ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2010, Vol. 84, No. 9, pp. 1576–1584. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Korshunov, A.P. Il’in, N.I. Radishevskaya, T.P. Morozova, 2010, published in Zhurnal Fizicheskoi Khimii, 2010, Vol. 84, No. 9, pp. 1728–1736.
1576
INTRODUCTION
Aluminum powders are extensively used as energy
admixtures to solid fuels and pyrotechnic composi-
tions and in the production of composition materials
and intermetallic compounds [1, 2]. An increase in the
activity of metal powders (a decrease in the tempera-
ture of sintering, oxidation, and ignition) as their dis-
persity increases is related to the size effect caused by
an increase in the fraction of nanoparticle surface
atoms. At the same time, interrelation between the size
of powder particles and their reactivity is not unambig-
uous. For instance, aluminum nanopowders (ANP)
passivated in air, as distinct from nanopowders of some
other metals (Fe, Ti), are not pyrophoric and are com-
paratively stable to oxidation during storage [2]. For
this reason, studies of size effect manifestations in
chemical processes are of obvious interest both from
fundamental point of view and for practical applica-
tions.
Works on the oxidation of aluminum nanopowders
are not numerous, their results are often contradictory
and cannot be used to determine the reason for the dif-
ference between the properties of aluminum nanopo-
wders and those of coarse-dispersion powders [2–13].
This is primarily related to the conventionality of the
term “nanopowders.” This term is usually applied to
high-dispersity powders with some (not regulated)
fraction of particles 100 nm and less in diameter. It
was, for instance, shown in [2–9] with the use of ther-
mogravimetry that a substantial increase in the rate of
oxidation of aluminum nanopowders in air compared
with coarse-dispersion powders was observed over the
temperature range 450–600°C, that is, below the
melting point of Al (T
m
= 660°С). Conversely, it was
found in [13] using mass spectrometry of separate par-
ticles that the oxidation of Al nanoparticles (~50 nm)
suspended in a gas flow did not occur up to 800°С.
A sharp increase in the rate of oxidation of alumi-
num nanopowders at 450–600°С was explained by
cracking of the oxide shells of particles caused by the
crystallization of an amorphous oxide layer in [2, 5,
13] and by sample ignition in [4, 9]. According to [13],
the rapid oxidation of aluminum nanopowders occurs
at the moment of metal melting. The expansion of the
metallic core of Al particles by 12% then increases
excess pressure inside particles to 88000 atm, which
contributes to oxide shell breaking. On the other hand,
the authors of [8] consider a mathematical model of
the dependence of T
m
of Al nanoparticles on their
diameter; this model takes into account the thickness
of the surface oxide layer but ignores the difference
between the molar volumes of crystalline and liquid
Al. An improved calculation procedure was suggested
in [14]; according to this procedure, the oxide shell of
Al particles should crack at all temperatures under lin-
ear heating conditions.
An analysis of the literature data shows that the use
of the approach based on the temperature dependence
of oxide shell characteristics does not clarify the char-
acter of the influence of the dispersity of Al powders on
their reactivity. There is no literature data on the influ-
ence of the special features of the structure of Al parti-
cles and particle-size distribution on the kinetics of
oxidation of powders. The purpose of this work was to
The Kinetics of Oxidation of Aluminum
Electroexplosive Nanopowders during Heating in Air
A. V. Korshunov
a
, A. P. Il’in
a
, N. I. Radishevskaya
b
, and T. P. Morozova
a
a
Tomsk Polytechnical University, pr. Lenina 30, Tomsk, 634050 Russia
e-mail: korshunov@tpu.ru
b
Department of Structural Macrokinetics, Tomsk Scientific Center,
Siberian Division, Russian Academy of Sciences, Tomsk, Russia
Received October 17, 2009
Abstract—The rules governing the oxidation of aluminum nanopowders obtained by the electrical explosion
of wires during heating in air under the conditions of linearly increasing temperature and in isothermal regime
were studied. The influence of the composition and structure of aluminum particle oxide coating and metallic
core on the parameters of the process and the phase composition and morphology of oxidation products was
determined. Thermal reaction conditions were shown to depend on thermogravimetry regime, and the
kinetic data were used to explain this dependence. The kinetics of oxidation was modeled taking into account
the aluminum particle-size distribution function. It was shown that the structures of particles of the nanodis-
perse and micron electroexplosive powder fractions were different.
DOI: 10.1134/S0036024410090244
PHYSICAL CHEMISTRY OF NANOCLUSTERS
AND NANOMATERIALS