Ceramic Raw Materials To Glasses

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Silicate structures
• The radius ratio for Si-O is 0.29 so silicon and oxygen form tetrahedral
coordination
• Each oxygen will left with -1 charge, resulting in SiO4-4 tetrahedral group
that can be bonded to other cations
• SiO4-4 forms the basic building block of the silicate minerals
• Pauling‟s rule state that Si+4 due to its high valence should be far
separated from other Si+4 ions. Thus, only corners oxygen atoms are
shared with other SiO4-4 groups.
Various ways of linking SiO4-4 tetrahedraons

• Six general types of Silicate groups depending upon the linking of SiO4-4
1. Nesosilicates
• Corner oxygens are not shared with other SiO4-4

tetradherons. SiO4-4 are isolated
• SiO4-4 are linked together by cations Mg+2, Fe+2 or Ca+2
• Example Olivine, almandine, zircon minerals.
Olivine structure
(Mg2SiO4)
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2. Sorosilicates
• One corner oxygen is shared with other SiO4-4 tetradherons.
• Disilicate group has two Si ions and 7 oxygens (Si2O7-6)
• Also called pyrosilicates
• Example: thortveitite (Sc2Si2O7), hardystonite, Ca2Zn(Si2O7).

3. Cyclosilicates
• Two of the oxygen of tetrahedron are shared and structure is

arranged in a ring
• Si6O18-12
• Example: Beryl - Be3Al2Si6O18
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4. Chainsilicates
• Two of the oxygen of tetrahedron are linked to form a long single

chain of linked SiO4-4 tetrahedrons, resulting silicates are called
isosilicates
• Example of isosilicate (single chain silicate): orthopyroxenes

(Mg,Fe)SiO3 or the clinopyroxenes Ca(Mg,Fe)Si2O6
• If two of chains of SiO4-4 linked together, so that each tetrahedron

share 3 of its oxygen ions, double chain silicates (inosilicates) will
form.
• Example of inosilicates are doubletremolite - ferroactinolite series -

Ca2(Mg,Fe)5Si8O22(OH)2.
Chain Silicates
Si2O6-4
Si4O11-6
Isochain silicate Doublechain silicate
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5. Sheet silicates (phyllosilicates)
• Three of the oxygen of tetrahedron are linked to form an infinite

sheet of shared SiO4-4 tetrahedron
• Basic structural group is Si2O5-2
• Examples: Clays, mica, talc minerals have basic building block of

two-dimensional sheet silicates
Si2O5-2
Phyllosilicates

6. Framework silicates (Tectosilicates)
• All corner oxygen of tetrahedron are shared with another SiO4-4

tetrahedron, then a framework structure develops
• Basis of 3-D structures
• Basic structural group is SiO2
• Examples: Quartz, cristobalite and tridymite are all based on frame work
structures.
Framework silicates
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Traditional Ceramic Raw Materials

• Clays
• Silica
• fluxes
Silica
SiO2 exists in three polymorphic forms
 Quartz
Tridymite
Cristobalite
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Quartz
• Framework silicates
• Every oxygen of tetrahedron is shared with other
tetrahedron
• Si-O-Si bonds joining neighbours are in the form of
spiral chains (helices)
Quartz
Not possible
Reality
In quartz the Si-O-Si bond angle joining tetrahedrons is between 140-153 ᵒ.
Quartz is stable up to temperature of 870 ºC
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Structure of Quartz
• Tetragonal structure consists of many spiral chains
• Tetragonal structure is stable up to temperature of 573 ºC
• Densest of all the silica forms having specific gravity 2.65
Quartz exhibit strong

piezoelectric effect that
is basis for its use for
quartz oscillaotrs, quartz
watches,etc.
Structure of Tridymite
• SiO4-4 tetrahedra forms rings
• Tridymite made up of layers of paired tetrahedra, with
successive layers alternating in stacking
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Structure of Tridymite
• Tridymite exhibit orthorhombic and hexagonal structure.
• Tridymite is stable between 870 ºC and 1470 ºC.
Structure of Cristobalite
• SiO4-4 tetrahedra forms rings
• Rings in both tridymite and cristobalite are slightly distorted
(more in later) and so the Si ions are not in the same plane
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• Cristobalite exhibits tetragonal or pseduocubic structure.
Less open structure than tridymite, this less open structure leads to
higher density of cristobalite (2.32) than tridymite (2.28)
Difference in packing of oxygen atoms in

tridymite and cristobalite
Cristobalite Tridymite
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Pressure-Temperature diagram of Silica
Conversions of Silica
• Conversions of silica from one crystalline form to another involves
breaking of Si-O bonds i.e. separating the tetrahedra and then
joining them again differently.
• Heating above certain temperature for a considerable time, it is

possible to gradually convert one form into another. These
reactions can be speeded up by catalyst (mineralisers) e.g., lime
promotes formation of cristobalite and iron compounds favour the
formation of tridymite.
• All three forms are stable at room temperature

• Volume expansion occurs in the conversion of one form to another
870 ᵒC
1470 ᵒC
Quartz Cristobalite Tridymite
Not reversible
At 1300 ºC, it takes 10 days to convert Form in the manufacture

100 % quartz to 100 % cristobalite. of silica bricks
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Conversions of Silica
• Conversions are very sluggish and reverse changes on cooling, i.e.,
from cristobalite and tridymite back to quartz, are so slow as to be
impractical.
• Change from quartz to tridymite is so slow and may not take place
at all without the presence of some impurity.
• By heating quartz to 1470 ºC or more, cristobalite forms.
• Cooling of cristobalite between 870-1470 ºC for considerable time,
tridymite forms.
• Rate of formation of one form to another also increases by
increasing the fineness of the material.
870 ᵒC
1470 ᵒC
Quartz Cristobalite Tridymite
Not reversible
At 1300 ºC, it takes 10 days to convert Form in the manufacture

100 % quartz to 100 % cristobalite. of silica bricks
Inversions in Silica
• All three forms of silica are relatively stable within the temperature
ranges. However, minor changes in structure within one form of
silica occur called inversions. (Require small energy changes)
• Two polymorphs of Quartz
573 ºC
α-quartz β-quartz
Si-O-Si bonds
Straighten slightly,
atoms become less
closely packed and
expansion occurs.
Linear expansion of 0.45 % occur on displacive phase transition of quartz,

this inversion leads to cracking of ceramic ware if the cooling occurs
rapidly through inversion temperature.
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• Transition in Cristobalite
220-280 ºC
α-Cristobalite β-Cristobalite
1 % expansion
• Transition in Tridymite
117 ºC 163 ºC
Tridymite (I) Tridymite (II) Tridymite (III)
0.1 % expansion
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 Inversions occur instantaneously but conversions take very long time.
 At inversion temperatures size change occur very rapidly. Such rapid

change can lead to cracking during firing if the temperature is taken
up or dropped too quickly through inversion temperatures during
firing.
 Sudden expansions are the cause of spalling in silica refractories.
 Linear expansion of silica at 1000 ºC is about twice that of clay, the

expansion of pottery body is often purposely increased by the addition
of flint.
Volume Expansion vs Temperature for various

polymorphs of silica
Vitreous silica expands only 0.05 %, substantially lowest than all other forms
of silica. It can withstand sudden changes of temperature without cracking or
shattering. Vitreous silica is therefore useful for making laboratory ware.
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Silica bricks
 Have high load bearing capability at elevated
temperatures.
 Used for sprung arches as roofs for open-hearth furnaces,
glass tanks, kilns and coke ovens, etc.
 Bricks are fabricated from ground ganister rock (quartzite)
containing 98 % silica to which is added 2 % CaO.
Fig. Quartz grain with

Cristobalite formed at
surface
Silica bricks
 Fired brick consists of shattered quartz grains that have
been completely transformed into cristobalite.
 Fire bricks have small amount of unconverted quartz (ca.
10 %) and nearly equal amounts of both cristobalite and
tridymite.
 Excessive quartz is deleterious.
 Long firing times favour formation of tridymite.
 Quartz first transforms into cristobalite, starting at grain
edges. This dissolves in the calcium silicate liquid phase
and precipitates as tridymite. During firing the amount of
quartz present continuously decreases, the amount of
crsitobalite initially increases and then decreases, and the
amount of tridymite continuously increases.
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Advantage of Inversion
“Cristobalite Squeeze” to prevent crazing of glaze (the
cracking of glaze due to failure in tension)
Glaze put into compression by Cristobalite squeeze
Other forms of Silica

 Silica gel
 Acidification of sodium silicate solutions result in
precipitated gelatinous mass, which can be extracted and
dried.
 Silica gel has no definite structure and is non-crystalline.
 Silica tetrahedra are joined randomly without any pattern.
 Vitreous silica
 Rapid cooling of liquid silica (melting point 1710 ºC) also
do not allow silica tetrahedra to arrange themselves in a
proper order, and so they join in a random manner to form
a glass (super-cooled liquid)
 Vitreous silica is also amorphous like silica gel
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Chemical properties of Silica

• Crystalline silica has good resistance to most of the aqueous
alkalis and acids, but not to hydroflouric acid.
• HF reacts with silica to form SiF4 (gas).
• Silica is attacked by fused alkalis and alkaline slags, forming

silicates. For example, silica is fused with sodium hydroxide to
form sodium silicate.
• Silica is not attacked by ferric oxide, hence silica bricks are used
in open-hearth steel furnaces.
• Silica gel is more reactive, because of its fine size.
• Silica gel is powerful water-absorbant (desiccant) and is attacked

by aqueous alkalis.
Occurrence of Silica
Silica occurs in nature as

• Quartzite rock and ganister
• Sand or sandstone
• Flint pebble
• Chalcedony
(crypto (sub-microscopic)-crystalline
• Opal quartz)
• agate
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Occurrence of Silica
Flint
• Form of silica, used in pottery and refractories
• Small crystals of quartz held together by water
molecules
• Slightly lower specific gravity than quartz (2.62)
• On calcining, combined water is driven off at about
400 ºC, this makes the large aggregates to loose
strength and become crumbly
• Occurs as nodules and pebbles on beaches adjacent
to Chalk, hence contain lime as impurity
• At 1100 ºC, quartz changes to cristobalite, this
conversion is promoted by the presence of impurities.
Clays
Formation
Decomposition of igneous rocks such as granite which
themselves formed by solidification of lava.
Composition of granite
Mica (K2O.3Al2O3.6SiO2.2H2O)
Quartz (SiO2)
Felspar (K2O.Al2O3.6SiO2) (least stable in air and water)
Decomposition/Kaolinisation of Felspar
K2O.Al2O3.6SiO2 + 2H2O Al2O3.2SiO2.2H2O

-K2O, -4SiO2 Kaolinisation
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Classification of Silicates
Clays
Kaolinite
• Crystalline material
• Crystals are flat and hexagonal in shape (2-D crystals)
• Sizes in the range of 1-10 µm in diameter
• Thickness of these crystals is less than 100 nm
• Residual clays have fewer impurities while sedimentary
clays have finer particles and highly contaminated with
other materials.
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Structure of Kaolins
• Clays are combination of two layer structures

Silica sheet (composed of silicon and oxygen atoms in the
form tetrahedron)
The [Si2O5]n2n- tetrahedral silica sheet.
Structure of Kaolins
• Gibbsite layer ( Al(OH)3 composed of aluminium atoms

and hydroxyl groups)
• Octahedrons join together and each OH groups is shared
with two aluminiums
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Octahedral Gibbsite sheet
The n[Al(OH)3] octahedral gibbsite sheet.
Dimensions of hexagonal rings in the silica and gibbsite sheets are

approximately same
Octahedral Gibbsite layers form sheets
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Clay mineral structure
Ions Molecules Sheets
Layers
Crystal
Sheet upon sheet = Layer
Layer upon layer = Crystal
Different clays are formed by layering silica and gibbsite sheets together
Formation of Kaolinite
• Condensation of silica and gibbsite layer in 1:1
The Stackings of Kaolin layers.
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Basal
spacing,
7.2 Ǻ
• Condensation of [Si2O5]-2 and Al(OH)3 layers occur by elimination of
hydroxyl groups in the gibbsite structure
• Structural formula of Kaolin mineral is Al2(OH)4. Si2O5
The combined tetrahedral and octahedral layers. The structure of the Kaolin minerals.
• Commonly written formula Al2O3.2SiO2.2H2O (H2O is not present as water

molecules but as hydroxyl groups)
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Forces of attraction in Kaolinite sheets

• Commonly written formula Al2O3.2SiO2.2H2O (H2O is not
present as water molecules but as hydroxyl groups)
• All types of Kaolinite have same basic structure but differ
in the manner of stacking to form crystal
• Weak Van der Waals‟ forces and hydrogen bonds between

the OH groups in gibbsite layer of one kaolin sheet and
the oxygens in the silica layer of next kaolin sheet
Kaolinite crystals
• The bonds between octahedral and tetrahedral layers and
in the a and b directions are very strong.
• Fewer layer can stack and this result in a very thin crystal
in c direction
• Crystal are long and wide with basal spacing 0.72 nm
• Hexagonal crystal result due to the inherited hexagonal
structures in both the tetrahedral and octahedral layers.
a
b
Fig. Hexagonal clay crystallite composed

of many stacked layers of kaolin sheets.
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Kaolinite crystals
Other types of Kaolin minerals

• All Kaolin minerals have same 1:1 stacking and the same
structural formula Al2(OH)4.Si2O5.
 Nacrite
Kaolin sheets lie directly over one another.
 Dickite
Atoms in Kaolin sheets are not directly over one another but
are displaced to fixed distance.
 Halloysite
Displacement between Kaolin sheets are completely
random.
Crystal size differ for various polymorph of Kaolin minerals

due to the difference in stacking of layers.
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Halloysite Nanotubes

Halloysite occurs in two forms: one hydrated, in which there is a layer of water
molecules between the layers, and one dehydrated. The hydrated form has a
basal spacing of 10A˚ (Fig. 4) and the dehydrated form, 7.2A˚ . The shape of
halloysite is elongate tubes (Fig. 5) whereas the shape of kaolinite is pseudo-
hexagonal plates and stacks .
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Physical Characteristics of Kaolinite
Hardness on Moh scale = 1.5

Fuse at = 1800 °C
Chemically inert
Hydrophilic and disperses in water
After thermal treatment or calcining can
be used as filler.
Kaolinit is soft and cause minimal wear
and tear of machinery or equipment
Kaolin Clays
Clays having Kaolin as the main clay mineral are called
Kaolin clays.
Types of Kaolin Clays
 China clay
 Ball clay
 Fire clay
 Brick clay
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China Clays
• Residual clays (primary clays) (deposited at place of
origin)
• Composition
Kaolinite mineral contaminated with silica, mica, felspar and
partly decomposed felspar
• Much finer than contaminated minerals can be readily
purified by sedimentation
• After purification it is obtained as white clay
• It is called white burning due to its low content of colouring
impurities, particularly iron and titanium compounds.
• Refractory clay due to low impurity content
• Used in production of white decorative ware and as
refractory clay, paper manufacturing and ceramic industry
Ball Clays
• Sedimentary clays (transport on relatively short distance)
• Finer size and high organic content
• Clay mineral is Kaolinite
• Much finer than china clay
• Due to its fine size it has higher plasticity and dry strength
• Higher impurity content than china clay
• Impurities cannot be removed easily due to their much finer
size
• The colour of unfired ball clay is due to organic matter (unfired
colour is poor guide to colouring impurities)
• Dark clay may fire to lighter colour
• Iron and titanium give the clay fired colour which vary from off
white to dark brown
• Lower refractoriness and fired colour are the disadvantages of
ball clay over china clay
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Fire clays
• Formed from felspar, Clay mineral is Kaolinite
• Mostly sedimentary clays (transported over longer
distance before being deposited)
• Found with or near coal measures
• It is purposed that vegetable life (later converted to coal)
had extracted alkali compounds from fireclay and gave
them high refractory nature
• Fine particle size, coarser than other clays
• Plastic
• Have colouring impurities like ball clays and fire to a buff
colour
• Mainly used for their refractory properties due to their low
alkali content
Brick clays
• Composed of variety of clays of varying compositions
• Clay mineral being Kaolinitic or illitic
• Very high iron content resulting in reddish fired colour
• Lot of impurities including gross amount of calcium
compounds
• Fluxes are not needed for firing due to high impurity
content and can be fired at low temperatures
• High organic matter reduce the fuel required for firing of
the ware
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Montmorillonites
• Montmorillonite is 2:1 (Silica : Gibbsite) layered smectite clay mineral.
• Smectite minerals are sodium montmorillonite, calcium
montmorillonite, saponite (magnesium montmorillonite), nontronite
(iron montmorillonite), hectorite (lithium montmorillonite), and
beidellite (aluminum montmorillonite).
• One layer of gibbsite is condensed with a silica layer with
replacement of hydroxyl groups.
• Two silica layers sandwiching between them a gibbsite layer
• Sodium montmorillonite occurs when the charge deficiency is
balanced by sodium ions and water and the basal spacing is 12.2A˚
Montmorillonites
• Instead of Gibbsite, Brucite Mg(OH)2 or Ferrous hydroxide
Fe(OH)2 can be present
• Condensation of a Silica layer on each side of Gibbsite
leads to the structural formula Al2(OH)2.2Si2O5 or
Al2O3.4SiO2.H2O (Pyrophyllite, a group of
Montmorillonite)
Silica
Al (OH)3 Gibbsite
Silica
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Formation of Kaolinite and Pyrophyllite
Si2O5
(OH)3 OH
Al2 + [Si2O5]-2 2(OH)- + Al2
(OH)3 Replaced (OH)3
Tetrahedral layer
or
Gibbsite layer
Al2O3.2SiO2.2H2O
+ Kaolinite
Tetrahedral layer
2[Si2O5]-2
Si2O5
4(OH)- + OH Al2O3.4SiO2.H2O
or
Replaced Al2 Pyrophyllite
OH
Si2O5
Montmorillonite minerals
Two major types of minerals are:
 Pyrophyllite (Bentonite clay form from volcanic ash)
 Talc
• Mg3(OH)2.2Si2O5
• Talc is also known as steatite, soapstone and French
Chalk
Brucite sheet
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Electrical neutrality in Montmorillonite
Al2 (OH)2 2Si2O5
Illite
• The structure is a 2:1 layer in which the interlayer cation is
potassium.
• One sixth of Si+4 is replaced by Al+3 ( Isomorphous substitution)
• Water molecule cannot penetrate between layers due to strong
interlocking ionic bond which holds the individual layers together.
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Physical Characteristics of Smectite

Surface area= 150-200 m2/g
Swelling capacity = 10-15 times in water
Ca and Na montrmorillonites have good
properties needed for bonding sands in
foundry molds. Those properties are green
compression strength, dry compression
strength, hot strength, flowability,
permeability, and durability.
Fine particle size and flake shape makes

impermeable membranes to the movement of
water.
Thixotropy:
Thixotropy is the ability to form a gel upon standing and to become fluid
when stirred or agitated.
This property makes sodium montmorillonite and hectorite excellent
suspending agents.
Sodium montmorillonite is the premier drilling mud and hectorite is used in
pharmaceutical and medicinal suspensions and in some high quality paint.
Comparison between Kaolinite and

Montmorillonite
Forces of attraction
Kaolinite has van der Waals‟ forces and hydrogen bonding
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Montmorillonite
Forces of attraction
Montmorillonite has no hydrogen bonding because outer
layers are silica layers .
Forces of attraction are only vad der Waals‟ forces so sheets
are weakly held together.
Basal spacing is 1-6 nm depending upon type of liquid
adsorbed between layers.
Swell in liquids.
Basal spacing is measured using XRD

Montmorillonite
Surface area
 Kaolinite has the external surface area i.e., basal planes
of hexagonal crystal and edges
• Monmorillonite sheets can be separated within the crystal

so not only external but internal area is also available.
• Montmorillonite has greater overall area than Kaolins.
• Due to high surface area they are used as adsorbents and
catalysts.
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Formation of Nanoclays
High Swelling characteristics of bentonite clays can be used
to produce nanoclays.
Bentonite clays swell in liquids due to very weak van der

Waals‟ forces between sheets.
Nanoclays are used as fillers to produce

compsites
- Nano Clays
 Clays are hydrophilic in nature, surface treatment
required to make hydrophobic
 Intercalated and exfoliated in polymers
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Intercalation and Exfoliation of clays
Determination of basal spacing of clays
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- Nano Clays
 Nanoclays addition into plastics increase strength, better
barrier properties and high heat distortion temperatures
are achieved at very low loading of filler.
 High levels of flame retardancy can be achieved.
Mica
• Mica is derived from talc or pyrophyllite by the isomorphous substituion.
• Replacing one in four of the Si atoms by Al in

Al2Si4O10 (OH)2
result in a charged lattice having formula
[Al2(Si3Al)O10(OH)2]-1
• Al is replaced in Silica layer
• If negative charge of one unit is balanced by the introduction of a

potassium ion, K+, the following formula results:
K+.Al2(Si3Al)-O10(OH)2 or KAl3Si3O10(OH)2 Potash mica or mucovite
• Replacement of two atoms out of four Si with two Al can result in a lattice
with -2 charge: [Al2(Si2Al2)O10(OH)2]-2
• A divalent cation can balance a charge like Ca+2
• Ca+2.Al2(Si2Al2)-2O10(OH)2 Calcium mica or margarite
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Mica
Potassium ions between layers in muscovite (potash) mica

• Micas can also be derived from Talc, e.g, K Mg3 (Si3Al)O10 (OH)2 Phlogopite
• Mica does not depend on van der Waals’ bonding , because positively charged
ions hold the negatively –charged units together.
• Bonding is still weaker than the other bonds in the lattice , and therefore micas
can be cleaved more easily along the unit planes than across them.
• Mica is used in capacitors, paints, optical devices, polymers, substrate for

deposition.
Calculation for finding Composition of Clays

A typical Ball clay consists of
• Kaolinite
• Quartz
• Mica
On performing chemical analysis we will find following:
Oxide Weight %
SiO2 51.13
Al2O3 29.30
Fe2O3 2.78
TiO2 2.08
CaO 0.15
MgO 1.68
Na2O 0.12
K2O 2.8
Ignition loss 9.54
Total 99.58
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Calculation of Alkalis
• Alkalis are present solely as micas. Taking two “ unit formula” of soda
mica , which can be written as Na2O.3Al2O3.6SiO2.2H2O.
• 𝑂𝑛𝑒 𝑝𝑎𝑟𝑡 𝑏𝑦 𝑤𝑒𝑖𝑔𝑕𝑡 𝑜𝑓 𝑁𝑎2𝑂 =

764.21
𝑜𝑟 12. 33 𝑝𝑎𝑟𝑡 𝑏𝑦 𝑤𝑒𝑖𝑔𝑕𝑡 𝑜𝑓 𝑠𝑜𝑑𝑎 𝑚𝑖𝑐𝑎
61.99
• The percentage of Na2O in this clay is 0.12 % and the percentage

soda mica is therefore 0.12 x 12.33 = 1.48 %
• 𝑂𝑛𝑒 𝑝𝑎𝑟𝑡 𝑏𝑦 𝑤𝑒𝑖𝑔𝑕𝑡 𝑜𝑓 𝐾2𝑂 = 8.46 𝑝𝑎𝑟𝑡𝑠 𝑏𝑦 𝑤𝑒𝑖𝑔𝑕𝑡 𝑜𝑓 𝑝𝑜𝑡𝑎𝑠𝑕 𝑚𝑖𝑐𝑎
• The percentage of K2O in this clay is 2.80 % and the percentage

potash mica is therefore 2.8 x 8.46= 23.72 %
Calculation of Alumina
• Alumina is combined in three minerals- Kaolinite, Soda mica and potash mica
• % of soda and potash mica is known (previous slide)
• Al2O3 can be calculated from their formulae and subtracting this amount from
the total alumina (29.3%) , we can find how much Al2O3 is present as Kaolinite,
and hence percentage of Kaolinite.
• Alumina in soda mica = 40.02 % ( 1 part of soda mica contains 0.4002 parts by
weight of Al2O3), So the percentage of Al2O3 combined as soda mica in clay =
1.48 x 0.4002 = 0.59 %
• Percentage of alumina in potash mica is 38.40 % and the percentage of Al2O3

combined in potash mica in the clay = 23.72 x 0.3840 = 9.11 %
• Total Al2O3 combined in the form of mica = 0.59 + 9.11 = 9.70 %
• The remainder of alumina (combined as Kaolinite) = 29.30-9.70 = 19.60 %

• 1 part by weight of Al2O3 corresponds to 2.532 parts by weight of Kaolinite
(Al2O3.2SiO2.2H2O). Therefore percentage Kaolinite in the clay = 19.60 x 2.532 =
49.63 %
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Calculation of Silica
• Silica is present as “free silica” or quartz and combined in three
minerals- Kaolinite, Soda mica and potash mica
• % of soda, potash mica and Kaolinite is known (previous slide)
• Silica combined as soda mica = 1.48 x 0.471 = 0.72 %
• Silica combined as potash mica = 23.72 x 0.452 = 10.72 %
• Silica combined as Kaolinite = 49.3 x 0.45 = 23. 08 %
• Total combined silica = 0.72 + 10.72 + 23.08 = 34.52 %
• Total silica from analysis (Table) = 51.13 %
• Free silica or quartz = 51.13- 34.52 = 16.1 %
Final Clay mineral composition
Mineral Weight %
Soda mica 1.5
Potash mica 23.7
Kaolinite 49.6
Quartz 16.6
Miscellaneous oxide 8.6
(Fe2O3, TiO2, CaO, MgO
and organic matter)
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Conversion Table
Fluxes
• Lowers the fusion temperature of the material or mixture
• Any materials ability to act as flux not only depends on its
own nature but it also depends on the material to which it
is added.
• Fluxes are higher in alkali or alkaline earth content.
• Addition of fluxes in clays lower the vitrification
temperature of clays.
• For producing high refractory clay products, clays should
have lower fluxing impurities.
• For non-refractory products used at room temperature,
fluxes must be added to reduce the firing temperature.
• Fluxes aid the formation of glass which if not present
make the resulting article very weak.
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Fluxes
Examples
• Hard paste porcelain (china clay 40 %, ball clay 10 % ,
feldspar 25 % and flint 25 %) used to make laboratory
ware. It has to withstand temperature of 1100-1200 ºC, so
relatively small amount of flux is added and the body is
fired to a high temperature (ca. 1400 ºC).
• Vitreous earthenware used for production of hotel
tableware (30 % china clay, 10 % ball clay, 22 % feldspar
and 35 % flint) and sanitary ware is not subjected to
higher temperatures, so more flux can be afforded. This
will allow glass formation in the ceramic body at low
temperature and provide necessary strength at a lower
firing temperature (1150 ºC)
Fluxes
Examples
• Stoneware clays These have enough natural flux and are
used without addition of fluxes. The natural fluxes are
present in mica, felspar, lime, magnesia and iron oxides,
and can be fired at 1200-1300 ºC to give a vitreous body
without addition of further flux.
• Building brick clays have enough fluxes to give strength to
the bricks when fired at about 1100 ºC.
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Various Fluxes
 Feldspar
• It has same structure as silica but some silicon is replaced by
aluminium and the resultant negative charge is satisfied by
sodium, potassium, calcium or barium.
• Orthoclase is KAlSi3O8 (Potash feldspar)
• Albite (NaAlSi3O8).(Soda feldspar)
• Anorthite CaAl2Si2O8 (Limefeldspar) (half of silicon in silica
replaced by aluminium, and the negative charge is satisfied by
calcium)
• Celsian BaAl2Si2O8
• High soda feldspar enable vitrification at lower temperatures in
a ceramic body than high potash feldspar. This result in
warpage during firing, since the liquid forms of lower viscosity
than that formed when potash feldspar is used.
• The flux should be uniformly distributed throughout the body. It
should be finely ground before mixing.
• Feldspars are used in ceramics, glazed, enamels and glasses.
Various Fluxes
 Cornish stone
• It consists of felspar, quartz, clay minerals, mica, fluorspar
and other minor impurities.
• Cornish stone is classified on colour basis ( hard purple,
mid purple and white)
• Purple variety has the highest content of felspar and white
variety has the lowest felspar.
• Purple variety is the strongest flux.
• The colour is due to fluorspar or calcium fluoride (CaF2),
which contains colouring impurity.
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Various Fluxes
 Bone Ash
• Calcined bone is tricalcium phosphate Ca3(PO4)2.
• It contains organic residue which gives some plasticity to
the body.
• It is used as in combination with felspar or cornish stone,
and enhances the translucency of the fired body.
• Oxen bones or other animal bones are used.
• The temperature of calcination determines how much
organic material is left in the bone, and therefore the
amount of plasticity the bone will contribute to the body.
• Over-calcined bone have very little or no organic material
remaining, and will contribute little to the plasticity of the
body. Under-calcined may contain excessive organic
matter which may cause the frothing in the body slip,
leading to faults in the product.
Thermal decomposition of Kaolinite

Four thermal decomposition reactions take place:
(i) Low temperature reaction take place at 400 ºC
Loss of adsorbed water at 100 °C
(ii) Intermediate temperature reactions, mainly between 400

and 650 ºC
Dehydroxylation (removal of –OH groups), starts at 400 ºC

and completes at 650 ºC (strong endothermic peak in DTA)
Mass loss corresponds to 13.96 % (theoretical value)
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Dehydroxylation is affected by various factors:
 Degree of disorder of kaolinite structure

 Pressure and partial vapour pressure of water
 Heating rate
 Particle size
Product of Dehydroxylation
Metakaolinite (almost amorphous, topotactic process in

which anionic arrays remain at their places and cations
reorganization occurs)

(iii) Metakolinite transforms to Spinel phase at ca. 950 ºC
(exothermic peak appears in Differential Thermal Analysis)
Al-Si spinel persists up to 1100 ºC.
Fig. Precipitation of
Al2O3 from spinel solid
solution on cooling
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(iv) Above 1100 ºC, Mullite phase forms and its amount
increases with increase of temperature from 1000 to 1300 ºC
Mullite
Mullite has needle like morphology, low porosity, low

shrinkage and high resistance to slag.
Typical composition (Al2O3= 75.2%, SiO2= 24.5%, and Na2O=
0.20%)
Fig. Mullite crystals forms in silica matrix by heating Kaolinite
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Triaxial Whiteware Compositions

Traditional ceramic composition consists of
• Clay
• Feldspar
• Flint Chemical composition of clays
Some triaxial whiteware compostions

Role of clay
• Providing fine particle size and good plasticity for forming
• Forming fine pores and more or less viscous liquid
essential to the firing process
Feldspar act as flux

• Forms a viscous liquid at firing temperature
• Aids in vitrification
Flint source of silica

• Remains unreactive during low temperature firing
• Forms high viscosity liquid at high temperature
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Ternary Phase diagram
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 Various compositions differ in terms of relative amounts
and kinds of feldspar and clay used.
 Increasing content of feldspar, increases amount of liquid
formed at eutectic temperature and vitrification proceeds
at lower temperature. As a result, there is more liquid in
the ceramic body, higher vitrification and higher
translucency obtained.
 Increasing amount of clay result in higher vitrification
temperature and the firing becomes more difficult and
expensive. However, forming processes becomes easier,
and the mechanical and electrical properties of resulting
body are improved.
 The amount and kind of clays used depends on the
forming processes and the final properties required in the
ceramic ware.

Examples
Dental porcelain
Required high translucency and are formed in small simple
shapes so high-feldspar-low-clay compositions are used.
Hard porcelain for artware and tableware

Must be formed into complicated shapes so high clay
content is required to ease forming.
A balance between china and ball clay is required for

producing desired properties.
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Firing of clay-feldspar-flint mixture
• Changes that occur during firing of mixture depends on
the composition and conditions of firing.
• The ternary eutectic temperature in the system feldspar-
clay-flint is at 990 ºC, whereas feldspar grains themselves
form a liquid phase at 1140 ºC.
• At higher temperatures an increasing amount of liquid is
formed which at equilibrium would be associated with
mullite as solid phase.
• Higher temperatures more liquid and shorter times of firing
and vice versa.

Firing of clay-feldspar-flint mixture
Quartz
• Initial mixture
Clay
Feldspar
• At 1140 ºC feldspar grains melts. Due to high viscosity

there is no change in shape until above 1200 ºC.
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• At 1250 ºC small grains (<10 µm) of feldspar disappears
Quartz
Clay
Feldspar

• Also at 1250 ºC, alkali diffuses out of the feldspar, mullite
crystals form in a glass Quartz
K diffuses out
Clay
K diffuses out
Feldspar
• Clay shrinks and fissures

Quartz
appear
Clay
Feldspar
Mullite
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• With further increase of temperature mullite crystals
continue to grow
• After firing at temperatures above 1400 ºC, mullite is
present as prismatic crystals up to about 10 µm length.
• Quartz remain as it is until temperature reaches 1250 ºC.
• High-silica glass around each quartz grain increases in
amount at higher temperatures.
High-silica glass
Quartz
Clay
Feldspar
Mullite

• By 1350 ºC quartz grains smaller than 20 µm are completely
dissolved.
• Above 1400 ºC little quartz remain, and the porcelain consists
of entirely of mullite and glass.
Fig. Quartz grains surrounded by a solution rim of high-silica

glass, the outlines of glass-mullite areas corresponding to the
original feldspar and the unresolved matrix corresponding to the
original clay can be clearly distinguished.
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• A quartz grain and the surrounding solution rim of silica-

rich glass.
The overall structure of quartz grains, solution rims, feldspar

relicts of glass and mullite, and fine mullite-glass matrices
can be seen.
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• The changes taking place during firing depend on time,
temperature and particle size.
• The slowest process is quartz dissolution.
• Above 1400 ºC , the structure consists of a mixture of
siliceous liquid and mullite.
• Liquid at the firing temperature cools to form a glass,
therefore resulting phases present at room temperature
are glass, mullite and quartz in amounts depending on the
initial composition and conditions of firing treatment.
• Compositions with larger feldspar content form larger
amounts of siliceous liquid at lower temperatures and
correspondingly vitrify at lower temperatures than the
compositions with larger clay contents.
Fig. Isothermal section of silica-leucite-mullite phase–equilibrium

diagram at 1300 ᵒC.
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Advantages of Triaxial Porcelains

• Quartz-clay-feldspar bodies are not sensitive to minor
changes in composition, fabrication techniques and firing
temperature.
• Interaction of phases continuously increase the viscosity
of liquid phase as more of it is formed at higher
temperatures.
• Interaction of quartz grains forms more liquid, but it is of
continuously increasing silica content and is consequently
more viscous.
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When to choose china clay and ball clay?
Most ceramic compositions contain both of them.
To obtain more forming ability, ball clay content can be
increased to increase plasticity. Since china clay is white
burning, a product with more translucency can be produced
with high content of china clay.
Since ball clay has high impurities, its addition makes

product less translucent and usually not white-burning.
Electrical porcelains are not critical to either forming or firing

operations. A balance between the clays is required which
can give most economical ware.
Secondary Phenomena during firing

Besides grain growth and densification (vitrification) several
other changes takes place in the ceramic compositions
which influence the quality of the final product.
Several changes which happen in ceramics are due to:
• Chemical reactions
• Oxidation
• Phase transitions
• Effect of gas trapped in closed pores
• Effect of non-uniform mixing
• Application of pressure during heating
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Oxidation
• The organic matter of the clays must be oxidised.

Plasticisers (organic binders) must also be oxidised.
• Organic matter char at 150 ºC and burn at 300 to 400 ºC so

heating rate should be slow.
• Faster heating rates will not allow complete oxidation and

vitrification can be achieved earlier.
• Organic matter trapped in ceramic will act as reducing agent at

higher temperatures.
• It only affect the colour of the ceramic material by giving black

core.

Oxidation
Fig. Shows the formation of black core in industrially fired
brick.
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Oxidation
Fig. Shows the formation of black core in industrially fired brick.
Black coring results from the reduction of iron oxide from hematite
Fe2O3 to FeO during the firing process
Cupric oxide, gives green colour under oxidising conditions, can
under reducing conditions, give a brilliant red known as rouge
flambé

Decomposition reactions
Decomposition of carbonates or hydrated compounds during
firing to form the oxide plus a gaseous produce (CO2 and
steam).
Hydrates decompose in the temperature range between 400

and 1000 ºC.
Carbonates decompose at 400 to 1000 ºC.
Sulphates decompose at 1200-1300 ºC.
At each temperature, there is an equilibrium pressure of

gaseous products, if this pressure exceeds further
decomposition does not take place. This leads to the sealing
of pores before complete vitrification.
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At higher temperature decomposition pressure increases
and this leads to formation of large pores, blistering and
bloating.
Blistering in ceramic coating

Bloating in ceramics
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Sulphates decompose at 1200-1300 ºC, they remain stable during

the firing process.
CaSO4 slightly soluble in water, higher the sulphate content higher

will be the amount of the soluble salts in ceramic body. This leads
to Efflorescence in ceramics (transfer of soluble salts to the
surface and forming of undesirable white deposit)
Remedy: Addition of Barium carbonate reacts with CaSO4 to

precipitate insoluble barium sulphate.

Formation of mullite and the silica glass or cristobalite result

in increased volume. Such decompositions are useful as
they can counteract a substantial shrinkage if the other
constituents are carefully selected.
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Phase transformations
Large volume changes during polymorphic transformations induce

stresses in the ceramics leading to cracking of wares.
Pure ZrO2 is not used to make refractory bricks due to huge

volume expansion at 1000 ºC from tetragonal to monoclinic phase.
Transformation to the required phases occur slowly, e.g., Silica

bricks.
By reducing the size of the grains, stresses in the individual grains

can be reduced. Properties of porcelains can be improved if the
fine-flint is used rather than coarse material.

Trapped gases
Trapped gases reduce density of ceramics.
Gases like water vapour, hydrogen, oxygen escape from closed

pores by solution and diffusion.
Gases like CO, CO2 and N2 have lower solubility and do not
escape from closed pores.
Sintering in air limits densification.
When high densities are required, as for optical materials or dental

poreclains requiring high translucency, vacuum or hydrogen
atmosphere is preferred.
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Non-uniform mixing
Improper mixing of raw materials can lead to less densification
and formation of more pores.
Forming methods should be improved.
Over firing
It occurs when higher firing temperature leads to poorer properties
or a reduced shrinkage.
There is always an optimum temperature of firing which gives

greatest density.
For vitreous ceramics, common cause of over firing is trapping of
gases in pores or the evolution of gases which cause bloating or
blistering.

Firing Shrinkage
Green ware contains 25-50 vol.% porosity.
The firing shrinkage is equal to the pore volume removed.
Firing shrinkage can be reduced by additions of non-shrinking

material to the mix.
Grog (prefired clay) is added to the fire-clay brick to reduce the

firing shrinkage.
In porcelain bodies flint is added.
Complete densification can lead to 35 % volume shrinkage or 12

to 15 % linear shrinkage and causes difficulty in maintaining close
tolerances.
Non-uniform shrinkage can cause cracks to open.
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Warping
It happens due to density variations in the green ware.
Higher shrinkage for the parts that had a low density than the
parts that had a high density in the green ware.
Pressure variations in pressed wares can cause different

degree of compactions at different sections of pressed parts.
Shrinkage at centre is more than the edges.

Warping
Temperature gradients during firing can produce warping in
the wares.
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Warping
In vitreous ware warping can occur under force of gravity.
This mainly happens in large heavy pieces.
Frictional force or drag of the ware against the setter. This

means bottom surface tends to shrink less than the upper
surface.

Warping
In vitreous ware warping can occur under force of gravity. This
mainly happens in large heavy pieces.
Frictional force or drag of the ware against the setter. This means
bottom surface tends to shrink less than the upper surface.
Remedies:
• Altering the forming methods (Uniformity of structure in initial
forming by minimizing pressure gradients, segregation and
porosity variation)
• Designing shapes in a way that compensates for warping
• Using setting methods in firing can minimize the effect of
warping.
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Setting methods for avoiding warping
Firing Cycle for Ceramics

 The term "firing cycle" can refer to the time required to
heat and cool ceramic products in a kiln, or it can
specifically refer to the time vs. temperature curve used
during firing.
 A complete firing cycle includes the entire temperature

profile from "cold to cold."
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A Sample firing curve
1000
Temperature (C )
815
540
260
37

Segment 1 (30-100 ºC)
Candling or preheat. A kiln is gradually heated to about 30-

100 ºC before the main firing begins.
Segment 2 (200-500 ºC)
“Binder burnout” phase
Removes binder and organic matter
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Segment 3 (500-1000 ºC )
Oxidation phase. Temperature depends on the type and

combination of materials.
Improper oxidation leads to structural weakness, discoloured
or black core.
Segment 4
Final heating before the “Soak temperature”.

Temperature can be rapidly increased. But it can overshoot
the temperature and result in over heating of ware.
Ramp at low rate is advised.

Segment 5 (Soak)
Temperature is held constant to allow the heat reach cooler

parts of the load.
Firing process takes place.
Segment 6 (rapid cooling part of the cycle)

At this temperature ceramics have a liquid (molten glass
binder).
Until this binder is sufficiently hardened (generally between
650-870 ºC), ceramic can be cooled very rapidly without
being damaged.
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Segment 7 (Annealing phase)
As Molten glass hardens, it develops internal stresses.

Worse in formulations that experience quartz inversions.
Annealing generally takes place when the glass bond is

between 760 and 530 ºC and the kiln temperature is
between 870 and 480 ºC. If the cooling progresses too
quickly at this stage, the internal stresses will cause the ware
to crack.

Segment 8 (Final cooling phase)
Faster cooling can be done without damaging the wares.

However, it also adds to cost.
Some potters prefer to have slow cooling rate to achieve

desired body or glaze effect.
Optimised firing
Ideal firing cycle will be different for every formulations and
trial and error is required to find right conditions of firing.
Problems such as black core or cooling cracks if appear try
to adjust various stages of firing cycle.
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Segment 8 (Final cooling phase)
Faster cooling can be done without damaging the wares.

However, it also adds to cost.
Some potters prefer to have slow cooling rate to achieve

desired body or glaze effect.
Optimised firing
Ideal firing cycle will be different for every formulations and
trial and error is required to find right conditions of firing.
Problems such as black core or cooling cracks are appearing
try to adjust various stages of firing cycle.
Life History of a Triaxial body
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Imperfections in Ceramics
Defects in ceramics are of two types:
 Atomic Defects
 Impurities in Ceramics
 Atomic Point Defects
• It is a vacancy or vacant lattice site
• All crystalline solids contain vacancies
• It is not possible to create crystal free of point defects
• Presence of vacancies increase the entropy of crystals
• In ceramics, defects for each ion type may occur
• For example, in NaCl, Na interstitials and vacancies and Cl
interstitials and vacancies may exist.
• Highly unlikely that anion go to interstitial sites (being very large
anion has to produce strain on the surrounding ions)
• The expression defect structure is often used to designate the
types and concentrations of atomic defect in ceramics. Because
the atoms exist as charge ions, electro neutrality must be
maintained.
• Ceramics defects occur in pairs
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Frenkel defect
Frenkel defect, Frenkel pair, or Frenkel disorder is a type of
point defect in a crystal lattice. The defect forms when an
atom or cation leaves its place in the lattice, creating a
vacancy, and becomes an interstitial by lodging in a nearby
location not usually occupied by an atom.
No Change in Charge
because cation maintains
the same charge as
interstitial
Point defects
Point defects are defects in crystal structure that occupy one spot
May be formed due to imperfect packing during solidification or by

atomic rearrangement
May arise due to thermal vibration of atoms at elevated

temperatures.
Three main types of point defects:
(i) Vacancies
(ii) Interstitials ions
(iii) Substitutional ions
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Frenkel defects
Effect of temperature on Point defects
The concentration of vacancies and interstitials increases

with temperature
The equation describes the relationship between vacancies

(interstitials) and temperature is:
Total number of atomic sites
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Equilibrium number of vacancies or lattice sites
Example
Calculate the equilibrium number of vacancies per cubic meter for copper
at 1000 ºC. The energy for vacancy formation is 0.9 eV/atom; the atomic
weight and density (at 1000 ºC) for copper are 63.5 g/mol and 8.4 g/cm3,
respectively.
solution
The number of atomic sites per cubic meter „N‟ for defect free copper is
𝑁𝐴 𝜌
𝑁= (1)
𝐴𝑐𝑢
Where NA is Avagador‟s number , ρ is density and Acu is atomic weight of copper
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Substituting (1) following equation
Total number of atomic sites
Schottky defect
The defect forms when oppositely charged ions leave their
lattice sites, creating vacancies. These vacancies are formed
in stoichiometric units, to maintain an overall neutral charge
in the ionic solid. The vacancies are then free to move about
as their own entities. Normally these defects will lead to a
decrease in the density of the crystal.
Charge neutrality is
maintained because for
every anion vacancy there
exists a cation vacancy
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Schottky defect
 Exists in pairs
 Point imperfections in ionic compounds in which cation-
anion pair is missing
 Similar to Frenkel defect, Schottky defects also depends
on and increase with temperature.
Example
Calculate the fraction of lattice sites that are Schottky defects
for cesium chloride at 534°C. Assume that the energy of
defect formation is 1.86 eV/cation-anion vacancy pair.
Number of Schottky defects, Ns

Number of defect free site, N
Energy barrier required to form Schottky defects , Qs
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Stoichiometry
A state for ionic compounds wherein there is exact ratio of
cations to anions as predicted by the chemical formula.
For example, NaCl is stoichiometric if the ratio of Na+ and Cl-

ions is exactly 1:1.
Both Frenkel and Schottky defects do not alter the ratio of

cation to anions in the crystal.
Non-Stoichiometry
 When the ratio of cations to anions is not exactly balanced.
 Exists in ceramic material in which ions have two or more valence
states.
 The electroneutrality disrupts and this is then balanced by some type of
defect.
FeO (Wustite) has iron in Fe+2

and Fe+3 states, the number of
each type of ion depends on
temperature and the ambient
oxygen pressure
Formula for FeO is Fe(1-x)O
x<1
Non-Stoichiometric crystal because ratio of O ion is more than Fe ions
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Impurities in Ceramics
• Impurity atoms form solid solutions in ceramic materials as they
do in metals.
• Substitutional and interstitial solid solutions can form.
• For interstitial solid solution, ionic radius of impurity must be
relatively small in comparison to anion.
• Substitutional impurities will substitute for host ion to which it is
most similar in an electrical sense.
• For example in NaCl, impurity Ca+2 ion substitutes Na+ and Cl-
substitutes O-2.
• For solid solubility, it is required that ionic charges and size must
be very nearly the same as those of one of the host ions.
• In the case of different charge of impurity from host ions, the
crystal must compensate for this difference in charge so that
electroneutrality is maintained within the solid (this can be
obtained by formation of lattice defects)
Example 13.4
If electroneutrality is to be preserved, what point defects
are possible in NaCl when a Ca+2 substitutes for a Na+
ions?
How many of these defects exist for every Ca+2 ion?
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Problem 13.32
If cupric oxide (CuO) is exposed to reducing atmospheres at elevated

temperatures, some of the Cu+2 ions will become Cu+.
(a) Under these conditions, name one crystalline defect that you
would expect to form in order to maintain charge neutrality.
(b) How many Cu+ ions are required for the creation of each defect?
(c) How would you express the chemical formula for this
nonstoichiometric material?
Solution
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Problem 13.32
(a) Suppose that Li2O is added as an impurity to CaO. If

the Li+ substitutes for Ca+2, what kind of vacancies would
you expect to form? How many of these vacancies are
created for every Li+ added?
(b) Suppose that CaCl2 is added as an impurity to CaO. If

the Cl- substitutes for O-2, what kind of vacancies are
created for every Cl- added?
Ceramics Phase diagrams

The Al2O3-Cr2O3 System
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The MgO-Al2O3 System
Limited solubility of Al2O3 in MgO below 1400 ºC which is due to difference in

charge and radii of Mg+2 (0.072 nm) and Al+3 (0.053 nm)

The MgO-Al2O3 System
Due to their corrosion resistance to basic slags, either preformed or in situ

spinel containing refractory castables are widely used as steel ladle linings.
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The ZrO2-CaO System
Volume expansion ~4-9%
Region of Partially
stabilized Zirconia (PSZ)
having CaO in the range of
3 to 7 wt.%)

Example
Calculating Volume Changes in Polymorphs of Zirconia
Calculate the percent volume change as zirconia transforms from a

tetragonal to monoclinic structure[9].The lattice constants for the
monoclinic unit cells are: a = 5.156, b = 5.191, and c = 5.304 Å,
respectively. The angle β for the monoclinic unit cell is 98.9º. The
lattice constants for the tetragonal unit cell are a = 5.094 and c =
5.304 Å, respectively. Does the zirconia expand or contract during
this transformation? What is the implication of this transformation
on the mechanical properties of zirconia ceramics?
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Example SOLUTION
The volume of a tetragonal unit cell is given by

V = a2c = (5.094)2 (5.304) = 134.33 Å3.
The volume of a monoclinic unit cell is given by

V = abc sin β = (5.156) (5.191) (5.304) sin(98.9) = 140.25 Å3.
Thus, there is an expansion of the unit cell as ZrO2 transforms from a

tetragonal to monoclinic form.
The percent change in volume

= (final volume - initial volume)/(initial volume) 100
= (140.25 - 134.33 Å3)/140.25 Å3 * 100 = 4.21%.
Most ceramics are very brittle and cannot withstand more than a 0.1%
change in volume. The conclusion here is that ZrO2 ceramics cannot be used in
their monoclinic form since, when zirconia does transform to the tetragonal form, it
will most likely fracture. Therefore, ZrO2 is often stabilized in a cubic form using
different additives such as CaO, MgO, and Y2O3.
Zirconia-refractory oxide ceramics

The ZrO2-MgO System
 Toughness and strength of Zirconia based ceramics can be
enhanced by taking advantage of their phase transformations.
 Zirconia compound ceramics are partially stabilized zirconia
(PSZ) which contains 9 mol % MgO.
 ZrO2-9 mol % MgO is sintered at 1800 ⁰C and then rapidly
cooled to room temperature resulting metastable cubic
structure.
 On reheating to 1400 ⁰C and held for a sufficient time, a fine
metastable submicroscopic precipitate with the tetragonal
structure is precipitated. This material is called PSZ.
 Transformation of tetragonal phase to monoclinic phase ,
cause volume expansion of the precipitate which retards the
crack propagation by a crack-closing mechanism.
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The ZrO2-MgO System

The ZrO2-MgO System
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Fracture Toughness of Ceramics
Material Density Fracture Toughness

Mpa (m)1/2
Al2O3 3.85 4
Si3N4 3.19 6.6
SiC 3.1 4
ZrO2, 9 mol% MgO 5.5 8+

The SiO2-Al2O3 System
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Practice Problems
12.36- 12.38
From W.D.Callister
Mechanical Properties of Ceramics

• Ceramics are relatively brittle.
• Ionic and covalent bonding held the crystals strongly
together and would not allow any plastic deformation in
ceramic materials.
• Tensile strength of ceramics are in the range of 0.69 MPa to
7 x 103 MPa for whiskers. Tensile strength of ceramics are
significantly lower than compressive. Compressive strength
of ceramics are 5-10 times higher than the tensile strength.
• Ceramics are hard and have low impact resistance primarily
due to ionic-covalent bindings.
• Plasticized clay can be deformable due to weak secondary
forces between layers of strongly ionic-covalently bonded
atoms.
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• Fracture of ceramic materials is transgranular (rather than
intergranular). Crack often grow along high density
crystallographic plane (cleavage planes)
• Flaws present in ceramics act as stress concentrators (as
proposed by Griffith)
• Local stresses at the cracks would be much higher than
applied stresses.

• Stress magnification by flaws
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• Stress magnification by flaws
Small crack length and large radius

give lower stress magnification.

• Fracture Toughness
Fracture will not occur as long as the right hand side of the equation
is less than plain strain fracture toughness of the material.
KIC values of ceramic materials are much smaller than for metals
(below 10 Mpa (m)1/2).
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• Static Fatigue
• Considerable variation and scatter in the fracture strength of ceramic

materials often observed.
• Specimen size and volume influence the fracture strength.
• Fracture strength can be enhanced by introducing residual compressive
stresses at the surface of ceramics.

Mechanical properties of Selected Engineering Ceramic Materials
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 Ceramics lack plastic deformation due to their ionic and covalent
bonds.
Deformation of Covalently bonded ceramics

• Since bonds are directional, on stressing covalent crystals exhibit
brittle fracture due to separation of electron-pair bonds without
their subsequent reformation.
Deformation of ionically bonded ceramics

• Single crystals deform plastically under compressive stresses
• Polycrystalline ionically bonded ceramics are brittle with cracks
forming at the grain boundaries.
Non-crystalline ceramics undergo viscous flow above Tg like liquids.

 The actual strength of ceramic material is lower than theoretical
values due to the structural defects such as:
(i) Surface cracks

(ii) Voids (porosity)
(iii) Inclusions
(iv) Large grains
• Size and volume fraction of pores are important factors affecting

strength of ceramics.
• Size of cracks/flaws is critical.
• Finer grain size ceramics have smaller-size flaws at their grain
boundaries and are stronger than large-grain size ones.
• Large ceramic parts generally fail at lower stresses due to their
higher probability of containing critical flaws.
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Bend test (Determination of Flexural modulus of ceramics is
recommended) for following reason:
• It is difficult to prepare and test specimens having the required

geometry;
• It is difficult to grip brittle materials without fracturing them;
• surface flaws often cause premature failures; and
• ceramics fail after only about 0.1% strain thus specimens must be
perfectly aligned in order to avoid the presence of bending stresses.
For these reasons a more suitable transverse bending test is used.

Bend test
In the bend test (or flexure test) a bar specimen having either a
circular or rectangular cross section is bent until fracture using
a three or four point loading technique.
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Bend test
For a 3-point bend test of a rectangular bar, the stress at fracture using
the bend test is known as the Flexural Strength or Modulus of Rupture
and is given by
Where σfs = Flexural Strength

F = Fracture Load
L = Length between outer supports
w = Specimen Width
h = Specimen Height
The results of the bend test are similar to stress-strain curves; however
the stress is plotted versus deflection rather than versus strain.
The modulus of elasticity in bending,

the flexural modulus, is determined
from the linear portion of the Stress-
deflection curve and is given by
Where
Force
Efs = Flexural Modulus

δd = Beam Deflection
F1 = 2/3 Fmax with δ1 at 2/3 F max
F2 = 1/3 Fmax with δ2 at 1/3 F max
Because cracks and flaws tend to remain closed in compression, brittle

materials are generally designed such that only compressive stresses act
on the part.
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Fracture in Ceramics
• After nucleation, crack propagates until a critical velocity is achieved (for glass
velocity is half than speed of light)
• On reaching critical velocity, crack may branch
• The site of nucleation can often be traced back to the point where a set of cracks
converges or comes together.
• Crack acceleration rate increases with increase of stress levels and increasing
stress
Microscopic Features of Crack
• During the initial acceleration stage of propagation crack is flat and smooth called
mirror region (highly smooth and reflective for glass and rougher with granular
texture in polycrystalline solids)
• The outer perimeter of the mirror region is roughly circular, with the crack origin at
its center.
• On reaching critical velocity crack, crack begins to branch.
• Roughening of crack occurs with two surface features-mist and hackle
• Faint annular region just outside the mirror is mist.
• Hackle is composed of striations or lines that radiate away from crack surface and
they intersect near crack initiation site and may be used to pinpoint crack location
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Microscopic Features of Crack
• Mirror radius give qualitative information regarding magnitude of

the fracture producing stress
• Smaller the mirror radius, greater the crack acceleration rate and
sooner the crack reaches its acceleration velocity
𝟏
• 𝝈𝒇 ∝
𝒓𝒎
Manufacturing Processes
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Processing of Ceramics
Processes Taking place in Ceramic industry
Raw Materials Selection
Purification
Size Adjustment
Ball milling/mixing
Product Shaping
Drying
Firing
How Ceramic processing is different from metal processing?
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Methods of Mixing
Dry mixing : for non-clay bodies
In case of non-clay bodies, binders and plasticisers or lubricating

materials (starch, waxes, PVA) are added to the dry mix.
No filter pressing. Soluble salts remain in the body. Interfere

manufacturing by reducing plasticity.
Wet mixing: for clay containing bodies
Water addition to obtain the exact consistency required for making.

Filter pressing required. It helps to remove much of soluble salts.
Hydroplastic forming
The ability of the clay to become plastic by

addition of water is used to produce heavy
clayware products.
Steps involved:
• Addition of water in the clay to obtain

required consistency.
• Pugging process ( removal of entrapped
air, often done under vacuum)
• Green product formation by extrusion or
simply filling up the mould.
• Drying and firing
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Hydroplastic forming
Extrusion is commonly used to make product by hydroplastic

forming technique.
Products: Bricks, pipes, tiles, blocks etc.
Slip Casting
• Used for pottery and fine ceramic bodies.
Slip: A free flowing suspension of a powdered ceramic material in a water is
termed slip. It should have high specific gravity and good fluidity so that it can
be pourable.
Steps :
• Making of Slip (various raw materials are made individually into slips, a
slip of the body can be prepared by mixing the right amounts of the
individual slips. This gives intimate mixing of materials).
• A known weight of the slip is poured into a plaster of Paris mould of the
required shape. (Water adsorbed into the porous mould, and as this
process proceeds, a layer of slip material is built up on the inside wall of
the mould and takes the shape of the mould.
• Casting is allowed to continue until the required thickness achieved.
• Mould is inverted and excess slip is drained
• Cast is allowed to partially dry in the mould. (shrinkage of the case allows
it be removed from the mould)
• Full drying and Firing.
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Slip Casting
Drain casting
Products: large or intricate shaped pieces (Sanitary

lavatory ware, art objects, and lab ware such as ceramic
tubes, etc).
Slip Casting
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Slip Casting
Suspension properties
• It is required for the material in suspension to remain suspended and not

to settle out.
• For slip casting, suspension should be of high concentration and yet be
fluid enough to pump through pipe lines, to pour into the plaster moulds ,
to flow into every corner of the mould and able to reproduce the shape
intended and to drain cleanly from the mould after casting.
• Agitation is necessary to keep particles in suspension.
• Casting-slips have to be made up at a higher concentration (30-40
ounces per pint ( ~840 g in 473 ml)) and relative density of 1.5 to 2.0 or
more.
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Two important properties of slips:
• Thixotropy: The property of suspensions to become more

viscous with time when left at rest is known as thixotropy. It
is desirable to leave a small amount of thixotropy in the slip
to give extra firmness to the cast and to keep reasonalby
high rate of casting. Too high a value of thixotropy produces
“flabby” or soft cast which is easily distorted.
• Fluidiity
Deflocculation
The process of making slip fluid enough to handle, certain chemicals
known as deflocculants are added in small amounts to the slip. The
process is called deflocculation.
In water clay behaves like the anion of a weak acid (e.g., acetate)
and some ionisation takes place,
water
M clay M+ + Clay-
The more M clay ionises, the more clay- produced and the less clay is left
as unionised M clay.
The charged clay particles will repel one another whereas the uncharged M
clay will not repel similar particles, coagulation of particles into aggregates
containing many particles will result.
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Packing of particles from flocculated and deflocculated suspension
Open structure Dense structure which

which is more is not easily
permeable to water penetrated by water
Properties Affected on Deffloculation
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Practical uses of the cation exchange properties of clays
• Flocculating exchangeable cation (H, Ca, etc) is replaced by
deflocculating cation (Na, K) are used in ceramic processing.
• In slip casting deflocculation reduces the viscosity of the
suspension enabling it to be used at high solids
concentration and workable fluidity.
• Deflocculants help to control fluidity of casting-slips.
• Sodium silicate and Calgon produce large complex anions in
solution can deflocculate a clay.
• Flocculation of a suspension can be useful as well. Glazes
require viscosity so that coating can be achieved.
• Flocculation can be achieved by addition of hydrochloric
acid or calcium chloride.
Plaster of Paris
• Calcined gypsum CaSO4.1/2H2O is prepared by heating (120-170 ºC)
naturally occurring gypsum CaSO4. 2H2O.
• On mixing with water, the hemihydrate rehydrates to dihydrate by
exothermic reaction and stiffening of the mass occurs.
• Plaster is used in making moulds and models owing to its low cost.
• Setting time of a plaster-water mixture can be prolonged to allow working
of moulds by addition of certain chemicals called retardants are used
(cold water and sugar can do the trick)
• Lower moisture content the quicker the set, stronger the plaster and the
lower will be porosity.
• Moulds require high porosity, sufficient strength and wear-resistance.
• Drying should be done below 60 ºC to remove excess water but not water
of crystallisation.
• Plaster mould absorb water. This water must be removed or the mould
will become saturated and will no longer perform its function.
• Mould drying is done overnight at gentle heat so that water of
crystallisation should not drive off.
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Tape Casting
• Used to make thin continuous sheets of flexible tape.
• Sheets are produced from slips.
• Slip consists of a suspension of ceramic particles in an

organic liquid that contain binders and plasticisers that are
incorporated to impart strength and flexibility to the cast tape.
• Polyvinyl butyral is commonly used binder.
• Layers of tape can be assembled into multilayer parts, such

capacitors or electronic packages, membranes for filtration,
fuel cell components, piezoelectric devices, heating elements,
etc.
Tape Casting
• Green tape is flexible tape that may be cut or into which

holes may be punched prior to a firing operation.
• Thickness: 0.1-2 mm
• Applications: Production of ceramic substrates used in
integrated circuits and for capacitors. Nanoparticle
based film, polymer based films for lithium-ion batteries.
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Tape Casting
Tape Casting
Commercial Tape Casting Machine
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Powder Processing
“Powder mass containing small amounts of water or
organic binder is compacted into desired shape by
pressure”
Process is used for fabrication of clay based or non-clay

based ceramics.
Electronic and magnetic ceramics as well as refractory

bricks are also fabricated by this method.
Advantages: High compaction (much denser products), low

porosity (large particle size distribution helps to minimize
voids).
Disadvantages: Expensive dies, intricate shapes not easy.
Powder Processing
Uniaxial pressing
Pressure is applied in a single direction. The formed pieces
takes on the configuration of the die.
Advantages: suitable for only simple shapes, mass production

of simple parts (production rate is high), inexpensive.
Disadvantages: pressure variations in the parts.
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Powder Processing
Uniaxial pressing
Pressure 60 to
830 MPa are If die pressing is
applied. carried at room
Hydraulic and temperature is
mechanical called
presses with Cold pressing
loads up to 750
tons are used.
Powder Processing
Hot pressing
“Pressing process is carried out at high temperature”
Hot pressing of SiC is carried at 2000 ºC.
Advantage: better compaction, high green density, higher strength

of the parts than cold pressed parts.
Disadvantage:
Graphite dies are used which needs oxidation resistant
coatings.
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Isostatic pressing
Powder compaction in multiple directions through a liquid
or gaseous medium surrounding the compacted part.
Advantages:
More complicated shapes are possible,

better compaction, no residual stresses in
the compacted part, uniform density,
homogeneous microstructure.
Cold Isostatic pressing
A flexible mould (polyurethane) is immersed in pressurised

liquid medium (water) is used in Cold Isostatic pressing.
Two methods of Cold Isostatic pressing

• Wet bag
In wet-bag isostatic pressing, powder is encased in a rubber
sheath that is immersed in a liquid which transmits the pressure
uniformly to the powder. Suitable for complicated parts.
• Dry bag
In dry-bag isostatic pressing, rather than immerse the tooling in
a fluid, the tooling itself is built with internal channels into which
high-pressure fluid is pumped. Suitable for simple shapes.
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Hot Isostatic pressing (HIP)
• Isostatic pressing is carried at increased temperature.

• Gas (Argon or nitrogen) is used as pressure medium.
• Combines compaction and sintering.
• Method can be used without mould (part is first consolidated
by cold isostatic pressing and then sintered to close porosity.
The part is then isostatically pressed at high temperature
without use of mould to increase the compaction density).
Ceramic tube made with hot Isostatic pressing (HIP)
Mandrel
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Injection moulding
• Mixing
• Injection
• Removal
• Debinding
• Sintering
Advantages:
Complex shaped small parts are produced by this method,
Faster moulding cycle, close tolerances can be met due to
consistent shrinkage.
Gel Casting
Ceramic powder is mixed with polymer monomers to form a
slurry. This is then transferred to a mould, mononmer
polymerises and forms a gel. The gel binds ceramic powder into
complex shaped-part.
Advantages:
Economical, large complex shapes can produced such as
turbine rotors.
Sintered corundum made by gel casting
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Gel Casting
Sintered corundum products made by

gel casting
Sintering
The process of bonding compacted particles without melting.
Or
The bonding of powders by solid-state diffusion in the absence of a separate

bonding phase
Or
Sintering is a method of producing products from powder, by heating the

material (below its melting point) until its particles adhere to each other.
Or
Coalescence of powder particles into more dense mass is termed

sintering.
Sintering is used in ceramic processing and powder metallurgy.
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Sintering
Process of Sintering
Powder compact have individual grains separated by between 25 and
60 vol.% porosity.
• At Initial stage of sintering neck forms

• Grain boundary forms
• Interstices between particles turns into pores
Both the size of and shape of the pores present change during
the firing process, pore become more spherical in shape and
smaller in size as firing continues.
Sintering
Process of Sintering
Neck like junctions form between adjacent particles as shown in SEM
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Sintering
Driving force for Sintering
For maximizing properties, transfer of material takes place from

one part of the structure to the other during sintering process.
The driving force for this material transfer/densification is the free-

energy change.
Both surface area and surface energy decreases with the

formation of new but lower-energy solid-solid interfaces.
e.g,. The net decrease in free energy occurring on sintering a 1-

micron particle size material corresponds to an energy decrease
of ca. 1 cal/g.
Sintering
Driving force for Sintering
On microscopic scale material transfer is effected by
• difference in pressure
• difference in free energy
across the curved surfaces.
Particle size play important role.
Small particles (large radius of curvature). Fine particles

(submircon sizes) are used for ceramic technology.
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Sintering
Parameters effecting Sintering process
• Particle size
• Shape
• Size distribution
• Impurities/dopants
• Secondary phases
• Consolidation/applied pressure
• Time and temperature
Sintering
Process of sintering
 Atomic diffusion takes place and the welded areas formed
during compaction grow until eventually they may be lost
completely
 Recrystallization and grain growth may follow, and the pores

tend to become rounded and the total porosity, as a
percentage of the whole volume tends to decrease
 In the pressing operation the powder particles are brought

together and deformed at the points of contact
 At elevated temperature - the sintering temperature - the

atoms can move more easily and quickly migrate along the
particle surfaces (Diffusion)
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Sintering
Process of sintering
 At the sintering temperature new crystallites form at the points

of contact so that the original inter-particle boundaries
disappear, or become recognizable merely as grain boundaries
(This process is called Recrystallisation)
 The total internal surface area of the pressed body is reduced
by sintering
Sintering
Mechanism of sintering
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Sintering
Relative density of alumina as a function of sintering time at

various temperatures of sintering
Sintering
Sintering temperature 1800 ⁰C for various alumina products
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Glasses
Definition of glass
“Inorganic product of fusion which has cooled to a rigid condition

without crystallisation”
 Glass is a ceramic material made from inorganic materials at

high temperatures.
 In contrast to crystalline ceramics, glass is produced from
constituents which are heated to fusion and then cooled to a
rigid state without crystallisation.
 A 3D network of atoms which lacks the repeated, orderly
arrangement typical of crystalline materials.
 Glasses are noncrystalline or amorphous structures.
 In a glass molecules have random orientation.
Glasses
Solidification behaviour of glass
 Glassy or non-crystalline materials do not solidify in the same

manner as do those that are crystalline.
 Viscosity of glass depends on temperature and decreases with
increase of temperature.
 The specific volume vs temperature curves are different for
crystalline and noncrystalline materials.
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Glasses
Specific volume versus temperature behaviour of
crystalline and noncrystalline materials
• Crystalline materials melt at
specific temperature (Tm)
• Have sharp change in specific
volume at Tm
• Glasses do not melt at specific

temperature
• Have continuous change in
specific volume vs temperature
• Exhibit glass transition
temperature (Tg)
Glasses
Continuous cooling transformation diagram for the
crystallisation of glass
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Glasses
Flow of noncrystalline ceramics
• Plastic deformation does not occur by dislocation motion
for noncrystalline ceramics because there is no regular
atomic structure.
• Non-crystalline ceramic material deform by viscous flow
as do liquids deform.
• Viscosity of non-crystalline materials is a measure of a
non-crystalline material‟s resistance to deformation.
Glasses
Flow of noncrystalline ceramics
• Glasses have extremely large viscosities at ambient
temperatures, due to strong interatomic bonding.
• As the temperature is raised, magnitude of bonding is
diminished, the flow of atom or ions become easier
resulting in decrease of viscosity.
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Glasses
Glasses
• Physical properties: hard, elastic, brittle, non-conductor
of electricity, transparent, etc.
• Chemical: resistant to most normal environments and
chemical but not to fluorine and very strong bases.
• In electrical industry glass is essential for various types of
lamps because of its insulative properties and ability to
vacuum tight enclosure.
• High chemical resistance of glass makes it useful for
laboratory apparatus and for corrosion resistant liners for
pipes and reaction vessel in the chemical industry.
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Glasses
Compositions and characteristics of some of the common commercial
glasses
Glasses
Soda lime glasses
Huge market for soda lime glasses. They are used in flat
glass (windows) and glass containers (beverage bottles).
Composition:
SiO2 = 74 wt.% (glass former)

Na2O = 16 wt.% (soda addition reduces melting point
dramatically, addition makes glass soluble in water)
CaO = 10 wt.% (act as stabiliser and also promotes
devitrification. Small additions stabilise glass against water)
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Glasses
Glass Additives
• Al2O3 (addition of ~1% increases durability of glass)

• SiO2 (glass former, higher content means lower thermal
expansion and better resistance to thermal shock)
• Soda, Na2O ( decreases the softening point of glass)
• CaO (decrease the softening point of glass but also
promotes crystallisation, addition of MgO (1-4 %) prevent
devitrification)
• Boron oxide (B2O3) (glass former like silica and increases
chemical resistance of glass)
• PbO (increases refractive index of the glass as well as
density; at 24-28 % PbO, the glass is considered as
crystal and in higher amounts creates x-ray absorptive
glass
Glasses
Glass Additives
• BaO (Increases refractive index of glass and absorptivity

of a glass without the harmful effect of PbO)
• Na2O and CaO ( Addition produces X-rays transmitive
glass for X-ray tubes)
• Cadmium ( a good neutron absorber used in nuclear
reactors can be added as oxide to make radiation
shielding glass)
• Transition metals with their unfilled d shell orbitals give
selective absorptivity when in a glass; for example
chromium oxide gives a green tint to a glass, Nd makes
glass purple.
• Reducing FeO to Fe2O3 in glass can transform a glass
into IR-transmittive glass
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Glasses
Calculation of glass composition
Soda-lime silicate glass is made from three raw materials:
• Silica (SiO2)
• Soda ash (Na2CO3)
• Limestone (CaCO3)
Oxide to total weight ratio called oxide factors are as follows:
Silica = 1
Na2O = 0.585 mass unit soda (Na2O) per mass unit of soda ash
CaO = 0.56 mass unit lime per mass unit of limestone
Glasses
Determination of glass batch composition. For example,
• 2000 g of Sand (SiO2)
• 800 g Soda ash (Na2CO3)
• 360 g Limestone (CaCO3)
Glass batch composition can be calculated by multiplying weight of raw
materials with oxide factors:
2000 x 1 = 2000 g of sand (SiO2)
800 x 0.585 = 468 g of Na2O
360 x 0.56 = 202 g of CaO
Total weight of glass = 2670 g
Glass batch composition
2000/2670 = 74.9 % silica
468/2670 = 17.5 % Na2O
202/2670 = 7.6 % CaO
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Glasses
Calculating the mass of raw materials needed to obtain a glass batch
composition of 16-10-74 batch of soda-lime silica glass (mass percents,
respectively).
Basis= 2670 g of glass
Amount of Na2O = 16 % x 2670 = 427.2 g

Amount of Na2CO3 = 427.2 g of soda/0.575 g of soda per g of soda ash
= 742.95 g
Amount of CaO = 10 % x 2670 = 267 g

Amount of Na2CO3 = 267 g of soda/0.580 g of lime per g of limestone =
460.34 g
Amount of SiO2 = 74 % x 2670 = 1975.8 g

Amount of SiO2 = 1975.8 g of soda/1 g of silica per g of sand = 1975.8 g
Glasses
Viscous deformation of Glasses
A glass behaves as a viscous liquid (supercooled) above its glass

transition temperature. Under stress, group of silicate atoms can slide
past each other, allowing permanent deformation of glass.
The equation relating viscosity to temperature for viscous flow in a glass

is
𝑄
𝜂 = 𝜂𝜊 𝑒 𝑅𝑇
Where 𝜂 is viscosity of glass (P or Pa.s)
𝜂𝜊 = pre-exponential constant (P or Pa. s)

Q = molar activation energy for viscous flow
R = Universal molar gas constant
T = absolute temperature
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Glasses
Viscous deformation of Glasses
Example
A 96 % silica glass has a viscosity of 1013 P at its annealing point
of 940 ⁰C and a viscosity of 108 P at its softening point of 1470
⁰C. Calculate the activation energy in kilojoules per mole for the
viscous flow of this glass in this temperature range.
Solution:
𝜂𝑎𝑝 𝑄 1 1 1013
= 𝑒𝑥𝑝 − = = 105
𝜂𝑠𝑝 𝑅 𝑇𝑎𝑝 𝑇𝑠𝑝 108
Q = 3.82 x 105 J/mol = 382 kJ/mol
Glasses
Effect of temperature on the viscosity of commercial
Glasses
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Glasses
Important reference points for the processing and heat
treatment of glasses
Working point: Visocity = 103 Pa.s. At this temperature

glass fabrication operations can be carried out.
Softening point : Viscosity = 107 Pa.s. At this temperature

glass will flow at an appreciable rate under its own weight.
Annealing point : Viscosity = 1012 Pa.s. Internal stresses

can be relieved at this temperature.
Strain point : Viscosity = 1014 Pa.s. Below this temperature

the glass is rigid and stress relaxation occurs only at a slow
rate. The region between the annealing and strain points is
commonly considered the annealing range of a glass.
Glasses
Forming methods for glasses
1. Pressing
Thick walled pieces such as Plates, dishes, etc.
Steel moulds with graphite linings are used for this purpose.
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Glasses
2. Blowing (production of glass jars, bottles and light bulbs)
Glasses
3. Drawing (production of sheets, rod, tubing and fibres)
Glass fibres are made by drawing or

Spinning method.
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Glasses
3. Drawing (production of glass sheets by float process)
Glasses
Heat treatment of glasses
1. Annealing
Thermal stresses (internal stresses) result due to difference

in cooling rate and thermal contraction between the surface
and interior regions.
Cooling the ceramic pieces at a slow rate.
Heating glass ware to the annealing point then slowly cooled

to room temperature.
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Glasses
2. Glass tempering
Rapid air cooling of the surface of the glass after it has been
heated to near its softening point.
The surface of the glass cools first and contracts, while the
interior is warm and readjusts to the dimensional change with little
stress.
Tensile stresses are built in the interior region of the glass and
compressive stresses on the surfaces.
Tempering process increases strength of the glass because

applied tensile stresses must surpass the compressive stresses
on the surface before fracture occurs.
Glasses
3. Chemically strengthened glass
Substitution of larger ions with the smaller ions on the surface of glass
will introduce compressive stresses at the surface and corresponding
tensile stresses at its centre.
The sodium aluminosilicate glass is immersed in a bath of potassium

nitrate at a temperature about 50 ⁰C below its stress point (~500 ⁰C) for
6 to 10 h, the smaller sodium ions near the surface of the glass are
replaced by larger potassium ions.
The method is suitable for thinner cross sections as the compressive

layer is much thinner.
Chemically strengthened glass is used for supersonic aircraft glazing

and ophthalmic lenses.
Gorilla glass (Corning) used in smartphones is toughened and scratch

resistant by the same method.
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Glasses
Crack growth is suppressed. Tempered glass has a higher resistance to

impact than Annealed glass and is about 4 times stronger than annealed
glass. Windshields for autos, safety glass for doors are produced by thermal
tempering (breaks into tiny beads that do not cut the skin)
Glasses
Crack growth is suppressed. Tempered glass has a higher resistance to

impact than Annealed glass and is about 4 times stronger than annealed
glass. Windshields for autos, safety glass for doors are produced by thermal
tempering (breaks into tiny beads that do not cut the skin)
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129
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Glasses
Glass-Ceramics
 Transformation of noncrystalline inorganic glasses to

crystalline form by the proper high temperature heat
treatment (devitrification) can produce a fine-grained
polycrystalline material which is often called glass-
ceramics.
 A nucleating agent (titanium dioxide) promotes the
process of crystallisation in glasses.
 Glass-ceramics have low coefficient of thermal expansion
and will not experience thermal shock. They have
relatively higher strengths and thermal conductivities.
 Glass-ceramics can be made transparent or opaque.
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Glasses
Glass-Ceramics
Typical heat treatment for producing Glass-ceramics
 Glass ceramics can be fabricated using conventional glass forming technique

followed by heat treatment.
 Commercial names for glass-ceramics are Pyroceram, Corningware, Cercor and
Vision.
 Common uses of these materials are tableware and ovenware, electrical
insulators and printed circuit boards, heat exchangers and regenerators.
Tile Composition (Emco)
Clay (KD-7) 35 %
CM-2 = 14 %
Potash feldspar (S-2) = 22 %
Soda feldspar (R-3) = 23 %
Silica Sand (Q-3) = 6 %
Sodium silicate = 6.15 (80 kg in 13 ton )
Sodium tripolyphosphate = 5.77 ( 75 kg in 13 ton)
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Glazes
Prepare following topics:
Definition, purpose of glazing, types of glazes, Frit glaze,
Methods of applications, defects of glazing (crazing,

peeling, crawling, blistering, etc.)
What is Porcelain Enameling??
See following link for details:

http://pottery.about.com/od/glazeproblems/tp/glazdefect.htm
http://en.wikipedia.org/wiki/Glaze_defects
Read booknotes provided
Glazes
Raw Glaze
5.76 g SiO2, 3 g Na2CO3, 0.8 g Iron oxide, 0.2 g china clay,
0.2 g bentonite
Frit Glaze
2 g SiO2, 1 g Na2CO3, 3.4 g feldspar, 2.4 g china clay, 0.2 g

bentonite, 1 g Fe3O4, 1 g BaO, 1 g Zinc Oxide
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Final Term Exam

Material to be prepared for exam:
• Slides provided
• Booknotes provided
• Question at the End of Chapter 12 and 13 (William D.
Callister Book)
12.26,12.28-12.38, 12.43-12.45, 13.1-13.5, 13.8-

13.11,13.19-13.25 (exclude 12.37 and 12.38(b))
After reading the material provided, you should be able

to answer these questions.
133

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• SiO4-4 forms the basic building block of the silicate minerals

Various ways of linking SiO4-4 tetrahedraons

• Corner oxygens are not shared with other SiO4-4

• SiO4-4 are linked together by cations Mg+2, Fe+2 or Ca+2

• Example Olivine, almandine, zircon minerals.

Various ways of linking SiO4-4 tetrahedraons

• One corner oxygen is shared with other SiO4-4 tetradherons.

• Disilicate group has two Si ions and 7 oxygens (Si2O7-6)

• Also called pyrosilicates

• Example: thortveitite (Sc2Si2O7), hardystonite, Ca2Zn(Si2O7).

Various ways of linking SiO4-4 tetrahedraons

• Two of the oxygen of tetrahedron are shared and structure is

• Example: Beryl - Be3Al2Si6O18

Various ways of linking SiO4-4 tetrahedraons

• Two of the oxygen of tetrahedron are linked to form a long single

• Example of isosilicate (single chain silicate): orthopyroxenes

• If two of chains of SiO4-4 linked together, so that each tetrahedron

• Example of inosilicates are doubletremolite - ferroactinolite series -

Isochain silicate Doublechain silicate

Various ways of linking SiO4-4 tetrahedraons

• Three of the oxygen of tetrahedron are linked to form an infinite

• Basic structural group is Si2O5-2

• Examples: Clays, mica, talc minerals have basic building block of

Various ways of linking SiO4-4 tetrahedraons

• All corner oxygen of tetrahedron are shared with another SiO4-4

• Basis of 3-D structures

• Basic structural group is SiO2

Traditional Ceramic Raw Materials

SiO2 exists in three polymorphic forms

In quartz the Si-O-Si bond angle joining tetrahedrons is between 140-153 ᵒ.

Quartz is stable up to temperature of 870 ºC

Quartz exhibit strong

Difference in packing of oxygen atoms in

Pressure-Temperature diagram of Silica

• Heating above certain temperature for a considerable time, it is

• All three forms are stable at room temperature

At 1300 ºC, it takes 10 days to convert Form in the manufacture

At 1300 ºC, it takes 10 days to convert Form in the manufacture

Linear expansion of 0.45 % occur on displacive phase transition of quartz,

 At inversion temperatures size change occur very rapidly. Such rapid

 Sudden expansions are the cause of spalling in silica refractories.

 Linear expansion of silica at 1000 ºC is about twice that of clay, the

Volume Expansion vs Temperature for various

Fig. Quartz grain with

Glaze put into compression by Cristobalite squeeze

Other forms of Silica

Chemical properties of Silica

• HF reacts with silica to form SiF4 (gas).

• Silica is attacked by fused alkalis and alkaline slags, forming

• Silica gel is more reactive, because of its fine size.

• Silica gel is powerful water-absorbant (desiccant) and is attacked

Silica occurs in nature as

K2O.Al2O3.6SiO2 + 2H2O Al2O3.2SiO2.2H2O

• Clays are combination of two layer structures

The [Si2O5]n2n- tetrahedral silica sheet.

• Gibbsite layer ( Al(OH)3 composed of aluminium atoms

Octahedral Gibbsite sheet

The n[Al(OH)3] octahedral gibbsite sheet.

Dimensions of hexagonal rings in the silica and gibbsite sheets are

Octahedral Gibbsite layers form sheets

Clay mineral structure

Ions Molecules Sheets