Diffusion of hydrogen in titanium alloys due to composition, temperature, and stress gradients

Abstract

A theoretical and experimental study was conducted to determine the combined effects on interstitial diffusion in metals of gradients in interstitial concentration, in solvent composition, in stress, and in temperature. The theory consolidates relationships, some of which have been previously published. It is based on macroscopic irreversible thermodynamics, and is applicable to anisotropic or Isotropic materials. Experiments were conducted and literature analyzed to determine the numerical quantities required to predict the change in hydrogen distribution with time for pure and alloy titanium, where the solvent gradient, stress gradient, and temperature gradient are constant with time. The diffusion driving forces for solute gradient, solvent gradient, and stress gradient are related to the effect of each factor on hydrogen activity. In addition, the material property which determines the diffusion driving force of a stress gradient for anisotropic material is a matter tensor analogous to the scalar partial molal volume used for isotropic material. The experiments, conducted with commercially pure titanium and titanium alloy, 6A1-4V, consist of measuring the effect of alloy additions and stress on the hydrogen activity in solid solution and the dilatation effect of hydrogen. Stress states tested were tension, compression, and torsion. The measurements were made by exposing titanium and the alloy to hydrogen at temperatures from 600° to 800° C, and measuring the equilibrium hydrogen gas pressure at various solid solution hydrogen contents. Both materials were tested with and without stress. Tension decreased the activity, compression increased it, and torsion had no effect. This is consistent with the stress effect theory of Li, Oriani, and Darken. The stress effect corresponds to an apparent partial molal volume of 1.7 to 2.2 cm³/mol, depending on the alloy and hydrogen content.