CRYSTAL-CHEMISTRY AND MAGNETIC-PROPERTIES OF THE K2NIF4 TYPE DILUTED SOLID-SOLUTION YCAAL1-XCRXO4 ESS-THAN-OR-EQUAL-TO-X-LESS-THAN-OR-EQUAL-TO-0.10) - EVIDENCE FOR CR3+ CLUSTERING
F. Archaimbault et al., CRYSTAL-CHEMISTRY AND MAGNETIC-PROPERTIES OF THE K2NIF4 TYPE DILUTED SOLID-SOLUTION YCAAL1-XCRXO4 ESS-THAN-OR-EQUAL-TO-X-LESS-THAN-OR-EQUAL-TO-0.10) - EVIDENCE FOR CR3+ CLUSTERING, Materials chemistry and physics, 34(3-4), 1993, pp. 300-305
The K2NiF4 type diluted solution YCa(Al1-xCrx)O4 (0 less-than-or-equal
-to X less-than-or-equal-to 0.10) is studied with respect to both crys
tal chemistry and magnetic properties, mainly in order to obtain some
evidence of Cr3+ segregation phenomena in the octahedral layers. The A
l3+ --> Cr3+ replacement results in a strong anisotropic variation of
the cell constants in terms of an increase and a decrease in the a and
c parameters, respectively, of the tetragonal cell. Such behaviour is
largely dependent on the M-0(apical) distances in the (Al,Cr)-O6 octa
hedra, as well as in the (Y,Ca)-O9 polyhedra, which show a coupling of
their variation. On the basis of the temperature (80, 400 K) and Cr3 concentration dependence of the magnetic susceptibility, which is use
d in the Heisenberg-Dirac-Van Vleck approach for modeling the magnetic
exchange interactions, a significant deviation of the Cr3+ distributi
on is found with respect to a statistical distribution. The amount of
Cr3+ clusters is lower than in the perovskite solid solution YAl1-xCrx
O3, owing to the lower dimensionality of the K2NiF4 type structure of
the YCaAl1-xCrxO4 series. The 2D character of the exchange interaction
s is found to be stronger than in pure chromite, YCaCrO4.