Digital Light Processing 3D Printing of Soft Semicrystalline Acrylates with Localized Shape Memory and Stiffness Control.

Multimaterial three-dimensional (3D) printing of objects with spatially tunable thermomechanical properties and shape-memory behavior provides an attractive approach toward programmable "smart" plastics with applications in soft robotics and electronics. To date, digital light processing 3D printing has emerged as one of the fastest manufacturing methods that maintains high precision and resolution. Despite the common utility of semicrystalline polymers in stimuli-responsive materials, few reports exist whereby such polymers have been produced via digital light processing (DLP) 3D printing. Herein, two commodity long-alkyl chain acrylates (C, stearyl and C, lauryl) and mixtures therefrom are systematically examined as neat resin components for DLP 3D printing of semicrystalline polymer networks. Tailoring the stearyl/lauryl acrylate ratio results in a wide breadth of thermomechanical properties, including tensile stiffness spanning three orders of magnitude and temperatures from below room temperature (2 °C) to above body temperature (50 °C). This breadth is attributed primarily to changes in the degree of crystallinity. Favorably, the relationship between resin composition and the degree of crystallinity is quadratic, making the thermomechanical properties reproducible and easily programmable. Furthermore, the shape-memory behavior of 3D-printed objects upon thermal cycling is characterized, showing good fatigue resistance and work output. Finally, multimaterial 3D-printed structures with vertical gradation in composition are demonstrated where concomitant localization of thermomechanical properties enables multistage shape-memory and strain-selective behavior. The present platform represents a promising route toward customizable actuators for biomedical applications.