Grain boundary segregation induced precipitation in a non equiatomic nanocrystalline CoCuFeMnNi compositionally complex alloy

Abstract Compositionally complex alloys (CCAs) in a nanocrystalline state often involve complex and poorly understood phase transformations which can consequently result in grain growth even at low temperatures. A detailed study of the microstructure and phase stability in CCAs is challenging due to the presence of multiple principal components. In view of these challenges the objective of the present study is to establish a systematic understanding of the phase evolution in a face centered cubic non equiatomic nanocrystalline CCA (CoCuFeMnNi). To accomplish this objective, we employed in-situ transmission electron microscope heating in combination with automated crystal orientation mapping (ACOM) and energy filtered transmission electron microscopy (EFTEM) to elucidate the sequence of phase decomposition of the high-pressure torsion (HPT) processed CoCuFeMnNi. Our analysis reveals a complex succession of grain boundary segregation and depletion steps leading to the formation of a FeCo-rich secondary phase. Our results show that prior to the formation of the secondary phase, Cu, Ni and Co segregate and Fe and Mn deplete at the grain boundaries. After the FeCo precipitation is triggered, Mn segregates to the grain boundaries along with Ni and Cu, whereas Fe and Co are depleted. The FeCo precipitates have a B2 crystal structure and typically exhibit a Kurdjumov-Sachs (K-S) and/or Nishyama-Wasserman (N-W) orientation relationships with adjacent fcc grains. Ex-situ heat treated CoCuFeMnNi analyzed by atom probe tomography (APT) revealed a highly heterogeneous segregation of the different elements to different grain boundaries. The FeCo-rich precipitates contain trace amounts of Ni, whereas Cu is rejected leading to the formation of a separate Cu rich phase. This complex segregation phenomenon is assisted by the high fraction of grain boundaries and triple junctions in the nanocrystalline material, which are critical for the phase evolution in this alloy, which is not frequently observed in the corresponding coarse-grained material.