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The existence of the so-called “enthalpy – entropy compensation effect” as an inherent property of a system is proven on the basis of a pure thermodynamic analysis. The compensation effect is documented for the example of grain boundary segregation and migration. It is shown that the changes of the values of characteristic enthalpy and entropy that fulfil the compensation effect are caused by the changes of grain boundary energy via the changes of grain boundary structure and system chemistry: Despite of the nature of such changes, a single linear dependence between the enthalpy and entropy should exist under the same mechanism of the process.

Enthalpy – entropy compensation effect in grain boundary phenomena