The cation tracer diffusion coefficients of Co and Ga were measured in (Co1-xGax)O as a function of dopant fraction, x, (0 to 0.03), log[O2 activity] (-7 to -0.67), and temperature (1100 to 1350C). For both diffusion coefficients, a non-linear dependence upon dopant fraction and a large effect of the Ga dopant upon the activity-dependence of the diffusion coefficients were found. The experimental observations were modelled in terms of a defect model which involved solute-vacancy pairs in 2 charge states, and triplets which comprised two Ga ions and a cation vacancy. By fitting the experimental data (tables 45 and 46), a binding energy for neutral pairs, {Ga.V'}x, was found which was small in comparison to the thermal energy, whereas the binding energy for singly-charged pairs, {Ga.V"}', was equal to about 0.5eV. The binding energy for the triplets, {Ga.V"Ga.}x, decreased from 1.1eV at 1100C to 0.76eV at 1350C. The mobility of free vacancies was some 50% larger for V" than for V'.
R.Schmackpfeffer, M.Martin: Philosophical Magazine A, 1993, 68[4], 747-65
Table 45
Diffusion Parameters for Co in (Co1-xGax)O at 1100 to 1350C
log [O2 activity] | x (at%) | Do (cm2/s) | E (kJ/mol) |
-0.67 | 0.00 | 0.0084 | 164 |
-0.67 | 0.32 | 0.0030 | 149 |
-0.67 | 0.79 | 0.0059 | 155 |
-0.67 | 1.64 | 0.014 | 164 |
-3.20 | 0.00 | 0.00079 | 151 |
-3.20 | 0.32 | 0.0018 | 156 |
-3.20 | 0.79 | 0.0041 | 161 |
-3.20 | 1.64 | 0.010 | 168 |
-7.00 | 0.00 | 0.0011 | 173 |
-7.00 | 0.32 | 0.000077 | 126 |
-7.00 | 0.79 | 0.000011 | 96 |
Table 46
Diffusion Parameters for Co in (Co1-xGax)O at 1100 to 1350C
log [O2 activity] | x (at%) | Do (cm2/s) | E (kJ/mol) |
-0.67 | 0.00 | 0.00032 | 123 |
-0.67 | 0.32 | 0.00034 | 123 |
-0.67 | 0.79 | 0.00056 | 129 |
-0.67 | 1.64 | 0.0041 | 152 |
-3.20 | 0.00 | 0.00020 | 135 |
-3.20 | 0.32 | 0.00029 | 132 |
-3.20 | 0.79 | 0.00058 | 136 |
-3.20 | 1.64 | 0.0030 | 154 |
-7.00 | 0.00 | 0.020 | 204 |
-7.00 | 0.32 | 0.00013 | 157 |
-7.00 | 0.79 | 0.000089 | 120 |