Pyrolysis Kinetics-Driven Resin Optimization for Enhanced Reliability in Ceramic Vat Photopolymerization Manufacturing

Thermal debinding represents a critical step that determines the overall success or failure in ceramic vat photopolymerization manufacturing (ceramic VPP), which involves the pyrolysis and subsequent removal of resin (binder). Despite its importance, research into the underlying mechanisms of resin pyrolysis has been largely overlooked. In this study, the multi-distribution activation energy model (M-DAEM) with the pattern-search method and local search algorithms and thermogravimetric data were employed to obtain the kinetic parameters of the resin cross-linked network in printed Si₃N₄ green bodies containing monomers with different functionalities, including HEA, HDDA, and PPTTA. High-quality global fitting results were achieved with R² values exceeding 0.9999 across all samples. The kinetics model was further utilized for the numerical analysis of the gas pressure inside the green body during the debinding process. This study indicates that monofunctional monomers can effectively reduce the activation energy of the primary pseudo-components, enabling pyrolysis to occur at a lower temperature and a lower rate, suppressing the peak value of gas pressure, and promoting high-quality debinding of the green body. This study can provide a reference for optimizing the resin formulation in ceramic VPP from the perspective of enhancing debinding performance.