3D printing of crack-free dense polymer-derived ceramic monoliths and lattice skeletons with improved thickness and mechanical performance

Previous research often failed to prepared polymer-derived SiOC ceramic components with dense and thick monoliths/skeletons based on additive manufacturing processes, due to the porosities and cracks generated during the pyrolysis process. Herein, we report a simple solution which combines the introduction of phenolic resin (PR) as an additive and the use of controlled strategy of pyrolysis, for the vat photopolymerization additively manufactured SiOC ceramics. As a result, crack-free dense monolith and lattice skeleton structural polymer-derived SiOC ceramics are successfully prepared despite the low ceramic yield of 19.3 wt% and large linear shrinkage of 50% generated after pyrolysis. The prepared dense monoliths possess a thickness of over 5 mm and the lattices show attainable maximum dense skeletons thickness of ~2 mm. The maximum dense thickness of the samples after pyrolysis is over 7 times that of other samples prepared based on additive manufacturing reported in the literature. As an indicator of dimensional retention, the specific dense thickness to ceramic yield ratio (T/Y) is deduced, resulting maximum values of 101.9 µm/(wt%) for lattice skeletons and 254.7 µm/(wt%) for monoliths. The former is even larger than that for dense monolith SiOC structures prepared by other conventional gel casting and isostatic pressing techniques with much higher ceramic yields of > 80 wt%, and is about 6.1 times the largest T/Y ratio (=16.7 µm/(wt%)) achievable in the AM-based works reported in the literature. This shows predominance of the current work over other types of polymer-derived ceramic structures prepared by additive manufacturing and even conventional methods. The lattice structures’ apparent density and specific strength reached 0.55 g/cm 3 and 6.6 × 10 4 N∙m/kg, respectively. The mechanical performance surpasses other structural polymer-derived ceramic structures with similar apparent density reported in the literature. Through the advanced characterization and analysis of material phase and morphology evolution during the pyrolysis process, the mechanism of defect-free densification is revealed. That is, the introduction of PR enables a highly smooth gas-releasing process due to the generation of ordered gas-releasing channels in the sample bodies during the pyrolysis process. As a result, the generation of cracks and defects was successfully prevented. Moreover, due to the high carbon residue of the PR, the samples containing 15 wt% PR in the preceramic state still possessed amorphous SiOC ceramics after pyrolysis at 1400 ℃, while 0 wt% PR samples showed SiC crystallization. Compared with similar materials reported, the ceramics prepared in this study exhibit enhanced structural and mechanical performance. The strategy investigated in the study can be a viable route for the additive manufacturing of high-performance crack-free and thick monolith and lattice skeleton SiOC ceramic structures based on vat photopolymerization.