This Review discusses stimuli-responsive liquid crystalline polymer networks and elastomers as materials with programmable mechanics for use in functional devices. Liquid crystals are the basis of a pervasive technology of the modern era. Yet, as the display market becomes commoditized, researchers in industry, government and academia are increasingly examining liquid crystalline materials in a variety of polymeric forms and discovering their fascinating and useful properties. In this Review, we detail the historical development of liquid crystalline polymeric materials, with emphasis on the thermally and photogenerated macroscale mechanical responses — such as bending, twisting and buckling — and on local-feature development (primarily related to topographical control). Within this framework, we elucidate the benefits of liquid crystallinity and contrast them with other stimuli-induced mechanical responses reported for other materials. We end with an outlook of existing challenges and near-term application opportunities.

Programmable and adaptive mechanics with liquid crystal polymer networks and elastomers

Recent progress in shape memory polymer: New behavior, enabling materials, and mechanistic understanding

Most covalent adaptable networks give highly interesting properties for material processing such as reshaping, recycling and repairing. Classical thermally reversible chemical cross-links allow for a heat-triggered switch between materials that behave as insoluble cured resins, and liquid thermoplastic materials, through a fully reversible sol–gel transition. In 2011, a new class of materials, coined vitrimers, was introduced, which extended the realm of adaptable organic polymer networks. Such materials have the remarkable property that they can be thermally processed in a liquid state without losing network integrity. This feature renders the materials processable like vitreous glass, not requiring precise temperature control. In this mini-review, an overview of the state-of-the-art in the quickly emerging field of vitrimer materials is presented. With a main focus on the chemical origins of their unique thermal behavior, the existing chemical systems and their properties will be discussed. Furthermore, future prospects and challenges in this important research field are highlighted.

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Vitrimers: permanent organic networks with glass-like fluidity

This review comprises a detailed survey of ongoing methodologies for soft actuators, highlighting approaches suitable for nanometer- to centimeter-scale robotic applications. Soft robots present a special design challenge in that their actuation and sensing mechanisms are often highly integrated with the robot body and overall functionality. When less than a centimeter, they belong to an even more special subcategory of robots or devices, in that they often lack on-board power, sensing, computation, and control. Soft, active materials are particularly well suited for this task, with a wide range of stimulants and a number of impressive examples, demonstrating large deformations, high motion complexities, and varied multifunctionality. Recent research includes both the development of new materials and composites, as well as novel implementations leveraging the unique properties of soft materials.

Soft Actuators for Small-Scale Robotics.

Windmills, cars, and dental restoration demand polymer materials and composites that are easy to process, assemble, and recycle while exhibiting outstanding mechanical, thermal, and chemical resistance. Vitrimers, which are polymer networks able to shuffle chemical bonds through exchange reactions, could address these demands if they were prepared from existing plastics and processed with fast production rates and current equipment. We report the metathesis of dioxaborolanes, which is rapid and thermally robust, and use it to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding. They show superior chemical resistance and dimensional stability and can be efficiently assembled. The strategy is applicable to polymers with backbones made of carbon-carbon single bonds.

High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis

A requirement for the reversible mechanical actuation of liquid-crystal elastomers is macroscale alignment. However, current processing techniques do not achieve reliable and robust alignment, which limits the practical use of these materials as actuators and artificial muscles. It is now shown that by introducing polymers with exchangeable covalent bonds, liquid-crystal elastomers can be easily processed and aligned, and subsequently remodelled.

Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds

Making dynamic three-dimensional (3D) structures capable of reversible shape changes or locomotion purely out of dry polymers is very difficult. Meanwhile, no previous dynamic 3D structures can be remade into new configurations while being resilient to mechanical damages and low temperature. Here, we show that light-activated transesterification in carbon nanotube dispersed liquid crystalline vitrimers enables flexible design and easy building of dynamic 3D structures out of flat films upon irradiation of light without screws, glues, or molds. Shining light also enables dynamic 3D structures to be quickly modified on demand, restored from distortion, repaired if broken, in situ healed when microcrack appears, assembled for more sophisticated structures, reconfigured, and recycled after use. Furthermore, the fabrication, reconfiguration, actuation, reparation, and assembly as well as healing can be performed even at extremely low temperatures (e.g., −130 °C).

Making and Remaking Dynamic 3D Structures by Shining Light on Flat Liquid Crystalline Vitrimer Films without a Mold

Assembling epoxy, one of the most common and widely used thermosets, by welding with remote control is extremely difficult and has not been realized so far, as epoxy cannot melt or be dissolved. Here we present a very simple but highly efficient solution by exploring the photothermal effect of carbon nanotubes (CNTs) to manipulate the transesterification reaction in vitrimers. The carbon nanotube dispersed vitrimer epoxy presented here can be welded by light within seconds or minutes. Moreover, various CNT–vitrimer epoxy materials with different chemical compositions and physical properties can be joined together. Furthermore, transmission welding can be used to weld CNT–vitrimers with other kinds of epoxy or thermoplastic polymers, which is not applicable to welding by direct heating and impossible to realize using the currently available photoweldable covalently cross-linked polymer networks. Additionally, these networks can be efficiently healed by light without the involvement of any glue or sealing agents.

Carbon nanotube–vitrimer composite for facile and efficient photo-welding of epoxy

Smart polymers have been playing indispensable roles in our lives. However, it is challenging to combine more than three stimuli-responses or functionalities into one polymer, not to mention integrating multi-stimuli responsivity and multi-functionality at the same time. Vitrimers, an emerging type of materials, are covalently crosslinked networks that can be reprocessed but are still infusible and insoluble. Herein, we show that simply introducing oligoaniline into a vitrimer results in a covalently crosslinked material that can respond to six different stimuli (heat, light, pH, voltage, metal ions and redox chemicals) and perform six functions (shape memory, welding, healing, recycling, electro-chromism and adsorption of metal ions). New properties, which cannot be found in either neat vitrimers or oligoanilines, are generated, including photo-heal-ability, photo-weldability, pH-induced shape memory, enhancement of the photo-thermal effect due to metal ions absorption and simultaneous multi-tasking operations. Furthermore, the material is low-cost and suitable for large-scale mass production.

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Multi-stimuli responsive and multi-functional oligoaniline-modified vitrimers

Photo-active shape memory polymers (SMPs) are considered as a promising candidate for converting light into mechanical energy. However, most known SMPs are only thermo-responsive. To achieve photo-activity, photo-responsive choromophores or fillers usually have to be incorporated from the very beginning of the material synthesis. Here, we introduce a novel post-synthesis approach to endow normal SMPs with photo-active properties using mussel-inspired surface chemistry. Without changing the original properties, the resultant polydopamine (PDA) coated SMPs show an efficient photo-active performance. The coating can be easily patterned and erased, which allows flexible light-triggered 3-D shape deformation of a planar SMP sheet. Moreover, owing to the high chemical activity, the PDA coating also provides a platform to optimize the surface properties of the photo-responsive SMPs through secondary surface modification.

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Yen Wei

Papers

Mouldable liquid-crystalline elastomer actuators with exchangeable covalent bonds

Making and Remaking Dynamic 3D Structures by Shining Light on Flat Liquid Crystalline Vitrimer Films without a Mold

Carbon nanotube–vitrimer composite for facile and efficient photo-welding of epoxy

Multi-stimuli responsive and multi-functional oligoaniline-modified vitrimers

Polydopamine coated shape memory polymer: enabling light triggered shape recovery, light controlled shape reprogramming and surface functionalization