Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Oxide Additive-Free α- → β-Si3N4 Phase Transformation at 1900 °C

Version 1 : Received: 11 October 2023 / Approved: 12 October 2023 / Online: 12 October 2023 (12:05:43 CEST)

A peer-reviewed article of this Preprint also exists.

Imamura, H.; Kura, K.; Kawata, T.; Honda, S.; Asaka, T.; Iwamoto, Y. Impurity Oxygen-Triggered α- → β-Si3N4 Phase Transformation at 1900 °C. Crystals 2023, 13, 1572. Imamura, H.; Kura, K.; Kawata, T.; Honda, S.; Asaka, T.; Iwamoto, Y. Impurity Oxygen-Triggered α- → β-Si3N4 Phase Transformation at 1900 °C. Crystals 2023, 13, 1572.

Abstract

Oxide additive-free α- ⇀ β-Si3N4 phase transformation of a high-purity commercial α-Si3N4 powder was investigated at 1600 to 1900 ℃ under nitrogen pressure of 980 kPa. The XRD analysis revealed that the α- ⇀ β-Si3N4 phase transformation proceeded mainly at 1900 ℃, and was completed by the extensive 1900 ℃-heat treatment for 20 h. This phase transformation temperature was 33 ℃ lower than the theoretical α-Si3N4 dissociation temperature and confirmed as completely different from that often discussed for the liquid phase sintering of α-Si3N4 powder by direct comparison with the phase transformation behavior of a reference powder, α-Si3N4 powder doped with 1 mol% Y2O3. The unique α- ⇀ β-Si3N4 phase transformation was further studied by a set of characterization techniques including elemental analysis, HAADF-STEM and STEM-EDS analyses. The results strongly suggested that the oxide additive-free α- ⇀ β-Si3N4 phase transformation was governed by the for-mation of metastable solid solution between α-Si3N4 and impurity oxygen of approximately 0.6 wt%, which promoted the dissociation below the theoretical α-Si3N4 dissociation temperature to afford thermodynamically favorable β-Si3N4. Along with the β-Si3N4 formation, the impurity oxygen was concentrated at the Si3N4 crystal grain boundaries and subsequently released from the sample via the grain boundary diffusion.

Keywords

Silicon nitride; Phase transformation; Oxygen impurity; Metastable solid solution; Grain boundary

Subject

Chemistry and Materials Science, Ceramics and Composites

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