Search Results (470)

Polyurethanes (PUs) are indispensable polymeric materials widely employed across diverse industrial sectors due to their excellent thermal stability, chemical resistance, adhesion, and mechanical durability. However, the intrinsic three-dimensional crosslinked network that underpins their performance also presents a fundamental barrier to reprocessing and recycling. Consequently, most end-of-life PU waste is currently managed through landfilling or incineration, resulting in significant resource loss and environmental impact. To address these challenges, this review presents an integrated perspective on sustainable PU systems by unifying green synthesis strategies with closed-loop recovery approaches. First, recent advances in bio-based polyols and phosgene-free isocyanate synthesis derived from renewable resources—such as plant oils, carbohydrates, and lignin—are discussed as viable means to reduce dependence on petrochemical feedstocks and mitigate toxicity concerns. Next, emerging chemical recycling methodologies, including acidolysis and aminolysis, are reviewed with a focus on the selective recovery of high-purity monomers. Finally, PU vitrimers and dynamic covalent polymer networks (DCPNs) based on urethane bond exchange reactions are examined as reprocessable architectures that combine thermoplastic-like processability with the mechanical robustness of thermosets. By integrating synthesis, recovery, and reuse within a unified framework, this review aims to outline a coherent pathway toward establishing a sustainable circular economy for PU materials. Full article

Façades account for approximately 15–20% of a building’s embodied carbon, making them a key target for material decarbonization. While bio-composites are increasingly explored for façade insulation, cladding systems remain dominated by carbon-intensive materials such as aluminum and fiber-reinforced polymers (FRPs). This paper presents findings from a study investigating the use of food-waste-derived bulk fillers in bio-composite materials for façade cladding applications. Several food-waste streams, including hazelnut and pistachio shells, date seeds, avocado and mango pits, tea leaves, and brewing waste, were processed into fine powders (<0.125 μm) and combined with a furan-based biobased thermoset resin to produce flat composite sheets. The samples were evaluated through mechanical testing (flexural strength, stiffness, and impact resistance), water absorption, freeze–thaw durability, and optical microscopy to assess microstructural characteristics before and after testing. The results reveal substantial performance differences between waste streams. In particular, hazelnut and pistachio shell fillers produced bio-composites suitable for façade cladding, achieving flexural strengths of 62.6 MPa and 53.6 MPa and impact strengths of 3.42 kJ/m² and 1.39 kJ/m², respectively. These findings demonstrate the potential of food-waste-based bio-composites as low-carbon façade cladding materials and highlight future opportunities for optimization of processing, supply chains, and material design. Full article

Metal–organic frameworks (MOFs), assembled from inorganic metal centers (metal ions or clusters) and organic ligands, possess distinctive features such as structural designability, high surface area, and tunable functionalities. In the past decade, MOFs have displayed substantial merits when utilized as innovative flame retardants in the realm of polymeric materials. A current focus is on the flame-retardant effects of MOFs in thermosetting plastics, yielding substantial achievements; however, systematic investigations into thermoplastic polymers, which are more widely used, remain limited. The flame-retardant mode of action for miscellaneous types of MOFs and their applications in polymeric matrices, with particular emphasis on recent advances in thermoplastic systems, are summarized. Furthermore, existing challenges and future perspectives are identified. Full article

Thermal management is rising in importance due to the evolving requirements of electronic devices, namely, compactness and performance. Polymers, particularly thermosets, exhibit low thermal conductivity, so that fillers are required to enhance the performance of thermosets and make them suitable for such applications. So far, various factors have been investigated in order to improve the thermal conductivity of thermosets, mainly based on single-filler systems. Given the variation in the geometry of different filler types, suggestions about the influence of geometry have also been made. However, the impact of the geometry of the filler type is rather unknown. Therefore, this paper investigates the use of copper (Cu) as a filler with high thermal conductivity and examines four different geometry types (three sphere types with different sizes, as well as platelets) in terms of their reaching a higher thermal conductivity in an epoxy matrix. Cu platelets showed the highest thermal conductivity values, even though they also exhibited high anisotropy. To understand their material behavior in more detail, a new method of inline viscosity measurement is further evaluated. This method allows consideration of local flow conditions and is therefore more precise than methods based on complex viscosity. Full article

A naturally sourced phenolic compound, umbelliferone, has been used to synthesize four monofunctional benzoxazines, two of which have been previously synthesized from aniline and furfurylamine. This study contributes two more—using benzylamine and phenethylamine—to provide insight into how the amine’s aromatic group and aliphatic chain length influence resulting properties. The proposed chemical structures of the novel monomers are confirmed by ¹H nuclear magnetic resonance (¹H-NMR) and ¹H-¹H nuclear Overhauser effect spectroscopy (NOESY). The polymerization behavior of each resin is determined by differential scanning calorimetry (DSC). The thermal degradation pattern and the flammability of each polymer are assessed by thermogravimetric analysis (TGA) and microscale combustion calorimetry (MCC), respectively. Char yields between 49% and 63% suggest the thermoset materials to be thermally stable and competitive for thermally demanding applications. All four polybenzoxazines demonstrate non-ignitable behavior, with heat release capacities below 100 J/g·K. Structure–property analyses on the two newly synthesized compounds have been provided to deepen our existing understanding of umbelliferone-benzoxazine systems, particularly regarding the effect of the aminic moiety on thermal properties. Full article

This work investigates the penetration behavior of SiC particles into Digital Light Processing (DLP)-printed thermoset substrates under low-pressure cold-spray conditions, aiming to enhance surface hardness and wear resistance. A coupled simulation framework was established in which particle acceleration was obtained from CFD using ANSYS Fluent, and high-speed impact and embedding were modeled through ANSYS Explicit Dynamics. Two particle diameters (25 μm and 60 μm) were examined across inlet pressures from 2 to 5 bar to evaluate both the continuous influence of pressure and the two-level effect of particle size. Mesh convergence was achieved at a resolution of d_p/20, ensuring numerical stability and computational efficiency. The results showed a strong dependence of penetration depth on pressure and particle size: for 25 μm particles, penetration increased from 0.76 d_p at 2 bar to 1.53 d_p at 5 bar, while 60 μm particles exhibited deeper absolute embedding due to their significantly higher kinetic energy. Response-surface analysis further revealed nonlinear pressure effects and a predominantly linear size-dependent shift. Experimental validation at 3 bar confirmed a penetration depth of approximately 1 d_p, demonstrating good agreement between simulation and physical observation. Overall, the validated workflow provides quantitative insight into particle–substrate interaction in thermoset polymers and offers a practical basis for controlled particle embedding as a surface-strengthening strategy in additive manufacturing. Full article

This study compares the chemical modification and polymerization behavior of canola, carinata, and crambe oils to evaluate their suitability as renewable building blocks for polymer synthesis. The vegetable oils were characterized in terms of fatty-acid composition and oxidative stability, and the data showed distinct profiles: canola with 0% erucic acid, carinata around 42.08%, and crambe reaching 56.25%, differences that end up influencing how each one responds during the modification steps. Epoxidation and acrylation were confirmed by ¹H NMR, ¹³C NMR, and FTIR-ATR, mainly through the disappearance of the olefinic peaks and the appearance of oxirane- and acrylate-related signals (some of them quite clear, others less pronounced). After acrylation, the oils were subjected to solution polymerization, forming bulk crosslinked materials, whose properties reflected their original fatty-acid profiles: the canola-based polymer reached the highest glass transition temperature (T_g), 47.73 °C, followed by the carinata-based polymer (T_g = 41.86 °C), while the crambe-derived polymer, with lower functionality due to its high erucic acid content, showed a much lower T_g of 20.26 °C. Altogether, these differences highlight how variations in fatty-acid composition subtly shape the efficiency of functionalization and the architecture of the resulting networks. The polymers obtained here point to potential uses in renewable coatings, thermoset resins, and other applications that depend on bio-based crosslinked materials. Full article

There are limited material choices for vat photopolymerization additive manufacturing processes that offer high dimensional accuracy. Acrylates and epoxies are commonly used, but their thermal properties are not suitable for applications requiring high-temperature performance. A possible solution is the use of high-performance thermosets, such as maleimide and cyanate ester, which are cured at high temperatures. Still, their use in vat photopolymerization methods has been limited due to the high temperature required. In this work, a photocurable formulation composed of multimaleimide monomers, a reactive diluent, and a cyanate ester was developed to improve thermal and mechanical properties and reduce cure shrinkage due to density changes during processing. In situ sequential interpenetrating polymer networks (IPNs) were investigated, in which the copolymerization of multimaleimide and a diluent occurs during printing, yielding a cyanate ester-swollen network with a sub-room-temperature glass transition temperature (T_g). The polymerization of the cyanate ester occurs during a high-temperature post-printing step. The resulting materials have a T_g above 250 °C (peak in the loss modulus), good fracture toughness (GIc of 100 J/m²), and overall cure shrinkage of less than 6%, with 1–2% occurring during the high-temperature post-curing step. Full article

This work presents a comprehensive literature review of the coefficient of linear thermal expansion (CLTE) of polymers and polymer composite materials (PCMs). It systematizes CLTE measurement methods for isotropic and anisotropic materials, including contact techniques such as dilatometry and thermomechanical analysis and non-contact methods such as digital image correlation, laser interferometry, diffraction-based techniques, and strain-gauge methods, with attention to their accuracy and fields of applicability. Furthermore, the review describes the principal mathemaical modeling approaches used to predict the CLTE of polymers and PCMs. The review also provides a comparative analysis of CLTE values for a broad range of thermoplastics (commodity, engineering, and high-performance grades) and thermosets, identifying the key factors that govern CLTE, such as the transition from the glassy to the viscous-flow state, the presence and anisotropy of a crystalline phase, and related structure–property effects. Special consideration is given to the factors determining the CLTE of polymer composites, including the properties of the polymer matrix, the nature, size, orientation and surface treatment of the filler, the architecture and reinforcement scheme of the composite, and the manufacturing process. The review also outlines application areas in which PCMs with controlled or reduced CLTE are required and illustrates these with specific examples. Thus, the article provides integrated view of the CLTE of polymers and PCMs, compiles reference data for CLTE values of various polymers and common composite fillers and offers practical recommendations for selecting polymer materials for fabricating goods that require high thermal dimensional stability. Full article

Dynamic covalent bonds within polymer materials have been the subject of ongoing research. These bonds impart polymers, particularly thermosets, with capabilities for self-healing and reprocessing. Concurrently, three-dimensional (3D) printing techniques have undergone rapid advancement and widespread adoption. Since polymers are among the primary materials used in 3D printing, networks featuring dynamic covalent bonds have emerged as a prominent research area. This review outlines approaches for incorporating dynamic covalent bonds into polymers suitable for 3D printing and examines representative studies that leverage these chemistries in material design. Polymers produced using these strategies demonstrate both self-healing and reprocessability, primarily via bond-exchange (metathesis) reactions. In addition, we discuss how the type and amount of dynamic bonds in the network affect the resulting material properties, with particular emphasis on their mechanical, physical, and thermal performance. In particular, the introduction of dynamic covalent bonds seems to significantly improve the degree of anisotropy, which has been the limitation of 3D printing techniques. Finally, we compile recent applications for objects printed from polymers that include dynamic covalent bonds. Full article

Carbon Fiber-Reinforced Polymer (CFRP) composites, widely used across industries, exhibit various damage mechanisms depending on the loading conditions applied. This study employs a structural health monitoring (SHM) approach to investigate the three primary failure modes, fiber breakage, matrix cracking, and delamination, in thermoset quasi-isotropic CFRPs subjected to quasi-static tensile loading until failure. Acoustic emission (AE) signals acquired from an experiment were leveraged to analyze and classify these real-time signals into the failure modes using machine learning (ML) techniques. Due to the extensive number of AE signals recorded during testing, manually classifying these failure mechanisms through waveform inspection was impractical. ML, alongside ensemble learning, algorithms were implemented to streamline the classification, making it more efficient, accurate, and reliable. Conventional AE parameters from the data acquisition system and feature extraction techniques applied to the recorded waveforms were implemented exclusively as classification features to investigate their reliability and accuracy in classifying failure modes in CFRPs. The classification models exhibited up to 99% accuracy, as depicted by evaluation metrics. Further studies, using cross-correlation techniques, ascertained the presence of fiber break events occurring in the bundles as the thermoset CFRP composite approached failure. These findings highlight the significance of integrating machine learning into SHM for the early detection of real-time damage and effective monitoring of residual life in composite materials. Full article

In this study, the blends of bio-based polybenzoxazine (V-fa type) and poly(ethylene glycol) (PEG) with PEG contents from 50 to 95 wt% and different molecular weights were developed to improve the flexibility of thermosetting polymers. Of these blends, PEG 8k at 80 wt%, which exhibited the best processability, was selected for further development via compositing with carbon black (CB) from 0 to 20 phr. Differential Scanning Calorimetry (DSC) analysis revealed that the melting temperature (T_m) increased from 70 to 83 °C and glass transition temperatures (T_g) increased from –53 to –48 °C at 20 phr. Thermogravimetric Analysis (TGA) demonstrated high thermal stability, with T_dmax (for all CB contents) presented at ca. 416 °C. Moreover, char yield was increased from 10% (without CB) to 28% (20 phr), reflecting improved decomposition resistance. Mechanical properties demonstrated that CB significantly reinforced the composites. The flexural modulus and flexural strength were increased from 117.18 MPa (without CB) to 456 MPa (10 phr) and from 2.42 MPa (without CB) to 3.94 MPa (2.5 phr), respectively. The SEM images confirmed uniform morphology and good filler dispersion. Conclusively, the composites of 8k PEG 80 wt% filled with 2.5 phr of CB provided an optimal balance of mechanical and thermal stability and engineering polymer applications. Full article

Thermoset composites provide excellent strength but pose major recycling challenges due to their crosslinked structure. In this study, epoxy–polyurethane–glass fiber (EPG) wastes were mechanically recycled into low-density polyethylene (LDPE), high-density polyethylene (HDPE), and polyamide-6 (PA6) matrices to produce second-generation thermoplastic composites (STCs). Fillers at 10–50 wt% were processed by single-screw extrusion and compression molding, and the resulting composites were comprehensively characterized. For LDPE, the tensile modulus increased by ~286–589% and tensile strength increased by 40–47% at 20–30 wt% loading, though ductility decreased at higher levels. HDPE composites showed a ~347% rise in modulus and ~24% increase in strength, but performance declined with more than 40 wt% filler. PA6 offered the most balanced outcome, retaining ~70% of its neat tensile strength while achieving an ~300% modulus improvement at 40 wt% loading. Thermal stability was strongly enhanced, with char residue at 700 °C rising from 0.4% to 38.7% in PA6 and from ~2.5% to 33–46% in polyolefins. In contrast, crystallinity decreased (e.g., LDPE 62.2% → 23.7%), and impact strength dropped at a loading above 30 wt%. Overall, the results demonstrate that EPG wastes can be reprocessed into functional composites without compatibilizers, with PA6 providing the most robust property retention at high filler contents. Full article

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 future 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. Full article

Cross-linked polymers are indispensable in advanced applications, but suffer from poor recyclability due to permanent covalent networks. Herein, we report recyclable supramolecular polyurea elastomers that integrate ureidopyrimidinone-based quadruple hydrogen-bonding motifs directly into the polymer backbone. The dynamic and reversible nature of these motifs imparts the SPUEs with remarkable malleability and reprocessability while preserving the robustness of conventional polyureas. The SPUEs display remarkable mechanical robustness, solvent resistance, and facile reprocessability through hot-pressing, producing homogeneous films with minimal performance loss. Impressively, tensile strength, elongation at break, and toughness retained high recovery after reprocessing, demonstrating excellent closed-loop mechanical recyclability. This work showcases supramolecular engineering as a powerful strategy to reconcile mechanical robustness with recyclability in cross-linked polymers, offering new opportunities for sustainable thermosets and elastomers in circular materials design. Full article