Photopatterning Crystal Orientation in Shape-Morphing Polymers.

Shape-morphing polymers have gained particular attention due to their unique capability of shape transformation under numerous external stimuli such as light, pH, and temperature. Their shape-morphing properties can be used in various applications such as robotics, artificial muscles, and biomedical devices. To take advantage of the stimuli-responsive properties of the smart polymers in such applications, programming shape change precisely through a facile synthetic procedure is essential. Programmable shape-morphing is readily obtained in hydrogels and liquid crystal polymer networks, but shape programming of semicrystalline polymers usually relies on low-resolution mechanical deformation. In this paper, a semicrystalline shape-morphing polymer with a controlled shape programmability was developed via photopatterning crystal orientation using a spatially controlled photopolymerization technique. The semicrystalline polymer network forms aligned crystallites at the boundaries between dark and bright regions during photopolymerization using a projector, which introduces an anisotropic stimulus response in the films. The semicrystalline polymer films with photoaligned crystallites expand 9-15% in the direction perpendicular to the patterned lines when heated above the melting temperature. Furthermore, spatially patterning the crystal orientation enables the formation of various complex 3D structures including a helical coil, a coil with a handedness inversion, a cone, a saddle, and a twisting flower. Finally, the magnitude of the shape transformation was controlled by varying the polymerization temperatures, and the actuation temperature was tuned by changing the amount of crystallinity in the polymer films. The simplicity and ease of control of our approach to program complex 3D structures from 2D semicrystalline polymer films make it a promising system for the aforementioned applications.