Formation of α/β-Si3N4 nanoparticles by carbothermal reduction and nitridation of geopolymers

Silicon nitride (Si₃N₄) particles with various α/β-Si₃N₄ ratios were fabricated from geopolymer (GP)-carbon compositions (M₂O·Al₂O₃·4.5SiO₂·12H₂O+18C), where M is an alkali ion (Na⁺, K⁺ and Cs⁺). They were made by carbothermal reduction and nitridation at 1400°, 1500°, and 1600°C for 2 hours under flowing nitrogen. Characterization of carbothermally reacted GP-carbon compositions was based on XRD, SEM-EDS, HRTEM, and selected area electron diffraction analyses. Depending on the alkaline composition of GP, the carbon content and the reaction temperature, a compositionally variable α/β-Si₃N₄ or SiAlON was achieved. Crystallization of the GPs gradually increased by heat treatment over 1400°C with corresponding weight loss. It was found that NaGP, KGP, and CsGP crystallized into a major phase of α-Si₃N₄, β-Si₃N₄, and SiAlON, respectively. Prolonged heating at 1600°C led to an increase in the α/β-Si₃N₄ ratio in NaGP due to the formation of aluminum nitride, while it led to a decrease in α/β-Si₃N₄ ratio in KGP. In the case of CsGP, SiAlON replaced the pollucite which mainly formed at lower temperatures. Transmission electron microscopy revealed that the needle-like particles were of ~0.5 µm in size and consisting of α/β-Si₃N₄ mixtures.