Types of Materials
Metals
High density
Medium to
high melting
point
Medium to
high elastic
modulus
Reactive
Ductile
Ceramic
s
Low
density
High
melting
point
Very high
elastic
modulus
Unreactive
Brittle
Polymers
Very low
density
Low melting
point
Low elastic
modulus
Very reactive
Ductile and
brittle types
Ceramics
Covalent or ionic
interatomic bonding
Often compounds;
usually oxides
New engineering
ceramics can also be
carbides, nitrides and
borides
Materials Data
Hard brittle solids - no
unique failure strength
because it depends on
crack size
Data can vary markedly
from manufacturer to
manufacturer
Strength may depend on
history after manufacture
(surface damage)
Some data are invariant structure insensitive e.g.
Melting point, Density,
Elastic Modulus
Others are highly
structure sensitive e.g.
Tensile Strength, Fracture
Toughness, Thermal
conductivity, Thermal
Expansion Coefficient
Processing of Advanced Materials
ceramic particle processing
Ceramic powder synthesis
Ceramic particle interaction in liquid
suspension
Ceramic powder packing
Ceramic forming and sintering
Reading List
Y. M. Chang, Physical Ceramics, John Willey
1997
D. Segal, Chemical Synthesis of Advanced
Ceramic Materials (Cambridge University Press
1991).
J. S. Reed, Principles of Ceramic Processing
(Wiley Interscience 1995)
T. A. Ring, Fundamentals of Ceramic Powder
Processing and Synthesis, Academic Press (1996)
Conventional Routes to Ceramic Powder
Precipitation from solution
Powder mixing
Fusion
Example 1: alumina production via
The Bayer Process:
Alumina occurs as the mineral bauxite and is
refined in the Bayer process whereby ore is
initially dissolved under pressure in sodium
hydroxide so that solid impurities ( SiO2, TiO2,
Fe2O3) separate from sodium alumina solution
Al2O3+2OH-+3H2O=2[Al(OH)4]Al OH 3 NaOH NaAlO 2 H O
2
2
This solution is either seeded with gibbsite (-Al2O3.3H2O)
after its neutralisation with CO2 gas.
NaAlO2 + 2H2O =Al(OH)3 + NaOH
2Al(OH)3= 2Al2O3 + 3H2O
Temperature, alumina supersaturation and amount of seed
affect particle size during crystallisation but, as for other
precipitation reactions, the production is agglomerated.
Production of yttria stablised zirconia from the minerals
baddeleyite (ZrO2) and zircon sand (ZrO2.SiO2)
Zirconia exists in three crystallographic forms while
monoclinic phase exists at room temperature for pure
zirconia phase. The monoclinic zirconia is a brittle material,
and toughening of zirconia can be achieved by
incorporation of oxide such as MgO, Y2O3 and CaO into
zirconia to achieve cubic phase and tetragonal phase.
Precipitation from solution
Powder mixing
1) Blending different oxide powders
2) The mixture is grinded or milled
3) Calcination
4) Firing with intermediate grinding
Example: YBa2Cu3O7-
From mixing Y2O3, BaCO3 and CuO, grinding and
heating at 1223K in air. Powder was then
pressed into pellets, sintered in flowing O2,
cooled to 473K in P2 and removed from the
furnace.
Fusion Route to Ceramics
Reactants are mixed as powders and melted, after which
nucleating agents were added. The temperature is then raised
until crystallisation occurs and the microstructure is developed.
These methods are limited by the melting point of reactants
while high temperature can lead to loss of volatile oxides.
Need for improved synthetic routes for advanced ceramics
1. Produce fine powder with low degree of
agglomeration which commonly occurs in
traditional methods.
2. Coatings and fibre productions which can not
achieved using conventional methods.
3. Remove inhomogeneity and voids which
occurs in ceramics produced with
conventional methods
4. Other starting materials for manufacture of
monolithic ceramics
Questions:
1. Compare different conventional ceramic processing
techniques and describe their limitations.
2. What materials can be produced using conventional
ceramic processing methods?
Liquid Phase synthesis by precipitation
Advantage: making pure products
Disadvantages:
1. Drying and calcination
2. Agglomeration and aggregation
Synthesis by precipitation:
Precipitation and Solubility
1. Precipitation due to evaporation
2. Precipitation due to high pressure
3. Precipitation due to reaction-induced supersaturation.
When a substance is transformed from one
phase to another, the change in the molar
Gibbs free energy at constant pressure and
temperature is given by
G 2 1
where is the chemical potential of phase
1 (solute) and phase 2 (solid).
The molar Gibbs energy change
can also be expressed as
a
G RTLn
RT ln S
a0
There are three main categories of
nucleation:
1.
2.
3.
Primary homogeneous
Primary heterogeneous
Secondary
Homogeneous nucleation occurs in the
absence of a solid interface; heterogeneous
nucleation occurs in the presence of a solid
interface of a foreign seed; and secondary
nucleation occurs in the presence of a solute
particle interface
Homogeneous nucleation
V RT ln S a
G v
vr
2
G r
RT ln S a r
*
std
When S=e=2.718
Standard Critical size
Angstrom
Surface energy (J/m2)
802
1.00
401
0.50
40
0.10
20
0.05
*
std
Nucleation rate ~ super-saturation ratio
as 1/S=0
2
J
long
A log S
J max
Heterogeneous nucleation
J T J hom o J hetero
Crystal Shape
h1 h2 hi
1 2 i
The shape of a crystal can be controlled by either
thermodynamics or kinectics. Only for crystals grown
under very, very low supersaturation ratio is a crystal
habit established by thermodynamics. For most other
crystal growth conditions, the kinetics of slowest
growing crystal faces give rise to a crystal shape.
Kinetic shape
Diffusion shape
Aggregate shape
Particles can aggregate by either Brownian or
shear induced aggregation.
Need for improved synthetic routes
for advanced ceramics
Produce fine powder
Coatings and fibre productions
Remove inhomogeneity and voids
Other starting materials for manufacture of
monolithic ceramics
Questions:
Define super-saturation S and explain why
S >>1 for nucleation in most of cases.
For producing crystal with equilibrium
shape, what level of S should be and
explain why?
