Effects of dopants with various valences on densification behavior and phase composition of a ZrO2–SiO2 nanocrystalline glass-ceramic

Effects of dopants with different valences on the densification behavior and phase composition of a ZrO₂–SiO₂ nanocrystalline glass-ceramic (NCGC) during pressureless sintering were investigated in this study. The raw powder of Ca²⁺, La³⁺, Ce⁴⁺ and Ta⁵⁺ ions doped ZrO₂–SiO₂ (referred to as Ca-ZS, La-ZS, Ce-ZS, Ta-ZS, respectively) and pure ZrO₂–SiO₂ (PZS) sample were synthesized by sol-gel method, followed by pressureless sintering. Compared with the PZS sample, doping of Ca²⁺ and La³⁺ ions significantly promoted the densification of the NCGCs. The “densification promotion” effect was attributed to the formation of oxygen vacancies and the decrease of SiO₂ viscosity due to doping of aliovalent cations. The dopants with various valences showed significant effects on the phase compositions of the NCGCs during sintering. Doping of Ca²⁺ ion accelerated the reaction kinetics between ZrO₂ nanocrystallites and amorphous SiO₂ to yield ZrSiO₄. The La³⁺ ion acted as destabilizer of t-ZrO₂, which resulted in a rapid tetragonal (t) to monoclinic (m) ZrO₂ phase transformation during sintering, while in the Ta⁵⁺ and Ce⁴⁺ ions doped sample, the phase transformation occurred gradually. All the doping ions increased the lattice parameters and the volume of t-ZrO₂ unit cell, while the effects of the doping ions on the lattice parameters of m-ZrO₂ unit cell were more complex.