Modification of mechanical properties and resolution of printed stereolithographic objects through RAFT agent incorporation

Stereolithography (SL) is an additive manufacturing technique that uses light to cure liquid resins into thin layers and fabricate 3-dimensional objects layer by layer. SL is of high interest for small-volume manufacturing and rapid prototyping because of its ability to relatively quickly create objects with intricate 100 mu m or smaller features. However, widespread adoption of SL faces a number of obstacles including unsuitable thermomechanical properties, anisotropic properties, and limited resolution and fidelity. In this work, we incorporate a reversible addition-fragmentation chain transfer (RAFT) agent into a glassy acrylate formulation to modify mechanical properties and improve resolution of objects printed using digital light processing (DLP) SL. Incorporating a small amount of a trithiocarbonate RAFT agent into the formulation leads to increased elongation and toughness accompanied by a small decrease in tensile modulus. To determine anisotropic properties of DLP SL, samples were printed in "horizontal" or "vertical" directions, where the long axis of the sample was printed in the x-axis or z-axis, respectively. RAFT samples printed in a vertical orientation exhibit a higher modulus than non-RAFT controls prior to post-cure in addition to a similar modulus with increased toughness upon UV post-cure due to the living/controlled nature of RAFT polymerization. Furthermore, incorporating a RAFT agent into the formulation allows significantly higher fidelity printing of a broad range of positive and negative features as small as 100 mu m. The RAFT formulation allows objects to be printed with significantly better fidelity than non-RAFT formulations, even when a radical scavenger is incorporated to mimic reaction rates observed from the RAFT formulation. Additionally, the RAFT agent significantly increases the critical energy parameter determined from the SL working curve, indicating an increase in gel point conversion. This work demonstrates the benefits of using controlled/living polymerization in a highly cross-linked acrylate system to improve toughness, modify anisotropic properties, and print high-fidelity features with enhanced properties in 3D printed materials.