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Advanced Ceramics Processing

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 CHAPTER 35
ADVANCED CERAMICS PROCESSING
Lisa C. Klein
Department of Ceramic and Materials Engineering
Rutgers University
Piscataway, New Jersey

1 OVERVIEW OF CERAMIC 3 ADVANCED PROCESSING 1117

PROCESSING 1113 3.1 New Energy Sources 1117
1.1 Microstructure 1114 3.2 New Shapes 1120
1.2 Motivation for Improvements 1114 3.3 New Precursors 1123
1.3 Manufacturing versus
Processing 1115
1.4 Back to Basics 1115 4 SUMMARY AND PROJECTIONS 1127

2 CONVENTIONAL PROCESSING 1115 BIBLIOGRAPHY 1127

1 OVERVIEW OF CERAMIC PROCESSING

Processing of ceramics is carried out through the consolidation of loose powders
to form polycrystalline objects. The majority of ceramics are sintered, using
solid-state sintering or liquid-phase sintering [See, e.g., Rahaman (1995),
Barsoum (1997)]. Generally, sintering occurs at temperatures below the melting
point for single-phase ceramics or below their liquidus for multiphase ceramics,
although a liquid phase may be present temporarily during sintering. The dis-
tinction that sets the majority of ceramics apart from the minority is the fact that
the majority is sintered below the melting temperature by solid-state transport.
The minority are those processed above the melting temperature, in particular,
glasses and glass-ceramics. Therefore, the key to successful processing of ce-
ramics is finding energy sources that can drive the transport processes.
In most cases, the source of energy is surface energy. The elimination of
surface energy, where surfaces of loose powders are converted to grain bound-
aries between particles, is what accounts for most of the energy available for
sintering. There are countless examples of ceramic products where the conver-
sion of this energy has resulted in a successful outcome. Nevertheless, there can
always be improvements in ceramic processing. Therefore, the focus of this
chapter is on new sources of energy to drive the consolidation and better, more
efficient uses of this energy to reach the goal of a well-consolidated, polycrys-
talline ceramic.

Handbook of Materials Selection, Edited by Myer Kutz

ISBN 0-471-35924-6 2002 John Wiley & Sons, Inc., New York

1113
1114 ADVANCED CERAMICS PROCESSING

1.1 Microstructure
When it comes to describing the outcome of processing in ceramics, the focus
of that description is the microstructure (Allen and Thomas, 1999). To put this
in perspective, the terms we use in describing microstructure need to be defined.
As such, microstructure is described in terms of grains, grain boundaries, and
porosity. For single-phase material, this is straightforward, but far more compli-
cated for multiphase materials. Because the starting point for processing is loose
powders or particles, the first feature in the microstructure is described as necks,
which are the contacts between particles. Next, we distinguish between a single
crystal, which is a perfect crystal without interruption, and a grain, which is
a single crystal of finite size. Once there is consolidation within a powder com-
pact, what was once called a particle becomes a grain. The regions of disorder
between these grains become grain boundaries. In the grain boundaries, we often
find a second phase, which is the remains of a liquid phase.
Another way of looking at the microstructure is focusing on the porosity,
which is the collection of voids. Initially, the porosity is interconnected. Grad-
ually, material transport fills in the voids, bringing more area of grains into
contact. Triple-grain junctions are the typical location of closed porosity. In the
end, the polycrystalline solid takes on its final microstructure through grain
growth and coarsening. In short, the goal of sintering is to turn the loose powders
into a well-consolidated polycrystalline solid.
With these terms, the features of the microstructure can be quantified. Quan-
tities such as pore volume, percent theoretical density, and grain size can be
used to draw the correlations we are familiar with in materials science. No
materials science student can graduate without learning the structure
processingpropertiesperformance paradigm known as SP3. The structure of
the material determines the properties, and the structure, in turn, is determined
by processing.
1.2 Motivation for Improvements
An alternative way to view ceramic processing is in terms of industrials needs.
Suppose there is a need, that can be satisfied by a ceramic product. The engi-
neering factors involved are shown in Fig. 1. The role of processing weighs
more heavily on the manufacturing side. Because issues of cost and reproduci-
bility balance the function of the product, the eventual implementation of the
ceramic product may hinge on whether or not the product can be made in a
practical way.

Fig. 1 Industrial issues relevant to ceramics.

2 CONVENTIONAL PROCESSING 1115

1.3 Manufacturing versus Processing

Is ceramic manufacturing comparable in scale to metals fabrication or compa-
rable in automation to pharmaceuticals production? The easy answer would be
no. What efforts have been made to introduce continuous production, automa-
tion, and continuous improvement into ceramic manufacturing? How much in-
telligent processing is used in ceramic manufacture? By intelligent processing,
we mean that we can insert diagnostics in the ceramic process that allow us to
evaluate physical properties during the process. The goal of intelligent manu-
facturing is achieved when we can correct the process to stay within acceptable
values of our physical properties before we reach the final product.
These questions about intelligent manufacturing are important to the health
of ceramic manufacture in a setting where at times more than one material or
design satisfy the industrial needs. Clearly, there are some ceramic products that
cannot be replaced by other material systems, but there are other ceramic prod-
ucts, such as glass containers, that are seriously threatened by other materials,
such as plastics. To answer these questions about ceramic manufacture, and, in
particular, about manufacture of advanced ceramics, requires a careful look at
individual segments of the industry. Moreover, they are useful questions to keep
in mind, as new processing technologies are introduced.
In terms of manufacturing a product that meets customer requirements, the
technical issues include quantitative specifications of properties, process im-
provement and zero defects. The nontechnical issues include government reg-
ulation and availability of investment for capital and product development.
Overall, the goal of manufacturing is to produce a high-quality product rapidly,
in an economical way, and in an environmentally acceptable manner.
1.4 Back to Basics
To improve processing means understanding the fundamental mechanisms dic-
tated by thermodynamics and kinetics. What goes on in ceramic processing is
listed in Fig. 2, connecting raw material to finished part. In taking raw material
to finished part, how many of these changes can be followed in real time? How
many of these changes are predictable, reproducible, and what is the accuracy
of the measurement that tells us that they are reproducible? These questions are
the real challenges of ceramic processing and ceramic manufacture.
2 CONVENTIONAL PROCESSING
As with any materials process, the unit operations we evaluate are powder prep-
aration, forming, consolidation, and sintering. For each step, it is necessary to

Fig. 2 Process-induced changes that link raw material to finished part.

1116 ADVANCED CERAMICS PROCESSING

Table 1 Examples of Structural and Functional Ceramics, Principally Single-Phase,

Produced by Sintering
Ceramic Property Application
Structural
ZrO2 High-temperature strength Furnace lining
Si3N4 Wear resistance Bearings
SiC Corrosion resistance Heat exchanger
TiC Hardness Cutting tools
Functional
BaTiO3 Ferroelectricity Capacitor
Al2O3 Electronic insulation Substrates for electronic packaging /
Spark plugs
BaO 6Fe2O3 Hard magnet Ceramic magnets
(Zn)Fe2O3 Soft magnet Transformer core
LiNbO3 Nonlinear optics Optical switches

understand the mechanisms and the extent to which we can model the steps with
thermodynamics or atomistics. A key question at each step is: What needs to be
measured and how can it be measured? Does the instrumentation exist that al-
lows us to follow a ceramic process in a continuous way? Are we measuring
the parameter directly or indirectly? When a process seems to be going out of
control, how can we fix it and can we fix it without going back to the beginning?
The steps in the fabrication of polycrystalline ceramics are divided between
those before firing and those during and after firing. Many excellent treatments
of ceramic processing have appeared over the last few years. A comprehensive
handbook on the subject treats each step in detail (Schneider, 1991). For con-
ventional ceramics (e.g., whitewares), ceramics produced in large volume (e.g.,
abrasives), and ceramics used at high temperatures (e.g., refractories), there are
textbooks that cover the processing and the applications [see, e.g., Reed (1995),
West and Hench (1990), Richerson (1992)]. Table 1 lists typical single-phase
sintered ceramics and their uses.
Some of the common steps in ceramic manufacture are shown in Fig. 3.
Rather than review what is now well known, this discussion will cover pro-
cesses that are new. These processes may not be suitable for production of all
ceramics in widespread use. Instead, these processes are variations of conven-
tional ways, in some cases, and radically new ways, in other cases, for making
ceramics. In all cases, the advantages of these processes over old methods will
be highlighted and evaluated.

Fig. 3 Unit operations in manufacturing ceramic part.

3 ADVANCED PROCESSING 1117

3 ADVANCED PROCESSING
When it comes to advanced ceramics, we can assume that there is value added
in the product that justifies advanced processing. If there is no value added, then
we might as well follow the methods developed thousands of years ago for
pottery. It would be foolish to suggest that we are abandoning pottery and
whitewares or that we ever will. To the contrary, whitewares constitute a major
part of the ceramic industry, and there are continuing improvements in their
manufacture, with respect to increasing their environmental friendliness, recy-
cling, performance, and economics.
The need for improving conventional processing has been well served [see,
e.g., Lange (1989), Lewis (2000), Sigmund et al. (2000)]. When it comes to
conventional powder processing, the needs are water-based systems to replace
organic-solvent-based systems, denser suspensions, better powder stabilization
schemes, and more in situ diagnostics. While addressing these issues is critical
to the health of the ceramic industry, the long-term survival and growth of ce-
ramics require some radical new processing schemes. The new technologies are
the basis for the remainder of this chapter. The interested reader will find that
conventional ceramics are treated thoroughly in many excellent textbooks [see,
e.g., Reed (1995)] and there is not enough room in this review for a full treat-
ment.
In looking for what is new in ceramic processing, three directions appear.
One can look for new energy sources for processing, such as microwave heating,
self-propagating reactions, mechanochemical processes, or reaction bonding.
One can look for new ways to control particle characteristics, such as size (e.g.,
nanoparticles), shape (e.g., equiaxed particles), metastable phases (e.g., rapid
solidification), or templating (e.g., seeding). Alternatively, one can look for new
building blocks, such as polymer precursors or solgel processing.
3.1 New Energy Sources
Microwave Processing
What is microwave processing? From the initial attempts in around 1979 to sinter
ferrites with microwaves, it has been know that certain materials show heating
effects through dielectric loss when irradiated with microwaves at a frequency
of 2.45 GHz. Ordinarily, microwaves, which are located on the electromagnetic
spectrum between infrared and radio waves, correspond to energies characteristic
of molecular rotation. This explains the usefulness of microwaves in reheating
food, which contains water molecules. In addition, selected ceramic composi-
tions show rapid heating through the use of microwaves. While materials with
low loss tangents are transparent to microwaves and materials, such as metals,
with high loss tangents reflect microwaves, it is the materials with intermediate
loss tangents that can benefit from microwave treatment. In the case of ceramics,
where an ion jump relaxation mechanism gives rise to polarization in an applied
electric field, there is the possibility to use microwaves to assist sintering [see,
e.g., Katz (1992), Clark and Sutton (1996)]. The advantages of microwave heat-
ing are experienced through volumetric heating, and rapid heating, resulting in
increased kinetics. The danger of microwave heating in ceramics is nonuniform
susceptibility, leading to localized hotspots, nonuniform grain growth, or ag-
1118 ADVANCED CERAMICS PROCESSING

glomeration. Microwave sintering has been investigated in oxide ceramics pri-

marily, as well as nonoxides. The greatest use of microwaves in ceramics
processing is in drying, but the use of microwaves in sintering is promising in
cases where volumetric heating and small grain size are desirable.
Self-Propagating Synthesis
What is self-propagating high-temperature synthesis, often abbreviated SHS? It
is a method for preparing composites that involves a chemical reaction that is
exothermic. Once the reaction is initiated, the conversion of chemical energy to
thermal energy is used to consolidate a powder compact into a composite. The
product of SHS is rarely homogeneous or free of pores, but the kinetics of the
consolidation is very rapid.
For example, a composite of Al2O3 ZrO2 Nb can be produced [see, e.g., Holt
and Dunmead (1991), Munir (1988), Yi and Moore (1990)]. Initially, reactant
powders are milled together and pressed into a simple shape. Beginning with a
compact of niobium oxide and an intermetallic such as Al2Zr, it is possible to
heat the compact to around 900C to ignite the reaction. An ignitable powder in
this case might be a mixture of aluminum, iron oxide, boron, and titanium on
the surface or in a layer in the compact. Reactions in the igniter layer at the
ignition temperature set off a self-propagating wave, which generates an adia-
batic temperature as high as 2300C. This temperature is sufficient to melt a
eutectic of Al2O3 and ZrO2. The wave propagation velocity depends on the
particle size and the presence or absence of liquid phase. The propagation is
rarely steady state, and while it is hard to control, it is reproducible. The resulting
composite contains Nb metal dispersed in an Al2O3 ZrO2 matrix. Depending on
the size of the starting powders, the ignition can generate stable wave propa-
gation through the compact that influences the matrix composition. The SHS
process, as practiced in ceramic matrix composites, has been described as burn-
ing a cigar in a bell jar. The approach has been expanded to many technologi-
cally important systems, well beyond the original class of thermite reactions.
Other ceramic composites produced by SHS include TiCNiAl and TiB2 NiAl,
as well as, compounds such as MgCr2O4 and MgAl2O4.
The advantages of SHS are the rapid nature of the process and the reduced
energy consumption. These advantages are balanced by the difficulty experi-
enced in controlling the process and the restriction to systems where exothermic
reactions occur. Nevertheless, there are many solidsolid and solidgas systems
that experience exothermic reactions once they are ignited, and further work is
being pursued.
Mechanochemical Synthesis
What is mechanochemical synthesis? It is a process that uses mechanical acti-
vation to bring about chemical reactions instead of using calcination at moderate
to high temperature to accomplish the same result [see, e.g., McCormick and
Froes (1998), Gilman and Benjamin (1983)]. For example, to prepare a multi-
component oxide such as lead zirconate titanate (PZT), it is possible to mix
powders of PbO, TiO2, and ZrO2, beginning with high-purity commercial pow-
ders, first in a ball mill in ethanol for 48 h, followed by drying, and finally in
3 ADVANCED PROCESSING 1119

a shaker mill at 900 rpm for up to 25 h (Lee et al., 1999). The high-energy
milling leads to mechanical activation. A schematic flowchart of the process is
shown in Fig. 4. At the same time, the surface area is increased, and the so-
called mechanical alloying of the powders yields crystal sizes that give broad-
ened X-ray diffraction peaks. The powders that exist following the milling do
not give crystal patterns for the individual components. Rather, the appearance
of the X-ray diffraction pattern suggests an X-ray amorphous or metastable form
of the PZT phase. When carried out properly, the mechanically activated powder
converts to crystalline PZT upon heating without the usual intermediate phases
of PZ or PT. In addition, the mechanically activated powder sinters more readily
than conventional powders. While the effects of high-energy ball milling are
generally favorable, there are some drawbacks associated with handling fine
particles, particle aggregation, and lead loss.
Originally, mechanochemical synthesis was designed for alloying metals and
intermetallics. Nowadays, many multicomponent ceramics, especially technolog-
ically important ferroelectric compositions, are prepared using mechanochemical
activation. The benefits are seen as (a) a particle size refinement, (b) partial
amorphization, and (c) and creation of distributed nuclei of the desired phase
during the mechanical treatment. The chemical part of mechanochemical
processing is said to be the chemical reactions that yield the nuclei of the equi-
librium phase, according to the phase diagram. The solid-state reactions occur
during the mechanical activation, rather than during thermal activation. This
claim is supported by the observation that the nuclei increase in number and
size as the time of the mechanical treatment increases, where thermally activated
growth would require much higher temperatures. Similarly, the exotherm ob-
served for the formation of perovskite in the thermal analysis of a conventional
powder is not observed for the mechanically activated powder because the per-
ovskite phase already exists. Consequently, the desired phase, typically perov-
skite, can be developed without significant pyrochlore, where conventional
processing may require high pressure and high temperature to develop perov-
skite.
Many ternary oxide systems have been investigated and the mechanochemical
treatment has been found to be beneficial. Where mechanochemical treatment is
not recommended is systems that are not reactive, those that show agglomeration
rather than size reduction, and those that require some additive to activate the
powder where the additive, in turn, becomes a contaminant. Alternatives to me-

Fig. 4 Schematic flowchart for mechanochemical processing of PZT.

1120 ADVANCED CERAMICS PROCESSING

chanochemical synthesis are, therefore, some of the other methods described,

such as solgel processing, hydrothermal synthesis, pulsed laser ablation, or
metal organic decomposition.

Reaction Bonding
What is reaction bonding? To answer this, a good example is an aluminum-
oxide-containing composite, referred to as reaction bonded aluminum oxide
(RBAO). This technique begins with a porous alumina preform that is infiltrated
with aluminum metal powders, or a compact of aluminum oxide and aluminum
metal powders [see, e.g., Wu et al. (1993)]. The aluminum metal is oxidized as
the compact is heated up to about 1000C and the compact densifies on contin-
ued heating to about 1400C and higher. The process is near-net shape in that
the part changes by sometimes as little as 1% in dimension. The mechanism for
the growth of oxide is the diffusion of oxygen through the polycrystalline alu-
mina. The oxidation kinetics can be controlled by additions of other oxides, such
as zirconia.
A variation of reaction bonding is the directed metal oxidation, or DIMOX,
process [see, e.g., Nagelberg et al. (1992)]. In this case, there is a growth front
presented by the breakdown of the alumina film on fresh aluminum melt. The
oxidation proceeds by diffusion of oxygen through the melt until the metal is
depleted. Similar to RBAO, the kinetics are controlled by alloy additions, in this
case, commonly MgO.
In all cases where reaction bonding is used, including earlier studies on re-
action-bonded silicon nitride (RBSN), there have to be favorable thermodynamic
conditions for the reactions to occur. The reactions bear some similarity to SHS.
The advantage of the process is the near-net shape capability for composites that
are difficult to densify by conventional means. The difficulty, however, is that
the approach is limited to a few reactive systems. Nevertheless, there are critical
applications for these materials, such as lightweight armor, that cannot be sat-
isfied in any other way.

3.2 New Shapes

Nanotechnology
What aspects of nanotechnology are relevant to advanced ceramic processing?
For a given application, there are now several suitable methods for preparation
of nanostructured materials with controlled chemical and physical characteris-
tics. One should ask, however, what is the critical nanograin size that enhances
a materials properties for a target application? These preliminary questions need
to be asked before entering the expanding area of nanopowders and nanomater-
ials.
The motivation for synthesizing nanostructured materials is the discovery of
physical and chemical behavior exhibited at this size dimension that is neither
described by single molecules nor by conventional materials [see, e.g., Siegel
(1991), Gleiter (2000)]. Nanopowders have been prepared using vapor- and so-
lution-based methods. The reason is that these methods can be adjusted to avoid
hard aggregation and morphology control problems.
3 ADVANCED PROCESSING 1121

One vapor phase technology is a combustion flame system, based on a flat-

flame burner, which is capable of synthesizing nonagglomerated nanopowders.
The temperature distribution in the flame precisely defines the zones of nucle-
ation, growth, and aging to enable the formation of monodisperse nanoparticles.
Equiaxed ceramic nanopowders with a narrow particle size distribution as small
as 10 nm have been prepared (Hahn, 1993, 1997).
One solution-phase technology is the hydrothermal method, where solutions
or suspensions are heated under pressure to precisely control the nucleation,
growth, and aging of the crystallites. In comparison to other solution-based tech-
nologies, hydrothermal methods offer the ability to prepare anhydrous crystalline
multicomponent oxides with controlled particle size. Similarly, hydrothermal
synthesis leads to control of nanopowder morphology.
Molecular-based technologies focus on the preparation of the nanostructured
mesoscale powders directly from the gas or solution phase. One molecular-based
vapor-phase technology is pulsed laser deposition in which ceramic material is
vaporized by a laser and vapor species are deposited on a substrate. This tech-
nology has been used primarily for thin-film preparation. Another uses combus-
tion flames or chemical vapors to deposit molecular species directly onto a
rotating or stationary substrate (Glumac et al., 1999). Solgel processing, an-
other molecular-based synthesis route, is treated separately.
It is also possible to hybridize various methods. For instance, a surface pre-
treated via pulsed laser deposition can be used to seed a nanostructure for a sol
gel powder. Combinations of hydrothermal synthesis and microwave heating
have been tried with promising results.
Nanopowders derived from vapor- and solution-phase sources can be proces-
sed in both dry and wet environments. Dry nanopowder assembly processing
encompasses spray deposition, fluidized bed, and fused deposition of ceramics.
Spray deposition methods include thermal spraying and cold gas dynamic spray-
ing. Thermal spray methods are suitable for powders that can endure the high
temperatures in the flame or plasma. Cold gas dynamic spraying projects par-
ticles at supersonic velocities and at low temperatures, so that particles form
bonds with a surface upon impact. This is effective for nanopowder agglomerates
with ductility. Another low-temperature dry nanopowder assembly process is
magnetically assisted fluidized-bed deposition. In this process, magnetic forces
fluidize magnetic particles, which in turn fluidize the desired nanopowders. This
process is very effective in coating large numbers of objects in a very uniform
fashion.
Wet nanopowder assembly processing affords the capability to disperse nan-
oparticles as singlets, something that cannot be achieved with dry nanopowder
assembly processing. There are three requirements for effective nanopowder as-
sembly processing: deagglomeration, dispersion, and particle assembly forma-
tion. For deagglomeration, processes such as eccentric rotating cylinder shearing,
impinging jets, and ultrasonic mixing are important technologies (Riman, et al.,
1998; Gelabert, et al., 2000). Dispersions based on a variety of polymer chem-
istries provide stability for nanopowder suspensions. To control the positions of
nanopowders in suspension, another approach is polymer self-assembly [see,
e.g., Brinker et al. (1999), Agarwal et al. (1997)].
1122 ADVANCED CERAMICS PROCESSING

Densification efforts focus on developing methods for controlling crack for-

mation and porosity while maintaining a nanoscale grain size. Conventional
solid-state and liquid-phase sintering lead to densification of nanostructured un-
fired mesoscale coatings at low firing temperatures. In one case, a metastable
ceramic nanopowder has been densified, by exploiting a pressure-induced phase
transformation, to produce a fully dense nanocrystalline material, where the final
grain size of the stable phase is comparable to or less than the particle size of
the starting powder. This was demonstrated for alumina and titania using low
temperatures (0.4 Tm) and high consolidation pressures (up to 8 GPa).
One final method, relevant also to layered manufacturing, applies advanced
laser rastering methods to densify nanopowders in two dimensions. Unlike pre-
vious work with laser sintering, the laser beam is designed to incorporate a
temperature distribution that induces, according to the patterned scanning of the
laser, densification normal to the surface in a continuous, defect-free fashion.
This leads to rapid densification times, localized heating, and the capability of
changing temperature quickly allows densification of complex, fine-scale pat-
terned structures. Thus, assemblies of nanopowders can be densified and the
remaining unfired materials can be removed by various means such as ultrasonic
cleaning.
Layered Manufacturing
What is layered manufacturing or solid freeform fabrication (SFF)? In recent
years, the cost of making machine tools or dies to make a prototype has become
exorbitant, and an alternative has been found that allows the preparation of the
part without dies, thus the name freeform. Using a computer-aided design
program, a solid object is cut into layers and a computer file is created that can
direct the building-up of the object layer by layer [see, e.g., Bandyopadhyay et
al. (1997), Song et al. (1999)]. One approach to solid freeform fabrication is
ink-jet printing. Borrowing the concept that is popular for creating written text,
an ink-jet printer can print the object layer by layer, to create three-dimensional
solids. In the form that this printing technology relates to ceramics, the required
steps are (a) the ink preparation, (b) the ink delivery through a nozzle, (c) the
break up of the ink stream into droplets, (d) the rastering of the nozzle over the
substrate, (e) the registry of successive layers, and (f) the consolidation of the
layers and sintering of the object to a fully dense ceramic.
Typical dimensions of each layer are 0.5 m. The finest nozzle is about 75
m, although micropen nozzles are being developed. A typical ink formulation
contains dispersant, binder, and plasticizer with 30 vol% ceramic powder. The
ink is forced through the nozzle and broken into droplets usually with electrodes.
The proper placement of the drops is critical to producing the desired dimensions
and aspect ratio in the object. Typically, the objects call for hundreds of layers.
Following the buildup of the object, the problems with drying and firing are no
different from those using more conventional processing and binder burnout.
Fused deposition of ceramics (FDC) is another useful technology for making
nanocomposites. This process uses a filament of inorganic particles dispersed in
a polymer as a means to deliver a molten stream of the composite onto a sub-
strate. The droplets can be as small as 125 m and can be deposited as multi-
layers for thicker coatings with a spatial positioning precision of 2.5 m.
3 ADVANCED PROCESSING 1123

Current instrumentation can process as many as four different filaments to allow

for the deposition of several materials on the same substrate.
To make nanostructured mesoscale coating depositions, we need to expand
the applications of ink-jet printing and FDC. These technologies should be useful
not only for deposition on a flat surface but also for administering multiple
components. This enables the assembly of neighboring components as well as
layered components of different nanostructures. Like fused deposition process-
ing, computers equipped with fast processors can be used to assemble complex
patterned structures for multifunctional systems.
Thus, one can envision multifunctional systems consisting of nanostructured
capacitors, resistors, conductors, and even patterned power sources. Because the
structures are computer generated, a large number of unique structures are pos-
sible.
Overall, the benefits of layered manufacturing include the ability to fabricate
complex shapes, fabrication without molds, automated fabrication, and near-net
shape processing. The potential drawbacks are the cost of the binder needed in
the initial layering, the dimensional accuracy, the binder burnout, and the trans-
ferability of a binder delivery system to a variety of ceramic materials. When
performance is more important than cost, then layered manufacturing used for
a low-volume product or small number of units may be competitive with con-
ventional processes such as forging, investment casting, or machining.

3.3 New Precursors

Polymer Precursors
What are the advantages of using preceramic polymers or precursors that py-
rolyze to ceramic? The advantage is the ability to use polymer forming methods
before carrying out the pyrolysis. The polymers are available as liquids, resins,
and thermosets. A typical preceramic polymer would be polycarbosilane, which
decomposes to SiC plus excess carbon and gaseous by-products such as hydro-
gen and hydrocarbons [see, e.g., Wynne and Rice (1984), Blum et al. (1989),
Wu and Interrante (1992), Greil (1995)]. Other preceramic polymers contain Si
Si (silane), SiN (silazane), or SiO (siloxane) bonds. There are suitable pre-
ceramic polymers for aluminum, zirconium, and titanium carbides, nitrides,
borides, and phosphides as well. The pyrolysis atmosphere may be nitrogen,
ammonia, argon, or air. Typically, the ceramic product is porous. Nevertheless,
suitable precursor chemistry and heat treatment can lead to dense materials.
Another benefit of the chemical approach is the high purity achievable and the
control over stoichiometry. In some cases, there are fewer steps involved with a
preceramic polymer than with powder processing. For example, the pyrolysis
can lead to a porous perform that requires infiltration by reaction bonding (as
in RBSN, reaction bonded silicon nitride), chemical vapor deposition (CVD), or
chemical vapor infiltration (CVI).

SolGel Processing
Of all of the advanced ceramic processing methods, why has solgel processing
become so prevalent? When solgel processing emerged about 20 years ago,
there were many that thought it was a laboratory curiosity without much future.
1124 ADVANCED CERAMICS PROCESSING

The cost of raw materials was frequently raised as being prohibitive. Some 20
years later, the interest in solgel processing has not diminished. Perhaps, the
reason is that there are many applications for solgel processing, where con-
ventional processing does not work as well, if at all. Certainly, in optical ma-
terials, ceramic membranes, and coatings, there are many outstanding examples
[see, e.g., Klein (1988, 1994)].
The solgel process refers broadly to room temperature solution routes for
preparing oxide materials [see, e.g., Brinker and Scherer (1990), Pierre (1998)].
In most cases, the process involves the hydrolysis and polymerization of metal
alkoxide precursors of silica, alumina, titania, zirconia, as well as other oxides.
The solutions of precursors are reacted to form irreversible gels that dry and
shrink to rigid oxide forms.
Twenty years ago, when the solgel process enjoyed resurgence in interest,
the emphasis was on the duplication of conventionally prepared ceramics and
glasses. Trying the solgel process was motivated by claims of the purity of the
starting materials and the generally lower temperatures for processing. Clearly,
the advantages of solgel processing outweigh the additional cost in enough
cases that the skeptics are satisfied for the moment.
In todays terminology, solgel processing is a form of nanostructure proc-
essing. Not only does the solgel process begin with a nanosized unit, a mole-
cule, it undergoes reactions on the nanometer scale resulting in a material with
nanometer features. The concept behind the solgel process is that a combination
of chemical reactions turns a homogeneous solution of reactants into an infinite
molecular weight oxide polymer. This polymer is a three-dimensional skeleton
surrounding interconnected pores. Ideally, the polymer is isotropic, homogene-
ous, uniform in nanostructure, and it replicates its mold exactly and miniaturizes
all features without distortion. The nanostructure and the nanophase porosity in
gels are, in fact, the features of interest, both scientifically and technologically.
The solgel process involves initially a homogeneous solution of one or more
selected alkoxides. Alkoxides are the organometallic precursors for silica, alu-
mina, titania, zirconia, among others. By far the most common system is one
composed of tetraethyl orthosilicate [TEOSSi(OC2H5)4]wateralcohol. Even-
tually, the solution reacts to a point where the molecular structure is no longer
reversible. This point is known as the solgel transition. The gel is an elastic
solid filling the same volume as the solution. Alkoxides react at different rates
according to the electronegativity of the cation.
Most studies of the solgel process deal with a single alkoxide. Each pre-
cursor has its own reaction rate and complicated interdependences of pH, con-
centration, and solvent. Even in the relatively straightforward case of alumina,
using aluminum-sec-butoxide (ASB), the expected reactions (14) are:

Al(OC4H9)3 H2O Al(OC4H9)2(OH) C4H9OH (1)

2(Al(OC4H9)2(OH) 2(AlO(OH)) yC4H9OH (2)
2(Al(OC4H9)2(OH)) 2H2O 2 Al(OH)3 2C4H9OH (3)
AlOOH or Al(OH)3 Al2O3 zH2O (4)

A catalyst is used to start reactions and control pH. The reactions are first hy-
3 ADVANCED PROCESSING 1125

drolysis to make the solution active (reaction 1), followed by condensation

polymerization (reaction 2) along with further hydrolysis. These reactions in-
crease the molecular weight of the oxide polymer (reactions 3 and 4) resulting
in either the monohydroxide AlOOH (boehmite) or the trihydroxide Al(OH)3
(bayerite). Nonaqueous solgel processes have been used to prepare most tran-
sition-metal oxides. In systems with multiple valence, the intermediate species
are oligomers that exist on the nanometer scale.
Aqueous colloidal sols also are used for solgel processing, recognizing that
the mechanism for accomplishing the solgel transition is quite different. In sols
such as Ludox, changing the pH or changing the concentration causes the ag-
gregation of sol particles. The sols can be gelled in such a way that the oxide
skeleton is a continuous linking of sol particles. These are discrete features that
make up the skeleton corresponding to the dimensions of the sol. The other
features are pores within secondary particles and pores between secondary par-
ticles. The chemical and structural differences between nonaqueous alkoxide
precursors and aqueous sol precursors become blurred at later stages of the sol
gel process.
Mixing as a first step applies to the single alkoxide, multiple alkoxide, and
colloidal sol processes. Absence of light scattering is a good indication of uni-
form mixing. Since the building blocks are nanometer in size, and smaller than
the wavelength of visible light, it is easy to follow, in a qualitative way, the
progress of the linking of building blocks. Gelling is often determined empiri-
cally as the time when the solution shows no flow. This is referred to as the
time to gel. For this step, viscosity is a good diagnostic for the transition from
a viscous liquid to a rigid structure.
Table 2 summarizes the shapes available by the solgel process. All of the
options are more or less porous materials. In all cases, it is important that the
porosity remain interconnected, whether the form of the material is essentially
one-dimensional such as a fiber, two-dimensional such as a film, or three-
dimensional such as bulk monoliths. These shapes can be divided into those that
show isotropic shrinkage from the preform to the final form and those that show
anisotropic shrinkage. Bulk materials fall into the isotropic category. Thin films
on substrates fall into the anisotropic category. High aspect ratio fibers also show
anisotropic shrinkage. Solgel thin films are exceedingly simple to prepare. A
solution containing the desired oxide precursors is applied to a substrate by
spinning, dipping, or draining. The process is able to apply a coating to inside
and outside of complex shapes simultaneously. The time to gel is short, indi-
cating film formation, drying and creation of pores must be rapid. When it comes
to dip coatings, 50 to 500 nm coatings are easy to make but thicker coatings

Table 2 Shapes Achieved by SolGel Process

Shape Composition Typical Application
Thin film Titaniasilica Interference Filter
Membrane Alumina Ultrafilter
Fiber Aluminazirconiasilica Reinforcement
Bulk
Xerogel Silica Lens
Aerogel Silica Thermal insulation
1126 ADVANCED CERAMICS PROCESSING

are more difficult. Similarly, fibers can be drawn out of low-water-content so-
lutions. The solgel process allows one to bait and draw a string of gel about
the same diameter as the desired fiber directly from the solution.
The solgel process based on casting and molding can make bulk objects.
The process can be used to make a microporous preform that is near-net shape.
This preform is called a monolith to refer to its continuity. Monolithic gels can
be formed from a colloidal sol or from an alkoxide solution. The main difference
between colloidal gels and alkoxide gels is their pore structures. Alkoxide gels
have small pores (10 nm), while colloidal gels have bigger pores or voids
between particles. Monolith fabrication is arguably the most challenging dem-
onstration of the solgel process.
Having selected geometry and designed the formulations accordingly, there
are several further steps common to monoliths, films, and fibers. First of all, the
gels must be dried. For monoliths, drying is more difficult because of the thicker
dimensions. Keeping in mind the nanostructured character of the material, sev-
eral drying treatments have been developed. One possibility is aerogels that are
dried in an autoclave by hypercritical techniques. That is, the solvent is removed
above its critical point. The resulting gel is about 10% dense and shows no
shrinkage. The more common case is xerogels that are dried by natural evapo-
ration. Xerogels are 60% dense and have reductions 4070% in volume.
Following reacting, gelling, and drying, gel materials have many of the char-
acteristics of the corresponding ceramic oxide, but they are more or less porous.
Interconnected pores, which remain open at the surface until the gels are fired
to temperatures well above 600C, allow the water and solvent to escape.
When the goal of the solgel process is a pore-free dense oxide, the final
stage of processing is sintering. The high surface area of gels is looked at as a
high driving force for sintering, so sintering is likely to occur at lower temper-
atures than in conventional powder compacts. This drive to remove porosity in
the end produces a material similar to conventionally processed materials.
Remember that high purity and uniform nanostructure are trademarks of the
solgel process. The challenge of the solgel process is to exploit the nano-
structure aspects of the process to derive real benefits. In single-component,
single-phase materials, by far the most important nanophase property is the po-
rosity. Porosity also means that there is surface area. Solgel processing has a
special contribution to multiphase material design and fabrication, in that the
porosity provides access to the nanoscale for processes such as liquid or vapor
infiltrations, physical or chemical depositions, and chemical reactions such as
pyrolysis or oxidation/reduction.
Because the solgel process is a low-temperature process, it is possible to
incorporate organic material. This is accomplished by infiltrating a previously
formed oxide gel with monomer, creating an organicinorganic copolymer with
a metal alkoxide, or simultaneously polymerizing monomer and metal alkoxide.
Because of the scale of mixing of the organic and inorganic phases, these ma-
terials are nanocomposites. The products of some of these syntheses can be
classified as sequential interpenetrating networks or simultaneous interpenetrat-
ing networks.
Among the features of solgel processing, the one that should stand out at
this point is its nanometer scale. In the long run, the advantages for the solgel
BIBLIOGRAPHY 1127

approach to nanophase ceramics materials are the simple processing steps, the
flexibility of solution chemistry, the low-temperature treatments, and small in-
vestment in equipment.
When considering where solgel materials are used, most of the applications
are substitutions of a solgel material for a ceramic obtainable by other means.
Nevertheless, there are some applications that are unique to solgel processing,
such as porous materials for membranes or infiltration and organicinorganic
hybrids.
4 SUMMARY AND PROJECTIONS
In the end, the choice of what method to use depends on many factors. Accord-
ing to the SP3 paradigm, performance is the ultimate test of synthesis and proc-
essing. Therefore, choices are made on the basis of how easily the process can
be optimized for chemical properties or physical properties. Other considerations
are the availability of the appropriate raw materials or precursors and the avail-
ability of the processing equipment. The advanced processing schemes in many
cases require high-temperature furnaces or reactive atmospheres. Difficulty gain-
ing access to this equipment or conditions may prohibit the use of an advanced
process. Similarly, problems of scale-up in size or number of components may
make a conventional process more straightforward than an advanced process.
Finally, time and cost are factors in the decision whether or not to use an ad-
vanced process. Nevertheless, there continue to be signs of progress in all of the
advanced processes described, with some, such as microwave processing, in
more widespread use than others, such as layered manufacturing. As with any
new technology, change is slow, but competition from other materials is a strong
incentive for advanced processing of ceramics.
Acknowledgments
Some of the ideas for this chapter come from the Materials Science Summer
Institute (MASSI) Intelligent Manufacturing of Nanostructured Ceramics,
June, 1996, sponsored by Rutgers University, Princeton University, and the Uni-
versity of Pennsylvania, and funded by NSF. My thanks go to the MASSI stu-
dents and co-organizer, Rik Riman, for outstanding ideas and discussions.
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