The effect of special grain boundary development via the grain boundary engineering process (GBE) was explored in a bimodal microstructured 316L austenitic stainless steel with an average grain size of 1.92 μm. The GBE process was carried out by the rolling-annealing method via two routes of low and medium applied strain, followed by a short annealing period in a single-step and iterative manner. The grain boundary character distribution was obtained by Electron Backscatter Diffraction (EBSD) analysis, and the intergranular corrosion resistance and the tensile behavior of the samples were examined. Microstructural characterization showed that applying low strain repetitively increased the coincidence site lattice (CSL) and Σ3 boundaries percentage and created large twin-related domains (TRD). The reduced sensitization was attributed to a high proportion of CSLs and large-sized TRDs by applying a low-strain route. In the early stages of the low-strain route, the grain boundary character distribution showed a high number of primary twin nuclei in coarse grains and a continuous network of single twin nuclei in smaller grains, creating a high percentage of Σ3-grain boundaries. The low applied strain and the absence of the necessary driving force for the recrystallization and GBs migration led to the formation of twin nuclei, which would assist with the reduction of microstructure energy. A high percentage of Σ3 boundaries and an increase in the percentage of triple points consisting of low energy boundaries were found to be influential factors in increasing elongation.
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