Latent nucleophilic initiators for melt processing phenolic–epoxy matrix composites

Phenolic–epoxy matrix compositions have been investigated for preparing tough, flame retardant fiber reinforced composites. Melt composite fabrication with these materials requires latent initiators for the curing reaction due to the high viscosities of the matrix resins. The objective is to provide a means for ensuring stability (i.e. no reaction) of the phenolic–epoxy matrix resins at 140°C while the matrix is applied to the fiber preforms, then to effect rapid reaction at the cure temperature of 180–200°C. We have investigated the strategy of embedding the initiators for matrix cure within the fiber sizing to achieve this goal. The cure times can be significantly reduced since high initiator levels can be employed with this approach. Reaction kinetics were investigated by differential scanning calorimetry to predict composite cure times. Monomeric initiators such as tris(2,4,6-trimethoxyphenyl)phosphine encapsulated in thermoplastic polyimide fiber sizings yielded promising results. Composite toughness and fatigue properties of these flame retardant composites are excellent.     

Aminimide as hardener/curing promotor for one part epoxy resin composition

Three kinds of aminimide compounds were examined as latent hardeners/promotors for epoxy resins. Since aminimides are thermolyzed to generate tertiary amine and isocyanate, the compounds are useful as polymerization initiators for the epoxy group as well as promotors for epoxy–acid anhydride reaction. The pot life was over 30 days at 40°C for a formulated one-part epoxy resin system. In comparison with epoxy resins cured with conventional hardeners, several interesting characteristics of the mechanical and electrical properties were observed. In particular, the epoxy resins cured by aminimides exhibited high tensile strength and high impact strength, which make them excellent curing agents for adhesive applications. The reasons for these unique properties are discussed.     

复合材料用中温固化环氧树脂体系的研究

研究了1^#、2^#两种复合材料用中温固化环氧树脂配方体系。对这两种固化体系的凝胶特性、放热特性、潜伏性促进机理、贮存稳定性及力学性能进行了比较。结果表明,1^#、2^#两种配方体系均可实现中温固化;1^#配方的潜伏性、贮存稳定性优于2^#配方;而2^#配方的NOL环性能、复合材料单向板材力学性能优于1^#配方,这可能是由于1^#配方体系中的双氰胺和促进剂取代脲A在环氧树脂中的分散不够均匀,从而影响了其复合材料的力学性能。     

Exploration of Epoxy Resins,Hardening Systems,and Epoxy/Carbon Nanotube Composite Designed for High Performance Materials: A Review

Epoxy resins, is an important class of reactive polymers, have been reported to be toughened by nanoparticles. Carbon nanotube is a tubular cylinder ofcarbonatoms having extraordinary mechanical, electrical, and thermal properties. In this article, present state of epoxy/carbon nanotube composite is given. Types of epoxy and hardening agents commonly used in composite processing have been thrashed out. Frequently used fabrication techniques are discussed with particular emphasis on evaluating dispersion state of nanotube. Epoxy/carbon nanotube composites offer substantially improved properties compared to traditional fiber-reinforced epoxy composites. Finally, potential relevance for efficiently transforming filler properties to matrix facilitating aerospace relevance is conversed.     

微波技术在环氧树脂及其复合材料中的应用

论述了近年来微波固化技术在环氧树脂及其复合材料固化中的应用,重点比较了微波固化与传统热固化后环氧树脂及其复合材料的力学性能、热性能和粘结强度的变化,并对环氧树脂复合材料微波固化的研究进行了展望。     

Glass Fiber Reinforced Composites and Thermal Study of Flame Retardant Epoxy Resin Systems Using Anhydride Curing Agents

Differential scanning calorimetric (DSC) curing kinetics of the epoxy systems composed of conventional, tetrafunctional, and phosphorylated epoxy resins were investigated using different anhydrides as curing agents and triethylamine as curing catalyst. The dynamic scans were analyzed to estimate the activation energy and the order of reaction for the curing process using some empirical relations. The thermal stability of the cured epoxy resins was studied by thermogravimetric analysis in nitrogen atmosphere at a heating rate of 10°C/min. Glass fiber reinforced composites were fabricated and evaluated for their limiting oxygen index, mechanical properties, dielectric properties, and chemical resistance. The incorporation of an epoxy fortifier showed significant improvement in mechanical properties.     

Preparation of Epoxy Resin Based on 1,5-Naphthalenediol and Its Application in Carbon Fiber-Reinforced Composites

A series of new epoxy resin base on 1,5-naphthalenediol were prepared to produce the heat-resistant carbon fiber-reinforced composites. The structures of the epoxy resins were characterized by Fourier Transform Infrared (FTIR) spectroscopy and Gel Permeation Chromatography (GPC) analyses. Dynamic curing behavior was investigated using Differential Scanning Calorimetry (DSC). The physical properties of the cured polymers were evaluated with Dynamic Thermal Mechanical Analyses (DMTA) and Thermogravimetric Analyses (TGA). The results showed that the cured polymer exhibited a higher glass transition temperature (T_g) of 251.1°C and better thermal stability. Such properties make the resin highly promising for heat-resistant composite applications.     

Thermo-mechanical behaviors of epoxy resins reinforced with nano-Al2O3 particles

This study examined the thermo-mechanical behavior of epoxy resins/nano-Al₂O₃ composites including the curing behavior, thermal stability, dynamic mechanical properties and thermal mechanical properties. The DSC curve peak temperature of the composites was decreased by the addition of nano-Al₂O₃. The thermal stability of the composites was similar to that of the neat epoxy resins. Dynamic mechanical analysis (DMA) indicated the glass transition temperature of the composites to be approximately 11 °C higher than that of the neat epoxy resins. The coefficient of thermal expansion (CTE) of the composites decreased with increasing nano-Al₂O₃ content.     

Polymerization of epoxy resins initiated by metal complexes

BACKGROUND: Processing parameters and material properties of epoxy resins can be vastly influenced by choice of curing agent. In this work, metal complexes were investigated as initiators for anionic and cationic epoxide polymerization. Systems for thermally induced and electron beam‐induced curing are described. RESULTS: Zinc or cobalt imidazole complexes of the type [M(imidazole)₂(anion)₂] are efficient initiators for anionic polymerization of glycidyl‐based epoxy resins. The complexes can be employed to prepare tailored resin systems ranging from fast curing systems at slightly elevated temperatures to systems with very high thermal latencies curable at temperatures far above 150 °C. Silver complexes [Ag(L)_n]SbF₆ (L = crown ether or alkene) are highly efficient initiators for cationic curing and low initiator contents of around 1% are sufficient to reach high degrees of crosslinking. The complexes are excellent initiators for both thermally induced and electron beam‐induced polymerizations. CONCLUSION: Metal complexes are powerful initiators for the homopolymerization of epoxy resins and can be designed not only for anionic and cationic polymerization but also for thermal and radiation curing. Based on this study and additional work, a library can be compiled which allows retrieval of optimized metal–ligand–anion combinations and adjustment of the initiators to the respective processing and material demands. Copyright © 2009 Society of Chemical Industry     

Modified Cyclohexanone-Formaldehyde Resin as an Epoxy Resin Curing Agent

Cyclohexanone-formaldehyde (CHF) resin was brominated and the brominated CHF (BCHF) was then reacted with excess aromatic diamines. The aminated CHF resins designated as ACHFs (modified ketone resin) were characterized and then applied as epoxy resin curing agents. Thus, the curing of the commercial epoxy resin diglycidil ether of bisphenol-A (DGEBA) by ACHFs was monitored by differential scanning calorimetric (DSC), based on the the DSC scans, the glass fiber-reinforced composites of DGEBA-ACHF systems were prepared and characterized by chemical resistivity and mechanical properties.     

One-component epoxy adhesive for repair of cell phone board

The development of a one-component epoxy adhesive for cell phone board repair was described. The most important goal of this study is to obtain long storage stability in conjunction with the curing reaction process at a relatively low temperature of 95 °C. Bisphenol-A type, bisphenol-F type, and NBR-based epoxy resins were used as the basic resins. Dicyandiamide (DICY) was used as a curing agent, and 2-methylimidazole (2MI) was used as an accelerator. 2MI was encapsulated using a copolymer of methacrylic acid and dodecyl methacrylate to achieve latent curing performance. After mixing the epoxy resin with DICY and encapsulated 2MI, this curing system showed excellent storage stability with almost no viscosity increase for 2 months at 20 °C, and full curing was achieved at 95 °C for 50 min. We determined the optimum formulation of the epoxy adhesive for adhesion of a cell phone board after the measurement of physical properties.     

A novel latent initiator for cationic polymerizations of epoxides: Composite catalysts containing aluminum complexes phase‐separated in epoxides

A novel latent initiator for cationic polymerizations of epoxides heterogeneous aluminum complex/phenol initiator (HAP) is reported. Phase transitions are newly employed for realizing the latent property. The initiator consists of 4,4′‐dihydroxydiphenylsulfone and aluminum tris(alkyl acetoacetate), with the alkyl group containing more than 18 carbons. The composite initiator is phase‐separated and dispersed uniformly in epoxy resins at room temperature. When the mixture is heated to a temperature greater than 70°C, the composite initiator makes clear mixtures with epoxy resins because of the phase change in the aluminum complexes. Homogeneous epoxy resins containing these composite initiators are ready for various types of processing, including impregnation and injection. Gelation occurs rapidly at temperatures greater than 100°C. The phase change in the initiator makes it possible for the epoxy compounds to have a long storage stability at room temperature and a high curing speed at greater than 100°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1046–1053, 2002     

Thermally curable adhesive tapes with complex catalyst system for fabricating semiconductor packages

Thermal curing of adhesive films was investigated to facilitate the fabrication of a reliable bonding for semiconductors. The formulated adhesive films contained acrylic polymer, epoxy resins, phenol resin, and an imidazole derivative that was the catalyst for curing the epoxy resins with phenol resin. The solubility, thermally latent characteristics, mechanical and adhesive properties of 2‐methylimidazole/boron trifluoride (2MZ/BF3), and 2MZ/aluminum trisacetylacetonate (AlAC) were investigated. It was found that 2MZ/BF3 and 2MZ/AlAC had excellent solubility in adhesive materials and they had excellent latent characteristics as thermal curing catalysts for epoxy resins, whereas conventional catalysts (2MZ and 2‐phenyl‐4, 5‐dihydroxymethylimidazole (2PHZ)) could not achieve both excellent solubility and thermally latent characteristics. The mechanical and adhesive properties of the post‐thermal‐cured adhesive film that contained 2MZ/BF3 or 2MZ/AlAC were comparable to those of the post‐thermal‐cured adhesive films that contained conventional catalysts. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Matrix formulation and interfacial enhancement of an aeronautical carbon fabric/epoxy composites fabricated via resin transfer molding (RTM) technique

Flexural strength and interlaminar shear strength of fiber-reinforced composites are among the most concerned properties in the aeronautical sector, which are ameliorated in combination through matrix formulation and interfacial enhancement in this study. A thermosetting matrix resin consisting of diglycidyl ether of bisphenol A and diglycidyl ester of aliphatic cyclo was formulated to cater to the requirements of carbon fabric/epoxy composites fabricated by resin transfer molding (RTM) technique. The toughness and thermal stability of the formulated epoxy resin were studied in consideration of the compromise among processability, thermal and mechanical properties for potential aeronautical applications. The processability of the matrix resin suitable for RTM technique was evaluated with respect to temperature-dependent and time-dependent viscosity. A regime for the curing and post-curing cycles was established according to the differential scanning calorimeter data. Air plasma is introduced herein as a technique to enhance the interfacial adhesion of carbon fabric/epoxy composites. Composites based on the epoxy system and plasma-treated carbon fabric were fabricated using the RTM technique. The reactive groups introduced by plasma treatment are responsible for the significant improvements of mechanical properties of the resulting composites. The microscopy pictures of the fracture surfaces confirm that the failure mode of carbon fabric/epoxy composites has changed initially from primarily adhesive failure to cohesive failure.     

聚三唑酯树脂的合成及其性能

通过酯化反应合成丁二酸二炔丙醇酯(DPS)、间苯二甲酸二炔丙醇酯(DPIP)、对苯二甲酸二炔丙醇酯(DPP),与三官能团叠氮化合物(TAMTMB)反应,制备了3种热固性聚三唑酯(PTAE)树脂,研究了树脂的加工特性、固化行为、树脂固化物的力学性能,制备和表征了T700单向碳纤维增强PTAE树脂复合材料。结果表明,PTAE树脂具有良好的加工性能,可在较低温度(80℃)下固化;固化后的PTAE树脂的玻璃化转变温度(Tg)受主链结构影响,3种树脂的Tg均高于140℃,浇铸体弯曲强度高于170 MPa,T700单向纤维增强PTAE树脂复合材料的常温弯曲强度高于1500 MPa。     

Effect of curing agent on the properties of mineral silica filled epoxy composites

Polymer materials have been used extensively as the organic substrate materials in electronic packaging industry. The mechanical, thermal, and morphology properties of the alternative low cost composites have been investigated in this article. One of the materials is epoxy resin cured by aliphatic amine, and the other is cured by aromatic amine. It was found that the physical, mechanical, and thermal properties of epoxy resins are strongly depended on the curing agents. Morphology changed differently in these two epoxy‐curing systems. Crosslink density obtained from rubbery modulus in dynamic flexural storage modulus showed aromatic amine functionality group that gives higher crosslink density and increased in physical, mechanical, and thermal properties. POLYM. COMPOS., 29:27–36, 2008. © 2007 Society of Plastics Engineers     

多面体低聚倍半硅氧烷在环氧树脂改性中的应用进展

综述了近几年多面体低聚倍半硅氧烷(POSS)在环氧树脂改性中的应用。POSS单独修饰环氧树脂,可提高其力学性能及热稳定性能;POSS协同9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物等功能性分子一起修饰环氧树脂,可增强其阻燃性能;POSS与碳纳米管、石墨烯等纳米材料共同修饰环氧树脂,可提高纳米材料在环氧树脂中的分散性,改善纳米复合材料的导电能力和黏结强度等性能;POSS与纤维共同修饰环氧树脂,可有效增强纤维与环氧树脂间的界面性能。最后展望了POSS修饰改性环氧树脂的未来方向:开发更简易的引入方式,引入更多样的官能分子,协同多种纳米材料修饰环氧树脂。     

Novel cycloaliphatic epoxy resins. II. Curing reaction with BF3MEA and its cured properties

The BF₃MEA curing reaction and the cured properties of novel cycloaliphatic epoxy resins (CE-resins), which were derived from an octadienyl compound, were studied. Gelation time and the DSC scan of the CE resins, with BF₃MEA hardener, proved that the reactivity of the CE resins is intermediate among the reactivities of the conventional resins; it was found that the CE resins react faster than DGEBA, but slower than the conventional cycloaliphatic epoxy resins. The pot life of the CE- (III) resin with BF₃MEA hardener proved to be over 30 days at a temperature of 20°C. The thermal properties are affected by the amount of BF₃MEA used and the curing conditions. CE-(III) showed the highest HDT of over 200°C with 2–3 phr of BF₃MEA. The flexural properties of CE-(I) proved to be flexible and tough. CE-(II) exhibited the highest strength and elongation, while CE-(III) had the same flexural properties as DGEBA. Furthermore, the blending of CE-(II) with DGEBA produced greater flexural strength and greater elongation than each original resin had. The thermal stability at elevated temperature and the water resistance of the cured CE resins proved to be inferior to those of DGEBA and novolac epoxy resin, probably due to the use of BF₃MEA. These results suggest the CE resin will provide a new application for a one-component curing system for composites. © 1993 John Wiley & Sons, Inc.     

Comparison between microwave and thermal curing of glass fiber–epoxy composites: Effect of microwave‐heating cycle on mechanical properties

The objective of this study was to compare the mechanical properties between epoxy composites cured by thermal heating and microwave heating. Epoxy‐anhydride resins reinforced with glass fiber were cured in a domestic microwave oven and in a thermal oven. Hardening agents included methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride. Microwave curing was carried out at various conditions, including 1‐, 2‐, and 3‐step heating cycle, whereby each cycle employed different power level and time. Mechanical properties were tested according to ASTM standards. It is found that the microwave‐cured composites produced mechanical properties as good as the thermally cured composites. The 2‐ and 3‐step heating cycle used in the microwave curing process produced better mechanical properties higher than those obtained from the microwaved 1‐step and thermally curing process. This is attributed to the slow increase in temperature during the beginning of the microwave curing process whereby the very low power level was applied in the first cycle of the multistep heating process. This affected the slower rate of viscosity increment, resulting in better wettability of the glass fiber with enhanced interfacial adhesion between the fibers and the resins. The viscosity of resins affected the homogeneity of the crosslinked structure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1059–1070, 2006     

Perspectives of Epoxy/Graphene Oxide Composite: Significant Features and Technical Applications

In this article, advancement in epoxy/graphene oxide composites is presented. These materials are comprised of graphene oxide (GO) as filler (carbon-based material, thermodynamically stable, two-dimensional, planar and layered structure). Due to improved properties (mechanical response, low density, electrical resistance, and thermal stability), epoxy resins are used in several applications. Graphene oxide proposes unique properties to epoxy composites as high surface area, thermal and electrical conductivity as well as mechanical and barrier properties, relative to neat matrix. The corresponding significance of epoxy/GO-based materials, related challenges, and potential exploitation regarding technical applications (aerospace, gas sensor, electronic devices, etc.) have been overviewed.