hP8-to-cP4 structural transition in Ni3In compounds at high temperature and pressure: Theoretical assessment of compression and phase stability information

IF 1.9 3区 材料科学 Q4 CHEMISTRY, PHYSICAL
Dalía S. Bertoldi , Susana B. Ramos , A. Fernández Guillermet
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Abstract

According to Webb et al. (1986) by heating the Ni3In (hP8) compound at 800–1200 °C under a pressure (P) of 6.5 GPa, a cP4 phase was formed, which reverted to hP8 when annealed at low pressure. A striking X-ray result is that the atomic volume (V) of cP4 was higher than that of hP8. Webb et al. determined the V versus P relations in samples quenched to room temperature and reported that the compressibility of the cP4 phase was significantly larger than that of the hP8 phase. These various findings have been theoretically analyzed in the current work by using ab initio density-functional-theory (DFT) calculations, including an account of the vibrational and electronic contributions to the thermodynamic properties. Calculations of the V versus P relations are used to reassess the compressibility relation between the cP4 and hP8 phases, and Gibbs energy calculations to characterize the relative stability of these structures. In particular, detailed comparisons are reported with the only information available on the thermal properties of the hP8 phase, viz., the Gibbs energy estimates obtained in CALPHAD-type phenomenological modeling of the Ni–In equilibrium diagram. The key qualitative result of the current work is that cP4 should be considered as a high-temperature phase, which might be stabilized by heating to the temperature chosen to anneal the hP8 material under pressure. On this basis it is suggested that the seemingly anomalous relative stability relations discussed by Webb et al. might be a consequence of considering only the effect of pressure on the cP4/hP8 relative phase stability.

高温高压下 Ni3In 化合物中 hP8 到 cP4 的结构转变:压缩和相稳定性信息的理论评估
根据 Webb 等人(1986 年)的研究,在 6.5 GPa 的压力 (P) 下于 800-1200 °C加热 Ni3In(hP8)化合物,形成了 cP4 相,在低压退火时又恢复成 hP8 相。一个引人注目的 X 射线结果是,cP4 的原子体积(V)高于 hP8。Webb 等人测定了淬火至室温的样品中 V 与 P 的关系,并报告说 cP4 相的可压缩性明显大于 hP8 相。在目前的工作中,我们利用原子序数密度函数理论(DFT)计算对这些不同的发现进行了理论分析,其中包括对热力学性质的振动和电子贡献的说明。V 与 P 的关系计算用于重新评估 cP4 和 hP8 相之间的可压缩性关系,吉布斯能计算用于描述这些结构的相对稳定性。特别是,报告详细比较了 hP8 相的热特性的唯一可用信息,即在镍铟平衡图的 CALPHAD 型现象建模中获得的吉布斯能估计值。当前工作的主要定性结果是,cP4 应被视为一种高温相,可以通过加热到 hP8 材料在压力下退火时所选择的温度来使其稳定。在此基础上,Webb 等人讨论的看似异常的相对稳定性关系可能是只考虑压力对 cP4/hP8 相对相稳定性影响的结果。
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来源期刊
CiteScore
4.00
自引率
16.70%
发文量
94
审稿时长
2.5 months
期刊介绍: The design of industrial processes requires reliable thermodynamic data. CALPHAD (Computer Coupling of Phase Diagrams and Thermochemistry) aims to promote computational thermodynamics through development of models to represent thermodynamic properties for various phases which permit prediction of properties of multicomponent systems from those of binary and ternary subsystems, critical assessment of data and their incorporation into self-consistent databases, development of software to optimize and derive thermodynamic parameters and the development and use of databanks for calculations to improve understanding of various industrial and technological processes. This work is disseminated through the CALPHAD journal and its annual conference.
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