GLASS INDUSTRY

Applied Chemistry

DR. Muhammad Salman

University of the Punjab



Introduction:

Glass is a solid solution of various silicates which are formed by rapidly cooling of molten mass
of salts.

Glass is not true solid by high viscosity (greater than 10^13 poise) which prevents the
crystallization to take place. Glass has no fixed melting point. It is an amorphous, transparent or
translucent mixture of silicates. The amorphous solid is not true solids and also no fixed melting
point and breaks with conchoidal fracture. Glass has all the characteristics of a transparent
amorphous solid. A true solid is obtained in crystalline state and has fixed melting point.

The glass is chemically a mixture of various compounds and composition is xR2O, YMO.6SiO2
(where X & Y are no. of molecules. R is an alkali metal & M is a divalent metal). These are
many varieties of glass, most of them being mixtures of silicates or breaks & silicates. 90% of
glass manufacturing belong to clay. “Soft glass or soda glass”

Properties which made the glass indispensable in modern civilization.

M e c h a n i c a l O p t i c a l C h e m i c a l T h e r m o d y n a m i c s Other
properties properties properties properties
Hardness Transparent No reaction Heat conduction moulability
compressive refractive index C h e m i c a l Co-efficient of expansion density
resistant
Tensile strength Dispersing power inexpensive

History:

The discovery of glass is very uncertain. As early as 6000-5000 B-C the Egyptians used to make
glass beads, jewelry etc. the window glass is reported 290 A-D. The hand-blown glass was
invented by twelfth century monk. During Middle Ages vience enjoyed monopoly in glass
industry.
Up to 16th century no glass was made in Germany, France, and England and even in USA. Plate
glass was made first time in France in 1668. Glass was started to be manufacturing in USA in
1608, no change in glass manufacturing took place in next 300 years. The only modification took
place that is purifying raw material and economy in fuel used. All glass manufacturing was
manual. Up to 1900 glass industry was consider as an art which was experienced by individual
workers. Towards the end of 19th century. Lubbers invented mechanical adoption of the hand-
blown window glass process.

In 1914, Foucault invented automatic mechanical process for glass sheet. In 1906, research group
in England perfected the float glass process. In 28th century automatic mechanical machines
speed up the production of bottles, bulbs, windows glass & mirrors.

Today glass industry is a highly specialized field, employing all the tools as modern science in
production, controls and development of many glass products.

Definition:

The glass can be defined by physically and chemically.

❖ Physical definition;

Glass can be physically define as:

“Glass is a rigid super cooled liquid having no definite melting point & sufficiently high
viscosity (more than 10^13 poise) to prevent crystallization.”

❖ Chemical definition:

Glass can be chemically define as:

“Glass is a union of non-volatile inorganic oxides resulting from the decomposition and
fusing of alkali and alkaline earth compounds, sand and other glass constituents.”

Composition of glass:
Glass is completely vitrified material or at least such a product its very small amount of non-
vitreous material in suspension. In spite of hundreds of new development in glass manufacturing
during last century. Lime, soda, silica constitute still from over 90% of all the glass in the world
as they did 2000 years back. The other minor constitute are B2O3, Al2O3, CuO, MgO, Na2O,
K2O, PbO, SO3, As2O3.

Role of different constituents in glass:

Constituents Role
K2O It Increase the softening & mobile melting point of glass.
PbO It Increases refractive index of glass. It is used for optical purpose and for cut
glass wires & making electric light bulbs. It is also used for neon sign tubes and
electric tubes because lead increase electric resistance of glass.
Fe2O3 or FeO It is used in ordinary glass and cannot transmit UV light. The iron free glass can
transmit UV light.
B2O3 It Increases the hardness and refractory properties of glass e.g. Pyrex glass.

Change in percentage of various compounds:

In ordinary glass change in % of various components effects properties of glass.

1-Alkali metals: if percentage of alkali metals increases, fusibility increases but resistivity
decreases.

2-Alkaline earth metals: if percentage of alkaline earth metals increases, fusibility decreases but
resistivity increases.

3-Silica: if percentage of a Silica increases, brittleness increases but resistivity decreases.

Commercial glass:

Commercial glass can be divided into six major classes:

➢ Vitreous silica
 ➢ alkali silicates

➢ Lime Glass

➢ Lead Glass

➢ Borosilicate glasses

➢ Special glass

1-Vitreous silica:

A glass made by fusing pure silica without a flux. Sometimes it is reflected as “quartz” glass. It is
very resistive thermally & chemically. It is characterized by low expansion and high softening
point, which imparts high thermal resistance to this glass.

SiO2 + Na2CO3 Na2SiO3 +CO2

(Water soluble)

(Sodium silicate)

Na2SiO3 + HCl SiO2 + 2NaCl + H2O

(Silica gel)

This glass is also extraordinary transparent to UV radiation.

2- Alkali silicates:

Two compounds water soluble glasses used only as solutions. The sand
& soda are simply melted together and the products designed as sodium silicates having a range
of composition from Na2OSiO2 to Na2O.4SiO2. This is also known as water glass, widely
consumed as an adhesive in fire proofing in the manufacturing of soaps & detergents and egg
preservation.

3-Lime Glass:
The ordinary type of glass used for a variety of application. It is used for windows, transparent
fixtures and for all types of containers. This type of glass usually contains SiO2= 69.72%, CaO=
12.5-13.5% & Na2O+ 13-15%. This type of glass melts with more difficulty but is more
chemically resistant. This type of glass was used to be a little colored due to impurities but now a
days due to the purification of raw materials, it is almost colorless.

4-Lead Glass:

The products obtained from lead oxide, silica & alkali for decorative and optical purpose. These
glasses have high refractive index and high dispersion power. Lead content may as high as 92%
(with a very high density). These glasses gave high electrical resistance hence used for electric
installations (bulbs, neon sign tubing & radiations). It is also used for shielding from nucleus
reactor.

5- Borosilicate glasses:

Glasses made up of boric oxide and silica are called borosilicate glasses, which are used for
optical and scientific work. Usually contain 10-13% boron oxide and 80-83% silica. These have
low expansion co-efficient, superior resistant to shock, excellent chemical stability and high
electrical resistance.

6- Special glass:

Special glasses include colored glasses translucent glasses, safety and laminated glasses, high
silica glass, photosensitive glass, phosphate and borate glasses.

Colored glasses:

Usually some additives are added to produce the desired colors. Mostly oxides & salts of Ti, V,
Cr, Mn, Co, NiCl4 are used. Color is also produced by colloidal particles precipitated with in an
originally colored glass by heating treatment. Colloidal gold is after used to produce gold ruby
glass. Color may also be produce by adding microscope or larger particles which may be colored
themselves like SeO2 used in traffic lights.
Opal and translucent glass:

These glasses are clear when in molten state but becomes opal or translucent in solid form due to
the separation and suspension of mixture particle in the medium which disperse the light passing
through them. They are commercially important as diffusing media in illumination, as containers
and as construction material. Fluorides are used as ingredients in such glasses.

Safety or laminated glass:

These glasses have composite structure consisting two layers of glass with an interleaf of plastic
or plasticized polyvinyl butyral resin. When such glass is broken these fragments remain sticking
with the interface layer. Another type is heat strengthened safety glass. This glass breaks into
small pieces without sharp edges pieces.

Fiber glass:

It consist very small fibers of glass invariably of the size 0.00005 inches diameter. It can be spun
into yarn, gathered into a mat, used in insulation, air filters and in other applications.

Photosensitive glass:

These glasses contain the compounds of photosensitive metals such as silver, gold and copper.
Sometimes cerium salts are used as photosensitizers. Colors variations in these glasses & directly
shades may be introduced by adding different compound during manufacturing.

Phosphate glass:

This glass contains phosphorous pentaoxide as a major ingredient wholly or partially replacing
silica. An important property of phosphate glass is its chemical resistance. Contrary to other
types of glass it can be safely used for hydrofluoric acid. It is used to carry uranium hexafluoride
in uranium separation procedures. Phosphate glass is also used in special optical, ultraviolet, heat
absorbing & fluorescent glass.

Raw material used in glass industry:

The different raw materials used in the manufacturing of glass are given below;

Raw material Function

Silica Sand for glass manufacturing should be almost pure quartz. Its iron content
should not be more than 0.045x for table ware & 0.015xfor optical glass as iron
affects the color of the glass.
Soda Na2O is principle supplied by soda ash. Other sources may be sodium
bicarbonate, salt cake and sodium nitrate. The latter is useful in oxidizing iron
and accelerating the melting.
Lime Important source of lime CaO or lime stone precipitate chalk and burnt lime from
dolomite CaCO3, MgCO3.
Feldspars Feldspar have the general formula R2O.Al2O3.6SiO2 where R2O represents
sodium oxide or potasiumoxide or a mixture of these two. The aluminum content
serve to lower the melting point of the glass.
Borax As a minor ingredient, supplies the glass with both sodium oxide and boric oxide.
It is seldom employed in window or plate glass but bora is added in container
glasses. There is a high index borate glass which has a lower dispersion value and
high refractive index than any other glass. This is a valuable optical glass. Borax
also lowers the expansion co-efficient and increase the chemical durability.
Salt cake Sodium sulphates along with other sulphates such as ammonium & barium are
the minor ingredient for many glasses. Salt cake is removed from the tank
furnace. Carbon is usually employed with sulphates to reduce them to sulphite.
Nitrate Sodium & potassium nitrate are helpful in oxidizing iron. So that is becomes less
noticeable in finished products. Potassium nitrate carbonates is employed in
many of the better grades of tables, decorative optical glass.
Cullet Cullet is the broken & crushed glass from old and imperfect articles, trim or
otherwise waste glass. It facilitate the melting and utilize the waste. It may be as
low as 10% of the charge r as high as 80% and so many minimize the cost of
production.
A r s e n i c o x i d e It is generally used to remove air bubbles from glass.
(As2O3)
Boric acid Boric acid is used in bottles, where only small amount of alkali required.
PbO The PbO increases refractive index of glass and such glass is used for optical
purpose.
Selenium Selenium is used in small amount in some glasses as decolorizer.

Refractory material:

Special refractory material such as sintered zircon, alumina, mullite, chrome alumina, zirconia-
Alumina, and silica etc. have been used in glass manufacturing.
Coloring material:

Coloring material Color

Manganese dioxide Violet
Cadmium sulphate Yellow
Cobalt oxide Black blue
Cuprous oxide Red
Chromium oxide green

Chemical reactions:

Na2CO3 + aSiO2 Na2O.aSiO2 + CO2

CaCO3 + bSiO2 CaO.bSiO2 + CO2

Na2SO4 + cSiO2 + C Na2O.cSiO2 + CO + SO2 OR

Na2SO4 + C Na2SO3 + CO

2Na2SO4 + C 2Na2SO3 + CO2

Na2SO3 + cSiO2 Na2O.cSiO2 + SO2

Manufacturing of glass:

Unit operations & processes:

• Transportation of raw material to plant

• Sizing of some raw materials (OP)

• Storage of raw materials (OP)

• Conveying, weighing & feeding of raw materials to furnace

• Reaction in the furnace to form glass

 • Fuel consumption to produce temperature for glass formation (PR)

• Heat saving by regeneration

• Shaping of glass products

• Annealing of glass products

• Finishing of glass products

Methods of glass manufacturing:

The manufacturing method of glass can be divided into following types:

o Formation of batch process

o Melting

o Shaping or forming

o Annealing

o Finishing

Formation of batch material:

The lamps (shaped mass) of injured such as lime stone, burnt lime, sand, domile, feldspar etc. are
crushed. Other ingredients such as quartz, sand ash are also obtain in similar way.

The required quantities are mixed uniformly in the form of coarse powder. This mixture of
ingredients are called as batten material.

The composition of typical soda-lime glass batch material is:

Sand 100 parts

Soda ash 285
Polomite 285
Lime stone 50
 Salt cake 90
Feld spar 90
Carbon 2
cullet 1000

Melting:

The process of melting can be explained as;

o Furnaces needed for glass manufacturing

o Formation of molten mass

Furnace needed for glass manufacturing:

The furnace are mainly of two types:

• Pot furnace

• Tank furnace

Pot furnace:

They constitute the most important part of a glass factory. The raw material are heated together
and a molten mass is obtained. A pot is crucible shape vessel manufacturing from high alumina
fire clay like mullite (3Al2O3.SiO2). Pot may be close or open type.

Diagrams
A number of pots (10-20) each with 2-ton capacity ae used. For optical glass only are pot is used
either rectangular or circular pot furnace are used. For casting thick plate glass, rectangular
furnace is used. Pots of different size are used according to the type and quantity of the glass.
Small pots hold 2-12 kg while bigger one hold capacity 2 tons & so on.

Regenerative system of heat economy is used to save large amount of heat. Close type is used
when glass is protected from the product combustion. Coal or coke is used for heating.

Regenerative system of heat economy is based on the principle that hot gasses one used again
and again. For this flow of air & fuel is reversed 20-30 minute interval. The batch materials are
put in the pot. They are place in a circle inside the furnace and heating burning reproduces gas
around them. The reaction take place in the furnace. When furnace fusion is complete, pots are
removed from furnace. Pot furnace. Pot furnaces are used for the production of high quality
glass, since charge protect from combustion.

Diagram:
 Heat Regenerative Pot Furnace

Tank furnace:

It consist f large tans built of fireless blocks, measuring 125*30*5 feet and delivers about 1400
tons per day. The batch material are fed into tank and produced/ gas is used as fuel in the furnace.
Siemen’s regenerative tank furnace is found to be more economical when large quality of one
type of glass is to be prepared. Such furnace is largely used in modern glass factories. In such
furnace the wall serve both to restrict and retain the heat and hold glass.

At one end of it added raw material and on other end glass is withdrawn. It is made from very
refractive material. The dome and arches are made of silica & bed is made of fire clay. Some
tank furnaces are known as dry tan have a capacity of 5-10 tones are heated either electro
thermally or by glass.

Diagram:
 Heat Regenerative Tank Furnace

In order to economize the heat, a regenerative system is used. The system work on two cycles.
The burning reached at 2800F whereas exile end at 1200F. Simultaneously air is being preheated
by passing u the other previously heated regenerative chamber and is mixed with fuel gas and
burned.

At regular intervals, the flow of air fuel mixture is reversed after every 20-30 minutes to
regenerate heat. Much heat is saved & high temperature is reached. The working temperature is
2200-2800F.

They reduce the effected of molten glass on the surface of furnace, water cooling pipes are used
frequently in modern furnace.

Formation of molten mass:

A mixture of ingredients after grinding add from one end to the furnace. These are heated and
during heating process, more and raw material is added. Some As2O3 is added for
decolorization. For cheap glass and MnO2, which imparts violet color to the glass.

Note: In pot furnace the process is discontinuous and used for optical glass. In tank furnace, the
process is continuous & useful sheet glass & bottle glass.+
Shaping:

Conversion of molten glass into some glass article is called shaping. Glass may be shaped either
by machine or had molding, depending item to item. Nowadays mostly shaping is done by
machine, sheet glass it made by continuous process. Article like bottle & electrical bulbs are
blown by automatic machines. Glass is last made by window the molten glass automatically.
Annealing:

To reduce strain, this necessary to anneal all glass objects, whether furnace by machines or hand
molding method.

Annealing induces two steps:

i. Holding a mass of glass above a certain critical temperature long enough to reduce
internal strain.

ii. Cooling the mass at room very slowly.

The annealing one is a carefully designed heating chamber in which the rate or cooling can be
controlling so as to meet the foregoing requirement.

Finishing:

All types of annealed glass must undergo certain finishing operations, which through relatively
simple are very important. These include cleaning, grinding, polishing, cutting, sand blasting,
canceling, grading & gaging. Although all of these are not required for each glass object but one
more is always necessary.

Process flow diagram: