Reversible Shape Transformation Research Articles

Reversible shape transformations through continuous deformations in soft responsive self-repairing solids using voxel techniques

Voxel modeling is a technique in which an object is represented by an array of cubes. One advantage in design-for-manufacturing is that selected voxels may be assigned desired responsive properties through additive manufacturing. It allows for achieving reversible shape transformation in soft responsive self-repairing solids within a strategic sequence. The first step in the sequence involves selecting an equivalent geometric shape. The second step involves mapping shapes to preserve properties during continuous deformation. The third step involves transforming the shape from one form to another. The fourth step involves defining changes in dimensions. The final step involves correlating the flow of stress with the stretch of the solid. This research also considers self-repair or self-healing as part of the transformation process because the splitting or joining of solids involves continuous deformation. The newly transformed shape can also be considered as the intermediate shape, or first shape for next transformation. This leads to a chain of shapes that are topologically equivalent, and interchangeable. The iterative steps involved in shape transformation finds applications in topology optimization, generative design, metastructures, among others. One application of shape transformation in these domains is that it serves as an alternative to material reduction techniques.

Fully Reversible and Super-Fast Photo-Induced Morphological Transformation of Nanofilms for High-Performance UV Detection and Light-Driven Actuators.

Flexible and highly ultraviolet (UV) sensitive materials garner considerable attention in wearable devices, adaptive sensors, and light-driven actuators. Herein, a type of nanofilms with unprecedented fully reversible UV responsiveness are successfully constructed. Building upon this discovery, a new system for ultra-fast, sensitive, and reliable UV detection is developed. The system operates by monitoring the displacement of photoinduced macroscopic motions of the nanofilms based composite membranes. The system exhibits exceptional responsiveness to UV light at 375nm, achieving remarkable response and recovery times of < 0.3s. Furthermore, it boasts a wide detection range from 2.85µWcm-2 to 8.30mWcm-2, along with robust durability. Qualitative UV sensing is accomplished by observing the shape changes of the composite membranes. Moreover, the composite membrane can serve as sunlight-responsive actuators for artificial flowers and smart switches in practical scenarios. The photo-induced motion is ascribed to the cis-trans isomerization of the acylhydrazone bonds, and the rapid and fully reversible shape transformation is supposed to be a synergistic result of the instability of the cis-isomers acylhydrazone bonds and the rebounding property of the networked nanofilms. These findings present a novel strategy for both quantitative and qualitative UV detection.

A Printable Magnetic-Responsive Iron Oxide Nanoparticle (ION)-Gelatin Methacryloyl (GelMA) Ink for Soft Bioactuator/Robot Applications.

The features or actuation behaviors of nature's creatures provide concepts for the development of biomimetic soft bioactuators/robots with stimuli-responsive capabilities, design convenience, and environmental adaptivity in various fields. Mimosa pudica is a mechanically responsive plant that can convert pressure to the motion of leaves. When the leaves receive pressure, the occurrence of asymmetric turgor in the extensor and flexor sides of the pulvinus from redistributing the water in the pulvinus causes the bending of the pulvinus. Inspired by the actuation of Mimosa pudica, designing soft bioactuators can convert external stimulations to driving forces for the actuation of constructs which has been receiving increased attention and has potential applications in many fields. 4D printing technology has emerged as a new strategy for creating versatile soft bioactuators/robots by integrating printing technologies with stimuli-responsive materials. In this study, we developed a hybrid ink by combining gelatin methacryloyl (GelMA) polymers with iron oxide nanoparticles (IONs). This hybrid ION-GelMA ink exhibits tunable rheology, controllable mechanical properties, magnetic-responsive behaviors, and printability by integrating the internal metal ion-polymeric chain interactions and photo-crosslinking chemistries. This design offers the inks a dual crosslink mechanism combining the advantages of photocrosslinking and ionic crosslinking to rapidly form the construct within 60 s of UV exposure time. In addition, the magnetic-responsive actuation of ION-GelMA constructs can be regulated by different ION concentrations (0-10%). Furthermore, we used the ION-GelMA inks to fabricate a Mimosa pudica-like soft bioactuator through a mold casting method and a direct-ink-writing (DIW) printing technology. Obviously, the pinnule leaf structure of printed constructs presents a continuous reversible shape transformation in an air phase without any liquid as a medium, which can mimic the motion characteristics of natural creatures. At the same time, compared to the model casting process, the DIW printed bioactuators show a more refined and biomimetic transformation shape that closely resembles the movement of the pinnule leaf of Mimosa pudica in response to stimulation. Overall, this study indicates the proof of concept and the potential prospect of magnetic-responsive ION-GelMA inks for the rapid prototyping of biomimetic soft bioactuators/robots with untethered non-contact magneto-actuations.

4D-Printed Hydrogel Actuators through Diffusion-Path Architecture Design.

Recently, smart hydrogels have garnered considerable attention as biomedical devices, and several approaches have been introduced for their fabrication, including the incorporation of stimulus-responsive additives, utilization of molecular imprinting techniques, and application of multilayered hydrogels. However, the nonuniform properties resulting from these approaches limit the practical applications of hydrogels by causing inconsistent performance and behavior. In this study, we propose a novel approach to manipulating the swelling kinetics of hydrogels by engineering their diffusion-path architecture. By simply adjusting the diffusion path length within the hydrogel, we achieved a significant change in swelling kinetics. This approach enables precise control over the diffusion and transport processes within the hydrogel, resulting in enhanced swelling kinetics when reducing the diffusion path length. Furthermore, by strategically designing the diffusion-path architecture of a 3D-printed hydrogel specimen, we can fabricate smart hydrogel actuators that exhibit reversible shape transformations during swelling and deswelling through a nonequilibrium differential swelling. The proposed approach eliminates the need to modify the spatial properties of hydrogel structures such as cross-linking density, polymer, or additive compositions, thereby achieving uniform properties throughout the hydrogel and creating new possibilities for the development of advanced 4D-printed biomedical devices.

Ligand-Directed Shape Reconfiguration in Inorganic Materials.

Polymer elastomers with reversible shape-changing capability have led to significant development of artificial muscles, functional devices, and soft robots. By contrast, reversible shape transformation of inorganic nanoparticles is notoriously challenging due to their relatively rigid lattice structure. Here, the authors demonstrate the synthesis of shape-changing nanoparticles via an asymmetrical surface functionalization process. Various ligands are investigated, revealing the essential role of steric hindrance from the functional groups. By controlling the unbalanced structural hindrance on the surface, the as-prepared clay nanoparticles can transform their shape in a fast, facile, and reversible manner. In addition, such flexible morphology-controlled mechanism provides a platform for developing self-propelled shape-shifting nanocollectors. Owing to the ion-exchanging capability of clay, these self-propelled nanoswimmers (NS) are able to autonomously adsorb rare earth elements with ultralow concentration, indicating the feasibility of using naturally occurring materials for self-powered nanomachine.

Permanent Shape Reconfiguration and Locally Reversible Actuation of a Carbon Nanotube/Ethylene Vinyl Acetate Copolymer Composite by Constructing a Dynamic Cross-Linked Network.

Given the rapid developments in modern devices, there is an urgent need for shape-memory polymer composites (SMPCs) in soft robots and other fields. However, it remains a challenge to endow SMPCs with both a reconfigurable permanent shape and a locally reversible shape transformation. Herein, a dynamic cross-linked network was facilely constructed in carbon nanotube/ethylene vinyl acetate copolymer (CNT/EVA) composites by designing the molecular structure of EVA. The CNT/EVA composite with 0.05 wt % CNT realized a steady-state temperature of ∼75 °C under 0.11 W/cm2 light intensity, which gave rise to remote actuation behavior. The dynamic cross-linked network along with a wide melting temperature offered opportunities for chemical and physical programming, thus realizing the achievement of the programmable three-dimensional (3D) structure and locally reversible actuation. Specifically, the CNT/EVA composite exhibited a superior permanent shape reconfiguration by activating the dynamic cross-linked network at 140 °C. The composite also showed a high reversible deformation rate of 11.1%. These features endowed the composites with the capability of transformation to 3D structure as well as locally reversible actuation performance. This work provides an attractive guideline for the future design of SMPCs with sophisticated structures and actuation capability.

Four-Dimensional-Printed Microrobots and Their Applications: A Review.

Owing to their small size, microrobots have many potential applications. In addition, four-dimensional (4D) printing facilitates reversible shape transformation over time or upon the application of stimuli. By combining the concept of microrobots and 4D printing, it may be possible to realize more sophisticated next-generation microrobot designs that can be actuated by applying various stimuli, and also demonstrates profound implications for various applications, including drug delivery, cells delivery, soft robotics, object release and others. Herein, recent advances in 4D-printed microrobots are reviewed, including strategies for facilitating shape transformations, diverse types of external stimuli, and medical and nonmedical applications of microrobots. Finally, to conclude the paper, the challenges and the prospects of 4D-printed microrobots are highlighted.

Programmable Complex Shape Changing of Polysiloxane Main-Chain Liquid Crystalline Elastomers.

Liquid crystal elastomers (LCEs) are shape-morphing materials whose large and reversible shape transformations are caused by the coupling between the mobile anisotropic properties of liquid crystal (LC) units and the rubber elastic of polymer networks. Their shape-changing behaviors under certain stimuli are largely directed by the LC orientation; therefore, various strategies have been developed to spatially modulate the LC alignments. However, most of these methods are limited as they require complex fabrication technologies or have intrinsic limitations in applicability. To address this issue, programmable complex shape changes in some LCE types, such as polysiloxane side-chain LCEs, thiol-acrylate main-chain LCEs, etc., were achieved by using a mechanical alignment programming process coupled with two-step crosslinking. Here, we report a polysiloxane main-chain LCE with programmable 2- and 3D shape-changing abilities that were created by mechanically programming the polydomain LCE with two crosslinking steps. The resulting LCEs exhibited a reversible thermal-induced shape transformation between the initial and programmed shapes due to the two-way memory between the first and second network structures. Our findings expand on the applications of LCE materials in actuators, soft robotics, and smart structures where arbitrary and easily programmed shape morphing is needed.

Adaptive Magnetoactive Soft Composites for Modular and Reconfigurable Actuators

AbstractMagnetoactive soft materials, typically composed of magnetic particles dispersed in a soft polymer matrix, are finding many applications in soft robotics due to their reversible and remote shape transformations under magnetic fields. To achieve complex shape transformations, anisotropic, and heterogeneous magnetization profiles must be programmed in the material. However, once programmed and assembled, magnetic soft actuators cannot be easily reconfigured, repurposed, or repaired, which limits their application, their durability, and versatility in their design. Here, magnetoactive soft composites are developed from squid‐derived biopolymers and NdFeB microparticles with tunable ferromagnetic and thermomechanical properties. By leveraging reversible crosslinking nanostructures in the biopolymer matrix, a healing‐assisted assembly process is developed that allows for on‐demand reconfiguration and magnetic reprogramming of magnetoactive composites. This concept in multi‐material modular actuators is demonstrated with programmable deformation modes, self‐healing properties to recover their function after mechanical damage, and shape‐memory behavior to lock in their preferred configuration and un‐actuated catch states. These dynamic magnetic soft composites can enable the modular design and assembly of new types of magnetic actuators, not only eliminating device vulnerabilities through healing and repair but also by providing adaptive mechanisms to reconfigure their function on demand.

Bioinspired shape shifting of liquid-infused ribbed sheets

The recent emergence of stimuli-responsive, shape-shifting materials offers promising applications in fields as different as soft robotics, aeronautics, or biomedical engineering. Targeted shapes or movements are achieved from the advantageous coupling between some stimulus and various materials such as liquid crystalline elastomers, magnetically responsive soft materials, swelling hydrogels, etc. However, despite the large variety of strategies, they are strongly material dependent and do not offer the possibility to choose between reversible and irreversible transformations. Here, we introduce a strategy applicable to a wide range of materials yielding systematically reversible or irreversible shape transformations of soft ribbed sheets with precise control over the local curvature. Our approach-inspired by the spore-releasing mechanism of the fern sporangium-relies on the capillary deformation of an architected elastic sheet impregnated by an evaporating liquid. We develop an analytical model combining sheet geometry, material stiffness, and capillary forces to rationalize the onset of such deformations and develop a geometric procedure to inverse program target shapes requiring fine control over the curvature gradient. We finally demonstrate the potential irreversibility of the transformation by UV-curing a photosensitive evaporating solution and show that the obtained shells exhibit enhanced mechanical stiffness.

Reversible Shape-Shifting of an Ionic Strength Responsive Hydrogel Enabled by Programmable Network Anisotropy.

Reversible shape-shifting hydrogels exhibit great potential in diverse fields. Repeatable programmability for the shape transformation has newly been enabled in thermally responsive hydrogels via engineering of the chain orientation of the polymer network, which substantially promotes the transformation capability. However, diversified responsive behavior and the enabling mechanism require further investigation. Herein, we develop an ionic strength (IS) responsive hydrogel enabling the programmable reversible shape transformation based on a semi-interpenetrating network of poly(acrylic acid) (PAA) and poly(vinyl alcohol) (PVA). Deformation of the hydrogel upon external force can be fixed due to crystallization of PVA that underwent cyclic freezing-thawing. Therefore, the chain orientation can be retained in the deformed area, enabling the programmable IS responsive actuation. In contrast to the thermally responsive actuation originated from the lower critical solution temperature phase transition, the IS responsive actuation does not accompany any phase change and the corresponding mechanism is proposed. Reversible bending providing an actuation angle as large as 80° can be achieved after optimization of the PVA content. The PVA crystals can be melted upon heating, and the responsive actuation can thus be reprogrammed. In addition, utilizing a digital light 3D printer, the hydrogels are further fabricated into arbitrary geometries, thus realizing more complex actuations. Overall, our work provides a general strategy to develop reversible shape-shifting hydrogels and paves the way for soft actuators.

Structuring Hydrogel Cross-Link Density Using Hierarchical Filament 3D Printing.

Polymer hydrogels, water-laden 3D cross-linked networks, find broad application as advanced biomaterials and functional materials because of their biocompatibility, stimuli responsiveness, and affordability. The cross-linking density reports material properties such as elasticity, permeability, and swelling propensity. However, this critical design parameter can be challenging to template locally. Here, we report a continuous processing scheme that uses laminar flow to direct the organization of cross-linking density across a single sample. Dilute and concentrated poly(ethylene glycol) diacrylate solutions are fed into custom serpentine millifluidic devices. These feature a modular sequence of splitting, rotation, and recombination elements, which create patterned streamlines that serve as a template for hierarchical concentration distributions. Poly(acrylic acid) microgels impart viscoplasticity, which stabilizes layered flow during multiplication and ensures reliable advection. The devices produce structured, seamless filaments, which are then arranged into objects using 3D printing, and photopolymerized to secure the heterogeneous distribution. The flow-encoded, multiscale architecture provides mechanical contrast, which is demonstratively exploited to program robust and reversible shape transformations, potentially useful in soft actuator and sensor applications. The unique structures achieved, and the geometrically dictated, chemistry-agnostic operating principles used to achieve them, provides a new means to engineer hydrogels to suit a variety of applications.

Stiffness Variable Polymers Comprising Phase-Changing Side-Chains: Material Syntheses and Application Explorations.

Stiffness variable materials have been applied in a variety of engineering fields that require adaptation, automatic modulation, and morphing because of their unique property to switch between a rigid, load-bearing state and a soft, compliant state. Stiffness variable polymers comprising phase-changing side-chains (s-SVPs) have densely grafted, highly crystallizable long alkyl side-chains in a crosslinked network. Such a bottlebrush network-like structure gives rise to rigidity modulation as a result of the reversible crystallization and melting of the side chains. The corresponding modulus changes can be more than 1000-fold within a narrow temperature span, from ≈102 MPa to ≈102 kPa or lower. Other important properties of the s-SVP, such as stretchability, optical transmittance, and adhesion, can also be altered. This work reviews the underlying molecular mechanisms in the s-SVP's, discusses the material's structure-property relationship, and summarizes important applications explored so far, including reversible shape transformation, bistable electromechanical transduction, optical modulation, and reversible adhesion.

Thermo- and near infrared light-induced reversible multi-shape memory materials for actuators and sensors

Smart materials with reversible shape transformation have drawn enormous interest for their potential applications in various fields.

Shape-programmable liquid crystal elastomer structures with arbitrary three-dimensional director fields and geometries

Liquid crystal elastomers exhibit large reversible strain and programmable shape transformations, enabling various applications in soft robotics, dynamic optics, and programmable origami and kirigami. The morphing modes of these materials depend on both their geometries and director fields. In two dimensions, a pixel-by-pixel design has been accomplished to attain more flexibility over the spatial resolution of the liquid crystal response. Here we generalize this idea in two steps. First, we create independent, cubic light-responsive voxels, each with a predefined director field orientation. Second, these voxels are in turn assembled to form lines, grids, or skeletal structures that would be rather difficult to obtain from an initially connected material sample. In this way, the orientation of the director fields can be made to vary at voxel resolution to allow for programmable optically- or thermally-triggered anisotropic or heterogeneous material responses and morphology changes in three dimensions that would be impossible or hard to implement otherwise.

Programmable and Reversible Self-assembly of 3D Architectures Actuated by Flexible Metal–Organic Frameworks

Respond rapidly and reversibly to external stimuli are critical to mimic biological systems. To design a multi-stimuli responsive actuator, we built a novel type of monolayer composite film that integrates the swellable metal-organic frameworks (MOF-88C) into the polymer P(VDF-CTFE). When exposed to polar solvent vapors (toluene, acetone, dichloromethane, and methanol), the composite-strip produces a reversible shape transformation derived from the intrinsic flexible of MOF crystal. Benefited to the active swelling MOF, the instant reversible bending (angle change >360° within 10 seconds) of the composite strip was realized at minute concentrations of dichloromethane vapor. Furthermore, to realized specific and programmable actuation, we use two fabrication strategies, templates and femtosecond laser system to control over swellable MOF crystals spatial distribution within the polymeric film. Interestingly, the composite film successfully mimicked natural plant tendrils, flowers that blooms or closes and soft robots that wriggle and grab objects. The composite material based on flexible MOF is a promising candidate for smart material of autonomous soft mechanical driving device.

Actuation of Three‐Dimensional‐Printed Nanocolloidal Hydrogel with Structural Anisotropy

AbstractPolymer hydrogels exhibit actuation properties that result in reversible shape transformations and have promising applications in soft robotics, drug delivery systems, sensors, and microfluidic devices. Actuation occurs due to differential hydrogel swelling and is generally achieved by modulating hydrogel composition. Here a different approach to hydrogel actuation that originates solely from its structural anisotropy is reported. For 3D‐printed single‐layer hydrogels formed by cellulose nanocrystals (CNCs) and gelatin methacryloyl it is shown that shear‐induced orientation of CNCs results in anisotropic mechanical and swelling properties of the hydrogel. Upon swelling in water, planar hydrogels acquire multiple complex 3D shapes that are achieved by i) varying CNC orientation with respect to the shape on the hydrogel sheet and ii) patterning the hydrogel with the regions of shear‐mediated and random CNC orientation. This study shows the capability to generate multiple shapes from the same hydrogel actuator based on the degree of its structural anisotropy. In addition, it introduces a biocompatible nanocolloidal ink with shear‐thinning and self‐healing properties for additive manufacturing of hydrogel actuators.

A Crystalline Three-Dimensional Covalent Organic Framework with Flexible Building Blocks.

The construction of three-dimensional covalent organic frameworks (3D COFs) has proven to be very challenging, as their synthetic driving force mainly comes from the formation of covalent bonds. To facilitate the synthesis, rigid building blocks are always the first choice for designing 3D COFs. In principle, it should be very appealing to construct 3D COFs from flexible building blocks, but there are some obstacles blocking the development of such systems, especially for the designed synthesis and structure determination. Herein, we reported a novel highly crystalline 3D COF (FCOF-5) with flexible C-O single bonds in the building block backbone. By merging 17 continuous rotation electron diffraction data sets, we successfully determined the crystal structure of FCOF-5 to be a 6-fold interpenetrated pts topology. Interestingly, FCOF-5 is flexible and can undergo reversible expansion/contraction upon vapor adsorption/desorption, indicating a breathing motion. Moreover, a smart soft polymer composite film with FCOF-5 was fabricated, which can show a reversible vapor-triggered shape transformation. Therefore, 3D COFs constructed from flexible building blocks can exhibit interesting breathing behavior, and finally, a totally new type of soft porous crystals made of pure organic framework was announced.

3D and 4D printable dual cross-linked polymers with high strength and humidity-triggered reversible actuation

We report a macromolecular design concept to develop humidity-responsive polymers with simultaneously improved mechanical properties and 3D printability, while still displaying fast, reversible and complex shape transformations.

On-demand shape transformation of polymer vesicles via site-specific isomerization of hydrazone photoswitches in monodisperse hydrophobic oligomers

Stimuli-responsive polymersomes exhibited reversible shape transformation upon irradiation with UV or visible light due to the E–Z isomerization of the hydrazone-based photoswitch resulting in a conformational change of the OPLA block.