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