Elastomeric Networks Research Articles

Adhesion of a nematic elastomer cylinder.

Reversible dry adhesion is exploited by lizards and insects in nature, and is of interest to robotics and bio-medicine. In this paper, we use numerical simulation to study how the soft elasticity of liquid crystal elastomers can affect its adhesion and provide a technological opportunity. Liquid crystal elastomers are cross-linked elastomer networks with liquid crystal mesogens incorporated into the main or side chain. Polydomain liquid crystalline (nematic) elastomers exhibit unusual mechanical properties like soft elasticity, where the material deforms at nearly constant stress, due to the reorientation of mesogens. Our study reveals that the soft elasticity of nematic elastomers dramatically affects the interfacial stress distribution at the interface of a nematic elastomer cylinder adhered to a rigid substrate. The stress near the edge of the nematic cylinder under tensile load deviates from the singular behavior predicted for linear elastic materials, and the maximum normal stress reduces dramatically. This suggests that nematic elastomers should display extremely high, but controllable adhesion, consistent with the available experimental observations.

Stepwise Curing Induced All-Stretchable Thermoelectric Generator of High Power Density.

In this study, a wearable and highly stretchable organic thermoelectric (TE) generator with a notable power density is developed. A highly stretchable and solution-processable TE/electrode pattern is realized by stepwise-curing elastomeric and conducting network. Significant advances in the TE or electrical properties are obtained for these stretchable patterns through post-activation treatment, which creates long-range charge transport pathways without degrading pre-established elastomeric networks. The TE and electrode patterns are solution-processed to a stretchable template, so that all-stretchable TE generator is realized. The fabricated TE generator maintains 90% of its maximum TE power output at 40% stretching stress and shows a stable TE power output after 200 stretching cycles. The TE generator maintains its stretchability in highly densified patterns, as the highly stretchable TE/electrode patterns enable good stretchability with little aid of the stretchable template. So, the TE generator has a high power density of 0.32 nW cm-2 K-2, one of the highest values among stretchable TE generators to date.

Injectable and photocurable precursors with their improved adhesive elastomeric films by nature-inspired marine mussels chemistry

Photocurable materials, capable of being delivered as liquids and rapidly cured in situ within seconds using UV light, are garnering increased interest in advanced minimally invasive procedures. Examining living organisms to extract novel principles and technologies, and subsequently applying them into synthetic materials to enhance their performances holds a central position in biomimetics (bioinspiration). In this exploration, we delve into the multifaceted world of marine mussel adhesion, emphasizing the pivotal role of 3,4-dihydroxy-L-phenylalanine (L-DOPA) in adhesive proteins. Simultaneously, we navigated the promising realm of elastomers derived from fatty acid dimers. 90° peeling test and fluorescence microscope indicate that the adhesiveness of the catechol-containing samples (5 % and 10 %) to the hydrophilic surface versus control samples were ∼ 4 and 8 times higher, respectively, as compared to within the tested group. Overall, our results suggest that the incorporation of methacrylated L-DOPA in the synthesis of photocured elastomeric networks leads to lower water contact angle and improved adhesiveness, creating new avenues for potential biomedical applications.

Achieving Efficient Intrinsically Stretchable Organic Photovoltaics with a Conjugated and Elastomeric Dual‐Network Morphology

AbstractStretchable organic photovoltaics (OPVs) are pivotal for advancing conformable electronics, yet achieving both efficient and intrinsically stretchable OPVs remains a significant challenge. The main issue is maintaining electronic and mechanical properties under deformation. Here, a ternary blend system, PTzBI‐oF:PYIT:EVA is presented, incorporating ethylene‐vinyl acetate (EVA) to establish a conjugated and elastomeric dual‐network morphology. The elastomer network dissipates applied stress, preserving the crystalline packing of the conjugated network and enabling improved mechanical stability of charge carrier generation and transport. Specifically, with 15% EVA content, the ternary blend achieved a power conversion efficiency (PCE) of 15.28% in rigid devices and exhibited a crack onset strain of 17.23%. Notably, the stretchable OPVs retained over 80% of their initial PCE under 30% strain. These findings underscore the potential of conjugated and elastomeric dual‐network morphology in developing high‐performance stretchable electronics for various applications.

The Theories of Rubber Elasticity and the Goodness of Their Constitutive Stress–Strain Equations

One of the most important challenges in polymer science is a rigorous understanding of the molecular mechanisms of rubber elasticity by relating macroscopic deformation to molecular changes and deriving the constitutive stress–strain equation for the elastomeric network. The models developed from the last century to today describe many aspects of the physics of rubber elasticity; although these theories are successful, they are not complete. In this review we analyze the main theoretical and phenomenological models of rubber elasticity, including their assumptions, main characteristics, and stress–strain equations. Then, we compare the predictions of the theories to our experimental data of polydimethylsiloxane (PDMS) rubber, in order to highlight the goodness of the reviewed models. The nonaffine and phenomenological deformation models verify the experimental curves in tension and compression in the whole investigated deformation range λ≤2. On the contrary, the affine deformation hypothesis is rigorously verified only in the deformation range λ≤1.

Modular design of Diels-Alder reversible networks for the facile production of highly tunable materials

Covalent adaptable networks (CANs) have attracted significant attention due to their potential to form crosslinked, yet reprocessable networks. Their ability to rearrange upon exposure to specific stimuli, in combination with properties such as self-healing can advance the development of novel materials, including for additive manufacturing. Thorough understanding of structure-property relations and processing potential will aid future application-driven research in network design as well as material selection. Therefore, a multitude of CANs were synthesized herein, by crosslinking epoxide-based oligomers via the furan-maleimide Diels-Alder reaction, to evaluate small systematic variations of (co)monomer composition, crosslinker length/flexibility and crosslinking density as vectors of tuning the CANs' thermomechanical properties. Networks with glass transition temperatures (Tg) spanning from <−40 °C up to >20 °C and Young's Moduli spanning from 0.2 MPa to >500 MPa were readily attainable. Crosslinker length/flexibility had a profound impact on the tensile properties, while changes in backbone composition provided insight into the impact of secondary interactions versus rigid moieties on mechanical performance. Self-healing at ambient conditions was demonstrated for elastomeric networks, with healing efficiency being enhanced when using longer crosslinkers. Finally, a cell viability and metabolic activity assay provided a preliminary in vitro demonstration of the biocompatibility of these materials.

Mechanistically Different Mechanochromophores Enable Calibration and Validation of Molecular Forces in Glassy Polymers and Elastomeric Networks.

Sterically distorted donor-acceptor π-systems, termed DA springs, can be progressively planarized under mechanical load causing a bathochromic shift of the photoluminescence (PL) spectrum. By combining theory and experiment, we here use a simple linear force calibration for two different conformational mechanochromophores to determine molecular forces in polymers from the mechanochromic shift in PL wavelength during multiple uniaxial tensile tests. Two systems are used, i) a highly entangled linear glassy polyphenylene and ii) a covalent elastomeric polydimethylsiloxane network. The mean forces estimated by this method are validated using known threshold forces for the mechanochemical ring-opening reactions of two different spiropyran force probes. The agreement between both approaches underlines that these DA springs provide the unique opportunity for the online monitoring of local molecular forces present in diverse polymer matrices.

Multi-stimulus perception and visualization by an intelligent liquid metal-elastomer architecture.

Multi-stimulus responsive soft materials with integrated functionalities are elementary blocks for building soft intelligent systems, but their rational design remains challenging. Here, we demonstrate an intelligent soft architecture sensitized by magnetized liquid metal droplets that are dispersed in a highly stretchable elastomer network. The supercooled liquid metal droplets serve as microscopic latent heat reservoirs, and their controllable solidification releases localized thermal energy/information flows for enabling programmable visualization and display. This allows the perception of a variety of information-encoded contact (mechanical pressing, stretching, and torsion) and noncontact (magnetic field) stimuli as well as the visualization of dynamic phase transition and stress evolution processes, via thermal and/or thermochromic imaging. The liquid metal-elastomer architecture offers a generic platform for designing soft intelligent sensing, display, and information encryption systems.

A multiscale anisotropic polymer network model coupled with phase field fracture

AbstractThe study of polymers has continued to gain substantial attention due to their expanding range of applications, spanning essential engineering fields to emerging domains like stretchable electronics, soft robotics, and implantable sensors. These materials exhibit remarkable properties, primarily stemming from their intricate polymer chain network, which, in turn, increases the complexity of precisely modeling their behavior. Especially for modeling elastomers and their fracture behavior, accurately accounting for the deformations of the polymer chains is vital for predicting the rupture in highly stretched chains. Despite the importance, many robust multiscale continuum frameworks for modeling elastomer fracture tend to simplify network deformations by assuming uniform behavior among chains in all directions. Recognizing this limitation, our study proposes a multiscale fracture model that accounts for the anisotropic nature of elastomer network responses. At the microscale, damage in the chains is assumed to be driven by both the chain's entropy and the internal energy due to molecular bond distortions. In order to bridge the stretching in the chains to the macroscale deformation, we employ the maximal advance path constraint network model, inherently accommodating anisotropic network responses. As a result, chains oriented differently can be predicted to exhibit varying stretch and, consequently, different damage levels. To drive macroscale fracture based on damages in these chains, we utilize the micromorphic regularization theory, which involves the introduction of dual local‐global damage variables at the macroscale. The macroscale local damage variable is obtained through the homogenization of the chain damage values, resulting in the prediction of an isotropic material response. The macroscale global damage variable is subjected to nonlocal effects and boundary conditions in a thermodynamically consistent phase field continuum formulation. Moreover, the total dissipation in the system is considered to be mainly due to the breaking of the molecular bonds at the microscale. To validate our model, we employ the double‐edge notched tensile test as a benchmark, comparing simulation predictions with existing experimental data. Additionally, to enhance our understanding of the fracturing process, we conduct uniaxial tensile experiments on a square film made up of polydimethylsiloxane (PDMS) rubber embedded with a hole and notches and then compare our simulation predictions with the experimental observations. Furthermore, we visualize the evolution of stretch and damage values in chains oriented along different directions to assess the predictive capacity of the model. The results are also compared with another existing model to evaluate the utility of our model in accurately simulating the fracture behavior of rubber‐like materials.

Dynamic Chalcogen Squares for Material and Topological Control over Macromolecules

AbstractHerein we introduce chalcogen squares via selenadiazole motifs as a new class of dynamic supramolecular bonding interactions for the modification and control of soft matter materials. We showcase selenadiazole motifs in supramolecular networks of varying primary chain length prepared through polymerization using tandem step‐growth/Passerini multicomponent reactions (MCRs). Compared to controls lacking the selenadiazole motif, these networks display increased glass transition temperatures and moduli due to the chalcogen bonding linkages formed between chains. These elastomeric networks were shown to autonomously heal at room temperature, retaining up to 83 % of the ultimate tensile strength. Lastly, we use post‐polymerization modification via the Biginelli MCR to add selenadiazole motifs to narrowly dispersed polymers for controlled topology in solution. Chalcogen squares via selenadiazoles introduce an exciting exchange mechanism to the realm of dynamic materials.

Dynamic Chalcogen Squares for Material and Topological Control over Macromolecules.

Herein we introduce chalcogen squares via selenadiazole motifs as a new class of dynamic supramolecular bonding interactions for the modification and control of soft matter materials. We showcase selenadiazole motifs in supramolecular networks of varying primary chain length prepared through polymerization using tandem step-growth/Passerini multicomponent reactions (MCRs). Compared to controls lacking the selenadiazole motif, these networks display increased glass transition temperatures and moduli due to the chalcogen bonding linkages formed between chains. These elastomeric networks were shown to autonomously heal at room temperature, retaining up to 83 % of the ultimate tensile strength. Lastly, we use post-polymerization modification via the Biginelli MCR to add selenadiazole motifs to narrowly dispersed polymers for controlled topology in solution. Chalcogen squares via selenadiazoles introduce an exciting exchange mechanism to the realm of dynamic materials.

Highly conductive and mechanically robust composite cathodes based on 3D interconnected elastomeric networks for deformable lithium‐ion batteries

AbstractDeformable lithium‐ion batteries (LIBs) can serve as the main power sources for flexible and wearable electronics owing to their high energy capacity, reliability, and durability. The pivotal role of cathodes in LIB performance necessitates the development of mechanically free‐standing and stretchable cathodes. This study demonstrates a promising strategy to generate deformable cathodes with electrical conductivity by forming 3D interconnected elastomeric networks. Beginning with a physically crosslinked polymer network using poly(vinylidene fluoride‐co‐hexafluoropropylene) and 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]), subsequent exchange with a 1 M LiPF6 electrolyte imparts elastic characteristics to the cathodes. The resulting LiFePO4 composite electrodes maintained their resistance under 500 consecutive bending cycles at an extremely small bending radius of 1.8 mm and showed high discharge capacity of 158 mAh g−1 with stable potential plateaus in charging and discharging curves. Moreover, flexible cells utilizing the composite electrodes exhibited superior operational stability under rolling, bending, and folding deformations.image

Flexible polymer networks: rubber elasticity and segmental orientation

Abstract Thermoreversible networks are very attractive materials because of a large variety of suitable thermoreversible chemical bonds which can be used for crosslinking. In future, to certain extent, they may replace so far used irreversibly crosslinked networks and contribute to more sustainable material concepts also in the field of crosslinked elastomers. This paper gives some theoretical basis for understanding the elastic deformation properties of crosslinked polymers and presents some experimental tools for studying deformation behavior not only on a macroscopic length scale but also on a segmental scale. Basic knowledge of these two topics is useful for chemists and material scientists when designing new sustainable elastomeric polymer networks.

Ultra-high conductivity double-conducting network elastomers with positive-negative pressure resistance constructed by self-assembly of fillers for intelligent sensing

Elastomers with ultra-high conductivity of metal grade have broad application prospects in the fields of skin electronics and special sensing. However, high conductivity of thin films can only be achieved at ultra-thin thicknesses. Achieving an overall conductivity of more than 106 S/m in a simple process remains a challenge. Here, we propose a strategy for the preparation of highly conductive porous elastomers (HCPE) by thermoplastic processing using a solid-phase transition double template (S-PTDT). The connected hole structure and dual conductive network constructed in the material overcome the contradiction between high conductivity and compliance with high filler content and become the most conductivity porous elastomer to date. Its overall conductivity reaches 4.4 × 106 S/m, while its Shore A hardness is only 26, even lower than that of the original material without filler. The unique positive and negative piezoresistive effects of the material enable it to accurately identify running posture and correct posture as an arch sensor. The muscle electrical intelligent sensing prepared by HCPE realizes the monitoring and judgment of muscle state and action standards in strength training, which shows its great application prospect in the field of intelligent flexible electronics.

A Flexible and Electrically Conductive Liquid Metal Adhesive for Hybrid Electronic Integration

AbstractElectrical and mechanical integration approaches are essential for emerging hybrid electronics that must robustly bond rigid electrical components with flexible circuits and substrates. However, flexible polymeric substrates and circuits cannot withstand the high temperatures used in traditional electronic processing. This constraint requires new strategies to create flexible materials that simultaneously achieve high electrical conductivity, strong adhesion, and processibility at low temperature. Here, an electrically conductive adhesive is introduced that is flexible, electrically conductive (up to 3.25×105 S m−1) without sintering or high temperature post‐processing, and strongly adhesive to various materials common to flexible and stretchable circuits (fracture energy 350 &lt;Gc &lt; 700 J m−2). This is achieved through a multiphase soft composite consisting of an elastomeric and adhesive epoxy network with dispersed liquid metal droplets that are bridged by silver flakes, which form a flexible and conductive percolated network. These inks can be processed through masked deposition and direct ink writing at room temperature. This enables soft conductive wiring and robust integration of rigid components onto flexible substrates to create hybrid electronics for emerging applications in soft electronics, soft robotics, and multifunctional systems.

On the theory of mechanically induced chemiluminescence in multiple network elastomers

Mechanophores, force-sensitive molecules, can be covalently linked into polymer networks to reveal the damage properties of polymeric materials under deformation. Recent works have introduced bis-adamantyl dioxetane (Ad) into multiple network elastomers. These mechanoluminescent cross-linking molecules can emit luminescence as they break. The experimental results can directly visualize the damage behaviors of multiple network elastomers and reveal the damage mechanism of these materials during deformation. In this work, we develop a constitutive model to describe the complex mechanical behaviors of multiple network elastomers based on observations from mechano-chemiluminescent experiments. The free energy density consists of the contributions from the filler network, the matrix network, and the entangled network. A new type of single-chain model is developed for the filler network, while the classic eight-chain mapping is adopted for the micro–macro transition. The chains in the filler network are progressively damaged under deformation to explain the stress-softening behaviors observed in the small and median strain regions of multiple network elastomers. The entangled network is rooted in individual fragments of the damaged filler network, which can be further damaged in the large deformation regime. The model can comprehensively capture the complex mechanical responses of multiple network elastomers with different values of the prestretching ratio of the filler network, including linear response, necking instability, and re-hardening phenomena in quadruple networks. By assuming that the luminescence intensity of the materials is proportional to the total percentage of damage from both filler and entangled networks, we quantify the relationship between damage and the luminescence intensity from mechanophores, which is further validated in quantifying luminescence intensity against different sets of experimental data on the uniaxial tension of multiple network elastomers. The model is further implemented for finite element analysis, demonstrating the ability to visualize and characterize the damage behaviors around a crack.

Non‐linear viscoelasticity of carbon black–fluoroether rubber mixture studied by large amplitude oscillatory shear tests

AbstractNon‐linear viscoelastic characteristics of carbon black (CB)‐filled fluoroether rubber mixture samples are investigated by large amplitude oscillatory shear (LAOS) tests. Three analysis approaches based on LAOS tests are then used to discuss correlations between rheological behavior and CB‐filling amount. Each non‐linear viscoelastic parameter of the mixture presents a three‐stage characteristic with increasing CB content, which are attributed to the alteration of CB–elastomer network structure, corresponding to the state where gum continuous phase, CB–elastomer mesophase, and excessive CB agglomerates predominate in the mixture compound, respectively. According to the findings in engineering experiments, a CB content of 35–40 phr is recommended, taking into account tensile, hardness, and aging properties. Excessive CB agglomerates are found to reinforce CB–elastomer networks at elevated temperatures. For cold‐resistance properties, structural changes in CB–elastomer network are proven to exert little effect on Tg, but a higher CB content was found to slightly enhance the cold‐resistance coefficient, probably due to the decrease in velocity fraction of gum rubber.Highlights LAOS tests were utilized to study the influences of CB on fluoroelastomer; Three‐stage alteration was observed in the mixture with increasing CB content; Correlation between CB content and the engineering properties was discussed.

Non-Aqueous Poly(dimethylsiloxane) Organogel Sponges for Controlled Solvent Release: Synthesis, Characterization, and Application in the Cleaning of Artworks.

Polydimethylsiloxane (PDMS) organogel sponges were prepared and studied in order to understand the role of pore size in an elastomeric network on the ability to uptake and release organic solvents. PDMS organogel sponges have been produced according to sugar leaching techniques by adding two sugar templates of different forms and grain sizes (a sugar cube template and a powdered sugar template), in order to obtain materials differing in porosity, pore size distribution, and solvent absorption and liquid retention capability. These materials were compared to PDMS organogel slabs that do not contain pores. The sponges were characterized by Fourier-transform infrared spectroscopy with attenuated total reflectance (FTIR-ATR) and compared with PDMS slabs that do not contain pores. Scanning electron microscopy (SEM) provided information about their morphology. X-ray micro-tomography (XMT) allowed us to ascertain how the form of the sugar templating agent influences the porosity of the systems: when templated with sugar cubes, the porosity was 77% and the mean size of the pores was ca. 300 μm; when templated with powdered sugar, the porosity decreased to ca. 10% and the mean pore size was reduced to ca. 75 μm. These materials, porous organic polymers (POPs), can absorb many solvents in different proportions as a function of their polarity. Absorption capacity, as measured by swelling with eight solvents covering a wide range of polarities, was investigated. Rheology data established that solvent absorption did not have an appreciable impact on the gel-like properties of the sponges, suggesting their potential for applications in cultural heritage conservation. Application tests were conducted on the surfaces of two different lab mock-ups that simulate real painted works of art. They demonstrated further that PDMS sponges are a potential innovative support for controlled and selective cleaning of works of art surfaces.

Printable Polar Silicone Elastomers for Healable Supercapacitive Strain Sensors

AbstractSoft strain sensors with high sensitivity and the ability to recover from damages are required in the emerging field of self‐healing soft robotics. Herein, printable supercapacitive strain sensors that can heal upon moderate heating (75 °C for 10 min) and exhibit a 30 times higher sensitivity than PDMS‐based sensors are developed. For the sensor's core layer and electrode, a nitrile‐functional polysiloxane that contains an active ionic initiator and can heal by siloxane equilibration at elevated temperatures is used. Supercapacitive strain sensors prepared from the elastomer are highly sensitive at low strains of 0–30%, enabled by the electric double‐layer formation of the ionic initiator. After healing, the sensors exhibit nearly unaltered performance in tensile testing. Due to the thermoreversible nature of the elastomer network, patterned core layers with different microstructures can be printed by direct ink writing. The capacitive sensors based on these microstructured films reach a higher sensitivity and linearity than those based on unstructured films. Finally, the sensor is integrated into a soft robotic finger and the sensor's ability to determine the bending angle is validated by motion capture. This technology can provide new opportunities to equip soft robotic devices with custom‐printed, healable strain sensors.

Extrudable Covalently Cross‐Linked Thio‐Urethane Liquid Crystalline Elastomers

AbstractLiquid crystalline elastomer networks cross‐linked by dynamic covalent bonds (xLCEs) possess the remarkable capability of being (re)processed during plastic flow at high temperatures, while also allowing for the (re)programming of their local alignment. However, the current generation of xLCEs cannot be extruded directly into filaments or injection‐molded into shapes capable of actuation. Here, a novel poly(thio‐urethane) (PTU) LCE thermoset is presented. The inclusion of dibutyltin dilaurate as a catalyst enables the manipulation of the elastic–plastic transition through two distinct pathways. The dissociative equilibrium exchange between the thio‐urethane linkage to form separate thiol and isocyanate competes with the associative exchange of thio‐urethane and a free isocyanate or thiol groups. The temperature of fast plastic flow onset is ≈160 ˚C, and the associated bond‐exchange activation energy is ≈54 kJ mol−1. The hydrogen bonding below the elastic‐plastic transition makes the elastomer robust and extremely ductile with a failure strain exceeding 600% and a Shore hardness A of 72, preventing any creep during cyclic thermal actuation. The versatility of this dynamically cross‐linked elastomer is successfully demonstrated by extruding it using a commercial twin‐screw extruder, injection molding it into required shapes, and hot‐pressing it into flat films or shapes.