Color-Changeable Four-Dimensional Printing Enabled with Ultraviolet-Curable and Thermochromic Shape Memory Polymers

Four-dimensional (4D) printing, which enables 3D printed structures to alter shapes over time, is attracting increasing attention because of its exciting potential in various applications. Among all the 4D printing materials, shape memory polymers (SMPs) have a higher stiffness and faster response rate and therefore are considered as one of the most promising 4D printing materials. However, the current studies of SMP-based 4D printing mainly focused on the deformation behavior and structural design of 4D printed structures. An additional function such as color change is desired for 4D printed structure, which would be potentially beneficial to the applications such as anti-counterfeiting, encryption, and bioinspired camouflage. In this paper, we report an ultraviolet (UV)-curable and thermochromic (UVT) SMP system that enables color-changeable 4D printing. The UVT SMP system is acrylate-based, thus highly UV-curable and compatible with PμSL-based high-resolution 3D printing technique. Thermochromism is imparted by adding the thermochromic microcapsules to the UVT SMP system, which allows the printed structures to reversibly change colors upon heating and cooling. To demonstrate its extraordinary thermochromic and mechanical performance, we use UVT SMP to print QR codes and multilevel anti-counterfeiting patterns which can hide the visible information at room temperature and visualize the information by encrypting, decrypting, and encrypting again steps with the shape-color recovery process. The development of UVT SMP will significantly advance current applications of SMP-based 4D printing, especially for anti-counterfeiting and safe data recording.