MTRL 382 M1 Ceramic Raw Materials and Powders

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M1 ARA1: Ceramic Raw Materials, Powders and Shaping
Compiled by Tom Troczynski
ATOMIC STRUCTURES AND BONDING [CM51-117] are the key determinants of all materials properties. Many
ceramics can be conveniently approximated as ionic solids, their atomic structures based on the electrostatic
interactions of rigid spheres. In reality, a non-metallic bond between dissimilar atoms is usually a mixture of
ionic and covalent bond [CM64]. Both ionic and covalent bond are classified as strong bonds, and therefore
most ceramics have high melting point, are stiff, hard, and are corrosion resistant. Both types of bonds do not
allow easy movement of dislocations under stress, and therefore (unfortunately) ceramics are also brittle.

SIMPLE OXIDE STRUCTURES can usually be described in terms of cations fitting into the tetrahedral and/or
octahedral sites of a densely packed sublattice of anions (typically oxygen, carbon, nitrogen) [CM76-80]. Atomic
bond and structure control single crystal material properties such as stiffness, fracture energy, strength, melting
point, conductivity etc. In engineering (real) materials microstructural features such as grain size, micro-
cracking or secondary phases (e.g. porosity) modify these properties. In engineering components, this is further
modified by the component geometry, joining of the ceramic part to other elements of the larger assembly etc.

Atomic structure of many oxides, e.g. of Mg, Ca, Sr, Ba, Cd, Mn, Fe, Co, Ni is the NaCl-type structure
[CM88]. It can be described as two interpenetrating FCC lattices of cations and anions, with all octahedral
sites filled. The important ceramic members of this family are MgO and CaO . Both are excellent refractory
ceramics, with melting points T
m
in excess of ~2500C; they are also resistant to basic slags substantially free of
alumina and silica.

Zinc blende ZnS, ZnO, diamond, SiC, BeO structures can be also described as two interpenetrating FCC
lattices, but with tetrahedral sites filled. This family includes BeO (one of the highest thermal conductivity
among all ceramics, k
th
> 200W/mK), SiC (wear resistant structural ceramic; abrasive; semiconductive); ZnO is a
varistor (variable resistor), used in protecting electronics from static discharge, and also as chemical sensor.

Structures based on simple cubic packing of oxygen (anions) include fluorite CaF
2
, where cations have
FCC packing, and anions fill the tetrahedral sites of the FCC cation sublattice [CM91]. ZrO
2
is an
important member of this class as one of the strongest/toughest structural ceramics, and also an ionic conductor

Antifluorite K
2
O is reverse of the fluorite structure of CaF
2
[Call390]. Antifluorite has FCC packing of anions
(e.g. oxygen) with cations in the tetrahedral sites. Examples include Li
2
O, K
2
O, Na
2
O which are fluxes for
glass and ceramics; rutile TiO
2
structure is also based on distorted FCC packing of oxygen, but because of their
large charge, the cations (Ti
4+
) fill only half of the available octahedral sites [CM93]. Although large amount of
TiO
2
is used as white pigment in paints and enamels, TiO
2
is also a semiconductor with photocatalytic property,
i.e. can be used in solar cells or for water purification.

The large and important family of titanates combines titania TiO
2
and 2-valence metal oxides such as CaO. In
such perovskite CaTiO
3
structure the anion (O) and the large cation (Ca) combine to form an FCC sublattice,
with the highly charged small cation (Ti
4+
) in the octahedral sites. The small central cation has tendency to shift
from symmetric co-ordination (e.g. under influence of external electric field), which results in a net electric dipole
of the unit cell. Accordingly, BaTiO
3
has an exceptionally high dielectric constant , i.e. is an excellent
ceramic for capacitors. Additionally, barium titanates are also piezoelectric and ferroelectric, and form
extensive solid solutions with other titanates (PbTiO
3
, SrTiO
3
) and with other oxides (ZrO
2
, SnO
2
). The
electrical properties of perovskite structures can thus be changed within wide limits, and constitute significant
fraction of the multi-billion dollar market for electronic ceramics.

SPINELS AB
2
O
4
have FCC oxygen sub-lattice and contain 8 molecules in the unit cell = A
8
B
16
O
32

[CM101]. The unit cell of so called normal spinel has therefore 32 oxygen ions, 32 octahedral sites (half
filled by B) and 64 tetrahedral sites (1/8 filled by A). The examples include: MgO
.
Al
2
O
3
= MgAl
2
O
4
(parent
mineral); ZnO
.
Fe
2
O
3
= ZnFe
2
O
4
; FeO
.
Al
2
O
3
= FeAl
2
O
4
; CoO
.
Al
2
O
3
= CoAl
2
O
4
; MnO
.
Al
2
O
3
= MnAl
2
O
4
;
NiO
.
Al
2
O
3
= NiAl
2
O
4
.

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For certain spinel structures the cations may shift between the A and B sites. Inverse spinel results in this
process, with general formula B (AB) O
4
. In inverse spinel A cations and half of B cations reside in the
octahedral sites, and half of B cations in the tetrahedral sites. This is the structure of most of ferrites, the
key materials for ceramic magnets and magnetic storage media, e.g. hard disks.

Examples of inverse spinels include: MgO
.
Fe
2
O
3
= Fe(MgFe)O
4
; NiO
.
Fe
2
O
3
= Fe(NiFe)O
4
CoO
.
Fe
2
O
3
=
Fe(CoFe)O
4
; FeO
.
Fe
2
O
3
= Fe
3
O
4
= Fe
3+
(Fe
2+
Fe
3+)
O
4
. Additionally, mixed spinel structure is also
possible, with wide variation in composition. The general formula of mixed spinel is (A
1-x
B
y
)(A
x
B
2-y
)O
4

Structures based on hexagonal close packing HCP of oxygen (or other anions) include wurzite ZnS, ZnO,
SiC, Al
2
O
3
[CM94]. In these structures half of the tetrahedral sites in HCP sublattice of anions are filled with
cations. In corundum Al
2
O
3
lattice 2/3 of the octahedral sites in the HCP sublattice of oxygen are filled with the
cations. Corundum, or alpha-alumina, is one of the most important structural ceramics.

ATOMIC STRUCTURES OF SILICATE CERAMICS involve silicon-oxygen SiO
4
tetrahedron [CM104],
OHFig. 1.1. The Si-O bond in the tetrahedron is largely covalent (>60% of covalent nature) and very strong.
Thus, in many silicates the SiO
4
tetrahedron behaves as individual unit of the structure, bonding to other
tetrahedrons through weaker intermediary ion (hence ionic bond), or directly to other SiO
4
tetrahedrons through
stronger covalent bond.

One of the reasons for large variety of silicate structures is that the Si-O-Si bond can easily rotate and its angle
varies therefore between 120 and 180 in various silicate structures, while each oxygen atom is connected to
a maximum of two silicon ions in all silicates. As a result, a large variety of open structures forms for silica-
containing ceramics, with none, one, two, three or all four corners of each SiO
4
tetrahedron shared with
other tetrahedrons, OHFig. 1.2. Ultimately, in 3D silicate structures all of the corners are shared and
therefore the resulting formula is SiO
2
(for pure silica) or SiO
2
.
Me
x
O
y
(for silicate compounds, such as
feldspars). On the other end of the spectrum of silicates there is a structure built of isolated tetrahedra in
which none of the SiO
4
corners is shared. The resulting formula will include SiO
4
4-
groups, their charge
balanced by other cations to the structure.
MULLITE is the most important component of fired aluminosilicate ceramics. It is a solid solution, with
compositional limits of 60-66 mole % Al
2
O
3
, density from 3.16 to 3.22 g/cc, melting incongruently at 1890C, to
Al
2
O
3
+ liquid [CM111,124], OHFig. 1.3. Its molecular composition can be represented ranging from
3Al
2
O
3
.
2SiO
2
to 2Al
2
O
3
.
SiO
2
. Mullite forms needle-shaped precipitates upon firing of clays, and thus
strengthens the ceramic body. Mullite is the only stable intermediate phase at atmospheric pressure in the
Al
2
O
3
-
SiO
2
system (OHFig. 1.3), with a complicated (defected) crystal structure. Pure mullite is excellent
refractory structural ceramic, due to its high melting point, needle-shaped crystallization pattern, with aspect
ratios up to 50:1, i.e. producing relatively high strength and toughness of the structure, and relatively low
thermal expansion coefficient of ~5
.
10
-6
1/K (this results in relatively high thermal shock resistance of mullite
ceramics). Unfortunately, many nominally mullite ceramics contain substantial fraction of other (e.g. lower-
melting point) silicates at grain boundaries, which deteriorate high-temperature performance of such material.

CLAYS are generally classified as layered silicates, having as part of their formula (Si
2
O
5
)
n
2n-
. Clay
minerals are hydrated aluminum

silicates, composed of layers of SiO
4
tetrahedra joined to layers of Me-O-OH
octahedra, OHFig. 1.4,

where Me = Al, Mg, Fe, i.e. trivalent or bivalent ions:

Al
2
(OH)
4
2+
+ (Si
2
O
5
)
2-
Al
2
(Si
2
O
5
)(OH)
4
= Al
2
O
3
.
2SiO
2
.
2H
2
O

The charge of such clay particle is balanced by weakly bonded alkali ions (Na
+
, K
+
), which can be easily
exchanged with other ions in the environments. In particular, if smaller ions with higher charges (Ca
2+
), are
exchanged for the large single-valence alkali ion, interaction of clay particles suspended in water becomes
easier and agglomeration results (viscosity of such suspension increases). Opposite happens when larger ions
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such as Na
+
, or very large silicate ions such as sodium silicate NaSiO
3
-
absorb on clay surface causing stronger
electrostatic repulsion and dispersion of clay particles in the suspension (with the resulting decrease of
suspension viscosity). The ability of clay particles to exchange ions with environment is an important
property, which is usually expressed (measured) through Cation Exchange Capacity (CEC).

Kaolinite (also known as china clay), is formed from the decomposition (weathering) of feldspars in the
presence of water and CO
2
, followed by sedimentation. Kaolinite is usually found as small particles <1 m. It is
a primary constituent of most pottery, paper, rubber fillers, paint, textiles. The morphology, particle size
distribution and chemistry of Kaolin clays are presented in OHFig. 1.5,6,7 and will be further discussed in class.


SILICA has three-dimensional structures [Call105], OHFig. 1.8,9, which include (in order of increasing
temperature):
o-quartz Q, also called low-quartz (<573 C), density d=2.65 g/cc
|-quartz Q, high- quartz (573-870C) d=2.63 g/cc
tridimite T, low, middle and high polymorphs (870-1470 C); low T,d=2.27g/cc,high T, d=2.29g/cc
crystobalite C, low and high polymorphs (1470 - 1710 C) low C d=2.33 g/cc; high C d=2.21 g/cc
silica glass (>1710 C); d=2.20 g/cc

The seven polymorphs of silica involve only three basic structures (Q, T, C). High Low inversions of quartz,
tridimite and crystobalite are displacive (in-phase) transformations, and therefore are reversible and rapid;
these transformations are not diffusional i.e. during transformation, atoms are displaced only a small distance
from their original positions (similarly like in martensitic transformation).

Between-phase transformations (Q T C) are reconstructive. This means that they are slow and
diffusional. Additional agents (e.g. solvents, liquid phases) are sometimes required to accelerate these
transformations to reasonable time (days); compare the following two phenomena of reconstructive
transformation in silica: crystobalite grows at 0.1 m/minute from a pure silica melt at 1680 C, whereas
crystobalite grows at 670 m/minute from a silica+0.3%Na
2
O melt at 1400 C.

The relatively low density of 2.2-2.65 g/cc of all forms of silica (e.g. when compared with other ceramics, such as
alumina of d=4 g/cc) indicates an open structure of silica, with large share of directional covalent bonding
involved (note that Al and Si have almost same atomic mass). However, the differences in density between the
several structural variants of silica (polymorphs) can cause cracking of silica bodies due to phase
transformations. Therefore, silicate materials designated to work at elevated temperatures (T>870C), e.g.
mainly silica and alumino-silicate refractories, should avoid quartz as one of the constituents. Usually, the
quartz crystobalite transformation is promoted during sintering of silica refractories with catalyst added (e.g.
CaO). The crystobalite does not transform back to quartz upon cooling of the refractory brick from the
manufacturing temperature (~1500C) because of reconstructive type of this polymorphic transformation. Thus,
once installed in place and slowly heated to the service temperature (e.g. several weeks of heating to ~1400C is
not uncommon), silica refractory containing crystobalite performs well.

The important difference between the vitreous and crystalline forms of silica is their coefficient of thermal
expansion. For silica glass o < 10
-6
1/K, while for crystalline silica o > 10
.
10
-6
1/K. Thus, thermal shock
resistance of vitreous silica is high and thermal shock resistance of crystalline silica is low.

FELDSPARS. One possible modification of the framework (3D) structure of silica is the substitution of Al
3+
ions
for the Si
4+
ions. Charge balance is maintained through acquisition of alkaline cations this process results in
formation of feldspars. They are low melting temperature (fluxing) silicate agents, important in the sintering
process of clay bodies. Feldspars are the most abundant minerals on earth. The layer (i.e. clays) and chain
silicates emerge by feldspar weathering. The most abundant feldspars include soda feldspar: Na(AlSi
3
O
8
) (
also known as soda ash or albite); potash feldspar: K(AlSi
3
O
8
) (known as orthoclase); and anorthite:
Ca(Al
2
Si
2
O
8
), OHFig. 1.10. The use of feldspars, silica and clays in processing of porcelains and other
traditional ceramics is illustrated in OHFigs. 1.11-15 and will be further discussed in class.

Other modifications of the 3D silicate network include a very large variety of technical glasses, the most
widespread (e.g. in construction) being the soda-lime-silica glass. Silica-based glass science and engineering
is a huge discipline thousands of variants of glasses are custom designed for diversified applications, from
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automotive and construction, to chemical and energy conversion, to optical glasses (reader is encouraged to
further explore CM Chapter 26, and the website of one of the largest producers of glass worldwide, Schott Glass
Inc, at www.schott.com, to appreciate diversification of glass applications).

In summary, silicates are largely diversified compounds containing SiO
4
tetrahedra as principal
components of their atomic structure. The ratio of silica to oxygen determines to a large extent the
character of the very large family of silicates. Therefore, the determination of the Si/O ratio for unknown
silicate materials leads to the identification of their atomic structures and thus properties, and thus is
frequently the first property determined for unknown silicate.

MINERALS-DERIVED RAW MATERIALS AND POWDERS used in production of ceramics have a very
significant impact on ceramics final properties. This is because there are no (or fewer) intermediate refinement
steps available for ceramics, as there are e.g. for metals. For example, the melting - solidification - plastic
deformation commonly used in processing of metals, is impossible for ceramics. Essentially, in ceramic
processing what goes in - comes out. The imperfections (e.g. impurities) in the raw materials remain as
imperfections in the final product. Thus a lot of effort goes into processing of ceramics before sintering, e.g.
processing of powders and shaping of the powders into useful products. This is generally known as science and
engineering of ceramic powder processing.

Ceramics have traditionally been based on oxide minerals, or other minerals that can be decomposed to yield
oxides, like hydroxides, carbonates, sulphides, halides, phosphates etc. Due to the predominance of oxygen in
the Earths crust, nearly half of all known elements occur as oxides, usually complex oxides, like silicates,
[CM345,6]. The series of relative abundance of the elements, which most frequently enter traditional ceramics,
includes: O, Al, Si, Ca, Mg, Ti, Na, K. Silica is the most abundant oxide on Earth: it contributes ~62 wt% of the
continental crust. Rocks with high proportion of SiO
2
(and typically also high content of alumina - as this is the
second most abundant component of the crust, constituting 16 wt%) are known as acidic rocks. Rocks with low
silica (and typically high content of magnesia [~3% of crust] and/or calcia [~6% of crust]) are defined as basic.
Alumina is rather uncommon in the basic rocks, and vice-versa: magnesia is uncommon in the acidic rocks.

The primary raw materials for traditional ceramics include clays, silica SiO
2
, and feldspars (K,Na)AlSi
3
O
8
.
None of the minerals used in the processing traditional ceramics can be treated as of fixed composition. For
example, the content of silica in kaolin clays typically varies in the range of 45wt% to 50wt%, and alumina 35wt%
to 40wt%, OHFig. 1.7. The balance includes volatile components (water and organics), of 10wt% to 15wt%.

A good example of use of the crude and industrial minerals are porcelains, usually referred to as triaxial
porcelains, as the content of the three main raw materials (i.e. clay, feldspar and silica) can be conveniently
plotted within triangular compositional diagram, OHFig. 1.12a,b,c. Ball clays (i.e. clays containing somewhat
larger amount of organic impurities) are usually combined with the purer kaolins (~50/50 by weight) to give the
plastic clay substance of the triaxial porcelain bodies, when mixed with water. The other two components of
the porcelains include feldspar (flux) and quartz (filler; usually in the form of fine silica sand).

Although compositions of various porcelains may vary widely, the rule of thumb composition is about
40wt% of each clay and sand, the remaining 20wt% being the feldspar flux. The phase transformations
during processing of porcelains can be can be followed using practical (non-equilibrium) data presented in
OHFig. 1.11-14 or equilibrium phase diagrams such as OHFig. 1.17,18. These will be further discussed in class.

ADVANCED (SYNTHETIC) CERAMIC POWDERS are intensively processed minerals, generally to obtain
precisely defined chamical composition and particle size (and size distribution). The important examples include:

ALUMINA powders [CM351] represent ~10% of the whole aluminium processing industry. The raw materials for
alumina are bauxites, which are hydrated aluminas (Al
2
O
3
.
nH
2
O, n=1,2,3) with some iron and silicon impurities.
The Bayer process is based on the reversible reaction of aluminium hydroxide with sodium hydroxide. In
the purification process, the bauxite (alumina ore) reacts with NaOH to produce a soluble form of NaAlO
2
, while
the insoluble impurity oxides sediment. The supersaturated solution of NaAlO
2
is seeded with gibbsite crystals
(n=3) to initiate precipitation of substantially pure aluminium hydroxide, which is subsequently decomposed to a
stable o- Al
2
O
3
through calcination at ~1200C. Hard, low density agglomerates of alumina result in this
process, so extensive deagglomeration and particle size reduction to micron-sizes (through milling) is
necessary to make this powder useful for advanced ceramics processing. The resulting alumina powders are
classified vs. particle size and content of sodium oxide impurities, OHFig. 1.20. The reactive powders have
average particle size below 0.5 um and 0.2-0.4wt% Na
2
O (low purity) or <0.05wt% Na
2
O (high purity).
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Refractory-grade aluminas are usually much coarser (several um or larger). Chemical purity of the powder
affects its sinterability and electrical and corrosion resistance of alumina at elevated temperatures.

ZIRCONIA Powders are obtained from Zircon Sand [CM353] (ZrSiO
4
), which is a common zirconia ore,
mined on a large scale in Brasil and Australia. The zirconia production process out of zircon is similar to that of
alumina. It is based on the conversion of a raw material (zircon) into a soluble precursor of zirconia Na
2
ZrO
3
,
and ZrOCl
2
, followed by pyrolysis to ZrO
2
. Before pyrolysis, soluble salts of oxides that stabilise high-
temperature polymorphs of zirconia can be added. These are typically salts of Y, Ca, and Mg.

Alternatively, the zircon sand can be initially pyrolized (decomposed to zirconia and silica) by passing it through
a plasma furnace reaching temperatures >10,000C. The resulting crude zirconia is separated from the
impurities through formation of soluble sodium zirconates and then chlorides which depompose to pure zirconia.

Due to the damaging phase transformations in pure zirconia, bi-valent or tri-valent oxides are often alloyed with
zirconia to stablise the high-temperature cubic or tetragonal phases, refer to the zirconia-yttria phase diagram in
OHFig. 1.21). If properly heat treated, such ceramic alloys as Partially Stabilised Zirconia PSZ or Tetragonal
Zirconia Polycrystals TZP, OHFig. 1.21, result in excellent (strong and tough) structural ceramic, of the
microstructure seen in OHFig. 1.22

SILICON NITRIDE [CM355] is one of the best structural ceramics for high-temperature applications, due
to its relatively high fracture toughness, strength and thermal shock / deformation resistance. Nitridation
of metallic silicon powder (or carbothermal reduction of silica in nitrogen environment) is a relatively inexpensive
route to produce silicon nitride. This powder, however, can contain a large amount of impurities, particularly
oxygen in the form of silica covering grains of silicon nitride. The reactions are:

3Si + 2N
2
Si
3
N
4
3SiO
2
+ 6C + 2N
2
6CO + Si
3
N
4


The problem of impurities carried into powder production stage by raw silica or silicon can be avoided in the
alternative chemical route, which is ~50% more expensive. The starting material is pure silicon tetrachloride,
which reacts with ammonia to produce easy to decompose silicon di-imide:

SiCl
4
+ 6NH
3
Si(NH)
2
+ 4NH
4
Cl Si(NH)
2
Si
3
N
4
+ 6NH
3


Ammonia can be recycled in this process. Calcination of silicon diimide leads to semi-crystalline silicon nitride.

SILICON CARBIDE powders by Acheson Process (Carbothermal Reduction of Silica) [CM354]
This process was developed around 1900s as a low - price route to hard, abrasive ceramics. Electric arc is
ignited through conductive coke and silica sand mixture, OHFig.1.23. The process relies on gas phase reactions
involving SiO gas, so the resulting SiC crystals are coarse and of variable purity, depending on their location in
the reaction zone. Although the overall reaction is SiO2 + 3C SiC + 2CO, the process is controlled by
intermediate gas-phase reactions involving gaseous form of silica SiO with carbon. Refinement of the resulting
coarse SiC crystals to sinterable SiC powders is an expensive process.

The cost of the coarse, ~ mm size macrogrits of SiC, which are a direct result of the Acheson process, is 10x
that of the raw materials (approximately $2/kg vs. $0.2/kg). The cost of abrasive - grade SiC with grains < 100
micrometers is up to 10x that of coarse macrogrits (approx. $10-20/kg vs. $2/kg), whereas the cost of sinterable
powder of submicrometer grain size can increase by another order of magnitude, to the range of $100/kg.
However, the cost of high precision advanced ceramic products of SiC is can reach $1000/kg. The four orders
of magnitude of cost increase, when moving from the raw materials to the finished products prevents
the penetration of consumer markets by advanced ceramics products.

BENEFICIATION OF CERAMIC RAW MATERIALS includes several processing steps before component
forming and sintering. The objectives of beneficiation are: (i) to reduce particles size and modify their size
distribution; (ii) to liberate impurities; (iii) to reduce the porosity of particles; and (iv) to disperse the
agglomerates. Equipment used includes large variety of crushers, mills, grinders. The typical ratio of the feed
size to the product size of milled particles is about 100 for most grinding equipment. For advanced ceramic
powders that must be ground to less-than micrometer, the feed size must be <0.1mm.

Generally, ball mills and vibromills (or attrition mills) are the most widely used for advanced ceramics.
Ball milling (BM) is a grinding process due to impact between tumbling media. However, some attrition can also
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take place in BM. The ball mill must operate below the critical angular frequency F
c
, at which centrifuging of
media takes place and all milling effectively stops. The range of sizes for different classes of particles is shown
in OHFig. 1.24, and the theoretical relationship between particle size and surface area of powder (assuming
spherical particles of same size) is shown in OHFig. 1.25. These will be further discussed in class.

LIQUIDS, IN PARTICULAR WATER, are commonly used for suspension of ceramic powders during
processing, dissolution/transport of additives and dispersion of powders. Water is obviously the most desired
processing liquid, due to environmental concerns and costs. Water is a polar liquid of high dielectric constant
(c = 80) and high surface tension ( I = 73 mN/m at 20C) and medium viscosity ( q = 0.001Pa.s = 1mPa.s = 0.01
Poise = 1 centy-Poise (cP) at 20C, but only 0.5 cP at 50C). Therefore water is a good solvent for polar and
ionic compounds.

Water for ceramic processing must be of sufficiently high quality. Generally "hardness" of water, caused by
dissolved salts of calcium, magnesium and iron, should be low. A quick test of water quality (or total dissolved
solids TDS [ppm]) is an electrical conductivity o [1/ohm.cm] measurement. Examples of conductivity
measurements are as follows:
well water : o ~ 670 1/ohm.cm, TDS = 270 ppm (mostly Ca & Mg salts), pH ~ 8
tap water : o ~ 650 1/ohm.cm, TDS = 260 ppm (mostly Na salts), pH ~ 8
industrial deionized water : o ~ 50 1/ohm.cm, TDS < 20 ppm , pH = 6 - 8
reagent deionized water : o ~ 1.0 1/ohm.cm, TDS < 2 ppm , pH ~ 7
H
2
O only water : o ~ 0.055 1/ohm.cm, TDS = 0 ppm, pH = 7

Oxides interact with water, resulting in spontaneous change of pH and surface charge, Fig. 1.26. Local negative
charges at the oxygen anions are satisfied by the attraction of protons, resulting in an oxide surface with zero-
local charge (note that effectively, oxides have a mono-layer of hydroxides on the surface):
a. {O-M-O-M-O]
-
+ H
+
[O-M-O-M-O-H]
0


In acidic environments, additional protons are adsorbed, resulting in a positive charge on oxide particles:
b. [O-M-O-M-O-H]
0
+ H
+
[O-M-O-M-O-H-H]
+


In basic environments, the reverse reaction takes place, resulting in negative local charges:
c. [O-M-O-M-O-H]
0
[O-M-O-M-O]
-
+ H
+


For high H
+
concentrations (low pH) the reaction 'b' proceeds to the right, creating an effective positive charge
on the surface of the ceramic particle. In basic environments (high OH
-
concentration, high pH) the reaction 'c'
proceeds to the right, creating an effective negative charge on the surface of the ceramic particle. These
reactions of oxides with water are reversible but can have slow kinetics at room temperature (e.g. showing
ageing effects).

Acidic oxides (SiO
2
, ZrO
2
) have a natural tendency to react with pure water (initial pH=7), releasing the
absorbed H
+
and creating a spontaneous negative charge on the oxide surface. Therefore, upon dispersion in
water, quartz, zirconia, as well as silica glasses, feldspars and clays, produce a mildly acidic
environment and spontaneous negative charging of the particles. If the pH is further decreased (i.e. the
concentration of H
+
is increased), protons re-adsorb on the particle surface resulting in a decreased surface
charge, down to zero at the IsoElectric Point IEP at relatively low pH (e.g. IEP for SiO
2
is at pH=2), and
positive surface charge at pH<IEP.

Basic oxides (MgO, CaO, Al
2
O
3
, ZnO, and to a lesser extent Fe
2
O
3
and Cr
2
O
3
) behave in opposite way: the
particles of these oxides dispersed in water spontaneously absorb H
+
, charge positively in pure water,
and therefore increase pH towards basic (as the concentration of OH
-
in the solution increases). A forced
increase of pH (e.g. through addition of ammonia water) will cause release of these absorbed protons,
decreasing surface charge down to zero at the IsoElectric Point IEP at relatively high pH (e.g. IEP for
CaO is at pH=10), and negative surface charge at pH>IEP.

For clay minerals a surface charge can be also created by the release of weakly adsorbed surface ions, such as
surface alkali ions (Na
+
, K
+
) from the surface of clay particles. The tendency toward alkali ion release is
MTRL 382 M1 Ceramic Raw Materials and Powders

Page 1-7
measured through the Cation Exchange Capacity (CEC, expressed in moles of the ions that can be
exchanged, per 100 grams of clay). Negative charge results on the faces of the clay particles. However,
edges of clay particles may attain different charge, depending on pH of the environment, e.g. positive
charges in acidic environments. OHFig1.27 is an excellent illustration of this phenomenon, and shows
absorption of charged gold nano-particles on oppositely charged edges of the broken clay particles. The
negatively charged faces may interact with the positively charged edges leading to a house of cards sub-
structure of the clay-water suspension, with relatively high viscosity.

The charged surfaces of clay particles selectively attract charged ions from the solution, particularly large ions
such as sodium silicate NaSiO
3
-
, resulting in the formation of a double ionic layer on the particles. Effectively
the particles are repulsed from one another (deflocculated), and a low viscosity slurry results. Deflocculation
is the process of particle dispersion produced by increased repulsive forces (electrostatic, steric) due to additives
(deflocculants) adsorbed on the particle surface. Coagulation is the reversible process of particle
agglomeration due to reduced electrostatic and/or steric repulsion forces. Ceramic powders have usually high
surface area and low solubility. Therefore, surface chemistry (rather than bulk chemical properties)
controls the behaviour of ceramic particles in liquids, especially ionic adsorption and particle charging,
and consequently dispersion/coagulation. The charge-control phenomena can be used for the deflocculation
(dispersion) of ceramic particles for a high surface charge, followed by coagulation (agglomeration) at no surface
charge (i.e. at Isoelectric Point IP) and therefore offer a powerful and simple technique for the dispersion and
coagulation of ceramic powders. These processes are of fundamental importance in forming of ceramic shapes
from slurries (wet forming), such as slip casting. This will be further discussed in Module 2 Forming of Ceramics.

BINDERS are chemicals or particles which form bridges between flocculated ceramic grains. Examples of
binders for ceramic powders include colloidal particle binders (such as cellulose or clays, which adsorb and
bridge larger ceramic particles) or molecular binders such as gums, starch, dextrine, paraffins, polyvinyl alcohol
(PVA), polyvinyl butyral PVB, sodium silicates, polymethylmethacrylate (PMMA). The polyvinyl alcohol (PVA) is
frequently used, as it is soluble in warm water, available with various molecular sizes: MW ~ 1000 to 100,000.
For PVA, OH groups of PVA provide adhesion to ceramic surfaces through the hydrogen bond. If PVA is
partially hydrolysed, it contains remnants of acetate groups (-COOCH
3
), and then it is also soluble in cold water.
Another group of binders includes polyvinyl butral (PVB) and polymethyl methacrylate (PMMA). These binders
are soluble in nonpolar liquids and therefore are usually used for processing of ceramics which react with water
(nonoxides) and/or in special forming techniques such as tape-casting and injection molding.

PARTICLE SIZE AND SIZE DISTRIBUTION of ceramic raw materials and powders strongly affect ceramic
forming and sintering, and thus final properties of ceramic components (example of such distributions for kaolin
clays is shown in OHFig. 1.6). Generally, for advanced applications ceramic powders with narrow particle
size distributions that can also be pressed to high green densities are preferred (note however that some
specialized applications require wide particle size distributions this is further exercised in Laboratory #2).
Unfortunately very fine (submicron) powders usually form low-density green ceramic bodies, unless specialised
techniques are used, such as slip casting or injection moulding.

A number of particles joined together by weak Van der Waals forces usually results in a low density soft
aggregate with ~10-30% solids. Some processing routes rely on soft agglomeration of fine ceramic powders
to improve powder flow during processing, for instance, to uniformly fill a mould cavity in dry pressing. Such
uniformly filled mould allows better sinterability, less distortion and higher strength of the final product. This is
commonly accomplished through spraying slurry of ceramic powder into chamber filled with hot gas, followed by
quick evaporation of the liquid from the individual droplets. This spray-drying process results in soft, free-
flowing, ~100 micron agglomerates of weakly bonded sub-micron ceramic particles, OHFig.1.28,29b.

Such soft agglomerates, desirable in ceramic powders, should be differentiated from hard (dense)
agglomerates, which are detrimental in ceramic processing. Hard agglomerates produce non-homogenous
green bodies and/or a non-homogenous sintering rate, because they reach full density long before it is reached
by adjacent material. Thus, adjacent material of lower density must shrink during sintering around the hard,
dense regions. This process leads to tensile stresses and radial cracks in the adjacent material.

Soft agglomerates can be re-dispersed using chemical methods, such as the introduction of a surface
electrostatic charge, or mild mechanical methods such as ultrasonic dispersion or ball milling. Soft agglomerates
are also destroyed during shaping operations (this will be further discussed in Module 2). Hard agglomerates
might be removed by extensive milling such as vibromilling. Those hard agglomerates which persist may be
removed from the system through sedimentation, where fine particles remain in suspension due to a surface
MTRL 382 M1 Ceramic Raw Materials and Powders

Page 1-8
charge and/or their lower sedimentation rate. Since both methods of de-agglomeration operate with liquid
dispersants, forming ceramics from a liquid suspension of powders (slip casting) produces one of the most
perfect green bodies. This is generally classified as colloidal processing of ceramics.

PARTICLE SIZE MEASUREMENT is an important operation in ceramic engineering. The raw materials for
ceramics are usually particulates with a wide distribution of sizes, usually between 0.1 to 100 micrometers
(traditional ceramics and refractories may use up to ~mm size particles). The average particle size and the size
distribution play a decisive role in the choice of ceramic processing techniques and consequently in the
properties of finished ceramic products. One of the simplest and most reliable techniques for particle size
determination is sedimentation in a low viscosity liquid in a gravitational field (for ~10 to ~100 m particles) or
under centrifuging (for 0.01 to 20 m particles). The sedimentation velocity v of a particle in a given gravitational
field depends on the particle's diameter and density and the properties of the liquid. Stokes law describes this
relationship:
v = (d
s
- d
w
)
.
g
.
D
2
/(18q)

where: q = water viscosity = 0.001Pa.s = 1mPa.s = 0.01 Poise = 1 centy-Poise at 20C; d
s
= solid density (i.e.
4.00 g/cc for Al
2
O
3
, 3.20 g/cc for SiC), g = 9.81 m/s
2
.

According to the above equation, it takes about 1 min for 10 m large alumina particles to travel 1 cm in
water. For most alumino-silicates (d
s
= 2.6 g/cc) similar particle will travel 1 cm in ~1.5 min, but if the particle is
1 m the time would be about 64 hrs. Thus for smaller particle sizes (<10 m) centrifuging is necessary to
accelerate sedimentation.

The particle size data are usually presented in the form of a histogram, as wt% vs. log (particle size), or in the
form of cumulative distribution (area under the histogram line), as in OHFig. 1.6. Many ceramic powders exhibit
log-normal distribution, i.e. log(particle size) is distributed normally. Simple verification of the log-normal
distribution is performed by plotting cumulative mass fraction vs. log(particle size) using the special normal
probability paper scale.

PROCESSING OF CERAMICS is much less forgiving, than processing of metals or plastics. In particular,
defects such as cracks introduced at the forming stage have little chance of being healed at the sintering
stage. This is why a lot of attention is being paid to develop methods of effective shaping of ceramic products
before sintering. Generally, the green body (i.e. un-sintered body) formation methods attempt to produce near-
final shape of the ceramic component, with minimal residual porosity. Simple die pressing of plastically
deforming metallic powders allows densification to the level of > 90% of theoretical density TD (equivalent to
<10% porosity). Unfortunately, ceramic powders resist plastic deformation, and best pressing methods achieve
densities on the order of 60% TD. Therefore, the remaining ~40% porosity must be eliminated during
sintering if fully dense article is required which is frequently the case for advanced ceramics. In some
specialised applications, such as filtration membranes, open porosity must remain after sintering and the design
specifications define the size and fraction of the open porosity.

PACKING DENSITY of ideal same-size spheres under sole effect of gravitation (e.g. no electrostatic or other
forces present) depends on their spatial arrangement, e.g. cubic packing results in fractional porosity P = 0.48,
and for dense hexagonal P = 0.26. Loose random packing produces P = 0.40 - 0.50. In reality the porosity is
much higher (P>70%) if the particles are angular or experience additional forces (e.g. electrostatic or Van der
Waals forces, significant for very fine submicron particles). The practical methods to increase powder packing
and decrease porosity at the stage of ceramic green body formation include:

1. GRADING powders by blending fractions of different particle size in order to fill gaps between coarse
fractions, OHFig. 1.28. Typically a ratio of 10/1 to 20/1 is necessary between two or three fractions of particles,
in order to maximise packing. As a result of grading, the packing factor (defined as the vol% occupied by
solids) will initially increase, and then decrease when the ratio of coarse fraction to fine fraction changes from 0
to 1. Note that properly graded blend can have porosity of less than 10% (!) even before sintering starts,
although to achieve this cm-size very coarse particles must be combined with um-size powder (this may be
acceptable though in some applications where strength is not an issue, e.g. in some refractory ceramics).
Having three fractions of particles (coarse, C, of packing factor = u
c
; medium M, packing factor = u
m
; fine
F, packing factor =u
f
), the theoretical maximum packing factor u
max
can be calculated from the Furnas model:
u
max
= u
c
+ (1 - u
c
) u
m
+ (1 - u
c
)(1 - u
m
) u
f

MTRL 382 M1 Ceramic Raw Materials and Powders

Page 1-9

The weights w
i
of the three fractions (per unit volume of the mix) at the theoretical maximum packing factor f
max

can be calculated from the following equations:
w
c
= u
c

.
d
c
; w
m
= u
m

.
d
m

.
(1 - u
c
) ; w
f
= u
f

.
d
f

.
(1 - u
c
)(1 - u
m
)
where d
c
, d
m
, d
f
are the densities of the coarse, medium and fine fraction of the particles respectively.

In the industrial practice the three fractions will differ in size by approximately factor of 7 to 10. This is still
modified by the distribution of the particle sizes of each fraction and the shape factors (the above models were
developed for spherical shapes). Normally the specifications would indicate wt% of the certain mesh size
particles, e.g. for grading refractory brick we may use 30 wt% of -6+20 mesh (3.2-0.82 mm), 30 wt% of -40+60
mesh (0.42-0.21 mm), and the balance 40 wt% of -200+325 mesh (0.074-0.045 mm). The packing density of
such mix will reach ~70% on vibration-assisted filling the mould and ~80% after pressing. Note that the packing
factor is a term widely used by industry, while packing fraction is used more frequently in R&D; both terms
mean the fraction of the volume occupied by the solids, or [1 minus fraction of the pores].

2. FLUID-ASSISTED PACKING of de-agglomerated (dispersed, colloidal) powders can be accomplished
through particles sedimentation or forced flow through a low viscosity (i.e. of viscosity coefficient q < 1 cP,
where 1 cP is viscosity of water at room temperature) suspensions of a ceramic powder in liquid. This is
possible even at very high loading of solids, i.e. solids volume fraction= 0.5 in the suspension, as long as the
powder is well deflocculated, i.e. individual particles separated by surface electrostatic forces or by surface
adsorption (solvents; polymers etc.). This is a key factor for effective slip casting of ceramic powders (refer to
later parts of this chapter).

3. DECREASED INTERACTION between particles, through their spheroidization, the addition of lubricants, or
an increase in average size. For example, the coefficient of friction of wet silica increases from 0.3 to 0.6 when
particle size is reduced from 1 mm to 0.01 mm.

4. BRUTE EXTERNAL FORCE through pressing of relatively dry powders: this approach must overcome
elastic spring-back and may result cracking of powder compacts; pressure gradients exist due to frictional effects
(powder/mould, powder/powder) and thus density gradients result. Irrespectively, this is quite frequent industrial
method of shaping powders as it is relatively simple, fast, and does not require much post-shaping operations
(e.g. machining).

FORMING OF CERAMICS is overviewed in OHFig. 1.29 and discussed in details below.

UNIAXIAL PRESSING OF DRY CERAMIC POWDERS, OHFig. 1.30, 1.31, is still the most common shaping
operation in ceramic industry. The powder preparation for dry pressing includes either dry milling, followed by
granulation, or wet milling followed by spray drying. Both methods must result in a free-flowing powder
composed of weak agglomerates. This is because moulds are typically filled by volume (and not by weight) and
therefore free-flow of powder is necessary to provide repeatable, complete filling of the mould. In order to
process such free-flowing granules, the um-fine (i.e. not-flowing) powders are mixed with 2-4wt% of organic
binders (such as Polyvinyl Alcohol PVA) and then agglomerated using a spray-drier. This results in 50 - 100
um semi-spherical particles, which are free-flow fed to dry pressing moulds. Upon filling the mould the
agglomerates pack to rather low (<0.3) packing fraction, and subsequently disintegrate under the forming
pressure (typically fairly high, i.e. up to 1T/cm
2
= 100MPa, sometimes reaching up to 300MPa). Even at this high
external pressure some interfaces or pores may persist due to the frictional pressure losses within the die, and
particularly if the agglomerates were too strong (e.g. too much binder used). These pressing defects may be
difficult to heal in the subsequent sintering process and form fracture initiation sites (flaws).

Uniaxial dry pressing results in significant gradients of pressure in the pressed body, OHFig. 1.32. The
gradients are proportional to the ratio of height/diameter of the pressed component, and can lead to gradients in
green density and loss of tolerances after the density equalizes throughout the body in sintering. Additionally,
the gradients of density cause gradients of elasticity of the pressed shapes, and thus lead to differential
strain under the pressing stress. Then, upon ejection from the mould, relaxation of this differential strain may
lead to fracture of the pressed component. The common defect of improperly dry pressed ceramic component is
therefore fracture, including laminations, end capping and ring capping, OHFig. 1.33.

During dry pressing, most of the compaction take place for pressures < 40 MPa (OHFig. 1.34), resulting in
~55vol% green density of technical ceramics such as alumina, ~75vol% of plastic ceramics such as wet
clay-containing body (e.g. tile). Some ceramics (such as KBr) may reach >90vol% density due to limited plastic
MTRL 382 M1 Ceramic Raw Materials and Powders

Page 1-10
deformation of the powders. Pressing of spray-dried granules needs to assure that the granules amalgamate
and do not leave behind any interfaces.

Addition of binders and lubricants improves dry pressing of ceramic powders. These soft organic substances
(polymers, such as PVA and PVB) form hydrogen bond with the hydrated surfaces of oxides and then act simply
as a temporary glue. A classic example (practised in the Lab experiments) is polyvinyl alcohol (PVA), which may
be plasticized (i.e. its glass transition temperature lowered below the pressing temperature) by addition of
polyethylene glycol (PEG). Good binder should flow easily during pressing and show little elastic recovery upon
stress relief (i.e. upon ejection of the component from the mould).

ISOPRESSING. In contrast to uniaxial pressing, ceramic components may be formed using isostatic pressure
delivered to surface of a component through a liquid medium, OHFig. 1.35-39. Practically, a flexible (rubber)
mould is filled with powder and sealed, and the setup submerged in the oil/liquid medium under pressure of 200-
300MPa. The uniform pressure assures uniform density of pressed component, and therefore isostatic
pressing offers significant improvement of density distribution over uniaxial pressing. The method can be highly
automated, the best example being isostatic pressing of spark plugs, OHFig.1.39 where the cycle takes about 1
second.

THE RHEOLOGY (i.e. flow pattern) of particle suspensions dominates the processing of plastic and wet ceramic
powders by extrusion, injection molding and casting (discussed below). Rheology affects green-body
strength, drying and firing shrinkage, and flaws distribution in the fired body. The rheology of ceramic systems
can be described in terms of the viscosity of the suspensions. The viscosity coefficient is defined as:
q = [shear stress (t)] / [velocity gradient dv/dr] or :
t = q
.
dv/dr = qd/dt
The CGS unit of q is poise P [(dyn
.
s/cm
2
) = 0.1 (N
.
s/m
2
)] in SI. 1 cP (centipoise) = 0.01 P, which is viscosity of
water at room temperature.

Several types of behaviours under stress can be identified for particle suspensions, OHFig. 1.40, i.e.:

Linearly viscous material flow usually occurs in liquids with simple molecular structures, such as water. For
such liquids q = constant, which is defined as Newtonian flow, stable against necking (this means for example
that continues fibres can be drawn from viscous Newtonian solution)

Non-linearly viscous material: the structure of the material can change during flow (e.g. due to flow), therefore
the shear stress is a non-linear function of shear strain rate:
t = w'
.
(d/dt)
b


In this case, the viscosity coefficient q varies with strain rate, and is defined as the slope of the t versus d/dt
line at any given value of the strain rate:
q = dt /d[d/dt)] = w
.
(d/dt)
b-1


If b < 1 the material is defined as a pseudoplastic; its viscosity decreases with the shear rate. This could occur,
for example, because of the structure of the flowing material gradually becoming more ordered. If b > 1 we have
bingham system, in which the viscosity increases with the shear rate.

The temperature dependence of viscosity can be in general described by the equation: q = q
0
.
exp(Q/RT)
where Q = the activation energy for viscous flow. A two-parameter equation for viscosity has been also verified
experimentally within narrow temperature ranges: log q = A' + B'/T . The following three-parameter equation for
viscosity has been verified experimentally over wide temperature ranges for glasses:
log q = A + B/(T - T
0
)
Suspension of ceramic powder in viscous (liquid) medium exhibits viscoelastic behaviour, governed by the
time-dependent response of a material to an externally applied stress, or time-dependent strain relaxation after
removal of the stress. For viscous material deformation rate is proportional to the applied stress, while
for elastic material amount of deformation is proportional to the applied stress.

The parameters of viscoelastic behaviour affect ceramic powders forming in presence of large amount of binders
(extrusion, injection moulding, tape casting). The strain rates in these methods of forming can vary within five
MTRL 382 M1 Ceramic Raw Materials and Powders

Page 1-11
orders of magnitude (e.g. from 1%/sec to 100,000%/sec), with strong impact on the flow properties of the
material which is being formed.

EXTRUSION is a plastic forming method limited to objects of constant cross section, preferably with high
symmetry, such as rods or tubes (but also bricks, including hollow channel bricks). An extruder is a machine
that forces material through a die by applying pressure. Two basic types include piston and auger type
extruders. Piston extrusion is a batch process typically used for small scale forming, i.e. pilot or lab trials.
Auger extrusion, OHFig. 1.42, is a continuous process that can incorporate a mixing stage with the forming
stage. The potential auger capacities are enormous, and therefore augers are used mainly in heavy clay,
refractories, and whitewares as well as in some technical ceramics applications.

An extrusion batch consists of ceramic powder, a solvent, binder, flocculants or deflocculants, lubricants, and
other additives. Mixing of all these is the most critical step of batch preparation for extrusion. The
purpose of mixing is to eliminate concentration gradients. The effectiveness of mixing can be improved when
dry powder and water (the solvent) are mixed in a high intensity mixer, giving a lower viscosity liquid phase.
The result is better wetting and mixing. Then binder powder is added and mixing continues to dissolve the
additives. Any excess solvent can be removed through filter pressing. This method is typically used in
whitewares. Clay has good plasticity when mixed only with water - no binders are necessary. Clay and water
are typically mixed with 20 - 30 volume % solids and filter pressed to produce higher proportions of solids. Once
optimized, extrusion may be used to mass-produce extremely complex shapes, such as catalytic support
substrates shown in OHFig. 1.43.

INJECTION MOULDING (IM), OHFig. 1.44, is a method for forming complex shapes at high rates, e.g. thread
guides, cutting tools, welding nozzles, and other small, high production volume parts. The ceramic IM machine,
OHFig. 1.45, is not much different than those used for polymer IM. In most cases, it is the last choice of
forming methods, used when no other forming process can produce the degree of complexity necessary,
when the production rate is high, and when the cost of the die(s) can be justified. It is especially attractive
for operations in which significant green machining is currently employed, for example for thread guides. IM has
the potential to eliminate green density variations and the accompanying distortions on firing. IM is usually
limited to parts, which have at least one dimension that is less than 1 cm. Those applications in which the
part dimensions are significantly larger than this (such as turbochargers) are generally not presently
commercially viable. Injection moulding will continue to be attractive mainly for high production volume, high
value-added parts in which the cost of mould design and construction and the long binder removal times can
be justified. IM process consists of 4 parts: (1) Mix preparation; (2) Part formation; (3) Binder removal; (4) Firing

IM involves simultaneous heat transfer and fluid flow, which may lead to defects. It is therefore desirable
to separate the two transport processes, the mould filling step and the setting step from one another, e.g. as
in gel casting.

Thick and thin sections in single IM part present significant problems. For most of the commercial injection
moulding technologies, binder removal is essentially a diffusion-controlled process. Thick sections require
more time to remove the binder than thin sections, because the time for removal is proportional to the thickness
squared. Therefore, by the time the thick section has had enough binder removed to be safe to put into
the furnace, the thin sections are devoid of binder and are thus quite weak. One way to deal with this lack
of mechanical strength is to use multiple binders, miscible with one another, and which can be removed at
different temperatures.

Binder removal is the most important and most difficult step in the injection moulding process. Binder
removal is a diffusion problem and is analogous to drying. It is affected by the particle size of the powder, the
packing arrangement of the powder, the viscosity and vapor pressure of the binder(s), the temperature, and the
gas pressure in the binder removal chamber. It is here that many defects are generated, including pores,
cracks, laminations, pin-holes and others. Binder removal time is long and can range from days to more
than a week, depending on the particular binder system employed. Removal can be assisted by using vacuum,
packing powders, pressure, and oxygen, again depending on the particular binder system.

Polymer removal proceeds firstly through capillary suction and flow into finer powder (large amount of binder in
initial stage), and is followed by thermal and oxidative degradation (smaller remnant amounts of organics in the
pre-firing stage or debinding stage). Debinding (polymer removal) is a difficult and time-consuming process,
and is a limiting feature of the IM technique, because: (i) gases released produce cracking and swelling,
delamination, blistering; (ii) heating rates are very small : < 2C/hr; (iii) temperature/time schedule is sensitive to
MTRL 382 M1 Ceramic Raw Materials and Powders

Page 1-12
component shape, composition, and variation in thickness; (iv) residual ash can interfere with sintering; (v)
component deformation can result during the process; (vi) the process limits component thickness to < 3 cm

IM defects may originate at any of the consecutive processing stages of mould filling solidification ejection
debinding sintering machining. IM defects typically include: Incomplete mould filling and weld lines
result from low fluidity, low temperatures, low injection speed or pressure, or improper gate location. Also:
cracks and voids result form non-uniform shrinkage, especially when the last liquid solidifies in the centre of the
component, but also if extensive orientation of polymer chains takes place.

TAPE CASTING OF CERAMICS has been developed in response to a demand for mass production of low
price, very thin (~0.25 mm) ceramic plates for the substrates for integrated circuits, multilayer capacitors, but
also for other specialised shapes (e.g. multilayer armors), OHFig. 1.46. Similarly as for injection moulding, the
most important initial processing step is preparation of the casting mix (slurry) consisting, on top of the
ceramic powder, large amounts of binder, plasticizers, dispersants and the solvent liquid.

In tape casting the slurry is cast on clean, smooth nonreactive surface, such as glass, stainless steel or polymer
(Mylar, Teflon, cellulose acetate), in a batch or continuous manner. The thin tape (generally < 1 mm, frequently
< 0.3 mm) is usually cast at 1-2 cm/s speed and at shear rate of 20-80 1/s. The pseudoplastic behaviour of
most formulations for tape casting causes the mix viscosity drop by an ~order of magnitude during the casting
process. Typically viscosity drops from ~3000 mPa s for the stationary slurry, to ~300 mPa s for the slurry
passing through the casting gate. After leaving the gate, the tape is dried while passed through the chamber
with counterflowing air, at temperature below the flash point of the flammable organic solvents. After drying the
flexible tape contains typically 50 vol% ceramic powder, 35 vol % organics and the balance 15 vol % porosity.
The organics burnout is easier than in the case of injection moulded parts because of small cross section
dimension of the tape.

SLIP CASTING (SC) allows to aggregate colloidal sol particles to a high green density cake (50-70% TD),
without losing the homogeneity of the suspension. The state of dispersion of colloidal particles (sol) depends on
the characteristics of the double layer (its thickness) as well as the density of particles in solution, so the
consolidation of sol can take place by modifying either one.

In a typical slip casting process, OHFig. 1.47, the consolidation is accomplished by an increase in the density
of the colloidal sol particles in solution through filtering the solvent from the sol. Thus, the term "colloidal
filtration" is sometimes used for slip casting (see below for further discussion of the principles of the Colloidal
Processing of ceramics). During slip casting the consolidation of colloidal particles arises due to an increase in
the particle density in solution upon filtration of the solvent. The filtration process can proceed through plaster
of Paris (gypsum) under capillary pressure P
c
= 0.1-0.2 MPa, or through a stronger polymeric membrane under
external pressures P
e
> 0.2 1.0 MPa. The goal of SC is to produce homogenous microstructures of single
or multiphase ceramic powders. The consolidated layer behaves as an additional filtering medium which is
increasing in thickness with time, so its parameters influence the mechanics of filtration.

SC being a diffusion-controlled process, the cast layer thickness L
c
depends on square root of the casting
pressure and time t, OHFig. 1.48. The constant a increases when the water-permeability of the cast layer
increases. This will happen when the cast layer has relatively high porosity, and is composed of relatively coarse
particles. This however is detrimental for subsequent sintering of the cast. SC process needs therefore to be
optimized such that the casting time is minimized while maintaining good sinterability of the article. Maximising
the solids content in suspension (through good dispersion of the particles, according to the principles of Wet
Colloidal Processing see below), and increasing the casting pressure helps to reduce the casting time. In fact,
recently, the widespread introduction of pressure casting techniques has occurred in the ceramic industry.

WET COLLOIDAL PROCESSING is defined for relatively low-viscosity suspensions of fine (sub-micron)
ceramic powders in water, typically in slip casting (but also other shaping methods and deposition of ceramic
coatings). It provides exceptional microstructural uniformity of the resulting ceramic green body (i.e. body
before sintering). It is also capable of forming complex geometries. Additionally, submicron grains inherently
involved in colloidal processing increase the driving force for densification, to result in desirable fine-grained
microstructures at relatively low sintering temperatures. Some special variants of colloidal processing, such as
sol-gel processing, allow forming of finished ceramic products (typically coatings) at 200-400C, and sometimes
even at room temperature. This allows composing ceramics with other materials, such as metals and even
organics, in the form of reinforcement, protective films etc.
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Colloids are dispersed systems (gas, liquid, or solid), containing at least one phase in the form of discrete
colloidal units, with at least one dimension between 1 nm and 1 m. Therefore colloids have very large
interfacial surface areas (up to 300 m
2
/g or even more) and significant fraction of molecules resides on the
surfaces of colloidal particles. Since sol particles are composed of relatively few (10
3
to 10
9
) molecules, the
large specific surface area of colloids means that their surface properties (rather than their bulk properties)
control their characteristics, in particular surface charge promoting attraction of ions or larger (polymer)
molecules from the solution, Fig. 1.49. Due to their size and surface charges, colloidal particles (sols) either do
not settle under gravity (i.e. remain in permanent suspension due to Brownian motion balancing sedimentation)
or they settle very slowly. The high total surface energy of the sol particles causes thermodynamic instability of
sol and thus promotes condensation due to van der Waals attraction, in absence of electrostatic repulsion.

The interparticle interaction energy is controlled by (i) Van der Waals dispersion forces (attraction); (ii)
surface charge and double layer formation (repulsion) (iii) solvation, i.e. adsorption of solvent molecules
(repulsion) and (iv) steric hindrance due to absorption of large molecules (repulsion). If the overall
repulsion exceeds attraction, OHFig. 1.50, individual sol particles remain in suspension. Otherwise, the particles
agglomerate and sediment or form 3D structure of a gel. The surface charge and a diffused layer of adsorbed
ions of the opposite charge around a particle result in an electrical potential which decreases exponentially
with distance x from the particle surface,OHFig. 1.51:
u = u
0
.
exp(-kx)
where 1/k = Debye length, and u
0
= surface potential (at x = 0). The surface potential u
0
[mV] is a function of
surface charge q and Debye length. For surface potentials lower than ~25 mV, it can be approximated as:
u
0
= q/(k
.
c
D
)
where q [C/m
2
] = surface charge density (typically 0.01 to 0.1 C/m
2
), c = the dielectric constant of solvent (c
D
=
80c
0
for water at 20C), and c
0
= dielectric constant of vacuum = 8.85
.
10
-12
C/Vm.

The thickness L of a double layer is defined at a distance from particle surface x =1/k = L. This is the distance
of e-times decay of surface potential (where e = 2.718... is a base of natural log function), according to the above
expression for surface potential u
0
. It is presumed that ions occupying the area inside the spherical shell
between x = 0 (the particle surface) and x = L (the double layer surface) are carried with the particle during its
movement in a solution. Equivalently, L coincides with the distance from the particles surface to the
hydrodynamic shear plane. The potential at x = L is therefore an important characteristic of the particle/solution
combination and is defined as the zeta potential Z:
Z = u(x=L) = u
0
.
exp(-1) = qL/{c
D
.
2.718}
where L [m] = double layer thickness, typically 1-10 nm. If typical values are inserted into the above equation,
the variation of zeta-potential between 5 mV and 500 mV is obtained.

It is experimentally found for most ceramic particles that the absolute value of zeta-potential |Z| < 100 mV.
Generally, a large Z is required (|Z|>30-50 mV) for sol stabilisation. To increase Z and improve sol stability,
a large surface charge q and a large diffused double layer thickness L is required, for any given
electrolyte. This is relatively easy accomplished by changing pH of the suspension, typically through additions of
nitric acid or ammonia. The effect of pH on Z and sol stability is shown in OHFig. 1.52. The pH for which Z=0 is
defined as Iso-Electric Point (IEP), a characteristic value for oxides dispersed in water, OHFig. 1.53. For
acidic oxides IEP lies in acidic pH range, and for basic oxides in the basic range, OHFig. 1.54.

DRYING OF CERAMIC BODIES is typically required after forming, and before sintering. This is an energy
intensive process, not easy to control because of the stresses produced due to differential shrinkage (e.g. due to
non - uniform removal of water). Drying involves complex processes of simultaneous mass and heat transfer.
The changing ratio of solids, water and pores during drying of clay is shown in OHFig. 1.55. The drying rate,
OHFig. 1.56, is initially constant (at constant temperature, humidity and air flow), as continuous film of water
covers all ceramic particles. As the continuous water film evaporates, the body shrinks and eventually particles
come to contact. At this point, water disappears from the surface, further drying is accompanied by diffusion
from body interior, and shrinkage essentially stops at the critical drying point. Beyond this stage the drying rate
drops, until all liquid is removed from the body. At the critical moisture content, rate of drying decreases as the
particles of ceramic come into contact and any further removal of solvent must overcome the capillary pressure.
END ARA1