Abstract
The kinetics of segregation embrittlement is controlled by phosphorus diffusion to the grain boundary, and this process can be described by the MacLean equation. The equilibrium state, corresponding to an infinite time of isothermal holding, has been the object of intensive study. On the other hand, only a few papers have presented a non-equilibrium analysis of segregation. In the initial states of the segregation process, a difference in the chemical potential of the impurity in the grain boundary and in the bulk produces a change of the free energy of the system and, correspondingly may cause a change in the work of fracture. Thus, if non-equilibrium segregation occurs, one can observe a decrease of the true surface energy of cracked surfaces and attendant grain boundary embrittlement. On the other hand, if the diffusion is a random process, the influence of the instantaneous level of grain boundary composition may play a major role in this kind of brittleness. The aim of the present paper is to analyze the influence of non-equilibrium phosphorus segregation at grain boundaries on the embrittlement of iron.
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