The self-diffusivities of iron and manganese,
DFe* and
DMn*, in Fe-Mn alloys containing from 1.04 to 33.98 at% Mn were determined in the γ phase (
FCC) region at 990∼1240°C by the residual activity method. At the same time, the interdiffusion coefficients, \Tilde{
D}, were determined by the Matano method in the temperature range between 850 and 1300°C, using diffusion couples of pure iron and 33.98 at% Mn alloy.
It was shown that
DFe* is smaller than
DMn* in the experimental concentration and temperature ranges. The Kirkendall markers in the interdiffusion couple were found to move towards the higher Mn-concentration side. The intrinsic diffusion coefficients,
DFe and
DMn, for the composition in the vicinity of 24 at% Mn were calculated, and it was also shown that
DFe is smaller than
DMn.
The values of \Tilde{
D} for 1177°C calculated using the experimental values of
DFe*,
DMn* and the activity coefficients applying Darken’s equation were shown to be in fairy good agreement with the experimental values of \Tilde{
D} in the composition range lower than 20 at% Mn. Moreover, for \Tilde{
D} in the composition range higher than 20 at% Mn, a better agreement between them was also obtained taking into account the effect of vacancy flow.
For each concentration, the activation energy for self-diffusion of iron,
QFe* was shown to be larger than that of manganese,
QMn*, and it was found that
QMn*<\Tilde{
Q}<
QFe* in the whole concentration, where \Tilde{
Q} is the apparent activation energy for interdiffusion.
QFe*,
QMn* and \Tilde{
Q} showed the minimum value at the respective compositions lower than 10 at% Mn. The calculated values of
QFe* and
QMn* using the empirical equation proposed by Toth
et al. were in good agreement with the observed values. The apparent activation energy for interdiffusion \Tilde{
Q}, was considered as the total of three components: temperature dependence of thermodynamic factor, temperature dependence of the effect of vacancy flow, and temperature dependence of
DFe* and
DMn*. It was shown that the vacancy flow produced an effect which decreased the calculated value of \Tilde{
D} in the whole range of composition.
The activation entropy
ΔS* for self-diffusion which was calculated from the experimental values of the frequency factor
D0*, was shown to be expressed by
ΔS*=α(
Q*⁄
Tm)+
ΔS0, where
Tm is the melting temperature,
ΔS0 is a negative term of the activation entropy which arises from the altered vibrational frequencies of the atoms constituting the saddle point configration, and α is a constant.
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