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.