Ceramic Powder Synthesis by Spray Pyrolysis
Gary L. Messing,* Shi-Chang Zhang,* and Gopal V. Jayanthi*
A variety of spray pyrolysis (SP) techniques have been
developed to directly produce ceramic powders from solu-
tions. This paper reviews the current status of these pro-
cesses in terms of the process parameters that enable the
formation of particles with controlled morphology and
composition. A model incorporating solute diffusion in the
droplet and solvent evaporation from the droplet surface is
presented to establish the critical parameters leading to
solid particle formation. The model illustrates that solid
particles can be obtained if solutes with high solubility and a
large difference between the critical supersaturation and
equilibrium concentration are used and if the process is
designed to avoid solvent boiling. It is demonstrated that
mixed metal oxide, non-oxide, and composite particles that
are solid, hollow, porous, or fibrous can be produced by
modifying the precursor characteristics, solution proper-
ties, and process parameters. The physical and chemical
flexibility of SP processes offers numerous opportunities for
the controlled synthesis of advanced ceramic powders and
films. However, production rates are limited by the need to
produce 4-pm-diameter droplets and to avoid subsequent
droplet coagulation. Developments in process controls,
atomization, and system design are required for wider com-
mercialization of SP-type processes.
I. Introduction
N UMEROUS solution techniques have been developed to syn-
thesize ceramic powders with improved physical and
chemical characteristics. Most solution-precipitated powders
must undergo subsequent calcination and milling steps, pro-
cesses that can negate some of the advantages of the solution
process. As a result, it is difficult to achieve the powder charac-
teristics that are increasingly in demand for high-performance
B. Ghate--contributing editor
Manuscript No. 194525. Received June I , 1993; approved September 22, 1993.
Supported by NASA through Battelle’s Advanced Materials Center for Commercial
Development of Space under Grant No. NAGW-81 I , and the Fluid, Particulate, and
Thermal Systems, and the Metals, Ceramics, and Electronic Programs of the National
Sc- Foundation under Grant No. CTS-9202418.
Member, American Ceramic Society.
‘a _ -* -.. . . . . _-.
.( - ,
. . ,
..
Particulate Materials Center, The Pennsylvania State University,
University Park, Pennsylvania 16802
ceramics (i.e., submicrometer particle size and low degree of
aggregation). In contrast, hydrothermally prepared powders can
be directly produced in the requisite physical and chemical
form. However, the high-pressure requirements and the general
difficulty in producing a wide range of multicomponent compo-
sitions often deters consideration of hydrothermal techniques
for the synthesis of ceramic powders. In principle, solution-
based aerosol processes, unlike most solution processes, inte-
grate the precipitation, thermolysis (i.e., calcination), and sin-
tering stages of powder synthesis into a single continuous
process. In this manner, the advantages of starting with a solu-
tion are complemented by providing unique control over the
thermolysis and sintering stages of inorganic particle formation.
A large number of terms’ have been used to distinguish the
various solution aerosol processes by either the mechanism of
aerosol generation or the type of precursor thermolysis reaction
(Table I). Spray pyrolysis (SP) has been widely used to describe
these processes. However, the use of pyrolysis is sometimes too
limiting and, in some cases, incorrectly describes the critical
thermal process during SP. For example, pyrolysis (i.e., thermal
decomposition) does not adequately capture the various oxida-
tion, nitridation, or reduction-based thermal processes that will
be increasingly important applications of SP-type processes.
However, the proliferation of new acronyms (including some
by the present authors) simply leads to more confusion in the
literature. Therefore, for the sake of simplicity and in keeping
with the prevalent use of “spray pyrolysis” in the literature, we
will use this term to describe all synthesis processes in which a
solution is atomized and thermolyzed to attain the requisite
phase.
Spray drying, a process similar to SP, has been used for many
years to produce pressing-grade ceramic powders and for
numerous other applications in the foods, chemicals, and mate-
rials ind~stries.‘~ SP synthesis differs from spray drying in the
use of solutions, the consequent process of precipitation or con-
densation within a droplet, and the use of significantly higher
temperatures (e.g., >3OO0C) to form the desired inorganic
phase by thermolysis. “Spray drying” of solutions followed by
calcination and milling was widely reported from the early
1970s to early 1980s as a means for preparing mixed metal
oxides. Johnson reviewed this literature and other powder syn-
thesis proce~ses.‘~ In this paper we focus on the more recent lit-
erature and advances in the field.
During SP, the solution is atomized into a series of reactors
(Fig. 1) where the aerosol droplets undergo evaporation and
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2708 Journal of the American Ceramic Society-Messing et al. Vol. 76, No. 1 I

Table I. Nomenclature for Spray Pyrolysis Processes

Term Authors

Solution aerosol-thermol ysis Jayanthi, Zhang, and Messing’

Evaporative decomposition
of solutions
Spray pyrolysis
Ultrasonic spray pyrolysis
Mist decomposition
Spray roasting
Chemical reactions
with aerosols
Plasma vaporization
of solutions
Aerosol decomposition
High-temperature aerosol
decomposition
Roy, Neurogaonkar, O’Holleran, and Roy’ and
Gardner and Messing4
Hirata and Kato’
Ishizawa, Sakurai, Mizutani, and Kato‘
lmai and Takami’
Ruthner’
Matijevic’
Pollinger and Messing“’
Kodas, Datye, Lee, and Engler’’
Moser and Lennhoff’’

solute condensation within the droplet, drying, thermolysis of
the precipitate particle at higher temperature to form a micropo-
rous particle, and, finally, sintering of the microporous particle
to form a dense particle (Fig. 2). Solution aerosol techniques
take advantage of many of the available solution chemistries
that have been developed for powder synthesis but then
uniquely control the particle formation environment by com-
partmentalizing the solution into droplets. In this manner, S P
ensures complete stoichiometry retention on the droplet scale,
at least, and, thus, is particularly advantageous for mixed metal
oxide synthesis. Furthermore, by controlling the type of ther-
molysis reaction, it is also possible to synthesize non-oxide
ceramic, metal, and composite particles.
A number of pre-1980 papers report the direct synthesis of
ceramic powders by heating solution aerosols. Neilson et a1.I5
reported the synthesis of metal oxides, mixed metal oxides, and
ferrite powders from metal chloride, sulfate, acetate, and nitrate
solutions atomized into oxygen or air-fuel flames. The particles
ranged from flakes and hollow shapes to submicrometer
spheres, but no correlations between process or solution condi-
tions and particle morphology were reported. Wenckus and
Leavitt16 reported the formation of ferrite powders from alco-
holic solutions of metal nitrates atomized into an oxygen flame.
Most other s t u d i e ~ ~ ~emphasized
’ ~ ~ ’ ~ ~ the
’ ~ compositional flexi-
bility for synthesizing ceramic powders but seldom was particle
morphology reported. However, when particle morphology was
reported, the powders consisted of hollow spheres.
Although Neilson et al. l5 demonstrated commercial-scale
potential for their flame decomposition process, it was
Ruthner’.’’ 22 who first commercialized the process. The
“Ruthner process” is based on the atomization of metal chloride
solutions into a vertical furnace that is operated at 700” to
1000°C. Solutions are atomized into the top of the furnace and
the generated powders are cyclone separated from the gas. A
wet scrubber is used to separate hydrogen chloride from the
exhaust gas. The powders consist of 25- to 400-p.m hollow par-
ticles which require milling if used for fine-grain ceramic pro-
duction. It is instructive to note that the Ruthner process was
developed originally for chlorine regeneration in the steel pro-
cess. More recently, Scimarec, Inc., in Japan:’ E. Merck, Inc.,
in germ an^,'^ and SSC, Inc., in the United States” now sell
ceramic powders produced by an SP-type process. Both Merck
and SSC further process by milling to obtain powders of the
desired characteristics.
As shown in Fig. 3 , a variety of particle morphologies have
been produced by S P processes. For fine-grain ceramic applica-
tions, a key issue concerns the process conditions leading to
volume precipitation within the droplet and the subsequent con-
version to a dense, solid particle rather than hollow, shell-like
particles (Fig. 4(A)). The completely filled particles formed
after precipitation were earlier d e s ~ r i b e d * ~as. *“solid”
~ to con-
trast their formation with the shell-like particles. Note, how-
ever, that the completely filled or “solid” particle is actually
nanoporous as a result of the porosity between the precipitated
salt nanocrystallites and the subsequent decomposition of the
salt crystallites. The latter is due to the lower specific volume of
the inorganic phase relative to the salt. It is also important to
understand how the precipitation conditions and precursor

Pressure Humiditv
Gauge Gauge”

Diffusion Drier Thermolysis Reactor Sintering Furnace

I I
I

P 1
Laser Particle
Size Analyzer

I
or
Reaction Gases Electric
Aerosol
Solution Atomizer Analyzer
Carrier Gas

Fig. 1. Schematic of SP equipment.

November 1993 Ceramic Powder Synthesis by Spray Pyrolysis
EVAPORATION PRECIPITATION
Fig. 2. Stages of SP process.
properties affect particle microstructure. Figure 4(B) illustrates
that there are a number of possibilities for synthesizing multi-
component and composite particles with a unique range of
microstructural characteristics.
To date, most SP research has focused on the preparation of
ceramic powders with specific chemical compositions. How-
ever, despite the importance of the powder physical characteris-
tics, there has been little attempt to understand or model the
processes and factors that affect the production of particles with
controlled size and morphology. Consequently, the production
capabilities and advantages of SP processes for advanced
ceramic powder synthesis, although quite promising, are only
now beginning to be realized.
One objective of this paper is to identify the technical prob-
lems that have limited the utilization of SP-type processes for
powder synthesis. By examining the underlying factors affect-
ing particle formation, we seek to determine future research
directions and process needs that will accelerate the acceptance
and commercialization of SP powder synthesis. Of particular
concern is the status of SP modeling for solid particle forma-
tion. We also review the literature to identify the opportunities,
challenges, and impediments for SP synthesis of ceramic pow-
ders with specific physical and chemical characteristics. We
conclude by briefly discussing other opportunities for advanced
materials synthesis by SP-type processes.
11. Spray Pyrolysis Process Steps
( I ) Precursors
Although true solutions, colloidal dispersions, emulsions,
and sols can be used as aerosol precursors, this paper focuses on
issues associated with SP of true solutions. Aqueous solutions
are commonly used due to ease of handling, safety, low cost,
and availability of a wide range of water-soluble metal salts.
The solute must have high solubility to increase the powder
yield of the process. Increasingly, alcoholic and organic solu-
tions have been studied due to the interest in the synthesis of
inorganic materials from metal organics that undergo gelation
or polymerization and for the synthesis of non-oxide ceramic
powders.
In general, metal chlorides and oxychlorides have the highest
water solubilities relative to other metal salts and are used for
the industrial production of MgO and ferrites.*’ The corrosive
nature of the product gases and the adverse effect of residual
chlorine on ceramic sintering decreases the general attrac-
tiveness of these salts for advanced ceramic powder synthesis,
but the technology for handling such systems is available.**
Other water-soluble metal salts-such as nitrates, acetates, and
sulfates-can also introduce impurities which may adversely
affect subsequent processing, sintering, or properties. For
example, Gardner and Messing4 showed that Mg(CH,COO),-
derived MgO contained free carbon after heating at 1000°C.
The presence of carbon from the precursor system has also been
shown to cause BaCO, formation in BaTiO, and barium-based
2709
DRYING DECOMPOSITION SINTERING
superconducting oxides and, thus, to adversely affect phase
development.
The low solubility of metal acetates and high decomposition
temperature of metal sulfates limit the use of these water-
soluble salts. Therefore, hybrid systems in which one of the
components is added via a solution and the remainder as parti-
cles have also been reported. For example A1,0,-15 vol% ZrO,
powders were producedz8 by using a dispersion of a-Al,O,
powder and ZrO(NO,),. To completely avoid the solute limita-
tions and to increase process yield, Scimarec, Inc., has devel-
oped a commercial SP process to produce mullite powder from
a sol mixture of AlOOH and SiO, .*3
The physical and chemical characteristics of soluble chcmi-
cal precursors strongly influence the characteristics of particles
formed by SP. Unlike most solution-precipitation processes
where the metal ions are precipitated as sparingly soluble salts
(e.g., hydroxides, oxalates, or carbonates), the dissolved precur-
sor salts precipitate during the evaporation stage of SP. As
shown later, the salt solubility and degree of supersaturation
influence whether solid or hollow particles are formed during
the evaporation stage of SP.
Charlesworth and Marshallz9 summarized how the perme-
ability and thermal character of metal salts affect particle mor-
phology when the boiling temperature of the solvent is
exceeded. For example, thermoplastic salts readily inflate,
whereas impermeable, rigid particles simply fracture into shell
fragments once the solvent boils. The thermal properties of the
precipitated precursor also impact subsequent particle evolu-
tjon30.3I during the thermolysis stage. For example, many metal
nitrates have low mefting temperatures (e.g., <2OO0C). If the
metal salt melts during thermolysis, then the reduction of the
product gas permittivity through the molten salt results in an
internal gas-pressure increase and “explosion” or foaming of
the particle. This process leads to hollow particles or particle
fragments of a broad particle-size distribution. Below we dis-
cuss the opportunity for forming porous AI,O, particles by this
type of process.
(2) Atomization
A variety of atomization techniques (Table 11) have been
used for solution aerosol formation, including pneumatic (pres-
sure, two-fluid, nebulizers), ultrasonic, and electrostatic. These
atomizers differ in droplet size, rate of atomization, and droplet
velocity. The velocity of the droplet when it leaves the atomizer
is important because it can determine the heating rate and the
residence time of the droplet during SP. The size of the droplets
produced with pneumatic or pressure nozzles decreases when
the pressure difference across the nozzle is increased. Two-fluid
atomizers represent off-the-shelf technology capable of atomiz-
ing large quantities of liquid at droplet velocities from 0.5 to 20
m/s but with minimum droplet sizes of only 10 pn3* Ultrasonic
nozzles, conversely, apply a relatively smaller amount of
energy, but efficiently couple that energy to achieve droplet for-
mation. Ultrasonic atomizers can easily produce droplets down
to 2 to 4 pm, but the atomization rate is limited to <2 cm’/min.
2710 Journal of the American Ceramic Society-Messing et al. Vol. 76. No. 11

Fig. 3. Various morphologies of particles produced by SP processes: (A) solid ZrO, particles derived from 0.1 M ZHC solution, (B) irregular ZrO,
particles derived from 1M ZAC solution, (C) AlzO,/platinum nanocomposite particles derived from 0.SM Al,(SO,),-H,PtCI, solution, (D) A1,OJ
platinum nanocomposite particles derived from 0 . S M AI(OBu’),-H,PtCI, solution, (E) catalyst particles derived from 0.1M NH,VO,-H,PO,xitric
acid solution, and (F) Y,O,-stabilized ZrO, discontinuous fiber derived from Z A C 4 wt%-PVOH-surfactant solution.

The concept of SP processes is to produce one particle per drop-
let. Because small particles are required for most advanced
ceramic applications, there is a serious need to develop tech-
niques that can atomize large quantities of small droplets at low
exit velocities. Indeed, it is for production reasons that compa-
nies have used pressure atomizers instead of ultrasonic
atomizers.
For a specific atomizer, the droplet characteristics depend on
the solution density, viscosity, and surface tension. The viscos-
ity of metal organic and organic acid precursors can range
orders of magnitude, depending on chemistry. The surface ten-
sion of organic-based systems (<40 dyne/cm (0.04 N/m)j is
generally less than water-based solutions (70 dyne/cm (0.07
N/m)j. These factors directly affect the droplet size during
atomization, and, thus, it is important that the initial droplet-
size distribution be determined to correlate the particle evo-
lution processes with the initial aerosol size. Later we will
demonstrate how the solution viscosity/surface tension char-
acteristics of the precursor solutions can be manipulated to
synthesize nanoparticles (<0. 1 p m in diameter) or discontinu-
ous fibers.
November 1993 Ceramic Powder Synthesis by Spray Pyrolysis 271 1

of solute diffusion. Therefore, to understand what factors con-

trol particle formation, a model incorporating both solute diffu-
sion and the rate of droplet shrinkage was developed.
(A) Evaporation of Liquid Droplets: A comparison of the
evaporation rate and temperature change of pure liquid droplets
Penneabihty
and solution droplets is helpful in identifying the effect of the
Pcimeabilit solute on particle formation by SP. The evaporation of liquid
0 droplets has been extensively studied and modeled for combus-
tion processes and atmospheric phenomena. The derived mod-
els form the foundation for calculating the rate of droplet-size
change as a function of temperature and relative humidity in the
initial evaporation stage of SP. The rate of evaporation of drop-
lets moving with the same velocity as the ambient is given by34

it Metal Salts
where p- and T, are the ambient vapor pressure and temperature
of the reactor, respectively. The subscript “d” refers to the same
parameters at the surface of the droplet, M is the molecular
weight of the gas and R, is the gas constant, R is the droplet
radius, and rn its mass. FuchP noted that Eq. (1) neglects the
initial change in the surface vapor concentration and the change
in the drop radius. Ranz and Marshall36experimentally deter-
mined the evaporation rate when there was a velocity difference
between the ambient and aerosol droplet. Note that, when the
droplets are <0.05 p,m in diameter, the vapor pressure must be
I C o 1I o i d -
Metal Salt corrected for the Kelvin effect.
( B ) Evaporation from Solution Droplets: In the initial
stage of drying, surface evaporation from a solution droplet is
the same as for a pure solvent except that the vapor pressure of
the liquid decreases as a result of the solute in the droplet.
Assuming the gas phase is ideal, the vapor pressure p d of a solu-
Fig. 4. Effect of precipitation conditions and precursor characteris- tion droplet is given by
tics on (A) particle morphology and (B) composite particle
microstructure.

where pTatis the saturated vapor pressure of the solvent at a

Table 11. Characteristics of Atomizers Commonly given temperature, xA the solute mole fraction at the surface of
Used for SP the droplet, and yA the activity coefficient which is dependent
Droplet size Atomization rate Droplet velocity on the nature of the solute; for ideal and dilute solutions, -yA can
Atomizer (w) (cm’/min) (m/s)
be assumed to be 1 . From electrodynamic balance experiments,
Pressure 10-100 3-no limit 5-20 Cohen et al.” found that the activity coefficient can vary sig-
Nebulizer 0.1-2 0.5-5 0.2-0.4 nificantly with the solute concentration during the evaporation
Ultrasonic 1-100 <2 0.24.4 of the solution droplets. Unfortunately, such data are not gener-
Electrostatic 0.1-10
ally available for the range of precursors currently used in SP.
(C) Temperature of Liquid Droplets: The droplet loses
heat as the latent heat required for evaporation and gains heat
(3) Evaporation Period when the temperature of the ambient is greater than the droplet
temperature. The rate of temperature change is given by
During the first stage of SP, the following physical phenom-
ena can occur simultaneously: evaporation of the solvent from
the surface of the droplet, diffusion of the solvent vapors away (3)
from the droplet in the gas phase, shrinkage of the droplet,
change in the droplet temperature, and diffusion of solute where K is the ambient thermal conductivity, A the latent heat of
toward the center of the droplet (Fig. 2). Before presenting the evaporation of the solvent, and S the specific heat of the liquid.
equations governing these phenomena, it is useful to compare Equation (3) neglects radiant heat transfer which is acceptable
the characteristic time constants’3 of these processes to identify if
the most important factors during SP. The characteristic time
refers to the time required for a process to reach steady state; the 4RaS,T,’
shorter the time, the sooner it reaches steady state.
<< 1 (4)
K
Table 111 shows that the characteristic time for diffusion of
the solvent vapor is much shorter than that for subsequent drop- where usb is the Stefan-Boltzmann constant. Heat transfer due
let shrinkage. Therefore, it is concluded that vapor diffusion to radiation could be comparable to the conductive and convec-
proceeds much faster than droplet shrinkage and reaches steady tive heat transfer if high ambient temperatures are used.
state before there is a significant change in the droplet size. By a (D) Temperature of Solution Droplets: Equation (3) can
similar argument, the temperature profile of the air and the be used for salt solutions if the specific heat and latent heat of
droplet can be assumed to reach steady state before droplet the solution do not differ significantly from the pure solvent
shrinkage. From this analysis, solute diffusion at high humidi- values. The solution droplet temperature will exceed the wet-
ties is concluded to be the slowest process, but, at low humidi- bulb temperature ( Twh)of pure water, because the vapor pres-
ties, the rate of droplet shrinkage may be comparable to the rate sure of a solution is less than that of pure water. Some observers
2712 Journal of the American Ceramic Society-Messing et al. Vol. 76, No. 11

Table 111. Comparison of Characteristic Times for Processes during SP

Characteristic times
Process Definition’ (relative to heat conduction)

Heat conduction in air t,, = R’ILY~ 1 .o

Heat conduction in a droplet t,, = R 2 / a , 90
Vapor diffusion in air t,, = R 2 / D , 0.86
Droplet shrinkage t , = R2p,lp,x,D, 20/x,
Solute diffusion in a droplet t,, = R 2 / D , -1 x 105
* D , is the diffusivity of solute in the droplet (cm’.s- I), D, the diffusivity of solvent vapor in air ( c m W ’ ) , R the droplet radius
(cm), tdgthe characteristic time constant for gas-phase diffusion (s), f,, the characteristic time constant for diffusion in the liquid
phase (s), fhg the characteristic time constant for heat conduction in the gas phase (s), f,, the characteristic time constant for heat
conduction in the liquid phase (s), I , the characteristic time constant for droplet shrinkage (s), x, the mole fraction of solvent
vapors far from the droplet, apthe thermal diffusivity in the gas phase (cm’.s I), a ,the thermal diffusivity in the liquid phase
(cm% I), ppthe density of the gas phase (g/cm ’),and p, the density of the liquid phase (g/cm -’).

suggest that the droplet surface temperature during the free sur- time dependence of the boundary conditions. To account for
face evaporation period can be equated to the temperature of the these factors, he modified the diffusion equation by making the
saturated solution (T,), and, thus, T, - Twbrepresents the following substitutions:
increase in droplet temperature due to the presence of the dis-
solved salts. During SP, the droplet temperature increases from
the solution feed temperature to the saturated solution tempera-
ture (T,), which is fixed by the humidity and temperature of the
furnace. Then, Eq. (6) can be written as
( E ) Solute Diffusion in a Droplet: The mean concentra-
tion of the dissolved salt C , increases concurrent with droplet (9)
shrinkage as follows:

c,, = C , (RKj with the boundary conditions

where C, and R, are the initial concentration and droplet radius,
respectively. The concentration of the solute in the droplet is
not uniform throughout the evaporation period, because the sol-
vent is lost from the droplet surface at a faster rate than the rate
of solute diffusion; thus, the solute concentration is higher at the
droplet surface than at its center. Choosing a spherical coordi-
nate system with the origin at the center of the droplet and
assuming that the solute concentration C depends only on the
radial coordinate r and time t , the solute concentration can be
evaluated by solving the partial differential equation
ac - D , a
_ concentration changes as a function of drying conditions for the
for the following initial and boundary conditions:
C = C, at t = 0
ac
_ -- 0 atr=O
ar
dC 1 dm
D , z = --
4 n r Z dt
at r = R(t)
When the droplet is moving relative to the ambient, the evap-
oration rate is faster on the leading surface of the droplet, and,
hence, the solute concentration is greater there. To determine
how the concentration profile changes within a droplet for this
case requires the inclusion of the dependence of the concentra-
tion on the spherical coordinates in the diffusion equation, a
major mathematical complication that is beyond the scope of
this paper.
An analytical solution to Eq. (6) is difficult, because the
droplet radius decreases with evaporation. Table 111 shows that
the characteristic time constant for droplet shrinkage can be
comparable to that for solute diffusion, and, hence, models that
assume constant radius are not realistic.”,’x Gardner“’ showed
that Eq. (6) can be solved by assuming that the rate of change of
the square of the radius of the droplet is constant.
van der Lijnao noted that the analytical solutions for Eq. (6)
do not effectively describe the concentration profile of the sol-
ute, because they do not consider the changes in diffusivity with
the solute conccntration, decreasing radius of the droplet, and
u =u, att=O
-r2s-
au
-
- _1_ _
dm
atz = Cr’ d r
az 4nr’ d t
Equations (l), (3), and (9) can be solved simultaneously by a
numerical, finite-difference method using an unequally spaced
grid with more points toward the surface of the drop than at the
center:”
( F ) Solute Condensation: To determine how the solute
evaporation stage of SP, we simultaneously solved the differen-
tial equations for solute diffusion and solvent evaporation using
a first-order explicit finite-difference scheme,’ in accordance
with the suggestion by van der Lijn. Once the concentration
profile in a droplet is known as a function of the drying condi-
tions, then the time at which the solute starts to precipitate can
be established. For heterogeneity-free solutions, we assumed
that homogeneous nucleation would occur when the solute con-
centration reached the critical supersaturation C,, at the surface.
(7) In reference to particle morphology, two cases for precipitation
are envisioned:
(i) If the solute concentration at the center of the drop is
greater than or equal to the equilibrium saturation (C,) of the
solute at the droplet temperature, then nuclei on the surface cat-
alyze precipitation throughout the droplet, i.e., volume
precipitation.
(ii) If the solute concentration at the center of the drop is
less than the equilibrium saturation of the solute at the droplet
temperature, then precipitation occurs only in that part of the
drop where the concentration is higher than the equilibrium sat-
uration, i.e., surface precipitation.
Note at this point that the true values of critical supersatura-
tion for the range of solutes used in SP are difficult to obtain,
mainly because most of the values in the literature are for het-
erogeneous nucleation. Exceptions to this are the results of
Cohen et al.,”’ who levitated solution droplets using an electro-
dynamic balance and found the critical supersaturation for
homogeneous nucleation.
The morphology of the particles can be predicted from the
model calculations of the solute concentration gradient and
November 1993 Ceramic Powder Synthesis by Spray Pyrolysis
the simple criterion for solid particle formation. For these cal-
culations, we chose values for zirconyl hydroxychloride
(ZrO(OH)CI, ZHC) because of our previous experience with SP
synthesis of ZrO, from aqueous solutions of ZHC and because
we have measured values for C , (5.7 mol/L) and C,, (8 mol/L)
for ZHC. The effects of the initial concentration of the droplet
and the ambient temperature on solid particle formation were
studied by calculating the solute concentration gradients in a
droplet at the onset of precipitation.
Figure 5 shows the solute concentration profile inside the
droplet when the surface reaches C,, for ambient temperatures
of 90" to 150°C. The horizontal C, line shows the equilibrium
saturation line. The C, line should change with increasing tem-
perature as a result of the solubility temperature dependence.
However, because the solubility temperature dependence is not
known, C , was assumed to be independent of temperature.
Also, the temperature of the droplet would not be expected to
change appreciably during the evaporation stage which leads to
precipitation, but instead would be expected to rapidly rise to
the furnace temperature after precipitation begins at the surface.
As shown in Fig. 5, the solute concentration is above C , for all
locations in the droplet only when the drying temperature is
90°C. In this case volume precipitation is predicted. For higher
temperatures, the radial distance at which the solute concentra-
tion goes below C , decreases. Figure 5 indicates that the thick-
ness of the precipitated layer can be adjusted by changing the
temperature. However, to retain the shell-like particle morphol-
ogy requires a mechanism to remove the remaining solvent
from the particle without disrupting the precipitate.
Figure 6 shows the effect of initial concentration on the sol-
ute concentration profiles inside the droplet at the time of pre-
cipitation. If the initial concentration is higher than the
equilibrium saturation, then volume precipitation should
always occur. When the initial concentrations are low, the sol-
ute concentration is more likely to be less than C , when the sur-
face reaches C,, . Although high initial concentrations are
suitable for volume precipitation, such saturated solutions are
likely to be heterogeneously nucleated during atomization and
thus not supersaturate to the same degree as suspended, drying
droplets.
Ambient T e m p e r a t u r e
Co = IM
3 ~ I I I ~ I I
0.0 0.2 0.4 0.6 0.8 1.0
r/ R
Fig. 5. Effect of ambient temperature on the solute concentration pro-
file inside a droplet during the evaporation stage.2
00 0.2 0.4 0.6 0.8 10
r/R
Fig. 6. Effect of initial concentration on the solute concentration pro-
file inside a droplet during the evaporation stage at 150"C.z
2713
Volume precipitation initially appears to lead to solid particle
formation, and surface precipitation seems to be the cause of
hollow particle formation. However, under certain conditions
this assumption may not be valid. For example, if there is too
little solute in the droplet at the time of precipitation, then all of
the precipitated solid crystallites may not touch each other. In
this case, it is possible that excessive porosity forms inside the
final particle, leading to low-density, hollow particles. Percola-
tion theory can be invoked to account for the space-filling
capacity of the precipitated solids. To form a continuous, three-
dimensional network of solids, the volume fraction of the pre-
cipitated solids at the droplet center should be higher than the
critical volume fraction 'p* (i.e., 0.16),", the percolation
criterion.
The solute concentration C (molb), the volume fraction cp of
the precipitated solids of density p (g/cm'), and the solute
molecular weight MW are related by
CMW
'p=looop
Thus, the solute concentration necessary to exceed the percola-
tion criterion at the droplet center is given by
IOOOp(p*
C" 2
-
MW
Based on volume precipitation and percolation criteria, we
conclude that solutes with a large difference between the criti-
cal supersaturation and equilibrium saturation, and with a large
equilibrium saturation, i.e., high solubility, are more likely to
yield solid particles during the evaporation stage of SP. Further-
more, high initial concentration results in volume precipitation.
In contrast with experience, the model predicts that the occur-
rence of volume or surface precipitation does not depend on the
initial droplet size.
In the above discussion, the size of the precipitated crystals in
the droplet was assumed to be small relative to the size of the
droplet. Based on precipitation theory, L e ~ n reported
g ~ ~ that the
degree of supersaturation influences the size and number of
crystals formed in the droplet. That is, solutes with a high
degree of supersaturation tend to form a large number of nano-
meter-sized crystallites, and, thus, the shape of the particle is
spherical. When the degree of supersaturation is low. the nucle-
ation rate is small relative to the growth rate, and, therefore,
only a few large crystals-and in some cases, even single crys-
tals-are formed.44The size and number of crystals determine
the size and size distribution of the pores and, hence, influences
further drying of the droplet.
(4) Drying
I ~
The drying of droplets containing precipitated salts signifi-
cantly differs from evaporation. According to Nesic and Vod-
nik$5 the rate of solvent removal in the presence of solids on the
droplet surface is given by (modified for drying in still air)
where R , is the droplet radius at the time of precipitation, 6 the
thickness of the crust, D,, the diffusivity of vapor through the
precipitate layer, and y the mass concentration of solvent vapor
(the subscripts d and 00 refer to the surface and the bulk vapor,
respectively). Because the vapor diffusivity through the pores
in the precipitate layer is much slower than the diffusivity of
solvent vapors in the gas phase, the resistance to mass transfer
increases significantly and the rate of evaporation decreases.
Note that Nesic and Vodnik treated diffusivity in the crust as a
constant and did not consider the effect of the size/size distribu-
tion, shape, or volume of the pores (parameters affected by the
solute supersaturation).
2714 Journal of the American Ceramic Society-Messing
When the solute starts to precipitate, the evaporation rate is
significantly reduced and the droplet temperature increases
steeply until it reaches the ambient temperature. Nesic and
Vodnik4' developed the following equation to account for the
change in heat transfer when solids are present:
~ I T R , K ( T-
K
, Td)
6
+ A-dm = mS- Td
dt dt
where K,, is the thermal conductivity of the crust.
The presence of solids on the droplet surface causes an addi-
tional resistance to the mass transfer of the solvent vapors,
whereas the additional resistance to heat transfer is small. This
leads to an increase in droplet temperature, because the evapo-
ration rate is slower. If the solute has a positive coefficient of
solubility and the particle temperature increases, then the solute
may redissolve; this is an effect that has not been considered in
any model. If the permeability of the precipitate crust is low and
if the ambient temperature is higher than the boiling point of the
solution, then the solvent may vaporize and form bubbles that
can cause inflation or even disintegration of the droplet. Predic-
tions of the time and the ambient temperature at which the solu-
tion reaches its boiling point require the solution of the
equations governing the drying stage of SP. If the pores are
small and the drying rates are high, then the capillary forces
between the solids and the liquid may cause a sufficiently high
stress to fracture the particle; this is a process analogous to that
proposed for sol-gel systems.46
(5) Droplet Coagulation
The above analysis treated SP as a single-droplet problem,
but liquid droplets can undergo coagulation-a process by
which two or more droplets collide and coalesce into a larger
droplet. This can occur as long as there is a liquid phase present.
There are no reports in the SP literature concerning the impor-
tance of coagulation phenomena on particle-size and morphol-
ogy development. However, the dynamics of coagulating
droplets (or particles) are well ~ n d e r s t o o dThe
. ~ ~ decay in the
particle number density, associated with the increase in the
average droplet size, can be described by
N,
-=-
1 reactions to internally thermolyze the dried particle. The SSC
hl t
"0
1 +I
7,
where No is the initial number of droplets, N , the number of
droplets at time t, T, = 2/pN0 the characteristic coagulation
time constant, and p the coagulation (collision) rate constant.
In Eq. ( 1 3 , Brownian motion is assumed to be the reason for
droplet collision and p is assumed to be constant. Both of
these assumptions are reasonable and allow for an estimate of
droplet coagulation times as a function of size and number den-
sity. Note that, for a constant volume of solution, N<,scales with
D;'. Thus, reducing the droplet size significantly increases the
probability of coagulation through its influence on 7,.
Figure 7 is a calculation of the time required for the coagula-
tion of 10% of the droplets. The curves demonstrate that the
coagulation time is relatively insensitive to temperature but
strongly dependent on the initial number density of droplets; the
higher the initial number density, the faster is droplet coagula-
tion. Based on these estimated atomization characteristics and
the short drying times for small droplets, it is expected that
coagulation can be suitably limited by maintaining the atomiza-
tion process to number concentrations between 10' and lo7
droplets/cm3.Coagulation during the thermolysis and sintering
stages of SP is assumed to be less important, because of the
smaller sticking coefficient of solid, inorganic particles. How-
ever, if the particle is heated to above its melting temperature,
then coagulation could be important. One important conclusion
from this analysis is that production rates are significantly lim-
ited if droplet concentrations of only lo7cm-3 are used to avoid
et al. Vol. 76, No. 11
10001 I I I 1
- I 900K I
0.I
I00 10' lo2 lo3 lo4
Droplet Diameter (nm)
Fig. 7. Coagulation time dependence on initial droplet number con-
centration, droplet size, and temperature."
droplet coagulation. Clearly, methods to limit coagulation are
needed for the commercial production of ultrafine particles.
(6) Thermolysis and Sintering
To date there has been little effort to model the thermolysis
and sintering stages of SP. In most SP papers these two stages
are conducted after SP as a consequence of insufficient droplet
residence time to complete the thermolysis reactions and sinter-
ing. Because the SP particles are reactive after thermolysis, it is
important to sinter them in situ to take full advantage of the SP
process. To date most reactor systems have been designed such
that thermolysis and sintering processes overlap; i.e., a conven-
tional, single-chamber spray drier is used. It is believed that the
processes of evaporation, thermolysis, and sintering should be
conducted in separate reactors to obtain maximum control of
the individual processes and because the time-temperature con-
ditions are significantly different. For example, thermolysis
reactions take place at 400" to 500"C, whereas sintering may
take place at > 1000°C. Overlap of these processes in a single
droplet could significantly affect densification of the particle.
Both the MerckZ4and SSCzsprocesses use in situ exothermic
process uses the exothermic reaction between metal nitrates and
urea, glycine, or sugar. The reaction provides sufficient heat
within the particle to completely form the high-temperature
ceramic phase. The rapid evolution of product gases results in
particle foaming, or low-density agglomerates which are then
milled to make them suitable for ceramic fabrication and sinter-
ing. The Merck process is similar in the use of nitrate solutions
plus organics for in situ generation of heat, but the details of the
process are not known.
There are no fundamental reasons why the nanoporous parti-
cles after thermolysis cannot sinter to full density in the aerosol
reactor. The characteristics of small pore size, purity, and small
crystallite size within the thermolyzed particle are the same
characteristics which have created interest in the low-tempera-
ture sintering of ceramics:' The fine nanocrystallites compris-
ing the particle (Fig. 8) should densify readily if exposed to a
suitably high reactor temperature. Sintering times of less than
5 s have been reported in the literature49for ceramic bodies with
significantly coarser crystallites and pores.
Particles densifying by solid-state sintering mechanisms do
not undergo interparticle sintering during SP, because the inter-
particle collision times are too short for neck formation by sur-
face diffusion, and the sticking coefficients of micrometer-sized
particles are small. Slamovich and LmgeS0showed that ZrO,
particles undergo intraparticle grain growth going from an ini-
tially microcrystalline particle to single-crystal particles.
The melting temperatures of most metal oxides are generally
outside the furnace capability of most SP processes, and, thus,
melting the particles to densify them is not always realistic.
November 1993 Ceramic Powder Synthesis by Spray Pyrolysis
Fig. 8. Microstructure of ZrO, particles synthesized by SP and heated
at 900°C.
Lyons et aL5' have recently shown that melting of thermolyzed
particles can be effective for compounds-such as V,O, and
Bi,O,-that have low melting temperatures. This approach is
not useful for most mixed metal oxides, because they phase
separate or incongruently vaporize if heated to their melting
point. Furthermore, if particles were melted at this stage, the
probability of coagulation and coalescence would significantly
increase. Kodas et al.".52showed that heating spray-pyrolyzed
YBa,Cu,O,_, (YBC) particles to 1000°C or near the melting
temperature of YBC (1015°C) results in equiaxed, single-
crystal particles. A plausible explanation for solid particle for-
mation at this stage involves the numerous liquid-forming reac-
t i o n ~ ' ~in the YBC system at <lOOO"C and liquid-phase-
assisted spheroidization of the inorganic particles. Solid V,O,
particles were produced by SP, by melting the thermolyzed
parti~le.'~
111. Applications
SP processes offer many opportunities to synthesize powders
with tailored physical and chemical characteristics. Based on
the principles presented above, we discuss the synthesis of solid
particles, hollow or porous particles, and nanoparticles (i.e.,
< l o 0 nm) by SP. The chemical versatility of SP is demon-
strated by reviewing the literature on multicomponent, non-
oxide, and composite powders. Finally, recent progress in the
use of SP-type processes for the formation of staple fibers and
thin films is discussed.
(1) Solid Particle Synthesis
Fabrication of advanced ceramics requires powders pos-
sessing a well-defined set of characteristics, including chemical
purity and homogeneity, < 1-pm particle diameter, dense parti-
cles, equiaxed shape, and freedom from particle aggregation.
The primary benefit of SP is the potential to directly produce
powders with these chardcteristi~s.~~'~~~~-'~ It is evident that a
major problem hindering the utilization of SP for powder syn-
thesis is the formation of hollow particles or broken shells.
Zhang and Messing'' demonstrated the importance of the rel-
ative saturation of the solute on solid particle formation by
atomizing 1M solutions of zirconyl nitrate (ZrO(NO,),, ZN zir-
cony1 chloride (ZrOCI,, ZC), and zirconyl hydroxychloride
(ZHC) into a -700°C furnace. At this concentration these salts
-
have relative saturations of 1 .O, 0.23, and 0.18, respectively.
Similar to other the ZN-derived powder (Fig. 9)
consisted of a mixture of <2-pm spherical particles and rela-
tively larger, thin-film relics of the initial droplets. Even though
the initial ZN solution is almost saturated and volume precipita-
tion is predicted, solid particles were not formed because the
salt solids volume fraction upon precipitation is only 0.085,
2715
which is much less than the percolation criterion of 0.16.
Smaller particle sizes were obtained with ZC and ZHC
(Figs. 9(B) and (C)) because of the lower initial relative satura-
tions. The ZHC-derived powder consists of I - to 3-pm-
diameter spherical particles with little evidence of surface pre-
cipitation or fragments. In contrast with ZN, the critical volume
fractions for ZC and ZHC are 0.250 and 0.328, respectively,
and, thus, both salts satisfy the percolation criterion.
To more closely evaluate the importance of initial solute con-
centration on solid particle formation, ZHC solutions with ini-
tial relative saturations from 0.009 to 1.4 (supersaturated) were
atomized with a two-fluid atomizer into a -700°C furnace
(Fig. 10). At relative saturations of 0.01 8 and 0.009, the parti-
cles are primarily solid spheres, whereas hollow particles and
shell fragments were obtained with solutions with higher
degrees of saturation.
The model predicts volume precipitation for high-concentra-
tion solutions and, hence, solid particle formation. However,
Fig. 10 illustrates that hollow particles are formed instead. This
discrepancy with the evaporation stage model can be attributed
to the high operating temperature during the evaporation stage
and subsequent solvent boiling once precipitation commences.
That is, as predicted by Eq. (14) and plotted in Fig. 1 l,*, the
reduction of evaporation rate and the high furnace temperature
cause the particle temperature to exceed the solvent boiling
temperature before the solvent is completely removed.
Odier et aLssobtained solid, spherical ZrO, particles by ultra-
sonic atomization of 0.08M to 0.67M (CJC, of about 0.018 to
0.15) ZC solutions. The mean particle diameter followed the
theoretical shrinkage predictions of Eq. ( 5 ) , indicating that the
solute concentration was relatively uniform because of slow
evaporation. The same groups6atomized droplets into a 700°C
furnace to obtain a heating rate of -3OO"C/s. The resulting par-
ticles were spherical shell fragments. When the furnace temper-
ature was adjusted to have a thermal gradient from 20" to 400°C
and a residence time of -5 s, solid particles were formed. When
PeblerbZultrasonically atomized a nitrate solution containing
0.02 mol/L zirconium and 0.004 mol/L yttrium into a multiple-
pass quartz reactor designed to extend the residence time to
15 s, they reported the formation of solid, spherical particles
with an average diameter of 0.4 pm.
To obtain volume precipitation, it is evident that slower
evaporation is necessary to avoid the development of a steep
concentration gradient within the droplet prior to precipitation
and at temperatures below the boiling temperature of the sol-
vent.2 Similar to the above experiments, furnaces have been
operated at high temperature in many SP studies to accommo-
date the fast droplet velocities associated with two-fluid atomiz-
ers. The rapid heating results in rapid evaporation and surface
precipitation. Consequently, powders produced with two-fluid
atomizers tend to be relatively large and consist of hollow parti-
cles and broken shells. Solid particles can be produced with
ultrasonic atomizers because the droplet velocity is very low
and the droplets are small, and a carrier gas can therefore be
used to obtain residence times of 10 to SO s during the evapora-
tion stage.6' In this manner, the evaporation rate can be reduced
and the conditions for volume precipitation obtained.
The temperature coefficient of solubility for a precursor can
influence solid particle formation when starting with dilute
solution droplets. For example, if the initial concentration is
low, the droplet temperature can exceed the wet-bulb tempera-
ture (Twb) of the pure solvent before precipitation (Fig. I I). To
illustrate this relation, the size of the droplet when precipitation
starts is marked by an "x" in Fig. 11. For salts with a positive
temperature coefficient of solubility, this means that the satura-
tion concentration in the droplet will be higher than the salt sat-
uration concentration at room temperature. The increase in the
saturation concentration postpones salt precipitation on the
droplet surface and results in more shrinkage and a higher sol-
ids content per unit volume at the onset of precipitation.
We evaluated the effect of the temperature coefficient of sol-
ubility by comparing Al,O, and BaO particle formation from
2716 Journal of the American Ceramic Society-Messing
AI,(SO,), and Ba(CH,COO)2 solutions of approximately the
same initial relative saturations.MAI(SO,), and Ba(CH,COOj,
have positive and negative temperature coefficients of solubil-
ity, respectively. At 100°C the relative saturation concentration
of AI,(SO,), decreases and the relative saturation concentration
of Ba(CH,COO), increases. Thus, an increase in the Ba(CH,-
COO), droplet temperature would cause precipitation to occur
earlier, resulting in hollow particles (Fig. 12).27In contrast,
solid spherical particles of 0.5- to 1.5-ym diameter were
obtained from the AI,(SO,), solution.
From the modeling of particle formation during SP and the
studies discussed above, we propose that the following solute
properties and operating conditions are necessary to obtain
solid particles from metal salt solutions:
(i) To satisfy the volume precipitation criterion, solutes
with a large difference between the solute critical supersatura-
tion and equilibrium saturation should be used.
(ii) The solute should have a high solubility and a positive
temperature coefficient of solubility to satisfy the percolation
criterion.
(iii) The precipitated solids should not be thermoplastic or
melt during the thermolysis stage of the SP process.
(iv) Ultrasonic atomizers or nebulizers are recommended
to generate aerosols with small droplet size and low velocity so
that low evaporation rates are achieved during the evaporation
stage of SP.
In contrast with reports on particle formation from metal salt
solutions, solid particles of a number of metal oxides have been
produced from metal alkoxide ~01utions.h.~~~~~" The difference in
the apparent ease of obtaining solid particles for inorganic salts
and metal alkoxides can be attributed to a fundamental differ-
ence in the mechanism of solute condensation. Metal alkoxides
and organic acid solutions undergo gelation or polymerization
at the gel point." The gel point of the solution can be reached
et al. Vol. 76, No. 11
Fig. 9. Particle morphologies of SP ZrO, particles obtained from 1M
solutions of (A) ZN, (B) ZC, and (C) ZHC.Z6
during SP by either heating or drying. Aging of the chemicals to
effect hydrolysis and condensation reactions prior to SP can
also affect particle formation by shortening the gelation time of
the sol droplet during SP. Although gelation may occur by dif-
ferent processes, the important distinguishing characteristic is
the formation of a continuous three-dimensional network and a
rapid increase in viscosity.
Solid particle formation from metal alkoxide or organic acid
solutions depends on the initial solution chemistry and the
degree of hydrolysis prior to atomization. During SP, heating
increases the alkoxide concentration and accelerates the solvent
evaporation and polymerization of alkoxide. Nogami et a1.&
demonstrated that the morphology of SiO, particles formed by
SP was strongly dependent on the tetraethoxysilane (TEOS)
polymerization degree. That is, powders prepared from solu-
tions with an intrinsic viscosity [q]less than 0.009 dL/g con-
sisted of both spherical and nonspherical particles, whereas
only spherical particles of 0.36 to 0.56 pm were formed when
[q] > 0.009 dL/g. When titanium isopropoxide was used: a
bimodal particle-size distribution of TiO, particles of 0.01 -pm
and 0.2- to 0.3-pm diameter was obtained. The small particles
result from the vaporization and condensation of some of the
titanium isopropoxide, whereas the larger particles were formed
by the precipitation/thermal decomposition of titanium isopro-
poxide droplets. Because metal organics have relatively high
vapor pressures, understanding the presynthesis chemistry is
essential if vapor condensation processes are to be avoided dur-
ing SP.
(2) Hollow or Porous Powder Synthesis
SP processes offer a number of opportunities for the synthe-
sis of either hollow or porous particles that may be useful for
thermal insulation or catalyst support applications. As sug-
gested by Fig. 5 and as predicted by the evaporation model,
November 1993 Cerurnic Powder Synthesis by Spray Pyrolysis
Fig. 10. Particle morphologies of ZHC-derived particles as a function of initial relative saturation: (A) 0.35, (B) 0.088, (C) 0.018. and (D) 0.009.20
Pure Water
I particles with open, macroscopic surface porosity can be
D/D,
Fig. 11. Change in temperature for droplets with different initial rela-
tive sat~ration.~~
precipitate layers of different thicknesses can be obtained
depending on the concentration gradient at the onset of precipi-
tation. If the precipitate shell has a sufficiently high permeabil-
ity for removal of the remaining solvent, then the shell can be
preserved and a hollow particle can be obtained. As far as we
know. no one has taken advantage of this possibility for con-
trolled hollow particle synthesis.
Porous materials that do not retain a dense surface can be
formed by using the opposite process conditions leading to
2711
solid particle formation such as by using metal salts that are
thermoplastic or have low melting temperatures. For example, a
number of nitrates melt before they decompose: A1(NO,),.9H2O
(74"C),59 Zn(N0,),.6H20 (45"C)," Cu(N0,),.3H20 (1 14°C):'
and Ba(NO,), (592°C).6yIf the metal nitrate melts before the
solvent is completely removed, the molten salt will inhibit
removal of the entrapped solvent. This is one reason why pow-
ders derived from metal nitrates often consist of porous or irreg-
ular particle^.^^,^^.^'-^^
Ciminelli and M e s ~ i n g ' ~have
, ~ ~ studied the formation of
A1,0, from A1(NO3),-9H,O solutions. When the concentration
at the surface reaches the critical supersaturation a crust forms
and the surface temperature of the droplet rises. At 76"C, the
A1(NO3),.9H,O salt dissolves in its own water of crystallization
to form a "melt" and releases nitrous oxide gases at >76"C. The
continual evaporation of water from within the droplet results in
an increase of the melt viscosity and eventually foaming of the
particle (Fig. 13(A)). Sproson and Messing' have reported that
formed by adding ethylene glycol to the solution (Fig. 13(B)).
-
This morphology develops as a result of ethylene glycol boiling
(Zb 198°C) when the metal salt is in a molten state.
(3) Ultrafine and Nanoparticle Synthesis
Research in the last 10 years has identified size-dependent
particle and microstructure properties in the submicrometer to
nanometer range as an important area for the development of
new materials and materials p r o c e s ~ e s .Based
~ ~ , ~ ~on inherent
simplicity and compositional flexibility, SP processes have the
potential to expand the availability and compositional range of
nanostructured particles. Nanoparticles can be directly synthe-
sized from droplets or by liberating the individual crystallites
comprising the SP-derived particles after the thermolysis stage.
2718 Journal of the American Ceramic Society-Messing et al. Vol. 76, No. 11

Fig. 12. Morphologies of (A) A1,0, particles derived from A1,(SO,),~16H2Osolution of CJC, = 0.022 and (B) BaO particles derived from
Ba(CH,COO)2solution of CJC, = 0.028.2’

Fig. 13. (A) Porous A1,0, particles derived from AI(N0,),.9H20 and (B) porous ZnO particles derived from Zn with 15 wt% polyethylene
glyco1.7h.”

To directly produce powders by SP requires control over

droplet formation, coagulation, and evaporation processes as
well as precipitation and decomposition processes. The final
oxide particle size D, after sintering can be approximated
(assuming the solute concentration is uniform at C,) by

where Dois the initial diameter of the solution droplet, C, the

the precursor theoretical
initial solution concentration, pprecurJar
density, ponldrthe oxide theoretical density, and W the oxide
yield of the precursor. Figure 14 illustrates that direct produc-
tion of nanoparticles by SP requires relatively dilute solutions
(i.e., low C,/C,) and small initial droplet size
Ultrasonic and electrostatic atomizers, and nebulizers have
been used to satisfy the requirement for small droplets. Droplet
size from ultrasonic atomizers can be controlled by the atomizer
frequency or by the solution surface tension and can be calcu-
latedb’from

r7S
d = 0.34 7
Initial Droplet Size (nm)

where p is the solution density (gicm’) and f is the frequency Fig. 14. Precipitate particle size as a function of solution concentra-
(s ‘1. tion and droplet size before calcination and sintering.”
November 1993 Ceramic Powder Synthesis by Spray Pyrolysis
Kato et al. obtained 220- to 280-nm Y-ZrO,h5 and 200- to
300-nm TiO,b particles by SP of O.035M zirconium alkoxide or
1 vol% titanium isopropoxide (Ti(j-OC3H7)J solutions using an
ultrasonic atomizer at 1.7 MHz. Odier et a1." obtained 180- to
200-nm ZrO, particles by atomizing a 0.018M ZC solution with
an ultrasonic atomizer operated at 2.5 MHz. Toghe et pre-
pared TiO,, SiO,, A1,0,, and cu-Fe,O, particles using an ultra-
sonic atomizer operated at 70 MHz. Slamovich and Lange'"
reported the synthesis of 0.2-pm Y-ZrO, particles by electro-
static atomization of nearly saturated ZC solutions.
The initial droplet size can be further reduced by adjusting
the surface tension of the precursor solution with either surfac-
tants or low-surface-tension solvents such as alcohols. By low-
ering the surface tension of a 0.05M ZHC solution from 73 to 32
dyne/cm with 5 wt% 1-butanol, the initial droplet size was
reduced from 3 to 2.3 Frn using an ultrasonic atomizer at 1.6
MHz. Although ZrO, particles of 660 nm should have been pro-
duced, 970-nm solid particles were obtained. The larger particle
size was attributed to coagulation of the droplets. The issue of
droplet and particle coagulation will require attention if SP pro-
cesses are to be used for direct production of nanoparticles and
ultrafine powders.
By using a nebulizer and impactor, we have been able to
form 50-nm ZnO and ZrO, nanoparticles (Fig. 15). The
impactor decreased the initial number density of droplets from
10' to lo3cm ' and preferentially removed the larger droplets
and thus decreased the median droplet size from 5 to 220 nm.
Particles formed by SP are usually composed of crystallites
substantially less than 100 nm in diameter after the thermolysis
stage. Therefore, instead of trying to form nanoparticles
directly, an alternative approach is to liberate the individual
crystallites comprising the SP-formed particles. Gardner and
Messing4demonstrated that 14-nm MgO nanoparticles could be
formed from Mg(CH,COO), but not from Mg(NO,),. Although
both salts yielded particles consisting of nanocrystallites, it was
proposed that the oxidation of the carbonaceous residue from
the acetate resulted in disintegration of the initial particle to
give unaggregated nanocrystallites. Similar results were
obtained for Zn0,31but the correlation between metal acetate
decomposition and nanocrystalline particle formation may not
be universal. Another approach for liberating the nanocrystal-
lites would be to use colloid or attrition-milling techniques for
SP particles that have been heated through thermolysis but not
sintered. Because large quantities of powder can be produced
using two-fluid atomizers, this approach may be the most viable
for the production of substantial quantities of nanoparticles,
given the limitations of current atomization technology and the
need to avoid coagulation.
Fig. 15. (A) ZnO and (B) ZrO, nanoparticles synthesized by SP.
2719
(4) Single Phase, Multicomponent Oxide Particle Synthesis
The aqueous coprecipitation of multicomponent systems is
always complicated by differences between the solubilities of
the solutes and the differences in the pH at which precipitation
occurs. These differences cause segregation of the solutes and
affect phase development during thermolysis. While SP tech-
niques localize compositional segregation to the droplet scale
during precipitation at least, these differences can still affect
phase formation in multicomponent systems if the relative solu-
bilities of the constituent salts differ significantly.
Odier et aL5' and Tohge e f a1." reported that it was not possi-
ble to synthesize phase-pure, superconducting YBC particles by
SP of metal nitrate solutions. This result was explained by the
differences in the metal nitrate solubilities and subsequent
sequential precipitation during evaporation of bulk solu-
tions. 11,8246 For SP to realize its potential for multicomponent
particle synthesis, chemical segregation within the droplet must
be avoided.
A number of organic acid- and metal alkoxide-based systems
have been developed for the synthesis of homogeneous, multi-
component oxide powders. The three-dimensional network
structure or higher viscosity of these precursor systems has
been shown to decrease or eliminate the extent of nonunifom
precipitation in mixed metal oxide ~ y s t e m s , ~ which
~ - ~ ' in turn
improves phase homogeneity. Y,O, homogeneity in SP-derived
Y-ZrO, particles has been demonstrated to be good by elemen-
tal mapping in TEM6' and by using the Williamson-Hall plot
method.h5
In another example, SP m ~ l l i t ewas ~ ~prepared by cohydro-
lyzing partially hydrolyzed TEOS and aluminurn isopropoxide
(Al(i-OC,H7)J. The physical characteristics of the particles
were similar to the ZrO, particles discussed above. Depending
on the degree of hydrolysis and whether a base or acid catalyst
was used, large differences in the relative volatility of TEOS
were observed; acid hydrolysis of TEOS plus copolymerization
with aluminum alkoxide yielded more chemically uniform
particles.
Kato6 used metal alkoxides as precursors for lead zirconate
titanate (PZT) and refluxing of the starting solution to obtain
compositional homogeneity in each PZT particle. Nonaka
et al.'" eliminated the heterogeneity of BaTiO, and SrTiO,
powders by increasing the concentration of the solutions or by
complexing Ti4+ions in the solution with H,O,. Starting solu-
tions were prepared from Ti(i-OC,H,), and Ba(NO,), or
Sr(NO,),. Pebler and Charlesh8synthesized phase-pure submi-
crometer YBC and Bi-Sr-Ca-Cu oxide particles from 0.06M
and 0.05M metal-ethylenediaminetetraaceticacid (EDTA) soh-
2720 Journal of the American Ceramic Society-Messing
tions, respectively. Although the solution characteristics (e.g.,
viscosity and solubility) and subsequent particle formation pro-
cesses were not reported, it is evident that the complexing agent
EDTA was necessary to reduce cation segregation during
precipitation.
We reported the synthesis of spherical YBC superconducting
powders69based on SP of an organic acid precursor solution.
The precursor was prepared by dissolving metal carbonates into
a citric acid/ethylene glycol solution, followed by heat treat-
ments to yield solid resins of different molecular weights. It was
concluded that a precursor with a high degree of polymerization
is an important requirement for the formation of solid particles
by SP of organic precursors. It is not clear whether segregation
was avoided by bonding in the precursor itself or was due to the
significantly slower diffusion of the chemical species in the vis-
cous matrix as predicted by the Stokes-Einstein equation.
Recent progress in precursor design to avoid chemical segrega-
tion in niulticomponent systems, such as YBC, offers promising
alternatives to simple metal salts for SP.
(5) Nonoxide and Metal Particle Synthesis
Only a few studies report the synthesis of non-oxide ceramic
powders by SP. Mizutani and Liu" reported that an oxygen-free
precursor possessing very low vapor pressure and soluble in an
oxygen-free solvent is required for synthesis of non-oxide parti-
cles. In their investigation, polysilazane dissolved in benzene
(6 X mol/L) was ultrasonically atomized and transported
with nitrogen into a 700°C furnace. Spherical, agglomerate-free
particles 0.38 pm in diameter were obtained. A pure a-Si,N,
phase was formed if the as-prepared powder was calcined at
1400°C in nitrogen. Lindquist et aLg2used a poly(boraziny1-
amine)-liquid-NH, solution as a precursor for SP synthesis of
BN powder under anhydrous and oxygen-free conditions. The
10 wt% polymer solution was atomized into a 1000°C furnace
in nitrogen. The white powder obtained was X-ray amorphous,
spherical, and had a particle size of -0.5 pm. The particles at
this stage were porous, and some appeared to be hollow. Subse-
quent calcining at 1600°C yielded dense, crystalline BN pow-
ders that were partially sintered.
There are only a few reports of metal powder synthesis,
except as part of composite powders. This is probably a conse-
quence of the pyrophoric nature of small metal particles and the
associated handling difficulties. However, Dornier Company in
Germany has reported" the production of tungsten alloy pow-
ders by SP from an aqueous solution of tungsten and other
metal salts. They also report that the alloy powder characteris-
tics were improved due to more homogeneous distribution of
the components.
Fig. 16. Nanocomposite particles of (A) A1,OJplatinum prepared from Al,(SO,),, (B) A1,OJplatinum prepared from boehmite, and (C) ZrOJplati-
num from ZHC.9'
et al. Vol. 76, No. 1 I
(6) Composite Particle Synthesis
Developments in the field of particulate composites and
nanoc~mposites'~ are impeded by the difficulty of uniformly
codispersing and mixing the individual powders. SP can fulfill
the emerging need for composite particles by directly producing
them with the requisite phase composition and distribution.
Combinations of polysilazanes, polyborazines, polysilanes,
metal alkoxides, and conventional metal salts create many new
possibilities for composite particle synthesis and design. Ther-
molysis atmosphere control may allow the synthesis of com-
posite particles of unique compositions.
Depending on the precursor characteristics, composite parti-
cle formation processes can be classified into four categories
(Fig. 4(B)).
( A ) Sequential Coprecipitation: If the difference in pre-
cursor solubilities is large, then the solute of lower solubility
will precipitate first. Depending on whether the particle can
continue to shrink, the other solutes will segregate to the surface
where they will heterogeneously nucleate. The composite parti-
cle will consist of relatively larger crystallites of the first phase
surrounded by smaller crystallites of the second phase. Figure
1 6(A)95illustrates such a case for Al,O,-platinum composite
particles synthesized from an aqueous solution of 0.5M
AI,(SO,), and H,PtCI, (2.5 wt% platinum) at 950°C. The pow-
der consists of 4- to 5-nm cubic platinum particles dispersed on
the surfaces of larger spherical y-Al,O, particles which are
composed of very small crystallites. Carim et aL9' prepared
nanocrystalline YBC-Ag composite particles by SP from a
nitrate solution of Y, Ba, Cu, and Ag and obtained <25-nm Ag
grains. Although the size of the aerosol-produced particles
ranged up to a few micrometers or more, the dimensions of the
individual grains composing the particles were typically 10 to
80 nm (for both YBC and Ag crystallites).
( B ) Simultaneous Coprecipitation: If the precursor solu-
bilities are nearly the same, then precipitation will occur almost
simultaneously. In this case, the composite microstructure will
consist of a uniform mixture of nanocrystallites. As an example,
a 0.5M ZHC and H,PtCI, (10 wt%) solution was atomized into a
furnace at 700°C using a nebulizer, and the powder was then
heated to 950°C at 10"C/min in air.95The TEM micrographs in
Fig. 16(C) show that the particle consists of a uniform mixture
of 16.5-nm t-ZrO, and 6.7-nm platinum crystallites.
Two other cases can b e considered as promising ways to pro-
duce composite particles. Gurav et aL9' recently reported that
highly disperse (20- to 100-nm) powders consisting of nano-
phase fullerene and rhodium were generated by aerosol ther-
molysis. The solution of mixed fullerene extract (Cm, C,,,) and
November 1993 Ceramic Powder Synthesis by Spray Pyrolysis
(( 1,5-COD)RhCI), in toluene was atomized and passed through
nitrogen in a hot-wall reactor. Nanocomposite particles were
formed at a reactor temperature of 550°C. XRD and TEM
showed that phase segregation can be controlled at the nanome-
ter scale to form ultrafine, nanocomposite particles of C, and
rhodium. TEM studies of the 50/50 wt% fullerene/rhodium
composite showed 3- to 5-nm rhodium crystallites.
Kanno and Suzukig8reported that t-ZrO,-SiO, composite
particles were produced by SP of an ethanol solution of TEOS
and ZC with an ultrasonic atomizer. The resultant ZrO,-SiO,
(1:l) particles were spherical and 0.8 to 1.0 km in diameter.
The formation mechanism of the Zr0,-SiO, composite particle
is similar to the simultaneous precipitation of two salts, but
SiO, is formed by gelation.
( C ) Colloid-Solution Precipitation: Hybrid systems
where one component is added as a colloid and the other as a
soluble metal salt or metal organic offer a number of advan-
tages in terms of yield, production rates, and phase-distribution
flexibility. Nanocomposite particles of y-Al,O, and platinum
(Fig. 16(B)) were produced by SP at 950°C from a hybrid sol of
H,PtCI, dissolved in a boehmite sol at pH 3. From XRD, the
platinum crystallite diameter was 3.9 nm and the y-Al,O, was
4.5 nm. The powder surface area was 203 m'/g.
(D) Vapor-Phase-Induced Precipitation: Some metal
salts, especially transition-metal salts, are easily precipitated in
the form of hydroxides or hydrous oxides when the solution pH
is changed.99As discussed earlier, the lower melting point of
AI(N0,),.9H,O (ANN) leads to formation of hollow and irregu-
lar AI,O, particles. However, the problem can be solved by
introducing NH, into the aerosol carrier gas before the droplet
reaches the melting temperature of ANN. In this manner
Al(OH), precipitates in the droplet to form a solid particle as
NH, dissolves in the droplets and increases the pH to 7. In a
similar manner, Gadalla et al. obtained a uniform mixture of
NiO and FeO hydrous oxide precipitates by reacting aerosol
droplets of the metal nitrates with NH,.
Another chemical precipitation process is based on the
hydrolysis of metal alkoxide droplets with water vapor.
Ingbrethsen et af.67obtained uniform, 0.1 -km-diameter spheres
of mixed Al,O,-TiO, (hydrous) oxides by the hydrolysis of alu-
minum sec-butoxide and titanium ethoxide aerosol droplets.
Recently, McCandlish et a1.lW reported a solution chemical
route called "spray conversion processing" to produce bulk
quantities of cobalt-WC powder. The process starts by mixing
the cobalt and tungsten on the molecular level with an aqueous
solution of ammonium metatungstate ((NH,),(H,W,,O,,).
4H,O) and cobalt chloride (CoCl,.nH,O). The solution was
spray dried to produce particles composed of a fine mixture of
the precursor salts. This precursor powder was reduced with
hydrogen and then reacted with CO to yield a cobalt-WC nano-
composite powder in which the WC particles were <50 nm in
diameter. The dense nanocomposite formed from this powder
was reported to be significantly stronger and tougher than
cobalt-WC composites fabricated from conventionally pro-
duced powders.
The availability of 100- to 1000-nm composite particles in
this size range avoids some of the difficulties associated with
nanoparticle processing. Yano et al."' used SP to prepare
A1,0,40% ZrO, particles from a nitrate solution. Although the
particles were hollow spheres of a few micrometers, the ZrO,
and a-Al,O, crystallite sizes were 60 to 150 nm, respectively,
after calcination at 1400°C for 1 h. This powder readily sintered
to >99% of theoretical density at 1200" to 1250°C. Note that
the precipitation conditions during SP plus the presence of a
second phase ensures that the particles will be nanocrystalline.
Another important advantage of SP for nanocrystalline powders
is that large quantities can be produced in contrast with current
vapor-phase technologies used to make nanosized (10-nm) par-
ticles. The potential for large-scale production of particles by
SP processes has already been e ~ t a b l i s h e d ~ ~for
- ' ~a. ~similar
~ faces. The important variables are the substrate temperature,
272 1
process but for applications in which small particle size and
controlled morphology are not critical.
(7) Fiber Synthesis
Analogous to fiber formation by dry spinning, we have dem-
onstrated that-by adjusting the precursor viscosity, surface
tension, and solution concentration-discontinuous fibers can
be produced by SP when using a two-fluid atomizer. A precur-
sor is spinnable if it is capable of undergoing large irreversible
elongations when subjected to a uniaxial stress.'02TOmaintain
the fiber morphology requires a chemical or physical mecha-
nism to stabilize the fiber in the extended state.
We have learned'03.'04that fibers of virtually any composition
can be formed during SP by changing the solution characteris-
tics so that it is spinnable and atomized with a two-fluid atom-
izer. The precursor is pumped with a peristaltic pump through
the central orifice of the two-fluid nozzle to form a ligament.
The precursor ligament is elongated by a high-velocity air jet
around the orifice and then stabilized by rapidly removing the
solvent when it enters the furnace.
To studyiMthe effect of precursor viscosity on ZrO, fiber for-
mation, zirconium acetate (Zr(CH,COO),, ZAC) solutions with
the equivalent of 23.5, 24.8, 26.6, and 27.4 wt% ZrO, plus 6
wt% poly(viny1 alcohol) (PVOH) were sprayed at 0.1 MPa into
a 750°C furnace. The maximum fiber fraction was obtained
with the 25 wt% ZrO, precursor solution which had viscosity of
0.122 Pas.
For low-viscosity solutions, the degree of fiber elongation is
controlled by cohesive fracture, whereas Rayleigh instability
controls formation at high viscosity. The ratio of the precursor
surface tension to viscosity determines the fiber formation
mechanism. To examine the controlling mechanism of fiber for-
mation over the low-viscosity range, ZAC solutions (25 wt%
ZrO,) containing 6 wt% PVOH with a viscosity of 0.120 Pa.s
and surface tensions from 56 to 40 dyne/cm (0.056 to 0.040 N/
m) were prepared by adding up to lo-, mol/L of a surfactant
(C,,H,,(OCH,CH,),,OH). As shown in Fig. 17, the fiber frac-
tion increases and fibers become longer and smaller in diameter
with decreasing y/q.
Apart from reducing the y/q ratio, the PVOH also functions
as a skeleton during fiber solidification. The skeleton formation
may be a combination effect of drying and coagulation of
PVOH caused b y the metal salt.'"5In a manner similar to hollow
particle formation, hollow fibers can be synthesized by control-
ling the operating and solution parameters.26At low solution
concentration, low solution flow rate, and low heating rate, the
fibers appear to be solid (Fig. 18(A)), but, at higher solution
concentration, higher flow rate, and higher heating rate, fibers
with diameters >2 pm are hollow (Fig. 18(B)).
(8) Thin Films
SP is also well suited for producing thin films of the desired
stoichiometry on large, nonplanar surfaces (e.g., wire^).'^,'"^
Vacuum deposition techniques yield films with smooth surfaces
which are useful for microwave applications, but granular films,
which can be fabricated by SP techniques, are needed for some
applications, such as light detectors."' Simplicity and economic
viability factors make film formation by SP deposition attrac-
tive. Since the pioneering paper by Chamberlin and Skarman on
CdS films for solar cells in 1966,'09the SP technique has been
applied widely to produce coating films of transparent conduct-
ing sulfide,"2 'I5 and selenide semiconductors."'
Typical film thicknesses range from 0.2 to 10 pm. Recently,
there have been a large number of reports published on the pro-
duction of superconductor films by SP.'w'o',' 1 7 ~ " x
In the SP deposition process, a precursor solution is atomized
into discrete droplets and subsequently transported to a heated
substrate. At the proper temperature the droplets or solid parti-
cles are decomposed and then sintered or melted on the heated
substrates. Viguie and Spitz"' classified SP deposition into five
processes according to the type of reaction on the substrate sur-
2722 Journal of the American Ceramic Society-Messing
Fig. 17. Effect of surfactant on formation of fibers: (A) ZAC and 6 wt% PVOH (7 = 112 mPa-s and y
PVOH with surfactant (q = 118 mPa.s and y = 40 dyne/cm).
Fig. 18. (A) Solid ZrO, fiber derived from ZAC plus 6 wt% PVOH solution of 24.8%ZrO, and (B) hollow ZrO, fiber derived from ZAC and 6 wt%
PVOH solution of 25.3% 210,.
carrier gas flow rate, solution flow rate, solution concentration,
droplet size, and nozzle to substrate distance.114.1'5 An ideal
deposition condition is when the droplet approaches the sub-
strate just as the solvent is completely removed."'
The surface temperature of the substrate is a critical factor for
SP film dep~sition,'"~~"'~~~'"~~~~ because it affects the processes on
the substrate, such as droplet drying, decomposition or melting,
crystallization, and grain growth. For example, Afify I"
observed that the crystallite size and strong preferred orienta-
tion of ZnO along the [002] plane is strongly dependent on the
substrate temperature, and, therefore, the resistivity of the film
increases with substrate temperature during deposition. In YBC
film synthesis, the film stoichiometry, phase composition,
microstructure, and film surface roughness greatly depend on
substrate temperat~re."'~Blancher'"' showed that YBC films
deposited from a nitrate solution at 800°C were composed of
highly uniform 1-pm grains and that they had a high degree of
orientation.
The atomization process is another critical factor in SP depo-
sition, because film formation depends on the processes of
droplet landing, reaction, and solvent evaporation, which are
related to droplet size and momentum. Lampkim12"showed
that, depending on droplet velocity and flow direction, a droplet
will either flatten, skip along the surface, or hover motionless.
Most SP film deposition is done from aqueous solution,
which is conducive to a low-cost process. However, some
investigators have developed processes using nonaqueous solu-
11.1 13.1 17.121
as the volatile solvent evaporates before striking
et QI Vol. 76, No. I 1
= 56 dyneicm) and (B) ZAC and 6 wt%
the substrate surface, leaving vapors to react at the s ~ r f a c e . " ~
The concentration of the SP precursors ranges from 0.01M to
0.3M. The metal nitrates and metal acetates are commonly
used, because of their low decomposition temperature, low
melting point, and low corrosivity. Some authors report that
precursors also affect the microstructure of films. For example,
Aranovich' I s demonstrated that zinc acetate- (Zn(CH,COO),)
derived ZnO films were much more uniform and smoother in
appearance than films derived from metal chloride or chloride
with H202solutions. Very smooth CdS surfaces were obtained
at low flow rates using acetate solutions, but chloride solutions
resulted in very smooth surfaces with columnar grains.120
IV. Summary
Spray pryrolysis (SP) is a versatile technique for production
of ceramic materials of a wide range of composition, size, and
morphology. Production of ceramic powders, films, or fibers
with controlled characteristics requires control over atomiza-
tion, coagulation, evaporation, thermolysis, and sintering pro-
cesses. The properties of the solution and the precursor,
including thermal characteristics, must be known, because they
can profoundly affect the maintenance of the particle morphol-
ogy through all stages of the process. Chemistry of the ceramic
phase can be adjusted by regulating the thermolysis atmosphere
and precursor chemistry. A number of challenges still face this
emerging field, depending on the specific synthesis objectives.
November 1993 Ceramic Powder Synthesis by Spray Pyrolysis
For example, issues associated with attaining solid particle for-
mation and limiting coagulation presently limit scale-up of SP
processes. One impediment to rapid development for this
method is the limited information about the fundamental char-
acteristics of precursor systems. Despite these limitations, SP
processes offer a wealth of opportunity for the production of
materials with new and novel characteristics.
Acknowledgments: We would like to acknowledge helpful discussions
with Robert Santoro and Michael Frenklach.
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November 1993 Ceramic Powder Synthesis by Spray Pyrolysis 2725

Dr. Gary L. Messing is Professor of Ceramic Science and Engineering and Director of
the Particulate Materials Center at The Pennsylvania State University. Dr. Messing
received his B.S. in ceramic engineering from the New York State College of Ceramics
at Alfred University and his Ph.D. in materials science and engineering at the Univer-
sity of Florida. He was a research scientist for two years at Battelle Columbus Labora-
tory before joining the Materials Science and Engineering Department faculty at Penn
State. Dr. Messing is coorganizer of the International Powder Processing Conference
series with H. Hausner and S. Hirano, an Editor of the Journal of the American Ceramic
Society, and has served as Chairman of the Basic Science Division. Professor Messing
received the Wilson Research Award at Penn State in 1992, a 1993 Richard M. Fulrath
Pacific Award (U.S. recipient), and is a Fellow of the American Ceramic Society.

Shi C. Zhang is a research associate in the Particulate Materials Center at The Pennsyl-
vania State University. Mr. Zhang graduated from Nanjing Institute of Chemical Tech-
nology, Nanjing, China, in 1966, majoring in ceramic science and engineering. From
1981 to 1983, he studied and worked at Rutgers University as a visiting scientist. He
was the director of the Advanced Ceramics Division in the China Building Materials
Academy from 1984 to 1986. Prior to joining Penn State in 1987,Mr. Zhang was named
as a member of the Expert Steering Board and chairman of the Powder Division, super-
vising the capital project “High-Temperature Structural Ceramics and Adiabatic
Engines,” by the Bureau of industrial Technology, State Science and Technology Com-
mission of China. From 1988 to 1991, he held a postdoctoral appointment at Penn State.
His principal areas of interest are synthesis and characterization of oxide, non-oxide,
and composite ceramic powders as well as other ceramic processes.
2726 Journal of the American Ceramic Society-Messing et al. Vol. 76, No.11

Gopal Jayanthi is a graduate student in chemical engineering at The Pennsylvania State

University. Mr. Jayanthi received his B.S. degree in chemical engineering at the Indian
Institute of Technology at Madras and his M.S. in chemical engineering from Texas
A&M University.