Ultrafast Shape-Reconfigurable Chiral Mechanical Metamaterial based on Prestressed Bistable Shells

Fast shape-reconfiguration with large morphing amplitude is crucial for intelligent materials/structures that require tunable functions and adaptivity to different environments. However, the morphing strategies are rare in combining ultrafast speed, large amplitude, and high energy-efficiency simultaneously. Herein, a class of 2D and 3D chiral mechanical metamaterials are proposed to tackle this challenge based on prestressed bistable metallic shells. The metamaterial is architected by cylindrical cores and slender bistable shells with an anti-chiral arrangement. The bistable shell has a flat extended shape and a rolled-up shape that can wrap on the connected cylindrical cores compatibly, and thus endow the metamaterials with a tunable morphing amplitude that can even extend to infinity. By experiments, simulations and theoretical modelling, it is demonstrated that the bistable shell can transform from the extended state to the rolled-up state with a transitional speed of 7.56 m s⁻¹, which provides the 2D and 3D metamaterials with 25.38- and 101.14-times body area/volume variation per second, respectively. Moreover, a smart trapper for capturing moving objects and a phononic structure with tunable band gaps are realized based on the metamaterials. This work provides a straightforward platform to design metamaterials and their derived systems with ultrafast and large-amplitude shape-reconfigurability.     

Combining 3D Printing with Electrospinning for Rapid Response and Enhanced Designability of Hydrogel Actuators

Porous structures have emerged as a breakthrough of shape‐morphing hydrogels to achieve a rapid response. However, these porous actuators generally suffer from a lack of complexity and diversity in obtained 3D shapes. Herein, a simple yet versatile strategy is developed to generate shape‐morphing hydrogels with both fast deformation and enhanced designability in 3D shapes by combining two promising technologies: electrospinning and 3D printing. Elaborate patterns are printed on mesostructured stimuli‐responsive electrospun membranes, modulating in‐plane and interlayer internal stresses induced by swelling/shrinkage mismatch, and thus guiding morphing behaviors of electrospun membranes to adapt to changes of the environment. With this strategy, a series of fast deformed hydrogel actuators are constructed with various distinctive responsive behaviors, including reversible/irreversible formations of 3D structures, folding of 3D tubes, and formations of 3D structures with multi low‐energy states. It is worth noting that although poly(N‐isopropyl acrylamide) is chosen as the model system in the present research, our strategy is applicable to other stimuli‐responsive hydrogels, which enriches designs of rapid deformed hydrogel actuators.     

Electrical Switching and Bistability in Organic/Polymeric Thin Films and Memory Devices

Recently, films created by incorporating metallic nanoparticles into organic or polymeric materials have demonstrated electrical bistability, as well as the memory effect, when subjected to an electrical bias. Organic and polymeric digital memory devices based on this bistable electronic behavior have emerged as a viable technology in the field of organic electronics. These devices exhibit fast response speeds and can form multiple‐layer stacking structures, demonstrating that organic memory devices possess a high potential to become flexible, ultrafast, and ultrahigh‐density memory devices. This behavior is believed to be related to charge storage in the organic or polymer film, where devices are able to exhibit two different states of conductivity often separated by several orders of magnitude. By defining the two states as “1” and “0”, it is now possible to create digital memory devices with this technology. This article reviews electrically bistable devices developed in our laboratory. Our research has stimulated strong interest in this area worldwide. The research by other laboratories is reviewed as well.     

A Magnet-Driven Soft Bistable Actuator

Bistable morphing structures are widely used as actuation mechanisms in soft actuators, soft robotics, energy absorbers, mechanical computers, optical lenses, metamaterials, and flexible electronics. However, untethered actuators, repetitive actuators, and hybrid-assembly (containing in-plane-assembly and out-of-plane-assembly) actuators remain challenging to realize using existing bistable structures, which hinders the novel application of such actuators in research, engineering, and daily life. This problem is solved by fabricating a magnet-driven soft bistable actuator (MSBA) unit. The self-buckling of the circular polydimethylsiloxane (PDMS) sheet ensures the bistability of the actuator and allows it to operate as an independent unit, free of external constraints. The reorientation of neodymium-iron-boron (NdFeB) microparticles embedded in the PDMS sheet enables the dome-shaped actuators to exhibit repetitive snapping under the stimulus of a direction-switching magnetic field. The potential of this MSBA unit in bionics, electronics, and biomechanics applications is demonstrated in systematic studies involving modification of the buckling deflection and magnetic moment density. The MSBA unit exhibits excellent performance in hybrid designs and intelligent systems.     

Nematic Liquid Crystals Embedded in Cubic Microlattices: Memory Effects and Bistable Pixels

The confinement of liquid crystals in geometries with frustrating boundary conditions gives rise to nontrivial effects such as bistability and memory. It is shown that large memory effects arise when nematic liquid crystals are embedded in cubic micrometer‐sized scaffolds made by two‐photon polymerization. The electric field alignment of the liquid crystals inside the porous medium is maintained when the applied field is above a threshold (approximately 2 V per micrometer of cell thickness). The onset of the memory is an on/off type process for each individual pore of the scaffold, and the memory typically starts emerging in one region of the structure and then propagates. The global memory effects in porous structures with controlled geometry are enhanced with respect to the case of random porous structures. This work is a proof of the “memory from topology” principle, which was previously suggested by computer simulations. These new materials can pave the way to new types of bistable displays.     

Light‐Coded Digital Crystallinity Patterns Toward Bioinspired 4D Transformation of Shape‐Memory Polymers

Spatially heterogeneous distribution of active components is key to the diverse shape‐morphing behaviors of biological species and their associated functions. Artificial morphing materials employing similar strategies have widened the design space for advanced functional devices. Typically, the spatial heterogeneity is introduced during the material synthesis/fabrication step and cannot be altered afterward. An approach that allows spatio‐selective programming of crystallinity in a shape‐memory polymer (SMP) by a digital photothermal effect is reported. The light‐patternable crystallinity affects greatly the shape morphing behavior. Consequently, a pre‐stretched 2D film with spatial heterogeneity in crystallinity can morph with time into designable 3D permanent shapes, achieving the 4D transformation. This approach utilizes a reprocessible thermoplastic SMP (polylactide) and the programming relies on a physical phase transformation (crystallization) instead of chemical heterogeneity. This allows repeated erasing and reprogramming using the same material, suggesting a versatile and sustainable means for manufacturing advanced morphing devices.     

Molecularly‐Engineered, 4D‐Printed Liquid Crystal Elastomer Actuators

Three‐dimensional structures that undergo reversible shape changes in response to mild stimuli enable a wide range of smart devices, such as soft robots or implantable medical devices. Herein, a dual thiol‐ene reaction scheme is used to synthesize a class of liquid crystal (LC) elastomers that can be 3D printed into complex shapes and subsequently undergo controlled shape change. Through controlling the phase transition temperature of polymerizable LC inks, morphing 3D structures with tunable actuation temperature (28 ± 2 to 105 ± 1 °C) are fabricated. Finally, multiple LC inks are 3D printed into single structures to allow for the production of untethered, thermo‐responsive structures that sequentially and reversibly undergo multiple shape changes.     

Designed Autonomic Motion in Heterogeneous Belousov–Zhabotinsky (BZ)‐Gelatin Composites by Synchronicity

Critical technologies from medicine to defense are highly dependent on advanced composite materials. Increasingly there is a greater demand for materials with expanded functionality. The state of the art includes a wide range of responsive composites capable of impressive structural feats such as externally triggered shape morphing. Here a different composite concept is presented, one in which a portion of the constituent materials feed off of ambient energy and dynamically couple to convert it to mechanical motion in a cooperative, biomimetic fashion. Using a recently developed self‐oscillating gel based on gelatin and the oscillating Belousov–Zhabotinsky (BZ) reaction, a technique is demonstrated for producing continuous patterned heterogeneous BZ hydrogel composites capable of sustained autonomic function. The coupling between two adjacent reactive patches is demonstrated in an autonomic cantilever actuator which converts chemical energy into amplified mechanical motion. The design of heterogeneous BZ gels for motion using a basic finite element model is discussed. This work represents notable progress toward developing internally responsive, bio‐inspired composite materials for constructing modular autonomic morphing structures and devices.     

Elastically and Plastically Foldable Electrothermal Micro‐Origami for Controllable and Rapid Shape Morphing

Integrating origami principles within traditional microfabrication methods can produce shape morphing microscale metamaterials and 3D systems with complex geometries and programmable mechanical properties. However, available micro‐origami systems usually have slow folding speeds, provide few active degrees of freedom, rely on environmental stimuli for actuation, and allow for either elastic or plastic folding but not both. This work introduces an integrated fabrication–design–actuation methodology of an electrothermal micro‐origami system that addresses the above‐mentioned challenges. Controllable and localized Joule heating from electrothermal actuator arrays enables rapid, large‐angle, and reversible elastic folding, while overheating can achieve plastic folding to reprogram the static 3D geometry. Because the proposed micro‐origami do not rely on an environmental stimulus for actuation, they can function in different atmospheric environments and perform controllable multi‐degrees‐of‐freedom shape morphing, allowing them to achieve complex motions and advanced functions. Combining the elastic and plastic folding enables these micro‐origami to first fold plastically into a desired geometry and then fold elastically to perform a function or for enhanced shape morphing. The proposed origami systems are suitable for creating medical devices, metamaterials, and microrobots, where rapid folding and enhanced control are desired.     

4D Printing of Hydrogels: A Review

3D printing permits the construction of objects by layer‐by‐layer deposition of material, resulting in precise control of the dimensions and properties of complex printed structures. Although 3D printing fabricates inanimate objects, the emerging technology of 4D printing allows for animated structures that change their shape, function, or properties over time when exposed to specific external stimuli after fabrication. Among the materials used in 4D printing, hydrogels have attracted growing interest due to the availability of various smart hydrogels. The reversible shape‐morphing in 4D printed hydrogel structures is driven by a stress mismatch arising from the different swelling degrees in the parts of the structure upon application of a stimulus. This review provides the state‐of‐the‐art of 4D printing of hydrogels from the materials perspective. First, the main 3D printing technologies employed are briefly depicted, and, for each one, the required physico‐chemical properties of the precursor material. Then, the hydrogels that have been printed are described, including stimuli‐responsive hydrogels, non‐responsive hydrogels that are sensitive to solvent absorption/desorption, and multimaterial structures that are totally hydrogel‐based. Finally, the current and future applications of this technology are presented, and the requisites and avenues of improvement in terms of material properties are discussed.     

Optoelectronic Duple Bistable Switches: A Bulk Molecular Single Crystal and Unidirectional Ultraflexible Thin Film Based on Imidazolium Fluorochromate

Optical‐electrical duple bistable switches are those that enable simultaneous conversion of both optical and electrical signals in one device to realize seamless integration. Herein, imidazolium‐FCrO₃ can be prepared into a large‐size single crystal and ultraflexible thin film with ultrahigh unidirectionality of (0 0 4) and is characterized through scanning electron microscopy (SEM), atomic force microscopy (AFM), powder X‐ray diffraction, etc. Both the thin film and crystal display synchronously eximious optoelectronic duple characteristics (dielectric and nonlinear optical second harmonic generation (SHG) bistable switching ON/OFF), with a record‐high SHG contrast of ≈250 (2.0 times that of KDP, potassium dihydrogen phosphate, exceeding all the known molecular materials/crystalline switches, revealing its potential to obtain high‐efficiency signal‐to‐noise ratio), sensitive dielectric bistability, and remarkable switching antifatigue. These attributes make imidazolium‐FCrO₃ a potential candidate in photoelectric seamless integration devices and flexible multifunctional devices.     

非均匀分布反馈半导体光放大器的动态双稳特性

分布反馈半导体光放大器(DFB-SOAs)具有较低的双稳上跳阈值，因而在光学信息处理方面有一定的应用前景。引入空间相移、啁啾等非均匀性后，其双稳特性可得到进一步改善。由于系统的传输速率受到脉冲下降沿形变及开启延时的限制，因此对其动态双稳特性的研究很有必要。从耦合模方程及载流子速率方程出发，数值分析了相移、啁啾分布反馈半导体光放大器的动态双稳特性。结果表明，相移使出射脉冲下降沿的形变及开启延迟随初始失谐量的减小呈现先恶化后缓和的趋势，引入啁啾可明显抑制脉冲下降沿的形变，但是增加了开启延迟所需的功率过载量。     

Programmed Shape‐Morphing Scaffolds Enabling Facile 3D Endothelialization

Rapid formation of a confluent endothelial monolayer is the key to the success of small‐diameter vascular grafts, which is significantly important for treating dangerous and even sometimes deadly vascular disorders. However, the difficulty to homogenously locate endothelial cells onto the lumen of small‐diameter tubular scaffolds makes 3D endothelialization greatly challenging. Here, novel shape‐morphing scaffolds enabling programmed deformation from planar shapes to small‐diameter tubular shapes are designed and developed by combining biocompatible shape memory polymer and electrospun nanofibrous membrane. Endothelial cells can be conveniently seeded and attached on the 2D surface of the scaffolds and subsequently self‐rolled into 3D organization at physiological temperature. Endothelial cell responses and functions are varied on the shape‐morphing scaffolds with different nanofibrous electrospun membranes as the inner layer, arisen from the inducement of scaffolds with different morphological, physical, and biochemical characteristics. Owing to excellent properties of the nanofibrous membrane fabricated by the coelectrospinning of poly‐ε‐caprolactone (PCL) and gelatin methacrylate (GelMA), the shape‐morphing scaffolds with a nanofibrous PCL/GelMA inner layer support desirable homogeneous endothelial cell attachment as well as the rapid formation of biomimetic cell–scaffold interaction and cell–cell interaction under the 3D cell culture condition, therefore offering a visible approach for facile 3D endothelialization.     

非线性法布里-珀罗腔的双稳态特性分析

应用传输矩阵的方法研究了垂直微腔多量子阱结构的双稳态特性,计算结果表明,分布布喇格反射器（ＤＢＲ）的高折射率介质紧挨着非线性介质（多量子阱结构）时更容易产生双稳态,我们计算了非线性法布里－珀罗腔的反射相位与入射光功率关系曲线,反射率与入射光功率的关系曲线,和作为反射镜的ＤＢＲ的对数对双稳态性质的影响等。     

Optical bistability in an L-band dual-wavelength erbium-doped fiber laser with overlapping cavities

The authors investigate the optical bistability in an L-band dual-wavelength erbium-doped fiber (EDF) laser with overlapping cavities. The bistable input-output hysteresis behavior of the two lasing wavelengths evolves in antiphase. The bistable region is tens of milliwatts wide. The bistability is essentially due to the homogeneous saturable absorption of EDF. The cross-gain saturation causes the bistabilities of the two lasing lines to evolve in antiphase with respect to each other. The gain clamping effect helps to widen the bistable region, which may be controlled by the cavity loss and by the EDF length.     

Kirigami‐Inspired Self‐Assembly of 3D Structures

Self‐assembly of 3D structures presents an attractive and scalable route to realize reconfigurable and functionally capable mesoscale devices without human intervention. A common approach for achieving this is to utilize stimuli‐responsive folding of hinged structures, which requires the integration of different materials and/or geometric arrangements along the hinges. It is demonstrated that the inclusion of Kirigami cuts in planar, hingeless bilayer thin sheets can be used to produce complex 3D shapes in an on‐demand manner. Nonlinear finite element models are developed to elucidate the mechanics of shape morphing in bilayer thin sheets and verify the predictions through swelling experiments of planar, millimeter‐scaled PDMS (polydimethylsiloxane) bilayers in organic solvents. Building upon the mechanistic understandings, The transformation of Kirigami‐cut simple bilayers into 3D shapes such as letters from the Roman alphabet (to make “ADVANCED FUNCTIONAL MATERIALS”) and open/closed polyhedral architectures is experimentally demonstrated. A possible application of the bilayers as tether‐less optical metamaterials with dynamically tunable light transmission and reflection behaviors is also shown. As the proposed mechanistic design principles could be applied to a variety of materials, this research broadly contributes toward the development of smart, tetherless, and reconfigurable multifunctional systems.     

Multistability in Bistable Ferroelectric Materials toward Adaptive Applications

Traditionally thermodynamically bistable ferroic materials are used for nonvolatile operations based on logic gates (e.g., in the form of field effect transistors). But, this inherent bistability in these class of materials limits their applicability for adaptive operations. Emulating biological synapses in real materials necessitates gradual tuning of resistance in a nonvolatile manner. Even though in recent years few observations have been made of adaptive devices using a ferroelectric, the principal question as to how to make a ferroelectric adaptive has remained elusive in the literature. Here, it is shown that by locally controlling the nucleation energy distribution at the ferroelectric–electrode interface multiple‐addressable states in a ferroelectric can be created, which is necessary for adaptive/synaptic applications. This is realized by depositing a layer of nonswitchable ZnO on top of thin film ferroelectric PbZr _x Ti_{(1– x )}O₃. This methodology of interface‐engineered ferroelectric should enable realising brain‐like adaptive/synaptic memory in complementary metal‐oxide‐semiconductor (CMOS) devices. Furthermore, the temporally stable multistability in ferroelectrics should enable the designing of multistate memory and logic devices.     

可变偏振光注入垂直腔面发射激光器的频率诱导偏振双稳

为了探索垂直腔面发射激光器偏振敏感的双稳演 化规律,进一步拓展其在光信息处理领域方面的应 用,本文采用自旋反转模型,数值研究了可变偏振光注入下1 550 nm垂直腔面发射激光器频率诱导偏振双 稳的特性。研究结果表明:在可变偏振角度光注入下,通过沿不同路径扫描频率失谐,垂直 腔面发射激光 器的两个正交偏振分量可在负失谐和正失谐区域产生频率诱导的偏振双稳。对于一确定的注 入强度,注入 光偏振角度的增加可导致负失谐区域的偏振双稳宽度逐渐扩展,而正失谐区域双稳宽度无明 显的变化;给 定适当的注入光角度,较大的注入强度更易于在负失谐区域展宽偏振双稳宽度。此外,在注 入光偏振角度 和注入强度均一定时,不同偏置电流情况下激光器偏振分量的频率诱导双稳宽度存在较大差 异,系统可以 通过合理地调节注入光偏振角以及偏置电流等参量实现对频率诱导偏振双稳的灵活控制。     

Bioinspired Electro‐Thermo‐Hygro Reversible Shape‐Changing Materials by 4D Printing

Hygromorph composites are moisture‐induced shape‐changing materials that are increasingly studied to develop autonomously actuated deployable structures. The morphing mechanism is based on the high affinity for moisture and the hygroexpansive nature of at least one component, combined with a bilayer microstructure. Among available hygromorphs, those consisting of cellulosic or hydrogel material‐based actuators trigger fast responses to moisture. Their stiffness however decreases significantly with the moisture content and that restricts their potential application as soft actuators. This work proposes a novel 4D printed multistimuli‐responsive structural material based on conductive carbon reinforcements and combined with a moisture sensitive polymer. These 4D printed materials possess a microstructure that provides the capability of natural actuators like pine cones. The actuation of these functional materials could be either triggered passively by the variation of the ambient moisture, or by electroheating, with the latter leading to the control of the moisture content in initially wet samples via Joule effects. This new class of functional materials shows an increase of the actuation speed by a factor 10 compared to other existing hygromorphs with the same responsiveness. When the electrical heating is turned off, passive cooling and moisture driven actuation is triggered in a full reversible mode.     

Hydrogen-Bonded Liquid Crystal Elastomers Combining Shape Memory Programming and Reversible Actuation

Materials that undergo shape morphing in response to external stimuli have numerous applications, e.g., in soft robotics and biomedical devices. Shape memory polymers utilize kinetically trapped states to, typically irreversibly, transfer between a programmed morphed shape and an equilibrium shape. Liquid crystal elastomers (LCEs), in turn, can undergo reversible actuation in response to several stimuli. This study combines the irreversible and reversible shape morphing processes to obtain LCEs that undergo shape-programming via the shape memory effect and subsequent reversible actuation of the programmed shape. This is enabled by an LCE crosslinked via dynamic hydrogen bonds that break at high temperatures and reform upon cooling, endowing the shape memory effect, while mild thermal or photothermal stimulation yields the reversible actuation. Through this combination, proof-of-concept robotic application scenarios such as grippers that can adjust their shape for grabbing different-sized objects and crawling robots that can morph their shape to adapt to constrained spaces, are demonstrated. It is anticipated that this work adds new diversity to shape-programmable soft microrobotics.