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1 INTRODUCTION
Mankind has used ceramics for thousands of years. The
oldest findings of ceramic objects date back more than
20 000 years with a larger scale production of bowls
and storage vessels starting from 6000 BC in China. All
ancient ceramics were based on clay but the properties varied greatly depending on the composition and
firing temperature. The traditional ceramics still form
the basis for dinner-ware, household items and works
of art, but it is the advent of advanced, non-clay ceramics that has sparked the current large interest in ceramic
materials. During the last 50 years, we have seen a
tremendous development of advanced ceramics for functional, biomedical and structural applications (1). Structural ceramics possess unique material properties such as
high strength from room temperature to very high temperatures (up to 1500 C), good wear, and erosion and
corrosion resistance in most environments. Functional
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ceramics are characterized by specific electrical, dielectric, magnetic and optical properties. Advanced ceramics
are currently being used in a large number of applications
such as cutting tools, heat engine parts, body implants,
sensors, capacitors and actuators, with new applications
continuously evolving.
Ceramics are brittle materials at moderate temperatures, which means that a ceramic material is prone to
catastrophic failure when the fracture stress is exceeded.
The strength of a ceramic material can be described by
the Griffith equation (1), as follows:
(9.1)
= Y KIC / C
where is the fracture stress, KIC the fracture toughness, C the defect size, and Y a factor that depends
on the position and shape of the defect. This relationship suggests that there are two ways of increasing the
strength of a ceramic material, namely by increasing the
fracture toughness or by decreasing the flaw size. A flaw
or defect can be thought of as an inhomogeneity in the
Strength, s
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2 POWDER PROCESSING OF
CERAMICS
Low toughness
Flaw size, c
material. These flaws can be cracks, inclusions, agglomerates or pores. If the fracture toughness is increased, the
strength of the material becomes more insensitive to flaw
size (Figure 9.1). This can be accomplished by the incorporation of a second phase such as whiskers, platelets or
particulates (1). In order to obtain the optimal increase
in fracture toughness and to avoid the formation of new
defects, the reinforcing phase has to be well dispersed
in the matrix.
Although high strength can be achieved by defect
minimization, the flaw size distribution can vary from
specimen to specimen, thus leading to a very broad
strength distribution, i.e. low reliability. For design
purposes, the scatter in fracture strength should be kept
at a minimum. Hence, the defect minimization has to
be so effective that defects above a certain size never
occur. The performance at high temperatures is also
controlled by the microstructure of the ceramic material.
The composition and the amorphous or crystalline nature
of the grain boundary phases often determine the creep
or slow crack growth tendency, which are the most
important mechanisms for failure at high temperatures.
The uniformity of the microstructure is also important
for the electrical properties of functional ceramics. For
example, a maximum dielectric constant of BaTiO3
is achieved when the final grain size distribution is
uniform and small. This is very important for multilayer capacitors where a high dielectric constant relates
to a small size and high efficiency of the capacitor.
203
from each other. A flocculated concentrated suspension, on the other hand, consists of clusters of particles
touching each other and, hence, creates an inhomogeneous suspension microstructure. This difference in
suspension microstructure and suspension rheology can
have a large impact on the behaviour during consolidation. For example, an inhomogeneous microstructure
can be expected to influence the filtration rate in pressure filtration and slip casting. Liquid flow is facilitated by the existence of larger channels between the
clusters.
This review intends to cover the field of colloidal
processing of ceramics. To support the understanding of
the underlying colloidal concepts, we will briefly introduce a background on the major particle interactions.
This is followed by a section on deagglomeration and
dispersion. An orientation on how the rheological properties of concentrated suspensions can be manipulated
is also given. The various colloidal consolidation routes
are presented and we also discuss the drying and burnout
behaviour.
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(9.2)
Material
Vacuum (Air)
Water
15.2
18.0
14.5
10.1
6.96
11.4
12.1
9.86
8.17
24.8
18.0
16.7
8.86
6.50
14.8
15.3
13.3
9.21
15.2
17.2
20.3
3.67
8.0
3.35
1.44
0.49
3.40
2.21
1.34
4.98
10.9
5.47
4.85
1.02
0.46
4.77
5.35
3.03
1.89
4.80
5.74
7.23
-Al2 O3
BaTiO3 (average)
BeO (average)
CaCO3 (average)
CaF2
CdS
MgO
Mica
PbS
6H-SiC
-Si3 N4
Si3 N4 (amorphous)
SiO2 (quartz)
SiO2 (silica)
SrTiO3
TiO2 (average)
Y2 O3
ZnO
ZnS (cubic)
ZnS (hexagonal)
3Y-ZrO2
MOH2 MOH + H
(9.3)
(9.4)
Both the pH and the reaction constant for the respective dissociation reaction control the net charge. The
point of zero charge (pzc) is the pH where the surface
concentration of (MO ) and (MOH2 + ) are equal. The
surface charge is negative at a pH > pHpzc and positive
at pH < pHpzc . Ions of opposite charge (counterions)
are attracted to the charged interface and form a diffuse
ion cloud adjacent to the particle surface. The thickness of this electrical double-layer is a very important
parameter, which determines the range of the doublelayer repulsion. The concentration and valency of the
1/2
0 kT
1
=
e2
ni zi2
(9.5)
(9.6)
Interaction energy
Double-layer
repulsion (VR)
EB
Distance, D
Secondary minimum
van der Waals attraction (VA)
Primary minimum
Figure 9.2. Schematic energy versus distance curves for double layer repulsion and van der Waals attraction. (Adapted from
ref. (15) with permission of The American Ceramic Society)
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8kT L
2L
F (D)
=
7
R
35 s 3
D + 2
7/4
D + 2
+5
12
(9.7)
2L
where s is the distance between the chain anchoring
points, L denotes the interaction range from each surface
and is the thickness of the highly compressed polymer
layer.
The term electrosteric stabilization is often used to
describe how polyelectrolytes act as dispersants. Electrosteric stabilization is a combination of a pure electrostatic repulsion and a polymeric repulsion where
the relative importance of the respective contributions
is closely related to the segment density profile at
the interface. If the polyelectrolyte adsorbs in a flat
conformation, the polymeric repulsion is short-range
in nature, and the stabilization mechanism is mainly
electrostatic. This is usually the case when the polyelectrolyte is highly charged, has an extended conformation, and the particle surface is oppositely charged.
With thicker adsorbed layers, having chains protruding into the solution, the polymeric contribution will
become more important. In addition to the steric contribution, there is always an electrostatic contribution
since the adsorption of a highly charged polyelectrolyte
on a weakly charged, amphoteric oxide surface usually
results in an increase of the net surface charge density.
4 DEAGGLOMERATION AND
DISPERSION
The deagglomeration and dispersion of ceramic powder
processing is crucial for obtaining a high reliability and
high strength in the final material. Any inhomogeneity
in the suspension, e.g. segregation, density gradients
or presence of agglomerates, is a potential flaw in the
sintered material. Hence, the agglomerates, which exist
in most starting powders, either have to be broken
down or removed. The definition of an agglomerate
depends on the chosen length scale and what is defined
as the primary unit. The crystallites, i.e. the single
crystal units in a powder, are typically quite small,
<100 nm, which means that the primary particles,
typically of a size between 0.5 and 1 m, are, in fact,
small agglomerates. These primary particles (more
correctly called primary agglomerates) constitute the
building blocks of secondary agglomerates of a typical
size between 50 and 200 m (Figure 9.3). With the
current interest in using finer and finer particles and
going into the so-called nanosized (<100 nm) range,
it becomes necessary to break down not only the
secondary agglomerates but also disintegrate the primary
agglomerates.
50 m
50 m
Mild
agitation
Primary agglomerate
Large
agglomerate
Primary
agglomerates
Primary
agglomerates
Crystallites
100 nm
Figure 9.3. Schematic showing the hierarchial structure of ceramic powders. (From E. Laarz, B. V. Zhmud and L. Bergstrom,
J. Am. Ceram. Soc., 83, 23942700 (2000), reprinted with permission from The American Ceramic Society)
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Fd 6vR
(9.8)
(9.9)
h = 2(rR)1/2
h(t) h
km t
(9.10)
(9.11)
km t 2
(9.12)
Fn E h
(9.13)
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5 RHEOLOGICAL PROPERTIES OF
CERAMIC SUSPENSIONS
(e)
(d)
(b)
sy
(9.14)
(e)
(d)
(c)
(b)
(a)
(c)
(a)
Figure 9.4. Classification of rheological behaviour under steady-shear conditions, plotted as shear stress and viscosity versus
strain rate; (a) Newtonian; (b) shear thickening; (c) shear thinning; (d) Bingham plastic; (e) nonlinear plastic. (From ref. (4) with
permission from Marcel Dekker Inc.)
0
b p
(9.17)
(9.16)
Viscosity (Pa s)
G = 0 /0
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101
0.50
100
0.48
10
0.45
0.42
102
101
100
101
102
103
104
Figure 9.5. Degree of shear thinning of silicon nitride suspensions at different solids content. (From L. Bergstrom, Colloids
Surf., A, 133, 151155 (1998) with permission from Elsevier
Science)
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(9.18)
n
(9.19)
r = 1
m
where m and n are used as fitting parameters. The best
fit of the experimental data to equation 9.19 shows that
the maximum volume fraction is drastically lower for
the SiCw suspension (m = 0.28) when compared to the
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105
Relative viscosity
10
0.6
Al2O3
SiCW
103
Si3N4
102
d = 5 nm
0.2
0.0
102
101
d = 20 nm
0.4
Flocculated,
thin layer
101
100
Flocculated,
thick layer
101
0.1
0.2
0.3
0.4
0.5
0.6
3
(9.20)
eff = 1 +
R
where is the thickness of the repulsive barrier and
R is the radius of the spherical particle. The effective volume fraction in an electrostatic system relates to
the particle size and the salt concentration through the
Debye length, / = 1/. Figure 9.7 illustrates the effect
of using two different thicknesses of the repulsive barrier
( = 5 and 20 nm) on the maximum packing density of
the solid particles. A thickness of 520 nm corresponds
to polymer layer thicknesses commonly encountered in
practical systems when using commercially available
dispersants. It is assumed that the spherical, monodisperse (coated) particles will pack to a maximum volume fraction of eff,m = 0.64 (random close packing).
Figure 9.7. The effect of particle size and the repulsive range
on the particle packing density. (From ref. (15) with permission
of The American Ceramic Society)
6 CONSOLIDATION
Dense, homogeneous green bodies can be prepared from
dry powder, suspensions or pastes. The green body
should be characterized by a high, uniform packing
fraction of particles, small and narrow size pores,
and a high degree of homogeneity, irrespective of the
forming method being used. The green body should also
possess a sufficient strength to allow handling without
shape distortion. The different forming methods utilize
solidliquid separation, particle flow and compaction,
solidification of the continuous medium or gelation to
produce ceramic components with different geometries
and microstructures. The features of the various methods
are outlined below.
(a)
Consolidated layer
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Ceramic slip
Mould
(b)
w
Supernatant
Cake
Rotor
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DC
+
Cathode Anode
Particle
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
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Barrel
Screw
Figure 9.10. Schematic representation of an injection moulding machine. (From ref. (4) with permission from Marcel
Dekker Inc.)
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Solid
0.1
0.01
Solid
Liquid
Liquid
0.001
3
7
pH
9
IEP
11
Figure 9.11. Stability diagram for an electrostatically stabilized alumina suspension as a function of pH and salt concentration. (Adapted from Graule et al., Ind. Ceram., 16, 3134
(1996))
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As cast
Green-body
shrinkage
and
deformation
Particle
contact
with
liquid
filling
the pores
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Liquid
Weight
Completely
dry
Figure 9.12. Schematic representation of the drying of a saturated powder body showing the weight loss with time. (From ref. (3)
with permission from Academic Press)
8 ACKNOWLEDGEMENTS
The author gratefully acknowledges the Brinell CentreInorganic Interfacial Engineering, and the Institute for
Research and Competence Holding (IRECO) for financial support. Wolfgang Sigmund, Brian Sundlof, Eric
Laarz, and Anders Meurk are thanked for stimulating
discussions.
9 REFERENCES
1. Richerson, D. W., Modern Ceramic Engineering Properties, Processing and Use in Design, 2nd Edn, Marcel
Dekker, New York, 1992.
2. Lange, F. F., Powder processing science and technology
for increased reliability, J. Am. Ceram. Soc., 72, 315
(1989).
218
3. Ring, T. A., Fundamentals of Ceramic Powder Processing and Synthesis, Academic Press, San Diego, CA,
1996.
4. Pugh, R. J. and Bergstrom, L. (Eds), Surface and Colloidal Chemistry in Advanced Ceramics Processing, Marcel Dekker, New York, 1994.
5. Reed, J. S., Introduction to the Principles of Ceramics
Processing, Wiley, New York, 1988.
6. Aksay, I. A., Microstructure control through colloidal consolidation, in Advances in Ceramics, Vol. 9, Mangels J. A.
and Messing, G. L. (Eds), American Ceramics Society,
Columbus, OH, 1984, pp. 94104.
7. Russel, W. B., Saville, D. A. and Schowalter, W. R., Colloidal Dispersions, Cambridge University Press, Cambridge, UK, 1989.
8. Israelachvili, J. N., Intermolecular and Surface Forces,
2nd Edn, Academic Press, London, 1992.