Mechanically Robust and UV-Curable Shape-Memory Polymers for Digital Light Processing Based 4D Printing.

4D printing is an emerging fabrication technology that enables 3D printed structures to change configuration over "time" in response to an environmental stimulus. Compared with other soft active materials used for 4D printing, shape-memory polymers (SMPs) have higher stiffness, and are compatible with various 3D printing technologies. Among them, ultraviolet (UV)-curable SMPs are compatible with Digital Light Processing (DLP)-based 3D printing to fabricate SMP-based structures with complex geometry and high-resolution. However, UV-curable SMPs have limitations in terms of mechanical performance, which significantly constrains their application ranges. Here, a mechanically robust and UV-curable SMP system is reported, which is highly deformable, fatigue resistant, and compatible with DLP-based 3D printing, to fabricate high-resolution (up to 2 µm), highly complex 3D structures that exhibit large shape change (up to 1240%) upon heating. More importantly, the developed SMP system exhibits excellent fatigue resistance and can be repeatedly loaded more than 10 000 times. The development of the mechanically robust and UV-curable SMPs significantly improves the mechanical performance of the SMP-based 4D printing structures, which allows them to be applied to engineering applications such as aerospace, smart furniture, and soft robots.

Highly stretchable hydrogels for UV curing based high-resolution multimaterial 3D printing.

We report a method to prepare highly stretchable and UV curable hydrogels for high resolution DLP based 3D printing. Hydrogel solutions were prepared by mixing self-developed high-efficiency water-soluble TPO nanoparticles as the photoinitiator with an acrylamide-PEGDA (AP) based hydrogel precursor. The TPO nanoparticles make AP hydrogels UV curable, and thus compatible with the DLP based 3D printing technology for the fabrication of complex hydrogel 3D structures with high-resolution and high-fidelity (up to 7 µm). The AP hydrogel system ensures high stretchability, and the printed hydrogel sample can be stretched by more than 1300%, which is the most stretchable 3D printed hydrogel. The printed stretchable hydrogels show an excellent biocompatibility, which allows us to directly 3D print biostructures and tissues. The great optical clarity of the AP hydrogels offers the possibility of 3D printing contact lenses. More importantly, the AP hydrogels are capable of forming strong interfacial bonding with commercial 3D printing elastomers, which allows us to directly 3D print hydrogel-elastomer hybrid structures such as a flexible electronic board with a conductive hydrogel circuit printed on an elastomer matrix.

Highly Stretchable and UV Curable Elastomers for Digital Light Processing Based 3D Printing.

Stretchable UV-curable (SUV) elastomers can be stretched by up to 1100% and are suitable for digital-light-processing (DLP)-based 3D-printing technology. DLP printing of these SUV elastomers enables the direct creation of highly deformable complex 3D hollow structures such as balloons, soft actuators, grippers, and buckyball electronical switches.

Multimaterial 4D Printing with Tailorable Shape Memory Polymers.

We present a new 4D printing approach that can create high resolution (up to a few microns), multimaterial shape memory polymer (SMP) architectures. The approach is based on high resolution projection microstereolithography (PµSL) and uses a family of photo-curable methacrylate based copolymer networks. We designed the constituents and compositions to exhibit desired thermomechanical behavior (including rubbery modulus, glass transition temperature and failure strain which is more than 300% and larger than any existing printable materials) to enable controlled shape memory behavior. We used a high resolution, high contrast digital micro display to ensure high resolution of photo-curing methacrylate based SMPs that requires higher exposure energy than more common acrylate based polymers. An automated material exchange process enables the manufacture of 3D composite architectures from multiple photo-curable SMPs. In order to understand the behavior of the 3D composite microarchitectures, we carry out high fidelity computational simulations of their complex nonlinear, time-dependent behavior and study important design considerations including local deformation, shape fixity and free recovery rate. Simulations are in good agreement with experiments for a series of single and multimaterial components and can be used to facilitate the design of SMP 3D structures.