Grain boundary diffusion and grain boundary structures of a Ni-Cr-Fe-alloy: Evidences for grain boundary phase transformations

Grain boundary tracer diffusion of Ni, Fe and Cr was studied in a Ni-base 602CA coarse-grained alloy. A co-existence of several short-circuit contributions was distinguished at higher temperatures in Harrison's B-type regime (773-873 K), which were related to different families of high-angle grain boundaries with distinct coverages by precipitates and segregation levels as revealed by HAADF-STEM combined with EDX measurements. Annealing at 873 K for 18 hours resulted in Cr23C6-type carbides coexisting with an α-Cr-Mn-enriched phase in addition to sequential segregation layers of Al, Fe and Ni around them. Curved and hackly grain boundaries showed a high density of plate-like carbides, whereas straight grain boundaries were composed of globular carbides with similar chemical composition variations and additionally with alternating layers of Cr and Ni in between the carbides, similar to microstructures after a spinodal decomposition. At lower temperatures, discontinuous interfaces with Cr and Cr-carbide enrichment dominated and the alloy annealed at 403 K for 72 hours contained plate-like Cr23C6-type carbides surrounded by a Ni-rich layer around them. The Ni grain boundary diffusion rates at these relatively low temperatures (formally belonging to C-type kinetics) showed an anomalous character being almost temperature independent. This specific diffusion behaviour was explained by a concomitant relaxation of transformation-induced elastic strains occurring on a longer time scale with respect to grain boundary diffusion. Thermodynamic insights into the probable mechanism of decomposition at grain boundaries are provided.