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

Synthesis-Processing-Property Relationships in Thermomechanics of Liquid Crystal Elastomers

ABSTRACTA novel liquid crystal elastomer (LCE) synthesized by melt polymerization, which exhibits the capacity of shape memory, is reported here for the first time. The method of synthesize the shape memory LCE has been explored. A facile two‐step method to synthesize these anisotropic materials to realize reversible shape change behavior is reported. The first reaction is the addition of nematic liquid crystal molecules to form a kind of liquid crystal polymer. Subsequently, the polymer is crosslinked to trap the order of the liquid crystal into a crosslinked LCE. The LCE exhibits liquid crystalline behavior which has shape memory with excellent fixity and recovery. Its shape memory and actuating properties also have been studied. When reheating the LCE to 165 °C, the shape will recover. The main chains and crosslinked bonds of the LCE contain ester groups, which are sensitive to alkaline and acidic condition. It turns out that the LCE is intact under acidic condition, but it can be degraded under alkaline condition. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 389–394

Programming shape changes in soft materials requires precise control of the directionality and magnitude of their mechanical response. Among ordered soft materials, liquid crystal elastomers (LCEs) exhibit remarkable and programmable shape shifting when their molecular order changes. In this work, we synthesized, remotely programmed, and modeled reversible and complex morphing in monolithic LCE kirigami encoded with predesigned topological patterns in its microstructure. We obtained a rich variety of out-of-plane shape transformations, including auxetic structures and undulating morphologies, by combining different topological microstructures and kirigami geometries. The spatiotemporal shape-shifting behaviors are well recapitulated by elastodynamics simulations, revealing that the complex shape changes arise from integrating the custom-cut geometry with local director profiles defined by topological defects inscribed in the material. Different functionalities, such as a bioinspired fluttering butterfly, a flower bud, dual-rotation light mills, and dual-mode locomotion, are further realized. Our proposed LCE kirigami with topological patterns opens opportunities for the future development of multifunctional devices for soft robotics, flexible electronics, and biomedicine.

Liquid crystal elastomers (LCEs) are promising building blocks for soft robots, given their large, programmable, reversible, and stimuli‐responsive shape change. Enhancing LCEs’ stiffness and toughness has been a longstanding desire previously explored by reinforcing them with fillers, crystalline microdomains, and interpenetrating polymer networks. While promising, these methods adversely affect molecular order and thermal strain. Here, a significant enhancement of the stiffness of LCEs is reported by loading them with low molecular weight liquid crystals (LMWLCs) without sacrificing thermal strain and molecular order. While pristine LCEs rapidly transition to a soft elastic plateau when strained from poly‐ to monodomain, LC‐loaded samples (LC‐LCEs) first experience a pronounced linear elasticity, followed by a soft elastic plateau at higher stresses. Further thermomechanical and X‐ray analysis confirm the emergence of an additional mesophase in polydomain LC‐LCEs, which evolves to short‐range smectic (cybotactic) during the poly‐ to monodomain transition. Monodomain LC‐LCEs show between 6.5‐ and 9.0‐fold stiffness enhancement with improved molecular order and thermal strain. Their work densities are more than double that of pristine LCEs, with active thermal stroke of up to 25% under loads of over 2000 times their weight. Such remarkable behaviors are attributed to the interplay between post‐polymerization phase separation of LCs and their strain‐enhanced smectic ordering. The results suggest that LMWLC inclusion can be a simple yet robust method to significantly improve the mechanical properties of LCEs.

Modeling the thermo-responsive behaviors of polydomain and monodomain nematic liquid crystal elastomers

The chemical response of liquid crystal elastomers (LCEs) offers substantial potential for applications in propulsion systems, micromechanical systems, and active smart surfaces. However, the shape-changing behaviors of LCEs in response to organic (isotropic) solvents remain scarcely explored, with most research focusing on liquid crystal (anisotropic) solvents. Herein, we prepared a series of aligned LCEs with varying crosslink densities using a surface alignment technique combined with an aza-Michael addition reaction, aiming to investigate their swelling behaviors in different isotropic solvents. We found that the rates of shape and volume variation modes, the elastic modulus of the LCEs, and the polarity of the solvent all significantly influence the swelling behavior. Specifically, when LCEs swell in acetone, dimethylformamide (DMF), and ethyl acetate, contraction occurs along the alignment direction. Conversely, extension along the alignment direction is observed when LCEs swell in toluene, anisole, and acrylic acid. Meanwhile, extension in the perpendicular direction is noted when LCEs swell in nearly all solvents. These shape changes can be attributed to the phase transitions of the LCEs. This research not only provides valuable insights into the swelling mechanisms of LCEs but also holds great promise for the development of solvent sensors and gas sensing applications.

This dissertation demonstrates the design of reversibly self-morphing novel liquid crystalline elastomer (LCE) antennas that can dynamically change electromagnetic performance in response to temperature. This change in performance can be achieved by programming the shape change of stimuli-responsive (i.e., temperature-responsive) LCEs, and using these materials as substrates for reconfigurable antennas. Existing reconfigurable antennas rely on external circuitry such as Micro-Electro-Mechanical-Systems (MEMS) switches, pin diodes, and shape memory alloys (SMAs) to reconfigure their performance. Antennas using MEMS or diodes exhibit low efficiency due to the losses from these components. Also, antennas based on SMAs can change their performance only once as SMAs response to the stimuli and is not reversible. Flexible electronics are capable of morphing from one shape to another using various techniques, such as liquid metals, hydrogels, and shape memory polymers. LCE antennas can reconfigure their electromagnetic performance, (e.g., frequency of operation, polarization, and radiation pattern) and enable passive (i.e., battery-less) temperature sensing and monitoring applications, such as passive radio frequency identification device (RFID) sensing tags. Limited previous work has been performed on shape-changing antenna structures based on LCEs. To date, self-morphing flexible electronics, including antennas, which rely on stimuli-responsive LCEs that reversibly change shape in response to temperature changes, have not been previously explored. Here, LCE antennas will be studied and developed. Also, the metallization of LCEs with different metal conductors and their fabrication process, by either electron beam (E-Beam) evaporation or optical gluing of the metal film will be observed. The LCE material can have a significant impact on sensing applications due to its reversible actuation that can enable a sensor to work repeatedly. This interdisciplinary research (material polymer science and electrical engineering) is expected to contribute to the development of morphing electronics, including sensors, passive antennas, arrays, and frequency selective surfaces (FSS).

This paper summarises the properties of archiral and chiral liquid crystalline (LC) elastomers, the latter of which have found interest due to their piezoelectric properties. In addition the formation of new LC elastomers by a radical polymerization of acrylate groups covalently linked to LC polymers was investigated. This was done concerning the progress of the crosslinking reaction, concerning the influence of the crosslinking on the LC phases and concerning the network properties (swelling ratio and elastic modulus) of the resulting elastomers. It turns out that the networks prepared in this way are very soft and their crosslinking density is low. This can be explained assuming that the radical polymerization of the acrylates leads only to short oligomers, due to steric restrictions. Photo crosslinking initiated by a photoinitiator in the LC phase creates a memory of the orientation before crosslinking.

During the last few years, liquid crystalline elastomers (LCEs) have been systematically produced by cross-linking liquid crystalline side-chain polymers. In these networks, a liquid crystalline molecule is fixed at each monomeric unit. LCEs exhibit a novel combination of properties. Due to liquid crystalline groups, they show anisotropic liquid crystalline properties similar to conventional liquid crystals (LCs); but due to the three-dimensional network-structure of the polymer chains, they show typical elastomer properties, such as rubber elasticity or shape stability. One exceptional property of this combination is demonstrated when a mechanical deformation to the LCE causes macroscopically uniform orientation of the long molecular axis of the LC units (the so-called “director”).This response of the LC-phase structure to an applied mechanical field is similar to the effect of electric or magnetic fields on low molecular weight liquid crystals (LMLC), as illustrated in Figure 1. Figure la shows an undeformed LCE. Because of the non-uniform orientation of the director, the sample scatters light strongly so the elastomer is translucent like frosted glass. On the other hand, applying a mechanical field the director becomes uniformly aligned and the sample is transparent (Figure 1b). Such a macroscopically ordered rubber exhibits optical properties very similar to single crystals. These propertie s of LCEs offer new prospects for technical application, e.g., in nonlinear and integrated optics.

The monodomain nematic liquid crystal elastomer (LCE) is a nonporous material with one-dimension (1D) negative thermal expansion (NTE) along the direction of orientation. This stimuli-responsive size change is comparable with the contractile response of a muscle fibre. Recently, LCEs have become more and more popular and increasingly investigated as a full-fledged class of stimuli-responsive materials. However, the nematic LCE is limited to a single, unidirectional deformation unless complex hybrid architectures are made. We develop here a special LCE based on a liquid crystal polymer with an extraordinary phase transition sequence, “re-entrant nematic (NRe) – smectic A (SmA) – nematic (N) – isotropic (I) phase”, along with “prolate – oblate – weakly oblate – spherical” chain conformation evolution. In the aligned LCE film, these conformational changes of polymer chain are observed with the naked eye through their macroscopic translations into a unique sequence of “contraction – expansion – second expansion” deformations. Notably, a switch from NTE to positive thermal expansion (PTE) occurs upon heating. Moreover, a bilayer actuator composed of aligned and non-aligned LCE layers can perform 2D to 3D shape transformation with “curling – uncurling – second uncurling” actuation sequence. This LCE capable of multiple deformations in response to a single stimulus paves the way to multimodal single-material actuators. It provides a new strategy for the development of advanced materials with adjustable and multidirectional deformations.

Swelling behavior and deformations of main chain liquid crystal elastomers (MCLCEs) have been reported. The swelling agent used here is a low molecular weight liquid crystal (LMWLC), 4-n-pentyl-4-cyanobiphenyl (5CB). Monodomain MCLCE swells anisotropically with the swelling degree q mono = 11.9 and polydomain MCLCE swell isotropically in 3D with q poly = 12.1. These values are much larger than observed in swelling side-chain LCEs (SCLCEs). In the stress-strain measurement, the plateau area is found among two steep areas. The electromechanical effects of monodomain MCLCE is also observed, and the results show that the maximum contraction in ∥ is about 7%. The threshold for the onset of the electromechanical effect is about 10 V, which is larger than observed in SCLCEs.

Patterns perceived as regular by humans are ubiquitous and can be classified into non-biological patterns like cloud formations and sand dune stripes, biological patterns like zebra stripes, and artificial patterns like tiles. This paper focuses on three examples of non-biological self-organized patterns: wrinkles on material surfaces, alignment defect structures in liquid crystals, and a layered structure in liquid crystal elastomers. These non-biological patterns exhibiting useful functions are advantageous due to their low fabrication costs compared to biological and artificial patterns.

To study the effect of the content of the nematic cross-linking units on the mesophase behaviors, the optical and mesomorphic properties of liquid crystalline elastomers (LCEs), aseries of LCEs have been synthesized by hydrosilylation reaction with poly(methylhydrogeno)siloxane, a cholesteric liquid crystalline monomer, and a nematic cross-linking agent. The chemical structures and properties of the synthesized LCEs have been investigated by use of various techniques. Homopolymer P0 bearing only cholesteric component displays a smectic A phase, but elastomers P1-P5 containing different content of nematic cross-linking units show a cholesteric mesophase. The reflection wavelengths of theLCEs show a weak temperature dependence at lower temperatures but a strong temperature dependence at higher temperatures. Furthermore, the maximum reflection wavelengths of the LCEs can be stabilized over a wide temperature range when the LCEs are heated, suggesting that the helical structure and pitch of the cholesteric phase can be stabilized with a polymer network.

Liquid crystal elastomers (LCEs), a class of elastomers combining liquid crystals with a polymer network, have garnered significant interest for applications in the field of soft robotics. However, the fracture and fatigue characteristics of LCEs remain poorly understood. This study presents a comprehensive investigation into the fracture and fatigue characteristics of LCEs, focusing on polydomain and monodomain variants subjected to different loading directions. The fracture energy (also called toughness) and fatigue threshold of polydomain and monodomain LCEs were quantitatively measured and compared with selected elastomers. Our experimental results demonstrate that polydomain LCEs exhibit superior fracture energy and fatigue threshold compared to monodomain LCEs. Within the monodomain category, LCEs subjected to parallel loading exhibit larger fracture energy than those under vertical loading, while their fatigue thresholds remain comparable. These findings enhance our understanding of the deformation and failure characteristics of LCEs, which are crucial for their applications in various fields.

Effects of network structure of main-chain liquid crystal elastomer on its thermal actuation performance