Search Results (84)

A thermoreversible dynamic covalent network was constructed in recycled polyethylene terephthalate (RPET) via Diels–Alder (DA) chemistry to enhance mechanical performance, reprocessability, and self-healing. Furan-functionalized RPET (RPET-3F) was first prepared from maleated RPET (RPET-MA), followed by crosslinking with bismaleimide (BMI) at different feed ratios. FTIR spectra confirmed the successful grafting of furan groups and the formation of DA adducts. With increasing BMI content, the gel fraction and crosslink density increased substantially, whereas the swelling ratio decreased, indicating the progressive development of a three-dimensional network. RPET-3F-2B showed the highest network integrity among all samples. DSC analysis revealed a distinct retro-DA dissociation peak at 143 °C and a recrosslinking peak near 124 °C, confirming the thermal reversibility of the DA network. Owing to the optimized network structure, RPET-3F-2B exhibited the best mechanical properties and excellent reprocessability, retaining stable performance after three hot-pressing cycles. After repeated reprocessing, its tensile strength remained 74% higher than that of RPET-MA, while the elongation at break was still improved by about 10%. Moreover, the sample showed efficient thermally induced self-healing at 150 °C, with surface cracks nearly disappearing after 4 h. These results demonstrate that DA chemistry offers a promising route to the high-value reutilization of RPET into recyclable, multifunctional polymer materials. Full article

The brittleness of bismaleimide (BMI) resin is a major issue that restricts its use as a matrix for advanced composites. Blending with thermoplastics constitutes an effective toughening approach that preserves the thermal resistance and mechanical properties of the resin. Reaction-induced phase separation is the primary toughening mechanism in thermoplastic-toughened BMI resin. However, the complex phase-separated structure causes the relationship between the glass transition temperature (T_g) and the curing degree to deviate from that described by the classical DiBenedetto equation. In this paper, two improved models, incorporating power-law correction and threshold inhibition, were constructed to address the phase-separation effect. An aerospace-grade BMI resin was toughened by a thermoplastic polyimide. The relationship between T_g and the curing degree was fitted by the DiBenedetto equation and the improved models. It was found that the adjusted coefficient of determination for the power-law correction and threshold inhibition models for the toughened resin increased to 0.978 and 0.995, respectively, whereas that of the DiBenedetto equation was only 0.612. This work provides a new, readily applicable empirical model for the prediction of T_g in thermoplastics-toughened thermosetting resins and offers theoretical support for optimizing the curing process and controlling the performance of multiphase resins. Full article

To clarify the effect of surface characteristics on the interfacial properties of T1100-grade carbon fiber (CF)/bismaleimide (BMI) composites, three CFs (F1, F2, and F3) with different surface treatments and sizing agents were studied. Surface physicochemical properties and sizing–resin reaction behavior were characterized; nano-infrared spectroscopy was innovatively used to quantify interfacial structure. The correlation among surface features, interfacial structure, and mechanical properties was established. All dry-jet wet-spun T1100 CFs show smooth surfaces with similar roughness, and mechanical interlocking contributes little to interfacial adhesion. F3 possesses the highest active carbon, oxygen content, and epoxy value. Its sizing agent exhibits strong reactivity with BMI, forming a ~200 nm thick interface and the highest interfacial shear strength (IFSS) of 95.9 MPa. Constructing a “thick and strong” interface promotes shear failure from brittle to tough, significantly enhancing 90° tensile and interlaminar shear strength (ILSS). This work provides guidance for interface design and engineering applications of T1100/BMI composites in aerospace primary load-bearing structures. Full article

The formation of recyclable polyethylene materials is significantly limited by traditional crosslinking methods, which involve solvent-heavy processes and permanent chemical bonds that cannot be undone. Herein, we report an environmentally friendly and scalable approach to construct a thermo-reversible polyethylene network (PE-g-DA) via solvent-free, one-step melt processing based on furan–maleimide Diels–Alder (D–A) dynamic covalent chemistry. Furan-functionalized polyethylene was dynamically crosslinked with bismaleimide during melt mixing, fully compatible with conventional polyolefin processing techniques. FTIR spectroscopy, temperature-dependent solubility, and differential scanning calorimetry collectively confirm the reversible formation and dissociation of D–A adducts, enabling thermal switching of the network structure. Equilibrium swelling experiments based on the Flory–Rehner model indicate that the crosslink density can be precisely controlled by varying the bismaleimide content. As a result, PE-g-DA exhibits significantly enhanced tensile strength while maintaining high ductility at moderate crosslink densities. Notably, the dynamic network allows efficient thermal reprocessing, with recycled samples retaining approximately 93% and 80% of their original tensile strength after the first and second reprocessing cycles, respectively. Moreover, intrinsic thermal self-healing behavior is directly visualized by scanning electron microscopy at 120 °C. This work demonstrates that combining dynamic Diels–Alder chemistry with solvent-free melt processing offers a practical and sustainable route to recyclable, reprocessable, and self-healable polyethylene materials with clear potential for large-scale industrial production. Full article

Hypersonic vehicles impose stringent requirements on lightweight structures to maintain mechanical integrity under extreme thermal environments. Bismaleimide (BMI)-based carbon fiber-reinforced polymer (CFRP) composites, featuring a high glass transition temperature and excellent thermal stability, are regarded as promising candidates for such applications. However, the high curing temperature and narrow processing window of BMI resins make it challenging to manufacture stiffened-shell structures with low defect levels and high fiber volume fractions. In this study, an integrated manufacturing route—hot-melt prepregging–filament winding–matched-metal mold forming—is proposed, and the key processing parameters are optimized via single-factor experiments and the Box–Behnken response surface methodology. The tensile strength of the laminate is selected as the response variable to evaluate the effects of the compression displacement (A), thermal consolidation/bonding temperature (B), heating rate (C), and cooling rate (D). The results reveal a unimodal dependence of the tensile strength on each parameter, with the significance ranking B > D > A > C; moreover, the A–B and A–D interactions are significant (p < 0.01). The established quadratic regression model exhibits good agreement with experimental data (R² = 0.974; R²_adj = 0.949). The predicted optimum conditions are A = 0.07 mm, B = 114.93 °C, C = 1.35 °C·min⁻¹, and D = 4.58 °C·min⁻¹, corresponding to a predicted tensile strength of approximately 2287 MPa. Validation experiments yielded 2291 MPa, in excellent agreement with the prediction. Microstructural observations indicate tight interlaminar bonding and a pronounced reduction in voids under the optimized conditions. Applying the optimized process to fabricate stiffened-shell demonstrators achieves a fiber volume fraction of >60% and a void content of <1%. This work provides a quantitatively defined processing window and parameter optimization basis for the high-quality manufacturing of BMI-CFRP stiffened-shell structures, with significant engineering relevance. Full article

Bio-based bismaleimide (BMI) resins can reduce environmental impact and impart intrinsic flame retardancy, but achieving a high glass transition temperature (Tg) remains challenging. Here, we replace the conventional petrochemical co-monomer O,O′-diallyl bisphenol A (DABPA) with a synthesized tri-allyl derivative of curcumin (AEC) in 4,4′-bismaleimidodiphenylmethane (BDM)-based resins. The AEC monomer, synthesized via exhaustive O- and C-alkylation of curcumin, acts as a trifunctional crosslinker. By systematically varying the imide:allyl molar ratio, we optimized the network properties. We optimize the network’s thermal and fire-safety properties. The optimized formulation (BDM: AEC = 1:0.87, denoted BA-0.87) yields 43.06% char at 800 °C and reduces the peak heat release rate (PHRR) by 13.2% compared to the conventional BDM/DABPA control (BD-0.87). Meanwhile, BA-0.87 passes UL-94 V-0 with no dripping and attains a Tg above 400 °C—nearly 100 °C higher than BD-0.87. These enhancements arise from curcumin’s rigid conjugated structure, which increases crosslink density and promotes char formation during decomposition. Our work demonstrates a viable, bio-derived pathway to engineer BMI resins that simultaneously improve thermal stability and intrinsic flame retardancy. Such resins are promising for demanding aerospace and high-temperature electronic applications that require both fire safety and stability. Full article

This study explores a disulfide-selective cross-linking strategy for natural rubber (NR) to formulate elastomeric materials with engineering-relevant mechanical properties. A disulfide-containing bismaleimide (BIS) cross-linker was synthesized from cystamine and maleic anhydride and compounded with NR. Three formulations were prepared: control (no inhibitor), CuCl₂-based, and copper(II) methacrylate (CuMA) based compounds, with BIS concentrations ranging from 3.55 to 8.88 phr. Rheological and mechanical testing revealed that CuCl₂ formulations suffered from molecular degradation, poor thermal stability, and mechanical brittleness due to oxidative reactions in the absence of antioxidants. In contrast, CuMA-based compounds exhibited intermediate molecular weights prior to curing, stable thermal behavior, and improved mechanical properties, including enhanced torque and tensile strength, indicating effective cross-linking and partial recyclability. The control formulations also performed reasonably well but did not match the mechanical strength of conventional sulfur-vulcanized NR. The results demonstrate that metal coordination, particularly with CuMA, can modulate disulfide metathesis kinetics and offer a pathway to thermally triggered network rearrangement. Overall, CuMA emerges as a promising candidate for developing high-performance, recyclable rubber materials, while CuCl₂ requires further stabilization strategies. This work establishes a baseline for future recyclability studies and advances the design of dynamic covalent networks in elastomers. Full article

Bismaleimide–triazine (BT) resins are widely utilized in various applications, with ongoing efforts to enhance their performance. In this work, a partially epoxidized polyhedral oligomeric silsesquioxane (PEOVS) containing vinyl and epoxy groups was successfully synthesized, and BT/PEOVS nanocomposites were prepared by blending PEOVS with BT resin. The results revealed that the unique structure of PEOVS significantly improved its dispersion within the resin matrix and enhanced the overall properties of the BT resin. The curing mechanism and properties of BT/PEOVS nanocomposites, with weight ratios of 99.5/0.5, 99/1, 98.5/1.5, 98/2, and 96/4, were analyzed using Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), dynamic mechanical analysis (DMA), thermogravimetric analysis (TGA), and dielectric measurements. The addition of PEOVS markedly improved the dielectric performance, with a 2% PEOVS content achieving a dielectric constant of 2.39 and a dielectric loss of 0.0036 at 1 MHz. Furthermore, the glass transition temperature and storage modulus were significantly enhanced, with a PEOVS content of 1.5% resulting in a glass transition temperature of 279 °C. The results demonstrate that incorporating PEOVS, featuring dual reactive functional groups, effectively enhances the comprehensive properties of BT resins, providing valuable insights into their modification and practical applications. Full article

Solvent processing hampers the reliability and energy density of self-healing binders for energetic materials. We report a solvent-free curing route for a Diels–Alder self-healing furanyl-terminated polybutadiene enabled by a functional external plasticizer, dibutyl phthalate (DBP), which acts not only to lower the viscosity of the binder but to disperse the high-melting bismaleimide, thereby driving crosslinked network formation. The 50 wt% DBP-plasticized film healed a pre-cut crack in 5 min at 120 °C and recovered nearly full mechanical properties after 24 h at 60 °C. Based on this binder system, a self-healing solid propellant with 80 wt% solid content was solvent-free cast into a dense and void-free grain that healed surface cracks within 5 min at 120 °C. This solvent-free approach overcomes the limitations of solvent-based processing and offers a viable fabrication route for self-healing energetic materials. Full article

Self-healing coatings can replace conventional coatings and are capable of self-healing and continuing to protect the substrate after coating damage. In this study, two types of self-healing resins were synthesized as coatings: Type-A via Diels–Alder crosslinking of furfuryl-modified diglycidyl ether bisphenol A with bismaleimide, and Type-B through epoxy blending/curing to form a semi-interpenetrating network. FTIR and Raman spectroscopy confirmed the formation of Diels–Alder (DA) bonds, while GPC tests indicated incomplete monomer conversion. Both resins were applied to glass and wood substrates, with performance evaluated through TGA, colorimetry (ΔE), gloss analysis, and scratch-healing tests (120 °C/30 min). The results showed that Type-A resins had a higher healing efficiency (about 80% on glass substrates and 60% on wood substrates), while Type-B resins had a lower healing rate (about 65% on glass substrates and 55% on wood substrates). However, Type-B is more heat-resistant, has a slower decomposition rate between 300 and 400 °C, higher gloss retention, and less color difference (ΔE) between wood and glass substrates. The visible light transmission of Type-B (74.14%) is also significantly higher. Full article

Chronic wounds disrupt natural healing and tissue regeneration, posing a major challenge in healthcare. Conventional wound care often lacks effective drug delivery, tissue integration, infection control, and patient comfort. However, injectable hydrogels offer localized, minimally invasive treatment and conform to irregular wound shapes. This study presents carboxymethyl cellulose (CMC)-based injectable hydrogels, prepared via Diels–Alder click chemistry using highly furan functionalized CMC (45%) and a bismaleimide crosslinker. The hydrogels showed a rapid gelation time (<490 s) under physiological conditions. The hydrogel exhibited favorable physicochemical and mechanical properties, as well as sustained curcumin release (∼80% in 5 days). In vitro studies confirmed excellent biocompatibility with NIH3T3 fibroblasts and notable antibacterial activity against E. coli, supporting its potential for wound healing applications. Full article

With the rapid development of information technology and semiconductor technology, the iteration speed of electronic devices has accelerated in an unprecedented manner, and the market demand for miniaturized, highly integrated, and highly intelligent devices continues to rise. But when these electronic devices operate at high power, the electronic components generate a large amount of integrated heat. Due to the limitations of existing heat dissipation channels, the current heat dissipation performance of electronic packaging materials is struggling to meet practical needs, resulting in heat accumulation and high temperatures inside the equipment, seriously affecting operational stability. For electronic devices that require high energy density and fast signal transmission, improving the heat dissipation capability of electronic packaging materials can significantly enhance their application prospects. In order to improve the thermal conductivity of composite materials, hexagonal boron nitride (h-BN) was selected as the thermal filling material in this paper. The BMI resin was structurally modified through molecular structure design. The results showed that the micro-branched structure and h-BN synergistically improved the thermal conductivity and insulation performance of the composite material, with a thermal conductivity coefficient of 1.51 W/(m·K) and a significant improvement in insulation performance. The core mechanism is the optimization of the dispersion state of h-BN filler in the matrix resin through the free volume in the micro-branched structure, which improves the thermal conductivity of the composite material while maintaining high insulation. Full article

The repair efficiency of various self-healing materials often depends on the ability of the prepolymer and curing agent to form mixtures. This paper presents a synthesis and study of the properties of modified self-healing polyurethanes using the Diels–Alder reaction (DA reaction), obtained from a maleimide-terminated preform and a series of furan–urethane curing agents. The most commonly used isocyanates (4,4′-methylene diphenyl diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), and hexamethylene diisocyanate (HDI)) and furan derivatives (furfurylamine, difurfurylamine, and furfuryl alcohol) were used as initial reagents for the synthesis of curing agents. For comparative analysis, polyurethanes were also obtained using the well-known “traditional” approach—from furan-terminated prepolymers based on mono- and difurfurylamine, as well as furfuryl alcohol and the often-used bismaleimide curing agent 1,10-(methylenedi-1,4-phenylene)bismaleimide (BMI). The structure and composition of all polymers were studied using spectroscopic methods. Molecular mass was determined using gel permeation chromatography (GPC). Thermal properties were studied using TGA, DSC, and TMA methods. The mechanical and self-healing properties of the materials were investigated via a uniaxial tensile test. Visual assessment of the completeness of damage restoration after the self-healing cycle was carried out using a scanning electron microscope. It was shown that the proposed modified approach helps obtain more durable polyurethanes with a high degree of self-healing of mechanical properties after damage. Full article

Thermal conductive composite materials have excellent electrical insulation properties, low cost, and are lightweight, making them a promising alternative to traditional electronic packaging materials and enhancing the heat dissipation of integrated circuits. Due to the differences in specific surface area and volume, thermal conductive fillers have poor interface connections between the polymer and/or thermal conductive filler, thereby increasing phonon scattering and affecting thermal conductivity. This article uses bismaleimide resin as the matrix and h-BN as the thermal conductive filler. The evolution laws of thermal conductivity and dielectric properties of thermal conductive composite materials were systematically characterized through multi-scale filler control and gradient filling design. Among them, h-BN with a diameter of 10 μm has the most significant improvement in thermal conductivity. When the filling amount is 40 wt%, the thermal conductivity reaches 1.31 W/(m·K). Full article

The glass transition temperature (T_g) was a pivotal parameter governing the thermal and mechanical properties of bismaleimide-based polyimide (BMI) resins. However, limited experimental data for BMI systems posed significant challenges for predictive modeling. To address this gap, this study introduced a hybrid modeling framework leveraging transfer learning. Specifically, a multilayer perceptron (MLP) deep neural network was pre-trained on a large-scale polymer database and subsequently fine-tuned on a small-sample BMI dataset. Complementing this approach, six interpretable machine learning algorithms—random forest, ridge regression, k-nearest neighbors, Bayesian regression, support vector regression, and extreme gradient boosting—were employed to construct transparent predictive models. SHapley Additive exPlanations (SHAP) analysis was further utilized to quantify the relative contributions of molecular descriptors to T_g. Results demonstrated that the transfer learning strategy achieved superior predictive accuracy in data-scarce scenarios compared to direct training on the BMI dataset. SHAP analysis identified charge distribution inhomogeneity, molecular topology, and molecular surface area properties as the major influences on T_g. This integrated framework not only improved the prediction performance but also provided feasible insights into molecular structure design, laying a solid foundation for the rational engineering of high-performance BMI resins. Full article