Dual‐Programmable Shape‐Morphing and Self‐Healing Organohydrogels Through Orthogonal Supramolecular Heteronetworks

Abstract

for applications in aerospace, smart devices, and biomedical materials. [1][2][3] Among these materials, shape-morphing polymers (SMPs) are particularly attractive because their forms can be programmed to perform transformations or motions in response to external stimuli (e.g., temperature, light, solvent, and electric fields). [3][4][5][6][7][8][9][10][11] Currently, two general approaches are used to obtain unparalleled shape-programming flexibility. The first involves geometric assistances to produce complex SMP shapes, such as kirigami and origami art, as well as 3D printing. [12][13][14][15][16][17] Alternatively, another approach is through the use of an innovational polymer network design, which employs functional components to expand the programmability of SMPs. [18][19][20][21][22][23] For example, SMPs with dynamic covalent polymer networks and reversible crosslinking netpoints exhibit unique shape reconfiguration and programmability. [18][19][20][21] However, despite these exciting prospects, most SMPs with the single control routes only allow complex temporary shapes to recover a former permanent state, ultimately limiting the versatility of these materials and our ability to control them for complex applications. Owing to the intrinsic restriction of the permanently crosslinked polymer network, such single programming inevitably lacks a mechanism Programmable materials that can change their inherent shapes or properties are highly desirable due to their promising applications. However, among various programmable shape-morphing materials, the single control route allows temporary states to recover the unchangeable former state, thus lacking the sophisticated programmability for their shape-encoding behaviors and mechanics. Herein, dual-programmable shape-morphing organohydrogels featuring supramolecular heteronetworks are developed. In the system, the metallo-supramolecular hydrogel framework and micro-organogels featuring semicrystalline comb-type networks independently respond to different stimuli, thereby providing orthogonal dual-switching mechanics and ultrahigh mechanical strength. The supramolecular heteronetworks also possess excellent self-healing properties. More notably, such orthogonal supramolecular heteronetworks demonstrate hierarchical shape morphing performance that far exceeds conventional shape-morphing materials. Utilizing this dual programming strategy of the orthogonal supramolecular heteronetworks, the material's permanent shape can be manipulated in a step-wise shape morphing process, thereby realizing sophisticated shape changes with a high degree of freedom. The organohydrogels can act as a biomimetic smart device for the on-demand control of unidirectional liquid transport. Based on these characteristics, it is anticipated that the supramolecular organohydrogels may serve as adaptive programmable materials for a variety of applications. Gel MaterialsProgrammable materials are capable of changing their inherent shapes or exquisite properties to adapt to complex environments a...

Adaptive Superamphiphilic Organohydrogels with Reconfigurable Surface Topography for Programming Unidirectional Liquid Transport

“…Figure a illustrates the overview of biomimetic surface design inspired by the peristome surfaces of pitcher plants and the groove surfaces of rice leaves. Combining with programmable shape morphing effect of heteronetworks, we can realize multiple biomimetic structure topography on the organohydrogel surfaces. As we mentioned before, the shape memory performance of these organohydrogels is deeply involved in accomplishment of the biomimetic surface topography; to confirm this acclamation, we measured the thermoswitchable mechanics and the shape fixity ( R f )/recovery ( R r ) ratio.…”

Asymmetric elastoplasticity of stacked graphene assembly actualizes programmable untethered soft robotics

“…Recently, a variety of flexible morphing systems have been developed with configurable soft materials by taking the advantage of various mechanisms such as asymmetric thermal expansion 5,6 , liquid crystalline transitions 7,8 , phase transitions [9][10][11][12] , and anisotropic swelling [13][14][15][16][17][18][19][20][21] , etc. To achieve shape programming and customization, numerous efforts have been made by applying specific chemical structures through a variety of polymeric materials including shape memory polymers (SMPs) [22][23][24][25] , vitrimer 26 , hydrogel [27][28][29] , organogel 30 . Application of two-way SMPs with a heterogeneous semi-crystalline structure or a broad melting transition realized reversible and controllable morphing behaviors [31][32][33] .…”

Kirigami‐Design‐Enabled Hydrogel Multimorphs with Application as a Multistate Switch

“…Transformations between distinct configurations, which are not multistable, could be realized by multistep shape memorization complemented with an external force. [ 31,32 ] It has also been demonstrated that a kirigami‐based parylene film could conformally wrap the heart of a mouse, so that the sensing functions of the flexible electronics on it was enhanced. [ 33 ] These structures are usually realized passively by applying mechanical forces to form 3D configurations.…”