Traditional Ceramics

Ceramics - Objectives
 Review the basics
◦ Definition, general properties
 Historical overview
 Crystal structures
◦ Ionic structures (simple, complex)
◦ Covalent structures
◦ Silicates
 clays
Ceramics
Ceramics
 worldwide market >$100 billion per year*
◦ glass 55%
◦ advanced ceramics 17%
◦ whiteware 10%

*excluding concrete – hydraulic cement production

is approx 3 billion tonnes p.a.
Ceramics and Human History
 fired clay pottery ca
10,000BC
◦ well developed techniques
by 6000BC
◦ hand formed (slab, coil
techniques)
 pottery wheel
◦ probably Mesopotamia, ca
3500BC
Ceramics and Human History
 glass, ca 3000BC , Egypt
 hydraulic cement, ca 200BC,
Rome
 porcelain 200AD, China
 silicon nitride 1857
 MgO steelmaking refractories
1880
20th Century
 1940 BaTiO3
 1950 SiAlONs
 1975 transformation toughening of ZrO2
 1986 high T superconductors
 Crystal Structures
 Begin with ionically
bonded structures
◦ Most ceramics have mixed
primary bonds
◦ Greater difference in
electronegativity gives
greater ionic character

http://www.chem1.com/acad/webtext/atoms/atpt-6.html
Pauling’s Rules for Ionic Crystals
 Neighbouring ions must be touching for stable
structure
◦ Radius ratio of cation to anion determines geometry
 Local electroneutrality must be maintained
 Shared edges, faces reduce stability
 If several cations, small, high valency ones tend not
to share edges, faces
 Number of types of ions tend to be small
Ionic Crystals

stable stable unstable

Critical Radius Ratios

Polyhedron Co-ord Number Minimum rM/rX

cube 8 0.732
octahedron 6 0.414
tetrahedron 4 0.225
triangle 3 0.155

 where rM is the cation (metal) radius and rX is

the anion radius
Ionic Crystals
 Geometry dependent
on ratio of cation radius
to anion radius (r/R)
 Greater ionic character
tends to give closer
packing
Simple Structures – AX
 one to one ratio of cation to anion
 many ceramic materials have these structures
AX Structure - CsCl

 Cl-
Note: This is not
a BCC structure.

Cs+

Cl-

Simple Cubic lattice – radius ratio=0.94

AX Structure - NaCl

2- FCC
interpenetrating
lattices.

MgO, FeO, NiO,

Some sulphides,
& carbides
AX structure – ZnS

Fcc lattice,
radius ratio =
0.34 for ZnS

GaAs, InP,
cubic SiC
 Al2O3 has trigonal
structure, but can be
represented as
hexagonal oxygen
lattice with Al ions in
octahedral interstices
 Perovskite (ABO3) Structure
 BaTiO3 is typical
 Below 120oC Ti4+ ion sits
off-centre, creating dipole
 Common amongst
ferroelectric, piezoelectric
ceramics

http://research.ncku.edu.tw/re/articles/e/20080411/i
mages/080304092145kgEFTR.jpg
Spinels (AB2O4 or AO.B2O3)

http://www.freewebs.com/diendanhoak26/hoahocvoco.htm
Summary - Structure of Crystalline Ceramics
Covalent Crystals
 more open structures
◦ Not close packed
 e.g. diamond
graphite
“Bucky balls”

22
Carbon
 Pure carbon -many polymorphs also exists in
the amorphous state.
◦ Diamond, similar to ZnS in structure
◦ Graphite is considered to be a crystalline ceramic
◦ Fullerenes, C60, recently discovered polymorph -
with interesting properties.
Diamond

 AX type crystal structure similar

to ZnS.
 Each carbon atom covalently bonded to four
other C atoms in a diamond-cubic crystal
structure
 optically transparent and extremely hard
(hardest natural material known)
 cruder or industrial forms used as abrasives,
indentors and coatings (especially thin films)
Diamond

25
 Graphite
 Layers of hexagonally arranged covalently bonded C
atoms
 Layers bonded by weaker Van der Wals bonds giving
easy slip
 Excellent as a dry lubricant, relatively high strength at
elevated temperatures, high thermal and electrical
conductivity, low thermal expansion, resistance to thermal
shock, and good machinability.
 Usage: electrodes, heating elements, crucibles, casting
molds, rocket nozzles, and other applications.
 Graphite

covalent bonds

secondary bonds

27
Fullerenes, C60
 Molecular form of carbon hollow spherical structure
resembling a geodesic dome
 Discovered 1985, have since been found to occur naturally
 In solid crystalline state, C60 molecules pack together in a
FCC unit cell arrangement, lattice parameter a =1.41nm.
 pure solid material density ~1.65 g/cm3
 relatively soft
 non-conducting (no free electrons)
Properties of Buckyballs
 If alkali metal anions, (e.g. K+) present (usually 3 per
C60 molecule), material (K3C60) displays characteristics
of a metal.
◦ In fact, K3C60 is considered to be the first molecular metal

 K3C60 buckyballs and similar molecular materials

become super conducting at about 18K

 Applications in low-power consumption, low-pollution,

magnetic-levitation and propulsion devices for mass
transit systems.
Carbon Nanotubes

30
 Silicates

 Earth’s crust ~65%

oxygen atoms, 25%
silicon
 Silica and silicates are
everywhere!
http://www.quartzpage.de/gen_ori.html
Radius ratio = 0.29, tetrahedral co-ordination
Silicates
 SiO44- tetrahedra can be combined in many
ways
 Joined at corners by oxygen = “bridging
oxygen”
◦ Number of bridging oxygens characterises
structure
 Primary bond has significant covalent and
ionic character
Kaolinite

http://originoflife.net/information/grap
hics/kaolinite.png

http://www.doctorspiller.com/ceramics_1.htm
 Molybdenite
MoS2

Sheet
Structures
Graphite
C

Talc
Mg3(Si4O10)(OH)2

K.S. Deffeyes, S.E. Deffeyes, Nanoscale:

Visualising an Invisible World, MIT Press, 2009
Non-Crystalline Ceramics
 commonly based on silicon dioxide (“silica”)
 random structure, lacks long range order
 “glass” structure
◦ Mainly ionic bonds

39
 Amorphous Ceramics - Glasses (Na20,
Ca0, K2O, etc)
• The viscosity of the material at ambient temperature is relatively
high, but as the temperature increases there is a continuous
decrease in viscosity.
• When the viscosity has decreased to the point that the ceramic
is a fluid, it is considered to have melted.
• At ambient temperature while it is still solid, it is said to be in the
“glassy” condition.
• There is no distinct melting temperature (Tm) for these materials
as there is with the crystalline materials.
• The glass transition temperature, Tg, is used to define the
temperature below which the material is a “solid” and defines a
practical upper limit on service temperature.
Crystalline vs Amorphous (Glass)

41
Specific volume of amorphous and crystalline
ceramics.

Liquid

supercooled
liquid

Crystalization
glass

Crystaline
solid

Tg Tm TEMPERATURE
 Defects in Crystalline Ceramics
• Vacancy
• Interstitial
• Dislocation
• Grain Boundary

Cation Interstitial
Anion Vacancy
Cation Vacancy

Schotky Defect Electro-

Frenkel Defect neutrality
 Microstructure
•Put a lot of atoms, unit cells together get
“microstructure”
grains

second phase

pores
cracks

45
 Ceramic Microstructures

Aluminium Silicon Nitride Rare Earth Doped

Oxide (14% porosity) Cerium Oxide

46
Mechanical Properties of Various Ceramics

a Sintered with about 5% porosity

Relative Hardness

B4C, SiC
WC, Al2O3

Glass
 Effect of Porosity on Stiffness

Where Eo is the theoretical modulus of elasticity with no

porosity, and P is the volume fraction of porosity.
Effect of Porosity on Strength

Where so is the theoretical modulus of rupture with no

porosity, P is the volume fraction of porosity, and n is an
empirical material constant
Fracture Toughness

Fracture Toughness (MPam)

Firing and Sintering
Objectives
 Describe stages in solid state and liquid phase
sintering
◦ Clay based ceramics
 Explain the driving forces for sintering
 Discuss parameters used to control the process
 Compare solid state and liquid phase sintering
 Describe and compare continuous and batch
furnaces
Sintering
 shaped green ceramic has particulate nature
◦ porous
◦ little strength
 increased strength and density achieved by
“sintering”
◦ solid state (diffusion)
◦ liquid phase (flow, dissolution)
Sintering
 application of heat (>0.5Tm)
 driving force is the lowering of surface energy
◦ surface area reduced
◦ can lead to shrinkage
◦ increased density
Stresses and Surfaces
 stresses associated with curved surface
◦ higher surface area per unit vol
 effective surface stress on sphere

4g
s=
surface energy

D diameter
Particulates
 inherent driving force for mass flow
◦ smaller particles, greater driving force
 heat allows for mass flow to occur
◦ move to reduce stress
 diffusion
 plastic flow
 viscous flow
Solid State - 2 Sphere Model

german p70
Neck Formation
 Densification and MassTransfer
E-C = evaporation-
condensation
VD = volume diffusion
SD = surface diffusion
PF = plastic flow
GB = grain boundary diffusion
Densification and Transport
 surface transport can cause neck growth
◦ evaporation-condensation
◦ surface diffusion
◦ volume (lattice) diffusion
 bulk transport gives neck growth and
densification
◦ grain boundary diffusion
◦ volume (lattice) diffusion
Stages in Solid State Sintering

R.M. German, Sintering Theory and Practice,Wiley Interscience, 1996, Fig 1.7
 Stages of Sintering
 Adhesion
◦ compacted particles
 Initial
◦ neck growth, significant
loss of surface area
◦ some densification
 Stages of Sintering
 Intermediate
◦ pore rounding and
elongation
◦ most open pores gone
◦ significant densification
◦ some grain growth
 Final
◦ pore closure
◦ minimal densification
◦ extensive grain growth
Stages in Solid State Sintering

German p12
Stages of Sintering
Stage Process Surface Area Densification Coarsening
Loss
Adhesion contact minimal (unless none none
formation high P is used)

Initial neck growth large, up to 50% small minimal

loss
Intermediate pore rounding, loss of most major grain growth and
elongation open porosity larger pores

Final pore closure, very little very little, slow extensive grain
densification growth and pore
growth
Grain Growth
 grain growth related to
curvature of grain
boundary
Grain Growth

barsoum p 329
Factors Affecting Solid State Sintering
 temperature
◦ diffusion is thermally activated
 green density
 uniformity of green density
 atmosphere
 impurities
◦ sintering aids
 size distribution
 particle size
Effect of Temperature
Effect of Grain Size and Pressure
Liquid Phase Sintering
 mixed powders heated
◦ solid state sintering during heating
 liquid forms
◦ liquid wets solid
◦ fills pores, reducing surface area
◦ higher diffusion rates
Stages in Liquid Phase Sintering
Stages in Liquid Phase Sintering
◦rearrangement
◦solution-
reprecipitation
◦final stage sintering
Densification with a Liquid Phase
Liquid Phase
Effect of Liquid Phase
Liquid Phase Sintering
 small amount of liquid forms
◦ lubricates grains, fills pores
 lower temperature required
 matrix phase bonds grains
 matrix phase often has inferior properties as
compared to grains
Tunnel Kilns
 allow continuous processing
 most are gas heated
 arrangement of ware important for heat
distribution
 typically 100 – 150m long
Tunnel Kilns
 Tunnel Kilns

http://www.made-in-china.com