Glass

Questio
is Glass?
n What
Glass is an amorphous solid. A material is amorphous when it has

no long-range order, that is, when there is no regularity in the

arrangement of its molecular constituents on a scale larger
than a few times the size of these groups. [...] A solid is a rigid
material; it does not flow when it is subjected to moderate
forces - Doremus

Glass includes all materials which are structurally similar to

a liquid. However, under ambient temperature they react
to the impact of force with elastic deformation and
therefore have to be considered as solids. -Pfaender

Glasses have numerous properties in common with

crystalline solids, such as hardness and elasticity of
shape [...]. The term 'amorphous solid state' has a more
comprehensive meaning broader than that of the
'vitreous state'. All glasses are amorphous, but not all
amorphous substances are glasses. Feltz, 1993

Glasses

Amorphous solids
No crystal structure
No long-range order
Resemble frozen liquids

Forming a Glass
Requirements

Material must have high viscosity at melting point

Material must have difficulty nucleating crystal

Procedure

Melt material to eliminate crystal structure

Cool material quickly through melting temperature
Form supercooled liquid
Cool until solid

Zachariasens rules glass formation

1. No oxygen atom may be linked to more
than two cations
2. The cation coordination number is
small: 3 or 4.
3. Oxygen polyhedra share corners, not
edges or faces.
4. For 3D networks, at least three corners
must be shared

Zachariasens rules glass

formation
Silica
covalent Si-O bond: sp3 hybrid
tetrahedral bonding
Pauling's packing rule:

r Si 4
0.4

0.29
2
rO
1.4
satisfies Zachariasen's rule #2.
Looking at the charge / CN = 4/2
satisfies Zachariasen's rule #1.
Crystal structure: sharing four
corners:
All Rules are Satisfied: SiO2 forms

Cation CN:Anion CN = 4:2

Zachariasens rules glass

formation
MgO
ionic Mg-O bond
Pauling's packing rule:

r Mg 2
0.72

0.51
2
rO
1.4
violates Zachariasen's rule #2.
Looking at the charge / CN = 6/6
violates Zachariasen's rule #1.
Crystal structure: edge sharing
polyhedra
Rules are NOT Satisfied: MgO does
not form a glass.

Cation CN:Anion CN =6:6

In general: *oxides with small cations (and

so- small CN's) form glasses;
partial covalent bonding hybridization,
low CN geometries
*oxides with large, low valence cations
(MgO, CaO, Li2O, Na2O,) do not form
glasses.
dominated by ionic bonding; higher CN's

What is the raw

material?
Sand - SiO2
Flux to lower T
eg. soda (1700
900C)
Stabilizing agent to
mitigate water
solubility of the glass
formed eg. CaO
normally added as
limestone

17%
72%

5%
6%

Silica Sand
Three of most common rock forming minerals
on earth
Chemically named: quartz sand / rock crystal
Properties:
Extremely heat durable
Chemical stack resistance

World
Silica

resources of
Sand

Silica sand resources is

abundant on the world.
Its extraction is limited by
geographic distribution
quality requirements
for some uses
environmental
restrictions
Extraction of theses
resources is dependent on
whether it is economic and
are controlled by the
location of population
centers
Fig. 1
http://minerals.er.usgs.gov/minerals/pubs/commodity/silica/780397.pdf

Quartz
Quartz is silicon dioxide (silica)
Is an excellent network former
Slow cooling forms regular network
Fast cooling forms irregular network
High viscosity at melting point
However, nucleates crystals easily
Melting point of Quartz is very high

Addition of Modifying ions

Continuous random network (CRN) of the glass
former is retained, but that network has been modified
by the addition of the second oxide.
These ionic compounds are called Glass Modifiers.

Bridging Oxygens link

glass forming tetrahedra.
Nonbridging Oxygens
form the ionic bonds with
the modifiers

The Solvay process for the

manufacture of Soda Ash
(NaHCO3).

Fig.6
cwx.prenhall.com/petrucci/medialib/ media_portfolio/22.html

Types / classes of glasses

Soda-lime
Lead glasses
Heat-resistant glasses
High-purity Silica glasses

Speciality, natural.

70% silica
+ Fe + Mn
Used as
surgical
blades in
heart
surgery

Soda-Lime-Silica Glass
Adding sodium oxide (soda) lowers melting point
Adding calcium oxide (lime) makes it insoluble
Sodium and calcium ions
terminate the network and
soften the glass
Soda-lime-silica glass is
common glass 90%
of all modern glass
66% sand; 15% soda; 10% lime

Lead Glass

Lime and soda replaced with PbO

High refractive index- clarity sparkle
Softer cut and engrave
Good electrical resistance - electronics

Heat-resistant Borosilicate Glass

Soda-lime-silica glass expands much when
heated
Breaks easily during heating or cooling

Boron-oxide-silica glass expands less

Tolerates heating or cooling reasonably well

Pyrex and Kimax are borosilicate glasses

Boron oxide replaces lime and most of soda
low thermal expansion coefficient
Al2O3 i.s.o. B2O3 aluminosilicate glass with
even better heat resistance

High-purity Silica
Highest quality most durable
3 processes melting pure SiO2; making 96% silica and
flame hydrolysis
Pure SiO2 pure silica melted @ 1900 C under
vacuum
96% - Vycor process borosilicate glass heated to
grow crystalline sodium borate channels
extracted hot HNO3 leaving 96% pure silica after
heat reduction @ 1200 C
flame hydrolysis SiCl4 in CH4 / O flame (1500
C, produces high-surface silica soot thermally
sintered to pure silica at 1723 C)

Speciality
Coloured glass MnO2 violet, CoO

blue, Cr2O3 - green

Opal glass white opaque or translucent
glassware colour due to scattering of light
from small particle usually NaF/CaF crystals
nucleating after a cooling and reheating
process
Frosted glass satiny look when exposed
to HF

4 HF SiO2 SiF4 2 H 2O

Speciality
Coated glass unique properties
- metal / metal oxides Ag+ + RA Ag mirror
- electrically conducting with SnO2 coating (thermal
SnCl4 hydrolysis)

Photosensitive glass glass that changes colour

upon exposure to light

phototropic darkens upon exposure to light and

returns to original clear sate afterwards.
AgCl/AgBr

The Process the

history

Historical Glass
Manufacturing process:
Historical method:
heating and blowing
shape the glass
products by hand
requires high skills &
is time consuming
therefore using glass
is considered as
luxury in our old world

The Process @ Consul

Tempered Glass
Tempering glass

Heat glass to softening point

Cool outside of glass quickly
Outside stiffens while inside is still hot
Shrinking inside compresses outside
Compressed outside stretches inside

Resists fractures because surface is compressed

Crumbles when cracked because inside is tense

The Float Process

The equilibrium thickness (T) is given by the relation:

where Sg, Sgt, and St are the values of surface tension at the three
interfaces shown in the diagram.

Glass Forming
Casting - molding
Pressing pressing second mold into molten
glass
Core-forming clay core dipped into molten
mass
Fusing fusing glass rods together around a
mold
Blowing blowing air into a glob

Glass Forming
Flat glass floating / rolling
Glass fibre continuous strands and
Crown process for glass wool

Optical fibres
Communications are increasingly based on
electro-optic systems in which telephones,
television and computers are linked by fibre optic
cables which carry information by light.
Making glass optical fibres is a highly
specialised aspect of glass manufacture. Optical
fibres consist of two distinct glasses, core of
highly refracting glass surrounded by a sheath of
glass with lower refractive index between the two
glasses, it is guided by total reflection at the
core-sheath interface to the other end of the
fibre.
In theory, a wide range of glasses can be used
as long as the difference in refractive index is
appropriate but the higher the refractive index of
the core relative to that of the sheath glass, the
greater the carrying capacity of the fibre. A
typical system available commercially comprises
a germanium doped silica core and a
borosilicate cladding.

Analysis & Testing

Analysis and testing is critical to all stages of the glass manufacturing process
from the initial starting materials, through the melting and forming to the
processes used for manufacturing the final product be it an automotive
windscreen, solar control or fire-glazing product

Consumption of Glass
Three largest consumers:
1.
2.
3.

glass packaging (43%)

domestic commodities
construction industry
glass package
43%

sheet glass
30%

plants and conduits

5%

electrotechnical needs
10%

housekeeping
12%

National Glass Usage

http://www.bisnis.doc.gov/bisnis/country/000727glass_samara.htm

Fig. 13

Glass Industries
The World Glass Industry has a gross production value
totaling $82.3 billion

Fig. 14
www.icem.org/events/ bled/matdocen.htm