(CH 211)

D r. H a m m a d K h a n
 Glass is everywhere
2

UV‐lamps, light protecting packaging packaging material for pharmaceuticals, labs Halogen/flash lamps

Transparency Chemical resistance Temperature resistance

• Impermeability: display industry, solar receiver, X‐ray tubes,

• Refractive index: fibre optics, light guides for endoscopy

solar receivers, flash lamps X‐ray tubes • Dielectric strength: diodes

Thermal expansion Electrically insulating • Mechanical properties: sprinklers in hotel room etc
Glass is everywhere
3

• The most common glasses are the soda-lime glasses, which are used to make most windows
and bottles. Other common glasses are borosilicate, aluminosilicate, borate, lead, phosphate,
halide and metallic glasses. Other glass products include ceramics and fiberglass.

• Hundreds of kinds of glass are now available. As manufacturers learned to control glass
properties and make glass more economically, they have developed glass suitable for more
and more applications.

• In addition to windows, bottles, laboratory glassware and light bulbs, glass is now used to make
solar heating panels, acid distillation columns, semiconductors, face plates for space suits, and
ports for underwater exploration vessels and space ships.
The future of glass is opening many opportunities
4
Research is opening up tremendous opportunities for the development of future glass products & the way we
currently use glass in various applications.

In China a smart window has been

Photovoltaic sunroof to provide electricity designed to save & generate energy
to hybrid & electric vehicles using VO2 as a transparent coating

Complex glass
Smart glass bottles & containers whose shapes & improved
colour changes depending on the liquid insulation properties
temperature (medicines, wines, to free architects
perishable products, etc.) from constraints

Architectural glass for temperature control,

self cleaning, aesthetics , fire control etc
What is Glass ?
5
→Physically, a rigid, super-cooled liquid having no definite melting point and a
sufficiently high viscosity to prevent crystallization.

→Chemically, the union of the non volatile inorganic oxides resulting from the
decomposition and fusion of alkali and alkaline earth compounds, sand and
other glass constituents, ending in a product with random structure.

Glass:
→is an amorphous material that lacks a long range periodic crystalline
structure
→has the mechanical rigidity of crystals, but the random disordered
arrangement of molecules that characterizes liquids so combines
some properties of crystals and some of liquids but is distinctly different
from both.
What is Glass ?
6

Glasses are energetically unstable in comparison with a crystal of the same chemical composition.

In general, when cooling a melted substance, crystallisation begins when the temperature falls

below the melting point. In glass this does not occur because the molecular building blocks (SiO4

tetrahedrons in silicate glass) are spatially cross-linked to one other. To form crystals, these

linkages must first be broken so that crystal nuclei can form. This can only occur at lower

temperatures, but at these temperatures the viscosity of the melt hinders the restructuring of the

molecules and the growth of crystals. In general, the tendency to crystallise (devitrification)

decreases with an increasing rate of cooling (within the critical temperature range below the

melting point) and with the number and type of different components in the formulation.
Composition of Glass 7

• Glass is composed and made principally by melting of the following

ingredients. sand, soda ash, limestone and cullet.

• Sand is pure silica or silicon dioxide (SiO2), is the primary ingredient

• Sodium Ash (NaHCO3) is added to reduce the melting point of
silica or sand. But its addition also makes the resulting glass
soluble in water.
• Lime stone/ Calcium Carbonate (CaCO3) is added to prevent
the glass from becoming soluble in water. Excess of calcium
oxide to a silica melt will cause devitrification At high temperatures:
• Cullet is a broken glass that is mixed with the batch and acts as a Sand (SiO2)→ SiO2
fusion agent for the entire mixture. It also helps to lower melting
NaHCO3→ Na2O
temperatures of raw materials
CaCO3→ CaO
 Composition
8
-4
• Basic Unit: SiO 4
Tetrahedron

-4
SiO 4 Si Al O O- Na+ ca+2
-2
O

• Quartz (SiO2) is crystalline

• Glass is amorphous
• Amorphous structure occurred by fusion of impurities i.e.,
alkali and alkaline earth metals (Na+, Mg+2, Ca+2, Al+3,…
• Impurities prevent the devitrification
Glass Structure
9

Glasses are energetically unstable in comparison with a crystal of the same chemical composition.

In general, when cooling a melted substance, crystallisation begins when the temperature falls

below the melting point. In glass this does not occur because the molecular building blocks (SiO4

tetrahedrons in silicate glass) are spatially cross-linked to one other. To form crystals, these

linkages must first be broken so that crystal nuclei can form. This can only occur at lower

temperatures, but at these temperatures the viscosity of the melt hinders the restructuring of the

molecules and the growth of crystals. In general, the tendency to crystallise (devitrification)

decreases with an increasing rate of cooling (within the critical temperature range below the

melting point) and with the number and type of different components in the formulation.
 Glass Structure
10
• Three categories of substances found in all glass

• Formers

• Makes up the bulk of the glass

• Examples: silicon dioxide (SiO2) in the form of sand,

B2O3 and P2O5

• Fluxes

• Change formers’ melting points

• Examples: Na2CO3,K2CO3, LiO, Al2O3

• Stabilizers

• Strengthen the glass and make it resistant to water

and chemicals

• CaO, MgO, PbO, BaO, ZnO, ZrO

RAW MATERIALS
11
• The raw materials for making glass are all oxides (contain oxygen). The composition of a sample can
be expressed in percentage of different oxides. As it turns out, silica is a very good solvent and can
dissolve far more oxides than just the above two (soda and lime) in it readily. The most common
cations found in glassware are sodium, calcium, magnesium, zinc and potassium. In fact, many
metal oxides can be added to silica melts to contribute different properties to the resulting glass.

Oxide should satisfy following conditions

• Every oxygen atom must be attached with 2-4 cations e.g. SiO2, B2O3, P2O5
and As2O5
• The oxygen polyhedral must share the corner position and not the edge.
• At least three corners of each tetrahedron must be share.

• The oxides used for glass manufacture are classified into following groups
Additives
12
• Alumina (Al2O3) is often added to soda lime glasses at around 1% to increase durability
• Silica (SiO2) not only forms the glass, but its weight percent is an indication of the thermal expansivity
of the glass; more silica means lower thermal expansion (thus higher resistance to thermal shock)
• Soda (Na2O) increases the viscosity of the glass melt at a given temperature but expensive
• Lime (CaO) contributes to the crystallinity of a glass and is relatively inexpensive as a raw material
• Boron oxide (B2O3) is a glass former like silica and increases the chemical resistance of the glass
• Lead oxide (PbO) increases the refractive index of the glass as well as its density
• Barium oxide (BaO) is a heavy ion and therefore increases the refractive index and absorptivity of a
glass without the harmful effects of lead
• Cadmium oxide (CdO), a good neutron absorber used in nuclear reactors, can be added as an
oxide to glass to make radiation shielding glasses
Additives
13
Addition of transition metal compounds to glass gives color to the glass. They are outlined below.

Yellow: Green: Purple:

Ferric Salts Ferrous & Chromium salts Manganese dioxide salt

Red:
Lemon Yellow: Fluorescent greenish yellow:
Nickel and cuprous salts Uranium oxide
Cadmium sulphide
Cu2O

Blue: Greenish Blue Color: Brown:

Cobalt Salts, CuO Copper Sulphate Iron

Opaque milky white: Ruby :

Cryolite of Calcium Auric Chloride
phosphate
Glass Manufacturing
14
1- Batch Preparation

2- Melting and Refining

3- Conditioning and Forming

4- Finishing
 Glass Manufacturing
15
Batch Preparation Approximate Compositions Used for
• Batch preparation stage involves weighing fine-ground Different Glass Products
Container Flat Fiber Laboratory
raw materials – that include formers, fluxes, stabilizers Constituent
Glass Glass Glass Ware

and sometimes colorants – according to recipe (in terms of weight percentage)

required for the final product and their subsequent SiO2 73 72 54 80

B 2O 3 10 10
mixing to achieve a homogenous composition
Al2O3 1.5 0.3 14 3
• Glass without iron impurities is sought for clear glass
CaO 10 9 17.5 1
pieces as presence of iron will cause the glass to
MgO 0.1 4 4.5 1
appear greenish while addition of lithium reduces the Na2O 14 14 5
melting temperature K 2O 0.6

• Due to its abrasive nature and larger particle size, cullet is usually handled separately from the primary
batch materials and may be fed to the furnace in measured quantities by a separate system
 Glass Manufacturing
16
Melting and Refining
• Melting
• Melting, the combination of the individual raw materials at high temperature (~1500 oC) to form
a molten glass, is the central phase in the production of glass.
• In continuous operations, the mixture of batch and cullet is continuously charged into the glass-
melting furnace at slow and controlled rate. The furnaces are natural gas or fuel oil fired and
operate at temperature upto 1800 oC.
• The following chemical reaction takes place and gives the glass in the liquid state. Impurities
called glass gal appear on the surface and removed. At this stage salts are added to get
colored glass.

• Two types of furnace are usually used

 Po t f u r n a c e
 Ta n k f u r n a c e
 Glass Manufacturing
17
 Po t f u r n a c e :
• In pot furnace, glass is melted in open or covered pots (closed
pots) of fire clay placed inside the combustion chambers of the
furnace made of ceramic material.
• In this furnace, the charge is fused in fire clay pots. The pots may
be opened or closed. The closed pots are used when the-glass is
to be protected from the products of combustion.

• The batch materials are put in the pots. They are placed in a circle inside a furnace and heated by
burning producer gas around them. When the fusion is complete the pots are removed from the
furnace and the fused plastic mass is taken out for shaping.
• Pot furnace is employed for the production of high quality glass, since the charge remains protected
from the products of combustion
 Glass Manufacturing
18
 Ta n k f u r n a c e :
• It consists of a large rectangular tank built of fire clay blocks. The batch
materials are fed into the tank and producer gas is used as a fuel in
the furnace
• In this process, cross flame regenerative type of gas or oil used. The
port is arranged along the side of the tank above the glass level those
on any one side is alternatively incoming and outgoing ports.

• Tank furnace is a continuous process and usually employed for the production of large
quantities of only one variety of glass at a time. e.g. manufacture of sheet glass container ware,
lamp shells and resistance glasses, continuous tank furnaces are generally used.
 Glass Manufacturing
19

The charge is heated at 1400°- 1500°C for 10-12 hours. The chemical reactions involved in both the
furnaces are:
Na2CO3 +aSiO2 Na2O.aSiO2+CO2

CaCO3+bSiO2 CaO.bSiO2+CO2

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

At 1400°C silica also in silicates of calcium and sodium

N a 2C O 3+ C a C O 3+ 6 S i O 2 N a 2S i O 3. C a S i O 3. 4 S i O 2+ 2 C O 2
 Glass Manufacturing
20
• Refining
• During the melting lot of frothing is caused owing to the evolution of the gases like CO2, SO2,
O2, etc. When the frothing subsides, the temperature is raised and the molten glass is allowed to
stand for some time. This is called refining, and its objective is to form a homogeneous mass free
from gas bubbles and bits of undissolved material or batch stones. Refining also takes place in
the melting tank.
• Glass melting is one of the most important and energy intensive processes in the manufacturing of
glass products, consuming 60 to 70% of the total energy used in glass production.
• Recuperative and regenerative furnaces, which allow for heating the incoming combustion air
with heat recovered from exhaust gases, are commonly used and these assist energy efficiency.
Glass Manufacturing
21
Conditioning and Forming
• Conditioning
• After completion of the refining stage the fairly homogenous, bubble-free glass leaves the tank
and enters the forehearths – the main channels that transport molten glass to the forming
machines.
• The main function of forehearths is to condition the glass; that is producing a stable glass with
desired glass temperature, evenly distributed both vertically and laterally, to be delivered to the
forming process.
• Conditioning in the forehearth is of critical importance, as deviations from the desired thermal
profile can cause undesirable differences in viscosity, and subsequently lead to visible defects in
the finished product.
Glass Manufacturing
22
Conditioning and Forming
• Forming
• The conditioned glass is delivered from the forehearth to the forming equipment at a constant
rate, also known as "pull rate". Glass may be shaped by either machine or hand molding.
• During the relatively short time the glass changes from a viscous liquid to a clear solid. The
design problems like flow of heat, stability of metals, and clearance of bearings should be
solved.
• Depending on the process, the viscous glass stream is either continuously shaped (floatglass,
fiberglass), or severed into portions of constant weight and shape (“gobs”) which are delivered
to a forming machine (container glass).
Glass Manufacturing
23

The molten glass is fabricated to require size and shape by either by hand or by
machine.

a) Blowing, b) Casting, c) Drawing, d) Pressing, e) Rolling, f ) Spinning

 Glass Manufacturing
24
Finishing
Different finishing treatments – such as annealing, toughening, and coating can be used to influence
product characteristics
• Annealing: It is a process of cooling slowly the newly shaped articles. If they are cooled quickly they
become brittle on account of the high internal strain. Annealing allows the molecules to arrange
themselves in such a way that there is no internal strain when the mass is cooled.
• Annealing is done in a temperature controlled kiln called lehr . At one end the temperature is a little
below the softening point of glass, i.e., 500-600°C and it gradually falls along the length of the oven so
inner and outer skins of a glass become rigid. At the other end the temperature is almost the same as
the room temperature.
• Immediately after shaping, the articles are introduced into the lehr at the hotter end and travel towards
the cooler end by means of a moving belt. It takes a few hours for the articles to move along through
the tunnel.
 Glass Manufacturing
25

• Glass annealing is critical to its durability as it removes the internal

stress caused by uneven cooling.
• Glass which has not been annealed is liable to shatter or crack when
subject to small change in temperature or mechanical shock.
• If glass is not annealed, it will retain many of the thermal stresses
caused by quenching and significantly decrease the overall strength
of the glass.

• The coating of glass surfaces (e.g. mirrors, strengthening of bottles, and coloring) gives glass new
physical, chemical, and optical properties. Lightweight glass containers are coated with organic
compounds to give the surfaces a degree of lubricity, thus preventing abrasion in handling. This adds
strength to the container and has enabled glass manufacturers to make a lighter and better product.
 Glass Types
26
Disadvantages: not resistant to high
temperature and thermal changes
Uses: bottles, jars, everyday drinking
glasses, and window glass. Most common commercial glass
and less expensive

Does not allow light at a

wavelength of lower than
400 nm (UV light) to pass. Composition: 60-75% silica, 12-
18% soda, and 5-12% lime

Glass containers are resistant

to chemical attack from
aqueous solutions so they will
not contaminate the contents
inside or affect the taste.
Smooth and nonporous surface: allows Light transmission
glass bottles and packaging glass to be
easily cleaned.
to be use in flat glass of
windows.
 Glass Types
27
Drawback: It doesn’t withstand
high temperatures or sudden
changes in temperature Composition: 54-65% SiO2, 18-38%
lead oxide, 13-15% soda or potash

Glass with high lead oxide

contents may be used as
radiation shielding glass Pb concentration: In moderate
amounts: increases durability

In high amounts: lowers the melting point and

High refractive index giving decreases the hardness giving a soft surface
high brilliance glass

These properties make it

appropriate for decorating
purposes
 Glass Types
28

It has greater resistance to thermal Composition: silica (70-80%), boric oxide (7-13%)
shock and allows for greater accuracy in and smaller amounts of the alkalis such as 4-8%
laboratory measurements when heating of Na2O and K2O, and 2-7% aluminum oxide.
and cooling experiments

Boron gives greater resistance to

thermal changes and chemical
corrosion.

Domestic
kitchens
It is used for
Laboratories
In the pharmaceutical Industrial chemical process
In bulbs for high-powered industry plants
lamps
Glass Types
29

Composition: It is used as resistors for

Aluminum oxide electronic circuitry

It is similar to borosilicate glass but it has:

 Greater chemical durability

 Can withstand higher operating temperatures

 Are more difficult to fabricate

Glass Types
30

It is resistant to heat
Furnace glass, for out windows on
shock up to
space vehicles
900°C.

Is a borosilicate glass melted, then processed to remove

almost all the non-silicate elements from the piece
Glass Types
31

It can sustain temperatures

up to 1200°C for short
Crucibles for growing periods
crystals

Pure silicon dioxide in

non-crystalline state Very difficult to fabricate, most
expensive of all glasses
 Waste Vitrification
32
• A new technology has been discovered to use recycle glass for radioactive waste management.
• The desired long-term storage form for nuclear waste is a relatively insoluble, compact solid. As a solid,
the waste becomes easier to store and handle; a small volume is desired because there are likely to be
few candidates for long-term storage spaces and thus space will be at a premium.
• Keeping the solubility low reduces the chances of groundwater contamination. The resulting solid is then
likely to be packaged, which provides additional barriers to contamination of the environment, but the
effects of radiation on the surrounding matrix packaging are not negligible

• Studies of archeological glasses have agreed with models

showing the immobilization of the important mobile nuclides
during the critical time period where they are highly
radioactive, encouraging the continued study and use of
Hazardous ISM (ion Virtified Final disposal
this methodology. This process is used to prepare waste for waste source specified media)
glass container
storage at a number of nuclear power plants in Europe.
 Waste Vitrification
33
• Amorphous borosilicates have been
identified as one option for nuclear waste
storage forms. To produce the glass, the
waste is dried, heated to convert the
nitrates to oxides, and then mixed with glass-
forming chemicals and heated again to
very high temperatures (approximately 1000
°C) to produce the melt.
• This is then poured into a containment vessel
where it cools to form a glass. The
containment vessel can then be sealed,
decontaminated, and placed into a long-
term (or temporary) storage facility.
 Waste Vitrification
34

Benefits of Vitrification:
Bottle Parts
35

• Finish is that part which receives the closure

• Smooth round shapes---easily formed Suitable on
filling lines
• Labeled at relatively high speeds Accurately
positioned in spot-labeler Greater strength-to-
weight ratios Better material utilization
 Bottle Defects
36

Flat shapes inherent problems.

“bird swing” and “spike” defects.

• Spikes --- glass projections inside the bottle

• Bird swing--- glass thread joining the two walls

Careful design to avoid stress points

 37

Thank you