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  1. Evaluating hydrogen permeation through medium-density and high-density polyethylene pipes to enable a hydrogen-compatible infrastructure

    As the United States and the global community pursue energy abundance and resilience, hydrogen is emerging as a critical energy carrier. The future of hydrogen transport depends on one thing: verifying that today’s pipelines are hydrogen ready. This study investigates the permeation behavior of medium-density polyethylene (MDPE) and high-density polyethylene (HDPE) pipelines under pure hydrogen gas environment at various pressures and temperatures. Using thermal desorption analysis (TDA) and direct pipe permeability measurements, hydrogen loss rates are quantified, revealing minimal permeation losses (< 10.5 g/km/day) under realistic operating conditions. Effects of temperature and pressure with Standard Dimension Ratios (SDR), were evaluatedmore » to determine their influence on permeation rates of MDPE and HDPE pipelines. In addition, ex-situ density and degree of crystallinity (DOC) of MDPE and HDPEs after hydrogen exposure were also investigated to understand pressure-dependency of polymer properties. The findings provide essential data for assessing polymer-based pipeline materials for safe and reliable hydrogen transport.« less
  2. Tandem CO2 valorisation to polycarbonate vitrimer and ethylene carbonate

    The need for renewably sourced polymers has intensified with the worsening of global challenges such as emissions and plastic pollution. Here, we report a CO2-based poly(cyclohexene carbonate) (PCHC) vitrimer cured with zinc stearate that directly addresses both issues. Enhanced zinc dispersion within the network enabled faster curing and reprocessing than possible with zinc acetate systems, while maintaining consistent Tg and mechanical integrity across multiple cycles. The vitrimer undergoes rapid glycolysis in ethylene glycol, valorisation into ethylene carbonate with up to 97% yield without additional catalyst. When applied to carbon fibre-reinforced polymers (CFRPs), applying this strategy enabled the development of sustainablemore » CO2-based CFRP that can undergo full resin valorisation and recovery of clean, damage-free fibres. Collectively, this tandem CO2 valorisation strategy—from vitrimer synthesis to fibre-reinforced composites and subsequent chemical valorisation—establishes multiple recycling and valorisation pathways and provides a promising routte for carbon capture and utilization as well as material recycling.« less
  3. Pultrusion and Vitrimer Composites: Emerging Pathways for Sustainable Structural Materials

    Pultrusion is a manufacturing process used to produce fiber-reinforced polymer composites with excellent mechanical, thermal, and chemical properties. The resulting materials are lightweight, durable, and corrosion-resistant, making them valuable in aerospace, automotive, construction, and energy sectors. However, conventional thermoset composites remain difficult to recycle due to their infusible and insoluble cross-linked structure. This review explores integrating vitrimer technology a novel class of recyclable thermosets with dynamic covalent adaptive networks into the pultrusion process. As only limited studies have directly reported vitrimer pultrusion to date, this review provides a forward-looking perspective, highlighting fundamental principles, challenges, and opportunities that can guide futuremore » development of recyclable high-performance composites. Vitrimers combine the mechanical strength (tensile strength and modulus) of thermosets with the reprocessability and reshaping of thermoplastics through dynamic bond exchange mechanisms. These polymers offer high-temperature reprocessability, self-healing, and closed-loop recyclability, where recycling efficiency can be evaluated by the recovery yield retention of mechanical properties and reuse cycles meeting the demand for sustainable manufacturing. Key aspects discussed include resin formulation, fiber impregnation, curing cycles, and die design for vitrimer systems. The temperature-dependent bond exchange reactions present challenges in achieving optimal curing and strong fiber–matrix adhesion. Recent studies indicate that vitrimer-based composites can maintain structural integrity while enabling recycling and repair, with mechanical performance such as flexural and tensile strength comparable to conventional composites. Incorporating vitrimer materials into pultrusion could enable high-performance, lightweight products for a circular economy. The remaining challenges include optimizing curing kinetics, improving interfacial adhesion, and scaling production for widespread industrial adoption.« less
  4. In situ investigation of high-pressure hydrogen-induced swelling in elastomers and its correlation with material properties

    The resistance of elastomeric materials to high-pressure hydrogen-induced damage is essential for ensuring the reliability of hydrogen infrastructure. Here, in this study, we systematically investigated the swelling behavior and hydrogen transport properties of four elastomer types – EPDM, NBR, FKM, and HNBR – using a custom in-situ view cell system capable of real-time monitoring during decompression from pressures up to 96.5 MPa. Each elastomer was formulated with and without fillers and plasticizers to assess the effects of formulation on swelling response. Thermal desorption analysis (TDA) was employed to determine equilibrium hydrogen content and diffusion coefficients, providing insight into gas uptakemore » and mobility within each material. Correlation analyses using Pearson and Spearman coefficients revealed that the diffusion coefficient showed a stronger relationship with swelling behavior than hydrogen content, highlighting the dominant role of hydrogen mobility. Filled elastomers, particularly those with carbon black, consistently showed reduced swelling due to enhanced stiffness and reduced diffusivity. These results deepen our understanding of diffuso-mechanical interactions in elastomers and support the rational design of sealing materials for high-pressure hydrogen systems.« less
  5. Reactive Modified Epoxy Resin and Its Miscible Blends Based on Recycled Oligomers from Solvolysis

    Chemical depolymerization of fully cured epoxy resin with 20% reactive modifier was successfully performed via a solvent-assisted solvolysis process into low molecular weight recyclable oligomers (RO) at 240 °C in a pressure vessel at 650 psi for 4 h. The thermoset epoxy resin was depolymerized into transparent brown viscous fluid with a higher viscosity than the uncured epoxy resin with approximately 93% yield. Different concentrations of the RO were homogeneously mixed with the pure epoxy resin, and their curing kinetics, viscosity, FTIR, mechanical properties, DMA, and cross-link density were investigated. The curing kinetics of the pure reactive modified epoxy resinmore » (baseline) and its mixtures with RO of different concentrations were investigated under both isothermal and nonisothermal conditions using small amplitude oscillatory shear flow. The elastic and viscous moduli (G′ and G″), complex viscosity (η*), and tan δ values were evaluated at different curing times and temperatures. The G′, G″, and η* increased dramatically, while tan δ decreased strongly by several orders of magnitude at the gel point. The zero-shear viscosity (η0) was determined from the angular frequency dependent on η* based on the Cross model for different blend compositions in the liquid state before curing. The composition dependence of η0 showed a positive deviation from the linear mixing rule and was well described by the Lecyar model. Here, the apparent activation energy of curing (Ea) was also evaluated according to the Arrhenius equation and was found to be 46 ± 2 kJ/mol regardless of the different contents of RO. For all blends up to 40 wt % RO, only one tan δ peak systematically shifting to lower temperatures with increasing content of RO was observed in the DMA measurements, indicating that the epoxy resin and the RO are miscible with up to 40 wt % RO.« less
  6. Carbon Fiber-Based Vitrimer Composites: A Path toward Current Research That Is High-Performing, Useful, and Sustainable

    In the polymeric material industry, thermosets and related composites have played a substantial role in the production of rubber and plastics. One important subset of these is thermoset composites with carbon reinforcement. The incorporation of carbon fillers and fibers gives polymeric materials improved electrical and mechanical properties, among other benefits. However, the covalently crosslinked network of thermosets presents significant challenges for recycling and reprocessing because of its intractable nature. The introduction of vitrimer materials opens a new avenue to produce biodegradable and recyclable thermosets. Carbon-reinforced vitrimer composites are pursued for high-performance, long-lasting materials with attractive physical properties, the ability tomore » be recycled and processed, and other features that respond uniquely to stimuli. The development of carbon-reinforced vitrimer composites over the last few years is summarized in this article. First, an overview of vitrimers and the methods used to prepare carbon fiber-reinforced vitrimer composites is provided. Because of the vitrimer nature of such composites, reprocessing, healing, and recycling are viable ways to greatly extend their service life; these approaches are thoroughly explained and summarized. The conclusion is our prediction for developing carbon-based vitrimer composites.« less
  7. An in-situ view cell system for investigating swelling behavior of elastomers upon high-pressure hydrogen exposure

    The transition to hydrogen as a clean and efficient energy carrier is impeded by challenges in the compatibility of hydrogen with materials used within hydrogen infrastructure. Elastomers, crucial in sealing components, often exhibit premature failures in high-pressure hydrogen environments due to excessive swelling. This study employs an innovative in-situ view cell system to assess the swelling behavior of hydrogenated nitrile butadiene rubber (HNBR) under various hydrogen conditions. The system, designed to withstand pressures up to 96.5 MPa, incorporates Digital Image Correlation (DIC) for strain measurements and volume estimation. Results reveal non-linear volume increases during depressurization, challenging conventional assumptions. Furthermore, investigationsmore » into peak hydrogen pressures and pressure-holding scenarios during decompression highlight complex swelling trends. The introduction of a novel computer vision (CV) method enhances precision in volume estimation, overcoming DIC limitations. The study provides insights into mitigating elastomer swelling, crucial for developing robust materials to support future hydrogen-driven energy systems.« less
  8. Phase field modeling of hydrogen release in nitrile-butadiene rubber composites after high-pressure hydrogen exposure

    Experimental data showed that a simple diffusion model doesn’t suffice to explain the hydrogen (H2) release kinetics in nitrile butadiene rubber (NBR) composites (one with no filler or plasticizer, one with plasticizer only, one with fillers and plasticizer, and one with fillers only) after exposed to hydrogen gas at a pressure of 27.6 MPa. In this work, we developed a phase field model that considers the effect of H2 gas bubble evolution on H2 release kinetics. With the model, we simulated the effect of thermodynamic and kinetics properties on the nucleation, growth, and shrinkage of gas bubbles and H2 releasemore » kinetics during and after decompression. Here, the results demonstrated that 1) the model built upon certain thermodynamic and kinetics properties of a given material can well describe its H2 release kinetics measured in experiments, and 2) the model can predict the gas bubble evolution, which is associated with the material property degradation and failures, with accurate thermodynamic and kinetics properties or H2 release data from experiments.« less
  9. Multi-scale imaging of high-pressure hydrogen induced damage in EPDM rubber using X-ray microcomputed tomography, helium-ion microscopy and transmission electron microscopy

    Ethylene propylene diene (EPDM) rubber has gained increasing interest for use in hydrogen infrastructure due to its excellent sealing performance and low temperature properties. However, severe structural damage has been observed in EPDM O-rings after exposure to high-pressure hydrogen. The origination and propagation mechanisms of this damage are poorly understood. Here, to address this knowledge gap, multi-scale imaging leveraging X-ray micro-computed tomography (micro-CT), helium ion microscopy (HeIM), and transmission electron microscopy (TEM) were used in this work to study a series of sulfur-cured ethylene propylene diene (EPDM) rubber materials with varying additives that were exposed to different hydrogen environments. Micro-CTmore » captured the substantial structural damage due to hydrogen exposure; it revealed an association between zinc oxide (ZnO) particles and damage initiation. Further studies by TEM and scanning TEM with energy dispersive X-ray spectroscopy (EDS) were focused on these particles at the micro-to nano-scale range. TEM indicated that hydrogen causes void formation at the interface between ZnO and the rubber matrix. HeIM enabled imaging of surface morphology of the material at high resolution pre- and post-hydrogen exposure while providing information on chemical composition and that cannot be captured by either micro-CT or TEM.« less
  10. Recyclable CFRPs with extremely high Tg: hydrothermal recyclability in pure water and upcycling of the recyclates for new composite preparation

    In recent years researchers have introduced different malleable and/or degradable thermosetting polymers to address the recyclability of traditional thermoset materials. Nonetheless, the mechanical properties and glass transition temperature (Tg) of these polymers are often compromised to achieve the desired depolymerization rate. In this work, a hydrothermally recyclable epoxy/anhydride thermosetting system with superior mechanical performance and high Tg (>200 °C) was developed for carbon fiber reinforced plastic (CFRP) applications, using triethanolamine as the co-curing agent and tetraglycidyl methylenedianiline (TGDDM) as the epoxy matrix. The hydrothermal recycling of such cured systems is achieved at relatively low temperature (200 °C) without the additionmore » of a catalyst. This mild recycling process decomposes the recyclable polymer matrix into an oligomer and imparts little damage to the valuable carbon fiber. The recycled carbon fiber and the decomposed polymer resin are reused to prepare a new CFRP. Here, this study has introduced a simple and practical approach for the preparation of recyclable CFRPs with high Tg and a pathway for highly efficient closed-loop recycling, which sets up a framework for the future design of sustainable polymer composites.« less
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