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Reactions:
During melting at high temperature the basic parts of the ingredients of glass (i.e. Na2O, K2O, CaO etc.) react with acidic part
(i.e. SiO2) to form silicates of the bases. In the borosilicate glass, however CaO is replaced by B2O3 . During the formation of
glass in conjunction with the silicate formation, CO2 and SO2 are also evolved.

The various reactions occurring during glass formation may be summarised as follows

(1) Na2CO3 + x SiO2 = Na2O. xSiO2 + CO2

(2) CaCO3 + y SiO2 = CaO. ySiO2 + CO2
(3) Na2SO4 + z SiO2 = Na2O. zSiO2 + SO2

The equation (3) may proceed as follows-

Na2SO4 + C → Na2SO3 + CO
2Na2SO4 + C → 2Na2SO3 + CO2
Na2SO3 + z SiO2 → Na2O. zSiO2 + SO2

Reaction involved during melting

(i) When sand (SiO2) is heated with soda ash, silica (SiO2) being an acidic oxide displaces carbonic acid from the
carbonate and sodium silicate is formed:

Na2CO3 + a SiO2 → Na2O. a SiO2 (NaSiO3) + CO2

When this is allowed to cool a solid glassy mass is obtained, which is known as water glass. Water glass is soluble in
water.

ii) On strong heating lime stone also reacts with silica and produces calcium silicate:

CaCO3 + b SiO2 → CaO. b SiO2 (CaSiO3) + CO2

When this melt is cooled a solid glassy mass is obtained. This is insoluble in water but soluble in acids.

iii) Similarly when a mixture of salt cake and silica is fused a glassy mass of sodium silicate is obtained which is also water
soluble.

Na2SO4 + c SiO2 + C → Na2O. c SiO2 + SO2 + CO2

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iv) But if silica is mixed with both soda ash and lime stone or salt cake, limestone and carbon, sodium calcium silicate is
formed which on cooling sets to a glassy solid mass insoluble in both water and acid.

Na2CO3 + CaCO3 + 6SiO2 → Na2O.CaO.6SiO2 + 2CO2

2Na2SO4 + 2SiO2 + C → 2Na2SiO3 + CO2 + 2SO2

Na2SiO3 + CaCO3 + 5SiO2 → Na2O.CaO.6SiO2 + CO2

The glass formation is a high temperature process in which a series of intermediate steps take place. The overall process
of glass formation can be subdivided into following stages:

(a) When the batch material contains only soda, limestone and silica

(i) Up to 600°C evaporation of water and volatilization of some oxides such as, As2O3, Sb2O3, PbO, B2O3 and salts such as,
NaCl, KCl, FeCl3, SnCl4, Na2SO4 etc. take place.

(ii) Within 700-900°C water soluble glass, sodium silicate is formed by the reaction between soda ash (Na2CO3) and silica
(SiO2): Na2CO3 + SiO2 → Na2SiO3 + CO2

(b) When the batch material is composed of salt cake, lime stone, silica and carbon:

(i) In between 600 - 800°C, salt cake (Na2SO4) reduces by carbon to Na2S.

Na2SO4 + 2C → Na2S + 2CO2

(ii) At 860°C the following reactions 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 acids.

Na2S + CaCO3 → CaS + Na2CO3

Na2CO3 + SiO2 → Na2Si O3 + CO2

CaS + Na2SO4 → CaSO4 + Na2S

CaSO4 → CaO + SO3

Na2S + SO3 → Na2O + SO2 + S

Na2O + SiO2 → Na2SiO3

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(iii) At 900°C and above decomposition of lime stone (CaCO3) takes place: CaCO3 → CaO + CO2

(iv) At 1000°C and above CaO reacts with silica to form calcium silicate.

CaO + SiO2 → CaSiO3

(v) At temperatures in between 1100 - 1400°C, salt cake reacts directly with silica to form sodium silicate.

Na2SO4 → Na2O + SO3

Na2O + SiO2 → Na2SiO3

2SO3 → 2SO2 + O2

(C) When the batch material contains red led, K2CO3 and silica as its components:

(i) At 600°C red lead decomposes to PbO and oxygen

Pb3O4 → 3PbO + 1/2 O2

(ii) At 670 -730°C lead oxide reacts with silica to form lead silicate.

PbO + SiO2 → PbSiO3

(iii) At 750°C K2CO3 decomposes to K2O and CO2 K2CO3 → K2O + CO2

At this temperature K2O reacts with silica to form potassium silicate: K2O + SiO2 → K2SiO3

Shaping of glass articles

After melting, the next step of glass manufacturing process is shaping. The manufacture of different types of glasswares
from the molten glass is called shaping.

Before the advent of modern technology, shaping for both blown glass wares and sheet or plate glasses were done by
manual labour. In this process air from the lungs is blown to a lump of molten glass taken at the tip of a blowpipe. A sheet
glass or window glass is prepared in this method by forming a cylinder by blowing. The top and bottom ends of the
cylinder are cut off and allowed to stand vertically on a stand. The hollow cylinder is then heated in an oven and then
flattened by opening it with a sharp knife.

This is a very tedious process and the quality of the article fully depends on the performance of the skilled labour. With
the advent of modern technology this tedious manual process has been entirely replaced by the continuous mechanical
process. In mechanical process collection of glass melt, giving shape of the article by blowing and with the help of mould,
removal of article from the mould after final shaping are all carried out continuously and automatically. In machine
moulding the important factor is to be considered is that the design of glass machine mould should be such that the entire
process should be completed in a very few seconds.

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Annealing of glass articles

Annealing is a very important step of glass manufacturing process. It consists of following three operations: (a) Heating the
glassware to a temperature (above critical temperature), which is known as annealing temperature. (b) Keeping the
glassware at the annealing temperature for sufficiently long time. (c) Cooling the glassware from the annealing temperature
very slowly and uniformly to room temperature.

Annealing is required for almost all glass wares (except glass tube) because during rapid or normal cooling there develops an
internal strain which causes thermal instability of glasswares. Glasswares crack or break on slight heating or locally cooling
or even on keeping for sometime. The internal strain is caused due to the lack of uniformity. The lack of uniformity results
from the insulating property of glass. During cooling the exterior surface of glass gets cold but the interior part of the glass
still remains hot, which causes internal strain. To avoid this non-uniformity or minimizing this internal stress the articles are
heated to a temperature (annealing temperature) at which if glasses are kept for some time the internal strain is removed.

Then if the articles are cooled very slowly, no internal strain develops. This is because of very slow cooling, both the
exterior and interior parts of glass ware cool uniformly. In glass industry annealing is usually carried out by passing the
glass wares through several hot chambers (lehrs), where glass wares are heated above its annealing temperature, kept for
some time and then the temperature gradually falls to room temperature. Annealing treatment makes the glasswares
more durable, resistant to shock and thermally stable.

Finishing of glass articles

This is the last step of manufacturing glassware. It includes cleaning, polishing, cutting, sand blasting, enameling, grading
etc. Although all these operations are not required for all glass wares, however, a few of these are required for almost all
glass wares.

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Special Glasses

1. Fused Silica Glass

2. 99.5% Silica glass

It is used for manufacturing relatively costly laboratory equipments such as prism, windows for optical instruments like
UV spectrophotometer. Infrared spectrophotometer etc.

3. 96% Silica glass

• 96% silica, 3% B2O3 and trace amount of other materials such as alumina and alkali

• less expensive than 99.5% silica glass but still it is more expensive than other types of glasses

• Low coefficient of expansion

• low thermal conductivity

• high capacity to resist changes at sudden fluctuation of temperature

• This glass is used for manufacturing laboratory apparatus such as condenser, crucible etc. which resist heat up to
800°C

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4. Alkali silicate glass

• Only two component glass

• Composition varies from Na2O.SiO2 to Na2O.4SiO2
• Water soluble glass is an example of this class
This glass is widely used as adhesive for manufacturing corrugated paper box. This is also used as fire proofing and egg
preservative agents. The higher alkaline variety of this glass is used as detergent and soap builders.
5. Sodalime glass

Soda-lime glass is widely used as glass containers, flat glass, table ware glass, bulbs, automobile, window glasses etc.
where high temperature resistance and chemical stability is not important.

6. Potash-lime glass

• Made from silica (SiO2), potassium carbonate (K2CO3) and calcium carbonate (CaCO3)
• Approximate composition K2O CaO SiO2
• Acids alkalis and other solvents less attack than ordinary soda lime glass
• Costlier than soda lime glass
• It is used for manufacturing chemical apparatus.

7. Borosilicate (Pyrex Glass)

• Boric anhydride B2O3 is used in place of lime
• 80-87% silica 10-20% B2O3 and less than 10% Na2O sometime contains 2-3% Al2O3 and small amount of ZnO
• high chemical resistance
• low coefficient of thermal expansion
• popularly known as Pyrex glass
• This glass is extensively used for manufacturing laboratory ware, industrial glass ware, table ware etc.

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8. Lead glass
This glass is specially used for optical work. A special variety of lead glass is used for
manufacturing high quality table wares. Lead glass containing high percentage (92%) PbO is
used for radiation protection. Lead oxide glass has high refractive index which provide them a
brilliant look. These are also used for manufacturing electronic tubes, cut glass articles,
imitation diamond, jewels, aristocratic table wares, optical instruments like prism lenses etc.

9. Oxide glass

10. Safety glass

• made by sandwiching thin plastic sheets between alternate sheets of glass under pressure and heat
• after sandwiching pressure is applied till the layers are merge into one another.
• 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
• the plastic sheets used for this purpose are pyroxylin or cellulose acetate, polyvinyl acetate or polyvinyl butyl acetate
etc
• This glass is particularly used for manufacturing window shield of high velocity auto vehicles.