Cross-linked Elastomers Research Articles

Oxidative Upcycling of Polyolefin Wastes into the Dynamically Cross-Linked Elastomer

Oxidative Upcycling of Polyolefin Wastes into the Dynamically Cross-Linked Elastomer

Room temperature self-healing and reprocessing elastomer with dynamic bonds for flexible wearable sensor

The production of room-temperature (RT) self-healing elastomers with good mechanical properties is significant for application in soft electronics, yet remains a challenge in material design. Herein, we present an effective and feasible approach to create RT self-healing cross-linked elastomers (CEs) through photo-initiated copolymerization. A key feature is the incorporation of 2,7-dihydroxynaphthalene and alicyclic diisocyanate into the polymer backbone as hard domains, along with the rational optimization of the soft segments. In addition, urethane-based H-bonding interactions, acting as sacrificial bond, contribute to the high toughness of the CEs. The resulting CEs exhibit desirable mechanical performances, including a tensile strength of 12.9 MPa, an elongation at break of approximately 1243 %, and a high toughness of 68.64 MJ m–3. Furthermore, by integrating a flexible PTMEG-based polymeric chain and hindered urea bonds into the backbone, the chain mobility and dynamic nature of the CEs are improved. The CEs are capable of reprocessing and self-healing at RT within 30 min upon scratching, with a self-healing efficiency in toughness reaching 99.64 %. The dynamic networks are evidenced by rheological test, stress relaxation analysis, as well as creep and recovery experiments. These CEs, characterized by their superior properties, hold promise for applications in flexible wearable electronics.

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.

Solid-state NMR of vulcanized natural rubber / butadiene rubber blends: Local organization and cross-linking heterogeneities

Elastomer blends, among which natural rubber (NR) and butadiene rubber (BR), are involved in many components of the automotive/tire industry. A comprehensive understanding of their mechanical behavior requires, among other features, a detailed description of the cross-link density in these mixtures. In the case of vulcanized immiscible blends, the distribution of the cross-link density within each of the NR- and BR-rich domains is key information, but difficult to determine using the conventional approaches used for one-component cross-linked elastomers. In this study, the vulcanization within NR/BR blends is investigated using a robust 1H double-quantum (DQ) MAS recoupling experiment, BaBa-xy16. Two kinds of cross-linked NR/BR blends were considered with two different microstructures for the BR component. The bulk organization of the resulting blends was first probed by analyzing the 1H spin-lattice relaxation behavior. In a second step, BaBa-xy16 was used to investigate, in a selective way, the cross-link heterogeneities within NR/BR blends. In particular, for immiscible NR/BR mixtures, the distribution of the cross-link density between both phases was compared and the observed differences were discussed.

Simulating loading–unloading hysteretic behaviors of nematic-genesis polydomain nematic elastomers

Nematic elastomers (NEs) are lightly cross-linked elastomers with nematic mesogens integrated in their polymer networks. Combination of large deformation capability with nematic-isotropic phase transition enables NEs to be the most promising soft materials for impact attenuation, actuation and soft robotics. In this paper, we focus on nematic-genesis polydomain NEs (N-PNEs) where mesogens are cross-linked at nematic states. N-PNEs are capable of absorbing and dissipating energy and easy to synthesize. We present a Voronoi diagram-based finite element model for specimen-scale N-PNEs, and investigate the cyclic tensile and compressive behaviors of N-PNEs at different strain rates. Our simulations reveal a smooth polydomain-monodomain transition during loading, accompanied by a full recovery of polydomain texture after the load is removed, indicating a memory effect of initial disordered mesogen alignment. The predicted behaviors align well with experimental observations, which validates our model. Furthermore, we assess the energy absorption and dissipation capabilities of N-PNEs compared to monodomain NEs, identifying conditions where N-PNEs exhibit superior performance. This study not only enhances our understanding of polydomain-monodomain transitions in N-PNEs, but also lays the groundwork for the development of N-PNE-based energy absorbers.

Gelatin-strengthened elastomer derived from polymerizable deep eutectic solvent for soft ionotronics

It is widely recognized that resolving the trade-off between mechanical toughness and recyclability in elastomers presents a significant challenge. This study introduces a novel gelatin-strengthened, supramolecular cross-linked elastomer (PCCA-G) synthesized through in situ photo-polymerization of a polymerizable deep eutectic solvent (PDES) system composed of choline chloride and acrylic acid. The research highlights the dual benefits of integrating gelatin into the PDES system in the absence of covalent cross-linker, notably enhancing mechanical properties and recycle ability. The PCCA-G3 % elastomers demonstrate exceptional transparency with a transmittance of 95.4 %, robust mechanical strength (approximately 4.99 MPa), and substantial strain capacity (1169 %). These properties make the elastomers ideal for loading-bearing sensor applications, capable of monitoring various human motions with high accuracy and sensitivity. Furthermore, the elastomers exhibit outstanding recycle properties via a simple solvation-evaporation process, maintaining performance after multiple cycles. This work addresses the critical need for environmental-friendly materials potentially reducing the ecological impact of widespread sensor usage. The adaptable nature of these materials also positions them as promising candidates for future developments in sensor technology and soft ionotronics.

Engineering of Reversibly Cross-Linked Elastomers Toward Flexible and Recyclable Elastomer/Carbon Fiber Composites with Extraordinary Tearing Resistance.

Carbon fiber (CF)-reinforced polymers (CFRPs) demonstrate potential for use in personal protective equipment. However, existing CFRPs are typically rigid, nonrecyclable, and lack of tearing resistance. In this study, flexible, recyclable, and tearing resistant polyurethane (PU)-CF composites are fabricated through complexation of reversibly cross-linked PU elastomer binders with CF fabrics. The PU-CF composites possess a high strength of 767MPa and a record-high fracture energy of 2012kJ m-2. The high performance of the PU-CF composites originates from the well-engineered PU elastomer binders that are obtained by cross-linking polytetrahydrofuran chains with in situ-formed nanodomains composed of hierarchical supramolecular interactions of hydrogen and coordination bonds. When subjected to tearing, the force concentrated on the damaged regions of the PU-CF composites can be effectively distributed to a wider area through the PU binders, leading to a significantly enhanced tearing resistance of the composites. The strong interfacial adhesion between PU binders and the CF fabrics enables the fracture of the CF in bundles, thereby significantly enhancing the strength and fracture energy of the composites. Because of the dynamic nature of the PU elastomer binders, the PU-CF composites can be recycled through the dissociation of the PU elastomer binders.

Motion-Accommodating Dual-Layer Hydrogel Dressing to Deliver Adipose-Derived Stem Cells to Wounds.

Current dressing materials cannot secure a cell survival-promoting wound environment for stem cell delivery due to insufficient assimilation to skin motion. The authors developed a novel motion-accommodating dual-layer hydrogel dressing for stem cell delivery into such wounds. Dorsal hand skin movement was evaluated to determine the potential range of deformation for a dressing. The outer hydrogel (OH) was fabricated with an alginate-acrylamide double-network hydrogel with a covalently cross-linked elastomer coat. The tough adhesive consisted of a chitosan-based bridging polymer and coupling reagents. OH material properties and adhesiveness on porcine skin were measured. An oxidized alginate-based inner hydrogel (IH) containing human adipose-derived stem cells (ASCs) was evaluated for cell-supporting and cell-releasing properties. The OH's function as a secondary dressing, and dual-layer hydrogel cell delivery potential in wounds were assessed in a rodent model. The dual-layer hydrogel consisted of OH and IH. The OH target range of deformation was up to 25% strain. The OH adhered to porcine skin, and showed significantly higher adhesion energy than common secondary dressings and endured 900 flexion-extension cycles without detachment. OH showed a similar moisture vapor transmission rate as moisture-retentive dressings. IH maintained embedded cell survival for three days with significant cell release on the contacting surface. OH showed less fibrotic wound healing than other secondary dressings in vivo. The dual-layer hydrogel successfully delivered ASCs into open wounds of nude mice (13 ± 3 cells/HPF). The novel dual-layer hydrogel can accommodate patient movement and deliver ASCs into the wound bed by securing the wound microenvironment.

Higher-Order Structural Analysis of a Transparent and Flexible High Thermal Conductive Liquid Crystalline Elastomer Sheet and Its Composite.

Transparency, flexibility, and high thermal conductivity are trade-offs. Specifically, we have investigated a cross-linked acrylic liquid crystal elastomer (LCE) that exhibits both transparency and flexibility while maintaining a high level of thermal conductivity. The transparent monodomain LCE sheet was achieved through a process of stretching an initially opaque polydomain sheet to 80% elongation and subsequently subjecting it to photocuring. The thermal conductivity in the stretching direction (x) of the monodomain LCE sheet was found to be 1.8 times higher than that of the prestretched polydomain sheet, consistent with findings from previous studies. However, in the orthogonal direction (y) to the stretching (x) direction, the thermal conductivity exhibited an even higher value, being 1.7 times greater than in the x-direction, with a value of 3.0 W/(m·K). This unique observation prompted us to conduct further investigation through higher-order structural analysis of these LCE sheets using 2D wide-angle X-ray scattering (WAXS) analysis. In the transparent sheet, the LCE molecules were aligned in the sheet in the stretching x-direction (monodomain structure) for the out-of-plane direction. However, in the in-plane x-direction, the molecular plane spacing exhibited random orientation at a period of 0.45 nm. In contrast, within the y-direction of the inner layer, the molecular plane spacing exhibited a uniaxial horizontal orientation at the same period length as in the x-direction. The heat energy entering into the y-direction once spreads to the x-direction, but it was considered that the reason for the higher thermal conductivity to the y-direction would be forming covalent bonds that function as new heat transmission paths, in the direction intersecting to the x-direction during photocuring. Therefore, we concluded that the synergistic effect of the high level of the ordered inner structure and covalent bonding structure due to cross-linking in the y-direction contributes to its higher thermal conductivity compared to that in the x-direction, which exhibits a random in-plane structure. Additionally, we have fabricated an LCE composite sheet filled with 75 vol % of alumina particles using a polydomain-type LCE as the base material. The composite sheet exhibits remarkable thermal conductivity in the thickness direction, measuring at 9.8 W/(m·K), while maintaining a flexibility characterized by an elastic modulus of 70 MPa. This thermal conductivity surpasses that of a nonmesogenic acrylic composite sheet with identical alumina particle filling, which measured at 3.9 W/(m·K), more than twice as much. The presence of the mesogen skeleton has been demonstrated to enhance heat transfer, even within soft composites, by facilitating the formation of an ordered structure.

Elasto-Plastic Materials based on EPDM Rubber, LDPE, Plasticized Starch and OMMT

This paper describes the development of new types of dynamically cross-linked thermoplastic elastomers based on ethylene-propylene-terpolymer rubber and low-density polyethylene, reinforced with plasticized starch and montmorillonite with a chemically modified surface. An octylphenol-formaldehyde resin in the presence of stannous chloride dihydrate was used as a vulcanizing agent. The samples were obtained on a Brabender Plasti-Corder mixer, at appropriate temperatures and rotation speeds, using the dynamic vulcanization method and the melt intercalation technique. The mixtures obtained were modeled in the form of plates with standard dimensions using specific molds and a laboratory-scale electrical press. The obtained samples were analyzed from the point of view of the physical-mechanical properties, the melt flow index, as well as from the structural and morphological point of view. It was observed that the characteristics of the samples are influenced by both the composition and the methods of obtaining used. According to the obtained characteristics, the new elasto-plastic materials can be used in fields such as the footwear industry (for the production of: soles, heels, protective boots), in the rubber and plastics industry, the automobile industry, agriculture or construction (when making gaskets, technical items, hoses, etc.). They can be easily processed into different finished products by methods specific to plastics.

Relationship between the poly(glycerol adipate) prepolymers chain microstructure and linear viscoelastic properties of the elastomers

This paper investigates the influence of the time of enzymatic polymerization of glycerol and divinyl adipate on the chain microstructure and the thermal and linear viscoelastic properties (LVE) of the poly(glycerol adipate) prepolymer (pPGA). The immobilized Candida antarctica lipase B (CALB) was used as a regioselective catalyst in the polytransesterification reaction. A series of pPGA prepolymers were synthesized at different duration times of 8, 24, 48 and 72 h and the degree of polymerization (DP) and degree of branching (DB) were determined based on a quantitative NMR analysis. Due to lack in the literature of the described relationship between the properties of the pPGA prepolymers and the PGA elastomers, the main goal of the research was to correlate the microstructure of the prepolymers with linear viscoelastic properties of the elastomers obtained by thermal crosslinking of the respective prepolymers. The respective pPGA prepolymers were cured at 110 °C for 5 days to obtain PGA elastomers. The LVE properties of the PGA elastomers were investigated based on the master curves of the storage (G') and loss (G") modulus. The differences in DP and BD for the pPGA prepolymers translated into the PGA elastomer crosslinking densities and the rubbery plateau modulus (G0). It was shown for the first time that the minor differences in the structure of the pPGA prepolymers (DP of 13 and 21, and DB of 8.4% and 9.7% for the pPGA prepolymers synthesized for 8 and 24 h, respectively) translate into significant differences in the LVE of the PGA elastomers (G0 of 116 kPa and 50 kPa for the PGA elastomers derived from pPGA8 and pPGA24 prepolymers, respectively).

Dynamic Adaptive Cross-linked Elastomers with Highly Robust, Recyclable, and Conductive Abilities toward Strain Sensors and Self-Sensing Actuators

Dynamic Adaptive Cross-linked Elastomers with Highly Robust, Recyclable, and Conductive Abilities toward Strain Sensors and Self-Sensing Actuators

Hydrophobic cyclodextrin dimer-assisted self-healing elastomer: movable crosslinks of pseudo-rotaxane with recyclable and separable functionality

A movable cross-linked elastomer derived from a pseudo-rotaxane by utilizing a dimer structure exhibits facile healing and good stretching.

Advancing Lithium Battery Performance through Gel Electrolytes: Investigating EC-Based Blends with HNBR and PEC for Enhanced Conductivity

Li-ion batteries (LiBs), the most established rechargeable energy storage devices, are currently at closing the gap of their theoretical capacity. That is the main reason why Lithium metal batteries (LMB) have recently regained interest, mainly because of the higher theoretical energy densities achievable with this technology. Therefore, the development of new electrode and electrolyte materials is essential for improving battery performance. Solid polymer electrolytes (SPEs) have been presented as safer alternatives for liquid electrolytes which are used commercially in these devices as they tend to be non-flammable, have enough mechanical strength to resist lithium dendrite growth, and do not leak. However, solid polymer electrolytes are less conductive than liquid electrolytes. Improved ionic conductivity in solid electrolyte materials can be obtained through the use of solid-state gel polymer electrolytes (GPEs). These materials combine the ionic conductivity of liquid electrolytes with the increased safety of SPE resulting in electrolytes with high ionic conductivity and good mechanical stability.1 This study introduces a novel approach to creating in-situ gel polymer electrolytes (GPEs) from solid polymer electrolytes (SPEs) using melt processing followed by sample heating. 2, 3This method capitalizes on the easy processability of SPEs. Initially, the SPE was prepared by blending two polymers with LiTFSI (bis(trifluoromethanesulfonyl)imide) through extrusion mixing. The sample was then converted into a GPE via a controlled heating step. Compared to the initial SPE, the resultant GPE possessed improved thermal and electrochemical properties. In this presentation, we will provide supportive data derived from IR, DSC, and NMR analyses to highlight the differences linked to changes in salt-polymer interactions in the GPE. Verdier, N.; Lepage, D.; Zidani, R.; Prebe, A.; Ayme-Perrot, D.; Pellerin, C.; Dolle, M.; Rochefort, D., Cross-linked polyacrylonitrile-based elastomer used as gel polymer electrolyte in Li-ion battery. ACS Applied Energy Materials 2019, 3 (1), 1099-1110.Ma, C.; Cui, W.; Liu, X.; Ding, Y.; Wang, Y., In situ preparation of gel polymer electrolyte for lithium batteries: Progress and perspectives. InfoMat 2021.Verdier, N.; Foran, G.; Lepage, D.; Prébé, A.; Aymé-Perrot, D.; Dollé, M., Challenges in Solvent-Free Methods for Manufacturing Electrodes and Electrolytes for Lithium-Based Batteries. Polymers 2021, 13 (3), 323.√

Elastomeric vitrimers from designer polyhydroxyalkanoates with recyclability and biodegradability.

Cross-linked elastomers are stretchable materials that typically are not recyclable or biodegradable. Medium-chain-length polyhydroxyalkanoates (mcl-PHAs) are soft and ductile, making these bio-based polymers good candidates for biodegradable elastomers. Elasticity is commonly imparted by a cross-linked network structure, and covalent adaptable networks have emerged as a solution to prepare recyclable thermosets via triggered rearrangement of dynamic covalent bonds. Here, we develop biodegradable and recyclable elastomers by chemically installing the covalent adaptable network within biologically produced mcl-PHAs. Specifically, an engineered strain of Pseudomonas putida was used to produce mcl-PHAs containing pendent terminal alkenes as chemical handles for postfunctionalization. Thiol-ene chemistry was used to incorporate boronic ester (BE) cross-links, resulting in PHA-based vitrimers. mcl-PHAs cross-linked with BE at low density (<6 mole %) affords a soft, elastomeric material that demonstrates thermal reprocessability, biodegradability, and denetworking at end of life. The mechanical properties show potential for applications including adhesives and soft, biodegradable robotics and electronics.

EFFECT OF HEATING ON STRUCTURAL PARAMETERS OF NITRILE BUTADIENE RUBBER IN THE PRESENCE OF CHLORINE-CONTAINING COMPOUNDS

A new class of active organic crosslinking agents for the vulcanization of NBR based on halogenmethyl-containing compounds has been found, allowing improvement significantly in the rheological and structural parameters of NBR. Gel content and Mooney viscosity in binary systems after plastification on rollers were studied. The sol fraction of cross-linked NBR (SKN-40+TCMCC) was found to be characterized by a bimodal MWD. Abnormally high value of W/ ns of sol fractions is associated with the bimodal nature of their MWD and indicates the presence of gel in the elastomer. The value of η of the sol fractions in cross-linked NBR was found to be insignificant. The sol fraction of cross-linked HCPX elastomer was shown to have lower values of the specified parameters and lower content of high-molecular-weight fractions. The branching density ρ of macromolecules of sol fraction of cross-linked NBR was 1.90-2.3·10-3, i.e. on average corresponded to one monomer unit and two hundred branching nodes per molecule

Hybrid Cross-Linking to Construct Functional Elastomers.

ConspectusElastomers have been extensively used in diverse industrial sectors such as footwear, seals, tires, and cable jacketing and have attracted more and more attention in emerging fields such as regenerative medicine, soft robotics, and stretchable electronics. Global consumption of natural and synthetic elastomers amounted to nearly 27 million metric tons in 2020. In addition, to further enhance the common properties of elastomers, it is highly desired to endow elastomers with functionalities such as reprocessability, biomimetic mechanical properties, self-healing ability, bioactivity, and electrical conductivity, which will significantly broaden their applications. The covalent or noncovalent cross-linked structure is the essential factor for the elasticity of elastomers. Traditional elastomers usually comprise a single type of cross-linked molecular network, for which it is difficult to modulate the properties and introduce functionalities. Inspired by the simultaneous existence of multiple cross-linked structures in proteins, researchers have employed a hybrid cross-linking strategy to construct elastomers. Various noncovalent interactions (e.g., hydrogen bonds, metal-ligand coordination, ionic interactions, and chain folding) and dynamic covalent bonds (e.g., disulfide bonds, oxime-urethane bonds, and urea bonds) have been integrated in elastomers. Accordingly, the properties and functionalities of elastomers can be tuned by regulating the types, ratios, and distributions of cross-links. The hybrid cross-linking strategy provides a versatile and effective way to construct diverse functional elastomers for broad applications in various important fields.In this Account, we present our recent progress on functional elastomers constructed by a hybrid cross-linking strategy, including their design, preparation, properties, and diverse applications. First, we provide a brief introduction of the basic concept of functional elastomers and outline general strategies and mechanics for functional elastomers constructed by hybrid cross-linking. Then, we classify hybrid cross-linked elastomers by their design strategies, including multiple cross-linking, topological design, chemical coupling, and multiple networks. The relationships between the functionalities and hybrid cross-linked structures are summarized. At the same time, we also introduce diverse applications of these hybrid cross-linked elastomers in biomedicine, flexible electronics, soft robotics, 3D printing, and so on. Finally, we discuss our perspective on open challenges and future development trends of this rapidly evolving field. This Account highlighting the diverse hybrid cross-linked elastomers not only provides insights into strategies for elastomer functionalization but also provides new ideas for material design and inspires a variety of new applications.

A mechanically robust and highly stretchable cross-linked dual-ionic conductive elastomer

A mechanically robust and highly stretchable cross-linked dual-ionic conductive elastomer

Thermally-triggered multi-shape-memory behavior of binary blends of cross-linked EPDM with various thermoplastic polyethylenes and their potential applications as temperature indicators

Shape-memory polymers (SMPs) are smart materials that can alter their configuration in response to external stimuli. They have shown promise in a number of application areas, including soft robotics or biomedical devices. Frequently, however, the materials needed are expensive, or labor-intensive synthetic processes are involved. In this contribution, we report a versatile and cost-effective manufacturing method for SMPs based on binary elastomer-thermoplastic-blends. These were produced from ethylene-propylene-diene monomer rubber (EPDM) combined with ultra-low-density polyethylene (ULDPE), propylene-ethylene copolymer (PP-c-PE), or high-density polyethylene (HDPE) as thermoplastic components. Atomic force microscopy revealed an immiscible two-phase morphology. Results of dynamic-mechanical thermal analysis showed that all polymer blends with a high thermoplastic load had efficient thermo-responsive dual-shape-memory, also demonstrated on macroscopic specimens. Furthermore, multi-shape-memory of elastomer/thermoplastic (40/60)-blends was investigated. Especially ULDPE-containing blends exhibited particularly promising multi-shape-memory features and stepless, controllable temperature response. Mechanistically, this is based upon the synergistic interaction of the cross-linked elastomer and the thermoplastic switching phase, consisting of different crystalline segments melting over a wide range from 60 to 125 °C. The continuous shape recovery over a broad temperature range could be used to create reusable test strips, e.g., for indicating exposure temperature in transportation chains or overheating protection.

Self-Healable and Reprocessable Silicon Elastomers Based on Imine-Boroxine Bonds for Flexible Strain Sensor.

Silicon elastomers with excellent self-healing and reprocessing abilities are highly desirable for the advancement of next-generation energy, electronic, and robotic applications. In this study, a dual cross-linked self-healing polysiloxane elastomer was facilely fabricated by introducing an exchangeable imine bond and boroxine into polydimethylsiloxane (PDMS) networks. The PDMS elastomers exhibited excellent self-healing properties due to the synergistic effect of dynamic reversible imine bonds and boroxine. After healing for 2 h, the mechanical strength of the damaged elastomers completely and rapidly recovered at room temperature. Furthermore, the prepared PDMS elastomers could be repeatedly reprocessed multiple times under milder conditions without significant degradation in mechanical performance. In addition, a stretchable and self-healable electrical sensor was developed by integrating carbon nanotubes (CNTs) with the PDMS elastomer, which can be employed to monitor multifarious human motions in real time. Therefore, this work provides a new inspiration for preparing self-healable and reprocessable silicone elastomers for future flexible electronics.