Ph. Bolt et al., FORMATION OF NICKEL, COBALT, COPPER, AND IRON ALUMINATES FROM ALPHA-ALUMINA-SUPPORTED AND GAMMA-ALUMINA-SUPPORTED OXIDES - A COMPARATIVE-STUDY, Journal of solid state chemistry, 135(1), 1998, pp. 59-69
The rates of metal aluminate formation in MeOx/Al2O3 systems (Me = Ni,
Co, Cu, Fe) at 500-1000 degrees C in O-2 or N-2 atmospheres were comp
ared, using both alpha-Al2O3 and gamma-Al2O3 substrates. Interfacial r
eaction to MeAl2O4 was assessed using Rutherford backscattering spectr
ometry and X-ray diffraction. The lateral homogeneity of the samples w
as investigated using scanning electron microscopy, The spinel formati
on rate follows the sequence FeAl2O4 < NiAl2O4 < CoAl2O4 < CuAl2O4. Th
is is explained in terms of thermodynamic limitations (FeAl2O4) and si
te-preference energies (CoAl2O4, NiAl2O4). The fast reaction to copper
aluminate was accompanied by a severe rupture of the top layer (simil
ar to 1 mu m) of the substrate, Penetration of transition metal ions i
nto gamma-Al2O3 substrates is notable at considerably lower temperatur
es than with alpha-Al2O3 substrates, mainly due to grain boundary diff
usion, Annealing conditions that favor the formation of transition met
al cations of a low valency (Co-2+, Cu+) are beneficial for reactions
to aluminates. (C) 1998 Academic Press.