Polymer-derived ceramics (PDCs) have many advantages in ceramic molding and ceramic properties, but because of the obvious volume shrinkage in the process of precursor transformation into ceramics, it is easy for defects to appear in the forming process of bulk PDCs. Herein, theoretical analyses and experimental studies were carried out to improve the quality of sintered samples and realize the parametric design of raw materials. Firstly, based on the HPSO/D4Vi cross-linking system, the mathematical model of the free cross-linking ratio was established, and the theoretical value was calculated. After that, the samples with different free cross-linking rates were heated at 450 °C and 650 °C for different holding times. It was found that the free cross-linking ratio (α) had a significant impact on the weight loss of the samples. When the difference of the α value was 10%, the difference of the samples' weight loss ratio could reach 30%. Finally, the morphology of sintered products with different α values was analyzed, and it was found that obvious defects will occur when the free cross-linking ratio is too high or low; when this value is 40.8%, dense and crack-free bulk ceramics can be obtained. According to analysis of the chemical reaction and cross-linking network density during sintering, the appropriate value of the free cross-linking ratio and reasonable control of the cross-linking network are beneficial for reducing the loss of the main chain element and C element, alleviating the sintering stress, and thus obtaining qualified pressureless sintered bulk ceramic samples.
Keywords: HPSO/D4Vi; SiOC ceramics; bulk ceramics; free cross-linking rate; polymer-derived ceramics.