Thermoset Matrix Research Articles

Allylation and Thermosetting of Acetosolv Wheat Straw Lignin.

The acetosolv extraction, allylation and subsequent cross-linking of wheat straw lignin to thermoset biomaterials is herein described. The extraction temperature proved to be of great importance for the quality of the resulting lignin, with moderate temperature being key for preservation of β-O-4' linkages. The allylation of the acetosolv lignin was carried out using three different synthetic strategies, resulting in selective installation of either benzylic or phenolic allyl ethers, or unselective allylation of various hydroxyl groups via etherification and carboxyallylation. The different allylation protocols employed either allyl alcohol, allyl chloride, or diallylcarbonate as allyl precursors where the latter gave the highest degree of functionality. The results also show that it is crucial to choose a functionalization protocol that is adapted to the functional groups present in the specific lignin used. Selected allylated acetosolv lignins were cross-linked using a thiol-ene approach and the lignin with the highest density of allyl groups was found to form a cross-linked thermoset material with properties comparable to kraft lignin-based analogues.

Toughened Vinyl Ester Resin Reinforced with Natural Flax Fabrics

Vinyl ester resins are widely used as thermoset matrix materials for laminated composites, particularly in naval and automotive applications, due to their strength, chemical resistance, and ease of processing. However, their brittleness limits their use, especially in cold conditions. This study investigates the toughness of core–shell rubber (CSR)-modified resins in composites with natural fibers. This research compares the properties of the neat resin matrix and the CSR-modified matrix. After optimizing the resin curing process with catalysts, various treatments were tested to analyze their mechanical and thermal properties. Using the vacuum bagging process, flax and glass fibers were used as reinforcements to assess the effects of matrix modifications. Flax fibers were chosen for their sustainability as a potential alternative to glass fibers. Mechanical testing was performed, comparing the performance of flax-based composites to those with glass fibers. Water absorption tests on flax composites followed the ISO 62 standard. Additionally, interlaminar shear strength and SEM micrography studies were conducted to examine the morphology and fiber–matrix adhesion, linking the microscopic structure to mechanical properties. Results indicate that while glass-reinforced composites have superior properties, flax composites offer a sustainable alternative, making them a promising choice for future applications.

Comparison of low-velocity impact damage in laminated composites for two thermoplastic material systems

Aircraft manufacturers are investigating thermoplastic material systems to produce parts more quickly and efficiently. Detailed damage data is needed to evaluate existing damage analysis methods, developed for thermoset materials, to predict damage in thermoplastic materials. Damage maps were created for two thermoplastic material systems subjected to low-velocity impact over a range of impact energies. In this paper, the damage maps were used to investigate and compare the damage response of the different material systems. Impact specimens were manufactured from TC1225 LMPAEK T700G from Toray Industries and APC AS4D/PEKK-FC from Solvay. The effect of the degree of crystallinity on the damage response was also investigated using a third set of specimens manufactured using the Toray material and a quenching process. Using a combination of data obtained from X-ray computed tomography and ultrasonic testing, damage maps were created for every interface and ply for selected specimens showing matrix cracks, delamination outlines, and fractured fibers. The LMPAEK specimens were found to have fewer and smaller delaminations than the PEKK specimens for impacts at the same energy. However, the LMPAEK specimens contained a larger number of fiber breaks. A similar trend was observed when comparing low-crystallinity LMPAEK specimens with the baseline LMPAEK specimens. The LMPAEK specimens often contained lines of fiber fractures in near-surface plies emanating from the contact region that were not present in the PEKK specimens. The different damage responses may indicate that the material selection will be a function of the application and loading.

An evaluation of progressive damage analysis methods for modeling low velocity impact of thermoplastic composites

State-of-the-art progressive damage and failure analysis (PDFA) tools for composites were developed for thermoset materials because of the prevalence of the material system within the aerospace industry and the need to address damage growth behavior of composites analytically. As the presence of thermoplastic materials has started to grow in the industry, it is necessary to be able to predict their behavior as well. However, it is unclear whether existing tools based on linear elastic fracture mechanics (LEFM) can be used to represent thermoplastics. One application area for PDFA tools is low velocity impact (LVI). This work presents two PDFA modeling methods originally validated for predicting damage of thermoset composites in low-velocity impact and evaluates their ability to model a thermoplastic material system in the same scenario. Both methods use MAT299, a continuum damage mechanics material model, to represent interlaminar damage and a cohesive tiebreak definition within LS-DYNA to represent delamination within a laminate. The results reveal that the cohesive tiebreak modeling method, while successful in modeling thermoset materials, is not currently capable of predicting the delamination response of thermoplastics. The larger strain energy release rates for the thermoplastic material in combination with a deficiency in the modeling method are believed to be the cause of the reduced delamination in the simulations. Potential routes for improving the delamination prediction in the simulations include adjusting the mode-mixity behavior, using a different cohesive approach for delamination, developing new best practices for cohesive behavior, and incorporating further non-linearity into the material model.

Reversible Schiff-base chemistry enables thermosetting smart composites with versatile properties

Fibre-reinforced polymer composites have become indispensable structural materials in modern life and global industry due to their superior specific properties and improved energy efficiency. However, the irreversibility of commercially available thermoset matrices, characterized by covalent cross-linking, poses challenges to both the recyclability and the enhancement of functionality. Herein, inspired by living tissues, we demonstrated recyclable, reprocessing, self-growing, and thermally/water modulated carbon fibre reinforced polyimine composites at low processing temperatures (≤110 °C, without any catalyst), realizing the intelligent composites. The tensile strength and average friction coefficients of our composites were 129.1 MPa and 0.52, respectively. Moreover, the chemical welding and self-growing mechanism of our system were deeply explored. The process enabled the recovery of clean and intact carbon fibres. We aim for this work to further deepen the understanding of dynamic polyimine networks with semi-aromatic skeleton, and facilitate the preparation of smart, adaptive and pluripotent composites.

Enhanced Thermal and Flexural Properties of Alkalized Date Palm/Kenaf Fiber-Reinforced Epoxy Hybrid Composites: A Comparative Study of Untreated and Treated Fibers

ABSTRACT This study evaluates the thermal and mechanical behavior of hybrid composites made from date palm (DP) and kenaf fibers (KF) in an epoxy thermoset matrix. Both DP and KF fibers are abundant and renewable, reducing environmental impact. KF offers high tensile strength and stiffness, improving composite strength and rigidity, while DP fibers offer toughness and impact resistance, enhancing durability. The composites were developed in 30%, 50%, and 70% DP-KF compositions using layup and hot-pressing methods. Fiber treatment through alkalization was analyzed for its impact on mechanical and thermal properties to find the optimal fiber ratio. The hybrid composites were subjected to DMA, TGA, and flexural tests. The treated composites exhibited fewer impurities and increased cellulose content, resulting in enhanced flexural performance. This improvement was evident through higher storage modulus, lower loss modulus, and reduced tan δ when exposed to thermal stress. The 30% DP and 70% KF composites exhibited best performance. The treated 30DP-70KF exhibited improvement in the flexural strength and modulus by 13.8% and 2.7%, respectively. TGA demonstrated that treated 30DP-70KF composites had a higher glass transition temperature (Tg) and better thermal degradation resistance. These findings highlight the potential of natural fiber hybrids in creating sustainable, high-performance composite materials for construction and industrial applications.

Mechanically neutral and facile monitoring of thermoset matrices with ultrathin and highly porous carbon nanotube films

We examine how the physical features of single-walled carbon nanotube (SWCNT) thin films can affect monitoring thermoset polymers during their manufacturing and application. Film thickness (23, 37 and 53 nm), electrode materials and configuration, and embedding within or surface application on a polymer were all investigated. During manufacturing monitoring, thicker films provided higher sensitivity than thinner ones (ΔR/R0 = 111% (53 nm) vs. 74% (23 nm)). Electrode material and configuration showed that sputtered gold contacts allow higher sensitivity and reliability compared with conductive silver adhesive, and that parallel electrode placement provides more distinct and discreet stage measurements compared to diagonal one. The opposite trend was noted for mechanical loading, where thinner films provide a higher piezoresistive response and embedded films outperform surface applied sensors (gauge factors between 23-86 and 4-10, respectively). All thin films accurately measured curing stages as well as mechanical changes and are shown to be self-adjusting when the force increases during mechanical loading. We show that manufacturing monitoring should rely on uniformly deposited electrodes and thicker films for identification of polymerization stages, whereas embedding thinner films in the matrix is recommended for highly sensitive deformation monitoring. This work outlines how simple, overlooked parameters can easily be varied to optimize the dual-stage monitoring performance of CNT-based sensors and helps to identify what parameters should be chosen for specific applications.

Advancements in Biofiller-Reinforced PLA Composites for 3D Printing: A Review

Additive manufacturing is key in realizing highly complex and high-performance composite materials. Among all the various kinds of functionality that could be added to a composite component, continuous fiber-reinforced composites have been drawing much attention because of their attractive combination of properties. The comprehensive spectrum of knowledge that ranges from the basics concerned with structure, morphology, synthesis, physical, and chemical properties finally reaches to this analytical study of advanced composites. Most generally, such a composite is structured on a thermoplastic or thermoset polymer matrix that embeds the load-carrying reinforcing fibers; probably best known are carbon, glass, and aramid fibers. These composites, which involve fibers continuously reinforcing, have high strength relative to their weight. They are also anisotropic, meaning they have qualities that vary from one direction to another – something which might be customisable for specific load cases. They warp and shrink less during their life in an outside environment than conventionally made bioplastics due to a fact that short fibers can provide reinforcement to them. This 3-D printing object is manufactured by special additive manufacture technology during the manufacturing process after compounding and extruding the fiber-reinforced composite filament. The final properties of 3D printed parts could be tailorable through changing variables such a fiber type, fiber length, volume fraction, polymer matrix material, orientation of fibers, and printing process parameters. These continuous fiber-reinforced 3D printed composites could achieve tensile strengths up to one GPa, have stiffness values reaching even a rating of countless Gpa, and have ad thicknesses in the range from about 1.4–1.8 g/cm³. This finding could be applied in basically all major industries, from aerospace and the automotive industry to sports gear. Such conclusions from the analysis may be useful in the selection of appropriate materials and techniques while even guiding the development of new applications with respect to such advanced composite materials.

Composite Recycling with Biocatalytic Thermoset Reforming.

Carbon fiber reinforced polymers (CFRPs, or composites) are increasingly replacing traditional manufacturing materials used in the automobile, aerospace, and energy sectors. With this shift, it is vital to develop end-of-life processes for CFRPs that retain the value of both the carbon fibers and the polymer matrix. Here we demonstrate a strategy to upcycle pre- and postconsumer polystyrene-containing CFRPs, cross-linked with unsaturated polyesters or vinyl esters, to benzoic acid. The thermoset matrix is upgraded via biocatalysis utilizing an engineered strain of the filamentous fungus Aspergillus nidulans, which gives access to valuable secondary metabolites in high yields, exemplified here by (2Z,4Z,6E)-octa-2,4,6-trienoic acid. Reactions are engineered to preserve the carbon fibers with much of their sizing so that the isolated carbon fiber plies are manufactured into new composite coupons that exhibit mechanical properties comparable to those of virgin manufacturing substrates. In sum, this represents the first system to reclaim a high value from both the fiber fabric and polymer matrix of a CFRP.

Comparison of mechanical and flammability properties of thermoplastic and thermoset matrix glass fibre woven fabric composites

This study aims to examine the mechanical and burning properties of composites made from twill (0°/0° and 0°/90° orientations) and plain fabrics using hybrid yarns produced by combining glass and polypropylene yarns with interwoven and intermingled methods. The properties of interwoven and intermingled hybrid fabric composites were compared with thermoset composites. Each composite (56% glass fibre content) plate is produced by combining eight fabrics with the same parameters using the press moulding technique. The effects of yarn and fabric weaving types on the results were examined in detail. When the results are examined, the breakage of glass fibres in intermingled hybrid yarns negatively affects the strength results. Therefore, composites made with intermingled hybrid yarn types and plain weave types of fabric had the lowest tensile strength value (132 MPa). The composite of twill woven fabrics produced with interwoven yarns arranged in 0°/0° orientation had the highest tensile strength of 315 MPa, and these results were very close to those of thermoset composites. Although the 0°/90° oriented twill composite showed a 2.3 times lower tensile strength value than the 0°/0° oriented twill composite, it had a 7.7 times higher value when bending strength values were taken into account. The main reason for this is that glass fibres contribute to the warp and weft directions. It has been observed that the composite consisting of plain fabrics woven with commingled hybrid yarns had the highest impact resistance. Additionally, when the combustion results were examined, it was concluded that the type of yarn and fabric weaving affected the burning rate. The slower combustion of hybrid commingled yarn composites resulted from fibreglass breakage during yarn production. These findings provide valuable insights into optimizing composite materials for specific applications, considering factors such as weaving pattern, fibre orientation, and mechanical performance.

Advanced Vitrimer with Spiropyran Beads: A Multi-Responsive, Shape Memory, Self-Healing, and Reprocessable Smart Material.

Thermosetting materials have limitations in terms of reshaping and recycling due to their irreversible bond structures, leading to significant plastic waste issues. Recently, epoxy vitrimers based on dynamic covalent bond exchange have been introduced as promising alternatives to traditional thermosets. Particularly, they demonstrate significant potential applications in the field of multi-responsive materials. In this research, a self-healable and mechano-responsive vitrimer (EB-V) is successfully prepared, incorporating epoxide spiropyran beads (ESP beads) derived from citric acid and epoxy derivatives. To enable self-reporting of cracks through color changes, ESP beads are covalently bonded to the vitrimer via an epoxy-carboxylic acid reaction. The photochromic properties of EB-V are demonstrated by color and fluorescence changes, and its tensile strength increased from 2.0 to 6.8MPa compared to the control sample. Dynamic mechanical analysis confirmed the covalent exchange reaction of the vitrimer, revealing its reconfigurable behavior and stress relaxation at elevated temperatures. Furthermore, EB-V exhibited exceptional properties, including self-healing and reprocessability. As a smart material, it holds great promise for a wide range of applications, such as sensors, actuators, 4D printing, and industrial safety diagnostics.

Polymers from renewable resources: Challenge of conventional thermoset materials and the need for sustainable thermoset polymers

Polymers from renewable resources: Challenge of conventional thermoset materials and the need for sustainable thermoset polymers

An Investigation into Mechanical Properties of 3D Printed Thermoplastic-Thermoset Mixed-Matrix Composites: Synergistic Effects of Thermoplastic Skeletal Lattice Geometries and Thermoset Properties.

This study aims to develop thermoplastic (TP) and thermoset (TS) based mixed matrix composite using design dependent physical compatibility. Using thermoplastic-based (PLA) skeletal lattices with diverse patterns (gyroid and grid) and different infill densities (10% and 20%) followed by infiltration of two different thermoset resin systems (epoxy and polyurethane-based) using a customized FDM 3D printer equipped with a resin dispensing unit, the optimised design and TP-TS material combination was established for best mechanical performance. Under uniaxial tensile stress, the failure modes of TP gyroid structures with polyurethane-based composites included 'fiber pull-out', interfacial debonding and fiber breakage, while epoxy based mixed matrix composites with all design variants demonstrated brittle failure. Higher elongation (higher area under curve) was observed in 20% infilled gyroid patterned composite with polyurethane matrix indicating the capability of operation in mechanical shock absorption application. Electron microscopy-based fractography analysis revealed that thermoset matrix properties governed the fracture modes for the thermoplastic phase. This work focused on the strategic optimisation of both toughness and stiffness of mixed matrix composite components for rapid fabrication of construction materials.

Co-molding High Temperature Erosion Coatings for Thermoset Polyimide Composites

High temperature (200-260°C) military composite engine components made of carbon fiber thermoset materials are susceptible to erosion damage. Evidenced by wear seen during operation, erosion protection remains a challenge for composites in the engine air flow path. In this paper, we investigate polyetheretherketone (PEEK), thermoplastic polyimide (TPI), and ceramic fabric (Nextel™) as potential high temperature erosion coatings for thermoset polyimide composite engine components. We evaluate the erosion protection materials for two qualities: (1) co-moldability with thermoset polyimide composite panels, and (2) erosion resistance to a sandblasting test. Autoclave and compression molding were used to test co-moldability with different manufacturing methods. The compression molding process was optimized to reduce surface defects using a pre-imidization step before the erosion protection layer was applied and final cure was completed. Co-molded test panels were cut into small coupons for sandblasting. After 60 s of alumina sandblasting PEEK had negligible mass loss, whereas the TPI and ceramic fabric had roughly the same erosion rate as the uncoated polyimide laminate.

Manufacturing of hexagonal cross-section thermoplastic matrix composite parts with automatic filament winding system

Thermoplastic filament winding is a flexible manufacturing method typically used in the production of cylindrical composite structures, allowing for in-situ consolidation without the need for a second consolidation step. The objective of this study is to produce non-cylindrical geometries, typically manufactured using thermoset matrix composites according to the literature, using the thermoplastic filament winding process. For this purpose, glass fiber (GF) reinforced polypropylene (PP) prepreg tapes were used to produce hexagonal cross-section thermoplastic composite parts. The critical process parameters; hot-air heater nozzle temperature, compression roller pressure, the linear speed of mandrel rotation, and corner radius of the mandrel, were determined using the Taguchi experimental design method. The interlaminar shear strength (ILSS) and maximum compressive strength (σmax) values were obtained as 211 MPa and 49.40 MPa as maximum, respectively. ANOVA analysis showed that the corner radius had the most significant impact on ILSS, while mandrel rotation speed and temperature were critical for σmax.

Enhancing the Fire Resistance of Ablative Materials: Role of the Polymeric Matrix and Silicon Carbide Reinforcement.

The primary characteristic of ablative materials is their fire resistance. This study explored the development of cost-effective ablative materials formed into application-specific shapes by using a polymer matrix reinforced with ceramic powder. A thermoplastic (polypropylene; PP) and a thermoset (polyester; UPE) matrix were used to manufacture ablative materials with 50 wt% silicon carbide (SiC) particles. The reference composites (50 wt% SiC) were compared to those with 1 and 3 wt% short glass fibers (0.5 mm length) and to composites using a 1 and 3 wt% glass fiber mesh. Fire resistance was tested using a butane flame (900 °C) and by measuring the transmitted heat with a thermocouple. Results showed that the type of polymer matrix (PP or UPE) did not influence fire resistance. Composites with short glass fibers had a fire-resistance time of 100 s, while those with glass fiber mesh tripled this resistance time. The novelty of this work lies in the exploration of a specific type of material with unique percentages of SiC not previously studied. The aim is to develop a low-cost coating for industrial warehouses that has improved fire-protective properties, maintains lower temperatures, and enhances the wear and impact resistance.

Comparison study of Izod impact properties on 3D printed thermoplastic and thermoset carbon fiber composite at different infill density

PurposeThis study aims to evaluate the low energy impact characteristics of 3D printed carbon fiber thermoplastic and thermoset polymer composite using the Izod impact test. The effects of infill density are examined on the Izod impact properties of 3D printed thermoset polymer and thermoplastic composite specimens. Furthermore, a thorough investigation is conducted into the effect of heat treatment using a hot-air oven on both types of 3D printed composite specimens. To characterize the impact characteristics of each specimen, the fracture surfaces caused by impact load are inspected, and the fracture mechanism is studied using scanning electron micrographs.Design/methodology/approachIzod Impact specimens of thermoset (epoxy resin) and thermoplastic carbon fiber of different infill density (70, 75, 80, 85, 90 and 100%) are fabricated using the different fiber impregnation 3D printing process. To carry out the heat treatment process, printing of composites is done for each infill design from both thermoset and thermoplastic composites and the impact characteristics of specimens are evaluated on a pendulum test-rig using the ASTM D-256 standard. Using a scanning electron microscope, each fracture zone underwent four separate scanning processes, ranging in size from 2 µm to 100 µm.FindingsThe impact resistance of the 3D printed thermoset and thermoplastic composite material is significantly influenced by the type of fiber placement and infill density in the matrix substrate. Because of the weak interfacial strength between the layers of fiber and polyamide 6, the specimen printed with continuous fiber implanted at the part exhibited reduced impact resistance. At 75% infill density, the impact specimen printed with coextruded fiber showed the highest impact resistance with a 367.02% greater magnitude than the continuous fiber specimen with the same infill density.Originality/valueThis work presents a novel approach to analyze the low energy impact characteristics and three-dimensional printing of carbon fiber reinforced thermoplastic and carbon fiber reinforced thermoset and thermoplastic composite material.

In‐situ preparation of modified‐halloysite/thermoset nanocomposites via thiol‐epoxy click chemistry

AbstractIn the current study, thermoset nanocomposites including halloysite nanotubes (HNTs) have been prepared through thiol‐epoxy click reaction at ambient conditions. Naturally available HNTs are first modified separately by epoxy and thiol groups and used as nanofillers in a mixture of trimethylolpropane triglycidyl ether and trimethylolpropane tris(3‐mercaptopropionate) ranging from 0 to 5 wt%. Fourier transformed infrared (FT‐IR) spectroscopy has been used to observe the characteristic bands of the pure and modified halloysite, neat thermoset, and HNT/thermoset nanocomposites. Thermal properties of epoxide‐modified and thiol‐modified halloysite nanotubes and also final thermoset nanocomposites have been investigated using thermogravimetric analysis (TGA) by comparing pure halloysite and neat thermoset, respectively. The dispersion of HNT nanotubes in thermoset matrix has been examined with scanning electron microscopy (SEM). In addition to the agglomerated/non‐agglomerated distribution, the present of HNT has been proved by EDX. The effect of HNT‐Epoxide and HNT‐Thiol loadings on mechanical properties has been examined by tensile test. All nanocomposites were found to exhibit better tensile strength than that of neat thermoset, called as reference sample. The most enhanced mechanical properties have been detected in the nanocomposite with 3% modified‐HNTs by weight because of the best dispersion, which promotes effective interactions between the nanotubes and thermoset matrix. Tensile strength of thermoset nanocomposites increased by 43% and 62%, while elongation at break increased by 58% and 149% when 3 wt% HNT‐Epoxide and 3 wt% HNT‐Thiol were added to the matrix, respectively. Further increase of HNT added to the matrix causes agglomeration of nanotubes and thus deterioration of mechanical properties.Highlights Pure HNT was modified and successfully converted into HNT‐Epoxide and HNT‐Thiol. In‐situ preparation of thermoset nanocomposites with modified‐HNTs was effectively achieved via thiol‐epoxy click chemistry. Mechanical properties increased significantly with both HNT‐Epoxide and HNT‐Thiol loading ratio up to 3 wt%. The presence and agglomerated/non‐agglomerated dispersion of modified‐HNTs in the thermoset matrix were verified by SEM–EDX analysis.

Topological Rearrangement-Induced Mesoscale Phase Redistribution to Enhance the Fatigue Resistance of Polymer Blends.

Maintaining a high modulus to simultaneously withstand deformation and increase fatigue resistance to restrict crack propagation in a material presents a significant challenge. In this work, a straightforward strategy was developed to address this issue in polymers. A dynamic network was incorporated into a permanent one prior to the formation of the latter, and two incompatible polymer networks were created to prevent common phase separation. The mechanical and fatigue resistance properties were substantially enhanced by the exact modulation of the soft and hard phase distribution by precise control over the densities of dynamic and permanent networks as well as the number of reprocessing steps. The experimental results demonstrated a nearly 9-fold increase in the fatigue life of polyurethane compared with traditional design methods and a 2.5 times increase in modulus. This strategy shows potential for the design of fatigue-resistant thermosetting and thermoplastic materials. The results offer new insight into the development of durable, high-performance materials that are reprocessable and compatible.

Development of intrinsically flame-retardant bio-thermosets with further enhanced thermal stability through a photo-thermal dual polymerization strategy

In response to safety and environmental concerns, there has been a significant increase in research focused on developing high-performance thermoset materials from sustainable sources. In this study, a sophisticated chemical design approach integrates coumarin and furan moieties into a bio-based UV-dimerizable benzoxazine resin. The newly obtained bio-benzoxazine exhibits a reduced curing temperature along with improvements in both thermal stability and flame-retardant properties compared to conventional thermosetting counterparts. Extensive characterization of the chemical structure of the UV-dimerizable bio-based benzoxazine is conducted through nuclear magnetic resonance, Fourier transform infrared spectroscopy, elemental analysis, and high-resolution mass spectrometry. The photo-dimerization processes are monitored using UV–Vis and NMR techniques. Additionally, the thermally activated curing behavior is scrutinized via differential scanning calorimetry and in situ FT-IR techniques. Remarkably, the fully polymerized bio-thermoset demonstrates exceptional thermal stability, possessing a Td10 of 410 °C and a Tg of 283 °C. Moreover, the resulting thermosets also shows very low flammability, as evidenced by a heat release capacity of 14.6 J·g-1·K-1 and a total heat release of 2.97 kJ·g-1. This study not only outlines a method to enhance the overall performance of bio-polybenzoxazines but also provides a direct and sustainable synthesis route for bio-derived, intrinsically non-flammable thermosetting materials.