Intrinsic heterogeneity of grain boundary phase transitions in the Cu–Bi system: insights from grain boundary diffusion measurements

Abstract

Abstract Diffusion of Bi and Ag in a series of polycrystalline Cu–Bi alloys is investigated using a radiotracer technique and applying the 207Bi and 110m Ag isotopes, respectively. Together with the previous measurements (Divinski S., Lohmann M., Herzig C., Straumal B., Baretzky B., Gust W. Grain-boundary Melting Phase Transition in the Cu−Bi System. Phys. Rev. B 2005, 71, 104104), a temperature–concentration interval of strong, by orders of magnitude, enhancements of Bi grain boundary diffusion rates is distinguished and the results are interpreted in terms of a grain boundary pre-wetting/wetting phase transition. Grain boundary diffusivity of Ag exhibits as well a step-wise increase with rising Bi content, mirroring the behaviour observed for the Bi tracer. However, contrary to the Bi tracer atoms for which grain boundary enhancement is observed at about 60 ppm of Bi in Cu–Bi alloys, this transition is revealed by the Ag tracer atoms at a significantly higher concentration, specifically between 90 and 100 ppm of Bi at 1080 K. The Ag diffusion rates in alloys with a moderate Bi content turn out to be not affected by the Bi-induced grain boundary phase transition and the measured grain boundary diffusion coefficients of Ag are nearly the same as those determined for pure polycrystalline Cu. This spectacular result suggests a strong heterogeneity of Bi segregation and Bi-induced phase transition for general high-angle grain boundaries in a given alloy. The behaviour is discussed in terms of the extrinsic grain boundary defects and their impact on mechano-chemical coupling which is accompanying the grain boundary phase transitions.