Vat Photopolymerization of High-Performance Materials through Investigation of Crosslinked Network Design and Light Scattering Modeling

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Virginia Tech

The reliance on low-viscosity and photoactive resins limits the accessible properties for vat photopolymerization (VP) materials required for engineering applications. This has limited the adoption of VP for producing end-use parts, which typically require high MW polymers and/or more stable chemical functionality. Decoupling the viscosity and molecular weight relationship for VP resins has been completed recently for polyimides and highperformance elastomers by photocuring a scaffold around polymer precursors or polymer nanoparticles, respectively. Both of these materials are first shaped by printing a green part followed by thermal post-processing to achieve the final part properties. This dissertation focuses on improving the processability of these material systems by (i) investigating the impact of scaffold architecture and polysalt monomer composition on photocuring, thermal post-processing, and resulting thermomechanical properties and (ii) developing a Monte Carlo ray-tracing (MCRT) simulation to predict light scattering and photocuring behavior in particle-filled resins, specifically zinc oxide nanoparticles in a rigid polyester resin and styrene butadiene rubber latex resin. The first portion of the dissertation introduces VP of a tetra-acid and half-ester-based polysalt resin derived from 4,4'-oxydiphthalic anhydride and 4,4-oxydianiline (ODPA-ODA), a fully aromatic polyimide with high glass transition temperature and thermal stability. This polyimide, and polyimides like this, find use in demanding industries such as aerospace, automotive and electronic applications. The author evaluated the hypothesis that a non-bound triethylene glycol dimethacrylate (TEGDMA) scaffold would facilitate more efficient scaffold burnout and thus achieve parts with reduced off-gassing potential at elevated temperatures. Both resins demonstrated photocuring and were able to print solid and complex latticed parts. When thermally processed to 400 oC, only 3% of the TEGDMA scaffold remained within the final parts. The half-ester resin exhibits higher char yield, resulting from partial degradation of the polyimide backbone, potentially caused by lack of solvent retention limiting the imidization conversion. The tetra-acid exhibits a Tg of 260oC, while the half-ester displays a higher Tg of 380 oC caused by the degradation of the polymer backbone, forming residual char, restricting chain mobility. Solid parts displayed a phase-separated morphology while the half-ester latticed parts appear solid, indicating solvent removal occurs faster in the half-ester composition, presumably due to reduced polar acid functionality. This platform and scaffold architecture enables a modular approach to produce novel and easily customizable UV-curable polyimides to easily increase the variety of polyimides and the accessible properties of printed polyimides through VP. The second section of this dissertation describes the creation and validation of a MCRT simulation to predict light scattering and the resulting photocured shape of a ZnO-filled resin nanocomposite. Relative to prior MCRT simulations in the literature, this approach requires only simple, easily acquired inputs gathered from dynamic light scattering, refractometry, UV-vis spectroscopy, beam profilometry, and VP working curves to produce 2D exposure distributions. The concentration of 20 nm ZnO varied from 1 to 5 vol% and was exposed to a 7X7 pixel square ( 250 µm) from 5 to 11 s. Compared to experimentally produced cure profiles, the MCRT simulation is shown to predict cure depth within 10% (15 µm) and cure widths within 30% (20 µm), below the controllable resolution of the printer. Despite this success, this study was limited to small particles and low loadings to avoid polycrystalline particles and maintain dispersion stability for the duration of the experiments. Expanding the MCRT simulation to latex-based resins which are comprised of polymer nanoparticles that are amorphous, homogeneous, and colloidally stable. This allows for validating the MCRT with larger particles (100 nm) at higher loadings. Simulated cure profiles of styrene-butadiene rubber (SBR) loadings from 5 vol% to 25 vol% predicted cure depths within 20% ( µm) and cure widths within 50% ( µm) of experimental values. The error observed within the latex-based resin is significantly higher than in the ZnO resin and potentially caused by the green part shrinking due to evaporation of the resin's water, which leads to errors when trying to experimentally measure the cure profiles. This dissertation demonstrates the development of novel and functional materials and creation process-related improvements. Specifically, this dissertation presents a materials platform for the future development of unique photocurable engineering polymers and a corresponding physics-based model to aid in processing.

Vat Photopolymerization, Polyimide, Additive Manufacturing, 3D Printing, Light Scattering, Monte Carlo Ray-Tracing