1

Glass
If sand or quartz is heated with other metal oxides or carbonates (other than Na & K carbonates) such
as lime, alumina or oxide of lead etc., mixture of silicates are obtained. When allowed to cool, they
solidify and do not dissolve in water, constitute what is known as glass. Glass has no definite
composition.
Physical definition of glass: Physically glass may be defined as a hard, rigid, super-cooled or under-
cooled, brittle, non-crystalline substance having no definite melting point and sufficiently high
viscosity to prevent crystallization. It is usually transparent, but sometimes it is opaque or translucent.
Chemical definition of glass: Chemically glass may be defined as a fused mixture of silicates, alkali
and alkaline earth compounds and other glass constituents (such as calcium oxide, magnesium oxide,
tin oxide, barium oxide, lead oxide. Glass is completely a vitrified product.
As seen above, glass has no definite composition. However, the major ingredients are sand, lime and
soda ash, and any other raw materials may be considered to be minor ingredients. Sand, lime and
soda ash still form over 90 percent of all the glasses of the world. Other ingredients, such as borax,
boric acid, aluminium oxide, zinc oxide etc. are added to give certain other properties to glass. So
these are called minor ingredients.
Physical properties of glass
(1) They are usually transparent, amorphous solids.
(2) Glass is completely vitrified product.
(3) They are hard and rigid and have no definite melting point.
(4) They have sufficiently high viscosity (greater than 1013 poise) to prevent crystallization.
(5) They insulator of heat and electricity.
(6) They can incorporate coloring materials preserving transparency.
Chemical properties of glass
(1) Glass is not attacked by air and oxidizing agents.
(2) Ordinary glass is readily attacked by alkalies, but very resistant to acids, except hydrofluoric
acid (HF). Glass is a silicate and HF acid reacts with it as follows-
Na2O.SiO2 + 6HF 2NaF + SiF4 + 3H2O
CaO.SiO2 + 6HF CaF2 + SiF4 + 3H2O
(3) Ordinary glass is alkaline in reaction. Water slowly reacts on glass to form NaOH. This
reaction is enhanced in the presence of acids. If bottles containing acids are kept for a long
time, silicic acid is formed and deposited on the glass of the bottles. The glass, known as
neutral glass of which pyrex is an example, contains small amount of alkali silicates.
(4) When fused with large excess of fusion mixture, glass decomposes into alkali silicates and
carbonates of other metals. If the resulting mass is cooled and treated with dilute HCl acid,
silicic acid as well as chlorides of metals are formed.
Raw materials
Different raw materials used in the manufacture of glass are given below.
1. Sand: Quartz sand containing no or little iron (<0.045% &<0.015% for table wares and optical
glass respectively) is used. Iron adversely affects the color of glass.
2. Soda ash: Anhydrous soda ash (Na2CO3) is used as a principal source of Na2O. Other Na2O
supplying source are sodium bicarbonate, salt cake and sodium nitrate.

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723

 2

3. Calcium oxide (CaO): CaO is supplied by limestone from dolomite (CaCO3.MgCO3), the
latter MgO introducing in the batch.
4. Salt cake: salt cake and other sulphates, such as ammonium and barium sulphates are
frequently used in almost all types of glasses. Such cake has been found to remove the
troublesome sum from the furnace. The removal of bubble is carried out by adding arsenic
oxide.
5. Feldspars: Feldspars have the general formula R2O.Al2O3.6H2O, where R2O is either Na2O or
K2O or a mixture of both.
6. Borax: Borax is used as a source of Na2O and B2O3. The latter increases the hardness and
refractory character of glass. Glass containing B2O3 can withstand sudden change of
temperature. B2O3 is added in the form of borax deca-hydrate (Na2B4O7.10H2O).
7. Cullet: Cullet is the crushed or broken glass from imperfect articles, trim or otherwise waste
glasses.
8. Selenium is used as a decolorizer in small amount in some glasses. The purpose of decolorizer
is to destroy the unwanted color. MnO2 is also used as a decolorizer.
9. Refractory Materials: Special refractory materials are used in glass manufacture. They include
sintered zircon, alumina, chrome alumina, zirconia-alumina, mullite, silica etc.

The above raw materials can be classified in the following groups:

(a) Fundamental materials: These are the sources of acidic as well as basic oxides. SiO2, B2O3, P2O5,
Al2O3, CaO, MgO, PbO, BaO, ZnO, FeO, Fe2O3, Na2O, K2O etc.
(b) Fluxes: Examples are: NaNO3, KNO3, B2O3, As2O3, Sb2O3, Na2B4O7 (borax), CaF2, (NH4)2SO4
etc.
(c) Coloring agents: Common coloring agents are copper oxide, cobalt oxide, iron oxide, manganese
oxide, gold oxide, nickel oxide, carbon, sulphur, selenium etc.

Methods of glass manufacture

The following steps are used for the manufacture of glass:

(i) Formation of batch material

(ii) Melting
(iii) Shaping or forming
(iv) Annealing and
(v) Finishing

Formation of batch material: The lumps of ingredients, such as limestone, burnt lime stone,
dolomite, feldspar, etc. are crushed to coarse powder. Other ingredients, such as quartz sand, soda ash
etc. are also obtained as proper particle size. The requisite quantities of different ingredients are
separately weighed and then mixed uniformly in the form of coarse powder. This mixture of powdered
ingredients is called batch material.

Melting: Glass melting furnaces are of two types- pot furnace and tank furnace. The batch materials
are melted either in pot furnace or tank furnace. Both furnaces can be regenerative type or recuperative
type. The purpose of regeneration or recuperation is to utilize the heat of the waste gases for heating
the incoming gas and air used for burning.

Pot Furnace- In this type of furnace, the glass is melted in either closed or open pots, placed inside
the combustion chamber of the furnace in a circle. A pot is a large monkey shaped crucible made from
high alumina fire clay. A pot is of about 2 (two) tonnes capacity. The number of pots generally varies

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723

 3

from 6-20 except in the case of optical glass, where only one pot is used. Pot furnaces are either
rectangular or circular in form. Rectangular furnaces with open pots are used for casting thick plate
glass and glass of special composition. Circular pot furnaces with covered pots are used for melting
relatively small batches of special composition. The furnace is generally fired on the regenerative
principle of heat economy, because this is the most economical system. However, preheating has also
been used in which empty pots are heated to about 1400oC and then the mixed charge is gradually
added in the hot pot until they become full of molten glass.

Tank Furnace- In tank furnace, batch materials are charged into one end of a large rectangular tank
built of refractory blocks. It also works on the regenerative principle of heat economy and is heated by
producer gas. In such type of furnaces, the walls serve both to restrict and retain the heat and to hold
the glass. Continuous tank furnace has been developed in which a layer of molten glass is maintained
by feeding the batch at the same rate as that at which it is withdrawn from the other end. The glass
forms a pool in the hearth of the furnace, across which the flame plays alternatively from one side to
the other. Small tank furnaces are called dry tank in which 5-10 tonnes of glass is melted and refined
in one day. These are heated either electro-thermally or by gas. The largest tanks are those used for the
manufacture of window glass. Some of these are 125×30 ft with a capacity of 1500 tonnes of molten
glass.

Shaping or Forming: The manufacture of different types of glass wares from the molten glass is
called shaping or forming. Glass may be shaped either by hand molding or by machine. Before
mechanization of shaping, glass wares were produced by manual labour, i.e. by blowing with the air
from the lungs. This process was known as manual process of hand moulding.

This tedious process has now been entirely replaced by continuous mechanical automatic process.
Forcault process and Colburn process have widely been used as mechanizes process for the
production of sheet or window glass.

Forcault process- In this process a drawing chamber is filled with glass from the melting tank. The
temperature of the melt is maintained at 980oC. The glass is drawn vertically from kiln through a so
called, debiteuse by means of a drawing machine. Each of the working machine pits is worked by one
drawing machine. The debiteuse is a lone fireclay boat with a slot in the center through which glass
flows continuously upwards, when the boat floats on the melt in each working pit. The debiteuse is
also provided with arms on two ends with the help of which it may be partially submerged into the
melt. By this plunging, a tongue of semi molten glass is formed above the boat. The tongue is
immediately caught by metal baits lowered into the glass through the slot at the same time that the
debiteuse is lowered. The metal baits starts drawing the glass continuously upward in the ribbon form
as fast as glass flows through the slot, and its surface is chilled by water cooled coils. The hard and hot
sheet or ribbon, still travelling vertically and supported by means of asbestos covered steel rollers then
enters through25 ft. long annealing chamber, or lehr.

In the Colburn process, drawing is started vertically, as in the above process, the vertically drawn
sheet is chilled, but after travelling for about three feet, the chilled sheet is heated and bent over a
horizontal roller by means of flames. The sheet is then moved to a flattening table through the
horizontal annealing lehr.

Annealing: Annealing is a process of slowly cooling hot glass articles to relieve internal stress after
they were formed. The process may be carried out in a temperature-controlled kiln known as a lehr. If
the articles manufactured above are cooled suddenly, glass being a bad conductor of heat, they
develop great internal strain and are likely to crack or break or shatter on heating or mechanical shock
or even on keeping some time. The internal strain is also caused by the lack of uniformity. In order to

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723

 4

avoid cause, all the articles should be kept above the critical or annealing temperature for a sufficiently
long time. Since glass is an insulator, rapid cooling will cool the surface more quickly than the internal
portion, causing an internal strain. To avoid this, glass must be cooled very slowly. Therefore, it is
necessary to anneal all types of glass, whether formed by machine or manually. Annealing is usually
carried out by passing the articles through several hot chambers (known as annealing chamber or
lehr) around the furnace, the temperature of which are gradually falling. Thus annealing makes the
glass articles more durable and resistant to shock and change of temperature.

The chamber in which glass ware is stacked and the chamber is heated up and cooled slowly by
closing the chamber from all sides is called annealing chamber or lehr. Annealing lehr, which are
commonly used for annealing, consists of a tunnel 60-75 ft long and 3-8 ft wide. In these, a track is
run for moving trolleys slowly from hot to the cold end.

Finishing: All types of annealed glass require finishing. Finishing is usually carried out by cleaning,
washing, grinding, polishing, cutting, sand blasting, enameling, grading, gaging. Washing and
cleaning are of course, applied to all kinds of articles, although the methods of finishing are adopted as
per requirements.

Chemical reactions

The basic part of the ingredients react with acidic part (i.e. SiO2) in the tank or pot furnaces (in which
batch materials are mixed and heated to form glass melt) at a high temperature to form silicates of the
bases. In the borosilicate glass, however, SiO2 is replaced by B2O3. CO2 and SO2 are evolved during
the formation of glass. When quartz or silica is heated with soda ash (Na2CO3) the silica, being an
anodic oxide, displaces the carbonic acid from the carbonate and a compound known as sodium
silicate is formed.
Na2CO3+ SiO2 Na2SiO3+ CO2

When this is allowed to cool, it solidifies to a glassy mass, known as water glass, which is soluble in
water.

The limestone also reacts with silica to give a glassy mass on cooling known as calcium silicate
which is insoluble in water but soluble in acids.
CaCO3 + SiO2 CaSiO3+ CO2

But if silica is simultaneously fused with Na2CO3 and CaCO3, sodium calcium silicate is obtained,
which sets to a glassy mass on cooling and it is insoluble in water and acid both.
Na2CO3 + CaCO3 + 6SiO2 Na2CaO.6SiO2 + 2CO2

Sometimes, a mixture of salt cake, sodium sulphate and charcoal is fused with sand and limestone to
get a glassy mass. Then the reactions are as follows-
2Na2SO4+ 2SiO2 + C 2Na2SiO3+ CO + SO2
Na2SiO3 + CaCO3 + 5SiO2 Na2CaO.6SiO2 + 2CO2

However, formation of glass is a high temperature process which takes place through a large number
of stages. The nature of the steps involved depends on the composition of the raw material and
temperature.

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723

 5

Refining of glass

Because of various reactions, gases are formed. These gases remain much in the melted glass and set
the melt to a state of ebullition, achieving thereby a uniform heat distribution throughout the melt.
They also serve to homogenize the composition of the melt. If the gas is in the form of small bubbles,
seeds are said to be there in glass. But if the gas is in the form of big bubbles, molten glass is said to
have boils. The process of removing these defects is called refining.

Refining of glass is done by-

1. Reducing the viscosity by raising the temperature of the molten glass.

2. Adding materials such as salt cake, borax, ammonium salts etc. to the melt.
3. Last traces of seeds can be removed by adding volatile substances such as As2O3 or NH4NO3
to the melt.

The volatile substance creates an upward rush of large bubbles which take up the fine bubbles and go
out.

Different types of glasses

i. Fused silica glass

ii. High silica glass
iii. Optical glass
iv. Borosilicate glass
v. Lead glass
vi. Soda-lime glass
vii. Coloured glass
viii. Opal glass
ix. Safety glass
x. Glass laminates
xi. Glass wool
xii. Photosensitive glass
xiii. Photo-chromic glass

Coloured glass: Coloured glasses are used for decoration, technical and scientific purposes. Coloured
glass is of three types.

(a) Colour is produces by the absorption of certain light frequencies by colouring agents in
solution. The colouring agents are the oxides of transition elements, such as the oxides of Ti,
V, Cr, Mn, Co, Ni and Cu. Colour is either due to chemical structural environment or due to
difference in the state of oxidation. For example, NiO is soluble in sodium lead glass yielding a
brown colour, but in potash glass it dissolves to give heliotrope. This NiO produces colour due
to chemical structural environment. Chromium oxides produce colour due to differences in the
state of oxidation. For example, they produce colours ranging from green to orange, depending
upon the properties of basic oxide, Cr2O3 to acidic oxide and the composition of the glass
(whether it is basic or acidic).
(b) Colour is due to colloidal particles precipitated within the colourless glass as a result of heat
treatment. For example, precipitation of colloidal gold produces gold ruby glass.
(c) Colour is due to microscopic or large particles which may be coloured themselves. For
example, SeO2 (selenium reds) used in traffic lights, lantern globes etc.

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723

 6

Safety glass: There are two main classes of safety glass. They are laminated and tempered or
strengthened glass. Laminated glass may be prepared by placing a non brittle plastic sheet between
two thin glass sheets. The three sheets are pressed together under moderate heat to seal the edges.
They are then heated under pressure in an autoclave to bring the plastic sheets in absolute contact with
the glass sheet. Ultimately the three sheets are made into one single sheet. The edges of the sandwich
may be sealed with a water resistant material. The plastics used for this purpose are proxylin or
cellulose acetate, polyvinyl acetate and polyvinyl butyracetal.

The tempered glass is very strong and tough, and posses high internal stresses. The already formed
glass vessel or sheet to be strengthened by tempering or annealing is heated to 800 oF, just below its
softening point, and then quenched in air or molten salt or oil. The quenching produces hard surface,
which resists bending and shattering forces. The interior pulls on the outside surface, putting it into
compression, and the interior develops compensating tension and provides a very good strength to the
glass. Such type of glass is used for doors and windows of automobiles and for pipes.

Glass laminates: For the manufacture of glass laminates, sheets of glass fabric are soaked in a
solution of phenol formaldehyde and placed one above another. The laminated sheets are then allowed
to cure under heat and pressure, as a result of which hard, light and strong laminated sheet are
obtained. Besides sheet, tubes and other shapes are also available commercially. It is used as a
material of construction, for making light weapons, and insulating materials, because it is highly non
flammable and insulator. The most important properties of laminated glass are:

i. It is shatter proof.
ii. It is shock proof and can withstand sudden chane of temperature and some pressure
without undergoing cracking.

A bullet resistant laminated glass is obtained by pressing together several layers of glass with vinyl
resins in alternate layers. The thickness of bullet resistant laminated glass varies from 12.7 mm to 76.5
mm and these are prepared specific purposes.

Glass wool: Glass wool is obtained by the action of steam jets on dripping streams of molten glass
down from small holes. The glass wool (which consists of innumerable tiny fine fibres) formed in this
manner is carried away by a conveyor belt on which it is hurled. Glass wool is fibrous wool like
material composed of intermingled fine threads of filaments of glass and has a number of important
properties. For example-

(a) It is non-combustible.
(b) It is fire proof.
(c) It has low electrical conductivity.
(d) It is heat proof.
(e) It does not absorb moisture.
(f) It is chemically resistant to a number of chemicals.
(g) It has a low density of 65 kg/m3.

Glass wool is used for heat insulation purposes in ovens, metal pipelines, motors, vacuum cleaners,
wall and roofs of houses. It is also used in the filtration of corrosive liquids such as acids and alkalis. It
is also used for sound insulation and for the manufacture of fibre glass.

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723

 7

Glass is a super cooled liquid substance

A liquid to crystal transition is a thermodynamic one; i.e. the crystal is energetically more favorable
than liquid below the melting point. The glass transition is purely kinetic; i.e. the disordered glassy
state does not have enough kinetic energy to overcome the potential energy barrier required for
movement of the molecules past one another. The molecules of the glass take on a fixed but disordered
arrangement. Glasses and super-cooled liquids are both meta-stable phases rather than true
thermodynamic phases like crystalline solids. In principle, a glass could undergo a spontaneous
transition to a crystalline solid at any time.

Fig: Density as a function of temperature in the phases of glassy materials

The situation at the level of molecular physics can be summarized by saying that there are three main
types of molecular arrangements.

1. Crystalline solids: molecules are ordered in a regular lattice.

2. Fluids: molecules are disordered and are not rigidly bound.
3. Glasses: molecules are disordered bur are rigidly bound.

Fig: Recuperative pot furnace

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723

 8

Fig: Recuperative gas fired tank furnace

Fig: A pot furnace of regenerative type

Fig: A tank furnace of regenerative type

Jewel Hossen, Lecturer, Dept. of Chemistry, RUET, [email protected], 01723-664723