4D printing has attracted tremendous interest since its first conceptualization in 2013. 4D printing derived from the fast growth and interdisciplinary research of smart materials, 3D printer, and design. Compared with the static objects created by 3D printing, 4D printing allows a 3D printed structure to change its configuration or function with time in response to external stimuli such as temperature, light, water, etc., which makes 3D printing alive. Herein, the material systems used in 4D printing are reviewed, with emphasis on mechanisms and potential applications. After a brief overview of the definition, history, and basic elements of 4D printing, the state‐of‐the‐art advances in 4D printing for shape‐shifting materials are reviewed in detail. Both single material and multiple materials using different mechanisms for shape changing are summarized. In addition, 4D printing of multifunctional materials, such as 4D bioprinting, is briefly introduced. Finally, the trend of 4D printing and the perspectives for this exciting new field are highlighted.

Shape-programmable soft materials that exhibit integrated multifunctional shape manipulations, including reprogrammable, untethered, fast, and reversible shape transformation and locking, are highly desirable for a plethora of applications, including soft robotics, morphing structures, and biomedical devices.Despite recent progress, it remains challenging to achieve multiple shape manipulations in one material system. Here, we report a novel magnetic shape memory polymer composite to achieve this. The composite consists of two types of magnetic particles in an amorphous shape memory polymer matrix. The matrix softens via magnetic inductive heating of low-coercivity particles, and highremanence particles with reprogrammable magnetization profiles drive the rapid and reversible shape change under actuation magnetic fields. Once cooled, the actuated shape can be locked. Additionally, varying the particle loadings for heating enables sequential actuation. The integrated multifunctional shape manipulations are further exploited for applications including soft magnetic grippers with large grabbing force, sequential logic for computing, and reconfigurable antennas.

Robust self-healing thermoplastic elastomers are expected to have repeated healing capability, remarkable mechanical properties, transparency, and superior toughness. The phase-locked design in this work provides excellent tensile mechanical properties and efficient healability at a moderate temperature due to the dynamic disulfide bonds embedded in the hard segments and mainly being locked in the viscoelastic hard microphase region. The self-healing elastomers exhibit a maximum tensile stress of 25 MPa and a fracture strain of over 1600%, which are quite prominent compared to previous reports. The nanoscale domains of the elastomer are smaller than the wavelength of visible light by microphase separation control resulting in colorless, nearly 100% transparency, and are as good as quartz glasses. The high dynamics of the phase-locked disulfide bonds renders a high healing efficiency of scratches on the surface within 60 s at 70 °C. The rapid scratch healing and complete transparency recovery of the elastomers provide new avenues in the highly transparent surface or protective films which finds potential applications for precision optical lenses, flexible display screens, and automobile or aircraft lighting finishes.

An epoxy ink and its 3D printing method were developed to allow printed parts to be recycled and reprinted.

The three-dimensional (3D) printing of flexible and stretchable materials with smart functions such as shape memory (SM) and self-healing (SH) is highly desirable for the development of future 4D printing technology for myriad applications, such as soft actuators, deployable smart medical devices, and flexible electronics. Here, we report a novel ink that can be used for the 3D printing of highly stretchable, SM, and SH elastomer via UV-light-assisted direct-ink-write printing. An ink containing urethane diacrylate and a linear semicrystalline polymer is developed for the 3D printing of a semi-interpenetrating polymer network elastomer that can be stretched by up to 600%. The 3D-printed complex structures show interesting functional properties, such as high strain SM and SM -assisted SH capability. We demonstrate that such a 3D-printed SM elastomer has the potential application for biomedical devices, such as vascular repair devices. This research paves a new way for the further development of novel 4D printing, soft robotics, and biomedical devices.