UV‐curing 3D printing technology is one of the technologies with the highest molding efficiency and accuracy in the field of 3D printing. At present, the main problems of UV‐curing 3D printing materials include the high curing shrinkage and the low toughness. In this work, free radical/cation hybrid curing system was developed, the effects of expansion monomer (DHOM, 3,9‐diethyl‐3′,9′‐dihydro‐xymethyl‐1,5,7,11‐tetraoxaspiro[5,5]undecanone) on the curing shrinkage, toughness, and other properties of the epoxy acrylate‐based UV‐curing 3D printing materials were investigated. The results showed that when the added amount of DHOM was 15 wt%, the best comprehensive performance of UV‐curing 3D printing materials was obtained. At this time, the curing shrinkage rate decreased from 6.13% to 3.47%. The main reason was that DHOM undergoes ring‐opening polymerization under the action of cationic photoinitiator, resulted in volume expansion. The impact strength increased from 9.61 to 12.13 KJ/m2, which was because that the ring‐opening reaction of DHOM reduced the curing shrinkage of the resin system and released the internal stress between the resin molecules.
Ultraviolet curing three dimensional printing (3DP), as an additive manufacturing technology, possesses relatively higher forming precision and faster forming speed, However, its low mechanical properties limit its applications. In this work, the morphology and properties of epoxy acrylate matrix 3DP materials modified by MethacrylPhenyl polyhedral oligomeric silsesquioxanes (MP-POSS) at different loadings (wt% = 0, 1, 3, 5, 7) were studied. The XRD and FTIR analysis indicated that MP-POSS chemically incorporated into the hybrid materials by copolymerization. The morphological analysis showed that POSS rich particles appeared when POSS loading was 5 wt%, the mean diameter of POSS rich particles increased with the increasing of POSS loadings, and the POSS rich particles agglomerated obviously when POSS loading reached 7 wt%. The tensile strength and the impact strength of the nanocomposites with 5 wt% POSS were increased to 48.9 MPa and 12.8 kJ/m 2 which were 150.9% and 162.1% compared with the unfilled materials. Analyzed with the SEM images of fracture surfaces, the mechanical properties may depend on the synergistic effect of reactive POSS nanocages and unreactive POSS rich particles. TGA and DTG curves showed the enhancement of the thermal stability of the nanocomposites at the later period of degradation process.
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