Glass

Glass is an amorphous, hard, brittle, transparent or translucent, super-cooled liquid, obtained by fusing a mixture of a number
of metallic silicates, most commonly Na, K, Ca and Pb. It possesses no sharp melting point, crystalline structure and definite
formula.
Glass is represented as xR2O. yMO. 6SiO2, where R = monovalent alkali metals like Na, K. M = diavalent metals like Ca, Pb,
Zn, etc. x & y = whole numbers.
Properties of glass: The physical and chemical properties of glass may be described as follows
(a) Physical Properties:
i. Glass are usually transparent amorphous solids.
ii. These are completely vitrified product.
iii. They are hard, rigid and have no define melting point.
iv. They possess very high viscosity (~1013 poise).
v. They are non-conductor of heat and electricity.
vi. They can incorporate pigments without losing their transparency.
(b) Chemical Properties:
i. Glass is very inert. Air and oxidizing agents do not attack glass. It does not react with acids except hydrofluoric acid.
ii. Glass reacts with HF to produce SiF4 and fluorides of metals
Na2O. SiO2 +6HF = 2NaF + SiF4 + 3H2O
Ca2O.SiO2 + 6HF = CaF + SiF + 3H O
2 4 2
iii. Ordinary glass is readily attacked by alkalis.
iv. Ordinary glass is slowly reacts with water to form NaOH. This reaction is enhanced in the presence of acids. Thus if
bottles containing acids are kept for a long time, silicic acid has been found to deposit on the glass of the bottles.
v. When glass is fused with large excess of fusion mixture, it decomposes into alkali silicates and carbonates of other
metals. If the resulting mass is cooled and treated with dilute HCl, silicic acid and chlorides of metals are formed.
 Raw materials of Glass
The main ingredient of glass are (a) SiO2, (b) Na2O / K2O, and (c) CaO / Bi2O3 / Al2O3, etc. Besides these ingredient many
other ingredient are used for the production of good quality of glass. Thereby, overall ingredients (raw materials) of all glasses
can be classified into the following types.
(a) Glass formers:
The raw material that are used essentially and extensively in the manufacture of glass are known as glass forming agents or
glass formers. Chemically glass is a mixed fused oxide. Therefore, the glass forming agents are mainly oxides for examples (i)
Silicon dioxide or silica, (ii) magnesium oxide, (iii) boron oxide, (d) aluminum oxide, and calcium oxide etc. Usually
commonly used glass such as bottle glass, window glass, and ordinary drinking water glass contains 70-75% silica as glass
former.
(b) Fluxes:
In order to lower the melting temperature of the silica some substances are added along with glass forming agents, these
materials are called fluxes. For examples borax, feldspar etc. In ordinary glass 12-17% fluxes and in borosilicate glass 4-10%
fluxes are used.
(c) Stabilizers:
To stabilize the characteristic properties of glass, the substances that are used along with glass formers and fluxes are called
stabilizer. During the production of glass, when high temperature liquid are cooled down to room temperature, they usually
form thick liquids and could not achieve the characteristic properties of glass. In some cases they form crystals at low
temperature. In most cases they form brittle glass. Such difficulties are avoided by using stabilizing agents. Examples of
stabilizing agents are (i) alumina (Al2O3), (ii) calcium oxide (CaO), and (c) magnesia (MgO) etc. In general 5-19*% stabilizer
are used in the manufacturing process of glass.
(d) Refining agents:
Since glass is a very high viscous liquid, in most cases small gaseous bubbles are trapped into the liquid batch. This produces
defects in the finished glass. In order to remove these gas bubbles from the molten glass batch some chemical are used.
These are known as refining agents. For examples (i) Na2SO4, (ii) NaNO3, (iii) NaCl, (iv) As2O3, and (v) CaF2 etc.
(e) Opalizing agents:
These are the materials, which allow the mixture of raw materials of glass to be melted in the normal way, and permit the
separation of fine crystals or droplets in the glass during manufacturing. This produces an opalescent appearance to the finished
glass. CaF2, Ca3(PO4)2, SnO, Na3AlF6, CoO etc. are used as opacifier.
(e) Cullet or broken glass:
The rejected articles and broken glass are crushed and recycled as the raw materials, which are called as cullet. Cullet reduces
the manufacturing cost of glasses as well as it takes active part in easy melting of raw materials of glass. Broken glass may have
different colours, which imparts impurities in the raw materials. Thus, MnO2, As2O3, Sb2O3 etc. are used to remove the
undesirable colour of glass.
(e) Colouring agents:
Glasses obtained from pure sand, lime and soda are colourless and transparent. But for some special uses particularly for
decorative purposes colour glasses are required. So to manufacturing coloured glass colouring agents are added along with
major and minor ingredients. The commonly used colouring agents are CuO, CoO, Fe2O3, MnO2, AuCl3, NiO, C and S etc.
 Manufacturing of glass
For the manufacturing of glass all the constituents of glass are separately ground, sieved and mixed in definite proportions.
The mix is then fused in a tank furnace or in a pot furnace. The overall manufacturing process of glass involves the following
steps.
(a) Primary preparation of raw materials:
Most of raw materials that are used for the production of glass contains different types of impurities like external impurities (
such as fibre, torn cloth, leaf, saw dust, ash, soil etc.) and internal ( such as iron, other magnetic materials etc.) impurities. The
external impurities are first remove by washing and by hand manually. The magnetic impurities are separated by using
magnetic separator or by chemical separation process. Then the raw material are ground into small size using different types
of crushing mill.
(b) Formation of batch materils:
Different types of raw materials (sand, soda ash and lime stone ) are mixed together in proper proportions and finely powdered
to form a homogeneous mixture, which is call batch material. During the formation of batch materials the quantity and quality
factors are considered carefully. The batch material of specific type of glass after crushing, washing, drying and mixing
thoroughly is transferred to the tank of tank furnace or to the pot of the pot furnace for melting.
(c) Melting:
The melting of raw materials is carried out in furnace where heat is liberated from combustion of fuel or heat is generated from
electric current. There are two different types of furnaces used for melting of raw material such as (i) pot furnace and (b) tank
furnace.
(i) Pot furnace: Pot furnace is usually used for small-scale production and manufacturing of special glass such as optical glass,
art glass etc. In pot furnace the batch materials are melted either in close or in open pots placed inside the combustion chamber
of the furnace in a circle. Thus the molten batch is protected from the products of combustion in pot furnace. Roof of the pot is
constructed with refractory material which also reflects the heat.
 Figure of tank furnace A cross-section of tank furnace
(ii) Tank furnace: The “batch” is melted in the tank using producer gas and air. It follows “regenerative system of heat
economy” . Air and fuel is passes through A & B and the burnt gases are deflected by the roof and “batch” gets melted.
Hot waste gas escapes through firebricks C & D and the direction of the fuel gas & air is reversed through C & D , which
absorbs the heat of the waste gas and burns. The waste gas now escapes through A & B.
The batch material for both pot and tank furnace is mixed with cullet as it lowers the melting temperature. The pot or tank of the
furnace is usually filled 3/4th of their height. They are heated to about 14000C. At this temperature the batch materials melt and
react to form molten glass. During the melting process following reactions occur

The molten mass is heated till its free from air bubbles. For colored glass desired pigment is added. The molten mass is then
cooled at about 800oC at later point of time.
(d) Shaping of glass articles: Once the sand is melted, it is either poured into molds to make bottles, glasses, and other
containers, or "floated" (poured on top of a big vat of molten tin metal) to make perfectly flat sheets of glass for windows.
Unusual glass containers are still sometimes made by "blowing" them. A "gob" (lump) of molten glass is wrapped around an
open pipe, which is slowly rotated. Air is blown through the pipe's open end, causing the glass to blow up like a balloon. With
skillful blowing and turning, all kinds of amazing shapes can be made.
(e) Annealing of glass articles: After shaping, glass articles are heated to a temperature above the critical temperature for
long time and then cooling them very slowly and uniformly to room temperature. Annealing eliminate the internal strain, lack
of uniformity due to very slow cooling rate.
(f) Finishing of glass articles: This is the last step of manufacturing of glass. It includes cleaning, grinding, polishing, cutting,
sand blasting, enameling, grading, decorating etc. Although all these operation are not required for all glass wares, however, a
few of these are required almost all the glass wares.

Shaping of glass articles Annealing of glass articles Finishing of glass articles

 Reaction involved during melting of glass raw materials
The glass formation is a high temperature process in which a series of reaction takes place. The nature of steps and chemical
reactions involved therein depend upon the composition of raw materials and temperature of the mixture at a particular stage
of glassification. The overall process of glass formation can be subdivided into following steps:
(a) When the batch material contains only soda, limestone and silica:

(i) Up to 6000C evaporation of water and volatilization of some oxides such As2O3, Sb2O3, PbO, B2O3 and salts such as,
NaCl, KCl, FeCl3, SnCl4, Na2SO4 etc. take palce.
ii) Within 700-9000C water soluble glass, sodium silicate is formed by the reaction between soda as (Na 2CO3) and
silica(SiO2).
Na CO + SiO Na2SiO3 + CO2
2 3 2

ii) In between 900-9600C calcination of lime and formation CaO and CO2 takes place.
CaCO3 CaO + CO2
iv) At and above 10100C, decomposition product of lime stone i.e. CaO reacts with silica to form calcium silicate.
CaO + SiO2 CaSiO3

(b) When the batch materials is composed of salt cake, limestone, silica and carbon:

(i) In between 600-8000C, salt cake (Na2SO4) reduces by carbon to Na2S.

Na2SO4 + 2C Na2S + 2CO2
ii. At 8600C the following reaction take place.
Na2SO4 Na2O + SO3
Na2S + SO3 Na2O + SO2 + S
Na2O + SiO2 Na2SiO3
At this stage lime stone reacts with Na2S to form mixed silicate of sodium and calcium, which is insoluble in both water and
acid. Na S + CaCO Na CO + CaS
2 3 2 3
Na2CO3 + SiO2 Na2SiO3 + CO2
CaS + Na2SO4 CaSO4 + Na2S
CaSO4 CaO + SO3
Na2S + SO3 Na2O + SO2 + S
Na2O + SiO2 Na2SiO3
iii. At 9000C and above decomposition of lime stone take place.
CaCO3 CaO + CO2
iv. At 10000C and above CaO reacts with silica to form calcium silicate.
CaO + SiO2 CaSiO3
v. At temperature in between 1100-1400, salt cake reacts directly with silica to form sodium silicate.
Na2SO4 Na2O + SO3
2SO3 2SO2 + S
Na2O + SiO2 Na2SiO3
(c) When the batch materials contains red led, K2CO3 and silica :
i. At 6000C red lead decompose to PbO and oxygen.
Pb3O4 3PbO + ½ O2
ii. At 600-7300C lead oxide reacts with silica to form lead silicate.
PbO + SiO2 PbSiO3
iii. At 7500C K2CO3 decomposes to K2O and CO2
K2CO3 K2O + CO2

At this temperature K2O reacts with silica to form potassium silicate.

K2O + SiO2 K2SiO3
 Different types of glass

Soda-lime glass
Soda-lime glass covers almost 95% of total glass manufactured. Its manufacturing cost is low. This glass composts of
following basic components.
(a) silica (70-74%)
(b) lime i.e. CaO (8-13%) and
(c) soda that contributes Na2O (13-18%)
To improve the quality and chemical resistance of the glass, a small amount of (~1%) Al 2O3 and (~3%) MgO are added.

Properties
• Low cost
• Resistant to water, acid and organic solvents.
• Attacked by HF acid
• Has less temperature resistance
• Moulded easily to any shape
• Poor thermal & chemical resistance
Uses
Window glasses, electric bulbs, bottles, jars, table wares etc.,
 Borosilicate (pyrex) glass
Borosilicate glass is developed specifically for use in laboratories and applications where thermal, mechanical and chemical
conditions are too harsh for standard, household-type soda lime glass. Some common names of borosilicate are Pyrex™ by
Corning and Duran™ by Schott Glass. Like most glasses, the main component of borosilicate glass is SiO 2. The big difference
is it has boron oxide and various other specialty elements instead of “soda and lime” to give it its outstanding qualities. The
composition of borosilicate glass is as follows
(a) silica (80-87%)
(b) Boron oxide i.e. B2O3 (10-20%) and
(c) Na2O ( >10%)
Some this glass contain a small amount of (~2-3%) Al2O3 and trace amount of ZnO.
Properties
• Substitution of alkali (Na2O) and basic alkaline
earth oxides(CaO) of the soda glasses by boron
and aluminium oxides results in low thermal co-efficient
• High softening point and excellent resistivity(shock proof)
• High chemical resistance

Uses
Industrial pipeline for corrosive liquids, gauge glasses,
superior laboratory apparatus etc.,
 Safety glass
Safety glass is made by sandwiching thin plastic sheets between alternate sheets of glass under pressure and heat. After
sandwiching pressure is applied till the layers are merged into one anther. When such composite glass breaks, it does not fly
like a splinter of glass (which is very dangerous) rather it converts into small pieces that are held with each other and takes the
form of a bed sheet. The plastic sheets used for this purpose are pyroxylin or cellulose acetate, poly vinyl acetate or polyvinyl
butyl acetate etc.
Tempered glass or toughened glass
Tempered glass undergoes an intense heating process immediately followed by rapid cooling. Tempered glass is made by
uniformly heating annealed glass to a temperature of up to 700°C. This extreme temperature shift causes the glass surface
and edges to compress, creating an extremely tough outer surface with a tensioned glass core. Such a glass is more elastic
and capable of withstanding mechanical and thermal shocks. When broken, tempered glass breaks into small particles along
circular edges, eliminating the risk of dangerous shards.
Characteristics of Tempered glass:
▪ Tempered glass is four to five times stronger than annealed glass of the same size and thickness against impact.
▪ Tempered glass has higher thermal strength, and it can withstand high temperature changes up to 250°C.
▪ Tempered glass is considered as safety glass. It is difficult to break and even in the event of a breakage, disintegrates into
small relatively harmless globules.
▪ Tempering does not alter the basic characteristics of glass such as light transmission and solar radiant heat properties of
normal glass.
Application of tempered glass:
Tempered glass is used in a wide range of applications, such as
▪ Industrial environments
▪ Safety glass (windshields, windows, and situations with exposure to projectiles)
▪ High-temperature environments and thermal stresses