Elastomeric Phase Research Articles

Designing Isocyanate‐Containing Elastomeric Electrolytes for Antioxidative Interphases in 4.7 V Solid‐State Lithium Metal Batteries

AbstractTo facilitate the use of solid polymer electrolytes (SPEs) with high‐nickel (Ni) cathodes in high‐voltage lithium (Li) metal batteries (LMBs), it is crucial to address the challenges of low oxidative stability and the formation of vulnerable interphases. In this study, isocyanate groups (−N═C═O) are incorporated to develop an SPE with a bi‐continuous structure, consisting of elastomeric and plastic crystal phases. This rationally designed SPE exhibits high ionic conductivity (0.9 × 10−3 S cm−1 at 25 °C), excellent elasticity (elongation at break of 330%), and enhanced oxidative stability (over 4.8 V vs. Li/Li⁺). A full cell, incorporating this SPE with a thin Li foil of 40 µm, and a high‐Ni LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode operating at 4.7 V vs. Li/Li⁺, demonstrates excellent cyclability, retaining 70% of its initial capacity after 200 cycles under a high C‐rate of 1C at 25 °C. The extended cycling of isocyanate‐containing SPE at 4.7 V vs. Li/Li⁺ is attributed to robust and compact inorganic‐rich interphases enabled by antioxidative −N−C═O components, as well as uniform Li deposition attributed to the bi‐continuous structured SPE. This study suggests that the isocyanate‐containing SPE system is a promising candidate for high‐voltage solid‐state LMBs by constructing stable interphases.

A perspective on the time‐dependent structure and properties of amorphous polymer

AbstractA molecular mechanism of viscoelastic deformation is presented. Amorphous polymers are characterized as a heterogeneous network of nanoscale cells. A “cell” is a homogeneous region within the network. Each cell phase fluctuates between the glassy and elastomer states with a period τ. The values of τ vary from cell to cell over several orders of magnitude and are strong functions of temperature. Whether a given cell responds as glassy or elastomeric depends on the ratio between its period of phase fluctuation (τj) and the period of observation (1/f), where f is the test frequency. We express this ratio, the Deborah number, as (τj × f), and present equations for modulus and energy loss as functions of (τj × f). The condition (τj × f) = 1 defines the glass transition of a cell, which arises cell‐by‐cell over a range of temperature, or over a range of time under stress. Viscoelastic deformation occurs if a cell changes phase while under stress. Energy stored during glassy state deformation is lost if the cell fluctuates to the elastomeric state. Stress is out of phase with strain, because strain rate controls the level of stress in glassy cells between phase fluctuations.Highlights A molecular mechanism of viscoelasticity is presented that does not involve viscous flow. Amorphous polymer is a heterogeneous network of nanoscale cells. Cells fluctuate in phase between glassy and elastomeric states due to their size. Time‐dependent properties are caused by time‐dependent structure. Energy is lost when glass phase cells under stress fluctuate to the elastomer phase.

Harnessing melt processing for the preparation of mechanically robust thermoplastic vulcanizate electrolytes

We report a new type of polymer blend electrolyte based on the principle of thermoplastic vulcanizates (TPV). TPV materials have been extensively used in the automotive and manufacturing sectors. However, to the best of our knowledge, TPV-based electrolytes have yet to be produced. These electrolytes, obtained via melt-processing, combine the high ionic conductivity and processibility of a thermoplastic phase with the improved mechanical strength of a crosslinked elastomeric phase. TPV electrolytes prepared with poly(caprolactone) (PCL) (thermoplastic phase) and hydrogenated nitrile butadiene rubber (HNBR) (elastomeric phase) are presented in this work. These materials deliver promising results in terms of ionic conductivity, electrochemical stability and mechanical strength. Further improvements in ionic conductivity are obtained by doping the TPV electrolyte with a flame-retardant solvent, triethyl phosphate. The crosslinked nature of the TPV allows both mechanical strength and electrochemical stability to be conserved upon doping which is not possible in non-crosslinked polymer blend electrolytes prepared with PCL and HNBR.

A Solid-Liquid Bicontinuous Fiber with Strain-Insensitive Ionic Conduction.

Stretchable ionic conductors are crucial for enabling advanced iontronic devices to operate under diverse deformation conditions. However, when employed as interconnects, existing ionic conductors struggle to maintain stable ionic conduction under strain, hindering high-fidelity signal transmission. Here, it is shown that strain-insensitive ionic conduction can be achieved by creating a solid-liquid bicontinuous microstructure. A bicontinuous fiber from polymerization-induced phase separation, which contains a solid elastomer phase interpenetrated by a liquid ion-conducting phase, is fabricated. The spontaneous partitioning of dissolved salts leads to the formation of a robust self-wrinkled interface, fostering the development of highly tortuous ionic channels. Upon stretch, these meandering ionic channels are straightened, effectively enhancing ionic conductivity to counteract the strain effect. Remarkably, the fiber retains highly stable ionic conduction till fracture, with only 7% resistance increase at 200% strain. This approach presents a promising avenue for designing durable ionic cables capable of signal transmission with minimal strain-induced distortion.

Higher order structures and toughening mechanisms for simultaneously polymerized polymethacrylate/polyurethane

AbstractAmorphous polymer/crystalline polymer blends can be prepared via the simultaneous polymerization of polymethacrylate/polyurethane combinations. The relationship between higher order structures and fracture mechanisms in these blends must be uncovered to elucidate the source of the increased fracture toughness of such materials. The present work involves the production of blended polymethacrylate/polyurethane and assess the internal structures of these specimens using optical and electron microscopy. These observations reveal the presence of both spherulites and elastomeric phases. The spherulites consisting of the polyurethane and are several micrometers in diameter whereas the phase‐separated polyurethane elastomeric domains are approximately 100 nm in size. Multiple cracks, crack bridging and plastic deformation around the precrack tips of loaded specimens are evidently responsible for the increased toughness of these blends. The former two phenomena are attributed to the presence of spherulites while the plastic deformation of the methacrylate matrix is ascribed to cavitation of the polyurethane elastomeric phases in response to loading.

Morphological evolution and property changes of acrylate rubber/polyacetal thermoplastic vulcanizates during dynamic vulcanization process

AbstractA new type of thermoplastic vulcanizates (TPV) that is resistant to hot oil, high temperature, and aging was prepared using acrylate elastomer (ACM) and polyoxymethylene (POM) as raw materials. The phase transition process and micromorphology development of the blends with the change of dynamic vulcanization (DV) time, and to illustrate the effects of the phase transition and the degree of elastomer phase crosslinking on the macroscopic properties of TPV were investigated. It was shown that ACM crosslinking occurs continuously during 0–8 min of DV, whereas the phase inversion process occurs predominantly during 0–3 min. In contrast, the cross‐section of the blends after phase inversion is flat, The constant elongation stress under small deformation, hardness, and permanent deformation after break are reduced, and the elongation at break, nonrelaxable modulus, and aging resistance are improved. The increase in the degree of vulcanization of the ACM phase resulted in a significant increase in the modulus of the blends under large deformation, an increase in the nonrelaxable modulus and relaxable modulus, an increase in the aging resistance, and a decrease in the elongation at tear were observed.

Formation of Interconnected Elastomeric Phase Unevenly Jammed by Nanosilica in the Plastic Matrix during Melt Processing

Formation of Interconnected Elastomeric Phase Unevenly Jammed by Nanosilica in the Plastic Matrix during Melt Processing

Polyolefin Blends with Selectively Crosslinked Disperse Phase Based on Silane-Modified Polyethylene.

Polypropylene-based multiphase compositions with a disperse elastomer phase provide superior impact strength. Making this property indifferent to processing steps requires stabilization of the morphology of these materials. Various approaches have been tested over time, each of which shows limitations in terms of performance or applicability. Using polyethylene (PE) homo- and copolymers capable of silane-based crosslinking as modifiers was explored in the present study, which allows decoupling of the mixing and crosslinking processes. Commercial silane-copolymerized low-density PE (LD-PEX) from a high-pressure process and silane-grafted high-density PE (HD-PEX) were studied as impact modifiers for different types of PP copolymers, including non-modified reference PE grades, LDPE and HDPE. Blends based on ethylene-propylene random copolymers (PPR) and based on impact- (PPI) and random-impact (PPRI) copolymers show improvements of the stiffness-impact balance; however, to different degrees. While the absolute softest and most ductile compositions are achieved with the already soft PPRI copolymer base, the strongest relative effects are found for the PPR based blends. Modifiers with lower density are clearly superior in the toughening effect, with the LD-PEX including acrylate as second comonomer sticking out due to its glass transition around -40 °C. The impact strength improvement found in most compositions (except at very high content) results, however, not from the expected phase stabilization. For comparable systems, particle sizes are normally higher with crosslinking, probably because the process already starts during mixing. Thermoplastic processability could be retained in all cases, but the drop in melt flow rate limits the practical applicability of such systems.

Elucidating the impact of microstructure on mechanical properties of phase-segregated polyurea: Finite element modeling of molecular dynamics derived microstructures

Phase-segregated polyureas (PU) have received considerable interest due to their use as tough, impact-resistant coatings. Polyureas are favored for these applications due to their mechanical strain rate sensitivity and energy dissipation. Predicting and tailoring the mechanical response of PU remains challenging due to the complex interaction between its elastomeric and glassy phases. To elucidate the role of PU microstructure on its mechanical properties, we developed a finite element modeling framework in which each phase is represented by a volume fraction within a representative volume element (RVE). Critically, we used separate constitutive models to describe the elastomeric and glassy phases. We developed a plasticity-driven breakdown process in which we model the glassy phase disaggregating into a new phase. The overall contribution of each phase at a material point is determined by their respective volume fractions within the RVE. We applied our modeling methods to two compositions of PU with differing elastomeric segment lengths derived from oligoether diamines, Versalink P650 and P1000. Our simulations show that a combination of microstructural differences and elastomeric phase properties accounts for the difference in mechanical response between P650 and P1000. We show our model’s ability to predict PU behavior in various loading conditions, including low-rate cyclic loading and monotonic loading over a wide range of strain rates. Our model produces microstructure transformations that mirror those indicated by small-angle X-ray scattering (SAXS) experiments. Fourier transform analysis of our RVEs reveals glassy phase fibrillation due to deformation, a finding consistent with SAXS experiments.

New recyclable and self-healing elastomer composites using waste from toner cartridges

Product recycling reintroduces what is discarded as waste and minimizes the environmental impact on our society. Among the different types of waste from electrical and electronic equipment, toner recycling often falls short, downcycling plastic components. This study introduces an innovative approach in which waste parts from toner cartridges are valorized to develop (recyclable and) self-healing elastomeric composite materials. The synergy between carboxylated nitrile rubber (XNBR) as the elastomeric phase and high-impact poly (styrene) (HIPS) as the thermoplastic phase derived from toner cartridge waste was explored and optimized. This combination resulted in the creation of a thermoplastic elastomer exhibiting robust mechanical properties and self-healing capabilities with a tensile strength of 6.6 ± 0.2 MPa and a temperature-driven mechanical recovery of 100%. Furthermore, the capacity of toner powder, an integral component of waste, to act as a reinforcing filler was confirmed, with a 50% increase in mechanical strength compared with the unfilled composite. Moreover, an increase in toner content (up to 20 phr) resulted in an optimal balance between tensile strength and self-healing capacity, surpassing the traditional antagonism between these properties. As a result, this research opens a new pathway in the field of self-healing composites and suggests a practical and environmentally friendly approach for managing electronic waste, effectively supporting the principles of Circular Economy.

Toward partially bio‐based thermoplastic vulcanizates based on poly (lactic acid) and chloroprene rubber

AbstractPolylactic acid (PLA)‐based thermoplastic vulcanizates (TPVs) were fabricated using dynamic and static vulcanization in the presence of untreated and surface‐treated zinc oxide (ZnO). Initially, the effect of chloroprene rubber (CR) as the elastomeric phase in the PLA‐based thermoplastic elastomer (TPE) was tailored. The CR content varied from 20 to 40 wt%, leading to 46%–70% and 19%–76% decrement in tensile strength and modulus, respectively, while elongation at break increased up to 9–13 times, highlighting the soft rubber phase's impact on ductility. Impact resistance testing showed improved toughness with CR addition, peaking at 20 wt% CR. Scanning electron microscopy (SEM) revealed matrix‐dispersed morphology with increasing CR droplet size, and co‐continuous morphology at 40 wt% rubber in BP6R4. In the next step, the optimized TPE was selected, and the focus shifted to investigate the effect of dynamic/static vulcanization on mechanical properties. It is revealed that adding modified ZnO (ZnO60) increased melt torque, but it decreased after 1.5 min. All vulcanized samples exhibited lower tensile strength and elongation at break but higher elastic modulus due to metallic particle reinforcement. ZnO particle agglomerates and rubber aggregations led to lower mechanical properties. These findings offer quantitative insights into vulcanization's influence on PLA‐based TPVs, informing partially biobased TPEs development and addressing vulcanization limitations.Highlights Fabrication of biobased thermoplastic elastomer (TPE) and thermoplastic vulcanizate (TPV) based on polylactic acid/chloroprene rubber (PLA/CR) shows the sustainable material prospect. The effects of dynamic/static vulcanization on TPE's behavior are investigated. Micro‐morphology analysis showed dispersed CR phase in TPEs when PLA content is <40 wt%. The addition of modified ZnO through static vulcanization minimized degradation. ZnO Agglomeration and CR aggregations caused subpar TPV mechanical properties.

Graphene assisted enhancement in the cyclic electromechanical properties of polyolefin based multiphasic conducting nano carbon black nanocomposites

Hybrid conducting carbon nanofillers and binary elastomeric-thermoplastic-blend based nanocomposites were synthesized to develop highly flexible matrices for strain sensing applications. The effect of graphene on the strain sensing characteristics of a thermoplastic-elastomeric blend which contains conducting carbon nano black (CCNB) above percolation threshold was investigated. The nanocomposites were crosslinked to different extent by high energy gamma radiation and the effect of elastomeric phase, graphene content and crosslink density on the strain sensing response of the nanocomposites was investigated. With incorporation of ethylene propylene diene monomer (EPDM), elongation at break increased around 2500% and the gauge factor by 200%. The graphene content had a profound effect on the electromechanical response and with the addition of 0.02 wt fraction of graphene around 300% increase in gauge factor was observed. With the increase in graphene content and radiation dose the elastic modulus also increased significantly. The relative change in the resistance with applied strain was reversible for all the nanocomposites and the mechanical hysteresis reduced with the addition of EPDM.

Balancing the Strength-Impact Relationship and Other Key Properties in Polypropylene Copolymer-Natural CaSO4 (Anhydrite)-Filled Composites.

To develop novel mineral-filled composites and assess their enhanced properties (stiffness, a good balance between mechanical strength and impact resistance, greater temperature stability), a high-impact polypropylene copolymer (PPc) matrix containing an elastomeric discrete phase was melt mixed with natural CaSO4 β-anhydrite II (AII) produced from gypsum rocks. First, in a prior investigation, the PPc composites filled with AII (without any modification) displayed enhanced stiffness, which is correlated with the relative content of the filler. The tensile and impact strengths dramatically decreased, especially at high filling (40 wt.%). Therefore, two key methods were considered to tune up their properties: (a) the ionomeric modification of PPc composites by reactive extrusion (REx) with zinc diacrylate (ZA), and (b) the melt mixing of PPc with AII surface modified with ethylenebis(stearamide) (EBS), which is a multifunctional processing/dispersant additive. The properties of composites produced with twin-screw extruders (TSEs) were deeply assessed in terms of morphology, mechanical, and thermal performance, including characterizations under dynamic mechanical solicitations at low and high temperatures. Two categories of products with distinct properties are obtained. The ionomeric modification by Rex (evaluated by FTIR) led to composites characterized by remarkable thermal stability, a higher temperature of crystallization, stronger interfacial interactions, and therefore noticeable mechanical properties (high tensile strength (i.e., 28 MPa), increased stiffness, moderate (3.3 kJ/m2) to good (5.0 kJ/m2) impact resistance) as well as advanced heat deflection temperature (HDT). On the other hand, the surface modification of AII with EBS facilitated the dispersion and debonding of microparticles, leading to composites revealing improved ductility (strain at break from 50% to 260%) and enhanced impact properties (4.3-5.3 kJ/m2), even at high filling. Characterized by notable mechanical and thermal performances, high whiteness, and a good processing ability, these new PPc-AII composites may be tailored to meet the requirements of end-use applications, ranging from packaging to automotive components.

New low‐temperature resistant shape memory elastomer: Ethylene‐octene copolymer/methyl vinyl silicone rubber composites

AbstractA new series of thermoplastic elastomers were fabricated in this study employing ethylene‐octene copolymer (POE) and methyl vinyl silicone rubber (MVQ) as the thermoplastic phase and the elastomeric phase, respectively. The effect of POE/MVQ blending ratios on the vulcanization, mechanical, and thermal properties, cold resistance, shape memory properties, and hydrophobicity of the thermoplastic composites was investigated. Moreover, specific properties such as low‐temperature impact (LTI), shape memory and hydrophobicity properties exhibited by the POE/MVQ thermoplastic composites were studied in detail. The results indicated that the POE/MVQ composites exhibited remarkable mechanical properties and LTI strength. With the MVQ content reaching 10 phr, their tensile strength reached 30.07 MPa, significantly higher than that of pure POE. Regarding shape memory properties, the shape fixing ratio and the shape recovery ratio were 97.6% and 94.3%, respectively, at the MVQ content of 40 phr.

Toughening and Stiffening in Thermoreversible Diels–Alder Polymer Network Blends

The thermophysical properties, mechanical behavior, and healing performance of Diels–Alder-based polymer networks can be tuned widely by changing the molar mass, functionality, and stoichiometric ratio of the multifunctional diene (e.g., furan) and dienophile (e.g., maleimide) monomers. Blending furan-functionalized monomers with a high and low molar mass opens a new dimension in tuning the properties of the resulting reversible polymer network blends (RPNBs), containing different ratios of elastomeric and thermoset phases, with low and high crosslink densities and glass transitions below and above room temperature, respectively. Increasing the thermoset content up to 20 wt % raises the gel transition temperature (Tgel), relaxation time (τ), rubbery plateau modulus, ultimate stress, and Young’s modulus of the stiffened elastomers, while the strain at fracture and self-healing efficiency remained mostly unchanged. Conversely, the addition of up to 20 wt % of the elastomer phase drastically toughens the thermosets because of stress dissipation, which can suppress the stress concentration in the phase-separated network blends. The blends showed higher stress and strain at break while retaining similar Young’s moduli. The toughness increases up to an order of magnitude at 50 wt %, compared to the pure thermoset. The phase-separated morphologies were evidenced by the presence of the Tg’s of the pure networks in DSC and DMA.

Highly Stretchable Printed Poly(vinylidene fluoride) Sensors through the Formation of a Continuous Elastomer Phase

Stretchable piezoelectric stress/strain sensing materials have attracted substantial research interest in the fields of wearable health monitoring, motion capturing, and soft robotics. These sensors require operation under dynamic loading conditions with high strain range, changing strain/loading rates, and varying pre-stretch states, which are challenging conditions for existing sensors to produce reliable measurements. To overcome these challenges, an intrinsically stretchable poly(vinylidene fluoride) (PVDF) sensor is developed through the polymer blending of PVDF and acrylonitrile butadiene rubber (NBR). Through precipitation printing and vulcanization, the resulting PVDF/NBR blends exhibit strong β phase PVDF and a blend morphology with submicron-level phase separation, but also strains up to 544%. Both the blend morphology and the mechanical properties indicate that this PVDF/NBR blend can be considered as a continuous elastomer phase above micron scale. After electric poling and adding electrodes, the PVDF/NBR blends have excellent piezoelectric properties to be used as both stretching mode strain sensors and compression mode stress/force sensors. The stretching mode sensors can measure strain up to 70% without strain rate and pre-stretch dependence, while the compression mode sensors have a loading-rate-independent linear voltage-stress relationship up to 4.8 MPa stress and a negligible pre-stretch dependence. Therefore, the PVDF/NBR sensors can provide accurate and reliable stress/strain measurements when attached to soft structures, which paves the way for sensing and calibration of soft robots under dynamic loading conditions.

Skin-Inspired Tough Elastomer with Moisture-Triggered Switchable Mechanical Properties.

Biological tissue usually exhibits good water adaptive mechanical properties, which can maintain high strength and toughness in both wet and dry states. However, synthetic tissue like hydrogel usually becomes hard and brittleness in its dry state. Here this challenge is met by exploring iron-catechol complex (TA-Fe3+ ) as a great platform combining extremely different polymers (elastomer and hydrogel) to construct new tissue-like soft composite materials with two different continuous phases, which have not yet been reported. In its dry state, the xerogel phase becomes a reinforced segment to increase the strength of PB without losing its toughness. In its wet state, this soft material becomes high performance hydrogel, where hydrogel phase absorbs high water and elastomer phase can sustain high loading. Such heterogeneous phase structures provide a good idea for designing the soft materials, exhibiting a trade-off between its high strength and toughness in both wet and dry states. Furthermore, its shape memory behaviors in both its wet and dry state, which shows a great potential application for complex adaptive shape transformation and engineering application like lifting of heavy objects under remote control due to high photo-thermal transition of TA-Fe3+ is explored.

Enhancing the Interface Behavior on Polycarbonate/Elastomeric Blends: Morphological, Structural, and Thermal Characterization.

A systematic study was performed to provide better understanding of the effect of elastomeric materials on the behavior of polycarbonate blends (PC). Thus, blends of PC with different amounts of elastomers, such as copolyether ester elastomer (COPE), acrylonitrile-butadiene-styrene (ABS), maleic anhydride-grafted ABS (ABS-g-MA), and styrene-ethylene-butylene-styrene (SEBS-g-MA) were prepared in a co-rotating twin-screw extruder. The materials were characterized by an electronic microscopy (SEM), an infrared spectroscopy (FTIR), and thermal (DSC) and thermo-mechanical (DMA) techniques. The incorporation of elastomeric phases was observed by changes in the FTIR band's intensity, whereas a new shoulder of the ester band of COPE at 1728 cm-1 indicates the occurrence of a transesterification reaction. Unmodified and modified ABS (5% and 10%) did not affect the glass transition temperature (Tg) of PC, while 1% SEBS-g-MA slightly increased this value. PC/10% COPE showed that a decrease in Tg of 25 °C has a result of better compatibilization between both phases, which is visible via SEM. SEM analysis identified three main toughening mechanisms, depending on the type of elastomer. Unlike any other study, this work deepens the knowledge, in a comparative way, to understand the elastomeric effect at the interface and consequently, on the mechanical behavior of PC systems.

STRUCTURE AND PROPERTIES OF THERMOPLASTIC PSEUDO-INTERPENETRATING POLYMER NETWORKS BASED ON NATURAL POLY-3-HYDROXYBUTIRATE AND NATURAL RUBBER

Thermoplastic film materials with a structure of pseudo-interpenetrating polymer networks (pseudo-IPNs) were created on the basis of natural semi-crystalline poly-3-hydroxybutyrate (PHB) and natural rubber (NR), the content of the NR was varied from 2 to 40 wt.%. Using the methods of Fourier Transform Infra-Red (FTIR) spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), structure-properties relationships were studied for PHB/NR thermoplastic pseudo-IPNs at different ratios of the components. Significant non-additive increase in mechanical characteristics compared to the individual PHB was found for PHB/NR pseudo-IPNs samples with a low content (up to 15 wt.%) of NR. For the sample with a content of 5 wt.% NR, the greatest increase (~18.4%) in strength at break was fixed (σb ≈ 22.5 MPa); for a sample with a content of 10 wt.% NR, the largest increase (~ 215%) in elongation at break (εb ≈ 48.8%) was observed. By FTIR spectroscopy, it was found that certain changes in the crystal structure of the PHB matrix occurred in the samples of pseudo-IPNs at increasing the NR content; however, no changes in the chemical structure of the components were detected. The SEM method revealed spherical domains of the dispersed elastomeric NR phase distributed in the PHB matrix in the samples of PHB/NR pseudo-IPNs. These observations evidence the microphase separation of the system components due to their thermodynamic incompatibility. It is worth to note that the sizes of the domains of the dispersed elastomeric phase naturally increased from ~10–20 μm for pseudo-IPNs PHB/NR = 85/15 wt.%, up to ~ 100 μm for PHB/NR = 60/40 wt.%. Using TGA method, it is established that PHB/NR pseudo-IPNs samples are characterized by high resistance to thermo-oxidative destruction, which non-additively increases with increasing the NR content. Destruction of PHB/NR pseudo-IPNs samples occur in two main stages: at I stage (Td ~ 240–285 °С) the main weight loss of the samples is occurred due to the destruction of macromolecules of the PHB matrix; at II stage (Td ~ 320–380 °С) the oxidative destruction of NR component takes place. Calculations have shown that with increasing the NR content, the maximum rate of thermo-oxidative destruction of pseudo-IPNs samples decreases compared to the individual PHB by 5–52 % with increasing the NR content from 2 to 40 wt.%. Therefore, it means that their resistance to thermo-oxidative destruction increases. The results obtained by DSC method have shown that the introduction of NR and changes of the components ratio significantly and non-additively affect all the thermophysical characteristics of the samples studied. This indicates a significant restructuring of the microphase (amorphous and crystalline) structure of pseudo-IPNs synthesized due to the interpenetration of the components into the microphases of each other and the formation of mixed PHB/NR microphases with different ratios of the components.

Role of Bicontinuous Structure in Elastomeric Electrolytes for High-Energy Solid-State Lithium-Metal Batteries.

Solid-state lithium (Li)-metal batteries (LMBs) are garnering attention as a next-generation battery technology that can surpass conventional Li-ion batteries in terms of energy density and operational safety under the condition that the issue of uncontrolled Li dendrite is resolved. In this study, various plastic crystal-embedded elastomer electrolytes (PCEEs) are investigated with different phase-separated structures, prepared by systematically adjusting the volume ratio of the phases, to elucidate the structure-property-electrochemical performance relationship of the PCEE in the LMBs. At an optimal volume ratio of elastomer phase to plastic-crystal phase (i.e., 1:1), bicontinuous-structured PCEE, consisting of efficient ion-conducting, plastic-crystal pathways with long-range connectivity within a crosslinked elastomer matrix, exhibits exceptionally high ionic conductivity (≈10-3 S cm-1 ) at 20 °C and excellent mechanical resilience (elongation at break ≈ 300%). A full cell featuring this optimized PCEE, a 35µm thick Li anode, and a high loading LiNi0.83 Mn0.06 Co0.11 O2 (NMC-83) cathode delivers a high energy density of 437Wh kganode+cathode+electrolyte -1 . The established structure-property-electrochemical performance relationship of the PCEE for solid-state LMBs is expected to inform the development of the elastomeric electrolytes for various electrochemical energy systems.