Photopolymerizations, in which the initiation of a chemical-physical reaction occurs by the exposure of photosensitive monomers to a high-intensity light source, have become a well-accepted technology for manufacturing polymers. Providing significant advantages over thermal-initiated polymerizations, including fast and controllable reaction rates, as well as spatial and temporal control over the formation of material, this technology has found a large variety of industrial applications. The reaction mechanisms and kinetics are quite complex as the system moves quickly from a liquid monomer mixture to a solid polymer. Therefore, the study of curing kinetics is of utmost importance for industrial applications, providing both the understanding of the process development and the improvement of the quality of parts manufactured via photopolymerization. Consequently, this review aims at presenting the materials and curing chemistry of such ultrafast crosslinking polymerization reactions as well as the research efforts on theoretical models to reproduce cure kinetics and mechanisms for free-radical and cationic photopolymerizations including diffusion-controlled phenomena and oxygen inhibition reactions in free-radical systems.

Material extrusion‐based additive manufacturing, also known as fused filament fabrication (FFF) or 3D printing facilitates the fabrication of cranial implants with different materials and complex internal structures. The impact behavior plays a key role in the designing process of cranial implants. Therefore, the performance of impact tests on novel implant materials is of utmost importance. This research focuses on investigating the dependency of the infill density and pattern on the impact properties of 3D‐printed poly(methyl methacrylate) (PMMA) sandwich specimens including internal rectilinear, gyroid, and 3D‐honeycomb (3D‐HC) structures. 3D‐HC structures show higher impact forces and dissipated energies as well as dynamic stiffness values compared to rectilinear and gyroid structures at the same infill density. 70% infill 3D‐HC and 100% infill rectilinear structures prove to be most promising. In addition, two different optimization techniques to further improve the impact properties of these specimens, namely a material and a topology optimization, are applied. Topology optimization shows promising results until first damage and material optimization regarding dissipated energies. However, both are not able to outperform the 3D‐HC pattern.

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