Aerosol Science and Technology

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Aerosol Processing of Materials

Abhijit Gurav , Toivo Kodas , Tammy Pluym & Yun Xiong

To cite this article: Abhijit Gurav , Toivo Kodas , Tammy Pluym & Yun Xiong (1993)
Aerosol Processing of Materials, Aerosol Science and Technology, 19:4, 411-452, DOI:
10.1080/02786829308959650

To link to this article: https://doi.org/10.1080/02786829308959650

Published online: 12 Jun 2007.

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Aerosol Processing of Materials
Abhijit Gurav, Toivo Kodas," Tammy Pluym, and Yun Xiong
Chemical Engineering Department, Center for Micro-Engineered Ceramics, Uniuersity of New Mexico,
Albuquerque, NM 87131
Recent advances in aerosol generation of materials are
reviewed. Gas-to-particle and spray processes (spray
pyrolysis) for powder generation and various routes for
film generation are discussed from the experimental
and theoretical perspectives. The range of materials
generated by these routes has increased in recent years
to include fullerenes and ceramic superconductors.
Many metals and various oxide and nonoxide ceramics
have also been added to the list of materials generated
by gas-phase routes. Established aerosol routes such as
vapor condensation have found widespread applica-
tions for generation of nanophase materials. The for-
INTRODUCTION
Aerosol generation of materials has seen
many new developments in recent years.
New aerosol processes have been devel-
oped, new applications have emerged for
existing aerosol processes, new chemical
approaches have been utilized, the range
of materials produced by existing pro-
cesses has been greatly expanded, and a
better theoretical understanding of the
processes has been obtained. An example
of a new process/application is produc-
tion of quantum dots (Flagan et al., 1991;
Saunders et a]., 1992; Sercel et al., 1992;
Wiedensohler et al., 1992). In one novel
approach, nanometer-sized metal parti-
cles are generated, classified in the gas
phase, and deposited, and then plasma
etching using the particles as masks is
used to form quantum dots of the sub-
strate material (Wiedensohler et al., 1992).
*To whom correspondence should be addressed.
Aerosol Science and Technology 19:411-152 (1991)
0 1993 Elsevier Science Publishing Co., Inc.
mation of quantum dots via aerosol approaches has
also been demonstrated. The theoretical understanding
of gas-to-particle conversion routes has advanced to
include the finite rate of particle fusion or sintering
occurring after collisions of particles. The modeling of
spray pyrolysis systems has provided insight into the
control of particle morphology and reactor design. In
this review, these recent developments in aerosol gener-
ation of powders and films via gas-phase and spray
routes are discussed with an emphasis on the material
chen~istriesinvolved and the synthesis of nanophase
materials.
In the other approaches, semiconductor
particles of materials such as CdS, ZnS,
and GaAs are produced directly in the
gas-phase (Fujita et al., 1985; O'Brian et
al., 1986; Flagan et al., 1991; Powell et a].,
1992). There are several examples of new
applications of existing aerosol processes
for materials processing. Vapor condensa-
tion has been studied for many years as a
method for particle formation, but has
only recently been exploited for genera-
tion of bulk nanophase ceramic materials
(Siege1 and Eastman, 1989). Several new
classes of materials such as fullerenes (a
new family of allotropes of carbon, e.g.,
C,,, C,,, etc.) (Rohlfing et al., 1984a;
Kroto et al., 1985; Kratschmer et al., 1990)
and ceramic superconductors (Chadda et
al., 1991; Ward et al., 1992a, b) have been
produced by existing aerosol routes (laser
reactors and spray pyrolysis, respectively)
in recent years. In addition, existing
aerosol methods have been used to pro-
duce novel materials from purified
412 A. Gurav et al.

fullerenes (Gurav et al., 1993). Although

Reactant A ( ~ ) A(g)
there have been a few recent reviews and Vapor
A(g) A(g)
book chapters on specialized aspects of

_
A(g) A(g)
aerosol processing of materials (Gleiter,
1989; Kodas, 1989; Segal, 1989; Kodas and Gas-Phase
Sood, 1990; Ichinose et al., 1992; Pratsinis
and Kodas, 1992), no recent articles have
gathered these advances into one source.
Reaction

B(g) B(g) Vaporization a

Solid

This article reviews recent develop-

ments in aerosol generation of powders
and films with an emphasis on new chemi-
cal approaches and the synthesis of
B(g)

Nucleation, Surface
Reaction, and
Coagulation
B(g) ~ ( g )
B(g) B(g)
8
Liquid

nanophase materials, and brings together

literature from diverse sources and disci-
plines to show the versatility and interdis-
ciplinary nature of aerosol routes to mate-
rials. Because of the depth and breadth of
this area, this review is restricted to devel-
opments related to materials generation
and does not address advances in mea-
surement techniques or basic aerosol sci-
ence and technology in general. The re-
view first discusses new developments in
powder generation by gas-to-particle con-
version. Next, spray routes (liquid/solid-
to-solid routes) to powders are reviewed.
This is followed by a discussion of aerosol
routes to films. Recent developments in
modeling are included for both spray and
gas-to-particle conversion routes where
they have had an impact on processes
used to produce materials.
Gas-to-Particle Conversion
Gas-to-particle conversion refers to pro-
duction of particles from individual atoms
or molecules in the gas phase. The physi-
cochemical processes constituting the
overall process are well understood quali-
tatively and are shown in Figure 1. Parti-
cle formation is driven by the cooling of a
supersaturated vapor or by the generation
of atoms or molecules by chemical reac-
tion of gaseous precursors. High tempera-
tures and hence high-energy sources such
as hydrocarbon flames, Joule (resistive)
heating, plasmas, sputtering, ion, electron,
Coagulation, I
Agglomeration,
and Coalescence
Powder
FIGURE 1. Gas-to-particle conversion process.
or laser beams, or hot-wall reactors are
often necessary. Depending upon the ki-
netics, thermodynamics, reactor design
and operating conditions, the product
atoms or molecules can form particles ei-
ther by uninhibited collisions (collision-
controlled nucleation) or by balanced
evaporation and condensation to and from
molecular clusters (evaporation-con-
densation controlled nucleation)
(Friedlander, 1977; Seinfeld, 1986). The
newly formed clusters grow by further
condensation of molecules and/or by co-
agulation with other clusters. A range of
particle sizes, from the nanometer- to the
submicrometer-scale, and spreads of the
size distribution, from nearly monodis-
perse to polydisperse, can be obtained.
Similarly, the extent of agglomeration,
particle shape, and composition can vary
greatly.
The primary advantages of gas-to-par-
ticle routes are small particle size (mi-
Aerosol Processing of Materials
crometer to nanometer range depending
on the process), narrow size distribution,
nearly spherical and solid particles, and
high purity. The disadvantages include
difficulties in producing multicomponent
materials, low production rates in some of
the processing routes (e.g., inert gas con-
densation), and problems associated with
hazardous gaseous reactants and byprod-
ucts. Another major disadvantage is for-
mation of hard agglomerates in the gas
phase which leads to difficulties in pro-
ducing high-quality bulk materials
(Kingery et al., 1976). However, some in-
sight has been obtained in recent years as
to the conditions required to eliminate
agglomerate formation (Wu et al., 1987;
Okuyama et a]., 1989; Nguyen and Flagan,
1991).
The use of gas-phase reactions of sin-
gle gaseous reactants to produce submi-
crometer-size titanium dioxide, silica, and
carbon black by flame synthesis is well
established. These processes have been
used at production levels of millions of
tons per year in several industries. The
gas-to-particle conversion route can also
be used for the generation of multicom-
ponent materials containing two or more
elements in addition to oxygen and nitro-
gen (Buchanan et al., 1980; Kagawa et al.,
1983a, b; Kagawa and Syono, 1985; Ono
et al., 1985, 1987; Pollinger and Messing,
1987; Akhtar et al., 1992b; Hung and Katz,
1992; Hung et al., 1992). However, it is
often difficult to produce multicomponent
materials with homogeneous chemical
compositions because differences in
chemical reaction rates of the reactants,
and in the vapor pressures and nucleation
and growth rates of the products may lead
to nonuniform composition from particle
to particle or within a single particle. For
this reason, coated particles or particles
with varying composition from particle to
particle are often obtained (Kagawa et al.,
1983a, b; Pollinger and Messing, 1987;
Hung and Katz, 1992; Hung et al., 1992).
413
Particles with these characteristics may be
desirable in some cases (e.g., mullite,
Moore et al., 1992). However, in most
other cases, chemical uniformity is re-
quired within each particle (Reed, 1988).
Many different types of flame, furnace,
plasma, and laser reactors have been used
to facilitate gas-phase reactions leading to
the formation of desired oxide or nonox-
ide materials. The sections below discuss
recent developments in material synthesis
using these gas-to-particle conversion
routes with an emphasis on the genera-
tion of nanophase materials and new
chemical approaches.
Nanophase Materials
The ability to manipulate matter and to
assemble structures on the atomic to
nanometer scale is currently a goal of
many researchers in physical and engi-
neering sciences. "Nanostructures," in a
broad sense of the word, are collections of
assemblies of atoms that have dimensions
in the range of 1-20 nm (Granqvist and
Buhrman, 1976; Gleiter, 1989; Siegel,
1990; Stroscio a n d Eigler, 1991;
Whitesides et al., 1991; Sundaram et al.,
1991; Ichinose et a]., 1992). For aerosols,
these include structures formed by depo-
sition of individual nanometer-size parti-
cles onto surfaces and bulk "nanophase"
or "nanocrystalline" materials which are
produced from nanometer-size particles.
In this section we discuss the processing
of the latter class of nanophase materials
via a variety of aerosol-based techniques.
The former topic, which is also termed
"quantum-dot generation," is discussed
later in the section on film formation.
Nanophase materials possess some
unique advantages with respect to proper-
ties and processing (Epperson et al., 1989;
Gleiter, 1989; Siegel and Eastman, 1989;
Hahn et al., 1990; Siegel, 1990; Pechenik
et al., 1992): (1) The ultrafine sizes of the
414
atomic clusters and their surface cleanli-
ness allow densification/sintering of
nanophase metals or ceramics at tempera-
tures substantially lower than those re-
quired for conventional materials. (2)
Nanophase materials have a large volume
fraction of atoms (20-50%) at the grain
boundaries. Hence, these materials can
deform easily at low temperatures via
grain boundary sliding (Coble creep) mak-
ing it easy to obtain desired shapes per-
haps without using conventional forming
processes. Conventional coarse-grained
ceramics are brittle; but in nanophase
form, they may become tough and elastic
or even superplastic (Karch et al., 1987;
Sherby and Wadsworth, 1989; Chen and
Xue, 1990). (3) The hardness and strength
of sintered nanophase ceramics are con-
siderably higher than those observed in
conventionally processed materials (Siegel
et al., 1988; Siegel and Eastman, 1989). (4)
Nanophase materials exhibit novel or un-
usual optical, electrical and magnetic
properties (e.g., superparamagnetism
(Shull et al., 1989; Deng and Chin, 1991;
Gangopadhyay et al., 1992; Lee et al.,
1992); increase in Curie temperature of
ferrimagnetic MnFe,O, (Tang et al.,
1991); stabilization of high-temperature
tetragonal crystalline phase at low tem-
peratures in ZrO, (Ramamurthi et al.,
1990)). It is also possible to obtain
metastable phases or alloys which cannot
be formed by conventional methods
(Glavee et al., 1991). Thus, nanophase
materials may provide unusual or im-
proved properties, net-shape forming of
materials, and processing at lower tem-
peratures.
The synthesis of nanophase particles
has been carried out most frequently by
physical methods such as gas-con-
densation (evaporation-condensation), dc-
and rf-sputtering, plasma processing, and
laser ablation. Nanophase materials have
also been generated by gas-phase reaction
A. Gurav et al.
routes using furnace reactors, and more
recently via spray pyrolysis which will be
discussed later. These aerosol methods are
reviewed in the following sections. Only
the key features of the processes are men-
tioned with references to pertinent re-
views.
Flame Reactors. Flame reactors involve
gas-phase reactions of precursors injected
into diffusion or premixed flames (Ulrich,
1971, 1984; Shon et al., 1979; Zachariah et
al., 1989). Oxides of Si and Ti, and most
other metals in the periodic table, have
been produced by the oxidation of the
respective halides in hydrocarbon flames
(see reviews by Kodas, 1989; Kriechbaum
and Meinschmit, 1989; Pratsinis and KO-
das, 1992). Additives can be introduced
into the flames to control the phase, shape,
and size distribution of the product
(Mezey, 1966; Haynes et al., 1979; Akhtar
et al., 1992a, b). Particle formation in
flame reactors follows the gas-to-particle
conversion mechanism described earlier.
The crystallinity of the powder and the
degree of particle agglomeration and coa-
lescence are determined by the residence
time and the temperature distribution in
the flame. Maximum temperatures in the
flame are often between 2000 and 3000 K.
Due to these high temperatures, this pro-
cess can be applied to volatile as well as
relatively non-volatile precursors. Primary
particles having a size of 1-500 nm are
formed. Product particles contain from a
few up to many thousand such primary
particles. Scale-up of this process has been
demonstrated for the production of car-
bon black, silica, titania, e t ~ .However,
due to the steep temperature gradients
present in the flames, this process offers
poor control over particle size and mor-
phology. The resulting product particle
size distributions are often broad (coagu-
lation controlled process) and hard ag-
glomerates are usually formed. This has
Aerosol Processing of Materials
seriously limited applications of ceramic
powders produced using flame reactors.
Funzace Reactors. These reactors in-
volve chemical reactions between precur-
sor vapors in a gas flow through a furnace
(see reviews by Kodas, 1989; Kodas and
Sood, 1990; Pratsinis and Kodas, 1992).
The precursors are introduced into the
furnace either as a gas or as an aerosol
formed from a solution or solid. The lat-
ter facilitates t h e introduction of low-
volatility precursors into the reactor
(Kagawa et al., 1983a; Powell et al., 1992)
and allows use of lower cost precursors
(Weimer et al.. 1991, 1992). Furnace reac-
tors provide excellent control over tem-
perature and flow velocity, and hence over
the product particle characteristics. Parti-
cle formation via gas-phase reactions in
furnace reactors is reasonably well under-
stood and detailed models have been de-
veloped for systems such as silicon parti-
cle formation by the decomposition of
silane (Wu et al., 1988; Nguyen and Fla-
gan, 1991), silica by the oxidation of SiCl,
(Kim and Pratsinis, 1988, 1989), and tita-
nia by oxidation of TiC1, (Landgrebe et
al., 1990; Pratsinis, 1990; Pratsinis et al.,
1990); and reaction of titanium isopropox-
ide (Okuyama et al., 1986, 1989; Kirkbir
and Komiyama, 1987). In addition, a large
body of more general models and model-
ing results is available and can be found
in recent reviews (Kodas, 1989; Kodas and
Sood, 1990; Pratsinis and Kodas, 1992).
Furnace reactors have been used to
produce a variety of materials in interest-
ing forms. Weimer et al. (1991, 1992) pro-
duced boron carbide via carbothernlal
reduction of boron oxide. Ultrafine amor-
phous TiO, having a particle size of 17-60
nm was produced in a furnace reactor by
vapor-phase hydrolysis of titanium te-
traisopropoxide (TTIP) at low tempera-
tures (257°C) (Shirnakawa et al., 1991).
Titanium dioxide particles having a size of
415
20-80 nm and density of 3.60 g/cm3 were
made by decomposition of titanium te-
traisopropoxide at 700°C using H e carrier
gas (Kirkbar and Komiyama, 1987).
Morooka et al. (1991) studied the oxida-
tion of TiC1, in a plug flow furnace reac-
tor at 950-1200°C and produced TiO,
particles in the range of 55-65 nm.
Organometallic compounds are volatile
and can react at relatively low tempera-
tures resulting in oxide or nonoxide com-
pounds. This has recently motivated their
use as precursors for several materials.
Adjaottor and Griffin (1992) synthesized
submicron A1N powders via vapor-phase
reaction of trimethyl aluminum and am-
monia at 700-llOO°C in a furnace reac-
tor. Sercel et al. (1992) produced crys-
talline nanometer-scale (10-20 nm) GaAs
clusters by vapor-phase reaction between
trimethyl gallium and arsine. Powell et al.
(1992) synthesized nanocrystalline ZnS us-
ing a single-source precursor containing
both zinc and sulfur in a single volatile
reactant.
Gas-Condensation M e t h o d . T h i s
method is the most extensively studied
and used technique for the synthesis of
nanophase materials. A material is evapo-
rated under a controlled inert atmosphere
followed by condensation to obtain small
clusters. This technique was pioneered in
1930 by Pfund (1930a, b) and Burger and
van Cittert (1930), and later by Harris et
al. (1948). Gleiter and co-workers (Gleiter,
1981) adapted this technique for forming
clusters that were subsequently consoli-
dated to make nanophase materials. It
has subsequently been used extensively to
produce bulk nanophase materials
(Gleiter, 1981; Siege1 and Eastman, 1989;
Averback et al., 1990).
The most common apparatus for the
synthesis of nanophase materials is shown
in Figure 2. It comprises an ultrahigh
vacuum (UHV) chamber fitted with evap-

Liquid Nitrogen
-izzz7
Evaporation
Sources
FIGURE 2. Vapor condensation process for
generation of nanophase materials. (Adaptcd
from Siegel and Eastman, 1989).
oration sources, a liquid-nitrogen-cooled
finger and scraper assembly, and an in situ
compaction unit to consolidate the pow-
ders produced and collected in the cham-
ber (Gleiter, 1989; Siegel and Eastman,
1989). The vacuum chamber is first
pumped to a vacuum > Pa and then
backfilled with a high-purity inert gas, typ-
ically a few hundred Pa of He. The sub-
stance (e.g., Ti, Al, or Cu) is evaporated
by resistive heating from a refractory
metal boat. A temperature corresponding
to a vapor pressure of -
10 Pa for the
precursor is chosen as the evaporation
temperature. The free convective plume
above the source results in cooling of the
gas mixture which results in formation of
small clusters. Average cluster diameters
usually range between 5 and 15 nm. The
clusters are carried by the free convective
A. Gurav et al.
currents of the inert gas to the liquid-
nitrogen-cooled finger where the particles
are collected by thermophoresis. After
evaporation, the inert gas is removed and
the particles are scraped from the cold
finger and funneled into a piston and anvil
device where they are compacted using
pressures of - 1-5 GPa. The main prob-
lem with this approach is that it is a
semi-batch and not a continuous flow pro-
cess, leading to low production rates. It
also cannot easily produce multicompo-
nent materials.
Oxide ceramics such as TiO, and Al,03
have been produced in a two-step process
(Siegel and Eastman, 1989). First ultrafine
metal particles were formed by evapora-
tion of Ti and A1 metals. Titanium parti-
cles were then oxidized to TiO, rutile
phase by the rapid introduction of pure
oxygen into the vacuum chamber at room
temperature. In order to produce Al,O?,
aluminum metal clusters were annealed In
air at 1000°C resulting in their transfor-
mation to the stable a-phase Al,O, with
a small increase in particle-size. Subse-
quent room-temperature consolidation
produced nanophase a-Al,03 with a grain
size of - 18 nm. Magnesium oxide having
ultrafine grain-size (5 nm diameter) was
produced by direct heating of MgO in a
vacuum chamber (Siegel and Eastman,
1989).
The main process parameters control-
ling the characteristics of the particles
produced are the inert gas pressure, the
evaporation rate, and the gas composi-
tion. The effects of varying these parame-
ters were first examined in detail by
Granquist and Buhrman (1976). They
demonstrated that the particle size can be
decreased by decreasing either the gas
pressure in the chamber or the rate of
evaporation of the precursor. The particle
size could also be decreased by using
lighter inert gases such as He rather than
Xe. Generally, in producing nanophase
materials, these parameters are adjusted
Aerosol Processing of Materials
to produce clusters having the smallest
size while still maintaining sufficient evap-
oration (production) rates.
The exploding-wire technique, which
can be considered as a vapor-con-
densation method, was used by Saunders
et al. (1992) to synthesize crystalline
nanophase GaAs clusters in the 5-10 nm
range. The clusters were formed by homo-
geneous nucleation of a vapor created by
the explosive vaporization of a bulk GaAs
wire in an inert atmosphere.
Although gas condensation and related
methods have been used for several years
to produce nanophase materials, several
challenges remain:
1. Chemical reactions between most met-
als and the refractory metal crucibles
cause changes in evaporation condi-
tions and failure of the crucibles.
2. The production of alloys, intermetallic
compounds, composites, and multicom-
ponent materials is difficult since the
thermodynamic activities and vapor
pressures are often quite different for
the constituents, resulting in difficulties
in controlling compositions.
3. Most ceramic materials have high melt-
ing points and very low vapor pres-
sures. Consequently, this approach is
limited to ceramics with low melting
points or high vapor pressures, such as
CaF, and MgO.
4. Post-oxidation of metallic clusters to
obtain oxide ceramics has seen limited
success since the resulting material is
often oxygen deficient and needs oxida-
tion treatments before or after com-
paction. Such treatments are undesir-
able since they usually cause agglomer-
ation, grain growth and/or surface
contamination.
5. Production rates are currently small
(milligram quantities) and the process
is essentially a batch-type reactor. Thus,
efforts to use continuous flow systems
are required.
417
Sputtering. The problem of low precur-
sor vapor pressures encountered for evap-
oration/condensation processes can be
overcome by using other methods to in-
troduce species into the gas phase. When
ions (e.g., Ar or Kr), accelerated to high
energies, are directed towards a surface,
atoms and clusters, both neutral and ionic,
are ejected. This method of vaporizing
materials is called sputtering (see review
by Gleiter, 1989). Yatsua et al. (1985)
reported the production of ultrafine parti-
cles by diode sputtering. Hahn and Aver-
back (1990) used magnetron sputtering to
synthesize nanoscale particles of Al, Mo,
Cu, Cu,,Mn,, Al,,Ti,,, and ZrO, with
diameters of 7-50 nm. The apparatus was
similar to that used for the gas-con-
densation method, except that it was fitted
with a dc/rf magnetron sputtering source
instead of a resistive evaporation source.
The grain sizes for Al, Mo, and Cu clus-
ters made at different operating condi-
tions were 30, 20, and 15 nm, respectively.
Oxide ceramics can be synthesized by
sputtering in different ways: (1)postoxida-
tion of metal particles prepared by dc
sputtering in an Ar atmosphere; (2) reac-
tive rf sputtering in an Ar-0, atmo-
sphere; and (3) direct rf sputtering of an
oxide target. Route 1 often leads to
grain-growth and agglomeration during
post-oxidation treatment. For example, the
grain size of the as-prepared Zr sample
increased from 20 to 30 nm on sintering
at 900°C (Hahn and Averback, 1990).
Hence, routes 2 and 3 are of particular
interest for the synthesis of oxide ceram-
ics. Recently Ying (1992) synthesized
nanophase Pt-TiO,_, cermet (composite
of a ceramic and a metal) having a grain
size of 11.1 and 7.9 nm, respectively, for
Ti0,-, and Pt. Chow et al. (1990) utilized
sputtering at high pressures (0.2-0.6 Torr)
to produce llanocomposites (particle di-
ameter < 15 nm) of Al and Mo. Haubold
et al. (1991) prepared tungsten samples
with 10 nm diameter crystallites.
418
Another advantage of sputtering is that
the composition of the product is the same
as that of the target. Hence, synthesis of
alloys and multicomponent ceramics is of-
ten possible. One drawback, however, is
that it usually produces small amounts of
clusters and the spread of the cluster size
distribution increases with decreasing
cluster size (Gleiter, 1989). For example,
production rates were - 100-180 mg/h
for pure metal cluster formation (Hahn
and Averback, 1990). The product yields,
however, reduced drastically when oxide
powders were made since the main depo-
sition of the particles was on the shield of
sputter source and not on the cold finger
(Hahn and Averback, 1990). Again, a ma-
jor challenge is scale-up while maintaining
powder quality.
Plasma Reactors. These methods use
plasmas to vaporize species followed by
condensation to form particles. Powders
or gaseous reactants are carried into a
plasma or arc discharge zone where com-
plete vaporization occurs. The vapor cools
rapidly while exiting the plasma and ultra-
fine particles form as a result of the high
supersaturation (see reviews by Kodas,
1989; Kodas and Sood, 1990; Pratsinis and
Kodas, 1992). Powders of Mn, Fe, Co, Zn,
and Mo with particle sizes in the range of
5-50 nm were synthesized by flowing re-
spective oxide powders through a low-
temperature plasma generated using pure
Ar or mixtures of Ar/H, or Ar/NH,
(Vissikov et a]., 1988). Nanophase nitrides
of Al, Si and Mg were synthesized by
passing the powders of respective metals
through an equilibrium electrical arc low
temperature plasma generated by Ar/N,
gas mixtures (Vissikov et a]., 1981;
Vissikov and Brakalov, 1983; Vissikov et
a]., 1988; Vissikov, 1992). Similarly, using
an oxidizing plasma (Ar/O,), ultrafine
SiO,, A1,0,, Fe,O,, and COO were syn-
thesized starting from SIC],, Al, FeCI,
A. Gurav et al.
nH ,O or FeSO, H,O and CoS (Vissikov
et a]., 1988). Ultrafine particles of differ-
ent metals, alloys, and ceramic-metal
composites (cermets) such as Fe-TiN and
Ni-TiN were produced in a 50% H,-50%
Ar plasma (pressure - 0.1 MPa) (Ohno
and Uda, 1984, 1989; Ohno et al., 1989;
Nakahigashi et al., 1992). Brock and Lim
(1991) have reported the formation of thin
carbon fibers and hollow tubes in corona
discharges in alkane-N, atmosphere.
An interesting development in plasma-
based processing methods is the synthesis
of diamond particles and films (Johnson
et a]., 1988; Angus et a]., 1991; Frenklach
et a]., 1989, 1991). Production of fine dia-
mond particles in a low-pressure mi-
crowave plasma reactor using acetylene-
Ar-diborane, and dichloromethane- and
trichloroethylene-0, mixtures has been
reported (Frenklach et a]., 1989, 1991). A
major challenge for plasma reactors is
elimination of hard agglomerates formed
by incomplete coalescence of particles that
have collided in the gas phase while main-
taining high production rates.
Laser Ablation. This method uses
high-power pulsed lasers to vaporize ma-
terials from target surfaces to provide high
supersaturations. The wavelength of laser
light has to be chosen depending on the
target material characteristics (see review
by Gleiter, 1989). For ablation of metals,
UV lasers (e.g., excimer lasers) are re-
quired as the reflectivity of many liquid
metal surfaces in the infrared or visible
range is close to 100%. To obtain pure
metal clusters, laser ablation is carried
out in inert gases. The resulting plumes
are composed of mostly neutral atoms
(Gleiter, 1989), whereas ions and clusters
are observed during laser ablation of com-
pounds such as YBa,Cu,O,_, (Izumi et
a]., 1991). The plume is entrained and
cooled by the carrier gas which results in
supersaturation and cluster formation.
Aerosol Processing of Materials
The resulting cluster size distributions are
often broad (Gleiter, 1989).
The laser vaporization or ablation tech-
nique is versatile and can be applied to
any material that can be fabricated into
an appropriate target. Clusters of transi-
tion metals (Dietz et al., 1981; Morse,
1986), main group metals (LaiHing et al.,
1987), alloys (Rohlfing et al., 1984b), and
semiconductors (Liu et al., 1986) have
been synthesized. Another approach com-
bines laser ablation of one metal with
simultaneous laser pyrolysis of a gaseous
precursor of another metal. Dem'yanenko
and Puretsky (1990) reported that
nanosecond excimer laser pulses could be
used to produce metal nanoclusters from
metal carbonyls. Recently, Johnston et al.
(1992a) have reported the synthesis of
6-14 nm A120, particles via laser abla-
tion of A1 in oxygen atmosphere using an
XeCl excimer laser. In another study
(Johnston et al., 1992b) an aluminum tar-
get was laser ablated (XeCl laser, 20 Hz)
in a nitrogen atmosphere resulting, after
post-processing, in phase-pure AlN with
an average particle size between 22 and
26 nm. The main disadvantages of laser
ablation based processes are low produc-
tion rates ( - 10 mg/h; Johnston et al.,
1992b) and high production costs.
Another class of processes which use
the energy of a laser to generate nan-
oclusters involves gas-phase reactions.
Formation of 3-10 nm clusters of Si has
been reported by room temperature pho-
tolysis of disilane with the output from an
ArF excimer laser operating at 193 nm
(Jasinski and LeGouses, 1991). Films and
particles of several pure metals, and ox-
ide/nonoxide ceramics have been formed
via gas-phase reactions driven by lasers
(Draper, 1980; Cannon et al., 1981a, b;
Ehrlitch, 1981; Bilenchi et al., 1982;
Haggerty, 1984; Jervis et al., 1985, 1987;
Cauchetier et al., 1987; Gupta et al., 1987;
Borsella et al., 1992). Gonsalves et al.
419
(1991) reported conversion of a liquid
organosilane precursor to intermediate
preceramic particles of Si,N,/SiC using a
high-power C 0 2 laser. This preceramic
material was converted to a composite
ceramic powder having a bimodal particle
size distribution with modes having mean
diameters of 44.8 and 119.43 nm. Pechenik
et al. (1992) fabricated transparent Si,N,
from nanosize, an~orphousstoichiometric
powders (mean particle size 16 nm) which
were made via laser-induced reaction be-
tween silane and ammonia. Highly dense
compacts having high hardness were sin-
tered at relatively low temperatures with-
out using any sintering aids or applying
pressure during sintering, approaches
which are necessary for sintering conven-
tionally synthesized Si,N, powders. This
demonstrates the advantages nano-par-
ticles offer with respect to subsequent
processing. The major drawbacks to this
class of processes are the complexity and
high cost of the equipment and the dif-
ficulty in scale-up.
It is noteworthy that one of the com-
mon methods of generating fullerenes in-
volves conditions similar to laser reactors
(Rohlfing et al., 1984a; Kroto et al., 1985;
Kratschmer et al., 1990). Substantial
amounts of fullerenes (primarily C60.and
C,, with small quantities of several hlgher
fullerenes) are present in the soot ob-
tained by laser vaporization of graphite.
Similarly, gram quantities of fullerenes
were synthesized during arc-discharges us-
ing graphite electrodes. Metal-incapsu-
lated fullerene particles were synthesized
using a composite of graphite and metal.
Recently, spectroscopic studies of conden-
sible compounds and soot from hydrocar-
bon combustion revealed the presence of
C,, and C,, (Howard et al., 1991). The
authors have reported optimal yields of 3
g of fullerenes per kilogram of fuel car-
bon burned in hydrocarbon flames. Thus,
fullerene generation occurs in aerosol re-
 A. Gurav et al.

actors where the sooty product contains a
mixture of different fullerenes and other
products. This area is only beginning to be
explored and offers major challenges for
aerosol scientists and engineers.
Novel Chemistries: Tailored Precursors
for Multi-Component Systems
Many materials including various semi-
conductors, ceramic superconductors,
metal silicides, mixed-metal oxides, metal
nitrides, glasses, etc. often contain two or
more elements that must be present in a
precisely controlled stoichiometry and
must be mixed at the atomic scale in
order to exhibit useful properties. If dif-
ferent precursors are used for different
components in gas-to-particle conversion
processes, inhomogeneities often result
Solid or Liquid
Precursors
because the chemical characteristics of all
the precursors and products are not the
same. The rates of chemical reactions and
thermodynamic properties, especially va-
por pressures and surface energies of re-
action products, determine the nucleation
and growth behavior of the different
products derived from the precursors.
These properties are so different from
precursor to precursor that the composi-
tion of particles formed in a multicompo-
nent system is often nonuniform from
particle to particle and within a single
particle (Kagawa et al., 1983a7b; Ono et
al., 1985, 1987; Pollinger and Messing,
1987; Hung and Katz, 1992, Hung et al.,
1992).
Figure 3 schematically explains the
origin of phase segregation or inhomo-
geneities in the case of a typical two-com-
ponent system with either a vapor-con-
Solid or Liquid Solid or Liquid
Precursor Precursor

1 I
Vaporization and

1
B(g) A(g)
Reactions forming A and B

A(g)
Vaporization
Vaporization

A(g) B(g)
B(g) A(g) B(g)
I Nucleation of A
C
C(g)
Reaction B(g)
I

Nucleation and Reaction

C Coagulation

.
D(9)

Nucleation and

Nucleation of B, '. . Coagulation

Formation of Desired
Product C=AB, and
Condensation of B
onto Particles of A and C,
r Coagulation

FIGURE 3. Particle formation in multicomponcnt systcm lcad-

ing to segregation of spccics: (a) vapor condensation and (b)
gas-phase reaction.
Aerosol Processing of Materials
densation or gaseous reaction route. One
of the components often nucleates first.
This is followed by successive nucleation
of other components which may occur on
the surface of existing particles or lead to
formation of new single-component parti-
cles. Starting with such a nonhomoge-
neous material, it is difficult to obtain
homogeneous material having precise sto-
ichiometry in different regions by subse-
quent processing steps such as reactive
sintering.
The tailoring of precursors for genera-
tion of multicomponent materials with
controlled properties has been investi-
gated recently for aerosol processes. This
approach has been used extensively for
liquid-phase routes. Mixed-metal alkox-
ides, oxalates or citrates have been exten-
sively used for the synthesis of multicom-
ponent glasses and oxides (titanates)
(Clabaugh et al., 1956; Kiss et al., 1966;
Mazdiyasni and Brown, 1970; Dislich,
1971; Hennings and Mayr, 1978; Bradley,
1989; Gupta and Cooper, 1989; Ma et al.,
1991). However, there are fewer reports
of the use of mixed-metal precursors for
gas-phase synthesis of multicomponent
materials. These are primarily for chemi-
cal vapor deposition (CVD) processes in
which problems similar to those found in
gas-to-particle routes are encountered.
Some of the examples include CVD of (1)
titanium, zirconium, and hafnium nitrides
from tetrakis(dialkylamido)metal(lV)
complexes (Fix et a]., 1991); (2) titanium
nitride from its chloride-amide-amine
complex (Winter et al., 1992); (3) 11/V1
semiconductors (ME, where M = Zn, Cd,
or Hg, and E = S, Se, or Te) from thio-
phosphinates (Takahashi et al., 1980;
Evans and Williams, 19821, thiocarbo-
mates (Frigo et al., 1989), thiolates
(Bochmann et al., 1990; Osaka and Ya-
mamoto, 1991); or alkylmetalthio-carba-
mates (Hursthouse et al., 1991, 1992; Ma-
lik and 07Brian,1991); (4) 111/V semicon-
ductors (ME, where M = Al, Ga, or In,
421
and E = P or As) from adducts such as
Me, In .PEt, (Bradley et al., 1988) or dinu-
clear complexes such as [R, MiR; El], and
R,M(R;E),MIR, (Jones et al., 1989); (5)
aluminum silicate from [AliOSiEt?),],
(Landry et al., 1992); (6) late transition-
metal silicides such as CoSi from
H ,SiCo(CO),, FeSi, from ( H ,Si),
Fe(CO), (Aylett and Colquhoun, 1977;
Aylett, 1989) a n d M n , S i f r o m
Mn2(CO),,( p S i H , ) (Stauf et al., 1988).
There are three methods (Figure 4)
involving tailored precursors that allow
control or prevention of phase-segrega-
tion or inhomogeneities in multicompo-
nent materials prepared via gas-phase re-
action routes: (1) single-source precursor
routes where a single, volatile precursor
contains all the required elements in the
correct stoichiometry required in the
product as for the CVD precursors men-
tioned above (Figure 4a); (2) employing
two or more separate precursors that have
been designed in a manner that results in
similar decomposition rates as a function
of temperature (Figure 4b); and (3) use of
two or more volatile species which react
with elimination of ligands thereby achiev-
ing the required stoichiometry in the
product (Figure 4c).
The single-source precursor approach
has been used to generate binary and
ternary materials by gas-to-particle con-
version. Zinc sulfide, a semiconductor ma-
terial, has been produced using a single-
source precursor (Powell et al., 1992). UI-
trafine particles (8 nm grain size) of ZnS
were synthesized by reaction of
Zn(S,CNEt ,),(tetramethylenediamine
[TMEDA]) at 500-700°C under nitrogen.
Ultrafine (30 nm size) Ge-Mn particles
were formed by reacting a single-source
volatile p r e c u r s o r 1 , l - b i s - ( p e n t a -
carbony1manganio)-3,4-din~ethylgermacyc-
lopent-3-ene at 600°C (Powell et a]., 1992).
Rice (1986) reported the synthesis of fine
Si/C/N powders by laser pyrolysis of an
organosilazane precursor. Similarly, Gon-
 A. Gurav et al.

Precursor Precursor Precursor Precursors

M'L ,
1 Vaporization Ln

I Vaporization

Reaction

-
M M' +
I Gas Phase
Reaction

Uganda M + Uganda M' +

I Gas Phase
Reaction

Ugands
-
M M' + Llgands

I
Nucleation Nucleation

e
I @
and
Coagulation

\*.
Coagulation

/ Coagulation
Nu"0n

@.e
e e@
Growth
0
@*
. .
@
Growth @@
1
and ,@
Coagulation

Coagulation

FIGURE 4. Approaches to controlling segregation during gas-

to-particle conversion: (a) single-source precursors, (b) matching
reactivity of precursors, and (c) requiring reaction of precursors
with each other.

salves et al., (1991) synthesized Si/C/N
nanoparticles by ultrasonic injection of an
organosilazane precursor into a laser re-
actor. However, in general, very few stud-
ies have examined the use of these and
related strategies for the generation of
multicomponent materials.
MODELING OF GAS-TO-PARTICLE
CONVERSION
The physicochemical phenomena encoun-
tered during gas-to-particle conversion in-
clude chemical reactions, nucleation, sur-
face reactions, evaporation, condensation,
and coagulation. Relative to spray pyroly-
sis, the gas-to-particle conversion route is
well understood and has been modeled
extensively (see references in Kodas and
Sood 119901 and Kodas 119891). There are
several new developments which are in-
teresting from both the practical and
modeling points of view. These include
control of aggregate structure and the ef-
fect of charged particles.
Aggregate Formation
Aggregates (agglomerates, nonspherical or
irregular particles) have long been en-
countered during aerosol manufacture of
materials such as carbon blacks, fumed
silica, and pigmentary titania (Ulrich,
1984). It is important to be able to model
and control aggregate formation as the
performance of particulate conlmodities
depends strongly on the morphology and
size of the particles. These factors deter-
Aerosol Processing of Materials
mine the electrical, optical and sintering
properties of materials produced from the
particles (Kingery et al., 1976). The reason
for aggregate formation has also long been
recognized, namely, the slow particle coa-
lescence (sintering, fusion) rate (Kingery
et al., 1976) with respect to the interparti-
cle collision r a t e ( U l r i c h a n d
Subramanian, 1977). However, due to the
simplicity of handling spherical geome-
tries and the difficulty in treating irregular
aggregate structures, theoretical studies of
aerosol dynamics have until recently been
largely confined to spherical particles.
Initial attempts on modeling aggregate
formation derived directly and logically
from aggregate characterization itself.
Medalia ( 1967) developed a two-dimen-
sional geometrical method for analyzing
aggregate shape from electron micro-
graphs and related it to the three-dimen-
sional aggregates using computer gener-
ated flocs. Adopting a constant "bulkiness
factor" from the above study, Ulrich and
co-workers (Ulrich and Subramanian,
1977; Ulrich and Riehl, 1982) modeled
fumed silica aggregate formation by ac-
counting for the effect of sintering on the
resulting aggregate structure which, in
turn, affected the particle collision rate.
However, they treated particle coales-
cence and interparticle collisions indepen-
dently by assuming the dominance of ei-
ther one of the two mechanisms during
any particular stage of particle growth.
Rosner and co-workers (Park and
Rosner, l989a, b; Tassopoulos et al., 1989;
Rosner and Tassopoulos, 1991; Rosner et
al., 1991; Castillo et al., 1991, 1992) have
done extensive studies on inertial and
thermophoretic effects on formation and
transport of aggregates in highly loaded
aerosol systems. Tassopoulos et al. (1989)
extended the ballistic aggregation and
diffusion-limited aggregation models
(Witten and Sander, 1981; Family and
Landau, 1984; Meakin et al., 1986) to
develop a discrete stochastic model simu-
423
lating the growth and microstructures of
aggregates in two- and three-dimensions
by several mechanisms, namely, Brownian
diffusion, impaction, and phoresis ither-
mophoresis, photophoresis, or elec-
trophoresis), occurring simultaneously.
However, this work lacked iterative com-
parisons of predictions from the model
and experimentally observed aggregate
microstructures. Although the model con-
sidered the effects of particle polydisper-
sity, mean-free-path, and spatial orienta-
tion (for nonspherical particles), it had no
provisions to incorporate certain situa-
tions encountered in practice, such as ag-
gregate growth for which the deposition
mechanisms evolve with time or aggre-
gates which gradually evolve due to, say,
sintering (Tassopoulos et al., 1989).
Recently, the concept of fractals has
been used to characterize aggregates
(Mandelbrot, 1983; Meakin, 1988; Avnir,
1989, Megaridis and Dobbins, 1990; Dob-
bins and Megaridis, 1991). A single fractal
dimension or power law exponent has
comn~onlybeen used to correct the colli-
sion rate and other transport behavior of
aggregates from those of ideal spheres
(Mountain et al., 1986; Kaplan and
Gentry, 1988; Rogak and Flagan, 1990;
Wu and Friedlander, 1993). However, this
results in the interdependence of coales-
cence and collision not being taken into
account. This is a crucial problem because
it is this interdependence that causes par-
ticles to undergo continuous time- and
size-dependent rearrangement throughout
their formation (Schmidt-Ott, 1988). In
addition, particle formation and growth by
collision alone occur through various size
regimes so that the growth kinetics may
not be described by a single fractal dimen-
sionality (Scheafer and Hurd, 1990).
Therefore, the particle shape or fractal
dimension also evolves as a function of
time and particle size. This point is sup-
ported by studies by Kaye (1991), who
examined the structure of fumed titania
424
through fractal analysis. Within any one
population of pigment powders, a range of
boundary fractal dimensions was found in
the two-dimensional projections of the
pigment particles. Weber et al. (1991) also
showed experimentally that silver parti-
cles produced by aerosol routes possess
size-dependent fractal dimensions. How-
ever, studies on flame-generated carbona-
ceous soot and silica indicated that while
the aggregate size and morphology are
determined by the operating conditions
and the region of the flame from which
the sample originated, the primary parti-
cle sizes ( - 10-50 nm) and fractal dimen-
sions (1.6-1.9) were narrowly confined
(Megaridis and Dobbins, 1990; Dobbins
and Megaridis, 1991). This is an important
result because it supports the assumption
of using a single fractal dimension which
drastically simplifies aerosol modeling.
Overall, however, a deterministic ap-
proach is needed to model particle growth
by simultaneous coalescence and collision.
Koch and Friedlander (1990a) first for-
mulated the problem of simultaneous coa-
lescence and coagulation by including a
coalescence term in the governing popula-
tion balance equation in addition to coag-
ulation. The coalescence contribution is
based on a particle sintering rate ex-
pressed by the surface area reduction rate
(da/dt), which is given as the ratio of the
difference in the surface area of an aggre-
gate (a) and a completely fused single
sphere (a,,,,) of the same volume over a
characteristic sintering time ( T ~ ) :
The charateristic sintering time depends
on the sintering mechanism which is de-
termined by the particle material proper-
ties, temperature, and particle size (Koch
and Friedlander, 1990b). However, this
approach did not account for the effect of
aggregate structure on particle collision
A. Gurav et al.
rate and the governing population balance
equation was solved only for the total
particle surface area and average primary
particle size.
Xiong and Pratsinis (1993) developed a
two-dimensional particle size distribution
model that solves the general aerosol dy-
namics equation explicitly using a sec-
tional method. Figure 5 shows how the
size and morphology of each particle can
be described using the particle volume (v)
and surface area (a). For an aggregate of
volume v, which is composed of i = v/v,
primary particles of volume v,, its surface
area lies between that of a completely
coalesced sphere, i2l3a,, and that of an
agglomerate of i primary particles just
touching one another upon collision, ia,.
The particle surface area fractal dimen-
sion (D,)can be obtained from v and a
(Eq. 2):
Both particle coalescence and collision
rates are related to the shape and size of
the particles. The predicted evolutions of
the particle volume and surface area dis-
tributions lead to a direct characterization
of the n~orphologyand average particle
size of the product powder, and to an
estimation of the surface fractal dimen-
sion of the particles from first principles.
The model was applied to gas-phase
synthesis of titania and silica powders
(Xiong et al., 1993a), and to the formation
of boron carbide particles by the rapid
carbothermal reduction process (Xiong et
al., 1992b). Figure 6 shows two snapshots
of the two-dimensional number distribu-
tion of titania particles formed by TiCl,
oxidation at 1700 K. For fully coalesced
particles the excess surface area is zero.
Figure 6 indicates that the particle num-
ber density is greatly reduced by coagula-
tion as the residence time increases from
1 to 1.6 s. Due to the rapid sintering of
Aerosol Processing of Materials

Volume:
vo iv,

Surface Area:
ao ia, > a >

Surface Fractal Dimension:

FIGURE 5. Descriptions of particle morphology using particle

volume and surface area. (Adapted from Xiong and Pratsiais,
1993.)

FIGURE 6. Two-dimensional number distribution of titania

particles formed by gas-phase TiCl, oxidation at 1700 K and
residence times (a) 1 s and (b) 1.6 s, respectively. (Adapted from
Xiong et a]., 1993a.l
426
FIGURE 7. Two-dimensional number distribution of (a) titania
and (b) silica particles formed by gas-phase oxidation of TiCl,
and SiCI,, respectively, at 1500 K and 1.6 s. (Adapted from
Xiong et al., 1993a.)
titania particles at these high tempera-
tures, the excess surface area is nearly
zero at both residence times indicating a
low degree of aggregation for those parti-
cles.
Figure 7, a and b, shows similar plots
for titania and silica particles formed by
the oxidation of TiCl, and SiCl,, respec-
tively, at 1500 K and 1.6 s. Comparing
Figures 7a and 6b, the effect of tempera-
ture on the particle sintering rate is seen.
The excess surface area of the TiO, parti-
cles at 1500 K is significant, indicating a
higher degree of aggregation than at 1700
K (Figure 6). Comparison of Figures 7, a
and b, reveals a stronger effect, in this
case, of particle material properties on
product powder morphology. Most of the
SiO, particles, in contrast to TiO, parti-
cles, have a high excess surface area and
small particle size at the same process
conditions. This prediction of a high
degree of aggregation for aerosol-made
silica powders is consistent with both in-
dustrial practice and experimental obser-
vations (Ulrich and Riehl, 1982; Xiong et
al., 1993a).
A. Gurav et al.
One drawback of this two-dimensional
sectional model is its complexity. Re-
cently, Kruis et al. (1993) developed a
simplified version of the above model by
assuming a monodisperse aggregate and
primary particle size distribution. This ap-
proach is useful for capturing some of the
key characteristics of aggregate formation
without going through the elaborate com-
putation of the detailed solution of the
two-dimensional aerosol dynamics equa-
tion.
The two-dimensional sectional ap-
proach also has several other difficulties.
The model cannot distinguish between
particles of different mass fractal dimen-
sions, but of the same surface fractal di-
mension or roughness. It is the former
rather than the latter fractal dimensional-
ity that determines the collision behavior
of the particles. Thus, a constant surface
area scaling factor, an adjustable parame-
ter, must be used throughout a simulation
to account for many unknowns related to
the particle structure. An improved ap-
proach would employ the mass fractal di-
mension in calculating the collision fre-
Aerosol Processing of Materials
quency function of aggregates. However,
the present approach cannot provide this
parameter and, consequently, this dimen-
sionality would just become another ad-
justable parameter. Another problem in
the two-dimensional aerosol dynamics
model is the use of a single particle sinter-
ing rate expression throughout particle
growth even though particle coalescence
may involve changes in the sintering
mechanism (Koch and Friedlander,
1990a).
An alternative approach which circum-
vents the problems described above is the
use of Monte Carlo simulations of cluster
formation to account for restructuring and
sintering (Akhtar et al., 1992a). Various
growth mechanisms such as monomer-
cluster, cluster-cluster, free-molecular
ballistic, and continuum Brownian (diffu-
sion-limited) aggregation can be utilized
together with simultaneous cluster sinter-
ing. This approach, however, is limited to
very small cluster sizes due to its compu-
tational intensity. However it can provide
detailed, microscopic structural character-
izations of the clusters from which both
the mass fractal dimension and the sur-
face area scaling factor as well as the
sintering rate can be deduced. These pa-
rameters, in turn, can be used in the de-
terministic two-dimensional simulation.
Preliminary simulations using the Monte
Carlo method indicated that sintering re-
sults in compact clusers on small length
scales in the initial stages. As clusters
become larger with time, the sintering
process slows down and the fractal dimen-
sion of the clusters decreases, consistent
with predictions from t h e two-
dimensional aerosol dynamics model.
Effect of Particle Charging on Aerosol
Coagulation
Particle charging is frequently encoun-
tered during commercial powder genera-
tion either due to the chemistry involved
427
or the use of ionic additives. Combustion
aerosols are examples where chemioniza-
tion is intrinsic to the formation of soot
particles (Burtscher, 1992). Additives are
also used during fuel combustion and in
gas-phase manufacture of powders to con-
trol the size, morphology, and phase com-
position of product particles. For example,
addition of trace amounts of various alkali
metals significantly reduces soot emission
(Haynes et al., 1979, 1981). Small addi-
tions of various halide metals during TiCl,
oxidation in the "chloride" process can
also reduce the size and polydispersity of
the product titania powder (Suyama and
Kato, 1976). A possible explanation for
these effects is that the alkali metal atoms
are easily ionized at the high flame tem-
peratures. Some of these metal ions pref-
erentially adsorb onto the particle sur-
faces and give rise to a unipolar or at least
an asymmetrical charge on the particles,
which hinders particle growth by coagula-
tion.
Xiong et al. (1992a) developed a simple
model to study the effect of ionic addi-
tives on aerosol coagulation using
Coulomb's law and Maxwell's images
method for calculating the electrostatic
repulsive forces between unipolarly
charged particles. A thermochemical equi-
librium calculation was performed to esti-
mate the charging ability of the alkali
metals based on their ionization potential.
The aerosol dynamic equation taking into
account electrostatic interactions between
titania particles in the presence of ionic
additives was solved by a sectional tech-
nique (Gelbard et al., 1980; Xiong and
Pratsinis, 1991). Figure 8 shows the evolu-
tion of (a) the geometric mean particle
diameter (d,,) and (b) the geometric stan-
dard deviation ( a ) of TiO, particles in
the absence and presence of 0.01 ppm
alkali metal chlorides. When no additives
are used, particle size increases rapidly by
Brownian coagulation and the corre-
sponding a approaches its self-preserving
 A. Gurav et al.

value (Friedlander, 1977). In the presence
of additives, however, coagulation is sub-
stantially reduced at different average
particle sizes depending on the charging
ability of the metal ions: 0.05 p m for
CsCl, 0.08 p m for KCl, and 0.17 p m for
NaCl. The spread of the size distribution
is also altered by the additives. Potassium
and cesium chlorides reduce the polydis-
persity of the particles substantially below
that of the self-preserving distribution.
Therefore, strong particle charging can
result in narrow size distributions and
small average product particle sizes.
In the above model, charging by the
metal ions was assumed instantaneous
with respect to particle-particle coagula-
tion. However, particle charging is also a
dynamic process (Pui et al., 1988). Oron
and co-workers (Oron et al., 1989; Oron
and Seinfeld, 1989a, b) solved the prob-
lem of simultaneous particle charging and
coagulation for low particle concentra-
tions and large particle sizes using a two-
dimensional sectional technique. The
model predicts the evolution of the charge
as well as the size of the particles and
takes into account electrostatic disper-
sion, ion recombination, and ion and par-
ticle production and loss. Except for its
large computational demand, the model
can be adapted to practical powder manu-
facturing processes where high particle
concentrations from molecular clusters to
micrometer-sized particles are usually in-
volved. A further improvement in model-
ing coagulation of charged particles would
be the incorporation of the particle shape
factor because charging depends greatly
on the particle geometry.
SPRAY PYROLYSIS
Spray pyrolysis is an aerosol process com-
monly used to form or process a wide
variety of materials in powder form (see

- No Additives
yun=O.O1 pprn, M:
.-----Na
--- K
0.25 - - - Cs 1.6-

0.20 -
1.5--
\
\
-,
.
\
1.4 - \
\
0.15 - \
\
a \
b1.3 - \
\

X
...
\
u \
0.10 - \

_---- 1.2 -
- - _,,
- 1--.

0.05 -
1.1 -

0.00 1 I * a 1 Z I * a i I 1.o 1 I * a i t I I I '

0.1 1 10 0.1 1 10
t, sec t, sec

FIGURE 8. Evolution of (a) geometric mean particle diameter

and (b) geometric standard deviation of titania particles in the
absence and presence of 0.01 ppm alkali metals.
Aerosol Processing of Materials
review by Kodas, 1989), including metals,
metal oxides, nonoxide ceramics, super-
conducting materials, fullerenes, and
nanophase materials. Spray pyrolysis is
also called aerosol decomposition (Kodas,
1989), spray roasting (Ruthner, 1983),
evaporative decomposition (Gardner et a].,
19841, spray calcination (Vollath, 19901,
Aman's process (Aman, 1956), and other
name variations in the literature. The pro-
cess involves the atomization of a precur-
sor solution into droplets which are then
directed through a heated region, usually
a reaction furnace, by a carrier gas. Inside
the furnace the solvent evaporates and
intraparticle reactions occur that form the
product material.
Spray pyrolysis offers several advan-
tages over conventional material process-
ing techniques. The main advantage is the
high purity of the product powder. In liq-
uid or solid-state processing, milling is
usually required to obtain a powder, which
introduces impurities. With spray pyroly-
sis the product purity is dependent only
on the precursor solution purity. Also,
particles produced by spray pyrolysis are
more uniform in size and composition than
those produced by many other techniques
due to the reaction being confined to a
micrometer scale (within the droplet) and
the lack of milling processes. Additionally,
multicomponent materials are easily made
by spray pyrolysis. Each droplet contains
precursors in the same stoichiometry as
desired in the product. This is an advan-
tage over gas-to-particle conversion routes
where it is difficult to condense several
reactants simultaneously from the vapor
phase in the desired stoichiometry. This is
especially important for systems such as
Pb-Bi-Sr-Ca-Cu-0, doped Ba-Ti-0, and
several other ceramics where it is com-
mon to have four or more elements in the
product material. Another advantage of
spray pyrolysis is the relative simplicity of
the process which has allowed scale-up to
ton quantities.
429
Several challenges, however, still exist
for spray pyrolysis. All the reactants for a
particular material must be able to coexist
in solution form in the proper stoichio-
metric ratio. Usually this is not difficult
and precursor solutions can be made from
inexpensive materials such as acetates and
nitrates. However, occasionally solubility
problems exist. Also, phase segregation
may occur for multicomponent materials
due to the different solubilities of the
precursors and should be eliminated, even
though the segregation is confined to the
size of the droplet. Single-source precur-
sors are one answer, but add to the ex-
pense of the process. Also, product gener-
ation rates are dependent on the droplet
output of the aerosol generator. Gener-
ally, if the atomizer produces a higher
output rate, the droplets, and thus the
product particles, become bigger and more
nonuniform, both of which are undesir-
able. Finally, a challenge is to obtain
greater control over the morphology of
product particles. Often hollow or frag-
mented particles are formed, which are
undesirable in most powder applications.
Solid particles are formed with proper
choice of precursor solution and control
of other process variables, but morphol-
ogy control is still largely an empirical
process.
This section will discuss the types of
materials produced by spray pyrolysis,
different droplet generation methods, at-
tempts at particle morphology control, and
the use of spray pyrolysis in the produc-
tion of nanophase materials.
Materials Produced by Spray Pyrolysis
The types of materials that can be pro-
duced by spray pyrolysis are limited only
by the precursors. Until recently little ef-
fort was directed at developing and using
new types of precursors. Metal acetate,
chloride, nitrate, lactate, citrate, and ox-
alate solutions were used extensively to
 A. Gurav et al.

produce a wide variety of materials precursors have been utilized to eliminate

(Akashi et al., 1967; Kanapilly et al., 1970;
Suyama and Kato, 1982; Chess et al., 1983;
Gardner and Messing, 1984; Imai et al.,
1984; Kato and Hirata, 1985; Y. Liu et al.,
1986; Sproson et al., 1986; Ivers-Tiffee
and Seitz, 1987; Seitz et al., 1987; Kodas
et al., 1988, 1989a, b; Pebler and Charles,
1988; Setaka et al., 1988; Dubois et al.,
1989; Odier et al., 1989; Rossetti et al.,
1989; Gadalla and Yu, 1990a, b; Pebler,
1990; Zhang and Messing, 1990; Ortega et
al., 1991). These precursors have the ad-
vantage of being inexpensive. However,
when forming multicomponent particles
from mixtures of the above solutions, dif-
ferent components will precipitate from
solution at different times causing phase
segregation (Figure 9a). Recently, new
this problem. Single-source precursors
have been used to produce powders with-
out phase segregation, since all compo-
nents of the material are contained within
a single molecule and thus precipitate
from solution at the same rate (Figure
9b).
Chandler et al. (1993) used the single-
source precursor X(diMeGlyc),Ti(O-Pr), ,
where X = Pb, Ba, Sr, and Bao,,Sro,,
(Chandler and Hampden-Smith, 1992)
to produce lead, barium, strontium,
and mixed metal titanates, and Pb(di-
Meglyc),Zro,,Ti0~,,(O-Pr), to form lead
zirconate titanate (PZT) powder particles.
These precursors are water-soluble and
formed unagglomerated, nanocrystalline,
phase-pure, submicrometer-sized titanate

(I> hiti: Yypiet

In Solvent Final
Particle
0 Solvent

i
Solvent
Evaporation

Precipitate
A I
@
Diffusion
and
Reaction
I Evaporation

1
Reaction
Further A => C Reaction
Evaporation A+B => D
B => E

A+B
Precipitate
8:": 1e

Solvenl B
Evaporates Precipitate
(a)
FIGURE 9. (a) Phase segregation during spray pyrolysis using
multi-source precursors; (b) single-source precursors for spray
pyrolysis.
 The use of colloidal precursors in spray
pyrolysis has also been investigated re-
cently, mainly as a means of morphology
control which will be
precursors to form
oore et al. (1992) produced
particles using colloidal silica
and aluminum nitrate. In contrast, hollow
particles were produced when ethyl sili-
cate was used instead of the colloidal sil-
ica (Kanzaki et al., 1985).
The processing of fullerenes and the
f o r n ~ a t i o n of nanocomposites with
rhodium have recently been investigated
by Gurav et al. (1993) (Figure 10). The
p r e c u r s o r s o l u t i o n s w e r e [(1,5-
COD)RhCI], (where C O D = cyclo-
octadiane) and mixed fullerene extract
(C6(,,C7(J in toulene. The Rh-fullerenes
produced consisted of agglomerates of
20-50 nm sized particles, while the pure
a crystallite size of - 10
nn1.
Other materials of industrial impor-
tance which have recently been produced
olysis are ceramic supercon-
types of superconducting
oxides have been pro uced including:
a,Cu,07~,(1-2-3) (Setaka et al., 1988;
Tchge et al., 1988; Kodas et al., 1988,
. TEM micrograph of 5050 wt.%
C,,,/Rh nanocomposite particles produced by
spray pyrolysis at 550°C using N, carrier gas.
(Adaptcd from Gurav et al., 1993.)
ebler and Charles, 1988, 1989;
1.. 1989a, b; Carim et al., 1989;
suchida et al., 1989; Gadalla and Uu,
1990a; Odier et al., 1990; Chadda et al.,
1991; Jin et al., 1991; Zachariah and
et al., 1989, 1991; Sarkar et al., 1990,
ard et al., 1992b), -Sr-Cu-O (Kodas
al., 198917). T1-Ca- CLI-O (Kodas el
al., 1989b), and ,CU,O, (1-2-4)
(Nishio et al., 1990; Chadda et al., 1991).
Superconducting powders are generally
produced by solid-state and liquid-phase
methods which require milling and heat-
ing cycles and often require carbon-con-
 A. Gurav et al.

GU . Solid particles of silver produccd at

600°C by spray pyrolysis. (Adapted from Pluym et
al., 1993b.)
Aerosol Processing of Materials
Droplet Generation
The atomization of the precursor solution
into droplets is an important step in spray
pyrolysis. The aerosol generator charac-
teristics determine the production rate
and droplet size distribution, and thus the
product particle size distribution. Numer-
ous generator types exist (Kerker, 1975)
and have different mechanisms and
droplet properties. The use of rotating
disk and rotating cup sprayers and air-
assist generators is well established and
has been discussed by Lefebvre (1989).
Collision nebulizers (May, 1973; Guss-
man, 1984) and TSI Constant Output At-
omizers are examples of the latter type of
generator.
Ultrasonic droplet generators contain a
piezoelectric transducer which vibrates
underneath a liquid when a high-
frequency electric field is applied, thus
causing droplet formation. Ultrasonic at-
omizers are commonly used in the labora-
tory, but give low production rates. Thus,
further studies must be conducted to de-
velop droplet generators which will be
practical for industrial applications.
Droplets can also be formed by electro-
static processes. When the surface tension
of liquid placed in an electric field bal-
ances the electrical force a stable cone is
formed called a Taylor cone (Taylor,
1964), and this cone emits a stream of
droplets. Such a phenomenon is called
electrostatic atomization or electrospray-
ing. Pioneering work was reported by
Slamovich and Lange (1988, 1990);
Cloupeau and Prunet-Foch (1989); and by
Bailey (1988). The characteristics of the
droplets produced by electrospray meth-
ods have been studied by numerous groups
(Grace and Dunn, 1992; Fernandez de la
Mora et al., 1990; Fernandez de la Mora,
1992; Meesters et al., 1991, 19921, and
submicrometer-sized droplets have been
produced (Park and Burlitch, 1992). The
433
main challenge here is scale-up to allow
larger liquid throughputs.
Levi et al. (1988) have adopted this
technique for electrohydrodynamic atom-
ization of alumina. The tip of a thin a,?,
rod was heated using an electron beam in
a vacuum chamber. Owing to the intense
electrical fields, the molten miniscus at
the tip of the rod adopted the form of a
Taylor cone and led to fine particles as
explained above. Again, scale-up is a ma-
jor problem which must be solved before
industrial applications are found.
Control of Particle Morphology
As stated previously, a disadvantage of
spray pyrolysis in some cases is the lack of
morphological control over the product
particles and the subsequent frequent for-
mation of hollow particles. Therefore,
much investigation has been devoted to
define the parameters controlling particle
morphology, and many attempts to con-
trol these parameters to produce solid
particles have been made (Leong, 1981,
1987a, b; Odier et al., 1990; Zhang et al.,
1990; Zhang and Messing, 1990; Tohge et
al., 1991; Lyons et al., 1992a; Ortega and
Kodas, 1992).
Hollow particles can be formed when a
solute concentration gradient is created
during evaporation. The solute precipi-
tates first at the more highly supersatu-
rated surface if sufficient time is not avail-
able for solute diffusion in the droplet. If
the crust that is formed is impermeable to
solvent, the pressure builds within the
particle upon further heating and ex-
ploded particle fragments can result (Fig-
ure 12). Hollow particles can also be
formed from precursors that melt after
drying if the gases evolved by reaction
cannot easily escape from the interior of
the particle and therefore expand the par-
ticle volume.
 A. Gurav et al.

Further
Further
Precipitation
Precipitation
and Solvent
and Solvent
Evaporation
Evaporation

Particle
Formation

Reaction

Porous
Particle
I Porous and
Hollow
Par
Bursting

00 0

Densification

Reaction
SOLID
PARTICLE * a -
Densification

0 ** *
BIMODAL
PARTICLE
SIZE
DISTRIBUTION

FIGURE 12. Evolution of dense or hollow morphology in

particles during spray pyrolysis.

The above studies have shown that
high-solubility precursors, low evapora-
tion rates, small droplet sizes, low solution
concentrations, long residence times, and
precursors that form permeable salts pro-
mote solid particle formation. Low solu-
tion concentrations and long residence
times are impractical for industrial pur-
poses, and thus the choice of precursor
with the desired physical properties is an
important parameter for morphological
control.
Zhang and Messing (1990) and Zhang
et al. (1990) studied the effects of salt
solubility and salt physical properties on
the n~orphologyof zirconia particles pro-
duced from five different salts. Two of the
salts (zirconyl chloride [ZC] and zirconyl
hydroxychloride [ZHC]) resulted in the
formation of solid ZrO, particles, while
the other three salts formed hollow parti-
cles. The ZC and ZHC solutions had lower
initial relative solution saturations than
the other solutions, and thus precipitation
Aerosol Processing of Materials
of the solute did not occur until evapora-
tion had reduced the size of the droplet.
Smaller droplet size upon precipitation
decreased the diffusion distance for the
solute and encouraged solid particle for-
mation. Also, Z C and ZHC salts are per-
meable which prevents particle expansion
and explosions (Figure 12), while the other
salts form a melt and become imperme-
able. Solutions with positive temperature
coefficients of solubility also favored solid
particle formation.
Leong (1981, 1987a, b) conducted an
extensive study on the morphological con-
trol of particles. Some control over parti-
cle morphology was possible by choosing
the proper precursor (high-solubility, per-
meable crust), and controlling the temper-
ature and humidity of the process.
Ortega and Kodas (1992) and Lyons et
al. (1992a) attempted to alter particle
morphology for systems which typically
produce hollow particles by using col-
loidal precursors and slowing the drying
rate by evaporating the droplets in a dry-
ing tube. The addition of colloidal seed
particles coupled with a slower drying rate
still produced hollow particles of ZnO
and MgO from nitrate precursors. How-
ever, the addition of large amounts of
TiO, particles when forming BaTiO, and
SrTiO, particles did affect morphology.
The normally hollow particles became
dense aggregates of smaller particles.
Therefore, limited control of particle mor-
phology was possible for particular sys-
tems.
Another method used to form solid
particles is aerosol-phase densification
(see Figure 12). Porous and hollow parti-
cles may densify upon heating due to one
or more sintering mechanisms (Kingery et
al., 1976) such as grain-boundary diffu-
sion, surface diffusion, volume diffusion,
viscous flow, or evaporation/condensa-
tion. Temperatures near the melting point
are necessary to densify the material, al-
though complete melting is not required.
435
Also, small particles promote densifica-
tion due to shorter diffusion distances.
Since droplets used in spray pyrolysis are
usually micron-sized or less, densification
is more favorable for this process than for
solid-state processes which generally have
larger particles. Examples of materials
which were produced in the form of solid
particles by aerosol-phase densification
include: Pd and PdO (Lyons et al., 1992b;
Pluym et al., 1993a), Ag (Pluym et al.,
1993b1, Ba,,,Ca,,,,TiO, (Ortega et al.,
1991), BaTiO,, and SrTiO, (Lyons et al.,
1992a).
Nanophase Materials by Spray Pyrolysis
Spray pyrolysis provides a route to
nanophase materials (Figure 13) and is
able to produce pure, chemically uniform,
multicomponent, nanophase particles in
gram or larger quantities from a variety of
precursors (Chadda et al., 1991; Lyons et
al., 1992b; Gurav et al., 1993; Pluym et al.,
1993a; Powell et al., 1993a, b). This tech-
nique involves droplet-generation, solvent
evaporation, precursor precipitation, and
decomposition of precursors within the
particles. The grain size is kept small by
operating at temperatures which are suf-
ficient for complete decomposition of pre-
cursors, but not high enough to cause
excessive grain growth. Carim et al.
(1989) g e n e r a t e d n a n o c r y s t a l l i n e
YBa,Cu,O,_,/Ag composite particles
with grain sizes of Ag and 1-2-3 phase of
10-80 nm. Gurav et al. (1993) produced
pure fullerene powders with crystallite
sizes of 10 nm, and Rh-fullerene particles
which were 20-50 nm in size with crystal-
lite sizes of 3-5 nm. Pluym et al. (1993a)
produced nanophase PdO particles with
crystallite sizes between 20 and 50 nm,
and Lyons et al. (1992b) made nanophase
PdO and V,O, with the same characteris-
tics ( F i g u r e 1 4 ) . N a n o p h a s e
YBa2Cu,0,_, was also formed by Chadda
et al. (1991).

-
Amorohous
Dried Salts
Solvent Evaporation
Reaction
Droplet
Increasing Temperature
DensificationISintering
and Grain-growth
Single-crystal
- Densificationl
Sintering and
Grain-growth
Polycrystalline
Another approach to synthesis of
nanophase particles was demonstrated by
Park and Burlitch (1992). A solution of
T i ( 0 -i-Pr),/ T i ( 0 -i-Pr),acac
(acac = acetyl-acetonate) was electro-
sprayed (electrostatic atomization tech-
nique) into a furnace reactor. Nanophase
TiO, particles having a mean size of 20
nm were obtained by controlling the con-
centration and hence the hydrolysis and
condensation. In this case, however, it is
not clear if the particle formation oc-
curred by gas-to-particle conversion or by
intraparticle reactions. The ability to pro-
duce a wide variety of nanophase materi-
als in large quantities by spray pyrolysis
may enable further progress in the study
of the properties of these materials.
SPRAY PYROLYSIS: MODELING
As pointed out above, morphological con-
trol is one of the major concerns in parti-
cle generation by spray pyrolysis. The
nature of the precursor (solubility, crys-
talline habit, and other factors) is the
dominant factor determining product
powder morphology (Leong, 1987a, b;
Zhang et al., 1990). In many cases, how-
ever, the choice of precursors is limited
due to either specific requirements of a
particular application or process con-
straints. Therefore, given the precursor
and solution chemistry, a theoretical un-
A. Gurav et al.
0dde
FIGURE 13. Generation of
nanophasc particles by spray pyroly-
sis. (Adapted from Lyons et al.,
992d
,&$?j.
iz;wi
$$;$$$%$;
...>..,.,..,..,.
Nanophase
r...:,
.
Particle
derstanding is required of the effect of
process conditions on particle morphol-
ogy. Among the few results on modeling
in the literature, almost all discuss droplet
evaporation up to the onset of solute nu-
cleation. In addition, these studies ad-
dressed spray drying conditions where
large droplets (100-1000 pm) were em-
ployed and did not account for the effects
associated with multiple particles, and
heat and water vapor transport. No rigor-
ous modeling has been done after initial
solute precipitation due to the complexity
of describing crystal growth and further
solvent evaporation to eventually form
dried particles (Sano and Keey, 1982).
Theoretical studies on droplet evapora-
tion began with the basic transport
(momentum, mass and heat) correlations
for droplets in a controlled air environ-
ment (Ranz and Marshall, 1952). The re-
sults explained many empirical observa-
tions on droplet evaporation such as that
the rate of change of surface area of a
pure liquid droplet is constant during
evaporation in still air (Charlesworth and
Marshall, 1960). These basic studies also
indicated the existence of a solute con-
centration profile inside the droplet for
many solution systems due to slow solute
diffusion compared to solvent evaporation
(Sano and Keey, 1982). Consequently,
precipitation often starts at the droplet
surface where the highest solute concen-
 . Nanophase PdO particles produced by spray pyrol-
ysis. (Adapted from Pluym et al., 1993a.)

tration is found, causing the formation of
orous or hollow particles (Figure 12).
Golli et al. (1974, 1977) s died the
evaporation of saline droplets. he effect
of the solute concentration change during
evaporation on droplet density and sol-
vent vapor pressure was obtained an
tated the droplet evaporation rate. Using
classical homogeneous nucleation theory,
the onset of solute nucleation can be pre-
438
dicted along with the solute concentration
and droplet size at precipitation (Melia,
1965; Richardson and Spann, 1984; Tang
and Munkelwitz, 1984).
Leong (1987a) presented a mathemati-
cal model for drying of solution droplets
up to the onset of nucleation incorporat-
ing these previous developments. De-
creasing the starting solute concentration
decreased the droplet size at precipitation
which is conducive to solid particle forma-
tion. This finding is consistent with experi-
mental observations (Leong, 1987b; Zhang
et al., 1990). Given the droplet size and
solution concentration, other process pa-
rameters such as air temperature and hu-
midity had a negligible effect on the
droplet size at the onset of nucleation.
Therefore, the particle morphology is
mainly determined by crystal growth and
subsequent physicochemical processes
(Leong, 1987a, b).
All the above studies addressed systems
with controlled gas conditions and mod-
eled the behavior of single droplet evapo-
ration. In practical spray pyrolysis pro-
cesses, however, a large number of
droplets are carried through the reactor
and the changes in carrier gas tempera-
ture and relative humidity as a result of
droplet evaporation cannot be ignored.
This is also important from an engineer-
ing perspective for reactor design and op-
eration.
Xiong and Kodas (1993) developed a
model describing the evolution of the
droplet size, solvent vapor concentration
in the carrier gas, and gas as well as
droplet temperatures along the reactor
axis. The model also accounts for the real
solution effects, solute concentration pro-
files inside droplets, and the onset of so-
lute nucleation. The model was used to
describe the evaporation of sodium chlo-
ride solution droplets up to the point of
precipitation in air in diffusion dryers and
hot reactors with axial wall temperature
gradients. Figure 15 shows the change in
A. Gurav et al.
o l # l ~ , c , 8 1 ~
0 20 40 60 80 100
Reactor Axial Distance (crn)
FIGURE 15. Evolution of NaCl droplet diame-
ter along the axis of a diffusion dryer for various
initial droplet sizes and molalities at an inlet air
humidity of zero, a droplet concentration of 5 X
lo6 no./cm3, and a constant wall temperature of
50°C. Circles denote the onset of solute nucle-
ation. (Adapted from Xiong and Kodas, 1993.)
NaCl droplet size along the axis of a dif-
fusion dryer for droplets of different ini-
tial diameters (d,,). The droplet size de-
creases gradually for large initial droplets
(d,, = 4 pm) and the droplets exit the
reactor far away from solute precipitation.
In contrast, small droplets dry rapidly and
precipitation occurs within the reactor.
Figure 16 shows how the point of solute
nucleation is determined by plotting both
the critical supersaturation ratio and the
actual saturation ratio for d,, = 2, 3, and
4 pm, respectively. For NaCl, the smaller
the initial droplets are, the smaller the
droplets are at the onset of nucleation.
However, the solute concentration at pre-
cipitation is the same for all initial droplet
sizes.
Figure 15 also shows the effect of vary-
ing initial droplet molality on the droplet
size evolution along the axis of a diffusion
dryer for d,, = 3 pm. For a given initial
droplet diameter, decreasing precursor so
lute concentration reduces the droplet size
Aerosol Processing of Materials

I I I ' l r I 1
- critical supersaturation ratio set of nucleation by varying process pa-
- - - - droplet saturation ratio
4- I rameters other than the solution concen-
I
I tration and initial droplet size is limited.
I
6
' Jayanthi et al. (1993) also modeled dry-
3- I
I
I
I
ing of droplets. Solutes with large differ-
I
I
I
I
ences between critical supersaturation and
I
I
I
I equilibrium saturation favored volume
I
2-
I
I I precipitation and solid particle formation.
I
I
High initial concentration and equilib-
rium saturation also favored volume pre-
cipitation. A percolation criterion was also
proposed: solid particle formation was fa-
vored by sufficiently high solute concen-
tration for precipitation to give a volume
fraction of the precipitate higher than the
Reactor Axial Distance (crn)
critical volume fraction.
FIGURE 16. Evolution of NaCl droplet solution A model has also been developed to
saturation ratio and critical supersaturation ratio describe evaporative losses of volatile
along the axis of a diffusion dryer for various metal oxides from particles (PbO, Biz?,,
initial droplet sizes (d,,) at an inlet air humidity MOO,, and V20,) during their generation
of zero, a droulet concentration of 5 X lo6 at the later high temperature reaction
no./cm3, a constant wall temperature of 50°C, stages of spray pyrolysis (Lyons et al.,
and an initial solution molality of 0.036 mol/kg. 1992c; Xiong et al., 1993b) (Figure 17).
Solute nucleation occurs when the droplet satu- These losses can have profound effects on
ration ratio crosses the corresponding critical the microstructure and morphology of the
supersaturation ratio. (Adapted from Xiong and
Kodas, 1993.)
product particles (Lyons et al., 1992a).
Moreover, evaporation of volatile metal
oxides from multicomponent materials
at the onset of nucleation and as a result such as Pb-Bi-Sr-Ca-Cu-0 and PbTiO,
is desirable for making solid product par- leads to modified stoichiometries resulting
ticles (Zhang et al., 1990). However, this in degraded properties of sintered ceram-

rate (mass d;). -

also results in a lower powder production

The effects of droplet concentration,

relative humidity of the carrier gas, and
reactor wall conditions on the droplet size
at the onset of nucleation were also inves-
tigated. Control of droplet size at the on-
ics. The model indicated that evaporative
losses of most of the metal oxides studied
are controlled by diffusional transport of
the metal oxide vapor to the reactor walls.
Some of the major remaining chal-
lenges for modeling are describing the
complex liquid- and solid-phase precipita-

Condensation
onto end
from walls
11
NOWParticle
Formation .
Solvent 1:; :
Bimodal
Particle Slze
Evaporation Dlstrlbutlon
and
lntreparticle FIGURE 17. Aerosol dynamics with
RosCtion
a volatile reaction product.
440
tion, diffusion and reaction processes.
Complex models are required because the
particles can change from single-phase
concentrated solution droplets, to porous
shells containing liquids to dry particles
during solvent evaporation. The solid-state
reaction processes occurring subsequently
at higher temperature also involve trans-
port processes through a porous material
in which reactions are occurring. The pore
size distribution changes with time due to
sintering processes, in a manner similar to
the changes in the agglomerates formed
by gas-to-particle conversion, further
complicating the problem.
FILM GENERATION
Aerosol routes offer a variety of ap-
proaches for film generation. These pro-
cesses have been used to deposit many
materials including ceramic superconduc-
tors, simple metal oxides, nonoxide ce-
ramics, metals, organics, and composites
at high rates at various temperatures. The
approaches can be divided into solution
droplet deposition, vapor deposition, and
molten or solid particle deposition pro-
cesses. However, a clear distinction is not
always possible as when both solid parti-
cles and vapor deposit as in particle-pre-
cipitation-aided CVD. The majority of the
work on film generation via aerosol meth-
ods has been done by research groups
from fields such as applied physics, mate-
rials science, and chemistry with the pri-
Films by Thin Films
Thin Films
Spray by Chemical
Pyrolysis Vapor
Deposition
A. Gurav et al.
mary goal being to achieve certain desired
characteristics in the films. These studies
often lack a systematic treatment of the
aerosol dynamics and also lack even the
distinction of the deposition mechanisms
involved in film generation. Therefore,
these processes offer great opportunities
for research groups working in aerosol
science and technology. The sections be-
low discuss routes to films involving liq-
uid-phase precursors and solid particle
deposition.
Liquid-Phase Precursors
Droplet Deposition (Spray Pyrolysis).
Processes using precursors in solutions for
generation of films are varied (Figure 18).
Spray pyrolysis involves deposition of
droplets containing reactants onto sur-
faces followed by solvent evaporation and
chemical reaction on the surface and is
discussed in this section. Volatile precur-
sors dissolved in liquids or solid particles
of volatile precursors can be used for
aerosol-assisted 0and discussed in the
subsequent section. Brief mention will also
be made of supercritical expansion of so-
lutions and aerosol jet etching.
In spray pyrolysis for film generation,
an aerosol of a solution is formed and
then deposited onto a surface where sol-
vent evaporation and chemical reaction
take place resulting in a film.
Some of the advantages of this process
include: simplicity and low cost (only sub-
strate heater and atomizer needed, atmo-
Thick Films
FIGURE 18. Film formation by
aerosol routes.
Aerosol Processing of Materials
spheric pressure), many choices for
liquid-phase precursors (for example, ni-
trates, chlorides, acetates, etc.), wide vari-
ety of multicomponent materials possible
(Pb-Bi-Sr-Ca-Cu-0, YBa,Cu,O,- ,), ori-
ented films, high deposition rates (0.1-1
pm/min demonstrated), scale-up demon-
strated (used industrially for coating
glasses and other materials). The primary
disadvantages include: porous films can be
formed, low purity in some cases, limited
to oxides, sulfides, selenides, and other
oxidation-resistant materials.
A variety of materials have been pro-
duced by droplet deposition. A particu-
larly large amount of work has been done
with various systems: CdS (Chamberlin
and Skarman, 1966; Gupta and Agnihotri,
1977; Ma and Bube, 1977; Cumberbatch
et al., 1987; Eboth6 et al., 1987); SnO,
(Garcia et al., 1982; Gonzalez-Oliver,
1986; Mulla et al., 1986; Orban de Xivry
et al., 1987; Omar et al., 1990; Afify et al.,
1991); ZnO (Aranovich et a]., 1979; Major
et al., 1983, 1985); YBa,Cu,O,_, (Kawai
et al., 1987; Chu et al., 1988a, b; Henry et
al., 1988; Saxena et a]., 1988; Langlet et
al., 1989; Derraa and Sayer, 1990; Golden
et al., 1990; Peng et al., 1991); and Pb-Bi-
Sr-Ca-Cu-0 (Cooper et al., 1988; Henry
et al., 1989; Hsu et al., 1989; Koo et al.,
1990). Applications of the technique are
for solar cells, oxide superconductor films,
photochemical cell electrodes, gas sensing
elements, antireflection coatings, and
thermal coatings (Tomar and Garcia,
1981; Kodas 1989). The types of precur-
sors that have been used most extensively
are metal chlorides and nitrates. Metal
acetates and alkoxides have been used to
a much lesser extent.
Droplet deposition systems typically
rely on the formation and deposition of
droplets in the 1-1000 p m range. Deposi-
tion rates as high as 1 pm/rnin have been
reported and film thicknesses of 1-10 p m
are common. The most commonly used
droplet formation technique is a two-fluid
441
atomizer in which the solution and a car-
rier gas are passed through under pres-
sure to form the droplets. Ultrasonic at-
omizers have also been used. Substrate
heating is typically carried out by placing
the substrate on a 200-500°C surface, of-
ten with a medium to promote heat trans-
fer between the substrate and heater. This
process is usually carried out at atmo-
spheric pressure, often without any enclo-
sure. In general, little is usually known
about initial droplet sizes and concentra-
tions, and the aerosol dynamics. Only a
few studies have examined theoretically
the behavior of these systems (Siefert,
1984a, b).
Aerosol-assisted Chemical Vapor Deposi-
tion. Deposition of high-quality thin films
of electronic materials is required for a
number of applications. Spray pyrolysis
(droplet deposition) cannot in many cases
produce dense oriented films. Physical va-
por deposition (PVD) processes such as
sputtering and evaporation require high
vacuum conditions and cannot coat sub-
strates with complex topographies. These
methods are often not feasible or too
costly for industrial applications where
large areas need to be coated. For these
reasons, and that they allow conformal
deposition over large areas at high rates
with relatively inexpensive equipment,
CVD processes are often employed.
An alternate method of depositing thin
films is aerosol-assisted chemical vapor
deposition (AACVD) (Figure 18). A solu-
tion containing volatile precursors is car-
ried in the form of an aerosol close to the
substrate that is to be coated. Before or
near the substrate, the precursors evapo-
rate into the gas phase. This is followed
by decomposition of gaseous molecular
precursors on the heated surface (CVD)
to deposit a thin film. Alternatively, the
solvent and precursors can be vaporized
in a hot-wall system before reaching the
substrate.

This approach has several advantages
for generation of multicomponent films
with thermally sensitive precursors. Be-
cause the precursors are held outside the
reactor at room temperature or even re-
duced temperature, thermal degradation
of the precursors does not occur. The
precursor delivery rates are constant with
time because the ratio and concentration
of precursors in the solution and the
droplet size and delivery rate do not
change with time. This allows the repro-
ducible deposition of multicomponent
films with constant composition as a func-
tion of deposition time. Conformal films
are also possible because deposition oc-
curs by CVD.
This process has several other advan-
tages: multicomponent films, controlled
stoichiometry, simplicity, wide variety of
materials, oriented or expitaxial films, high
deposition rate, many choices for precur-
sors, doping possible, conformal coverage.
One disadvantage is that a solvent is pres-
ent in many cases and may be incompati-
ble with the precursors or the chemistry
of film formation. Again, this problem has
been overcome in most cases by suitable
choice of the solvent.
A number of materials have been fabri-
cated in thin-film form using AACVD in-
cluding In,O,, SnO,, F<o,, Cr,O,,
Al,O,, Y,O,, V,O,, VO,, TiO,, ZrO,
(Blandenet et a]., 19811, Al,O, (DeSisto
et a]., 1990), CuO (DeSisto et a]., 1989),
MgF, (Joosten et al., 1985), InSe and
In,Se, (Gysling et a]., 1992), A,0,
(Lambeck et a]., 1986, yFe,O,-Fe,O,
(Langlet et a]., 1986) BaTiO, (Lee and
Pressure
Pressure
Generator
A. Gurav et al.
Park, 1990), ZnS (Maatman et a]., 1988),
Cr,O, (Qian et a]., 1990). Little informa-
tion is available in general on deposition
rates. Temperatures of 300-600°C have
most commonly been used. Ultrasonic at-
omizers have been used most extensively
for droplet generation.
A material that has been studied exten-
sively is YBa,Cu,O, (Driessen et a].,
1989; Koukita et al., 1989; Lackey et al.,
1990; Tang et a]., 1990; DeSisto et al.,
1991; Matsuno et al., 1992; Salazar et al.,
1992). Most studies have relied on warm-
wall or hot-wall reactors for precursor
evaporation. The use of organometallic
precursors has allowed substrate tempera-
tures of 300-500°C and as high as 900°C.
Deposition rates as high as 5 pm/min
have been obtained while producing high
quality films. The most commonly used
precursors are metal p-diketonates such
as metal tetramethylheptanedionates (di-
pivaloylmethanoates), but metal alkox-
ides, acetates, and chlorides have also
been used.
Figure 19 shows a typical system used
for generation of films by AACVD
(Salazar et a]., 1992). The aerosol droplets
were atomized using a TSI constant out-
put atomizer. The solution consisted of
Y-, Ba-, and Cu- tetramethylheptanedion-
ates in toluene. The droplet diameter was
on the order of 1 pm. A hot-wall reactor
was used to evaporate the precursors while
a substrate heater was used to heat the
substrate to a higher temperature.
These processes have not been investi-
gated theoretically or experimentally as
far as the aerosol dynamics are con-
gauge
FIGURE 19. Aerosol assisted chemi-
Filter cal vapor deposition for film genera-
tion. (Adapted from Salazar et al.,
1992.)
Aerosol Processing of Materials
cerned. Little is known about how to de-
sign and operate these systems in order to
achieve high quality films. Most of the
work in this area has concentrated on
empirically optimizing film quality by vary-
ing temperature, precursor properties, and
solution concentrations.
Supercritical Expansion of Solutions, and
Aerosol Jet Etching. Supercritical expan-
sion of solutions relies on expansion of a
solution of precursors from the supercriti-
cal state to the gaseous state with accom-
panying particle formation and deposition
of particles, droplets, and/or vapor onto a
surface (Tom and Debenedetti, 1991).
Thus, droplet deposition, particle deposi-
tion, physical vapor deposition, and CVD
are all possible. SES has several attractive
features including the ability to handle
thermally sensitive precursors and the
ability to produce unique phases. Other
advantages to this approach include: the
ability to dissolve species that are not
usually soluble and that it is a low temper-
ature process. The primary disadvantages
are that this is a complex process which is
not thoroughly understood, a limited
number of combinations of solute and
solvents are available, and incorporation
of solute into the product often occurs.
Several materials have been produced by
this approach. Silicon dioxide particles and
films, for example, can be formed by dis-
solving SiO, into supercritical H 2 0
(Peterson et al., 1986; Matson et al., 1987a,
b). Deposition rates of 1 pm/min have
been obtained. Numerous organic materi-
als have also been processed (Yeo et al.,
1993). Debenedetti and co-workers have
done extensive studies on modeling ho-
mogeneous nucleation and particle forma-
t i o n u s i n g s u p e r c r i t i c a l fluids
( D e b e n e d e t t i and K u m a r , 1986;
Debenedetti, 1990; Tom and Debenedetti,
1991).
Aerosol jet etching involves the forma-
tion of aerosol droplets containing molec-
443
ular species such as acids (HF, HCl) which
can react with a substrate to form volatile
species (Chen et al., 1987, 1990; Jurcik et
al., 1990). The substrate is usually heated
which results in rapid reaction and de-
sorption of volatile products containing
the atoms that compose the substrate. The
droplets are usually deposited by inertial
impaction. Films of SiO, and Hg,-,Cd,Te
have been etched. Anisotropic etching was
obtained because the droplets travel only
in the vertical direction. Etch rates of up
to 1 pm/min have been obtained for
SiO, at temperatures below 50°C. These
etch rates are of the same magnitude as
those obtained in conventional plasma
etchers which require vacuum systems to
operate. Recently, Ahonen et al. (1993)
have reported the application of an
aerosol jet technique to develop and sub-
sequently etch photoresist coatings over
large surface area substrates which are
difficult to coat uniformly using conven-
tional spin-coating or immersion tech-
niques.
Solid Particle Deposition
Inertial and Electrostatic Particle Deposi-
tion. Films consisting of particles can be
formed by a variety of deposition mecha-
nisms including impaction, diffusion, sedi-
mentation, thermophoresis, and elec-
trophoresis. Inertial particle deposition
has been used to form ceramic filters,
sensors, and hard coatings. Typically a
carrier gas stream is directed at a surface
resulting in a flow field approximating
stagnation point flow. Particle deposition
takes place by impaction, in the absence
of temperature gradients. Vacuum sys-
tems have also been used to increase de-
position efficiencies.
The primary strength of solid particle
deposition by impaction is for generation
of thick films. Typically, post processing is
required to densify the porous films. The

structure of these films before and after
densification has not been studied exten-
sively. Under suitable conditions, high de-
position rates can be obtained. The disad-
vantage of this approach is that porous
polycrystalline films are formed.
Solid particle deposition has been used
to form coatings of several materials in-
cluding ceramic superconductors-
YBa,Cu,O, (Koguchi et al., 1990);
YBa,Cu,08 (Murakami et al., 1991); Bi-
Pb-Sr-Ca-Cu-0 (Matsuno et al., 1988;
Baker et al., 1989); SnO, (Adachi et al.,
1988). Deposition rates as high as 1-5
,um/min have been obtained. The parti-
cles have been formed by virtually all
available methods including liquid-phase,
solid-state, and gas-phase routes.
A novel use of gas-to-particle conver-
sion and electrostatic particle deposition
w a s r e c e n t l y d e m o n s t r a t e d by
Wiedensohler et al. (1992) (Figure 20).
Particles of Ag were produced by vapor
condensation, classified using a differen-
tial mobility analyzer, charged, and de-
posited onto InP substrate. The deposited
particles were then used as an etch mask
to allow generation of quantum dots.
In general, solid particle deposition has
not been exploited as much as spray py-
rolysis but the possibility of quantum dot
formation should motivate further studies
of this class of processes.
Deposition chamber
Etching chamber
A. Gurav et al.
Themzophoretic Aerosol Deposition.
Thermophoretic particle deposition relies
on the thermophoretic velocity of parti-
cles in a temperature gradient. The most
well-known example is optical fiber pre-
form fabrication by particle formation and
deposition by thermophoresis (modified
chemical vapor deposition, MCVD)
(MacChesney et al., 1974; Biswas, 1986;
Fiebig et al., 1986; Kim and Pratsinis,
1988; Biswas and Pratsinis, 1989). An-
other example is formation of thick films
of superconducting ceramics by deposi-
tion of ceramic particles formed by aerosol
decomposition (Kodas et al., 1989b). This
process has also been used to produce
Bi-Sr-Ca-Cu-0 films (Matsuno et al.,
1988). This approach has the main advan-
tage that high deposition rates can be
obtained. Difficulties include providing
uniform deposition over large areas and
producing dense films after post-
processing of the coatings.
Particle-Precipitation-aided C W . Parti-
cle-precipitation-aided CVD involves
forming solid particles in a CVD system
and depositing the particles onto a sub-
strate in parallel with deposition by CVD.
The system is designed so as to provide a
temperature gradient towards the sub-
strate to drive the particles onto the sub-
strate. Particle precipitation CVD has
FIGURE 20. Quantum dot forma-
(DMA)
tion by particle formation classifica-
tion, deposition, and plasma etching.
(Adapted from Wiedensohler et a].,
1992.)
Aerosol Processing of Materials
been used to form films of AIN and TiO,
at rates of 10-1000 p m / h (Shimogaki
and Komiyama, 1986; Komiyama et al.,
1987; Dekker et al., 1992). These rates are
much higher than those obtained with
conventional CVD processes. The precur-
sors included TiCI,, Zr(C,H,O),, AICl,,
and Ti(OC,H,),. These systems have not
been modeled.
SUMMARY AND CONCLUSIONS
The range and versatility of aerosol pro-
cesses for the generation of powders and
films have expanded greatly in the last few
years. For example, aerosol routes are
now routinely used to generate nanophase
materials by vapor condensation and to
form superconducting ceramics by spray
pyrolysis. These are examples of existing
routes that have been applied to new ma-
terials. Entirely new applications of
aerosol technology have also emerged as
for the generation of quantum dots, dia-
mond powder and films, and fullerenes.
Thus aerosol routes to materials have the
potential to provide numerous new indus-
trial applications in addition to existing
processes such as TiO, pigment genera-
tion, optical fiber fabrication, and carbon
black production.
In order to fully realize the potential of
aerosol methods for materials processing,
considerable research efforts are needed
in certain poorly understood areas. For
example, there is a need to develop physi-
cal or gas-phase reaction routes for the
generation of multicomponent materials
with controlled stoichiometry. Use of
novel precursors, either single-source or
multisource with tailored chemical prop-
erties needs to be exploited for the syn-
thesis of these multicomponent materials.
These materials are currently unavailable
in the form of high quality powders, and
generation of useful quantities and pro-
cessing studies could lead to significant
improvements in materials properties. De-
445
velopments are required in aerosol-based
methods to produce substantial quantities
of ultrafine or nanophase materials. U1-
trafine structures (particles, patterned
films, etc.) of magnetic, semiconducting,
metallic, and superconducting materials
are highly promising for future nano-tech-
nologies, and the aerosol community can
make many contributions for scale-up,
controlled processing, and in situ charac-
terization of such materials. The area of
film generation has, so far, been domi-
nated by physicists, materials scientists
and chemists, and efforts are needed to
understand and model the aersol dynam-
ics and identify the mechanisms governing
film formation to obtain better quality
and reproducible films. Apart from film
generation, further modeling studies sub-
stantiated by experiments are required on
nucleation, agglomeration, and morpho-
logical evolution of particles under realis-
tic or practical conditions of materials
processing. Finally, emphasis needs to be
placed on scale up of aerosol processing
methods to larger levels of production of
metals and oxide/nonoxide ceramics while
maintaining powder quality.
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Received March 8, 1993; accepted July 9. 1993