by
Hassan Z. Harraz
hharraz2006@yahoo.com
OUTLINE OF TOPIC 6:
Glasses
Raw Materials:
a) Silica sand
b) Limestone
c) Soda ash
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
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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
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Glass
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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
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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
Minimum
SiO2
99.7
Maximum
Fe2O3
0.013
Maximum
Cr2O3
0.00015
99.6
98.8
97.0
99.0
0.010
0.030
0.25
0.10
0.0002
0.0005
-0.0001
Opthalmic glass
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).
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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:
Calcination Process
Calcined lime
Hydrated lime
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Naturally:
Synthetically:
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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.
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17%
5%
72%
6%
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Glass
silica sand
soda ash
lime
other ingredien
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www.glassforever.co.uk/howisglassmade/
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Glass
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The Process
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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
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Glass
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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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Glass
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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.
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Glass Properties
Specific volume (1/r) vs Temperature (T):
Crystalline materials:
Specific volume
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
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Viscosity [Pa
s]
10 14
strain point
annealing range
10 10
10 6
10 2
1
200
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Tmelt
600
1000 1400
1800 T(C)
Glass
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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
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Glass
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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
Uses
Soda lime glass is used for flat glass, containers,
lightening products.
It is used where chemical durability and heat
resistant are not needed
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SiO
Flame
2H2O + SiCl4
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+ 4HCl
Glass
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v) Specialty Glasses
Coloured glass:
MnO2 violet,
CoO blue,
Cr2O3 - green
Opal glass:
Frosted glass:
satiny look when exposed to HF
4 HF SiO2 SiF4 2 H 2O
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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
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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
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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.
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b) Tempered Glass
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What is the difference between (regular) annealed glass and tempered glass?
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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)
Glass
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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.
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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
Fig 4: Phase relation ships for part of the system SiO2-CaO-Na2O at atmospheric pressure (weight%).
The system includes the following crystalline phases:
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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
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Recycling of Glass
Recycle of glass is mostly used for packaging
Recycle process
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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
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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
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www.vitrification.com/ vitrification.htm
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