Photochemical Design for Diverse Controllable Patterns in Self-Wrinkling Films.

Harnessing the spontaneous surface instability of pliable substances to create intricate, well-ordered, and on-demand controlled surface patterns holds great potential for advancing applications in optical, electrical, and biological processes. However, the current limitations stem from challenges in modulating multidirectional stress fields and diverse boundary environments. Herein, this work proposes a universal strategy to achieve arbitrarily controllable wrinkle patterns via the spatiotemporal photochemical boundaries. Utilizing constraints and inductive effects of the photochemical boundaries, the multiple coupling relationship is accomplished among the light fields, stress fields, and morphology of wrinkles in photosensitive polyurethane (PSPU) film. Moreover, employing sequential light-irradiation with photomask enables the attainment of a diverse array of controllable patterns, ranging from highly ordered 2D patterns to periodic or intricate designs. The fundamental mechanics of underlying buckling and the formation of surface features are comprehensively elucidated through theoretical stimulation and finite element analysis. The results reveal the evolution laws of wrinkles under photochemical boundaries and represent a new effective toolkit for fabricating intricate and captivating patterns in single-layer films.

Photo-Dissociable Fe3+-Carboxylate Coordination: A General Approach toward Hydrogels with Shape Programming and Active Morphing Functionalities.

An extendable double network design for hydrogels with programmable external geometries and actuating trajectories is presented. Chemically cross-linked polyacrylamide as the first network penetrated with linear alginate chains is prepared for demonstration. The coordination of Fe3+ ions with carboxylate groups in alginate chains acts as the second network, and its dissociation through photoreduction is utilized to realize the photoresponsive shape memory property; the shape fixity ratio and shape recovery ratio both exceed 90%. The gradient dissociation of Fe3+-carboxylate coordination under UV facilitates 3D programming of hydrogel geometry. On another aspect, the resulted cross-linking gradient differentiates the extent and rate of solvent-induced volume change of the PAAm network, endowing the hydrogel with photo-programmable solvent-driven actuating behavior. Furthermore, by inducing the formation of Fe3+-carboxylate coordination within the entire network for shape programming and cross-linking gradients in specific regions as active joints, hydrogels with designed actuating behaviors based on specific 3D shapes are realized. The shape memory and active morphing functionalities enabled by photo-dissociable Fe3+-carboxylate coordination in PAAm hydrogel can be generally extended to other hydrogels.

Programmable 3D Shape-Change Liquid Crystalline Elastomer Based on a Vertically Aligned Monodomain with Cross-link Gradient.

A liquid crystalline elastomer (LCE) as a kind of stimuli-responsive materials, which can be fabricated to present the three-dimensional (3D) change in shape, shows a wide range of applications. Herein, we propose a simple and robust way to prepare a 3D shape-change actuator based on gradient cross-linking of the vertically aligned monodomain of liquid crystals (LCs). First, gold nanoparticles grafted by liquid crystalline polymers (LCPs) are used to induce the homeotropic orientation of the LC monomer and cross-linkers. Then, photopolymerization under UV irradiation is carried out, which can result in the LCE film with a cross-link gradient. Different from the typical LCEs with homogenous alignment that usually show the shape change of extension/contraction, the obtained vertically aligned LCE film exhibits excellent bendability under a thermal stimulus. The nanoindentation experiment demonstrates that the deformation of LCE films comes from the difference in Young's modulus on two sides of the thin film. Simply scissoring the thin film can prepare the samples with different bending angles under the fixed length. Moreover, using a photomask to pattern the film during photopolymerization can realize the complex 3D deformation, such as bend, fold, and buckling. Further, the patterned LCE film doped with multiwalled carbon nanotubes modified by LCPs (CNT-PDB) can act as a light-fueled microwalker with fast crawl behavior.

2D-to-3D Shape Transformation of Room-Temperature-Programmable Shape-Memory Polymers through Selective Suppression of Strain Relaxation.

Although shape-memory polymers (SMPs) can alter their shapes upon stimulation of environmental signals, complex shape transformations are usually realized by using advanced processing technologies (four-dimensional printing) and complicated polymer structure design or localized activation. Herein, we demonstrate that stepwise controlled complex shape transformations can be obtained from a single flat piece of SMP upon uniform heating. The shape-memory blends prepared by solution casting of poly(ethylene oxide) and poly(acrylic acid) (PAA) exhibit excellent mechanical and room-temperature shape-memory behaviors, with fracture strain beyond 800% and both shape memory and shape recovery ratio higher than 90%. After plastic deformation by stretching under ambient conditions, the material is surface-patterned to induce the formation of an Fe3+-coordinated PAA network with gradually altered cross-linking density along the thickness direction at desired areas. Upon subsequent heating for shape recovery, strain release is restricted by the PAA network to different extents depending on the cross-linking density, which results in bending deformation toward the nonpatterned side and leads to three-dimensional shape transformation of the SMP. More interestingly, by sequentially dissociating the PAA network via UV or visible light-induced photoreduction of Fe3+ to Fe2+, residual strains can be removed in a spatially controlled manner. Using this approach, a series of origami shapes are obtained from a single SMP with a tailored two-dimensional initial shape. We also demonstrate that by incorporating polydopamine nanoparticles as photothermal fillers into the material, the whole shape transformation process can be carried out at room temperature by using near-infrared light.