SUMMARY

The research is aimed at exploring the thermo-mechanical properties of thiol-ene polymers in bulk form, investigating the ability of thiol-ene polymers to behave desirably as photolithographic media, and providing the first characterization of the mechanical properties of two-photon stereolithography-produced polymer structures. The thiol-ene polymerization reaction itself is well-characterized and described in the literature, but the thermomechanical properties of thiol-ene and thiol-ene/acrylate polymers still require more rigorous study. Understanding the behavior of thiol-ene networks is a crucial step towards their expanded use in bulk forms. Additionally, the thiol-ene polymerization reaction mechanism exhibits unique properties which make these polymers well suited to photolithography, overcoming the typical dichotomy of current materials which either exhibit excellent photolithographic behavior or have controllable properties. Finally, before two-photon stereolithography can create mechanisms and devices which can serve any mechanically functional role, the mechanical properties of the polymers they produce must be quantitatively characterized, which is complicated by the extremely small scale at which these structures are produced. Characterization of bulk materials was both mechanical and chemical. Fourier transfer infrared spectroscopy revealed functional group conversion information and sol-fraction testing revealed the presence of unconverted monomer and impurities, while dynamic mechanical analysis (DMA) and tensile testing revealed the thermomechanical responses of the systems. Nanoindentation was employed to characterize the mechanical properties of micrometer-scale polymer structures produced by two-photon stereolithography. Optical and electron microscopy were exploited to provide both quantitative and qualitative evaluations of thiol-ene and thiol-ene/acrylate performance in small-scale polymerization regimes.