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Thermodynamics of coherent interfaces under mechanical stresses. I. Theory

机译:机械应力下相干界面的热力学。一,理论

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We present a thermodynamic theory of plane coherent solid-solid interfaces in multicomponent systems subject to nonhydrostatic mechanical stresses. The interstitial and substitutional chemical components are treated separately using chemical potentials and diffusion potentials, respectively. All interface excess quantities are derived using Cahn's (1979) generalized excess method without resorting to geometric dividing surfaces. We present expressions for the interface free energy as an excess quantity and derive a generalized adsorption equation and an interface Gibbs-Helmholtz equation that does not contain the interface entropy. The interface stress tensor emerges naturally from the generalized adsorption equation as an appropriate excess over bulk stresses and is shown to be generally nonunique. Another interface property emerging from the generalized adsorption equation is the interface excess shear. This property is specific to coherent interfaces and represents the thermodynamic variable conjugate to the shear stress applied parallel to the interface. The theory reveals a number of Maxwell relations describing cross effects between thermal, chemical, and mechanical responses of coherent interfaces. In Part II of this work, this theory will be applied to atomistic computer simulations of grain boundaries.
机译:我们提出了在非静力学应力作用下的多组分系统中平面相干固-固界面的热力学理论。分别使用化学势和扩散势分别处理间隙和替代化学成分。所有界面多余量都是使用Cahn(1979)的广义多余方法得出的,而无需求助于几何分割面。我们给出了界面自由能作为过量的表达式,并导出了一个广义吸附方程和一个不包含界面熵的界面Gibbs-Helmholtz方程。界面应力张量从广义吸附方程中自然地出现,比整体应力适当地过量,并且被证明通常是不唯一的。从广义吸附方程式得出的另一种界面性质是界面过量剪切。此属性特定于相干界面,代表与平行于界面施加的剪应力共轭的热力学变量。该理论揭示了许多麦克斯韦关系,描述了相干界面的热,化学和机械响应之间的交叉效应。在这项工作的第二部分中,该理论将应用于晶粒边界的原子计算机模拟。

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