Silicon nitride is a solid compound which can be formed by direct reaction between silicon and nitrogen. It appears in three distinct phases characterized by their crystalline structure, namely:
- The α and β phases, which are the most common, display hexagonal crystal structures (corner-sharing, tetrahedral SiN4 with strong Si-N bonds resulting in a rigid, layered 3D framework). Both these phases are synthesized at normal pressures; the α phase forms at low temperatures with the transition into the β phase occurring between 1,400°C and 1,600°C.
- The γ phase, which only forms at high temperatures and pressures.
Sintering Additives
Sintering is a heat treatment process commonly applied to powders. In order to control the formation of microstructures — i.e., the formation of covalent bonded structures resulting in material toughness — the introduction of sintering additives during production is crucial. Rare earth and metal oxides such as Yttrium oxide (Y2O3) and Aluminum Oxide (Al2O3) are common sintering additives.
In one study, it was observed that:
- Despite fractional increases of β-Si3N4 (from 7.67 to 57.34 wt%) during the initial α to β phase transformation, average grain size and hardness (ca. 20 GPa) remain unchanged. Thereafter, grains adopt a rod-like structure accompanied by a substantial increase in fracture toughness (from 3.36 to 7.11 MPaM1/2).
- During second stage sintering, β-Si3N4 reaches 100.00 wt% accompanied by a rapid increase in grain size. This results in a fractional increase in fracture toughness (from 7.11 to 7.61 MPaM1/2) against a noticeable reduction in hardness (from 20 GPa to 16.80 GPa).
It has been shown that introducing a high-hardness second phase — such as silicon carbide (SiC), titanium carbide (TiC), or titanium nitride (TiN) — improves the fracture toughness and hardness of silicon nitride engineering materials. This shows that bimodal microstructured ceramics (α- and β-phases) can be tailored for the production of optimally performing materials.