Effect of Thermal Vacancy on Thermodynamic Behaviors in BCC W Close to Melting Point: A Thermodynamic Study

As temperature increases, the thermal vacancy concentration in pure metals dramatically increases and causes some strongly non-linear thermodynamic behaviors in pure metals when close to their melting points. In this paper, we chose body-centered cubic (bcc) W as the target and presented a thermodynamic model to account for its Gibbs energy of pure bcc W from 0 K to melting point by including the contribution of thermal vacancy. A new formula for interaction part was proposed for describing the quadratic temperature behavior of vacancy formation energy. Based on the experimental/first-principles computed thermodynamic properties, all the parameters in the Gibbs energy function were assessed by following the proposed two-step optimization strategy. The thermodynamic behaviors, i.e., the strong nonlinear increase for temperature dependence of heat capacities at high temperatures and a nonlinear Arrhenius plot of vacancy concentration, in bcc W can be well reproduced by the obtained Gibbs energy. The successful description of thermal vacancy on such strongly non-linear thermodynamic behaviors in bcc W indicates that the presently proposed thermodynamic model and optimization strategy should be universal ones and are applicable to all other metals.