AEROSOL SYNTHESIS OF NANOSTRUCTURED

MATERIALS

Olivera B. Milosevic

Institute of Technical Sciences of

the Serbian Academy of Sciences and Arts,
Belgrade, Yugoslavia

INTRODUCTION

The scientifical and technological interest in nanostructured materials is currently

tremendously increasing. I ·) The basis of this interest is related to the extraordinary
properties that powders and materials at the nanometer or subnanometer scale exhibit,4.6
Such properties result from their structure that distinguish them from conventional
polycrystalline materials by the size of the crystallites that compose them as well as a large
volume fraction of interface and grain boundaries. The nanostructured materials research
efforts emphasize the synthesis routes for the generation of ultrafine powders with control
over particle size, shape, composition and morphology as the key issue in advanced
materials synthesis. I The aerosol synthesis route enables the generation of new
nanoparticles and nanomaterials either as coatings or powders as single, complex metal
oxides, nonoxides or metals by adjusting the precursor chern istry .i The starting-point of the
aerosol synthesis of nanostructured materials is the generation of discrete droplets of the
starting solution (aerosol) and control over aerosol decomposition in a high temperature
tubular flow reactor.8 •9 The successive processes of solvent evaporation, drying, solute
precipitation and decomposition proceed through heterogeneous gas-liquid/solid reactions
in dispersed system ensuring high surface reaction and limiting any compositional
segregation to the droplet leve1. 9 By controlling the precursor solution chemistry,
processing parameters and mechanisms of particle formation through either the surface or
volume precipitation of droplets it is possible to tailor the powder size, morphology,
chemical and phase compositions . The condition for aerosol generation ultrasonically with
special emphasis on the various particle morphology synthesis is reviewed in this paper.
The importance to model the phenomenon of mass and heat transfer occurring during the

Ad vanced Science and Technology of Sintering, ed ited by Stojanovic et al.

Kluwer Academic/Plenum Publishers, New York. 1999 103
evaporation/drying stage is discussed from the viewpoint of the parameters leading to a
certain particle morphology. It is demonstrated that aerosol synthesis of nanostructures can
be realized in a controlled manner by adjusting the aerosol droplet size and precursor
chemistry.

NANOSTRUCTURED MATERIALS-SYNTHESIS,
STRUCTURE, PROPERTIES RELATIONSHIP

Nanophase materials are characterized by ultrafine metastable structure that contains

great concentration of defects either as point defects or disclocations, grain boundaries,
interfacial boundaries etc. Those materials differs structurally and propertywise either from
amorphous or crystalline state of the same chemical composition. It has been already shown
that nanocrystalline materials, nanoglasses, alloys with ultrafine structure and
nanocomposites are of special scientifical as well as applicative interest. Submicronic
materials, with grain sizes between 100 and 1000nm exhibiting properties deviating from
those of micron sized materials, represent the subject of intensive research too . Quanum
dots or quantum crystallites (semiconductor crystallites in the range between 1 to l Onm that
4
show three dimensional quantum size effect) also have a growing research interest.
In accordance to the proposed atomic structure of nanocrystalline materials, they are
composed of numerous small crystals less than 100nm in diameter, forming the crystalline
component and the network of boundaries. I The boundaries exhibit a broad spectrum of
interatomic spacings, ranging from 15 to 40% . It was shown that the atomic density is
reduced up to 30% in the boundary regions , in relevance to the neighboring crystals . I
Consequently, nanocrystalline materials are characterized with a high content of grain
boundaries (50%) and with the different grain boundaries structures inside one boundary,
that do not appear in the coarse grained materials. I This unique structure results in very
special and extraordinary properties they exhibit and indicates that nanostructures will gain
in great importance in the near future .
Research in the field of nanophase materials have seen a tremendous increase in
academic and industrial interest in the last decade as the consequence of their potentially
useful physical and chemical properties.' For instance, it is evident higher electrical
conductivity in ceramics and magnetics; increase in hardness and strength of metals and
alloys; 10 increased ductility and formability of ceramics ; II quantum-dots effects in
semiconductors; significantly modified magnetic behavior as well as superparamagnetism,
spin-glass behavior and magnetic viscosity, revealed in nanocomposite magnetic
s
materials . , 12 Decreasing the Curie temperature) by 40K in nanostructured (",70nm) nickel,
3
enhanc ing the diffusivity':' by a factor of 10 for nickel and alumin ium with grain sizes
between 70 and 30nm, increasing ductility of brittle ceramics, permitting large plastic
deformations at low temperatures.l" hardness and chemical resistivity observed for the
ceramics generated in the nanocrystalline form, high-temperature stability of Si3N4/SiC
micro/nano-composite'' represent several examples of the modifying characteristics for
nanophase materials. In the case of nanophase Ti0 2 with grain sizes between 2 - 20nm ,
enhanced ductility, sinterability, plastic deformation and high atomic diffusivities have been
observed. IS Significant changes in thermal expansion coefficient, magnetiic susceptibility,
saturation magnetization, superconducting properties are also associated with
1O
nanocrystalline solids. Although the mechanisms responsible for such behavior are far to
be clearly understood in all details, they are possible the consequence of the higher
boundary area in nanophases implying the structure importance in designing and modifying
the properties. Certain materials structure responsible for nanostructures behavior appears

104
during materials synthesis procedure through powder generation as well as sintering
process . This implies that the demands in synthesis of nanostructures are directed to such
structure tailoring that results from the synthesis-structure-properties relationship.

NANOPHASE PARTICLES GENERATION

One of the basic problems that has to be solved in order to permit the technological
application of materials with ultrafine to nanometer-sized grains is the availability of their
synthesis. In addition, in order for nanophase materials to be commercially viable , the
production route must be controlled and reproducible. Several methods has been currently
used in nanophase particle synthesis such as mechanical attrition," various chemical
methods like sol-gel or coprecipitation' " as well as aerosol synthesis. In aerosol synthesis
two approaches to powder preparation can be roughly distinguished: gas-to -particle route
and droplet -to-particle roote .'
Gas-to-particle refers either to the gas phase reaction'f or to the gas-condensation
associated with a chemical reaction in aerosols. 19 These methods, although often need high-
energy sources like plasma, sputtering, ion, electron or laser beams offer several
advantages for powder synthesis. It is possible to generate small particle size, either in
micronic to nanometer range, narrow size distribution, high purity particles etc. However,
some disadvantages relate to the generation of multi component systems.
Droplet-to-particle route refers to the heterogeneous gas-liquid/solid chemical reactions
in dispersed systems (aerosols). Such mechanism enables high surface reaction,
stoichiometric retention as well as segregation suppression to the droplet scale. It was
already shown that great variety of materials, including multicomponent ones, can be
obtained in accordance to this method, often called as ultrasonic spray pyrolysis."
The process involves formation of descrete droplets of precursor solution in the form
of aerosol and control over their thermally induced decomposition and phase
transformation?OAerosol is most frequently formed ultrasonically, using high-frequency
(lOOKHz- lOMHz) ultrasonic beam" directed to the gas-liquid interface. Liquid
atomization and aerosol formation occur for the certain values of the acoustic waves
amplitude, where the average droplet size depends mostly on the solution properties
(viscosity, surface tension, density etc.) as well as the ultrasound frequency . It was already
shown that this technique is suitable for the aerosol formation with the narrow size of
droplet distribution. In the same time, the average aerosol droplets can be kept small
enough (around or bellow 2 urn for the aerosol frequency of2.5MHz ),20 enabling synthesis
of submicronic as well as nanosized particles.
The aerosol is carried out by the flowing gas stream into high-temperature tubular flow
reactor. The flow rate of the carrier gas represents one of the most important process
parameters enabling the supporting atmosphere as well as the aerosol flow rate and the
droplets residence time to be controlled. During the process, aerosol droplets undergo
evaporation, drying and solute precipitation caused by the mechanisms of heat and mass
transfer inside the droplets and between the droplets and surrounding gas. Dried particle
decomposes consequently in a single step process and through heterogeneous reactions in
dispersed system. Depending on the process parameters - temperature and residence time,
either amorphous or crystalline particles can be obtained . (figure 1). It was shown that
proper adjusting of the mentioned parameters enables synthesis of nanophase,
polycrystalline or single - crystal particles by controlling over the mechanisms of grain
growth and sintering," Figure 2 a represents typical composite nature of ZnO particles, the
average particle size of 200 nm, derived ultrasonically (ultrasound resonant frequency 2.5

105
 Sing le crys tal

Polycr ystalline _

- .....
® ...
0 ...
Amorp ho us
Nanophase
.»
~ § Dri ed particle
E--~
~ :§.
.g ~ t dm/dt=F(D,L\p, L\T, 0)
dT/dt=<p(D. L\T . 0 )
E ~

~~ Aeroso l d roplet
~~
....._----------+
Residence tim e, t

Figure 1. The opportunities of ultrasonic spray pyrolysis in various particles synthesis

MHz) from dilute nitrate solution. Prolonged residence time implies crystallization of ZnO
particles (figure 2b). Another example is obtaining fully dense, spherical, crystalline silver
22
particles from nitrate solution for prolonged residence time, providing particle further
densification and decomposition.
The crystallinity of the aerosol derived particles depends upon the precursor choice
too, as shown for the case of Fe203 particle synthesis for magnetic application.i'' The
composite particle nature is observed for the nitrates - derived spherical particles, with the
average size less than 200nm in contrast to the monocrystalline character of y- Fe203
chloride-derived particles.
Nanophase particles can be generated in accordance to this method by properly
controlling over the initial aerosol droplet size, the mechanisms of the droplet collision and
coalescence as well as by suppressing the excessive grain growth and grain coarsening. As
a result, it is possible to obtain either nanoparticles directly from nano-sized droplets or to
obtain submicronic sized particles, that offer a composite nanograin particle structure?4,2S
Nanocomposite structure of various examined ultrasonically derived particles are revealed
for oxide fuel cells" as well as for manganese, copper and nickel oxide particles prepared
by low pressure aerosol spray pyrolysis.r" Submicronic single - phase manganese - ferrite
particles (with particle size less than 200 nm ) are obtained in accordance to aerosol spray
pyrolysis for the aerosol droplets of around Illm.27 The particles exhibit nearly bulklike
magnetic properties and multi domain particle structure. Single-phase polycrystalline
structure of particles ranging from 100-1OOOnm is observed also for strontium ferrite
powders,28 comprised of crystallites <100nm. The choice of precursors, their thermal and
decomposition behav ior play an important role in nano particles synthesis. In the case of
nitrate derived iron oxide , composite particle structure is formed where the secondary
particle is comprised of 6nm sized primary particles. However, for Fe(III)-acetylacetonate
as precursor, it was proved nano-sized particles synthesis directly .f In the case of Sn02
particles synthesis ultrasonically (ultrasound resonant frequency 1.7MHz) from tin sulfate
as a precursor solution, the microstructure hierarch y in composite particle formation,
including nanoparticles appearance, is clearly proved by detailed TEM, XRD and SEM

106
Figure 2. Composite (a) and single-crystal nature (b) of ZnO particles obtained ultrasonically at 2.5MHz
from nitrate solution concentration of 0.004 mol/l

observation.i'' Namely , the material includes primary crystallites, the mean size in the range
10-100nm gathering together into clusters-grains , ranged 100-200nm in diameter. These are
themselves gathered into spherical agglomerate s, or so called "secondary particles" the
mean size of around 1000nm.

CONTROL OF PARTICLE MORPHOLOGY AND MODELING

From the viewpoint of the application of the as-generated particles, either as powders
or precursor material s for advanced materials synthesis, particle morpholog y is of great
interest. Aerosol synthesis in accordance to ultrasonic spray pyrolysis enables synthesis of
various particle morphology , either as hollow or dense spheres. It is presumed that certain
particle morphology are formed during the evaporation/drying stage.i" Namely, the
following physicochemical phenomena are encountered during evaporation/drying stage:
evaporation of the solvent , diffusion of the solvent and solute away from the droplets and
inside the droplet, respectively, changing in droplet temperature and crust formation. They
are governed by the basic laws of heat and mass transfer so several models describing the
above mentioned phenomena are developed and can be applied in prediction of particle
morp hoogy.
I 20"303 1 Depen d'mg on eit
. her th i ute concentration
e so rormed im the
' gra dilent IS c.
droplet or not (figure 3), the solute can precipitates either mostly at the droplet surface or in
7
the droplet interior. As a result of the solute precipitation at the droplet surface, the
precipitate crust is formed, leading to the formation of diffusion barrier. Depending on the
crust properties , either hollow or fragmentary porous particles are formed as presented at
figure 3a for ZnO particles derived from nitrate precursor. Obviously, core shell particles
morphology are the result of salt surface precipitation where as-obtained Zn-nitrate core is

107
rigid enough to pass the gaseous products of nitrates decomposition. This leads to pressure
built-up inside the particle and to the formation of exploded particles for such droplet
geometry. Similar particle morphology can be also obtained if the conditions for droplet
32
collision and droplet coalescence are fulfilled . In accordance to the previously
reported,30,32,33 the droplet collision can be suppressed if the droplet number density are
below 107/cm3 as proved in the case of ZnO, BaTi03 as well as Bi-Pb-Sr-Ca-Cu-O
powers,
d generated Wit . h vanous
vari aeroso I fl OW rates .33 '34
The appearance of surface precipitation is the case for the most inorganic salts, if the
obtained core is rigid enough and if the relationship between the droplet geometry-
residence time is not properly adjusted. However, it is possible to obtain solid particles even
from inorganic solutions.r'' such as nitrates or chlorides by enabling suffic ient residence
time for decomposition as well as gases diffusion and particle shrinkage . Proper adjusting
of the droplet geometry as well as the residence time lead to solid particle formation, as
presented at figure 4, for the case of nitrate -derived ZnO particles from a.Smolll solution.
The problems regarding droplet collision and consequently droplet coalescence or
agglomerated particles formation are often associated with ultrasonic spray pyrolysis, since
7
reducing droplet size significantly increases the probability for collision. Agglomerated
particles are undesirable especially for afterwards sintering purposes, causing hard
agglomerates formation and inducing local grain growth and inhomogeneity. Figure 3c
represents agglomerated particles in a multicomponent Bi-Pb-Sr-Ca-Cu-O system where
the mechanisms of sintering and neck formation are obvious. However, those agglomerates
are formed in the process of droplet-to-particle transition followed by liquid phase
formation and liquid binding model agglomeration during thermolysis."

I. One particle per one droplet

r., concentratio=-l
gradient
Surface precipitation Volumeprecipitation

A) B)
t II. Droplet collision

L>ropletcoaUescence

Agglomerated
C) ~ particles

Figure 3. Schematic of the control of particle morphology during ultrasonic spray pyrolysis

108
 Figure 4. Nitrate -derived solid ZnO particles synthesis by ultrasonic spray pyrolysis at 2.5MHz.

On the contrary of the reports on the mechanisms of particle formation from inorganic
salts, solid particles are often generated from metal alkoxides or organic solutions if they
undergo Rolymerization process . Several examples relate to the synthesis of microporous
zirconia, 1 spherical Sn02 as well as TiOi Sn02 particles in the range from 200-800nm
from SnCl 4 and TiCl 4 - SnCl 4 aqueous solutions.i" respectively and BaTi03 particles
obtained ultrasonically from TiCI4-BaCI 2 alcohol/water solution ." The mechanism for solid
particle formation is proposed through polymerization - gelation process of the precursor
salts during evaporation / drying stage, leading to the formation of three- dimensional
network , volume precipitation and solid particles . Particularly, in the case of BaTi0 3 , the
mechanism is discussed in term of Ti(lV) ions hydrolysis in droplets during evaporation
and consequently BaCl2 precipitation on such obtained three-dimensional network . The
obtained particles are spherical , with smooth surfaces and with the mean particle size of
about 500nm (figure 3b).
Another feature that strongly alter the particle morphology is transferring ions into gas
phase in the case of volatile precursors." In this case the particles are formed both from gas
as well as liquid (solid) phase, leading to the broad size of particle distribution and to the
differences in particle morphology. From the viewpoint of difficulties for the stoichiometry
retention in the case of multicomponent systems, this feature has to be controlled carefully .

AEROSOL GENERATION OF FILMS

Aerosol synthesis has been widely used in various films generation, either as droplet
and particle deposition or aerosol assisted CVD technology. It was shown that coating s and
films can be obtained in various systems , like superconductors, metal oxides , nonoxides ,
38
metals, composites etc. and on various substrates, like glass, ceramic, metal, alloys etc.
Especially in the case of aerosol assisted CVD (Pyrosol process) , the process involves
deposit ion of droplets containing evaporative reactants and subsequently evaporation and
reaction on the substrate surface." The materialsconcemed for film formation in the latter
case are metals (noble and transition metals), sulphides (eg. ZnS, CdS) as well as various
oxides ." It was shown that high quality of deposits, the thickness from IOOnm to several
microns, that are widely used as sensors, capacitors, films for optics and magnetics ,
transparent electrodes as well as biomaterials can be obtained in accordance to aerosol
synthesis .39, 40

109
CONCLUSION

This paper reviewed various approaches for the nanostructured materials synthesis with
special emphasis to aerosol synthesis . The method of ultrasonic spray pyrolysis is discussed
from the viewpoint of the ability to synthesis of various particle morphologies . Recent
developments in synthesis of particles and films are discussed. The mechanisms of particle
morphology are focused with the special emphasis to the materials and precursor chemistry
involved.

ACKNOWLEDGMENT

This work is realized through the project "Prognosis of materials properties from the
viewpoint of the synthesis- structure-properties relationship", financed by the Ministry of
Science of Republic Serbia as well as through the collaboration with RBI, Instruments and
measures, Meylan , France. The influence and support of academician M .M.Ristic are very
much appreciated . The assistance of Prof. I. Arsentyeva and Prof. Lj. Zivkovic in
providing TEM and SEM analysis is gratefully acknowledge .

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