Defect-regulated synthesis of ZrB2 powders via carbon thermal reduction and elucidation of its hot-pressing densification mechanism

Abstract

Through defect modulation, ZrB2 powder was controllably synthesized using the carbon thermal reduction (CTR) method, with boron powder serving as a novel additive. Thermodynamic data for the ZrO2-B2O3-C system in the presence of boron were calculated using HSC thermodynamic software. Additionally, TG-DSC thermal analysis combined with XRD was used to investigate the reaction process. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) were used to analyze the defect structure and grain surface characteristics of the reaction products. The results indicate that the reaction of B with ZrO2 and C exothermically alters the nucleation environment of ZrB2 grains. The helical dislocations generated act as a source of crystal growth steps, promoting the growth of smooth interfaces and leading to a transformation of the ZrB2 grain growth mechanism. Quantitative calculations of the dislocation density of ZrB2 powders, using the convolutional multiple whole profile fitting (CMWP-fit), suggest that the inclusion of boron as an additive can modulate the defect concentration of the products. ZrB2 powders with varied dislocation densities were achieved through meticulously controlled synthesis methods, followed by subsequent densification via hot pressing sintering. The results indicated that the relative density of ZrB2 ceramics increased from 83.9 % to 96.7 % as the dislocation density of the powder increased from 2.7 × 1013 m−2 to 7.6 × 1014 m−2 with the rise in boron content from 0 wt% to 3 wt%. In addition, the defects create extra sintering-driving forces that induce a shift in the densification mechanism from grain boundary diffusion to dislocation slip during hot-pressing sintering. This shift results in an increase in the apparent activation energy from 105 kJ/mol to 210 kJ/mol.