Soft elasticity enabled adhesion enhancement of liquid crystal elastomers on rough surfaces.

The fabrication of pressure-sensitive adhesives (PSA) using liquid crystal elastomers (LCE) that are tolerant to substrate roughness is explored in this work. Traditional soft adhesives are designed by maintaining a balance between their cohesive strength and compliance. However, rough surfaces can significantly affect the adhesion strength of PSAs. Lowering the stiffness of the adhesive by reducing the cross-linking density or using additives can improve contact on rough surfaces. But this also decreases the cohesive strength and affects the overall performance of the adhesive. Additive-free LCE-based adhesives are shown to overcome these challenges due to their unique properties. Soft elasticity of LCE and low cross-link density contribute to their high compliance, while moderate cross-linking provides finite strength. The effect of contact time and substrate roughness on the adhesive performance is evaluated using probe-tack, indentation, lap shear, and static loading experiments. The unique combination of properties offered by LCE can lead to the development of roughness-tolerant adhesives, thereby broadening the application scope of PSAs.

Ultrafast universal fabrication of configurable porous silicone-based elastomers by Joule heating chemistry.

Silicone-based elastomers (SEs) have been extensively applied in numerous cutting-edge areas, including flexible electronics, biomedicine, 5G smart devices, mechanics, optics, soft robotics, etc. However, traditional strategies for the synthesis of polymer elastomers, such as bulk polymerization, suspension polymerization, solution polymerization, and emulsion polymerization, are inevitably restricted by long-time usage, organic solvent additives, high energy consumption, and environmental pollution. Here, we propose a Joule heating chemistry method for ultrafast universal fabrication of SEs with configurable porous structures and tunable components (e.g., graphene, Ag, graphene oxide, TiO2, ZnO, Fe3O4, V2O5, MoS2, BN, g-C3N4, BaCO3, CuI, BaTiO3, polyvinylidene fluoride, cellulose, styrene-butadiene rubber, montmorillonite, and EuDySrAlSiOx) within seconds by only employing H2O as the solvent. The intrinsic dynamics of the in situ polymerization and porosity creation of these SEs have been widely investigated. Notably, a flexible capacitive sensor made from as-fabricated silicone-based elastomers exhibits a wide pressure range, fast responses, long-term durability, extreme operating temperatures, and outstanding applicability in various media, and a wireless human-machine interaction system used for rescue activities in extreme conditions is established, which paves the way for more polymer-based material synthesis and wider applications.

A molecular interpretation of the toughness of multiple network elastomers at high temperature.

SignificanceSoft materials can be toughened by creating dissipative mechanisms in stretchy matrixes. Yet using them over a wide range of temperatures requires dissipative mechanisms independent of stretch rate or temperature. We show that sacrificial covalent bonds in multiple network elastomers are most useful in toughening elastomers at high temperature and act synergistically with viscoelasticity at lower temperature. We do not attribute this toughening mechanism only to the scission of bonds during crack propagation but propose that the highly stretched network diluted in a stretchy matrix acts by simultaneously stiffening the elastomer and delaying the localization of bond scission and the propagation of a crack. Such a toughening mechanism has never been proposed for elastomers and should guide network design.

Twisting for soft intelligent autonomous robot in unstructured environments.

Soft robots that can harvest energy from environmental resources for autonomous locomotion is highly desired; however, few are capable of adaptive navigation without human interventions. Here, we report twisting soft robots with embodied physical intelligence for adaptive, intelligent autonomous locomotion in various unstructured environments, without on-board or external controls and human interventions. The soft robots are constructed of twisted thermal-responsive liquid crystal elastomer ribbons with a straight centerline. They can harvest thermal energy from environments to roll on outdoor hard surfaces and challenging granular substrates without slip, including ascending loose sandy slopes, crossing sand ripples, escaping from burying sand, and crossing rocks with additional camouflaging features. The twisting body provides anchoring functionality by burrowing into loose sand. When encountering obstacles, they can either self-turn or self-snap for obstacle negotiation and avoidance. Theoretical models and finite element simulation reveal that such physical intelligence is achieved by spontaneously snapping-through its soft body upon active and adaptive soft body-obstacle interactions. Utilizing this strategy, they can intelligently escape from confined spaces and maze-like obstacle courses without any human intervention. This work presents a de novo design of embodied physical intelligence by harnessing the twisting geometry and snap-through instability for adaptive soft robot-environment interactions.

High Thermal Conductive Liquid Crystal Elastomer Nanofibers.

Liquid crystal elastomers (LCEs), consisting of polymer networks and liquid crystal mesogens, show a reversible phase change under thermal stimuli. However, the kinetic performance is limited by the inherently low thermal conductivity of the polymers. Transforming amorphous bulk into a fiber enhances thermal conductivity through the alignment of polymer chains. Challenges are present due to their rigid networks, while cross-links are crucial for deformation. Here, we employ hydrodynamic alignment to orient the LCE domains assisted by controlled in situ cross-linking and to remarkably reduce the diameter to submicrons. We report that the intrinsic thermal conductivity of LCE fibers at room temperature reaches 1.44 ± 0.32 W/m-K with the sub-100 nm diameter close to the upper limit determined in the quasi-1D regime. Combining the outstanding thermal conductivity and thin diameters, we anticipate these fibers to exhibit a rapid response and high force output in thermomechanical systems. The fabrication method is expected to apply to other cross-linked polymers.

Elastomer Composites with High Damping and Low Thermal Resistance via Hierarchical Interactions and Regulating Filler.

Modern microelectronics and emerging technologies such as wearable electronics and soft robotics require elastomers to integrate high damping with low thermal resistance to avoid damage caused by vibrations and heat accumulation. However, the strong coupling between storage modulus and loss factor makes it generally challenging to simultaneously increase both thermal conductance and damping. Here, a strategy of introducing hierarchical interaction and regulating fillers in polybutadiene/spherical aluminum elastomer composites is reported to simultaneously achieve extraordinary damping ability of tan δ > 1.0 and low thermal resistance of 0.15 cm2 K W-1, which surpasses state-of-the-art elastomers and their composites. The enhanced damping is attributed to increased energy dissipation via introducing the hierarchical hydrogen bond interactions in polybutadiene networks and the addition of spherical aluminum, which also functions as a thermally conductive filler to achieve low thermal resistance. As a proof of concept, the polybutadiene/spherical aluminum elastomer composites are used as thermal interface materials, showing effective heat dissipation for electronic devices in vibration scenarios. The combination of outstanding damping performance and extraordinary heat dissipation ability of the elastomer composites may create new opportunities for their applications in electronics.

Biomass and Transparent Supramolecular Elastomers for Green Electronics Enabled by the Controlled Growth and Self-Assembly of Dynamic Polymer Networks.

Determining the optimal method for preparing supramolecular materials remains a profound challenge. This process requires a combination of renewable raw materials to create supramolecular materials with multiple functions and properties, including simple fabrication, sustainability, a dynamic nature, good toughness, and transparency. In this work, a strategy is presented for toughening supramolecular networks based on solid-phase chain extension. This toughening strategy is simple and environmentally friendly. In addition, a series of biobased elastomers are designed and prepared with adjustable performance characteristics. This strategy can significantly improve the transparency, tensile strength, and toughness of the synthesized elastomer. The synthesized biobased elastomers have great ductility, repairability, and recyclability, and they show good adhesion and dielectric properties. A biobased ionic skin is assembled from these biobased elastomers. Assembled ionic skin can sensitively detect external stimuli (such as stretching, bending, compression, or temperature changes) and monitor human movement. The conductive and dielectric layers of the biobased ionic skin are both obtained from renewable raw materials. This research provides novel molecular design approaches and material selection methods for promoting the development of green electronic devices and biobased elastomers.

Autonomous Underwater Self-Healable Adhesive Elastomers Enabled by Dynamical Hydrophobic Phase-Separated Microdomains.

High-efficient underwater self-healing materials with reliable mechanical attributes hold great promise for applications in ocean explorations and diverse underwater operations. Nevertheless, achieving these functions in aquatic environments is challenging because the recombination of dynamic interactions will suffer from resistance to interfacial water molecules. Herein, an ultra-robust and all-environment stable self-healable polyurethane-amide supramolecular elastomer is developed through rational engineering of hydrophobic domains and multistrength hydrogen bonding interactions to provide mechanical and healing compatibility as well as efficient suppression of water ingress. The coupling of hydrophobic chains and hierarchical hydrogen bonds within a multiphase matrix self-assemble to generate dynamical hydrophobic hard-phase microdomains, which synergistically realize high stretchability (1601%), extreme toughness (87.1 MJ m-3), and outstanding capability to autonomous self-healing in various harsh aqueous conditions with an efficiency of 58% and healed strength of 12.7 MPa underwater. Furthermore, the self-aggregation of hydrophobic clusters with sufficient dynamic interactions endows the resultant elastomer with effective instantaneous adhesion (6.2 MPa, 941.9 N m-1) in extremely harsh aqueous conditions. It is revealed that the dynamical hydrophobic hard-phase microdomain composed of hydrophobic barriers and cooperative reversible interactions allows for regulating its mechanical enhancement and underwater self-healing efficiency, enabling the elastomers as intelligent sealing devices in marine applications.

Mechanically Ultra-Robust Fluorescent Elastomer for Elaborating Auxetic Composite.

Fluorescent elastomers are predominantly fabricated through doping fluorescent components or conjugating chromophores into polymer networks, which often involves detrimental effects on mechanical performance and also makes large-scale production difficult. Inspired by the heteroatom-rich microphase separation structures assisted by intensive hydrogen bonds in natural organisms, an ultra-robust fluorescent polyurethane elastomer is reported, which features a remarkable fracture strength of 87.2 MPa with an elongation of 1797%, exceptional toughness of 678.4 MJ m-3 and intrinsic cyan fluorescence at 445 nm. Moreover, the reversible fluorescence variation with temperature could in situ reveal the microphase separation of the elastomer in real time. By taking advantage of mechanical properties, intrinsic fluorescence and hydrogen bonds-promoted interfacial bonding ability, this fluorescent elastomer can be utilized as an auxetic skeleton for the elaboration of an integrated auxetic composite. Compared with the auxetic skeleton alone, the integrated composite shows an improved mechanical performance while maintaining auxetic deformation in a large strain below 185%, and its auxetic process can be visually detected under ultraviolet light by the fluorescence of the auxetic skeleton. The concept of introducing hydrogen-bonded heteroatom-rich microphase separation structures into polymer networks in this work provides a promising approach to developing fluorescent elastomers with exceptional mechanical properties.

Thermally Conductive Elastomer Composites with High Toughness, Softness, and Resilience Enabled by Regulating Interfacial Structure and Dynamics.

The emerging applications of thermally conductive elastomer composites in modern electronic devices for heat dissipation require them to maintain both high toughness and resilience under thermomechanical stresses. However, such a combination of thermal conductivity and desired mechanical characteristics is extremely challenging to achieve in elastomer composites. Here this long-standing mismatch is resolved via regulating interfacial structure and dynamics response. This regulation is realized both by tuning the molecular weight of the dangling chains in the polymer networks and by silane grafting of the fillers, thereby creating a broad dynamic-gradient interfacial region comprising of entanglements. These entanglements can provide the slipping topological constraint that allows for tension equalization between and along the chains, while also tightening into rigid knots to prevent chain disentanglement upon stretching. Combined with ultrahigh loading of aluminum-fillers (90 wt%), this design provides a low Young's modulus (350.0 kPa), high fracture toughness (831.5 J m-2), excellent resilience (79%) and enhanced thermal conductivity (3.20 W m-1 k-1). This work presents a generalizable preparation strategy toward engineering soft, tough, and resilient high-filled elastomer composites, suitable for complex environments, such as automotive electronics, and wearable devices.

Fully Recycled Polyolefin Elastomer-Based Vitrimers with Ultra-High, Universal, Stable, and Switchable Adhesion.

Achieving both robust adhesion to arbitrary surfaces and thermal-switchable/recyclable properties has proven challenging, particularly for commodity polyolefins. Herein, a simple and effective route is reported to transform polyolefins elastomer (POE) into a fully recycled epoxy-functionalized POE vitrimers (E-POE vit) with ultra-high, universal, stable, and switchable adhesion via facile free radical grafting and dynamic cross-linking. The resultant E-POE vit exhibits increase in adhesion strength on glass exceeding three to ten times compared to those commonly used polymers, due to the synergy of dense hydrogen (H)-bonds and strong interfacial affinity. In addition, E-POE vit also displays strong adhesion on diverse surfaces ranging from inorganic to organic while maintaining good stability in various harsh environments. More importantly, temperature-sensitive H-bonds allow E-POE vit to switch between attachment-detachment at alternating temperatures, resulting in reversible adhesion without adhesion loss, even after 10 cycles. Moreover, E-POE vit is able to be fully recycled and reused more than ten times via thermo-activated transesterification reactions with negligible change in structure and performance. This work may unlock strategies to fabricate high-performance commercial polymer-based adhesives with adhesion and recyclable features for intelligent and sustainable applications.

Innovative Synthesis of Photo-Responsive, Self-Healing Silicone Elastomers with Enhanced Mechanical Properties and Thermal Stability.

Photo-responsive materials have garnered significant interest for their ability to react to non-contact stimuli, though achieving self-healing under gentle conditions remains an elusive goal. In this research, an innovative and straightforward approach for synthesizing silicone elastomers is proposed that not only self-heal at room temperature but also possess unique photochromic properties and adjustable mechanical strength, along with being both transparent and reprocessable. Initially, aldehyde-bifunctional dithiophene-ethylene molecules with dialdehyde groups (DTEM) and isocyanurate (IPDI) is introduced into the aminopropyl-terminated polydimethylsiloxane (H2N-PDMS-NH2) matrix. Subsequently, palladium is incorporated to enhance coordination within the matrix. These silicone elastomers transition to a blue state under 254 nm UV light and revert to transparency under 580 nm light. Remarkably, they demonstrate excellent thermal stability at temperatures up to 100 °C and show superior fatigue resistance. The optical switching capabilities of the silicone elastomers significantly affect both their mechanical characteristics and self-healing abilities. Notably, the PDMS-DTEM-IPDI-@Pd silicone elastomer, featuring closed-loop photo-switching molecules, exhibits a fracture toughness that is 1.3 times greater and a room temperature self-healing efficiency 1.4 times higher than its open-loop counterparts. This novel photo-responsive silicone elastomer offers promising potential for applications in data writing and erasure, UV protective coatings, and micro-trace development.

Fiber Actuators Based on Reversible Thermal Responsive Liquid Crystal Elastomer.

Soft actuators inspired by the movement of organisms have attracted extensive attention in the fields of soft robotics, electronic skin, artificial intelligence, and healthcare due to their excellent adaptability and operational safety. Liquid crystal elastomer fiber actuators (LCEFAs) are considered as one of the most promising soft actuators since they can provide reversible linear motion and are easily integrated or woven into complex structures to perform pre-programmed movements such as stretching, rotating, bending, and expanding. The research on LCEFAs mainly focuses on controllable preparation, structural design, and functional applications. This review, for the first time, provides a comprehensive and systematic review of recent advances in this important field by focusing on reversible thermal response LCEFAs. First, the thermal driving mechanism, and direct and indirect heating strategies of LCEFAs are systematically summarized and analyzed. Then, the fabrication methods and functional applications of LCEFAs are summarized and discussed. Finally, the challenges and technical difficulties that may hinder the performance improvement and large-scale production of LCEFAs are proposed, and the development opportunities of LCEFAs are prospected.

Easy Processable Photomechanical Thin Film Involving a Photochromic Diarylethene and a Thermoplastic Elastomer in Supramolecular Interaction.

A novel supramolecular photoactuator in the form of a thin film of centimetric size has been developed as an alternative to traditional liquid crystal elastomers (LCE) involving azobenzene (AZO) units or photochromic microcrystals. This thin film is produced through spin coating without the need for alignment or crosslinking. The photoactuator combines a photochromic dithienylethene (DTE) functionalized with ureidopyrimidinone (UPy) units, and a telechelic thermoplastic elastomer, also functionalized with UPy, allowing quadruple hydrogen bonding between the two components. Upon alternating ultraviolet (UV) and visible light exposure, the film exhibits reversible bending and color changes, studied using displacement and absorption tracking setups. For the first time, the photomechanical effect (PME) is quantitatively correlated with photochromism, showing that DTE units drive the movement under both UV (photocyclization) and visible (photoreversion) light. In situ illumination techniques reveal that the PME arises from photoinduced strain within 160 nm UPy-bonded DTE domains, which expand and contract by approximately 50% under UV and visible light, respectively. The semicrystalline nature of the elastomer and a robust supramolecular network connecting both components are critical in converting microscopic photostrain into macroscopic actuation.

Ultra-Fast Fabrication of Mechanical-Water-Responsive Color-Changing Photonic Crystals Elastomers and 3D Complex Devices.

The traditional fabrication of opal-structured photonic crystals is constrained by the rate of solvent evaporation, a process that is not only time-consuming but also labor-intensive. This study introduces a paradigm shift by incorporating silica nanoparticles (SiNPs) with high zeta potentials and hydrogen bonding capabilities into an elastomeric matrix, resulting in a novel non-close-packed structure. This innovation circumvents the limitations of conventional methods by enabling the rapid formation of photonic inks (PI) into vibrant and luminous photonic elastomers (PEs) within seconds. These PEs demonstrate remarkable mechanochromic properties, exhibiting dynamic color changes across the visible spectrum in response to tensile and compressive deformations. Furthermore, the presence of hydroxyl groups endows the PEs with superior water-responsiveness, which can be finely tuned through the ink formulation. The elimination of solvent evaporation dependency facilitates the fabrication of macroscopic photonic crystal devices with complex geometries using digital light processing (DLP)-based 3D printing. This approach ensures exceptional optical performance and high customization potential. The resulting PEs hold significant promise for applications in smart wearables, soft robotics, and advanced human-machine interface technologies.

Fibrous MXene Synapse-Based Biomimetic Tactile Nervous System for Multimodal Perception and Memory.

Biomimetic tactile nervous system (BTNS) inspired by organisms has motivated extensive attention in wearable fields due to its biological similarity, low power consumption, and perception-memory integration. Though many works about planar-shape BTNS are developed, few researches could be found in the field of fibrous BTNS (FBTNS) which is superior in terms of strong flexibility, weavability, and high-density integration. Herein, a FBTNS with multimodal sensibility and memory is proposed, by fusing the fibrous poly lactic acid (PLA)/Ag/MXene/Pt artificial synapse and MXene/EMIMBF4 ionic conductive elastomer. The proposed FBTNS can successfully perceive external stimuli and generate synaptic responses. It also exhibits a short response time (23 ms) and low set power consumption (17 nW). Additionally, the proposed device demonstrates outstanding synaptic plasticity under both mechanical and electrical stimuli, which can simulate the memory function. Simultaneously, the fibrous devices are embedded into textiles to construct tactile arrays, by which biomimetic tactile perception and temporary memory functions are successfully implemented. This work demonstrates the as-prepared FBTNS can generate biomimetic synaptic signals to serve as artificial feeling signals, it is thought that it could offer a fabric electronic unit integrating with perception and memory for Human-Computer interaction, and has great potential to build lightweight and comfortable Brain-Computer interfaces.

Integrating Benzoxazine-PDMS 3D Networks with Carbon Nanotubes for flexible Pressure Sensors.

Shapeable and flexible pressure sensors with superior mechanical and electrical properties are of major interest as they can be employed in a wide range of applications. In this regard, elastomer-based composites incorporating carbon nanomaterials in the insulating matrix embody an appealing solution for designing flexible pressure sensors with specific properties. In this study, PDMS chains of different molecular weight were successfully functionalized with benzoxazine moieties in order to thermally cure them without adding a second component, nor a catalyst or an initiator. These precursors were then blended with 1 weight percent of multi-walled carbon nanotubes (CNTs) using an ultrasound probe, which induced a transition from a liquid-like to a gel-like behavior as CNTs generate an interconnected network within the matrix. After curing, the resulting nanocomposites exhibit mechanical and electrical properties making them highly promising materials for pressure-sensing applications.

A Facile Approach to Construct Novel Polyesters as Soft Midblock for Thermoplastic Elastomers.

The development of innovative synthetic strategies to create functional polycaprolactones is highly demanded for advanced material applications. In this contribution, we reported a facile synthetic strategy to prepare a class of CL-based monomers (R-TO) derived from epoxides. They readily polymerize via well-controlled ring-opening polymerization (ROP) to afford a series of polyesters P(R-TO) with high molecular weight (Mn up to 350 kDa). Sequential addition copolymerization of MTO and L-lactide (L-LA) allowed to access of a series of ABA triblock copolymers with composition-dependent mechanical properties. Notably, P(L-LA)100-b-P(MTO)500-b-P(L-LA)100 containing the amorphous P(MTO) segment as a soft midblock and crystalline P(L-LA) domain as hard end block behaved as an excellent thermoplastic elastomer (TPE) with high elongation at break (1438±204 %), tensile strength (23.5±1.7 MPa), and outstanding elastic recovery (>88 %).

Separating Charge Centers of Chain Segments in Dielectric Elastomer through Steric Hindrance Engineering.

Theoretically, separating the positive and negative charge centers of the chain segments of dielectric elastomers (DEs) is a viable alternative to the conventional decoration of chain backbone with polar handles, since it can dramatically increase the dipole vector and hence the dielectric constant (ε') of the DEs while circumvent the undesired impact of the decorated polar handles on the dielectric loss (tan δ). Herein, a novel and universal method is demonstrated to achieve effective separation of the charge centers of chain segments in homogeneous DEs by steric hindrance engineering, i.e., by incorporating a series of different included angle-containing building blocks into the networks. Both experimental and simulation results have shown that the introduction of these building blocks can create a spatially fixed included angle between two adjacent chain segments, thus separating the charge center of the associated region. Accordingly, incorporating a minimal amount of these building blocks (≈5 mol%) can lead to a considerably sharp increase (≈50%) in the ε' of the DEs while maintaining an extremely low tan δ (≈0.006@1 kHz), indicating that this methodology can substantially optimize the dielectric performance of DEs based on a completely different mechanism from the established methods.

Room-Temperature Self-Healing and Recyclable Self-Crosslinked Isosorbide-Based Adhesive Bioelastomer.

Recently, renewable bio-based materials have received more and more attention due to environmental issues such as global warming and ecosystem destruction. In the present work, a series of isosorbide-based bioelastomers poly(isosorbide carbonate-co-butanediol aliphatic esters)s (PICBAs) are synthesized by a facile and economical two-step melt polycondensation. Due to the slightly self-crosslinking reaction of isosorbide, PICBAs exhibit excellent tensile strength and self-healing ability, the mechanical properties of PICBAs can recover over 95% after 48 h under room temperature. In addition, PICBAs can stick different substances, such as glass, rubber, plastic, and stones, and show better adhesive performance than 3M commercially available double-sided tape. Consequently, isosorbide-based bioelastomers PICBAs are of great potential to be used as environmentally friendly pressure-sensitive adhesives (PSA) in the future.