Amine-cured Epoxy Research Articles

Mitigating aging infrastructure risks: An optimized epoxy resin system for water supply pipeline rehabilitation

Urban water supply networks are crucial for ensuring the delivery of safe drinking water to urban populations; however, the aging infrastructure in these systems has led to a rising incidence of leaks and frequent pipeline failures, posing serious risks. Traditional repair approaches encounter limitations in terms of efficiency, durability, and environmental safety, particularly when employed in potable water pipelines. To address these challenges, we developed a novel multi-component amine-cured epoxy resin system specifically optimized for in-situ curing under ambient conditions. This study comprehensively examines the mechanical properties, water absorption behavior, and curing kinetics of this resin system, formulated to reduce volatile organic compound emissions while enhancing durability under prolonged water exposure. Experimental findings demonstrate that the E2 formulation exhibited superior tensile strength, flexural properties, and fracture toughness relative to other formulations, with a two-stage water absorption model accurately predicting resin behavior in moisture-laden environments. Moreover, finite element modeling and laboratory testing confirmed the influence of bubble defects on mechanical performance, and a negative pressure defoaming technique effectively reduced defect volume, resulting in a 17.6% improvement in tensile strength. Collectively, this research advances the practical application of rapid-curing resins, offering a resilient, safe, and sustainable solution for the rehabilitation of aging water pipeline networks.

Flame retardant, transparent, low dielectric and low smoke density EP composites implemented with reactive flame retardants containing P/N/B

For the purpose of investigating the modified flame-retardant epoxy resin (FREP) with the low smoke density release during combustion, the flame retardant containing P/N/B elements named DBT was synthesized with the raw materials of 4-Acetylphenylboronic acid, 3,5-diaminotriazole and DOPO. The DBT was added as a co-curing agent to an amine-cured epoxy resin system, and based on the DSC results of the resin, it was revealed that -NH- in the structure of the DBT was capable of facilitating EP curing. With the introduction of DBT, the transparency of FREP samples was slightly affected. On account of the excellent flame retardancy exerted by the DBT in the FREP system, the FREP samples reached the V-0 grade in UL-94 testing with an LOI of 35.9% at 5 wt% DBT addition. Meanwhile, the results of the cone calorimetry test demonstrated that in comparison with the epoxy resin, the PHRR, THR and av-EHC of the EP/DBT7.5 sample decreased by 34.0%, 35.4% and 18.68%, respectively. The DBT was effective in reducing the smoke density of EP, and the EP/DBT7.5 sample attained the HL1 level for DS (4) and VOF4. The chemical analyses for residual char revealed that DBT was mainly employed for flame retardancy and smoke suppression by forming P/B-containing chars in the condensed phase. There was no loss of mechanical properties of the FREP samples as the rigid groups were present in the DBT structure. Furthermore, it was noted that the FREP samples exhibited a decrease in dielectric loss and dielectric constant as the content increased.

Analysis of bio-based epoxy resins: Impact of amine hardeners on thermal, thermomechanical, optical and electrical properties of epoxidized resveratrol with high Tg

Epoxidized resveratrol (RES) has been cured with different amines in order to compare their possibilities to obtain high-temperature resistance of bio-based epoxy resins. Materials obtained from the bio-based monomer present glass transition temperatures (Tg) among the highest ever reported for an epoxy-amine curing system, with extremely high char residue, making them excellent candidates for extremely high-temperature applications. Particularly, epoxidized RES stoichiometrically cured with 4,4′-sulfonyldianiline (DDS) reached 297 °C, measured as the tan δ peak by DMTA, and two other materials, using 4,4′-methylenedianiline (DDM) and 4,4′-diaminodicyclohexylmethane (CAA) as curing agents, exceeded 300 °C. In fact, the material begins to degrade before the chains are fully relaxed, so they are thermosetting that never go completely into the rubbery state. Additionally, this resin improves the direct current (DC) insulating character (~1015 Ωcm) while decreasing the optical band gap (~2 eV) when compared to other epoxy resins available, which is of great interest for photovoltaic applications. Moreover, some of the materials presented a very high char residue proportion when heated (>40 wt% at 800 °C under nitrogen atmosphere), presenting good fire-retardant properties.

Encapsulated inorganic pigments in epoxy composite microspheres using emulsion synthesis

Inorganic pigments are a commonly used colorant with various applications and promising prospects. However, the implement of organic pigments is hindered by poor dispersion stability in coatings due to non-uniform morphology and size. Herein, encapsulated pigments of Cobalt Chrome Green CoCr2O4 (PG 26), Cobalt Blue CoAl2O4 (PB 28), Titanium Chrome Yellow TiCrSbO6 (PB 24) in epoxy microspheres are obtained via an oil-in-water emulsion polymerization. The morphology, particle size, thermal properties, glass transition temperature (Tg) and color performance of the composite microspheres were characterized by different analytical techniques. The average particle size varied with pigments types and loadings. When the content of CoCr2O4 and CoAl2O4 is in the range of 15 wt%-30 wt%, and TiCrSbO6 content is between 15 wt%-25 wt%, the composite microspheres exhibit a narrow particle size distribution, regular morphology, and smooth surface. The size followed the rule of CoAl2O4/epoxy (20–26 μm) > CoCr2O4/epoxy (14-16μm) > TiCrSbO6/epoxy (6–9 μm). Besides, according to the aggregation-induced emission (AIE) principle, the relationship between fluorescence intensity and reaction time was investigated, thus deducing the curing process of the epoxy groups with m-xylenol dimethylamine (MXDA). The kinds of three inorganic fillers exhibit varying effects on the diffusion process of MXDA. TiCrSbO6 promotes the progress of the epoxy-amine curing reaction. Notably, CoCr2O4 microspheres exhibited stable green value (a*) and color saturation (C*), TiCrSbO6 microspheres showed increased yellow value (b*) and saturation (C*), and CoAl2O4 microspheres enhanced blue value (b*) with minimal change in lightness (L*). Overall, this study provides a comprehensive understanding of the properties of inorganic pigment/epoxy composite microspheres and highlights their potential for improved dispersion stability in coating applications.

Seamlessly embedded microcapsules in self-repairing coatings: Improved compatibility and enhanced corrosion resistance recovery

Microcapsules, with polyether amine as the core repairing agent and polyether amine-cured epoxy as the shell, were prepared via the multiple emulsion polymerization and applied in an epoxy/polyether amine coating system on carbon steel surfaces. The microcapsules and the coating substrate have the same composition and are seamlessly connected by chemical bonds, akin to the direct injection of liquid healing agents into the substrate. When the repairing agent flows out, it will crosslink and cure with the epoxy groups in the substrate to achieve no difference self-repair. The characteristics of microcapsules were studied by scanning electron microscope (SEM), Fourier transform infrared (FTIR) and Thermal gravimetric (TG). The mechanical properties and corrosion resistance recovery of coatings loaded of coatings with different weight percentages of loaded microcapsules were investigated using tensile testing, electrochemical impedance spectroscopy (EIS) and neutral salt spray test (NSS). Results indicate that the 7 wt% microcapsules composite coating shows a 37.7 % increase in tensile strength and a 71.4 % increase in fracture toughness over pure epoxy coating. After immersing in saltwater for 7 days, the scratch sealing efficiency can reach 99.85 %. The coating system not only improved the compatibility between microcapsules and the substrate, but also enhanced the toughness of thermosetting brittle epoxy materials, giving it long-lasting anti-corrosion capability.

Investigating the effect of chemical structures on water sorption and diffusion in amine-cured epoxy resins by molecular dynamics simulations

Mechanical degradation of polymer materials by moisture ingress is inevitable due to their chemical and physical properties. In this regard, it is necessary to better understand the mechanisms governing interactions between water and polymer. In this research, the sorption and diffusion of moisture in epoxy systems with different chemical structures of amines (DGEBA/DDS and DGEBA/DDM) has been investigated by molecular dynamics simulations. For the validation, the physical properties of the simulation models and the calculated values of the diffusion coefficient and equilibrium water content have been compared with the existing data and acceptable results have been obtained. The study results of polymer systems showed that both the polarity and the average radius of nanopores played an effective role in diffusivity and equilibrium water content values. It was also found that the interactions between water and polymer molecules at the water-polymer interface played an important role in the initiation of the moisture sorption process. The results of the simulation during the hydrothermal aging process showed that moisture first entered the pores in the epoxy network, then diffused deeper into the polymer, and finally, with a change in the polymer structure, caused water-polymer hydrogen bonds with stronger strength.

Efficient degradation of amine cured epoxy resin via the cleavage of C-N bond by amphiphilic dodecylbenzenesulfonic acid

Amine-cured epoxy resin (EP) is often compounded with carbon fiber (CF) used for wind power blades due to its excellent performance. However, the insolubility and infusibility of service-life-expired carbon fiber reinforced epoxy resin (CFREP) hinder its sustainable recycling. We reported a new strategy for efficient degradation of EP and CFREP with 0.5 mol% amphiphilic dodecylbenzenesulfonic acid (DBSA) in aqueous system. It was found that the strong lipophilicity of DBSA accelerated its enrichment on EP surface, and further promoted the diffusion of DBSA and H2O to the resin bulk phase. As a result, the degradation ratio of the EP powder reached 100 % at 190 °C only in 10 h. The characterization of FT-IR and NMR proved that the degradation mechanism of EP was the selective cleavage of C-N bond catalyzed by H+. The resin degradation products (RDP) containing active hydrogen were used to prepare polyurethane (PU) with good mechanical properties. This method achieves complete recycling of waste CFREP in aqueous systems.

Hydrolytic degradation and biomineralization of amine-cured epoxy resin based on glycidate

Hydrolytic degradation and biomineralization of amine-cured epoxy resin based on glycidate

Mechanical and electrical performance of glass fiber reinforced plastic insulation for cryogenic application in fusion magnet irradiated in fast breeder reactor

In a superconducting (SC) magnet fusion reactor, the insulation material used has to withstand significant fluxes of neutrons and neutron-induced gamma radiation. Epoxy-based glass fiber-reinforced plastic (GFRP) composites are the insulation system for fusion magnets and are highly demanding. This insulation system requires excellent mechanical and electrical performance under mixed neutron and gamma radiation at cryogenic temperatures. The insulation material developed consists of boron-free S-glass fiber impregnated with a two-component modified Diglycidyl ether of Bisphenol-A (DGEBA) epoxy resin. An anhydride-cured DGEBA resin system is not suitable for cryogenic temperatures. Therefore, to overcome this thermal stress issue in cryogenic components of SC magnets, a high-toughness, flexible, aromatic amine-cured epoxy resin system was developed for the insulation system. In order to assess the radiation resistance for mechanical and electrical properties, the composite samples were irradiated in the fast breeder test reactor (FBTR) at IGCAR, Kalpakkam, India. The irradiation experiment was carried out for a neutron fluence of 1.0E+21 n/m2 and a gamma dose of 0.4 MGy at a full reactor power of 32 MWt. The tensile strength, interlaminar shear strength, and breakdown strength measurements were investigated before and after irradiation at room temperature and 77 K. The test results indicate that no significant degradation was observed in the properties of the irradiated samples up to the above-mentioned radiation doses.

Base-Mediated Depolymerization of Amine-Cured Epoxy Resins

Base-Mediated Depolymerization of Amine-Cured Epoxy Resins

Evaluation of healable epoxy matrices as covalent adaptive networks in uniaxial compression

Vitrimers provide dynamic bonding that can allow a degree of self-healing capability in cross-linked resins. A commercial amine-cured epoxy resin, Prime 27, showed a compressive yield stress, measured in compression, of 88 ± 2 MPa and a compression modulus of 3.41 ± 0.03 GPa. This base resin was modified by incorporating various proportions of two commercial vitrimers, either Thioplast EPS35 (an aliphatic epoxy-terminated polysulfide) or Vitrimax T130 (an imine-cured DGEBA epoxy resin). The addition of increasing amounts of Thioplast EPS35 into the resin led to a rapid drop in the glass transition temperature of the matrices and also a reduction in compressive performance. After an initial test in quasi-static, uniaxial compression, samples containing vitrimers were heated for 1 h at 100 °C and then subjected to a second compression test; all of the matrices loaded with Thioplast EPS35 were able to recover their full initial compression performance. Addition of increasing amounts of Vitrimax T130 to the same commercial epoxy resin did not cause any change in its glass transition temperature. However, after initial compression testing, followed by heating (1 h at 100 °C), only the formulation containing 40 wt% Vitrimax T130-loaded matrix regained its full initial compressive performance. Optimal results in terms of healing capability, measured as the recovery of the initial compression performance during a second identical test, following a heating step, were achieved by incorporating 10 wt% of EPS35 or 40 wt% Vitrimax T130, with little to no drop in glass transition temperature. For these selected formulations, the incorporation of 10% Thioplast EPS35 in Prime 27 gave a yield stress of 83 ± 2 MPa and a compression modulus of 3.13 ± 0.02 GPa, while the addition of 40% Vitrimax T130 gave a yield stress of 79 ± 2 MPa and a compression modulus of 3.30 ± 0.02 GPa.

Statistical and Artificial Neural Network Coupled Technique for Prediction of Tribo-Performance in Amine-Cured Bio-Based Epoxy/MMT Nanocomposites

This study explores the effects of four independent variables—the nanoclay weight percentage, sliding velocity, load, and sliding distance—on the wear rate and frictional force of nanoclay-filled FormuLITETM amine-cured bio-based epoxy composites. An experimental design based on the Taguchi method revealed diverging optimal conditions for minimizing the wear and frictional force. These observations were further validated using a Back-propagation Artificial Neural Network (BPANN) model, demonstrating its proficiency in predicting complex system behavior. Material characterization, conducted through Scanning Electron Microscopy (SEM) and Energy-dispersive X-ray Spectroscopy (EDS), illustrated the homogeneous distribution of the nanoclay within the FormuliteTM matrix, which is crucial for enhancing the load transfer and stress distribution. Atomic Force Microscopy (AFM) analysis indicated that the incorporation of nanoclay increases the surface roughness and peak height, which are important determinants of the material performance. However, an increase in the nanoclay percentage decreased these attributes, suggesting an interaction saturation point. Due to their augmented mechanical properties, the present study underscores the potential of amine-cured bio-based epoxy systems in diverse applications, such as automotive, aerospace, and biomedical engineering.

Association between Serviceability and Recyclability of Amine-Cured Epoxy Thermosets

Association between Serviceability and Recyclability of Amine-Cured Epoxy Thermosets

Thermo-mechanical and insulating robust epoxy vitrimer for fully recyclable fiber reinforced composites relied on salen agent

Environmental concerns raise the urgent demand of recyclable materials for electrical and electronic applications. Epoxy and its glass fiber reinforced composites are the most widely used materials in these areas, but are generally unrecyclable. Herein, we reported a recyclable epoxy vitrimer and its glass fiber reinforced composite by using salen agent and DGEBA-type epoxy to ensure its molecular design flexibility and industrial adaptability. Comparing with the conventional amine-cured epoxy, the obtained epoxy vitrimer shows a higher glass transition temperature of 140 °C, a superior tensile strength of 86.7 MPa and an enhanced breakdown strength (180 MV m−1). Furthermore, based on the reversible imine-imine and amine−imine exchange reactions, the epoxy vitrimer could be recycled by both mechanical and chemical methods. An admirable recycling efficiency was achieved based on electrical properties. Moreover, its corresponding glass fiber reinforced composites could be recycled in a closed-loop way while the reclaimed fabric was comparable to its origin. This study demonstrates the potential application of salen agent to develop fully recyclable electrical insulating component and opens a window to further improve the material properties of epoxy vitrimer based on the great design flexibility of salen agent.

Tuning the properties of bio-based epoxy resins by varying the structural unit rigidity in oligomers and curing procedures

Bio-based epoxy resins, which will replace petroleum-based ones, are gaining attention. In this work, three magnolol-based epoxy oligomers with varied structural unit rigidities (biphenyl, monophenyl, and aliphatic chains) were synthesized. Both the processability and the reactive activation of curing systems improved as structure unit rigidity decreased. “First-time curing resins” had only an epoxy-amine curing network, while “second-time curing resins” had dual curing networks. The structural unit rigidity regulated the thermal properties of first-time curing resins, which decreased with decreasing rigidity. However, P-MHQ-EP-n/DDM-1 had better mechanical properties than DGEBA/DDM, e.g., its impact strength (6.2 kJ/m2 vs. 4.5 kJ/m2) increased by 37.8%, indicating that moderate structural unit rigidity allows for good deformation and absorbs impact energy due to chain mobility. The second-time curing resins with increased crosslinking sites had better heat resistance (with a Tg increase of over 71.6%), thermal stability, and char residue in comparison to the first-time curing resins. More impressively, P-MBP-EP-n/DDM-2 and P-MHQ-EP-n/DDM-2 obtain a LOI values greater than 39.0% and UL 94V-0 ratings because they have high-rigidity structural units and high crosslinking densities. In conclusion, well-balanced biobased epoxy resins could be made by regulating the structure-unit rigidity of epoxy oligomers and curing procedures.

Interfacial Enhancement by CNTs Grafting towards High-Performance Mechanical Properties of Carbon Fiber-Reinforced Epoxy Composites.

The problem of interfacial interaction between carbon fiber (CF) and the matrix is the key to the failure of CF-reinforced plastic (CFRP). A general strategy to enhance interfacial connections is to create covalent bonds between the components, but this usually reduces the toughness of the composite material, which in turn limits the range of applications of the composite. In this study, carbon nanotubes (CNTs) were grafted onto the CF surface using the molecular layer bridging effect of the dual coupling agent to prepare multi-scale reinforcements, which significantly improved the roughness and chemical activity of the CF surface. By introducing a transition layer structure between the carbon fibers and the epoxy resin matrix to moderate the large modulus and scale differences between them, the interfacial interaction was improved while enhancing the strength and toughness of CFRP. We used amine-cured bisphenol A-based epoxy resin (E44) as the matrix resin and prepared the composites by the hand-paste method and performed tensile tests on the prepared composites, which showed that, compared with the original CF-reinforced composites, the modified composites showed an increase in tensile strength, Young's modulus and elongation at break by 40.5%, 66.3% and 41.9%, respectively.

Catalytic disconnection of C–O bonds in epoxy resins and composites

Fibre-reinforced epoxy composites are well established in regard to load-bearing applications in the aerospace, automotive and wind power industries, owing to their light weight and high durability. These composites are based on thermoset resins embedding glass or carbon fibres1. In lieu of viable recycling strategies, end-of-use composite-based structures such as wind turbine blades are commonly landfilled1–4. Because of the negative environmental impact of plastic waste5,6, the need for circular economies of plastics has become more pressing7,8. However, recycling thermoset plastics is no trivial matter1–4. Here we report a transition-metal-catalysed protocol for recovery of the polymer building block bisphenol A and intact fibres from epoxy composites. A Ru-catalysed, dehydrogenation/bond, cleavage/reduction cascade disconnects the C(alkyl)–O bonds of the most common linkages of the polymer. We showcase the application of this methodology to relevant unmodified amine-cured epoxy resins as well as commercial composites, including the shell of a wind turbine blade. Our results demonstrate that chemical recycling approaches for thermoset epoxy resins and composites are achievable.

A cure kinetics investigation of amine-cured epoxy by Rheo-Raman spectroscopy

In a companion paper, fluorescence lifetime imaging revealed a heterogeneous morphology at macroscopic and molecular length scales in a bis-epoxide blend composed of diglycidyl ether of bisphenol-A (DGEBA) and diglycidyl ether of 1,4-butanediol (DGEBD) cured with meta-phenylenediamine (m-PDA) with a strategically integrated mechanophore. This macroscopic heterogeneity most likely originates during the crosslinking process, which motivates measurements of both the reaction progress and the mechanical properties under controlled cure schedules. Rheo-Raman spectroscopy provides simultaneous measurements of Raman spectra to monitor vibrational modes relevant to the crosslinking process and rheology to track the viscoelastic shear modulus during crosslinking. Here, rheo-Raman measurements confirm that the molecular level heterogeneity is influenced by reaction kinetics differences of the two miscible bis-epoxides with m-PDA. In the companion paper the macroscopic heterogeneity was linked to the self-association of oligomers in DGEBD through interchain hydroxyl-hydroxyl hydrogen bonding. Rheo-Raman studies also revealed that this self-association slows down the overall cure-kinetics of the DGEBD/m-PDA and DGEBA/DGEBD/m-PDA curing reaction, thereby supporting the link between the macroscopic heterogeneity and oligomers in DGEBD.

Protonation of Strained Epoxy Resin under Wet Conditions via First-Principles Calculations Using the H+-Shift Method.

A significant challenge in adhesive bonding is the accelerated breaking of stretched adhesives under wet conditions, which is known as cohesive failure. One group of commonly used adhesives consists of the amine-cured epoxy resins. Based on deprotonation free-energy calculations of the unstrained resin in water, it has recently been proposed that these adhesives can undergo failure through breakage originating at the protonated amine group under neutral or acidic conditions [J. Phys. Chem. B 2021, 125, 8989-8996]. In this study, we comprehensively investigated the degree of protonation of the amine group under both stretched and compressed conditions by devising a robust first-principles protonation calculation method applicable to strained materials. It was found that the amine group was partially protonated in neutral water at 298 K and that the amine group was protonated when the epoxy resin was stretched to a greater extent in water, and vice versa. These findings support the physicochemical cause of cohesive failure due to protonation of the amine group in the stretched amine-cured epoxy resins.

Ionic Liquids as Alternative Curing Agents for Conductive Epoxy/CNT Nanocomposites with Improved Adhesive Properties

Good dispersion of carbon nanotubes (CNTs) together with effective curing were obtained in epoxy/CNT nanocomposites (NCs) using three different ionic liquids (ILs). Compared to conventional amine-cured epoxy systems, lower electrical percolation thresholds were obtained in some of the IL-based epoxy systems. For example, the percolation threshold of the trihexyltetradecylphosphonium dicyanamide (IL-P-DCA)-based system was 0.001 wt.%. The addition of CNTs was not found to have any significant effect on the thermal or low-strain mechanical properties of the nanocomposites, but it did improve their adhesive properties considerably compared to the unfilled systems. This study demonstrates that ILs can be used to successfully replace traditional amine-based curing agents for the production of electrically conductive epoxy/CNT NCs and adhesives, as a similar or better balance of properties was achieved. This represents a step towards greater sustainability given that the vapor pressure of ILs is low, and the amount needed to effectively cure epoxy resins is significantly lower than any of their counterparts.