Characterizing Atomic Interactions in Interstitial Non-Stoichiometric Compounds by Statistical Thermodynamics: Engineering Usage of Estimated Values of Statistical Thermodynamic Parameters

• 作者: Nobumitsu Shohoji
• 来源期刊: 现代物理(英文)
• 学科: 化学
• 关键词: Statistical Thermodynamics NON-STOICHIOMETRY INTERSTITIAL Compound HYDRIDE Nitride Carbide PHOSPHIDE Sulfide
• 年，卷（期）: xdwlyw_2017,（3）
• 页码范围: 365-381
• 页数: 17页
• 分类号: O6

摘要

Statistical thermodynamics allows us to estimate atomistic interactions in interstitial non-stoichiometric compounds MXx through analysis of experimentally determined pressure-temperature-composition (PTC) relationships for MXx being in equilibrium with X2 in gaseous state?(X=H,N,P or S)?or for non-stoichiometric carbide MCx being in equilibrium with excess C. In case of analysis for MCx, chemical activity a(C) of C in place of partial pressure p(X2) of X2 gas must be known. On statistical modelling of crystal lattice structure for MXx, an a priori assumption of constant nearest-neighbour X-X interaction energy E(X-X) within a homogeneity composition range at arbitrary temperature T was accepted to determine number θ of available interstitial sites for occupation by X atoms per M atom. Values of interaction parame-ters estimated as such appear rational and realistic noting consistency of the values for M’s in the same group in the Periodic Table of the Elements and compatibility with enthalpy values evaluated by conventional thermodynamic approach. Engineering insights gained for MXx through analysis of atomistic interaction parameter values evaluated by the statistical thermodynamics are reviewed comprehensively in this paper. M might be substitutional alloy A1-yBy composed of constituents, A and B, or MZz containing another interstitial constituent Z besides X. Insights acquired from this line of statistical thermodynamic analysis appear to be of pragmatic use for advanced alloy design as shall be demonstrated hereafter.