Molecular Dynamics Simulation of Cumulative Microscopic Damage in a Thermosetting Polymer under Cyclic Loading.

To develop durable composite materials, it is crucial to elucidate the correlation between nanoscale damage in thermosetting resins and the degradation of their mechanical properties. This study aims to investigate this correlation by performing cyclic loading tests on the cross-linked structure of diglycidyl ether bisphenol A (DGEBA) and 4,4'-diaminodiphenyl sulfone (44-DDS) using all-atom molecular dynamics (MD) simulations. To accurately represent the nanoscale damage in MD simulations, a bond dissociation algorithm based on interatomic distance criteria is applied, and three characteristics are used to quantify the microscopic damage: stress-strain curves, entropy generation, and the formation of voids. As a result, the number of covalent bond dissociations increases with both the cyclic loading and its amplitude, resulting in higher entropy generation and void formation, causing the material to exhibit inelastic behavior. Furthermore, our findings indicate the occurrence of a microscopic degradation process in the cross-linked polymer: Initially, covalent bonds align with the direction of the applied load. Subsequently, tensioned covalent bonds sequentially break, resulting in significant void formation. Consequently, the stress-strain curves exhibit nonlinear and inelastic behavior. Although our MD simulations employ straightforward criteria for covalent bond dissociation, they unveil a distinct correlation between the number of bond dissociations and microscale damage. Enhancing the algorithm holds promise for yielding more precise predictions of material degradation processes.

Latest Advancements in the Development of High-Performance Lignin- and Tannin-Based Non-Isocyanate Polyurethane Adhesive for Wood Composites.

The depletion of natural resources and increasing environmental apprehension regarding the reduction of harmful isocyanates employed in manufacturing polyurethanes (PUs) have generated significant attention from both industrial and academic sectors. This attention is focused on advancing bio-based non-isocyanate polyurethane (NIPU) resins as viable and sustainable substitutes, possessing satisfactory properties. This review presents a comprehensive analysis of the progress made in developing bio-based NIPU polymers for wood adhesive applications. The main aim of this paper is to conduct a comprehensive analysis of the latest advancements in the production of high-performance bio-based NIPU resins derived from lignin and tannin for wood composites. A comprehensive evaluation was conducted on scholarly publications retrieved from the Scopus database, encompassing the period from January 2010 to April 2023. In NIPU adhesive manufacturing, the exploration of substitute materials for isocyanates is imperative, due to their inherent toxicity, high cost, and limited availability. The process of demethylation and carbonation of lignin and tannin has the potential to produce polyphenolic compounds that possess hydroxyl and carbonyl functional groups. Bio-based NIPUs can be synthesized through the reaction involving diamine molecules. Previous studies have provided evidence indicating that NIPUs derived from lignin and tannin exhibit enhanced mechanical properties, decreased curing temperatures and shortened pressing durations, and are devoid of isocyanates. The characterization of NIPU adhesives based on lignin and tannin was conducted using various analytical techniques, including Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), matrix-assisted laser desorption/ionization with time-of-flight (MALDI-TOF) mass spectrometry, and gel permeation chromatography (GPC). The adhesive performance of tannin-based NIPU resins was shown to be superior to that of lignin-based NIPUs. This paper elucidates the potential of lignin and tannin as alternate sources for polyols in the manufacturing of NIPUs, specifically for their application as wood adhesives.

Design of Experiments-Based Fire Performance Optimization of Epoxy and Carbon-Fiber-Reinforced Epoxy Polymer Composites.

The fire performance of epoxy and carbon-fiber-reinforced polymer (CFRP) composites with and without fire retardants (FR) (i.e., ammonium polyphosphate (APP), aluminum trihydroxide (ATH), melamine (MEL), expandable graphite (EG)) was investigated. A design of experiment (DoE) approach was applied to study the single- and multifactorial effects of FR. The fire performance of epoxy and CFRP was evaluated by limiting the oxygen index (LOI) and heat release, which were obtained by limiting the oxygen index test and cone calorimetry. It was found that mixtures of 70 wt.-% epoxy, 24.6 wt.-% of APP, and 5.4 wt.-% MEL resulted in the highest LOI level of 45 within tested groups for epoxy resin and also for CFRP specimens (LOI level of 39). This mixture also resulted in the lowest average heat release rate (HRR180s) of 104 kW·m-2 and a spec. total heat release (THR600s) of 1.14 MJ·m-2·g-1, indicating the importance of balancing spumific and charring agents in intumescent systems and synergy thereof.

Development of Epoxy and Urethane Thermosetting Resin Using Chlorella sp. as Curing Agent for Materials with Low Environmental Impact.

In the current system, the disposal of plastic materials causes serious environmental pollution such as the generation of carbon dioxide and destruction of the ecosystem by micro-plastics. To solve this problem, bioplastics, biomass and biodegradable plastics have been developed. As part of our research, we have developed novel bioplastics called "cell-plastics", in which a unicellular green algal cell serves as a fundamental resource. The production of the cell-plastics would be expected to reduce environmental impact due to the usage of a natural product. Herein, to overcome the mechanical strength of cell-plastics, we used thermosetting epoxy and urethane resins containing Chlorella sp. as the green algae. We successfully fabricated thermosetting resins with a Chlorella sp. content of approximately 70 wt% or more. IR measurements revealed that the chemical structure of an epoxide or isocyanate monomer mixed with Chlorella sp. was modified, which suggests that the resins were hardened by the chemical reaction. In addition, we investigated the effect of thermosetting conditions such as temperature and compression for curing both resins. It was revealed that the Young's moduli and tensile strengths were controlled by thermosetting temperature and compression, whereas the elongation ratios of the resins were constant at low values regardless of the conditions.

A Molecular Dynamics Simulation for Thermal Activation Process in Covalent Bond Dissociation of a Crosslinked Thermosetting Polymer.

A novel algorithm for covalent bond dissociation is developed to accurately predict fracture behavior of thermosetting polymers via molecular dynamics simulation. This algorithm is based on the Monte Carlo method that considers the difference in local strain and bond-dissociation energies to reproduce a thermally activated process in a covalent bond dissociation. This study demonstrates the effectiveness of this algorithm in predicting the stress-strain relationship of fully crosslinked thermosetting polymers under uniaxial tensile conditions. Our results indicate that the bond-dissociation energy plays an important role in reproducing the brittle fracture behavior of a thermosetting polymer by affecting the number of covalent bonds that are dissociated simultaneously.

Role of MWCNTs Loading in Designing Self-Sensing and Self-Heating Structural Elements.

This work proposes nanocomposites with carbon nanotubes characterized by self-sensing and self-heating properties. Recently, a growing interest in these two properties has been found in many industrial sectors, especially in the aerospace and automotive fields. While the self-sensing function allows diagnosing the presence of micro-damage in the material thanks to the detection of residual resistance, the self-heating function is exploited to properly tune the heating performance in terms of the heating rate and final temperature values. An electrical percolation value of around 0.5% by weight of carbon nanotubes was found by electrical characterization. The AC conductivity of the nanocomposites, in the range of 100 Hz to 1 MHz, evidences that beyond a CNTs amount of 0.5% wt/wt, they are characterized by a purely resistive behavior. The self-sensing analysis displayed a gauge factor value of 4.1. The solid thermal stability up to 300 °C makes the material suitable as a heating element at high temperatures. SEM investigations and temperature maps evidence a good dispersion of the conductive filler in the epoxy matrix and, consequently, good isotropy in heat distribution. As regards the trend of electrical resistance by varying the temperature, the electro-thermal investigation has shown the presence of both Positive Temperature Coefficient (PTC) and Negative Temperature Coefficient (NTC) behaviors with a predominance of NTC as soon as the temperature becomes closer to the glass transition temperature of the epoxy resin.

Improvements in Mechanical and Shape-Memory Properties of Bio-Based Composite: Effects of Adding Carbon Fiber and Graphene Nanoparticles.

Shape-memory carbon fiber (CF) polymer composites reinforced with graphene nanoplatelets (GnPs) as a filler based on a bio-based V-fa/ECO copolymer were prepared at different graphene GnPs and CF mass fractions using the hand lay-up and hot-pressing methods. The obtained composite specimens were subjected to flexural, dynamic mechanical, and shape-memory analyses. The obtained results revealed that the flexural strength and modulus were improved by the addition of the GnPs and CF due to the improvement in the interfacial adhesion and fiber reinforcement with up to 3 wt.% GnPs and 60 wt.% CF. Additionally, appreciable improvements in the shape-memory performance were achieved with the addition of the GnPs, where values of up to 93% and 96% were recorded for the shape fixity and recovery, respectively. The shape-memory performance was affected by the fiber mass fraction, with the composites retaining the shape-memory effect albeit with a significant drop in performance at higher fiber mass fractions. Lastly, the specimens at 40 wt.% CF and 3 wt.% GnPs were determined to be the optimum compositions for the best performance of the bio-based SMP composite.

Development of a Novel Biobased Polyurethane Resin System for Structural Composites.

Polyurethanes are gaining increasing interest for their use as structural components subjected to cyclic loads, such as leaf springs. Thermoset polyurethane (PUR) based technology offers some advantages, such as fatigue resistance, low viscosity, and fast curing. However, current PUR formulations present two major drawbacks: their petrochemical origin and high reactivity. The aim of this work was to develop a novel biobased PUR (BIO-PUR) with the required mechanical properties and processability for manufacturing structural composites by resin transfer moulding (RTM). For this purpose, a high functionality and high hydroxyl index castor-oil-based polyol was used combined with a biobased glycerol (BIO-Gly) to increase the crosslinking density and improve the final properties of the BIO-PUR. The viscosity and reactivity of the different systems were studied by means of rheology tests and differential scanning calorimetry (DSC). Thermal and mechanical properties were studied by dynamic mechanical analysis (DMA) and flexural tests. Furthermore, the RTM process of a representative part was simulated and validated through the manufacturing and testing of plates. The properties of the BIO-PUR resin systems were strongly influenced by the addition of biobased glycerol and its effect on the crosslinking density. The combination of a high functionality and hydroxyl index biobased polyol with the biobased glycerol resulted in a high-performance BIO-PUR with the required reactivity and final properties for structural applications.

Development of Electrically Conductive Thermosetting Resin Composites through Optimizing the Thermal Doping of Polyaniline and Radical Polymerization Temperature.

This work developed an electrically conductive thermosetting resin composite that transitioned from a liquid to solid without using solvents in response to an increase in temperature. This material has applications as a matrix for carbon fiber reinforced plastics. The composite comprised polyaniline (PANI) together with dodecyl benzene sulfonic acid (DBSA) as a liquid dopant in addition to a radical polymerization system made of triethylene glycol dimethacrylate with a peroxide initiator. In this system, micron-sized non-conductive PANI particles combined with DBSA were dispersed in the form of conductive nano-sized particles or on the molecular level after doping induced by a temperature increase. The thermal doping temperature was successfully lowered by decreasing the PANI particle size via bead milling. Selection of an appropriate peroxide initiator also allowed the radical polymerization temperature to be adjusted such that doping occurred prior to solidification. Optimization of the thermal doping temperature and the increased radical polymerization temperature provided the material with a high electrical conductivity of 1.45 S/cm.

Preparation of BMI monomers containing phosphate and phosphonate structure to enhance the flame retardant and toughness of BMI.

Aiming at enhancing the toughness and fire safety of bismaleimide (BMI), BMI monomers containing phosphate and phosphonate structure (BDTP and BDTDP) were designed and prepared. With incorporation of 5 wt% BDTP and BDTDP, the peak value of heat release rate (PHRR) of BMI/BDTP-5 and BMI/BDTDP-5 decrease by 59.4% and 52.4%, respectively. The total smoke production (TSP) of BMI/BDTP-5 and BMI/BDTDP-5 are of 8.3% and 13.1% reduction, respectively. Meanwhile, BMI/BDTP-5 and BMI/BDTDP-5 possess UL-94V-0 rating, which indicates that BMI is endowed with better flame retardant performance by modification of designed BMI monomers. Besides, the impact strength of BMI/BDTP-5 and BMI/BDTDP-5 increase by 146.3% and 90.2%, respectively. The comprehensive performance of BMI/BDTP-5 is better than that of BMI/BDTDP-5. And the effect of phenyl phosphate structure in BDTP and phenyl phosphonate structure in BDTDP on BMI performance is explored.

Improving Fracture Toughness of Tetrafunctional Epoxy with Functionalized 2D Molybdenum Disulfide Nanosheets.

In this work, improved fracture toughness of tetra-functional epoxy polymer was obtained using two-dimensional (2H polytype) molybdenum disulfide (MoS2) nano-platelets as a filler. Simultaneous in-situ exfoliation and functionalization of MoS2 were achieved in the presence of cetyltrimethylammonium bromide (CTAB) via sonication. The aim was to improve the dispersion of MoS2 nanoplatelets in epoxy and enhance the interfacial interaction between nanoplatelets and epoxy matrix. Epoxy nanocomposites with CTAB functionalized MoS2 (f-MoS2) nanoplatelets, ranging in content from 0.1 wt% up to 1 wt%, were fabricated. Modified MoS2 improved the fracture properties (81%) of tetrafunctional epoxy nanocomposites. The flexural strength and compressive strength improved by 64% and 47%, respectively, with 0.25 wt% loading of f-MoS2 nanoplatelets compared to neat epoxy. The addition of f-MoS2 nanoplatelets enhanced the thermomechanical properties of epoxy. This work demonstrated the potential of organically modified MoS2 nanoplatelets for improving the fracture and thermal behavior of tetrafunctional epoxy nanocomposites.

Fabricating a Repairable, Recyclable, Imine-based Dynamic Covalent Thermosetting Resin with Excellent Water Resistance by Introducing Dynamic Covalent Oxime Bonds.

The sustainable production of adaptive, recyclable and imine-based dynamic covalent thermosetting resins (DCTRs) presents an opportunity for polymer scientists to address the prevalent environmental and energy concerns associated with current petroleum-based plastics. However, the imine-based DCTRs easily decompose in the presence of water, which can weaken the mechanical properties in imine-based polymers. In this study, we designed oxime-imine DCTRs that are stable in the presence of water and exhibit good mechanical properties. In the presence of one kind of amino group catalyst, the oxime-imine DCTRs could be completely recycled. Additionally, these well-designed oxime-imine DCTRs have good mechanical properties, high glass transition temperatures (166 °C), and good thermal stabilities. Taken together, this work offers a sustainable solution for the design and manufacture of high-value degradable materials intended for applications in which recyclability and reusability are indispensable.

Quantifying the Shape Memory Performance of a Three-Dimensional-Printed Biobased Polyester/Cellulose Composite Material.

A biobased composite material with heat-triggered shape memory ability was successfully formulated for three-dimensional (3D) printing. It was produced from cellulose nanocrystals and cellulose micro-powder particles within a bioderived thermally cured polyester matrix based on glycerol, citric acid, and sebacic acid. The effect of curing duration on the material's shape memory behavior was quantified by using two thermo-mechanical approaches to measure recovery: (1) displacement in three-point bending and (2) angular recovery from a beam bent at 90° in a single cantilever setup. Extending curing duration increased the material's glass-transition temperature from -26°C after 6 h to 13°C after 72 h of curing. Fourier-transform infrared spectroscopy confirmed the associated progressive conversion of functional groups consistent with polyester formation. Slow recovery rates and low levels of shape recovery (22-70%) were found for samples cured less than 24 h. Those results also indicated a high dependence on the measurement approach. In contrast, samples cured for 48 and 72 h exhibited faster recovery rates, a significantly higher recovery percentage (90-100%) and were less sensitive to the measurement approach. Results demonstrated that once a sufficient curing threshold was achieved, additional curing time could be used to tune the material glass-transition temperature and create heat-triggered 3D-printed products.

Hydrophobic Shape-Memory Biocomposites from Tung-Oil-Based Bioresin and Onion-Skin-Derived Nanocellulose Networks.

The fabrication of smart biocomposites from sustainable resources that could replace today's petroleum-derived polymer materials is a growing field of research. Here, we report preparation of novel biocomposites using nanocellulose networks extracted from food residue (onion skin) and a vegetable oil-based bioresin. The resin was synthesized via the Diels-Alder reaction between furfuryl methacrylate and tung oil at various ratios of the components. The onion-skin-extracted cellulose nanofiber and cellulose nanocrystal networks were then impregnated with the resins yielding biocomposites that exhibited improved mechanical strength and higher storage modulus values. The properties of the resins, as well as biocomposites, were affected by the resin compositions. A 190-240-fold increase in mechanical strength was observed in the cellulose nanofiber (CNF) and cellulose nanocrystal (CNC)-reinforced biocomposites with low furfuryl methacrylate content. The biocomposites exhibited interesting shape-memory behavior with 80-96% shape recovery being observed after 7 creep cycles.

FIMEC Test to Evaluate the Water Uptake of Coated and Uncoated CFRP Composites.

This study focuses on the application of the FIMEC (flat-top cylinder indenter for mechanical characterization) indentation test to evaluate the effect of water uptake on the mechanical properties of high-performance materials, in particular CFRP (carbon fibre reinforced polymer) composites. Coated and uncoated samples were analyzed. Silicon-based and siloxane coatings were formulated and applied to CFRP to reduce the moisture absorption of the material. The FIMEC test was adopted to study the reduction of the stiffness of CFRP plates for different ageing in water. The evolution of mechanical properties is reported as a function of the water uptake. IR analyses and weight variation measures were used as supporting data. Experimental results show that the FIMEC test is suitable to assess the stiffness reduction due to the aging in water and to identify coatings able to minimize the water uptake.

On the Nature of Epoxy Resin Post-Curing.

Post-curing is intended to improve strength, elevate glass transition, and reduce residual stress and outgassing in thermosets. Also, experiments indicate post-curing temperatures lead to ether crosslinks and backbone dehydration. These results informed molecular dynamics methods to represent them and compare the resulting thermomechanical effects. Diglycidyl ether of bisphenol A (DGEBA)-diamino diphenyl sulfone (DDS) systems were examined. Independent variables were resin length, stoichiometry, and reaction type (i.e., amine addition, etherification, and dehydration). Etherification affected excess epoxide systems most. These were strengthened and became strain hardening. Systems which were both etherified and dehydrated were most consistent with results of post-curing experiments. Dehydration stiffened and strengthened systems with the longer resin molecules due to their intermediate hydroxyl groups for crosslinking. Changes in the concavity of functions fit to the specific volume versus temperature were used to detect thermal transitions. Etherification generally increased transition temperatures. Dehydration resulted in more transitions.

Aromatic Hyperbranched Polyester/RTM6 Epoxy Resin for EXTREME Dynamic Loading Aeronautical Applications.

The effects of the addition of an aromatic hyperbranched polyester (AHBP) on thermal, mechanical, and fracture toughness properties of a thermosetting resin system were investigated. AHBP filler, synthesized by using a bulk poly-condensation reaction, reveals a glassy state at room temperature. Indeed, according to differential scanning calorimetry measurements, the glass transition temperature (Tg) of AHBP is 95 °C. Three different adduct weight percentages were employed to manufacture the AHBP/epoxy samples, respectively, 0.1, 1, and 5 wt%. Dynamical Mechanical Analysis tests revealed that the addition of AHBP induces a negligible variation in terms of conservative modulus, whereas a slight Tg reduction of about 4 °C was observed at 5 wt% of filler content. Fracture toughness results showed an improvement of both critical stress intensity factor (+18%) and critical strain energy release rate (+83%) by adding 5 wt% of AHBP compared to the neat epoxy matrix. Static and dynamic compression tests covering strain rates ranging from 0.0008 to 1000 s-1 revealed a pronounced strain rate sensitivity for all AHBP/epoxy systems. The AHBP composites all showed an increase of the true peak yield compressive strength with the best improvement associated with the sample with 0.1 wt% of AHBP.

Curing Kinetic Parameters of Epoxy Composite Reinforced with Mallow Fibers.

Knowledge about the curing behavior of a thermosetting resin and its composites includes the determination of kinetic parameters and constitutes an important scientific and technological tool for industrial process optimization. In the present work, the differential scanning calorimetry (DSC) technique was used to determine several curing parameters for pure epoxy and its composite reinforced with 20 vol % mallow fibers. Analyses were performed with heating rates of 5, 7.5, and 10 °C/min, as per the ASTM E698 standard. The kinetic related parameters, that is, activation energy (E), Avrami's pre-exponential factor (Z), and mean time to reach 50% cure (t½), were obtained for the materials, at temperatures ranging from 25 to 100 °C. Response surfaces based on the mathematical relationship between reaction time, transformed fraction, and temperature were provided for optimization purposes. The results showed that the average curing time used for the production of diglycidyl ether of bisphenol A/triethylenetetramine (DGEBA/TETA) epoxy systems or their composites reinforced with natural mallow fibers can be considerably reduced as the temperature is increased up to a certain limit.

Amino-Functionalized Lead Phthalocyanine-Modified Benzoxazine Resin: Curing Kinetics, Thermal, and Mechanical Properties.

Phenol-diaminodiphenylmethane-based benzoxazine (P-ddm)/phthalocyanine copolymer was prepared by using P-ddm resin as matrix and 3,10,17,24-tetra-aminoethoxy lead phthalocyanine (APbPc) as additive. Fourier-transform infrared (FTIR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA) were used to investigate the curing behavior, curing kinetics, dynamic mechanical properties, thermal stability, and impact strength of the prepared copolymers. The kinetic parameters for the P-ddm/APbPc blend curing processes were examined by utilizing the iso-conversional, Flynn-Wall-Ozawa, and Málek methods. The P-ddm/APbPc blends exhibit two typical curing processes, and DSC results confirmed that the blending of APbPc monomer can effectively reduce the curing temperature of P-ddm resin. The autocatalytic models also described the non-isothermal curing reaction rate well, and the appropriate kinetic parameters of the curing process were obtained. The DMA and impact strength experiments proved that the blending of APbPc monomer can significantly improve the toughness and stiffness of P-ddm resin, the highest enhancements were observed on 25 wt.% addition of APbPc, the recorded values for the storage modulus and impact strength were 1003 MPa and 3.60 kJ/m2 higher, respectively, while a decline of 24.6 °C was observed in the glass transition temperature values. TGA curves indicated that the cured copolymers also exhibit excellent thermal stabilities.

A Review on Styrene Substitutes in Thermosets and Their Composites.

In recent decades, tremendous interest and technological development have been poured into thermosets and their composites. The thermosets and composites with unsaturated double bonds curing system are especially concerned due to their versatility. To further exploit such resins, reactive diluents (RDs) with unsaturated sites are usually incorporated to improve their processability and mechanical properties. Traditional RD, styrene, is a toxic volatile organic compound and one of the anticipated carcinogens warned by the National Institute of Health, USA. Most efforts have been conducted on reducing the usage of styrene in the production of thermosets and their composites, while very few works have systematically summarized these literatures. Herein, recent developments regarding styrene substitutes in thermosets and their composites are reviewed. Potential styrene alternatives, such as vinyl derivatives of benzene and (methyl)acrylates are discussed in details. Emphasis is focused on the strategies on developing novel RD monomers through grafting unsaturated functional groups on renewable feedstocks such as carbohydrates, lignin, and fatty acids. This review also highlights the development and characteristics of RD monomers and their influence on processability and mechanical performance of the resulting thermosets and composites.