Chapter 1: Part A

---------------------------------
General 4.spects of
Adhesion and Adhesives
---------------------------------
 I.A.I Introduction
An adhesive is defined as a substance capable of holding materials together by
surface attachment [ 1]. Adhesive is the general term and includes cement, glue, paste,
mucilage, etc. and these terms are all used essentially interchangeably. The materials
being joined are commonly referred to as the substrates or adherends. The term adhesion
refers to the state in which the two substrate surfaces are held together by interfacial
forces which may consist of valence forces leading to specific adhesion, or interlocking
forces leading to mechanical adhesion, or both. A number of publications, including
handbooks, pertaining to adhesion and adhesives are currently available l 2-11 ].

I.A.2 Importance of Adhesives in Today's World

Adhesives which have existed for thousands of years, have gained tremendous
industrial importance during the past few decades and are now considered as engineering
materials with an ever-increasing bonding applications ranging from household articles
of everyday use to supersonic aircrafts and satellites. There is hardly a product
manufactured today that does not utilise an adhesive either in its construction, packaging,
transportation, display, storage or advertisement. It has now come to the stage where a
properly selected adhesive can join together any two entirely different materials.

I.A.3 Advantages and Limitations of Adhesive Bonding

For an adhesive to be useful, it should not only hold materials together, but
should also withstand operating loads and environments and last the life of the product.
Many of the earlier natural adhesives (derived from vegetable, animal or mineral
substances) were later replaced by synthetic polymer adhesives owing to their stronger
adhesion and greater resistance to adverse environments. The number and types of
synthetic polymer adhesives have proliferated to an uncountable level. The significant
progress that has taken place in the science and technology of adhesion and adhesives
over the past 60 years, or so, is mainly due to the advantages that adhesives offer
compared to other more traditional techniques for fastening materials such as brazing,
welding, rivetting, bolting, etc. The important advantages of adhesive bonding are

1
 Table LA.I Important Advantages and Limitations of Adhesive Bonding Compared to
Traditional Joining Techniques

Advantages Limitations
* Ability to join similar or dissimilar, thin or * Does not permit visual
thick materials of any shape examination of the bonded area
* Provide uniform stress distribution * Need for careful surface
* Provide increase in design flexibility preparation and rigid process
* Damp vibration, absorb shock, resist control
fatigue and cyclic loads * High cure temperature, long cure
* Seal the joint against a variety of times, holding fixtures, etc. may
environments be needed
* Provide an attractive strength/weight ratio * Upper and lower service
* Often the most convenient, fast and temperatures and environmental
cost-effective technique limitations to be taken care of

compiled in Table 1.A.1. However, as with any technology, there are some limitations
as well, which are also given in the table.

1.A.4 Components of Adhesives

Modern-day adhesives are often fairly complex formulations of components
that perform speciality functions. The primary component of an adhesive is the binder
which provides the adhesive and cohesive strength to the bond. The binder is usually an
organic resin, but can be a rubber, an inorganic compound or a natural product. The other
components are hardener, solvent, modifier, filler, diluent, accelerator, inhibitor,
reinforcement, etc. depending on the specific end requirements.

1.A.S Requirements for a Good Bond

The establishment of intimate molecular contact at the interface is necessary
for developing strong adhesive joints. To achieve this, the following necessities should
be taken care of:

2
l.A.5.1 Cleanliness of the Surfaces to be Joined: The substrate surface should he free
from foreign materials such as dirt, oil, moisture and weak oxide layers. This can be
achieved by proper surface treatments like solvent wiping, vapour degreasing, abrasive
cleaning, chemical etching, etc. Before actual bonding operation, the effectiveness or
surface preparation can be checked by water break-free test in which the properly cleaned
surface will hold a continuous film of water rather than a series of isolated droplets.
1.A.5.2 Wetting and Spreading of the Adhesive on the Substrate: For an adhesive to
wet a solid surface, it should have a lower surface tension than the critical surface tension
of the solid [ 12]. Good wetting results when the adhesive flows into the valleys and
crevices on the substrate surface.
l.A.5.3 Proper Setting of the Adhesive : Once the wetting process is complete, the
adhesive should set (harden) by a suitable method such as solvent evaporation, cooling
or chemical reaction. The process of hardening increases the bulk strength of the adhesive
leading to an increase in the strength of the joint.
l.A.5.4 Proper Selection of the Adhesive: The adhesive should be selected so as to suit
the specific end requirements of the bonded joint. The factors to be considered include
the nature of the substrate, service requirements, production requirements, environmental
conditions, special functions, if any (like thermal or electrical conductance), cost and
safety aspects [13].
l.A.5.5 Proper Design of Joint: A joint should be designed to get maximum strength
for a given area of bond by securing uniform stress distribution over the whole bonded
area so as to take advantages of the desirable properties of the adhesives and to minimise
their shortcomings.

l.A.6 Criteria for Optimum Bond Strength

A generalised form of the dependence of the measured strength of an adhesive
bond, Fmeas , on the various physical, chemical and other factors is represented by the
equation
where, M represents the mechanics of the adhesive bond, W"' is the work or adhesion, ,�·
and Gare the complex Young's and shear moduli respectively of the adhesive, G, is the
fracture resistance of the material, iJH,1111 is the strength of interfacial chemical bonds,
( 01 - 02 ) is the solubility parameter difference, y is the surface roughness and 7J(t) is the
viscosity profile of the adhesive during cure [14]. F111 "11, is also dependent upon the
handling properties of the adhesive. Many of the above variables are interdependent and
many confounding relationships exist.

1.A.7 Theories of Adhesion

The mechanisms of adhesion are still not fully understood and many theories
of adhesion based on the physical and chemical phenomena taking place at the adhesive-
substrate interface are described in literature [15].
1.A.7.1 Adsorption Theory : is well accepted and has been discussed in depth by
Kemball [16], Huntsberger [17], etc. It states that, provided sufficiently intimate
molecular contact is achieved at the interface, the materials will adhere because or the
interatomic and intermolecular forces which are established between the atoms and
molecules in the two surfaces. These forces can be of the primary type (ionic, covalent
and metallic bonds) or the more common secondary type (van der Waal 's bonds).
1.A.7.2 Mechanical Theory: proposes that mechanical interlocking of the adhesive into
the irregularities of the substrate surface is the major source of intrinsic adhesion [18 J.
However, the attainment of good adhesion between smooth surfaces exposes this theory
as not being of general applicability.
LA. 7.3 Electronic Theory : is due primarily to Deryaguin and co-workers [ 19 J. It states
that when the substrate and adhesive having different electronic band structures arc
brought in intimate contact, an electrical double layer is formed and the electrostatic
forces resulting from such junction potentials contribute significantly to the intrinsic
adhesion.
1.A.7.4 Diffusion Theory : by Voyutskii [20], states that the intrinsic adhesion or
polymers to themselves (autohesion), and to each other, is due to mutual diffusion of

4
polymer molecules across the interface. This requires that the chain segments or the
substrate and adhesive possess sufficient mobility and are mutually soluble.
l.A.7.5 Weak BoundaryLayer Theory: was first described by Bikerman [21 J, wherein
the strength of an adhesive joint is interpreted in terms of the rheological strength of a
discrete boundary (interfacial) layer that exists between the adhesive and adherend. The
theory proposes the existence of a finite boundary layer composed of adsorbed adhesive
molecules that differ in nature from those constituting the bulk phase. A strong joint
results if the boundary layer can withstand the external forces, whereas, a poor joint is
formed because of a weak boundary layer which may be caused by entrapped air,
impurities or low molecular weight species that concentrate near the surface.

l.A.8 Classification of Adhesives

Since a large variety of adhesives is currently being used for different bonding
applications, there is no adequate single system of classification for all the products.
Adhesives can be generally classified based on the function, physical form, origin,
chemical composition, end use, etc.
l.A.8.1 Function : Adhesives are classified into structural and non-structural types
based on their primary function in the joint. As per ASTM D-907, a structural adhesive
is defined as a bonding agent used for transferring required loads between adherends
exposed to service environments typical for the structure involved [I]. A structural bond
is one which stresses the adherend to the yield point, thereby taking fult advantage of the
strength of the adherend. Accordingly, a dextrin adhesive used with paper ( eg. postage
stamps) and which causes the failure of the paper if stressed, forms a structural bond. The
stronger the adherend, the greater the demands placed on the adhesive. Thus, few
adhesives qualify as structural for metals. Structural adhesives are often based upon
monomer compositions which polymerise to give high-modulus, high-strength adhesives
between relatively rigid adherends [usually more than 1000 psi (pounds per square inch)

epoxies, phenolics, acrylic resins, etc.

5
 A non-structural adhesive (holding adhesive) is not required to support
substantial loads but is primarily intended to hold light-weight materials in place. A
failure in a non-structural adhesive joint will not cause the total failure of the structure.
Examples are gums, certain rubber-based adhesives used to fill gaps, etc.
l.A.8.2 Physical Form: Adhesives are classified as (a) liquid adhesives which can be
easily applied by spray, brush, etc. (b) paste adhesives which can be applied using spatula
or trowels (c) tape and film adhesives which are especially useful in bonding honey-comb
structures and thin materials, and (d) powder or granules which can be melted or
dissolved in proper solvent and applied like the liquid type.
l.A.8.3 Origin : Adhesives are classified as natural and synthetic based on their origin.
(a) Natural ones include vegetable- and animal-based adhesives and gums. They arc
inexpensive, easy to apply and have a long shelf life. They develop tack quickly but have
low strength properties and hence the application is limited to paper, foil, light wood, etc.
(b) Synthetic adhesives are polymer-based which can provide high strength to the joint.
l.A.8.4 End-use: Based on the adherends bonded, they can be metal adhesives, wood
adhesives, rubber adhesives, etc. Based on the environment for which they are intended,
they can be acid-resistant adhesives, high temperature adhesives, low temperature
adhesives, etc.
l.A.8.5 Chemical Composition : Synthetic adhesives can be classified as thermosetting,
thermoplastic, elastomeric or alloys based on their chemical composition [22].
l.A.8.5.1 Thermosetting Adhesives: They form bonds that are essentially infusible and
insoluble through the action of heat, catalyst or a combination of these. As cured
thermosets are densely cross-linked, they can function as structural adhesives with good
heat- and solvent resistance. They are available as one-part and two-part systems.
Examples are epoxies, phenolics.
l.A.8.5.2 Thermoplastic Adhesives: They are fusible and soluble. They can soften when
heated and are subject to deformation under stress. They do not cross-link upon cure but
harden upon cooling from a melt or by evaporation of the solvent. Thermoplastics are
usually meant for temperatures up to about 65 ° C and their applications are confined to

6
low-load, unstressed joints which are not subject to severe environmental conditions, as
in packaging. Examples are polyvinyl alcohol, polyvinyl acetates, cellulose acetate.
l.A.8.5.3 Elastomeric Adhesives :They are based on natural or synthetic elastnmeric
polymers having high elongation and toughness. They are supplied as solutions, latex
cements, dispersions, pressure sensitive tapes, etc. and are generally noted for their high
degree of flexibility and good peel strength. Examples are natural rubber, nitrile rubber,
silicones.
l.A.8.5.4 Polymer Alloys: These are made by combining resins of two or more different
chemical groups chosen from thermosets, thermoplastics or elastomers. The thermoset
resin chosen for its high strength is plasticised by the second resin which is usually a
thermoplastic or elastomer, thus making the alloy tougher, more flexible and more
resistant to impact. Such alloy/blend adhesives are used where the highest and strictest
end-use conditions must be met, sometimes regardless of cost, as in military applications.
Examples are epoxy-phenolics, epoxy-nylon, nitrile-phenolics.

l.A.9 Adhesive Joint Design

The components that are to be connected by adhesive bonding must have
specially designed joints. The four basic types of stresses commonly encountered in
adhesive joints are normal (or direct), shear, peel and cleavage [23]. For getting improved
joint efficiency, it is necessary that the bonded area be as large as possible within
allowable geometry and weight constraints and that the adhesive should be stressed in the
direction of its maximum strength. The bonded joints perform best under tension,
compression or shear loading, not as well under cleavage and relatively poorly under peel
loading [24].

l.A.10 Evaluation of Adhesive Joint Strength

Evaluation of an adhesive joint by various test methods helps in the prediction
of the behaviour of a joint made using a particular adhesive. The strength of an adhesive
joint is determined primarily by the mechanical properties of the adherend and adhesive,
residual internal stresses, degree of true interfacial contact, the joint geometry and the

7
details of mechanical loading. A uniform stress pattern in an adhesive joint is seldom
produced by the application of an external force and fracture initiates where the local
stresses exceed local strength.
1.A.10.1 Destructive Testing : A variety of destructive testing methods are available
[25], from which one has to choose the most appropriate test that can simulate the actual
stress, its direction, environmental conditions and rate of loading. ASTM D-1002
describes the single lap shear test used for metallic substrates. This is the most commonly
used and useful test since it is simple, cheap and that a lot of data are available for
comparison. Peel test involves the controlled stripping of a flexible adherend that is
adhesively bonded to either a flexible or rigid adherend. Most common types are T-peel,
180° peel and the climbing drum peel test for sandwich structures, described in ASTM
methods D-1876, D-903 and D-1781 respective I y. ASTM D-897 describes the popular
pi-tensile test for wood and metal substrates.
An analysis of the mode of failure in the joint is extremely valuable to decide
where, and to what extent, the failure occurred. The joints may fail adhesively or
cohesively. Adhesive failure is interfacial bond failure between the adhesive and the
adherend, whereas cohesive failure occurs when fracture allows a layer of the adhesive
to remain on both surfaces. When the adherend fails before the adhesive, it is cohesive
failure of the substrate. Cohesive failure within the adhesive or on the adherend is the
ideal type of failure, where the limiting strength of the material in the joint has been
reached. The mode of failure is often expressed as percentage cohesive I adhesive failure.
The analysis of mode of failure helps in identifying the weak link in the joint so that
remedial action can be taken.
l.A.10.2 Non-Destructive Testing : The objective of any form of non-destructive test
is to correlate the joint strength with some physical, chemical or other parameter which
can be measured without causing damage to the bonded assembly. Ultrasonic resonance,
acoustic tests, thermal methods, radiography etc. are some of the important non­
destructive tests being practised [26].

8
l.A.11 Structural Adhesive Families
Structural adhesives can produce high-strength, load-bearing joints with good
creep resistance and most of the thermosetting adhesives belong to this class.
Thermosetting polymers are presently employed almost exclusively, either as the basis
for the structural adhesive compositions or as the matrix resins for composites. This
dominance of thermosetting polymers may be ascribed to several reasons: (a) the typical
precursors are low molar mass resins which contain relatively polar chemical groups
which can be polymerised by the addition of a curing agent or catalyst and/or the
application of heat or light; (b) relatively low viscosity during the processing steps and
the presence of reactive polar groups in the resin lead to good wetting and high intrinsic
adhesion at the adhesive/substrate or matrix/fibre interface; (c) a variety of curing agents
may be employed to suit a wide range of processing requirements; (d) when polymerised,
thermosetting polymers give rise to amorphous, highly cross-linked structures resulting
in many useful properties for engineering applications such as high modulus, high
strength, low creep and good performance at elevated temperatures [ 18]. However,
because of their high brittleness, the impact and flexure properties of thermosets are
usually poor, but these can be modified by alloying with suitable thermoplastics or
elastomers.
The structural adhesives are available as one-component (long shelf-life), two­
component (limited pot-life), solvent based liquid, solid powder, film (unsupported) and
tape (supported) forms. The one-component group may be heat-cured or cured by surface
or anaerobic catalysis, while the two-component group is usually cured at lower
temperatures. The market areas of interest for structural adhesives are transportation,
construction, rigid bonding and consumer products [27]. The structural adhesive
applications include bonding of metal-to-metal honeycomb sandwich structures,
structural plastic laminates, fibre-reinforced composites, etc., particularly used in
spacecraft, aircraft and marine industries.
The chemistry of structural adhesives is essentially the chemistry of the
thermoset epoxy and phenolic resins. A brief description of these resins along with other

9
important structural adhesive classes is given below.

1.A.11.1 Amino Resins

The condensation products of formaldehyde with urea or melamine constitute
the only important members of the amino resins [28]. With high functionality for urea
and melamine (4 and 6 respectively), these resins cure to form highly crosslinked three
dimensional structures. The melamine resins offer better heat-, chemical- and moisture­
resistance than the urea resins.

1.A.11.2 Polyurethanes
Polyurethanes are characterised by the presence of urethane linkages and arc
prepared by the reaction between a polyisocyanate and an active hydrogen compound
such as alcohol, amine or thiol which yield urethane, urea and thiocarbamate linkages
respectively [29J. The general reaction leading to the synthesis of a polyurethane is
depicted in Scheme 1.A.1. Polyurethanes are often formulated so as to produce a
segmented polymer consisting of soft and hard segments. The soft segment is composed
of a long chain polyol, such as polyether or polyester diol. The hard segment is formed
from a polyisocyanate and a short chain polyol or diamine chain extender. The inherent
toughness and wide range of physical properties displayed by polyurethanes can be
attributed to its two-phase morphology, in which the hard domains serve to reinforce the
polymer and provide sites for multi functional crosslinking. The soft segment is primarily
responsible for the elastic and low temperature properties of the polymer.

OCN -R-NCO + HO- R'-OH

Diisocyanate Dial
l

f-o-R'-0-CO-NH-R-NH-CO�

Polyurethane

Scheme 1.A.1 Synthesis of Polyurethane

10
 Polyurethane structural adhesives have made significant progress in recent
times and they offer a unique combination of properties like good bond durability,
substantial adhesion to a wide variety of substrates, ability to perform extremely well at
lower temperatures, good chemical resistance, formulating flexibility, high peel strength
and very good impact resistance [30]. The limitations are their poor elevated temperature
performance, only moderate bonding strength to metals and also limited shelf-stability
due to the moisture sensitivity of the free isocyanate groups, if present in them.

1.A.11.3 Acrylic Resins

Acrylic based adhesives are solvent-free, reactive engineering adhesives and
include cyanoacrylates, anaerobics and modified-acrylic adhesives. They are
characterised by high peel strength, shear strength and chemical resistance and are
tolerant of a variety of substrate contaminants, particularly, oil. Acrylics are polymers
and copolymers which are mainly based on acrylic and methacrylic acids and their
derivatives, especially the acid esters. Polymerisation is started by a free-radical initiator,
often a peroxide, and then the monomers polymerise rapidly at room temperature to form
the final polymer. Anaerobic materials are single component liquids that can be stored
at ordinary temperatures in the presence of oxygen and then polymerise rapidly to solids
on being confined between two surfaces that exclude air. Anaerobic products are
extensively used for thread-locking, sealing and bonding of bearings and shafts [31 J.
Cyanoacrylate adhesives are better known as 'super glues' or 'instant glues' and
occupy a rather unique position because of their speed of cure, strength and case of use
[32). Cyanoacrylate monomer can be made to polymerise by a free-radical mechanism,
but the strongly electronegative nitrile and carboxyl groups attached to the ex-carbon
make it very susceptible to anionic polymerisation, which can be initiated by relatively
weak bases. The processes of polymerisation initiation and propagation proceed by the
reactions as shown in Scheme l .A.2. Usually, small amounts of thickening agents arc
also added to control viscosity.

1l
 CN
.,--tI -
CN initiation
A- CH
!
CH,=( + A
-
- \COOR COOR
Cyanaoacrylatc base propagation
/

CN CN

A-{CH,-7�CH2-f-
C � 11 COOR
polymer

Scheme 1.A.2 Anionic polymerisation of Cyanoacrylates

1.A.11.4 Epoxy Resins

Epoxy resin adhesives are probably the most versatile of all high-strength
adhesives. They comprise a group of cross-linkable materials which possess the reactive
oxirane functional group. Epoxies can be cured by a variety of hardeners like aliphatic
and aromatic amines, acid anhydrides, phenols, carboxylic acids, ureas, inorganic acids
and bases, mercaptans, heterocyclic compounds, etc., and a knowledge of the chemistry
or curing permits the user to cure epoxies at a wide range of temperatures and to control
the degree of crosslinking [33]. The structure of the most commonly used epoxy resin,
diglycidyl ether of bisphenol A (DGEBA) and its cure reaction with an aliphatic primary
amine curing agent are shown in Scheme 1.A.3. Depending on the chemical structure or
the resin, hardener and the curing conditions, it is possible to obtain toughness,
mechanical properties ranging from extreme flexibility to high strength and hardness,
chemical-, heat- and electrical-resistance [34J. The popularity of epoxies as adhesives is
due to a number of reasons: (a) the presence of highly polar groups like oxirane,
hydroxyl, amine, etc. provide high specific adhesion to many materials like metals, glass
and ceramics; (b) when the resin is properly cured, the cohesive strength within the
glueline is very high, leading to good strength for the joint; (c) they cure without the
release of any condensation by-product and this makes it possible to bond the epoxies
with only contact pressure; (d) they exhibit very low shrinkage during cure and hence the

12
 DGEBA

Diepoxy

Cured polymer

Scheme l .A.3 Epoxy resin structure and cure with amine

joint will have reduced stress concentrations; (e) they can be readily modified in many
ways, some of which are alloying with other suitable resins, incorporating diluents,
extenders, fillers, specialized additives, etc [35,36].
Epoxy resins when cured produce highly brittle matrices with poor peel and
impact resistance. Much work has been carried out to toughen the epoxies by the
incorporation of a secondary phase of dispersed rubbery particles [37-41 J. Reactive liquid
rubbers like carboxyl terminated butadiene acrylonitrile copolymer (CTBN) [37-411,
thermoplastics like poly(aryl ether ketones) [42], acrylic elastomers [43] and pre-formed
core-shell polymers are found to be effective in improving the toughness of epoxy
systems.
The high temperature capability of conventional DGEBA resins is limited to
about 150 ° C. However, this property can be enhanced by increasing the degree of
crosslinking by a suitable choice of multi functional epoxies and curing agents.
Relatively high glass transition temperatures (Tg >200° C) have been reported with

13
polyfunctional epoxy resins like triglycidyl derivative of p-ammo phenol [ 44 J,
tetraglycidyl ether of glyoxal phenol novolac resin and tetra glycidyl derivative of
methylene dianiline (structures given in Scheme l .A.4) [ 45]. The high crosslinking and
brittleness of such cured resins together with the propensity of epoxies to absorb
considerable quantities of water which reduce the Tg, have greatly diminished the
prospects of this approach to achieve high-temperature capability [46 J. Thus, even the
most stable epoxy adhesives can be used for long-time exposure only up to service
temperatures not exceeding 180 ° C [47]. For speciality applications such as optical
devices on-board the satellites, systems with low coefficient of moisture expansion
(CME) such as dicyclo pentadiene phenol epoxy are preferred [48J.

(c)

Scheme 1.A.4 Structures of some polyfunctional epoxies: (a) triglycidyl ether of p­

amino phenol, (b) tetraglycidyl ether of glyoxal phenol novolac and (c) tetraglycidyl
ether of methylene di aniline

l.A.11.5 Polyaromatic Resins

The polymers based on heterocyclic-aromatic, resonance-stabilised structures
like polyimides, polybenzimidazoles, polyphenylquinoxalines, polybenzoxazoles,
polypyrrones, etc., having good thermo-oxidative stabilities have been classified as high­
temperature resistant structural adhesives, capable of withstanding temperatures greater

14
than 300°C [49-51]. To be used successfully as an adhesive, the thermally stable polymer
must be processable under moderate conditions with no volatile evolution, good shelf
life, tack, compatible with the adherends and should have good, durable properties [ 521.
Only a few high temperature polymeric adhesives are commercially available because of
an elusive market and an unfavourable combination of price, processability and
performance. Such polymers are often made and used for specialized applications and are
generally not available commercially.
Among the numerous high-temperature resistant polymers, the polyimides (Pl)
have by far achieved the greatest commercial success due to their ability to maintain
acceptable mechanical properties at elevated temperatures together with a measure of
thermal stahility for long-term use at temperatures around 300 ° C 153,541. Pnlyimides arc
prepared from aromatic tetra carhoxylic dia11hydridcs and aromatic diami11cs (Scl1c111c
l .A.5) and the Pl adhesives are of 3 types (a) condensation, (b) thermoplastic, and (c)
imide prepolymers [55]. Condensation Pis have long-term use temperature up to 300 ° C
retaining about 50% of its room temperature strength; but their processing disadvantages
have limited their wider use. The family of condensation polyimides derived from
tetracarboxylic acid 2,2-bis (3 ',4'-dicarboxyphenyl) hexafluropropane and phenylene
diamines were shown to be suitable for aerospace bonding applications up to 3 71 °C [ 56].

0 0
II 11
/�c,
0
'C 0 C
0
/ +
II II
() 0
Pyromellitic anhydride 111-Phenylcne diamine

-H20
1='11- Jno0c

Polyamic acid Polyimicle

Scheme 1.A.5 Synthesis of Polyimide

15
LARC-TPI (NASA) is an example of a thermoplastic PI adhesive based on benzophcnone
derivative (structure given in Scheme 1.A.6), which can produce large area void-free
adhesive bonds. Extensive studies have been carried out on this adhesive for bonding
applications 111 aerospace as well as industry [57]. Polyimidesulphones,
polysiliconeimides and polyetherimides are the recent developments in thermoplastic Pl
adhesives that have shown promise. Polyetherimides were shown to have exceptional

Scheme 1.A.6 Structure of LARC-TPI (NASA)

adhesive properties for temperatures up to 204 ° C [58-60]. An alternative route to

enhanced processability is based on imide prepolymers, where the oligomers having the
stable cyclic imide structure are preformed and can be further cured via the unsaturated
end groups in them through addition reactions. 3 main types belonging to this class which
showed potential as high-temperature adhesives are based on norbornene (cg. NASA
LARC-13) [61J, acetylene (eg. Thermid IP-600) [62J and maleimide (eg. Hysol EA 9655)
[ 63 J functionality. Among these, the bismaleimides have been studied extensively.
The double bonds in maleimide groups can undergo free radical and anionic
homo- and copolymerisations. Thus, with a diamine, bismaleimide undergoes Michael
addition followed by free radical crosslinking (Scheme 1.A.7). Bismaleimides offer
possibly the greatest benefits in terms of enhanced processability similar to epoxies.
However, their thermal stability and long-term capability in the 200-300 ° C range are
limited and hence essentially fill the gap between the epoxies and the condensation and
thermoplastic Pis. Non-methylenedianiline (MDA) condensation and addition polyimides
avoid the toxicity and carcinogenicity issues related to MDA and their performance has
been reported to be comparable to their MDA-containing counterparts [64,65].

16
 � 0
��-R-N ) �I H2N �R' -NH2
O <?- -
0 0

HN-R ' N H�\- R-N �I

l
"ir . 19N
-R- N
)

�(
Diamme
� '1/
Addition product (�
"11
<?-
( 0 0 O
BMI
'?
y� __ . R-
HN - ' NH�\-R- N �
O 0
)
Polymerisation N R N
� � "I�
(
�/
O Cured polymec � O

Scheme 1.A. 7 Bismaleimide-diamine crosslinking

1.A.11.6 Phenolic Resins

The phenolic resins are an important class of thermosetting resins. They are
dealt with in detail in Part 8 of this chapter.

1.A.12 Recent Trends in Adhesives

Adhesion is an inter-disciplinary and ever-growing field and recently there has
been a better recognition of adhesion technology as a basic science. The fundamental
disciplines of chemistry, materials science and solid mechanics are involved in adhesion
and L.H. Lee has dealt with the theoretical aspects of adhesion in his recent publications
in 2 volumes [66,67J.
The resins which form the mainstay of the industry such as the epoxies,
phenolics and acrylics have been studied extensively for their adhesive properties. The
developments in the chemistry and properties of such structural adhesives have led and
supported the spread of these materials from the high-technology aerospace industries
into all types of general engineering applications. However, the latest research in
adhesives is always triggered by the challenging needs of high-tech aerospace industries.
Efforts are ongoing to develop polymers for high temperature adhesive and
composite aerospace applications such as supersonic aircraft [68]. Such adhesives must

17
possess both processability for bonding as well as durability for elevated temperature
service. Out of the several heterocyclic-aromatic polymers, the polyimides are considered
the state-of-the-art material for high temperature adhesive applications and a number of
recent studies are devoted to improving the processability as well as high temperature
capability of different types of polyimides.
The development and evaluation of Pis based on phenylethynyl terminated
imide oligomers have shown their suitability for bonding applications on titanium
substrates up to 204° C, with good processability and thermo-oxidative stability [69-71 J.
Similarly, excellent adhesive and composite properties were reported for a PI prepared
from 3,3',4,4'- biphenyl tetracarboxylic dianhydride and an 85:15 molar ratio of 3,4'­
oxydianiline and 1,3-bis (3-aminophenoxy) benzene [72]. A recent report highlights the
excellent performance of a phenyl ethynyl terminated polymer PETI-5 as a high­
temperature matrix resin and adhesive [731. Scheme 1.A.8 depicts the synthesis route to

H,"lQJ_o-©J._ NH:
H ,
�°i)�
NH , +
�
0
re + 2
i?
�
M-
--©J

s5 mole % 15 mole% NMP 23 ° C 91 mole% 18 mole%

N2 l 35%solids

0 0 0 O
- C=�Arf.�� frl�rr��=c---©
- �OOH HOO�OOH HOO�
©

1Cydodehyd,ahoc

0 0 0 0

� ��+��,-j�= --©J
C= C

Random imide Oligomer containing terminal phenylethynyl groups

350-371 ° C
1 Where Ar=
1 hour

Crosslinked resin _©J-� or -©J-�°10r

Scheme 1.A.8 Synthesis route to PETI-5

18
PETl-5. Also, modified polyetherimides with 4-phenylethynyl phthalic anhydride end­
capper were synthesised, which yielded highly imidised, controlled molecular weight
materials with excellent thermo-oxidative stability, solvent resistance and adhesion to
titanium substrates [60]. Recent efforts focus on the development of non-MDA
condensation and MDA-free addition polyimides. Toughened bismaleimide resins find
good aerospace bonding applications for short term use at 232° C and long term use up
to 163 ° C [74,75].
The use of single-component, hot-melt thermoplastic adhesives has grown
rapidly in recent years [76]. Polysulfones and polyetherketones having high Tg are the
important members of this class. A polyarylether ketone has been reported to perform
exceptionally well as a hot-melt adhesive [77].
Several studies have demonstrated the use of silane coupling agents as adhesion
promoters which improve the bond performance, durability and insensitivity to
contamination [78,79]. For the purpose of enhancing fibre/matrix interactions and
improving adhesion in composites, chemical modification of fibre surfaces was found to
be successful. New methods of surface treatments avoiding hazardous chemicals [80,81],
adhesive bonding via exposure to microwave radiation [821,etc. are also given due
importance in adhesive technology.

1.A.13 References

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3. C.V. Cagle (Ed), Handbook of Adhesive Bonding, McGraw-Hill Book Company, New
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4. Irving Skeist (Ed), Handbook of Adhesives, 211 Edition, Van Nostrand Reinhold
"

Company, New York ( 1977)

5. Adhesives, Adherends, Adhesion, Nicholas J.De Lollis, Robert E. Kriges Publishing
Company. Inc., Huntington, New York ( 1980)
6. J. Shields, Adhesives Handbook, 3"1 Edition, Butterworth & Co., London (1984)

19
7. A.H. Landrock, Adhesives Technology Handbook, Noyes Publications, New Jersey
(1985)
8. S.R. Hartshorn (Ed), Structural Adhesives: Chemistry and Technology, Plenum Press,
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9. A.J. Kinloch, Adhesion and Adhesives: Science and Technology, Chapman and Hall,
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10. Hal F. Brinson (Technical Chairman), Engineered Materials Handbook, Yol.3 :
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12. A.J. Kinloch, Adhesion and Adhesives: Science and Technology, Chapman and Hall,
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13. J. Shields, Adhesives Handbook, 3"1 Edition, Butterworth & Co., London, 23-29 (1984)
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(Ed), Plenum Press, New York, 17-19 (1986)

20
28. C.A.A. Rayner, in Adhesion and Adhesives, R.Houwink and G. Salomon (Eds), Elsevier
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21
48. U. Tatsunobu, Y. Keisaburo and Y. Teruhiro, (Mitsui Toatsu Chemicals), Japan Kokai
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22
71. P.M. Hergcnrothcr, R.G. Bryant, B.J. Jensen, J.G. Smith, Jr., and S.P. Wilkinson, 39'"
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72. B.J. Jensen, T.H. Hou and S.P. Wilkinson, 40" Int. Natl. SAM!'/:· 5,)•mp., 1072 (1995)
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75. K.A. Olesen and R. Falabella, 40'" Int. Natl. SAMPE Symp., 1183 (1995)
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79. M.R. Haddock and G.L. Anderson, 3<J" Int. Natl. SAMPE' Symp., 2752 (1994)
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23