kermesquaderni SCIENCE

AND CONSERVATION
FOR MUSEUM
COLLECTIONS
edited by
Bruno Fabbri

NARDINI EDITORE

kermesquaderni
Redazione
Federico Messina

ISSN 2036-1122
ISBN 978-88-404-4218-1

Stampa digitale
2012 – Nardini Editore

© 2012 Nardini Editore

www.nardinieditore.it

Questa pubblicazione è protetta dalle leggi sul copyright e pertanto ne è vietato qualsiasi uso improprio.
 SCIENCE AND CONSERVATION
FOR MUSEUM COLLECTIONS

INTRODUCTION

1 - PREVENTIVE CONSERVATION

1.1 Introduction

1.2 International standards and guidelines

1.3 Environment-material interaction

1.4 Microclimate and monitoring

1.5 Handling works of art

1.6 Exhibition criteria

1.7 MUSA project: intermuseum network for conservation of artistic

heritage

Bibliography

Acknowledgements

2 – STONE ARTEFACTS

2.1 What conservation means

2.2 Natural Stones

2.3 Artificial stones

2.4 Deterioration of the stone

2.5 Cleaning of stone artefacts

2.6 Consolidation and Protection

2.7 Case studies

Bibliography
3 – MOSAICS

3.1 Manufacturing techniques

3.2 History of the mosaic

3.3 Degradation of mosaic

3.4 Restoration of mosaics

3.5 Case study

Bibliography

4 – CERAMICS

4.1 Ceramic technology

4.2 Technological classification of ceramics

4.3 Alteration and degradation processes

4.4 Ceramic conservation and restoration

4.5 Case studies

4.6 Examples of restoration

Bibliography
Acknowledgements

5 – CLAY TABLETS

5.1 Defnition

5.2 Deterioration

5.3 Conservative intervention

5.4 Case study: Syrian tablets

Bibliography

Acknowledgements
6 – GLASS

6.1 General information

6.2 Processing techniques

6.3 Glass deterioration

6.4 Glass conservation and restoration

6.5 Case studies

Bibliography

Acknowledgements

7 – METALS
7.1 Origin of metals

7.2 Manufacturing techniques

7.3 Conservation state of metals

7.4 Conservative intervention for metals

7.5 Case studies: Recovery of metallic artefacts from terracotta containers

Bibliography

Acknowledgements

8 – GOLDSMITH ARTEFACTS

8.1 Goldsmith’s metals

8.2 Enamels

8.3 Precious stones

8.4 Alteration and degradation

8.5 Conservative intervention

8.6 Case studies

Bibliography
9 – WOOD ARTEFACTS

9.1 Characteristics of the wood

9.2 Working techniques

9.3 Degradation of wood

9.4 How to start restoring

9.5 Restoration of a small inlaid table

9.6 Restoration of a commemorating wooden tablet

9.7 The restoration of a seventeenth-century wooden crucifix

Bibliography

10 – ICONS

10.1 The construction of icons

10.2 Degradation and damages of icons

10.3 Methods of conservation and restoration of icons

10.4 Examples of conservative interventions

Bibliography

11 – TEXTILE FINDS

11.1 Morphology, characteristics and properties of textiles

11.2 Decay of textile fibres

11.3 Conservation treatments of archaeological textiles

11.4 Conservation practice: two case histories

Bibliography

Acknowledgements

12 – LEATHER AND ANIMAL SKIN OBJECTS

12.1 Introduction
 12.2 Skin

12.3 The tanning process

12.4 Parchment

12.5 Leather degradation

12.6 Conservative intervention

12.7 Examples of conservative interventions

Bibliography

13 – INORGANIC MATERIALS OF ORGANIC ORIGIN

13.1 The materials

13.2 The restoration operations

13.3 Cases of study

Bibliography

Acknowledgements

14 – ANALYTICAL TECHNIQUES
14.1 General information

14.2 Optical microscopy

14.3 Spectroscopic techniques

14.4 Radiochemical techniques

14.5 Chromatography

14.6 Electron microscopy

14.7 Thermal analyses

14.8 Open porosity measurements

14.9 Analysis of microbial colonization

Bibliography

Acknowledgements
 SCIENCE AND CONSERVATION ... – INTRODUCTION 8

INTRODUCTION

HOW THE IDEA OF A BOOK WAS BORNE

In the years 2009 and 2010 a long refreshing course for restorers of Syrian Directorate
General of Antiquities and Museums was made at the Archaeological Museum in
Damascus, Syria. The course was organized and managed by the Institute of Science and
Technology for Ceramics (ISTEC), of the Italian National Research Council (CNR), which
has its main office in Faenza, in collaboration with a private Syrian organization. In
particular, CNR-ISTEC planned and managed the scientific program, while the Syrian
organization mainly devoted itself to the logistic problems.
The course included the study and conservation of a lot of different types of artefacts and
materials, which were taken into account from a theoretical and practical point of view.
The lessons were partly given by personnel of CNR-ISTEC, but for the main part of the
lessons, especially the practical ones, it was necessary to contact external private
professionals. A total of more than twenty experts contributed to the success of the
enterprise.
During the progress of the course, a common difficulty emerged for all the teachers, due to
the lack of suitable didactic material for the trainees. In fact, there are many publications at
disposal, but they generally are mono-thematic and a high number of books would be
necessary in order to cover all the subjects of a course. In addition, it was not possible to
utilize books in Italian language, so that all the experts had to prepare the suitable
documentation for their own speciality in English language. Due to this situation, the idea
was borne that it would have been possible to re-arrange and complete this didactic
material and to realize a book, of which the main characteristics were to be poly-thematic,
in English language, and including about fifteen types of archaeological materials,
sometime very different from each other.

CONTENT OF THE BOOK

The book takes into consideration archaeological artefacts made out of the most common
materials, like stones (both natural and artificial), mosaics, ceramics, glass, metals, wood
and textiles. But all these important materials are accompanied by less diffuse artefacts and
materials, like clay tablets, goldsmith artefacts, icons, leather and skin objects, bones and

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ivory, coral and mother of pearl. Each type of artefact and/or material is treated from at
least four different points of view:
- Composition and processing technology
- Alteration and degradation causes and mechanisms
- Procedures for conservative intervention
- Case study and/or examples of conservative intervention
In this way, the importance of science and diagnostics in the field of conservation emerges,
together with the fact that it is not possible to avoid scientific analyses of the
archaeological finds if one wants to achieve the best results from the conservation point of
view. In addition, it becomes clear that the choice of the conservation systems is strictly
connected to the results of the analyses.
Of course, the high number of materials and the great difference between their
conservation problems would require a great number of pages, if they were treated in a
deep way. Such a solution is not practical and not economic, therefore the solution was to
treat all the subjects in a not deep, but complete and precise way. As a consequence, the
book is subdivided into chapters devoted to different materials, together with two
transversal chapters: one devoted to the general principles of the preventive conservation
and the other one to the description of the most useful analytical techniques. In such an
approach, special reference has been made to the needs of the museums and to the use of
non-invasive analytical techniques.

THE TARGET
Due to its general features, the book is mainly addressed to students and young restorers or
conservation scientists all around the world, because it is written in English. The book can
be usefully read by expert professionals too, because nobody knows everything and the
experts often need to learn something of the materials not included in their specific
knowledge. All these people will find the essential on a lot of different ancient materials,
all that is necessary to face up to specialist mono-thematic publications. After reading this
book, they will be able to choose what really they need in order to become experts of new
types of artefacts.
Of course, the reading of this book needs the knowledge of the English language, even
though at a not very high level, because the text is written in a simple English form. This
was possible because it mainly deals with technical items, which can be often described

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with simplicity. We hope that not too many errors will be discovered when reading the
book, while the reader will discover that the lecture is very easy.
The English language facilitates the reading by people of all the world, while the digital
publication of the book makes its diffusion cheaper, allowing to avoid its printing and the
subsequent distribution by mail.

THE AUTHORS
As said before, the training course for restorers in Syria had many experts, and each one of
them treated only the materials of his competence. Therefore, all these experts were
contacted in order to ask them to collaborate for realizing this book. In addition, some
other experts were contacted in order to increase the subjects treated in the book or to
substitute those already contacted experts who were not in condition to collaborate. At the
end, 24 experts accepted to contribute with their experience for obtaining a good product,
because these contributors have very different experiences and activities. As it is shown
from the list reported in the following Table 1, all they are Italian experts, or work in Italy,
so that the book can be seen as an example of the Italian vision in the conservation of
Cultural Heritage.
In order to appreciate the variety of the authors, it can be observed that many of them work
in public institutions, while others are professionals. Another difference comes from their
sector of activity: about half of them are restorers, while the others are conservation
scientists, and they have a particular experience in studying materials and degradation
processes. In this way, all the aspects of each material treated in the book could be faced.
As a consequence of what said above, each chapter of the book generally results from the
contribution of two or more collaborators, but each author remains the responsible of what
he wrote. For this reason, the contributions of the authors are detailed in the table
following (Table 2).

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Table 1 – List of the experts who collaborated to the realization of the book.
Surname and name Profession Institution Town E-mail address

ABU AYSHEH Moh’d Restorer/Archaeologist Freelance Brisighella (Ra) [email protected]

AGNINI Elena Restorer Freelance Faenza (Ra) [email protected]
AMATO Francesca Art historian Freelance Florence [email protected]
BANDINI Giovanna Art historian/Restorer Superintendence Rome [email protected]
BERTAZZOLI Enrico Restorer Freelance Faenza (Ra) [email protected]
CRISTOFERI Elena Restorer MIBAC-SBAP Ravenna [email protected]
DE NUNTIIS Paola Researcher CNR-ISAC Bologna [email protected]
FABBRI Bruno Researcher CNR-ISTEC Faenza (Ra) [email protected]
GUALTIERI Sabrina Researcher CNR-ISTEC Faenza (Ra) [email protected]
INGUI’ Giuseppe Restorer Freelance Marineo (Pa) [email protected]
MACCHIAROLA Michele Researcher CNR-ISTEC Faenza (Ra) [email protected]
MALTSEVA Daria Restorer/Art historian Freelance Pisa [email protected]
MAMBELLI Roberto Teacher Restoration school Ravenna [email protected]
MARIANI Bruna Restorer Freelance Lucca [email protected]
PALLA Franco Professor University Palermo [email protected]
PERON Francesco Restorer Freelance Milan [email protected]
PERTEGATO Francesco Restorer Freelance Ferrara [email protected]
PINTO FOLICALDI Barbara Restorer Vatican Museums Vatican State [email protected]
PONTI Fabio Architect Freelance Naples [email protected]
RUFFINI Andrea Researcher CNR-ISTEC Faenza (Ra) [email protected]
SCIANNA Nicolangelo Restorer Freelance Forlì [email protected]
SIANO Salvatore Researcher CNR-IFAC Florence [email protected]

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Table 2 – Detail of the contributions of each author to the book.

Author Paragraphs
CHAPTER 1 – PREVENTIVE CONSERVATION
DE NUNTIIS Paola 1.1.1 – 1.2 – 1.3 – 1.4.2 – 1.4.3 – 1.4.4 – 1.5 – 1.7
PALLA Franco 1.1.2 – 1.4.1
PONTI Fabio 1.6

CHAPTER 2 – STONE ARTEFACTS

ABU AYSHEH Moh’d 2.1 – 2.6 – 2.7.1
AMATO Francesca 2.2 – 2.3.1 – 2.3.2
MACCHIAROLA Michele 2.3.3 – 2.3.4 - 2.4 – 2.7.2
MAMBELLI Roberto 2.5

CHAPTER 3 – MOSAICS
ABU AYSHEH Moh’d 3.1 – 3.2 – 3.3 – 3.4 – 3.5.1
MACCHIAROLA Michele 3.5.2

CHAPTER 4 – CERAMICS
AGNINI Elena 4.4 – 4.6.2
BANDINI Giovanna 4.6.1
FABBRI Bruno 4.1 – 4.2 – 4.5.1 – 4.5.2
GUALTIERI Sabrina 4.3 – 4.5.1

CHAPTER 5 – CLAY TABLETS

BERTAZZOLI Enrico 5.2 – 5.3.1 – 5.3.2 – 5.3.3 – 5.3.4 – 5.3.5
FABBRI Bruno 5.1 – 5.3.3 – 5.3.4 - 5.4

CHAPTER 6 – GLASS
AGNINI Elena 6.4 – 6.5.1
AMATO Francesca 6.1 – 6.2
FABBRI Bruno 6.5.2
MACCHIAROLA Michele 6.3

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CHAPTER 7 – METALS
AMATO Francesca 7.1 – 7.2
FABBRI Bruno 7.5
MARIANI Bruna 7.3 – 7.4.1 – 7.4.2
PINTO FOLICALDI Barbara 7.4.3 – 7.4.4

CHAPTER 8 – GOLDSMITH ARTEFACTS

AMATO Francesca 8.2 – 8.3
PINTO FOLICALDI Barbara 8.1 – 8.4 – 8.5 – 8.6

CHAPTER 9 – WOOD ARTEFACTS

AMATO Francesca 9.1 – 9.2
INGUI’ Giuseppe 9.3 – 9.4 – 9.5 – 9.6
PERON Francesco 9.7

CHAPTER 10 – ICONS
MALTSEVA Daria 10.1 – 10.2 – 10.3 – 10.4

CHAPTER 11 – TEXTILE FINDS

PERTEGATO Francesco 11.1.1 – 11.1.2 – 11.1. 3 – 11.2 – 11.3 – 11.4
PALLA Franco 11.1.4

CHAPTER 12 – LEATHER AND ANIMAL SKIN OBJECTS

SCIANNA Nicolangelo 12.1 – 12.2 – 12.3 – 12.4 – 12.5 – 12.6 – 12.7

CHAPTER 13 – INORGANIC MATERIALS OF ORGANIC ORIGIN

CRISTOFERI Elena 13.1 – 13.2 – 13.3.1 – 13.3.2
FABBRI Bruno 13.3.3

CHAPTER 14 – ANALYTICAL TECHNIQUES

FABBRI Bruno 14.1.2 – 14.1.4 – 14.3.1 - 14.4.3
GUALTIERI Sabrina 14.2.3 – 14.8
MACCHIAROLA Michele 14.2.1 – 14.2.2 – 14.4.1 – 14.4.2 – 14.6 – 14.7
PALLA Franco 14.9
RUFFINI Andrea 14.1.1 – 14.1.3 – 14.3.2 – 14.3.3 – 14.3.4 – 14.3.5 –
14.3.6 – 14.5
SIANO Salvatore 14.3.7

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1 – PREVENTIVE CONSERVATION

1.1 Introduction

1.1.1 The concept of preventive conservation

Since the XIX century the problem of artwork conservation has become a growing concern
due to environmental changes (air pollution) and, in confined environments, increased
public enjoyment.
The following is a brief summary of the milestones in the development of the concept of
‘Preventive Conservation’:
• In the late 1960s, the science of conservation developed as a result of cultural
heritage damage caused by floods in Florence and Venice.
• In 1963, C. Brandi proposed a new concept of restoration as “ protection, hazard
removal and ensuring favourable conditions”.
• The Carta del Restauro di Venezia (1964) used terms such as: “systematic
maintenance, preservation of the environment, no separation of the monument from
its environment, restoration as a exceptional process”.
• In “Problems of Preservation” (1973), G. Urbani presented a “conservation
program” focused on the relationship between heritage and environment.
• In the 1970s, ICCROM (International Centre for the Study of the Preservation and
Restoration of Cultural Property) defined preventive conservation as a discipline
encompassing a series of actions required to enhance the conservation status of a
monument over time.
• In 1987, the ICR (Italian Central Institute for Restoration) proposed the “Carta del
Rischio” (Risk Charter) for cultural heritage, with the aim of creating a
computerized database to simplify access to information on risk factors for
materials, their conservation status, environmental aggression, and maintenance.
Artistic heritage is subject to deterioration: over time materials lose their ability to respond
and adapt to different environmental parameters (natural and man-made damage).
Degradation is a cumulative process evolving in a non-linear and irreversible fashion. The
same causes may produce different effects depending on the type of object and its previous

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history. The combination of different causes, past or present, produces synergistic effects.
The aging of materials is an irreversible process that cannot be stopped, but only
accelerated by inadequate conservation or neglect, or slowed by protecting objects or
artefacts from the harmful effects of degradation agents.
Prevention begins with knowledge. The aim of this chapter is to identify key simple steps
to achieve preventive conservation addressing the increasing difficulties of cultural
heritage due to changing environmental social and cultural conditions: prolonged exposure,
outdoor and indoor air pollution, transfers of works of art, and the presence of visitors. The
presence of large uncontrolled numbers of visitors in museums, for example, can
compromise works of art. Each visitor is a source of particles, gases and heat affecting the
museum environment. One visitor in an exhibition hall produces:
- 50-100 g/h of water vapour
- 100 watt/h of heat
- 50 ml/h of carbon dioxide
- 0.2 g/h dust (microorganism, fibres of clothing, organic fragments)
Numerous rules and recommendations are available, both at national and international
level, concerning the conservation of artworks. The literal application of recommendations
is not sufficient, and the procedures to follow must be assessed on a case-by-case basis. In
other words, the rules are “indications” that must be interpreted and modelled explicitly to
each object, knowing its nature and history.
The involvement of all museum staff and visitors will be essential to prolong the existence
of the works entrusted to them.

1.1.2 Preventive conservation program and climatic history

A crucial step in a cultural heritage preventive conservation program is to define the
compatibility of environmental parameters, particularly in the indoor environment. In order
to stop or to slow the rate of artefact deterioration, attention focuses on:
• research on the climatic history of the artefact related to the characteristics of materials,
and any previous restorations and the current state of conservation/degradation;
• analysis of specific environmental parameters which the works of art are exposed to;
• determining the capacity of the environment to preserve artefacts;
• identifying the parameters [temperature, relative humidity, radiation inside the visible

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range (UV/lumen ratio), air speed] that the corrective action must provide;
• analysing the particulate matter both on surfaces and in environmental aerosol.
In addition to planning a methodology for environmental analysis, useful to yield
information on hazardous conditions for the artefacts, it is important to pay attention to
possible health risks for operators and users of cultural assets stored in confined
environments.
To describe the climatic history of an artefact, it is particularly important to fillin a specific
detection form that accompanies the traditional cataloguing card. The detection form will
summarize:
• the last location of the object;
• notes on conservation;
• environmental measurements;
• monitoring equipment;
• deterioration events.

1.2 International standards and guidelines

There are many national and international documents (standards, guidelines, technical
standards and not) for the conservation of works of art. Some are general, others are rough
guidelines often written by people with no scientific training and background, so that their
application and compliance are complicated by myriad laws, standards, guidelines and
rules, which sometimes contradict each other. Some of those rules are derived from
regulations drawn up for other areas outside cultural heritage, and there are difficulties of
comprehension, both for user understanding and the basic knowledge of the subject matter.
Not just the literal application of the recommendations must be assessed, but also the
procedures to follow in each specific case. The responsibility then goes back into the hands
of those appointed by the museum curator or director to take concrete action to tackle the
various conservation issues, selecting and critically adapting the many documents currently
available.
The choice of procedures for preventive conservation requires multidisciplinary expertise
that is normally achieved by a university science degree at least. Currently, however, the
options for preventive conservation are the prerogative of staff in the cultural heritage

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sector primarily persons with training in art history. So training should be modified to
include a significant scientific component.
The head of the museum must be aware of the importance of preventive conservation, and
organize training and transfer of advanced concepts to the staff through basic training
courses. The implementation of conservation practices requires staff to be educated on the
principles and procedures in a understandable and simple way.
This section surveys the international law, standards and guidelines to show the different
approaches. Each country has special institutions working to define various standards
based on experience in the specific area. They are technical standards with protocols that
define goals, procedures and limits. In Italy the national body in charge of unifying all the
national standards is UNI.
Recently, an agreement between UNI and the Ministry of the Cultural Heritage has
allowed experts in the field of cultural heritage to draw up specific regulations for
operators in the sector. At supranational level the European agency is CEN (European
Committee for Standardization) and regulations are made at international level by ISO
(International Organization for Standardization). They are private organizations with
voluntary membership. Once published, standards are not free but must be purchased, also
through websites. There are numerous UNI regulations on cultural property, specifically
those dealing with environmental monitoring, measurement methods, analysis and
reference values for storage (Table 1.1).
In addition to the technical rules in Italy national legislation has established regional
standards for accessibility to the regional museum systems, and hence to financial
contributions (D.M. 10/05/2001, Atto di indirizzo sui criteri tecnico-scientifici e sugli
standard di funzionamento e sviluppo dei musei, Art. 150, comma 6, D.Lgs. n. 112 del
1998).
At European level a working group “Environment” of CEN/TC 346/WG4 has been set up.
At international level reference is made to ISO-11799 (2005) “Information and
documentation - document storage requirements for archive and library materials”.
Mention should also be made of the major international conservation institutions such as
UNESCO, ICOM, ICCROM, the Canadian Conservation Institute, the Institute for Cultural
Heritage of the Netherlands, the European Confederation of Conservators-Restorers’
Organizations, and others.

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Societies that do not work exclusively in the cultural heritage field, but must be taken into
consideration include: the American Society of Heating, Refrigerating and Air-
Conditioning Engineers (ASHRAE), and National Information Standards Organization
(NISO, USA). Particularly useful for our field are the ASHRAE Handbook: “Applications
2003 – Museum, Libraries and Archives”, ANSI/NISO Z39.79-2001 “Environmental
Conditions for Exhibiting Library and Archival Materials”, NISO TR01-1995
“Environmental Guidelines for the Storage of Paper”.

Table 1.1 - UNI standards dealing with environmental monitoring for Cultural Heritage.

UNI TITLE

Documentation - Climatic conditions for storage of graphic

UNI 10586, 1997
documents and characteristics of lodging

Works of art of historical importance - Ambient conditions for

UNI 10829, 1999
conservation - measurement and analysis

UNI 11131, 2005 Cultural Heritage - Field measurement of air humidity

Conservation of Cultural Property - Specifications for

UNI EN 15757, 2010
temperature and relative humidity to limit climate-induced
(ex UNI 10969, 2002)
mechanical damage in organic hygroscopic materials

UNI EN 15758, 2010 Conservation of Cultural Property - Procedures and instruments

(ex UNI 11120, 2004) for measuring temperatures of the air and the surfaces of objects

1.3 Environment-material interaction

1.3.1 Atmospheric aerosol

Air pollution is no longer confined to cultural heritage located outdoors, but also affects
the inside of buildings (up to 40% of the outdoor pollution) and, hence, museums, rooms
and showcases. Dust, vapors and gases produced by traffic and other human and natural
activities can be trapped inside, but also transformed. It is therefore necessary to
understand what happens in the atmosphere and what is meant by atmospheric aerosol. The
atmospheric dispersion of particles in liquid or solid phase is called atmospheric aerosol.
The fraction of airborne particles of biological origin (for instance fungal spores) is called
bio-aerosol.

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The atmosphere is constituted by 78.1% N2, 20.9% O2, 0.1% Ar; the remaining 0.1%
consists of several trace gases: CO2 (360 ppm), CH4 (2 ppm), N2O (0.3 ppm), CFC (3 ppb),
O3 (0.1 ppm), NO2 (0.1 ppm), C6H6 (0.1 ppb). The gas concentration can be expressed in
weight (mass/volume; µg/m3) or in volume (volume/volume; % = percentage; ppm = part
per million; ppb = part per billion).
The natural sources of aerosol include: land, ocean, volcanoes, fires, forests, pollen and
fungal spores. Those of human industry are transport, power plants, agriculture,
deforestation and waste. Gas (CO, SO2, NOx, VOC) and dust (heavy metal, carbon
compounds, polycyclic aromatic hydro-carbons) in the urban atmosphere cause serious
damage to health, but the threshold levels utilized for health are not applicable to cultural
heritage.
Pollutants can be divided into:
- primary, produced directly from the sources, like SO2 produced by thermal power
plants, industry and traffic, or NO2 produced by traffic, power stations, industry,
agriculture and livestock;
- secondary, formed in the atmosphere by reaction between primary pollutants and
the primary constituents of the atmosphere. We speak of homogeneous reactions
when reactions occur in the same gas phase, while heterogeneous reactions occur
between gas and liquid (water droplets) or gas and solid (solid particles).
Polluting particles differ in shape (fractals of diesel, spherical particles of carbon), size and
composition. Figure 1.1 shows the distribution of diameters idealized for different types of
aerosol. Urban aerosol is characterized by small size and high concentration, unlike bio-
aerosol that has a low concentration and large size.
Figure 1.2 shows the dynamic evolution of an airborne system. Rainout is the process that
determines the removal of particles from the atmosphere as they are absorbed by water
droplets or by ice. The process is called washout when the droplets fall to the ground
incorporating particles encountered on the way. The particles can act as condensation
nuclei around which droplets or ice crystals are formed. Coalescence is the process by
which droplets containing particles merge during contact or impact to form a single drop.
Wet deposition includes all the processes used to capture pollutants in the atmosphere due
to the interaction of water in liquid or solid phase (rainout and washout). Dry deposition
indicates the different processes (chemical, biological, physical) that occur in the absence

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of rainfall and are continuous in time. The result is the removal of pollutants from the
atmosphere, but this is followed by their enrichment in soil, water bodies and on cultural
heritage surfaces. The removal efficiency of aerosols from the atmosphere by rain depends
on their size and the distance between the clouds and the Earth’s surface. Fog droplets can
absorb six times more aerosol than that absorbed by drops of rain.

Figure 1.1 – Particle size distribution for different types of aerosol.

Figure 1.2 – Dynamic evolution of an airborne system.

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The factors determining the amount of dry deposition are turbulence, the chemical and
physical properties of pollutants and the nature of their surface. Figure 1.3 shows the
components that allow ideal particles to float in the air.
The transport of air masses is influenced by meteorological parameters: turbulence and
atmospheric stability, wind, horizontal movements, thermal gradient for vertical
movements.

Figure 1.3 – Forces acting on airborne particles.

The efficiency of capture of a surface is given by the number of particles captured from the
surface per unit of particles deposited, depending on the characteristics of the surface, i.e.
composition, porosity, if wet or dry, smooth or rough.

1.3.2 Biological aerosol as a potential deteriorating agent

Atmospheric aerosol is a suspension of liquid, solid or multiple-phases of condensed matter
ranging from 0.001 to 100 µm approximately in size. Particle size is determined by the
formation processes and subsequent atmospheric chemical and physical transformations.
On the basis of the size-distribution, aerosol is divided into three categories:
 nuclei mode (0.005 to 0.1 µm)
 accumulation mode (0.1–2 µm)
 coarse mode (>2 µm).

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Biological aerosol or bio-aerosol is a fraction of organic aerosol including dead or alive

(e.g., bacteria, fungi, virus) fragments, or by-products of biological activities, such as semi-
volatile organic compounds and micro-molecules. Bio-aerosol can range from: single
spores (fungus spores), pollen grains (emitted by in flowering vegetation), algae, bacteria,
virus, biological aggregates, materials produced by biological activity or attached to non-
biological particles. Aerosol of biological origin (cells, fractions of cell, organic matter of
different origin: animal, plant and microbial) forms a significant portion of atmospheric
aerosol, sometimes reaching close to 50% of all aerosol particles.
Biological materials account for 25%-40% in weight of airborne particulate. Bio-aerosol is
also called Primary Biological Aerosol Particles (PBAP). PBAP-PM10 mass is dominated
by fungal spores, plant debris is also important. The contribution of PBAP is very small in
winter, but may reach 5% of PM10 or more when vegetation is active. The annual emission
factor based on total vegetation land area is 24 kg/km². The annual European emissions are
more than 200,000 tons.
Bio-deterioration can be defined as the irreversible loss of value and/or information of
works of art as a consequence of attack by living organisms. The action of the airborne
microorganisms produces not only an anti-aesthetic effect but also the progressive loss or
transformation of the physical and chemical properties of the materials.
Successful colonization by any biological community on organic and inorganic materials
depends on the composition of the material, its state of conservation and the existence of
favourable environmental and climatic conditions (temperature, humidity, natural and
artificial radiation, ventilation, and inorganic and organic pollutants). The relative intensity
of the biological attack on different materials is shown in Table 1.2.
The sources of bioaerosol are outdoor and indoor. Outdoor sources are mainly Primary
Biological Aerosol (PBA) from natural sources present in the environment and secondly
anthropogenic bioaerosol. Indoor sources include PBA incoming from outdoors and
Secondary Biological Aerosol generated from colonies growing on materials and surfaces
present in the indoor environment. A large quantity of dust (organic and inorganic particles
and fibres) is transported by visitors and staff and deposited in the indoor environment.
Biological particles are mainly transported through the air circulation and secondly by
contact between objects. Many materials can act as good substrate for the growth of
colonies when water is available.

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Table 1.2 – Intensity of the biological attack on different materials.

Auto- Hetero-trophic
Algae
Micro-organism trophic Bacteria Fungi Lichens Mosses
(Cyanobacteria)
Bacteria (Actinomycetes)
Organic Material
Wood − ** *** + + −
Paper − ** *** − − −
Textiles − * **/*** − − −
Parchment − * **/*** − − −
Painting − * **/*** − − −
Synthetic material − * ** − − −

Inorganic Material
Stone ** * * *** *** **/***
Mural painting * * ** *** * +
Glass * − − * * −
Metal * − − * + −
Legend: − = absent; + = rare; * = occasional; ** = common; *** = frequent.

Re-suspension of the viable biological particles in the indoor environment plays an

important role for the rapid spread of pathogens. The biological particles are deposited onto
surfaces by some important physical processes:
- gravitational deposition,
- impact due to air movements,
- thermophoresis (gradient of temperature from air and surface),
- electrophoresis (electric particle charge in relation to the surface electric charge).
The conditions of deposition are strictly related to the particle features and to the kind of
physical process. Gravitational deposition mostly involves large particles whereas
thermophoretic deposition mostly involves small particles.
Several methods have been developed to analyze and measure airborne biological particles
to identify them by their morphological, physical and chemical characteristics.
Many devices are in use for sampling airborne particles. Each is best suited for a limited
particle size range and all operate on a few basic principles. Bioaerosol samplers are often
similar to the instruments used for the collection of other kinds of airborne particles. The
treatments and assay methods differ and require special procedures depending on whether
the material is viable or non-viable. No devices are currently available for automatic

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measurement of bioaerosol. Figure 1.4 shows the different devices for sampling airborne
particles:
- gravitational settling (non volumetric): a simple Petri dish with culture media
(Figure 1.4, left);
- suction: a volumetric sampler for morphological identification of viable and non-
viable particles (Figure 1.4, centre);
- sampler for cultural identification of viable particles (Figure 1.4, right).

Figure 1.4 – Different devices for sampling airborne particles: gravitational settling (left),
Hirst sampler for morphological identification of particles (centre), SAS (Surface Air
System) sampler for cultural identification of viable particles.

Airborne micro-organisms are always present in the air of open and closed spaces.
Continuous monitoring of humidity and air temperature is important to prevent biological
attacks. Equal importance is given to the calculation of the dew-point temperature that will
disclose the presence of water on surfaces, structures and objects due to condensation of
water vapour. Figure 1.5 shows some examples of biodeterioration of cultural heritage:
details of damage and biodeteriogens as colonies and magnified by SEM or OM
microscopy.

1.3.3 The pollution factor

The deterioration of stone has increased dramatically in the urban environment during the
last century. The degradation of materials depends on different parameters like relative
humidity, temperature, radiation, mechanical stress and pollution. The effects of multi-
pollutants on construction materials are studied using three different approaches:
- analysis of damage on monuments,

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- simulation in a microclimatic room,

- exhibitions in the field on different materials in different places.

Deuteromycete: Aspergillus sp.

Deuteromycete: Cladosporium sp.

Alternaria Aspergillus-Penicillium Cladosporium

Epicoccum

Figure 1.5 – Images of fungi that cause major damage to cultural heritage: colonies on Petri
dish and samples observed by OM (colour) and SEM (black and white).

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The types of degradation are recognizable as white areas and black areas on marble and
limestone monuments (Figure 1.6). The white areas are characterized by washout, while
the black areas are due to formation of an alteration crust. The white areas are located on
surfaces wetted by rainwater and subjected to intense runoff. The black areas are located
on surfaces wetted by rainwater, but protected from runoff. There are also grey areas that
are surfaces completely protected from rainwater.

Figure 1.6 – Degradation on marble, white areas and black areas

The stone surface in the white area is eroded and thinned by the mechanical action of rain
water. In addition the stone dissolves due to acid attack. In polluted areas gaseous
pollutants, mainly SO2 and NOx, are deposited slowly in the absence of precipitation (dry
deposition, see paragraph 1.3.1). Rain normally has a cleaning effect due to carbonic acid
dissolved in the rain. The wet deposition on stone surfaces is related to the phenomenon of
acid rain.
The black areas are the areas where the products of interaction between atmospheric
deposition and materials accumulate (black crusts), by studying the layers of alteration the
alteration mechanisms that occur on monuments as a result of multi-pollutant areas can be
identified. SO2 is oxidised to SO3 and H2SO4 originates during raining that determines the
dissolution of CaCO3 from the stone material and the formation of gypsum (70% vs 1%
contained in the white areas). The process of gypsum (CaSO4. 2H2O) formation is called
sulphatation. Figure 1.7 shows optical and electron microscopy images of black areas.

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Figure 1.7 – Magnification of the black area at optical (left)

and scanning electron (right) microscope.

The lamellar crystals of gypsum give a greater porosity to the new surface. Carbon
particles are also trapped between the slats of gypsum crystals and give the crust a typical
black colour. In hydraulic mortars gypsum reacts with the hydrate silicates and determines
the formation of Thaumasite and Ettringite, whose crystalline structure favours swelling
and fracturing of the original material resulting in severe damage.
Very often some of the effects of degradation are misinterpreted; for example the black
patinas of biological origin are mistaken for black crusts (e.g. fungal melanin, lichens,
algae, cyanobacteria). Black biological patinas can be found in places with frequent
presence of run-off, where the formation of black crusts is impossible, and in places where
the drying and aging of the cyanobacteria that colonize the rocks lead to a darkening of the
surface, mainly due to chemical changes (e.g. chlorophhyll). The interaction between
anthropogenic and biogenic deposits further complicates the situation of materials.
Bioaerosol is often sticky, so the following deposit is easily retained. In highly polluted
areas it may be difficult to detect microbial infections, even if present.

1.3.4 Degradation factors of artwork materials

Two degradation factors affect works of art. The first regards the type of materials, the
second the damage: physical, chemical and biological damage.
Materials can be divided into two main categories:
a) inorganic materials, such as metals, alloys, ceramics, glass, stone and mortar,
b) organic materials, such as paper, wood, leather, rubber, plastics, paintings and
textiles.

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Inorganic materials
Inorganic materials are the part of heritage generally least susceptible to deterioration in
museums, archives and historic buildings, but also subjected to slow but inexorable aging.
The main environmental hazards are:
- climate: inadequate relative humidity, temperature and light,
- pollution by gas and dust: deposition of aerosols on surfaces from internal and
external sources, corrosion, formation of crystalline structures on the surface,
oxidation and carbonation,
- microbiology: formation of bacterial and algal coatings under conditions of high
water availability and light surfaces.
Inorganic materials are theoretically more tolerant than organic substances to the limit
values of relative humidity, light and temperature but their relative waterproofing, with the
exception of stone, marble and plaster, causes the formation of water condensation (dew)
on the surface of materials. Water condensation and dust deposited on the surface can lead
to aggressive chemical reactions with dissolution of the substrate. In these cases frequent
dusting and climate control are recommended.
Outdoor urban pollution (particles and gases) is particularly aggressive against these
materials due to the chemical reactions that frequently generate crystalline products that
can grow within the microscopic gaps producing fissures, fractures and detachments.
Organic materials
Organic materials constitute a substantial part of the cultural property in museums,
archives and historical buildings. They are the materials most vulnerable to deterioration
and show the following types of damage:
– Paintings: discolouration, cracks, soiling,
– Textiles: reduced strength, colour change and fading,
– Paper: embrittlement, discolouration and stains,
– Wood: breakage, decomposition and sputtering surface,
– Leather: weakening and surface sputtering,
– Rubber and polymers: embrittlement and discolouration.
Environmental hazards
The main environmental hazards are:
- Climate: relative humidity, temperature and light are all important factors that must be

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monitored in museums. The restriction of fluctuations in relative humidity is important

for the preventive conservation of organic materials. Light and ultraviolet radiation
should be monitored for photosensitive materials.
- Pollution by gas and dust: deposition aerosols on surfaces from internal and external
sources. Aerosol lifted by visitors and floor-cleaning machines, corrosion, formation of
patinas that reduce readability, oxidation, suitable substrate development of different
biological forms. Monitoring results show that the indoor and outdoor museum
pollutant concentrations depend on the type of building and its use.
- Microbiology: fungal attacks on objects displayed in glass cases or placed in storage with
high humidity are very frequent in museums. The presence of bacteria may be an
additional risk.
Control of environmental conditions
It is important to control environmental conditions to avoid the attack of deposited
bioaerosol. However, attention should be paid to avoid overdrying materials, using water
as a structural medium like wet sand sculpture (i.e. paper). Experience suggests that RH
should never fall below 40% or exceed 65%. Rapid excursions (within 30 minutes) of
relative humidity have little impact on wood and books, but prints are more sensitive if not
adequately protected.
More dangerous are cyclical RH fluctuations in the 24 hours that allow the wood to enter
into equilibrium with the environment resulting in shrinkage and swelling, which may
detach the painted surface.
The physical deterioration of artwork is due to radical changes in materials through the
action of hygrothermal cycles, while chemical deterioration occurs mainly on the surface.
These problems are added to biological deterioration that is caused by all the physical and
chemical processes induced by the growth of microorganisms deposited on the surfaces.
Relative humidity influences:
- size and shape (RH high = bulge = biodeterioration; RH low = shrinkage = cracks
and breaks)
- the speed of deteriogenic chemical reactions
- biodeterioration sources.
Air Pollution can:
- cause the loss of surface material

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- encourage the development of microorganisms

- leave traces of pollutants on surfaces
- change the appearance of objects
Temperature can:
- promote chemical reactions
- accelerate the physical processes
- encourage the expansion of materials
- alter colour pigments
- increase the surface temperature of objects
Vibration and noise can cause:
- damage or destruction of crystals and unstable glass
- detachment of unstable parts

1.4 Microclimate and monitoring

1.4.1 Explorative and continuous monitoring

The correct preservation of historical and artistic heritage in the site where the works of art
are conserved requires monitoring of potential interactions between the environment and
works of art. For this purpose a continuously working external meteorological unit should
be installed for the complete monitoring of climatic parameters such as temperature,
humidity, wind speed and direction, and barometric pressure.
Generally, the measurement in an indoor environment can be divided into two steps:
- Explorative monitoring: First a short-term measurement is made using portable
equipment to identify the area/s for detecting the environmental parameters and eventually
for microbiological sampling. At the same time a technical-information form is filled in for
each environment (including information acquired during the documentation action).
- Continuous monitoring: After having identified the location to monitor environmental
parameters, continuous monitoring can be performed by instruments, establishing the most
appropriate schedule.
Both Explorative and Continuous monitoring can survey the temperature and relative
humidity, lighting, amount of ultraviolet radiation and surface temperature in relation to
the timing and modality of access to cultural assets. Long-term measurements can be

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carried out by sensors, connected to the equipment by cable or by a cordless system.

Considering the complexity of the process involved in artwork deterioration, a range of
parameter variations that could be “acceptable”, and a narrower range that could be
“optimal” can be devised. Finally, internal parameters can be recorded by a wireless
network for data storage (using a local computer or a remote processing centre) and must
be compared to the external climatic parameters recorded simultaneously. The results
allow proper conservation to be planned for cultural heritage preserved in that
environment.

1.4.2 Analyzed parameters and analysis systems

The indoor environment can be characterized by physical parameters. These parameters are
measured using specific equipment and standard procedures. The main physical parameters
to be measured in a museum are: temperature, relative humidity, ventilation and radiation
(natural or artificial). Secondly, vibration, dust and airborne particles must be monitored.
Temperature
Depends on the object under consideration and not its history, and varies with the
temperature of adjacent structures (thermal equilibrium), measured with different types of
thermometer and expressed in Celsius degrees (°C). The different operating principles of
thermometers are: liquid (mercury and alcohol), gas, metal deformation
(hygrothermograph), electrical resistance (Pt100), thermocouple and infrared. Related to
the concept of temperature is that of heat. Heat flow is the quantity of heat, i.e. the amount
of energy entering or leaving the body in a process of heat exchange. Heat flow is achieved
through conduction, convection and radiation. Items at different temperatures, will slowly
tend to reach equilibrium. The thermal insulation of buildings helps to limit heat exchange
during winter to the outside and during summer internally.
Relative humidity
Relative humidity expresses the ratio between the amount of water vapour in the air and the
amount that, at the same temperature, would be needed as steam condenses into water
droplets. Humidity is the parameter that most affects biodeterioration, which generally
occurs when values exceed 65%. Low relative humidity must be considered equally as
dangerous as excessive moisture (water becomes part of the structure of the material,
cellulose fibres in paper or wood). If dehydrated, these materials lose their elasticity.

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Relative humidity is not evenly distributed in an environment, but is related to the

distribution of temperature. Where significant differences in temperature occur, such as
close to walls, doors, windows and heat sources, there will be marked variations of relative
humidity.
Humidity and temperature measurements
Both humidity and temperature can be measured by several types of instruments based on
different operating principles:
- hair hygrometer (RH) Lambrecht,
- mechanical thermohygrometer,
- pocket digital thermometer,
- thermohygrometer with mini-datalogger (2 sensors T - RH, 32.000 store data,
Tinytag),
- Assman psychrometer.
The control of relative humidity values is a high priority activity compared to controlling
lighting and temperature. Continuous measurement data are essential to the diagnosis. The
choice of instrumentation and management measures is extremely important.
Illumination
Illumination is the amount of light radiation striking the surface. All exhibition premises
are equipped with natural or artificial lighting. Some light sources are harmful to
conservation of works of art. Radiation useful for viewing the work is visible, but the other
components of both natural and artificial light are harmful because they are still energetic.
The damage caused by light includes:
- colour changes and fading
- cracking
- failure of media
- yellowing
In addition, warm air forms movements involving dust and biological particles, which are
then deposited on a cool surface. Illuminance, radiance, luminance, ultraviolet radiation
must be measured. It is very important to pay attention to where the sensor is positioned,
the action of sunlight entering through windows and artificial lighting. The intensity of
light should be monitored and measured before the final placement of objects. Often
aesthetic criteria of construction and engineering take precedence over those of

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conservation. Ignition systems to environmental presence can be useful to extend the life of
an object and save energy and money when the number of visitors is low. In choosing
artificial lighting the “colour temperature” and “tone” characterizing each type of lamp
must be taken into account. The choice of light source should consider both the amount of
light reaching the object and the quality of light (emission spectrum).The choice of the
lamp should be evaluated taking into account the characteristics given in the product data
sheets. The following types of lamps are available:
- incandescent lamps
- halogen light bulbs
- discharge lamps
- fluorescent
- LED (light emitting diode)
- fibre optics.
Ventilation
Ventilation in the exhibition halls is essential to have a uniform distribution of temperature
and humidity but should not be excessive (not exceeding 0.1 meters per second) and
should be made with filtered air to limit the movement and deposition of dust. The same
treatment should be reserved for store rooms, often underestimated. Precision instruments
such as the hot wire anemometer should be used to measure air flow.
Dew point
The dew point or dew temperature is the temperature to which air should be warmed to
condense it into dew. The dew point temperature is not a parameter measured directly but
calculated by measuring the air temperature and relative humidity. The measurement of
dew point serves to highlight condensation on surfaces.
Monitoring systems
Monitoring systems with sensors linked by radio to a data-logger are currently available to
manage the timing of measurements, data storage and transmission of data to a local
computer or a remote processing center (Figure 1.8). They are advantageous because:
- installing the system is less costly because it is cable-free
- the choice of sensor location is less constrained and sensors can be repositioned in case of
a change in exhibition environments
- distance network transmission is rapidly expanding.

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Figure 1.8 – Monitoring instruments: thermohygrometers (left)

and photo radiometers (right).

1.4.3 Macroenvironments
Macroenvironments are understood as the museum itself and its rooms. The buildings that
house museums and archives can be divided into three categories:
- Buildings constructed ad hoc with air conditioning systems regulating temperature,
relative humidity and ventilation. If well managed, the risk of physical chemical and
biological damage processes is very small. Possible problems derive from the incorrect
detection of climate parameters due to a plant design not suitable for museums.
- Buildings constructed ad hoc with no air conditioning, built in different eras and with
different criteria (historic buildings, museums dating back to the late 1880s) with various
microclimatic situations. Possible problems are that temperature can be adjusted, while
humidity is adjusted only in dehumidification.
- Buildings or premises used for other purposes (convents, schools, housing, etc.) and later
adapted. Possible problems include poor or inadequate insulation, and management of
heating shared with other institutions with different needs.
Often, due to lack of space, highly diverse and less appropriate environments (humidity, no
ventilation, poorly lit, etc.) are used with different climatic conditions, which often
facilitate the deterioration of materials.
The same building may have different environmental situations depending on:
- location of the rooms (basement, intermediate floors, roofs) and their exposure,
- presence or absence of windows and skylights,
- intended use of the rooms (exhibition rooms, lockers, study rooms, offices etc.).
- type of heating, cooling or air conditioning, type of lighting,

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- presence and activities of staff and visitors.

In buildings without air conditioning, into which unfiltered air is blown, two other factors
have an impact on the retention of materials: chemical and biological pollution which
differ in relation to the location of the museum. Industrialization and urbanization of the
area in which the museum is located and its proximity to the sea or parks determine the
prevalence of certain chemical or biological compounds.
Degradation processes are also supported by:
- significant fluctuations of temperature and moisture due to incorrect adjustment,
- the quantity of material present in the rooms,
- the presence of capillary rise of water resulting in high relative humidity,
- poor ventilation of the rooms, promoting condensation,
- interruption of use of air drying, forced air heating or air conditioning systems,
- exceptional events (floods, water leaks, broken plumbing, heating, sanitation ...)
The objects in museums experience vibrations whose frequency can damage their
structure, especially if large and placed at high levels in urban buildings close to roads with
heavy traffic such as buses, or railways and airports. The remedy is to design shock
absorber supports. Noise and vibration in museums can cause damage or destruction of
crystals or glass in unstable conditions, the detachment of unstable parts and disturb
visitors.
Store rooms are very important places in museums because many objects remain there for
a long time waiting to be exhibited or lent to other museums. Different types of material
require different levels of temperature and relative humidity conditions that entail the
preparation of different storage environments. Frequent inspections are necessary to
control the environment and the conditions of objects. Continuous microclimatic
monitoring is therefore important to filter the incoming air, schedule regular cleaning,
check that there is adequate air circulation and there are no damp patches on walls, ceilings
or floors, check if windows are covered and if the works in storage are protected from dust,
perform periodic aerobiological sampling, especially if the rooms are humid (RH> 65%),
and monitor the presence of insects.
Light in store rooms should be managed as follows:
 artificial light and natural light will not enter,
 the lighting will be used only when necessary,

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 the lighting level must be high when it is necessary to examine the objects,
 a level of 500 to 600 lux is required to see the details of the surfaces, but only for a
few minutes.

1.4.4 Microenvironments
Microenvironments are understood as showcases, showcases and climaboxes (Figure 1.9).
Objects in museums are protected, especially from dust, by containers called showcases,
display cases and climaboxes. Showcases are equipped with doors that open normally,
sometimes dust-tight but not air-tight. Caskets are inspected only by designated staff.
Climaboxes are containers built to protect a single artwork by adjusting the internal RH.

Figure 1.9 – Microenvironments: showcases, caskets and climaboxes.

Temperature, relative humidity, lighting, air pollutants and parasites should be tested even
in small containers using passive systems. Relative humidity can be controlled and
measured inside the containers using desiccant substances such as silica gels without cobalt

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salts or PROSORB and ART SORB, respectively, which are used for relative humidity
from 40% to 60% and 60% to 80%. The relative humidity can also be controlled using
organic materials like cotton.
Temperature, relative humidity, illuminance and air pollutants should be tested in the box
using electronic instrumentation allowing the insertion of sensors inside the containers
without having to make changes to the structures, or humidity indicator cards that can be
inserted in the glass case and show the maximum value of moisture reached, or small
instruments with digital display to put inside windows.
Light is controlled by measuring illuminance (lux) and UV (µwatt/m2). It is better to have
external lights for the container to avoid warming, changes in RH at the time of start-up
and shut down, and trapping insects attracted by light inside the containers.
Pollutants can be controlled by minimizing the entry of air using building materials in the
container with low or zero emission of pollutants, inserting substances to purify the air
inside the window.
If the container is well sealed, insects will not enter, but in any case it will be important to
lay traps for insects and put filters in the openings.
If necessary, showcases, display cases and climaboxes may be equipped with active
systems for humidity control and internal pressure, but these are recommended for use only
when absolutely necessary due to their high purchase and maintenance costs.
The choice of suitable materials ensures better preservation of objects placed inside
windows and showcases. The design of the windows should be taken as a priority
consideration for a better visibility and enjoyment of the exhibits, also from an academic
point of view. Placing artwork in a showcase with the wrong microclimate means
accelerating the processes of deterioration and aging.

1.5 Handling works of art

Handling works of art for exhibitions is the most risky type of event to the integrity of the
transferred works.
For this reason many institutions lend their paintings only if they receive a declaration of

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conformity on the environmental conditions of the rooms used for temporary exhibitions.
Based on the microclimatic monitoring conducted in the rooms, the declaration ensures
that the conditions required by the lender are respected (in percentage terms) and therefore
in compliance with requests. Figure 1.10 shows an example of a declaration of conformity
processed by ISAC-CNR before a recent temporary exhibition.
Damage can be provoked by unsuitable micro-climatic conditions, manipulation, and
mechanical stresses (for instance landing aircraft). The first and most important problem is
to maintain the micro-climatic conditions of the original location. Operationally, we can
split the transfer into the following steps: preparation work and transport, stay at the
temporary exhibition, preparation for return and transport, and relocation in the place of
origin.

Figure 1.10 – Declaration of conformity, example of a document utilized by ISAC-CNR

for a recent exhibition.

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Is important to ensure constant temperature and humidity conditions throughout all phases
of the transfer, making sure that:
- all packaging operations take place in the same environment in which the artwork
is kept,
- boxes and packaging material have been acclimatized in the same environment for
at least a day,
- filling materials sensitive to atmospheric moisture, such as paper, cardboard and
rags are used. A new generation of desiccant materials (such PROSorb) is available
able to keep a certain percentage of relative humidity within certain limits of
volume and characteristics of cases and time spent,
- the conditions within the package are recorded throughout the duration of transport,
inserting, in agreement with the carrier, a micro datalogger capable of continuously
monitoring temperature and humidity inside the case (Figure 1.11).

Figure 1.11 – Instruments for measuring temperature and humidity inside the storage
case during transportation: Tinytag and Black Box.

Acclimatization phase
Once the objects reach their destination, it is essential for the boxes to be placed promptly
in a room with characteristics similar to those of local shows, to mitigate the differences in
temperature and humidity between the external environment and the interior of the
packaging. Then objects can be unpackaged, the datalogger retrieved and the data
downloaded, and the objects arranged in their final place of exhibition.

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During the construction of an exhibition, pictures and tables should not be placed in contact
with the wall (an air gap of 3 cm for small items and 5 cm for large objects must be left), or
in the vicinity of jets of air circulation. At least one measurement of illumination should be
made on the objects, and solar radiation prevented from reaching the artwork during the
exhibition. Finally continuous monitoring of temperature and relative humidity is essential
to ensure the providers of compliance with the materials during the exhibition.
Documentation
Before and after the exhibition forms and reports should be prepared to be sent to supplier
museums. The documentation before the exhibition should collect information essential to
the safe movement of works and for the organization that takes care of the transfer. The
cards must contain information on the host structure and the state of conservation of the
material provided.
The documentation after the exhibition should give provider museums information on
repackaging and acclimatization procedures of the works after the return, and provide a
declaration of compliance stating the artworks was conserved within the required limits.
Despite the large amount of national and international attention to the issue of preventive
conservation, we are still far from having reached standard storage conditions to be
observed for many types of cultural heritage. It is not uncommon to receive requests for
compliance with limits for conservation of material that differ from those reported by the
rules and recommendations available today. Table 1.3 lists several international
recommendations for painted panels.

1.6 Exhibition criteria

In working out some guidelines in order to realize a museum better, one becomes quickly
aware of how wide the existing material on the subject and how great the risk of making
repetitive any form of method suggested and examined. But simply putting ourselves in the
shoes of the visitor and imagining how we would like space and exhibition were organized
in a museum, everything suddenly becomes clearer and we have no more doubts about
what we would find in order to understand at the highest level the value of what we visit
and enjoy the emotions that it sends.

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Table 1.3 – Recommendations for painted panels.

MUSEUM T °C RH % MUSEUM T °C RH %
Great Britain < 25 45 - 65 France 16 - 20 50 - 60
Great Britain 17 - 23 45 - 65 Austria 20 - 22 50 ?
Great Britain 18 - 24 40 - 60 Spain 20 - 24 50 - 60
The
USA 20 - 21 45 - 55 15 - 25 53 - 57 ?
Netherlands
USA 19 - 25 45 - 55 Vatican 18 - 20 55 - 60
USA 16 - 26 45 - 60 Milan 19 - 20 50 - 60
USA < 25 45 - 55 Modena 15 - 20 50 - 60
USA 19 - 23 45 - 55 Parma 15 - 20 50 - 60
Canada 18 - 22 45 - 55 Pesaro 16 - 22 50 - 60
Ireland 18 - 22 50 - 60 Florence 15 - 20 50 - 60
France < 22 45 - 55 Naples 19 - 24 50 - 60
UNI (IT) 10829 19 - 24 50 - 60

All this must always happen in the greatest possible respect to the protection and
conservation of exhibits. The ever-present risk in who designs is that, being a creative
person, he tends to indulge in forms of leadership that threaten to steal the scene to the
actors, which in this case are the exhibits. Therefore the goal to be centered is the creation
of an environment that enhances and facilitates the understanding of what is on display,
and does not detract attention or compete with the artwork that is exhibited.
The most important elements that make work at the best the “machine” of the exhibition,
when used carefully, and that ensure a good level of protection and preservation of the
artworks, are:
- the quality of the light and how it is used; the light also affects the microclimate of the
environment;
- the materials, including their colours, that make up the container which houses artefacts,
as well as its structure;
- the space with its implications made of sizes and distances;
- the meaning of the route, both physical and mental, that is not only a space to walk in a
while, but it will be the place to find the events of history represented in the objects;

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- the chronological route, as a tape that accompanies the succession of objects, and the
mutual influence of the artworks;
- the technology that currently offers opportunities for consultation and interaction until
recently unimaginable.

1.6.1 The light

The light allows us to see the objects, but can also damage and alter the microclimate of
the environment and its choice is extremely delicate because it involves not only the
quality of exposure and the creativity of the designer, but also affects the same
preservation of works. That’s just the first dilemma to face: natural or artificial light?
Usually people who visit an exhibition tend to prefer natural light, but natural light is not
stable, because it depends on: prevailing weather conditions, season, time of day when the
visit takes place, kind of opening to the outside of the space that hosts the artworks. So,
according to these variables natural light requires a series of measures for diminishing or
increasing it. These actions have costs that far outweigh the savings derived from the non-
use of artificial light.
The artificial light, conversely, can be configured by programming its intensity as a
function of the sensitivity of the object exposed, so avoiding any effects that might damage
it. In addition, it can be modulated so as to amplify or mitigate the contrast between
artwork and background, depending on whether it deals with painting rather than sculpture,
black and white photo rather than colour photo, modern art with sharp colour tones rather
than classical art with soft and delicate effects.
As light affects the fruition quality of the artwork is obvious, just think of distracting
reflections from light created when investing pictures and paintings (especially if protected
by glass) and how much the direct light from a spotlight wisely addressed may enhance the
three-dimensional shapes of a statue or a sculpture in general. Although it is always risky
to generalize, in most cases we can say that, in the presence exhibitions of paints is
preferable to use diffuse light coming from above, while in the presence of marble statues
and groups, a well-designed use of direct light can help to better enjoy the plasticity of
forms. Do not forget that, illuminating an object rather than another, we influence the
visitor’s attention and, in a sense, we accompany him on a precise chronological or logical
sequence that can be variously motivated. For example, if we want that a sculpture is

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observed before another one, it will be sufficient to put an ignition device that
automatically sends a beam of light on it first and then on the next.
The use of ignition devices using photoelectric cells, which are activated when the visitors
are arriving, allows to highlight the object so avoiding being distracted by other nearby
objects, and addressing the focus where we want and when we want it to happen, with a
substantial energy saving. In addition, the lighting of a lamp placed for the benefit of a
object, which applies only to the passage of the visitor and turns off on in absence of
visitors, greatly limits the warming of the room, reducing the risk of damage to the
exhibits.
The use of fibre optics, as well as that of the LED light sources, currently provides us with
great opportunities and variety of action, without any infrared and ultraviolet emissions
that are filtered upstream, and without generation of heat.
In conclusion we can say that the artificial light, with its greater flexibility, can be better
controlled than the natural one, both for the prevention of the risk of damage and alteration
of the artworks and for the role of emphasis and guidance that can play within the space of
a museum.

1.6.2 Materials and colours

Material and colours are strongly linked to each other, and together inextricably interact
with light: let us think how much the visual and emotional effect of a monument or an
archaeological site changes if lit by yellow sodium lamps rather that white neon lights. To
fully evaluate the importance of lighting in relation to colour, just remember that in
absence of light all colours are equal, i.e. blacks.
The materials, intended as constructive elements, can be used and treated in endless ways
that can alter their appearance. If we think of a few of them (glass, aluminum, steel,
copper, white plaster, brick, concrete, wood, marble, ceramic tiles), immediately for each
of them we imagine a different colour or we have a different and exclusive feeling. We
could go on much longer, but that is enough to make us immediately aware that imagining
a single object on display on a background made from time to time with one of the
materials listed, we shall experience a different feeling for each scenario imagined.
The same goes for colours: white, ivory, cream, pink, orange, yellow, light and dark green,
light and dark blue, brown, dark red, light gray, dark gray, black. Every background

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combined with a same object increases or decreases its apparent brightness, making us a
different effect, forcing us to focus our attention in a different way; it relaxes us or excites
us, it saddens us or exalts us. This interplay of material and colour is a crucial point for the
design of interior exhibition space, and should be used in a wise way to enhance the story
that we want to tell with our exposure and for the emotional journey in which we want to
lead the visitors.
Intense colours, used as a background, will impose their own personality to the whole
environment, and thus risk to attract attention and visual energy, while a soft background
with an average capacity of reflectance (where the white colour has the highest reflectance
factor and black the lowest) will be more restful to the eye of the visitor and will be less
protagonist and less competitive in comparison with the exhibited objects.
Please note that in dealing with the component “building material” of the building
museum, we limit ourselves to his perception experienced from “within”, that is as it
appears from the internal space and how it interacts with the artworks exhibited in it. It is
obvious that the building seen from the outside, with its constructive materials, enters a
totally different dynamics, that is the report with the outer space represented from the city
with its many components and conditionings, something that would take us off topic and
would require an analysis of different kind. The close connection between the building
material with its own capacity to reflect and return in different way the amount of light
received, and the effect this has on the artwork exhibited and the human eye, provides
another starting point in designing museum spaces.
The halls and paths that are home to the artworks will be treated differently from the
transition and disengagement spaces between an exhibition area and the other, allowing the
visitor to reduce “the stress of visiting a museum” and allowing the eye to rest and to
loosen the concentration every time you are in an area not strictly dedicated to the
contemplation of objects.

1.6.3 Space, sizes and distances

The concept of the exhibition space for the museum is linked inseparably with that of the
exhibition that we will face later. Instead, in this area you want to emphasize, again
according to the principles of conservation and prevention of damage to the artworks, the
importance of calculating the average contemporary influx of visitors and the relative size
of the space needed to accommodate them.The method can start from the tie given by a

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space that already exists and that can not be changed, or from the case when we are in
condition to design the same space. In the first case we will speak about the control of the
influx, kept within the limits tolerated by the space, acting in such a way that overcrowding
does not seriously affect the microclimate of the room. In the second case we will ensure
that the areas destined to the observation of the artwork are sufficient as it regards size and
comfort, so that the object can be seen and understood without causing any damage to it.
A preliminary feasibility study, performed on homogeneous museums to ours for type of
host city, population, tourism, geographic latitude and longitude, average educational level
of population and type of exibition occurred, will give us a reliable estimate of peak flow
throughout the year and we will not be unprepared to cope with any periods of great
affluence.
All this will contribute to the planning and staging of the “ideal museum” to which we
must always strive for, although we will never be able to reach it. The “ideal museum” is
the space that guarantees both the “perfect preservation” of an artwork and its “perfect
enjoyment” by the visitor.
Proxemics is the discipline that studies the space and distance in relationships between
people and their impact in their reports and communications. Proxemics can help us in
sizing flows and spaces in the exhibition halls, taking into account the four interpersonal
areas defined and codified by the anthropologist Edward T. Hall:
• the intimate distance (0-45 cm),
• the personal distance (45-120 cm) for the interaction between friends,
• the social distance (1.2-3.5 m) for communication between acquaintances,
• the public distance (over 3.5 m) for public relations.
These parameters can help us in defining the space to be devoted to the placement of an
artwork, in relation to the number of visitors expected to admire it contemporaneously, as
well as with reference to relations between them, that is if they are among foreigners,
friends, colleagues or otherwise. All this is clearly designed to put who visit an exhibition
in a comfortable situation, and it determines, together with the other factors considered, the
success or failure of an exhibition.
We all have fixed in our memory, if only once we happened to live it, the hasty visit that
we were allowed to do to the “Mona Lisa” by Leonardo in the halls of the Louvre in Paris.
Moreover, after queuing up to admire her, the visit was also disturbed by the reflections of

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light present on the glass placed for her protection. Therefore, it can be argued that, as
partial compensation for a long wait, then we should at least have a comfortable and
rewarding visit to the opera, or, however, to a faster visit should not match exhausting
expectations. Putting the visitor in a state of “stress due to visiting the museum”
discourages him in the desire to the approach to culture, frustrating those persons which
with their accurate work of research, seek to bring to the attention of all the excellence of
the creativity and sensitivity of human beings.

1.6.4 Physical and mental path

The path in a museum exhibition is a narrative space and, as such, must follow the logic
and timing of the narrative language. All this interacts with the specific four-dimensional
architecture, where the three spatial dimensions are combined with the fourth dimension
represented by time, which becomes the instrument of exploitation and creation of the real
architectural space.
The visitor must be enabled to move in the museum path following the narrative logic that
the designer of the exhibition wants to transmit, as we must move within a book, reading
the lines in succession, and turn the pages in sequence. An improper arrangement of the
exhibits or a wrong indication of the way to follow would have the same effect as a book
read by jumping carefully from one line to another and from one page to another. If the
viewer was forced to move in a illogical way, or he freely chose a wrong succession of
reading, he will read a story different from that we want to communicate, or worse, will
not be able to grasp the full meaning of the narrative.
Let us imagine getting close to that classical marvel that is the Acropolis of Athens; let us
examine the map and we immediately understand how the path can guide and limit the
fruition of what appear to our view (Figure 1.12).
Following the path uphill to the entrance, we see that, now in its final stretch, it proceeds in
the direction of the Temple of Athena Nike, with the entrance of the Propylaia on the left.
Arriving near the Temple, the path turns almost 165 degrees to the left, leaving behind the
Temple, and giving us the surprise of the Propylaea this time on our right; then finally,
with an additional curve on the right, we are at the front of the Propylaea, which, once
crossed, will reveal to us the Parthenon and other wonders. In this case the path has
literally animated the works, showing them to us in various perspectives. The Greek

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masters with this sublime work show us what is meant by path, i.e. a place of surprises and
unexpected events, never with a dead time of transfer from one space to another.

Acropolis

Ionic columns

Uphill road

Temple of Athena
Nike

Figure 1.12 – Map of the entrance to the Acropolis of Athens.

Let us imagine, now, to be in a room where the statues on display depict the various
emperors of ancient Rome, and that we want to associate with each one of them a brief
history of the events during their reign, showing how these events have taken place and
also how they affected the techniques of creative arts.
The importance of a correct reading of the works in chronological order is evident. Let’s
suppose that you have a room that does not have enough space to exhibit artworks in linear
sequence in a single row, but for reasons of space must exhibit works in two symmetrical
rows (Figure 1.13).
Without a proper indication, the visitor is indecided about which path to follow among the
many possible, with the risk of “reading” the show in a disordered or wrong manner.
With proper use of light indicators or through explanatory graphs or just a simple

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numerical sequence, we will put the visitor in condition to follow without doubt the right
path to “read our story”.

Figure 1.13 – Solutions for the path when the artworks are exhibited in parallel rows.

1.6.5 The time as a chronological tape

The concept of time that we examine in this context is similar to a chronological journey of
the artworks shown, which also has a vision of what is happening while the artworks are
realized. If, for example, we are admiring a classical Greek artwork dated 480 BC, which
was found away from the motherland, undoubtedly is of help for better understanding the
artwork, making us more excited, to know that:
- in that year the most dramatic of the Persian wars took place, in which Leonidas with 300
Spartan warriors faces the huge army of Xerxes at Thermopylae,
- the destruction of Athens had then favoured the reconstruction of the Acropolis with the
criteria of the classicism contained and anticipated in the object that we are admiring.
So it is essential to place the artwork in a specific historical-temporal context, accompanied
by information about what had happened before, what was happening at that moment and
what would have happened immediately afterwards, in historical, political, social and
artistic terms.
Other information that can enrich the visitor’s knowledge relates to all the work of the
experts which has preceded the exhibition which is visited:
- how and by whom a specimen has been found,
- what technique has been used to restore the specimen, and what was its original context.

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The framing of the artwork, as part of the world view that prevailed when it was made,
makes us better understand its value. The value of a work can be represented by:
- its capacity to fix the more typical and representative characters of the history of taste
when he saw the light,
- its subversive and revolutionary potentiality to undermine these characters, and to
propose major turning points in the artistic communication process.
This is definitely one of the most demanding and important tasks to face by who organizes
an exhibition; completeness and clarity of the framework will determine the final quality of
work.

1.6.6 Technology
The current level of evolution of technology is opening up huge opportunities for museum
exhibition, because it is a fundamental support in the preservation of the artworks thanks to
the possibilities reached in monitoring and tele-control of the climate, and in the lighting
and security. But technology also adds potentialities really striking in the interactive
fruition of artworks.
The architectural and urban reconstruction with 3D graphics of some archaeological sites
leaves very surprised, and with interactive information you can reach the ideal level of
knowledge exchange with the visitor to a museum.
A monitor placed next to the specimen on display, which contains the data previously
mentioned, mostly with reference to the historical-temporal context, will allow the visitor
to access information that most interests him, putting him in a position to choose whether
to deepen the historical aspect rather that the political or artistic one relative to the artwork
visited, or to know the history of its discovery or to view a virtual reconstruction of its
original appearance and the context in which it lived.
Over the millennia, which have written his history, man has changed infinite forms of
expression and communication of his emotions, but their substance has not changed.
Therefore, a correct guide to follow in our work is to ensure that those coming after can
find what we would want to find for us.

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1.7 MUSA Project: intermuseum network for

conservation of artistic heritage

The MUSA project’s watchword is “preventive conservation”. The MUSA project

stemmed from the need to conserve exhibits in the best possible condition in museums, art
galleries, libraries, churches and underground archaeological sites. Unfortunately objects
are not “naturally” preserved but tend to deteriorate. So it is very important to survey the
quality of the air “enveloping” works of art displayed in museums controlling the physical,
chemical and biological parameters of the air by target analysis campaigns and with the aid
of microclimatic instrumentation. In addition, the project was stimulated by recent
legislation establishing the standards and targets of quality that museums, libraries and
historical archives will have to achieve in the near future, in particular the Italian
Ministerial decree dated 10/05/2001.
The MUSA project (www.isac.cnr.it/musa) set up a network exploiting the Internet and
wireless communication technology to monitor buildings containing works of art using a
remote-controlled system. The experimental phase, lasting about two years, finished on
31/12/03 and involved three pilot sites. Thirty museums in the Emilia–Romagna region
(Italy) were involved in the project (Figure 1.14), which ended at the end of the year 2009.

Figure 1.14 – Web page of the MUSA project.

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The network offers museum curators and technical staff a practical means of tackling
preservation of cultural heritage by automatically measuring the physical parameters of
peripheral sites. The parameters measured are those fixed in the cited decree:
- Temperature and Relative Humidity for physical parameters,
- Bacterial, Fungal and Total Microbial load for biological parameters, expressed as
Colony Forming Units per cubic meter of air (CFU/m3).
The aerobiological measurements are carried out with the Andersen sampler (6 stages) in
different seasons and in rooms with risk situations.
The main philosophy of the MUSA project is to verify the resistance of various types of
materials in relation to the environmental conditions. The system will be particularly useful
for those sites without conservation experts to report situations at risk or ongoing hazards.
All parameters monitored are transmitted in real time from the peripheral sites to a central
archive (database) providing analyses and forecasts on the trend of environmental
conditions. The participating museums periodically received clear reports with
recommendations for easy application:
- to rationalize and optimize restoration,
- meet the requirements of the microclimate monitoring systems to access credit and loans,
- certification of the showrooms at temporary exhibitions,
- undertake a process of optimization of energy requirements.
The system is implemented through:
- a telematic network exchanging data and information from and to the museum sites
connected,
- local use of wireless communication technology for environmental data,
- real time transmission and reception of data via internet communication technology from
the museums to the Data Management Centre and vice versa.
A simulation of a remote-controlled system: every museum in the world transmit for
instance T and RH data by an automatic system to the data management centre in Italy that
will provide analyses and forecasts on the trend of environmental conditions sending
reports, graphs, alarm messages and restoration procedures. Alarm messages indicate the
possible micro-environmental risk situations that might occur (or are already present) for
the preserved works of art. The recovery procedures suggest recovery actions to achieve
optimal parameters for the proper storage of artwork materials. Another important form of

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help offered to the museums is to check the correct operation of remote equipment and
when necessary, provide remote assistance and notify any abnormalities.
The graphic interface of the database consists of a website, a useful tool for connecting
remote sites with the operation centre (CNR-ISAC). The Data Management Centre collects
and archives all the data of the individual museums that can be requested via the web
anytime and anywhere with network connection.
In conclusion, project’s last phase was concentrated on the study of relations between
materials and biological and physical parameters and the search for the threshold within
which works of art must be maintained for their optimal conservation in relation to their
constituent materials. The research project conducted by ISAC-CNR in Bologna for about
10 years has become a service available to anyone anywhere in the world (MUSARTIS®
PEGASOFT: Art Care Innovation. www.musartis.it).

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comma 6), G.U. 19 ottobre 2001, n. 244, S.O., 223 pp.
NISO TR01, Environmental Guidelines for the Storage of Paper Records, by W. K.
Wilson, NISOPress, Bethesda, Maryland, USA, 1995, 21 pp.
Padfield T., Role of Standards and Guidelines, in W.E. Krumbein, P. Brimblecombe, D.E.
Cosgrove and S. Stainforth (eds.), Durability and Change, Wiley, New York, 1994, pp.
191-199.
Palla F., Marineo S., Lombardo G., Anello L., Characterization of bacterial community in
indoor environment, in: Fort, Alvarez-Burgo, Gomez-Heras, Vazquez-Clavo (eds.),
Heritage, Weathering and Conservation, Taylor & Francio Group, London, UK 2006,
pp. 361-365
Palla F., Biotecnologie per la caratterizzazione di aerosol biologici nelle biblioteche,
Bollettino ICR – Nuova Serie 14, 2007, pp. 54-57
Pitzurra L., Microbial envariomental monitoring of the refectory in the monastery of St.
Anna in Foligno, Italy, Aerobiologia, Kluwer Academic Publishers, 15, 1999, pp. 203-
209.
Reddy M.K., Suneela M., Sumathi M., Reddy R.C., Indoor air quality at Salarjung
museum, Hyderabad, India, Environmental monitoring and assessment 105, Springer,
2005, pp. 359-367.
Ruge A. (a cura di), Manuale europeo delle professioni museali, ICOM-ICTOP, 2008, 29
pp.
Sabbioni C., Zappia G., Gobbi G., Pauri M.G., Deterioration of ancient and modern
buildings materials due to environmental factors, in: Structural Repair and
Maintenance of Historical Buildings, C.A. Brebbia and R.J.B Frewer (eds.),
Computational Mechanics Publications, Southampton, 1993,pp. 235-242.
Sabbioni C., Ghedini N., Bonazza A., Favoni O., Atmospheric pollution effects on
hydraulic mortars, Pollution Atmospherique, Numéro Spécial Octobre 2007, pp. 55-62.
Saiz-Jimenez C., Microbial Melanins in Stone Monuments, Science Total Environment,
167, 1995, pp. 273-286.
Saiz-Jimenez, C. Deposition of anthropogenic compounds on monuments and their effects

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on airborne microorganisms, Aerobiologia 11, 1995, pp. 161–175.

Sivuchin D.V., Corso di Fisica Generale, Vol. 2, Mir, Moscow, 1986, 583 pp.
Thomson G., The Museum Environment, Butterworths, London, 1986, 293 pp.
UNI 10586, Condizioni climatiche per ambienti di conservazione di documenti grafici e
caratteristiche degli alloggiamenti, Milan, Italy, 1997, 12 pp.
UNI 10829, Beni di interesse storico e artistico - Condizioni ambientali di conservazione -
Misurazione ed analisi, Milan, Italy, 1999, 24 pp.
UNI 11131, Beni culturali - Misurazione in campo dell’umidità dell’aria, Milan, 2005.
UNI EN 15757, Conservation of Cultural Property - Specifications for temperature and
relative humidity to limit climate- induced mechanical damage in organic hygroscopic
materials, Milan, Italy, 2010, 18 pp. (replaces UNI 10969: 2002, retired).
UNI EN 15758, Conservation of Cultural Property - Procedures and instruments for
measuring temperatures of the air and the surfaces of objects, Milan, Italy, 2010.
(replaces UNI 11120: 2004, retired).
Van Balen K., Toumbakari E.E., Blanco-Varela M.T., Aguilera J., Puertas F., Palomo A.,
Sabbioni C., Riontino C., Zappia G., Environmental Deterioration of Ancient and
Modern Hydraulic Mortar (EDAMM), Protection and Conservation of European
Cultural Heritage, Research report 15, Luxemburg, 2003.
Warscheid Th., Braams J., Biodeterioration of Stones: a review, International
Biodeterioration & Biodegradation, 46, 2000, pp. 343-368.

Acknowledgements

Special thanks go to Salvatore Barbaro and Rosa Chisesi - C.I.R.I.A.S. University of

Palermo, for collaboration on the microclimate study.

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2 - STONE ARTEFACTS

2.1 What conservation means

2.1.1 Strategy for conservation

Conservation is a duty of protection that each one of us has in relation to the environment,
its cultural heritage, its diversity and identity respect to other ethnic groups, religions and
social status.
Generally it means to promote and contribute to conservation of material and immaterial
works: our culture and our custom, our art that have been passed down and that we must
deliver to the future generation. This is achieved through steps involving the materials
constituting the artifacts and the environment conservation.
We must know the materials, their behavior, their interactions with the environment to
having correct vision of the specific conservative needs.
In principle there are three times correlated with the conservation of artifacts:
- ancient, where the knowledge of the materials was of great relevance to workers
and artists;
- intermediate, characterized by the exchange of books, collections and museums;
- modern, where it exceeds the traditional materials and traditional methods with the
study of the dynamics of degradation and the behavior of ancient materials and
synthetic ones used for the restoration.
The requirements of knowledge regarding modern treatments are: thorough knowledge of
the constituent materials, knowledge of the ‘excursus vitae’ of the artifact; knowledge of
conservation and awareness of the treatments received by the artifacts over the years.
Based on the knowledge mentioned before, derived from the interpretation of data and
intersection from scientific analytical processes and research of historical sources, we can
develop the most advantageous strategy for conservation.
In any type of artistic work, there are technological or restoration operations that involve
the use of natural and synthetic materials, traditional or innovative, always with

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interactions or physical or chemical contact with the materials constituting the artifacts.
They are typical of the type of each work of art.

2.1.2 Preliminary studies

Preliminary study allows us to understand and have full and complete knowledge of the
work of art to be restored. This study is summarized in a number of preliminary researches
concerning the publications that cover the issue of interest, findings, architectural
components and archaeological sites to be retained; historical photos and archival reports
and/or techniques on any conservative intervention made in the past. The preliminary study
also includes:
- graphic survey: plants, share, sections, any significant relief in scale 1:1, paintings
of areas of particular interest;
- photographic survey: general photographs, photographic survey of the conservation
condition before the restoration, photos documenting particular areas to be studied
carefully.
The survey (two-dimensional and/or three-dimensional) must be finalized to the
knowledge of the work of art, assuming, for example, that our reference unit for a wall
structure is ashlar stone.
The use of non-destructive investigation methodologies is useful for the analysis on sight,
the photographic and reflectographic relief, which contribute significantly to the
knowledge of the areas and materials and are able to highlight the differences just
perceptible or completely invisible to naked eye, and often help in the identification of
significant restorations, various states of degradation, etc..
The most significant parameters through which to articulate the visual observation are:
geometry of the object, types of materials, colors, size and performance, size and
characteristics of the eventual joints of mortar in the interstices, composition, iconography,
conservation status and points of sampling.
There are various non-destructive methods for the relief of the color in terms of both
quality and quantity: the traditional relief and digital photography using band kodak as a
color reference, for a more faithful reproduction of the areas concerned. The method of
visual comparison relies on the comparison between the colors under consideration and a
set of standard samples, such as the Munsell book of color (1488 samples of color); the

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instrumental relief is based on the elaboration of the measure of diffuse reflectance from
the surface of the sample.

2.1.3 Morphologies of alteration and degradation

THE ITALIAN STANDARD UNI 11182/2006

This Italian standard provides the definitions of terms used to indicate the different forms
of alteration and micro-organisms visible macroscopically. The document permits the
detection of the state of conservation of the stone surface and the definition of the causes,
while the extent of the alteration will be detected later by diagnostics. In this context,
alteration is a modification of the material that does not necessarily imply a deterioration
of characteristics in conservative terms, while degradation is a modification of the material
that involves a deterioration of characteristics in conservative terms. We list below the
terms of alteration and degradation with their definition.
- Absence: loss of three-dimensional elements (in the arms of a statue, in a loop, mosaic
floor tiles).
- Alveolization: presence of cavities of variable shape and size, such alveoli, often
interrelated and uneven distribution.
- Biological colonization: presence, macroscopically detected, of micro and/or macro-
organisms (algae, mosses and lichens).
- Biological patina: thin and homogeneous layer, consisting primarily of micro-organisms
of varying texture, color and adhesion to the substrate (Figure 2.1).
- Boundary of migration: limit of the migration of water, usually upwards, which is
manifested by the formation of efflorescence and/or loss of material. It is generally
accompanied by change of color saturation in the area below.
- Casting: tracks vertically performed; frequently they are several in parallel.
- Chromatic alteration: natural variation of the parameters that define the color of the
material. It generally covers the entire surface of the materials concerned; when the
alteration occurs in a localized area, it is preferable to use the term stain.
- Crust: modification of the surface layer of stone, of variable thickness, generally hard,
distinguishable from the underlying parts for the morphological characteristics and often in
color. It can also detach spontaneously from substrate that generally appears disrupted
and/or powder.

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Figure 2.1 – Biological patina on a building in Rimini: macrophoto on the left

and microphoto on the right.

- Deformation: change in shape that involves the entire thickness of the material.
- Differentiated degradation: loss of material from the surface, indicating the heterogeneity
of the texture and structure; in the case of plaster can take a characteristic form similar to a
small rose.
- Disintegration: de-cohesion with the fall of material in form of powder, or tiny
fragments. Sometimes the term ‘pulverization’ is used as a synonymous.
- Efflorescence: formation and appearance of crystalline powder, usually white, on the
surface.
- Encrustation: stratiform compact deposit, generally adherent to the substrate. The deposit
is defined concretion when it is preferentially developed in a direction not coinciding with
that of the stone surface and takes the form of stalactite or stalagmite.
- Erosion: removal of material from the surface which in most cases is compact.
- Exfoliation: formation of one or more laminar portions, called ‘sheets’, with very reduced
thickness and sub-parallel between them.
- Film: superficial layer of transparent or semitransparent substances, which are consistent
with each other and unrelated to the stone material (for example protective film, film with
aesthetic function, etc.).
- Fracture or slot: discontinuity in the material that implies the mutual displacement of the
parties. In the case of incomplete fracture, in Italy we use the term cricca; when the
phenomenon occurs in the glassy coating of ceramic materials, we use the term cavillo.
- Graffiti vandalism: affixing of colored paint on the surface of the work.

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- Lacuna (gap): discontinuity with loss of material, for example part of a plaster or a
painting, piece of ceramic body or ceramic coating, mosaic tiles, etc.
- Patina: natural modification of the surface; it is not connected to particular phenomena of
degradation and is perceived as a variation of the original color of the material.
- Pitting: Degradation that occurs with the formation of blind holes, numerous and close
together. The holes mainly have cylindrical shape with a maximum diameter of a few
millimeters (Figure 2.2).

Figure 2.2 – Pitting in mosaic tesserae.

- Posting: a) mortar: discontinuity between layers of plaster, both among themselves and
with respect to the substrate, that usually preludes to the fall of the layers themselves; b)
ceramics: discontinuity between coating and ceramic body or between two coatings.
- Stain: localized color variation of the stone surface (especially marbles); it is related to
the presence of foreign material (water, oxidation products of metallic materials, organic
substances, paints, and microorganisms).
- Superficial deposit: accumulation of materials of various nature, such as dust, soil, guano,
on the surface. The deposit has variable thickness, generally poor coherence and poor
adhesion to the material below.
- Presence of vegetation: presence of herbaceous plants (higher plants).
- Swelling: localized lifting of the material surface, variable in shape and texture depending
on the state of conservation.

DOCUMENTATION OF THE CONSERVATION STATE

The morphologies of alteration and degradation must be graphically represented by
thematic tables, also the constituent materials must be marked in such a way that helps in

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understanding and interpreting the conservation status of an artifact prior to conducting any
intervention. So is important and fundamental the graphic and photographic documentation
of conservation status of the artifact before conservative intervention.
The diagnostics along with the archival documents are to be considered our point of
departure for a project of conservation and without which it is not possible to perform a
correct conservative intervention.
The thematic charts of conservation status are the identity card of the artifact and this
should highlight the types of materials, morphology of deterioration and alteration and
their location.

2.1.4 The principles of conservation

In principle, every intervention of conservation can be divided into three main phases:
cleaning, consolidation and protection; not necessarily all three are present and not always
the sequence of execution is the one cited above. Reasons of safety for the artifact
sometimes recommend its pre-consolidation before cleaning it. Generally the conservative
intervention terminates with its detailed documentation.

CLEANING
Cleaning is the removal of materials, unrelated or not, in different state of aggregation and
of different nature (crust, concretion, patinas, deposits, vegetal and animal organisms)
which disrupt or prevent the enjoyment of any aesthetic or material level of the artifact.
In fact its action or a too vigorous cleaning may also remove historical patinas, reducing
the artifact to a mere material object, deprived of its past. Often enough in recent times, a
thorough cleaning was carried out that affected the work, such as a polychrome surface.
This is an outdated view of cleaning, the “renewal” of a surface; today, cleaning means
“thinning” of the surface patina of an artifact. The purpose of cleaning, in terms of
conservation, is to remove what is harmful to the stone: soluble or insoluble salts, layers of
various materials intentionally used and not suitable or no longer functional, infesting
vegetation, dirt, etc., respecting the upper layer of the artifact. And this should occur
without producing harmful substances for the conservation of the materials, or micro
abrasion on the surfaces.

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The main cleaning methods can be grouped into: physical, chemical and mechanical (see
paragraph 2.5). Before performing the cleaning operations, the following preliminary
operations should be made:
- detailed analysis of the consistency of the materials,
- analysis of reaction products,
- pre-consolidation (reversible) if there is a need.
Water is among the most common solvents for cleaning operations, although in some cases
it is incompatible with certain substrates, because most artistic materials are insoluble in
water (metals, stones, textiles, organic materials). In addition, because many substances are
conveyed by water, this last can operate equally well in their removal.

CONSOLIDATION AND PROTECTION

The term “consolidation” indicates a treatment designed to improve the cohesion and
adhesion between the constituents of a artifact. Consolidation must restore the structural
continuity of the material and recover the primary characteristics of matter, or at least bring
them close to their initial values. It must not exaggerate in the continuity, or block the
existing porosity. Of course all of this while respecting the meaning of the artifact and its
iconographic aspect. The consolidation should bring benefits to the structure of the
material, but without exceeding in this, otherwise you can get imbalances and very
dangerous tensions in the structure. Consolidation should not alter the appearance of the
materials of the artwork (increasing the reflectivity, colour saturation) and respect the
characteristics of the materials.
The inorganic consolidants have considerable affinity with the stone, as regards the
physical properties, and they last more than the organic materials, but the improve of
mechanical properties induced by inorganic consolidants is much lower. With inorganic
consolidants you can not weld cracks whose walls are distant less than 50-100 microns.
This is because the hardening of the inorganic compounds is too rapid; in addition there
may be the clogging of the pores near the surface. Difficulties in penetration there are also
for organic consolidants, in particular those with large polymer molecules. The distribution
of the consolidant within the stone also depends on the concentration of the solution, the
type of solvent, the contact time, pressure and temperature of the working environment.
Each material undergoes processes of transformation caused by environmental imbalance.
The protection interventions are designed to make these transformations less likely or

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slower. The protection offered by chemicals is to reduce the penetration of water inside the
porous structure, making the surface and the walls of the pores hydrophobic; consequently
are reduced all the phenomena that develop in the presence of water, such as transport and
crystallization of salts and the phenomenon of freezing/thawing.

DOCUMENTATION OF THE CONSERVATIVE INTERVENTION

Finally, it is of fundamental importance the graphic and photographic documentation of the
various conservative interventions performed on an artifact. The graphical documentation
can be done through tables showing the themes and highlighting the areas of intervention
and the type of intervention performed.
You must make an extensive photographic documentation during the operations for the
conservation and restoration; at the end of each work, there must be a report, which is a
technical-scientific summary of what was done to the artifact, with lots of graphic and
photographic documentation. In addition the results of the work must be made public, with
conferences, scientific meetings and subsequent publication, so that the work is found to be
consultable from interested persons and not. This documentation helps the restorer to apply
the most appropriate methodologies to obtain excellent results. In addition, it will be of
paramount importance to perform other conservative interventions in the future.

2.2 Natural stones

2.2.1 Definition
Natural stones can be divided into three groups depending on their origin:
- Igneous rocks: very hard rocks deriving from the solidification of a magma inside the
earth’s crust or a lava on the earth’s surface, with different structures (micro or macro
crystalline, porphyritic or vitreous), often intensely coloured and with a precious aspect,
such as basalt, porphyry, granite and diorite.
- Sedimentary rocks: formed from deposited material, more or less tender, such as
sandstone, limestone, gypsum and tuff.
- Metamorphic rocks: deriving from a re-crystallization in solid state of pre-existent rocks
due to heavy change of temperature and/or pressure, more or less tender, sometimes easily
workable. Included in this group are all types of marble, white and not. Marble is a

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metamorphic rock with carbonate composition (calcite and/or dolomite) deriving from
metamorphism (contact or regional) of pure carbonate rocks.
A rock as building material (mainly for ornamental functions) is chosen according to its
aesthetic (for example color) and technical (for example workability) properties.
Over the centuries sedimentary rocks (limestone, sandstone, clays, etc.) were mainly used
either as building materials either as raw material for producing mortars and ceramic
products. In fact these rocks are easily available and simple to be extracted.
Also marbles (metamorphic rocks) were often used as ornamental stone, while the use of
other rocks is less frequent due to hard supplying, difficult working and other.
In a limestone, three principal components can be identified, which are used to classify the
different types of limestone:
- granules (framework)
- micrite (matrix, granules < 30 micron)
- cement (carbonate crystals due to chemical precipitation).
The most complete and used classification for limestone (and dolomite) is Folk
classification (Figure 2.3), that takes into account both the nature of the principal
components and the texture of the rock.

% Allochemical granules Allochemical granules

allochemic > 10%
Sparite micrite
< 10% Allochemical

calcite > sparite Allochemical granules granules

al granules < 1%

> micrite calcite 1-10%

Intraclasts >
25%

Micrit Cement with

e sparite
Figure 2.3 – FOLK classification of limestone.

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2.2.2 Sculpture
One of the characteristics that the sculptor wants to find in the stone is the compactness, ie,
the block must have the same resistance in all directions, in order not to have breaks along
eventual lines of weakness. Some natural defects, such as the so-called “hairs of the
marble”, which were often unexpected and which forced the sculptor to abandon the block,
are to be avoided.
There are three groups of tools, which are commonly used for sculpture (Figure 2.4):
1) chisels of various forms (beams, gouge, cuneo), beaten with clubs to remove splinters;
2) drills, used for making holes,
3) abrasives (natural pumice, emery), used for polishing the surface.
Large pointed chisels are used to give the first roughing to the block. Shapes are outlined
with a scalpel (“gradina”), whose end has three teeth, which leaves characteristic signs,
known as “tracks”, with round or squared section, and with various types of abrasive.

Figure 2.4 – Tools for sculpture.

USING A MODEL
The preparation of a model is not strictly necessary; the sculptor can in fact carve the block
directly, without making any prior preparation. But it has often been used because, once
the material has been removed, there is no turning back.
The model can be graphic, sometimes with four main views (front, rear and two sides), or
three-dimensional in plaster or terracotta. It may be of equal size to the sculpture that the
artist want to achieve, or smaller. It often happened that the artist made the model and then
the workshop prepared the sculpture. The degree of completeness of the model varied,
depending on whether there was an intervention of the artist on the final sculpture. The use

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of a model allowed the series production, which was very important for example in the
Hellenistic and Roman period. To produce a large number of replicas, a sort of semi-
industrial system was organized: parts of the statues were made by different craftsmen and
assembled later with metal nails. The execution of the most important parts, like the face,
was realized by the artist. Unfortunately, sometimes the parts coming from different
workshops have different colours.
The use of a model requires the “counting of points”. This technique was firstly used in
ancient Greece, which invented the use of the plumb line. The distances between the wire
and the surface of the model were reported on the block, where the sculptor drill holes as
deep as the distances measured. The stone in excess was removed with the chisel until the
desired surface.
In the Renaissance, graduated instruments were used to calculate the points. Leon Battista
Alberti, in the book “De Statue” speaks of a “definitor”, a graduated circle fixed to the top
of the model, in a horizontal position, with a turning arm (Figure 2.5). To detect a point,
you turn the arm from which a plumb cable drops. This cable touches the surface of the
model and then it is possible to report three measures: 1) the angle marked by the turning
arm above the graduated circle, 2) the distance between the centre of the circle and the
point of contact of the plumb, 3) the distance between the point to be noted and the
pavement. In the case of large cavity that cannot be reached by the cable, a straight
horizontal arm is used, that starts from the plumb cable. Vasari, in the book “Vite”, speaks
about a simpler but more used technique: a combination of a vertical and a horizontal arm.

Figure 2.5 – The “definitor” system by Leon Battista Alberti for the sculpture.

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2.2.3 Painting and polishing

In antiquity the stone was coloured directly or, more often, on the preparation of plaster. In
the fifth century BC in Greece the “ganosis” was diffused, that consists in coating with
wax. In the Middle Ages only a few parts of the stones were coloured. Since 1400, the
natural stone was preferred, without colouring, with slight polishing obtained rubbing with
a wet cloth and a mixture of pumice in powder and sulphur, or using oxalic acid.
The practice of painting on stone is in vogue especially in the 1500. The initiator of this
technique seems to have been Sebastiano del Piombo (Figure 2.6). Its diffusion is related to
the use of oil painting on various supports.
The paintings that have a stone support always are small, because of the softness and
fragility of the material. The preparation, which was often realized only in the areas that
had to be painted, consists on a single coat of oil. The colours are those of the oil painting
(orpiment, lead black, cinnabar, lacquer, blue or green ash, indigo, carbon black, verdigris)
mixed with walnut oil, linseed oil and turpentine.

Figure 2.6 – Pietà by Sebastiano del Piombo, 1517, Viterbo, Civic Museum: painting on
stone. After: http://it.wikipedia.org/wiki/Pietà_(Sebastiano_del_Piombo).

Since 1800 the stone is also used as a support for press. The lithographic matrix is a porous
limestone, which is cut into slabs of various sizes, often between 5 and 10 cm, and heavy
even several tens of kilograms. The slab of stone can be re-utilized: when you have
finished printing, you can renew the surface of the slab decreasing its thickness. The

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surface is perfectly smoothed if the signs are executed in ink; it is rubbed with sand and
water to make it rough if you paint with the brush.
To increase the number of print pages as more as possible, a preparatory process of the
stone was added: covering with a light layer of a solution of Arabic gum and nitric acid in
water, which makes the surface more porous. This layer is dried for a few hours and then
removed with water.
Today, the stone slabs have been replaced by porous metals such as zinc and aluminium,
that give the same performance, but are cheaper and easier to handle.

2.2.4 Tarsia or commesso

The term “tarsia”, from Arabic “tarsi”, indicates the technique of combining between them
different components and supports. Unlike other techniques that combine different
materials between them, such as niello, agemina, cloisonné, champlevé, the tarsia is
characterized by the combination of components constituted of the same material, although
of different colour.
It is possible to distinguish two forms of tarsia in which precious stones are used. In one
case the stone is inserted in the supporting material, while in the other the stones are
juxtaposed with each other and put on a common basis. The first case in antiquity was the
most common.
The support could be metal, wood or ivory, and the artwork can also be called
“incastonatura” (embedding), a technique similar to enamel cloisonné. There were two
main methods of this type of tarsia: ihzu and tamlu (Asian words). The first was to fix the
stones by means of calcium carbonate in small holes with walls in relief. The second
method consists in engraving the support by digging a spot for the insertion of the stone so
that this last was at the level of the basic plan.
The term “stone tarsia” indicates the coverings of floors, walls or part of furniture. Thin
slabs of stone and coloured marble are used, cut and stuck to each other to form
decorations in a compact area. In this tarsia, unlike the mosaic, the components are not
regular and not all the slabs have the same shape and size and the mortar does not appear
on the surface. In the Roman world, the technique was widely used.

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2.3 Artificial stones

2.3.1 Stucco
“Stucco” is a mixture of lime, marble powder, washed sand, and casein, mixed in various
proportions according to its function, and the materials available. After being moulded and
dried, the amalgam is applied to stable supports, especially wood. The best colours are the
mineral colours and the binder usually is glue.
When used with the function of filling or finishing, the mixture should be soft and achieve
compactness after moulding; with the function of decoration, the mixture must have
plasticity, fineness, malleability. Used for parts in relief is added to the rest through metal
tips.
The stucco is used in Mediterranean countries and eastern countries for ornamental
architecture, because the material is easy to find and to work; in addition the climate is
warm, condition that favours its conservation. In Egypt the masks of mummies were made
in stucco, as well as elements such as pilasters, pilaster strips in Greece and Roman
Empire. In Islamic countries and in those of their influence (North Africa, southern Italy
and Spain) stucco is associated with the technique of engraving (see 8.3.5).
After the twelfth century, stucco became a complementary element to painting and
sculpture in wood. In the first case the chalky plaster serves as a preparation to the pictorial
layer, while in the sculpture it was used to hide the suture zones of a statue or to moulding
the parts in relief, such as leaves, then fixed with iron tips or wooden sticks. In both cases,
the stucco should be a fine paste.
In the Renaissance, the stucco became again an architectural complement. The will to
imitate the ancient artifacts brings to experiment materials and develop the technique: in
the mixture the portion of sand is replaced with marble powder and the stucco becomes
more soft. For the exterior - due to rain, ice and wind - a special kind of stucco was
prepared, whose paste is made by means of an infusion of elm peelings, Greek hay, and
mallow peaks mixed with eight parts of a marble mortar, a part of sulphur and two parts of
powdered pumice.
The stucco gains a scenographic role in rococo architecture of the seventeenth and
eighteenth centuries. Austria and southern Germany are very famous for their

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experimentation, where the stucco imitates the most varied materials. For the most
voluminous decorations, the plasterer added chopped straw.

2.3.2 Scagliola
The “scagliola” was invented in the 1600 in Carpi (Modena, northern Italy). The scagliola
is obtained from natural gypsum, “selenite”, present in abundance in the Northern
Apennines (northern Italy) through cooking (about 300 °C), and fine grinding. The fine
powder obtained is then mixed with glue made from pieces of tanned leather, in order to
have a workable paste, which is then coloured and polished with pumice, walnut oil or
flax. Pastes of scagliola have allowed to imitate all types of marble and these imitations
were used for flat surfaces.
Scagliola is also used in the “tarsia”. In this case the base is made by a mixture of plaster
and water, placed in a container to solidify, or it is a composition of straws. On this base, a
layer of scagliola of a few millimetres is placed; after drying, it is carefully polished; on it,
is possible to make the design by dusting. The design is then engraved and the exceeding
scagliola is removed, creating ruts. Coloured scagliola is then deposited over the whole
surface, but it will remain only in the ruts, when the other parts will have been smoothed.
Every time you want a new colour, you can engrave ruts and deposit a layer of new
scagliola.

2.3.3 Mortars

DEFINITION
A mortar is a mix of inorganic or organic binder, aggregate mainly fine, water and eventual
organic or inorganic additives (or simply a mix of binder and water) in precise ratios in
order to give:
- an appropriate workability to the fresh mixture,
- opportune physical properties (porosity, permeability, etc.) and adequate mechanical
characteristics (strength, deformability, adherence) after setting, as well as a good
durability.
Binders can be aerial or hydraulic. Aerial lime and gypsum are aerial binders; hydraulic
lime and cement are hydraulic binders. Aerial binders can harden only in the air, while
hydraulic binders can also under water.

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The aggregate is the skeleton of the mortar and it reduces its volume change during the
setting phase.
The aggregate can be composed of:
• sand (from river, from quarry, from coast)
• crushed rocks
• natural materials with pozzolanic activity (e.g., pozzolan, fossil siliceous sand)
• artificial materials with pozzolan activity, like “cocciopesto”
• Fragments from hardened mortars.
Additives are organic or inorganic substances, often present in small quantities, that
modify one or more properties of a mortar.

AERIAL BINDERS: AERIAL LIME

Aerial lime is obtained by the calcination (about 900 °C) of very pure limestone. The
calcination produces the formation of quicklime (CaO) according to the reaction:
Limestone (CaCO3) ⇒ quicklime (CaO) + CO2
CaO for being used as binder has to be hydrated in order to transform it in slaked lime
(Ca(OH)2) according the following reaction:
CaO + H2O ⇒ Ca(OH)2 slaked lime
The setting process of slaked lime is due to its reaction with CO2 present in air and
evaporation of water according to this reaction:
Ca(OH)2 + CO2 ⇒ CaCO3 + H2O
Aerial lime can be distinguished in “rich” (fat) and “poor” (thin), depending on the amount
of impurities (dolomite, silica, clay minerals, etc.) of the calcined limestone: respectively
<2% and between 2% and 8%.
Among the poor limes we can mention the magnesium lime, which is obtained by
calcination, and subsequent hydration, of dolomitic limestone, that is calcium carbonate
(CaCO3) with a lower amount of double carbonate of calcium and magnesium (CaMg
(CO3)2). The calcination, the subsequent hydration, and the setting process of a dolomitic
limestone produce the development of magnesium phases: magnesite, hydromagnesite,
brucite, nesquehonite. A mortar prepared with a magnesium lime can be easily recognized
on the basis of the presence of one or more magnesium phases above mentioned.

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AERIAL BINDERS: GYPSUM

Gypsum, the most ancient binder, is obtained through the cooking of rocks containing
gypsum at low temperature (130-150 °C). The firing produces a partial loss of water and
the formation of calcium sulphate hemihydrate:
CaSO4 • 2H2O ⇒ CaSO4 • 0.5H2O + 1.5H2O
Setting process is due to re-hydration of calcium sulphate hemihydrate in air:
CaSO4 • 0.5H2O + 1.5H2O ⇒ CaSO4 • 2H2O

HYDRAULIC BINDERS: HYDRAULIC LIME

Hydraulic lime is obtained by calcination, at 1000-1100 °C, of marly limestone, where clay
concentration is between 8 and 20%, and a subsequent suitable process of hydration.
Hydraulic lime is composed of calcium hydroxide (Ca(OH)2), and several types of calcium
silicates or calcium aluminium silicates deriving from the reaction of a fraction of calcium
oxide and the amorphous residues of the argillaceous minerals destroyed during the
calcinations phase (Figure 2.7). The hydraulic properties of this binder are due to the
presence of these silicates.

Marly limestone (clay 8-20%)

Calcination (1000 – 1100 °C)

°°C)
destruction of argillaceous minerals
CaCO3 ⇒ CaO + CO2
reaction between amorphous clay mineral residues and a fraction of CaO

CaO + calcium silicates and calcium aluminum silicates (hydraulic fraction)

Hydration

HYDRAULIC LIME
Ca(OH)2 + calcium silicates and calcium aluminum silicates

Figure 2.7 – Hydraulic lime: production scheme.

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The hydraulic lime has two setting mechanisms:

- aerial, due to the carbonation of the calcium hydroxide,
- hydraulic, due to the hydration of the silicates.
Of course the hydraulic characteristics of these binders are closely linked to the
concentration of clay present in the calcinated raw materials. The hydraulic properties can
be expressed by the Hydraulic Index (H.I.), which is the ratio between the sum of the
percentages of SiO2, Al2O3, and Fe2O3 (clayey fraction) and those of CaO, and MgO
(carbonate fraction). The hydraulic properties increase with the value of H.I.

SiO2 + Al2O3 + Fe2O3 (clay fraction)

H.I. =
CaO + MgO (carbonate fraction)

HYDRAULIC BINDERS: CEMENT

Cement is obtained by firing, at high temperatures (1400 °C or more), natural or artificial
mixtures composed of limestone, marly limestone and clay, so that the mixture has the
following chemical composition: CaO 60-66%, SiO2 16-21% and Al2O3 4-12%. The firing
process causes the melting of the mixture and, after cooling, a hard material, partially
vitrified, called “clinker” is obtained. Then the clinker (calcium silicate, calcium
aluminate, calcium iron-aluminate) is pulverized and different additives, natural or
artificial, are added to it in order to change some of its properties.
The setting process of the cement is due to a complex system of hydrolysis and hydration
reactions. This binder does not contain an aerial fraction.

HYDRAULIC MORTARS
A mortar with hydraulic characteristics can be obtained by means of an hydraulic binder
(hydraulic lime and/or cement) or through mixing aerial lime + aggregate with pozzolanic
activity (natural or artificial) + water.
In the past, until the middle of the 18th century, the hydraulic binders were not known.
Therefore mortars with hydraulic characteristics were obtained in the following ways:
- aerial lime + “cocciopesto” (fragments and dust of terracotta)
- aerial lime + pozzolana (sand of explosive volcanic origin).

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During the setting phase, cocciopesto and pozzolana react with the aerial lime giving rise
to hydrated calcium silicates and hydrated calcium and aluminium silicates, which are the
responsible of the hydraulic properties of the mortar.
Rarely hydraulic mortars were obtained with metakaolin and sand instead of cocciopesto
and pozzolana.
Hydraulic mortars based on metakaolin were the result of a sophisticated building
technology. They required the production of metakaolin by means of firing (about 600 °C)
of kaolin (clayey rock) and a perfect mixture with aerial lime in precise proportions.
During setting process, the aerial lime easily reacts with the metakaolin giving rise to the
formation of calcium and aluminum silicates in hydrated form.
Before the 18th century, there was the fortuitous and unconscious production of hydraulic
limes. In fact the presence of hydraulic mortars based on hydraulic binder was detected in
several medieval or late antique age sites.
The production of hydraulic binders, in the past, was due to the presence of marly
limestone in the area of the site, to high temperatures of calcination and to a not careful
hydration process.
According to the kind of the binder (Italian standard UNI 10924), we can distinguish the
mortars based on:
a) aerial lime;
b) gypsum;
c) hydraulic binders;
d) aerial lime and materials with pozzolanic activity;
e) organic binders;
f) clay binders;
g) Other (e.g. two or more types of binders).

PLASTER
Plaster is a wall coating composed of different mortar layers, applied in a precise sequence.
After hardening, it has protection function and surface finish.

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2.4 Deterioration of the stone

2.4.1 Introduction
Each material situated in a environment gets to balance with it. If the environment changes,
and the new environment has physical-chemical characteristics very different, the situation
appears imbalanced. Then the material will get to balance with the environment through
physical-chemical transformations, with worsening of the material properties. The
transformation suffered by the material in order to reach a new balance with the
environment is called “deterioration”. Therefore, the deterioration is due to the
combination of intrinsic characteristics (linked to the material) with extrinsic
characteristics (linked to the environment). Intrinsic characteristics are: composition
(chemical and mineralogical), structure, type of finishing working (polishing, protection
treatments, etc.), positioning during setting up.
The extrinsic characteristics linked to the environment in which is located the artefact can
be subdivided in: physical, chemical, biological, anthropic. There is never a deterioration
process due to only one of the causes aforesaid. These causes of deterioration generally act
together with different intensity. The study of weathering mechanisms is important because
understanding the causes of the symptoms leads to understanding the conservation needs
and leads us to informed and effective solutions.
Buildings are elements of our environment, and there are multiple causes for their
continuous alteration. When the alterations entail physical or structural consequences on
the material, they are named decay. The buildings suffer different stresses during their
multi-secular existence: physical and chemical, mechanical, human or natural, all provoke
continuous alterations to the structures. The issue to be dealt with now for a coherent
planning of the conservation activities is what kind of decay do these factors produce. The
identification and documentation of the present decay, interpreted in correlation with its
genesis, will guide us in searching solutions in order to modify or stop causes and effects.
There are different opinions and approaches in an attempt to classify causes and symptoms
of decay. The problematic for creating distinct categories is that a strong interaction exists
between natural and anthropogenic factors, as also between causes and symptoms, in stone
or brick structures. In addition, natural and artificial stones are porous materials. Therefore
the most significant causes of decay derive from the presence of water and from the
variations of temperature. Water can penetrate into the walls either by direct contact (e.g.

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rainfall) or as rising damp due to the absorption of underground waters. Water and
variation of temperature are strictly related to all other causes of decay. Anyway, water can
be considered as the main chemical cause of decay.

2.4.2 Physical causes

THERMAL STRESSES
In porous materials, the absorption of water is sometimes followed by a change of its
volume. Therefore, the wetting of the walls, in combination with the thermal variations,
can create irreversible damages to the buildings. The damages caused by the thermal
stresses may be either invisible to the human eye when they occur in the inside parts or
manifest themselves on the surface of the material with micro-cracks. The result of such
movements is the augmentation of the porosity and permeability of the building’s
materials.

MECHANICAL STRESSES
The buildings suffer mechanical stresses for two associated reasons. Firstly due to ground
movements: the ground should always be considered part of the structure with which it
interferes continuously. Secondly due to the fact that the buildings are made of different
materials and every material reacts differently to thermal stresses, thus producing at the
same time mechanical stresses to the other components.

FROST ATTACK
Another very important factor in the degradation of stones and mortars is the freeze/thaw
cycle. The rigid structure of the stones suffers the pressure of ice forming, capable of
creating fractures and, in extreme cases, the collapse and complete loss of the material.
The attack by frost affects more materials with very marked weaknesses along the natural
bedding plans and those with large porosity (e.g. the limestones are more susceptible than
the sandstones). Often, the attack by frost weakens the internal structure leaving the
surface apparently undamaged.

SALTS
Also the damages derived from salt crystallization are related to the wetting and drying
cycles in stone masonries. Rising damp and rain can affect the whole structure introducing

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soluble salts and organic solutions by capillary action. In drying conditions, when water
evaporates, we have the crystallization of the salts deposited in the internal parts or the
external of the material.
The salts on the surface create an aesthetic disturbance, and are usually easy to remove.
More threatening for the material is the growth of salts deposited within the pores as it
generates tensions that can overcome the tensile strength of the stone and cause structural
failures.

2.4.3 Biological causes

Different organisms and micro-organisms stimulate different decay. Intrusive vegetation,
not only obscures the visual perception of the surface but often it transfers acidic moisture
on the surface and in depth causing the mineral decay.
Higher plants can create serious damages on the surface and in the internal part due to their
roots, that are fed with the mineral components of stone and bricks.

2.4.4 Anthropic causes

POLLUTION
A polluted environment is another decay factor. The problem, already present from
antiquity, but accentuated in the last century, relates to the chemical alteration of the
minerals constituting the stones, the mortars or the bricks.
Where the pollutant particles present in the atmosphere are deposited on the buildings,
depending on whether our surface is protected or not, we have two opposite main
phenomena. Constructions and structures not sheltered, which are subjected to many cycles
of precipitation, can suffer due to the abrasive power of the water. So, many areas are
attacked and run-off channels are created. On the other hand, the protected parts favour the
genesis of black crusts, especially in calcareous stones (see 2.4.5).

PREVIOUS INTERVENTIONS
To conclude the observations on the major causes of decay, not of less importance is the
human factor and especially the approach of the previous interventions to the historical
buildings.

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In the past century, during conservation and maintenance treatments, quite often the
cements presented above accelerate their action along the time and, very often, the
decomposition of the material can be observed.

2.4.5 Anthropic deterioration: black crusts

The black crust is a characteristic deterioration layer present on carbonatic surfaces in
greatly polluted areas, which is due to the interaction between atmospheric particles
(anthropic origin) and stone surface. The black crusts can be considered the accumulation
areas of atmospheric particles (natural and anthropic) and products of the stone degradation
reactions. Black crusts are formed in wet areas but sheltered from intensive flow of water
(Figure 2.8, left). They are mainly composed of gypsum produced by wet and dry
deposition of sulphur which is present in the atmosphere and the subsequent sulphation of
the calcium carbonate present in the stone substratum. The sulphation of the carbonate
rocks (limestone, marble, etc.) and of the mortars can occur by two mechanisms:
• Direct mechanism
CaCO3 + H2SO4 + H2O ⇒ CaSO4•2H2O + CO2 (wet deposition: SO4--)
• First, in presence of water, there is the formation of emi-hydrated calcium sulphate
(CaSO3•0.5H2O), followed by the oxidation into hydrated calcium sulphate, that is
gypsum (dry deposition: SO2).
The responsible components of the black colour of these layers of deterioration are the
carbonaceous particles deriving from the incomplete combustion of fossils fuels. These
particles, in accordance with their high specific surface (Figure 2.8, right) and small
contents of heavy metals (Pb, Zn, V, Cu, etc.), act as catalyst in the sulphur oxidation.
Sometimes the carbonaceous particles can produce directly crystals of gypsum. In addition,
products of natural deposition (soil dust, biological particles, sea-spray etc.) are usually
present in the black crusts. Summarizing the components of the black crusts are:
 Gypsum (main component, due to the sulphation process)
 Carbonaceous particles
 Soil dust (mainly quartz)
 Sea-spray (in maritime areas)
 Biological particles
 Carbonate and silicate granules belonging to the substratum

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 Organic components (biological or anthropic origin).

Figure 2.8 – The head and the face of the statue, on the left, show evident black crusts.
On the right, a carbonaceous particle observed by scanning electron microscope.

2.5 Cleaning of stone artefacts

2.5.1 General rules to observe during the cleaning
Cleaning must be controllable in every stage, gradual and selective. “Controllable” means
that the actual effect of the cleaning must not depend on the operator. The use of the
scalpel, for example, is strictly connected to the way the restorer works, while a pack, once
the contact time and the concentration of the components are defined, has a final effect
which is independent from the operator. “Gradual” means that the operator must be able to
stop his action at any time during the cleaning. “Selective”: this word has been used mainly
with reference to the preservation of the covering layer; sometimes it is necessary to clean
the dirt without even damaging this layer.
Cleaning must avoid production of materials dangerous for conservation (for example:
water-soluble salts). This rule has been introduced to handle cleaning with aggressive
chemical substances (acids and bases). Cleaning must avoid every kind of alteration of the
surface (for example: micro-fractures, abrasions, scratches). This rule has been introduced
to regulate the cleaning with mechanical instruments (micro sand-blaster, scalpel, etc.).
There are three kinds of cleaning for the stone materials: physical, chemical, mechanical. If
needed, they must be applied in the exact order listed above which also refers to the
increasing aggressiveness on the surface.

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2.5.2 Physical cleaning

In this operation the dirt must be dissolved and the operator must find the solvent for
dissolve. In order to choose the correct solvent you need to follow the principle that “the
similar dissolves the similar”, which scientifically means that the solvent must have a
polarity similar to that of the dirt.
There are 3 ways to find the suitable solvent to clean the dirt, clearly with different costs:
1) Make a chemical analysis of the substances to remove and, from their formula, find out
the polarity; this is obviously the most scientific method, the most precise, but also the
more expensive and not suitable for most of the operators. It is normally used for very
important jobs.
2) Discover, after a careful observation, the kind of dirt which is on the surface (after a
preliminary washing with water, very polar solvent, on the surface there will remain
wax, fat and resin). Of course this method implies that the operator is quite
experienced. For this method, the Teas diagrams are used which, if correctly applied,
can lead to good results. The use of these diagrams is briefly explained below.
3) Make tests on the surface in order to evaluate the polarity of the dirt, as explained later.

THE TEAS DIAGRAMS

The Teas triangle is a ternary diagram (Figure 2.9) where in the 3 sides are mentioned the
values of Fp (polar), Fh (hydrogen bonding) and Fd (non polar): these are the so-called
solubility parameters which define a value of polarity of a specific substance (for example
the ethyl alcohol has 19, 45 and 36 respectively). These parameters are useful models to
make reasonable forecasts on the efficiency of a solvent towards the substance to be
dissolved. In the same diagram you can represent resins, waxes, fats, etc., so that it is
simple the comparison between solvent and substance to be dissolved (Figure 2.10).
You can practically operate like this: you can try to melt the dirt which is at the edge of the
examined area with a certain solvent; if this does not dissolve the dirt, you try with another
one, on the opposite side; if even this doesn’t work, you can mix them both at 50% (so
having an intermediate polarity) or you can carry on trying with other percentages.
Normally, in the most complicated cases, you will use a mixture in equal parts.

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Figure 2.9 – Representation of some solvents in the Teas diagram, where in the 3 sides are
mentioned the so-called solubility parameters Fp (polar), Fh (hydrogen bonding) and Fd
(non polar).

Figure 2.10 – Representation of different substances in the Teas diagram.

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TESTS ON THE SURFACE

Various tests can be made on the surface to clean, using mixtures of solvents whose
polarity is known (the parameter Fd is considered the more indicative). When the mixture
dissolves the dirt, you have a precise indication on the polarity of the substances to
remove. One of the most widely used test is to Feller, by using three solvents: acetone,
toluene and cyclohexane, and preparing 13 mixtures in the proportions shown in table 2.1.
These mixtures contain toluene, a toxic solvent, therefore should be used only to make the
solubility tests (where the exposure to fumes is minimum) not for the total cleaning of the
work, where there are longer exposure times and fume volumes much bigger. Once that the
suitable mixture to dissolve the dirt has been found, a solvent of low toxicity for the
cleaning can be selected, which has a similar Fd to that of the mixture found by the test.

Table 2.1 – Composition of the mixtures for the Feller’s test.

Mixture % Volume of
n. Fd Cyclohexane Toluene Acetone
1 96 100 0 0
2 92 75 25 0
3 88 50 50 0
4 84 25 75 0
5 80 0 100 0
6 76 0 87.5 12.5
7 72 0 75 25
8 68 0 62.5 37.5
9 64 0 50 50
10 60 0 37.5 62.5
11 56 0 25 75
12 52 0 12.5 87.5
13 47 0 0 100

Even though it is quick and practical, this test reaches the Fd 47 polarity value, leaving
unexplored a considerable area of a higher polarity. For this reason, many people use a
new test, by utilizing the Ligroin product, a nearly a-polar solvent, and not toxic, which

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covers a wider polarity interval (Fd = 97 to 36) and is easily found in the Italian market.
Test mixtures are prepared using three solvents (Acetone, Ethanol and Ligroin) as shown
in table 2.2.

Table 2.2 – Composition of the mixtures by using Ligroin instead of toluene.

Volume % Solubility parameters
Mixture
Ligroin Acetone Ethanol Fd Fp Fh
L 100 97 2 1
LA1 90 10 92 5 3
LA2 80 20 87 8 5
LA3 70 30 82 11 7
LA4 60 40 77 14 9
LA5 50 50 72 17 11
LA6 40 60 67 20 13
LA7 30 70 62 23 15
LA8 20 80 57 26 17
LA9 10 90 52 29 19
A 100 47 32 21
LE1 90 10 91 4 5
LE2 80 20 85 5 10
LE3 70 30 79 7 14
LE4 60 40 73 8 19
LE5 50 50 67 10 23
LE6 40 60 60 12 28
LE7 30 70 54 13 33
LE8 20 80 48 15 37
LE9 10 90 42 16 42
E 100 36 18 46
AE1 75 25 44 29 27
AE2 50 50 42 25 33
AE3 25 75 39 21 40

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2.5.3 Chemical cleaning

In this phase you have to act on what is left out on the surface, after the physical cleaning,
which normally has good success with substances of organic type. The chemical cleaning
consists in transforming the dirt, usually salts and salt deposits, into soluble substances
with water and so easily removable from the surface with rinses. This kind of cleaning, if
not attentively and correctly made, can damage the surface. In effect if strong acids and
bases are used, these mixtures can transform the salt deposits but they also attack the
surface of the artwork.

USE OF AB57 MIXTURE

To avoid the damages frequently caused by the restorers, in the 70’s the Italian Central
Institute for Restoration studied a cleaning mixture to use for the chemical cleaning of the
stone materials, named AB57, whose composition for a water litre is the following:
Ammonium bicarbonate NH4HCO3 30 g
Sodium bicarbonate NaHCO3 50 g
Disodium or tetrasodium salt E.D.T.A. 25 g
Desogen 10 cl
Carboxymethylcellulose 60 g
Its preparation is very simple: the various substances are dissolved in water, then mixed
with CMC (Carboxymethylcellulose), which makes a high density mixture with very good
properties as an excellent water retention. This poultice is applied to stone and frescoes
surfaces (Figure 2.11). The various ingredients which constitute the cleaning mixture react
with the salt deposits of the surface, especially calcium carbonate.

Figure 2.11 – Application of the cleaning mixture AB57 on a stone surface.

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The ammonium bicarbonate reacts with calcium carbonate according to the following
reaction:
2 NH4HCO3 + CaCO3 => Ca(HCO3)2 + (NH4)2CO3
Calcium carbonate is transformed into calcium bicarbonate, which is about 100 times more
soluble in water; furthermore the ammonium carbonate ((NH4)2CO3) immediately
decomposes into NH3, CO2 and H2O, so that it forms little bubbles which mechanically
favour the detachment of the deposits from the surface.
The second component of AB57 (sodium bicarbonate) reacts with calcium carbonate
according to the following reaction:
2NaHCO3 + CaCO3 => Na2CO3 + Ca(HCO3)2
Also in this reaction the calcium carbonate is transformed into bicarbonate, but sodium
bicarbonate is more aggressive than calcium bicarbonate. The produced Na2CO3 is a very
soluble salt, but in this case it does not decompose and remains on the surface: it must be
removed with several rinses.
The third component (EDTA) reacts with calcium carbonate tearing out the calcium atom,
because it is a strong chelating agent and it tends to form strong bonds with metal atoms,
especially with calcium.
The fourth component (Desogen) is a surfactant which improves the wettability of the
cleaning mixture. In fact water is a very polar solvent, and the presence of the tensoactive
reduces the superficial tension, increasing the contact area with dirt and thus making the
penetration easier.
The mixture AB57 is normally suggested for cleaning stone because, as shown in the
above-mentioned reactions, it acts attacking the carbonates. To this regard it needs to point
out that often artefacts of carbonatic composition have to be cleaned (marble, travertine,
marlstone, mortars, etc). In this case deposits of CaCO3 can be found on a surface of
CaCO3. In this particular situation, in order to avoid the risk to attack also the main
surface, it is therefore necessary to modify the composition of the mixture AB57. The main
thing is to decrease the quantity of the most aggressive reagents (EDTA and NaHCO3) and
to increase that of NH4HCO3, which has a softer action.
To get a correct cleaning in this particular situation it is necessary to find the most suitable
mixture by making tests with at least three mixtures of different composition, with low,
medium and high aggressive level, respectively. Once the most efficient mixture has been

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found, it is very important to determine the correct timing of contact with the poultice. This
must be taken away before that a significant attack to the salt deposits occurs. A longer
time can bring to a reaction also with the calcareous surface. However you need to
consider that the deposits, being of secondary form, are less compact compared to the
surface, and normally this last needs a longer time to begin to react. There are no precise
rules to formulate the cleaning mixture suitable for calcareous surfaces; three formulas are
given in order of increasing chemical aggressiveness:
1) NH4HCO3 saturated solution
2) NH4HCO3, 60 g, plus EDTA, 10 g
3) NH4HCO3, 60 g, plus EDTA, 10 g, plus NaHCO3, 10 g.
The tests of cleaning should be made following the previous order as follows: for every
cleaning mixture prepare a pack on a small area of the surface in a square shape of 20 cm
side, which well represents the kind of dirt. Subdivide the pack into four squares and after
6 hours take away the first one and check if the dirt has been attacked. If not, take away the
second square after 12 hours and so on, as shown in Figure 2.12. In case you fail with that
mixture, you try with the intermediate one and, if necessary, with the most aggressive one.
This is the most correct way of operating to find out the best kind of pack and the correct
contact time.

6 12 12
hours hours hours
18 24 18 24 18 24 24
hours hours hours hours hours hours hours

Figure 2.12 – Scheme for the realization of the tests for establishing the most suitable
mixture for cleaning surfaces of artefacts made of calcareous rocks.

USE OF IONIC EXCHANGE RESINS

In the chemical cleaning you can also use ionic exchange resins, products widely used in
the water treatments. Resins of this type can exchange their acid (H+) or basic (OH-)
groups with the cations or anions of the salt deposits.

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The chemical mechanism of the reactions can be so schematized:

H
a) Cationic resin + CaCO3 = Cationic resin Ca + CO2 + H2O
H
OH
b) Anionic resin + CaSO4 = Anionic resin SO3 + Ca(OH)2
OH

These resins are powders that, mixed with water, give rise to a gelatinous substance that
can be applied on the surface with brushes or packs; this substance does not penetrate the
pores and is easily removable (Figure 2.13).
The cationic resins bind a metal and free H+ ions, so creating an acid environment: this you
have to consider when operating on a calcareous surface, considering also that the resin
can start to bind also calcium of the surface if the contact time is too long.
On the contrary anionic resins bond to the anionic part of the salt and free OH- ions, so
creating a basic environment, which does not create any particular problem. These resins
are very suitable for cleaning black crusts (see reaction b); SO4 is torn from the calcium
sulphate, so destroying its structure and even if it deals with calcareous stone, this is not
attacked.

Figure 2.13 – Removal of ionic exchange resins from the black crusts on a stone surface.

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2.5.4 Mechanical cleaning

MANUAL CLEANING
This type of cleaning is performed by means of simple manual tools, such as spatulas,
scalpels, brushes, cutters, and sanders.

MICRO SAND-BLASTER
The use of a micro sand blaster (Figure 2.14) is the mechanical cleaning method, certainly
the most popular for cleaning of even big size deposits. If properly used, the micro sand
blaster can clean according to the general rules described in 2.5.1.

Figure 2.14 – Micro sand-blaster for mechanical cleaning.

This kind of cleaning is based on the abrasive action of various kinds of particles which are
blasted by a compressed air jet on the surface to clean. The parameters that influence this
kind of work are:
1) hardness of the bullets
2) shape and size of the bullets
3) jet pressure
4) diameter of the exit nozzle
5) distance nozzle-surface
6) application time of the jet.
The hardness of the bullets is fundamental because, to avoid damaging the surface, you
have to remember that the bullet must be harder than the deposit to eliminate but equal or

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less than the surface to clean. In the market there is a wide range of products to use as
bullets: silica, spheres of marble and glass and various kinds of wood sawdust, as the coat
of peach stone, walnuts, and other. These powders can have round or sharp shapes and, of
course, different diameters.
The other parameter to control is the pressure of the jet on the surface: to avoid damages,
the pressure should never be more than 1.5 Bar. The usual pressure of the machine is 3-6
Bar which, at a distance of 30-40 cm from the surface, produces a pressure of more than
1.5 Bar. To avoid this inconvenient, there are on the market special nozzles (JOS method),
which throw the bullets with a helical movement at low pressure (0.1-1 Bar). The
traditional and JOS methods are compared in Figure 2.15 and Table 2.3. The JOS system is
much better than the traditional, both for low pressure and because the bullets hit the
surface with a less dangerous direction.

Figure 2.15 – Comparison between the throwing of the traditional (left) and JOS (right)
method for micro sand-blaster.

Table 2.3 – Comparison between the properties of traditional and JOS methods
for micro-sand blaster
Compressor Distance from Pressure on the Bullet size
Method
pressure (Bar) the surface (cm) surface (Bar) (µm)
Traditional 3-6 30-40 > 1.5 400

2 35-40 0.5 300

JOS
0.5 20 0.2 300

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ULTRASONIC DEVICE
This method is used to remove small deposits. It is quite slow, but it absolutely does not
damage surfaces. The ultrasounds, generated from a small source (Figure 2.16, left),
compress and expand the air that, when reaches the deposit makes it vibrate and after some
time manages to detach it from the surface (if it is of small dimensions). The method is
recommended to work with a wet surface because the ultrasounds spread more efficiently.

Figure 2.16 – Cleaning apparatus for ultrasounds treatment (left)

and device for the atomizing system (right).

ATOMIZING SYSTEM
A very simple and non-destructive way of cleaning stone surfaces is to use atomized water
(Figure 2.16, right), which combines a good washing with the removal of soluble salts
from the surfaces. Water chemically acts by dissolving gypsum and secondary calcite, the
main binder materials of crusts, which can be thus easily removed. The strong pressure of
the liquid produces extremely small drops, improving the water penetration into dirt and
therefore the cleaning efficiency. Due to their small size, drops are practically not
subjected to gravity, thus allowing to reach with their cleaning effect even those areas
which are very difficult to reach. Another advantage, though secondary, is the physical
cleaning produced by the atomizing of the droplets and by the water steam over the
surfaces of the artefact.

LASER TECHNOLOGY
The use of laser technology has given excellent results when applied to the restoration of
artwork, and researchers are still at work to further widen the possibilities of laser

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applications in the restoration field. Particularly the Nd-Yag laser, used with the Q-switch
mode, assures a high cleaning effect, without any kind of thermal or mechanical effect,
thus preserving the integrity of the substratum.
So laser cleaning proves to be:
a) selective: the laser beam is absorbed by dirt without affecting the substratum
b) graduated: the beam power can be varied according to the operator’s needs.
At the moment, laser apparatus, such as the one indicated in Figure 2.17 (left), is mainly
used to remove black crusts on light colour stones.
Once certain parameters are fixed, such as length and power of the impulse, the radiations
are absorbed by the crust, which is eventually vaporized if brought to very high
temperature in a short time (4000-5000 K). When radiations reach the marble or the light
colour stone, they are reflected as if they were a normal white light, without causing any
damage.

Figure 2.17 – An example of source apparatus for laser beam (left)

and conductivity meter (right).

2.5.5 Measurement of soluble salts

The instrument used to calculate amount of water soluble salts in artistic artefacts is a
conductivity meter (Figure 2.17, right). To this purpose, the soluble salts are extracted by
preparing and applying a carboxymethylcellulose poultice on the stone surface (see 2.5.3,
Use of ionic exchange resins). The water soluble salts, present inside the stone, go up into
the poultice during evaporation.

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The carboxymethyilcellulose, when is completely dry, is placed in a beaker with distilled

water on a magnetic stirrer (Figure 2.17, right). With the conductivity meter it is possible
to know the amount of soluble salts in solution.

2.6 Consolidation and Protection

2.6.1 Reasons and aims of treatment

The term “consolidation” indicates a treatment designed to improve the cohesion and
adhesion between the constituents of a stone material. The decision to consolidate an
artifact is fundamentally related to the cohesion of the constituent material.
The consolidation can be necessary for two main reasons:
- loss or decline of cohesion of the material, with a decrease of mechanical and
chemical-physical characteristics that determine the intrinsic properties of a
material (Figure 2.18);
- loss or lack of adhesion between layers or parts of the artifact, for example the
layers of a fresco.

Figure 2.18. – Example of material to be consolidated: deteriorated marble.

In other words, the materials to be used for consolidation should bring structural benefits to
the material constituent the artifact, by regenerating the structural continuity of the stone

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material, and restoring the primary characteristics of the material, at least near to the initial
value. But they must not exaggerate in this, otherwise may generate imbalances and
tensions between stone material and consolidated parts, very dangerous for the structures.
Practically, they must not have complete continuity nor create blockages of the porosity. In
addition the consolidation should comply with the stone materials and everything should
be done in the respect of the significance of the artifact, without altering its appearance
(increase of reflectance and saturation of the colors) as well as its iconography.
The materials used for the consolidation treatment must have the following characteristics:
- reversibility:
the added material can be removed; this is important especially in case of
preconsolidation;
- compatibility:
the added material coexists with the original without causing excessive stress;
- durability:
the added material retains its characteristics for a long time;
- security:
the products used must respect the surrounding environment, during and after the
application, and the safety and health of operators.
The consolidating materials may be of organic and inorganic nature. The inorganic
consolidants have considerable affinity with the stone, regarding the physical properties,
and have a duration exceeding with reference to organic ones. The improvement of
mechanical properties induced by inorganic consolidant is lower and it is not possible to
weld the cracks if the distances between the walls are more than 50-100 microns. Where
the taking of the inorganic compound is too rapid, there may be clogging of the superficial
pores. Also for organic consolidants there are difficulties in penetration, since they are
polymers with large molecules.
Each stone undergoes processes of transformation which are caused by the imbalance with
environment. The aim of protection interventions is to make less likely or slow these
changes, and the aim can be achieved by acting either on the environment either on the
stone materials.
The aim of protection, made with chemical substances, is to reduce the penetration of
water inside the porous structure, so that are reduced all the phenomena that develop in the

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presence of water, such as transport and crystallization of salts and the phenomenon of
freezing/thawing.

2.6.2. Inorganic consolidants

CALCIUM HYDROXIDE
The consolidation by using calcium hydroxide in aqueous suspension derives from the
formation of calcium carbonate by reaction with carbon dioxide of the air:
Ca(OH)2 + CO2 CaCO3 + H2O
Treatments with calcium hydroxide have been used in particular in the 20th century with
unsatisfactory results. These treatments form a thin layer (“sacrificial layer”), non-
transparent, which represents a system of protection for the stone material. So, the
principal function of calcium hydroxide is that of protective rather than consolidant.

BARIUM HYDROXIDE
Analogously to calcium hydroxide, barium hydroxide reacts with carbon dioxide to form
barium carbonate:
Ba(OH)2 + CO2 BaCO3 + H2O
The Ba and Ca ions have a similar ionic radius, so that barium can be substituted by
calcium. Barium carbonate has a coefficient of expansion similar to that of calcite (CaCO3)
and a low solubility. The porosity of the stone material is reduced only partially, without
any formation of a layer impermeable to water vapor. It cannot weld cracks larger than 50
microns. The bleaching of the surface can be drawback, which can be avoided by removing
the excess of hydroxide on the surface.

ETHYL SILICATE AND SILICON RESINS

These two products are intermediate between organic and inorganic consolidants. The
ethyl silicate and the silicone resins, in presence of water, will hydrolyze giving rise to the
formation of hydrated silica, that precipitates as amorphous material and can bind to the
minerals of the stone material or can condense with hydroxyl groups of these materials.
Thereafter, the hydrated silica undergoes a slow process of dehydration and
polymerization. The ethyl silicate available commercially is dissolved in a solvent (usually
ethanol) and contains a catalyst of hydrolysis. The low molecular weight and the low

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viscosity of the solutions favor penetration. The complete polymerization occurs after
about three weeks after the treatment.

2.6.3. Organic consolidants

GENERALITY
All consolidant organic polymers are synthetic. Their molecules are obtained from basic
molecules or “monomers”. If the monomers are equal it is a “homopolymer”, if there are
two or three different types you have a “copolymer”.
The structure of molecules can be linear or three-dimensional. The polymers with a linear
structure are “thermoplastic”, i.e. they soften and melt by heating. Many have a certain
solubility at room temperature in organic solvents, and in theory are removable. In the
polymers with reticulated structure, the monomers are able to fasten other chains with
cross links; therefore, these resins are known as “thermo-hardening” (they burn at high
temperatures). They are irreversible, have high mechanical resistance, less flexibility and
high fragility, high adhesive power, strong internal cohesion.
The resins were born in the years 30-40 of the last century and are made from polymer,
solvent, stabilizer, plasticizer, charge (inert material), colorant, emulsifier. They can have
all these components, or even just the two fundamental: polymer and solvent. All resins are
soluble in organic solvents but not in water. The stabilizer delays the degradation of the
resin, the emulsifier lets you to mix the resin with water (primal) and the plasticizer makes
the resin less fluid; the colors, which are in the mixture, must not react with the resin or the
stone.

ACRYLIC, EPOXY AND POLYESTER RESINS

Acrylic resins like Paraloid B-72, Paraloid B-44, Primal B-60, Primal AC33 are
thermoplastic materials, soluble in organic solvents, with good resistance to aging, to
chemicals and to light. They have good adhesion, but are not structural adhesives.
The depth of penetration is not greater than 0.5-1cm, and it depends on the type of solvent
that is used (acetone or thinner neutral).
The epoxy resins are thermosetting materials; for reaction with the hardener is obtained the
final product. They have a good chemical resistance, are resistant to water and organic
solvents, less well to UV radiation; have good mechanical properties and are excellent as

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an adhesives. Unlike other resins, the epoxy can’t catalyze if you add an excess of
hardener.
The reaction of the polyester resins proceeds rapidly, so that the workability time is 5-15
minutes, and hardening is achieved within 30 minutes. The resin/catalyst ratio is not as
stringent as for the epoxy, so that often, to accelerate the reaction at low temperature, just
increase the catalyst. The reaction proceeds with a decrease of the volume, which can also
get 8 to 9%; this makes these resins unsuitable to be used for structural reinforcement,
contrary to the epoxy resins. Polyester resins are sensitive to yellowing and to absorption
of water; after cross-linking, they cannot be dissolved in solvents, but their removal can be
done by swelling with ethyl acetate or acetone.

SILICONE AND POLYURETHANE RESINS

Silicone resins are called R.T.V. followed by a number, that indicates the plasticity and
density of the resin. The formation process is always the same, only changing the
plasticizer. They does not enter into the stone, but they have a good adhesion with the
material.
Lastly the polyurethane resins (foam) are used in various operation of conservation.

2.6.4 The application methods for the consolidants

For the artifacts of considerable size to be treated in situ, basically there are two methods
of application: by brush and by spray.
For small objects processed in the laboratory, it is better to treat them in other ways, for
example by capillarity up to complete immersion. The object is placed in a covered
container where it is immersed only for a small part in the consolidating solution, that is
kept at constant concentration. Then the level of the solution is increased at regular
intervals until completely to cover the object.
The treatment by complete immersion, at room temperature and room pressure, is similar
to the previous one, except that the level of solution can be increased immediately or
gradually to allow the solution to come out from the manufacture.
The treatment under vacuum requires a container with the escape routes for the air and
entrance of the solution, and a suction pump capable of achieving a suitable depression.
Thus the artifact is dried and de-gassed, in order to facilitate the entrance of the

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consolidating solution within the capillary channels. Normally you leave the artifact
immersed for 24 hours.
The distribution of the consolidant within the stone depends on many factors, like the
concentration of the solution, the type of solvent, the time of contact, pressure and
temperature in the work environment, pore size distribution of the stone.
In addition to the choice of the application method, the depth and regularity of penetration
of the consolidant depends on the type and size of the artifact to be treated, and its
conservation status in various areas.

2.6.5 Protective materials

In the past, the products used as protective materials were beeswax, vegetable oils and
natural resins. The protection is much more effective when it will penetrate deep and is not
prevented the evaporation of water coming from the inside.
The most important requirements for protective products are: minimal influence on the
optical properties of the material, stability to chemicals (in particular pollutants), stability
to UV radiation, impermeability to water, permeability to water steam, reversibility when
the protection has lost its effectiveness, absence of harmful by-products, and easy
applicability.
There are different products for different aims of application: water repellent and
waterproofing, against the growth of organisms, antagonist of ultraviolet and visible
radiations, ‘sacrifice’ surfaces as those “graffiti resistant”, and products which are against
erosion.
Some historical materials for protection of stone artifacts are: surface painting, protein
material (milk, white and yolk egg, glue), lime plaster, dried materials, paint (oils and
resins) and waxes; while the modern materials are: microcrystalline waxes, synthetic
acrylic and acryl-vinilic resins, siloxane, silanes and mixtures thereof with acrylic resins
(Dry film 104). These resins are very diverse than those used for the consolidation as it
regards polymeric formulation and mechanical characteristics, because they must form
consistent and elastic superficial films.
Finally there are some materials which give rise to the formation, on the surface of
limestones, of artificial layers which reduce the contact with the harmful materials. One of
these materials is the ammonium oxalate, which forms calcium oxalate. Such a film

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reduces the porosity, rather than to close it. It is not reversible, but highly compatible with
the substrates.
The ammonium oxalate, used in saturated solution (5-6%) in de-mineralized water (Table
2.4) is able to react with the superficial calcium carbonate, transforming it into calcium
oxalate:
CaCO3 + (NH4)2C2O4 = CaC2O4 + NH3 + CO2 + H2 O
Ca-carbonate + Ammonium oxalate = Ca-oxalate + ammonia + carbon dioxide + water

If gypsum is present, the reagent develops also an effective de-sulphuring action:

CaSO4 + (NH4)2C2O4 = CaC2O4 + (NH4)2SO4
Gypsum + Ammonium oxalate = calcium oxalate + ammonium sulphate

Table 2.4 - Physical-chemical characteristics of ammonium oxalate

to be used for protection.
Chemical formula (NH4)2C2O4 H2O •

Molecular weight 142.11 g/mol

Purity degree 99%
Content of volatile components 5% (maximum)
pH of a 5% solution 6-7
Content of metals (Na, Fe) <100 ppm
Content of chlorides <50 ppm
Solubility in water at room temperature 5%

The protective layer generated by reaction is thin but homogeneous, stable in acid
environment, breathable and transparent.
The solution must be applied as poultice with the cellulose pulp, interposing a sheet of
Japanese paper between the pack and the stone surface, the duration of applications should
be tested from case to case; generally it is 24 hours, but only of the order of 5 hours for
frescoes.

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2.7 Case studies

2.7.1 Traditional production of lime in Middle East

The construction techniques of ancient furnaces for limestone and the production of lime
and slaked lime in the Middle East have remained unchanged over time until the present
day. The research here presented was to document the types of kilns and traditional
operations for the production of lime in some countries like Yemen, Syria, and Egypt.
The materials for combustion generally vary with time: from wood in antiquity, to coal in
the fifteenth century, to fuel oil or manure of animals like in Yemen.

YEMEN
In Arabia Felix “Yemen”, in particular in the valley of Wadi Hadramut, lime (local name
“The Nura”) is generally produced by local limestone rocks, very rich in calcium
carbonate. The rock pebbles are baked in cylindrical ovens (“Miafi”), about 3 m high, 2 m
in diameter, made with raw bricks. They are open from the top and have a small opening
for introducing the fuel. Their form recalls the ovens described by Catone in the second
century B.C. For combustion, different materials are used: animal manure, old tires for car
and matchwood. These ovens are intermittent and must continuously be fed with the fuel to
keep the heat inside for two days, until to complete the baking of lime (decarbonation) and
the formation of quicklime.
After baking and cooling, the pebbles of quicklime were extracted and carried in another
place specially prepared for the slaking. They form a plan (“Al Mahkt”) covering an area
of 2.5 x 2 m or more, then sprayed with water, after which it begins to beat with cylindrical
sticks of wood until the total hydration of lime. Sometimes a mechanical equipment is used
inside the cylindrical cistern to ‘power down’ the calcium oxide pebbles (Figure 2.19).

Figure 2.19 – Steps of the lime production in Yemen: use of dung for burning (left),
manual hydration of quicklime (centre), slaked lime for sale (right).

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After that, the slaked lime is put on the market, especially for production of plasters (local
sand and lime) that are applied in brick made buildings to create a raw surface of sacrifice
for architecture of Yemen, which is materially very poor. Only the house of those who
have hence greater economic possibilities is adorned with the addition of colored oxides in
the mortar.

SIRYA
In Sirya, after a period of research, two old furnaces, abandoned for over one year, were
discovered in the area of Al Karma, after the route of Al-Zabaltani, in the outskirts of
Damascus (Figure 2.20).

Figure 2.20 – Lime production in Syria: the furnace in Al-Zabaltani.

The furnaces have circular form and are constructed of rough pieces of limestone rocks.
They are open from the top and have a small opening at the bottom for feeding the furnace.
Their diameter is about four meters, while the height is about eight meters. Both the
furnaces inside were plastered with clay. Each of them has a capacity of 75-100 tons of
limestone rocks. The stones were brought from the areas of Al-meza (along the road to
Lebanon) and Hama, where many rocks rich in calcium carbonate are present. Kernels of
apricot, residues of the olive mills and sawdust were used as combustible in the kilns. The
product of these furnaces can be sold as pebbles of calcium oxide (quicklime), or as slaked
lime. Unfortunately, these kilns were abandoned after the death of the owner.
Always in Damascus, near to Suq Al Hamid, at Bap al-Jabia, a old kiln was demolished
some years ago and a deposit for lime from Hama was built in the place of the kiln. The

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owner of this kiln made us aware that, in the city of Hama, north of Damascus, there is an
entrepreneur of lime, called Ziad Al-Kalas, who is doing this job for many years and also
his ancestors were workers of the lime. Very probably for this reason, that family took the
surname “Kalas”, which in Arabic means ‘those who work the lime’.
At Hama, Al-Sarihin is the area of production of lime. Here the furnaces are constructed
below ground, with local stone and plastered with clay. Their diameter is about four meters
while their height is six meters. They are open from the top and have a small opening from
the back for feeding the kilns. The raw material is brought from quarries at the south of
Hama, it is reduced in blocks of small/medium size (30-50 cm) and put inside the furnace
in particular way, in order to obtain a vacuum in the centre of the oven, which will be the
combustion chamber. They are continuously fed for seven days, also with the help of air
pumps, to enable the flame to reach the top of the furnace. Exhausted or burned fossil fuels
are used as combustible. After the baking (calcination of the calcareous stones) and the
subsequent cooling, the pebbles of quicklime are removed from the furnace and hydrated
in order to obtain lime ready to be used.
The capacity of these furnaces varies between 30-50 tons of stones. In Syria, the lime is
used for the preservation of historic monuments, especially for the ancient mosques, and in
different sectors of industry.

EGYPT
In Egypt, specifically in the village of Turt Al-Bald, outskirts of Cairo “Shaq Al-Thuban”,
there is a large craft area for working marble; at the end of this area, there are several
operating quarries of limestone. In vicinity of the quarries of limestone, are located kilns
for the production of lime (Figure 2.21).

Figure 2.21 – Lime production in Egypt: openings for feeding ovens (left), preparing oven
for cooking (centre), quicklime and hydrated lime for sale (right).

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Here the construction of the furnaces is different than Yemenis and Syrians ones. In Egypt,
the kilns have a rectangular shape, built with local stone and are open from above and
frontally; in the back there are three openings (40 x 70 cm) for the introduction of flames.
The ovens are constructed on the surface, with a base of 7 x 6 m and a height of about 3 m.
Once transported to the site by means of trucks, the stones are crushed until you get the
size required (10-45 cm). Subsequently, you begin a ordered arrangement of the stones
inside the ovens, so that the ones of larger size are placed at the bottom, keeping free the
openings at the rear; after which you will introduce the small stones until filling the
furnace. Each oven has a capacity of 90-100 tons of limestone.
The next step is the ignition of the furnace, with fuel oil that feeds ovens from the back.
The cooking cycle, till the complete decarbonation of calcium carbonate has a duration of
24 - 30 hours. After that you let cool the calcium oxide (quicklime), it is then hydrated
(lime) and placed on the market.

2.7.2 Development of restoration mortars

The use in restoration interventions of mortars based mainly on Portland cement was very
common until few years ago. The spread of cement mortar and reinforced concrete was
due to the easiness of application, to the low costs and the rapid hardening. But, because of
their chemical-physical incompatibility with the original materials and their scarce
durability, the use of these restoration mortars was often one of the main causes of damage
for the archaeological and architectural heritage. The main deterioration processes, due to
the use of cement or reinforced concrete, are: efflorescence of salts, disintegration,
detachments.
Now we are aware of the damages suffered by archaeological and architectonic heritage
because of the use of cement mortars in restoration interventions, therefore fortunately a
progressive abandonment of cement in restoration works is taking place.
At present in Italy the use of Portland cement in conservation interventions is unusual.
Premixed mortars, hydraulic lime mortars, or strange bio-compatible products have taken
the place of cement mortars. Unfortunately the composition of the binders, and the physic-
mechanical characteristics of the restoration mortars are often ignored by restorers and
conservation managers. In addition there isn’t a specific European standard for restoration
mortars.

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In this climate of general confusion there is a proliferation of products (binders and

premixed mortars) sometimes worse than the classical cement mortar. Unfortunately the
progressive abandonment of the cement in conservation works hasn’t been joined by the
development of opportune restoration mortars.
The parameters to take into account in order to develop suitable restoration mortars are:
- Compatibility with the materials present in the monument or in the archaeological
structure. In order to assure the compatibility we have to characterize the ancient
materials and evaluate their conservation conditions. Also the knowledge of the
composition and of the mechanical properties of the restoration mortars is
indispensable,
- Function: for example mortars for injection, for plastering, etc.,
- Environment in which the artifact is located (internal, external, highly polluted, etc.).
In addition a restoration mortar should have to be removable from the artefact,
recognizable from the original materials and obviously non-poisonous for the restorers.
In Italy, at present, the hydraulic lime mortars are the most employed in the restoration
interventions. The only European standard on building limes is EN 459-1, that recognises
three different limes with hydraulic properties:
– HL (hydraulic lime)
– NHL (natural hydraulic lime)
– FL (formulated lime).
Unfortunately only NHL, according to this standard, is obtained by the calcination of
marly limestones, while the other two limes can be a mixture of calcium hydroxide and
cement. The previous standard classifies the hydraulic degree according to the compressive
strength and the lime (Ca(OH)2) content (Table 2.5). It doesn’t take into account the
hydraulic index.

Table 2.5 – Hydraulic degree for NHL according to EN 459-1.

Ca(OH)2 Compressive strength (MPa)

Hydraulic
degree (%) 7 days 28 days
2 ≥ 35 - 2-7
3.5 ≥ 25 - 3.5 - 10
5 ≥ 15 ≥2 5 - 15

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In order to develop restoration mortars compatible with original materials, easily

removable and at no high costs, several commercial hydraulic limes were examined by
CNR-ISTEC in Faenza. The analyses highlighted that all the binders had unexpectedly
high concentrations of calcite (aggregate), likely due to low baking temperatures
(~1000°C), or to a deliberate addition of CaCO3 in order to obtain values of compressive
strength in accordance to European standard EN 459-1. In addition, elemental and
mineralogical analyses showed that natural hydraulic limes (for example NHL 3.5)
produced by different firms are classified by EN 459-1 in the same manner, even though
they have chemical-mineralogical compositions remarkably different, other than different
values of hydraulic index.
Subsequently three mortars were prepared by using three commercial binders, and then
examined in order to identify their mineralogical composition and evaluate some
mechanical properties (in particular adhesive strength and flexural strength).
Considering the high concentrations of calcite detected in the binders, the mortars were
prepared in this way: one part of binder, two parts of aggregate (powder of limestone), and
water with a percentage of about 20% by weight of the other two components (binder and
aggregate).
The mortars were examined two months after their preparation. In order to evaluate the
adhesion properties of the mortars, small models of mosaic were made (six for every
binder). Tests of adhesive strength were carried out on these mosaics in accordance to a
procedure standardized by the CNR laboratories in Faenza (Figure 2.22).

Figure 2.22 – Instrument used in order to determine the adhesive strength of the mortars.

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Based on the analytical data (absence of clinker, low hydraulicity degree, negligible
concentrations of soluble salts and the best mechanical properties), the ease of use, the
quick times of setting and the final colour, a mortar prepared with the best NHL 3.5 was
prepared, with the same ratios of the ones investigated. This mortar was tested in a
conservation intervention of two floor mosaic fragments coming from the Late Antique
Villa in S. Giusto (North Apulia, Italy), from where they had been lifted few years before.
The restoration mortar was successfully used for re-laying and connecting the two mosaic
fragments on a movable support of aluminium with a honeycomb structure. After this test,
different NHL mortars were successfully used for in situ conservation interventions in the
Archaeological Park of Classe near Ravenna (Italy). The restoration mortars were applied
for plastering, for filling lacunae and for reinforcing wall remains (Figure 2.23).

Figure 2.23 – Archaeological Park of Classe, Ravenna (Italy). In situ conservation by NHL
mortars: reinforcing of wall remains, filling of lacuna.

More recently mortars based on NHL 5 were used for re-laying about 250 mosaic
fragments (about 240 m2 of mosaic), coming from the floor of the Church “A” of the Late
Antiquity of S. Giusto (Lucera, southern Italy), on movable supports (Aerolam) (Figure
2.24).

2.7.3 Archaeometric case studies of stone materials

Big archaeometric studies of natural and artificial materials coming from three different
Italian archaeological sites are shown: San Severo (Classe, Ravenna), Torretta Vecchia
(Collesalvetti, Livorno), Pietratonda (Civitella-Paganico, Grosseto).

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Figure 2.24 – Restoration of the mosaics from the Church “A” of S. Giusto (Lucera,
southern Italy) by mortars based on NHL 5.

SAN SEVERO (CLASSE, RAVENNA)

The complex of San Severo is part of the archaeological area of Classe near Ravenna
(north-eastern Italy). In the San Severo site, structures of various age are present, from
Roman period to Middle Ages. Many mortar samples were collected from remains of wall
structures with known age. The samples were analyzed by different analytical techniques
according to the analytical sequence specific for mortars showed in the chapter 3,
paragraph 3.5.2. The results highlighted that:
- mortars of the Roman period have hydraulic characteristics due to the presence of
pozzolana among the aggregate, and the ratio binder/aggregate is 1:3;
- mortars of the Late Antiquity are hydraulic or weakly hydraulic, due to the presence
of “cocciopesto” among the aggregate; the ratio binder/aggregate is 1:2;
- mortars of the Middle Ages have aerial characteristics; in addition production
techniques of the lime and preparation manner of the mortars were not very
accurate; the ratio binder/aggregate is 1:2.

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As a consequence, masonries in San Severo can be easily dated on the basis of the
characteristics of the aggregate in the mortars: pozzolana for Roman mortars, cocciopesto
for Late Antiquity mortars and sand (without pozzolana and cocciopesto) for Medieval
mortars.

TORRETTA VECCHIA (COLLESALVETTI, LIVORNO)

Torretta Vecchia is a Roman archaeological site located in Tuscany (Central Italy). All
mosaics in this site are located in the bath sector: frigidarium, corridor and related rooms.
A specific archaeometric-technological study was carried out on all the mosaics in Torretta
Vecchia site, and the structures of all mosaic floors were detected. In particular three
different stratigraphies were identified:
- mosaic of the Frigidarium (FR1). From the bottom, the following layers can be
distinguished: 1) stones + bricks, 2) clay, 3) bricks, 4) lime + coarse aggregate, 5)
lime + thin aggregate, 6) bedding mortar, T) mosaic surface (tesserae);
- mosaics F, C, C1 (corridor) and L1 e L5 (rooms adjacent to C1 and F, respectively).
From the bottom: 1) terracotta slabs (rarely stone), 2) foundation mortar, 3) bedding
mortar, T) mosaic surface (tesserae);
- mosaics D-D1 (north sector of the corridor) and L3 (room next to D). From the
bottom: 1) foundation mortar directly on the ground, 2) bedding mortar, T) mosaic
surface (tesserae).
The analyses of mosaic materials (stone and glass tesserae, bedding mortars, foundation
mortars and brick fragments present in the structure of the same mosaics) were performed
according to the sequence shown in chapter 3, paragraph 3.5.2. They highlighted the
following results:
- similar lithologies used for obtaining the stone tesserae in the different mosaics
(generally local provenance, and a biunique correspondence between colour and
lithology)
- foundation mortars with similar composition and characteristics (same raw
materials and preparation manner)
- bricks with similar compositional and textural characteristics.
The mosaic floors were built at the same time, while there are three different structures
(Frigidarium, foundation with bricks and without) that could be justified by different
function of the floors.

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PIETRATONDA (CIVITELLA PAGANICO, GROSSETO)

In the archaeological site of Pietratonda three different sectors can be identified: residential
sector (AREA 1), productive sector (AREA 2), and baths (AREA 3). Mortars, plasters and
bricks coming from the different sectors were analyzed, together with clay samples from
Pietratonda’s area (XRD, XRF, DTA-TGA). The data obtained showed:
- only in productive sector were found hydraulic mortars (bedding mortars and
plaster), whose composition includes metakaolin;
- in the other sectors were found aerial or weakly hydraulic mortars due to the use of
cocciopesto;
- all the bricks were obtained by firing (850–900 °C) carbonatic clays, while the local
clays analyzed are not carbonatic.
Then the productive sector probably belongs to a different building phase and the bricks of
Pietratonda were not produced using local clays. Very probably the choice to apply in the
productive sector hydraulic mortars, based on lime and metakaolin, with high hydraulicity
degree and high mechanical properties, is due to the specific functions and characteristics
of this sector, where mortars and plasters were required, with high mechanical properties
and high durability in wet conditions.

Bibliography

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Alberti L.B., De statua, M. Collareta ed., Livorno, 1998.
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Bellocci G. et al., Nuovi materiali per lo scavo, il restauro e la conservazione dei beni
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Borgioli L., Polimeri di sintesi per la conservazione della pietra, Il Prato ed., Saonara
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Am. Assoc. Petrol. Geol. Mem., I, 1962, pp. 62-84.
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3 – MOSAICS

3.1 Manufacturing techniques

3.1.1 What mosaic is

Mosaic is the art of creating decorative images through the assemblage of small colored
pieces of stone, glass or other materials. Mosaic is used for decorating both flat and curved
architectonic surfaces, both inside and outside. Usually a distinction is made between wall
mosaics and floor mosaics, due to the different realization technique.
The human being since always has demonstrated the pleasure to decorate surfaces by using
small pieces of colored stone, and this makes it impossible to establish the origin of mosaic
with certainty. Also the origin of the term ‘mosaic’ is not yet established and several
hypotheses are suggested. A hypothesis indicates a origin from the Greek musaikòn, that
means ‘patient work worthy of the Muses’. Somebody suggests a origin from muzauwaq
that means ‘decoration’ in Arabic language; somebody else sees a connection with the
name Moses, and mosaic would mean ‘belonging to Moses’.
The decorative pieces of stone or other colored materials can be natural or artificial. In the
second case they must be opportunely prepared according to specific processing
techniques. In any case, the single pieces must be fixed to the surface to be decorated, so
that suitable application techniques have been adopted along the time.

3.1.2 Mosaic implementation

For the realization of the ancient mosaic in the shop of the artist the following facilities
were used: hammer, chisel, pliers, tiles (stone, glass, etc.), binder (lime), aggregates of
different sizes (sand, marble powder) and water.
Towards the end of the fourth century A.D., the Codex Theodosius reveals that in the late-
Hellenistic period several specialists cooperated in the execution of a mosaic:
Pictor imaginarius (the cartoonist), which was expected to provide the design and
composition “trying out the system, tracing the lines of the composition, and the procedure
for the implementation, so that he was the responsible for the realization of the
iconographic plan”;

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Parietarius, had the task of transferring the idea of the composition on the floor or wall
surface;
Musivarius, who inserted the tiles into the bedding mortar;
Lapidarius structor and Coctor calcis, laborers for the preparation of backgrounds and
materials of stone and glass.
In principle, with some exceptions, according to Vitruvio, a floor mosaic was composed of
three layers of preparation: after leveling the surface, and if not large enough it was
compressed, you begin to prepare the layers.
The first one from the bottom is called statumen (river stones and / or brick), the second
layer rudus (coarse mortar) and the third one nucleus (mortar similar to the previous, but
with fine aggregate) and finally the decorative tiles. Often mosaic floors did not comply
with the rule described by Vitruvio; constant feature is the presence of a layer of mortar
(sovra-nucleus) that consists almost exclusively of lime, with a thickness less than 5 mm.
The thickness of the various layers of preparation is different for each floor mosaic and can
change as needed in each ambient.
In general, the mosaics are made in “daily”, namely a piece of the mosaic decoration made
within one working day by a ‘musivarius’. The size of this “daily” varies according to:
setting time of the binder (bed layer) in which the tiles were inserted, the degree of
difficulty of the mosaic and the skill of the mosaicist. As for the history of performance
techniques, we have little evidence from the sources. Most of the information therefore
derives from direct observation of extant mosaic works.
For the diversity of support structures and composition of the preparatory layers, it is
useful to distinguish the mosaics in relation to the architectural structure to which they are
applied: floors, walls, ceilings or vaults. Apart from differences in the execution, time to
time dictated by the nature of the soil or the variety of available materials, with sufficient
accuracy it is possible to outline the phases of a floor mosaic, which remained largely
unchanged for centuries. The ground, after being dug, leveled and highly compressed
(Figure 3.1), was generally covered with three preparation layers, as was described by
Vitruvius in the first chapter of the seventh book. The first layer from the bottom
(statumen) is usually composed of a thick layer of large stones and / or materials without
clay binder; the second one (rudus), consisting of lime and sand or gravel, was beaten by
teams of workers with the mallet; the third layer (nucleus) was composed by the same

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mortar above, but with fine-grained aggregates. Obviously, the thickness of each layer
varies depending on the type and intended use of the space and the nature of the underlying
soil.

Figure 3.1 – The mallet to beat the ground and the roller for levelling the layers of mortar.

After that the preparation of the substrate has been completed, to better realize the
composition, the mosaicist draws the sketch of the figure (sinopia) with mortar applied
with a brush. Then a bedding layer (sovra-nucleus) is spread, less than 5mm thick, only
consisting of lime (sometimes with a small fraction of fine aggregate) in which the tesserae
are inserted (Figure 3.2).

4
3

Figure 3.2 – Vertical section of a Roman floor mosaic: 1-clay; 2-cobblestone and brick
chips; 3-lime mortar with aggregate of average size; 4-mortar with fine aggregate;
5-tesserae.  The  thickness  of  the  layers  is  indicated  on  the  left  in  cm.  

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The preparation of the base bed was made “daily”, i.e. only the necessary during a working
day; the measure of the “daily” was variable in accordance with the drawing to be carried
out, the skill of the mosaicist and the setting time of the mortar bedding. After the
completion of the mosaic, the floor was plastered with mortar of marble dust, sand and
lime to obtain a compact surface. It was then carefully polished, before with a pumice
stone, and then with beeswax or with other things. Instead, regards the technical
implementation of wall mosaics, the architectural and aesthetic necessities require that it
runs differently than the floor mosaic, especially as it regards the layers of preparation and
the processing accuracy of the surface. In general, the technique foresees the creation of a
first layer of mortar, called “ariccio”, composed by lime and coarse inert material, directly
applied on the wall to eliminate its lacunas and asperities. The thickness of this layer is
variable and depends on the imperfections it has to hide. After the application of this layer,
the surface appears uniform. Then a second layer of mortar was applied, a bit thinner that
the previous one: it is composed by lime containing inert material with variable grain size.
This layer, about 2 cm thick, has the function to sustain the following layer, whose direct
application to the wall is impossible because of its characteristics.
A characteristic of the second layer is the property to give elasticity and thickness to the
support of the mosaic, guaranteeing the physical stability to the decorations and the
transpiration of humidity. Usually in the first or in the second layer we can find straw in
the side of the mortar. The third and last applied layer is called layer of “allurement” and
there the tesserae are inserted when the mortar is still fresh (Figure 3.3). Its composition is
made of lime with very small fragments of inert materials. Its thickness varies from 3 to 5
mm, a thickness sufficient to ensure proper anchoring of the tiles.

3.1.3 Materials for mosaics

STONE MATERIALS
Due to the proximity of the Greek provinces, the customs and arts of the Greeks arrived in
Rome. This began when in 146 BC Lucio Mummio, Roman consul, took and sacked
Corinth and brought to Rome many works of art.
From 59 BC foreign marbles were imported and mosaic floors were spreading. Giulio
Cesare ordered that the camps had floors of this type, so in a few years, the spread of
multi-colored stones in Rome was very rapid.  

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Figure 3.3 – Mausoleum of Galla Placidia (Ravenna, Italy) where you see lines of
composition, pattern of implementation and the notches of the
trowel (on the left); section of a mosaic wall    (on  the  right).  
 
1
In Rome, marble from around the world was used for statues, columns and bas-reliefs, to
enrich not only the public buildings, but every single private house. The walls and floors of
the most beautiful temples and palaces were lined with imported marble, cut into different
shapes or tiles of various colors. For luxurious floors decorated with slabs of marble or
with compositions in opus sectile or tesselatum, the artists utilized colored marble of
exceptional beauty. The marbles were sent from each province: Spain, Mauritania,
Numidia, Tripolitania, Egypt, Asia Minor, Greece, etc.
In the big public buildings, thermae, and villas in the provinces far from Rome, where all
these rocks could not arrive, mosaic artist employed local stones.

THE GLASS
The amorphous solid material, commonly called glass, is characterized by the fact that it
has a long-range structural order, contrary to the typical crystalline solid substance (see
Chapter 6). The principal component of the glass is silica, which is defined component for
vitrification. Silica is found in nature in form of quartz in quartzite and quartz sand, that are
the main sources of silica.
The high fusion point of silica (about 1700 °C) limits its use in pure form; in fact, in
ancient times it was not possible to reach temperatures above 1000 °C. It was therefore
                                                                                                                         
1
The term marble is used here as historical and commercial sense. From a petrographic point of view, marble
is a carbonatic metamorphic rock derived from a structural change of sedimentary carbonate rocks.

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necessary to introduce certain substances that are able to change some physical and
chemical characteristics, such as the “melting”. Alkaline compounds are added to lower the
fusion point of the mixture; those most commonly used were sodium compounds, while in
more recent times were also used potassium compounds.
These compounds facilitate the production of a melted phase at relatively low
temperatures, but produce easily alterable glass. In the glassy mixture it is necessary to
introduce “stabilizer” substances in order to increase the hardness and decrease the
perishability of the glass. Calcium oxide (CaO) or magnesium oxide (MgO), but also lead
oxide (PbO), are among the most common stabilizers in ancient glass.
The glass, with its various shades of color and its sheen, is the most fascinating aspect of
the ancient mosaics. The glass is used almost exclusively for the construction of wall
mosaics, with some exceptions for floor mosaics.
Works in mosaic made with glass honored marble temples and public buildings, the floors
and walls of the villas in Rome and in the most distant provinces as well.
The nature of glass mosaic tessera is very complex; in reality, this category includes
various types of glass-based materials, with very different physical and chemical
properties. This diversity is demonstrated by the use of terminology sometimes confusing
and not universally recognized.
The metallic-leaf tessera is a tile in which a thin sheet of beaten metal (gold and silver) is
heated, placed on a glass substrate (a few millimeters thick) and another glass layer, called
folder (less than one millimeter thick), covers the metallic leaf to protect it from oxidation
and to increase the brightness.

OTHER MATERIALS
Besides the use of stone materials and glass for the creation of wall or floor mosaics, in
some cases it has been observed the use of different materials, such as terracotta, ceramics,
precious stones, shells, nacre, etc.

THE BINDERS (MORTAR FOR SUBSTRATES)

In ancient mosaics, they used mortar-based binders, that are inorganic materials capable,
when mixed with water, to join together the different components (see Chapter 2).
The mortar is a mixture of organic or inorganic binders with predominantly fine
aggregates, water and any addition of organic and/or inorganic additives (or only a mixture

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of binder and water) in such proportions as to give a workable dough, at the fresh state,
with suitable physical characteristics (porosity, permeability, etc.), mechanical properties
(strength, deformability and adherence), and opportune appearance and long durability
when hardened.
The complex of chemical and physical reactions that lead to the consolidation of the binder
takes the name of “setting reaction and hardening”. The first reaction is the transformation
of the material from ‘liquid’ to ‘solid’ that confers adhesion in a quite short time. The
complete process, however, occurs in many hours and sometimes several days, and leads to
the transformation of the binder in a very hard substance.
The binders, according to their characteristics, are divided into aerial binders and hydraulic
binders. The aerial binders (lime and gypsum) are mixed with water, but they harden in
presence of air. The hydraulic binders, on the contrary, require water, but they also harden
in water.

3.1.4 Definition of mosaic typologies

FLOOR MOSAIC
In the ancient world the floor mosaic was common in public and private buildings of every
social class, sometimes using recycled materials. In this chapter reserved for the mosaics, it
seems appropriate to list and describe in summary the main and most famous types of
ancient mosaic.

- Pebble mosaic: is a floor mosaic made of small and coloured pebbles laid on a layer of
lime or clay. In the most refined examples the details of the figures are rendered
with thin strips of lead or terracotta (Figure 3.4).
- Cocciopesto: floor mosaic made of mortar and cocciopesto (pieces of terracotta and
lime), red colored, sometimes with tesserae, irregular in shape and size, distributed
randomly. It was used to cover both pavements and cisterns (Figure 3.4).
- Opus Signinum: cocciopesto floor with lime cement, decorated with tesserae of
limestone to produce simple geometric designs (Figure 3.4).
- Opus Sectile:   floor or wall decoration made of polychrome marble slabs with different
thickness, cut in geometric shape, and laid in lime mortar to produce simple or
complex designs (Figure 3.5).

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Figure 3.4 – Typologies of floor mosaic: pebble mosaic (on the left),
cocciopesto (in the centre) and opus signinum (below).
 

Figure 3.5 – Typologies of floor mosaic: opus sectile.

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- Opus Scutulatum: floor characterized by the insertion of irregular fragments of

polychrome marbles and stones (scutulae) on a background of white limestone
tesserae (Figure 3.6).
- Opus Mixtum: floor decoration characterized by the interaction of different mosaic
typologies (scutulatum, sectile and segmentatum) enclosed by a black background
of opus tessellatum in white limestone (Figure 3.6).
- Opus Tessellatum: all types of floor mosaic, monochrome and polychrome, geometric or
figurative, realized with marble or stone tesserae quite large in size (Figure 3.7).
- Opus Incertum: floor mosaic made with tesserae irregular in form and size, placed in
lime mortar in diconnected way to form geometric or figurative design (Figure 3.7).

Figure 3.6 – Typologies of floor mosaic: opus scutulatum (on the left)
and opus mixtum (on the right).

Figure 3.7 – Typologies of floor mosaic: opus tessellatum (on the left)
and opus incertum (on the right).

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- Emblema: polychrome mosaic of small dimension produced in the workshop with small
tesserae, on its own base to facilitate its successive placement in another place
(Figure 3.8).
- Asaroton: floor mosaic used in the decoration of triclinia; produced using small tesserae,
it represents the floor of a dining room on which there are the remains of a banquet
such as: fishbone, fruit peelings and bones. The Greek term means an upswept
floor. Plinio attributes the invention of this subject to Soso of Pergamo, a
Hellenistic mosaicist lived in the second century AD (Figure 3.9).

Figure 3.8 – Typologies of floor mosaic: emblema.

 
Figure 3.9 – Asaroton, a typology of floor mosaic (on the left), and opus musivum, the
only wall mosaic typology (on the right).

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WALL MOSAIC
- Opus musivum: a wall or vault mosaic, realized with glass and stone tesserae and nacre,
which has a very rough surface in comparison with the floor mosaic (Figure 3.9);
‘musivum’ refers to the art of decorating nymphaea with shells, pumice and stone.

3.2 History of the mosaic

3.2.1 The origins of the mosaic

In the Old Orient was very widespread and developed the inlay technique, but it is not real
mosaic. Very unusually shaped mosaic tesserae were used in the Sumerian city of Uruk
(third millennium B.C.). They were made up of cones of clay with their base left at its
natural state or decorated with red or black painting. Inserted in the walls still fresh with
the base outwards, they formed interesting decorative figures. Because of its complexity,
the mosaic of clay cones did not widespread and it lasted for a short time.

3.2.2 Mosaics in the Greek world

In the Greek world, the oldest forms of mosaic are those obtained with small colored
pebbles on a dark background to form floral decorations or meandering tendrils around
mythological figures or animals, like those in Olinto, dated back to 348 B.C. (Figure 3.10).
Mosaics with pebbles and shells appeared in primitive form since the eighth century B.C.
at Gordion, Crete and Asia Minor, but they developed thanks to more sophisticated
techniques in the fifth century in Athens, Sparta and Corinth. Later, in the mosaics in
Olympia, Alexandria, and Sicily, appeared tesserae cut in the shape of a cube (tessellatum).

Figure 3.10 – Greek mosaics: “Lion Hunt” (4th century B.C., Pella, Macedonia) on the left;
mosaic in Olinto on the right.

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3.2.3 The mosaic in the Hellenistic period

In the Hellenistic period (2nd half of the 4th century to 2nd half of the 1th century), an
important school of mosaic artists developed, which was located in Pergamon. The most
beautiful works were described by Plinio who defined admirable the “Asarotos” performed
between 197 and 159 B.C. by Sosos, master of Pergamo. In the Asarotos, which literally
means “unswept floor”, the remains of a meal on a homogeneous background are depicted,
and the work is considered as a trompe l’oeil ante litteram. This theme was later taken over
by the Romans. The contact with the Italian school in this period (1st and 2nd century B.C.)
and the frequent trips of the same masters in various areas make the classification of
Hellenistic works difficult.

3.2.4 Roman mosaics

The use of mosaics in Rome, according to Plinio, was introduced in the Silla age. The first
wonderful examples are certainly those of Pompeii. The mosaics of the House of the Faun
date back to the 2nd century B.C., and represent very different issues: the battle of
Alexander, a cat eats a bird, fish (Figure 3.11). The style of these works could be called
Baroque; it preferentially deals with complex themes and the sophisticated technique
indicates a virtuosity of execution.
This style is adopted in all schools with Hellenistic influence and is so marked as to
suggest non-Italic performers, almost a “Koine” of Alexandrian master in the service of the
Romans. To this style one must also refer the mosaics of Palestrina, S. Lorenzo in
Penisperna in Rome, the “Lion of Teramo” and many others.

Figure 3.11 – Examples of Roman mosaics in Pompeii: the battle of Alexander, a cat who
is eating a bird, and fish (2nd century B.C.)

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During the transition period from late antiquity to the early Christian age, the mosaic
spreads much. It is commonly used on the floor before moving, especially in Christian
buildings, to wonderful wall decorations. Polychrome mosaic still prevails, though the
technique differs somewhat from that of opus vermiculatum.
At the beginning of the century, mythological scenes still prevail, which then leave the
place to more static representations, often of people in front attitude. Stylized depictions of
landscapes and trees also appear, but the prevailing tendency is the realization of geometric
figures. Some passages of the famous mosaics of Piazza Armerina (Sicily, Italy) are to be
attributed to this period between third and fourth century, while the wall and vault mosaics
go back to the early Christian age. The techniques used here were needed for different
reasons both practical and expressive. The bottom of the mortar was not smooth like a
floor, but more rough and uneven, and due to the rough surface of the tesserae the mosaic
also takes a different appearance determined by the reflaction of light on the irregularities
of the stones.
There are no texts that describe the technology used for early Christian, Byzantine and
medieval wall mosaics, but there are many studies on the monuments. The wall was
covered with three layers of lime mixed with marble powder, or at a lesser extent brick
powder. To allow a easy adhesion between successive layers, cavities were made on the
rough surfaces (in form of diamond or ladder) or hooks and even nails were inserted. The
third layer, the finest one, was the bed destined to host the tesserae; it was realized in small
portions at a time, so that the mosaic master could arrange the tesserae before the mortar
hardens.
On this bed the preliminary sketch (sinopia) was made. Traces of sinopia sometimes found
on the first or the second layer can not be considered other than the evidence of the tests
performed by the artist. The color given to the sinopia had perhaps intended to attenuate
the impact of the fund, which appeared, the work done, in the interstices between the
tesserae.
The technical realization was no longer differentiable as in the Roman period; the
distinction between vermiculatum and tessellatum mosaics disappears, because in the same
mosaic the tesserae have different sizes and shapes depending on the extent of the mosaic
area.

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The use of glass tesserae made it possible to produce an infinite number of color tones and
allowed to refine the techniques. In addition, one continued the use of tesserae of marble
and other stones, especially to simulate the color of the meat. It also employed mother of
pearl and terracotta tiles.
The golden or silver color was obtained by applying a sheet of precious metal on pieces of
glass, then covering the surface with a transparent glass paste and finally baking the whole.
A widespread technique was to intersperse tiles upside down, eventually monochrome tiles
with different colors in order to achieve particular effects of reflection, or punctuation. In
the Christian buildings clearly changed the theme of the mosaics: the apses are usually
adorned with the figure of Christ and the Apostles (only with Pope Damasus, in the 4th
century AD, passed to honor the cult of figures of the Saints became usual).
In the fifth century techniques, themes, and styles seem canonized, for which large holy
figures are static, stylized, in a rigidly frontal and hieratic attitude, and almost always on
dark and nebulous backgrounds. We remember the apses of S. Maria Maggiore, S.S.
Cosma and Damiano, and S. Theodore in Rome, and also the ‘triumphal arch of S. Paul
outside the walls and the Oratory of S. Giovanni Evangelista still in Rome.

3.2.5 Mosaics in Ravenna

A separate chapter is the copious production of mosaics in Ravenna. They developed
between the fifth and sixth century by bringing together the Byzantine art and the early
Christian one. The pictures that we found in older works (mausoleum of Galla Placidia,
Neonian Bapstistery) of the monuments of this area still appear realistic, while the later
representations (Baptistery of the Arians, S. Apollinaris New) lose depth and shine with
bright colors on contrasting backgrounds usually monochromatic (mostly gold).
The particular expression of the figures and the use of chromatic techniques with sharp
contrasts, based primarily on the edges, suggest the influence of the new masters clearly
inspired by Byzantine art. Byzantine is that sense of serenity and contemplation that
spreads over all the figures of S. Vitale, and that is also reflected, although certainly by
other hand, in the mosaics of S. Apollinaris in Classe.

3.2.6 Byzantine mosaic

The optimum effect was undoubtedly achieved by the pictorial expression in Byzantine
wall mosaics from the sixth century onwards. The decoration of churches was canonized

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by location and choice of icons. The mosaics were destined to the upper part of the church
and were interspersed with architectural structures that marked the areas decorated as
backgrounds. This scheme was in response to a basic concept that wanted to separate in the
Church a spiritual area (the dome and the presbytery, compared to the heavenly vault),
earmarked for the Christ Pantocrator (Figure 3.12) and the Virgin Mary, and a terrestrial
area (the naos and the narthex) destined to images of the life of Christ and the Virgin.
Secondary apses were destined to saints, martyrs and so on.
Beautiful is the harmony achieved from the walls and structures (scale) covered by multi-
colored marbles with the mosaics of the vaults and domes. The Byzantine art reached such
refinement by delegating to the reflection of the mosaics, especially gold and silver ones,
the special function of expanding space and light. Due to these characteristics, enhanced by
the technique of embedding the tesserae according to certain angulations, mosaic art came
to play a crucial expressive role. There is no doubt that even the best paintings could not
achieve the same effect as in the wonderful movement of Byzantine polychromy, hence the
belief that the mosaic has not to be considered a minor art.
In the Byzantine era we distinguish a first period (565-726), during which the iconographic
and thematic scheme, first synthetic, is refined and matured; at the height of that era, the
function of the Saints’ images was enhanced till to reach central roles.

Figure 3.12 – Christ Pantocrator in St. Sophia, Istanbul.

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In the Iconoclastic periods (726-787 and 814-843) clearly images disappear, replaced by
simple symbols (mostly the Cross), animals, plants, birds and so on. The first images that
reappear in the post iconoclastic era are isolated figures that revive the classic scheme and
then produce complex scenes, ordered by complete cycles. It is at this stage (ninth century)
that they expressed the greatest mastery of the “sloping tesserae”, which usually
characterize two-dimensional backgrounds and make vibrant the surfaces, surrounded by
tesserae with a more pronounced color (for example St. Sophia in Istanbul).
From the tenth century the figures tend to assume strong plastic characteristics, with
emphasis on the nuances of the images, so that they seem to come alive and take shape.
The lines reach more grace in the boundaries to the “painting”, so that the results are of
particular effectiveness and realism of the twelfth century. We remember the mosaics of
the Dafne Villas in Turkey (Figure 3.13), and the Dome of the Cathedral of Monreale and
Cefalù in Italy. At this time we reach the full capacity of the mosaic expression in
Byzantium.

Figure 3.13 – Some of the mosaics of Daphne Villas in Turkey.

3.2.7 The Roman and Gothic mosaics

The influence of Byzantium and the reflections of this art outside were numerous. In Kiev,
Georgia, Syria and Palestine there are examples of great significance.
In Italy, works and schools (perhaps for the presence of masters of Byzantium) focused in
Sicily (Palermo, Cefalù, Monreale) (Figure 3.14), Campania (Naples, Salerno, Capua),
Lazio (Montecassino, Rome), and Veneto (S. Marco in Venice and Torcello island).
Unlimited design themes from local cultures merged to take unique characteristics. The

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same iconography, to express these issues outside the orthodox domain tends to overcome
the classical scheme, as if to be in competition with the glories of Byzantium. With sure
originality, is part of this period the extensive activity of the Roman masters Cosmati, very
skilled in inlay technique, opus sectile and also in the mosaic in general.

               
Figure 3.14 – Mosaics in the Cathedral of Monreale (left) and Cefalù (right) (Sicily, Italy).

From the “thirteenth century” we can see the beginning of the decline of the Byzantine
mosaic. The mosaic begins to be replaced by the painting, aimed at the discovery of new
effects of depth and luminosity performances. The painting became the guide for mosaic
art, which in particular tries to imitate its virtuosity, producing tiny pieces of mosaic and
placing them in a secondary level.
Only in Venice mosaic had longer life than anywhere till the advent of the new aesthetic
principles of the Renaissance. Due to continuous operations and the subsequent restoration
one can now say that the basilica of S. Marco represents a real “store of the Medieval and
Renaissance mosaic”, as well as Pompeii for the Roman period.
Some mosaics in the Basilica of S. Marco in Venice and St. Maria on the island of Torcello
(Figure 3.15), where great works were realized throughout the twelfth and thirteenth
century, demonstrate that there was born without a doubt the most important school of
mosaic at the time.

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Figure 3.15 – Venetian mosaics in S. Marco basilica (left) and Torcello island (right).

The school in Florence, which operated in the Baptistery of S. John since 1225, originated
from its teaching and certainly its influence was decisive for the Roman school.
Notwithstanding the relation of subordination to painting, the mosaic is still widely used
throughout the fourteenth century especially for the facades of churches, and this occurs
almost exclusively in Italy (Rome, Pisa, Siena, Orvieto and again S. Marco in Venice). The
few episodes abroad in this century and in the previous one (Westminster, Saint Denis,
Prague, etc.) are the testimony of the rare cases of “export” of Italian art.
The diffusion of the principles of the Romanesque and Gothic style effectively excludes
the use of wall mosaic. There’s still some spread of the floor mosaics in which the
composition is based mostly in opus sectile with mosaic textures. But, especially from
northern Italy and Nordic regions, the development of the manufacture of colored floor
ceramic tiles is soon an alternative to the expensive mosaic decorations.

3.2.8 Mosaics during the Renaissance and subsequently

During the Renaissance, the mosaic art is increasingly seen as subordinate to painting.
There is no longer any originality; tracing the strokes of frescoes with tiny tesserae, mosaic
tries to compete in virtuosity but eventually decays to imitative and secondary roles. In the
fifteenth century and in the sixteenth century, the masters of mosaic are usually artists who
entrust with their designs in craftsmen, who then realize the works.

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There are many examples of mosaic reproducing famous paintings, such as the Dormitio
Virginis by Mantegna, paintings of Tiziano, Tintoretto, Veronese and so on.
In 1516 Raffaello, with the Venetian master Luigi da Pace, realizes one of his works for
the cupola of the Chigi chapel in S. Maria del Popolo in Rome. In Venice the most
important work is done in the fifteenth century with the decoration of the vault of the
chapel of Males in S. Marco by Paolo Uccello. Referring to the activity of this era, Filarete
cites the proliferation of furnaces in Venice, specialized in the production of glass tesserae.
But equally important event of the Renaissance is considered the beginning of the
decorations of S. Peter in Rome by Muziano of Brescia, who opened a shipyard very active
until the nineteenth century.
Pope Urban VIII decided to reproduce some paintings in Rome with mosaic to preserve
them from decay; all the techniques and the research were then refined for the sole purpose
of imitating the best performances of the artists and thus perpetuate the misunderstanding
of mosaic as “eternal painting”.
In the seventeenth century, in the S. Peter Basilica, Paolo Cristofori created the copy of the
“Burial of Petronilla” by Guercino and the “Communion of S. Jerome” by Domenichino;
in Naples G.B. Calandra in 1624 reproduced paintings by Guido Reni. But the seventeenth
century should be credited with having initiated the search for new results in the
production of glass paste. The completion of these productions in the eighteenth century
reached such a level of refinement to lead to amazing results. In 1731 Alessandro Mattioli
invented a manufacturing process that will provide at least 15,000 colors for the Vatican
mosaic tesserae. Also in the eighteenth century, you will get the “flowing glaze”, which
allow you to produce tesserae with a thickness also less than a millimeter. Were these new
techniques to achieve “perfection” in the reproduction of paintings and to facilitate the
dissemination of the fine mosaics (Figure 3.16).The results fueled the spread of the mosaic,
which returned to life and regained interest. In 1752, a mosaic school was imported to St.
Petersburg from Rome, and a workshop was implanted in Palermo, at the court of Charles
Bourbon. In 1803 the opening of a laboratory was inaugurated in Milan under the guidance
of Giacomo Raffaelli, who is considered the inventor of the flowing tesserae. In 1811, in
Naples there is a mosaic workshop, as well as in England, where the workshop of South
Kensington Museum was opened.

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Figure 3.16 – Some mosaics of the 17th century in the Basilica of San Clemente in Rome.

In 1848 Czar Nicola I created a laboratory in Rome for Russian students, that then moved
to St. Petersburg in 1850. The activity of this laboratory was remarkable, especially in
terms of quantity, and it is responsible for the reproduction of many paintings. In 1876 was
inaugurated in Paris the National School of Mosaic; at the end of the century and the
beginning of the next, several families of mosaic craftsmen from north-eastern Italy open
mosaic laboratories in Paris, Berlin, Vienna, Copenhagen, London, New York, Nimes,
Nice, Lille, and other localities.

3.2.9 The Oriental mosaic

In Orient, apart from rare examples found in the Sasanian art (Iran), one can follow the
development of mosaic observing the many decorations of Islamic art. Among these, of
great value is the Dome of the Rock in Jerusalem (Figure 3.17), with floral ornaments of
the Syriac-Hellenistic style, but also with original themes of Islam (candelabra, trees of
life, palm trees dotted with jewels, etc.).
Another important work of Islam is the Great Mosque of Damascus (700-715 AD) (Figure
3.17) with an amazing panel depicting a fictional town in many meticulous details.
Well developed in the Mamluk period (1200-1300) and until the peak of the sixteenth
century was a mosaic of glazed ceramic, which reached its zenith under the Safavid rule
(tomb mosque of Saih Safi at Ardabil, Iran, Figure 3.17).

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India was very strong influenced in the Islamic period and the best examples of mosaic
were produced mostly in the Daccan and in the central regions in general. Here mosaic of
glazed ceramic found employment on a large-scale, preferring in the seventeenth century
the use of square tiles.

     
Figure 3.17 – The Rock in Jerusalem, the Mosque of Damascus (700-715 A. D.) and the
Tomb mosque of Saih Safi at Ardabil, Iran.

3.3 Degradation of mosaic

The mosaic is made up of several layered components including two/three or more
preparation layers and the surface layer of tesserae:
- the first preparatory layer from the bottom is made of large stones laid on the
ground, previously leveled and rammed. This layer only exists if the mosaic has
been constructed on a natural soil;
- the second preparatory layer, which is spread over the first one, this layer is made
of a lime mortar with large aggregate;
- the third preparatory layer is spread over the second one in a thin thickness, and it
is made of a mortar with fine aggregate;
- the fourth preparatory layer is called “bedding layer”; it is a thin layer of very lime-
rich mortar, and is applied in stages over the third preparation layer;

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- tesserae of different materials (stone, brick, glass, etc.) are inserted in the previous
layer before the mortar sets and hardens, so that the mosaic surface is composed of
tesserae with mortar that fills the interstices between the tesserae.
Obviously, these materials in contact with the micro- and the macro-environment, or
because of human intervention, are subjected to numerous types of alteration and
degradation phenomena, sometimes irreversible. When stone materials are the principal
constituents of the mosaic, the various morphologies of alteration and degradation
affecting it are very similar to those treated in the section devoted to degradation of natural
and artificial stone materials in the Chapter 2. One can easily find lacuna, alveolization,
fracture, pitting, superficial deposit, deformation, microbiological organism, and so on. But
there are some degradation morphologies which are specifically related to the particular
structure of the mosaic or have an original appearance linked to it. These degradation
morphologies will be illustrated below.
Mobile tesserae (Figure 3.18, left): degradation that occurs when there is a loss of adhesion
between the tesserae and the mortar; it is usually caused by disintegration of the mortar
with the consequent possibility of detachment and loss of some tesserae.

                               

Figure 3.18 – Mobile tesserae (left) and scaling (right).

Scaling (Figure 3.18, right): degradation that occurs with total or partial separation of parts
of the work (scales), often connected with discontinuities in the original material; generally
the scales are made of apparently unaltered material, and have a irregular thickness.
Encrustation (Figure 3.19, left): compact degradation layer, generally adherent to the
substrate, consisting of inorganic or organic material. When preferentially connected to the
mortar, this degradation phenomenon follows the borders of the tesserae.

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Efflorescence (Figure 3.19, right): surface formation of generally whitish salts, that have
crystalline or powdery or filamentous appearance. The salts generally come from the
mortars, because these are very porous, so that the borders of the tesserae are well
evidenced.

Figure 3.19 – Encrustation (left) and efflorescence (right).

Disintegration (Figure 3.20, left): it deals with a degradation characterized by detachment

of granules or crystals.
Differential Degradation (Figure 3.20, right): type of degradation to be put in relation with
the compositional or structural heterogeneity of the materials, mainly the tesserae; often
the result is the formation of two different levels, one for the more resistant material, that is
practically correspondent to the original level, and a lower level corresponding to the less
resistant tesserae.

Figure 3.20 – Disintegration (left) and differential degradation (right).

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Stain (Figure 3.21, left): alteration that occurs with formation of accidental pigmentation
localized on the surface; it is related to the presence of foreign material (rust, copper salts,
organic substances, paint, etc.) mainly on the surface of the tesserae.
Chromatic alteration (Figure 3.21, right): type of deterioration that occurs as a consequence
of the variation of one or more parameters of the color; it can occur with different patterns
depending on Figure 3.21 is connected to the transformation of the red glass into green
compounds which cover the surface of the tesserae in mosaics of Pompeii.
Detachment (Figure 3.22): interruption of continuity between the different layers of the
mosaic, both among themselves and respect to the base.

Figure 3.21 – Stain (left) and chromatic alteration (right).

Figure 3.22 – Two different manifestation of the degradation type called “detachment”.

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Metallic elements (Figure 3.23, left): presence of structural reinforcements belonging to

the new support of a re-laid mosaic.
Presence of vegetation (Figure 3.23, right): the presence of herbaceous shrubs or trees in
mosaic works assumes a characteristic appearance, due to the fact that the vegetation
preferentially takes root in the mortar layer and comes out through the layer of the tesserae.

Figure 3.23 – Metallic elements (left) and presence of vegetation (right).

3.4 Restoration of mosaics

3.4.1 The restoration of floor mosaics in situ

The conservation work is influenced by environmental factors such as humidity,
temperature, pollution, light, contact materials, and other.
In the case of mosaics buried for a long time a relatively stable balance was maintained,
which is suddenly broken with the discovery and the mosaic is subjected to new
conditions, generally much more dangerous for its preservation compared to previous ones.
A very important operation for a re-discovered floor mosaic is the cleaning of the surface,
which leads to the first revelation of the artwork and makes it known from various points
of view: conservation status, nature of material, artistic and aesthetical value. Cleaning is
normally done manually, with broom, brushes, sponges and water; then we proceed with
the other types of necessary interventions, as the application of mortar to hold the
peripheral edges and those of gaps, and the pre-consolidation of the substrate through
injections. These operations are designed to prevent loss of materials of the artwork.

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In the case of the mosaics preserved in situ is of fundamental importance the development
of a good conservation plan. When you can not proceed immediately with the safeguard
operations, waiting for a permanent protection, it is opportune to cover the mosaics. This
intermediate operation may provide the implementation of a temporary coverage, or
permanent when an intervention can not be planned in a defined time. The materials placed
in contact with the surface of the mosaic should be inert with respect to the materials of the
mosaic, ensuring reversibility, durability, good drainage, resistance to mechanical,
chemical and biological stresses.
The operation of restoration in situ may include the following phases:
- photographic and graphic documentation
- preliminary investigation with analytical methodologies: optical microscopy in reflected
light, to observe the structure of the samples and define their state of conservation; use of
Munsell tables, for the definition of color; optical microscopy in transmitted and polarized
light, to define the mineralogical and petrographic characteristics of the materials
constituting the mosaic, the volumetric ratio binder/aggregate of the mortars and to
determine form, size and nature of the granules constituting the aggregate; diffractometric
analysis (XRD) for the identification of the mineral phases; thermal analysis (DTA-TGA),
for the quantification of calcite, an estimate of the organic matter and of the nature of the
binder in the mortars; chemical analysis (ICP or XRF), for the definition of the elemental
composition of the glass.
- study of alterations (UNI 11182/2006, Cultural heritage - natural and artificial stone
materials-Description of the type of alteration, Terms and definitions).
- intervention stages: cleaning (physical, chemical and mechanical); consolidation of the
preparatory layers and the mosaic tissue; integration of the lacunas, and surface protection.

3.4.2 The restoration of a wall mosaic in situ

Normally, the wall mosaic is kept indoors. Rarely you remove a wall mosaic and therefore
you proceed with in situ conservation work.
The structure of a wall mosaic is generally easier than that of the floor mosaic. Normally
on the wall was applied a first layer of mortar made of lime and aggregate (sand, marble
dust, pozzolana, fragments of straw, etc..), and on this layer was placed the bedding mortar

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of lime with or without inert. This last layer was wetted in order to define the “preliminary
sketch” with colored areas to guide the laying of mosaic tesserae.
The tesserae in the wall mosaics are basically of four types: stone, glass, nacre and
ceramics. The more specific problems are those affecting the glassy tesserae, which are
very sensitive to various types of degradation.
The cleaning of the wall mosaics is generally performed through a chemical action, that is
mostly removal of soluble salts; for more resistant encrustations, cleaning is done through
mechanical operations. In the consolidation of degraded tesserae you can use acrylic or
silicone resins.
Regarding the preparation layers, which generally suffer problems of adhesion loss of the
tesserae, the detachments and cavities in the support layers are usually filled by injecting
mortar.
In the past and even today, to consolidate the preparation layers, is also used to anchor the
implementation in the areas of mosaic decoration with big detachments, because the simple
injection of filling the cavity may cause a danger of collapse, due to the heaviness of the
detached layers.
While in the past the use of metal was encouraged, now special ceramics or plastic
materials suitable for this use are preferred.

3.4.3 The restoration of the mosaics on cement support

The industrial manufacture of cement has been started in the second half of the nineteenth
century. The application of this binder in the field of restoration lasted until a few years
ago, supported from the mistaken idea that saw it as the material for a definitive
restoration.
In particular the high mechanical resistance of this material has suggested the lifting of the
mosaics and their re-laying in situ on a cement support. As a result, more and more often
you has had to intervene on these restorations because of the occurrence of damages,
sometimes so severe to cause partial or total loss of the mosaic. This was due to the
deterioration (oxidation and swelling) of the cement that is characterized by high
coefficient of thermal expansion, and presence of a high concentration of soluble salts.
The numerous interventions on mosaics lifted and re-layed on concrete supports allowed to
observe the various techniques for implementing them.

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In the twenties and thirties of the twentieth century, metallic grids with welded joints were
specially prepared for each slab. In more recent interventions, generally there is a greater
carelessness, with the iron rods irregularly placed, often bound and almost in contact with
the base of the tesserae, making it even more damaging.
In addition, over time there has been a tendency to completely eliminate the spaces
between the tesserae, and to replace the original mortar. This was done to make the artifact
thinner and therefore lighter and easier to handle. In this way, the state of conservation of
mosaics which have just been re-layed few decades ago is often worse than that of mosaics
restored using the same technique in the first half of the twentieth century.
The process of intervention on the mosaics re-layed onto concrete must be tailored to each
case; it is important to accurately identify the level of the iron grid and implement its
removal all at once. Of course it is a risky action for the layer of tesserae, which sometimes
can cause great damage and possible loss of tesserae.
The technical intervention is started pasting several layers of cotton canvas onto the mosaic
surface, utilizing animal or vinyl glue.
The mosaic is turned over and placed on a table. By the use of diamond wheels, parallel
incisions are made up to a depth of just a few centimeters (or a few millimeters) from the
base of the tesserae in two perpendicular directions.
The different squares of the support so obtained are removed using hammer and chisel,
then proceeding in a mechanical way to remove residual cement in contact with the base of
the tesserae.
The mortar which is present in the interstices between the tesserae, whether original or
cement, must be maintained: the original must be kept for obvious reasons, and cement is
so tenacious that its elimination would lead to severe damage for the tesserae.

3.5 Case study

3.5.1 Restoration of mosaics in the Basilica of St. Leucio (Italy)

PRELIMINARY OBSERVATION
The Basilica of S. Leucio in Canosa di Puglia (Italy), built in the sixth century A.D. on a
Hellenistic temple, has a double tetra-conical plant inspired by the Syrian style, which is

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present in Italy only here and in the basilica of S. Lorenzo Maggiore in Milan. The basilica
underwent a number of restoration works already starting since shortly after its
construction, due to static instability that damaged the structure.
The current restoration has involved the floor mosaic panels which were already
considered in the years 1962-’63 and in 1985; in that occasion they were lifted, restored
and then re-layed in the apse, in the inner western area of the canopy, in elevated places
compared to the original floor of the basilica.
The fragments involved in the operation of restoration and conservation were positioned in
space in front of the west apse more elevated of the original floor in the basilica and
surrounding the tabernacle (Figure 3.24). They have underwent a significant degradation,
due to the exposure to the direct action of weathering, which has produced an advanced
state of oxidation of the reinforcing bars, loss of cohesion between mortar and tesserae, as
well as cracking of the mosaic decorations.

Figure 3.24 – Design of the basilica of S. Leucio (left), remaining of the basilica (centre)
and detail of the floor mosaic (right).

Widespread on the surface of all the mosaics is the presence of lichens, moss and algae
(Figure 3.25); these species of microorganisms are the cause of chemical and physical as
well as aesthetical degradation. The chemical degradation is due to the production of acids
by lichens, leading to a chemical attack of the raw materials which constitute the mosaic
tiles, while the physical action is exerted by the thallus that link the lichens to the substrate,
that is the tesserae.
The tesserae mainly consist of brick fragments, which were produced with raw materials
coming from clay sediments near river Ofanto; some are made of imported marble (or

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materials for reuse), given the lack of outcrops of marble in central-southern Italy, and
many tesserae consist of limestone from local quarries.
The biological alteration was present on the surface of tiles with calcareous gray and white
colored Aspicilia species, with some orange thallus of Caloplaca and other black kind of
the genus Verrucaria; the thallus is rather thin and does not penetrate much in depth.

Figure 3.25 – Lichens, moss and algae on the surface of the mosaic.

CONSERVATIVE INTERVENTION
The first phase of work included the photographic documentation of the general
archaeological context and the conservation state of the mosaics with attention to the
different degradation morphologies. The preliminary cleaning with biocide allowed to
make clear the geometric pattern and colors of the tesserae, and thus making possible most
of the graphic documentation of the mosaics.
Then a linear plot was realized by contact (Figure 3.26, left). It is important because it will
serve as support for the drafting of thematic tables documenting the state of conservation
of the mosaics before the conservative intervention both in the original parts and those
reconstructed in previous restorations. The consolidation of the mosaic decorations, with
application of double cotton gauze and glue diluted in water, ensured stability to the
tesserae. Then the transportable fragments were moved to the restoration laboratory for the
total removal of cement and iron reinforcement on the back (Figure 3.26, right, and 3.27).
With regard to large mosaic fragments, we proceeded by cutting them into smaller and
movable fragments with two rows of tesserae in order to facilitate cutting and splitting
between a section and the adjacent ones.

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Figure 3.26 – Realization of a linear plot (left)

and removal of cement from the back of the mosaic (right).

Figure 3.27 – Back of the section after the removal of concrete.

Then we applied a layer of hydraulic mortar, consisting of:

- sand as inert in two different particle sizes,
- pozzolana to provide greater physical-mechanical resistance,
- natural hydraulic lime, with a small percentage of acrylic emulsion mixed with water
to ensure greater workability; this mixture is consistent with the mosaic materials in
terms of physical-chemical properties and at the same time reversible.

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After throwing a first layer, which was not pulled, a network of synthetic fibers with
apertures of 0.5 cm per side was laid. A second layer of mortar was then applied with a
wooden straight bar sliding along the wooden rails, providing the final thickness of the
mosaic of 2.5-3 cm at all points for each mosaic fragment (Figure 3.28).
After the carbonation of the mortar, about seven days, we passed to gluing of strips of
mosaic on mobile devices, the choice of them focused on a media type of alveolar
aluminum and fiberglass. It deals with a sandwich of two sheets of glass fiber woven
(thickness of 0.5 mm) embedded in a epoxy resin and made to adhere to an internal
structure made of honeycomb aluminum with cells of 6.35 mm side and a thickness of 2.5
cm.

Figure 3.28 – Application of new hydraulic lime-based mortar on the back of the mosaic.

Of course the cellular supports were reinforced from the rear with aluminum tubes (size 6
x 3 cm), to ensure greater stability to the mosaics, allowing you to move them in future
without problems. Turned the fragments in the direction of the tesserae, the cotton gauze
was removed (Figure 3.29), and the cleaning of the mosaic surface was made with
sorghum brushes, scalpels, and jets of water vapor to remove any residue of the acrylic
resin.
Tesserae were reinforced with local treatments and the ultimate use of a consolidant. We
suggested the method of integration of the gaps with the same color of the mosaics (Figure
3.30).

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Figure 3.29 – Removal of the cotton gauze from the mosaic surface.

Figure 3.30 – The mosaic fragment after restoration.

3.5.2 Analytical sequence for studying mosaics

INTRODUCTION
A mosaic is composed of a sequence of preparation layers, of a bedding mortar layer, and
surface layer made of tesserae (or slabs). In the study of a floor or wall mosaic it is very
important to distinguish the different layers. A floor mosaic can have a complex structure;
sometimes we can find a mosaic set up on another older. The structure of the wall mosaics
is certainly more simple than the one of the floor mosaics. In fact it is generally composed
of two preparation layers, the bedding mortar and then the tesserae.
The various mortars have different functions: foundation, stucco.
Mosaic tesserae can be made of stone, glass, ceramics and other (shells, Egyptian blue,
etc.). Glass tesserae prevail in the wall mosaics, even though they can be often identified

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also in floor mosaics. Stone tesserae are generally obtained by cutting carbonate rocks,
especially sedimentary (limestone and dolomite), subordinately metamorphic rocks
(marble). Marl, sandstone, volcanic rocks and flint are definitely less frequent.
Sedimentary carbonate rocks are frequently encountered because they are easily workable;
in addition they show a large number of colors.

ANALYTICAL SEQUENCE FOR TESSERAE

The tesserae are studied by means of different analytical methodologies that allow their
documentation, colour identification and petrographic classification; in particular:
- Munsell Rock Colour Chart: classification of the color,
- XRD: identification of the crystalline phases,
- reflected light microscopy: documentation, sample appearance, deterioration forms,
- transmitted polarized light microscopy on thin section: mineralogical-petrographic
analysis, classification,
- DTA-TGA: quantification of the calcite,
- SEM-EDS: micro-structural observations, chemical analyses of small surface areas,
- ICP-AES or XRF: whole chemical composition.
In order to obtain an accurate documentation of the sample, the description of the structure
and deterioration forms, and the determination of the chemical composition of the whole
sample (useful for the classification) or small surface areas of the glass tesserae, the
analytical sequence for studying stone tesserae is:
• polishing of the tessera surface by ultrasound bath,
• classification of the color by comparing the tesserae with Munsell Colour Chart,
• observation at the stereo microscope, for documenting the sample, describing the
structure, and identifying the deterioration forms,
• cut of a tessera into two pieces,
• grinding of one piece into powder suitable for performing XRD and DTA-TGA,
• preparation of a thin section by using the other half; the material remaining after
preparation of the thin section is kept as a testimony,
• observation of the thin section (mineralogical microscope),
• micro-morphological and micro-structural observations, chemical analyses of small
surface areas (SEM-EDS),
• chemical composition of the whole sample (ICP-AES or XRF)

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The analytical sequence for studying glass tesserae is slightly different, because XRD
analysis is useless. So, first the tessera is observed by reflected light microscopy, and then
cut into two pieces. One piece is cleaned by ultrasound bath in order to classify the color
by Munsell Chart and to perform new observations by stereo microscope, before grinding
this piece for the chemical analyses (ICP-AES). The other half piece is cut again into two
parts, so that one of them is used for performing SEM-EDS analyses and the other one is
preserved as a testimony.
Ceramic tesserae or fragments, which are present in different layers of the mosaics, are
generally made of simple terracotta. They can be studied following the analytical sequence
typically used to analyze ceramic materials. Practically it coincides with that illustrated for
the stone tesserae. In fact, these analytical techniques allow the documentation of the
sample, the attribution of the color, the determination of the chemical composition
(important for the identification of the raw materials), and the mineralogical-petrographic
characteristics (useful for reconstructing the paste composition and the firing degree).

ANALYTICAL SEQUENCE FOR MORTARS

Mortars (bedding and foundation layers) are studied by means of several analytical
methodologies that allow the documentation of the sample, to identify the composition of
the binder and of the aggregate, the determination of the shape and of the dimensions of
the aggregate, the recognition of the characteristics of the mortar (hydraulic or aerial), the
evaluation of the ratio binder/aggregate, and finally the description of the micro structural
characteristics, and the determination of the chemical composition of different surface
details or of single crystals.
In particular the analytical techniques used are:
 reflected light optical microscopy (documentation, sample structure, evaluation of
the ratio binder/aggregate
 mineralogical microscope (binder/aggregate ratio, mineralogical-petrographic
characteristics)
 XRD (identification of the crystalline phases)
 DTA-TGA (quantification of calcite, portlandite and gypsum; evaluation of the
organic matter; characteristics of the mortar (hydraulic or aerial).
 SEM-EDS (micro morphological and micro structural observations, chemical
analyses of surface single points).

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The analytical sequence for studying mortars is:

• cleaning and polishing of the mortar
• observation of the sample (stereo microscope)
• cut of the mortar in different pieces
• grinding of one piece (XRD, DTA-TGA)
• cutting of an other piece in thin section (mineralogical microscope)
• observation of a small piece (SEM-EDS).

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Macchiarola M., Abu Aysheh M.S., Fiorella G., Fontanelli R., Conservazione
musiva e conoscenza: un binomio imprescindibile. Esempi d’interventi in situ
e in laboratorio, in: “The 10th Conference of the International Committee for
the Conservation of Mosaics” (ICCM), Palermo, 2008, in press.
Macchiarola M., Fontanelli R., Nicolardi D., Studio archeometrico di materiali
musivi e interventi conservativi di pulitura, consolidamento e protezione per il
mosaico in situ, in: Atti IX colloquio “AISCOM”, Ravenna, 2005, pp. 685-
692.
Mondelo R.P., Torrescarro M., El mosaico romano de Casariche (Sivilia), in:
“BSEAA”, 51, 1985, pp. 143-155.
Neal D.S., Roman mosaics in Britain: an introduction to their schemes and a catalogue of
paintings, A. Sutton ed., London, 1981.
Pedelì C., Pulga S., Pratiche conservative sullo scavo archeologico: principi e
metodi, All’insegna del Giglio, Florence, 2002.
Podini M., Abu Aysheh M.S., Macchiarola M., Un nuovo mosaico con Oceano da
Suasa (AN): aspetti archeologici, tecnologici e conservativi, in “AISCOM”
XI, Ancona, 2006, pp. 611-622.
Racagni P. (a cura di), La basilica ritrovata: i restauri dei mosaici antichi di San
Severo a Classe, Ravenna, Ante Quem, Bologna, 2010.
Racagni P. (a cura di), I restauri di RavennAntica: esperienze di valorizzazione del
mosaico antico, Ante Quem, Bologna, 2011.
Roncuzzi I., Fiorentini E., Mosaico. Materiali, tecniche e storia, MWeV, Ravenna,
2001.

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Ruffini A., Fiori C., Vandini M., Caratterizzazione chimica di vetri musivi antichi.
Parte I: metodologie d’analisi e risultati, in: “Ceramurgia” XXIX, n.4, 1999,
pp. 285-298.
Ruffini A., Fiori C., Vandini M., Caratterizzazione chimica di vetri musivi antichi.
Parte II: elaborazione dei dati analitici, in: “Ceramurgia” XXIX, n.5-6, 1999,
pp. 361-368.
Smith D.J., Roman mosaics in Britania before the Fourth Century, in: “CMGR” II,
La mosaique Greco-Romanie II, Paris, 1975, pp. 269-289.
UNI 11182/2006, Beni culturali - Materiali lapidei naturali ed artificiali -
Descrizione della forma di alterazione, Termini e definizioni, UNI, Milano,
2006.
Verità M., Tecniche di fabbricazione dei materiali musivi vitrei, in: “Medieval
mosaics: light, color and materials”, E. Borsook and F. Gioffredi Superbi eds.,
Silvana Editoriale, Milano, 2000, pp. 47-64.

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4 – CERAMICS

4.1 Ceramic technology

4.1.1 Clay materials

The manufacturing cycle of the ceramic products, starting from suitable raw materials,
which are some specific types of clays, includes three main necessary steps. After
preparing a suitable mix of clay and water, they are: shaping, after that we obtain an object
usually indicated as “green”; drying, after which we have the “dry” piece; firing, that gives
rise to the final object.
The clay minerals are the principal mineralogical phases of the clays. They have a
crystalline structure that is constituted by two basic structural units, whose repetition in the
space gives rise to the various clay minerals. The two structural units are:
- tetrahedron SiO4
- octahedron Al(OH)6 or Mg(OH)6
Both them are electrostatically not saturated, being the first with four negative free charges
and the second with three (with Al) or four (with Mg) free charges. The free charges of the
tetrahedrons are progressively diminished by joining together six of them, so that they
make an hexagonal form. The tetrahedrons are joined putting in common two of their
oxygen atoms, so decreasing their free electric charge. Then, several hexagons are joined
together in the same way, so forming a planar structure, which is called tetrahedral sheet.
In the same way, three octahedral units originate an hexagon, and the joining of several
hexagons gives rise to the formation of the octahedral sheet.
The clays can be characterized from three points of view: grain size distribution,
mineralogical composition, chemical composition.
The particle size is mainly concentrated in the field of the clay fraction (less than 2 micron)
and of silt fraction (between 2 and 64 micron), while the sand fraction (>64 micron) is
usually less than 5%. The clay minerals are always very fine, so that they are mostly
included in the fraction less than 2 micron.
The principal minerals which can be present in the ceramic clays are usually subdivided

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into four groups, according to Table 4.1.

Table 4.1 – Principal minerals which constitute the ceramic clays

CLAYEY MINERALS OXIDES/HYDROXIDES

Illite K2-XAl4(Si6+XAl2-XO20)(OH)4 Quartz SiO2

Chlorite (Mg1-YFeY)6-XAl2XSi4-XO10(OH)8 Hematite Fe2O3
Smectite (Montmorillonite) Goethite FeOOH
4SiO2.0.85Al2O3.0.33MgO.0.15Na2O.0.5H2O Limonite ~2Fe2O3.3H2O
Kaolinite Al4(Si4O10)(OH)8

FELDSPARS CARBONATES

Albite (sodic feldspar) NaAlSi3O8 Calcite CaCO3

Orthoclase (potassic feldspar) KAlSi3O8 Dolomite CaMg(CO3)2

There are two groups of ceramic clays, which are distinguished by the presence/absence of
carbonate minerals.
The carbonate-rich clays have an average composition given by about:
- 45% clay minerals, of which illite ~30%, chlorite ~8%, smectite ~7%, and kaolinite in
traces,
- 30% of quartz and feldspars, subdivided into quartz ~25%, feldspars ~5%; no
difference can be individuated in the frequency of sodic and potassic feldspar,
- 5% of iron oxide or hydroxide,
- 20% carbonates, which can be subdivided into calcite ~15% and dolomite ~5%.
In the case of non-carbonatic clays, we have about:
- 55% clay minerals, subdivided into illite ~35%, chlorite ~10%, smectite ~10% and
kaolinite in traces,
- 40% quartz and feldspars, subdivided into quartz ~30%, feldspars ~10%; no difference
can be individuated in the frequency of sodic and potassic feldspar,
- 5% of iron oxide or hydroxide.
Among the many other minerals which can be present in the raw clays, mica is the most
diffuse, being represented mainly by muscovite (white mica), while biotite (dark mica) is

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less frequent.
As it regards the chemical composition of the ceramic clays, it depends on the chemical
composition and abundance of their minerals. As it can be seen in the table 4.1, the most
important minerals are made of less than ten chemical elements and the most frequent and
abundant are silicon and aluminum, and calcium when it deals with carbonatic clays. The
presence of mica does not change this general rule, because muscovite is constituted by the
same elements of illite. As a consequence, the chemical composition of the ceramic clays
can be expected similar to those reported in Table 4.2, where each element is evaluated as
percentage of its oxide.
In addition to the elements that appear in the mineral formula, titanium, manganese and
phosphorus are generally taken into consideration, because they are present in the clays as
impurities. Finally, we have to explain the parameter I.L. in table 4.2. It represents the
volatile elements, which leave the clay during firing up to 1000 °C, in particular water
from the clay minerals and carbon dioxide from the carbonates.

Table 4.2 – Average chemical composition of Italian clays for brick and tile production.
Clay type SiO2 Al2O3 TiO2 Fe2O3 MnO MgO CaO Na2O K2O P2O5 I.L.

Carbonatic 45.2 11.9 0.7 5.1 0.1 2.9 14.9 0.8 2.3 0.1 16.3
Non carbonatic 71.5 12.9 0.6 4.7 0.1 1.5 0.9 1.0 2.0 0.1 5.1

4.1.2 Shaping techniques

Shaping is the processing methodology which permits to give a shape to a suitable ceramic
clay mixture. The addition of water to the clay raw material is necessary in order to obtain
a suitable physical state for the shaping operation. The water content depends on the
shaping technology to be used. It is possible to operate with three different physical states
of the clay/water mixture: plastic, fluid, dry.
A ceramic body at plastic state contains an amount of water sufficient to give cohesion
between the particles of the ceramic powder: the obtained paste can be deformed without
rupture. The water amount is comprised between 20 and 30%. The ceramic bodies at
plastic state are the most frequently used since the beginning of the ceramic production in
the Neolithic time.

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The cohesion capacity is called ‘plasticity’; it is due to the presence of clayey minerals, in
particular to their capacity of absorbing water molecules on their surface. The presence of
water guarantees the cohesion between the particles and a lubricant action between them.
Smectite is the most plastic mineral, followed by illite, kaolinite and chlorite. Quartz,
carbonates and feldspars have no plasticity. The aplastic component of the paste is called
‘temper’. All the non-clayey minerals of the ceramic pastes can be used as temper, for
example in form of natural or artificial sand. A very particular temper material is given by
“chamotte”, that is ceramic material ground till the dimension of a sand.
A ceramic body with an amount of water insufficient to guarantee cohesion between all the
particles of the ceramic powder is at ‘dry state’. The water amount is less than 10%; this
water gives rise to the formation of aggregates, so avoiding the volatilization of the
powder. These ceramic bodies can be shaped only by using the modern pressing technique.
When the amount of water is more than 40% approximately, they say that the ceramic
body is at ‘liquid state’. This type of mixture is used only with the slip casting technique
since the middle of the XVIII century.

COLOMBINO AND SLAB TECHNIQUE

As it can be seen in the Figure 4.1, the ‘colombino’ technique operates by hand assembling
thin sticks of paste in a suitable way and then eliminating the discontinuities between them.
Instead of sticks, the slab technique foresees the assembling of thin slabs of plastic clay.

Figure 4.1 – Illustration of the ceramic shaping with the ‘colombino’ technique.

b
l
u
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WHEEL SHAPING
As it can be seen in the Figure 4.2, this technique utilizes an instrumentation constituted by
two rotating discs, one for placing the ceramic paste to be shaped and the other for giving a
rotation to the system. This technique is known from the third millennium B.C. and
Ancient
represented the most shaping
important shapingtechniques
technique till :today.
Wheel shaping

10

Figure 4.2 – Scheme of operation of the wheel shaping technique in a modern version.

SLIP CASTING
Slip casting is the only shaping technique which utilizes the ceramic body at liquid state
(barbotine). This technique is very useful for manufacturing complex forms which have
not circular sections. Barbotine is introduced into a porous mould, which absorbs part of
the water forming a thin layer of solid material adherent to the internal surface of the
mould. When the right thickness of the solid layer has been achieved, the mould is
emptied, and the object is extracted after a short solidification phase.

4.1.3 Drying
The drying is the technological phase during which the processing water is eliminated from
the shaped object through evaporation, without provoking any damage. At the beginning,
the grains are separated by inter-granular water; evaporation occurs on the surface of the
object and the water moves from inside to the surface. The total volume decreases till the
grains come in contact between them; this first phase is called ‘phase of shrinkage’: it
needs attention and is time consuming. In the second phase, the evaporation continues, but
the total volume does not decrease; this phase is called ‘phase of porosity’ and is less

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BOURRY DIAGRAM OF DRYING

dangerous than the previous one. In general the two phases are connected by an
intermediate phase.
The drying evolution is well illustrated by the Bourry diagram (Figure 4.3).

Shrinkage

Water Porosity
Volume

Clay

Hours

Figure 4.3 – Illustration of the drying evolution through the Bourry diagram:
A= phase of shrinkage; B= intermediate phase; C= phase of porosity.

LEATHER HARDNESS
Physical state of a partially dried object, when the piece is sufficiently hard to resist to
mechanical stresses, due to particular operations of the ceramic processing cycle (e.g.
application of slip or decoration), but still sufficiently humid to permit such operations and
to join together independently shaped pieces.

4.1.4 Firing
Firing is the thermal treatment which promotes irreversible physical-chemical
transformations, in order to obtain a product with suitable aesthetical, mechanical, and
chemical properties. The firing cycle includes both the heating and cooling phase.
The main characteristics of the firing process are:
- maximum temperature,
- heating and cooling rate,
- firing atmosphere (oxidant or reductive),
- soaking time at the maximum temperature.
The heating and cooling rates, and the firing atmosphere can be varied several times,

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according to the reactions, which occur in the ceramic paste, and to the aesthetical effects
to be obtained. But the possibility of controlling the firing parameters (temperature and
atmosphere) depends on the type of firing system at disposal. In the most ancient firing
systems they could not be controlled, mainly because:
- the thermal insulation is very poor, so that very different temperatures can be measured
for different vases, and also in various points of the same artefact, depending on their
position and orientation with regard to the heat source;
- there is no separation between combustion area and firing area, so that the firing
atmosphere is greatly influenced by the combustion of the wood and the atmosphere will
tend to be reductive during the heating, but oxidant during cooling, when the combustion
has been stopped.
The gradual evolution of the firing systems led to a better control of both temperature
(insulation of the firing system) and firing atmosphere (separation of the firing zone from
the combustion area.

DESTRUCTIVE CHEMICAL REACTIONS

The first reactions which occur during the heating phase are destructive reactions, which
destroy the primary minerals; among these reactions the most important are:
1) at 100-200 °C, illite and smectite loss some of their water content,
2) at 300-350 °C, iron hydroxides loss their water content,
3) at 400-500 °C, in presence of oxidant atmosphere, the organic substances oxidize
producing carbon dioxide and steam,
4) in the interval 500-700 °C approximately, all the clayey minerals completely loss
their water content,
5) at 573 °C, the SiO2 phase stable a low temperature (α-Quartz) transforms into the
phase stable at higher temperature (β-Quartz), with an increase of volume more
than 10%; this reaction is reversible, so that during cooling β -Quartz transforms
into α-Quartz with a decrease of volume,
6) at 700-850 °C, the carbonates decompose with the liberation of carbon dioxide,
7) at about 950 °C melting of eutectic compositions with feldspars begin, while the
theoretical melting temperatures for feldspars are: sodic feldspar = 1120 °C,

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potassic feldspar = 1200 °C, plagioclases >1200 °C.

RECONSTRUCTIVE CHEMICAL REACTIONS

The residues of the destructive reactions give rise to the formation of new crystalline
phases. The principal reactions involve the residues of the decomposed carbonates,
together with silica and alumina from the clayey minerals. As the firing temperature
increases, the following new compounds form:
1) CaO + SiO2 = CaSiO3 (wollastonite),
2) 2CaO + Al2O3 + SiO2 = Ca2Al2SiO7 (gehlenite),
3) CaO + MgO + 2SiO2 = CaMgSi2O6 (diopside, mineral of the pyroxene group),
4) CaO + Al2O3 + 2SiO2 = CaAl2Si2O8 (anorthite, calcic plagioclase); the same
reaction can be written as: Ca2Al2SiO7 (gehlenite) + Al2O3 + 3SiO2 = 2CaAl2Si2O8,
that means that anorthite can also form at expenses of gehlenite,
5) at 750-800 °C, in oxidant environment, Fe2O3 starts to crystallize.

RAKU TECHNIQUE
This firing technique is characterized by a very rapid cooling phase, which is obtained by
extracting the shaped artefact from the kiln when it is still at high temperature, and putting
it into water at room temperature. In addition, before immersion into water, the object is
put in contact with organic material, in order to lead the chemical elements of the glaze to
their reduced state.

4.1.5 Characteristics of the fired paste

CHEMICAL AND MINERALOGICAL COMPOSITION

A part from the elimination of the volatile elements, the chemical composition of the fired
paste is the same of the unfired paste; on the contrary, the mineralogical composition has
changed. The mineralogical composition is very simple when non-carbonatic clays are
used: very abundant quartz, remarkable amounts of feldspars and small amount of
hematite, together with a large amount of amorphous phase, may be some 20-30%. On the
contrary, when carbonatic clays are used, the fired paste shows several new compounds
(gehlenite, diopside, anortite), other than primary quartz and feldspars, and practically no

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amorphous phase.

DIMENSIONS OF THE ARTEFACTS

The chemical reactions which occur during firing give rise to a significant shrinkage,
mainly due to the elimination of water and other volatile compounds. The shrinkage due to
firing can be some units percent, and it is much lower than the shrinkage during drying.
The thermal expansion of the ceramic artefacts does not influence their final dimensions,
because the expansion during heating is compensated by the contraction during cooling.

COLOUR
The colour of the fired products depends on:
- the presence of iron, which is usually between 4 and 8% Fe2O3 in the ceramic clays; it is
the main responsible of the colour, because its oxides are intensely red or black coloured;
- the presence of calcium, because the calcium silicates formed during firing, particularly
gehlenite and diopside, can include some iron, so that the amount of free iron forming iron
oxides decreases; therefore the red or black colour is intense when calcium is low and vice-
versa;
- the firing atmosphere, that can be oxygen-rich (oxidant) or oxygen-poor (reductive)
depending on the firing system; oxidant atmosphere favours the formation of red coloured
hematite (Fe2O3); in reductive atmosphere there is the formation of magnetite (Fe2O3.FeO),
which is black; if the atmosphere varies during firing, for example during heating and
cooling, layers of different colours (red and black) with different tonalities can form;
- the presence of NaCl, which favours the formation of new alkaline silicates during firing,
which can inglobate iron; the whitening effect is particularly developed near the surface,
and gives rise to the formation of the so called ‘ghost coating’ (see 4.1.6).

MECHANICAL RESISTANCE
The mechanical resistance is generally measured as resistance to compression and/or
bending strength; this last is about 20% of the resistance to compression (Figure 4.4). The
mechanical resistance is inversely proportional to porosity.

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MECHANICAL RESISTANCE
sample

P
- COMPRESSION
~ 1000 kg/cm 2

P
- BENDING
~ 200 kg/cm 2

Figure 4.4 – Schemes of determining the mechanical resistance.

POROSITY AND PORE SIZE DISTRIBUTION
With the exception of stoneware and porcelain, all the ceramics are porous. Measured with
the mercury intrusion porosimeter, open porosity is of the order of 30-40%, while is less if
measured as water absorption, because water molecules do not enter the smallest pores.
The dimensions of the pores vary in a large interval, as it can be seen in Figure 4.5.
Stoneware and porcelain have less than 1% open porosity, but they can have very high
Pore size distribution
levels of closed porosity, up to 25-30% by volume.

Volume
(mm 3/g) Volume
(%)

Pore radius (micron)

Figure 4.5 – Frequency istogram and cumulative frequency curve of the pore size
distribution of a ceramic material analyzed by mercury intrusion porosimeter.

4.1.6 Ceramic coatings

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TYPES OF COATINGS
The development of ceramics by the man pursued two different objectives that are the
improvement of both aesthetical and technical characteristics.
The most important way was the application of more and more sophisticated coatings, with
the main goal of impermeabilizing the ceramic surface, because all the fired pastes were
very porous. There are four different types of ceramic coatings:
A) Clay-type, obtained with suitable clays
1) Engobe, porous
2) Slip, non porous
B) Glassy-type, characterized by a complete impermeability
3) Transparent glaze
4) Opaque glaze

APPLICATION OF THE COATING

The raw powder of the coating can be applied on the surface of the artefact, after
dispersion in water, with three different application techniques: immersion, pouring or
brushing. Depending mainly on the type of coating, the application can be made when the
ceramic paste is at leather hardness, or dried or fired; in the first two cases, paste and
coating will be fired with a unique process (single firing), while in the last case, there will
be two firings, one for the paste and the second for the coating (double firing). When
decorations are applied on the surface of the coating, in most cases they are fired together
with the coating, but certain decorations need a subsequent specific firing at lower
temperature.
Independently on the application technique used, a layer of powder coating is formed on
the surface of the object due to water sucking by the porous paste, that is the same
mechanism that has been seen speaking about the shaping technique called “slip casting”.
The thickness of the layer is very uniform when the immersion technique is used, much
more uniform than in the case of the other two techniques. In any case, the thickness is of
the order of some ten microns in case of clay-type coatings, and some hundred microns for
glassy ones.

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COMPOSITION OF THE COATINGS

Due to their nature, the clay-type coatings have a mineralogical and chemical composition
very similar to those of the ceramic pastes. The phase composition is mainly constituted by
quartz, feldspars and iron compounds in case of coloured coatings. On the contrary, the
chemical composition of the glassy coatings is very different from that of the ceramic
pastes. In addition, they are completely or almost completely transformed into glass, with
no or very small amounts of crystalline phases (transparent and opaque glaze respectively).
The chemical elements that compose the glazes can be subdivided at least into five groups,
each with a specific task (Figure 4.6). The basic component (SiO2), the modifier or melting
elements, and the stabilizer element (Al2O3) are always present. There are several
colouring elements, each one with a particular colour, also depending on the chemical
composition of the glassy matrix. For example:
- Iron (Fe): red, brown, green, blue;
- Manganese (Mn): brown, violet, light red, black;
- Copper (Cu): gree, blue, turquoise, red;
- Cobalt (Co): blue;
- Chromium (Cr): green, yellow, red, brown;
- Antimony (Sb): yellow, orange.
CHEMICAL ELEMENTS OF THE GLAZES

1. Basic Components of the frame (SiO 2)

2. Modifiers (Na +, K+ , Mg 2+ , Ca 2+, Pb 4+ )

3. Stabilizers (Al 3+ )
4. Opacifiers ( Sn4+ ) Mixing of the components
5. Colouring
(Co, Mn, Cu, Fe,
Cr, Sb)
GLAZE POWDER

Figure 4.6 – Task of different chemical elements which can be contained

10
in a glaze.

LEAD GLAZES AND ALKALINE GLAZES

Most of the ancient glazes contain lead and/or alkaline elements (sodium and/or potassium)
as modifier elements. Lead glazes have a lower melting temperature (600-750 °C)
compared with alkaline glazes (750-1050 °C). Lead glazes are very brilliant, very

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transparent and deeply penetrate the ceramic paste. Alkaline glazes are more suitable when
colouring elements are present. In addition, the presence of alkalis can change the final
colour for a same colouring element, for example copper (green or turquoise) and
manganese (violet or black).

COMBINATION OF COATINGS
Different types of coatings can be applied in the same artefact, where each one develops a
different task, depending on its characteristics. So, four combinations are possible:
- porous clay type coating before, and transparent glaze as external surface,
- porous clay type coating before, and opaque glaze as external surface,
- opaque glaze before, and transparent glaze as external surface,
- porous clay type coating before, then opaque and transparent glazes in the order.

GHOST COATING
Sometime the external surface of the artefacts is light coloured, while the ceramic mass
shows a red or orange/yellow colour. As a general rule, the observer deduces the presence
of a light-coloured clay-type coating, but sometimes it is not true. The light colour may be
due to the action of sodium chloride during firing. Sodium chloride had been introduced
into the ceramic mass dissolved in the processing water (for example by using sea water).

4.2 Technological classification of ceramics

4.2.1 Classification criteria

Three are the main classification criteria for ceramics:
- formal, based on the shape of the artefact
- functional, based on the use of the artefact
- technological, based on the manufacturing technique of the artefact.
While formal and functional criteria are well established since a long time, technological
classification is still in discussion. For this kind of classification, the following parameters
are usually considered: colour and porosity of the clay-based ceramic paste, presence and
type of coating, firing atmosphere. These parameters can be applied with relative facility

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even with simple macroscopic observations, eventually with the help of a small
magnifying lens, provided that the observations are performed on fresh fracture surfaces.
The colour is used to distinguish the coloured (red or grey) bodies from the “white” ones.
The distinction between porous and non porous bodies is very easy. The best system is to
evaluate the water suction by the body. To this purpose a drop of water can be put on the
ceramic surface for observing whether the water is sucked by the ceramic paste or not.
Instead of water, saliva can also be used. If the surface is clean, the observer can also put
his tongue into contact with the artefact: he will feel the sensation of strong adhesion of the
tongue to the ceramic mass in case of porous material. In addition, non porous bodies show
the typical fracture of a glass. The presence or absence of any coating is not always easy to
be recognized. A useful help can derive from the comparison of the colour on the natural
surface and on the fracture surface. In addition, the brilliance of the coating can be used to
distinguish between “clayey coatings” and “glassy coatings”. The definition of the firing
atmosphere can be made specifying if the colour has a red or grey tonality, corresponding
to oxidant or reducing atmosphere respectively. Starting from the above observations,
many different ceramic typologies can be recognized according to Table 4.3.

Table 4.3 – Technological classification of the ceramic materials.

FIRING CERAMIC
CERAMIC PASTE COATING
ATMOSPHERE TYPOLOGY
1) Terracotta
2) Polichrome
terracotta
Coloured Porous Oxidant
3) Coarse ceramics
Absent
4) Thin walled
ceramics
1) Reduced ceramics
Reducing
2) Bucchero
Porous slipped
Porous slip Oxidant
ceramics
1) Non porous red
Oxidant slipped ceramics
Non porous slip 2) Sigillata
Non porous black
Reducing
slipped ceramics
Discontinuos, Red or black figures
Ox/Red/Ox
non porous slip ceramics

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Transparent glazed
Transparent glaze
ceramics
1) Porous slipped,
Porous slip + transparent glazed
Transparent glaze ceramics
2) Sgraffito ceramics
Oxidant Majolica and lustre
Opaque glaze
majolica
Compact Stoneware, glazed
Absent or
or less stoneware, salt
transparent glaze
porous stoneware
Hard earthenware, Soft
Porous Transparent glaze
earthenware
White
Transparent glaze Hard porcelain, soft
Compact Ox/Red/Ox
or absent porcelain
Very quartz
rich, more 1) Stonepaste
Opaque or
or less Porous Oxidant 2) Siliceous Faenza
transparent glaze
coloured (or Egyptian fajence)
paste

4.2.2 Typologies with coloured porous body without coating

TERRACOTTA AND POLYCHROME TERRACOTTA

Terracotta is the simplest type of ceramics. Practically it is a ceramic typology made with
the clay as it is found in nature, with coloured and porous body, without coating, usually
fired in an oxidant atmosphere. The ceramic paste is made of not treated clay, so that the
surface is quite irregular. The firing temperature generally is below or around 900 °C. The
statues of the famous Terracotta Army in China, (221-206 B.C.) are a great example of this
typology (Figure 4.7).
Terracotta decorated with unfired colours (Figure 4.7) is called polichrome terracotta. The
pigments are generally organic and the artefacts are not re-fired after painting.

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Figure 4.7 – The Chinese Terracotta Army (on the left); a religious scene with statues
made of polichrome terracotta (on the right).

COARSE CERAMICS
Terracotta characterized by the presence of large inclusions (up to some millimetres) inside
the paste, which were voluntary added by the potter to reduce the shrinkage of the paste
during the ceramic processing, and to improve the thermal shock resistance of the artefact
during its use as cooking ware. The commonest inclusions are made of calcite, silicates and
chamotte (Figure 4.8). When calcite is used, the firing temperature cannot exceed 800 °C.

THIN WALLED CERAMICS

Terracotta characterized by very thin walls, up to about 2 mm. These small thicknesses put
into evidence the great ability of the potter in the shaping technique, mainly through
moulding. Artefacts of this type (vases, cups and glasses) are very common in northern
Italy in the Roman period, between II century BC and II century AD.

Figure 4.8 – Thin sections of coarse ceramics with calcite (left)

or silicate (right) inclusions.

REDUCED CERAMICS AND BUCCHERO

Reduced ceramics are typologies with porous paste, without coating, and characterized by
a grey colour obtained by firing in reducing atmosphere at least around the maximum
temperature and in the first phase of cooling. Bucchero is a particular type of this typology;

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it is completely black coloured and shows a brilliant surface. These characteristics are
obtained in a strongly reductive atmosphere, due to the presence of volatile carbonaceous
particles in the combustion fumes. Bucchero is a typical production of the Etruscan people
in Italy before the beginning of Rome’s power.

4.2.3 Coloured porous body and clay-type coating

BLACK SLIPPED CERAMICS

Ceramic typology with fine porous and coloured paste, with a coating made of a very thin
‘argillaceous’ layer (Figure 4.9), which is compact and typically black coloured due to
firing in oxidant atmosphere and then in reducing atmosphere, around the maximum firing
temperature, so that the body is red coloured, while the slip is black coloured. Its
production started in the central southern part of Italy (Figure 4.9, left).

CERAMICS WITH RED OR BLACK FIGURES

Ceramic typology with fine porous and coloured paste, with a coating made of a very thin
‘argillaceous’ layer, which is applied in a discontinuous way, in order to draw the figures
you want (black figures) or cover the area that contains the figures (red figures) (Figure
4.9, right). The result is obtained through a oxidant atmosphere followed by reducing
atmosphere around the maximum temperature, and then oxidant atmosphere during
cooling. The reducing atmosphere induces a black colour in the paste and in the coating as
well; on the contrary, during cooling in oxidant atmosphere only the ceramic paste turns to
red because the black coating is impermeable and cannot be oxidized.

Figure 4.9 – Thin section of black slipped ceramics (on the left),

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and ceramics with red figures (on the right).

SIGILLATA
Ceramic typology with fine porous coloured paste, with a coating made of a very thin and
compact ‘argillaceous’ layer. Both paste and coating are usually red-orange coloured;
decorations are present, which are obtained by moulding (Figure 4.10). Sigillata is a typical
valuable Roman production, obtained through very oxidant firing at a temperature as high
as 900-1100 °C.

Figure 4.10 – Examples of sigillata ceramics.

4.10 – Examples of sigillata ceramics.

4.2.4 Typologies with coloured porous body and glassy coating
TRANSPARENT GLAZED CERAMICS
Ceramic typology with fine porous and red coloured paste, with a coating constituted by a
coloured or not coloured transparent glaze.

POROUS SLIPPED, TRANSPARENT GLAZED CERAMICS, AND SGRAFFITO CERAMICS

Ceramics with a colourless or coloured transparent glaze applied on another coating, which
generally is a white porous engobe layer (Figure 4.11). The white surface of the engobe
can be used as a basis for decoration, which is then protected by a colourless transparent
glaze, that also increases the aesthetical value of the decoration. When the decorations or
part of them are obtained by incising the engobe up to uncover the red support, the product
is called sgraffito ceramics (Figure 4.11). These products are manufactured through double
firing:
1st firing = paste + engobe: the engobe had been applied when the support was at leather

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hardness,
2nd firing = painted decorations + transparent glaze.

Figure 4.11 – A fragment of ‘Sgraffito’ ceramics and its photo in thin section.

MAJOLICA AND LUSTER MAJOLICA

Typology with fine, yellow-orange and porous ceramic paste, with a layer of opaque glaze
(Figure 4.12). Sometimes there is a white porous engobe under the glaze, and/or a
transparent glaze layer on the opaque glaze, in order to protect the decorations painted on
the opaque glaze surface. Majolica is usually processed through double firing: at about 950
°C the first one, and some 30-40 °C less, the second.
Luster majolica is a kind of majolica with a metallic effect on the surface of the glaze
(Figure 4.12), which is obtained by treating the surface with metals (copper, silver or gold)
and re-firing the object at a temperature as low as 500-600 °C (low-fire firing).

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EWARE (Gres)
Figure 4.12 – Examples of majolica and lustre majolica artefacts, and a photo under the

ogy with a more ormineralogical less microscope in thin section.

e, which4.2.5 is Stoneware
compact (Gres)or
hanks toCeramic
its high quantity
typology with a more or less coloured paste, which is compact or less porous
because it contains a glassy phase (20-40%), more frequently without coating (Figure
se (20-40%), more
4.13). A special impermeabilization treatment, which was common in the past centuries,
was realized by introducing sodium chloride into the kiln at the maximum temperature
hout coating; a special
(around 1100 °C), so promoting the formation of a surface layer of completely melted

ation treatment, which

material (salted stoneware).

in the past centuries ,

by introducing sodium
he kiln at the maximum
~ 1100°C), so promoting
of a surface layer of
al ( salted stoneware )
19
Figure 4.13 – Stoneware artefacts.

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4.2.6 EARTHENWARE
Ceramic typology with a white porous body, with non-coloured or coloured transparent
glaze. The paste can be obtained by two different types of mixture, which are always
constituted of iron-poor raw materials:
- clay, sand and feldspar (about 55:30:15 respectively). The artefacts are produced in
double firing: the paste is fired at about 1250 °C, then the transparent glaze is fired
at 1100-1150 °C (hard earthenware) (Figure 4.14 on the left);
- clay, sand and limestone (rock mainly made of calcite) (about 50:30:20
respectively). It needs two firings: the first is for the paste (about 1000 °C) and the
second for the glaze at 900-950 °C (soft earthenware) (Figure 4.14 on the right).

Figure 4.14 – Hard earthenware (on the left)

and soft earthenware (on the right).
4.2.7 PORCELAIN
Ceramic typology with a very fine, white and compact body, often translucent because it is
prevalently constituted by a glassy phase which surrounds the crystalline phases.
Depending on the nature of the glassy and crystalline phases, there are different types of
porcelain, obtained with different formulations of the paste.
The type of porcelain obtained with a mixture of kaolin, feldspar and quartz (50:25:25
approximately), fired at 1300-1400 °C in an oxygen-poor atmosphere, is the most valuable
and it is called hard porcelain (Figure
4.15); mullite is its typical crystalline
phase, which

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Figure 4.15 – Artefacts of hard porcelain (on the left)

and soft porcelain (on the right).

forms during firing. Generally, a transparent glaze is applied, which has the same
components of the paste, but with less kaolin and/or quartz and more feldspar, so that it
results more fusible. The glaze is applied on the surface of the porous product obtained by
a pre-firing at 800-900 °C.
Soft porcelain is fired at lower temperature, about 1200 °C, and its composition is very
variable. There are at least two types of soft porcelain: one of them is manufactured with a
paste containing alkaline and/or earth-alkaline compounds (some lead can also be present),
which melt during firing and link the grains of the body (Figure 4.15); the second one,
typical of the English production, is obtained by using bone ashes, which are mainly made
of calcium phosphate, with the task of producing the melted phase (bone china or
phosphatic porcelain).

4.2.8 SILICEOUS CERAMICS

Ceramic typologies with a light coloured porous body, whose chemical composition is
represented by about 80% of silica, with a generally coloured transparent glaze. Two types
of artefacts are known with this characteristics: small Egyptian statues or other (Egyptian
fajence), and Islamic architectonic ceramics (stonepaste).

4.3 Alteration and degradation processes

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4.3.1 CAUSES OF ALTERATION

An ancient object is subjected to different factors that can modify its original
characteristics, starting from the moment of its realisation up to its recovering. The
interaction with the surrounding environment, in fact, can promote physical and chemical
modifications of the archaeological objects. This issue is treated in particular in the
Chapter 2, so that here the more general questions will be just mentioned, while some
processes specific for ceramics will be treated more deeply.
The modifications can be distinguished into alteration and degradation. Alteration
provokes transformation in the chemical and mineralogical compositions, but does not
apparently compromise the integrity of the artefacts. It depends on the artefacts
characteristics:
- porosity, the most important element because favours the interaction with all the
elements that “live” in the environment,
- the crystalline/glassy phase ratio,
- the composition, shape and size of the crystalline grains,
- the presence of coating, because the behaviour of paste and coating is quite
different, and the interface between paste and coating represents a point of
weakness.
Opposite to alteration, degradation compromises the integrity and the original
characteristics of the artefacts, causing mainly a mechanical disintegration.
The soil solutions are the main spreading vehicle of the alteration agents by considering
that the majority of ancient finds are in archaeological sites, that means buried
underground.
By considering all the environmental situations, four are the main causes of the
degradation phenomena, usually linked to each other:
- Humid pathology: The contribution of water is fundamental. Water solutions containing
salts, ions and other particles can come from the environment by means of percolating
water, rain, etc. or, as well as arising for capillarity in case of architectural ruins. The
situation is harmful for both glazed and not glazed ceramics.

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- Structural movements: These movements can originate inside the artefacts (Figure 4.16),
but in the majority of the cases are determined by external causes, for example
earthquakes.

Figure 4.16 – Ceramic sculpture with cracks provoked by structural movements

originated inside the artefact.

- Anthrophic interventions: Old and not well executed restoration works fall in this
category. Anthropic interventions also include the mass tourism that provokes changes of
the micro-climatic conditions.
- Other causes: These can include the interactions between different materials that
constitute the cultural assets (for example mortars and bricks), and the manufacturing
defects (such as the so-called “calcinello”).

4.3.2 PHYSICAL DEGRADATION

Physical degradation is the result of mechanical stresses acting on the artefacts. The factors
causing physical degradation can be schematized as in Table 4.4, where their importance is
related with the type of environment where ceramics rest before their recovery.
Table 4.4 – Importance of the causes of physical degradation
in different environments.
Factor Environment of permanence
Underground Air Underwater

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Indoor Outdoor
Frost/thaw +++
Soluble salts + + +++ +
Humidity + + +
Thermal shock + +++
Fluent water + +++
Wind +++
Weight +++ + + +
Vibrations +++ + + +
IR radiation + +

Frost/Thaw is to be considered practically only for outdoor exposed artworks, because the
water present inside porous structure of ceramic object varies its physical state in relation
with the climate. In particular, the increment of the water volume during the passage to the
solid state provokes internal forces of compression and traction.
The same could be said for the soluble salts, whose migration through the pores or
fractures of a ceramic paste favours the crystallization of deposits over or under the
external surface, or immediately under the glaze in the cases of glazed ceramics. In
extreme situations, you can arrive to the complete detachment of surface portion of the
artefacts, or glaze layer in the case of glazed materials. The problem of the soluble salts
also exists for objects buried underground or underwater, even though it appears only after
their recovery.
The variations of relative humidity and the consequent phenomena of condensation and
evaporation favour a gradual and constant infiltration of the water under the surface of the
ceramic object causing development of mechanical stresses that can diffuse in the whole
artwork.
Ceramics are subjected to thermal shocks, such as the majority of the materials, due to
rapid and noticeable variations of temperature, for example from day to night or from
summer to winter. Of course, these variations are practically possible only outside.
Fluent water has an abrasive action on the surface of the artefacts, which occurs
particularly underwater. The mechanical action of wind is similar to fluent water, but it acts
in air (outside) instead of underwater. In addition to corrosion, it is possible that deposits of
pollutants are formed on the artistic surfaces.
Most archaeological finds come from underground where the weight of the soil over the

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objects exerts a significant pressure, so that cracks and deformations are possible even
though the resistance of the ceramic materials to compressive forces is good.
The vibrations deriving from human actions, such as traffic, drillings, etc., can cause
instability; they can act on historical buildings as well as on archaeological sites.
IR radiation is a possible cause of degradation: its focusing on the object can cause a
localised increase of temperature and consequently the formation of stresses.

4.3.3 CHEMICAL MODIFICATIONS OF THE PASTE

The chemical alteration is the result of several modifications that change the original
composition of an artefact. They can be caused by human or environmental interferences
during the “life” of an object. It is well known, for example, the presence of carbon in
vessels used as cooking pots, whose visible consequence is a surface blackening, with
variable intensity depending on the position referred to the heat source.
In the ceramics, the chemical transformations can affect both paste and coating, even
though the paste modifications are more frequent. Apparently these modifications do not
give serious problems, because the transformations are often not visible at naked eyes, and
the physical integrity of the object is preserved. Anyway, it is important to know these
types of alterations, because the archaeological objects are sources of a lot of information
that permits to reconstruct several points of their working processes. The chemical
composition is particularly important for provenance studies, while the mineralogical
patterns permit to define the range of the firing temperatures.
Among the many possibilities of chemical changes, the most sensible seem to be the
alkaline elements (Na, K and Rb) and the earth-alkaline ones (Ca, Sr and Ba), with an
increase or decrease of concentration depending on the type of alteration process.
Several examples of pollution of manganese have been also found, but the pollution of
phosphorus certainly is the most common especially in the oldest ceramics, where it can
attain very high concentrations. This last type of chemical pollution is here commented in
detail.
Phosphorus contents in the clayey raw materials are usually much less than 0.5% P2O5,
due to the presence of phosphate minerals. Therefore, if a chemical composition of an
archaeological ceramic find shows higher phosphorus contents (up to 10% P2O5), doubts

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about the chemical integrity of the artefact have to arise. The macro-pores in the ceramic
fragments accept the solutions containing phosphorus and some chemical elements of the
ceramic paste, such as calcium, iron and aluminum interact with it to form new phosphate
compounds.
But what is the provenance of the phosphorus?
Taking into account that phosphorus pollution only occurs in buried ceramics, the most
likely hypothesis is that the phosphorus comes from bones, which are often found in
underground archaeological deposits. The bones are constituted by calcium phosphate and
they can be attached by soil solutions and release phosphorus. For this reason the more
polluted finds are the oldest ones, in particular Neolithic ceramics. It is also possible that
the vessels can have been used as container for food or for funeral purposes such as
cinerary urns. Another source of this pollutant element can be the fertilizers used in the
agriculture.
Apart from the source of phosphorus, it is also interesting to know how it is fixed into the
ceramic paste. Phosphorus precipitation from soil solutions is related to environmental
conditions, particularly to pH and Eh, which are controlled by changes in the water
content, movement of water-level in the ground, the presence of organic matter, and
bacterial activity.
Summarizing, first it is necessary to have acid soil solution able to attach bones and then
the solutions change their characteristics in order to favour the deposition of phosphorus.
The ceramic fragments provide the cations necessary to fix the phosphorus.
In some cases, such as the Neolithic ceramics from Sammardenchia (Italy), the
macroscopic aspect changes. The finds show big vacuoles, which could be erroneously
interpreted as result of the technological process, but in reality due to the dissolution of
calcite grains by acid solutions, which facilitate the mobilization of phosphorus and its
precipitation within these secondary cavities. SEM investigations have revealed local
chemical composition with about 50% of iron oxide, 20-25% of P2O5 and 10-15% of
aluminum oxide, other than minor amounts of silica and calcium oxide. These data suggest
a significant presence of vivianite, a hydrate iron phosphate (Fe3(PO4)2.8H2O), crystallized
to form a honeycomb structure (Figure 4.17).

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Figure 4.17 – SEM micrograph of phosphorus-polluted ceramics: the three points indicate
some of the analyzed positions, where the results suggest the presence of vivianite.

4.3.4 MINERALOGICAL MODIFICATIONS OF THE PASTE

The ancient ceramic objects recovered from archaeological excavations were for a long
time in contact with soil solutions and pollutants. This interaction can provoke
transformations in the mineralogical composition of the artefacts, other than in the
chemical composition. The mineralogical transformations mainly occur in the ceramic
paste. In any case water has a basic role; in form of rain, as well as percolating water and
humidity, it is the trigger for the transformation processes. In addition, water is a vehicle
for acids, carbon dioxide, soluble salts and other types of pollutants.
The main mineralogical modifications occurring in a ceramic paste are explained below:
- rehydration,
- transformation of gehlenite,
- secondary calcite from carbonation,
- calcite from external contribution.
Rehydration. In the ceramic paste can be present relicts of argillaceous minerals, probably
because the firing process did not favour their complete utilization for reconstructive
chemical reactions. This phenomenon mostly occurs in terracotta and raw ceramics.
The argillaceous relicts are very reactive and when they meet water they interact with it
and re-hydrate. The water molecules are captured by the argillaceous relicts that partially
reconstruct their micro-structure. It is a sort of re-argillification, with a partial
reconstruction of the starting mineral phases. At the end there is a very little crystalline

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phase with a structure similar to smectite.

How is it possible to recognize this situation?
Sometimes in XRD spectra a broadened peak is present in correspondence of the smectite
angles. In addition, TG-DTA curves show dehydration process with a loss of weight that
occurs gradually in a large temperature range, from 200 to 400 °C approximately.
The broadened peak in the XRD and the large temperature range in thermal analysis are
attributable to the weak bonds in the new crystalline structure. The weakness is confirmed
by the disappearing of this peak after re-firing at very low temperature (<400 °C).
Transformation of gehlenite. This reaction is typical of calcareous ceramics and occurs in
presence of humidity or water, not in arid environments.
During firing the carbonate minerals present in the original raw mixture are destroyed and
participate to the formation of new calcium silicate phases such as gehlenite, pyroxene,
anorthite. Among them, gehlenite is the less stable phase, so that it can be attacked by soil
solutions and it undergoes the following main transformation:

Gehlenite ⇒ Wairakite + Calcite + Gibbsite

At a first stage, the hydration of gehlenite gives rise to the formation of wairakite, which is
a hydrate alumino-silicate of calcium, together with calcium hydroxide and aluminum
hydroxide:
4 Ca2Al2SiO7 + 18 H2O ⇒ CaAl2Si4O12 • 2 H2O + 7 Ca(OH)2 + 6 Al(OH)3
Through reaction with the carbon dioxide present in the air, the calcium hydroxide
transforms into calcite:
Ca(OH)2 + CO2 ⇒ CaCO3 + H2O
The interpretation of XRD spectra permits to recognize this type of alteration.
Usually a diffractogram of well-fired and preserved ceramic body made with calcareous
clays shows a mineralogical pattern with a combination of new calcium silicates like
pyroxene, gehlenite, anorthite and wollastonite. On the contrary, when a diffractogram of
an altered paste is interpreted, it is possible to observe wairakite and/or calcite together
them. It is also possible that gehlenite is even absent. This is an anomalous situation,
because calcite and wairakite cannot exist at the temperatures necessary for the formation

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of calcium silicates such as pyroxene and anorthite (>850 °C). Therefore, the situation has
to be interpreted as a consequence of alteration processes mainly due to the action of water.
In these cases, next to a rather noticeable mineralogical transformation, there is no change
of chemical composition, apart from the acquisition of water and carbon dioxide which are
included in the ‘loss on ignition’ (LOI) or ‘ignition loss’ (IL).
Secondary calcite from carbonation. As mentioned above, during firing the carbonates,
mainly calcite, present in the clayey raw materials, are destroyed in order to permit the
formation of calcium silicates. So, if calcite is recognised into the ceramic paste, it is
possible that it is secondary calcite. In other words, the observed calcite is not the same
mineral that was present in the raw material. It is likely the result of an interaction with the
environment after firing, as in the case of transformation of gehlenite.
A type of secondary calcite is formed by carbonation of CaO, which remains free in the
ceramic paste, as residue of the destruction of primary calcite.
During firing, the destruction of carbonates provides calcium oxide (CaO) that combines
with silica (SiO2) and aluminium oxide (Al2O3) of the argillaceous minerals. If the CaO
amount is slightly in excess respect to the other oxides, or the firing time and/or the firing
temperature are not sufficient, there will be any residual CaO. This “free CaO” in the paste
can react with carbon dioxide (CO2) present in the environment, just after firing or during
the use of the artefact, so that new crystals of calcite are formed. First CaO interacts with
H2O in order to form Ca(OH)2; then Ca(OH)2 reacts with CO2 and transforms into calcite.
This type of calcite can be recognized by crossing the results of different investigation
methods, in particular the results of XRD and thin section observations at the optical
microscope. The small sizes of the new grains homogeneously distributed into the paste, in
fact, do not permit to recognize calcite. You can be sure that there are grains of new
crystalline phases, but you cannot identify their composition. So it is necessary to confirm
or not the attribution by using XRD technique.
The formation of secondary calcite through carbonation of ‘primary calcium oxide’ does
not alter the original chemical composition of the paste, so that it is possible to use the
chemical data for provenance studies.
Calcite from external contribution. Water solutions rich in calcium bicarbonate Ca(HCO3)2
transport it into the soil and inside the vacuoles of porous ceramics. In suitable

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environmental conditions, the instability of the bicarbonate favours the precipitation of

calcite inside the pores of the ceramic body. The precipitation of calcium carbonate occurs
according the follow reaction:
Ca (HCO3)2 ⇒ CaCO3 + H2O + CO2
Sometimes the new grains are in form of acicular crystals that start from the rim toward the
centre of the pore, sometimes completely filling it.
In order to recognise this type of secondary calcite, it is useful to combine different
analytical techniques: optical microscopy in thin section, XRD and XRF for example.
The observation in thin section is very useful because the calcite from external contribution
re-crystallizes inside macro-pores and fractures of the ceramic body (Figure 4.18).

Figure 4.18 – An example of secondary calcite from external contribution,

observed in thin section at the mineralogical microscope.

Secondly, the XRD technique is useful to confirm the presence of calcite. Finally, the
chemical analysis can also give an indirect but decisive contribute. In fact, a group of
ceramics, recovered from one archaeological excavation and belonging to the same
typology, usually should have the same or quite similar chemical compositions.
Conversely, in case of ceramics containing post-depositional calcite, the chemical
composition randomly varies from a sample to another. In fact, the precipitation of calcite
is not uniform, depending on the position of the finds in the ground.

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The presence of calcite from external contribution significantly modifies the whole
chemical composition of the ceramic pastes, also because other elements can be present in
the soil solutions and trapped into the ceramic paste, even though in less amounts.
This makes it is very difficult to know the original chemical composition of the shards, so
that the possibility of using these chemical data for provenance study is strongly
compromised.
The calcite from external contribution and from carbonation are easily distinguishable
between them, because the first is concentrated inside the macro-pores while the calcite
from carbonation is in micro-crystals widely dispersed in all the ceramic body.

4.3.5 CHEMICAL ALTERATION OF THE COATINGS

The ceramic coatings are subjected to alteration/degradation phenomena as the ceramic
pastes, but they have a different structure and/or composition, so that the effects also are
different. Usually, during burial, the glassy coatings can change their chemical
composition more easily than the argillaceous coatings. Sulphuration and phosphatation
are the main chemical alteration processes involving the coating layer of buried glazed
ceramics.
Sulphuration. This phenomenon affects lead glazes, both opaque and transparent. The
sulphuration appears as a blackening of the object surface, that quite completely hides
every decorative elements (Figure 4.19).
From the chemical point of view, it is a patina characterized by a high sulphur content.
Usually, no crystalline compound have been found, but sometimes the XRD investigations
revealed the presence of lead sulphide (galena).

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Figure 4.19 – Appearance of sulphurated lead glazes.

In order that the sulphuration occurs, it is necessary to have reducing conditions in the
burial environment. This is possible when the ceramic objects and rubbish of organic
materials are in the same place. The presence of organic materials permits the growth of
bacteria that metabolize sulphur ions for producing hydrogen sulphide (H2S). This last then
interacts with the elements present in the glaze layer, specifically lead, and amorphous lead
sulphide (PbS) forms, which is black in colour:
PbO + H2S ⇒ PbS + H2O
Depending on the available time, the lead sulphide could partially crystallize as galena.
The thickness of the blackened layer and its consistence depends on the closeness to the
pollutant source and on the duration of reducing conditions in the surrounding
environment. It is possible, in fact, that different fragments of a unique artefact can have
been subjected to different levels of sulphuration and blackening, which will appear very
evident after reassembling several fragments of the same object.
Several laboratory tests evidenced that it is possible to annul this blackening effect,
through a chemical treatment consisting in the use of hydrogen peroxide (oxygenated
water, H2O2), or by means of a thermal treatment at relatively low temperature (<350 °C).
The final result is apparently the same, that is the lightening of the surface. But by using
hydrogen peroxide, the cleaning is limited to the top part of the glaze layer, while the
heating treatment acts on all the thickness of the blackened parts.
Phosphatation. This type of alteration consists in the formation of thin patinas on the glaze
surface and provokes an iridescence of the glaze, with a subsequent loss of its brightness.
These crystalline or amorphous patinas are mainly characterised by hydrate phosphate of
calcium and lead and are the results of leaching processes by soil solutions. These remove
the more unstable elements releasing the transported cations, for example phosphorus,
which combine with some components of the glaze (calcium and lead), so fixating on the
surface. The Table 4.5 shows that it deals with is a very deep alteration of the original
chemical composition of the ceramic glazes, because phosphorus is practically absent in
the original glazes, and the content of silica is generally lowered.

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4.4 Ceramic conservation and restoration

4.4.1 EXAMINATION OF THE ARTEFACT AND RECORDING

The first examination of the object is done with the naked eye. If the object allows, handle
it carefully and look at it. All observations are to be recorded in new record or checked
with an existing written and photographic record.

Table 4.5 – Chemical composition of phosphorus polluted ceramic glazes.

SAMPLE
COMPOUND
PO3 PO7 PO14
PbO 30.75 44.26 54.66
SiO2 41.38 9.07 3.78
Al2O3 2.34 3.49 6.43
TiO2 0.03 0.06 0.10
Fe2O3 0.36 0.52 0.74
MgO 0.39 2.09 0.79
CaO 10.33 27.01 19.83
Na2O 0.40 0.47 0.59
K2 O 0.41 0.57 0.22
P2 O5 13.61 12.42 11.64
SO3 0.00 0.00 1.21
Ca5.5Pb4.5(PO4)6(OH)2 +++ +++ +++
Pb(CO3)2.2H2O +
Pb3O2CO3 +
Quartz +++ + ++

The written and photographic record is something that must always accompany the object.
The better and more precise the record is, the easier it is for the next conservator, scientist
or researcher to benefit from it.
If further investigation is necessary, this will be done with ultraviolet, infrared, x-ray aided

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examination as well as scientific analysis.

It is essential to keep clear records and documentation relating to the condition and
treatment of objects. In many collections, pro forma lists that just need to be checked are
useful; drawings are helpful as well as photographic recordings.
In an archaeological context, where objects have been excavated and may have required
some emergency on-site treatment, good written and photographic records are extremely
valuable for later work in the conservation studio.
Numbering is often important for archaeological objects as soon as they are excavated. A
temporary number may be temporarily placed on the object itself, or on the packaging, or
even as a label attached to the object. It may be necessary to put a number directly on to
the object either on the excavation site or in the conservation studio. The numbering needs
to be done in a way that is easily located but not obtrusive. A small rectangular area can be
painted with a primer such as Paraloid B-72 and on it the number can be written with a
stable marker or with drawing ink. This prevents the marker ink being absorbed into the
body of the object.
For a long time ancient repairs have been neglected by archaeologists and conservators.
This is also something that should be carefully documented as belonging to the history of
the object.
To the pottery repairs belong the use of metal staples that keep together the fragments or
cracks, through holes drilled into the ceramic and joined together by metal thread, and also
sometimes the use of alien fragments.

4.4.2 PLANNING A RESTORATION INTERVENTION

It is important to establish what sort of ceramic material the object is made of, for example,
unfired, low fired or high fired. If it is glazed, how stable is the decoration? Is it unfired?
The characteristics of the ceramic will influence the choice of the treatment.
The surface of ceramic is often contaminated by concretions of lime, gypsum or siliceous
materials which may obscure any decoration.
A principal cause of damage to ceramic objects that have been excavated is due to the
presence of soluble salts which are absorbed by the pottery whilst in the ground. The salts
can physically break the ceramic apart, so that the surface will exfoliate away and if this

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process is allowed to continue the whole object may be destroyed.

4.4.3 CLEANING
Before attempting to remove any surface deposit, the chemical nature of the concretions
should be established.
Incrustations can be removed mechanically as well as chemically. It is important to make
tests first, to make sure the object is not harmed and to choose the appropriate method.
If the excavated object is still wet or damp, the surface dirt should be removed as soon as
possible before it dries and it is drawn into the body.
Surface dirt can be cleaned first using a soft brush. The surgery scalpel and dental drill are
often a valid instrument to take away some surface deposit. Particularly for unglazed
pottery, several kinds of rubber powders and sponges have been developed for removing
surface dirt.
Some deposits can be removed with ultrasonic tools.
For carbohydrates, proteins and fats in the ceramic, enzymes can be used to enable to be
washed away.
Soluble salts which are a potential cause of deterioration may be removed by prolonged
soaking in distilled or deionized water. At regular intervals the water should be measured
to see if the treatment has been completed and is without salts.
Incrustations of calcium carbonate or calcium sulphate formed on the surface can be
removed using acids.
Care must be taken using acids. The ceramic should be thoroughly soaked in water first,
and the acids applied with a dropper, pipette or paper pulp in sufficient quantity to remove
only the concretion. It must be remembered that in using an acid to remove deposits we are
creating at the same time soluble salts: to objects treated in this way therefore must be
given a prolonged washing.
There are also lead sulphite blackening that can be removed if necessary, the eventual
cleaning should be carefully evaluated because it might not always be necessary.

4.4.4 CONSOLIDATION
If an object has been excavated it may require temporary reinforcement.
Cyclododecane (C12H24), a solid hydrocarbon that sublimes at room temperature, can be

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used as a temporary consolidant for weak or brittle material also straight after excavation.
Cyclododecane can be heated and applied as a melt, using a brush or heated spatula, or
dissolved in non-polar or aromatic solvents and used by spray, brush or injection.
If the object requires consolidation, then the consolidants may be applied by brush,
airbrush, pipette, injection, with compresses or by immersion. The choice of consolidants
and the method of application will depend on the condition of the object. The correct
choice of the method is extremely important as the consolidant is going to remain in the
object forever.
Experience showed that solvent based consolidants such as Paraloid B-72, acrylic resin or
polyvinylacetate in acetone or toluene are better than emulsions.

4.4.5 BONDING
The chosen adhesive needs to be reversible, non yellowing, stable, and easy to apply. It
must not affect the ceramic body in any way. Equally, it must have enough strength to hold
the fragments together without shrinkage.
The viscosity of the adhesive chosen is also important.
The correct density will depend on the porosity of the ceramic.
It should remain stable within the parameters of the Class A resin (which is for 100 years).
The best results are given by a solvent-based adhesive, which is the acrylic adhesive such
as Paraloid B-72 (known as Acryloid B-72 outside Europe). Paraloid B-72 has been found
very stable and reversible in its wide range of use in conservation.
On the other hand, in the last 2 decades there are publications in international conservation
journals about the instability of the cellulose nitrate, which is unfortunately still widely
used for bonding archaeological ceramics.

4.4.6 INTEGRATION OR FORMAL RESTORATION

There are various arguments for and against the use of fillings.
The decision to use fillings, and to what extent, will depend on the importance of the piece,
the historical context of the object, the extent of the collection, the money and time
available, the future handling, storage and display. If the object requires reconstruction, the
general rule is that the material chosen needs to be reversible and have good aging
properties. The best material used is based on a particular industrial plaster. The best filler

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is Polyfilla powder for indoor (also called Moltofill innen) based on calcium sulphate. It
does not shrink, it is easy to shape and remains workable for longer; is easy to mix with
pigments and can be easily painted. It also allows further filler to be added once the first
application has set. In some cases only large gaps should be filled but not missing chips.
The best solution is to fill the area to the same level as the original surface and not a few
millimeter below it. In the archaeological world, the decision was often taken to fill lower
in order to highlight the difference between old and new. This gap often attracted dirt and
by making the filling lower, the original border got damaged or weakened.
It is worth mentioning that in some cases detachable fills can also be made.

4.4.7 CHROMATIC RESTORATION

In some cases, pigments are already put into the powder of the filling material, in order to
obtain a suitable homogenous colour. In this case no painting is necessary, sometimes the
surface only needs a protection coat depending on the surface to be obtained.
In most cases it is right to choose a background colour to paint on the fill. This makes the
fills distinguishable from the original whilst at the same time being discreet. In other cases
the retouching of the decoration might close break lines or even go further and complete
iconographic motifs if they are known.
There is no general rule; it really depends on the demands of the collection.
If it is necessary to retain the reconstruction of the decoration, it needs to be closely
matched to the original but easily distinguishable on closer examination.
From an aesthetic point of view, it is important that the gaze of someone looking at the
objects slips away and does not hang anywhere.

4.4.8 CATALOGUING AND PHOTOGRAPHIC DOCUMENTATION

Examination should be done when the object arrives in the museum, studio or collection. It
is important to record all observations before any treatment begins: how it was transported,
packed, its general condition, the size and number of fragments and anything else of
relevance.
The photographic and graphic record plays an important part.
Digital photographic recording makes everything easier nowadays, the recording is easy
and data can be immediately entered in a data base.

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If possible black and white photos and colour slides should also be made because, if
properly stored, they last a long time. A scale of millimetres should appear in each
photographic record and possibly with the reference numbers of the object.

4.4.9 HANDLING AND PACKAGING

The package, already done at the site, is very important because sometimes it is the
definitive one for the object. Also important is to place the object in the container and pay
attention to possible wrong climate that could be created within it. It is therefore important
to choose the right material for storing items, depending on what kind of storage room is
available, which also takes into account whether the object is dirty, heavy, etc.. The best
material for containers are boxes made of polypropylene. It is important that the boxes are
easy to handle and therefore not too large, rigid, impact resistant, that do not chemically
interact with the exhibits, resistant to weathering, moisture and biodeterioration. It is very
important that the object is always accompanied by a fact sheet with information about the
origin, the excavation data, with the dates of discovery and storage, conservation status and
everything is useful to know it immediately.
For excavated ceramic objects it is important that the relative humidity remains below
55%, in order to prevent mold.
If inventorying data is to be written on the surface of the find, in this case a small
rectangular area should be painted by brush with a primer such as Paraloid B-72 diluted in
solvent. Once dry, the inventory number or data can be written on it with a stable marker
or drawing ink.

4.5 Case studies

4.5.1 SYRIAN PAINTED POTTERY

DESCRIPTION OF THE PROBLEM

The material is represented by fourteen large fragments coming from a Ugarit
archaeological site and dates back to the XII century B.C. (medium Bronze Age). Two
main questions were individuated with reference to these samples:

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a) Is there a slip applied on the surface of ceramics with the aim of giving a light
colour to the surface and therefore a good evidence to the decorations?
b) Is the composition of the red and brown decorations always the same or there is a
difference between red and brown?
Depending on the colour of the surface and of the decorations, two homogeneous groups
were observed, for a total of 11 fragments (Figure 4.20), while three are different, also
between them, and were neglected. The characteristics of the two groups are as follows:
1) very light coloured surface (beige) with brown decorations: fragments SAMA1,
SAMA2, SAMA3, SAMA4, SAMA5 and SAMA11;
2) light coloured surface with red decorations: fragments SAMA1, SAMA7, SAMA8,
SAMA9 and SAMA10.

SAMPLING
To answer the previous questions, four pieces (two for each group) were selected for
observing them in thin section:
- Group 1: SAMA3 and SAMA4
- Group 2: SAMA7 and SAMA8
After breaking of the specimens for the thin sections, new observations were made on the
fresh surface, also with the help of a stereomicroscope, in order to confirm or modify the
observations already made on the old rupture surfaces. As it regards the coloured
decorations, it was decided to analyze them through portable EDS-XRF, because this
technique is non destructive.

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Figure 4.20 – The two groups of painted pottery selected for sampling.

OBSERVATIONS AT THE OPTICAL MICROSCOPE

Observations at the stereomicroscope were made on the fresh fracture surface of the
ceramic samples SAMA3, SAMA4, SAMA7 and SAMA8. In particular it was confirmed
that there is not a clear border between the superficial light-colored paste and the internal
red-colored ceramic paste. This would mean that there is a superficial whitening
phenomenon, but not the application of a white slip layer.
At the mineralogical microscope, in thin section, all the samples observed look similar to
each other. The paste is red in color, grain-size distribution is serial, the maximum
dimension is around 250 micron, that is fine sand; the non plastic grains (around 15%) are
made of rounded mono-crystalline quartz, mica (muscovite more than biotite) and feldspar.
The matrix is isotropic; iron nodules and argillaceous rock fragments are also present.
Towards the outer surface, there is a layer, with a thickness around 500-700 microns,
which presents a great amount of mica lamellae and it is clearly distinguishable from the
paste due to the lighter color and the scarcity of non plastic grains. Nothing similar is
present towards the inner surface.

X-RAY FLUORESCENCE ANALYSIS

Through the X-ray fluorescence analysis (Figure 4.21), it was possible to realize that all the
decorations are made with a iron-rich pigment, for both the two series of samples. In

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particular, no manganese was observed apart from the usual traces that are in clays. In
addition, it was possible to ensure that the calcium concentration is very high and similar
inside and outwards.

Figure 4.21 – Analysis of the red colored decoration and two of the obtained spectra.

CONCLUSIONS
The presence of the lighter colored layer could be interpreted as a coating maybe made
with the same clayey raw material used for the paste, after separation of the coarse
fraction, with concentration of the finer clay fraction. This assumption derives from the
greater abundance of mica in the lights layer than the internal parts. The light color of the
layer could be due to the use of sea-water that during firing allows to obtain a lighter color.
The sodium chloride, present in the sea-water, during the drying step migrates toward the
surface and so its presence during firing provokes the whitening.
Because a light surface layer is clearly present only on the outer surface of the artefact, it is
possible that the sea-water was used only for the external surface treatment (realization
and/or application of slip by brush or by hand) and not as water for mixing the clay for the
ceramic paste. It is worth mentioning that the archaeological site is near the sea and thus
the supply of sea water was very easy.
All the decorations contain only iron as coloring element. As a consequence, the different
tonalities of color should be interpreted as the result of a different firing atmosphere: more
oxidant in case of red colored decorations and vice-versa. The reddish color of the paste
under the decorations is in agreement with this hypothesis.

4.5.2 INLAID ISLAMIC CERAMICS

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In the Timurid period most of the wall ceramic coverings were made by the technique of
the inlay work. One of the oldest example is given by the funerary monuments in the
cemetery of Sahi Zinde in Samarkand (Uzbekistan), which date from the second half of the
14th century to the beginning of the 15th century (Figure 4.22). Then the technique quickly
Sahi Zinde, Samarkand
spread throughout the Islamic world, from neighboring countries like Iran today, where the

Ceramic tarsia
Imam Mosque in Isfahan is one of the best known examples.

Figure 4.22 – Inlaid ceramic coverings in the Sahi Zinde monumental cemetery in
Samarkand, Uzbekistan (half 14th century – beginning 15th century).

This architectonic product needs a suitable ceramic paste which could be easily cut into
very different and often very complicated shapes. Its chemical composition, compared with
that of a brick and local clay (Table 4.6) shows that it is characterized by a large amount of
silica, while the brick paste is very similar to the local clay.
Of course, the high content of silica is due to a high content of quartz (around 70%). This
means that the paste has not strong ceramic linkages, which ensure the possibility to cut the
fired paste without particular difficulty. This special composition of the ceramic paste,
suitable for inlay works, is named ‘stonepaste’.
The large amount of quartz also gives a light color to the ceramic paste, thereby allowing
variously colored glazes have better efficacy. Both transparent and opague glazes could be
applied on the unfired support, because very small amount of gases developed from the

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paste.

Table 4.6 – Chemical composition of ceramic pastes and clays from Samarkand.

Stonepaste Brick Local

Oxide clay
SZ7 SZ8 SZ10
SiO2 82.53 80.70 60.42 63.30
Al2O3 4.30 4.89 12.00 12.02
TiO2 0.12 0.14 0.71 0.69
Fe2O3 0.84 1.00 4.89 4.38
MnO 0.06 0.05 0.10 0.09
MgO 3.52 3.65 4.09 3.25
CaO 5.87 6.07 13.10 11.56
Na2O 1.30 1.84 1.56 1.53
K2 O 1.28 1.42 2.87 2.95
P2 O5 0.18 0.24 0.26 0.23
Total 100.00 100.00 100.00 100.00
I.L. 1.44 0.90 10.04 11.87

As it regards the chemical composition of the glazes in Samarkand (Table 4.7), it can be
seen that the transparent glazes are very different from the opaque glazes. These last are
lead-alkaline glazes (12-13% PbO, 10-12% Na2O+K2O) and contain tin oxide (6-7%
SnO2), while transparent glazes are lead-free as well as of tin. Tin oxide develops the
function of opacifier and lead is added together with tin oxide in order to favour its
opacifying power.

Table 4.7 – Chemical composition of transparent and opaque glazes from Samarkand.

Transparent glazes Opaque glazes

Element
IK2 IK8 IK8 IK10 IK4 IK1
blue white blue blue turquoise turquoise

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SiO2 77.54 79.13 77.74 70.37 59.00 58.87

Al2O3 2.82 2.54 2.49 3.22 2.36 2.68
TiO2 0.10 0.10 0.10 0.12 0.09 0.10
Fe2O3 2.07 0.95 2.34 2.79 0.76 0.87
MgO 2.12 2.68 2.37 2.52 2.14 2.00
CaO 3.65 4.34 3.91 5.02 3.50 3.57
Na2O 8.16 6.69 6.27 10.33 7.90 10.03
K2 0 2.15 1.89 1.97 3.09 2.10 2.28
PbO 0.07 0.86 0.82 0.91 12.96 11.63
SnO2 0.01 0.35 0.33 0.01 7.04 5.76
CuO 0.01 0.01 0.03 0.06 1.75 1.70
CoO 0.34 0.05 0.67 0.32 0.01 0.01
As2O3 0.34 0.05 0.54 0.34 0.00 0.00
MnO 0.05 0.03 0.03 0.04 0.04 0.04
P2 O5 0.27 0.26 0.25 0.39 0.25 0.30
SO3 0.30 0.07 0.14 0.47 0.10 0.14

4.6 Examples of restoration

4.6.1 RESTORATION AND PRESENTATION OF AN ETRUSCAN BUCCHERO

The intervention illustrated herein involves a one-handled jug, or oinochoe, in Etruscan
bucchero, dated at the second half of the VI century B.C., produced in the city of Chiusi (a
city of Etruscan origin in the province of Siena, Italy). This artefact, which came from a
private collection, was seriously damaged after falling from a height of over 2 metres
(Figure 4.23). As a result, this archaeological find, when delivered to the restorer, was in
such a fragmentary state (about 125 pieces) as to make it difficult to correctly identify its
original form, which had been substantially compromised.

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Figure 4.23 – View of the fragments of the oinochoe on the external (left)
and internal (right) surfaces.

Furthermore, an initial ‘inspection’, aimed at evaluating the state of conservation, indicated

that the artefact had already undergone two previous restorations, as demonstrated more
specifically by:
- the presence of at least two kinds of glue, one of which, likely the older one, was resinous
and found only along the crack between globular body and foot of the oinochoe;
- the inner surface of numerous shards totally coated in grey plaster with shreds of paper;
- the several fracture lines, which showed traces of colophony and several signs of filling;
- the missing parts previously reconstructed; in fact, some limited zones were not made of
earthenware, but rather of plaster mixed with animal glue and black ink.
First of all, the various fragments of these plaster-animal glue-ink “fillings” came loose
after being soaked in warm water (45°-50° C). Once dried, the surfaces were carefully
dabbed clean with pads dampened in a solution called 3A, containing water (30%), alcohol
(35%), and acetone (35%), and then further cleaned with benzene, trichloroethylene, and
petroleum ether. In fact, the water-alcohol-ketone solution is capable of removing the
plaster, ink, and animal glue residue, and colophony (the latter of which was used locally
as an adhesive), while the aliphatic hydrocarbon and aromatic solvents remove wax and
other fatty substances (including, probably, even shoe polish) used in the past to give the
surface of the bucchero greater sheen and a more intense black hue.
At this point, following standard consolidation by applying acrylic resin (Paraloid B72)
dissolved in 2-3% acetone, the assembly phase and gluing the numerous fragments
together began. This operation was the most complex of the entire intervention, mostly due
to the extensive filing, carried out during a previous restoration, presumably during the

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XIX century, found on several edges of the shards (to the point that some of these shards
no longer made precise contact with the adjacent pieces).
Therefore, first the parts resulting from the most recent and devastating fall (thereby with
“freshly” broken edges that fit perfectly together) were glued with a polyvinyl butyral resin
(Mowital B60H in pure alcohol) spread repeatedly over the abovementioned cracks.
Successively, the gluing of fragments presenting abrasions and/or filing of the joints was
organised as follows. The various shards were arranged, taking into account a series of
elements like: the existing potential points of contact; the decoration; the thickness; the
curvature; the potter’s turning lines visible on the back. Then, the pieces were temporarily
glued together with sporadic drops of cyanoacrylate resins (Figure 4.24, left) and (once the
correct position had been verified) were definitively glued with two-part epoxy resin being
allowed to run into the spaces between the pieces: before, a coat of acrylic primer had been
applied to the fracture lines to facilitate a potential reversal of the gluing process.
Upon conclusion of the reassembly and gluing of the fragments, the problem of the
reconstruction of the missing pieces (that had been previously and ineptly reconstructed
with plaster, glue, and ink) was dealt with, as well as restoration of the areas where
vigorous filing had abraded the ceramic material. This procedure was necessary not only
for aesthetic reasons, but mainly to guarantee the overall static and structural stability of
the artefact. Therefore, all these ‘spaces’ were filled with a mixture of dental plaster (70%)
and fine scagliola (30%) suitable moulded and finished (Figure 4.24, right). Successively,
the surface was coloured to minimise the differences between the reconstructed and
original parts of the artefact, always guaranteeing easy distinction between reconstructed
and authentic zones. More specifically, the following procedure was used in applying the
‘a puntinato’ chromatic treatment. The missing parts were duly integrated and shaped
before being tinted uniformly with an acrylic base color, fundamentally ‘black anthracite’,
to emulate the color of the bucchero (even if of a slightly lighter tone). The second step
was to ‘spray’ multiple fine ‘pinpoints’, done with the use of hard-bristled tooth brush. The
shades of the pinpoints vary from intense black to dark grey, with sporadic pinpoints of
dark blue, dark red, and ochre yellow, depending on the shades of color perceptible on the
original earthenware. This method of spraying ‘pinpoints’ takes into account the
‘suggestions’ indicated by the artefact itself. In fact, the oinochoe in bucchero, following

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close observation, has not a uniformly black surface, but rather various shadings, even if
extremely subtle.

Figure 4.24 – Assembling and gluing stages (left); reconstruction and filling phases (right).

Therefore, the application of colors with this method of using small and variegated
pinpoints (overlapping and/or combined) served both to better blend the colors of the
original earthenware with those applied to the reconstructed areas, while also facilitating
the identification of the reconstructed areas and distinguishing them from the authentic
ones thanks to this colored “dusting”. Furthermore, the “a puntinato” method resulted in
the replication of the characteristic sheen of the bucchero, always by means of spraying
minuscule pinpoints of pearl white color (Figure 4.25).

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Figure 4.25 – Details on the pictorial restoration on the reconstructed zones

with the “puntinato” method.
Thanks to this restoration, it was once again possible to comprehend, and therefore
appreciate, the artefact that would have otherwise been compromised by such a devastating
event; consequentially, the recovery of the ‘form’ also allowed the recovery of the
‘essence’ of this work (Figure 4.26).

Figure 4.26 – The oinochoe upon conclusion of the restoration.

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4.6.2 RESTORATION OF THREE MAJOLICA PLATES OF THE 15TH CENTURY

The conservation work illustrated here is about three majolica plates, tin glazed terracotta,
dated 15th century. These three artefacts, which are from a private collection, were broken
and dirty. Plate number 1 was broken into five fragments, number 2 in three fragments,
number 3 in two fragments (Figure 4.27, at the top). All three plates had encrustations
along the fractures and had missing areas.
The owner has kindly made available the three plates as case studies, in order to show
three different ways of decoration of the missing areas. The reconstruction of the missing
pieces in this case was necessary for aesthetic reasons, but at the same time to guarantee
the overall static and structural stability of the artefact (for plate 1 and 2). The task was that
no original glaze should be covered by the retouching.
The first cleaning was done by washing with distilled water using a soft sponge and
brushes. The glaze was then cleaned with cotton swabs wetted with a solution of 5%
ammonium hydroxide in distilled water.
The incrustations along the breaks were removed mechanically with hand tools because
otherwise a perfect alignment of the fragments was not possible. The assembly of the
fragments was done with the reversible adhesive acrylic resin (Paraloid B72) diluted in
acetone (Figure 4.27, in the middle).

Plate 1 Plate 2 Plate 3

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Plate 1 Plate 2 Plate 3

Figure 1 – The three majolica plates dated 15th century: before, during and after restoration
(over, in the middle an below respectively).
There is no general rule about how far one should go with the retouching of the missing
areas; it really depends on the demand of the collection. The three plates were a good
example to show three options (Figure 4.27, at the bottom):
- for one plate it was chosen a ground color to be painted on the fill, to make the fill
distinguishable from the original but at the same time discreet;
- in the second case, above the ground color, the inpainting of the decoration was applied;
in any case the retouching of the decoration ends near the fracture lines;
- in the third case it was decided to go further and complete the iconographic motifs
because the chromatic integrations are easily reversible; in this case the decoration was
closely matched to the original, but is easily distinguishable by close examination. No
original glaze was covered by retouching.

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ACKNOWLWDGEMENTS
Many thanks to the National Museum of Damascus (Syria) for the use of the image of
some archaeological ceramic fragments and the correspondent analytical results.

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5 – CLAY TABLETS

5.1 Definition
The clay tablets are slabs of unfired or fired clay used in the past as a writing medium for
documents on various subjects in order to conserve them for a more or less long time. They
can be of various size and shape, starting from few centimetres to half a meter or more.
The largest tablets are approximately rectangular with a plane shape, while the smallest
ones are biconvex in shape and can be held in the palm of the hand. In fact, they were
shaped by mixing the clay in the palm of a hand.
Only a minority is constituted by a clay envelope enclosing the true tablet. The clay tablets
were used by the Mesopotamian civilizations (Sumerian, Babylonian, Assyrian and Hittite)
since the second half of the fourth millennium B.C., and most of them are written in
cuneiform characters, which were generally imprinted with a blunt reed stylus (Figure 5.1).
Cuneiform script is one of the earliest forms of writing, which emerged around the 33th
century B.C. It included about one thousand characters in the Early Bronze Age, but only
about four hundreds in the Late Bronze Age. The latest known tablet in cuneiform
characters dates back to 75 A.D.
The tablets were imprinted when the clay paste was at plastic state, that is sufficiently soft
to impress the characters of the writing, and with a sufficient mechanical resistance that
allowed to resist to the stresses of writing.

Figure 5.1 – A Babylonian tablet (87 B.C.), which describes

the arrival of the comet of Halley.

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After impressing the text, the tablets were dried by exposition to the sun, and sometime
fired in order to make them much harder and durable, in particular the largest ones and
destined to be kept for a very long time.
The compositional characteristics of the clays used for the tablets are the same of the clays
for ceramics and one can find everything in the correspondent Chapter 4. There,
information can be found also with reference to the significance of ‘plastic state’ of a clay
and the behaviour of the clay during drying as well.
The tablets may be personal or business letters, can represent legal documents or parts of
books as well. The clay tablets that function as checks, provided by the famous Code of
Hammurabi, the Babylonian king who reigned from 1792 to 1750 B.C., are a fine example
of use of this type of artefact in commercial field.
After a certain time, most unfired tablets became useless, so that they were destroyed and
the clay reused for new tablets. Therefore, it is clear that the tablets produced in the past
are much more numerous than those recovered. Notwithstanding this, at least five hundred
thousand tablets are today kept in museums, and others are continuously retrieved from the
archaeological excavations in the regions where they were used.
Cuneiform writing lasted several centuries; then, during the Iron Age, it was completely
replaced by alphabetic writing.

5.2 Deterioration
The clay tablets are found in regions where the climate is generally dry, so they are often in
good condition. In fact, the main deteriorating consequences of unfired clay tablets are due
to the interaction with water. This occurs when the burial environment is humid, because
the clay minerals are highly sensitive to the action of water and can absorb it in large
quantity. As a consequence, they will get plastic or even muddy, so suffering different
kinds of damage. If it deals with many tablets, all coming from the same store, they will be
piled randomly and will join together to become practically non-detachable from one
another. Of course, in this case you may lose the opportunity to read the entire text
imprinted on the clay surface. In addition, the tablets undergo significant deformations, and
the cuneiform characters with them, so that even the characters that are in sight could

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become readable with high difficulty.

The alternation of wet and dry phases also leads to swelling and contraction phenomena,
which can give rise to deformations, formation of fissures, fragmentation of a tablet in two
or more pieces, and even to structural weakening and subsequent pulverization.
When tablets are humid, particles of the burial soil can adhere to them, and after recovery
many of these particles remain adherent to the surface. The elimination of these particles
surely is one of the most difficult cleaning operations. Obviously, the removal of soil
particles is necessary in order to highlight the angular form of the characters of the
cuneiform writing.
The problem of soluble salts also applies to raw clay tablets, because they are very porous
even though they rapidly become little permeable in contact with water solutions. But the
duration of burial and then the contact with water is so long that all the clayey mass can be
infiltrated by the solutions which circulate in the soil.
The problem of soluble salts likely is more hard for cooked clay tablets, because they are
less sensitive to water and their permeability virtually does not change. In such a way, all
the mass of the tablets can be rapidly soaked with water and its evaporation concentrates
the soluble salts near and on the surface. The crystallization of these salts, mainly chlorides
and sulphates, generates internal tensions in the tablets and little by little they undergo a
gradual detachment of material starting from the surface. This effect adds to that of the
hydration / dehydration of clay minerals, thus increasing the speed of the degradation
process.

5.3 Conservative intervention

5.3.1 Intervention during the excavation

During an archaeological excavation it is possible to find only one or few clay tablets, but
more frequently small or big archives are encountered. Three different types of clay tablets
can be present:
- unfired clay tablets,
- fired tablets,
- originally poorly fired clay tablets, or badly cooked clay tablets as a consequence of
accidental conditions such as the fire of the rooms where they were stored.
Most of the recovered tablets are unfired, because only a minority of tablets was destined

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to be fired, and the majority was stored in form of dried clay. During the recovery,
however, it is difficult to determine with certainty whether they had been baked or not.
The unfired cuneiform tablets can be distinguished from the archaeological ground with
difficulty, because this last often formed through the collapse of the walls where the tablets
were kept. In fact, in most cases the walls were built by using clayey material. The main
difference comes from the fact that the tablets were usually manufactured with depurated
very fine clay.
It is very important to recognize the single artefacts inside the ground, so that it is possible
to separate them from each other. Of course, you have to avoid the forced separation of the
tablets which adhere between them due to the humidity in the ground. In these cases it can
be sufficient to carry out a natural drying for obtaining an ‘automatic’ detachment. But the
drying should be gradual in order to avoid further cracking and fragmentation of the
tablets. To this purpose, it is opportune to protect the objects from the sun during the
excavation. It can not be excluded that at the beginning of the twentieth century it was just
the recovery of fired or partially fired tablets to suggest to cook the unfired clay tablets for
their better conservation. Both in past and in recent times, somebody has realized the firing
of the clay tablets on-site just at the time of excavation.
The procedure of the preservation work can be a little different in the case of raw and
cooked clay tablets. In addition, there are two different approaches regarding intervention
on the uncooked tablets: on one side the supporters of the opportunity to cook the tablets to
give them a high mechanical strength, on the other side the supporters of the opportunity to
keep the tablets as they are, that is uncooked.
The different procedures are summarized in Figure 5.2, where documentation is not
considered, because it is very important and should be realized in every step of the
intervention.

5.3.2 Preliminary cleaning

Preliminary cleaning of the recovered tablets should be executed after drying the objects,
when most part of the soil particles spontaneously detach due to the shrinkage occurring
during drying. In addition, the drying favours an increase of the mechanical resistance of
the tablets, so that they can better support the mechanical stresses caused by the tools used
for cleaning them.

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CLAY
TABLETS

DRYING AND
UNFIRED PRELIMINARY FIRED
CLAY TABLETS CLEANING CLAY TABLETS

CHEMICAL CONSOLIDATION
CONSOLIDATION BY FIRING

DESALINATION

CLEANING
AND MENDING

HOUSING

Figure 5.2 – Schematization of the different procedures proposed

for the conservation of fired and unfired clay tablets.

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Another positive effect of drying before cleaning refers to the soluble salts which are
usually present in the clay tablets. These salts come out and crystallize on the surface of
the residual burial soil that covers the artefacts, so that they are at least partially eliminated
during the preliminary cleaning together with the same soil particles. From this point of
view, this procedure constitutes a good way for realizing a first phase of desalination. On
the other hand, the salt crystallization can weaken the structure of the tablet; therefore the
preliminary cleaning should be performed with caution, avoiding the occurrence of too
strong stresses. Of course, fired or partially fired tablets need less caution than the unfired
ones.
Preliminary cleaning should be always carried out at the stereomicroscope by means of
scalpel and acuminated wooden instruments, paying attention to fix all the areas at risk
with acrylic adhesive.
Finally, in order to avoid greater damages, carbonate deposits and thick deposits of salt
crystals should not be removed, even though they partially or completely impede the
readability of the text. Analogously, eventual roots should be cut near the surface and not
extirpated from the artefact.
In case of tablets originally baked or today cooked, when the cuneiform images are almost
illegible, the use of some soft form of sand blasting can be taken into account in order to
remove debris and minute particles from the surface without causing any damage.

5.3.3 Consolidation of unfired tablets

It is very difficult to successfully treat the unfired tablets, and the use of an
adhesive/consolidating should be done after a careful evaluation by an expert conservator
of clay tablets and ceramics, with the aim of evaluating the general characteristics and
particularly the conservation state of the tablets.
In addition, it would be very useful to be sure that the tablets are really unfired. This
information can be quite easily achieved by analyzing them by means of X-ray
diffractometry.
Unfortunately it deals with a destructive technique, but this should not be a big problem
when a lot of homogeneous archaeological material was recovered. Alternatively, an
expert researcher can obtain good indications by analyzing the tablets by means of UV/Vis
spectroscopy, which needs only few milligrams of specimen.

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CHEMICAL CONSOLIDATION
Since a lot of time, firing is a very usual practice for the consolidation of unfired clay
tablets. When this practice was introduced, the studies on the conservation treatments were
at an initial stage, while today it is sometime possible to realize conservation procedures
that can allow the unfired clay artefacts be well conserved without applying thermal
treatments. In addition, it needs to consider that the number of recovered tablets is very
high and it would not be possible to cook all them in a relatively short time.
Environments with controlled temperature and relative humidity can be sufficient for the
conservation of the tablets without any other intervention, because these conditions prevent
the leakage of the soluble salts. On the other hand, it is evident that a perfect control of
these environmental parameters is practically impossible, so that some conservation
intervention is advisable.
After the preliminary cleaning, the restorer will proceed to reassemble the fragmented
objects, if they are. It is suggested to pre-consolidate the fracture surfaces by applying a
diluted solution of paraloid B70 in acetone or ethyl silicate. Then, the joining of
fragmented portions can be executed by using acrylic glues, which are preferable in
comparison with the vinylic ones, because they are more resistant to humidity action. If
there are points with more or less deep fractures, they will be treated with infiltrations of
medium concentrated paraloid B70. Alternatively, you can try to consolidate the tablet by
using ethyl silicate, which is generally utilized for consolidating unfired clay bricks.
In general, the consolidating treatments of unfired clay tablets are possible accordingly to
the high open porosity of the unfired clay, even though the penetration will be not very
high because the treatment rapidly makes the surface impermeable. Of course, it needs that
the clay is not humid, because the water would make the surface of the clay artefact
impermeable and would preclude any penetration of the consolidating solution. The
consolidation treatment can be carried out by immersion for some hours, or for less than
one hour when it is realized under partial vacuum.
The research about the conservation treatments of the unfired tablets is quite scarce, and it
would be hoped for an increase of activity in this field. Some research groups are
evaluating how to use the nanotechnologies and the nano-materials to this purpose. In
particular, they are planning to experiment nano-limes and nano-silica as consolidating
materials, because they are inorganic compounds and would not change the composition of
the clay tablets in a significant way. This would be particularly true when it deals with

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tablets made of carbonate-rich clays, as frequently happens.

On the other hand, nano-limes have been already successfully used for the consolidation of
stone, mortar, plaster, fresco, and wall painting. The particles of nano-lime have an average
size of the order of one hundred nano-meters and are sold in form of suspension in
different solvents. Treatment with these products will result in the evaporation of the
solvent and formation of calcium hydroxide. In presence of humidity, the calcium
hydroxide converts into calcium carbonate, through reaction with atmospheric carbon
dioxide, as occurs in the traditional mortars. This means that the treatment should be
carried out before the complete drying of the clay tablet, unfortunately when the object has
not its maximum mechanical resistance. The drying will be completed after consolidation
of the treated tablets.
Notwithstanding the fineness of the particles, it seems that the penetration of the nano-lime
suspensions is not very high. The result will be a good consolidation of the superficial parts
of the clay tablets, which, however, are the ones more likely subjected to wear.

CONSOLIDATION THROUGH FIRING

Unfired clay is little resistant against the action of water, because it is easily disaggregated
and many clay minerals are easily attacked and altered. In addition, clay artefacts have a
low mechanical resistance. On the contrary, fired clay (terracotta) is mechanically resistant
and less attached by water than unfired clay. Having this in mind, since the beginning of
the twentieth century is common practice to cook the raw clay tablets, in order to
consolidate them. Tablets were sometimes baked at the time of excavation by using metal
boxes filled with sand, even though more recently the on-site cooking was more controlled.
But such a type of practice should not be considered a normal conservative intervention,
because it completely modifies the composition of the objects and the nature of what is
conserved is very different from that of the unfired items. This is not in line with the
principles of conservation; in fact, this type of treatment is not practiced in any other kind
of artefacts.
The firing of clay tablets should be considered an exceptional type of intervention to be
implemented when you cannot do otherwise in order to retain the ability to read what is
written on the tablets. Fortunately, usually a large number of tablets are found together, so
you can keep many of them raw, as evidence of the initial condition of those cooked. On
the other hand, the work of cooking is very long and in the case of a large collection of

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clay tablets could take years. Preferably, will be fired those tablets or fragments that show
the presence of deposits of calcium carbonate or other salts which cannot be mechanically
removed, unless some parts are held together just by the salts. After cooking, if still
present, probably the deposits will be more easily removed, mechanically or chemically.
The cooking of well dried clay tablets is usually carried out in programmable kilns with a
very low thermal gradient and several steps before reaching the maximum temperature, so
that cooking can last up to one week. Depending on the authors, the maximum firing
temperature may vary greatly, from 675 to 800 °C.
In this way they try to reduce to the minimum the breaking of tablets, due to the chemical
reactions which occur during heating and cooling (see chapter 4, and in particular 4.1.4 and
4.1.5). The main result of these reactions will be a significant reduction of the dimensions
of the tablets, with the possibility of breaking if the contraction does not occur
contemporarily in all the positions of a tablet.
Another factor that may affect the outcome of cooking is the technique of manufacturing
the tablets. Where they were processed using a homogeneous clay paste, there is a good
guarantee of success. On the contrary, when the tablets were manufactured by
superimposing several layers of clay, likely these layers can separate during cooking.
Anyway, you can never completely avoid the occurrence of fractures due to their presence
at a latent state. In fact, the proportion of broken tablets after firing is always very high and
often beyond repair. For this reason someone cooks the tablets immersed in sand contained
in suitable container. This safety measure should avoid, in case of detachment, the
fragments move away from each other and thus can easily be relocated successfully. In any
case, also the tiniest fragments must be recovered and reattached, especially when they
have characters engraved on the surface, and their loss would make the reading very
difficult. In this case it is opportune to cook the fragments separately and attach them
together after cooking, because the thermal treatment would burn the adhesives used.
These adhesives are the same used for pottery (see 5.3.4 and also Chapter 4).
Because the clay tablets often break further during the cooking process, it is advisable to
take pictures of the tablets before cooking them. Then the pictures will be used as guides
for understanding the precise position of the fragments, as they were pieces of a puzzle. An
acrylic adhesive is suitable to join the fragments.
The practice of firing the tablets has become very common, but there are not enough

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studies available to determine which are the best conditions especially with regard to the
maximum firing temperature. In fact, the above mentioned temperature of 675-800 °C does
not take into account the composition of the clay, namely the presence or not of
carbonates. In their absence, 675-800 °C can be retained a valid temperature, because it
ensures the complete destruction of clay minerals and the achievement of a sufficiently
stable physical state.
On the opposite case, that is in presence of carbonates (for example calcite), cooking at
750-800 °C could result in the partial or complete decomposition of calcite, with a more or
less abundant residue of calcium oxide. In fact this temperature could be non sufficiently
high to ensure the formation of stable compounds and the residual calcium oxide will then
be transformed into calcite again (see Chapter 4, namely 4.1.4 and 4.3.2). This reaction
implies an increase in volume which can lead to the fragmentation or even the
pulverization of the tablets.
In conclusion, it would be opportune to know the mineralogical composition of the tablets,
and to establish the treatment temperature taking it into consideration. It would be even
better to look for the clay used for manufacturing the tablets and to use it to test the best
firing temperature for the tablets.

5.3.4 Conservation of fired tablets

The restoration of clay tablets usually is simple when they were well cooked and today
they are nothing else than a terracotta.
A viscous solution of Paraloid B70 is relatively not toxic and easy to use for reattaching
the detached fragments; a more diluted solution of the same product can act as
consolidating for the weak parts close to the junction. The two solutions (viscous and
diluted) can be contained in small polythene bottles with a spout, from which their
application on the clay tablets is easy.
All the conservative interventions must be done after having well-dried the items, because
they acquired a high level of moisture during the burial. Somebody uses to re-fire the
tablets, but this would definitively compromise the possibility of dating them through
thermo-luminescence analysis. Therefore this practice is not advisable.
Perhaps to facilitate handling of the tablets is opportune to apply a film of Paraloid B70 in
solution; other than to consolidate the item, it would have the function of protecting the

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surface during the study.

In conclusion, the fired clay tablets can be treated as you act in case of ceramics, and you
can refer to Chapter 4.
Sometime the clay tablets are partially cooked as a consequence of accidental events (for
examples fire) after their use. In this case the tablets coming from the same excavation
would present very heterogeneous cooking level, with large differences among objects and
part of a single object. Such a situation does not allow to treat the tablets as if they were
cooked; on the contrary, it is advisable to consider them as if they were raw.

5.3.5 Extraction of the soluble salts

Both uncooked and cooked clay tablets very frequently contain soluble salts, which
accumulated during the burial period into the porous structure of this type of artefact. In
case of uncooked tablets it is better not to perform any desalination treatment before
consolidation, because the material is soft and the artefact could be easily damaged, so
making the readability of the inscriptions more difficult or even impossible. As a general
rule the desalination treatment should be done after consolidation, avoiding the firing of
the clay tablets, even though the desalination treatment is easier for the cooked ones.
The extraction of the soluble salts from the smallest tablets can be carried out in distilled or
de-ionized water kept in slow motion, changing the water several times and measuring the
content of salt in the used solution by means of silver nitrate or a conductivity meter till the
disappearance of the salts.
Alternatively they can be soaked in custom designed desalination systems where water is
constantly circulating. Generally a long time, of the order of a month, is necessary for
completing the treatment. At the end many clay tablets may have broken into two or more
pieces, so you need to mend them with the help of photographs taken before the
desalination treatment. For the largest tablets, the desalination can also be achieved by
using ion exchangeable resins, as it has been illustrated for stone (see Chapter 2).
In any case, it is advisable to think of the possibility not to desalinate the tablets and to
keep them in suitable environment, impeding the formation of efflorescence and associated
cracks. This is certainly difficult to realize, but today there are the means to do it, without
recourse to firing, by controlling temperature and relative humidity in the deposits or in the
exhibition rooms.

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5.3.6 Housing and digitizing

The problems of the reaction between clay minerals of the unfired clay tablets and
atmospheric water are greatly related to their conservation. In many cases also the presence
of carbon dioxide in the environment can become very important because it could start
carbonation reactions of the calcium contained in the tablets.
This is especially true in the case of tablets cooked in order to consolidate them, when you
get highly reactive calcium oxide, ready to form calcium carbonate again. Carbonation
occurs with a great increase in volume of the particles and the birth of internal tensions.
Therefore, housing projects for clay tablets are very important and requested, according to
what has been illustrated in Chapter 1 (Preventive conservation).
Sometimes, clay tablets are housed in small plastic or metallic boxes, stuffed with cotton
batting in order to give protection to the tablets. But cotton batting is rather abrasive with
reference to unfired clay tablets and, in addition, this type of housing appears rather
unprofessional and un-presentable.
In order to manipulate the clay tablets as little as possible, several institutions started to
register their collections decades ago using conventional photography. But these
registration methods are insufficient because the clay tablets are objects in three
dimensions. This is why in recent times several three-dimensional projects of digitization
of the clay tablets have been proposed.
Of course these methods are still expensive and not available for all researchers involved in
the study of cuneiform texts. However, they are rapidly developing systems cheap enough
and also easy to use in the field.

5.4 Case study: Syrian tablets

5.4.1 The archaeological material

The material comes from Tell Mari, Hariry, Derelzoor (Syria), and dates back to the
beginning of the II millennium B.C. (Figure 5.3). It deals with thousands of small tablets,
about 5 cm long and large, and about 2 cm thick.
The main conservation problems of these tablets come from the apparent formation of grey
coloured soluble salts, also during the conservation in the museum, which produce the
break-up of the clay; the sample MA-1 (=Th07-05) well represents this problem (Figure

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5.3 and 5.4). In order to try to solve the problem, it would be necessary to know the nature
of the soluble salts, to understand the mechanism of their formation, and how to eliminate
them for stabilizing the artefacts.

Figure 5.3 – The two sides of some clay tablets from Tell Mari (Syria).

5.4.2 Laboratory investigations

The first investigation was made by observing the tablet MA-1 at the stereomicroscope. It
was observed that this tablet shows a radial cracking, which concerns a superficial layer of
clay, apparently due to the internal growth of a white transparent crystal or aggregate of

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crystals.
Semi-quantitative chemical analyses were performed by EDS-XRF through measures in
the area of the defect and in a well preserved area of the same side of the sample MA-1
(Figure 5.4).
It was expected that the comparison between the results of the two areas would have given
the possibility to deduce the qualitative composition of the whitish material present under
the clay at the convergence point of the cracking lines.
The analyses were carried out with 30 KV and 20 µA and the signal was recorded for 60
seconds. The results, reported in Table 5.1, show only two intense peaks, referable to iron
(Fe) and calcium (Ca) respectively.

Figure 5.4 – The red raw indicates the defect where an EDS-XRF analysis was carried out;
another analysis was made on the same side at the centre of the tablet.

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Table 5.1 – Results of the XRF analyses of the clay tablet MA-1.
Sample Fe Ca K Mn Ti S Ni Si P Cr Cl Sr V Zr
Clay 4,000 2,200 180 200 120 15 65 35 35 35 20 35 30 35
paste
Defect 2,400 2,100 110 90 80 75 35 20 30 20 15 40 25 20
area

All the other peaks are low or very low, taking also into account the background intensity,
and they can be attributed to: potassium (K), manganese (Mn), titanium (Ti), sulphur (S),
nickel (Ni), silicon (Si), phosphorus (P), chromium (Cr), chlorine (Cl), strontium (Sr) and
zirconium (Zr). All these elements are present in low or very low percentages, excluding
silicon. Due to its low sensitivity, the detection of silicon means that its concentration is
very high, of the order of 50-60% SiO2.
In the defect area, the main part of the elements (Fe, K, Mn, Ti, Ni, Si, P, Cr, Cl, Zr) shows
a drastic decrease of their peak intensity; calcium remains at the same level, while sulphur
and strontium show an evident increase of intensity.
These results indicate that only calcium, sulphur and strontium are contained in the
material under the cracking, while all the other elements detected by the analysis in this
point are attributable to the contribution of the surrounding clay. In addition, because the
intensity of calcium is the same in the two analyzed points, it is possible to affirm that
calcium is a big component of the internal “crystal”. In fact the contribution to the intensity
of calcium by the internal crystal compensates to the lack of intensity due to the smaller
exposed portion of clay, which contains a large amount of calcium.
In spite of the low intensity of the sulphur line, it can be stated that also sulphur is a main
component of the material under the cracking, because sulphur has a low sensitivity with
this type of analysis. On the contrary, the low intensity of strontium indicates that it is
present only in minor amount.
In conclusion, the internal crystal would appear to be constituted by calcium and sulphur
with minor amounts of strontium. Therefore, it can be hypothesized that it deals with
gypsum (CaSO4.2H2O).
With the aim of confirming this hypothesis, a small amount of whitish material was taken
from another tablet, which was already damaged and broken, and submitted to
mineralogical analysis by X-ray diffractometry (XRD). This analysis fully confirmed the
hypothesis, showing a lot of gypsum accompanied by traces of quartz, calcite and

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plagioclase. Of course, these last are present due to impurities of the clay paste in the
analyzed sample.

5.4.3 Conclusions
After attaining the above conclusion on the nature of the whitish material which is present
under the clay at the convergence of the cracking lines, it would be very interesting to
continue the research, in order to individuate the growth mechanism of gypsum inside the
tablet even during its conservation in the museum. Three hypotheses can be suggested:
- gypsum is present in the raw clay used for the preparation of the clay tablets, and it
accumulates due to the humidity action,
- gypsum forms due to a reaction between calcium and sulphur already present in the
raw clay in separated compounds,
- gypsum forms due to a reaction between calcium present in abundance in the raw
clay, in form of calcium carbonate, and sulphur coming from the surrounding
environment (pollution?).
According to these hypotheses, a research project could be planned for analysing the raw
clay materials outcropping in the area of the archaeological site from where the tablets
come, and to evaluate the air quality inside the museum. In addition, it would be opportune
to know whether the tablets are fired or simply dried in the sun.
In conclusion, it can be discussed about interventions of consolidation, necessary to restore
the compactness of material, but clay tablets show many unsolved problems. Therefore we
have reached the awareness that such a particular material still requires deeper and more
accurate studies.

Bibliography

Ambrosi M., Dei L., Giorgi R., Neto C., Baglioni P., Colloidal particles of Ca(OH)2:
properties and application to restoration of frescoes, Langmuir, 17, 2001, pp. 4251-
4255.
Baglioni P., Giorgi R., Soft and hard nanomaterials for restoration and conservation of
cultural heritage, Soft Matter, 2, 2006, pp. 293-303.
Bater M., Abed Esfahani A., Paidar H., Structural studies of Haft Tappeh’s cuneiform

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tablets, Iranian Journal of Cristallography and Mineralogy, 13, 1, 2005, pp. 1384. (In
Arabic language).
Brooks S., A new approach to the design of kiln furniture for the firing of cuneiform
tablets, Iraq LIX, 1997, pp. 203-207.
Cohen J., Duncan D., Snyder D., Cooper J., Kumar S., Hahn D., Chen Y., Purnomo B.,
Graettinger J., Digitizing cuneiform, 5th International Symposium on Virtual Reality,
Archaeology and Cultural Heritage (VAST 2004), M. Mudge, N. Ryan, R. Scopigno
eds., The Eurographics Association, 2004, pp. 135-143.
Gerasimova N.G., Vinogradova V.P., Research and restoration of cuneiform tablets,
Khudozestvennoe nasledie, 36, 6, 1980, pp. 83-89. (In Russian language).
Giorgi R., Dei L., Baglioni P., A new method for consolidating wall paintings based on
dispersions of lime in alcohol, Studies in Conservation, 45, 2000, pp. 154-161.
Giorgi R., Maglioni M., Berti D., Baglioni P., New methodologies for the conservation of
cultural heritage: micellar solutions, microemulsions, and hydroxide nanoparticles,
Accounts of Chemical Research, Vol. 43, n. 6, 2010, pp. 695-704.
Goren Y., Mommsen H., Klinger J., Non-destructive provenance study of cuneiform tablets
using portable X-ray fluorescence, Journal of Archaeological Sciences, 38, 3, 2011, pp.
684-696.
Liégey A., Etude pour le dessalement de tablettes cuneiforms en terre crue, In: Journées
d’études de la SFIIC: Le dessalement des Matériaux poreux: Tes Journées d’études de
la SFIIC, Poitiers 1996, ed. International Institute for Conservation of Historic and
Artistic Works Section Francaise de l’Institut International de Conservation (SFIIC),
1996, pp. 105-113.
Thickett D., Playing with fire: Characterization of clay types used in fabricate cuneiform
tablets and their thermal behaviour during firing-based conservation treatment, 12th
Triennal meeting Iccom Committee for Conservation, Volume II, James & James,
London, 1999, pp. 809-810.
Thickett D., Odlyha M., The contribution of thermoanalytical techniques to the
conservation treatment of cuneiform tablets in the British Museum, Thermochimica
Acta, 365, 1-2, 2000, pp. 167-175.
Thickett D., Odlyha M., Ling D., An improved firing treatment for cuneiform tablets,
Studies in Conservation, 47, 1, 2002, pp. 1-11.

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Willems G., Verbiest F., Moreau W., Hameeuw H., Van Lerberghe K., Van Gool L., Easy
and cost-effective cuneiform digitizing, 6th International Symposium on Virtual Reality,
Archaeology and Cultural Heritage (VAST 2005), M. Mudge, N. Ryan, R. Scopigno
eds., The Eurographics Association, 2005.

ACKNOWLEDGEMENTS
Many thanks to the National Museum of Damascus (Syria) for the use of the image of
some clay tablets and the correspondent analytical results.

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6 – GLASS

6.1 General information

6.1.1 Origin
Glass is a rigid, non-crystalline and transparent material resulting from a treatment at high
melting temperature (melting point 1300-1500 °C; partial melting at 1000 °C was achieved
in antiquity) of a mixture of silica (vitrifying element, extracted from sand, river pebbles,
quartz), calcium carbonate and sodium or potassium (flux elements). From the casting of
this mixture a product is obtained called the fries. The fries can be added to accessory
elements and then placed on a second fusion.
Plinio tells the story of how some Phoenician traders used sodium carbonate (nitrun) to
light a fire on the sandy shore of a river. They saw how the present nitrun fed the flames
and melted with siliceous sand, producing an unknown material that became brilliant after
cooling. It is likely that the production of glass was born in the Mesopotamian area and in
Egypt (the oldest artefacts come from Syria from the fifth millennium BC), and from there
it spread to China and the Far East. From the beginning, the working technique was
difficult and so the glass was considered a semiprecious material, used in jewellery along
side gems. Glass making then spreads to imperial Rome, with the technique of blowing.
Later, in the Middle Ages comes the separation of the sodium glass in the Mediterranean,
and potassic glass appears within the French-German Countries. At the end of the tenth
century the glassworks of Venice started, transferring to Murano from 1291.

6.1.2 Structure and composition

Glass is an amorphous solid obtained by the melting of mixtures with siliceous
compositions and by a subsequent fast and controlled cooling. The fundamental structural
unit of glass is the SiO2 tetrahedron. In glass the tetrahedrons are arranged in a disordered
manner and the bonds amongst them are variable; also in quartz the SiO2 tetrahedron is the
fundamental structural unit, but here the tetrahedrons are arranged in a regular manner and

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bounded among them by precise bounds (Figure 6.1)

Silica (SiO2), a fundamental component of glass, is called “network former”. The main
sources of silica in nature are silicate rocks such as quartz sands and quartz sandstones.
Quartz has a high melting point (about 1700 °C) and the kilns in the past were not able to
reach these temperatures. At that time, it was necessary to add a flux that lowered the
melting point of the glass batch. Fluxes were alkali compounds (Na or K). Historically, the
main sources of flux were:
• Natron (Na flux)
• Ash of maritime plants (Na flux)
• Ash of continental plants (K flux)
Natron = evaporitic deposit mainly composed of hydrated sodium carbonate.
Ash of maritime plants (called “allume catino”) is mainly composed of sodium and
calcium carbonate, with reasonable quantities of Mg and K, and perceptible concentrations
of phosphorus.

Tetrahedron SiO2

Q G
Figure 6.1 – Glass disordered network (G) and regular reticular structure of quartz (Q).

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Ash of continental plants is particularly rich in potassium (K).

Their use changes according to the historical period and geographic area.
Flux lowers the melting point but weakens the bonds inside the glass network, making the
glass more alterable. It becomes indispensable to add a new component (stabilizer) to the
glass batch in order to strengthen the bonds inside the glass network. The stabilizers used
in ancient glass were calcium oxide and magnesium oxide. The role of the stabilizer is to
strengthen the internal bonds so that the glass becomes less alterable. Flux and stabilizer
are called “network modifiers” according to the role they play.
In summary, the principal components of a glass are: network former, flux and stabilizer.
A glass (like mosaic glass) can be coloured and opaque. Then in a glass colouring and
opacifiers, the so called “accessory components”, can be present.
Furthermore, in ancient glass obtained by natural materials it is possible to detect a lot of
elements linked to the impurities of the raw materials (Al, Ba, Mg, K, Fe, etc.). These
elements can be called “fortuitous components”. Another important element is the lead.
This has different functions in glass technology (flux, colouring and opacifier).
Colouring elements in ancient glass are simply copper, iron, manganese and cobalt. An
enormous quantity of colours could be obtained according to the presence of these
elements, their firing atmosphere, firing temperature and the presence or absence of lead.
Opacifier elements were antimony and tin.
Opacity in a glass could be obtained by means of primary opacifiers or of secondary
opacifiers. Primary opacifier is an opaque material in granules (often quartz) added to the
melt during its cooling. Secondary opacifiers are minute crystals that are formed from the
melt during its cooling (opacifier elements).
The presence of bubbles also contributes to increase the glass opacity.
Until the 8th century A.D., Hellenistic, Roman and Byzantine glasses were produced by
siliceous-calcareous sand coming from the mouth of river Belus or Volturno plus natron as
flux. In Mediterranean Europe during the 9th century the substitution of natron with
allume catino (ash of maritime plants) begins for glass production. Between the 9th
century and the middle of the 12th century two fluxes (natron and allume catino) coexist.
From the end of the 12th century there is exclusive use of allume catino as flux in the glass
production. The success of the allume catino was sometimes followed by the use of new
network formers (quartz pebbles, new sands). Of course there are some exceptions in the

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general evolution of the glass technology over its long history. In fact glass that is
particularly difficult to produce such as red, yellow or white opaque is often the result of
precise recipes and production techniques that are not in agreement with the compositional
and technological characteristics of the other coeval glass. For example red opaque glass
can be detected, which was produced with a Na flux obtained by ash or marine plants in
Roman period.
The identification of the chemical composition is fundamental for characterizing ancient
glass. In fact chemical composition gives precise information on raw materials and on
production technologies. In order to easily show the results of chemical analyses, ternary
(for example, the ternary diagram of the principal components Si, Na and Ca, or of the
fortuitous components Al, Mg and K) or binary diagrams (e.g. K/Mg) are generally used. It
is possible to distinguish a glass produced by a sodic flux obtained by natron from a glass
with a sodic flux obtained by maritime plant ash, taking into account the percentage of
K2O and MgO. In particular, in natron glass K2O and MgO are ≤1%; while the
concentrations of K2O and MgO are >2.2-2.5% until 6-7% in glass made with ash of
maritime plants.

6.1.3 Classification referred to composition

SODIC AND POTASSIC GLASS

Glass obtained with soda or potassa as flux. Soda ash is obtained from the calcination of
algae and marine plants, while potassa is extracted from the ashes of the forest trees,
usually beech and flint. Sodic glass is also called “long glass” because it remains plastic for
a long time, it is lighter than potassium glass, has no resonance and has a yellowish or
brownish tone.

CRYSTALLINE AND CRYSTAL GLASS

Crystalline glass is a very transparent, very light and thin sodium glass. It is obtained using
vitrification of the pebbles of Ticino that are rich in quartz and with few impurities. The
stones are first crushed and subjected to thermal shock and numerous cleanings. The
resulting powder is mixed with high amount of flux, which is also cleaned several times in
the water. Crystal glass, more commonly called just “crystal”, is the glass of superior
quality and represents an evolution of potassium glass, purified from impurities that made

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the green. Made of silica, potassium and lead oxide, it is a transparent, lightweight, thin,
shiny and bright, with high refraction index of light, hard and heavy glass. Because of its
hardness it is characterized by incised decorations and facets.

GLASSES THAT IMITATE OTHER MATERIALS

1) chalcedony glass (tin oxide is added to the mixture as opacifier, while various metal
compounds are added in order to create multi-coloured streaks).
2) strass glass (potassium glass in which the lead component is greater, and in which
coloured substances are added to imitate precious stones).
3) milky-glass (opaque white and glossy glass, imitating the porcelain. It is obtained by
combining the mixture with the sodium manganese dioxide as a whitener and the tin oxide
as opacifier).

6.2 Processing techniques

6.2.1 Forming
Each forming technique starts from the “bolo” which is the melted glass.
Casting. Casting the bolus within closed clay mould, which give both the form and the
decoration. This technique only allows the production of objects with a full shape, that is
without cavities inside them.
Moulding. Casting the bolus in the interspaces between two identical twin moulds, or
casting it into one mould and modelling it in the same mould, still hot.
Cold cutting. After solidification, the glass can be worked on using grinding, cutting and
engraving.
Blowing. The glass is removed from the crucible and rolled on a slab of metal, to give it a
cylindrical shape. The bolus is then attached to a glassy long hollow metal tube, named
“rod breath”, through which the glazier inflates the air to create the bubble. Often the piece
is heated and blown several times. The blowing may be carried out without tools or with a
metal mould. To shape the blown glass according to the desired shape forceps and scissors
are used.
Ice glass. It recalls broken ice. It is obtained by immersing the semi-finished piece in cold
water and then again in the furnace: the temperature changes cause the cracks. The piece is

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then further blown and polished.

Murrine. The first step is to prepare murrine sticks, each with different colours, and weld
them together to obtain one stick in several colours. This large cylinder is then heated and
stretched in order to obtain a much longer and thinner one, that has the same colours and
composition of the beginning. Once cooled, the cylinder is cut into round pieces, that are
enclosed by a glass ring then arranged in a plane surface and heated till they are welded.
Such a disk is cooled and then reheated and worked as one piece, in order to reach the
desired shape.
Filigrana. This technique employs strings of glass used for the entire length. Often the
filigrana technique regards the insertions of strings of opaque glass into transparent glass.

6.2.2 Decoration
Enamel painting. Cold-drawing of the enamel (powdered glass obtained from enamel
ingots powdered and then mixed with metal oxides and a fat binder), cooked in the oven at
a moderate temperature (500 °C) to melt and fuse the glass with enamels.
Cold paintings, grisaille. They use powdered glass combined with metal oxides diluted in
wine or liquid resin. Then the mixture is warmed in order to obtain coloured glass.
Incision. Working with special tools directly on the body of the objects. It removes
material, so it is possible on hard, thick glasses, such as lead crystal. It can be done using:
- grinding wheel, producing furrows on the wall of the object.
- diamond tip, producing scratches or tiny dots under the action of the diamond. It is
applied to glass with thin walls.
- sand blasting, recent system (last quarter ‘700), which is to scratch the wall with a
continuous stream of sand at high speed.
Applied decoration. Glazed decorative elements are applied to the object in relief. This
happens when the parts are not completely solidified.
Golden glass. The gold leaf is applied to a glass surface and then engraved. It is then
covered with a thin layer of glass that protects the gold. The whole complex is slightly
heated in order to close the glassy layers and enclose the gold leaf.

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6.2.3 Glass windows

The glass window is a mosaic of glass pieces of different colours. Sometimes a preparatory
drawing on paper of the same dimension of the glass window is prepared. It is cut and used
as a guide in the process of cutting the glass. The slabs can be achieved in two ways:
1) the bolus can be blown as a bottle, obtaining cylinders cut in their length and then
flattened on a surface of stone;
2) The second system consists on a fast rotation performed by two glass makers that
use two tolls at the same time in order to obtain a big glass disk.
The pieces of glass are cut by means of hot tips or diamond tips. At the end these pieces
are inserted into a lead frame, strengthen by means of a large iron frame.

6.2.4 Egyptian blue

While not a glass in the strict sense, the Egyptian blue is treated in this chapter as it seems
to be the most suitable part of the book. In fact, the name “Egyptian blue” is given to a
blue glass paste, whose color is due to the presence of crystals of cuprorivaite as well as
other crystalline compounds. It is used as pigment in painting (in powder form) and to
obtain blue mosaic tesserae, that were utilized, especially in the 1st century A.D., for
covering fountains.
Egyptian blue is obtained by the calcination of a mixture composed of quartz, calcium
carbonate, copper carbonate and small quantities of natron (900-950 °C). During the
baking in oxidizing atmosphere the calcination of CaCO3 and copper carbonate is followed
by the reaction amongst calcium oxide, copper oxide and quartz (SiO2). This reaction
produces the formation of Cuprorivaite (blue in colour, CaCuSi4O10). The presence of
natron in the mixture favours the synthesis process. Egyptian Blue is composed of
Cuprorivaite (responsible for the blue colour), quartz and sometimes small quantities of
silica phases of high temperature in a sodium rich glass paste (Figure 6.2).

6.3 Glass deterioration

The main deterioration process of the glass is the leaching (removal) of the alkaline flux
(Na and K) due to hydrolysis by water. In this way the H+ ion enters in the glass structure
in the place of Na+ or K+.

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Figure 6.2 – Egyptian blue tessera.

The ionic radius of H+ is smaller than Na+ and K+ ones; for this reason a reduction
phenomenon takes place in the external part of the glass structure. With the passing of the
time exfoliation process can develop due to this phenomenon. In addition the complex
mechanism of reflections and refractions of the light that goes across the thin sheets
constituting the exfoliation gives rise to iridescence. Then exfoliation and iridescence are
deterioration forms closely connected to a chemical process which is the leaching of the
alkaline flux (Figure 6.3).
Other deterioration phenomena are the precipitation of soluble salts (in fractures and
bubbles inside the glass), that can lead to the disintegration of the glass, and sulphation
phenomena (formation of sodium sulphate on the glass surface).

6.4 Glass conservation and restoration

6.4.1 Examination of the artefact and its documentation

It is important to record all the data belonging to the object. The box container should carry
the following:

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A) Labelling

Figure 6.3 – Glass deterioration: exfoliation (left) and iridescence (right).

B) All the excavation data

For the object itself a catalogue should be prepared with information about the site
including:
C) Where the object comes from: county, city, road
D) The name of the archaeological site
E) The date when the excavation took place, under whose scientific direction, from
which company
F) Coordinates of the site, data, drawings, photographic record
The first visual examination is very important. The use of good light and microscope
magnification makes the examination easier.
The result of the observations should be written in the report at the time they are done.
Drawings and a photographic record are very important, as well as the list of any treatment
done, and a scale check list giving priority to the conservation treatment and fragility of the
object.
It is useful to prepare a check list containing data fields, for example, whether the surface
is iridescence, has a brittle surface, has a craquelè, is sweating or weeping; all this to
determine the kind of body, the transparency or opacity, the colour, the thickness, as well
as indications of fabrication techniques and other useful information.

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6.4.2 Planning a restoration intervention

First, it is important to ask and answer the following questions.
Is a conservation treatment necessary? How fragile is the object to get the treatment?
Which kind of effects can be expected from the treatment? How often should the treatment
be repeated? Instead of a treatment is there a way to use any prevention? What is the final
destination of an object, the storage room or an exhibition or should it be just made
presentable for a publication?

6.4.3 Cleaning
It is crucial to examine the object or the fragments with complete attention. The fragility of
the body and the surface of the object must be clear. The materials chosen will depend on
the substances to be removed.
A standard procedure for “healthy” glass – that is, not having any glass disease and any
kind of cold painted decoration or gold – would involve cleaning the glass with distilled
water – if necessary, with an added non-ionic detergent.
The weathering on archaeological glass should not be removed under any circumstances
because this would also remove what is left from the original surface of the glass.
All glass or glass fragments that can be safely washed should be washed, including some
glass with glass crizzling, unless it is too fragile or has dangerous and/or unstable cracks
and repairs. Here the experienced conservator should judge what is best.
The fragments edges should be cleaned before gluing - if possible using acetone or ethanol.

6.4.4 Consolidation
Also for glass as well as for ceramics Cyclododecane can be used as a temporary
consolidant for weak or friable material on excavation as well as in the conservation study.
Following the excavation of glass pieces or fragments, it is important that they are taken
out of any plastic bags and stored in an atmosphere neither too humid nor too dry.
Any attempt done by researchers and conservators to consolidate the exfoliating surface of
the glass did not give good results. Archaeological glass with lifting weathering layers may
require a little fixing and/or consolidation with a dilute solution of Paraloid B-72 in about
10%-15% weight/volume in acetone.
When attempts at impregnation of the glass with various materials were also made in the
previous decades, it was found that the sealing of the surface of finely fissured glass gave

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various problems. The only method of preserving the glass as far as possible is to store it at
all times in a controlled climate (see 6.4.8).

6.4.5 Assembling and bonding

The best adhesive for glass may not jet exist! However, a solvent based adhesive like the
acrylic polymer Paraloid B-72, as well as some epoxy adhesives can give the best results in
restoring glass. (This fact follows several decades of experience by conservators and draws
on scientific publications from all over the world).
Glass divides into two categories as far as bonding is concerned: healthy glass and
weathered glass (also called with glass disease). For healthy glass the best adhesives are
epoxy adhesives, for glass that has a strong or less strong weathering must be decided
individually which material to choose. It is important to add that modern glass can also
suddenly suffer from glass disease, which can be caused by the environment in the storage
or by the wrong materials used for the exhibit cases.
The best epoxy adhesives for glass are adhesives with the same refractive index of the
glass, transparent, non yellowing, chemically inert, with an expansion coefficient as close
as possible to that of the artefact, with mechanical resistance to tensile stress and tear, with
resistance to microbiological attack, reversible, or at least removable through swelling with
solvents without damaging the original.
The experience of the last decades demonstrates that the best non-yellowing epoxy resins
on the market are: Hxtal Nyl-1 and Epo-Tek 301-2. These have proven to be stable over a
long period of time and have the parameters of class A resin; this means that they should
remain stable for 100 years.
The technique used for the gluing is very important. The fragments must first be taped or
fixed together in order to support firmly the fragments while the adhesive is setting and
this can take several days.
The best method is to use tape. The choice of tape used depends on the surface of the glass,
whether it is weathered or not. In some cases transparent tape, which is elastic and has a
good sticking capacity on the surface, might be the best; in other cases, medical tape used
for the human skin might be better.
Strips of tape should be used, made with scissors, cut lengthwise and then crosswise. The
length or thickness of the strips will depend on the size of the fragments and the thickness

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of the glass. The strips can be also very small, depending on the size of the fragments and
should be held and fixed with tweezers. The strips might be also of 1 or 2 millimetres, if
possible not thicker than the glass thickness to allow the epoxy adhesive to flow
underneath. The tape strip should be attached on the surface of one fragment and pulled
onto the other fragment placed across the break. All the strips should be put at right angles
to the line of the break. It is not always necessary to put the strips on the front and the back
of the object. If the object is round then the strips can only be put on one side, in this case
on the outside.
This method enables the object to be stuck completely together in a perfect alignment, only
held by the strips. At this point the adhesive can then be applied by capillary action along
the breaks.
The filling of the adhesives in the break is done by capillary action. The resin is applied
carefully along the upper half of the crack and is drawn in by capillary action. As soon as
the resin penetrates, the crack immediately becomes invisible.
Any excess of the epoxy resin on the surface must be cleaned away before the adhesive has
set by using a cotton swab dipped in acetone.
It is important to mention an alternative to the tape. For fragments that are difficult to fix,
or may be damaged on the surface by applying the tape because they suffer with the glass
disease, there are small metal pieces, which can be made individually to make a bridge
across the join.
The best metals to us are stainless steel or brass. These can be bent like a rounded “W” and
can be glued on with a small drop of cyanoacrylates adhesives. Also small clamps as well
as other self constructed aids can be used.
The broken object itself will determine the most appropriate method. Sometimes the
surface allows the use of both tape and clamps.
Under no circumstances should heat be used to speed up the process of setting of the epoxy
or on the glass.
For archaeological glass that has weathering it may be good to use an acrylic polymer
solvent-based adhesive such as Paraloid B-72 for the bonding. Archaeological glass that
suffers with glass disease should not be taped.
The tape would remove parts of the surface weathering or leave an imprint on the surface.
Therefore a different method must be used. Paraloid B-72 is the correct adhesive as long as

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an absolutely transparent result is not required.

A small amount of adhesive B-72 should be applied to one of the broken edges and joined
with the edge of the matching piece. All the pieces will then be joined by piece-by-piece
assemblage. In case it is difficult to hold the fragments, small metal clamps, as mentioned
above, might be used. Deciding when to remove the excess adhesive will depend on the
fragility of the glass.
It may be wise to remove it only once it has set. The prerequisite for good results in glass
restoration are a mixture of experience, skill and intuition.

6.4.6 Filling in missing areas

Filling in gaps in glass is generally a very difficult task.
The matching of the colour of the glass and the actual filling of the missing area requires
great precision, technique and a lot of time. In the case of modern glass, filling in missing
areas might be considered in some cases if the piece is very important aesthetically.
The best materials for replacing missing areas on glass are resin-based fillers: the above
two epoxy’s mentioned above: Hxtal Nyl-1 and Epo-Tek 301-2.
In most cases is possible to achieve a close or identical match between the glass and resin
by using dyes, or finely ground pigments.
There are various types of materials for making a simple backing or a double-sided mold
for the resin, are such as plasticine, tape, dental waxes, silicone rubbers and various other
supports.
A successful cast, with the right colour, shape and free of bubbles is very difficult to make.
In many cases the cast has to be worked with drills and sand paper and then polished which
places stress on the object.
Where archaeological glass is concerned, it may be desirable for long term aesthetic
reasons to leave the object with the missing areas not filled with resins. If a support is
necessary to give structural stability, it can be made out of glass, Plexiglas, metal or other
materials, instead of resin.
In many museums collections of archaeological glass, we see how the reconstructed or
restored areas have badly aged. This has frequently led to heavy yellowing, shrinking and
breaking not only of the resin but also the glass attached to it.
Most of the epoxy resins that have been used in the past 30-40 years have already changed

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colour and transparency and are more visible and disturbing than if the glass had been left
without reconstruction of the missing area.
Add to this the stress placed on the object that has to be treated with a releasing agent,
various modelling materials like Silicon and is then often scratched by modelling and
shaping the epoxy resin fill.
As an alternative for very damaged objects, a digital reconstruction can be made and
placed alongside the original object or a modern copy can also be created.

6.4.7 Recording and photographic documentation

As soon as the objects arrives in the museum, studio ort collection, should be examined. It
is important to record all observations before any treatments begins: how it was
transported, packed, its general condition, the size and number of fragments and anything
else of relevance.
The photographic record plays an important part.
Traditionally, black and white still photos have been the preferred record for objects in
museum collections because if properly stored would last a long time. However, it must be
pointed out that digital photographic recording is now become more widespread and can be
easily incorporated in the record. If possible also colour slides should be made because if
properly stored these can last a long time. A scale of millimetres should appear in each
photographic record and with the reference data of the object.

6.4.8 Packaging and storing

Fragile objects should be packed in acid-free tissue and put in an inert cardboard box.
The most effective storage for glass conservation, especially from an excavation site, is in
a stabile environment at a moderate temperature (18°-30°) with the humidity kept between
40-55%, protected from pollution and strong lighting, not only from the sun but also from
the artificial light.
The materials used to make storage cupboards and exhibition display cases need to be free
of solvents and adhesives. These could give off negative exhalations over many years and
infect previously healthy glass. This is also valid for modern glass, whereby glass disease
caused by airborne chemicals were found in some collections.
We know that paper labels attached to the glass surface, which were widely used in the
past, do affect the glass. Therefore it is wise to use, as for the ceramics, a safe system to

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write on the surface. A small rectangular area should it painted by brush with a primer such
as Paraloid B-72 diluted in solvent. Once dry, the inventory number can be written on it
with a stable marker or drawing ink.

6.5 Case studies

6.5.1 Restoration of archaeological glass from Forlì (Italy)

The ex Monte di Pietà building is owned by and headquarters of the Fondazione della
Cassa dei Risparmi in Forlì (Italy). The restoration and renovation of this building and the
excavation of the 800 square meter site brings to light the story of a historically important
15th Century urban settlement in the city of Forlì. Between 2004 and 2005, ceramic, metal
and quite a lot of vitreous material were excavated at the ex Monte di Pietà.
The excavated glass included many fragmented vessels, for example, drinking glasses and
bottles of various sizes. The fragments of a cup on a high foot (Figure 6.4) constituted
quite a rare find as did some receptacles like urinals which were also used for scientific
observation of urine. Following their excavation:
- all the fragments were placed in plastic bags and given an excavation location number;
- all the fragments were very dirty with the excavation earth (Figure 6.5);

Figure 6.4 - Cup with high foot upon conclusion of restoration.

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Figure 6.5 - State of conservation (left)

and group of fragments (right) prior to conservation.

- all the fragments were of various dimensions, colour and thickness;

- in the conservation laboratory the glass fragments were placed in flat dishes and each
fragment was washed with water and a soft brush;
- most of the fragments showed to some extent the symptoms of the glass disease,
iridescence, craquelè and flaking of the surface;
- the hardest task was sorting out all the fragments (Figure 6.6).
This labour intensive work required much patience and a good eye to recognise the
fragments belonging to each other. The skill lay in separating out the glass rim fragments
from pieces of the body and base and laying them all out on trays in as near as possible
their correct position.
At the same time the fragments with an identical or a similar colour were also kept in
groups. In order to do this was important to look at the glass colour not only placing the
fragment on a white sheet of paper but also by looking at the cut of the glass.
The thickness of most of the glass fragments, especially belonging to drinking glasses was
about 1mm to 1.5 mm thick The colour of the glass ranged from greens to almost
transparent whites. Some surfaces had typical finishes of drinking glasses.
To glue the fragments, epoxy resin Epo-Tek 301-2 was chosen because it enabled very thin
fragments to be held together. Attempts were undertaken with Paraloid B-72, but with poor
results. Filling the break with the adhesive was done by capillary action. The resin was
applied carefully along the upper half of the crack. As soon as the resin penetrated, the
crack immediately became invisible.

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Figure 6.6 - Group of fragments after cleaning.

The missing lacunae were not filled up. This is because many of such museum restorations
show widespread discoloration of the resin fills. We must remember the physical stress
placed on the glass by moulding, casting, sanding and polishing of the resin.
Some representative objects were chosen for public exhibition, for example, two urinal
(Figure 6.7), some drinking glasses, necks of bottles. Special Perspex supports were made
to hold the glass objects that were shown in the exhibition in May 2009 in Forlì.

Figure 6.7 - Urinals upon conclusion of restoration.

6.5.2 Analysis of a glass ball

This is just a very simple example on how non destructive analytical techniques can be
usefully utilized in an archaeological museum, in particular ED-X-ray fluorescence.
A glass ball was discovered by the restorers of the Archaeological Museum in Damascus
during the examination of metal artefacts, which were there stored since a long time. It

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deals with a ball of approximately 1.5 cm in diameter with a hole of about 4 mm in

diameter.
The surface is blue coloured for the main part, and the internal surface of the hole as well,
but there is a large surface area which is white both outside and inside the hole (Figure
6.8). The restorers made the hypothesis that it deals with the clapper of a bell (about 10 cm
high and 6 cm in diameter), which was found together the drilled glass ball.

Figure 6.8 – Archaeological glass ball.

Analyses were performed by energy dispersive XRF (30 KV, 20 µA, 60 seconds) in the
white and blue zones, in order to explain their different colour; the results are reported in
Table 6.1.
The elements detected are always the same, with silicon, copper, calcium and potassium
prevailing on the others, which are represented by iron, chlorine, titanium and phosphorus.
Of course, the intensity of the silicon peak is low, but its content is high, due to its very
low sensitivity to the adopted analytical technique.
Therefore, the sample under examination seems to be a calcium-alkaline glass, which was
produced by a not well homogeneous mixture of the raw materials. In fact, the white zone
shows a particularly low content of calcium, which is not compensated by the higher
amount of potassium. Possibly, the scarcity of calcium does not guarantee the complete
fusion of the mixture and copper cannot develop its typical blue colour.

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Table 6.1 – Semi-quantitative chemical composition of the glass ball by EDS-XRF.

Area Ca Cl Cu Fe K P Si Ti

Blue 1512 29 1685 115 315 20 43 38

White 802 52 1360 142 414 15 43 39

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Kühn H., Erhaltung und Pflege von Kunstwerken und Antiquitäten, Band I und II, Keyser,
München, 1981.
Messiga B., Riccardi M.P., A petrological approach to the study of ancient glass, in: Per.
Mineral., 70, n. 1, 2001, pp. 57-70.
Newton R., Davison S., Conservation of glass, London Butterworths, 1989.
Plenderleith H. J., Werner A.E., The conservation of Antiquities and Works of Art, 2nd

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Edition, Oxford University Press, London, 1974.

Tennant N.H., ed., The conservation of glass and ceramics, James & James, London, 1999.
Tite M.S., Bimson M., Cowell M.R., The technology of Egyptian blue, in: Early vitreous
materials, British Museum Occasional Paper 56, London, 1987, pp. 19-47.

ACKNOWLEDGEMENTES
Photography by Elena Agnini is published courtesy of the Italian Ministry of Heritage and
Culture.
Many thanks to the National Museum of Damascus (Syria) for the use of the image of an
archaeological glass ball and the correspondent analytical results.

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7 – METALS

7.1 Origin of metals

7.1.1 Natural and artificial metals

Metals exist in nature in form of minerals (oxides or other substances), so that they must be
extracted. Only a few exist in the native state, like gold, silver and copper.
In Latin, gold was called “aurum”, that means “shiny sunrise”; in nordic languages “gold”
means “yellow”; it is the metal of the Sun. Its chemical symbol is Au.
In nature, gold is wild or native, in form of flakes (Figure 7.1) or nuggets or within quartz
rocks. In the latter case is alloyed with silver (gold-silver alloy = electro) or copper, which is
extracted with the method of “salgemma”. Characteristics: High density, melting point at 1063
°C, ductile, malleable, low hardness, unalterable.
In Greek language, silver (symbol Ag) was called “argos”, that means “light, brilliant”; or
from other terms “plata”, “silver” that have reference to its brightness; it is the metal of Diana
or of the Moon. It occurs naturally in its native state or free, or is inside minerals of lead or
copper, from which is extracted by the method of ‘cupellation’. Characteristics: ductile,
malleable, low hardness, durable, low resistance to corrosion.
In Latin, copper (Cu) was named “aes” or “cuper” from Cyprum, that had the most
conspicuous mines of the world; it is the metal of Venus. In nature, copper is in its native state
or free (Figure 7.1) or as an impurity in minerals containing sulphur. Characteristics: ductile,
malleable, low hardness, low resistance to corrosion.
In Latin the name of lead is “plumbum”, that means “heavy”. It is the metal of Saturn. Lead
(Pb) occurs in nature in the form of mineral and is extracted through ‘cupellation’.
Characteristics: ductile, malleable, low hardness, low resistance to corrosion.
Tin (Sn) is the metal of Jupiter; its Latin name is “stannum”. In nature it exists as tin oxide and
is extracted through ‘cupellation’. Characteristics: ductile, malleable, low hardness, low
resistance to corrosion.

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Figure 7.1 – Native gold (on the left) and copper (on the right).

Iron (Fe) can be found in nature in the form of iron oxide and is extracted through
‘cupellation’. Characteristics: ductile, malleable, low hardness, low resistance to corrosion.
In addition to natural alloys, there are the artificial ones, made for their chances of workability.
One of these is pewter, made of tin (73 to 90%) and copper, with additional antimony (Sb) and
bismuth Bi), or antimony and lead, or antimony and zinc (Zn). Tin has bright colour and is
also durable; therefore, this alloy was used for the production of artefacts instead of silver. To
increase the fusibility, an amount of lead was often added.
Bronze (from Germanic “brun”, that means dark) and brass (from Latin “luteum”, flat, for the
flat shape on which it is worked), are two alloys made of Cu with minor amounts of white
metals, like tin and zinc, which lower the melting point and increase the fluidity of the more
abundant metal. The colour varies depending on the proportion between the component
metals. Both in the bronze and in the brass, you may find the addition of lead, which increases
the malleability of the alloy.

7.1.2 Copper and copper alloy

Copper, a reddish-yellow metal that is malleable, ductile, and has a brilliant lustre when
polished, was first used in antiquity in its native, or un-combined form. The greatest
proportion of copper used in antiquity, however, was obtained from smelting the many
minerals containing this element. Although easily worked, it is too tender to be suitable for
tools, weapons, or implements. But it is possible to harden copper by hammering it while it is
cold. As copper takes the desired shape, it hardens and becomes more brittle. In this way,

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usable cutting and working edges can be fashioned. Cold-working of copper was known and
practiced in antiquity. Copper can also be hardened by alloying it with various other metals, a
procedure that was practiced in antiquity as well.
Addition of 1% to 10% of tin to copper produces an alloy known as bronze. If the tin content
is raised to approximately 30%, the alloy becomes whiter and is called speculum. Speculum is
a hard, tough metal, which needs a high polish; it was used primarily for making mirrors and
coins. The addition of up to 40% of zinc to copper produces brass, which becomes more
yellow, the higher the proportion of zinc is.
The properties of these alloys vary with the percentages of copper to tin and zinc.

7.2 Manufacturing technique

7.2.1 Direct manufacturing techniques

These techniques were used to make and to decorate simple objects (plates, cups, pots, etc.),
but also for the monumental statuary before the improvement of the fusion techniques.
Spinning: getting twisted strands, or hammering a sheet, or passing a sheet through a
perforated plate.
Lamina: getting laminas through hammering on a flat or curve surface. In order to compose a
large statue, it was necessary to model several sheets and then mount them on a core of wood
with pivots of copper or bronze. The wooden support was coated with bitumen, so that the
sheets will adhere perfectly. The processing of the lamina implies the technique of “re-firing”.
As a result of beating, the metal becomes harder and to continue the work it is necessary to
heat the sheet and then let it cool down slowly, so it regains its original elasticity without
changing shape.

7.2.2. Fusion
This technique requires the preparation of the model, which is the most important phase of the
process of fusion.

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FUSION IN SIMPLE OR MULTIPLE FORMS

The fusion is done in forms made of stone or ceramic. The forms could be open, for the
realization of flat items such as weapons and tools; the three-dimensional objects can be made
of two or more shells. To save the metal, especially the precious one, a core of earth is placed
inside the form.

LOST-WAX FUSION
1) Indirect: it creates a clay model from which to make a plaster mould and then to create any
number of models in wax.
2) Direct: creating a full wax model or wax coated on clay. In both cases the pattern is lost. It
can be full or empty. The wax is then eliminated through holes.

STAFF FUSION
A technique used since the Renaissance to melt reliefs, medals, and generally small objects.
“Staff” is called the box or metal frame in which is placed the foundry sand used for forming.

ELECTROPLATING
Technique that uses electrolysis in the mass production of metal objects. Its discovery dates
back to 1836-38. The method consists of depositing by electroplating a metal on the inner
surface of a form. The form is used as the cathode, while the anode is made by a slash of the
same metal.

7.2.3 Joining techniques

FOLDING AND RIVETING

The edges of the metallic sheets are folded and hammered (folding) or the edges of the
overlapped laminas are drilled and joined with hammered rivets and pivots (riveting).

WELDING
With addition of materials (brazing) or without addition of materials, just warming the metals
to join (autogen).

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7.2.4 Decorative techniques

Chipping: tracing furrows through chisels (chisels with round cut), without removing material.
The chisel is beaten by a hammer, it lowers the surface without removing material.
Bulinatura or engraving: track furrows by removing material, engraving with chisels with
rectangular or triangular cut.
Punching or stamping: technique based on the action of a bar of iron or lead, on whose tip is
carved the design to impress. Techniques typical of coinage.
On relief: direct decorative techniques on a metal lamina. It consists in hammering the back of
the lamina fixed to a support of wood or clay. The technique is called “Toreutics”, although
the term generally indicates the techniques associated with the processing of metals (from the
greek “toreus”, chisel).
Granulation: Typical technique for decorating the surface of metal objects with small spheres,
obtained by melting scrap metal in crucibles with charcoal or by dripping molten metal in
water or oil. These spheres were then welded on a base with glue, animal bones, or resins, or
welded with low-melting alloys.
Filigree: typical jewellery technique for decorating the surface of metallic objects with gold
wires attached to the lamina with adhesives or by welding with low-melting alloys.
Agemina: technique that involves inserting metal wires through hammering them in furrows.
This wires can be of the same metal or another metal.
Damaschinatura: consists of inserting metal laminas in furrows or delimitated areas.
Niello: making a layer of hot dark coloured sulphides of Ag, Cu or Pb, pulverized and
dispersed in a matrix of wax, and then insert it in incisions on the surface of the object.
Combination of metals and other materials:
1) Cloisonné: put strips in the metal surface so as to surround the alveoli intended to receive
precious stones or glass or enamel; 2) Champlève: the alveoli are arranged inside the lamina
with chisels or moulds; 3) Inlay; 4) Crisoelephantine technique: use of ivory and gold.

7.2.5 Finishing
Rasping: rubbing with scraper or rasp the object just after casting, to perfect it. The presence
of fusion defects can have several causes.

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Burnishing or polishing: rubbing the surface with a hard tool in order to smooth the roughness,
to darken the colour and polish the surface.
Gilding:
1) a gold leaf covers the surface. It is applied warm or with stucco or plaster;
2) fire gilding or amalgam: a mixture of gold and mercury was brushed onto the surface and
heated; at about 400°C the mercury evaporate, leaving the gold layer;
3) galvanic gilding: electrochemical procedure, whereby the metal is covered with gold;
4) “Mecca”: a sheet of tin is applied to the metallic support; it is then painted with a special
varnish (Mecca), so as to appear gold. For the gilding both the leaf and the support must be
prepared.
Plaque: precious metal laminas are welded on sheets of less precious metal; “simple” if
conducted on a single side, “dual” on both.
Coating: black cuprite was laid on bronze surfaces to give them dark colour and compact
aspect.

7.2.6 Sculpture
For a long period, the monumental metal sculpture was made with the primitive technique of
hammering metal laminas, while the use of moulds and fusion was only applied to small
statues. Only toward the end of the sixth century in Greece, with the fusion technique are
produced even monumental statues. After that, this technique becomes the only used for the
production of metal sculptures.
The most important metal used in sculpture is copper, because it is abundant in nature, and
also for its characteristics. Because copper has a melting point high enough (1085°C) and a
low degree of fluidity in the molten state, it is not particularly suited to casting in forms. But
the addition of white metal to copper, such as tin and zinc, gives alloys, bronze and brass,
respectively, with lower melting point and increased fluidity.
Bronze with 5% tin retains the red colour typical of copper, with 10% the colour is dark
yellow, between 10 and 25% is pale yellow, more than 25% is silvery.
To make the alloy more economical, tin is partially replaced with lead, which makes the alloy
more suitable for the working technique in cold state, as well as heavier and darker.

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7.2.7 Decoration on copper laminas

OIL PAINTING
The copper lamina was used as pictorial support from the second half of the sixteenth century.
Reasons for its spread:
1) conviction of durability,
2) invention of the places where to produce mechanically thin metal laminas,
3) introduction of relief printing, obtained by an engraved matrix,
4) diffusion of the oil painting,
5) easy preparation.
Disadvantages:
a) flexibility of the lamina;
b) small dimension;
c) poor adhesion of colours;
d) bubbles, cracks and detachment if you use a binder;
e) corrosion of the slab.

ENGRAVING (CHALCOGRAPHY)
In chalcography the ink goes into the furrows, corresponding to the blacks on the sheet, and is
removed from the parties that don’t affect the surface, corresponding to the whites. That’s why
it is called “engraving print”.
The diffusion of this technique was a few decades later than the xylography; it was born
between 1430-50 in Germany and in Italy. It remains popular until the nineteenth century
when it is supplanted by the lithographic technique. Chalcography replaces xylography for the
fact that the signs of engraving on copper can be thin, very close to each other and crossed in
all directions. The thickness of the layer of copper, obtained from a perfectly flat and clean
surface, ranges from 1 to 2 millimeters.
The signs can be traced by means of various tools:
1) “bulino”, with a characteristic triangular-shaped tip, which causes rigid-edged furrows; it is
used almost parallel to the surface;
2) “dry-point”, a steel tool in the form of a robust needle with a circular section, used in a

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vertical position determining very deep but not very wide furrows, with edges characterized by
the presence of curled pieces of metal.
Both these techniques are of direct engraving on metal and therefore with limited possibilities
of making curvatures. Otherwise there are indirect techniques, which employs a chemical
attack:
3) etching, in which the incision is carried out on a layer of varnish on the metal lamina, while
the incision of the metal is done by the chemical action of a dilute acid (usually nitric acid);
4) aquatint, which gives an effect of granulation of the slab in order to get the impression of
perspective. The granulation is done with acid.
The paper used for the incision on copper has to be soft and elastic, so that it can enter into the
furrows and catch the ink. To make it softer, the paper is wetted before passing under the
press, which means a shrinkage of about 1-2%.

7.3 Conservation state of metals

7.3.1 Metals from excavation

Every material has a stable form in relation to the environment in which it exists. When it is
buried, an object is situated in a new microclimate, possibly one vastly different from its
previous state. The material of which the object is made will adapt to these new conditions, so
that it will undergo a process of modification to approach a stable relationship, or equilibrium,
with the new environment. As the material approaches equilibrium, the rate of change will
decrease and eventually stop when equilibrium is actually reached. This stability will remain
constant as long as the object remains buried in the ground.
Iron, copper and copper alloys undergo to big corrosion in acid environment and in presence
of saline solutions, while they have a good preservation in alkaline environment. On the
contrary, lead shows a reasonable preservation in saline environment, while it has a poor
preservation in both acid and alkaline environment.
When it is absolutely necessary to undertake a treatment, keep in mind that whatever is done
in the field by a non conservator almost certainly must be undone in the laboratory. This

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underscores the importance of the principle of reversibility, an importance concept in any

conservation treatment. This means that any treatment applied to an object must be reversible,
that is it must be capable of being reversed or removed at a later date with no resulting damage
or change to the object. It should make no difference whether the reversal process takes place
several hours later, several days later, or as long as a year or more.
Reversibility is especially important for field conservation because one is often forced to carry
out procedures under less than ideal conditions.
It must always be kept in mind that any treatment applied to an object, including mere
cleaning, can contaminate it and invalidate any subsequent analysis, whether it is for dating
purposes or elemental analysis. If any kind of analysis will be required at a later date,
representative samples of the material should be taken carefully and set aside. Even if analysis
is not immediately envisaged, it is wise to set aside samples automatically so that testing can
be done later. Moreover, to the experts who make the analysis should be given a copy of the
complete conservation record of the object.

7.3.2 Bronze conservation state

Excavated objects of copper alloy can exhibit a variety of colours of corrosion products. Green
is by far the most common one, but blue, black, red and reddish brown are found, as well as
mottled combinations of all of them. Copper alloys frequently are found well preserved but
suffer drastically if buried in saline soil. Chlorides will form an unstable corrosion product
which, in presence of moisture and oxygen, will set into motion a self perpetuating system of
corrosion. Within only a few hours of excavation, this corrosion can lead to what is called
bronze disease, a form of corrosion producing a fluffy, powdery material varying in colour
from emerald to pale green. Bronze disease can cause considerable damage to copper alloys,
resulting in deep pitting and disintegration of the metal.
Preservation of copper alloy objects is further complicated by the presence of decoration
composed of other metals or other materials. On freshly excavated objects, it may be difficult,
if not impossible, to distinguish such coatings, especially if the object is heavily corroded.
When the copper underneath corrodes, corrosion products form on top of the gilded, silvered,
or thinned surface. Because the object is covered with these products, it is easily assumed to

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be made exclusively of copper. The layer of gold, silver or other materials may have been
disrupted if the corrosion of the copper alloy substrate is particularly extensive; as a result, it
may be lost within the corrosion.

7.3.3 Cupreous metal corrosion

The cupreous metals are relatively noble metals that normally survive in very hostile
conditions, including for burial underground or submersion in salt water, where they often
completely oxidize.
Cupreous metals react to the environment and form similar alteration products, such as
cuprous chloride (CuCl), cupric chloride (CuCl2), cuprous oxide (Cu2O), and the green- and
blue-coloured cupric carbonates, malachite [Cu2(OH)2CO3] and azurite [Cu3(OH)2(CO3)2]. In
a marine environment, the two most commonly encountered copper corrosion products are
cuprous chloride and cuprous sulphide. The alteration compounds of copper alloys, however,
can be more complex than those of pure copper. The chlorides can be found in the soil, in the
sea, in the air (in the acid rain), in every state of water (even in the form of moisture) and
gases which are normally found in an unpolluted atmosphere. The first step of this corrosion
by the hydrochloric acid is the formation of the cuprous ion:
Cu >> Cu+1 + e-
Cu+1 + Cl- >> CuCl (unstable nantokite)
2CuCl + H2O >> 2HCl + Cu2O (cuprite)
2HCl + 2Cu >> 2CuCl + H2
Cuprous chloride (nantokite) is a very unstable mineral compound. When cupreous objects
that contain cuprous chlorides are exposed to the air, they inevitably continue to corrode
chemically by a process in which cuprous chloride is hydrolyzed in the presence of moisture
and oxygen and forms hydrochloric acid and basic cupric chloride.
The hydrochloric acid in turn attacks the un-corroded metal and form more cuprous chloride:
4CuCl + O2 + 4H2O >> 2Cu2(OH) 3Cl + 2H+ + 2Cl-
The reactions continue until no metal remains. This chemical corrosion process is commonly
called 'bronze disease'. Any conservation of chloride-contaminated cupreous objects requires
the chemical action of the chlorides to be inhibited either by removing the cuprous chlorides

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or converting them into harmless and very stable cuprous monoxide (C2O, cuprite). If the
chemical action of the chlorides is not inhibited, cupreous objects will self-destruct over time.
The bronze disease manifests itself either as a powdery green substance on the surface of the
metal or as a warty or waxy film over the surface of the artifact. It may simply resemble a
natural patina to the untrained eye. However, while a patina is not destructive, bronze disease
certainly is.
Copper objects in sea water are also converted to cuprous and cupric sulphide (Cu2S and CuS
respectively) by the action of sulphate-reducing bacteria. In anaerobic environments, the
products of copper sulphide are usually of lower oxidation state, as well as the iron sulphide
and the silver sulphide. After recovery and exposure to oxygen, the cuprous sulphide
undergoes subsequent oxidation to a higher oxidation state, i.e., cupric sulphide.
After removal of a marine incrustation, articles made of copper are inevitably covered by a
black layer, of variable thickness, of powder of copper sulphide which confers an unsightly
appearance. Occasionally, the process of corrosion pit the surface of the artefact, but this is
more common in copper alloys where tin or zinc are corroded preferentially. The stable layer
of copper sulphide does not affect the object after his recovery from the sea as do the chlorides
of copper.

7.3.4 Record of the conservation state

When any conservation treatment is undertaken, whether in the field or in the laboratory, it is
imperative to make detailed and accurate records of everything done to the object. To the
archaeologist, the treatment applied may seem obvious, but it may not be so to the conservator
in the laboratory who will eventually work on the object. Considerable time and effort of the
conservator, not to mention possible damage to the object, can be avoided if you do a proper
documentation in the field.
A treatment report should include a brief but clear description of the object, the materials of
which it is made, and the condition in which was found. Any weak areas, cracks, and the like
that might not be readily visible should be indicated. It is always helpful to include sketches
and photographs to indicate these weak areas and the position of cracks.
Clearly you must record what was done to the object, how it was done, and under what

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conditions.
Be sure to state what specific materials were used, including the full trade name and grade, the
solvents used and in which concentrations.

7.3.5 Principal diagnostic techniques

Historical artefacts and works of art deteriorate over time because of exchange of energy and
matter interactions with the surrounding environment. These processes are complex from a
chemical-physical point of view and can lead to changes in the original appearance of an
object, as well as to weakened structures, corrosions and other alterations. Without any
intervention to stop or slow down the degradation, you could completely lose the artefact. The
implementation of conservation and restoration first of all involves recognising a work of art
as a physical object possessing both aesthetic and historical value. This is followed by work
(such as cleaning, consolidation and protection) that is based on full respect for the original
work of art in its historical context, on the principle of the reversibility of any intervention,
and on the stability and safety of the used materials.
Scientific research gives a significant contribution to the conservation of our heritage.
Several methods are used to explore the bulk, microscopic and surface properties of the
artefacts, including both traditional and advanced analytical techniques. Before a piece is
restored, conservators use scientific investigations to learn about the materials and techniques
used to create it. This allows them to make sure that they use materials that are compatible
with the originals and that the intervention is effective and durable. Other investigations
include the study of alterations and their origin, the identification of previous restorations,
assignment of provenance and dating.
Science is also used to develop and test new conservation methods and to create innovative
diagnostic tools. All these studies are by their nature multidisciplinary, bringing together
specialists from the arts and the sciences to exchange ideas and develop creative and
sustainable solutions.
The importance of scientific support for conservation of cultural property has long been
recognized. Since then the analysis of constituent materials remains one of the main concerns
not only to improve the knowledge of the object and its context, but also to understand the

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deterioration processes and identify proper conservation treatments.

The fact that archaeological and historical objects are often unique, artistically relevant and
not easily movable clearly encourages the use of non-destructive techniques and portable
instruments.
On this ground X-ray fluorescence (XRF), which is an elemental analytical technique, is one
of the most widely explored. Though early applications date back to the 50’s and 60’s,
portable or, at least transportable, XRF spectrometers started being effectively used in early
70’s, when semiconductor detectors became available. Carrying the object to the laboratory
was no more necessary: thanks to the feasibility of in situ investigations the application of
XRF was virtually extended to any type of object. In recent times a significant improvement in
portability of spectrometers has been produced by both thermoelectrically-cooled detectors
and miniaturized X-ray tubes.
Opposite to ceramics, metals do not keep a close chemical connection between the raw
materials and the alloy, moreover they can be re-melted; this precludes in general the
possibility of giving a compositionally-based provenance. Nevertheless differences in
elemental composition can be significant of different fabrication contexts; for instance not
original parts can be identified in statues, doors and other complex objects. Used in
combination with microstructural techniques, elemental analysis can provide information on
the fabrication technology, with special regard to casting, soldering and repairing.

7.4 Conservative intervention for metals

7.4.1 Prevention measures

Corrosion products of copper alloy can be extremely tricky and difficult to remove. Their
removal, therefore, should be undertaken only by a trained conservator. If little or no metal
remains, the entire object can disintegrate if cleaning is attempted by an inexperienced person.
Injudicious cleaning can irreparably damage an object; it can destroy not only surfaces and
decorative details, but also organic and environmental evidence preserved by the corrosion.
Small textile fragments can be found adhering to object of copper alloy; in which case you

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must stop the process of biological deterioration of the fibres by the toxic ions of copper.

7.4.2 Mechanical cleaning

Do no pull object of copper alloy out of the ground because they snap and break easily. The
object can be removed from the ground following general procedures. First, carefully remove
all dirt surrounding the object, being sure not to scratch the surface, gently undercut the object
and, when it is completely free, carefully pick it up in the palm of the hand. Place it in a paper
envelope until it can be properly packed in the dig house.
The paper envelope is only a temporary measure, but it will allow the object to dry out. A
object of copper alloy should not be placed directly into a polyethylene bag when it is still
damp. Moisture will collect on the inside of the bag and keep the object wet, which can easily
initiate or exacerbate the corrosion process.
Always handle objects of copper alloy carefully. There may be little metal left, and dirt and
corrosion can easily hide cracks and splits. Unnecessary handling causes considerable damage;
so, handle the object as little as possible. All the objects of copper alloy, especially the long
and thin ones, should be carefully supported at all times.
If the metal is shattered or badly corroded with deep cracks, we must consolidate it using a
solution of acrylic resin. Do not use an emulsion because the water in it could initiate or
exacerbate the corrosion process. Any method of lifting blocks can be used to lift fragile
objects in copper alloy.
Principal mechanical instrument for cleaning: scalpel, micro sand-blasting machine, ultrasonic
device, precision rotary micromotor.

7.4.3 Chemical cleaning

The chemical cleaning aims to eliminate fouling, stains and thickenings caused by the
corrosion products and also to reclaim and stabilize zone with high presence of chlorine.
Cleaning is completed by several dips in deionised water in order to extract and neutralize
harmful presence of salts. This method inhibits the electrochemical corrosion, turning them
into unstable corrosion products and stopping the cathodic and anodic processes.
Most of the archaeology’s masterpieces found under ground, near water, oxygen and chlorine

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anion, are really damaged by those elements as they lead up to a total oxidation of the original
metal with a stratified unstable and separated structure.
The first action to do is to dry the surface, possibly with treatment by means of infrared rays.
The better way to conserve pieces, in this case, is to dip them into a reducing solution of
sodium sulphite which preserves them by the akagenit (β-FeOOH) fallen into the holes and
difficult to be removed. After the removal of soil and the weaker fouling, you can stabilize the
surface through deionised water or chemical products.
Chemical agents usually used for this kind of cleaning are:
- Descaler (ammonium acetate),
- complexing (E.D.T.A.),
- organic acids and their salts (citric acid, ossalic acid, ammonium citrate, etc.),
- inorganic acids (orthophosphoric acid).
An alternative to the above mentioned products can be considered the use of tannic acid
solution, all over again after the chlorine extraction.
Treatments realized by rust converters have the double aim to stabilize and protect.
It is quite always preferable to utilize mechanical cleaning after water dives because in such
way it is better controllable, even if worked surfaces could be damaged by the operator.

7.4.4 Final protection

To limit the damages produced by corrosive agents, mainly of atmospheric type, some
evaluations have to be carried out:
- how aggressive is the atmosphere in the place;
- how much is damaged the masterpiece and what is necessary for the future conservation;
- which products are better to protect them.
For what concern the first step is necessary to check the daily and yearly relative humidity
reports. Then analyze the atmosphere, check predominant winds, the temperature and the rain
trends during the year. Once achieved all these controls, it is possible to decide whether to
apply a protective layer of varnish or not, in order to isolate the surface from environmental
attack.
Varnish could be passive, if it is used only to protect the surface, otherwise active if it

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develops a cathodic effect, when made with zinc or aluminium pigments.

The commonly used varnish is composed by binder, which could be done with resins or oils to
be film-forming, or made by solvents or thinners, to melt the resins and let it be more viscous
for the application, or plasticizer, to let it be more elastic and at least with pigments, to have a
covering effect or protective with zinc or aluminium.
If using inhibitor protections, commonly polar organic substances, in order to create thin
oriented layers over the surface, it is possible to prevent the attack of aggressive agents
changing the potential of corrosion or increasing the surge. The most used inhibitors are the
organic amines (zinc naphthenat), alkaline salts of sulphanat oils.
It’s better not to use inhibitors for outdoor iron masterpieces, but you can use them in indoor
places, mixing them with oils, waxes or acrylic products.
Different method can be used for copper or copper alloys, where you can use inhibit both for
outdoor and indoor pieces. The most used one is BTA (Benzotriazole) and its derivatives. This
product together with copper ions creates a stable link.
From the point of view of the reversibility of the varnish, it must be deemed that it is easier to
clear away the nitrocellulose one, while the inhibitors are quite impossible to be removed.

7.5 Case study: Recovery of metallic artefacts

from terracotta containers

In the archaeological museum in Damascus (Syria) there were two terracotta vases which
contained a lot of metallic artefacts (Figure 7.2); they date back to the half of the third
millennium B.C., and come from Tell Mabtoh (Hasaké, Syria). The archaeologists would want
to examine the metallic artefacts, so that the question is “How to conserve these two artefacts
and at the same time to study their content?”. First of all it was decided to increase the
knowledge of the content performing preliminary analyses by means of non destructive
techniques, such as radiography and X-ray fluorescence.
The radiographic investigations with increasing power permitted to observe that the vases are
full of metallic tools, in a number much higher than that visible from outside, but it is not

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possible to say how many they are and which is their dimensions and shapes. The chemical
analysis by means of portable XRF (30 KV, 20 µA, acquisition time 60 seconds) confirmed
the impression that it dealt with copper tools, with impurities represented for the most part by
iron. Anyway, the presence of small amounts of tin cannot be excluded, but not more than 2-
3%.

Figure 7.2 – Terracotta container with metal artefacts inside.

As a consequence of these results, it was decided that it was opportune to recover the metallic
tools for their specific characterization. The following plan of what to do was defined:
- Conservation of one terracotta vase as it is, a part from moderate external cleaning,
- Opening of the second terracotta vase by breaking it into two parts,
- Progressive recovery of the metallic tools,
- Restoration of the broken terracotta vase,
- Cleaning of the recovered metallic tools,
- Adequate documentation of all the operations,
- Study and conservation of the cleaned metallic tools.
All the operations for opening the container into two parts were executed very slowly and with
some worry; anyway the objective was attained without any inconvenient (Figure 7.3). When
the content appeared to the observers, the surprise was great and any doubt about the
opportunity of the operation disappeared. The surprise was also greater while the recovery of

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the metallic tools proceeded, due to their large number and the variety of forms (Figure 7.4).
When all the content was extracted, it was possible to classify 189 metallic objects of various
dimensions and shape, even though most of them were arrows.

Figure 7.3 – Opening of the terracotta vase into two parts.

The metallic objects were completely covered by layers of alteration compounds (Figure 7.5),
typical of archaeological copper artefacts, so that it was impossible to observe the original
surface. Therefore, all the metallic objects were mechanically cleaned and then chemically
treated accordingly to the usual procedure for this type of metal.
It was at the end of this step of the intervention plan that the satisfaction of archaeologists and
restorers for their decision to open one of the terracotta containers reached the maximum level.

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Figure 7.4 – Recovery of the metallic tools from inside the terracotta vase.

Figure 7.5 – Alteration products of the metallic objects observed at the optical microscopy.

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After cleaning, in fact, several artefacts showed very interesting incised symbols, as it is
shown in Figure 7.6.
Likely the interpretation of these inscriptions will be useful in order to answer the question
about the significance of the two terracotta vases full of metallic tools.

Figure 7.6 – Some cleaned metallic tools with incised symbols.

Bibliography

Agricola G., Un dialogo sul mondo minerale e un trattato sull’arte dei metalli, P. Macini and
E. Mesini (eds.), Bologna, 2008.
Barrio J., Chamón J., Pardo A.I., Arroyo M., Electrochemical techniques applied to the
conservation of archaeological metals from Spain: a historical review, in J Solid State
Electrochem, 13, 2009, pp. 1767–1776.
Biasini V., Cristoferi E., A study of the corrosion products on sixteenth and seventeenth
century armour from the Ravenna National Museum, in Studies and Conservation 40,
1995, pp.250-256.
Biringuccio V., De la Pirotechnia, Venezia 1540, A. Mieli (ed.), Società Tipografica Editrice
Barese, 1914.
Buccolieri G., Analysis of selective laser clearing of patina in bronze coins, Arco Edizioni,
Catania, 2006.
Cristoferi E., Istruzione preliminare all’intervento conservativo dell’oploteca del Museo

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Nazionale di Ravenna, in Quaderni di Soprintendenza n.1 (QdS 1), Ravenna, 1995,

pp.53-58 and 103-105.
Cristoferi E., Metallo e tessuto: l’intervento conservativo alla brigantina dell’Oploteca di
Ravenna, in Quaderni di Soprintendenza n.2 (QdS 2), Ravenna, 1997, pp. 39-42 and
117-121.
Cristoferi E., Il restauro dell’Oploteca del Museo Nazionale di Ravenna: borchie e ribattini,
l’’anima’ dell’armatura, in Quaderni di Soprintendenza n.5 (QdS 5), Ravenna, 2002, pp.
96-105.
D’Angelo D., Storia del restauro archeologico, appunti a cura di D. D’Angelo e S. Moretti,
contributi di M.T. Abbate, Alinea, Firenze, 2005.
Degrigny C., Use of electrochemical techniques for the conservation of metal artefacts: a
review, in J Solid State Electrochem, 14, 2010, pp. 353–361.
Formigli E., I grandi bronzi antichi: le fonderie e le tecniche di lavorazione dall’età arcaica
al Rinascimento, Atti dei seminari di studi ed esperimenti, Nuova Immagine, Siena,
1999.
Fuga A., Tecniche e materiali delle arti, Electa, Milano, 2004.
Hind A.M., British Museum. A guide to the process and schools of engraving. London, 1933.
Lalli C., Analisi scientifiche e problematiche di restauro e conservazione del bronzo di
Lussino: un caso particolare nel restauro di sculture in bronzo, Linea Grafica, San Salvo
(CH), 2008.
Maltese C., Le tecniche artistiche. Mursia, Milano, 1973.
Maltese C., I supporti nelle arti pittoriche. Storia, tecnica, restauro, Mursia, Milano, 1990.
Marabelli M., Ancient metal object in outdoor exposure: causes, mechanisms and
measurements of damage, in: Science, technology and cultural heritage, Oxford 1991.
Marabelli M., Conservazione e restauro dei metalli d’arte, Bardi ed., Roma, 2007, 205 pp.
Mazzeo R., Patine su manufatti metallici, in Atti del workshop “Le patine: genesi, significato,
conservazione”, promoted by ICVBC, Nardini Editore, Firenze, 2004.
Michelucci M., Il restauro archeologico tra tutela e valorizzazione, Linea Grafica, San Salvo
(CH) 2008.
Oteri M.A., La reversibilità nel restauro archeologico, Riflessioni su alcuni esempi di Sicilia e

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Magna Grecia, Marghera Edizioni, Arcadia Ricerche, 2003.

Pini R., Siano S., Salimbeni R., Pasquinucci M., Miccio M., Tests of laser cleaning on
archeological metal artefacts, in: Journal of Cultural Heritage, Vol. 1, Supplement 1,
2000, pp. S129-S137.
Salvi A. (ed.), Meteo e metalli: conservazione e restauro delle sculture all’aperto, dal Perseo
all’arte contemporanea, Nardini Editore, Firenze, 2007.
Scott D.A., Copper and Bronze. In: Art, corrosion, colorants, conservation, The Getty
Conservation Institute, Los Angeles, 2002.
Vlad Borrelli L., Restauro archeologico, storia e materiali, Roma, 2003.

ACKNOWLEDGEMENTS
Many thanks to the National Museum of Damascus (Syria) for the use of some images taken
during the recovery operations of metallic artefacts from a terracotta container.

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8.1 Goldsmith’s metals

Goldsmith’s artifacts are created in part for devotional purposes, a desire to manifest power
and cultural enrichment; each one of these motivations induces the client to request long-
lasting and possibly precious materials from the artist.
These banal motivations may in fact be the luck of these hand-manufactured objects
leading to their realization, maintenance, and often their survival. This is due to what these
objects had represented, for whom they had been created, and even for the materials they
had been made of.
The main characteristic differentiating the Goldsmith’s artifacts from those simply made of
metal is not only the fact that they are made of precious metals, but also the fact that they
are composed of many other precious elements: enamels, stones, coral, wood and amber.
Gold and silver are the principal metals for goldsmith artefacts, but copper and bronze also
are often used. The principal characteristics of these metals can be seen at chapter 7,
together with their manufacturing techniques.

8.2 Enamels

8.2.1 Material
Developed independently from the glass, enamel was born later than the glass in the fifth
century B.C. in the Celtic area. It became widespread coming from Byzantium throughout
medieval Europe between the eleventh and sixteenth century, when real schools of enamels
were created (the Rhine, the Meuse, and the most significant for the industrial production
and the distribution of manufactured goods, the Limoges). In the sixteenth century it loses
the characteristics of an independent technique and becomes a variant of painting.
This is a technique that takes inspiration from jewellery and glass manufacture. A glass
mixture is prepared, mostly coloured: 50% silica, 35% red lead (minium), 15% sodium or
potassium + metal oxides which are the colouring matter. The mixture is completed with

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additives such as borax, soda, magnesium to give to the product greater hardness, stability
and elasticity. The glass paste, prepared in small loaves, is cut and pulverized.
The glass powder is wetted with water and applied to a metal lamina (gold, silver, bronze,
copper and recently iron). The adhesion of the enamel occurs through recasting in muffle
(without contact with the fire), or through cold process, using resins and mastics in which
the powder is dispersed. To adhere better to the enamel, the metal supports were
sometimes made wrinkled.
The next step is cooling, to make a fixed texture of the glass. If necessary, a levelling stage
and a polishing stage are performed.

8.2.2 Technological typologies

- cloisonnè, it consists in the insertion of wet pastes of coloured glass on the metallic
lamina inside small strips in relief, which are obtained by welding little metallic strips
(cloison) curved in the shapes of little pools. In order to fix the strips to the laminas, a
provisory resin is used. With the firing, the pressure of the enamels and the warm
temperature definitely attach the strips, burning the resin.
- plique a jour, similar to cloisonnè, with the difference that after the firing the little strips
are removed, leaving only the semitransparent enamels.
- champlevè, here the pools are produced engraving the metallic lamina, without adding
any material.
- bassetaille, a drawing was made directly on the metallic lamina and then the vitreous
paste is applied on it, without hiding the drawing due to the transparency of the
enamel.
- email de ronde bosse, the enamel is applied on the lamina worked in relief.

8.3 Precious stones

8.3.1 The materials
Some natural minerals are used to make jewellery and art objects by virtue of structural
features such as colour, transparency, brightness, hardness and rarity. Typically, these
minerals are divided into three groups:
1) precious: rare and characterized by great hardness and brightness (diamond, corundum,
ruby, sapphire, emerald);

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2) semi-precious: moderately rare, generally transparent and coloured (amethyst and

topaz);
3) gems: mainly non-transparent, compact, with a micro-crystalline structure (onyx, agate,
turquoise, lapis-lazuli).
One of the characteristics of these minerals is the hardness, so that they occupy the highest
steps of the Mohs scale. The Mohs Scale, which takes its name from the Austrian
mineralogist Friedrich Mohs, is an empirical criterion for assessing the hardness of
materials. It takes as reference the hardness of ten numbered minerals and such that each is
able to scratch that which precedes it, and is scratched from the one that follows it (Figure
8.1).

Figure 8.1 – The minerals of the Mohs scale.

The crystalline form of a gem is a feature undoubtedly related to its chemical composition,
but not always determined only by this, because it is known that the same substance can
occur in one or more different crystalline phases (polymorphism). Similarly, it is not the
chemical composition to determine the physical characteristics of a material, but its
crystalline form. There are minerals with the same chemical composition, but different
colour, density, hardness, transparency, refractive index, scattering coefficient.
The use of these stones date back to ancient times, in prehistory, when they were used in
their natural state, without processes, if not rudimentary. To go back to embryonic forms of
processing, such as cutting and polishing, we must go back to the times of the historic
civilizations of the rivers of Mesopotamia, to which is attributed the invention of the
carving and engraving of stones.

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“Glyptic” indicates the art of carving and working gems to obtain items for use and
decoration (from the Greek γλύφειν = carving). This technique differs from others that use
precious minerals, for example jewellery and certain kind of mosaic, as a consequence of
direct processing on the stone, while other techniques use stones placed in a more complex
system.
Artistic techniques on gems are fairly simple and are transmitted almost unchanged to this
day, if we exclude the processes of mechanization. The techniques are characterized by
different procedures depending on the structural characteristics of the stones and on the
ornamental use. The glyptic includes essentially two groups of products: the carved gems
in negative and the carved ones in relief. But there are stones that require only the cut.

8.3.2 Synthetic and false stones

The synthethic stones are those produced chemically imitating the composition and the
structure of natural gems, and therefore the physical aspect. The false stones have nothing
in common physically and chemically with the natural products, imitating the only colour.
They are obtained with glass pigmented with metal oxides, or with other natural stones of
poor quality.

8.3.3 The cutting

The cutting is practiced by means of circular saws, or rotating grinding wheels, usually in a
metal material, whose hardness varies in relation to that of gems (in descending order of
hardness: steel, copper, tin, lead). An oily mixture of abrasive corundum or diamond
facilitates the work of cutting. The process is very simple and consists in setting the stone
to be cut to a mobile support, then submit it to the rotating grinding wheel (the rotation
varies from a minimum of 2000 to 3000 rounds per minute and increases depending on the
hardness of the stone). The cut can be applied at random on the stones, for example to
highlight certain structural characters (“cabochon” cut). Or it can be planned in order to
obtain regular faces (“geometrical cut”). Increasing the number of faces, it is possible to
multiply the effect of brightness, amplifying the angles of incidence and the refraction of
light.
The cut must be made with precision, faces and angles must be chosen carefully.
Sometimes the ancient cutting was less precise, almost always obtained empirically, not
always reaching the effect of maximum brightness. The results were improved with the

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progress of scientific knowledge concerning the physical structure and the optical
properties of the minerals. For example, the modern cutting takes into account another
characteristic of the mineral, discovered by physics: not all the points inside the crystals
are equal, but some parts can present weakest links (“cleavage”). These parts are the ones
that the cutter preferably follows, reducing the possibility of waste or breakage.
The cutting technique is mostly applied to gems with high refractive index, such as
diamond. Diamond occupies a unique position in human history. It is pure and bright, and
its hardness, the highest ever in the Mohs scale, makes it a symbol of eternity and strength.
These concepts are inherent in the word diamond, that comes from the greek Adamas,
“unchangeable, indestructible, wild”. Diamonds are formed deep in the earth’s crust and
then transported to the surface along with other minerals, under the pressure of magma
movement. The diamond is composed of pure carbon atoms arranged in a tetrahedron, and
in the raw state appears predominantly dull and unattractive. It should be appropriately cut
to highlight the high refraction coefficient and consequently the great dispersion of light
(Figure 8.2).

Figure 8.2 – Different cuts of the diamond.

The ancients did not know how to work the diamonds and were limited to basic operations
of cleaning or smoothing. Later, in the fifteenth century, was made the first attempt to cut:
it seems that in 1475 a French was able to produce a diamond with 33 facets and was an
Italian to realize 58 facets. Today it is possible to see multi-faceted cuts. The most famous
diamond is colourless or with light colours, which is the most valuable and most rare, but

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there are also a variety of diamond yellow, green, blue, pink, red and black.
The diamond powder used as an abrasive comes from diamonds not used for cutting, due
to the presence of defects in the natural stone.

8.3.4. Carving and engraving in negative

Until the Hellenistic age only the carving and engraving of gems in negative was practiced.
The engraved gems in the past were usually used as seals (Figure 8.3).
The technique consists on practicing incisions on the surface of the minerals by means of
peaks of various shapes, depending on the design to be carried out. Tips may be of metal or
rocks harder than the gems to be worked, usually diamond or corundum. Other instruments
used: grinding wheels, drill, chisels, hammers, blades, abrasive quartz and garnet mixed
with oil or water, clamps and forceps. The action leaves opaque tracks of the tips, so that
the stones need to be polished with powdered pumice or tin oxide.

Figure 8.3 – Examples of carving and engraving in negative.

Carving by means of acid attack is practiced for example in quartz, taking advantage of its
siliceous composition. The stone is covered with a thin layer of wax; the decoration is
made engraving the wax with a tip; the hydrofluoric acid attacks the quartz in the parts
where the wax was removed from the tip, remaining intact the parts still protected by the
wax. The longer you leave the acid, the deeper is the incision. Using the acid in aqueous
solution, the incision is glossy, while it remains opaque when acid is used in gaseous form.

8.3.5 Carving and engraving in relief

From the Arabic word gama’il (flower bud), the cameo is an artistic object made by

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carving and engraving a stone in relief, using a two tone layered gem (typically onyx,
sardonic, agate), or producing the bichrome effect overlapping the precious stones with
coral or shell (Figure 8.4).
The stones at the base are usually dark, to create contrast. The procedure for the realization
of a cameo is all manual and still now processed by craftsmen. The first phase consists in
the choice of the shell suitable for the engraving and carving action. Later, is practiced the
cutting of the convex part of the shell and then its shaping, eliminating the unnecessary
parts (“scoppatura”). Finally, the “aggarbatura”, which consists in giving to the piece the
desired shape (usually round or oval) using a special grinding wheel. After that the piece
can be mounted on a spindle of wood with hot mastic composed of Greek pitch, wax and
scagliola.

Figure 8.4 – Examples of carving and engraving in relief.

After this operation, the “scrostatura” consists in abrading the external part of the shell in
order to leave the light-coloured part as surface. Finally the artist draws on the surface the
wanted subject.
Only at the end, the shell is attached to the cut gemstone with glue. Working cameo has
experienced its greatest peak in the Renaissance.

8.4 Alteration and degradation

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Goldsmith’s artifacts, even if composed of noble metals, suffer changes and deterioration
as all other objects do.
In order to manipulate the metal, it must never be pure, but instead be an alloy with less
noble metals able to fluidify according to the specific work needing to be done. The less
noble elements experience a natural oxidation and the most sensitive of these objects made
with different materials are altered by incorrect thermal-hygrometric regulation in the
environments where they are housed.
Beyond the metal alterations in alloy we cited in chapter 7, we can add silver oxidation, a
light and superficial oxidation (Figure 8.5), and silver sulphide, a more tenacious and
thicker encrustation due in great part to the atmospheric pollution (Figure 8.6).

Figure 8.5 – Small silver jar (MV12131), Vatican Museums: silver oxidation.

Silver oxide (Ag2O) has typically aesthetic consequences; indeed the black-yellowish
tarnish is caused by contact with the air, and it is easily removed with a light mechanical
cleaning. Instead, the most damaging sulphur effects come from atmospheric pollution
although they are also a result of objects being found in sulphur rich earth at various
archaeological sites (2Ag + H2S ---> Ag2S + H2). This alteration causes a strong metal
corrosion, which causes also the mineralization with subsequent weakening of the material.

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Figure 8.6 – Silver strainer (MV65426), Vatican Museums: silver sulfide.

Fortunately, as far as it concerns gold, there are no evident alterations with the exception of
those coming from the deterioration of the other metals surrounding the gold. In gilded
works, the formation of alterations underneath the level of gold causes a lifting off of it
even though there is the risk of losing the golden finish, which was intended at the moment
of its creation as a protective function of the underlying metal against the atmosphere and
other altering agents.
Further degrading can be caused by mechanical actions since frequent damage is
experienced following bumps or structural changes not consistent with the original
construction of the works.

8.5 Conservative intervention

8.5.1 Introduction
The nature itself of the artifacts requires a delicate and refined composition that will need
to be applied even at the moment of the maintenance work.
This type of maintenance was often entrusted to people who sought to bring back the
original form of the piece as if it had just left the hands of the goldsmith who created it;
however, this is also the case today as a result of a lack of culture. This type of work
requires the use of strong natural and artificial cleaners being difficult to remove and
favouring the reformation of oxidation if not sulphuration.

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This use had often caused structural damage that required new reinforcing soldering; this
soldering unfortunately would immobilize some of the original elements that were
supposed to be taken apart for maintenance work.
Conservative restoration of goldsmith artifacts today is still considered a niche sector, even
if it is a opinion not always shared. This art dates back to the 1800, and belongs to the
category called “minor art”, which today has been substituted by the expression “applied
art”. As such, it was not a subject of conservative study like the most fortunate “major arts”
around which a thick historical artistic fabric was constructed; at the same time technical
and conservative knowledge was developed that today are within reach of everybody.
“Decorative art” has been handled as an object of daily life, appreciated by a small circle
of scholars and experts. This has impeded the debate even on their conservative method
often leaving to the “sensitivity” of the owner the choice of the result to be achieved.
Only in the last 20 years, we have tried to apply the theory of art restoration in this
aforementioned sector by developing guidelines and common methodologies based, as
other art, on Brandi’s theory, thereby making uniform the interventions from
archaeological artifacts to modern ones.

8.5.2 Dismounting
When the work of art allows for it, its disassembly is the principle operation that permits
an in-depth study of its executive method and a differentiating restoration among the
various elements the piece is composed of (Figure 8.7).

Figure 8.7 – Lateran Cross (SGL288), San Giovanni in Laterano, Rome: disassembly.

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It was exactly the conservation of the piece itself at the base of the choices surrounding its
construction, making it possible to intervene on every singular element of the work of art
needing help without damaging the rest of the piece. This is a reason why these pieces
were almost always able to be taken apart completely, as Valadier said, because they were
“the architectonic constructions in miniature”.
The reassembly requires the arrangement of the elements (or pieces) as they were at the
time of the disassembly since they were hand-made by artisans, and each one was different
from the other. What is required is a constant graphic and photographic mapping during
the work phase and an attentive highlighting of the inscribed numbers on every element by
the goldsmith in the construction phase.
The disassembly must not create any damage to the individual elements which would
cause difficulty in repositioning them (e.g., the opening of riveted hinges or fracture of a
metallic flap). The intervention of the art restorer, therefore, stops at the point in which his
or her work becomes more damaging than beneficial.

8.5.3 Cleaning
Having all the pieces taken apart, the restorer can step in and begin in a balanced and
separate way, according to the composition of the materials and the type of alteration
present.
At first, a degreasing bath in ketone solvents is made in order to remove possible protective
products that were used in previous maintenance interventions. If a full immersion is not
possible, attempts to obtain similar results can be undertaken by padding the elements with
the solvents. Both silver oxide and copper salts are sensitive to immersion actions in
Rochelle salts; this solution may be milder or stronger according to the percentage of
dissolved salts in the de-ionized water and the time the salts are left in such solutions.
If the encrustation of the excavated objects is very strong and tenacious, one can add a
percentage of E.D.T.A. to the solvents. Without the possibility of immersing the work, one
can intervene with a piezoablator. Once the encrustation is removed, the work needs to be
finished off with sodium bicarbonate which will be explained below.
Excellent results have been obtained by using laser cleaning. Indeed, the ray has a very
good mechanical action on dark encrustations often found on metals, and it makes a
detachment of the entire patina without scratching the original metallic layer underneath.

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The structuring or layout of the laser depends on the type of patina having formed, which
can be different according to the composition of the alloy and the environmental agents
with which it came into contact. Therefore, in order to reach the optimal result, several
samplings need to be taken in order to get to the desired results.
Before proceeding with the mechanical cleaning with wooden chisels, a bath with surface
active agents will help the next step. At this point, if the patina is very thin, the chemical
cleaning can be balanced with the mechanical one through the use of dissolved sodium
bicarbonate in water with the aid of wooden chisels or soft sponges. This paste of sodium
bicarbonate will have a light chemical reaction but a fundamentally abrasive one, so it
should be used delicately. At the end of this process, one should proceed with long rinses
in de-ionized water and finally with a drying with infrared rays.
Nowadays, a laser cleaning of the surface is more common and favours a dry cleaning or
possibly with little water with careful attention paid not to use too much force on the
surfaces which are often weakened by the alterations. The intensity of the ray is easily
regulated depending on the stubbornness of the surface encrusting that needs to be
removed. After the removal of the encrustation, this process subsequently requires a
homogenization of the sodium bicarbonate cleaning since the ray may leave a light
oxidation on the non-noble elements of the silver alloy.
Unfortunately, the aid of such machinery is not widespread since the equipment is costly,
but also due to the environments where such operations are carried out.

8.5.4 Consolidating
After the cleaning, a consolidation or even integration will occur in order to finish with the
protection of each and every single element. Some elements require a consolidation
especially if they are a structural part of the piece.
The most used methods so far are mechanical with hinged metal rivets, but the reversibility
in these cases is difficult given the invasiveness of the operation; subsequently, epoxy bi-
component resins are utilized. However, the durability of these materials is always
conditioned on the methods and places where the pieces are housed since they are sensitive
to the thermo-hygrometric variations. The use of the micro-welding laser has been
introduced in the last few years in order to obtain micro-consolidation with a strong seal
without any noticeable alteration of welded materials except for under a microscope.

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8.5.5 Integrating
Some of these consolidations require, however, even the necessity to reconstruct some of
the missing parts, and in a particular way for structural needs when the missing of one
element may call into question the very nature of the work itself by limiting its use as well
as its exposition. The integration of the metals is carried out mostly with bi-component
pigmented epoxy resins; sometimes even with metallic dust should the weight of it not be
dangerous for the piece’s intactness. Otherwise, you can use compatible metals, if not the
same of the work itself, attached in a mechanical way or with resins if not exposed to
excessive force. This integration will be recreated similarly to the model with such a finish
so as to distinguish it from the original without rendering it aesthetically invasive.

8.5.6 Conclusive operations

Because of the very nature of metals, contact with oxygen causes a surface alteration.
This natural occurrence can never be totally avoided, however, it can be at least slowed
down by housing the works of art in thermal-hygrometrically controlled environments and
protecting the surfaces with synthetic wax, silicon or nitrocellulose gloss.
These types of products create a film that limits the direct contact with oxygen and
consequently the oxidation of the metals itself. However, even these materials are exposed
to alterations, and from time to time need to be substituted with new products. This
necessity requires the consideration of which protective products to use, because they need
to be able to be removed without causing any damage to the work underneath.

8.6 Case studies

8.6.1 Disassembly

THE LATERAN CROSS

The cross (SGL288, Treasure Museum of the Basilica of San Giovanni in Lateran, Rome,
Figure 8.7) was completely taken apart because its wooden interior was damaged and its
ability to stand was compromised. The nails that kept in place the gold-plated silver layers
had been mostly substituted during the maintenance work with iron and some brass nails.

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Thanks to this operation, many of the stamps inscribed by the 18th century goldsmith were
found on many layers on the backside of the piece.
The piece’s structure in walnut was assisted with walnut plugs and the original nails in
silver still found inserted in the wood were substituted with brass ones (Figure 8.8) in order
to differentiate between the modern ones and the antique ones.

Figure 8.8 – The Lateran Cross: original silver nail and the brass one substituting it.

AMBER SALT SERVICE

Even these salt services (MV61841-61845, Vatican Museums, Figure 8.9) were
disassembled in order to effectuate a cleaning on the metals without damaging the amber
otherwise sensitive to solvents for metallic elements.

Figure 8.9 – An example of amber-made salt shaker of the Vatican Museums.

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GOBLET/GLASS
This goblet (MV61858, Vatican Museums, Figure 8.10) could no longer guarantee its
integrity to stand erect since its stem was fractured and, therefore, could no longer be
upright. It was disassembled in order to give space to a silver tube which went to connect
the two parts internally, thereby ‘reinforcing’ the original stem.

Figure 8.10 – Goblet of Vatican Museums (MV61858).

VARA OF SAN SILVESTRO OF TROINA

Even the Vara of San Silvestro of Troina (Figure 8.11) needed a complete disassembly
since every element was in need of cleaning in ketonic solvents in order to remove the
altered gloss from a prior restoration; in that restoration the correct disassembly had not
been made since the original numeration of the goldsmith was evidently neglected.

Figure 8.11 – Vara of San Silvestro of Troina.

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THE IMMACOLATA
This statue (San Biagio Church, Acireale, CT, Figure 8.12) was taken apart in order to
homogeneously clean the thin layers of silver, and they were replaced in a way to plug the
gaps that were created by a previous incorrect reassembly and placing new ones where the
original ones were not sufficient.

Figure 8.12 – The Immacolata in the San Biagio Church in Acireale, Italy.

8.6.2 Cleaning

BOWL
This archeological bowl, kept in the National Archaeological Museum of Damascus, Syria,
presented a strong sulphuration, and above all a thick encrustation (Figure 8.13).
In this case, a cleaning with a piezoablator had good results, and it was followed by a
sodium bicarbonate rinse in water.

STRAINER
This strainer (MV65426, Vatican Museums, Figure 8.6) was not able to withstand
damaging mechanical actions due to its fragility and its diffused fractures. In order to
remove the thick crust of silver sulphide, it was decided to use a laser and subsequently to
uniform the cleaning with sodium bicarbonate in water by padding (Figure 8.14).

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Figure 8.13 – Encrustation and sulphuration of the goblet

of the National Archaeological Museum of Damascus.

Figure 8.14 – Strainer (MV65426) after cleaning

(the strainer before cleaning is in Figure 8.6).

8.6.3 Consolidation

CHALICE (MV61790, VATICAN MUSEUMS)

This chalice was taken apart with its pieces cleaned according to their specific nature. The
enamels of the crux were heavily fractured with many parts missing, and therefore, needed
an adequate consolidation using the same nitrocellulose gloss that was used to protect the
silver layer on which they were created (Figure 8.15).

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Figure 8.15 – Chalice of the Vatican Museums (MV61790).

PYX WITH LEAD NAILS

The pyx (MV61794, Vatican Museums) presents a strong deterioration in one of its lead
elements and the beginnings in another (Figure 8.16). It seems to have been caused by the
internal wood that was placed on the inside of the copper stem. From an analysis carried
out in the diagnostic laboratories of the Vatican Museums, it was determined that the wood
put in contact with lead can cause “cancer” in the latter manifesting itself with the
pulverization of the material. The nails were taken out, cleaned with pure alcohol and
consolidated with paraloid B72 (3%) and at the end reset after the cleaning of the pyx and
the removal of the internal wood.

BOWL
The archaeological bowl, kept at the National Archaeological Museum of Damascus had a
fracture along its edge. The encrustation strengthened the underlying very weak surface
which at the moment of its removal during the cleaning had a fragment detachment (Figure
8.17). In order to reposition the fragment in its place, the cleaning was terminated and
consequently consolidated with a bicomponent epoxy resin.

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Figure 8.16 – Pyx of the Vatican Museums (MV61794).

Figure 8.17 – Bowl of the National Archaeological Museum of Damascus.

8.6.4 Integration

MANDYLION OF EDESSA
The silver frame of the Mandylion of Edessa (VAT1000, Papal Sacristy, Vatican City) was
disassembled and restored. Each element was taken apart in order to distance them from
the ancient Christ image so as not to damage it.
During this phase, it was noted that the enamel of the collet petals of the frame were not
originally heated, and therefore they are modern, and the gold plate that covered the hidden
face of the original riza is therefore also modern. The silver plated copper strings that
fixated the pearls to the crown were as well modern (Figure 8.18).
These were in fact strung with modern iron strings whose alteration stained the pearls and

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the ancient fasteners that originally guaranteed the attachment were shattered during the
maintenance work. To make up for this damage, the aforementioned strings were used. It
was considered to eliminate them, and using the openings of the ancient fasteners, some
silver screws were welded with a laser blocking the bolts, making it possible to continue
with the maintenance without causing any damage.

Figure 8.18 – Silver frame of the Mandylion of Edessa.

THE PALIOTTO OF PIETRO PIFFETTI

The Paliotto of Pietro Piffetti (Papal Sacristy, Vatican City) is composed of a wooden
structure on which a multitude of sheets of mother of pearl, ivory, decorated in turtle shell
and various woods are attached. The trimmings created by these polymetric elements are
highlighted and enriched by brass lines that have at the same time the function of
absorbing the shocks of movements that such hard elements must endure being layed on
the “live” surface of wood (Figure 8.19).
Therefore, in addition to integrating the sheets of mother of pearl, ivory and turtle, and
having consolidated almost all the sheets whose Cervione glue had lost elasticity and

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adhesion, it was decided to integrate even the brass line in a circular shape instead of a
square one for an aesthetic and mechanical end.

Figure 8.19 – A Paliotto of Pietro Piffetti (Vatican City).

8.6.5 Protection and reassembly

The end result of any restorative operation of Goldsmith artifacts is the protection of the
metallic surfaces with a gloss that slows down the natural oxidation, and the object’s total
reassembly. The protection may be done with microcrystalline wax or with nitrocellulose
gloss, which are both removable. According to the nature of the artifact, it is preferable to
choose one way or another.
The fundamental rule of the reassembly is to follow painstakingly the mapping followed at
the moment of the disassembly, and even sometimes this needs to be called into discussion
if one realizes that the original structure may have been modified in a previous
intervention. That which can happen in the case where we observe the goldsmith’s mark or
engraved numbers at the moment of construction or should some element not coincide with
its adjacent part. We, therefore, try to reassemble following the hypotheses of original
construction in the hopes that the piece did not suffer any large variations so that it will
easily coincide together.
The Immacolata (Church of San Biagio, Acireale, CT) was therefore reassembled
following the mapping of the disassembly, but making small changes or allowances for
some of the lamina that were placed badly in a prior restoration (Figure 8.12 and 8.20).

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Figure 8.20 – The Immacolata in the Church of San Biagio

in Acireale, Catania (Italy).

The Crucifix (MV61794, Vatican Museums) had been reassembled by inverting the order
of the composed parts and therefore, it was reset in the correct positioning (Figure 8.21).

Figure 8.21 – Crucifix of the Vatican Museums (MV61794).

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Bibliography

AA.VV., Il gotico nelle Alpi 1350-1450, catalogo della mostra, Trento, 2002.
Acidini Luchinat C. (a cura di), Grandi restauri a Firenze. L’attività dell’Opificio delle
Pietre Dure 1975-2000, Firenze, 2000 (specifically p. 77 and 141).
Bulgari C.G., Argentieri, gemmari e orafi d’Italia, 5 Vol., Palombi editori, Roma, 1980.
Dolcini L., La fortuna del cristallo di rocca nel Medioevo. Guida alla consultazione della
bibliografia, in: “Technology and Analysis of Ancient Gemstones”, T. Hackens, G.
Moucharte, eds., Proceedings of the meeting in Ravello, Italy, 1987, Belgium, 1989.
Dolcini L., Il restauro delle oreficerie: considerazioni di metodo, in: Ori e Tesori
d’Europa, Atti del convegno di Udine, Italy, 1991, Udine, 1992.
Dolcini L. (a cura di), Il restauro delle oreficerie. Aggiornamenti, in: “Appunti del Museo
Bagatti Valsecchi”, Milano, 1996.
Giulietti S., Lo smontaggio delle oreficerie, in due esperienze di restauro, in: Ori e Tesori
d’Europa, atti del convegno di Udine, 1991, Mondadori Electa, 1992, 478 pp.
Hall J., Dizionario dei soggetti e dei simboli nell’arte, Longanesi, Varese, 1993, 430 pp.
Innocenti C. (a cura di), In margine al Reliquiario di Castignano: considerazioni
sull’oreficeria e il suo restauro, in: Il Reliquiario della Santa Croce di Castignano. Il
Restauro, Firenze, 1999, 80 pp.
Innocenti C., Un’esperienza senza precedenti nel restauro delle oreficerie, in: La Sfera
d’Oro: il recupero di un capolavoro dell’oreficeria palermitana, V. Abbate, C.
Innocenti, eds., Napoli, 2003, pp. 99-109.
Krauss H., Uthemann E., Quel che i quadri raccontano, Varese, 1994.
Lesage R. (ed.), Dizionario pratico di Liturgia Romana, Parigi, 1956.
Lipinsky A., Oro, argento, gemme e smalti - tecnologia delle arti dalle origini alla fine del
Medioevo, Olscki ed., Firenze, 1975, 516 pp.
Maltese C. (a cura di), Le Tecniche Artistiche, Varese, 1973.
Maltese C., AA.VV., Le tecniche artistiche, Mursia, Milano, 1994.
Matteini M., Moles A., La chimica nel restauro, Nardini Editore, Firenze, 1989.
Montevecchi B., Rocca S.V. (a cura di), Suppellettile ecclesiastica I, in: Dizionari
terminologici (4 volumi), Firenze, 1988.
Pinto Folicaldi B., La Croce Astile della Collegiata di Sant’Orso in Aosta: modifiche

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strutturali, estetiche ed iconografiche attraverso i secoli, tesi di laurea Opificio delle

Pietre Dure, Firenze, 2003.
Pinto Folicaldi B., La Croce Di San Giovanni: studi, indagini e restauro, tesi di Laurea in
Tecnologie per la Conservazione e il Restauro dei Beni Culturali, Università degli
Studi della Tuscia, Viterbo, Italy, 2009.
Proja G.B., Immagini reliquie e benedizioni, Città nuova ed., Roma, 2005, 100 pp.
Santi G. (a cura di), Arte e liturgia, Cuneo, 1993.
Singer C., Holmyard E.J., Hall-Trevor A.R., Williams J., Storia della tecnologia, Torino,
1966.
Varazze (da) I., Legenda Aurea, a cura di A. e L. Vitale Brovarone, Venezia, 1999.

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9 – WOOD ARTEFACTS

9.1 Characteristics of the wood

Wood is one of the oldest materials used by humans, because it is easy to find and it is
relatively easy to be manufactured. The man used it to build houses and furniture, as well
as to create everyday objects and ornaments.
The chemical composition of wood is made up of approximately 50% carbon, 44%
oxygen, 6% hydrogen; minor amounts of other chemical elements can be present, in
particular nitrogen (not more than 1%), Ca, K, and Mg compounds (the sum of which is
generally less than 1%) and traces of pigments. The main elements are combined together
to form mainly cellulose, hemicellulose and lignin in different proportions depending on
the type of tree. Coniferous plants show 40-50% cellulose, 20% hemicellulose and 25-35%
lignin, while broadleaf plants have approximately the same percentage of cellulose, but
less lignin (17-25%) and a variable percentage of hemicellulose (15-35%).
The compactness of the wood depends on the speed of growth and deterioration of the
cells, so that the wood can be divided into “hard” and “tender”; oak, walnut, boxwood,
pear, and cherry are hard woods, while pine, poplar, linden, and fir are tender. The types of
wood used for artistic purposes are the medium-hard ones, resistant to animals and less
sensitive to temperature changes.
The wood is characterized by a strong anisotropy, that means that the behaviour differs
depending on the direction, due to its fibrous structure. If we look at the cross section of a
trunk, we can distinguish clearly a number of tissues arranged in concentric bands (Figure
9.1). This implies a different behaviour to variations in temperature and humidity and
determines different rheological properties (elasticity and plasticity). The wood is affected
by the climate changes, so that it swells with moisture and heat, and it tends to form cracks
when it dries. This last phenomenon also occurs when the wood dies, after killing the tree,
because its cells lose water.
The wood can show further heterogeneity due to the presence of natural defects:
- nodes, that are branches incorporated into the wood during the growth of the
circumference of the trunk; they have a mass volume different from that of the

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surrounding wood, and then retire differently during aging (Figure 9.2),
- onion structure, that is a gap between two consecutive growth rings, caused by frost or by
a high temperature; this defect may emerge during aging,
- star cracks, which consist in radial cracks caused by the tensions of plant growth or by
the different behaviour of the central part of the trunk and the rest (Figure 9.2),
- eccentric heart, that is a conspicuous irregular growth rings which are eccentric due to
the fact that the plant is grown in steep slopes or in very windy areas,
- bags of resin, which constitute tree’s natural defences when it suffers an injury.

Figure 9.1 – Section of a trunk of wood.

Figure 9.2 – Some natural defects of wood: nodes and star cracks.

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9.2 Working techniques

9.2.1 Cut and seasoning

The trunk can be reduced to axes according to different patterns of cut, parallel to the
length of the trunk (Figure 9.3). Each cut, according to the point where it takes place, has a
different name. After cutting, the wood loses quickly the water present in the cell cavity.
All axes tend to embark, but the central axis is more stable.
The natural seasoning ensures the greatest stability; it is achieved by piling the boards and
interposing strips to allow air circulation. Since it would take a long time, the artificial
drying is used, which occurs in special environments, real furnaces with controlled
humidity and temperature. At this stage the wood continues, but more slowly, to lose water
until it reaches equilibrium with the environment around 17-23% humidity. At this stage
the wood is deprived of substances carried by the resin flowing into the wood.

Figure 9.3 – Scheme of different positions where a trunk can be cut for achieving axes.

9.2.2 Paintings
When necessary, the first stage is the assembly of several well seasoned axes, with casein
and mortar, reinforced with wood and pivot: pivot’s head is planted on the side of the
surface to be painted and then covered with a layer of wax. Rigid wood axes fixed on the
back must be avoided because they prevent the natural movement of wood; flexible
wooden armatures should be used. The connected axes are covered with strips of canvas.
The preparation of the surface to be painted begins with the application of a first coat of
glue on the canvas and then a layer of plaster and glue, smoothed after drying. The process
was then repeated several times until you have a preparation chalk/glue of 1-2 mm, on

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which lies the film of painting. The most important types of painting are:
Encausto: the wax is used as a binder for colour. The pigments are moistened in hot
beeswax lying on the wood. The colours are kept liquid through braziers and applied by
brush, with a hot spatula. Solidifying, the pigments are captured. Encaustic painting is very
opaque, thick and creamy.
Tempera: a mixture of glue with mineral filler (usually chalk) is used to build cohesion
between painting and wooden support. The glue is diluted in water, causing a temporary
swelling of the surface. Therefore, there should be a period of drying, after which the
mixture comes into contact with the wood. Then the colours are applied. The tempera can
be meagre or fat. Meagre if the binder is egg yolk, milk, animal tissues, fig latex, animal
glues. Fat if the binder is composed of oils and varnishes.

9.2.3 Sculpture and intaglio

As for stone, sculpture of wood consists in definitively removing portions of material. The
wooden sculpture was often painted or covered by other materials (metal, leather, etc.).
An artefact is preferably derived from a single block of wood, but some parts are made
from other blocks and then joined.
After carving, the obtained object may be left “raw” or covered with a thin layer of colour
diluted in water, and then polished or painted.
Also the ‘intaglio’ technique for wood is similar to that of the stone. The tools used are
chisels, gouges, mallet (Figure 9.4).
After an accurate design and sometimes three-dimensional model in clay, the block is
moulded with a saw, then finished with a great gouge and the artefact completed with the
help of other tools. The polishing is performed with walnut oil or flax, or with lacquer,
rubbing with linen cloths.

Figure 9.4 – Tools used for the ‘intaglio’ technique for wood.

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9.2.4 Inlay
Marquetry is an ancient technique that can also be called inlay (“rimesso” is the Italian
word) when it concerns wood. It consists in inserting and pasting elements of the same or
different material, with mastics or organic glues, on a purposely prepared surface, to create
geometrical drawings (like “certosino”) or figurative drawings, both on complete surfaces
and on panels. This is the art of painting with wood.
This art develops a lot in Italy in the 14th century just with a painstaking form of inlay
work, known in Italy as “certosino”. This is a composition of geometrical drawings,
realized through small sections of wood, detailed with light and dark pieces, which were
fitted together into a corresponding opening. At first, inlayers shaded the pieces blackening
them, besides alternating them; initially they made use of a red-hot iron, afterwards they
dipped the small sections of wood into scorching sand, and subsequently they began to boil
the same small inlaid sections with vegetable oils or herbal essences.
At the beginning of the 17th century the wood inlay regained favour thanks to the great
Dutch cabinet-makers, who introduced the new technique of ‘marquetry’ (marquetterie in
French) into France; unlike inlay, marquetry lies on the plane.
This is a technique decoration based on the colour contrast of different woods, but also
metallic plates, silver flakes of mother of pearl, ivory, tortoiseshell, and other. The inlay is
made with very fine views. Ultimately, there are two types of inlay (Figure 9.5):
Certosino: you use small pieces of solid woods, light- and dark-colored fixed to the basic
structure with mastic.
Marquetterie: overlapping sheets of various woods with equal thickness and size; with a
single cutting operation is obtained the desired design.

Figure 9.5 – Wooden artefacts with ‘certosino’ (left) and ‘marquetterie’ (right) technique.

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9.2.5 Gilding
The gilding techniques concerning wood are two:
leaf gilding, which involves the application of gold leaf on a surface properly treated;
dust gilding, which is technically identical, but it uses gold dust instead of gold leaf.
Gilding is a difficult technique: we think that an inexperienced person can not possibly
realize this technique only reading these pages, or even a more exhaustive book than this.
Only the experience gained working alongside a good artisan allows people to get
satisfactory results.
This technique, certainly difficult to realize because of the awkwardness of the extremely
fascinating process, requires different stages and it takes several days to complete the
inlaid work. However the outcome surely rewards patience of the restorer trying one’s
hand at this ancient art that lasts from more than a century.
The process have remained the same for a very remote time. Modern technology adds a
change in terms of rolling gold, that is not hand-wrought by the “gold beaters” anymore,
on the contrary it is processed in a factory.
The following necessary materials and tools can be found in a well-stocked paint shop, or
in a Fine Arts shop, or in a shop specialized in the field of restoration:
materials: plaster of Bologna, rabbit-skin glue (known as “colla Lapin”), fish-glue sheets,
Armenian bole (also known as “bolus armenus” or “bole armoniac”), pure gold foils.
tools: gilder’s pad, gilder’s knife, gilder’s brush, burnisher, bain-marie pan, various
brushes, fine-grained sandpaper (120, 180, 240).
In any case, gilding requires that the support is made perfectly smooth, with the surface
pores closed; of course this operation must be carried out on a cleaned surface, free of dust.

9.2.6 Ebanisteria (cabinet making)

Woodworking technique fairly recently (since the seventeenth century), especially for
furniture, initiated by the introduction of the use of ebony, a solid wood with fine grain.
Actually ‘ebanisteria’ can include all the highly specialized works, using precious woods.
Typically, this work provides a structure or a veneer, the first made from hardwoods such
as walnut, oak or pear tree, and the second by precious sheets of woods such as ebony or
mahogany and other exotic woods.

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9.2.7 Xilography
Xilography comes from the greek words ‘xulon’ = wood and ‘grafein’ = to write.
In a matrix of wood the surface of the not engraved parts receives the ink and makes the
sheet black, while the carved parts remain white. That’s why this technique is called “print
on relief”.
For the xylography, blocks of hard woods are used, cut along the wood fibers. The
instruments used to engrave are various types of knives and gouges. On the well seasoned
and polished tablet of wood, the drawing with pencil and then ink is made.
This design will be the reverse of the image that is wanted. With a short cutter you start to
carve the wood, keeping close to the design.
When the whole design is surrounded by the groove, you proceed to remove the wood in
the parts that should be white, using gouges of various sizes. And then a pad or a roller
passes over leaving the ink. The print is then made by hand or with a flat press. The earliest
prints were almost always completed by adding a coat of colour. But then the colours were
added in the same printing process.
Initially, many pieces of wood with different inks were printed simultaneously, as many as
were the desired colours. But the colours were flat. At the beginning of ‘500 a procedure
based on the use of different matrices was introduced, which produces effects similar to
drawings in ink and watercolour on coloured paper.

9.3 Degradation of wood

9.3.1 General information

Wood, contrary to the common convictions, shows a remarkable intrinsic degradation
resistance. Or rather, the only element ‘time’ doesn’t play a leading role in bringing about
a change in the features of the materials.
The outside agents alone, in particular among them the biotic agents (bacteria, fungus,
insects), can be cause of degradation, provoking serious aesthetic/artistic/functional
problems and grave difficulties in terms of preservation, especially in the area of expertise
of cultural goods.
The settlement and the development of the biotic agents is strongly influenced by the
environmental conditions; bacteria and fungus generally need a very moist environment to

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succeed in destroying wood, while insects are more harmful than them, because they do
not need particular environmental conditions.
There are a lot of insects interested in works of art, but the most common xylophagous
insects belong to the orders of Coleoptera (commonly called beetles), Isoptera (also known
as termites), Lepidoptera, and Hymenoptera. The first three are really involved in the
restoration field.
Each species has distinctive biological and ethological features. It is essential that the
restorer has a good knowledge of these orders of insects to protect and preserve works of
art from them.

9.3.2 Coleoptera
“Woodworm” (“tarlo” is the Italian noun) is the common noun to identify various types of
Coleoptera (beetles), which feed on wood (Figure 9.6). Some beetles can be found more
easily today than in the past, because the temperature within our houses, thanks to the
heating system in wintertime, is in favour of their production cycle; in fact in these
favourable conditions they are able to reproduce themselves three times a year.

Figure 9.6 – The common woodworm: insect of Coleoptera family (beetles).

The female of the common woodworm (Anobium punctatum, “woodworm of furniture”)

lays eggs into cracks, holes, erosions of the wood and into all the points of the furniture,
where the newborn grub will have the opportunity to feed itself, beginning to dig its tunnel.
It follows that the well-polished and preserved parts of our furniture aren’t a favourable
environment for woodworms, therefore it is very important to devote some time to take
care of the furniture so as to protect them against these undesired insects.
Grubs, once they have entered the wood, live into it, wood-feeding themselves and digging

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long tunnels, which naturally follow the grains of the wood. The life cycle of these insects
also lasts several years, and at the end of that (generally in the spring and in the autumn
seasons), the fully grown insect go towards the outside. It follows that, contrary to what
people think, the hole we normally see and which inform us of the presence of woodworms
in our furniture, isn’t the entrance hole, but it is the exit hole.
Therefore when we see the small opening, the damage has already committed.
Among the most common species, which infest furniture, there are the woodworms of the
family of Anobium. These come out when they are fully grown, in particular in the months
of May or July. During these periods people can listen peculiar and regular tapping against
the surface, that the male of the woodworm provokes hitting the wooden surface with its
head.
In this case we have to do with loving calls. For this reason, the woodworm of this species
is also called “death watch beetle” (it belongs to the Xestobium refovillusom species).
Another insect of the family of the Cerambycidae, also known as “capricorn beetle”,
become very acclimatized in our houses. The woodworm of this family is very voracious
and it doesn’t despise resinous or hard woods. These insects are hardly identified, because
they spend all their life into the wood, where they mate and reproduce themselves. The
only clue is the typical sound, which people can listen when this insect feeds itself.
Another type of Xylophagous insect belongs to the Lyctus kind. It is recognizable for the
distinctive form of the exit holes (round holes, which are 2-3mm wide) where the female of
this species lays eggs. This happens between April and May months.

9.3.3 Isoptera
Termites belong to the order of the Isoptera. They are social insects, in fact they live in
colonies, composed of until two million of members; they are afraid of light, so they work
within, provoking a complete emptying of the artifact at the expense of cellulose. There is
no exterior signal of their corrosive action and very often people notice their presence
when the damage is irreparable.
There is a partition into castes: fecund male and female on the one hand, worker and
soldier on the other; the development of the different castes is organized through a differed
feeding. The final development of a colony, complete of all castes, takes three or four
years.

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The queen lays eggs as much as thirteen million a year; only in certain periods some sexed
species appear, swarming outside in springtime; they mate, they lose their wings, then they
come back into wood and they create a new colony.
The relation between the members of the colony are regulated by secreted chemical factors
called pheromones: there are pheromones of alarm, of trace, and of mating.

9.3.4 Damage analysis of woodworm

Woodworms don’t attack by chance, but they look for the thicker parts, which provide
them with a larger quantity of food. They search the soft sections of the rings marking the
age of the wood, or the signs of these circles in wood having large grains. Woodworms dig
perpendicular to the surfaces, with curvilinear and branched development.
Woodworm presence is revealed by small dust drifts, which suddenly appear on the floor,
under the furniture or inside it. If we take a look at the supposable point, where we think
the hole is, we will soon find it. The exit holes of the Xylophagous insects are very
evident: the recent holes have a clear outline, because they have done not long before
(Figure 9.7, left). When we see holes having a dark outline, or partially closed with wax,
we can easily consider that they are holes caused by the passage of some woodworm long
time ago, but also in this case we can not overlook them (Figure 9.7, right).
Damages, which the woodworm can do, include both small holes, scattered everywhere
without compromising the quality of the furniture, while sometimes the excavation can
cause the crumbling of entire parts. At times the insect digs its tunnel beneath the surface,
making the outer layer thin and breakable: this type of damages is provoked by the
Anobium Punctatum (‘or furniture beetle’) and Capricorn beetle.

Figure 9.7 – Recent (left) and old (right) exit holes of the Xylophagous insects.

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In this case we must pay attention to use abrasive paper, because we run the risk of
removing this light wrap, leaving into the open an irrecoverable unaesthetic tunnel. The
latter just called “long woodworm” becomes an alarming sign for not declared
falsifications. In fact, in the world of the falsification, the furniture is made with salvaged
materials and they are passed off as original. The adaptability of wood for new furniture
makes often possible to find more or less deep woodworm’s tunnels.
For this reason, we must be suspicious in relation to a presumed authentic furniture. We
must show the doubt to the dealer and we must demand explanations about the presence of
the “long woodworm”. Certainly, if it is not the case of a falsification, it is a case of
misguided attempt of restoration.
Generally, the main woodworms which infest beams and wooden artifacts are the so-called
Capricorn of the conifers and broadleaved Capricorn.

9.3.5 Corrosive wear

It is quite easy to find old or even ancient wooden material (beams of old houses, some
period furniture that can not be restored) and to assemble or rebuild or alter a piece,
placing it in a previous age to its origin. A system which can help us to bring into the open
the fraud, will be the corrosion.
The latter should appear on all the parts of the object or of the furniture, obviously
appearing more marked in the lowest parts, because these are more subjected to use: in the
case of furniture placed on the floor, there will be a lot of damages in the low parts,
because of bumps, rodents, or floor washing. In the external parts, which are exposed to
severe weather conditions (light, water, sun) some deep cracks will develop; if these are
authentic, they will follow the direction of the fiber of the wood.
The drawer runners will be corroded by the continuous running.

9.3.6 Warping
If a wooden surface is exposed to the environmental changes (heat, dampness, etc), it will
warp, so that the surface of the furniture will take a concave or convex form.

9.3.7 Patina
Patina on wood is the element that reveals the age, the history and the authenticity of an
object, and it is the result of different components, which form it in the course of the time.

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Wooden fibers, having different structure visible with magnifying lens, have a shiny and
transparent look, almost a crystalline aspect, but they change their physical features
through the action of the atmospheric agents. The several operative phases for the
manufacture of a furniture also affect the appearance of the wood; in fact in this last case
the wooden fibers are deprived of some pigment and resin.
Besides the natural ageing process, we have to consider the dust settled in the small
crevices of the varnish (oils, wax, etc), used for the polishing phase. Then the deterioration
of these organic materials will occur due to the attack by bacteria living in the air. Finally
we have to take into account the life of the object that brings about the formation of the
precious patina (coating). It is possible to fake the patina; in this case it gives the furniture
a velvety look, which appears smooth and dry to the touch. This false look can not be
confused with the greasy coating, made up by wax or old-fashioned varnishes, which is
very often used by the forgers to cover the surfaces.

9.4 How to start restoring

9.4.1 Leading scheme and operation plan

In this paragraph we take the matter of how to start restoring of an object or a furniture into
consideration. In particular, we examine the various basic operations or procedures
enforceable for each artifact having different style and age, distinguishing the interventions
that, after a choice, can be more appropriate for the piece subjected to our cares.
Since each restoration needs a defined procedure, a general leading scheme makes easy to
choose the technical, practical, and operative phases, which will be applied to the object
being restored. The artifact must be observed with great attention, so that we can
understand:
● the age, and the compositional style,
● the thought of the artist, or the artisan, who is the maker of the artifact; this is an
important element because the deepening of this knowledge can make it possible to
perform an intervention in harmony with the artifact,
● if the artifact is authentic, fake or compromised by previous interventions, or even, if
it is in so bad conditions that any restoration could be excessive, due to working time
and/or materials cost,

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● the extent of the damages, which can be defined as:

- considerable; if the damages concern artistic objects, they are resolvable only with
experience and ability,
- considerable, but concerning less noble or rural artifacts; the patient collector can
act alone if he has an adequate preparation,
- of limited extent, therefore quite easily solvable. Then follows a valuation of the
artifact, estimating the damage on which the restorer has to professionally act.
At this watchful analysis follows the typological choice of the restoration and of the
materials suitable for the achievement of the work.
The plan of operation includes the following phases:
a) reinforcing (replacing pieces),
b) cleaning,
c) pest control (disinfestation),
d) integration of stucco-works or holes,
e) painting or coloring,
f) polishing and finishing,
g) final phase of protection.
Not always the restoration requires all the above working phases; for this reason it is
important to choose according to the criteria related to the different restoration techniques.
In fact the restoration of wood shows several aspects, and the attitude towards this artistic
and handicraft area changes over the time. The causes of this change are different, for
example the taste, the coming of new technologies and new materials, the more or less
idealist thought of the restorer, and the social, economic, and commercial aim of the
intervention.

9.4.2 Restoration typologies

Scientific restoration: it is employed for the renovation of the work of art; this type of
restoration includes the interventions that ensure the observer about the authenticity of
each section of the archeological find, excluding any intrusion on an artistic or formal
level. For example, the archeological find acquires the original stylistic form, but the
integrations are not hidden through and through, so that the restoration is clearly visible.
Aesthetic restoration: this technique is used in full obedience of the compositional and

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structural elements but also artistic and decorative features of the work of art. Following
specific and well defined criteria, the restorer intends to return the work of art its
original aspect: obviously after a meticulous study of the compositional elements and
after considering an accurate video-graphic and graphic documentation.
Commercial or supplementary restoration: it is used to reach the prearranged purpose in
the shortest possible time. Nowadays this type of restoration is more than ever applied,
giving rise to fakes and, above all, negatively acting on the work of art. Taking this type
of restoration into consideration in a completely negative way, it is important to
remember the supreme thoughts of some ancient masters: Vasari, Suardo, Melani, who
give us strict judgments about the restorer’s work.
Deviant restoration: this type of restoration changes the aspect of the object in a significant
way, only and exclusively for profit. In this case, the restoration mainly aims at a rapid
profit, without scruples and without worrying about the state of the furniture.
Primitive restoration: it is a restoration work for objects which are currently used by the
possessor; therefore they are restored so that they can still be used, without worrying for
the aesthetic aspect of the restored artifact.
Destructive restoration: it is used to make the artifact, or a section, credibly authentic,
especially if the object has a certain value; therefore it is used for profit.

9.4.3 Curative treatments for wood

Among all the building materials, wood is the one that suffers more for degradation
problems, due to the action of woodworms, fungi, and bacteria. Like other materials of
organic origin, wood also needs proper curative interventions.
All kinds of artifacts (beams, wooden ceilings, truss, furniture, painted tables, parquet,
stairs, frames) can be and have to be treated by choosing the most appropriate of the
following treatments:
Microwave treatment: ecological system for wood treatment, which does not use any
chemicals, it has no residual effect, and it does not need to leave home.
HP technique: an odorless curative product is injected into the wood, which ensures the
elimination of any woodworms infestation. This product makes the wood water-
repellent, and protects wood against the dampness. Furthermore it forbids the so-called
“shrinkage” in a dry climate, and protects wood from fungi, algae or bacteria. Finally, it

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does not remove gildings and does not corrode tempera paintings.
Micronization: a special product is micronized on the surface of the wooden artifact
through a particular pump.
Toxic fumigation gases: The fumigation using toxic gases penetrates into the structures of
the wood to reach the crevices, where termites build their nests; because of the inherent
risks, this treatment is subjected to particular regulations.

9.5. Restoration of a small inlaid table

9.5.1 Description of the work of art

Object: small table completely inlaid with ‘intarsio’ technique, 85x60 cm (Figure 9.8).
Age: beginning of the 20th century.
Artist: unknown artist (masters in the art of “ebanisteria” of Palermo).
Compositional stylistics: geometrical/Empire/restoration/floral.
Architectural composition: foot central column supporting the square top and three legs in
the form of lyre at the base of the column.
Property: private.
Year of restoration: 2010.
Description of the inlay: the small table has in the lower part three small feet double-s-
shaped, which are inlaid in the crest part; in the central part there is the column foot
completely inlaid; in the upper part the square top shows a geometrical inlay, which
represents Saint George killing the dragon.

Figure 9.8 - Small inlaid table before (left) and after (right) restoration.

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Executive technique: the small table shows various inlay techniques; the lower part is an
example of the “certosino” technique, while the upper part shows geometrical and
figurative techniques with different wooden typologies.
Wooden typologies present on the small table (Figure 9.9):
Ebony: very dense black wood, coming from Africa.
Walnut: this wood tends towards a dull brown color with dark grains. It is a native
Sicilian tree and its wood is widely used.
Mahogany: sturdy and hard wood, having a reddish brown coloring.
Acer: heavy wood having light color; it is a native Sicilian tree.
Beech: it is a semi-hard wood, having light color.
Chestnut: strong wood, light brown in color, almost tawny yellow; it is a native Sicilian
tree.
Ashwood: strong wood having light color; it is a native Sicilian tree.
Olive tree: hard yellowish wood with back grains, suitable for inlay works. It is a
native Sicilian tree.
Rosewood: very fine wood, widely used in France and England.

Figure 9.9 – Some wooden qualities in the small table.

Retaining and supporting structure (Figure 9.10): the retaining structure of the top of the
small table is made up of three walnut sections: chestnut planks surround the
perimeter; in the central part there are two walnut planks, and, in the middle of them,
the screw lodging for the central leg. The median part consists of walnut wood, which
is decorated with small inlaid works in the “certosino” style, characterized by various

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wooden typologies that create a geometric pattern. The wood of the three lyre-shaped
legs is dark walnut; in this lower part walnut wood is inlaid with geometrical
“certosino”, creating a fishbone structure.

Figure 9.10 – Retaining and supporting structure of the table.

9.5.2 State of preservation

At a first general glance of the artifact, we can notice a disparate preservative condition.
The wooden structure appears in a decent state of preservation, and the same thing for the
surface inlays. There are clear signs of chromatic changes and abrasions on the surface of
the small table, caused by the wearing effect of time and by its use. However the small
table on the whole keeps very well the stylistic features and the good readability.
The anthropological elements strongly influenced the state of preservation of the artifact
and its continuous use created many structural/static problems. The wood of the support
presents an extended attack of active Xylophagous insects; the flickering holes are clearly
visible to the naked eye, both on the support and on the inlaid sections. It can be possible to
see some previous restoration works on the three legs supporting the small top.

9.5.3 Restoration work

The restoration activity follows the watchful observation of the artifact, to point out and
elaborate all the information useful for a further knowledge of the work of art and in
support of the most appropriate planning of the restoration work.
The cognitive researches constitute the base for the execution of a restoration work,
conducted according to scientific criteria and in respect of the work of art, its materials and
its history. All the information gathered in this cognitive stage is added into a register,

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well-supported by a complete photographic documentation of the whole restoration

activity. This documentation consists of four main stages of study: executive techniques,
constituent materials, preservation state, previous actions and restorations.
The restoration work foresees a preliminary removal of the dust and additional deposits
with the brush, on the whole surface of the top and of the legs of the small table (Figure
9.11, left). For the removal of the fatty dusts, it was necessary the use of a padding with a
non polar neutral solvent (white spirit), used on the complete surface.
Then, given the presence of several flickering holes of woodworms, as a preventive
measure, the wooden support was disinfected with biocide products (Figure 9.11, right).
This was done covering the surface by brushing and through injections on the direction of
the artifact, to forbid a possible infestation of biodeteriogen organisms (mycological
organisms).

Figure 9.11 - Removal of the dust and additional deposits with the brush (left)
and disinfection with biocide products (right).

After this preventive treatment, a ‘pvc’ hermetic chamber was built for the small table; in
particular, the artifact was placed in the chamber and it was treated with an anti-
woodworm permethrin-based product for a month (Figure 9.12, left).
Subsequently, was made to the manufacture a injection of Paraloid B72, a 7% melted in a
mixture of thinner nitric paint and acetone, having the same quantities.
Then the small wooden sections, lifted from the table top, were pasted with an organic
glue, consistent with the original one (rabbit-skin glue).
It was necessary to close all the present holes on the surface of the small table, provoked
by the attack of the woodworms, to avoid the inclusion of dangerous dusts for the

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preservation of the artifact. This was done through some beeswax (Figure 9.12, right),
making uniform the whole surface. At the end of the restoration work, a layer of neutral
protective beeswax was applied on the whole surface, in order to protect it and make it
smooth and shiny.

Figure 9.12 - Treatment with an anti-woodworm permethrin-based product (over)

and closure of surface pores with beeswax (below).

9.6 Restoration of a commemorating wooden tablet

9.6.1 The artifact and its conservation state

The artefact is a polychrome commemorating wooden tablet, containing tri-dimensional
inscriptions and composed by three planks with a frame, kept in the Archaeological
Museum in Damascus (Syria).
Thanks to a document found in the archives, it was possible to date the piece of art to the
XIV century AD (Figure 9.13). The results of the analysis of the conservation state of the
artwork are reported in table 9.1.

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Figure 9.13 - Polychrome commemorating wooden tablet (XIV century AD).

Table 9.1 – Results of the analysis of the conservation state of the wooden tablet.
Type of damage Front Back
Remarkable surface dust layers + +
Cleavages, holes and breakages +
Detachments of colour layers from the wooden surface +
Lack of colour and blanks on all the surface +
Colour cracks on all the surface +
Many whitewashing traces on the frame + +
Traces of different colour layers on all the surface due to previous +
restorations, and a glossy protective film that fixes dust and dirt and
provokes many detachments and losses

9.6.2 Description of the intervention

Due to the high documental value of the tablet, the bad conditions of the colour film and
the important paint losses (around 50%), we proposed a highly reversible conservative
intervention. Then, because of the complexity of the case, we decided for a diagnostic
campaign to identify and confirm the original layers and to distinguish them from later
paintings. Furthermore we had to understand the composition of the glossy film, which at a
first glance at the microscope, looked like an alkyl varnish utilised for planking.
The intervention on the front surface included:

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- First consolidation test.

- First consolidation and emergency fixings of the detached parts using sturgeon glue
injections of all the surface, according to the test results.
- Emergency plastering of all the surface using French plaster and local plaster, whose
recipe was modified due to the conservative needs of the highly unstable colour flakes.
- Cleaning test to remove the attached dust.
- Cleaning of all the surface by using solution of Contrad 2000, 20% concentration; it was
strongly recommended to move slowly and precisely.
- Final consolidation of all the detachments.
- Plastering with local plaster only in those gaps that can improve the reading of the
artifact and of the inscriptions.
- All the plastering and the white traces were retouched with small slightly opaque water-
colour lines.
- Before removing the glossy varnish, we thought it is mandatory to delay any decision
after the execution of the scientific analysis to identify its nature and precisely choose
the best solvent to remove it.
On the back surface the following interventions were made:
- Dry cleaning test;
- Cleaning of the entire surface from dust, using soft brushes and Wishab sponges.
- Cleaning tests made with surface-acting agent and de-mineralized water. That was made
in order to identify timings, methods and right concentrations.
- Whole surface cleaning, according to the tests.
- Mechanical removing of the whitewashing traces using lancets.

9.7 The restoration of a seventeenth-century crucifix

9.7.1 The artwork and its conservation state

The artwork is a seventeenth-century wooden polychrome crucifix, by unknown author,
located in the last bay of the right aisle in the Church of Santa Maria in Bethlem in Pavia
(Italy). The crucifix has a total height of 495 cm, and underwent restoration in the years
2003 to 2004 with the collaboration of the Superintendence for the Historical and Artistic
Demo-ethno-anthropological Heritage of Milan (Figure 9.14).

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Figure 9.14 – The wooden polychrome crucifix in the Church of Santa Maria in Bethlem
(Pavia, Italy) before (left) and after (right) restoration.

The sculptural work in question has a great expressive power and a side profile of a
particular beauty. The sculpture of the Christ might have realized shortly before 1600. The
cross does not seem coeval with the figure of Christ, but it could have been replaced later.
The radial pattern at the intersection of the arms of the cross, as well as the cartouche with
the inscription INRI, is made of copper, now very oxidized and difficult to date.
The work was impaired by the following pathologies:
• infestation of Xylophagous insects;
• significant deposits of particulate matter, and fat fumes;
• repainting scattered everywhere;
• relevant fissures between the torso and arms;
• lack of three phalanges of the right hand, and one finger of the left hand;
• loss of color, and subsequent application of gypsum, on the stomach, on the loincloth,
and on the knees (in the vicinity of such failures, there are many small unstable parts of
matter);
• presence of a thick layer of paint on the loincloth;
• layer of transparent varnish, such as for boats, given on the entire cross.

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9.7.2 Diagnostics and methodology of intervention

During the intervention of restoration it was established that the cross is not contemporary
with the figure of Christ, as well as the radial pattern and the cartouche; the latter are not
made of brass, as had been supposed, but in copper, and their execution is certainly of
recent times.
The first observations, carried out at a small distance, have also allowed us to discover that
the back of the sculpture is completely hollow from the head until the pelvis (for reasons of
manufacture). The cavity was then occluded and modeled with felt impregnated with
gypsum and then painted. In the marginal areas of this filling, many gaps were found, as
The
well as unstable fragments of fill material due to movements of the wooden support.
chemical and physical analyses have also found that the Christ has been subjected to
interventions three times, and each intervention was carried out with a new plastering and
subsequent application of renewed colors.
They found a total of 18 different layers of paint and plaster, often uneven and incomplete;
the concave shape of the flakes of color, in section, leads one to suppose that the problem
lies in the wooden support. This support is a piece of linden wood, and in particular the
piece in question fails to reach the full stability of the fibers and therefore you have
constant movement of matter and detachment of what has been put on.
With these assumptions, even taking into account that the traces of original color are scarce
and that the color is very delicate because the binder is protein, it was decided to keep all
the repainting, removing only the last two layers, which are very dark and have a oleo-
resinous composition.

9.7.3 Restoration intervention

After excluding the removal of Christ from the cross to avoid the risk of losing the stability
of the arms, the restoration was conducted by implementing the following phases:
- photographic campaign before the intervention;
- stratigraphic investigations combined with physical-chemical analyses for the
identification of the original colors;
- execution of thematic tables on the conservation state;
- disinfestation by woodworms with Permectar, in a specially built room;
- application of veils in all the unstable colored parts (Figure 9.15);

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- injecting a rabbit skin glue, diluted to 5-7%, below the unstable flakes and at the
perimeter of the gaps, all already covered with veils;
- dry cleaning with very soft brushes and a small aspirator;
- re-adhesion of the flakes of color and soldering with thermo-cautery;
- removal of veils with luke warm water and cotton wool;

Figure 9.15 – Application of veils in all the unstable colored parts.

- testing to evaluate the consistency of the oleo-resinous layer to be removed and the
materials to be taken;
- repair of the damaged parts between torso and arms, and of the fingers, with a mixture of
gypsum (90%) and glue (10%);
- cleaning the entire surface with a swab and synthetic saliva to soften the layer of oily
varnish, then removed with a mixture of lavender and alcohol (Figure 9.16);
- execution of the necessary fillings with gypsum of Bologna admixed with rabbit glue

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(5%);
- integration of the painted parts, with the use of water colors, according to the striped
technique (‘rigatino’ technique);
- application of a thin protective layer of microcrystalline wax over the entire work;
- cleaning of the metal components to remove the oxidized material, straightening, final
protection with microcrystalline wax, and reassembling of the metal components;
- complete photographic documentation after the restoration.

Figure 9.16 – Cleaning with a swab and synthetic saliva to soften the layer of oily varnish,
then removed with a mixture of lavender and alcohol.

Throughout the time of restoration intervention, thirteen thematic tables were prepared to
document all information and the intervention phases:
• materials constituting the artwork,
• collection points of the samples analyzed,
• lifting positions of the surface finishing layers,
• application of emergency veils,
• application of veils and consolidation,
• fillings and plastic reconstructions,
• pictorial integrations.
Two thematic tables are shown as an example in Figure 9.17: they refer to the phase of
application of veils and consolidation.

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Figure 9.17 – Two examples of the thematic tables prepared during the intervention:
application of veils and consolidation on the right (over) and left (below) side.

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Bibliography

Althofer H., La questione del ritocco nel restauro pittorico, Casa Editrice Il Prato,
Saonara, Padova, 2002, 64 pp.
Amati F., Restauro ligneo secondo le regole d’arte, Di Baio editore, Milano, 1995.
Bennet M., Scoprire e restaurare mobili antichi, Fratelli MELITA Editori, La Spezia,
1995.
Cremonesi P., L’ uso di tensioattivi e chelanti nella pulitura di opere policrome, Casa
Editrice Il Prato, Saonara, Padova, 2004, 135 pp.
Druy E., Tecniche e segreti dei grandi ebanisti del passato, Istituto Geografico De
Agostini, Novara, 1990.
Ferrozzi V., Cremona M., Antiche tecniche decorative e moderni metodi di restauro,
Zanichelli, Bologna, 1993.
Gambetta A., Funghi e insetti nel legno. Diagnosi, prevenzione, controllo, Nardini editore,
Firenze, 2010, 160 pp.
Giurato R., Finitura e lucidatura nel restauro del mobile, Il Castello editore, Cornaredo,
Milano, 2007, 112 pp.
Hayward C.H., Il restauro dei mobili antichi, Il Castello editore, Cornaredo, (Milano),
2003, 144 pp.
Liotta G., Gli insetti e i danni del legno. Problemi di restauro, Nardini editore, Firenze,
1994, 152 pp.
Matteini M., Moles A., La chimica nel restauro. I materiali dell’arte pittorica, Nardini
editore, Firenze, 2007, 408 pp.
Ordonez C., Del Mar Rotaeche M., Ordonez L., Il mobile. Conservazione e restauro,
Cardini editore, Firenze, 1996.
Perugini G., Il restauro dei dipinti e delle sculture lignee. Storia, teorie e tecniche, Del
Bianco Editore, Colloredo Montalbano (Udine), 2004, 311 pp.
Pieresca G., Il Legno e l’arte di costruire mobili e serramenti, Hoepli Ed., Milano, 1991,
466 pp.
Rodd J., Restauro e manutenzione dei mobili antichi, Fratelli MELITA Editori, La Spezia,
1993.

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Trevisan M.G., Il restauro dei mobili e degli oggetti d’antiquariato, De Vecchi editore,
Milano, 1991.
Trevisan M.G., Ragazzo E., Guida al restauro dei mobili antichi, De Vecchi editore,
Milano, 2009, 152 pp.
Turco A., Coloritura verniciatura e laccatura del legno, Hoepli Ed., Milano, 1985, 652 pp.
Vaccari A.V., Dentro il mobile - storia, antiquariato e restauro del mobile italiano,
Zanichelli Ed., Bologna, 2005, 360 pp.

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10 – ICONS

10.1 The construction of icons

10.1.1 Introduction
In this context the “icon” is considered as an image on a wooden basis. Cases such as painting
on metal, on stone, on canvas, etc, are not considered here.
Methods and principles of conservation of traditional icon painting, that is Russian icons,
originating from Byzantine, are assumed as a basis. However, besides Russia and Greece
which are first of all associated with icon painting, this art exists in other countries such as
Serbia, Bulgaria, Rumania, Poland, Ukraine, Belarus, as well as Egypt (Coptic icons),
Ethiopia, Near East (Melchites icons).
Despite the similarity of processes of manufacturing icons, in each of these regions there were
local features of painting techniques and the applied materials, changing throughout centuries.
This should be considered when choosing methods of restoration, preliminary having studied
sources describing their peculiarities and data of technical examination. For example, for the
Greek icons characteristic are mixed techniques with application in multilayered structures of
various materials, including wax.
East icon painting was not always made using egg tempera, but also glutinous binding media.
Moreover, it was not always varnished with protective layer, what made it very sensitive to the
influence by water solutions, including the process of consolidation. In icons originating from
Eastern Europe countries we find gypsum grounds, which react differently to consolidation.

10.1.2. Technique and materials

Icon supports are made of well dried seasoned wood, mainly soft, low resin kinds with
homogeneous structure. There was enough width of one board for small icons; for large icon
panels the boards were stuck together. On the reverse side (and later on both plank ends) of the
panel slats were inserted, made, as a rule, from harder wood, for preventing the deformation of
the wood panel (Figure 10.1, left). On the front side, the central part of a board was carved

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out, dividing the surface into a hollow area (kovcheg) and borders; the sloped edge between
hollow area and borders is called luzga (Figure 10.1, right).
Before application of the ground on the glued board a piece of cloth, the so-called pavoloka,
was often pasted. Sometimes pieces of this cloth were pasted to cover the joints of the boards,
knots and other defects of the wood. Since the end of 18th century on cheap icons a cloth could
be replaced in paper.

Figure 10.1 - Reverse side of the panel with slats (left);

grounded panel with kovcheg, luzga and borders (right).

The icons ground, known as levkas, was prepared from collagen glue (animal or fish glue) and
“gesso” (gypsum, chalk, or their mixture). It was applied in thin layers one over the other in
several stages, after which it was dried and polished.
Then a preparatory sketch on the levkas, with a brush by hand, or mechanically copied from
model manuals, was drawn. To make the sketch contours visible through the painting and
gilding layers, they were often incised in the ground; this was called grafja.
A traditional technique of icon painting is egg tempera in which as binding media the
emulsion on the base of an egg yolk is used. There are other but rare binding media, like gum,
animal glue, and vegetable glue. The basic pigments used in icon painting were of mineral

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origin; organic pigments, as a rule, are less resistant to external action, but due to their
transparency and colour intensity they considerably enriched the palette of icon painters.
A protective layer was put on the ready image, for this purpose oil-resin varnishes of various
composition were applied. Olifa (drying oil), prepared on the base of linseed oil boiled with
siccatives, was the most widespread protective coating in the Russian icon painting.

10.2 Degradation and damages of icons

All materials constituting the multilayered structure of an icon are subject to climatic
influences, and cycles of temperature-humidity that lead to degradation. As on the whole the
icons manufacturing processes are similar to early Italian works of art, we will not consider a
problem of conservation of a wooden support and of influence of insects and microbiological
factors, since they are considered in the corresponding chapter “Wood artefacts”.
One of the main consequences of changes in temperature-humidity cycles are layer decohesion
and detachments on different levels: pavoloka can separate from the board, levkas from the
board or from pavoloka (blisters or longitudinal deformations are formed, Figure 10.2 left and
right), paint film from levkas (Figure 10.3); besides we can observe internal layer detachments
within the ground. These damages which have been not corrected in due time, lead to losses of
levkas and paint layer.

Figure 10.2 - Detachments of levkas with pavoloka (left), and detachments of levkas (right).

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Figure 10.3 - Flaking of the paint layer.

The most widespread degradation of levkas and paint layer is the formation of cracks-
craquelure in the course of drying and ageing of constituting materials (Figure 10.4, left and
centre). Excess of glue in levkas provokes rigid craquelure with the raised edges (Figure 10.4
right).

Figure 10.4 - “The Mother of God of Kikkos” (Greece, XVIII century, private collection):
deep craquelure (left), superficial craquelure (center),
and craquelure with the raised edges (right).

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Other serious problem is darkening of a protective film of olifa or varnish (Figure 10.5). This,
as we already mentioned, because of poor legibility of the image often led, on the one hand, to
periodic “washings” of painting with strong alkalis, which damaged it; on the other hand to
partial or full renovation of painting and formation in due course of multilayered structures
with application at different times of inserts of levkas, where it has lost, and overpainting
(Figure 10.6).

Figure 10.5 (on the left) - Quadripartite icon (Russia, XIX century, private collection):
darkened protective coating.
Figure 10.6 (on the right) - “Selected saints with the Scenes from the Life of St. Nicholas”
(Russia, middle of XVI century, State Russian Museum, Saint Petersburg).

When a new protective layer is put on the old one or when there is excessive thickness of
olifa, its deformation and formation of roughness on the surface are observed (Figure 10.7,
left).
In some case the surface coating does not darken, but loses the transparency and dims, for
example due to films of the egg white (applied in Ukrainian and Belarus icon painting), or
shellac coating under the influence of moisture (Figure 10.7, right).

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Figure 10.7 - Roughness of the surface film (left); destruction of the surface film under the
influence of moisture (right).

10.3 Methods of conservation and restoration of icons

10.3.1 Consolidation of layer detachments of pavoloka,

levkas and paint film
According to traditions of Russian school of conservation, for the consolidation of icons,
materials similar to those employed for their manufacturing are used, that is sturgeon and
rabbit skin glues. These glues are water soluble, therefore they may be reused after softening;
they provide reliability of fixing, are elastic enough and do not introduce alien elements into
the icons. Before the use it is necessary to warm them up in bain-marie at temperature not
above 60-70 ˚С, since at higher temperature and longer warming the glue loses its properties.
If the object is intended to be stored not in a museum with constant climatic conditions, but in
damp places, a preservative should be added into the water solution of glue.
If detachments of the pavoloka or levkas from the board are observed, but the ground is stable

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and homogeneous, on the places requiring consolidation we put a preventive piece of tissue-
paper on 5% glue. In case of the closed blisters of the ground we make two holes with a needle
on opposite edges of the blister and introduce 7-10% warm glue using a syringe. If there are
losses of levkas, the glue can be introduced directly through them. After absorbing of the glue,
while the ground is still damp and elastic, the blister should be thoroughly put down with
Teflon spatula. If it is necessary, after drying of the ground the glue can be introduced again.
A little bit dried up, but still elastic, ground is finally leveled with Teflon spatula and dried up
through an absorbent paper with a warm small iron (at temperature not above 45-50 ˚С). At a
considerable thickness of the ground or in case of detachment of pavoloka on the fixed place it
is recommended to put some weight.
If the painting surface is dust covered or the ground is powdered, for the best wettability and
deep penetration of the glue, the surface is preliminarily impregnated with ethyl alcohol in
water (approximately 1:1) by means of a brush, and then is kept until full evaporation of the
alcohol.
Superficial thin flaking of the levkas as well as paint film (Figure 10.8) is consolidated by
means of impregnations with warm glue. Glue of low concentration (from 1.5 to 3%
depending on density and degree of degradation of the levkas) is used to provide its best
penetration and uniform distribution through the whole thickness of the ground. As plasticizer
for increasing elasticity of the glue, some honey is added to the solution (in the ratio 1:1 by
weight of dry glue). After each impregnation it is necessary to wait as long as absorbing of the
glue is completed, and to repeat the procedure until formation, on the dried surface, of a thin
glue film, that means sufficient saturation of the ground with the glue.
Each subsequent impregnation is made after complete drying of the previous portion of the
glue. After the last impregnation, while the ground and the paint layer are not completely dried
out and keep elasticity, the surface is stuck with pieces of tissue-paper (their size about 10-15
х 20-25 cm) and dried with warm small iron, pressing thoroughly every flake (Figure 10.9).
Before putting it on the surface, the tissue-paper is moistened with the brush to avoid
formation of folds which during drying with the iron can be printed on the surface. If it is
necessary to consolidate a large area, the work is carried out on separate areas of the surface
that allows to dry the surface uniformly with the iron and to prevent its premature drying.

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Figure 10.8 - “Saint Trifon” (XX century, private collection): flaking of the paint layer,
before (left) and after consolidation (right).

A special kind of consolidation is the one through steaming. This method is applied in case of
rigid detachments of levkas, resisting to softening with impregnation of glue, or with bad
penetration of the glue through the surface. Its peculiarity involves the application of abundant
warm glue (usually 3% since it is put once) on the treated position, then a piece of tissue-paper
is put on it, and the surface is gradually warmed through a Teflon film with a small iron till
complete absorbing of the glue. Lastly the surface is dried through absorbing paper as after
common consolidation.
When paint film and all the thickness of the levkas are dried completely (not less than 24
hours) the protective tissue-paper is removed with a wad of cotton wool, which was moistened
in hot water and hardly wrung out. The rest of the glue is carefully removed with a similar
wad and then the surface is dry-cleaned.
During the consolidation of the icons with water sensitive surfaces, synthetic materials can be
used.

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Figure 10.9 - Icon surface covered with tissue-paper in course of consolidation.

10.3.2 Removing of surface grime

Surface grime includes deposits of dust, soot from candles, mould, remains of insects and their
excrements (especially when accumulated under metal covers of icons), splashes of paint, wax
drops etc.
They can be removed from the surface only when you are certain that levkas and a paint layer
have no flaking. If the icon was already consolidated, considerable part of surface grime was
removed when the protective tissue-paper was detached.
From the surfaces well protected with oil-varnish or olifa covering, the surface grime can be
removed with a damp wad.
If the protective varnish coating is transparent and uniform, the removal of surface grime can
be the conclusive process of the object restoration (Figure 10.10). Resistant deposits of surface
grime can be easily removed with ox gall, whose residue is cleaned off with a damp wad.
Wax drops at first are thinned with a scalpel, and then removed with a cotton wool wad
moistened in turpentine.

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Figure 10.10 - Removal of surface grime.

10.3.3 Cleaning
Cleaning of a paint surface depends on the nature of the protective film (its thickness,
uniformity, and dimness degree), and presence of over-painting.
Prior to the beginning of works it is necessary to carefully examine the icon under the
microscope to have a clear idea of the sequence of layers and the applied materials.
For cleaning, the following solvents are applied: ethyl alcohol (often mixed with turpentine in
different proportions or with addition of spike oil), ethylene glycol, monomethyl ether,
dimethyl sulphoxide, etc.
Nowadays gels are being introduced into practice, which bind molecules of solvent and
prevent its deep penetration into the layers.
The chemical analysis of a surface film helps to define its components and correctly to choose
the solvent. All cleaning works are carried out under a microscope that provides the control of
the condition of the surface and allows to avoid damages.

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THINNING OF THE SURFACE FILM

Cleaning does not produce the full removal of the protective film, but only its thinning; the
thin layer of the original film which remains on the surface attests the work done was correct
and the author’s painting was not damaged during the cleaning (Figure 10.11).
Cleaning always begins on a test segment on the least important area of the image (as a rule,
on the background or borders) for choosing the methodology.
Solvent selection begins with the less effective ones, and, in case of their inefficiency,
gradually raising the treatment degree. The sign of effectiveness of a solvent is the colouring
of the wad, which was moistened in solvent, in yellowish colour of the darkened varnish
during cleaning of the segment chosen for test.

Figure 10.11 - Quadripartite icon (Russia, XIX century, private collection):

thinning of the surface film.

Thin layers of soft varnish can be thinned by means of a cotton wool wad moistened in
solvent. Extra care should be taken of the late icons of the 19th - early 20th centuries as their
paint layer has not yet polymerized completely and is very sensitive to the solvents.
Considerably thick and strong protective coating should first be softened by solvent. It is an

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expedient to use a compress of flannel, moistened in solvent and well wrung out. The
compress of flannel is put on a test segment and, based on the degree of its action, the
optimum time of application is chosen. It is important to watch the protective film not
dissolving the whole layer. The softened layer of varnish or olifa coating is removed with a
cotton wool wad and then, by means of a microscalpel under a microscope, varnish layer left
is leveled. If necessary, during the work the surface is humidified with turpentine which is
neutral to old painting (CESMAR recommends to replace turpentine with ligroin).
Various pigments have different degrees of adhesion with the protective film, therefore on
different segments it is necessary to vary the time of treatment and sometimes the choice of
the solvent.
When the protective coating is not uniform, with the presence of clots and roughness, it is
forbidden to apply solvents, in order not to damage a paint layer under a thin varnish film. It is
necessary to preliminarily level the surface film mechanically with a scalpel, or abrade it with
pumice or emery paper.

REMOVAL OF OVERPAINTING
When there are overpaintings or partial re-paints, before starting their removal it is necessary
to carry out complete diagnostics of the icon (using a microscope and methods of technical
examination) for defining the safety level of the layer of author and the expediency of the
cleaning.
Over-painting can be:
- continuous, covering all painting surface;
- partial, laying on the most damaged segments (including the re-painting on inserts of
the restoration ground in lacunas of the original material) or on the parts where for renovation
high qualification was not required, especially on the background and on the borders of icons
(Figure 10.12).
Irregularities of the surface before re-painting can be covered by a new priming.
Sometimes the older image is completely covered by a thick layer of levkas and then over-
painted; in such cases also the composition of the image changes (Figure 10.13).

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Figure 10.12 - “Sinaxis of Archangels” (Romania, XIX century, private collection):

icon with overpainting on the background (left), and after the cleaning (right).

Figure 10.13 - “The Mother of God of Tolga” (Russia, XIX century, private collection): test of
cleaning, original painting (fragment of the composition “Entrance to Jerusalem”) under the
layers of the new ground and overpainting.

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On a test segment, you should make a cleaning layer-by-layer for discovering type and
sequence of overpainting layers, intermediate layers of olifa or varnish, features of authentic
painting (Figure 10.14). It is expedient to carry out this cleaning mechanically, without
application of solvents before defining materials and methods of original painting, not to
damage layers which can be especially sensitive to treatment with solvent.

Figure 10.14 - “ The Mother of God of the Sign” (Russia, XVIII century, Icons Museum
of Peccioli, Italy, collection of Francesco Bigazzi): the segment of stratification
on the border; original painting is covered with blackened olifa, then repainted and covered
with a protective layer also darkened.

Then studying the method to remove the superimposed layers and to thin the original surface
film is done. The oil overpainting is easily removed with alcohol-turpentine solution. Selection
of solvents for the removal of egg tempera overpainting is defined by its thickness and
pigmentary composition. In general the work is being done as described in the previous
section “Thinning of the surface film”. Especially solid layers, for example ochre, if they lay

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on intermediate layer of olifa, is recommended to abrade mechanically with pumice or emery

paper to reduce time of solvent action. Approaching the original surface it is necessary to use
solvents with special cautious so that not to damage the finishing coating impregnated with
olifa and hence particularly vulnerable.

CASES OF LIMITED APPLICATION OF SOLVENTS OR THEIR COMPLETE EXCLUSION

Works on cleaning icons under a microscope, which have been conducted since the 70s, have
enabled to make a number of observations, which have led to restrict the application of
solvents or, in some cases, to their complete elimination.
The application of coloured lacquers (mainly green and various shades of red) for more
decorative effect in icons painted in the 17-18th centuries is well known. In these cases
restorers as a rule show due care, being aware of their sensitivity to solvents. But researches
have also revealed the application of yellow organic lacquers in icons of the 13th century (for
example, in the flesh paint of the “Mother of God on a throne with Sts. Nicholas and
Clement”, collection of the State Russian Museum, Saint Petersburg), and of yellowy-brown
lacquer in the icon painting of the 16th century. These lacquers are not easily distinguishable
under a layer of darkened olifa, and the restorer should be especially attentive at the initial
stage of research to reveal them, as short-term action of solvent results in their complete
disappearance.
As a rule, cleaning of icons is sophisticated when the background gilding is simulated by
means of yellow lacquer on leaves of white metal (tin, aluminum, silver; Figure 10.15).
Besides coloured lacquers, special sensitivity to solvents is inherent to oil painting. Along with
pure oil technique applied in late icon painting, researches confirmed the application (since the
17th century) of a mixed technique in which egg tempera and oil layers alternate.
A special case of cleaning the icons executed in oil technique is the removal of the pebbled
olifa film from their surface. In similar situations, in order to avoid damage of the thinnest
paint layer, it is recommended to use a mechanical thinning of the surface coating working
with microscalpel under a microscope (Figure 10.16).
Another contraindication to application of solvents for cleaning icons is a great olifa content in
the ground (the recipes are known, recommending to add a little olifa during preparation of

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levkas for its better plasticity). Visually such grounds may be recognized based on their
yellow-brownish tint. During the application of solvent, it penetrates into the ground through
cracks of craquelure and causes ground softening resulting in weakening of cohesion with the
paint layer. This leads to losses of paint.

Figure 10.15 (on the left) - “The Mother of God of Kazan” (Russia, XIX century,
private collection): cleaning of the background gilding simulated
by means of the yellow lacquer on leaves of tin.
Figure 10.16 (on the right) - Test of cleaning of the oil painting covered
with pebbled olifa film.

10.3.4 Filling of lacunas in the ground and in the paint layer

To prevent absorption of moisture by groundless wooden support and to prepare the object for
the following retouching, the lacunas of the levkas (and of the paint film if it is thick enough)
are filled with a restoration ground. It is prepared from the same materials, as were used at
icon manufacturing, that is chalk and sturgeon or rabbit glue.

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Before application of a new ground the lacunas are saturated with warm 2-3% glue and, after
drying, with the glue of higher concentration to form a thin film of glue on the surface. Doing
this it is necessary to avoid accumulation and overflow of glue, as well as soaking of edges of
the old levkas. Then warm 8-10% glue is mixed up with chalk to obtain homogeneous dense
paste, which is put with a palette knife. When the levkas is thick, the restoration ground is put
layer on layer to provide uniform drying and to avoid its cracking. The level of the new
ground should be above the original one because during drying it shrinks, and then it will be
thinned when polished. Dry inserts of the ground are polished with a flat surface of natural
cork slightly moistened with water, or with a fine-grained emery paper without water. During
polishing it is necessary to be careful not to damage the surrounding surface of the painting.
The finished inserts of the restoration ground are covered with a thin layer of mastic or
dammar varnish mixed with turpentine in the approximate ratio 1:4, for protection against
washing out during retouching and prevention of the absorption of paint in the ground (Figure
10.17).

10.3.5 Retouchings
To achieve integrate perception of a work of art retouchings of losses of the painting are
carried out. Some main principles are observed:
- retouchings are carried out strictly within the borders of losses of the original painting;
- retouchings are carried out with reversible materials (as a rule, with water colour) which are
easily deleted without risk of damaging the original paint layer;
- retouching should be easily distinguishable and should not create the impression of
resemblance with the original texture. Therefore different restoration schools use various
methods: retouchings with points, strokes etc. (Figure 10.18).
- the lost details of the image are not reconstructed.

10.3.6 Application of protective varnish

After restoration a thin protective film of a suitable varnish is applied on the icon surface. For
this purpose mastic varnish is used. It is mixed with turpentine in the ratio from 1:5 to 1:2,
depending on nature of the surface and absorption capacity of the varnish. A thin layer of the

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varnish is applied with a gauze-cotton wad, and after drying in case of necessity the procedure
is repeated to obtain a uniform film.

Figure 10.17 (on the left) - “The Mother of God of Kazan, Resurrection, St. Nicholas and
selected saints” (Russia, XIX century, private collection): inserts of the restoration ground.

Figure 10.18 (on the right) - “The Mother of God of Bogolyubovo” (Russia, XIX century,
private collection): retouching with points.

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10.4 Examples of conservative interventions

10.4.1 Icon “The Mother of God of Korsun”

(Russia, 17th century, private collection)
The icon has arrived for restoration with extensive detachments of the ground and of the paint
layer, while considerable parts of the levkas with painting were lost (Figure 10.19, left). A part
of fallen off fragments was kept in a small bag (at the top of the photo in the above figure),
and some pieces of the ground were randomly glued with synthetic glue. The borders and the
background of the icon were covered with a silver oklad (cover of the icon) with traces of
gilding. Because of its poor condition it was not expedient to dismantle the oklad (also
because its restoration was not stipulated in the present work), so only the grime was removed
from its surface.
Before consolidation, the painted part of the icon was impregnated with ethyl alcohol mixed
with water (1:1) to remove the dust from the surface and to improve the penetration of the
glue. Consolidation was done by repeated impregnations with 1,5% warm sturgeon glue.
Places for fallen fragments of the levkas were chosen in accordance with their colour,
thickness, features of craquelure, etc., then the fragments were glued with 7% glue. After
protecting the large blister (on the left of the face of the Virgin) with tissue-paper, 5% glue
was injected with a syringe.
When all surface was protected with a tissue paper and dried with a small iron, the silver
nimbus of the Virgin with Christ was dismantled (Figure 10.19, right).
The grime and the dust which were accumulated under it were removed with a soft damp
brush, and then consolidation of the damaged levkas was done on this part too. After removal
of tissue-paper, the fragments of levkas previously pasted with synthetic glue were moistened
with acetone. Then the softened glue was removed, and fragments were fixed with 7%
sturgeon glue. Finally a covering with tissue paper and drying with a small iron were done.
The painting examination with a microscope and test cleanings showed the presence of two
layers of overpainting on clothes; in addition, on the flesh painting some other layers applied
in different times were revealed. Removal of overpainting on clothes and on the background
was done by means of compresses with ethylene glycol monomethyl ether.

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Figure 10.19 - “The Mother of God of Korsun” (Russia, XVII century, private collection):
before conservation (left) and after consolidation with nimbus dismantled.

On the flesh painting, owing to non-uniformity of distribution and fragmentary preservation of

the original paint layer, the cleaning was carried out mechanically with a microscalpel under
the microscope. On old inserts of the ground, in lacunas of the author’s painting, the
overpainting was preserved, which are not too much differing in colour from the original.
Such preservation of the intermediate re-paintings enables to reduce the area of restoration
retouchings and gives the idea of the history of the icon’s life.
Examination through a microscope showed, that the olive-color background belongs to the
first renovation of the icon, under which a gilding is visible. Probably, originally the icon had
no metal cover. However, because now all the background is covered with the silver oklad,
and the authentic gilding poorly remained, this over-painting was preserved.
Lacunas of the levkas were filled with the ground with small addition of a dry ochre pigment,
that neared the tone of the inserts to the coloring of the original painting and facilitated the
retouchings process (Figure 10.20, left).
Retouchings were done with water colours. According to the task set by the owner of the icon,
some details of the image were re-constructed during retouching on the basis of the remained
contours and of fragments of the authentic painting (Figure 10.20, right).

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Figure 10.20 - “The Mother of God of Korsun” (Russia, XVII century, private collection):
after cleaning, with inserts of restoration ground (left), and after complete conservation
treatment (right).

10.4.2 Icon “Last Judgement”

(North Russia, middle of the 16th century, private collection)
The icon represents a fragment of the composition “Last Judgement” (Figure 10.21, left),
lateral parts of a board are lost. Through examination, two continuous layers of over-painting
and numerous inserts of different times were revealed (Figure 10.21, right). A feature of this
icon is the wide application of mixed techniques: the background is covered with a thin
transparent layer of light-yellowish lacquer, but at the bottom in the scenes of infernal tortures
the backgrounds are executed in a brown lacquer over a pale-green layer of copper-green
colour; mountains are painted in light ochre with shades of brown mineral pigment; under-
tints are softened and enriched with a layer of brown lacquer (Figure 10.22, left). Some other
details of the image are also painted with yellow lacquer. Such abundance of coloured
lacquers, sensitive to the application of solvents for cleaning, led to the choice of a mechanical
way of cleaning under a microscope on the above-stated parts.

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Figure 10.21 - “Last Judgement” (North Russia, middle of the XVI century, private
collection): before conservation (left), and in course of cleaning (right).

Cleaning was done layer by layer. The surface over-painting was removed with ethylene
glycol monomethyl ether with a wad; intermediate (second) over-painting was first softened
with compresses impregnated with ethylene glycol monomethyl ether and then removed with
microscalpel under a microscope, and after that the underlaying protective film was thinned.
The work was carried out with great (16-fold) magnification, as the original surface has a
visibly pronounced relief, caused by craquelure with rigid raised edges; there was risk of
damaging their top in the course of work. This relief and the abundance of minor losses of the
fragile coloured lacquer led to the need to level the surface up to the previous renovation; this
was done by covering with a layer of a liquid ground. The presence of strong animal glue over
the old protective coating had made it very hard and fragile; therefore, in order to avoid chips
and tiny losses during the cleaning, the surface was slightly moistened with ox gall or water
with alcohol (1:1). The same solution was used for softening layers of the re-priming before
their removal, since this ground had been impregnated with olifa and could not be softened
with water only.
In the course of the work, another feature of the techniques of execution of the icon was
revealed: details painted with cinnabar appeared to be very unstable not only to solvents, but

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also to water solutions. According to ancient sources, cinnabar was sometimes prepared with
vegetable glue binding. Therefore, before the filling of the lacunas in levkas with the inserts of
the ground, the areas with cinnabar details were protected by a thick layer of mastic varnish,
which was removed upon termination of the process.
Minimal retouching was done with water colours, some losses of the levkas were preserved
without filling them with restoration ground (Figure 10.22, right).

Figure 10.22 - “Last Judgement” (North Russia, middle of the XVI century, private
collection): brown lacquer for modeling the shades of under-tint layer on the mountains (left),
and after conservation (right).

Bibliography

AA.VV., The Conservation of Icons: An Approach Towards Problems, Methods and

Materials Used in Conservation Laboratories Worldwide, Proceedings of the
International Meeting of the Icons’ Working Group, Athens, 10-15 October 1995,
ICOM-Greece, Athens, 1999.
Avillez M., Vourvopoulou C., Conservation of a Greek icon. Technological and

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 SCIENCE AND CONSERVATION ... c. 10 – ICONS 344

methodological aspects, Article from: e_conservation, the online magazine, N. 6,

September 2008, pp.37-55.
Bentchev I., Haustein-Bartsch E. (herausgegeben von), Ikonen: Restaurierung und
naturwissenschaftliche Erforschung: Beiträge des Internationalen Kolloquiums in
Recklinghausen, 1994.
Bobrov Yu.G., Bobrov F.Yu., Conservation and restoration of easel tempera painting,
Moscow, 2008 (in Russian language).
Filatov V.V., Conservation of works of Russian icon painting, Мoscow, 2007 (in Russian
language).
Harrison L., Ambers J., Cartwright C., Stacey R., Hook D., Entwistle C., Sacred to Secular:
the care and conservation of Orthodox icons at the British Museum, in: The Object in
Context: Crossing Conservation Boundaries, D. Saunders, J.H. Townsend, S. Woodcock
eds., International Institute of Conservation of Historic and Artistic Works, London,
2006, p. 317.
Harrison L., Ambers J., Cartwright C., Stacey R., Orthodox icons at the British Museum: an
approach to ethical conservation practice, Proceedings of the International Meeting
“Icon: Approaches to research, conservation and ethical issues”, Archaeology and Arts
Magazine, S. Stassinopoulos and A.Lambraki (eds.), Athens, 2006, pp. 131-133.
Jolkkonen N., Fullenwider H.F. (eds.), Icon Conservation in Europe. Proceedings of the
meeting in Frankfurt am Main, 24-28 February 1999, The Valamo Art Conservation
Institute, Uusi-Valamo, Finland, 1999, 160 pp.
Jolkkonen N., Nikkanen H. (eds), Changes in Post-Byzantine Icon Painting Techniques,
ICOM Committee for Conservation Interim meeting on the Icon research area,
Copenhagen, Denmark, 14-17 October 2001, The Valamo Art Conservation Institute,
Uusi-Valamo, Finland, 2001.
Naumova M.V., Conservation of Icons. Methodical recommendations, Grabar Art
Conservation Center, Moscow, 1993 (in Russian language).
Wolde, S., The Preservation and Conservation of Art Works in Present-Day Ethiopia,
Proceedings of the First International Conference on Ethiopian Art. London, England:
Royal Asiatic Society, 1986, pp. 131-135.

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11 - TEXTILE FINDS

11.1 Morphology, characteristics

and properties of textiles

11.1.1 Fibres
Textile objects of historical interest are made by fabric, frequently combined with other
materials (for instance garments or upholstery). Fabrics in their turn are obtained
interlacing yarns of four natural fibres: cotton and linen (cellulosic), wool and silk
(proteinous).
Fundamentally fibres are built up by polymerisation (also called condensation), that is the
combination of molecules until long chains are formed. The morphology of the fibre
corresponds to the nature of these fibrous structures: one or more molecular chains,
arranged parallel to each other (or else spiralling around the axis of the fibre) and relatively
stable.

CELLULOSIC FIBRES (COTTON AND LINEN)

They are obtained by polymerisation of molecules of ß-glucose, the structural formula of
which can be simplified according to Figure 11.1.
Linen or very strong cotton fibres are made up by straight chains of at least 2,200
molecules.

Figure 11.1 – Simplified structural formula of molecules of ß-glucose.

PROTEINOUS FIBRES (WOOL AND SILK)

Wool fibres are made up by polymers of 18 different amino acids. Being amphoteric, these
have a terminal acid group (-COOH) and a basic one (-NH2): the acid group of a molecule
can combine with the basic group of another and, through the elimination of a molecule of

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water, constitutes a bond called peptidic that is at the base of the process of polymerisation.
The general structural formula of an amino-acid is reported in Figure 11.2.

Figure 11.2 – Structural formula of amino-acid.

In the case of cystine, the amino-acid from which wool is mostly formed, the radical R
forms a further bond, beyond the peptidic, that links two adjacent molecular chains. The
keratin formula presents, instead, two chains of amino-acid, going helicoidally, joining
across a transverse bond made up of two atoms of sulphur. The presence of this second
bond determines a three dimensional structure due to the forces of lateral attraction, which
confers to the wool a resistance to the solvents capable of splitting the only peptidic bond
that characterises its behaviour, giving stability and durability. Its extensibility must, at
least be partially, owed to the helicoidal form of the molecule.
Silk is a continuous filament, each one composed of two filaments of fibroin surrounded
by a coating of sericin. Fibroin and sericin are also produced by the polymerisation of
about 15 amino-acids, the formula differing according to the area of provenance of the
fibre. Silk differs from wool because it does not contain keratin and therefore has no
transverse bonds with double atoms of sulphur. Its great mechanical resistance depends on
the high crystallinity of the fibre.
The performance and look of textile fibres and, therefore, of the yarns made from them,
depends on their characteristics such as length, shape, density, surface structure and
crystallinity.
The length of the fibre is correlated with mechanical resistance to many stresses, in
particular to tension.
The surface conformation of the fibres substantially determines the reaction to light: fibres
with smooth surface reflect the greater part of light with which they are invested, while
those with rough surface absorb it.

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The degree of crystallinity of the fibre influences its response to changes of humidity with
the environment (moisture regain figure) and its mechanical resistance. A fibre with a low
level of crystallinity tends to absorb humidity with great ease because this change mostly
affects the surfaces and amorphous parts of the fibre; at the same time each fibre has less
resistance to mechanical stress.
The density of the fibres (weight per unit of volume) determines the way in which the
threads and textiles drape.

11.1.2 Yarns (or threads)

Reactions of textiles to mechanical stress are closely related to their structure, obtained
through two fundamental stages: the assembly of the fibres into yarns and the creation of
the textile by interweaving.
In the yarn numerous fibres lye parallel to each other, to a certain degree with the help of
twisting. In this new situation the fibres are submitted to a forced cohesion and the thread
reacts as a system to the application of tension, twist, bending and their combination. The
character of this system is the basis of the strength of the thread: its resistance is founded
on the combination of the individual elements of which it is comprised.
By contrast the weakness of one or more elements is automatically transferred to the whole
system.
From the mechanical point of view the peculiar function of the twist, in contrast with the
technical construction of many other materials, is that of producing its effects without
substantially compromising the flexibility of the yarns. It is true also that a thread with
high twist, in comparison with other conditions, is stronger but less flexible than the one
with less twist.

METAL THREADS
So called silver and gold threads are obtained by twisting a soft laminate of metal in a
spiral around a core thread, usually of silk. Sometimes the laminate is applied to a support
of a membrane of parchment or paper. The metal laminate is usually made from an alloy,
such as copper and silver for example, covered by a layer of a richer alloy, such as copper
with silver and gold. In this way the brilliance of silver and gold is obtained with less cost
of noble metal, but the characteristics of the metal corrosion tend to get worse more
rapidly.

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11.1.3 Textiles
A textile, in the narrowest sense, is the result of interweaving between one group of threads
(the warp), disposed parallel to each other and a yarn (weft) which runs at right angles to
these from one side (the selvage) to the other.
Like other techniques of interlacing threads, weaving gives rise to a coherent system, the
strength of which is founded on the evenness of the distribution of stress on the threads that
take part in its formation.
As for the yarn, then, the weakening of each of the components and the eventual
breakdown puts a load on the entire textile and can rapidly result in a tear.

MECHANICAL PROPERTIES
Altogether, mechanical properties determine the reaction of threads and textiles to
mechanical stress.
The most significant to emerge from this examination are resistance to tension,
extensibility, flexibility, elasticity and plasticity.
• The resistance to tension of a fibre is conventionally measured by the weight
necessary to break it, being directly proportionate to the length of the molecule, to
the level of crystallinity and to the compactness of the bundle of molecules.
• Extensibility is the lengthening of a fibre under tension that it can suffer without
breaking. Wool can elongate easily by 10%; silk, cotton and linen much less.
Normally fibres extend more easily when they are wet.
• Flexibility is the most proper characteristic of textiles; it is tied to the shape, weight
and density of the fibres. The decrease of flexibility is the source of much damage
suffered by textiles.
• Elasticity is the measurement of the stretch of which a fibre is capable under
tension that vanishes when the tension is removed. It is a property that tends to
diminish with age and use.
• Plasticity of a fibre under tension measures the amount of stretch that remains when
the stress is removed. Normally it is correlated with fineness of the fibre. Wool is
the most plastic among the natural fibres, and its plasticity becomes greater under
the action of heat and humidity.

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11.1.4 Fibres identification

OPTICAL MICROSCOPE OBSERVATION

The analysis of fibres constituting historical artefacts (textile and paper) plays an important
role in order to reconstruct their history and for a correct conservation strategy.
According to their origin fibres are generally divided in natural fibres and techno-fibres;
usually, the analytical interest is towards to natural animal and vegetal fibres, that represent
the main support of a wide range of artefacts. Animal fibres are wool (from sheep, goat,
camel) and silk produced by some insects. Vegetable fibres are cellulose based and are
distinguished in fibres from seeds (cotton), from stems (hemp, flax), from leaves and fruits.
Optical microscopy is one of the most common scientific method for examination of
material structures otherwise invisible to the naked eye, by using reflected or transmitted
light through a magnification from 10 to 500 times. Moreover, fibres analysis can be
performed by Scanning Electron Microscope (SEM), usually after coating the sample by
thin layer of electrically conductive materials (gold).
Microscope analysis makes possible fibres identification through their structural profiles,
and shed some light on state of its conservation (e.g. detection of presence of microbial and
insect activities).
First of all it is necessary to prepare the sample by removing the extraneous substances
from the fibres surface by means of organic solvents (trichloroethylene, ether). If the fibres
are heavily sized with starch or coloured, it is necessary to treat them in a test-tube with a
boiling solution (1% sodium carbonate, 3% hydrochloric acid). After this treatment, the
fibre looses the colour but for a better microscopic resolution, it is recommended to dye the
fibres by a iodine-sulphuric reagent.
For paper samples it is necessary to manually tear the sample in small pieces, then boil
them to obtain homogeneous fibre suspension. Then a small amount is stratified on a slide,
let dry on warmed surface and proceed through the chemical treatments.
The fibre structural morphology can be described as follows:
Wool. Wool fibre has irregular, roughly cylindrical, multi-cellular structure with tapered
ends. Through microscope observation, three basic layers are distinguished: epidermis
(outer layer), cortex (middle layer) and medulla (inner layer). Medulla is seen only in
coarse and medium wool fibres and by a highly powerful microscope.

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Silk. In raw silk fibre, two filaments can be distinguished with an elliptical shape under
microscope observation. Wild silk, or tussah fibre, has different morphology than the
cultured silk. It is flattened, coarse, thick and broader fibres have fine, wavy lines all across
its surface, whereas cultured silk is composed by narrowed fibres with no marks.
Cotton. The cotton fibre is a single elongated cell. Under microscope it looks like flat,
spirally twisted ribbon like tube with rough granular surface. Its colour can change from
white to reddish. Fibre length is between 10 and 60 mm.
Hemp. Hemp fibre looks like having multiple sided cylindrical filaments with between 30
and 70 mm in length. Fibres are slightly flattened with longitudinal stripes and rare
transverse irregular stripes. Their colour is between ivory and beige. In the raw hemp the
fibres are covered by encrusting substances like lignin.
Flax. Flax fibre shows multiple sided cylindrical filaments with fine pointed edges. The
filaments are spaced by nodes, looking like a bamboo stick. Hemp fibres are between 6 and
50 mm in length. Distinguishing between flax and hemp is not easy: hemp has a more
irregular and flattened shape, and with multiple nodes. Moreover the outside layer is less
transparent than the flax and the ends are rounded instead of pointed.

CHEMICAL TESTS
Fibres analysis through chemical tests is based on the assumption that they react with
chemical reagents in different ways according to their chemical composition and structure.
Chemical spot tests are destructive but they are widely used because they allow the
identification of specific elements of the sample with a minimal amount of material. Some
of the tests are listed below.
Burn test. Animal fibres burn slowly with a smell similar to burnt hair or feather, leaving
abundant black brittle residue; natural vegetal fibres burn quickly, smelling like burnt
paper, and leave soft and fine ashes that turn to dust if touched.
Sodium hydroxide test. Let the sample boiling for 30 minutes in 10% NaOH: the animal
fibres (wool and silk) dissolve; cotton forms soda-cellulose; flax remains practically
unaltered; hemp and vegetal fibres containing lignin become yellow.
Treatment with acids. Concentrated sulphuric acid (H2SO4) induces the decomposition of
all the fibres except wool, which dissolves only if the acid solution used is hot. With
concentrated nitric acid (HNO3), wool becomes yellow-orange and then dissolves; silk
becomes yellow; vegetal fibres do not change colour and do not dissolve.

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Schweitzer test. Wool dissolves in a different way than silk; cotton swells before
dissolving; hemp dissolves slowly in relation to its contaminator.
Iodine-sulphuric test. Two solutions are needed for this test. The first contains 1 g of
potassium iodide (KI) and 0.5 g of iodine-powder, dissolved in 100 ml of water. The
second solution is obtained mixing 40 ml of bi-distilled water with 20 ml of glycerine, than
adding 60 ml of concentrated sulphuric acid, drop by drop and under cooling and stirring.
Fibres or part of them containing lignin turn their colour into yellow, while cellulose based
fibres turn their colour in blue.
Cotton fibres turn into blue as well, while in flax fibres the outside layer turns into blue,
transverse stripes turn into dark blue and the inside layer turns into yellow. Raw hemp
turns into green-blue in the middle and yellow on the outside because the presence of
lignin. Treated hemp, without lignin, turns into green.
Fluoroglucinol test. The reagent is prepared adding concentrated hydrochloric acid (HCl)
to a 1% fluoroglucine in alcohol solution. Fibres stain in red, but the colour is strongly
related to the lignin content:
cotton = no stain (no-lignin); flax = slightly pink; hemp = dark red.
Lugol’s iodine test. Dissolve 2 g of zinc chloride (ZnCl2) into 10 ml of distilled water and
2 g of potassium iodide (KI) in 5 ml of distilled water; mix the two solutions together (it is
important to add some iodine grain). This reagent is able to stain the fibres as follows:
cotton = red/purple; flax = dark purple; fibres with lignin = dark yellow; silk = yellow.

11.2 Decay of textile fibres

Textile fibres suffer, equally with all organic materials, an unstoppable process of
molecular decay, by reason of their intrinsic nature.
The process of polymerisation or condensation is reversible: the presence of certain
external conditions can determine the inverse reaction, called hydrolysis (or de-
polymerisation), that happens through the absorption of molecules of water: the internal
bonds of the chains weaken and these break into shorter chains. Different methods of
chemical testing confirm that the more the chains shorten the more, proportionately, the
fibres weaken.

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11.2.1 Decay in archaeological microclimate

In the microclimate of archaeological contexts some of the main phenomena of fibres
decay, such as photochemical degradation and damage produced by pollution, became
negligible; on the contrary they suffer irreparable damage, sometimes till complete
destructions, due to thermal and hygro-chemical factors.
In conditions of high humidity, fading of colour and weakening of the fibres is
accentuated; while too dry an atmosphere causes loss of flexibility, elasticity and resistance
to tension. Experience shows that in very humid environment, the possibility of
biodegradation from attack by micro-organisms and insects is increased while the risk of
damage of a physical nature is lessened. Insect attack is a great danger for proteinous
fibres; when they prosper in a textile they weaken it on the one hand by eating it and on the
other by depositing excrement. This is often acid in nature, which can cause further
deterioration.
Also important is the acid/basic balance in archaeological sites, mainly because they are
frequently wet or damp. Wool and silk react better than cotton and linen in an acidic
situation and/or a damp or waterlogged one. In a similar condition the laminates of metal
threads, in particular those of copper and of its alloys, are attacked through electrolytic
phenomena favoured by high humidity; on the other hand any membrane (the underlying
proteinous layer of some gold threads) is attacked by water and alkaline conditions.
The influence of temperature on the conservation of textiles is almost negligible if they are
kept within the middle range; proteinous fibres are more sensitive than cellulosic ones at
high temperatures and silk more than wool.

11.2.2 Typology and chronology of textile finds

Textiles are, among all organic materials, the most rare archaeological finds because of
their extreme perishability. By side their saving and first aid operations are frequently very
problematic and risky.
As far as their age is involved, archaeological textile can be classified as: pre-historic,
antique and late-antique, medieval.
Generally speaking, they are mainly the remains of garments worn by the dead body, or
items of the outfit for the deceased. Inside the grave their surviving becomes extremely
difficult. Frequently a high level of humidity, if not the presence of water, promotes fibre’s
de-polymerisation by hydrolysis and microbiological and insects attack. For these reasons

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the most plentiful findings of ancient textiles came from geographical areas with a dry
climate, as in Egypt; or where inserting textiles in the graves is very set in the social habits,
as in different countries of Latin America. More recently large quantities of archaeological
textiles came out from excavations in China and Central Asia. Sometimes a very cold
climate created good condition for survival, as it happened in the site of Moščevaja Balka
(Northern Caucase).
In Europe too little fragments have been found in burials, frequently including gold or gilt
threads. They are mainly taken from tombs of personalities of high rank, both secular or
religious.
Sometimes tiny portions of natural fibres interlacing survive from the pre-history,
incorporated in salty incrustations of metal objects, or completely mineralized
(carbonized), or simply as traces left on plastic materials, like clay or mud.
Since till the dawn of civilization weaving has been the most complex technology practised
by human beings, and frequently the same interlacing gives rise both to the fabric and to its
decoration, no matter how little a find is: it brings up this production proceeding, as much
important as its age. Once again, since textiles have always been longed for wealth and
status symbols, and very easily transportable, they have to be considered privileged means
to investigate the traffic of goods in relation to power and economy centres.
In Europe the most ancient textile finds come frequently out in the course of circumstances
different from normal archaeological excavations, such as the opening of tombs of dynastic
or church characters or saints. These are often buried inside sarcophagus, where the
environmental conditions are not the same as in a grave, even if comparable to that. During
the three last decades an intense activity of studying and conserving of this kind of objects
has been undertaken. Among them the following ones are worthy to be mentioned:
- the liturgical vestments found in some of the sarcophagus in S. Apollinare in Classe
at Ravenna (7th century);
- the costumes of noble men and women from the site of Moščevaja Balka (Northern
Caucase; 8th-9th century);
- the burial vestments of Saint Ulrich († 973) discovered in the Augsburg cathedral;
- those of Pope Clemens the 2nd († 1047) from his tomb in the Bamberg cathedral;
- the burial garments worn by St Antoine († 1231) in the Basilica del Santo in Padua;
- the large collection of vestments found inside the dynastic sepulchres in the

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Panteón Real of Burgos (13th century);

- the garments of Cangrande della Scala († 1329) taken from the sarcophagus of the
Scala family in Verona;
- the mantle of Sigismondo Pandolfo Malatesta († 1468) removed from his tomb in
the St. Francis church at Rimini;
- the textiles found in the sarcophagus of the bishop Moricotti (15th century) in the
Cimitero Monumentale of Pisa;
- the female dress found in a tomb of the Calvinist church of Boldva (Hungaria; 1560
ca.);
- the grave garments of Cosimo de’ Medici, of his wife Eleonora of Toledo and of
their very young son Garcia, taken from the family tombs in Florence (16th
century);
- the overdress associated to the mummified body of Sainte Eustochia Calafato in the
Montervergine’s Monastery at Messina (second half of 16th century).

11.3 Conservation treatments of archaeological textiles

Methodology and practice of conservation do not depend on the context of provenance of
the find, but just on its condition. That is from one hand the decay’s degree of the fibres
and, from the other, the level of integrity of the object as such. Anyway be aware that,
generally speaking, as old a piece is, as rare it is supposed to be. From another point of
view, it does not matter how deteriorate a piece is: it always brings up information if it met
somebody able to single out and interpret the historic and technical evidence and the traces
of structure. Gathering and studying these information is the first aim of the conservation
of archaeological items; sometimes the only one, aside is the preservation of the material
as much undisturbed as possible. When its reconstruction even partial is not possible, the
graphical one is a recommended complement.
The importance of this side of the question is such to come first of the recovery of the
aspect of a item. This too have to be considered non purely from the aesthetic point of
view, but more properly as the possibility to appreciate its shape, to recognise its structure
and guess its function.

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The practice of conservation has to follow the general rule of doing everything that is truly
and strictly necessary, but nothing more than that.
The first decision to be made is: does the survival of the piece require to dismantle or
remove something and, in that case, what? Facing the conservation of garments and
clothes, with no sufficient knowledge of their structure and dressmaking it is easy to lose
some of this aspect, which are particularly important not only for the garment under
treatment but for the entire class of these objects. It will never be sufficiently stressed to
avoid undoing any seam and part of their structure. Most of all must be blamed their
disassembling to the purpose to recover easily any separate flat component (unfortunately
this also has been frequently made).
The final result of such a practice would be an object which has lost its specific
authenticity, that is a replica built with original components. The same is true for any
three-dimensional piece.
In general terms one can describe the conservation proceeding of an archaeological textile
through the following steps: excavation, disinfestation, documentation, cleaning and
consolidation.

11.3.1 Excavation
All objects which have survived into the ground, or in a similar situation, for any length of
time became accustomed to their surrounding environment; so when they are brought to
the open air the processes of decay undergo a drastic acceleration; this has to be limited as
much as possible.
Remember that textiles are less clear in the ground and more brittle than many other
objects. Do not try to clean them immediately. In the handling never consider them self-
sufficient but prearrange a proper support. If the textile is dry maintain it dry and pack in
acid-free tissue paper or perforated polyethylene bag and store flat. If it is waterlogged
keep it in the same condition, with its surrounding mud, pack it in a sealed polyethylene
bag and store in a cool place. If it will require time to bring it to a stable store check
frequently that it does not dry out; if necessary use a humidity-chamber. Don’t forget that
textiles sometimes survive simply as a track on another material; it is always worthwhile to
preserve this track.

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11.3.2 Disinfestation
In a heavy humid atmosphere moulds and other micro-organisms proliferate. In order to
neutralise those still alive and contrast future developments, products already tested to this
purpose can be found in every country.
They do not have to be used to impregnate the textiles but to saturate a sealed chamber in
which they have previously been introduced. With light attacks, a current of air can
sometimes be enough; but be careful because when the level of humidity becomes too low
the brittleness of the piece grows up. Among the disinfestants, ethyl alcohol can frequently
be used: it is efficient against many micro-organisms, it does not interfere chemically with
the fibres molecules and very little with their humidity content.

11.3.3 Documentation
One of the first steps is the gathering of information. The result of a conservation project is
frequently as good as thorough preliminary studies and documentation are. This cannot
obviously be considered settled once forever; important pieces of information are normally
singled out only when a certain familiarity with the object has been reached.
The activity related to the documentation frequently needs the piece to be handled and
everybody can realize, in a while, how much dangerous this can be to the aim of its
preservation without an adequate temporary support and a sufficient experience.
Facing three-dimensional objects information can be collected following a general scheme
as this:
a) shape of the object; b) its use and function; c) its structure; d) material or materials of
which it is made of; e) decorations, if present.
A suitable knowledge of the main interlacing techniques and kind of textile objects can be
very helpful.
In the course of excavations photos cannot be considered enough in themselves; drawings
help to collect what an expert eye appreciates but slips out of the object glass.

11.3.4 Cleaning
Three are the main methods for the cleaning of historical textiles:
• vacuuming;
• washing;
• treatment with organic solvents (non polar).

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VACUUMING
The first cleaning means to eliminate mechanically as many foreign substances as possible,
particularly soil. A careful vacuuming for many finds is the only opportunity and not
always advisable. The degree of chemical degradation must be previously assessed and, in
case of brittle fabrics, a low power vacuum cleaner has to be used, meanwhile the piece has
to be saved from any mechanical stress that can injure it. For pieces which are particularly
fragile and/or very important it is advisable to work under magnification.

WASHING
It is a dynamic physical-chemical process, represented by the equilibrium:
dirt textile + water → textile + watery solution containing dirt
A part from being irreversible, washing exposes the piece to an inevitable risk, since a
textile handled when wet is more damageable. So it must be avoided if there is lack of
adequate equipment and proper experience. Archaeological textiles which can be safely
washed, in water or aqueous detergent solution, are rare; for deeply mineralised fibres it
can be a disastrous shock. On the contrary many textile finds from Egypt and Pre-
Columbian America, thanks to a correct washing, can get to a relaxation of the fibres, a
correct value of pH and content of humidity. But remind: dyes are almost certainly stable
in textiles from Egypt but check carefully those of the Pre-Columbian ones.
The first property of water is the capability to penetrate by capillarity into the fabric: its
molecules enter among the fibres, spacing them out, in this way they reach the hidden dirt.
That makes possible the action of intermolecular forces between the solid dirt and liquid. If
the solid combines with water to make a hydrogen bond it is called hydrophilic. Thanks to
this property water can solubilize, swell and soften organic substances of which the
molecules contain a sufficient number of polar groups (normally a hydroxyl group):
sugars, salts, starches, gelatine, many of the dyes. Beyond this, water has the ability to
separate many inorganic substances into ions, thus favouring their chemical combination
with other substances. That assumes great importance in the aim of separating a second
category of foreign substances in textiles.
But water alone is not effective against a large range of substances like grease and oily
compounds, so an effective washing solution makes necessary the join of some additives.
To this purpose a recipe has been prepared ready and tested by Judith H. Hofenk-de Graff
at the Central Laboratory for Objects of Art and Science in Amsterdam, widely used in

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textile conservation. The general formula advisable for non particularly degraded pieces,
contains:
- a detergent or surfactant (amphoteric compound), non-ionic or anionic;
- a sequestrant that is an organic or inorganic compound which helps the detergent to make
soluble complexes with polyvalent metallic ions;
- sodium carboxymethyl cellulose, a compound that absorbs the dispersed particles and
acts as a porter to carry away the dirt, preventing it from re-depositing on the textile.
The formula mostly used contains: 1 g/l of a non ionic detergent, 0.5 to 1 g/l of a
sequestrant, and 0.25 g/l of sodium-carboxymethyl cellulose, in distilled water. Many
variations have been suggested by the Dutch scientist since its first formulation (1968), in
relation to the kind of fibres, the severity of the decay, the dyes stability, the availability or
not of deionised water. Someone suggests a final rinsing containing an emollient
substance, frequently a 5 to 10% solution of glycerol.
But water, being partially polar (split in H+ and OH-), can react directly with fibres and
dyes too: some of the molecules of the chain can hydrolyse damaging the textile. For this
reason washing can have drastically negative effects, especially when, to improve its
efficacy, the detergent aqueous solution contains additives that make the pH go up, a
condition that can weaken the proteinous fibres, such as wool and silk.
A second phenomenon is caused by the washing: the swelling of fibres that can be
responsible of loss of colours (fairly easily on cotton and silk) and wool’s felting. On the
other hand it could cause fibres realignment giving rise, in the course of drying, to a natural
flattening. It can bring the pH up to the centre of the scale (6 to 7) and recover a correct
level of humidity inside the fibres.
Lastly, since water is such an effective solvent, it often contains relevant quantities of free
ions (above all calcium, magnesium and chlorine). This water, called hard, forms a
insoluble scum with soap following a reaction of exchange between the ions of calcium
present in the water and the potassium ions from the soap. That is why the water to be used
for washing historic textiles must be purified: distilled or de-ionised.
The practice of washing mostly adopted follows a sequence of operations, such as:
preliminary tests; proper washing; rinsing; drying.
• To verify if the piece can safely stand the watery treatment you have to observe its
reactions to different mixtures of ethyl alcohol and water, with an increasing

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percentage of this one, using a sprayer in a little portion of it.

• To test the stability of dyes: take little specimens of dyed yarns from the object, put
them on a sheet of blotting paper, imbibe them with the washing solution, cover
with a polyethylene sheet and leave over-night; if all the colours are with no doubt
stable it is possible to go on.
The pH has to be previously monitored too, because the final neutral position has to
be reached gradually and, even worse, because a too low starting value can bring
the textile after washing to a fibres pulp.
• To be safely washed a textile has to be flattened on a smooth, slightly inclined,
plane; with archaeological finds this operation requires frequently a long time, first
spraying a mixture (1:1) of ethyl alcohol and deionised water and trying to unfold
step by step the creases. When flat, cover the piece with a layer of nylon net, start
the proper washing with just deionised water and, if truly necessary, with detergent
solution. Remember that any chemical introduced has to be extracted by rinsing
and this will always means a risky handling.
• The aim of rinsing is to extract and carry out both the solubilized dirt and the
chemical components of the washing solution. Spraying the water on the top of the
textile and leave it drain along the inclined surface is more safe and effective than
submerging it in a basin.
Since the washing produces a lowering of the pH, the rinsing can be considered
finished when its value is stable between 6 an 7. For the reason seen above
deionised water has to be used.
• To improve the drying the textile can first be padded with a sheet of blotting paper
or absorbent textile, put on top of the nylon net. After having taken away carefully
this latter, the piece will dry naturally on the plane at room temperature;
evaporation of the water can then be facilitated by a current of cold air. Till it is wet
the piece can be gently put in a more correct shape and threads orientation.

TREATMENT WITH ORGANIC SOLVENTS

Cleaning with organic non polar solvents is based, substantially, on the same phenomena
of washing, that is to solubilize, emulsify and carry away the foreign substances from the
textile, but without triggering chemical reactions with the fibres and swelling them. It is
rarely practised with archaeological textiles, unless they are deeply contaminated with

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grease dirt. Treatment with organic solvent can be realized in a basin on which the textile
is submerged by the solvent, better if crossed by a current of air which maintains it in a
slight movement. It remains less effective than washing, it is not able to neutralize the pH
and can impoverish the natural fat content of wool. Keep in mind that the use of organic
solvents is strictly under provisions of the law.

11.3.5 Consolidation
The aim of consolidation is to give back to an object enough strength to stand the stress of
being safely handled, studied, exhibited in a Museum window or kept in storage. To do this
one has to adapt to the remaining flexibility of each object, due to its degree of fibre’s
decay, the few basic techniques of textile conservation, each one with advantages and
disadvantages: storage; support by means of one or more stitching techniques; sandwich
between two layers of fabric; support by adhesion; coating.

STORAGE
Obviously it is the less risky solution but with contraindications; first of all it does not
make possible to appreciate the objects. Therefore it has to be taken into consideration if a
more invasive technique is worth to be applied if it can recover at least partially the shape
of an object; especially when complex and/or three-dimensional objects are split a part in
fragments. On the other hand the pre-historic fragment can rarely survive without being
coated.
In spite of being a minimal intervention it requires at least: a good familiarity with
archaeological finds, the availability of materials chemically inert, storage space ad
equipment.
Every piece must be adequately hold; flat textile of large dimensions can be rolled on
cylinders (6 to 20 cm in diameter), according to their thickness and residual flexibility.
Rolling very degraded textiles can aggravate the situation; these need to be preserved flat
or folded as less time as possible, avoiding squashed creases.

SUPPORT BY STITCHING
When a textile has not been involved in a deep alteration of the fibre morphology but, even
if still maintaining a fairly good flexibility and strength, it is damaged by a loss of
integrity, its consolidation normally means to lay it on a new fabric, which acts as a

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support, and stitch it down. The support can be localized in the damaged sections, or
complete under the entire object. To make the holes become as less disturbing as possible
the support fabric would have to have thickness, texture and shining similar to those of the
old one, and be subsequently dyed in a colour which matches that or those of the piece to
be consolidated.
Using support fabrics of natural fibres is, in general terms, preferable; but fabrics of man
made fibres (techno-fibres), particularly polyester, polypropylene and their mixture with
cotton, have, under the same performance, a much lighter weight and a much greater
lastingness.
Stitching operation can be made in two ways: over a rigid plane using a curved needle; by
means of frame built on the principle of the traditional one to embroider, on which one
works with one hand on top and the other underneath, using a straight needle. In both cases
the support fabric has to be put with warp and wefts aligned with those of the object, and
adapted to its possible deformations and not vice versa. The stitch mainly used is couching,
drawn from the gold embroidery technique; but many other stitches are used.

SANDWICH
If the molecular decay got forward to the point that cannot stand, without further
damaging, the actions of a needle crossing the old textile, this can be placed between a
support layer, with the characteristics seen in the previous treatment, and a protective layer,
as transparent as possible (nylon net, silk organza, polyester gauze). Stitching normally
runs outside the external perimeter, along the splits and the internal perimeter of holes.
Dyeing both layers in appropriate makes the colours losses less visible and the upper layer
more transparent.
The treatment cannot be applied on three-dimensional objects.
Strictly speaking it does not give rise to a true consolidation: if the piece is not maintained
flat on a plane its effectiveness is truly poor. For very brittle fragments, as the pre-historic
ones, a sandwich between a padded wood ground and a glass is sometimes effective.

SUPPORT BY ADHESION
In the case of a textile chemically degraded at such a point that it could not stand a
mechanical treatment, a different approach is to support it by using an adhesive instead of
the stitching. In spite of contrary opinion the application of this technique needs as much

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experience and ability as the one based on stitching; and one must admit that many of the
past criticisms have been largely motivated by wrong or too scarcely experienced
applications. Last but not least since the first apparition of the method, products used are
substantially upgraded and many objects have received a specific treatment. The result is a
general improvement and a more proper use of the technique.
The adhesive used to this purpose can be a natural substance, like starch, hydrolyzed; more
practical and widespread are thermoplastic resins.
These can be applied in different ways: as a film on a fabric like polyester gauze or silk
organza, or coating a nylon net, or producing a film on a sheet of siliconized paper, later
transferred on the preset support fabric. The coupling of the piece to consolidate and the
adhesive interface is usually obtained following a process called “heat-sealing”, which acts
heating the resin till it is plasticized and exerting a pressure suited to the residual strength
of the textile.
Experience makes possible to treat in this way also three-dimensional objects, without
taking them to pieces, working on subsequent portions of the textile kept flat, till all the
surface has been supported.
For large scale objects a hot vacuum table of appropriate dimensions can make the
operation quicker, safer and more homogeneously effective. Once supported by adhesion
the treatment can be completed with a further support, to fit the loss, using moderately the
stitching technique made possible by the first consolidation.

COATING
Coating is used when it is necessary to give back a certain strength to a textile which has
suffered such an extreme decay process that is no more able to stand its own weight and
maintain its shape. Archaeological finds are frequently in this condition.
Consolidation is obtained using impregnating substances; these create inside the molecules
of the fibres new links to substitute the broken ones, without which they run into the risk of
disintegration.
Polyvinyl alcohols and Paraloid B72 have been mainly used in the past; at present they
have been replaced by emulsions of polyvinyl acetate or by an acrylic resin (Plexsisol). As
far as little objects are involved, the application of aeriform resins shows a great
consolidation efficacy and almost negligible effects on their aspect (see 11.4.2).

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11.4 Conservation practice: two case histories

The two following case histories represent the extreme situations that a conservator has to
face. The first one is a large dimension’s garment, the fabric of which was severely
degraded in the sections that were under the buried and almost in good condition
somewhere else.
On the other hand its level of integrity made possible not only to single out its shape,
dressmaker structure and dimensions, but also to recover it physically as a garment, even if
with some uncertainties. On the contrary the second case is a very small fragment,
relatively recent (13th-14th century) which was truly in danger of disintegration in a middle
term time.
These differences have obviously brought to different treatments; and not because of the
dimensions but because of their different states of conservation. In the first case the
traditional techniques based on the stitching was still a possible practice, even if with many
cautions, and followed by a protective sandwich. For the second object an experimental
process has been adopted, already used in medical and aeronautical fields to make
chemical proof metal prosthesis and pieces of equipment, and successfully tested on
archaeological clay object.
Five years after the treatment had been applied and published, a research carried out on a
similar polymer looks as if its durability - that means the efficacy of the treatment in time -
once considered extremely long, was substantially reduced.
Nevertheless the case is introduced because this fragment is one of many objects exposed
to a risk of rapid destruction. In such situations the only possible option to store them
practically undisturbed is the application of the best techniques known at the moment. This
attitude is based on the belief that conservation, as any other human activity, is not free
from the necessity of making decisions; and that, in spite of any dutiful effort, our
scientific knowledge of the phenomena which cause the behaviour of the objects is rarely
exhaustive and indisputable to such a level to let us operate choices in a total certainty.

11.4.1 An Egyptian shawl/mantle (11th-12th century)

HISTORICAL SETTING
Dimensions: 294 cm wide and 132 cm in height (plus 16 cm of the superior appendix,

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which, however, has lost its outer edge). Fabric: wool tapestry weave, originally white,
with hairs on the right face. Decorations: crosses in red and blue, with tresses on the wrong
face.
Found in the region of Fayoum, it is a late version of the shawl, since ancient times a
garment quite common in the Mediterranean area. Generally woven to shape in a piece,
with fine wool threads, it has a rectangular shape and, according to paintings of dynastic
Egypt, it can be worn in many different ways, wrapping it around the body; it was also
used as a bed cover or as a shroud. The shawl is characterized by three narrow decorative
bands in the weft direction, one in the centre and the other two close to the side hems. At
least since 7th century, these bands were sometimes decorated with inscriptions, both in
Coptic or Arabic, often invoking protection by God.
Because of the dimensions of these garments, frequently very large, they survived always
in state of fragment; this fact has been made worse by the antiquarian market that
preferably preserved the decorated sections, discarding the rest. The piece is exceptional
first of all because it is whole. In fact, even if large areas are missing it has been possible,
placing the fragments in their right positions, to recover its completeness, the correct shape
and dimensions.
Judging from the present knowledge there is a also a peculiarity that makes this peace
unique. Since the fabric is heavy and relatively little flexible, it was not draped around the
body but worn on the shoulders with the centre of one of the larger sides on the back of the
neck. Because of the weight of the fabric it tended to slip down from the shoulders,
producing a lightly triangular opening to the front. The problem has been solved with a
solution that represents a little but meaningful evolution from the traditional garment
woven to shape, toward a more elaborate tailoring technique. Four little sections of textiles
- two long rectangular strips and two trapezoidal - have been joined to the front edge,
which possibly overlapped partially to guarantee a good closure. For this reason the
garment has a very special importance as a source of information about the costume’s
history, not only because of its structure, but also for its stitching largely untouched.

STATE OF CONSERVATION
Like many other textiles coming from graves, the fabric that has been in contact with the
body deeply degraded by effect of the biological fluids. The result is the loss of large
portions of it, meanwhile others are at present completely mineralised and, as a

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consequence, very brittle. On the contrary other areas are in relatively good conditions.
Between the two extremes all the possible levels of degradation, revealed by differences in
colour, can be recognized.

TREATMENT
As a result of a previous treatment the fragments were mounted on a replica of the three-
dimensional cope used at present, made with a strong plain-weave linen fabric (Figure
11.3). Being the garment substantially misinterpreted, most of them were obviously out of
place and shape and dimensions of the piece totally obscured.
As a first operations the linen fabric has been cut in correspondence of the missing areas,
in order to be able to move at least the largest fragments, and accommodate them more
correctly on the basis of: orientation of warp and weft, positions of the decorations, hems,
and other technical details. The shape of the shawl was in this way first recognized,
together with the system of the front closing (Figure 11.4), thanks also to a further
fragment found almost by chance among others stored textiles. After an exhaustive
photographic documentation the object was then put back to storage, to have time to study
similar pieces in other museums’ collections.

Figure 11.3 (on the left) – The fragments of the shawl/mantle as mounted
in the previous treatment.
Figure 11.4 (on the right) – A detail showing part of the neckline, before conservation.

Coming back to the problem three years later, the new examination of the piece has
confirmed the first hypothesis and suggested simply a few little adjustments. The
fragments for which it was possible to locate with no doubts the right positions were

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removed from the previous linen support and placed on the new one, a cotton rep fabric,
which has a grain similar to that of the original fabric, dyed in a colour which matches
those of the object (a range between a light yellow-beige and a dark reddish brown). The
other fragments, pulled off from the linen fabric, were placed on polyethylene sheets and
moved on top of the support to find the correct location. Only for very few of them there is
still a certain dubiousness. All the fragments have then been stitched down (with the
couching technique) and covered with a dyed nylon net, to maintain in position those that
are in danger to break and disintegrate and to avoid abrasions when the piece will be
handled (Figure 11.5). The supplementary section corresponding to the front opening have
been reconstructed in shape but not in dimensions (Figure 11.6) because of the lack of
information in the remaining bits.Eventually the shawl/mantle has beer rolled on a
polyethylene cylinder, with the right face outside, and protected by means of sheets of
white paper and a layer of strong cotton/polyester fabric.

Figure 11.5 – The mantle after conservation.

11.4.2 Treatment of an Italian fragment (13th-14th century)

The fragment, a few centimetres square of a silk ribbon (Figure 11.7), brocaded with a gold
thread (Figure 11.8), has been discovered in 1988 in one of the tombs inside the church of
the Benedictine Abbey of S. Fruttuoso (Camogli, Italy). It was probably part of the
decoration of a liturgical garment, made in the course of a period of particular splendour in
the history of the Abbey, such between thirteenth and fourteenth century.

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Figure 11.6 – Detail of the neckline of the mantle, partially restored.

Figure 11.7 – The fragment of gold brocaded ribbon, tablet woven, after cleaning.

STATE OF CONSERVATION
In spite of its apparent solidity the textile showed at the microscope a propensity of
disintegration at the edges (Figure 11.9), a symptom of a very advanced molecular decay
of the fibres. The prolonged permanence in relatively stable thermohygrometric conditions,
which have favoured its survival, has however provoked a mineralization process, in the
course of which salts, mould particles, dust and insects hides have been incorporated
(Figure 11.10).

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Figure 11.8 (on the left) – SEM micrograph of the gold laminate wound around a silk core.

Figure 11.9 (on the right) – Detail showing the extreme brittleness
of the silk core (photo SEM).

Figure 11.10 – The dusty surface of the gold laminate (photo SEM).

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TREATMENT
Once taken away from the confined environment of the tomb, the danger of disintegration
of the specimen, due to the almost complete loss of mechanical resistance, was such that
normal cleaning procedures could not be taken into consideration. The solvents or
detergents solutions (even water itself), used as a rule either in the removal of the soluble
encrustations or of the solid particles harboured in the weave, would have made soluble or
carried away the degraded products of the fibres too, thus definitively compromising the
solidity of the material.
Only a prudent mechanical cleaning was possible. In order to realize the operation with no
risks, it was necessary to fix the fragment on a rigid seat which allowed it to be safely
moved; the cleaning was then carried out with a sharp wooden tool and the help of a
binocular microscope (20x) and of a micro-aspirator. It got back, at least partially, to the
shining of the metallic threads that give rise to the typical lozenges pattern of the tablet
weaving.
Once cleaned it was evident that any intervention of support, either mechanical or by
adhesion, would not have had any possibility of success.
An accentuate bending, in fact, would have made the extreme resource which is the
imprisonment between a padded ground and a rigid transparent surface, too risky.
Moreover one wished to avoid solutions which would have substantially altered the aspect
of the material: for this reason, propositions like the incorporation of synthetic resins were
discarded.
Previous experiences whose results were revealed positive and are confirmed by similar
research published by the specialized literature, have led us to choose a particular treatment
which requires the use of a paraxililenic product (Galxyl C). The technique consists in
coating the object with a very thin layer obtained through polymerisation of monomer
vapours of paraxililene, which closely follows the object’s surface. The film obtained in
this way is extremely resistant, of high chemical inertness, completely transparent and
colourless. The option of a treatment which, because of its stability has a very difficult
reversibility was based on the consideration that, in the absence of any consolidation, the
life expectation of a so brittle textile is limited to a few decades, if not a few years.
Since the paraxililenic based polymers are insoluble in the common organic solvents and
thus cannot be applied as solutions, the application requires a longer process and a special
peace of equipment (Figure 11.11). One starts from the dimer of paraxililene, which is a

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solid crystal at room temperature, manageable with no special precautions.

The object to be treated is placed in the coating chamber where vacuum is applied up to the
achievement of about 0.1 mm Hg; the dimer is heated up to 150 °C in the sublimater
making it pass to the vapour phase; the dimer is than introduced in the pyrolytic area at
about 680 °C, where it changes in paraxililenic monomer; the reactive monomer enters
successively in the coating chamber, maintained at room temperature, where it is deposited
on all the cold surfaces, it condenses and meanwhile polymerizes producing a thin
continuous coating, free of irregularities, of the same thickness (4 µm) in every point of the
surface of every thread. After the treatment the visual aspect of the specimen is practically
unaltered and the reached consolidation can be appreciated acting a bland surface rubbing.
Thus it can handled with sufficient safety and preserved without special precautions.

Figure 11.11 – Graphic scheme of the coating process.

Bibliography

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medieval textiles, Preprints of the Interim Meeting (Palermo 1998), Rome, 1990.
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ACKNOWLEDGEMENTS
Marco Di Bella and Valeria Rosselli for their help during the fibres identification
procedure are gratefully acknowledged.

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12 – LEATHER
AND ANIMAL SKIN OBJECTS

12.1 Introduction
Leather is a product derived from animal skin. It has been utilized by human beings since
prehistory, as is documented in cave paintings and by the finding of flint and ivory tools
likely used for skin processing. The original use was for clothes: the skins removed from
the animals were used for protection against low temperatures or as ornament. Recent
evidence of this was found with the Similaun man discovered in the ice in Alto Adige,
northern Italy. Along with the body, the ice preserved his clothes made of skins all dated
back to five thousand years ago, though the use of animal skins, as documented in cave
paintings is much older. At that time animal skin was probably utilized in its natural state
after flaying the animal and drying the skin.
Unfortunately, dried skins could only be used for a short time, because they rapidly
decompose in hot and humid climates or become rigid in cold climates. The rotten smell of
the decomposing skins did not likely offend the nostrils of our ancient ancestors. The skin
was probably discarded when fungi and bacteria made the material fragile and possibly
because it could then spread to human skin. In addition rigid skins were not suitable as
clothing, so they could no longer be worn. As a consequence, people learned that the skin
must be treated in order to maintain its elasticity and impermeability, that means that it
must be tanned.

12.2 Skin

Skin is a biological tissue, which can be defined as a specific community of cells and
substances derived from similar cells, with common morphological characteristics and
having the same function.
The category of epithelial animal tissue can be subdivided into glandular and covering
tissues. The latter are tissues comprising tightly connected cells, in geometric forms and

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are well defined. The covering epithelium tissue can line internal cavities without any
connection with the outside, for example the blood vessels or cavities connected with the
exterior, like the digestive and respiratory tract, and can even cover external surfaces
where it is called the epidermis. The tissue is formed differently depending on its specific
functions:
- a simple single, plate-like layer in the airways and blood vessels
- a simple, single cube-like layer (polyhedral shaped cells), in the digestive system
and excretion ducts in glands
- a multi-layered plate composed of three layers (deep, intermediate and external) in
areas that have contact with air.
Surface cells can be alive and continuously moistened (saliva for the mouth, mucous
secretions in the pharynx, oesophagus and vagina, and lachrymal fluid for the cornea) or
dead if transformed into corneum. The cells directly in contact with the air and those in the
intermediate layer are subjected to a corneum transformation, which forms a continuous,
sometime very thick, keratin sheath, or forms specific organs such as reptile scales, antlers,
nails, or bird beaks.
The skin is the external covering of an animal’s body and is composed of three very
distinct layers (Figure 12.1):
- epidermis - the outermost layer is composed of the various layers of epithelium
cells, including the dead cells and those active in the deeper layer, or strato
germinativum. This layer equals 1% of the total thickness of the skin;
- dermis - with a thickness that varies from animal to animal, it can equal 85% of the
total skin, contains blood vases and nerve endings. It is composed of two layers, the
papillary and reticular dermis.
- hypodermis - or subcutaneous fatty tissue, connects the skin with the organs under
ti. It represents 14% of the total thickness of the skin.
The connective tissue of the dermis is a dense connective tissue, rich with fibres. There are
three types of connective fibres:
- collagen fibres - are made up of small bundles of fibres 0.2-0.5 µm thick which are
cemented together by a substance, called mucin, which dissolve in acids or boiling
water. Each fibre comprises proto-fibres, which are created by long poly-peptic
chains. Each chain is composed of amino-acids: proline, hydroxiproline, and

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glycine. Three chains united together in spiral form, create the basic unit of
collagen which is called tropocollagen;

Figure 12.1 – Cross-section of skin.

- reticular fibrils - these differ from the previous in their ability to divide or join to
other fibres during the anostomosis process; they are made of a different
scleroprotein, reticulin; like collagen, it can be dissolved in boiling water, or other
alkaline solutions;
- elastic fibres - are found in lower quantities than the previous fibres, have a totally
different chemical composition and physical properties; they are formed by the
protein elastin, which is insoluble in boiling water and acid solutions. It can be
dissolved only in a highly alkaline environment.
Connective tissues can undergo two types of transformations: swelling and shortening.
Swelling can be caused by increased water content (acid or alkaline solutions) in the space
between the fibrils; this is known as osmotic swelling and is substantially reversible. On
the contrary, a swelling due to neutral salts or non-ionic reagents, called lyotropic swelling,
is irreversible because it disturbs the organization of the proto-fibrils. Shortening is caused
by heat, which shortens the collagen fibrils and makes the process irreversible.
The combination of water and heat destroys the skin and forms gelatin (animal glue).

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12.3 The tanning process

12.3.1 Tanning in ancient times

Prehistoric human beings became aware that the skin of the killed animals could be
suitable for many applications. They also understood that it had to undergo a process to
avoid decay, so that it could be used for a long time maintaining its elasticity, resistance
and impermeability. This process is called tanning. It is only possible to speculate about
the primitive tanning process, such as the discovery of the effect smoke from fires inside a
cave had on a flayed skin. Tanning through smoke exposure is still used today in some
regions of the Orient. Another assumption is the use of fats by rubbing them directly on the
skin; this type of tanning is still utilized by the Eskimos.
These primitive treatments cannot actually be called tanning, but a type of pseudo-tanning.
During the actual process of tanning all the parts which tend to rapidly putrefy, the
epidermis and hypodermis, have to be eliminated. The epidermis can be left only when the
skin belongs to a animal with thick fur which needs to be conserved. Therefore, only the
derma is tanned, in other words, transformed into leather. We can define tanning as the
process which fixes the collagen fibrils and impedes their decomposition, maintaining its
characteristic resistance to water and heat.
Early attempts at tanning utilized the degenerative action of bacteria, trying to control their
effect. Historical documentation shows us that there were tanneries in ancient
Mesopotamia where the skins were dipped into solutions containing fermenting
substances, such as flour, grape juice, milk and salt. The enzymatic action of the bacteria
was very difficult to control, so it was necessary to check the state of the skins and repeat
the process, washing it in clean water before each enzyme bath. Baths of fermented urine
were also used, but it was even more difficult to control the bacterial growth. Immersion
into fermented solutions was also practiced by the Egyptians, and this procedure was still
occasionally utilized until the 17th century.

12.3.2 Operations prior to proper tanning

DRYING
After the animal has been killed and flayed, the integument is laid to dry in aerated
environment, far from the sun rays in order to avoid an excessive drying of some parts of

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the object. Speed drying, in fact, can leave humid parts inside with subsequent bacterial
formation and severe damage. In the past, the tanning occurred just a short time after
drying, but after the spread of the process it was necessary to learn storing and conserving
methods for the dried product. Like today, the conservation of the dried skins was carried
out by salting. The skins are sprinkled with solid salt on the hypodermis side (flesh side)
and stacked up. The salt dissolution determines the loss of about 30% out of the total
water.
The conserved hides are ready to undergo the various tanning steps. All kinds of animal
skins can be tanned, but ovine, caprine and bovine are the most utilized, today like in the
past. The skin of other mammals can more rarely be used depending on the geographic
area.

SOAKING
Reviving a dried skin means restoring its characteristics which it had just after flaying. So
that the tanning is effective, and that all the tanning materials are fixed to the collagen
fibrils, it is necessary that the fibrils are very rich with water. The soaking phase is simply
leaving the dried skins immersed in clean water. In antiquity, this operation was done
directly in the water flow from rivers or streams. Then basins were used making it
necessary to change the water and the skins must be beaten. Apart from absorbing water,
during this phase, the animal skins were cleaned, eliminating the salt and the dirt.
Only in the 19th century were basins substituted by big wooden barrels, which rotated on
their axis by hydraulic power. Inside the barrels, the skins were delicately beaten by the
rotating action (Figure 12.2).

LIMING
The liming is the impregnation of the skins with lime. Such a treatment has the aim to free
the integument from those parts that are not transformed into leather, the epidermis and
hypodermis. The lime is an earth-alkaline compound which has the property to attack the
keratin; in addition, the fibrous structure of the derma reacts more easily with the tanning
substances. Therefore, through liming it is possible to achieve the separation of the
epidermis with the hair side, the loss of the hypodermis through saponification of the fats,
and the swelling of the dermis.

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Figure 12.2 – Internal view of a barrel with some skins during the reviving.

HAIR REMOVAL
The liming has produced a chemical relaxation between epidermis and derma. As
mentioned earlier, this detachment can also be obtained through a biological route,
meaning a controlled decay of the skin using fermented baths. In both cases, one must then
proceed to the physical separation of the two parts. In antiquity, the separation was done by
hand; the skin was placed on a inclined plane and the leather worker completely removed
the hair and the epidermis using a convex half-moon knife held with two handles. Today
the same operation is performed by machines. At the end of this phase, the skin looks like
Figure 12.3.

THE FLESHING
After the hair removal, the skin is washed and the treatment continues with the fleshing.
This operation is very similar to the hair removal, but it is made on the opposite side, that
is on the flesh side. Then, when the skin is very thick, it is possible to make the split and
separate the derma into two or more thin leather pieces from the single skin.
Ovine, caprine and bovine skins, the most used, are split into two parts to increase yields
and to obtain more elegant and easy to handle leather objects. In modern times, with the
use of appropriate machines, more layers are obtained from the skins of big animals. For
example, before the elephant became a protected animal, up to ten layers could be obtained
from its skin. After fleshing, the skin is reduced to only the derma.

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Figure 12.3 - Section of skin after hair removal.

THE MACERATION
Fleshing is followed by maceration, which eliminates all the keratin and epidermis residue.
This type of processing is limited to the ‘light’ skins from sheep and goats, and is preceded
by a lime elimination phase to remove all the traces of lime if liming was used. This work
was done on an inclined plane using the knife and by compressing the skin to bring out all
traces of lime.
In the Medieval Ages, maceration was performed with animal dung (birds and dogs),
thanks to the action of the organic acids and bacteria which produces enzymes. Since the
17th century maceration with dung was replaced by bran and oat chaff to obtain
fermentation with formation of lactic acid, acetic acid and other acids. Today maceration is
executed by means of enzymes, of which the most used ones comes from the pancreas.

12.3.3 Proper tanning

After the above operations have been completed, the skin is limited to the only derma, and
it looks white, flaccid and slippery, even though the flesh side (internal part that was in

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contact with hypodermis and muscles) and the flower side (external part that was
immediately under the epidermis) can be recognized. Proper tanning is carried out on this
material, so leather consists only of an appropriately treated derma.
Different methods of tanning exist, depending on the substances used. In each case the
purpose of tanning is to fix the collagen in order to avoid its degradation, mainly because
of water and heat. The resistance to these factors is measured as temperature of
gelatinization, which may vary from case to case.

VEGETAL TANNING
Vegetal tanning is one of the most ancient procedures and it is still employed today to
obtain leather suitable for soles, saddles, horse harness, linings, and book-binding.
This system involves the use of materials of vegetal origin, that contain tannin in variable
percentages depending on the vegetal species and the part of the plant which is utilized.
Favoured by the acidity of the bath, the tannin is fixed irreversibly to the collagen.
Tannins are phenolic compounds, which are classified into two groups:
- hydrolysable tannins, or pirogallico tannins
- condensed tannins, or catechin tannins.
Sometimes the same plant can contain both types of tannin, for example the oak tree. Bark,
wood, leaves and fruits are the parts of a plant which contain different tannins and in
variable percentage. In particular, the vegetable growths (gall nuts) which are formed due
to insect bites have a high tannin content.
The oldest form of vegetal tanning was done in pits which were prepared lining them with
sturdy wood. A first layer of humidified bark was placed on the bottom, and the skins were
posed on it with the flesh side facing down. Then a new bark layer was placed on the
flower side of the skin and on the bark a new layer of skins with the flower side facing
down. They proceeded by alternating the directions of the skins, always separated by bark
layers until the pit was full. The last layer was a bark layer which was covered with wood
boards to the purpose of closing the pit and keeping the skins stopped. Finally, water was
poured until the pile of skins and bark was completely covered.
In this first stage the material was left for a minimum of two months, then the skins were
recovered, cleaned and placed in another pit with the same above described system. Here
the skins stayed another few months. They repeated the procedure of changing the pits six
or more times, so that the entire process lasted 2-5 years in order to obtain high quality

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tanning. After extraction from the last pit, the skins were washed with fresh water and then
left to dry. After some time, they noticed that it was possible to save material if they didn’t
use new bark every time. In addition, the reuse of old tannin-poor bark led to a slower
tanning with best results.
The skins extracted from the last pit were washed and hung out to dry.
The selection of the vegetal substances to be used for tanning was made not only
depending on the type of tannin present, but also in consideration of the final quality of the
leather: the leather obtained by using oak was more compact and harder, while the one
obtained with valonia was more spongy. Also the colour varies from pink to light green
depending on the vegetables used.
Today, by using extracts of tannin and utilizing the rotating barrel, tanning has become
much faster, from 8 to 20 days. The yield of a tanning process is the following: 100 kg of
dried skins yield 115 kg of leather, while 100 kg of soaked skins produce 50 kg of leather.

MINERAL TANNING
Mineral tanning is realized by using mineral compounds of aluminium, iron, chromium,
and zirconium. Before tanning, the macerated skin has to undergo a treatment with strong
acid solutions, e.g. sulphuric acid, to which salts are added to avoid swelling. This
treatment has the function of eliminating the last lime residues and to permit a rapid and
deeply effective tanning action. When the tanning is not carried out immediately, the acid
treatment allows the skin to be conserved for a certain time.
The most ancient tanning was realized with aluminium, usually in form of rock alum,
which is a sulphate of aluminium and potassium. Rock alum has been known since ancient
times and was mainly used in the tincture process. In contrast to vegetal tanning, tanning
with alum does not always lead to a complete fixation of collagen, because it is based on
the stability of the protein-metal salt in the collagen-aluminium complex. The leather
obtained is soft, elastic and ivory-white coloured, but not very resistant to water, which can
restore the skin to a state prior to tanning. This could be called pseudo-tanning, but the
above mentioned characteristics of the leather treated with alum made it desirable for
producing gloves and book covers. The most utilized are lamb and kidskin, pigskin was
also used in ancient times.
More recently, tanning with alum was performed in two steps. The first step is as above,
but with the addition of sodium chloride, which has two objectives:

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- to avoid the swelling of the skin due to the action of sulphuric acid formed through
hydrolysis,
- to favour the absorption of aluminium oxide, that plays the role of tanning
The second treatment was carried out in the barrel by means of a mixture of albumen, egg
yolk, sodium chloride and flour; it lasted about 45 minutes.
Tanning with iron can be ignored because it was used rarely and only as a substitute of
chromium due to its lower cost. Tanning with zirconium can be skipped as well, because it
is now in development. On the contrary, it is worth saying something about tanning with
chromium.
Chromium salts have been recently introduced, in fact the first attempts were made by
Americans in the year 1855. Schultz (1883) and Dennis (1893) patented the successful
system that most skins are still treated with.
Tanning with chromium, primarily utilized for bovine skins, is done through one or two
baths inside the tank; then a maturation period follows on the inclined plane. After that the
skins are pressed in order to squeeze most of the liquids retained, and shaved on the flesh
side to make the thickness uniform. Finally the skin will be neutralized by weak alkaline
compounds (bicarbonate) to prepare it for the tincture process.
Leather tanned with chromium shows a fine flower side and a compact fibrous tissue; it is
water, wear and tear resistant; and it has a tensile resistance higher than that of the leather
obtained with vegetal tanning.

TANNING WITH OIL

Like smoking, tanning with oil was among the first techniques used, but then it practically
disappeared. Therefore, it is not worth describing in detail. It was executed using fish oil or
animal fats, and it served to obtain suede leather.

12.3.4 Dyeing
Speaking of tanning and its various systems and materials it was said that vegetal tanning
does not always produce leathers of uniform colour, and that different shades are obtained
depending on the vegetable substances employed. Leathers tanned with alum are white and
generally these were left unaltered, while those treated with chromium are yellowish.
Therefore, sometimes you must run the dye after tanning, in order to obtain a uniform
product. Today dye is indispensable to make the leather look appropriate depending on its

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subsequent use. To dye the leather you can use natural or synthetic dyes.
Natural dyes are obtained from some kinds of wood:
- ‘campeggio’; through the so-called haematin, it produces blue and black shades,
- red (or Brazilian) wood; it gives ‘brasilina’, that produces pink and red shades,
- ‘fustello’ (or yellow) wood; that contains ‘fustina’ and produces yellow to brown
shades.
Synthetic dyes can be subdivided into:
- basic dyes, used for the leathers that underwent vegetal tanning,
- acid dyes, used for all leathers, but mainly for those undergoing chrome tanning.
Tinting can be done by brushing on only one side, or by immersion with the use of a tank.

12.4 Parchment

12.4.1 Definition
Another important product derived from skin is the parchment which has had several uses
even though the most important use is as writing support.
Parchment is a skin that was made stable through almost exclusively mechanical
operations instead of proper tanning. Parchment is obtained, for the most part, from all
types of sheep skins, goat and more rarely calf which is common in German parchments.
The flesh side of a dried skin is very similar to parchment, therefore, the first parchment
was likely created as a dried skin with the hair removed, even though it wouldn’t have
lasted long before decomposing. It was probably created by chance after drying an un-
tanned skin, that had undergone all the preliminary operations of hair removal and
fleshing. Certainly, at the beginning it was not produced as a writing support, but to satisfy
other needs related to rural life, such as sieves, musical instruments, etc. The legend says
that parchment was borne in Pergamon, a city of Asia Minor, in the 2nd century B.C., but
its origin is much more ancient. In Pergamon it definitely spread as writing support, when
its manufacturing quality improved.
The manufacture of parchment achieved its maximum development in the Middle Ages
and it has remained unaltered till today.

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12.4.2 Manufacturing
According to the most ancient method for manufacturing parchment (8th century), the skins
were immersed into lime water for three days, so that the hairs were removed from the
epidermis and the fat layer of the hypodermis dissolved. After air-drying, stretched on a
frame, the skin was scraped with a convex crescent knife and then rubbed with powdered
chalk.
Parchment manufacturing reached its height during Medieval times and has remained
virtually unchanged even today.
Dried skins undergo a series of preliminary operations identical to those mentioned in
tanning: soaking, liming, hair removal and fleshing. In antiquity, liming was performed by
putting the skins in stone pits with the lime solution and turning them from time to time for
5-10 days. Today, by using the rotating cylinder, the liming stage lasts 2-3 days only.
After hair removal, the skin is washed and dried keeping it stretched on a wood frame by
means of nails (for the thick skins) or ropes for small and thin skins in order to avoid
lacerations. While the skin is under tension, the residues of fat substances and hairs are
eliminated by scraping with a convex crescent knife; scraping is executed on the hair side
or flower side, while fleshing on the other side. Drying under stress makes the collagen
fibres arranged in aligned layers, and the plane sheet maintained even after the skin is
removed from the frame.
The manufacture is completed by treating the flower side of the parchment with a piece of
pumice stone. In Italy, probably during the 8th century, the pumice stone was substituted by
chalk, while they continue to use pumice stone in Germany; pumice stone will be used
again in Italy in the 18th century. The scraping also has the function of reducing the
thickness of the parchment. But the request of thin parchment was better satisfied by using
a skin from a newborn or stillborn lamb; vellum was probably parchment obtained from a
calf foetus. Today machines can split skins to obtain thin parchment from any animal,
though goat is usually used.

12.5 Leather deterioration

Leather degradation can occur due to intrinsic and external causes. Intrinsic causes are
connected to tanning and the links formed between the tanning substances and the collagen

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fibres. The block of collagen plaits is stable between pH 3 and 6; outside this parameter the
links loosen and the fibres are more easily degraded. Water is the most important
deteriorating agent, which causes swelling of the fibre tissue and removes the tanning
substances. Alum tanned leather is particularly sensitive, because water alone is able to
break the links between the aluminium compounds and the collagen fibres.
If any acid accumulated inside the derma due to erroneous tanning processes, it causes a
softening of the leather, and if pH goes down to 3, the tanning looses its efficacy.
Contemporaneously, the acid corrodes the fibres making the leather brittle till its
destruction. Alkaline substances also lead to the same damage, because they increase the
pH value over 6.
Intrinsic causes of damage are completed by defects of the starting skin, due to the
presence of injuries or diseases present in the skin before tanning, if the affected piece was
discarded.
Among the external degrading substances, other than water and heat, atmospheric pollution
must be taken into account. In particular, sulphur dioxide is absorbed by leather and starts
a series of oxidant reactions which leads to the formation of ammonium sulphate. When
these substances are above 10% inside an antique leather, this compound surely indicates
an advanced state of decay.
Also the reaction between collagen and atmospheric water is favoured by the presence of
acid, so that a very acid leather, kept in a very humid environment, is a high risk for
conservation.
Among the external degradation factors there are the biological ones of micro-organisms
and insects.
Micro-fungi mainly develop when humidity is more than 65%; they cause the formation of
stains and leather degradation particularly in dyed leather. Chromium tanned leather is the
most resistant; unfortunately ancient leather was almost exclusively prepared through
vegetal tanning.
Some species of insects prefer leather for their diet, the most common and frequent are
Beetles such as the Dermestidae: their larvae eat the leather and dig deep channels (Figure
12.4).
Some woodworms, for example Anobidae, prefer wood and paper, but can also eat leather:
the holes produced in leather covered books by the larvae during their transformation into

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adult insect are well noted. Finally one must mention termites, which eat any organic
product, Blattodea, which erode the leather surface, and ravenous mammals such as mus
muscumlus and the like.

Figure 12.4 – Example of a book cover eroded by Dermestidae grubs.

12.6 Conservative intervention

12.6.1 Prevention
The general principles for the lasting conservation of leather objects, or partial leather
objects, derive from the previous analysis of the degradation factors. First of all it is
necessary to keep the objects in stable climatic conditions. Sudden changes in temperature
or the presence of high humidity can produce the dangerous phenomenon of condensation,
so that the small water drops are adequate for the development of fungi and microbes from
the spores present in the dust deposited on the surface of the objects. Therefore, the objects
must be protected from dust, which also contains insect eggs and polluting substances. The
best conditions are less than 65% relative humidity and a temperature around 18 °C.

12.6.2 Leather analysis

Before the final placement of the objects, the leather should be investigated by analyzing it
in order to establish whether it needs to be restored and how. Therefore, the objects should

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be well cleaned to eliminate the dust, that could alter the analytical data.

NON DESTRUCTIVE AND MICRO-DESTRUCTIVE ANALYSES

There are only three types of analysis which do not need to take a sample:
- to recognize the type of animal of which the skin was part,
- to measure the water content,
- to measure the pH value.
Direct observation with a stereo-microscope on the hair side, is used to determine the
unique characteristic hair pattern of each mammal.
The measurement of the water content is executed by means of an instrument equipped
with micro-electrodes which are inserted in the leather and, through the voltage difference,
indicate the percent of water contained. The pH measurement is realized by means of an
electrode in contact with the leather. Its measurement in a distilled water solution obtained
by introducing some powdered leather would be more precise, but this is a micro-
destructive method.
The search for ammonium sulphate is a micro-destructive investigation too, but there is no
alternative. One can utilize the same solution obtained for measuring the pH value, by
adding some drops of distilled water solution containing 0.1% of nitric acid and 1% of
barium chloride. The presence of ammonium sulphate is demonstrated if the leather
solution becomes milky white.

DESTRUCTIVE ANALYSES
This chapter should be excluded a priori, because it is almost never possible to destroy
significant parts of any cultural object. Only in the case of leather covers can you
sometimes sacrifice a sample taken from non visible parts, in order to determine the type
of tanning, the temperature of denaturing, and the content of fats.

12.6.3 Restoration
After photographic documentation of the current state of an artefact, the elimination of
dust is the first operation that must be done. The results of the analyses will indicate the
most appropriate methods for the conservative intervention, which begins with adjusting
the water content in the range 12-20% at 21 °C and 50% RH conditions.
Then, the first operation is cleaning. Droppings of insects and other encrusting substances

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can be mechanically removed under the stereo-microscope; a wet surface cleaning with
methyl-cellulose or neutral detergent is done depending on the level of dirtiness and decay.
The next step is the suturing of tears or the integration of lacunae; it must be always done
with leather of the same type of animal and tanning, by using the part of the skin identical
to the missing one. For example, if the lacuna is on a skin from the animal’s back, you will
use a new leather part coming from the back, and not from other parts of the animal. This
solution will prevent tensile differences between original and added parts. In addition, you
will have the best aesthetical result, because the leather texture changes in the different
parts of the body.
If a leather object is very damaged, due to microbe or insect attack, it needs a
reinforcement, that can be done with pure cotton or with very thin leather. There is not a
general rule: the use of cotton or leather should be decided on, case by case depending on
the type of artefact and degradation problems.
Lubrication is the last phase of the intervention: there are several industrial products, but
one can also prepare a solution according to known recipes.

12.7 Examples of conservative interventions

12.7.1 Seal container

It deals with a seal container made of painted leather (8 x7.5 cm, XV century), kept at the
Medieval Museum in Bologna (Italy). One can see (Figure 12.5) the extreme dryness of
the leather, with losses of colour and fragmentations on the lower part on the right. The
two valves were probably initially joined by two wood or ivory small cylinders.
After an accurate cleaning, the object was left in climatic cell for 30 days at a temperature
of 16 °C with 50% relative humidity. In this way the leather has slowly absorbed the lost
water and has become more malleable. So, it has been possible to restore the fractures and
to fix the colours by introducing Paraloid B72 under the pictorial film and joining it to the
leather surface. In order to maintain fixed the two parts, a modern material like two
Plexiglas bars was selected (Figure 12.6).

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Figure 12.5 – View of the seal container before restoration:

two halves interior and exterior details.

12.7.2 Book covers

The second example presented here refers to three leather covers from books kept at the
Manfrediana Library in Faenza, including a cinquecentina. The first case is a book from
the year 1552 (Z.N. 006 004 017), the cover of which has been already shown in Figure
12.4. It is evident that the leather was so eroded as to be the limit of its resistance, but the
cover, that depicts two hands crossed, is very important due to its impressed golden
Figures. Therefore it was decided to proceed with its reapplication after lining it with split
leather, vegetal tanned and dyed as the original; the result is shown in Figure 12.7.

Figure 12.6 – Recto and verso of the seal container after restoration.

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Figure 12.7 – Leather cover eroded by Dermestiae,

reapplied to the book after restoration.

The second example of leather cover refers to a incunabulum of the year 1483 (inv. 1158,
BCF, inc. 84). In this case the leather cover lined wood planes which had been attacked by
xylophagous insects of the species Anobidae. Then erosion was transferred from the wood
into the leather, which had been weakened due to repetitive mechanical use and it had
lacunas in various areas (Figure 12.8, left).
Before leather restoration, the volume underwent disinfestations with ethylene oxide in
autoclave, to neutralize possible eggs still present. Then the leather was separated from the

Figure 12.8 – Leather cover on wood axis, before (left) and after restoration (right).

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wood. The analytical results demonstrated that it was vegetal tanned goat leather;
therefore, the leather was cleaned with methyl-cellulose and a neutral detergent, and
integrated with new leather of the same type (Figure 12.8, right).
The last example of restoration of a leather cover is presented due to its particular damage
connected to a tanning defect and its conservation in very humid environment. It deals with
a manuscript volume (Index Zauli Naldi, 18th century, Manfrediana Library in Faenza),
whose front cover was broken and detached from the wood, while the back cover was
almost completely missing (Figure 12.9). The analyses revealed that it had been vegetal
tanned and its pH was 2.8.
In this case the cover was cleaned and humidified on the flesh side with calcium
bicarbonate to increase the pH. The usual integration with new non dyed vegetal tanned
leather completed the work (Figure 12.9).

Figure 12.9 – Volume Index Zauli Naldi before any intervention (left)
and after restoration (right).

12.7.3 Upholstery of a telescope

This ancient Campani telescope, dated back to 1700 ca., is kept at the Specola Museum in
the University of Bologna, It is composed of six tubes inserted into one another; the closed
telescope is 134 cm long, and 9.5 cm in diameter; when open, the length reaches 474 cm.
The tubes are paper made with wooden slats; the five smaller tubes are coated with leather

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in their initial section, and with marbled paper in all the remaining length. The external
tube is completely covered with leather, and the analyses demonstrated that it was made
from two vegetal tanned skins of goat. The leather surface is decorated with golden
stamping.
The telescope has come to us in bad conditions, with tears and lacunae on the external
tube, as well as the initial coating of the other tubes (Figure 12.10).

Figure 12.10 – External tube (over) and detail of the head of a minor tube (under)
of the Campani telescope.

The conservative intervention has consisted of thorough cleaning with methylcellulose and
neutral detergent, followed by the arrangements of lacunae and tears. The last operation
was lubrication with a mixture of oil of ox foot and anhydrous lanolin (Figure 12.11).

Figure 12.11 - Details of the leather coating of the Campani telescope,

before (left) and after (right) restoration.

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Bibliography

AA.VV., La Conceria in Italia dal Medioevo ad oggi, edito dalla rivista “La Conceria”,
Milano, 1994.
Berardi M.C., Il cuoio, in Conservazione dei materiali librari archivistici e grafici, vol. I,
M. Regni e P.G. Tordella (a cura di), Allemandi, Torino, 1996, pp.93-100.
Bravo A.G., Storia del cuoio e dell’arte conciaria, Associazione Italiana dei chimici del
cuoio, Tipolitografia Bongi, San Miniato, 1996.
Brunello F., Storia del cuoio e dell’arte conciaria, Fenice S.p.A., Tipografia Rumor,
Vicenza, 1991.
Calloni C., Istologia, Giunti, Firenze, 2007.
Caniglia V., Maffè S., Chimica e tecnologia nella fabbricazione del cuoio, Levrotto &
Bella, Torino, 2001.
Caniglia V., La pergamena, oggi come duemila anni fa, Ananke, Torino, 2001.
Casaburi V., Metodi di analisi e ricerche delle industrie del cuoio presso la R. Stazione
Sperimentale per l’industria delle pelli e delle materie concianti, S.I.E.M., Napoli,
1938.
Di Febo A., Il trattamento del cuoio, in «CABNEWSLETTER», 3, 1992, pp. 5-6.
Di Febo A., Il trattamento del cuoio/2, in « CABNEWSLETTER», 4, 1993, pp. 5-8.
La Lande J., de, L’art de faire le parchemin, Parigi, 1762.
La Lande J., de, L’art du tanneur, Parigi, 1764.
La Lande J., de, L’art du Corroyeur, Parigi, 1767.
Leghissa S., Compendio di citologia e istologia, Utet, Torino, 1966.
Motta P., Anatomia microscopica, Piccin, Padova, 1984.
Plenderleith H.J., Werner A.E.A., Il restauro e la conservazione degli oggetti d’arte e
d’antiquariato, Mursia editore, Milano, 1986.
Reed R., Ancient skins, parchment and leather, London, New York, 1972.
Regni M., I cuoi dorati e dipinti: tecniche e conservazione, in Conservazione dei materiali
librari archivistici e grafici, vol II, a cura di M. Regni e P. G. Tordella, Allemandi,
Torino, 1996, pp.407-420.
Schultz S. J., The leather manufacture in the United States, New York, 1876.
Scianna N., The use of lipids to protect the leather of ancient book bindings, in connection

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with the action of microorganisms, in: Proceedings of the 13th World Congress of the
International Society for Fat Research, Section Lipids and Works of Art, Marseille,
1976, pp.75-78.
Scianna N., Solving cases: book and paper artefact restoration, Brepols, 2010.

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13 – INORGANIC MATERIALS
OF ORGANIC ORIGIN

13.1 The materials

13.1.1 General information

This section is about a range of little-known raw materials, but always employed for
making artefacts using specific and very particular production technologies. All these
materials are usually defined as inorganic, but they have an organic origin. They are bone,
ivory, coral, and mother of pearl. These materials have been dealt together because are
formed by inorganic matter intimately combined with a small fraction of organic matter
and because their conservation and restoration operations are similar.
As far as conservation concerns it is important to respect the chemical, physical and
structural differences that distinguish everyone of these materials. Bone and ivory have a
proteic nature and are part of the load-bearing frame of vertebrates of the Cordata phylum
and in particular of Mammalia class. Coral and mother of pearl are calcareous formations,
which support and protect the invertebrates of the Cnidaria phylum and the Mollusca
phylum.
Artefacts of bone and ivory, coming from an archaeological site, suffer a loss of their
original appearance because of a regression of the organic substance in their chemical
composition. Similar artefacts, not coming from soil but placed in a museum without
suffering any aggressive treatment, preserve a good look and can regain their vitality if
subjected to adequate operations.
Coral and mother of pearl have a very low percentage of organic substance in their
chemical composition. For this reason, in archaeological sites with not acid soil they
maintain their original appearance, while in museum collections, without regular
maintenance, can loose their good original look.

13.1.2 Bone
Bones are the components of the skeleton, which is the support apparatus of all the
vertebrates. In the great class of Mammalia, the most frequently used bones for getting

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manufactured articles are those belonging to the Ungulate order.

Moreover it is correct to associate to the bones also the antlers of the Mammalia of the
Cervidae family, as material for this type of use. In fact, the antlers are an external
development of the skeleton of these animals and, in particular way, of the bone of the
skull in some kinds of Cervidae. For a long time, bones and antlers have been used for the
predisposition of utensils and elegantly you can work them for the realization of artistic
articles and coverings of value for other types of material: wood and metal. Their use is
linked to the availability in the geographical zone of production.
The hard tissues of the vertebrates of the Equidae and Bovidae families, because of their
good characteristics, were the most commonly used; both the longest and the largest bones
were exploited. To obtain artefacts, even bones of animals of smaller size were not
disdained, as well as larger and light ones of the order Cetacea, although they are very
spongy. The matter that constitutes the hard tissues of vertebrate is formed by the
mineralization of connective tissues. That is why we can find, in bones, an inorganic
component that varies from 57 to 60% and 43 to 40% of an organic component. The
percentages, however, can be very different depending on many factors.
The chemical composition of bone is defined by a predominantly inorganic fraction,
consisting mainly of calcium phosphate and calcium carbonate associated with minor
amounts of other salts. This mineral component comes in the form of microscopic crystals
known as hydroxyapatite, with chemical formula Ca5(PO4)3(OH). This calcium phosphate
hydrate is intimately combined with the organic portion, which consists of collagen fibers
contained in an amorphous substance of protein complexes.
The material that makes up the bones shows a structure with lamellar systems, organized in
different levels of growth (Figure 13.1). The typical conformation highlights areas of
compact tissue where are more or less visible nutritional channels, and less compact areas
that have the characteristic sponginess. The bones have a low hardness (2-3 on Mohs scale,
see chapter 8, paragraph 8.3.1) and can be easy to work with specific technical solutions.
The material to be processed is selected and drawn from strategic parts of the skeleton.
Usually the parts used are the ones where you can make the most of the original size of the
bone in comparison to the model of the artefact to be realized and, in particular, where are
less frequent those elements characterizing the bone, as the cavities, the alimentary canals,
the most porous and spongy parts (Figure 13.2).

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Figure 13.1 – Crossing section of bone.

Figure 13.2 – Longitudinal sections of caw bones whit the alimentary canals.

The antlers of Cervidae family, as it has already been specified, are a modification with
external development of bones of the animal’s skull. The chemical composition of antler is
comparable with that of the bones of the skeleton, but some differences are given due to a
different internal structure as a result of specific development needs. This therefore results
in a lower hardness than the bones. Each year the antlers grow on small permanent
protuberances of the frontal bones named pedicles. For this reason, the morphology of this
material is coarser and may vary depending on the physical development of the animal
(Figure 13.3). Although seemingly the material of the antler is compact as that of the bone,
it is immediately distinguishable by the more heterogeneous and shapeless outside, and
mainly for a higher internal porosity.

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Figure 13.3 – Crossing section of antler.

13.1.3 Ivory
The ivory is a differentiated form of dentine, the material that makes up the teeth of most
vertebrates belonging to the mammalian class. The teeth are a specialized form of bone
tissue and are composed mostly of dentine. The dentine, arranged around a cavity of the
pulp, is provided with a protective layer. In the upper part, i.e. the area more exposed to
use, is covered by the enamel, while in the lower zone, in correspondence of the root, is
covered with cement.
Ivory, for its warm appearance, its excellent strength, ductility, and ease of processing, was
considered a very sought material, already very rare in Roman times.
The animals from which the ivory was mainly obtained were the great pachyderms, among
which we should remember the mastodon and the mammoth, whence comes the so-called
“fossil ivory”, and the most recent examples of African and Asiatic elephants. It was also
used the material obtainable by the big canine teeth of the Mammals belonging to the
Hippopotamidae family, and most of the ungulate Suidae family like pig, wild-boar, wart-
hog, babirusa and peccary (Figure 13.4). Among the marine Mammals they used to use the
tusks of the walrus, the canine tooth of narwhal, and various types of teeth and whalebone
of the Cetacea order.
However, the term “ivory” has often wanted to state only the most valuable dentine
obtained from the tusks of elephant, from which we obtained a dense and compact
material, with a silky look, which has a radial reticular structure (Figure 13.5, left),
consisting by a tubular system (canalization) (Figure 13.5, right).

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Figure 13.4 – Transversal section of terrestrial and marine Mammals: elephant,

hippopotamus, wart-hog, walrus, narwhal, and sperm whale.

Figure 13.5 – Ivory artefact whit radial lines (left) and crossing section of ivory (right).

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Each type of ivory has a different aspect, structural characteristics that vary, and a
transverse section which is very characteristic. All types of ivory, as well the bone, have a
chemical composition, where the most important part of mineral salts is combined with an
organic substance, in varying percentages depending on many factors. The inorganic part is
mainly composed of calcium and magnesium phosphates, and is however attributable to
the formula of hydroxyapatite, Ca10(PO4)6(OH)2, since the unit cell consists of two
molecules. The organic matrix consists of collagen fibers and protein complexes.
Ivory is easy to work for its limited hardness. In fact, the dentine is softer than bone,
because what makes the teeth resistant are enamel and cement, which in the processing of
artifacts are usually removed. For its protein nature, ivory is anisotropic, has a medium
degree of porosity, and a degree of hygroscopicity which can vary depending on the animal
it comes from and the processing method used for the production of the artefact.

13.1.4 Coral
Corals are marine animals included in the Cnidaria group. Considered for a long time a
marine plant, instead coral is a colony of tiny polyps that build a protection of limestone
composition that takes complex forms. The coral is, therefore, hard exoskeleton due to a
calcareous secretion of several species of tiny polyps. Depending on the species, these
marine animals are able to build reef formations of different shape and color (Figure 13.6).

Figure 13.6 – Form and transversal section of coral.

Corals have form of a tree, varying in color from dark red to pink to white. They consist of
two distinct parts: an inner harder and compact that acts as a support, and an external, more
tender (leather hardness), where the polyps are. This sort of outer shell, called ‘cenosarco’,

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through a system of small channels, connects together all the individuals composing the
colony. The inside of the branches, used for the production of manufactured goods, is
called ‘ceppo’ and is made mostly of calcium carbonate (CaCO3) in the form of calcite
produced by the secretion of polyps.
The chemical composition of the ‘ceppo’ also includes minor amounts of magnesium
carbonate, and variable amounts of calcium sulphate, iron oxide, and phosphates. All the
differences found by the analyses published in the literature are due to different species of
corals examined. Part of the organic component (around 1.35%) is not yet well determined,
but it was associated with the presence of pigments. The structure consists of needle-like
particles, radially arranged in layers perpendicularly to the axis of growth. This particular
structure defines the radial transverse section of the coral.
The hardness of the material is variable depending on the species of coral and can be
evaluated between the 3rd and 4th degree in the Mohs scale (see paragraph 8.3.1).
The material used for the production or for the coating of artifacts is carefully selected and
taken so as to maximize the form of branches and branch points of the coral formations.
The coral, regardless of its color, has a mat appearance, but, with a good manufacturing
process, it can acquire a considerable luster.

13.1.5 Mother of pearl

The mother of pearl is a material produced by animals that live in the water and that belong
to the Mollusca group.
In particular, the mother of pearl is present and is easily visible in some Bivalve Mollusca
and some Gasteropoda Mollusca living in freshwater and saltwater. This material is part of
a protective structure that we all know as shell, and which shows itself in many shapes and
colors (Figure 13.7).
More exactly the shells are formed by the secretion capacity of the epithelium of the
mollusk and by the overlapping of the layers of growth. This process is able to form a hard
and rigid structure that the mollusk uses for protection. The layers that make up the
thickness of a shell show different characteristics. The outer layer, called ‘periostraco’, is
the oldest layer of the shell, where the typical colors are located. The innermost layer, in
contact with the shellfish, called mother of pearl, is the newest layer of the shell and has a
light color with iridescent shine.

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Figure 13.7 – Two kinds of mother of pearl with two different colours.

The chemical composition of a shell is given by a high percentage of calcium carbonate

(calcite, CaCO3), which in the inner part is in the form of lamellar crystals of aragonite.
Calcium carbonate is connected to a small organic part, formed mostly by ‘conchiolina’
(C32H48N2O11), which is a scleroprotein with a high water content.
The percentages of the three components vary depending on the area of the shell, the type
of mollusk and the geographical area of origin. Depending on the characters just mentioned
also the hardness varies.
In the past, the mother of pearl was obtained only from the shells of some species of
mollusks. Its value is due to a good workability, but especially to a shiny and iridescent
appearance, due to the stratified structure (Figure 13.8).
The mother of pearl is also the matter that constitutes the pearls. Also the pearls are of
various shape, size and color.
The pearls are formed by the same secretion that forms the mother of pearl, which
incorporates any foreign particle that is accidentally introduced into the valves of the shell.
In this way the mollusk isolates and makes ineffective the foreign body. Over time, the
deposit of secretion becomes increasingly large, with the same characteristics of the
mother of pearl. Therefore, the pearls are the product of a reaction implemented by the
mollusk as a defense. Of course, the cultivation of pearls involves the introduction of
artificial particles within a particular species of mollusks.
The defense mechanism will immediately coat the foreign body, which is extracted from
the mollusk when it has reached the desired thickness and then the desired size of the pearl
to be produced.

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Figure 13.8 – Mosaic tesserae made of shiny and iridescent mother of pearl,
and detail of their surface.

13.2 The restoration operations

The principles required to operate on an artifact with cultural value are common to all
types of matter, but it should be stated that for this particular type of products made from
inorganic materials of organic origin is even more necessary to have an excellent
knowledge and use much caution, because of their delicacy. It is well known that if you
restore the matter of a work and not working properly, you may worsen the conservation
state and even lose information that an ancient artifact may give us. Before developing the
restoration project is necessary, therefore, to acquire a set of data that should lead to the
complete knowledge of the artifact in question (Table 13.1).
The conservation state, defined by alteration and degradation that affect the appearance of
the artifact, can be defined based on previously published specific denominations.
For products made with the above mentioned materials is certainly more difficult to find
evidences on the technology of production, which, however, would open a vast and
interesting chapter. It should be borne in mind that the production techniques over the
centuries have changed, and their study is only now becoming predominant over the
restoration project.
A wrong restoration could remove a high percentage of data that can be transmitted from
the cultural object. The restoration intervention will be oriented to avoid excessive changes
of the properties that characterize the work (Table 13.2).
Table 13.1 – Plan of the preliminary phase of study.

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Historical context
Cognitive
Material characterization
investigation
Production technique
Anamnesis of the Transformation related to the matter and production technique
conservation state Transformation related to the life of the work
Diagnostic Determination of the nature of matter
investigations Determination of alteration and degradation
Photographic and graphic documentation, and mapping
Testing and verification of the tools and products that you intend to use

Table 13.2 – Plan of the operative phase.

Microclimatic characters
Thermohygrometric conditions
Preservation Light radiations
Air quality
Biodeteriogens
Pre-consolidation, consolidation
Cleaning
Restoration Bonding
Grouting, integration
Protection
Written, graphic and photographic documentation
Maintenance

Due to the material of which is made this kind of artifacts, it is important to detect even the
slightest trace present on the surface. For this reason, most operations are performed with
the aid of the microscope. Tools and products must be used with infinite caution.
As for the products to be used for cleaning, to avoid introducing substances that may alter
the original chemical composition, it is preferable to intervene with mechanical methods
because the blade of the knife, if used with extreme lightness, is harmless in respect of
these delicate materials. It may be possible to act with volatile solutions prepared with
different percentages of water, alcohol, and acetone depending on the case to be addressed.
The previously tested aliphatic solution, called “3 A”, can not be purchased already made,
but it should be prepared with the individual components in different percentages
depending on the needs to which to cope.
The same caution is required in the pre-consolidation, the consolidation and bonding

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necessary in situations of disruption and breakage of the material. The resins used must be
very tough and indispensably reversible with water, alcohol or acetone.
Fillings and integrations are to be avoided. If they are really necessary to give firmness and
support for the piece, they must be obtained with the help of a material that is softer than
the material forming the article and with a proper tonal gradation to the case. To do this
you can prepare the pastes to color, or pre-colored, that are placed in contact with the
original matter of the work by means of a primer. In addition, the color must have a tone
that is not invasive, and does not quickly darken.
Very important is also the storage environment of the work that must meet certain
parameters related to temperature, humidity and light. The literature provides many details
about it, but it is better to specify that, in relation to humidity, sometimes even inadequate
values can be considered suitable if they maintain the continuity already gained from the
material of the artifact.

13.3 Cases of study

13.3.1 Recovery and restoration of an archaeological artifact

In an archaeological site is not usual to find ancient artifacts made with the materials
discussed in this chapter. As already specified in the preceding paragraph, the state of
conservation of artifacts made of bone and ivory, found in soil, is different from that of
objects made of coral and mother of pearl. Surely the discovery of artifacts in coral and
mother of pearl is rarer and in any case limited to the decorated surfaces of artifacts made
with other materials. In addition to the small size, the difficulty of the discovery is related
to the difficult recognition of these materials. As for the artifacts of bone and ivory, the
identification is definitely easier, but the material aspect is very different and dependent on
the type of soil in which the artifact remained.

THE IVORY FROM PHOINIKE

The ivory artifact was found September 24, 2003, in the grave 41 (S5 Lower Town,
US192) at the necropolis of the Hellenistic-Roman town of Phoinike in southern Albania.
The Italian Archaeological Mission directed by prof. Sandro De Maria (University of
Bologna) was working in this archaeological site since 2000. After the first surveys made

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by Luigi Maria Ugolini between 1926-1927, the research has been resumed, either in the
urban area, either in the territory belonging to the town.
The necropolis, excavated and studied by prof. Giuseppe Lepore, is at the base of the
southern slope of the hill on which stands the ancient town of Phoinike. In this area there is
a succession of burials ranging from the Hellenistic period (second half of the fourth
century BC.) to the imperial Roman age (the most recent attestations concern the beginning
of the third century AD).
The tomb 41, or ‘burial of the surgeon’, was obtained into the space between two tombs of
the Hellenistic period and it contained two separate depositions: a double inhumation,
attributable to a 40 year old man and a woman of 30, and a incineration attributable to a
man of about 35 years. The dating of the finding seems to lie in the Flavian-Trajanic age
(late first century to early II century AD) and states an interesting case of coexistence of
different rituals in the middle imperial age (Figure 13.9).
The two individuals in the inhumation burial had been deposed in a unique wooden box
and with the head northward. Abundant and of great interest was the outfit that had been
laid at the feet of the burial: at south-west there were toilet items relevant to the woman,
and in any case referring to the female world, among which a gilded bronze pin with a
decorative element made of mother of pearl, while to the south-west there were items
related to the man, that included an interesting set of surgical instruments from which it
derived the name of the burial.
It is precisely in the context of the surgeon burial, that the ivory under study was found. In
a predominantly calcareous soil, light in color but with variable appearance due to the
presence of residues of the burial, iron tools were identified along with a stone ‘tabula
scriptoria’ with its stylus in bone, and in particular a iron pincer and two bronze scalpels
which had to be placed within a container. Of the container, with cylindrical shape, has
been found only the precious cover made of ivory material. It was presumably obtained
from a section of African elephant tusk. Due to the size of the diameter (about 8 cm) and
given the evident cleavage of the material (the reticular structure and radial typical of the
elephant tooth is more resistant to cleavage), it is also possible to envisage the use of ivory
from the canines of hippopotamus, very much in use at that time because of the already
difficult availability of elephant ivory, in any case wanted for his more evident whiteness.

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Figure 13.9 – Tomb n. 41 with multiple burial and detail of where the ivory was found.

The ivory of Phoinike, definable as a lid for pyx, has been restored on the occasion of
classes during the 2005-2006 edition of the Master Degree course on “Science for the
conservation-restoration of cultural heritage” organized by Dr. Rocco Mazzeo, Professor of
Chemistry for Cultural Heritage at TE.CO.RE., University of Bologna, Ravenna Campus.
The restoration was carried out as a practical example from 19 to 23 June 2006.
The finding, with shape of a lid, was received still incorporated into the soil of excavation
(Figure 13.10, left). By a first visual analysis of the find, one could see that the material
had a color that was altered by staying in a soil rich in elements relevant to a inhumation
burial and it appeared significantly flaked.
The first intervention was to perform a cleaning of the surface of ivory, to remove the
excavation soil and to allow an adequate pre-consolidation with acrylic resin, in order to
avoid the loss of the flaking parts. Despite this and because of disconnections, many
flaking parts did not reach a sufficient adhesion, so it was necessary to apply, with glue,
gauze perfectly adherent to the entire surface (Figure 13.10, right).
Applied on the visible side of the artifact, it has ensured the complete fixation of all flaking
parts and allowed to operate in the lower side of the artifact without any problems. The
removal of the soil was performed with a scalpel. Then, punctual micro-washes were
carried out with the solution “3A” (acetone, alcohol and water in equal parts), immediately
followed by a fast drying.

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Figure 13.10 – The ivory artefact in the archaeological soil (left),

and gauze adherent to the surface of the ivory artifact (right).

Consolidations and adhesions were made with acrylic resin to ensure good reversibility.
The subsequent application of gauze, on the cured side of the artefact, has allowed the
removal of the previously applied gauze and the execution of the same cleaning operations:
micro-washing, drying, consolidation and adhesion even on that side of the artefact.
Each operation was carried out with extreme precision and speed in particular, in order not
to lose sight of the integrity of the artefact. The small flaked pieces looked all equal, but at
the end of the work a decoration formed by ovals appeared on the surface of the ivory,
which had been realized as bas-relief (Figure 13.11, left). A graphic representation could
evidence the important ornament, which was dug on an abundant portion of material
(Figure 13.11, right).

Figure 13.11 – Ivory fragments before gluing (left)

and drawing of the ivory artefact (right).

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13.3.2 Interventions of structural reconstruction

The artefacts coming from collections, if well preserved, have a more realistic and
recognizable appearance. In the exhibition ambit, it can happen that you must intervene on
the shape of an artefact to ensure a linkage between the detached parts, to compensate the
loss of supports, or to reconstruct missing parts in order to deliver its correct reading to the
artwork.

THE ‘DITTICO DI MURANO’

In the hall of the ivory material of the National Museum of Ravenna, is exposed the so-
called ‘Dittico di Murano’ (inv. 1002), which is actually a cover of gospels, dating to the
sixth century. It was restored in the Restoration Laboratories of the Soprintendenza per i
Beni Architettonici e Paesaggistici of Ravenna in November 1989 (Figure 13.12).
The artifact, executed in African elephant ivory, is composed of five panels of considerable
thickness, which were originally held together through a series of tenon and mortise joints.
During its lifetime it suffered damage and structural changes until it has lost its original
unit. Due to the loss of the functions of connecting of the various panels, it had been
placed, in an unknown time, on a wooden board to which it was glued through a thick
sheet of paper that should probably serve as a cushion or protection against the wood.

Figure 13.12 – ‘Dittico di Murano’ before and after restoration,

which includes its structural reconstruction.

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After analysis of the conservation state, a restoration work was planned, which is
extremely respectful of the characteristics of the different parts to be joined and tolerant of
the physical characteristics of flexibility caused by climatic changes. After the total
reclamation of carved surfaces, it was decided to free the artwork from foreign materials,
and in particular to study a system of rejoining that made possible all movements to which
the ivory could be subjected.
The disassembly of the different parts of the ‘dittico’ has allowed us to observe and
identify the original conjunctions of the structure, discriminating the holes made during
repairs to which the artefact had been subjected over time. The original system foresaw
that the central plate, provided with tenons on all four sides, get stuck between the four
external plates. In addition, the original method of joining was concealing the mechanisms
linking the ivory sheets, leaving undisturbed the iconographic program represented.
All holes drilled for the subsequent rejoinings, however, were remarkably clear, because
they interrupted the serial design of the frames, and interfered with the background of the
representations.
After careful study of the ancient functionalities of the covering, it has been put in place a
system of assembly that even satisfied the exhibition requirements. The reconstitution of
the unit of the artefact was obtained by respecting the joints of ‘tongue’ type, characteristic
of the original mounting system, without introducing any attachment point between the
different panels. It was therefore necessary to introduce an element that can create a
support without interfering with the artifact in order to ensure a clear ‘reading’ of the
artwork (Figure 13.13). For this reason we have chosen a Plexiglas support. The favorable
conditions, offered by this synthetic material, are transparency and a low coefficient of
expansion.

Figure 13.13 – Drawing of the complete longitudinal

section of the ‘Dittico di Murano’ and its support.

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The joining of artifact and support was given to the action of magnets that have the
advantage of providing a good bond without creating constraints (Figure 13.14). The
magnets inserted into the holder are six. They exert attraction on correspondent washers,
which are isolated from ivory through felt pads, and are fixed by flat-head screws carefully
coated with Teflon. This system has enabled reassembly of the artefact with movable
joints, properly insulated and fully reversible (Figure 13.15).

Figure 13.14 – Fixing system for the ‘Dittico di Murano’.

Figura 13.15 – Detail (over) and drawing (below) of the working system of the magnet.

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THE PASTORAL OF THE NATIONAL MUSEUM OF RAVENNA

Exhibited in the hall of the ivory material of the National Museum of Ravenna, the pastoral
concerned (inv. 1115) is an artifact that consists of a crook in ivory, of the thirteenth
century, and a polychrome stick of the fifteenth century, divided into independent sections
according to a typology suitable for traveling (Figure 13.16).

Figure 13.16 – Drawing of the pastoral in the top (crook) and low part with joint system.

The artifact was restored in April 1990 in the Restoration Laboratories of the
Soprintendenza of Ravenna. Before the conservative intervention, the pastoral showed
significant structural damage due to loss of material and especially the loss of his duties as
disassembly and reassembly.
The stick, 165 cm long, is composed of 21 elements of different length and sloping
downward. The strong chromatic effect of the artefact is caused by the different materials
used for the realization. The bi-chromatic alternation of ebony wood and bone is made
precious with a floral decoration painted in red, black and gold (Figure 13.17).

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Figure 13.17 – Detail of the pastoral with decorated bone and ebony,
and microscopic image of pigments on bone.

The possibility of disassembly was provided by fixed conjunctions, and by eight screw-
junctions that were obtained between the ebony and the beech, which constitutes the inner
core of the elements in bone.
In addition to degradation due to wear relating to its use, the object showed remarkable
tampering due to several repairs over time. The materials inserted to recreate the union of
different parts were nails and metallic wires, bonds with irreversible polyester resin, and
the insertion of wedges of light wood. All these insertions, in addition to providing a fixed
but shaky union, were the major cause of the significant structural damages present (Figure
13.18).
A careful graphic documentation was then necessary for a thorough study and for the
elaboration of the executive project. The resolutive project had to return the pastoral to its
original function, with the possibility of disassembly and reassembly.
So, it was decided the complete disassembly of the pastoral in all its parts and especially to
eliminate all foreign materials (Figure 13.19). After having predisposed an accurate
protection, that would have allowed handling the original parts, the work of disassembly
began.

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Figure 13.18 – Detail of old fixing connections among the elements.

Figure 13.19 – Drawing of the original joining system among the elements.

The bold intervention of structural reconstruction has provided the remake of the original
assemblage by means of screw-type mortises and tenons. In the parts in ebony, the thread
of the mortises was reset, and was rebuilt the internal structure of bone parts with beech
wood. Each interior remake in beech was provided with a screw-threaded tenon that is
adapted to the threaded mortise of the ebony parts. All work was carried out with the help
of a skilled turner who reconstructed the screwing originally planned, so that each side
could match perfectly (Figure 13.20). The return of a solid structure made it possible to
proceed with the normal stages of restoration, which has returned to the artifact its original
identity.

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Figure 13.20 – Turning of the wood elements for joining system.

13.3.3 Analysis of a stain on ivory artefact

Among the most important pieces kept in the National Archaeological Museum in
Damascus, there is a ivory head, dated 13th century B.C., from Ugarit (Syria), with a metal
crown on the forehead. Since some time, a light blue coloured stain is growing above the
right eye, just few millimetres under the crown. So, the light blue stain was analyzed by
energy dispersive XRF (30 KV, 20 µA, 60 seconds), as it is shown in Figure 13.21.

Figure 13.21 – XRF analysis of a light blue stain on the forehead of a ivory head.

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Three different measurements were done: two in light blue area and one on the crown
metal. Results are shown in Table 13.3. As expected, the ivory is constituted by calcium,
with unusual concentrations of iron and copper, while the other detected elements are
negligible.
The metallic crown is mainly made of copper, with minor amounts of gold and iron, and
traces of calcium, arsenic, sulphur and silver. This metal can be recognized as ‘shakudo’, a
Japanese term which indicates an alloy of copper with gold (around 4-5%).

Table 13.3 – Chemical composition of the ivory head (relative intensities).

Light blue stain
Element Metallic crown
Position 1 Position 2
Ca 5458 5056 252
Fe 694 467 1425
Cu 419 659 16106
P 43 78 ---
K 75 67 ---
Ti 59 55 ---
S 36 51 70
Mn 39 41 ---
Au (Lα) --- --- 1120
As --- --- 108
Ag --- --- 19

According to these results, the anomalous contents of iron and copper in the ivory are
evidently due to diffusion of iron and copper coming from the crown. In addition, if the
composition of the crown is taken into account, it can be noted that the diffusion of iron is
proportionally greater than that of copper.
In conclusion, the growth of the light blue stain on the ivory head is due to the diffusion of
iron and copper from the crown, favoured by the fibrous microstructure of the ivory. The
stain appeared and grew after a cleaning treatment, carried out just one or two years ago.
So, probably it is the consequence of the use of not suitable chemical reagents and/or a not
well washing at the end of the treatment.

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Bibliography

Cavenago Bignami Moneta S., Gemmologia, Hoepli, Milano, 1965.

Cristoferi E., Il restauro del “Dittico di Murano”. Studio per la ricomposizione strutturale
di un avorio del Museo Nazionale di Ravenna, in: KERMES, 1991, n.12, pp. 34-39.
Cristoferi E., Gli avori. Problemi di restauro, Nardini Editore, Firenze, 1992.
Cristoferi E., La materia e la tecnica, in: “La collezione degli oggetti in avorio e osso”, L.
Martini ed., Museo Nazionale di Ravenna, Poligrafico e Zecca dello Stato, Roma,
2004.
Cristoferi E., Conservare e restaurare: l’intervento come progetto, in: QDS, Quaderni
della Soprintendenza per i Beni Architettonici e Paesaggistici di Ravenna n.6, 2006.
Cristoferi, E., Conservare e restaurare: un esempio di intervento, in: “Eburnea Diptycha. I
dittici d’avorio tra Antichità e Medioevo”, M. David ed., Edipuglia, Bari, 2007.
De Maria S., Gjongecaj S., “Phoinike I. Rapporto preliminare sulla campagna di scavi e
ricerche 2000, Firenze, 2002.
De Maria S., Gjongecaj S., “Phoinike II. Rapporto preliminare sulla campagna di scavi e
ricerche 2001, Bologna, 2004.
De Maria S., Gjongecaj S., “Phoinike III. Rapporto preliminare sulla campagna di scavi e
ricerche 2002-2003, Bologna, 2005.
De Maria S., Gjongecaj S., “Phoinike IV. Rapporto preliminare sulla campagna di scavi e
ricerche 2004-2006, Bologna, 2007.
De Maria S., Gjongecaj S., “Phoinike V. Rapporto preliminare sulla campagna di scavi e
ricerche 2007-2009, 2011.
Jedrzejewska H., Principi di restauro, Fiesole, Firenze, 1983.
Mac Gregor A., Bone Antler Ivory & Horn. The Technology of Scheletal Materials Since
the Roman Period, Croom Helm, London & Sydney; Barnes & Noble Books,
Totoma, New Jersey, 1985.
Monesi V., Istologia, Piccin ed., Padova, 1977.
Matienzo L.J., Snow C.E., The chemical effects of hydrochloric acid and organic solvents
on the surfaces of ivory, in: Studies in Conservation, n.31, 1986, pp. 133-139.
Villavecchia – Eigenmann, Nuovo dizionario di merceologia e chimica applicata, Hoepli,
Milano, 1973.

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ACKNOWLEDGEMENTS
Superintendent, Arch. Antonella Rinaldi, for the use of photographic material from the
photographic archive of SBAP in Ravenna (the photos were taken by Paolo
Bernabini).
Prof. Sandro de Maria and prof. Giuseppe Lepore for the use of photographic material of
the tomb 41 in Phoinike (Department of Archaeology of Ravenna – University of
Bologna).
Prof. Rocco Mazzeo for the use of photographic material of the intervention on the ivory of
Phoinike (Faculty TE.CO.RE. in Ravenna – University of Bologna).
The National Museum of Damascus (Syria) for the use of the image of a ivory artefact and
the correspondent analytical results.

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14 – ANALYTICAL TECHNIQUES

14.1 General information

14.1.1 What analytical techniques are

An analytical technique is a method that is used to determine the value of a certain
characteristic of the material, for example the amount of a chemical compound or the
concentration of chemical elements. There is a wide variety of techniques used for
analysis, from a simple analytical balance to very advanced techniques using highly
specialized instrumentations. As an example, the most common techniques used in
analytical chemistry are listed in Figure 14.1.
The analytical techniques are characterized by their invasiveness, type of information
supplied, physical state of the sample, being portable or not, resolution, how much sample
it needs, expression of the result, what materials can be analyzed, costs of instrumentation
and analysis.
The contribution given by analytical investigation to the knowledge of the cultural heritage
can be related to:
- technological information,
- provenance studies,
- conservation and restoration,
- dating or authentication of a finding.
Some examples have been shown in the previous chapters.

14.1.2 Invasive and not invasive techniques

For conservation and restoration activities, it is very important to know when it is
necessary to take a sample and to bring it into the analytical laboratory or not. In addition,
when a sample is needed, it is important to know if it will be destroyed or not, and in
which amount.
As a consequence, the analytical techniques can be classified into:
- destructive, when the sample or most part of it is destroyed during the analysis:
optical microscopy with transmitted light (for the observation of thin sections),

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wavelength dispersion X-ray fluorescence (WDS-XRF), X-ray diffractometry

(XRD), ionic chromatography;
- micro destructive, when only few milligrams of sample are destroyed: thermo-
differential and thermo-gravimetric analyses (TGA-DTA);

ANALYTICAL TECHNIQUES

Optical or Radiochemical
spectroscopic - Neutronic Activation
- UltraViolet/Visible Parting Electrochemical - X-Ray Diffraction
- InfraRed - X-Ray Fluorescence
Thermal
- Atomic Emission - Chromatographic - Ion-selective
- Atomic Absorption techniques - Thermal electrode
- Colorimetry analyses

Figure 14.1 – List of the most common techniques for analytical chemistry.

- invasive but not destructive, when they need a sample that will not be destroyed:
scanning electronic microscopy with energy dispersion microprobe (SEM-EDS),
infrared spectroscopy (IR), ultraviolet/visible spectroscopy (UV/Vis), optical
microscopy in reflected light (stereomicroscopy);
- not invasive, when there is not the need of a sample and the analyses can be done
directly on the artwork: colorimetry, energy dispersion X-ray fluorescence (EDS-
XRF), Raman spectroscopy.
In addition we can distinguish:
 qualitative analyses = only identification of chemical elements or minerals or other,
 quantitative analyses = quantification (%, mg/l, etc.) of the detected chemical
elements, minerals, and so on,
 semi-quantitative analyses = only an approximate evaluation of the detected
chemical elements, minerals, etcetera.
The needs of each technique with reference to the preparation and amount of sample to be

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analyzed will be outlined in the subsequent specific paragraphs.

Most of the analyses are performed in scientific laboratories where a precise and/or heavy
analytical apparatus can be appropriately located and set up. These equipments usually
need a very stable support, because they include very delicate parts. In addition, sometimes
it is necessary to cool them by water circulation, or they need to work under vacuum, and
so on. Therefore, in most cases it is necessary to take samples from the artwork, or from
the monument, and to analyze them in laboratory. Of course, it deals with invasive and
often destructive analytical techniques.
When it is not possible to take samples, the analyses cannot be performed, unless it is a
‘transportable’ instrumentation, and it is possible to bring it in the place where the object to
be analysed is. This is possible when the analytical instrument is not to much heavy and/or
bulky, and it does not need any special plant, other than a source of electricity. Usually it
deals with non invasive analytical techniques.
Among the transportable instrumentations, a special category deserves to be highlighted,
i.e. the ‘portable’ instruments. These are very interesting and useful, because they are light
enough to be held in hand and easily approached to the object to be investigated. The
energy source of these instruments generally is a battery, so that their time of operation is
conditioned by the duration of the battery. Therefore, it is opportune to have a reserve
battery to be used while charging the other.
Not many analytical techniques permit to perform ‘in situ’ analyses, but in recent years
their number is growing steadily, even though some of them are not so precise as the
correspondent laboratory instrumentations.

14.1.3 Definition of chemical analysis

Chemical analysis is the identification, in case determination, of the chemical elements
present in a material, without considering how they are combined (crystalline phases,
organic substance, etc.). As said before, also chemical analysis can be:
 qualitative = only identification of chemical elements,
 quantitative = quantification of the detected chemical elements,
 semi-quantitative = only a very approximate quantitative evaluation of the detected
chemical elements.
In a chemical quantitative analysis, the detected elements can be grouped on the basis of

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their concentration:
 main elements >1%,
 minor elements 0.1 - 1%,
 trace elements < 0.1 %.
The results of a chemical quantitative analysis are generally expressed in form of
percentage of the oxides of the different elements, with the addition of the ‘loss on
ignition’ (LOI), which includes all the volatile component under 1000 °C, mainly water
and CO2.
The preparation of a sample for chemical analysis must be particularly careful. In
particular we have to pay great attention to the grinding level and the precision of the
weighing. Of course no pollution of the specimen must always be assured.
Some techniques for chemical analyses require the specimen in solution, so that it is
necessary to know how to dissolve the sample.

14.1.4 Planning the sampling

The sampling (number of samples, collecting points, characteristics of the samples, etc.)
have to be carried out according to the aim of the analytical study.
The sampling must be representative, so that the number of samples to collect is closely
influenced by the different situations, for example:
 types of materials constituent the artifact or the archaeological or architectonic
structure,
 visible deterioration phenomena to investigate,
 extension of the archaeological-architectonic structure to study.
The sampling must take into account the conservation requirements of the
artifact/monument or of the archaeological structure.
The sampling must be carried out taking care to avoid being too invasive and producing
aesthetic damages. Only the minimal amount of material should be taken, according to the
kind of analytical program of investigation.
Sometimes scarce availability of money and/or time can reduce the number of samples and
then the sampling can be little representative.
The documentation of the sampling is fundamental. For this purpose is indispensable to
give a code to each sample and to describe its characteristics and the collecting point. Wide
photographic documentation illustrating the collecting area of each sample is very useful.

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In addition the collecting points have to be indicated on a map or a photo. Sometimes the
location of the sample can be simply indicated by a free-hand sketch.
According to the consistence and the structure of the material, the samples can be
fragments or powders, and different appropriate tools and sampling techniques can be
required: chisels of different dimensions, scalpels, drill for coring, brushes (for powdering
material). Of course a fragment can be composed of different parts (as in case of plasters,
glazed ceramics, mosaics) and each part will be analyzed separately.
The sampling should be carried out by, or in presence of, the professional who will analyze
the samples. Anyway, only a perfect understanding with the scientist conservator and/or
the restorer can bring to good solutions for all the situations.
The samples will be kept in plastic containers (transparent or opaque) of appropriate size.
On each container the identification code of the sample should be written by indelible
marking pen.
Analytical methodologies, typical of the exact sciences (physics, chemistry, etc.), applied
to the study of ancient materials can provide precise information about the provenance of
the raw materials, the production technologies, dating, the identification of the
deterioration products and of the deterioration mechanisms (diagnostic). Of course the
knowledge of the ancient materials and of their deterioration processes are fundamental
support for a correct conservation intervention.
Before starting the sampling, it is necessary to know and/or to do several things, according
to the following list:
- to define as well as possible the problem linked to the conservation intervention,
- to have an idea of the composition of the artefact,
- to define the state of conservation: alteration and degradation types,
- to individuate the analyses to perform at a first stage of the study,
- to decide if only non invasive analyses can be made or not,
- to define the type and the number of samples which seem necessary,
- to define the exact points for non invasive analyses,
- to prepare all is necessary to collect samples for destructive analyses; the sampling
must be carried out with the more suitable instruments in order to have the
necessary amount of sample with the minimum invasiveness,
- to give a code to each sample; the code should individuate both the single sample

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and the group to which it pertains,

- to prepare the instruments for documenting the sampling operations,
- to prepare the containers for the samples collected.
Of course, the practical realization of these points depends on the type of artefact under
observation and the type of material of which is made.

14.2 Optical microscopy

Optical microscopes can be subdivided in reflected light microscopes and transmitted light
microscopes. In the reflected light microscope (stereo-microscope) the image is obtained
through the light reflected by the surface of the specimen and enlarged by means of lens
(objectives and oculars). In the transmitted light microscope (mineralogical microscope)
the light passes through the sample, which was made transparent through an opportune
reduction of its thickness.

14.2.1 Stereomicroscopy
Reflected optical microscopy is useful for detecting the structure of the sample (Figure
14.2) and for identifying the deterioration forms. In addition, by means of a stereo
microscope it is possible a photographic documentation of the sample. This last operation
is very important because the other analytical methodologies performed for characterizing
the samples are generally micro-destructive. A complete photographic documentation
allows us to preserve the memory of the sample.
Reflected optical microscopy is the first analytical technique that we have to carry out for
the characterization of materials (stone, mortars, ceramics, glass, etc.). The stereo
microscope suitably equipped (support, jointed arm, lighting system, etc.) is very useful for
observing details of big and composite samples (wall painting fragments, mosaic
fragments, pieces of wood artefacts) or whole artefacts (icons, coins, ceramic vases, glass
objects etc.). Of course the use of this microscope can be also useful for carrying out in
better manner several restoration operations (cleaning, plastering, repainting) on small
objects or on details of bigger ones.

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Figure 14.2 – Stereo microscope (mod. Olympus SZX9) on the left, and smoothed bedding
mortar and foundation mortar observed by stereo microscope (on the right).

To better observe the structure and the components of a sample, it can be useful to prepare
a polished section, because in this way all the surface of the sample is simultaneously in
focus. Polished sections can be prepared by using increasingly fine abrasives in presence of
water, unless there is a risk of loss of soluble compounds; in this case it is necessary to
work dry.

14.2.2 Mineralogical microscope

Mineralogical microscope is a transmitted light microscope that uses polarized light and is
equipped by accessories useful for observing phenomena due to the birefringence (or
double refraction) of minerals (Figure 14.3).
In a mineralogical microscope, from the bottom, can be recognized these main parts:
 lamp,
 first polarizer,
 revolving plate with a central opening in the middle, on which the sample (thin
section) is put,
 lenses (objectives) with different magnifications,

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Figure 14.3 – Mineralogical microscope with a thin section inserted under the objective.

 second polarizer (analyzer). The vibration direction of the light obtained by the
analyzer is rotated of 90° in comparison with the vibration direction of the first
polarizer. The second polarizer can be put in the optical system of the microscope
or can be taken off, while the first is fixed,
 Amici’s lens,
 two ocular lenses,
 connection for camera.
Mineralogical microscope allows the identification of the minerals according to optical
characteristics that it is possible to observe in ‘thin section’ (25-30 micron) under different
polarized light conditions.
In order to identify these optical characteristics three different conditions of observation
are possible in this particular optical microscope:
 with parallel nicols
 with crossed nicols
 with crossed Nicols in converging light, Amici’s lens inserted, maximum
brightness and magnification (used only for very specific mineralogical studies).
Each observation condition gives us optical information useful for identifying the minerals
present in the thin section of the sample.

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In particular by parallel nicols (nicols //):

• shape and size of the crystals,
• colour: the crystals can appear coloured or colourless,
• pleo-chromatism: during the rotation of the plate of the microscope some crystals
change their colour (pleo-chromatism),
• cleavage traces: one or two systems of parallel lines that can be observed in a
crystal,
• relief: some crystals appear in relief in comparison with others or the matrix.
While by crossed nicols (nicols X):
 interference colours: not real colours that appear when we insert in the optical
system the second polarizer (analyzer). Each crystal of every mineralogical species
present in the thin section shows a new colour (interference colour),
 extinction: rotating the plate, the interference colours change from the highest
brightness to dark (extinction); direction and type of extinction can be measured,
 gemination: presence of set of crystals with the same composition and structure
(same mineral) grown according to specific crystallographic rules; you can easily
measure the extinction angle, which is typical for a given mieral,
 pores: they can be identified because they appear white with parallel nicols, and
dark with crossed nicols (even rotating the plate).
By the use of handbooks, in which are reported the optical properties of the minerals, it is
possible to recognize those present in the thin section of the sample. In addition several
photographic atlas, in which are shown photos of different rocks taken by mineralogical
microscope, can be consulted.
By the use of the mineralogical microscope it is also possible to observe the texture of the
thin section: if the crystals or granules are in contact with each other, or if they are
submerged in a matrix, or bounded by a cement; if the crystals/granules are orientated, if
there are microfossils (sedimentary rocks), and so long. On the basis of the mineralogical
composition and the texture is possible to classify the rock fragments.
Mortars can be considered artificial sandstones with a framework (aggregate) composed of
granules from natural and/or artificial stones bound by a carbonate and/or gypsum cement
(ancient and traditional mortars). In modern and contemporary mortars (mortars based on
cement) an amorphous-micro crystalline cement composed of different calcium silicate

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hydrated and calcium aluminum silicate hydrated can be present in the place of the
traditional carbonate/gypsum binder.
By means of the mineralogical microscope it is possible to recognize the shape, the
dimension and above all the petrographic characteristics of the aggregate, the composition
of the binder, the evaluation of the porosity, the probable presence of reaction borders
between the binder and some granules of the aggregate (“cocciopesto”, volcanic granules,
etc.) and finally the reconstruction of the ratio binder/aggregate (by volume).
As said before, the observations at the mineralogical microscope need the preparation of
the sample in form of ‘thin section’, i.e. a slice of sample with a thickness of 30 microns
approximately. A thin section is prepared from a fragment of material through a gradual
reduction in thickness to the desired value. The thickness should be uniform, and the two
opposite surfaces of the slice perfectly flat and parallel. This is a difficult task, and it is
usually carried out in specialized laboratories by means of appropriate machines.
Of course, a so thin slice of sample is not auto-sustaining, so that it is placed on a suitable
support and covered with an extremely thin protective glass. Therefore, the preparation of
a thin section includes the following steps:
- cut a suitable piece of sample, with the cutting surface oriented in the most suitable
direction for the observations to do,
- polishing of the cutting surface as smooth as possible,
- gluing of the polished surface on a sample-holder, which can be constituted of a small
rectangular glass plate, about 1 mm thick, 5 cm long and 3 cm wide; the glue is a resin,
- abrasion of the sample parallel to the surface of the glass slice, up to a thickness of about
30 microns,
- coverage of the sample with an extremely thin glass plate.

14.2.3 Observation and interpretation of ceramic thin sections

The examination of thin-sections under polarising microscope allows to observe textural
features of the argillaceous matrix (colour, fineness, homogeneity, isotropy, etc.), of the
grains and macro-pores larger than 50 microns approximately (shape, size, roundness,
preferential orientation, etc.), as well as the identification of the minerals and their
abundance, the grain packing and size distribution of crystalline plastic inclusions (temper)
contained in the ceramic paste.

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All this information can be used to reconstruct the life of the artefact, from the origin to the
recovery. In fact, the abundance and mineralogical composition of the a-plastic inclusions
can provide information on the technological process used in the artefact production: the
paste preparation, the nature of the temper and its possible origin, the surface treatments
(smoothening, polishing, application of slip, painting, etc.) and the firing conditions.
The quality of mineral and/or rock fragments (for example magmatic rock fragments), their
distribution and amount and other physical properties of the a-plastic inclusions can
provide information on the provenance of the artefact, also taking into account the
geological data from the presumed area of origin.
At the beginning of the observation, it is important to distinguish the three main
components that compose the microstructure of a ceramic paste:
- Matrix or groundmass: the fine component of the paste, that derives from the
clayey materials (much less than 50 µm in size);
- Skeleton or framework or temper: usually it derives from sandy grains originally
present in the clay or intentionally added by the potter (>50 µm in size);
- Voids: the macro-pores (>50 µm) present in the ceramic paste.
To this purpose, visual comparators are used, which also take into account the dimensions
of the grains, so that it is possible to immediately note the fineness of the ceramic paste.
The second step is to observe the features of the matrix; you should look at its colour and
homogeneity, the presence of argillaceous rock fragments (ARF) and/or iron nodules, an
eventual changing distribution of micro-crystalline grains in the matrix.
An important parameter is the isotropic behaviour, because it is indicative of the firing
level: more isotropic is the matrix, more fired is the ceramic. In fact, during firing the
clayey minerals become amorphous and change their appearance. So, an anisotropic matrix
indicates a low firing temperature, and vice-versa. The colour of the matrix can be useful
to define the firing atmosphere: red colour indicates an oxidant atmosphere, while grey or
black colour an oxygen-poor atmosphere (reductive). In the first case, the oxygen inside
the kiln favours the oxidation of the iron present in the clay; in the second this oxidation
does not occur or is incomplete.
Subsequently, the attention has to be devoted to the grain-size of the temper that composes
the framework. The conventional size range starts from <63 µm (silt) up to >500 µm
(coarse sand). By considering the distribution of the temper in this range, two types of

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distribution can be distinguished: serial, that means all the sizes are represented, or hiatal,
when there is a gap in the distribution range of the temper.
What does it means? Usually a serial distribution of the temper is indicative of the use of
“natural” raw material. On the contrary, hiatal distribution could indicate a human
intervention in the preparation of the clay paste, because the coarse fraction may have been
intentionally added by the potter for realising a special product for a specific use. In the
last case, it is also important to observe the shape of the grains, more precisely the level of
roundness of their borders: sharp border usually indicates sand obtained by breaking rocks,
while rounded grains are typical of sands resulting from natural processes, for example due
to wind or water transportation.
Another important step is to recognize the mineralogical composition of the temper. In
general, the attention has to be devoted to: quartz (single grain and in crystalline
aggregates), K-feldspar, plagioclase, calcite (micrite and sparite), biotite, muscovite,
pyroxene, amphibole, volcanic rock fragments, flint fragments and fossils relicts.
The macro-pores are the result of the different steps of the ceramic working process. They
can form during shaping due to residual air bubbles, or can be leaved by the burning of
organic matter present in the clay or by the decomposition of carbonate grains (such as
calcite). By the way, sometimes macro-pores produced by air bubbles can be oriented
parallel to the surface, such as argillaceous lamellar particles; it is possible to interpret this
information as the use of wheel during the shaping process.
On the surface of some ceramics it is possible to highlight surface treatments, when the
surface layer shows a different appearance in comparison with the ceramic body (see
paragraph 4.5.1).
As regard the coated ceramics, after distinguishing the type of coating (clay-type or glassy
type), the observer has to describe the presence of one or more coating layers, the
microstructure (presence of bubbles, cracks, pigments, not-dissolved crystals, new
crystalline phases), the thickness (an average value has to be measured), and finally the
extension of the interface, that is the interaction zone between paste and glaze.
All this information has importance from a technological point of view. Similar thickness
on the two sides of the fragment indicates that the application was likely made
simultaneously, dipping the artefact into the glaze suspension; on the other hand, different
thickness values indicate application in two times, likely by sprinkling or by brush.

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The thickness of the interface zone may be related to the number of firings. In fact, glazed
ceramics can be single or double fired. The interface zone is very thick (more than 40 µm)
in case of single firing, because body and coating interact much with each other. In case of
double firing, the interface can be practically invisible, because the paste has reached its
stability during the first firing and it interacts little with the glaze during the second firing.

14.3 Spectrocopic techniques

Spectroscopy was originally the study of the interaction between radiation and matter as a
function of wavelength (Figure 14.4). Later the concept was greatly expanded to comprise
any measurement of a quantity as function of either wavelength or frequency.
Spectrometry is the spectroscopic technique used to assess the concentration or amount of
a given species. Spectroscopy/spectrometry is often used in physical and analytical
chemistry for the identification of substances through the spectrum emitted from or
absorbed by them.

14.3.1 Measurement of colour

The color of an object depends on the frequencies absorbed by the object itself in the field
of radiation perceived by the human eye. The range of frequencies to which our eye is
sensitive is from about 400 to about 700 nm, so that this range is called the ‘visible’.
The object that reflects light energy evenly throughout the visible range has a white color.
If some energy is absorbed uniformly throughout the range, the color is a shade of gray,
becoming black when all the energy is absorbed.
When the reflection (or absorption) of energy is not uniform, the object has a different
color depending on the frequencies absorbed more. The graph of variation of the energy
absorbed from the surface of an object in the visible range is the ‘color spectrum’ of that
object (Figure 14.5, left). The spectrophotometer is the measurement instrument able to
record a spectrum.

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Figure 14.4 – Different interactions between radiation and matter

depending on the radiation wavelength.

In 1931, an international commission (CIE = Commission Internationale de l’Eclairage)

established that a color could be defined as the sensitivity of the human eye to spectra of
three colors: red, green and blue. So, they introduced the possibility to define a color with
numbers, rather than adjectives. In this way, each color became defined in the same way by
anyone, without subjective margins. In the same year, in fact, it was introduced the so-
called ‘chromaticity diagram’ (Figure 14.5 right), where each color could be detected by
two chromaticity values (x, y), while a third value indicated the ‘clarity’ of the color.
Subsequently, the definition of the color underwent further development, first with the
introduction of the Hunter L, a, b system, then elaborated by the already mentioned
Committee CIE in 1976. The new color space CIE L, a*, b* (or simply CIELab) differs
from the previous system for the method of calculating the three parameters.
CIELab space is defined by three coordinates (Figure 14.6), two on the horizontal axis (a*,
b*) and the third on the vertical axis (L). The three variables are:
a* = axis of contrasting colors green (-a) and red (+ a);
b* = axis of contrasting colors blue (-b) and yellow (+ b);
L = clarity of color, ranging from 0 (black) to 100 (white).

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Figure 14.5 – Eample of colour spectrum (left) and chromaticity diagram (right).

After 1976, some new parameters have been introduced, for example to define differences
in ‘tone’ and ‘saturation’, but the CIELab method is currently the most used, and the
colorimeter is the instrument for measuring color according to this system. The instrument
illuminates the sample at an angle of 45°, while a detector records, through the
interposition of filters, how much red, green, blue and yellow is absorbed by the sample, so
as to provide the parameters L, a, b. These data can then be plotted to show the differences
between different samples.
The two types of instrumentation (spectrophotometer and colorimeter) on the market for
color analysis, therefore, have very different performances. The colorimeter has the
advantage of providing numerical data, but the spectrophotometer has the advantage of
providing the full spectrum and to allow a better identification of the differences. The
choice of an instrument rather than the other depends on the purpose for which it is used.
In the field of restoration, the colorimeter can provide sufficient information to assess how
an intervention might have altered the characteristics of the material. In addition, the
colorimeter is a portable instrument that is well suited to the needs of this sector, and the
technique of measurement of color using colorimeter is neither destructive nor invasive.

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Figure 14.6 – The HunterLab and CIELab space; the different way of calculating
the three parameters are indicated.

14.3.2 Raman spectroscopy

Raman spectroscopy is a spectroscopic technique used to study vibrational, rotational, and
other low-frequency modes in a system. It relies on inelastic scattering, or Raman
scattering, of monochromatic light, usually from a laser in the visible, near infrared, or near
ultraviolet range. The laser light interacts with phonons or other excitations in the system,
resulting in the energy of the laser photons being shifted up or down. The shift in energy
gives information about the phonon modes in the system. Infrared spectroscopy yields
similar, but complementary information.
Typically, a sample is illuminated with a laser beam. Light from the illuminated spot is
collected with a lens and sent through a monochromator. Wavelengths close to the laser
line, due to elastic Rayleigh scattering, are filtered out while the rest of the collected light
is dispersed onto a detector.
Spontaneous Raman scattering is typically very weak, and as a result the main difficulty of
Raman spectroscopy is the separation of the weak inelastically scattered light from the
intense Rayleigh scattered laser light.
Raman spectroscopy is a non destructive analytical technique. Portable instruments also
exist, but they are less sensitive than the laboratory instruments. When fitted with a

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microscope, the laboratory instrumentation becomes able to perform micro-analyses

(micro-Raman spectroscopy).
An example of Raman spectra is shown in Figure 14.7, for organic and inorganic
compounds.

Figure 14.7 - Example of Raman spectra: a) albumine, b) casein, c) gelatine,

d) sturgeon glue, e) fish glue (on the left) and. some inorganic materials (on the right).

14.3.3 Infrared spectroscopy

Infrared spectroscopy (IR spectroscopy) is the subset of spectroscopy that deals with the
infrared region of the electromagnetic spectrum. It covers a range of techniques, the most
common being a form of absorption spectroscopy. Infrared spectroscopy exploits the fact
that molecules have specific frequencies at which they rotate or vibrate corresponding to
discrete energy levels (vibrational modes). As all spectroscopic techniques, it can be used
to identify compounds or investigate sample composition. Correlation tables for infrared
spectroscopy are tabulated in the literature.
The infrared portion of the electromagnetic spectrum is divided into three regions: the
near-, mid-, and far-infrared, so named for their distance from the visible spectrum. The
far-infrared, approximately 1000–30 µm, lying adjacent to the microwave region, has low
energy and may be used for rotational spectroscopy. The mid-infrared, approximately 30–
2.5 µm, may be used to study the fundamental vibrations and the associated rotational-
vibrational structures. The higher energy near-IR, approximately 2.5–0.8 µm, can excite

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overtone or harmonic vibrations. The infrared spectrum of a sample is collected by passing

a beam of infrared light through the sample. The examination of the transmitted light
reveals how much energy was absorbed by the sample at each wavelength. This can be
performed by means of a monochromatic beam, which changes in wavelength over time.
In such a way, a transmittance or absorbance spectrum can be produced, showing at which
IR wavelengths the sample absorbs. Analysis of these characteristics of absorption reveals
details about the molecular structure of the sample.
The same spectrum can be obtained by using an instrument based on Fourier transform to
measure all wavelengths at once. Fourier transform infrared (FTIR) spectroscopy is a
measurement technique for collecting infrared spectra. Instead of recording the amount of
energy absorbed when the frequency of the infra-red light is varied by means of a
monochromator, the IR light is guided towards an interferometer. After passing through the
sample, the measured signal is the interferogram. Performing a mathematical Fourier
transform on this signal you may obtain a spectrum identical to that from conventional
dispersive infrared spectroscopy.

14.3.4 UV-Vis spectroscopy

Many atoms emit or absorb visible light. Visible absorption spectroscopy is often
combined with UV absorption spectroscopy in UV/Vis spectroscopy. Ultraviolet-visible
spectroscopy involves the spectroscopy of photons in the UV-visible region. This
technique is complementary to fluorescence spectroscopy, in that fluorescence deals with
transitions from the excited state to the ground state, while absorption measures transitions
from the ground state to the excited state.
UV/Vis spectroscopy is routinely used in the quantitative analysis of solutions of transition
metal ions and highly bonded organic compounds.
Solutions of transition metal ions can be coloured (i.e., absorb visible light) because
electrons can be excited from one electronic state to another. The colour of these solutions
is strongly affected by the presence of other substances. For instance, the colour of a dilute
solution of copper sulphate is very light blue, but adding ammonia intensifies the colour
and changes the wavelength of maximum absorption.
Organic compounds, especially those with strong bonds, also absorb light in the UV or
visible regions of the electromagnetic spectrum. In order to analyze them, they are

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dissolved into water (water soluble compounds). For non water soluble compounds, you
can use ethanol, because this solvent has very weakly absorption at most wavelengths.
Solvent polarity and pH can affect the absorption spectrum of an organic compound.
Tyrosine, for example, increases its absorption when pH increases from 6 to 13 or when
solvent polarity decreases.
The Beer-Lambert law states that the absorbance of a solution is directly proportional to
the concentration of the absorbing species in the solution:
A = -log10(I/I0) = Є · C · L
where:
A = measured absorbance,
I0 = intensity of the incident light at a given wavelength,
I = transmitted intensity,
L = path length through the solution,
C = concentration of the absorbing species,
Є = constant value, known as molar absorption or extinction coefficient, for each species
and wavelength, at a particular temperature and pressure; sometimes is defined in terms of
natural logarithm instead of the base-10 logarithm.
Thus, for a fixed path length, UV/VIS spectroscopy can be used to determine the
concentration of the absorber in a solution:
C = A/Є·L
The instrument used for the analysis is called UV/vis spectrophotometer, whose basic parts
are: a light source (often a tungsten filament, 300-2500 nm), a monochromator, a sample
holder, and a detector (Figure 14.8).

Figure 14.8 – Scheme of the working principle of a UV/Vis spectrophotometer.

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The spectrophotometer measures the intensity of light passing through a solution (I), and
compares it to the intensity of the incident light (Io). The ratio I/Io is called transmittance
(T), and is usually expressed as a percentage; the absorbance (A) is calculated based on the
transmittance: A = -log(T/100).

14.3.5 Emission spectroscopy

Emission spectroscopy is a spectroscopic technique which examines the wavelengths of
photons emitted by atoms or molecules during their transition from an excited state to a
lower energy state. Each element emits a characteristic set of discrete wavelengths
according to its electronic structure, so that the elemental composition of the sample can be
determined by recognizing these wavelengths. Emission is the process by which the energy
of a photon is released for example by an atom whose electrons make a transition between
two electronic energy levels (Figure 14.9). The emitted energy is in the form of a photon.

Figure 14.9 – Absorption and emission of radiations.

There are many ways in which atoms can be brought to an excited state, each one of them
characterizes a different analytical technique. Interaction with electromagnetic radiation is
used in fluorescence spectroscopy, protons or other heavier particles in particle-induced X-
ray emission (PIXE) and electrons or X-ray photons in energy-dispersive X-ray
spectroscopy (EDS) or X-ray fluorescence (XRF). The simplest method is to heat the
sample to a high temperature, after which the excitations are produced by collisions
between the sample atoms.
Emission spectroscopy, which developed in the late 19th century, is often referred to as
optical emission spectroscopy (OES), due to the nature of the emitted light.

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14.3.6 ICP-AES
Inductively coupled plasma-atomic emission spectroscopy (ICP-AES) is a spectral method
used to determine very precisely the elemental composition of samples, and to quantify the
concentration of each element.
The inductively coupled plasma (ICP) is a type of plasma in which the energy is supplied
by electrical currents which are produced by electromagnetic induction. Plasma
temperatures can range between 6,000 K and 10,000 K, and are comparable to those of the
surface of the sun.
ICP-AES uses high-energy plasma from an inert gas, like argon, to burn very quickly the
analytes. ICP-AES works through the emission of photons from analytes that are brought
to an excited state by the use of high-energy plasma. The colour that is emitted is
indicative of the elements present, and the intensity of the spectral signal is indicative of
their concentration.
The plasma source is induced when passing argon gas through an alternating electric field
that is created by an inductively coupled coil. When the analyte is excited the electrons try
to dissipate the induced energy moving to a ground state of lower energy. Doing so, they
emit the excess energy in form of light, whose wavelength depends on the energy gap
between the excited energy level and the ground state. This is specific to each element
according to the number of electrons that the element has, and the orbital that is filled by
the electrons.
By detecting the light at specific wavelengths, it is possible to determine what elements are
present. In addition, one can create a calibration curve (intensity vs. concentration) by
using solutions of known concentration, compare the intensity in a sample of unknown
concentration with the calibration curve, and determine the concentration of the analyte.
An ICP-atomic emission spectrometer is composed of two parts: the ICP and the optical
apparatus. The ICP is generated in a torch that consists of 3 concentric tubes of silica glass
and a coil of the radio frequency (RF) generator which surrounds part of this torch (Figure
14.10, left). Argon gas is typically used to create the plasma.
When the torch is turned on, an intense magnetic field from the RF generator is activated.
The argon gas flowing through is ignited with a Tesla unit, which typically is a copper strip
on the outside of the tube. The argon gas is ionized in this field and flows in a particular
rotationally symmetrical pattern towards the magnetic field of the RF coil. A stable, high

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temperature plasma of about 7000 K is then generated as the result of the inelastic
collisions created between the neutral argon atoms and the charged particles (Figure 14.10,
right).

Figure 14.10 – Structure of a torch for the generation of a plasma source (left)
and a lighted torch (right).

A peristaltic pump delivers the sample solution into a nebulizer where it is atomized and
introduced directly inside the plasma flame. The sample immediately collides with the
electrons and other charged ions in the plasma and is broken down into charged ions. The
various molecules break up into their respective atoms which then lose electrons and
recombine repeatedly in the plasma, giving off the characteristic wavelengths of the
elements involved. One or two transfer lenses are then used to focus the emitted light on a
diffraction grating where the radiations that compose it are separated.
The light intensity is then measured with a photomultiplier tube at the specific wavelength
for each element involved. The intensity of each line is then compared to previous
measured intensities of known concentrations of the element and its concentration is then
computed by extrapolation along the calibration line.
The analysis by ICP-AES requires a sample in form of solution. Therefore, when solid

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samples (like stone, ceramics, glass, clay) are to be analyzed, it is necessary to dissolve
them in order to obtain a diluted solution. There are two principal ways for the dissolution
of solid samples: acid attack or alkaline fusion. The samples to be analyzed contain a
significant amount of silica, so that you cannot dissolve them by using hydrofluoric acid,
which would cause the loss of silica in form of silicon fluoride. Therefore, alkaline fusion
is recommended. The melting can be obtained by heating at about 1,000 °C a mixture of
sample (for example 0.1 g) and flux in proportion 1:10 approximately; the flux can be a
mixture of lithium tetra-borate and lithium borate. Then, the melt can be dissolved with
aqueous solution of nitric acid.
The ICP-AES is a destructive analytical technique, but the amount of sample needed is
very low, so that this technique is very useful in order to analyze many different materials.

14.3.7 Laser induced plasma spectroscopy

Laser induced plasma spectroscopy (LIPS), also named laser induced breakdown
spectroscopy (LIBS), is a micro-analytical elemental technique based on the spectral
characterisation of the plasma plume produced by focusing a pulsed laser beam on the
material to be analysed. The technique does not require any preparation of the artefact
under study. It is micro-destructive but often non-invasive, since the analysis is carried out
on a very small quantity of laser ablated material, which does not imply any relevant
invasiveness issue in most cases. As schematised in Figure 14.11, the basic set up of LIPS
includes a pulsed laser, focusing (L1) and gathering (L2) optics, spectrometer, and personal
computer.

Fig. 14.11 - Schematic set up of the LIPS technique.

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A low energy (10-100 mJ/pulse) Q-switched Nd:YAG laser is typically used to excite the
plasma emission. The very high peak intensity associated with its short pulse duration (5-
10 ns) and tight focusing (10-100 µm spot diameter) produces material ablation, ionisation
and then a rapidly expanding luminescent plasma plume. The spectral lines of the latter are
characteristic of the atomic species composing the material under analysis.
The lifetime of the plasma ranges from a few to several microseconds according to the
irradiation parameters and material composition.
During the early hundreds of nanoseconds the optical emission is characterised by a
continuum spectrum, then atomic lines become visible with an increasing signal/noise ratio
and finally the noise gradually disappears. One of the main concerns of LIPS is the
selection of the optimum time delay between laser irradiation and spectral acquisition. In
order to maximise the signal/noise ratio also double pulse lasers and gated spectrometers
including intensified CCD sensors (iCCD) are used in complex laboratory setups.
However, simplified portable devices using single pulse compact Q-switching Nd:YAG
lasers and low-cost spectrometers appear to be more promising as a powerful and easily
accessible archaeometric tool.
In principle, LIPS can allow detecting and recognising all the elements whether using a
multichannel optical spectrometer with sufficiently wide range, high resolution, and high
sensitivity.
Besides qualitative analysis, preliminary calibrations using suitable reference samples also
allow relative quantifications based on the measurements of line intensity ratios. In this
respect, apparatuses including double pulse lasers and iCCD detectors are up two orders of
magnitude more sensitive than low-cost portable devices, which are usually employed to
measure the main atomic components with a sensitivity of some thousands of ppm.
The micro-scale material volume analysed for each laser shot is determined by the spot
diameter (10-100 µm) and ablation rate (0.1-10 µm/pulse). Usually, several spectra are
collected in each measurement spot, whose elaboration allows achieving quantitative
elemental depth profiles along penetration depths up to the order of millimetre with a high
spatial resolution.
Depth profile analysis can be considered the main feature of LIPS since it provides the
main advantage with respect to other surface elemental techniques, such as X-ray
fluorescence (XRF), electron microprobe (SEM-EDX/WDX), and particle induced X-ray

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emission spectroscopy (PIXE). Depth profiling has a fundamental importance whenever

material stratifications and substantial compositional differences between surface material
layers and the bulk underneath are encountered.
The introduction of LIPS dates backs to the origin of the laser technologies while its
significant potential application in archaeometrical investigations was thoroughly proven
along the last fifteen years.
The studies reported concern pigments, metal alloys, glasses and ceramics. However, today
copper, silver, and gold alloy artefacts represent the more successful and promising
applications. Museum collections and large bronzes such as the Etruscan masterpieces
named the Arringatore and the Chimera from Arezzo from Florence’s National Museum of
Archaeology, as well as a number of Renaissance masterpieces were thoroughly
characterised along the last years using portable LIPS.
As an example, Figure 14.12 shows a detail of the spectrum and the tin depth profile of a
Roman bronze figurine. As it can be seen, a surface enrichment of tin content of a factor
2.5 was observed in this case, which decreased to the bulk value after about 400 laser
pulses. Such a strong compositional modulation, which was determined by long-term
corrosion, represents a peculiar feature of archaeological bronzes, which can be revealed in
a non invasive way using LIPS.
It is also worth noting that surface enrichment/depletion phenomena of the metal alloys
have been recently recognized as a key feature for distinguishing between genuine ancient
copper alloy artefacts and modern counterfeits.

Figure 14.12 - Examples of plasma emission spectrum (left)

and tin depth profile (right) of a Roman bronze figurine.

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14.4 Radiochemical techniques

14.4.1 X-ray diffractometry

The identification code of X-ray diffractometry is XRD. This analytical methodology
enables the identification of crystalline phases (minerals) present in the specimen.
Generally it is a micro-destructive and semi-quantitative analysis, but sometimes it can be
not destructive, when the specimen has a perfectly flat surface.
The instrument used for carrying out this analysis is the diffractometer, which gives the
results in graphic form (diagram), which is called diffractogram.
The physical principle on which this analytical methodology is founded is the Bragg
equation, which says: a sheaf of parallel planes of a crystalline structure causes the
reflection of a monochromatic X-ray beam only for some angles of incidence, according to
the equation: 2d senθ = λ, where:
λ = wavelength of the incident x-ray beam
d = distance between two adjacent parallel planes
θ = angle of incidence.
The Bragg equation can be easily obtained by observing the geometric scheme reported in
Figure 14.13. Two X-ray beams will be in phase between them when the difference
between their paths (AB + BC) corresponds to the wavelength (λ), or multiple of it:
λ = AB + BC = 2d senθ

Figure 14.13 – Geometric scheme for obtaining the Bragg equation.

From this equation it is possibile to calcolate the ‘d’ value, after measuring the reflection
angle (θ) for a prefixed wavelength (λ): d = λ /2senθ.
Each mineral has a crystalline reticulum with a precise composition and structure, so that

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each crystalline phase is characterized by a precise set of “d” values. In this way it is
possible a mineralogical analysis on the basis of the attribution of a set of calculated “d”
values.
A scheme of diffractometer is shown in Figure 14.14. The powdered specimen rotates,
while the X-ray source is fixed. When, for a sheaf of reticular planes in a mineral the
equation of Bragg is satisfied, a reflection occurs; than the reflected ray is captured by the
detector, which measures its intensity.

Figure 14.14 – Working scheme of a diffractometer.

Fig. 14.15 – Diffractogram with “d” values calculated by computer

according to the Bragg equation.

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At the end of the analysis, the instrument gives a diagram (diffractogram) which is
composed by an irregular base line from which more or less intense peaks can be identified
(Figure 14.15). Each peak corresponds to a reflection by a sheaf of parallel planes of a
crystalline phase in the sample. The value of “d” in correspondence with each peak can be
easily calculated by the Bragg equation.
The interpretation of a diffractogram means to identify the different “d” values and to
attribute them to the several minerals present in the analysed sample. The attribution of the
peaks to different minerals is possible by means of manuals and cards (now in digital
format) that show all the “d” values and the intensity of the peaks of each mineral.
XRD analysis is generally semi-quantitative. The relative amounts of the identified
minerals can be shown by a different number of crosses. For example:
+++++ = very abundant, ++++ = abundant, +++ = not very abundant, ++ = reasonable, + = scarce.
X-ray diffractometry is a typical laboratory instrumentation, so that it is invasive because it
needs a powdered sample, even though of small size. In very recent times, portable
instrumentation has been developed that allows a non destructive mineralogical
characterization of materials in the cultural heritage field.

14.4.2 X-ray fluorescence spectrometry

The X-ray fluorescence spectrometry (XRF) is a technique of qualitative and quantitative
chemical analysis. It exploits the emission of X-rays by the sample when hit with an
adequate energy. This energy is supplied by a source of X-rays with a broad spectrum of
wavelengths, mostly continuous, so as to be able to excite most of the chemical elements.
The X-ray radiation emitted from the sample, however, is discontinuous and is
characteristic of the elements present in the sample. The recognition of the different
wavelengths (λ) and their attribution to a specific chemical element is obtained by means
of an analyzer crystal that rotates during the running and on which the total X-ray
fluorescence emitted by the sample is collimated. The identification of the different
wavelengths allows for the qualitative analysis of the sample, while the intensity of the
radiation allows the quantitative analysis.
The measurement of λ is done according to the equation of Bragg (2d senθ = λ), the same
shown for the x-ray diffractometry. In XRD the wavelength (λ) is constant and known, so
that it is possible to determine the values of ‘d’ and recognize the correspondent minerals.
In XRF, on the contrary, there is a crystal with well known ‘d’ value, so that it is possible

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to calculate the wavelengths of the x-ray radiation emitted by the sample (wavelength
dispersion system = WDS). A scheme of a WDS-XRF spectrometer is shown in Fig. 14.16.

Rotation of the detector

Detector
Sample

Fluorescence
radiation Primary
radiation
Collimators

X-ray
Tube
Analyzer
crystal

Figure 14.16 – Scheme of X-ray fluorescence spectrometer.

WDS-XRF is a non-destructive analytical technique, if the sample is analyzed in the form

of pressed powder (tablet). However, the results are better when the analysis is performed
on the sample mixed with a flux (lithium tetra- and meta-borate), melted and cooled to give
rise to a glass disk, commonly called ‘pearl’. In this way, the technique becomes
destructive, other than invasive. In addition, the amount of sample analysis must not be
ignored, because it is about 1 gram. However, the WDS-XRF technique remains the most
interesting for the precise chemical analysis of solid samples (stone, ceramics, glass,
metals), taking into account the speed of analysis and the ability to analyze virtually all
elements, from traces to the highest percentages.

14.4.3 Transportable and portable XRF spectrometry

Energy dispersion system-XRF is a very useful analytical technique in the field of the
cultural heritage, because it allows to analyze the artifacts in situ without destroying
material. The general principal is the same of WDS-XRF, that is to recognize the elements
which have emitted X-ray radiations when the sample is hit by a X-ray beam, and to
transform their intensity into concentration values. This is made possible by changing the
recognition system of each emitted radiation: energy dispersion instead of wavelength
dispersion.
Only the energy dispersion system permits to realize transportable or portable

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instrumentations, which can perform in situ analyses. The transportable instruments have
to be mounted near the artifact to be analyzed, while the portable instruments have a
battery as energy source, can be kept by hands and placed in contact with the object.
Anyway, EDS-XRF is particularly useful for the analysis of metals, because the metallic
elements are the most sensitive (Figure 14.17). But all the elements become sensitive
enough if the instrumentation can be used in contact with the object to be analyzed, or
argon is continuously insufflated into the space between instrument and object.

Figure 14.17 – Analysis of an ancient bronze coin by means of transportable XRF.

Of course, EDS-XRF has also some disadvantages, which mainly derive from the fact that
it analyzes just the surface layer of the sample, so that the result does not represent the real
composition of the artifact, unless it is very homogeneous from the core to the surface. As
a consequence, this type of instrumentation is very useful in order to analyze the alteration
layers, as well as for a speedy campaign of qualitative analyses.

14.5 Chromatography

14.5.1 General information and terminology

Chromatography is the collective term for a set of laboratory techniques for the separation
of mixtures. It involves passing a mixture dissolved in a “mobile phase” through a
stationary phase, which separates the analyte to be measured from other molecules in the
mixture based on differential partitioning between the mobile and stationary phases. Subtle
differences in partition coefficient of the compounds will result in differential retention on
the stationary phase and thus separation.
Chromatography may be preparative or analytical. The purpose of preparative

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chromatography is to separate the components of a mixture for further use (and is thus a
form of purification). Analytical chromatography is done normally with smaller amounts
of material and serves for determining the existence and possibly also the concentration of
analyte(s) in a sample. The analyte is the substance to be separated.
A bonded phase becomes a stationary phase when it is covalently bonded to the support
particles or to the inside wall of the column tubing.
A chromatogram is the visual output of the chromatograph. In the case of an optimal
separation, different peaks or patterns on the chromatogram correspond to different
components of the separated mixture. Plotted on the x-axis is the retention time and plotted
on the y-axis a signal (for example obtained by a spectrophotometer, mass spectrometer or
a variety of other detectors) corresponding to the response created by the analytes which
exit the system. In the case of an optimal system the signal is proportional to the
concentration of the specific analyte separated.
A chromatograph is an equipment that enables a sophisticated separation, e.g. gas-
chromatographic or liquid-chromatographic.
Chromatography is a physical method of separation, in which the components to be
separated are distributed between two phases, one of which is stationary (stationary phase)
while the other (the mobile phase) moves in a definite direction. The effluent is the mobile
phase, which leaves the column. A immobilized phase is a stationary phase, which is
immobilized on the support particles, or on the inner wall of the column tubing.
The mobile phase may be a liquid (LC = liquid chromatography), a gas (GC = gas
chromatography), or a supercritical fluid (SFC = supercritical-fluid chromatography). The
mobile phase includes the sample to be analyzed and the solvent that transports the sample
towards the chromatographic column (the stationary phase), which interacts with the
sample. The retention time is the characteristic time it takes for a particular analyte to pass
through the system under set conditions.
The sample may consist of a single component (solute) or it may be a mixture of different
components. In the course of an analysis, the phase containing the analytes of interest is
referred as the sample, whereas everything which is separated from the sample, before or
in the course of the analysis, is referred as waste.

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14.5.2 Liquid chromatography

Liquid chromatography (LC) is a separation technique in which the mobile phase is a
liquid, and can be carried out either in a column or a plan. At present day, liquid
chromatography generally utilizes very small filling particles and a relatively high
pressure. It is referred as high performance liquid chromatography (HPLC).
The sample is forced through a column by a liquid (mobile phase) at high pressure. The
column is filled with particles, irregularly or spherically shaped, or with a porous
monolithic layer (stationary phase).
HPLC is historically divided into two different sub-classes based on the polarity of the
mobile and stationary phases. When the stationary phase is more polar than the mobile
phase (e.g. toluene as the mobile phase, silica as the stationary phase), the technique is
called normal phase liquid chromatography (NPLC).
In the opposite case (e.g. water-methanol mixture as the mobile phase and C18 =
octadecylsilyl as the stationary phase), it is called reversed phase liquid chromatography
(RPLC). Ironically the “normal phase” has fewer applications and RPLC is therefore used
considerably more.

14.5.3 Ion exchange chromatography

The ion exchange chromatography uses a ion exchange mechanism in order to separate the
analytes. It is usually performed in columns, but can also be used in planar mode.
The ion exchange chromatography uses a stationary phase, which is electrically charged,
with the aim to separate compounds including amino acids, peptides, and proteins. In
conventional methods, the stationary phase is a ion exchange resin, characterized by
functional groups which have a charge such that they can interact with oppositely charged
groups of the compound to retain.
Ion exchange chromatography is commonly used to purify proteins.
In the field of the cultural heritage, it is very useful and currently used for analyzing the
quantitative chemical composition of soluble salts previously extracted from solid samples
like natural stones, mortars, clay bricks, ceramics.
This technique can analyze the various cations (Na+, K+, NH4+, Ca++, Mg++, etc.), as well
as the anions (Cl-, F-, NO3-, SO4--, etc.).

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14.6 Electron microscopy

Particles or specimen details under 1 micron can be observed only by electron microscopy,
which has a higher resolution power than optical microscopy.
Electron microscopy uses an electron beam and lenses that are adjustable magnetic fields.

14.6.1 Scanning electron microscopy (SEM)

In SEM observations the magnified images of specimen details are obtained by electrons
emitted by the surface of the sample (secondary electrons).
An incandescent filament gives out electrons. By means of a system of electro-magnetic
lenses these electrons (primary electrons), transformed in a thin sheaf, are addressed on the
specimen. The area of the surface hit by the primary electrons gives out electrons
(secondary electrons) that are used for obtaining the enlarged image of a detail of the
surface of the sample.
SEM analyses give us three-dimensional images, in addition the preparation of the sample
is very simple and doesn’t modify the morphology of the sample. In this way micro-
morphological and micro-structural studies are possible. A scanning electron microscope
can reach magnifications about 20,000 times.
Scanning electron microscopy can be equipped with an instrument (energy dispersive X-
ray spectrometer, code: EDS) that enables to detect the chemical elements present on the
superficial layer of the sample.
When the primary electrons hit an area of the sample the atoms present in this area give out
secondary electrons (used for obtaining the image of the sample) and x-ray radiations
(fluorescence x-rays) which wavelengths and associated energies are typical of the
chemical elements that emitted them. If we have an instruments enable to detect the energy
of these X-rays, we can easily recognize the elements present on a surface layer of the
sample. By EDS microanalyses is possible to carry out chemical analysis of surface details
of the sample, and to know the distribution of chemical elements on the surface of the
sample.
In Figure 14.18 a SEM-EDS instrument is shown.

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Fig. 14.18 – SEM-EDS instrument, mod. Cambridge Stereoscan 360.

14.6.2 Transmitted electron microscopy (TEM)

In TEM analyses the electron beam goes across the specimen. If the sample is not
transparent to electrons a cast of the specimen surface, obtained depositing a thin film
made of a suitable material, is observed.
TEM observations give us bi-dimensional images that can reach maximum magnification
about 100,000 times.
An incandescent filament gives out electrons. These electrons are captured, transformed in
a thin beam and sent on the specimen by a system of electro-magnetic lenses. The electron
beam after crossing through the specimen is captured and elaborated by an other system of
electro-magnetic lenses that gives us the enlarged image of a detail of the sample.
TEM analyses are not frequently used in cultural heritage sector.

14.7 Thermal analyses

The thermal analyses are analytical techniques that study the physical-chemical
transformations of the material due to variations in temperature (heating and/or cooling) of
the specimen.
Inside this big family of analytical techniques only differential thermal analysis (DTA) and
thermal gravimetric analysis (TGA) will be taken into account, because these two

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analytical methodologies are used very much from several years in the cultural heritage
sector, especially in the study of mortars.
DTA and TGA request the heating of the sample with a constant rise in temperature.
All the physical and/or chemical transformations of the materials are always associated
with variations in energy, that is heat exchange between sample and environment.
In particular heat absorption by the environment corresponds to a endothermic reaction,
while heat cession to the environment to a exothermic reaction. In addition, often the
transformations of the material produce variations in weight, generally loss of weight.
DTA-TGA analyses allow the identification and often the quantification of the thermo-
unstable compounds. In addition, in mortar study these analyses also identify the hydraulic
or aerial characteristics.
Differential thermal analyses indicate variations in temperature during the test between the
specimen and an inert material (generally alumina) present in the same oven and warmed
in the same manner.
Thermal gravimetric analyses indicate variations in weight of the specimen during the test,
expressed in percentage with reference to the initial weight of the sample.
The apparatus for differential and gravimetric analyses is shown in Figure 14.19. It is
composed of a oven and a precision balance connected to a small staff on the base of
which there is the housing for two small crucible. In one of these crucibles (made of
alumina or platinum) few milligrams of powdered specimen are put, while in the other
crucible few milligrams of powder of alumina are put. During the test, the inert material
(alumina) always has the same temperature of the oven. When the sample doesn’t change it
has the same temperature of the alumina, but when during the test the specimen undergoes
a transformation, its temperature is different from that of the alumina. In particular in
correspondence of endothermic transformations the temperature of the specimen is lower
than the temperature of the inert material; while in correspondence of exothermic reactions
the temperature of the specimen in the oven is greater than the temperature of alumina. The
differences of temperature between sample and alumina are measured by two
thermocouples.

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Container-
keeper rod

SAMPLE INERT

Termocouple

Figure 14.19 - Scheme of DTA-TGA apparatus.

In differential thermal curve an endothermic reaction is generally shown by a peak in down

direction, while an exothermic reaction is shown by a peak in high direction. Each
substance changes at precise temperature; then comparing the DTA curve of the sample
with the DTA curves of known substances, the identification of the different compounds
present in the samples is easily possible.
When the sample doesn’t lose weight during the test the TGA curve is quite horizontal.
While in correspondence of a weight loss the curve is inclined.
In a DTA-TGA analysis performed at the same time, by means of the weight loss in
correspondence of the reactions and simple stoichiometric calculations it is possible to
obtain the quantification of the substances identified in the samples. Therefore the
combination of DTA and TGA is a quantitative analysis.
In Figure 14.20 is shown a thermogram DTA-TGA of a marble covered by a black crust.

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Figure 14.20 – DTA-TGA thermogram of a marble covered by a black crust.

Gypsum and calcite are the substances identified and quantified.

14.8 Open porosity measurements

The open porosity is an important parameter for diagnostic purposes for several materials,
stones and ceramics in particular. The porosity of an artefact is the sum of the pores,
fractures and cracks, and it can be determined by visual or physical methods. Visual
methods (optical and electronic microscopy) permit to describe dimension and shape of the
pores and it is possible to count the number of pores and define a percentage of them.
Physical methods (dipping the material in a liquid, water or mercury) permit to determine
the percentage or the volume of the liquid absorbed.

14.8.1 Water absorption

Dried samples, previously weighted (Wd), are put into a container filled with
demineralised water. After 2 hours boiling, when the water is not so warm, the samples are
slightly dried with a rag and then weighted again (Ww). The difference of the two weights
is the amount of absorbed water. In this way, it is possible to determine the total open
porosity of the artefact, given by the pores larger than 0.01µm approximately, that is the
percentage of water that a material is able to absorb:

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W.A. (wt%) = 100 (Ww-Wd)/Wd

with: W.A. = water absorption; Ww = wet weight; Wd = dry weight.

14.8.2 Mercury intrusion porosimetry (MIP)

Mercury intrusion porosimetry allows the determination of the open porosity and
dimensional distribution of the pores.
The specimen (a small piece of about 1 g) is put in a bulb, in which vacuum is made. Then
mercury is put in the bulb. Step by step an increasing pressure is applied to the mercury
that in this way can enter in pores gradually finer. The instruments can measure the volume
reduction of mercury after every increase of pressure.
There is an equation (equation of Washburn) that, supposing pores in the shape of
cylinders, binds the radius (r) of the transversal section of the pore to the pressure (P)
which mercury needs for entering the pore. Equation of Washburn in simplified form:
r = 7.36/P
where “r” is expressed in micron and “P” in atmospheres.
According to this equation by means of a mercury intrusion porosimeter it is possible to
determinate the total open porosity (total decrease of the mercury during the test) and the
dimensional range of the pores (radius) between 18 Å (4,200 atmospheres) and 100 micron
(<1/10 of atmosphere). The results can be shown in graphic form of histogram or
cumulative curve (Figure 14.21).

Pore radius (micron)

Figure 14.21 - Result (histogram and cumulative curve) of a mercury intrusion

porosimetry analysis for the external layer of a plaster.

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14.9 Analysis of microbial colonization

Biodeterioration of works of art is a complex process involving a high number of microbial

species in both inorganic and organic materials. Particularly, fungi and bacteria (frequently
associated with green algae, cyanobacteria, lichens), wide-spread in biosphere
environments, are the main microorganisms related to the deterioration of cultural assets.
Moreover, complex microbial communities may emit mixed aerosol into indoor
environments with human (visitors, professionals) health damaging proprieties, that may
persist in the environment.
In order to identify the components of microbial populations colonizing the surfaces of
works of art and dispersed in the aerosol, it is possible to perform the investigation by
different methodologies, such as microscopy, in vitro culture and molecular biology
(Figure 14.22).

SAMPLING

MORPHO-MOLECULAR
ANALYSES

MICROSCOPY MOLECULAR
in vitro CULTURE
TECHNOLOGIES

Optical Nutrient Agar DNA extraction

Fluorescence Sabouraud PCR reaction
Scanning Electron TSA Cloning/Sequencing
Confocal Laser Sequence analysis
Scanning

DETECTION - IDENTIFICATION

Figure 14.22 - Methodologies that can be used in order

to analyze microbial populations.

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14.9.1 Sampling
Non invasive sampling on surfaces of work of art can be done by using biological tools
such as sterile swabs, adhesive tape and Nylon H+ membrane (Amersham). This methods
is mainly utilized to collect the particles and the microbial colonies present on the surfaces
(Figure 14.23).

A B C

Figure 14.23 - Sampling on paper and leather specimens by Sterile swab (A), Nylon
membrane fragment (B), Aluminium stab for SEM analysis (C).

Specifically, for indoor environments, the aerosol sampling can be performed by portable
(or fixed) instrumentation, such as AirPort MD8 sampler, equipped with disposable
gelatine filter (Figure 14.24); flow rate and sampling time are selected in relation to the
volume of the environment analysed.

A B

Figure 14.24 - Portable equipment from Sartorius: AirPort MD8 (A);

sterilized disposable gelatine filter (B).

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Gelatine filter represents a very good method for sampling and for the following
identification procedure, because it maintains the viability of the collected microorganisms
and the filters are completely water-soluble. Therefore microbes can be cultivated in/on
different nutrient media (in vitro culture) or microbial genomic DNA can be directly
extracted (molecular technologies).

14.9.2 Characterization of fungi by Optical Microscopy

In order to recognize fungal contamination, agar medium plate (Sabouraud) can be
inoculated by swab, nylon membrane or gelatine filter fragments (Figure 14.25). The agar
Sabouraud, is a selective medium for fungi; it contains 1.5% agar, 4% dextrose, 1%
peptomycol and cloramphenicol (16 µg/ml). Both pH value and antibiotic presence inhibit
the growth of most bacteria. Agar plates are incubated at 30 °C at least for 3 days and the
colonies are analyzed through their macroscopic and microscopic morphology. A simple
method to examine fungi morphology is the “adhesive tape method” (Figure 14.25):
- put few drops of Lugol’s solution onto a slide (Lugol’s solution consists of 5 g iodine (I2)
and 10 g potassium iodide (KI) mixed with 85 ml distilled water, to make a brown
solution with a total iodine content of 150 mg/ml);
- delicately push the adhesive side of the tape on the mould surface;

A B

Figure 14.25 - A) Fungal colonies growth on agar medium, inoculated by gelatine

membrane fragment. B) Penicillium sp. structure stained by Lugol’s solution,
observed by optical microscope (40X magnitude).

- wet this side with Lugol’s solution to achieve the coloration of fungal hyphae;
- observe by optical microscope.

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14.9.3 Electron microscopy (SEM, CLSM) observations

In order to establish the presence of microorganisms by electron microscopy, both
scanning (SEM) and confocal laser scanning (CLSM) provide a valuable contribution to
the characterization of microbial consortia, highlighting the possible deteriogen action
(Figures 14.26, 14.27 and 14.28).

A B

Figure 14.26 - SEM micrographs of microbial structure:

A) bacteria from liquid culture;
B) chains of Actinomycetes spores from mosaic mortar.

A B

Figure 14.27 - SEM micrographs of micro-structures, from waterlogged

wood specimen, artificially coloured in laboratory by Photoshop:
A) Fungal spores (green) and mycelium (yellow);
B) Pyrite framboids (yellow) and Diatomeae (green).

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A B

Figure 14.28 - CLSM micrographs of biofilms from hypogean environment (A)

and mosaic mortar (B); cyanobacteria and green algae are recognizable.

14.9.4 In vitro culture

Sterile swab and nylon membrane fragments (surfaces) or gelatine filter fragments
(aerosol) can be used to inoculate agar plate, performing the in vitro culture analysis on
Nutrient–agar (general medium) (Figure 14.29) or Sabouraud (fungal growth medium)
(Figure 14.30).

Fig 14.29 – Bacteria colonies growth on Nutrient agar plate inoculated by swab
(surface sampling).

Fig 14.30 – Fungi colonies growth on Sabouraud agar plate inoculated

by gelatine filter fragments (aerosol sampling).

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14.9.5 Molecular biology technologies

The study of microbial communities in a work of art, performed by microscopy
observation and/or in vitro culture does not provide comprehensive information on the
composition. That is due to the fact that only the morphological profiles can be detected by
microscopy and that less than 1% of environmental organisms can be cultured in
laboratory by standard techniques. Therefore, straightforward and precise methodologies
are needed for studying microbial colonization of cultural heritage. In recent years
molecular biology and the new biotechnologies, have been used in the field of cultural
heritage diagnosis, at the aim to identify biological damages and to establish the
consequential conservation/restoration strategies. Moreover, this approach minimizes the
sample amount, and optimizes the diagnostic studies on microbial colonization because it
allows the specific identification of microbial species.
Molecular biology provides a sensitive study on microbial contamination of works of art,
based on the analysis of specific DNA genomic sequence. It is performed by the technique
of in vitro amplification (able to increase specific target sequence of microbial genomic
DNA), named Polymerase Chain Reaction (PCR).

MICROBIAL DNA SOURCES

Microbial particles (MP) can be sampled by swab, nylon membrane or gelatine filters
fragments. In order to recover the MP, swabs or nylon membrane fragments were re-
suspended in 500µl of 1X TE solution (10 mM Tris-HCl pH 7.5 / 1 mM EDTA) incubating
at 4 °C for four hours; subsequently MP are collected by microfuge centrifugation at
14,000 rpm for 10 min.

MOLECULAR IDENTIFICATION
Reliable detection and characterization of microbial taxa by molecular analysis is based on:
i) microbial genomic DNA extraction; ii) set up amplification profiles of specific target
sequences (molecular markers) by polymerase chain reaction (PCR); iii) determination of
base composition of PCR products (sequencing); iv) sequences analysis by using dedicated
software (bio-informatics) and design of relative dendrograms.
Microbial particles represent one of the source of microbial genomic DNA, that can be
extracted by using specific laboratory protocols or commercial kits. Routinely, we utilize
QIAamp DNA Stool mini kit (QIAGEN) or Genomic DNA Purification kit (Fermentas),

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properly modified in relation to the samples characteristics (Figure 14.31).

1 2 3 4 5 M

Fig 14.31 – Agarose (0.8%) gel electrophoresis. Genomic microbial DNA extracted from
isolated bacteria and fungi colonies (lines 1-2), directly from MP sampled
by gelatine filter (line 3), nylon membrane (line 4), sterile swab (line 5).
M = molecular marker λ-Hind III.

Standard PCR amplification profile provides 30-40 cycles of amplification, in

thermocycler, with the following steps:
1) denaturing at 95 °C for 30 seconds;
2) primer annealing at 50-60 °C for 1 minute;
3) polymerization at 72 °C for 1 minute.
These steps are preceded by a denaturing step at 95 °C for 4-8 minute, and followed by a
final polymerization step at 72 °C for 7 minutes, to ensure that all PCR products were full-
length and 3’-adenylated.
Primers for target sequence amplification can be designed on the basis of the rRNA genes/
rDNA intergenic sequences, called Internal Transcribed Spacer (ITS).
The identification of taxa is performed by sequencing of the PCR fragments, in order to
determine the DNA nucleotide composition, followed by the homology research by the
algorithm BLASTN in nucleotide data bank (NCBI-NIH – USA, EMBL-Germany), which
allows to draw the corresponding dendrograms (Figure 14.32).
In conclusion, molecular technologies provide a non invasive sampling and a direct
analysis of microbial DNA target sequences. It provides a repertoire of techniques with
high specificity and speed of execution that implements significantly the microbiological
analysis. Combining the results from microscopy, in vitro culture and molecular analyses
we are able to describe the almost complete composition of microbial consortium. This is

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essential for understanding the microbial deterioration in indoor environments, in order to

control the microbial development and the related potential illness for visitor and/or
professionals.
So, the precise identification of fungal and/or bacterial species, related to the environment
and to the constitutive materials of the artefacts, leads to the definition of the indices of
“Attention” and “Risk” for both deterioration of cultural assets and health of the
users/operators.

M 1 2 3 C- 4 5

Fig 14.32 – Agarose (2%) gel showing the PCR-products obtained by amplification of ITS
regions. DNA fragments between 220 bp and 500 bp in length (lines 1-3, 4-5) are shown.
Negative control = C-; molecular marker 100bp DNA ladder = M.
Sequencing and sequences homology analysis identified four different microbial taxa.

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ACKNOWLEDGEMENTS
Especially thanks go to Francesco Paolo Mancuso, Antonietta Vella (DBS, University of
Palermo) and Roberta Russo (Italian National Research Council, IBIM, Palermo) for
collaboration in microbiology and molecular biology analyses.
Many thanks are also due to Anna M. Mannino (SEM) and Giovanni Morici (CLSM)
University of Palermo, for microscopy investigations.

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NARDINI EDITORE ® Alcuni titoli in libreria e presso la casa editrice. Per ordini e informazioni: [email protected]; www.nardinieditore.it

PERIODICI ARTE E RESTAURO Il colore negato e il colore ritrovato. Storie

diretta da Andrea Galeazzi e procedimenti di occultamento e descialbo
KERMES. LA RIVISTA DEL RESTAURO - trimestrale Umberto Baldini, Teoria del restauro e unità delle pitture murali, a cura di Cristina Danti
e Alberto Felici
di metodologia Voll. I-II
BOLLETTINO DELL’ISTITUTO CENTRALE PER IL RESTAURO-ISCR-
semestrale Ornella Casazza, Il restauro pittorico nell’unità ARTE E RESTAURO/FONTI
di metodologia
Mauro Matteini, Arcangelo Moles, La chimica Ulisse Forni, Il manuale del pittore restauratore -
nel restauro. I materiali dell’arte pittorica e-book, introduzione e note a cura di Vanni Tiozzo
KERMESQUADERNI Giovanna C. Scicolone, Il restauro dei dipinti con- Ricette vetrarie muranesi. Gasparo Brunoro e il
temporanei. Dalle tecniche di intervento tradiziona- manoscritto di Danzica, a cura di Cesare Moretti,
Tecniche e sistemi laser per il restauro dei beni Carlo S. Salerno, Sabina Tommasi Ferroni
culturali, a cura di Roberto Pini, Renzo Salimbeni li alle metodologie innovative
Bruno Fabbri, Carmen Ravanelli Guidotti, Il restau- Il mosaico parietale. Trattatistica e ricette
I restauri di Assisi. La realtà dell’utopia dall’Alto Medioevo al Settecento, a cura
(con CD-rom), a cura di Giuseppe Basile ro della ceramica
di Paola Pogliani, Claudio Seccaroni
Conservazione preventiva delle raccolte museali, Vishwa Raj Mehra, Foderatura a freddo Susanne A. Meyer e Chiara Piva, L’arte di ben
a cura di Cristina Menegazzi, Iolanda Silvestri Francesco Pertegato, Il restauro degli arazzi restaurare. La raccolta d’antiche statue (1768-
The Painting Technique of Pietro Vannucci, Called Cristina Ordóñez, Leticia Ordóñez, Maria del Mar 1772) di B. Cavaceppi
il Perugino, a cura di Brunetto G. Brunetti, Rotaeche, Il mobile. Conservazione e restauro
Claudio Seccaroni, Antonio Sgamellotti Cristina Giannini, Roberta Roani, Giancarlo Lanter- ARTE E RESTAURO/STRUMENTI
Villa Rey. Un cantiere di restauro, contributi na, Marcello Picollo, Deodato Tapete, Dizionario
per la conoscenza, a cura di Antonio Rava del restauro.Tecniche Diagnostica Conservazione Vincenzo Massa, Giovanna C. Scicolone, Le vernici
Le patine. Genesi, significato, conservazione, per il restauro
Claudio Seccaroni, Pietro Moioli, Fluorescenza X.
a cura di Piero Tiano, Carla Pardini Prontuario per l’analisi XRF portatile applicata Maurizio Copedè, La carta e il suo degrado
Monitoraggio del patrimonio monumentale a superfici policrome Francesco Pertegato, I tessili. Degrado e restauro
e conservazione programmata, Tensionamento dei dipinti su tela. La ricerca del Gustav A. Berger, La foderatura
a cura di Paola Croveri, Oscar Chiantore valore di tensionamento, a cura di Giorgio Capriot- Dipinti su tela. Metodologie d’indagine
Impatto ambientale. Monitoraggio sulle Porte ti e Antonio Iaccarino Idelson, con contributo di per i supporti cellulosici, a cura
bronzee del Battistero di Firenze, Giorgio Accardo e Mauro Torre, ICR di Giovanna C. Scicolone
a cura di Piero Tiano, Carla Pardini e intervista a Roberto Carità Chiara Lumia, Kalkbrennen. Produzione tradiziona-
Raphael’s Painting Tecnique: Working Pratique Monumenti in bronzo all’aperto. Esperienze di con- le della calce al Ballenberg/ Traditionelle Kalkher-
before Rome, edit by Ashok Roy, Marika Spring servazione a confronto (con CD-rom allegato), a cura stellung auf dem Ballenberg (con DVD)
Pulitura laser di bronzi dorati e argenti, di Paola Letardi, Ilva Trentin, Giuseppe Cutugno Anna Gambetta, Funghi e insetti nel legno.
a cura di Salvatore Siano Manufatti archeologici - CD-rom, a cura Diagnosi, prevenzione, controllo
Il Laser. Pulitura su materiali di interesse artistico, di Salvatore Siano
a cura di Annamaria Giovagnoli Cesare Brandi, Theory of Restoration, a cura ARTE E RESTAURO/ESPERIENZE
Sebastiano del Piombo e la Cappella Borgherini di Giuseppe Basile con testi di G. Basile, P. Philip- Dario F. Marletto, Foderatura a colla di pasta
nel contesto della pittura rinascimentale, a cura pot, G.C. Argan, C. Brandi (ed. inglese // ed. russa) fredda - Manuale
di Santiago Arroyo Esteban, Bruno Marocchini, La biologia vegetale per i Beni Culturali.
Claudio Seccaroni Vol. I Biodeterioramento e Conservazione, ARTE E RESTAURO/@NTEPRIMA E-BOOK
Basic Environmental Mechanisms Affecting Cultural a cura di Giulia Caneva, Maria Pia Nugari,
Heritage. Understanding Deterioration Mechanisms Ornella Salvadori // Vol. II Conoscenza e Valorizza- Federica Dal Forno, La ceroplastica anatomica e il
for Conservation Purposes, edited by zione, a cura di Giulia Caneva suo restauro. Un nuovo uso della TAC, una possi-
Dario Camuffo, Vasco Fassina, John Havermans Lo Stato dell’Arte 3 // 4 // 5 // 6 // 7 // 8 // 9 // 10, bile attribuzione a G.G. Zumbo
Giambattista Tiepolo. Il restauro della pala di Congressi Nazionali IGIIC Luigi Orata, Tagli e strappi nei dipinti su tela.
Rovetta. Storia conservativa, diagnostica e studi Codici per la conservazione del Patrimonio storico. Metodologie di intervento
sulla tecnica pittorica, a cura di Amalia Pacia Cento anni di riflessioni, “grida” e carte, Mirna Esposito, Museo Stibbert. Il recupero di una
Indoor Environment and Preservation. Climate a cura di Ruggero Boschi e Pietro Segala casa-museo con il parco, gli edifici e le opere
Control in Museums and Historic Buildings, edit by La protezione e la valorizzazione dei beni delle colllezioni
Davide Del Curto (testi in inglese ed italiano) culturali, a cura di Giancarlo Magnaghi Maria Bianco, Colore. Colorimetria: il sistema di
Roberta Roani, Per la storia della basilica di Santa L’eredità di John Ruskin nella cultura italiana colore Carlieri-Bianco
Croce a Firenze. La “Restaurazione generale del del Novecento, a cura di Daniela Lamberini Non solo “ri-restauri” per la durabilità dell’arte, a
tempio” 1815-1824 La diagnostica e la conservazione cura di D. Benedetti, R. Boschi, S. Bossi, C.
Adele Cecchini, Le tombe dipinte di Tarquinia. dei manufatti lignei (CD-rom) Coccoli, R. Giangualano, C. Minelli, S. Salvadori, P.
Vicenda conservativa, restauri, tecnica di Strumenti musicali antichi. La spinetta ovale di Segala
esecuzione Bartolomeo Cristoferi, a cura di Gabriele Rossi Cecilia Sodano Cavinato, Un percorso per la
Caravaggio’s Painting Tecnique, edited by Marco Rognoni (in italiano e in inglese) valorizzazione e la conservazione del patrimonio
Ciatti, Brunetto G. Brunetti Meteo e Metalli. Conservazione e Restauro delle culturale. Il museo Civico di Bracciano
sculture all’aperto. Dal Perseo all’arte contempora- Encausto. Storia, tecniche e ricerche, a cura di
QUADERNI DEL BOLLETTINO ICR nea, a cura di Antonella Salvi Sergio Omarini (in italiano e in inglese)
Marco Ermentini, Restauro Timido. Architettura Il restauro della fotografia. Materiali fotografici e
Restauri a Berlino. Le decorazioni rinascimentali cinematografici, analogici e digitali, a cura di
lapidee nell’Ambasciata d’Italia, a cura di Giuseppe Affetto Gioco
Leonardo. L’Ultima Cena. Indagini, ricerche, restau- Barbara Cattaneo
Basile (testi in italiano, tedesco, inglese)
ro (con CD-rom), a cura di Giuseppe Basile Science and Conservation for Museum Collections,
ARCHITETTURA E RESTAURO e Maurizio Marabelli edited by Bruno Fabbri
Dendrocronologia per i Beni Culturali e l’Ambiente.
Dalla Reversibilità alla Compatibilità // Il recupero a cura di Manuela Romagnoli CON IL CENTRO CONSERVAZIONE
del centro storico di Genova // Il Minimo Interven- E RESTAURO “LA VENARIA REALE”
to nel Restauro // La fruizione sostenibile del bene Valentina Russo, Giulio Carlo Argan. Restauro,
critica, scienza collane dirette da Carla Enrica Spantigati
culturale // Il Quartiere del ghetto di Genova
Marco Ermentini, Architettura timida. Piccola enci- ARCHIVIO
QUADERNI DI ARCHITETTURA clopedia del dubbio Restauri per gli altari della Chiesa di Sant’Uberto
diretti da Nicola Santopuoli e Alessandro Curuni Consigli. Ovvero l’arte di arrangiarsi in cantiere e alla Venaria Reale, a cura di Carla E. Spantigati
Federica Maietti, Dalla grammatica del paesaggio in bottega, // Tips. Finding your Way Around Sites Delle cacce ti dono il sommo impero. Restauri per
alla grammatica del costruito. Territorio e tessuto and Workshops a cura di Alberto Felici e Daniela la Sala di Diana alla Venaria Reale (con DVD inte-
storico dell’insediamento urbano di Stellata Murphy Corella (in italiano e in inglese) rattivo), a cura di Carla E. Spantigati
Il rilievo per la conservazione. Dall’indagine alla I ruderi e la guerra. Memoria, ricostruzioni, restau-
valorizzazione dell’altare della Beata Vergine del ri, a cura di Stella Casiello CRONACHE
Rosario nella chiesa di San Domenico a Ravenna, Archeometria e restauro. L’innovazione tecnologica, Restaurare l’Oriente. Sculture lignee giapponesi
a cura di Nicola Santopuoli a cura di Salvatore Siano per il MAO di Torino, a cura di Pinin Brambilla
Barcilon ed Emilio Mello
CON L’ASSOCIAZIONE GIOVANNI SECCO SUARDO - ARTE E RESTAURO/PITTURE MURALI Kongo Rikishi. Studio, restauro e musealizzazione
QUADERNI DELL’ARCHIVIO STORICO NAZIONALE E Direzione scientifica: Cristina Danti della statuaria giapponese - Atti della giornata
BANCA DATI DEI RESTAURATORI ITALIANI Cecilia Frosinini internazionale di studi
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diretti da Giuseppe Basile e Lanfranco Secco Suardo
I: secc. XVII-
Alberto Felici, Le impalcature nell’arte per l’arte.
Palchi, ponteggi, trabiccoli e armature per la realiz-
Il restauro degli arredi lignei - L’ebanisteria pie-
montese, a cura di Carla E. Spantigati, Stefania De
XX/Vol. II: secc. XIX-XX, a cura di Giuseppe Basile zazione e il restauro delle pitture murali Blasi