Low ionic conductivity, inadequate interfacial stability, and complex electrolyte-membrane fabrication procedures have long stood as the core bottlenecks restricting the advancement of polymer-based solid-state batteries. In this study, we develop an in situ thermally initiated polymerization strategy to fabricate PDOL/PMMA composite matrices, which are further synergistically tailored by incorporating Li7La3Zr2O12 (LLZO) ceramic filler and fluoroethylene carbonate (FEC). This design yields a composite quasi-solid electrolyte capable of concurrently optimizing ionic conduction and interfacial stability. Within the multicomponent system: the flexible PDOL domain establishes interconnected continuous pathways for lithium-ion migration, the rigid PMMA component affords robust mechanical reinforcement, the LLZO inorganic filler may regulate local ion coordination and anion migration through polymer/ceramic interfacial interactions and accessible surface sites, thereby contributing to the elevated lithium-ion transference number and strengthens the electrolyte’s capability to suppress lithium dendrite propagation, meanwhile, FEC undergoes preferential reductive decomposition at the surface of the lithium metal anode, generating a compact SEI layer rich in lithium fluoride (LiF) that effectively inhibits parasitic interfacial side reactions. The results demonstrate that the composite quasi-solid electrolyte achieves a room-temperature ionic conductivity of 4.42×10-4 S cm-1, a Li+ transference number of 0.82, and an electrochemical window of 4.7 V. Lithium symmetric cells can stably cycle for over 1600 h at 0.1 mA cm-2. This work confirms the critical role of synergistic optimization between inorganic fillers and polymer matrices in enhancing the overall performance of composite electrolytes, and provides a green and practical fabrication strategy for the engineering of solid-state lithium batteries.
Polyethylene terephthalate (PET) has a wide range of applications in human life due to its high-cost performance, but its poor brittleness and flame retardancy limit its scope of application, especially in the ultra-thin configuration required for advanced electronic products. Here, focused on the flame-retardant PET-based copolyesters with advantages in industrial prospects, a one-pot, two-step method is utilized to incorporate 1,4-cyclohexanedimethanol (CHDM) and pre-modified Dihydro-10-[2,3-di(hydroxycarbonyl) propyl]-10-phosphaphenanthrene-10-oxide (DDP) with terminal hydroxyl groups (named DDP-EG) into the PET main chain, resulting in the formation of a PEDCTs copolyesters with improved overall performance. The phosphorus-containing and halogen-free flame retardant DDP-EG embedded in the polymer backbone can achieve free radical quenching in the gas phase and catalytic charring formation in the condensed phase. PEDCTs exhibit remarkable flame resistance and fire protection, maintaining a UL-94 V-0 rating at 0.8 mm thickness, while enhancing the limiting oxygen index to 32.0%. The PHRR (peak heat release rate) decreases by 49.0%, and the total heat release (THR) diminishes by 31.0%. In addition, the fire safety parameter FGI dropped from 8.03 to 4.59, and the FPI increased from 0.042 to 0.105. Moreover, PEDCTs maintained a high light transmittance (89.6% at 700nm) and an elongation at break of 150%.
Mechanism by which process parameters affect the shape memory properties of 4D-printed objects remains unclear. In this study, laser powder bed fusion (LPBF) was employed as the printing technique to systematically investigate the relationship from poly(l-lactic acid) (PLLA) raw material preparation to process-properties mapping. It was found that increasing the laser energy density led to a lower shape recovery ratio of PLLA scaffold with a lower crystallization, wherein the crystalline phase acted as netpoints remembering the permanent shape. And the phenomenon that crystalline phases were breaking down into fewer and smaller crystalline phases under a high laser energy density was intuitively observed. The mechanism was proposed that the laser broke the crystalline phase of PLLA powder during printing and enabling control over the netpoints and thereby influencing the shape memory properties of PLLA scaffold. Furthermore, based on the above mechanism, multi-phase composite scaffolds with pixel-level distribution of amorphous and semi-crystalline phases were fabricated using a single semi-crystalline PLLA as the raw material by tailoring LPBF process parameters. In conclusion, this study revealed that laser-induced breaking of PLLA crystalline phase governed the shape memory properties and provided a new paradigm for multi-phase printing via LPBF.
Interfacial delamination is a common failure mode in fiber fabric/flexible polymer composites. Using aramid fiber fabric/thermoplastic polyurethane composites as a representative system, this study develops a multiscale model to predict interface peel strength. Guided by the model, an interface mechanical interlock structure is designed and geometrically optimized. Experiments demonstrate that the optimized mechanical interlock structure increases the interfacial peel strength by a factor of 9.6. The proposed multiscale modeling framework and mechanical interlock design strategy provide guidance for the interfacial strengthening of fiber fabric/flexible polymer composites.
Haloferax mediterranei is a promising archaeon for producing the high-value-added biopolymer poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). However, its metabolic engineering has been largely hampered by the scarcity of efficient genome-editing tools. Here, we developed a versatile genome-editing platform by harnessing the endogenous type I–B CRISPR-Cas system. This toolkit enables highly efficient and precise gene deletion (>90% efficiency), multiplex editing, gene insertion, and large-scale chromosomal deletions (up to 24.9 kb). Additionally, we implemented a Cas3-mediated bidirectional deletion strategy facilitated by recombination inhibition. Using these tools, we constructed genome-reduced chassis with deletions of up to 43.5 kb, which exhibited superior PHBV synthesis without compromising cell growth. One optimal strain, ES1Δ123Δ24.9, achieved a PHBV production of 27.44 g/L from glucose in a 7-L bioreactor, with a conversion rate of 0.38 g PHBV/g glucose—the highest reported carbon source conversion rate among archaeal PHBV producers to date. These genome-reduced H. mediterranei strains represent an advanced chassis for the production of PHBV and other valuable biochemicals.
This work proposes the development of modified alkyd coatings based on the open-loop chemical recycling of fiber-reinforced polymer (FRP) composites from end-of-life (EoL) wind turbine blades. Epoxy-based glass FRP composites are efficiently depolymerized by a catalyst-assisted mild solvolysis process using a biobased diol, achieving complete resin dissolution and recovery of clean fibers. The resulting organic recyclate, rich in hydroxyl-terminated epoxy-derived oligomers, is directly employed - without further purification or modification steps - as a reactive macromer for the synthesis of industrial alkyd resins. Modified alkyds containing up to 17 wt% recycled fraction are formulated into pigmented anticorrosive coatings and applied on steel substrates. Comprehensive characterization shows that recyclate contents up to 10 wt% do not adversely affect coating processability, curing, mechanical properties, outdoor durability, or corrosion protection, as confirmed by electrochemical impedance spectroscopy. These results demonstrate a viable and scalable route for the high-value reuse of chemically recycled FRP materials in protective coatings, enabling a synergistic circular economy link between the wind energy and coatings industries.
Polylactic acid microplastics (PLA-MPs) pose a persistent risk in the aquatic environment due to incomplete degradation under natural conditions. Here, a FeMg-LDH-modified oxychar composite (OC-LDH) was prepared via low-temperature partial oxidation and evaluated as a persulfate (PS) activator for the degradation of PLA-MPs. During oxychar synthesis, FeMg-LDH promoted the activation of O2 and left more oxygen-containing functional groups (OCFGs) on the surface of OC-LDH. In batch degradation experiments, OC-LDH achieved the highest weight loss (50.2%) of PLA-MPs in 30 days, outperforming oxychar and FeMg-LDH alone and indicating a synergistic effect between the two components. Moreover, OC-LDH maintained about 84% of its initial activity after three reuse cycles, with Fe leaching below 0.3 mg/L. Mechanistically, the active species attack the PLA backbone (ester) before oxidizing terminal C–H groups. Quenching experiments and EPR confirm that the PS activation proceeded through both radical pathways (SO4·- ·OH, O2·-) and non-radical ones (1O2, electron transfer). XPS points to Fe(II) and OCFGs (especially CO) on the OC-LDH as the key reaction sites. Meanwhile, the oxychar matrix also helped to disperse LDH, promoted Fe(II)/Fe(III) redox cycling and improved electron transport, all of which boosted PS activation. Overall, this work offers a recyclable catalyst design and practical insight into the synergistic roles of oxychar and LDH in PS activation for PLA-MPs remediation in water.
Rapid growth in wearable health-monitoring systems is accelerating demand for flexible, safe, and environmentally responsible energy-storage components. Nevertheless, conventional liquid electrolytes pose leakage and flammability risks, so they are poorly suited to skin-contact, mechanically deformable devices. Fossil-derived polymer electrolytes can deliver robust performance, but are typically persistent, which complicates end-of-life management of polymer wastes. Despite rapid advanced materials development, the literature lacks a comprehensive design-to-performance pattern connecting the green polymers chemistry with ion-transport mechanisms and wearable-device requirements. Renewable polymer-based electrolytes offer a compelling portfolio for designing safer and more sustainable wearable energy devices with higher potential for biocompatibility and reduced environmental consequences This review addresses strategies for manufacturing and application of renewable polymer electrolytes, demonstrating how microstructure and bonding in such systems improve ionic conductivity, electrochemical stability, and mechanical robustness under deformation. We also summarize device-oriented performance of renewable polymers in flexible batteries, supercapacitors, and biosensing platforms, followed by outlining research portfolio for sophisticated wearable device demonstrations. In particular, hybrid electrolyte systems, greener synthesis and processing routes, and recyclability-by-design aspects of wearable energy systems are reviewed toward innovative sustainable developments.
Controlling the condensed structures is crucial during polymer processing, while chain structure significantly influences the condensation process. In thermoplastic polymers, the high rigidity and unique topology of polyetherketoneketone lead to interchain locking, severely hindering segmental motion and close packing, limiting its performance. Here, we report a chain softening strategy to reduce the disentanglement barriers and promote segment movement, achieving full and dense condensation of chains. The softener 1,2-dichloroethane reduces the torsional energy barrier and gyration radius of polyetherketoneketone chains by inducing electron density shifts via intermolecular interactions. The solution exhibits a broad relaxation time distribution and rapid stress relaxation. After chain softening, the porosity of polyetherketoneketone condensates significantly decreases, and the fiber density is comparable to that of the hot-pressed sheet. Upon removing 1,2-dichloroethane, the chains in the fiber re-interlock due to the recovery of rigidity and topologicity, thereby giving it excellent performance. This method of controlling condensed structure by changing molecular physical properties has positive implications for polymer processing.
Covalent organic frameworks (COFs) have emerged as premier candidates for advanced functional materials due to their permanent porosity, high crystallinity, and tunable chemical structures. However, their inherent rigidity and poor processability often limit their direct application in flexible and integrated devices. Integrating COFs with hydrogel matrices offers a synergistic solution, combining the molecular-level precision of COFs with the superior mechanical flexibility, high water content, and biocompatibility of hydrogels. This review systematically summarizes the recent progress in COF/hydrogel composites, focusing on interface design strategies including physical blending, in-situ growth, and covalent cross-linking. We highlight how these design principles modulate the synergistic effects between the components to enhance ion transport, catalytic activity, and mechanical durability. Furthermore, we provide a comprehensive overview of their multifunctional applications in environmental remediation (heavy metal and organic pollutant removal), energy storage (zinc-ion batteries and supercapacitors), biosensing (wearable strain sensors and clinical diagnostics), and biomedical engineering (diabetic wound healing and bone tissue regeneration). Finally, the current challenges and future perspectives of COF/hydrogel composites are discussed, aiming to provide a roadmap for the development of next-generation soft-matter materials.
To address the failure of hard–soft interfaces in conventional inorganic–organic protective coatings under deep-sea alternating loading, a polymer microsphere-based composite coating was fabricated by a one-step process. The coating showed strong adhesion to the substrate (about 26.49 MPa). Based on the falling-ball impact process, a method was proposed to evaluate the elastic response of coating materials, from which the first flight time (FFT) was obtained and the elastic energy coefficient (EEC) was calculated. For a composite coating with a thickness of 80 μm and a microsphere content of 20 vol%, the FFT reached 418 ms, which was 138% of that of a pure PU coating. The elastic energy coefficient (EEC) reached 2.53. An elastic energy storage–release model was proposed to clarify the interfacial enhancement mechanism between microsphere-enabled energy storage and matrix-mediated energy release. After alternating loading from 0 to 20 MPa, the coating showed an EEC of 2.41, which was 6 times higher than that of an inorganic microsphere coating. The adhesion strength remained above 17 MPa. The coating also maintained stable elastic performance under marine engineering conditions (ultraviolet radiation, artificial seawater). This work provides a new perspective for the design of protective coatings for deep-sea alternating loading.
Windows represent critical weak points in building energy efficiency, making effective thermal management essential for modern low-carbon energy conservation. However, mainstream energy-saving window solutions are often constrained by technical complexity and lack application flexibility. Herein, we developed a high-performance transparent thermal management film with broad application potential through a simple solution-blending strategy combined with spectral design. The spectrally selective film achieves high near-infrared shielding (>90%) and ultraviolet shielding (>95%) to inhibit solar heat gain, while maintaining high visible light transmittance (>60%) and low haze (<12%). A heat-transfer model was established to distinguish absorption- and reflection-dominated insulation mechanisms, quantitatively confirming the thermal performance and cost advantage of the film. Outdoor tests show that the film achieves a maximum temperature reduction of 10.2 °C. Simulations further reveal annual cooling-energy savings of 33.1–37.1 MJ·m−2 in tropical and arid regions, indicating significant potential for reducing building-related carbon emissions. This work demonstrates a cost-effective, high-performance solution for building energy conservation.
CO2 based-Poly(propylene carbonate phthalate) (PPC-P), a CO2-based polymer, is esteemed for its commendable mechanical properties, biodegradability and high transparency, positioning it as a promising material for sustainable packaging. However, its inherent brittleness and poor toughness significantly restrict its practical applications. This study addresses this limitation by incorporating ultra-high molecular weight poly(ethylene oxide) (UHMW-PEO) as an effective toughening agent. To overcome the melting processing challenges posed by the extremely high melt viscosity of UHMW-PEO, a novel hybrid methodology integrating solution blending, gradual dilution and melt blending is successfully implemented. The resulting blends exhibit excellent compatibility between PPC-P and UHMW-PEO because of the incorporation of entanglements introduced. Remarkably, the addition of a small amount of UHMW-PEO yields a toughened PPC-P material with an optimal balance of tensile strength, ductility and transparency. PPC-P/5%PEO formulation is selected for blown film extrusion, producing films that retain exceptional transparency (> 90%), robust barrier properties and a high tensile strength (∼ 22 MPa), while simultaneously exhibiting outstanding ductility (∼ 400% elongation at break) and impressive tear resistance (∼ 63 kN/m). These findings underscore the potential of this eco-friendly blend as a high-performance material for packaging articles.
To limit increasing amounts of water pollution and to further the Circular Bioeconomy paradigm, there is a need for the development of sustainable and cost-effective adsorbents. Currently, there is much research being conducted on the use of biopolymers-based GHs in treating wastewater, however, most of the literature is focused on their materials properties so that little insight is provided into how the structure of hydrogels relates to their adsorption characteristics, reuse potential and practicality in real-life situations. Therefore, this review provides a critical overview of green hydrogels based on renewable resources and the waste generated during their production, using a structure-property-performance format. This paper will discuss the influence of polymer chemistry, functional group distribution, crosslinking techniques and network architecture on the adsorption capacity, selectivity, mechanical stability and regeneration potential of GHs. The assessment of the removal of the major classes of pollutants has been systematically evaluated in terms of the dominant adsorption mechanisms that could occur. Additionally, the green synthesis approaches are critically analyzed for their sustainability, durability, and scalability. Furthermore, the key limitations have been identified to highlight the gaps between laboratory studies and practical application. By bringing together a comparative analysis of different approaches, the mechanistic basis for adsorption, and application-based challenges, this review provides design principles and directions for future work to rationally develop next-generation, green hydrogel adsorbents for sustainable wastewater remediation.
Polylactic acid is steadily gaining market share as a compostable, bio-based alternative to petroleum-based thermoplastics. However, its use in high-performance applications remains limited due to its brittleness, low heat-distortion temperature, and rapid hydrolytic and thermal oxidative breakdown. Over the past 25 years, researchers have developed various methods to address these challenges, including modifying molecular chain architecture, controlling supramolecular compatibility and crystallinity, and reinforcing macro- and nano-scale structures. This review examines these strategies across different length scales. It critically evaluates how multimodal approaches, such as chain extension, dynamic networking, compatibilization, plasticization, nanofiller integration, and fiber-reinforced blends, can deliver synergistic improvements in durability while supporting principles of the circular economy. By comparing results on mechanical, thermal, recyclability, and aging, the review also identifies research gaps, particularly in long-term aging under real-world conditions and in end-of-life sorting infrastructure. At the end of this review, a roadmap is proposed for translating laboratory breakthroughs into scalable industrial applications.
Electrospinning enables the fabrication of nanofibrous membranes with high surface area, tunable porosity, and good mechanical performance. Nevertheless, the vast majority of studies still rely on potentially carcinogenic solvents, such as chloroform (CHF) and dichloromethane (DCM), particularly for polymers like polylactic acid (PLA) and polycaprolactone (PCL). This use reflects a technological lock-in, where hazardous protocols persist despite well documented risks for human health and environment. In this study, acetone, ethanol, and water were investigated as green or green-acceptable alternatives to commonly used solvents for producing electrospun functional membranes. Thermodynamic compatibility was first assessed using Hansen Solubility Parameters (HSP), and their experimentally validated by evaluating solution stability and processability under standard electrospinning conditions. Rheological and morphological analyses confirmed that green solvent-based solutions with adequate proportions allowed producing fibers are comparable to the membrane prepared using hazardous solvent, with additional tunability in terms of fiber diameter and overall morphology. Mechanical testing and wettability measurements further showed properties that are fully comparable to the reference systems, while functional oil absorption tests demonstrated capacities up to 25 g/g with confirmed reusability over five cycles. Finally, the study provides evidence that the long-standing solvent lock-in in electrospinning can be realistically overcome. Crucially, this was achieved without altering the standard process parameters and while obtaining membranes with comparable performances, or in some cases superior, to those fabricated with hazardous solvents.
Molecular dynamics simulations are employed to investigate the nanoscale properties of asphalt binder, a polymer-based composite material. However, nanoscale nonlinear viscoelasticity and fatigue damage remain poorly understood, and molecular simulation parameters still lack a robust quantitative link to macroscopic mechanical performance. Progress in cross-scale prediction of asphalt mechanical properties is severely limited by the lack of molecular-scale methods to capture key parameters (e.g., dynamic modulus). This study develops a dynamic loading modelling algorithm to characterize the viscoelastic and fatigue damage behavior of the asphalt materials at the nanoscale. The results show that the dynamic modelling can obtain stable stress-strain data with characteristic viscoelastic hysteresis behavior. The simulated dynamic shear modulus master curves capture differences among molecular components and reproduce the relative magnitudes observed experimentally. Despite a nine orders of magnitude difference in temporal and spatial scales between the asphalt binder models and actual materials, high-frequency simulations deviate by less than 0.5 orders of magnitude from macroscopic data from the SHRP report. Under constant temperature and loading frequency, the asphalt molecular model exhibits the typical stage mechanical responses: linear viscoelastic, nonlinear viscoelastic, and fatigue damage. Input stress amplitudes of 0.4 GPa and 0.7 GPa serve as thresholds for these stages in the AAM-1 asphalt binder model. Energy dissipation remains nearly constant during viscoelastic stages but increases in the damage phase, accompanied by microstructural evolution such as void growth and increased fractional free volume, reflecting progressive structural degradation and reduced deformation resistance. These findings advance the understanding of molecular-scale dynamic mechanics in asphalt binder, provide quantitative insight into stage-specific viscoelastic and damage behavior, and offer a foundation for cross-scale constitutive modeling and prediction of macroscopic mechanical performance.
Polymer nanocomposites (PNCs) offer lightweight materials with enhanced mechanical, thermal, barrier, and functional properties, but their complex architectures pose significant challenges for sustainable end-of-life (EoL) management. This review provides a critical and comparative analysis of current recycling strategies for PNCs incorporating inorganic, carbon-based, in-situ generated polymeric, and hierarchically structured nanofillers. Mechanical, chemical, solvent-based, and emerging thermal approaches are systematically evaluated with respect to property retention, morphological stability, and nanofiller behaviour during repeated processing cycles.Beyond summarizing existing methods, this review identifies key structure–recyclability relationships that govern performance loss, filler migration, and phase instability, highlighting how nanofiller chemistry, dimensionality, and interfacial interactions dictate recyclability outcomes. Particular emphasis is placed on all-polymer nanocomposites (APNCs), which are critically assessed as a promising pathway toward closed-loop recycling due to their intrinsic chemical compatibility, while also addressing unresolved challenges related to fibrillar morphology preservation during reprocessing.By comparing recycling efficiencies across nanofiller classes and processing routes, this review delineates design principles for recyclable nanocomposites and identifies gaps that limit industrial implementation. The analysis demonstrates that optimized nanofiller loading, compatibilization strategies, and controlled processing histories can significantly mitigate degradation and enable functional reuse. Overall, the review provides actionable insights for designing next-generation PNCs aligned with circular economy principles rather than treating recyclability as an afterthought.
The participation of dynamic covalent bonds gives Vitrimer materials the ability to "reshape and regenerate". However, the relatively low bond energy of the dynamic covalent bond which vulnerability results in vitrimer materials showing low tolerance during use, thus seriously limits their wide application. In this study, we proposed a molecular network enhancement strategy based on cross-linking expansion and through-space conjugation. Dynamic imine bonds were introduced into the vanillin-based bio-basic benzoxazine resin to achieve the material remodeling and recycling under hot pressing process. Using the through-space conjugation of the benzene ring inside the polybenzoxazine network and the extended cross-linking density of the furan groups, the mesh size inside the material network structure could be reduced by 62.8%, and the mass loss after 24 h of soak in acidic conditions was only 4.85%, and its Young's modulus reached 3049 MPa, and the glass transition temperature was as high as 195.9°C. More importantly, we have proposed the synthesis mechanism of benzoxazine monomer and the differences in the synthesis mechanism of polybenzoxazine under different substituent amine sources. This work provides a reference for the preparation of polymer densification and the development of functional polybenzoxazine materials in the future.
Fire-warning systems (FWSs) attract increasing attention due to their potential for highly-efficient fire management, which have made some significant progress recently. Graphene oxide (GO) is one of the prime candidates on account of the insulate-to-conductive transformation under high temperature attack, it is precisely the electrical transformation can be captured for serving as a warning response. In this review, composition-engineered GO-based FWSs are reasonably sorted out and comprehensive analyzed, which constitutes a significant segment of FWSs research. Specifically, the evaluation covers the diversity of fabrication methods, variety of composition-engineered GO-based FWSs, the core fire-warning performance, as well as the relevant working mechanisms, etc. Furthermore, given the state-of-the-art in composition-engineered GO-based FWSs, the present challenge and the emerging perspectives are proposed, providing a guidance for tackling the main issues and promising developing direction of the next-generation of composition-engineered GO-based FWSs.
