GLASS
1.What is Glass?
The term Glass signifies an amorphous solid substance. When crystalline quartz is
heated in specially designed electric furnace to a temperature at about 1650oC. It
melts a colourless liquid solution containing chiefly silica and some outer selected
components (like Na, Ca, Pb, K etc.). On the other hand if this liquid is cooled rapidly
the quartz can be obtained as a colourless, clear, glassy mass called supercooled
liquid.
Glass do not have crystalline internal structure. They usually are hard,
brittle and transparent and supercooled liquid. When glass is cooled from the hot
molten state, it gradually increases in viscosity without crystallisation over a wide
temperature range. Cooling is controlled to prevent crystallisation or high strain.
Quartz glass is therefore widely used in the manufacture of various kinds of
laboratory apparatus. The glassy quartz also passes into crystalline form when
heated for some time at a temperature of about 1150oC.
When quartz or silica is heated with sodium carbonate, a compound
known as sodium silicate is obtained. When it is allowed to cool, it solidifies to a
glassy mass called water glass and it is soluble in water.
Chemically, glass may be defined as a fused mixture of silicates, alkali
and alkaline earth compound and other glass constituents such as calcium oxide,
magnesium oxide, barium oxide etc.
Physical properties of glass:
1.They are usually transparent amorphous solids.
2. Glass is vitrified product.
3. They are hard and rigid and have no definite melting point.
4. They have high viscosity.
5. They are insulator of heat and electricity.
6.They can incorporate colouring material preserving transparency.
7. Possesses high compressive strength and since it doesn't have any crystalline
structure.
Chemical properties
1. Glass is not attacked by air and oxidizing agent
2. Ordinary glass is readily attacked by alkalis but very resistant to acid except
hydrofluoric acid. Glass is a silicate and HF reacts with it to form SiF4 gas and
fluorides of metals.
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 NaOH.
This reaction is enhanced in the presence of acids. If bottles containing acids are
kept for a long time, silicic acid has been found to be deposited on the glass of the
bottles , the glass known as neutral glass of which porex glass is an example which
contains very small amount of alkali silicate.
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, silicic acid as well as chlorides of metals are formed.
Characteristics of glass:
A)Hardness (B)Transparency (C)Dispensive capacity (D)Destructive capacity
(E)Low coefficient of cubical expansion (F)High electrical insulation (G)Low thermal
conductivity (H)Capacity of absorbing decorative colours without ions of
transparency (I)Chemical inertness under ordinary conditions
Raw materials of glass
(A) Major ingredient (around 97%)
i. Silica (SiO2 )(around 70%) formers make up the largest percentage of the
mixture to be melted. In typical soda-lime-silica glass the former is silica (silicon
dioxide) in the form of sand. Silica content in sand required for the best table ware
and optical glass should be at least 99.9%.
ii. Soda or soda Ash (around 15%) Na2CO3 act as flux. Fluxes lower the
temperature at which the former will melt. Soda (sodium carbonate) and potash
(potassium carbonate) both alkalis are common fluxes. Potash glass is slightly more
dense than soda glass. It helps in accelerating the melting.
iii. Lime or limestone (CaCO3) (around 10%): It provides CaCO3 (Calcium
carbonate) often called calcined limestone which is a stabilizer. Without stabilizer
water and humidity attack and dissolve glass.
B. Minor ingredient (around 3%):
1. Potassium carbonate (K2CO3): It acts as a flux. Fluxes lower the
temperature at which the formers will melt soda (sodium carbonate) and potash
(potassium carbonate). Both alkalis are common fluxes. Potash glass is slightly
denser than soda glass.
2. Borax (Na2B4O7.10H2O): It is a minor ingredient which supplies B2O3.
Besides its high fluxing power, borax lowers the coefficient of expansion of glass
and add to its chemical durability. It increases the hardness or refractory
character of glass.
3. Feldspar: It is naturally occurring mineral with a formula Na2O3.Al2O3.6SiO2
(soda feldspar) or K2O.Al2O3.6SiO2 (potash feldspar). Feldspar is used as a flux
i.e. to lower the melting point and to retard denitrification.
4. Salt cake (Na2SO4): Salt cake is used in small quantities as refining agent
addition of sulfate up to about 2% in the the batch makes the glass bubble free
earlier than the corresponding sulfate free glass.
5. Arsenic oxide (As2O3): It is generally used to remove air bubbles from the
glass.
6. Lead (II) oxide: Lithrage (PbO) or red lead (Pb3O4) is used for production of
heavy and high-quality flint glass which is used in optical instruments, tableware
and decorative articles.
7. Phosphorus (V) oxide (P2O5): It is used as Na2HPO4 or Ca3(PO4)2 and is
added in tableware glass for importing bright appearance.
8. Cullet: It is crushed glass from imperfect for defective articles or their trimming.
It makes the melting easy and also utilisation of waste mixture of raw materials
from which glass melt is produced. It also decreases the cost of production to a
lesser or greater extent.
Colouring materials: Coloured glasses are obtained by adding certain
metallic oxide or salts in the fused mass various colouring agent and the
corresponding shades are grouped as follows.
Red:- CdO (1.4%), Se (1%)
Ruby red:- (i) Colloidal gold or ruby gold
(ii) Cu2O
Light yellow:- Cerium oxide (2%), Titanium oxide (TiO2)
Deep blue: Cobalt oxide (CoO) (0.1%)
Greenish: Copper (II) oxide (CuO)
Emerald green: Cr2O3 (0.13%), CoO (0.001%)
Amber: FeS (0.3%)
Black: MnO2+Fe2O3
Yellow: CdS
Fluxes: KNO3, NaNO3,B2O3, As2O3, Sb2O3, CaF2
Fundamental materials: SiO2, B2O3, P2O5, Al2O3, CaO, MgO, PbO, Fe2O3, Na2O
Decolourisers: MnO2, As2O3, Sb2O3, NiO
Oxidising agent: NaNO3, KNO3, BaO2, Pb3O4
Reducing agent: Coal, coke, zinc, aluminium
Opacifier: Na3AlF6, Ca3(PO4)2, SnO2
Different glasses mixture or batch materials:-
1. Coloured bottle glass: Sand(SiO2), soda (Na2O3), limestone(CaCO3), dolomite
2. Window glass: Sand, soda ash, Salt cake, limestone, coal
3. Gold Ruby glass: Sand, red lead, potash, borax, gold chloride
4. Vegetable green glass: Sand, soda, iron oxide, arsenious oxide, limestone
potassium chromate
5. Amber yellow glass: Sand, potash, soda, limespar, Sulphur, arsenious oxide
6. White glass: Sand, red lead, soda, NaNO3, NaCl
7. Dark blue glass: Sand, soda, limespar, Cobalt oxide
8. Chemical glassware: Sand, hydrated alumina, limespar, KNO3, soda ash,
magnesia calcined borax
9. Amber coloured bottle glass: Sand, soda, limestone, Salt cake, graphite
Glass manufacturing consists of following high level States
(I) Formation of batch material
(II) Melting a.pot furnace
b.tank furnace
(III) Forming and shaping
(IV) Annealing and finishing
(I) Formation of batch materials:-
In order to make clear glass the right set of raw materials is required. This
consists of silica sand (SiO2), sodium oxide (Na2O) from soda Ash, calcium oxide
(CaO) from limestone/dolomite(MgO) and feldspar (Al2O3 ) are mixed together in
the right proportion. These mixed ingredients are called Batch material.
(II) Melting: The melting of batch components takes place in furnishes. The
selection of furnace depends upon the quantity and type of glass being produced.
The homogeneous mixture known as batch is fused with some broken glass called
“Cullet” in any of the two types of furnaces.
Glass furnaces are of two types- (i) Pot furnace (ii) Tank furnace. The
glass melt is produced from the batch either in pot furnace or in tank furnace.
But furnaces can be regenerative type. The purpose of regeneration is to
utilise the heat of waste gases for heating the incoming gas and air used for burning.
The batch melts and fuses at 1700℃. The homogeneous mixture is
melted either pot furnace or tank furnace.
These reactions are involved in both furnace and charged is heated at
1600-1700℃.
Na2CO3+SiO2 Na2SiO3+CO2
2Na2SO4+2SiO2 2Na2SiO3+O2+2SO2
CaCO3+SiO2 CaSiO3+CO2
At 1600℃ silica also in silicates of calcium and sodium.
Na2SiO3+CaSiO3+4SiO2 Na2SiO3.CaSiO3.4SiO2
(glass)
The use of silica glass is wide but melting temperature of silica is too high. To
reduce the processing temperature of silica, different types of flux such as Na2CO3
and K2CO3 can be used. The addition of fluxes to silica reduces the overall cost of
glass processing but results in degradation of properties. Different property modifiers
on intermediates such as boron, sodium, magnesium, titanium and calcium can be
used to modify the properties of glass. Colourants are used to control the colour in
the final glass. The amount of iron oxides present in the glass results in unintentional
change in colour of glass. The other types of colorants used are gold and silver.
These types of colourants change glass colour by forming colloids in glasses. Finally
fining agents such as arsenic, antimony oxides, potassium and sodium nitrates are
added to raw materials to remove bubbles from the melt as the raw materials melt
and react inside the furnace. Carbon dioxide and water emission takes place which
causes formation of bubbles. The high temperature and low viscosity is maintained
to rise the gas bubbles at the upper surface of the melt and hence removed from the
melt. Fining is important because it controls the homogeneity of glass by eliminating
bubbles. Batch particles’ size and their mixing in proper proportion are other factors
that provide homogeneity in glass structure.
(III) Forming and shaping: The viscous mass obtained from melting is
poured into moulds to get different type of articles of desired shape by either blowing
or pressing between rollers. Glass forming permits molten glass to be shaped into
flat sheets and filament by controlling the viscosity. For example viscosity of the
glass must increase slowly as the temperature drops to produce full lead crystal and
the viscosity of the glass must increase rapidly as temperature drops to manufacture
glass fibre. Depending upon the applications there are different processes of forming
the glass. Heating is continued till clear molten mass is free from bubbles is obtained
and it is then cooled to about 800℃. Molten glass is converted to desired shape by
blowing or moulding or pressing between rollers-“forming and shaping”
Lump is introduced into a mould
Inflated by blowing air into it from mouth
Sheet glass or window glass is prepared by this manual process of hand
moulding
(IV) Annealing and finishing:-
Annealing is necessary to cool glass in a controlled manner through predetermined
temperature gradient is called annealing. The longer the annealing period, better the
quality of glass. Finishing the articles obtained that are subjected to a number of
operation such as cleaning, polishing, grinding, rounding ages for bringing them to a
usable “finishing” glass articles are then allowed to cool gradually at room
temperature by passing through different chambers with descending temperature.
This reduces the internal strain in the glass.
To avoid this, glass must be cooled very slowly process of slow cooling
which is used to reduce strain, is known as annealing. It is therefore necessary
process for types of glass weather formed by machine or hand mould method. For
every type of glass there is a definite annealing temperature and if glass is
maintained as near this temperature as possible strain is rapidly removed.
The chambers in which glassware is stacked and the chamber is heated
up and then cooled slowly by closing the chamber from all sides is called annealing
chamber. Annealing lehrs is heated at hot end by directly fired hearths or gas fired
hearths. Lehrs have also been heated electrically.
The design of glass making furnace depends upon the following
important factor-
(a) kind of fuel to be used
(b) method of working of glass articles
(c) Composition and properties of molten glass
(d) required productivity of the furnace
Modern glass making furnaces are classified according to the following factors.
(a) Operating principal
(b) Design of furnace space
(c) Method of heating
(d) Direction of gas flow
Glass making furnace are divided into periodic pot and tank furnaces and
continuous tank furnaces.
Periodic furnaces: All melting stages occur in the same furnaces but
are separated in time periodic furnace used for special glass, coloured glass etc.
Continuous furnaces: All the stages of melting occur simultaneously in
different sections of the furnace. It is used for manufacture of plate, container ware,
industrial glass, glass fibre, medical glassware etc.
On the basis of method of heating the glass making furnace are
classified as flame furnaces, electrical furnaces, flame electric
furnaces.
Flame furnaces: Thermal energy is produced by combustion of gaseous or liquid
fuels.
Electrical furnaces: Heat is produced by electrical current.
Flame electrical furnace: It is combined method of flame and electricity employed
for producing heat.
Continuous tank furnaces are usually preferred because they have
higher efficiency and higher productivity
Pot furnace is used in glass making are mainly with the lower flame and
removal of waste gases through the furnace bottom. Single and two pot furnace are
generally used in making optical and industrial glasses.
Multi-pot furnaces have been used in making coloured and crystal
glasses.
In glass making, continuous tank furnaces are more common than
periodic tank furnaces.
