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This review outlines the essence of a progressive study on the glassy inter-granular film (IGF) in a model ceramic system, the low-CaO-doped HIPed high-purity Si 3 N 4 . This was initiated from the finding of a systematic variation of equilibrium IGF thickness following the dopant chemistry, manifesting its fundamental important to ceramic processing. By employing analytical transmission electron microscopy to measure the local chemistry in IGF, however, significant discrepancy was found between trends of local IGF chemistry and thickness. A stable IGF composition was revealed in this system, while a bi-level distribution of Ca segregation establishes a correspondence between the IGF structure and the surface crystallography. The detection of similar levels of nitrogen in IGF through the whole series further supports the presence of a rather stable IGF chemistry. After the saturation of dopants in the stable IGF, extra CaO was found to re-distribute in pockets by enrichment at tips, leading to a liquid phase separation with the Ca-rich phase wetting the entrance zone contacting IGF. The perspective for establishing a comprehensive correlation between the inter-granular phases and the bi-modal microstructure induced by faster growth of basal facets is briefly discussed to pave the way for future work.

Inter-granular glassy phases in the low-CaO-doped HIPed Si 3 N 4 ceramics: a review