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Thermodynamics of Solid and Fluid Surfaces

Thermodynamics of Solid and Fluid Surfaces
J. W. Cahn

One hundred years ago, Gibbs developed a thermodynamics of both fluid and solid surfaces that included such topics as adsorption, heat and mechanical surface effects, curved surfaces, homogeneous and heterogeneous nucleation, stability and even grain boundaries. Since this monumental paper, almost everything that has been written has been within the framework of what he bequeathed to us. Some of these papers are easier to read, others are easier to apply, but few match the logic, rigor and scope of the original.

In this paper I will touch briefly on some of the topics which I believe are of interest to metallurgists. In the next two sections I will discuss two more general formulations of planar fluid surfaces. The first avoids the pedagogic problems of the locations of the dividing surface, but is otherwise physically equivalent to Gibbs' formulation. It is also more easily applicable. The key change is that, instead of defining excess quantities by comparing the actual system with a hypothetical system not containing the surface, the present development concentrates on the actual system thereby avoiding the dividing surface and the comparison system. There have been several other developments along these lines which have obvious advantages. The second formulation, based on gradient energy, has been developed in the style of Gibbs. It is equally rigorous but attempts to deal with the surface in greater detail. The fourth section develops the full variation for planar solid-fluid surface including strain and orientation changes. The fifth section discusses twelve Maxwell-type relations for surface thermodynamic variables for solid-fluid interfaces.

Publisher: TMS
Product Format: PDF
Pages: 377-399
Date Published: September 1, 1998
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