In recent years, vat 3D printing has emerged as a prominent technique for fabricating complex high-resolution structures. However, the performance of printed components is strongly influenced by the properties of photopolymerizable resins. To address the growing demand for advanced materials with enhanced mechanical, thermal, and other functional properties, nanocomposite resins incorporating metal oxide nanoparticles have been explored. This dissertation investigates the preparation, 3D printing, and performance of nanocomposite photopolymerizable resins reinforced with semiconducting metal oxide nanoparticles, focusing on their impact on the photopolymerization reaction and photoactivity. This study explores the influence of nanoparticles such as ZnO, alumina-doped ZnO, and TiO2 on both free-radical and cationic photoinitiation mechanisms, revealing how nanoparticle concentration, type, and band gap energy affect the monomer conversion and curing efficiency. Different analytical techniques were employed to evaluate the effect of the nanoparticles on the photocuring reaction and its kinetics, with real-time FTIR providing the most reliable results. AZO nanoparticles had a significant positive effect on the photopolymerization of acrylate resin, whereas ZnO nanoparticles did not exhibit similar improvements. TiO2 nanoparticles in anatase and rutile forms were found to influence free-radical polymerization differently, with rutile nanoparticles showing better performance under 405 nm light, while anatase nanoparticles performed better under 365 nm light. In the cationic mechanism, anatase nanoparticles acted as more effective photosensitizers, improving monomer conversion and reaction kinetics. Additionally, the thermomechanical, electrical, and dielectric properties of vat 3D printed nanocomposites were evaluated, highlighting the nanoreinforcement effect and identifying a percolation threshold in electrical properties.
These findings provide valuable insights into the roles of semiconducting metal oxide nanoparticles in photoinitiation and photosensitization, offering guidance for optimizing vat 3D printing processes and enhancing the functionality of 3D printed structures. This dissertation advances the field of vat photopolymerization by contributing to the development of high-performance materials with broad applications across various industries.