Vat photopolymerization of silica reinforced styrene-butadiene rubber elastomeric nanocomposites

Abstract

Compared to their unfilled counterparts, elastomeric nanocomposites offer tailorable combinations of properties, including improved mechanical properties, increased durability, and enhanced thermal and electrical conductivity. However, the high viscosity caused by the presence of both the high molecular weight elastomer and the inclusion of fillers complicates additive manufacturing (AM) of elastomeric nanocomposites. This is especially challenging in vat photopolymerization (VP) AM, which requires resins that possess low viscosity (< 10 Pa·s) and exhibit sufficient storage modulus (∼ 104 Pa) when photocured. To address this process limitation, the authors have previously demonstrated decoupling the relationship between viscosity and molecular weight via VP of a photocurable composite latex resin. In this approach, a photocurable matrix is photocured as a scaffold around the latex particles, which provides sufficient modulus for the printed "green" part. Following a dehydration post-processing step, the latex particles coalesce to provide the final elastomeric mechanical properties without compromising feature resolution.In this work, the authors explore the effects of the addition of silica nanoparticles (10, 15, and 20 wt.%) on (i) the printability of photocurable styrene-butadiene rubber (SBR) latex resin and (ii) the mechanical properties of the resultant printed composites. The printable photocurable silica-SBR colloidal resin is realized by balancing the viscosity of the resin, the modulus of the cured green body, the silica nanoparticles content for reinforcement, and the high SBR content for elastomeric behavior. Specifically, the photocurable colloidal resin's viscosity is controlled by formulation design, while high silica nanoparticle content in the final part is achieved through evaporation of unreactive diluent. Characterization of the printed SBR nanocomposites with 20 wt.% silica reinforcement elucidated significant enhancements in the tensile strength (53 % increase), Young's modulus (671 % increase), and Shore A hardness (108 % increase) compared to printed SBR without filler reinforcement. To the authors' knowledge, this is the first report of 3D printing rubber nanocomposite using VP.