Main-Chain Nematic Side-Chain Smectic Composite Liquid Crystalline Elastomers

A composite liquid crystalline elastomer is designed, combining main-chain and side-chain mesogenic polymers in the network, and resulting in micro-phase separated regions of nematic and smectic ordering in the macroscopically homogeneous elastomer. A range of different fractions of the components is explored, from fully nematic main-chain system, across to fully smectic side-chain elastomer. Thermal phase transitions of both phases coexisting in the material are detected by calorimetry, and the nematic/smectic structure investigated by X-ray scattering. The tensile stress–strain data reveal the key effect of such a multi-phase composite, where the nematic fraction adds ductility while the smectic fraction increases the modulus and mechanical stiffness. Varying the composition, the authors are able to optimize the mechanical properties of this material type.     

Light‐Driven Liquid Crystalline Networks and Soft Actuators with Degree‐of‐Freedom‐Controlled Molecular Motors

Design and fabrication of photomechanical soft actuators has attracted intense scientific interest because of their potential in the manufacture of untethered intelligent soft robots and advanced functional devices. Trifunctional and monofunctional polymerizable molecular motors are judiciously designed and synthesized. Novel light‐driven liquid crystalline networks (LCN) are prepared by crosslinking overcrowded‐alkene‐based molecular motors with different degrees of freedom into the anisotropic LCN. The photoisomerization and thermal helix inversion of light‐driven molecular motors are reversible when only the upper part of the molecular motor is linked to the network, endowing the LCN film with remarkable photoactive performance. However, photochemical geometric change of the light‐driven molecular motor does not work after crosslinking both the upper and lower part of the motor by polymer chains. Interestingly, it is found that the fastened motor can transfer the light energy into localized heat instead of performing photoisomerization. The light‐driven molecular‐motor‐based LCN soft actuators are demonstrated to function as a grasping hand, where the continuous motions of grasping, moving, lifting, and releasing an object are successfully achieved. This work may provide inspiration to the preparation of next‐generation photoactive advanced functional materials toward their wide applications in the areas of photonics, optoelectronics, soft robotics, and beyond.     

Microstructured Nematic Liquid Crystalline Elastomer Surfaces with Switchable Wetting Properties

Inspired by the lotus leaf, scientists have developed many superhydrophobic surfaces, some of which show remarkable switching between hydrophobic and hydrophilic state under external stimuli. However, the switch usually relies on the change of chemical properties rather than on the modification of the topographic structure of the surface. In this paper, the roughness‐change‐related switchable wetting properties of microstructured responsive surfaces made of nematic liquid crystalline elastomers (LCEs) is reported. First, various carbonate LC monomers and side‐on LCEs are synthesized with low nematic‐to‐isotropic transition temperature, T_NI. Then, LCEs prepared from 3″‐vinylcarbonyloxypropyl 2,5‐di(4′‐octyloxybenzoyloxy)benzoate monomer, with T_NI of 76 °C and contraction of 34% are used to construct a surface covered with micropillar arrays by using a replica molding technique. The contraction of the micropillars induces a reversible roughness change of the microstructured surface. Water contact angle of this microstructured surface changed with temperature, indicating a successful approach at building a surface with switchable wetting properties.     

Microstructured Photopolymerization of Liquid Crystalline Elastomers in Oxygen‐Rich Environments

Liquid crystal elastomers (LCEs) are soft materials that undergo large anisotropic shape change in response to stimuli. Rational organization of the local director field can impart spatial control of the strain profile, enabling stretch‐based deformation capable of nearly 20 J kg^?1 of output force. LCEs are increasingly being considered in end‐use applications in robotics, therapeutics, and optics. Here, a new synthetic approach is introduced to prepare LCEs composed of main chain mesogens via the cationic photopolymerization of the epoxy liquid crystal monomer (LCM). This examination details the optical, mechanical, and thermal properties of epoxide‐based LCEs as a function of spacer length (3, 6, or 11 carbons). The oxygen insensitivity of the cationic photopolymerization of these monomers makes this approach particularly attractive for implementation with emerging additive manufacturing techniques. This contribution focuses on microstructuring LCEs via 2‐photon direct laser writing (2P‐DLW). A custom heated cell facilitated 2P‐DLW of the aligned LCE epoxy resin melts to fabricate diverse geometric arrays. Enabled by the orthogonality of the reaction chemistry, hybrid and microstructured material compositions are prepared via the encapsulation of LCE epoxy micropatterns with free‐radical polymerization of acrylate‐based LCEs. The distinct thermomechanical response of the hybridized and microstructured LCE composites enables local and spatially controlled actuation.     

一种丙烯酸酯型侧链液晶高分子的合成及液晶性的研究

依据液晶分子结构理论,选择联苯基作为介晶基元,六亚甲基为柔性间隔基,合成了一种丙烯酸酯侧链型液晶高分子。对于合成的中间及目标产物通过FTIR、1HNMR等进行了结构的表征。对于聚合物采用GPC法测量了其分子量,并通过DSC、POM、XRD和计算机模拟等手段研究了其液晶性。研究表明合成的聚合物分子量-Mn=2523、-Mw=2826,具有较宽的温域(45.3～95.2℃),且为典型的近晶A相液晶。     

Microfluidic Synthesis of Liquid Crystalline Elastomer Particle Transport Systems which Can Be Remote‐Controlled Magnetically

Here, the microfluidic synthesis of liquid crystalline elastomer (LCE) particles, which can be remote‐controlled magnetically and used as transport systems, is presented for the first time. Ferri‐magnetic, rod‐shaped Fe₃O₄ nanoparticles are functionalized with poly(methyl methacrylate) to make them compatible with organic LCE precursor compounds. Their influence on the LCE precursor alignment is studied and thermoresponsive as well as photoresponsive LCE microparticles containing 0–6 wt% Fe₃O₄ are synthesized with a microfluidic device. Thermal and photochemical actuations of these particles are investigated. Their magnetic addressability is studied with a recently developed magnetic setup, by which the particles can be guided on liquid surfaces in the centimeter range–but with a precision in the submillimeter range. This allows the performance of reversible light‐ or heat‐controlled actuations at desired positions. The potential of synthesized LCE particles as transport systems is demonstrated by the transport of plastic, textiles or copper, which can be pushed just due to magnetic forces or transported in general by taking advantage of the phase dependent “stickiness” of LCEs. These studies open doors to novel applications of LCEs as microrobots using magnetism as a control.     

Mechano-Optical Sensors Fabricated with Multilayered Liquid Crystal Elastomers Exhibiting Tunable Deformation Recovery

Advances in tuning the mechanoresponsive behavior of liquid crystal elastomers have facilitated the development of next-generation applications such as reconfigurable photonic/electronic materials, energy-harvesting devices, and flexible sensors. However, the molecular-level control of mechanical responses remains difficult, with limited tunability achieved for recovery processes after stimulus removal. Herein, a design concept is proposed for facilely tuning the recovery of both the macroscopic deformation and molecular orientation change of liquid crystal elastomers using layered materials that exhibit the desired mechanoresponsive behavior. Changing the layering materials (a polydimethylsiloxane film with elastic response to a polymethylpenten film with plastic response) alters the relaxation time from <1 s to >6 months. To demonstrate this concept, highly sensitive, stretchable mechano-optical sensors with fast and ultraslow recovery times are developed that enable an applied strain to be quantitatively detected in real time or memorized with high spatial resolution, even with a conventional camera. This material design concept for arbitrarily controlling the recovery response can provide a platform for stimuli-responsive applications.     

Photoinduced Topographical Feature Development in Blueprinted Azobenzene‐Functionalized Liquid Crystalline Elastomers

All‐optical deformation and recovery of complex topographical features is demonstrated within elastic sheets composed of main‐chain type azobenzene‐functionalized liquid crystalline elastomers (azo‐LCEs). The azo‐LCEs are synthesized via an orthogonal, two‐step reaction between commercially available LC monomers and n‐butylamine. By employing surface alignment, the local orientation of the nematic director is spatially complex (“blueprinted”). Exposing the blueprinted LCE films to light as an actinic stimulus generates a photomechanical response which yields reversible shape changes between 2D and 3D shapes. The deformation of azo‐LCEs strongly depends on the azobenzene concentration as well as the network structure (i.e., crosslink density). Blueprinting complex director profiles within azo‐LCEs yield reconfigurable elastic sheets that can be addressed both remotely and selectively which may have benefit in a variety of applications in aerospace, medicine, and optics.     

3D-Printed Photoresponsive Liquid Crystal Elastomer Composites for Free-Form Actuation

Direct ink writing of liquid crystal elastomers (LCEs) offers a new opportunity to program geometries for a wide variety of shape transformation modes toward applications such as soft robotics. So far, most 3D-printed LCEs are thermally actuated. Herein, a 3D-printable photoresponsive gold nanorod (AuNR)/LCE composite ink is developed, allowing for photothermal actuation of the 3D-printed structures with AuNR as low as 0.1 wt.%. It is shown that the printed filament has a superior photothermal response with 27% actuation strain upon irradiation to near-infrared (NIR) light (808 nm) at 1.4 W cm⁻² (corresponding to 160 °C) under optimal printing conditions. The 3D-printed composite structures can be globally or locally actuated into different shapes by controlling the area exposed to the NIR laser. Taking advantage of the customized structures enabled by 3D printing and the ability to control locally exposed light, a light-responsive soft robot is demonstrated that can climb on a ratchet surface with a maximum speed of 0.284 mm s⁻¹ (on a flat surface) and 0.216 mm s⁻¹ (on a 30° titled surface), respectively, corresponding to 0.428 and 0.324 body length per min, respectively, with a large body mass (0.23 g) and thickness (1 mm).     

Reconfigurable Three-Dimensional Mesotructures of Spatially Programmed Liquid Crystal Elastomers and Their Ferromagnetic Composites

Reversible programming of 3D soft mesostructures is desired for many applications including soft robotics and biomedical devices. The large, reversible shape changes of liquid crystal elastomers (LCEs), which result from the coupling between the alignment of liquid crystal (LC) molecules and the macroscopic deformation of polymer networks, have attracted much attention for such applications. Here, a facile and versatile strategy is introduced to create reconfigurable, freestanding 3D mesostructures of LCEs and magnetic LCE composites that are inaccessible with existing techniques via spatially programming LC molecules through mechanical buckling. Demonstrations include experimental and theoretical results of more than 20 reconfigurable 3D LCE mesostructures of diverse configurations, from coils and spirals to structures that resemble fences and frameworks, with characteristic feature sizes and thicknesses ranging from micro to macro. The large, reversible shape-switching behaviors of these structures over multiple cycles are also demonstrated. An LCE gripper is shown to grab/release objects of both regular and irregular geometries. Furthermore, a robot of ferromagnetic LCE composites that simultaneously responds to magnetic and thermal stimuli for diverse biomimetic behaviors, especially crawling underneath a narrow crack, illustrates the integration of other functional materials to LCEs for multifunctional systems.     

Light-Guided Dynamic Liquid Crystalline Elastomer Actuators enabled by Mussel Adhesive Protein Chemistry

Light-guided soft actuators with dynamic polymer networks have drawn much attention in recent years. However, the application of such actuators is limited by their synthetic strategies, polymer structures, and shape-morphing modes. This work reports a new class of liquid crystalline elastomer (LCE) actuators crosslinked by mussel-inspired catechol-Fe (III) complexes. The actuators are mechanically strong while being self-healable, shape-reprogrammable, and reprocessable. Importantly, the formation of catechol-Fe (III) complexes enables the single-component LCE network to exhibit outstanding photothermal effects without any light-absorbing additives. Thus, actuators with designable structures and complex shape-morphing capabilities can be readily programmed with mechanical force coupled with either environmental heating or NIR light irradiation. Furthermore, the material platform provides a robust and flexible way to fabricate actuators with different dimensional structures varying from 1D to 3D. The LCE shows great potential in robotic fields, and as a proof-of-concept, a crawling robot, C-Bot, is specially designed. The robot is capable of moving untethered both on solid-substrate and water surfaces under the guidance of light based on the mechanisms of shape-morphing and Marangoni propulsion, respectively. Surprisingly, different from the vast majority of previously reported LCE-based robots, the C-Bot is strong enough to carry a heavy load while moving.     

Microstructured Actuation of Liquid Crystal Polymer Networks

Smart microstructured materials enable functions such as actuation, detection, transportation, and sensing with potential applications ranging from robotics and photonics to biomedical devices. Of the many materials systems, liquid crystal polymer networks (LCN) are fascinating owing to their ability to exhibit reversible macroscopic deformation driven by a molecular order–disorder phase transition. LCN have been increasingly explored for their utility in the design and fabrication of smart actuating devices capable of complex shape changes or motions upon external stimulation of humidity, heat, light, and other stimuli, and recent studies in this field show that their actuation complexity can be enriched and actuation performance enhanced by having some sort of microstructures. Herein, the recent progress in microstructured actuation of LCN materials with substructures in scale ranging from micrometer to millimeter is reported, placing the emphasis on the main approaches to generating a microstructure in LCN, which include patterned LC director fields, patterned chain crosslinking in LCN with uniaxial orientation of mesogens, 3D/4D printing, and replica molding. The potential applications in microstructured 3D actuators and devices as well as functional LCN surfaces are also highlighted, with an outlook on important issues and future trends in smart microstructured LCN materials and actuators.     

Reversible and Rapid Laser Actuation of Liquid Crystalline Elastomer Micropillars with Inclusion of Gold Nanoparticles

It is highly desirable for liquid crystal elastomer (LCE) based microactuators to activate and actuate in a highly controlled fashion without perturbing the surrounding environment. To reach this goal, in this study, a novel experimental protocol is developed to successfully incorporate gold nanosphere (AuNS) and gold nanorod (AuNR) into polyacrylate based LCE elastomer to fabricate LCE/AuNR and LCE/AuNS micropillars or microactuators. The effect of gold nanoparticle inclusion has been studied by spectroscopy (UV–vis‐near‐infrared), microscopy (transmission electron microscopy), thermal analysis (differential scanning calorimetry and thermogravimetric analysis), and x‐ray scattering (wide‐angle x‐ray scattering and small‐angle x‐ray scattering). Finite element analysis is performed to examine the feasibility of utilizing the photothermal effect of AuNR/AuNS to enable photothermal actuation of LCE/AuNR and LCE/AuNS micropillars. The comparative experimental studies on the thermal and photothermal actuation behavior of the LCE, LCE/AuNS, and LCE/AuNR micropillar suggested that AuNR is an excellent candidate for developing high‐performance LCE actuators with photothermal actuation capability. With inclusion of less than 1 wt% of AuNR, the very high maximum actuation strain (30%) and rapid response (a few seconds) have been achieved in LCE/AuNR micropillar actuators under 635 nm laser irradiation.     

液晶聚合物薄膜的介电性能

研究了两种液晶聚合物薄膜的介电性能。结果表明,液晶聚合物的介电常数随频率的增加而缓慢变小,高温下的介电常数较大。介电损耗在一定的温度范围内（室温至３５０℃）出现峰值,峰值位置随频率的增加向高温方向移动。     

一种超支化分子液晶性的研究

超支化聚酯是以3，5－二羟基甲苯和3，5－二羟基苯甲酸为原料，采用“一锅煮”的方法合成而得。通过热示差、偏光显微镜、X衍射等手段全面地探讨了聚酯的液晶性。表明该聚合物在83.4-134.6℃较宽的温度区间表现出典型的向列型液晶性质。     

含柔性长链的二元胆甾相新型液晶的制备及其性能研究

以胆甾醇和长链二元酸为原料，合成了一种柔性长链的新型小分子二元胆甾相液晶，并对其相转变过程进行了深入分析。红外光谱、核磁共振谱、质谱和元素分析证实了其分子结构，差示扫描热分析（DSC）谱图和偏光显微镜（POM）观察图像等一致表明其相转变过程完全符合胆甾相液晶的特征。说明胆甾相液晶分子的刚性大小与胆甾相液晶的形成没有直接关系，胆甾相液晶基元是其形成有序排列的决定因素。     

Control of the Properties of Micrometer‐Sized Actuators from Liquid Crystalline Elastomers Prepared in a Microfluidic Setup

In this article new results on the preparation of monodisperse particles from a liquid crystalline elastomer in a microfluidic setup are presnted. For this, droplets from a liquid crystalline monomer are prepared in a microfluidic device and polymerized while they are flowing inside a microtube. The parti­cles obtained by this method possess an internal orientation, which gives them actuating properties. When they are heated into the isotropic phase of the liquid crystalline material they show a reversible change in shape whereby they change their length in one direction by almost 100%. It is shown how the variation of experimental parameters during their synthesis impacts the properties of these micro‐actuators. Influence over their primal shape, the strength of their shape changing properties, their size, and their mechanical properties is demontrated. From the systematic variation of experimental parameters a deep understanding of the complex processes taking place in a flowing droplet of a liquid crystalline material is obtainted. Additionally NMR analysis and swelling experiments on these actuating materials are provided.     

聚乙烯醇侧链液晶的结构与液晶性研究

研究了聚乙烯醇侧链液晶主链分子量和液晶基元等结构因素对其液晶性的影响，结果表明随着聚合物的分子量增加，导致复合物清亮点温度下降。但是在液晶主链尚未被液晶基元饱和之前，随着液晶基元相对主链摩尔比的增加，样品形成较为完善的氢键结构。