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Topic 6: GLASS

A short series of lectures prepared for the Third year of


Geology, Tanta University
2013- 2014

by
Hassan Z. Harraz
hharraz2006@yahoo.com

OUTLINE OF TOPIC 6:
Glasses
Raw Materials:

a) Silica sand
b) Limestone
c) Soda ash

Glass Manufacturing Process


Glass Forming
Glass Structure
Glass Properties
Glass Types:

i) Soda-lime glasses
ii) Lead glasses
iii) Heat-resistant or borosilicate glasses
iv) High-purity silica glasses
v) Specialty glasses
Heat Treating Glasses:

a) Annealing glass
b) Tmpered glass
Chemistry of Glass Manufacture
Recycling of Glass
Virtification

Question

What is Glass?
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

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

Taxonomy of Ceramics
Glasses
optical
composite
reinforce
containers/
household

Refractories
Clay
products

Abrasives

-bricks for
high T
(furnaces)

-sandpaper
- cutting
- polishing

-whiteware
- bricks

Cements
-composites
- structural

Advanced
ceramics
engine
- rotors
- valves
- bearings

Adapted from Fig. 13.1 and discussion in Section 13.2-6, Callister 7e.

-sensors

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

13 March 2014

Glasses
A glass can be defined as an inorganic product which has
cooled to rigid structure without crystallization.
Glass is hard material normally fragile and transparent
common in our life.
Glass-ceramics have an amorphous phase and one or more
crystalline phases and are produced by a so called "controlled
crystallization" in contrast to a spontaneous crystallization

It is composed of mainly:
Sand
Alkali
Glass-ceramics are mostly produced in two steps:
First, a glass is formed by a glass manufacturing process.
The glass is cooled down and is then reheated in a second
step. In this heat treatment the glass partly crystallizes
Two prime characteristics of glass are their optical transparency
and the relative ease with which they may be fabricated.
Amorphous solid materials
No crystal structure
No long-range order
Resemble frozen liquids

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

RAW MATERIALS
Raw materials used in lime-soda glass
Raw Materials
Soda ash (Na2CO3)
Limestone (CaCO3)
Silica sand (SiO2)

Approximate
Proportion (wt %)
25
10
65

Provides

Approximate Proportion
in glass (wt %)
18
7
75

Soda (Na2O)
Lime (CaO)
Silica (SiO2)

a) Silica sand

Silica sand suitable for glass manufacture is however relatively


rare, because of the need for a high degree of chemical purity.
The essential requirements for silica sand for glass manufacture
are that it must be even grain size - more than 90% of grains must
lie in the range 125-500m, and its chemical composition must
meet the requirements shown in Table 4.
Table 4: Required chemical composition of silica sand for glass manufacture
Glass

Minimum
SiO2
99.7

Maximum
Fe2O3
0.013

Maximum
Cr2O3
0.00015

Tableware, crystal and borosilicate glass


Colourless containers
Coloured containers
Clear flat glass

99.6
98.8
97.0
99.0

0.010
0.030
0.25
0.10

0.0002
0.0005
-0.0001

Opthalmic glass

Fig.1: High pure silica sand raw


materials

a) Silica sand
The discolouring impurities iron and chromium occur within the non-quartz mineral fraction of the
sands.
Iron can occur as haematite, giving the sand a red colour, or as oxy-hydroxidcs (giving a yellow or brown
colour) as well as in silicate minerals.
Chromium occurs as the heavy mineral chromite (FeCr2O4), which is stable during glass manufacture,
and so rather than resulting in a discoloured glass, it persists as solid inclusions within the finished
product, which can cause it to be brittle. This is especially important for float glass manufacture, where
persistence of chromite grains can render useless substantial lengths of glass strip. Because of the
difficulties involved in the chemical determination of minor amounts of Cr it may be appropriate simply
to count the number of grains of chromite detected optically within a sample of known weight in order
to classify a sand as suitable for float-glass.
Alumina is a natural impurity in glass sands, arising from the presence of feldspars, mica or clay
minerals, and varies from 0.4% to 1.2% Al2O3 High values in this compositional range are preferred
because they help to reduce melting temperatures (yet another component is added) and involve no
negative effect on glass colour or other physical properties. The occurrence of aluminium as an
impurity may also be beneficial by reducing the need to add aluminosilicates (feldspar, aplite or
nepheline syenite) for the manufacture of certain glasses.
Great care is taken to consider the minor components of a glass, as small traces of impurities may have
a major positive or negative effect on the quality of the finished product. For example, the presence of
traces of iron may give a pale green colour (often visible when examining a pane of glass end on), and
this can be tolerated in some applications (such as container glass).
Other minor components might have beneficial effects on the qualities of the glass produced. For
example, addition of lithium (reduces the temperature required to melt the glass, and so yields savings
in energy costs.

b) Limestone
Limestone is required twice in glass manufacture - once to produce
sodium carbonate and secondly as an ingredient in the batch to be
melted.
As an ingredient in batches to be melted to produce glass, limestone
purity is critical. In particular, Fe contents have to be very low, and the
amount of MgO, as in dolomite, has to be known. In some glasses MgO is
added using pure dolomite, but the amounts have to be controlled.
Like CaO, MgO causes immiscibility in glass melts; the miscibility gap in the
system SiO2-MgO is wider than that in the system SiO2-CaO (Fig.4).

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

Limestone Cycle
Limestone
CaCO3

CO2
Calcium
Hydroxide
Ca(OH)2 - WET

H2O

Milk of Lime

Heat

Lime
H2O

H2O
Slurry

CO2

Hydrated
Lime
Calcium hydroxide

(Ca(OH)2 - DRY

Calcium
oxide
(CaO)

Lime (CaO)
Include hydrated lime & quicklime
Only quicklime can use to make glass

Extraction of Lime

Quarry of limestone
Transported to crush plants
Undergo Calcination process:

heating limestone or chalk (CaCO3) in kiln till 900oC


CO2 is emitted in this process and calcium oxide
(lime) is produced.

Calcination Process

Calcined lime

Quicklime/Burnt lime/White wash is obtained by heating


limestone at temperatures above 900oC in a Kiln:
CaCO3 heat CaO + 2CO2

Hydrated lime

Calcium Hydroxide/Slaked Lime is a dry powder, resulting from


the controlled slaking of Calcined Lime with water in a Hydrator:
CaO + H2O Ca(OH)2

Precipitated Calcium Carbonate

Carbonation of Hydrated lime, also known as purified, refined or


synthetic Calcium carbonate:
CaO + H2O + CO2 CaCO3 + H2O

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Prof. Dr. H.Z. Harraz Presentation

Glass

10

Vertical Lime Kiln

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Prof. Dr. H.Z. Harraz Presentation

Glass

11

c) Soda Ash (NaHCO3)

Anhydrous sodium carbonate


Texture: soft
Color: grayish & white
Appearance: lump / powder in nature

Naturally:

Erosion of igneous rock form sodium deposits


Transport by waters as runoffs & collect in
basins
When sodium comes in contact water/ CO2,
precipitates out sodium carbonate.

Synthetically:

Extraction of Soda Ash(NaHCO3),


Manufactured synthetically through Solvary
process by using salt, ammonia & limestone

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

12

The Solvay process for the manufacture of Soda Ash (NaHCO3)

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

Impurity
The Na2O and CaO decrease the softening point of this glass from 1600oC to 730oC
So that soda lime glass is easier to form.
An addition of 1 4% MgO is added to Soda lime glass to prevent cracks.
Magnesium can be substituted for a proportion of the calcium content by the use of
dolomite instead of limestone
In addition of 0.5 1.5% Al2O3 is used to Increase the durability. Alumina is a
widespread component of glasses in addition to soda ash and silica, and helps
improve resistance to weathering.
Boric oxide (to produce heat-resistant glasses such as 'Pyrex' and 'Vycor') and
Lead oxide (for lead crystal tableware).
Potassium can be substituted for some of the sodium with the use of feldspar, aplite
or nepheline syenite.
fluorides.: used to produce Opaque glasses .
Lithium (Li2O) is added to the glass composition: The amounts required are very
small, frequently ~1 to <4%. Lithium is added to glasses for several reasons, because
it reduces liquidus temperatures; it improves moulding properties (reduces
viscosity); it improves thermal properties ('Pyrex', ceramic hobs) and it improves
strength.

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

14

Ingredients To Obtain Glass


What is the raw material?
There are following main
ingredients used in the
manufacturing of glass:

Percentage of Ingredients in Glass

17%
5%

72%

6%

Sand (SiO2), Quartz, or Silica sand 72%


Flux to lower T e.g. Soda or Soda
Ash (NaHCO3) 17%; (1700 900oC)
Stabilizing agent to mitigate water
solubility of the glass formed e.g.
CaO normally added as Limestone
{Lime 5%}

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

silica sand
soda ash
lime
other ingredien

15

Glass Manufacturing Process


1. Silica sand, limestone, soda ash and cullet (recycled glass or
broken glass) are keep dry and cool in a batcher house in
silos or compartments
2. Mixing and weighting into proper proportion
3. Send to furnaces in hoppers:
operated by natural gas
heat the mixture at 1300-1600oC into soften or
molten state
4. Molding (or Casting ): molten glass flows to forming
machine to mold into desire shapes
5. Annealing lehrs : reheating the glass in an oven
to ensure even cooling of glass for strengthening of
the products
6. Cooling process: Cool for 30 min to an hour for safe to
handle.
7. Glass products are then decorated, inspected again and
finally packaged and shipped to our customers.

www.glassforever.co.uk/howisglassmade/

Glass Furnace Cooling Systems

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

16

The Process

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

17

Glass Forming
1)
2)
3)
4)
5)

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

Flat glass floating / rolling


Glass fibre continuous strands and Crown
process for glass wool

13 March

Prof. Dr. H.Z. Harraz Presentation

Glass

18

Glass Fabrication Methods


PARTICULATE
FORMING

GLASS
FORMING

CEMENTATION
plates, dishes, cheap glasses
-mold is steel with graphite
lining

Pressing:
Pressing
operation

Gob

Fiber drawing:

Parison
mold

Compressed
air

Blowing:
suspended
Parison

wind up
Finishing
mold

Adapted from Fig. 13.8, Callister, 7e. (Fig. 13.8 is adapted from C.J. Phillips, Glass: The
Miracle Maker, Pittman Publishing Ltd., London.)

Blow Molding
Softened
glass

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Pressed Glass Processing


Softened
glass

Prof. Dr. H.Z. Harraz Presentation

Glass

20

Float Glass: The Process

Modern Plate/Sheet Glass making:

Image from Prof. JS Colton, Ga. Institute of Technology

Glass Structure
Basic Unit:
4SiO 4 tetrahedron
Si 4+
O 2-

Glass is amorphous
Amorphous structure
occurs by adding impurities
(Na+,Mg2+,Ca2+, Al3+)

Impurities:
interfere with formation of crystalline
structure.

Quartz is crystalline
SiO2:

Na +
Si 4+
O 2-

(soda glass)
Adapted from Fig. 12.11, Callister, 7e.

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

22

Glass Properties
Specific volume (1/r) vs Temperature (T):
Crystalline materials:

Specific volume

crystallize at melting temp, Tm


have abrupt change in spec. vol. at
Tm

Liquid
(disordered)

Supercooled
Liquid

Glasses:

Glass
(amorphous solid)
Crystalline
(i.e., ordered)

Tg

Tm

solid

do not crystallize
change in slope in spec. vol. curve at
glass transition temperature, Tg
-- transparent
- no crystals to scatter light

Adapted from Fig. 13.6, Callister, 7e.

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

23

Glass Viscosity vs. T and Impurities


Viscosity decreases with T
Impurities lower Tdeform

soda-lime glass: 70% SiO2


balance Na2O (soda) & CaO (lime)
borosilicate (Pyrex):
13% B2O3, 3.5% Na2O, 2.5% Al2O3

Viscosity [Pa

s]

Vycor: 96% SiO2, 4% B2O3


fused silica: > 99.5 wt% SiO2

10 14

strain point
annealing range

10 10
10 6
10 2
1
200

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T deform : soft enough


to deform or work

Tmelt
600

1000 1400

1800 T(C)

Adapted from Fig. 13.7, Callister, 7e.


(Fig. 13.7 is from E.B. Shand, Engineering Glass,
Modern Materials, Vol. 6, Academic Press, New
York, 1968, p. 262.)

Prof. Dr. H.Z. Harraz Presentation

Glass

24

Glass Types
Five common types of glass:
i) Soda-lime glasses
ii) Lead glasses
iii) Heat-resistant glasses OR
Borosilicate
iv) High-purity Silica glasses
v) Speciality glasses

13 March 2014

There are the following types: Fused silica glass


96% silica glass
Soda lime glass
Lead silicate glass
High lead glass
Boron silicate glass
Alumina borosilicate glass
Low alkali glass
Alumina silica glass
Glass ceramics

Prof. Dr. H.Z. Harraz Presentation

Glass

25

i) Soda-Lime-Silica Glasses
65% sand; 15% soda; 10% lime
In this glass component are:
71 73% SiO2
12 14% Na2O
10 12% CaO

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
The Na2O & CaO decrease the softening point of this
glass from 1600oC to 730oC, So that soda lime glass is
easier to form.
An addition of 1 4% MgO is added to Soda lime glass
to prevent cracks.
In addition of 0.5 1.5% Al2O3 is used to Increase the
durability

Soda-lime-silica glass is most commonly produced


glass which accounts for ~95% of all the glass
produced in the world.
Soda-lime-silica glass expands much when heated
Breaks easily during heating or cooling

Uses
Soda lime glass is used for flat glass, containers,
lightening products.
It is used where chemical durability and heat
resistant are not needed

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

26

ii) Lead Glasses

Lime and soda replaced with lead oxide (PbO)


Contains lead oxide (PbO) to improve refractive index
High refractive index- clarity sparkle
Softer cut and engrave
Good electrical resistance - electronics

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

27

iii) Heat-resistant (or Borosilicate) Glasses


Contains Boron oxide, known as
Pyrex.
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 - B2O3 aluminosilicate glass
with even better heat resistance

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

28

iv) High-purity Silica Glasses


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 (1500C,
produces high-surface silica soot thermally
sintered to pure silica at 1723 C)

SiO

Flame

2H2O + SiCl4
13 March 2014

+ 4HCl

Prof. Dr. H.Z. Harraz Presentation

Glass

29

v) Specialty Glasses
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
13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

30

v) Speciality (Cont.)
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.
light
AgCl/AgBr

Ag+ X-
Ag
+
X
dark
colorless

Blue-grey

Non-silicate glasses are becoming increasingly important for special optical


purposes,
for example in the use of glasses prepared from CaF2, AlF3 and P2O5
for infrared optics or the use of fluoride glasses for optical fibres

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

31

Heat Treating Glass


Annealing:
removes internal stress caused by uneven cooling.

Tempering:
puts surface of glass part into compression
suppresses growth of cracks from surface scratches.
sequence:
before cooling

hot

surface cooling

further cooled

cooler
hot
cooler

compression
tension
compression

Result: surface crack growth is suppressed.

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

32

a) Annealing Glass
Annealing is a process of slowly cooling glass to relieve internal
stresses after it was formed.
The process may be carried out in a temperature-controlled kiln
known as a Lehr.
Annealing glass is critical to its durability.
Removes internal stress caused by uneven cooling.
Glass which has not been annealed is liable to crack or shatter
when subjected to a relatively small temperature change 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.

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

33

b) Tempered Glass

The tempering process consists of the following steps:


1) First the glass is washed and then heated.
2) In order to temper glass, it must reach 1100F (the softening point for glass.)
3) The glass is then cooled with cold air. Quenching with forced cold air sets up the tension and compression
zones.
4) The tempered glass continues down the rollers to cool more and be packed for shipping. Glass to be tempered
must be cut to size before the tempering step.
A flow chart in the next slide provides a summary of the tempering process.

Tempered Glass: The Process

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

34

b) Tempered Glass (Cont.)


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

13 March 2014

Glass expands when heated


Quenching freezes this expansion on the
outside
Center cools more slowly, and contracts. Sets up
tension and compression zones.
Tempered Glass is required for door products and
some windows installed near doors. If tempering
is done improperly then distortion can result.
Tempered glass is stronger than annealed glass.
If annealed glass (raw float) has a strength factor
of 1, tempered glass would be 4.

Prof. Dr. H.Z. Harraz Presentation

Glass

35

What is the difference between (regular) annealed glass and tempered glass?

Annealed (regular) Glass


Advantages:
Cost
Limitations:
Breaks in sharp pieces
Not as strong as
Tempered Glass
Size limitations

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Tempered Glass
Advantages:
4 times the stronger than
annealed
Breaks into small, harmless
pieces.
Qualifies as Safety Glazing
Limitations:
Must be cut to size before
tempering
Optical distortion (roller wave,
strain pattern)

Prof. Dr. H.Z. Harraz Presentation

Glass

36

Examples of todays glass products:


Containers (jars and bottles)
Flat glass (windows, vehicle
glazing, mirrors, etc.)
Lighting glass (fluorescent
tubes, light bulbs, etc.)
Tableware (drinking glasses,
bowls, lead crystal, etc.)

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Laboratory equipments (test

tubes, cylinders, measuring


flasks, etc.)
TV tubes and screens
Decorative glass
Fiberglass
Optical glass
Vacuum flasks

Prof. Dr. H.Z. Harraz Presentation

Glass

37

CHEMISTRY OF GLASS MANUFACTURE


In general terms, soda-lime-silica glass manufacture involves melting the required

raw material mix at 1600C, which yields a very fluid melt, from which gases can
escape (especially carbon dioxide produced by the decomposition of carbonate raw
materials).
The glass is then worked to produce the articles required at about 1000C, followed
by annealing at 500-600C.
Example; the float glass process, used to produce flat panes of glass suitable for
windows, illustrates this well (Fig.3).

Fig.3: Diagram of the float glass process, showing the way a continuous ribbon of glass is drawn from the melting furnace, through
the float bath (which gives the perfect surface to the sheet) and then is annealed and allowed to cool before preparation for sale.

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

38

CHEMISTRY OF GLASS MANUFACTURE (Cont.)


A glass is little more than a rapidly quenched liquid
The term 'Glass' can be applied to many different materials, but in common
usage it refers to quenched silicate liquids, , which behaves as a solid but
retains the molecular structure of the liquid.
The production of commercial glasses is therefore dictated by the
application of phase diagrams which allow the melting behaviour of
particular compositions to be predicted and the optimum conditions for
glass manufacture to be identified.
The appropriate phase diagram is that for the system SiO2-CaO-Na2O (Fig.4).

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

39

CHEMISTRY OF GLASS MANUFACTURE (Cont.)


Name
Cristobalite
Tridymite
Quartz
Pseudowollastonite
Sodium silicate
Sodium disilicate
Sodium calcium silicate
Sodium calcium silicate

Sodium calcium silicate

Formula

Abbreviated formula

SiO
2
SiO
2
SiO
2
CaSiO
3
NaSiO
3
Na Si O
2 2 5
Na CaSi O
4
3 9
Na Ca Si O
2 2 3 9
Na Ca Si O
2 3 6 16

S
S
S
CS
NS
NS

2
N CS
2 3
NC S
2 3
NC S
3 6

Point O is the ternary eutectic,


at 725C, with the composition
5.2% CaO , 21.3% Na2O and
73.5% SiO2

Fig 4: Phase relation ships for part of the system SiO2-CaO-Na2O at atmospheric pressure (weight%).
The system includes the following crystalline phases:

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

40

CHEMISTRY OF GLASS MANUFACTURE (Cont.)

Liquidus phase relationships within the three-component system SiO2-CaO-Na2O go well beyond those relevant for glass
manufacture.
Consequently, Figure 4 focuses on the silica-rich corner of the triangular diagram, as this includes most glass compositions. In
this region, the silica mineral on the liquidus is cristobalite, tridymite or quartz (depending on temperature), with very steep
temperature gradients particularly towards more sodic compositions. Towards the lime apex, a field of two liquids is drawn; in
this field, liquid compositions separate out into two contrasting liquids, one silica-rich and one lime-rich.
These two liquids are immiscible in the same way that oil and water are immiscible, and like a good mayonnaise they are
opaque to light and can be quenched to produce an opaque white solid. The other liquidus fields show shallower temperature
gradients.
On the boundaries between them arrows are marked to show the "downhill direction". These all converge on a single point,
where the temperature at which liquid can exist is lowest, which is a ternary eutectic. The ternary eutectic composition can be
read from the compositional axes and corresponds to 5% CaO, 21% Na2O, and 74% SiO2. The minimum temperature can be
read from the contours is 725C.
In order to decide on the optimum blend of ingredients required to make a soda-lime-silica glass, the ternary liquidus diagram
can be used to indicate the temperature required to initiate melting. The ternary eutectic composition is therefore the one
which appears to be ideal for glass manufacture, as it will begin to melt at the lowest temperature, saving energy and
manufacturing costs. Melting is carried out at 1600C to give enough superheat to ensure that all of the solid grains within the
raw materials dissolve within the liquid and to ensure that the viscosity of the liquid is sufficiently low that gases can escape.
Compositions which are more silica-rich have a rapidly rising liquidus temperature, and may not completely melt, leaving a
glass which contains crystals of a silica mineral or bubbles and appears frosted. It is therefore important to use this and similar
diagrams not only to design batch mixes but also to diagnose problems which arise when glasses are not correctly made.
The sources of soda and lime are respectively sodium carbonate (soda ash) and limestone (dolomite is used if magnesium is
needed). These materials decompose on heating with the loss of carbon dioxide. Thus, in the formulation of batches consisting
primarily of silica sand, limestone and soda ash, proportions must be corrected to take into account the loss of carbon dioxide
so that they correspond to the compositions required for the finished glass. In order to carry out this correction, relative
atomic masses (atomic weights) are used to determine the proportions of CaO within CaCO3 and Na2O in Na2CO3:
Relative atomic masses: Ca = 12 ; O = 16 ; Na = 23 ; Ca =40
Relative molecular masses:
CaO = 56 ; Na2O = 62; CO2 = 44, CaCO3 = 100; Na2CO3 = 106
Therefore;
100 tonnes of limestone (CaCO3) yields 56 tonnes of CaO and 44 tonnes of CO2. and
100 tonnes of soda ash (Na2CO3) yields 100 x 62/106 = 58 tonnes of soda and 42 tonnes of CO2

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

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

Fig. 14

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

42

Recycling of Glass
Recycle of glass is mostly used for packaging
Recycle process

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

43

Virtification
Definition:
a new technology has been
discovered to use recycle glass for
radioactive waste management

Process:
melt glass together with
radioactive waste in barrels or
some other container
glass will then bind up with
radioactive contamination into a
huge glass block
radioactive waste is bond by the
glass and become immobilized
keep radioactive waste from
interacting with water, stop
spreading the waste
Fig. 20
www.vitrification.com/ vitrification.htm

13 March 2014

Prof. Dr. H.Z. Harraz Presentation

Glass

44

Good & Bad of Virtification


Volume percent of vitrified product
compared to the original waste volume

Benefit of virtication:
Prevent radioactive waste
pollution
Minimize the amount of glass
waste produced
Increase the efficiency of glass
use (to stabilize hazardous
waste)
High volume reduction of waste
Landfill space can be saved

Fig. 21

13 March 2014

www.vitrification.com/ vitrification.htm

Prof. Dr. H.Z. Harraz Presentation

Glass

45