INORGANIC SYNTHESIS AND INDUSTRIAL
Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 9, pp. 1488−1497.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © N.I. Radishevskaya, V.I. Vereshchagin, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 9, pp. 1436−1445.
An IR Spectroscopic Examination of the Composition
of Oxyhydroxide Films on the Surface
of Micron-Sized Aluminum Powders
N. I. Radishevskaya and V. I. Vereshchagin
Department of Structural Macrokinetics, Tomsk Scientiﬁ c Center, Siberian Division,
Russian Academy of Sciences, Tomsk, Russia
Tomsk Polytechnic University, Tomsk, Russia
Received December 3, 2010
Abstract—The composition of oxyhydroxide coatings formed on the surface of micron-sized ASD-1 and ASD-4
aluminum powder in air was examined in relation to the degree of dispersity and the impurity level and content
of the powders. The mechanism of formation of the oxyhydroxide layer on the aluminum surface was presented.
Modern ceramics decoration techniques extensively
employ spinel-based pigments which are characterized
by resistance to heat, moisture, light, and attacks by
molten glazes and are environmentally friendly. Using
the self-propagating high-temperature synthesis (SHS)
route, ﬁ nely dispersed spinel-containing pigments were
synthesized, which technique expanded the range of
option available for ceramic pigment preparation [1–3].
Relevant studies showed that the crystal structure and
color of spinel are strongly affected by the structure
of the oxyhydroxide coating formed on the aluminum
surface, which component makes possible proceeding
of the SHS process and contains nanostructured oxide
and hydroxide phase formations. The latter also strongly
affect the temperature parameters of SHS, which fact
was hardly taken into account previously.
In this context, it was of interest to examine the
formation of aluminum oxides and hydroxides on the
surface of ASD-1 and ASD-4 commercial aluminum
powders, resulted from heat treatment at various
temperatures in air.
Aluminum is a typical amphoteric element which
crystallizes in face-centered cubic structure with
the lattice parameter a = 4.4 Å and has no allotropic
modiﬁ cations. The most common oxidation state of
aluminum is +3, but the unﬁ lled 3p- and 3d-orbitals
makes possible formation of additional donor-acceptor
bonds by the aluminum atoms. The Al
ion with its small
= 0.057 nm) is very prone to complexing. It
forms not only anionic but also cationic complexes, e.g.,
an aqua complex [Al(OH
and hydroxo complex
. Aluminum(III) may have the coordination
number 4 and 6 .
In our work we used dispersed commercial aluminum
powders ASD-1 and ASD-4 obtained by molten
aluminum spraying  and examined the powders
calcined in a mufﬂ e furnace at temperatures ranging
from 200 to 1100°C at intervals of 50°C. The resulting
oxide layers on the aluminum surface were identiﬁ ed
by IR spectroscopy in the 4000–400 cm
a Nicolet 5700 (US) IR Fourier-transform spectrometer
using a diffuse reﬂ ection accessory (KBr pellets), as
well as by X-ray phase analysis on a Shimadzu XRD-
7000S (Japan) and DRON-UM1 diffractometers. The
mass-spectroscopic examinations of the ASD-1 and
ASD-4 powders were carried out in the temperature
range 20–1100°C by differential thermal analysis on
an STD Q600 instrument (heating rate 10 deg min
coupled with mass spectrometry on a Prolab VG