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Plasma Spheroidization of Ceramic Particles

Article  in  Chemical Engineering and Processing · February 2005

DOI: 10.1016/j.cep.2004.02.015

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 Chemical Engineering and Processing 44 (2005) 221–224

Plasma spheroidization of ceramic particles

Z. Károly∗ , J. Szépvölgyi
Institute of Materials and Environmental Chemistry, Chemical Research Center,
HAS, P.O. Box 17, Budapest 1525, Hungary

Received 30 August 2003; received in revised form 18 December 2003; accepted 11 February 2004
Available online 19 June 2004

Abstract

Formation of spherical, micron-sized ceramic particles was investigated in an RF thermal plasma reactor. It has been concluded that a
wide size distribution of feedstock powders gives rise to either excessive evaporation of smaller grains or insufficient melting of bigger ones.
Ceramic spheres with more or less voids inside can also be prepared starting from powders pretreated in special ways.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Plasma reactor; Ceramic particles

1. Introduction 2. Experimental

Spherical particles proved to be superior in several ap-
plications owing to their favorable properties. Thus, they
are used in thermal spraying for their excellent flowabil-
ity, in powder metallurgy because of their excellent repro-
ducibility in manufacturing parts with controlled porosity
and as a filler material, as well. Metal microspheres can
be easily produced by melt atomization. Similar method
in the case of ceramics is impractical. Micron-sized ce-
ramic particles, however, can be smelted by thermal plas-
mas that provide exceptional conditions for spheroidization
due to its high temperature. In terms of purity and resi-
dence time of the particles in the hot temperature core, RF
plasmas provide better conditions as compared to arc plas-
mas.
The present report describes the preparation of spherical
ceramic particles of different kind and of different size in an
inductively coupled RF thermal plasma reactor. The effect
of plasma gases and the type of the feedstock materials on
the microstructure of the formed particles was studied in the
experiments.
∗ Corresponding author. Tel.: +36 1 325 7933x415;
fax: +36 1 325 7892.
E-mail address: karoly@chemres.hu (Z. Károly).
The experimental apparatus consisted of a TEKNA-type
induction plasma torch (PL-035LS) with a quartz confine-
ment tube of 25 mm and a water cooled steel chamber con-
nected to a cyclone. The plasma plate power of 21 kW was
provided by a four turn, water cooled induction coil from an
RF generator operating at an oscillator frequency of 3 MHz.
High purity argon was used both as plasma and sheath gas
with flow rates of 20 and 60 l min−1 , respectively. In order
to raise the low enthalpy and heat conductivity of the argon
plasma gas, hydrogen was also mixed into the sheath gas
with a proportion of 10% (v/v).
The starting powders were fed with a PRAXAIR powder
feeder through an injection probe to the top of the plasma
flame by argon carrier gas (3 l min−1 ) with a constant feed
rate of 10 g min−1 . The outlet of the quartz injection tube of
an inner diameter of 2 mm, was located 10 mm below the
top of the induction coil.
Commercial alumina (ALO-Ex30 and ALO-GB1 from
AJKA Alumina Co. Ltd., Hungary), aluminum-hydroxide
and silica powders were investigated. Impurity levels of the
powders were below 0.5%. In some tests, minor amount of
NaNO3 and Na-silicates were, however, blended into the
silica aggregates. The sodium-silicates were used as binding
agents of primary particles, while NaNO3 was applied to
release gas (O2 and N2 ) at temperatures higher than 720 ◦ C.
Both the raw materials and the produced powders were
characterized for density, particle size distribution, specific

0255-2701/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.cep.2004.02.015
222 Z. Károly, J. Szépvölgyi / Chemical Engineering and Processing 44 (2005) 221–224
surface area, phase composition (XRD) and microstructure
(SEM). Density was determined by means of picnometry.
The particle size distribution by volume of grains was de-
termined by a Malvern Master Particle Sizer. The specific
surface areas were measured with a conventional volumetric
instrument by BET method. A Philips Xpert XRD appara-
tus was used for X-ray diffraction measurements. Standard
X-ray powder techniques were used with Cu K␣ radiations
generated at 40 kV and 30 mA. The microstructural (SEM)
investigations were performed on a JEOL JSN50A appara-
tus. Cross-section images of the particles were made by em-
bedding them into resin that was followed by their cutting
by diamond blade.
3. Results and discussion
According to the scanning images of particles spheroidiza-
tion took place effectively (compare Figs. 1 and 2). A
spheroidization rate as high as 90% could be achieved.
It was previously shown [1] that increasing feed rate en-
tail declining spheroidization efficiency. This phenomenon,
however, could not be experienced with increasing mean
Fig. 1. SEM image of alumina feedstock particles.
Fig. 2. SEM image of alumina particles after spheroidization.
particle size of the feedstock powder. Besides spheroidiza-
tion melting usually caused an increase in density that fell
close to the theoretical one (ρ = 2.32 g cm−3 ) at silica pow-
ders. However, the higher was the size of the feedstock par-
ticles, the density of products remained increasingly below
the theoretical one. This can be attributed to the fact, that
above a certain size particles have not got enough time to
be melted on the whole. Thus, the core remains unaffected.
Considerable changes in the size of silica after processing
cannot be observed (Fig. 3), whereas the specific surface
area of products was increased and it was higher with de-
creasing mean particle size of the feedstock. Particles below
the mean size are prone to be evaporated completely to be
condensed again in the nanosize range in the cooler parts
of the plasma reactor. These nano-sized particles usually
cover the surface of bigger ones. Decreasing the power or
reducing the residence times would decrease evaporation
rate, however, it would also jeopardize the spheroidization
of bigger particles.
Spherical alumina can also be formed from commercial,
low cost aluminum-oxides or even from aluminum-hydr-
oxides. In the latter case energy of the plasma should provide
not only the enthalpy of melting but that of dehydration and
subsequent phase transformations of alumina as well. Under
the aforementioned conditions particles below 45 ␮m have a
good chance to be spherodized. Presumably the wide particle
size distribution of starting gibbsite powder accounts for the
less spheroidization rate of 70%.
Application of agglomerated alumina powders as feed-
stock material gives rise to spheroidization too. Density of
product particles falls much below the theoretical one (ρth ,
Al2 O3 = 3.95 g cm3 ), while significant increase in the grain
size can be observed in case of alumina (Fig. 4). Scanning
images of these powders, however, show they mainly con-
sist of hollow particles. Formation of hollow particles and
the size enlargement can be attributed to the expansion of
gases located in the interior of melted droplets. The gases
Fig. 3. Main characteristic of silica product powders (S denotes specific
surface area, ρ represents apparent density).
 Z. Károly, J. Szépvölgyi / Chemical Engineering and Processing 44 (2005) 221–224 223

Fig. 4. Comparison of the particle size distribution of feedstock material (straight line) and product (dashed line) (ρ represents apparent density).

are hindered from leaving after the development of a coher-

ent outer melted layer. The final size of these cavities are de-
termined by the freezing temperature of the oxide melt that
is approximately TF = 0.8TM [2,3], where TM is the melt-
ing point of particular oxide. The overpressure in the voids
can be calculated by this formula: P = (2σ/r), where σ
denotes the surface tension of melt and r denotes the radius
of the hollow. From the above formulas it can be calculated,
that the molar quantity of gas in the resulted voids are in the
same order of magnitude than that of the gas in the porous
structure of the starting grains. It is the case if the raw ma-
terial is made from primary particles of several microns by
spray drying or agglomeration. When the goal is to prepare
hollow spheres some gas-blowing agents can be blended to
the grains in order to provide substantial gas volumes. These Fig. 6. SEM image of a hollow microsphere of thick wall.

supplementary materials facilitate bubble generation by re-

leasing gas at a certain temperature by decomposition. This
process was applied to make hollow silica particles in ex-
periment 4 (Fig. 5). Density of particular powder is a mean
value that does not characterize each particle. The wall of
individual particles may differ in considerable extent, as this
can be recognized by comparing Figs. 5 and 6. While the
density of particles having thin shells is less than 1 g cm−3 ,
that of the solid particles can reach even the theoretical value.

4. Crystallinity

Freezing of the melted particles takes place rapidly be-

Fig. 5. SEM image of a hollow microsphere. cause of the extremely high temperature gradients being
 224 Z. Károly, J. Szépvölgyi / Chemical Engineering and Processing 44 (2005) 221–224
Fig. 7. XRD pattern of spheroidized alumina powders.
characteristic to thermal plasmas. According to XRD pat-
terns, majority of silica particles were transformed into
amorphous state on plasma treatment, only 1–2% remained
quartz.
Several papers report [4] that liquid alumina solidifies not
in the thermodynamically most stable phase of ␣-Al2 O3 ,
but rather in the form of ␥-Al2 O3 . This is attributed to the
fact that the solidified phase structure is basically deter-
mined by the relative critical free enthalpies of nucleation of
alternative crystal structures. Consequently, not surprising,
that considerable part of spheroidized particles composed
of ␥-Al2 O3 and other metastable phases (such as ␦, ␪) of
alumina (Fig. 7). The latter were formed from the ␥ phase
according to the usual route of phase transformation on cal-
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cinations, assuming that the temperature history of given
particle makes it possible. For bigger particles (>30 ␮m) the
heat effect of crystallization may promote additional phase
changes.
5. Conclusions
The RF thermal plasmas are suitable tools for making ox-
ide ceramic microspheres, either dense or hollow. The mi-
crostructure of the product can principally be influenced by
the structure of feedstock materials and to a less extent by
the plasma operating conditions. Highly porous raw materi-
als and/or the presence of blowing agents facilitate formation
of hollow spheres. By varying the process conditions, one
can primarily affect the thermal history of particles, hereby
the degree of evaporation.
References
[1] N.M. Dignard, M.I. Boulos, Sphericity analysis method for the in-
duction plasma processing of powders, in: Proceedings of the ISPC
14, Prague, 1999, pp. 2211–2217.
[2] R. McPherson, J. Mater. Sci. 8 (1973) 851.
[3] P. Florian, D. Massiot, B. Poe, I. Farnan, J.-P. Coutures, Solid State
Nucl. Mag. 5 (1995) 233.
[4] T. Ishigaki, Y. Bando, Y. Moriyoshi, M.I. Boulos, J. Mater. Sci. 28
(1993) 4223.