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J. Korean Ceram. Soc. > Volume 47(1); 2010 > Article
Journal of the Korean Ceramic Society 2010;47(1): 39.
doi: https://doi.org/10.4191/kcers.2010.47.1.039
Theoretical and Experimental Studies on the Kinetics of Cation Redistribution Processes in Complex Oxides
Jianmin Shi, Klaus-Dieter Becker
Institute of Physical and Theoretical Chemistry, Technische Universitat Braunschweig
ABSTRACT
The kinetics of cation reequilibration have been studied theoretically and experimentally in complex oxides after an external perturbation of equilibrium by temperature jumps. A general kinetic model for cation redistribution amongst non-equivalent sites in complex oxides is derived based on a local homogeneous point defect mechanism involving cation vacancies. Temperature-jump optical relaxation spectroscopy has been established to investigate cation kinetic processes in spinels and olivines. The kinetic model satisfactorily describes the experimental absorbance relaxation kinetics in cobalt containing olivines and in nickel containing spinels. It is found that the kinetics of cation redistribution in complex oxides shows a strong temperature- and composition-dependence. Activation energies for cation redistribution in Co-Mg olivines are found to range between 200 and 220 kJ/mol whereas an energy barrier of about 230 kJ/mol is observed in the case of nickel gallate spinel.
Key words: Complex oxides, Kinetics, Cation distribution, Optical spectroscopy, Spinel, Olivine
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