Epoxy-based composite adhesives with improved lap shear strengths at high temperatures for steel-steel bonded joints

High-performance room temperature-cure epoxy structural adhesives utilizing simplified formulation are developed. The developed structural adhesive consists of diglycidyl ether of bisphenol A (DGEBA) and novolac epoxy blend as a base resin, micrometer-sized silica particles as a reinforcing filler, and triethylenetetramine as a curing agent. The developed ambient temperature-cure epoxy structural adhesive with optimized formulation exhibits outstanding properties including high glass transition temperature of 95°C, high thermal stability with degradation temperature at 5% weight loss of 364°C, exceptionally high rubbery plateau modulus of 320 MPa, good flame-retardant characteristics with limiting oxygen index of 40, and high single lap shear strength for single lap steel-steel bonded joint of 548 MPa at the temperature of 80°C. The silica-filled DGEBA/novolac epoxy composite adhesive is a potential candidate for applying as a structural adhesive for construction with long-term durability.     

Adhesion Improvement of Bio-Based Epoxy in Environmentally Friendly and High-Performance Natural Fiber-Reinforced Composites

Developing robust bio-based epoxy against petroleum-derived epoxy is necessary for environmentally friendly and high-performance natural fiber-reinforced composites. A bio-based vanillin epoxy (VE) is synthesized from the lignin-derived vanillin, and a thermoset resin is prepared after mixing it with a 4,4′-diaminodiphenyl methane (DDM) hardener. Further, it is infused in high-cellulose-containing alkali-treated jute fiber (TJF) mats through a simple approach to enhance the adhesion between the VE-DDM and TJF. Bio-based VE-DDM resin shows better compatibility with TJF than petroleum-derived bisphenol A diglycidyl ether (DGEBA) epoxy. The bio-based VE-DDM/TJF composite demonstrates the T_gis ≈165 °C, tensile strength is ≈83.12 ± 3.80 MPa, and Young's modulus is ≈2.86 ± 0.10 GPa with excellent flexural strength (138.72 ± 3.81 MPa) and flexural modulus (8.01 ± 0.11 GPa). It also shows merits regarding hydrophobicity, reduced water absorption ability, durability, and chemical resistance in an acidic medium. The natural fiber-reinforced VE composites pave the way to produce environmentally friendly and high-performance composites for structural applications.     

Epoxy–imide resins from N‐(4‐ and 3‐carboxyphenyl)trimellitimides. I. Adhesive and thermal properties

Epoxy–imide resins were obtained by curing Araldite GY 250 (diglycidyl ether of bisphenol‐A and epichlorohydrin; difunctional) and Araldite EPN 1138 (Novolac–epoxy resin; polyfunctional) with N‐(4‐ and 3‐carboxyphenyl)trimellitimides derived from 4‐ and 3‐aminobenzoic acids and trimellitic anhydride. The adhesive lap shear strength of epoxy–imide systems at room temperature and at 100, 125, and 150°C was determined on stainless‐steel substrates. Araldite GY 250‐based systems give a room‐temperature adhesive lap shear strength of about 23 MPa and 49–56% of the room‐temperature adhesive strength is retained at 150°C. Araldite EPN 1138‐based systems give a room‐temperature adhesive lap shear strength of 16–19 MPa and 100% retention of room‐temperature adhesive strength is observed at 150°C. Glass transition temperatures of the Araldite GY 250‐based systems are in the range of 132–139°C and those of the Araldite EPN 1138‐based systems are in the range of 158–170°C. All these systems are thermally stable up to 360°C. The char residues of Araldite GY 250‐ and Araldite EPN 1138‐based systems are in the range of 22–26% and 41–42% at 900°C, respectively. Araldite EPN 1138‐based systems show a higher retention of adhesive strength at 150°C and have higher thermal stability and T_g when compared to Araldite GY 250‐based systems. This has been attributed to the high crosslinking possible with Araldite EPN 1138‐based systems arising due to the polyfunctional nature of Araldite EPN 1138. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1729–1736, 2000     

Synthesis of a Sustainable and Bisphenol A-Free Epoxy Resin Based on Sorbic Acid and Characterization of the Cured Thermoset

In the present study, an epoxy compound, 1,2-epoxy-6-methyl-triglycidyl-3,4,5-cyclohexanetricarboxylate (EGCHC) synthesized from sorbic acid, maleic anhydride, and allyl alcohol is proposed. Using commodity chemicals, a bio-based carbon content of 68.4 % for the EGCHC resin is achieved. When cured with amine hardeners, the high oxirane content of EGCHC forms stiff cross-linked networks with strong mechanical and thermal properties. The characterization of the epoxy specimens showed that EGCHC can compete with conventional epoxy resins such as DGEBA. A maximum stiffness of 3965 MPa, tensile strength of 76 MPa, and T_g of 130 °C can be obtained by curing EGCHC with isophorone diamine (IPD). The cured resin showed to be decomposable under mild conditions due to the ester bonds. The solid material properties of EGCHC expose its potential as a promising bisphenol A, and epichlorohydrine free alternative to conventional petroleum-based epoxies with an overall high bio-based carbon content.     

Preparation of high peel strength and high anti-aging epoxy adhesive that used for bonding aluminum alloy without surface treatment

In the case of bonding of aluminum alloy, surface pretreatment have been widely adopted for adherends so as to achieve superior adhesive performance. However, the strict surface treatment of the aluminum alloy cannot be implemented without special equipment and the mechanical properties, corrosion resistance and aging resistance of the common adhesives cannot meet the demand without surface treatment. Here, acrylic oligomer modified by carboxyl terminated organosilicon and nano alumina were used to modify an epoxy formulation based on a classical DGEBA monomer to produce a high peel strength epoxy adhesive that can be used without surface pretreatment. The peel strength and the shear strength of the adhesive could reach 7.18?N/cm and 18.75?MPa, respectively, and could be well maintained under ?70?°C and 100?°C. The novel adhesive also has good heat aging resistance, water resistance and artificial seawater resistance. SEM and XPS were used to investigate mechanism of aging resistance of modified adhesives without surface treatment.     

含氮杂环二胺固化双酚F环氧胶粘剂的研究

以1,2-二氢-2-(4-氨基苯基)-4-[4-(4-氨基苯氧基)-苯基]-二氮杂萘-1-酮(DHPZ-DA)为固化剂,采用示差扫描量热法(DSC),TGA,红外光谱及剪切强度测试研究了双酚F环氧树脂/DHPZ-DA粘接体系固化行为及耐热性。由Kissinger和Ozawa方法计算得到固化体系的表观活化能分别为80.1 kJ/mol和84.3kJ/mol。由Crane方程求得的表观反应级数为0.93。该胶粘剂体系Tg>200℃,当双酚F环氧树脂与DHPZ-DA固化剂的物质的量比为10∶4时,其室温剪切强度与150℃老化24 h后的剪切强度均大于12 MPa,表现出良好的耐热性。     

硅改性BPA-PA酚醛环氧树脂导电胶的合成及性能

以双酚A多聚甲醛酚醛树脂（BPA-PA酚醛树脂）、二甲基二甲氧基硅烷和环氧氯丙烷为原料,通过酯交换反应和亲核取代反应得到硅改性BPA-PA酚醛环氧树脂。采用傅里叶变换红外光谱（FTIR）、X射线光电子能谱（XPS）分析进行结构确证。结合非等温DSC、T-β外推直线和FTIR分析研究了最佳固化工艺条件。探讨了不同硅烷添加量对硅改性BPA-PA酚醛环氧树脂性能的影响。最后以硅改性BPA-PA酚醛环氧树脂为基体树脂,加以导电填料和助剂,制备出中温型导电胶。对导电胶进行拉伸剪切强度、体积电阻率和热重测试分析,结果显示：自制硅改性BPA-PA酚醛环氧树脂导电胶拉伸剪切强度达到20.18MPa、体积电阻率达到7.44×10^-4Ω·cm,残炭量达到68.89%。相对市售E-51环氧树脂所制导电胶,自制硅改性BPA-PA酚醛环氧树脂导电胶拉伸剪切强度提高5.73MPa,体积电阻率降低3.86×10^-4Ω·cm,残炭量提高7.49%。     

Evaluation of a structural epoxy adhesive for timber-glass bonds under shear loading and different environmental conditions

This article presents a study of timber-glass adhesive joints. It examines the shear specimen and shear tools preparation process and the evaluation of the results backed up with an overview of existing similar studies. The chosen adhesive was a cold-curing two-component structural bonding epoxy resin (Mapei Adesilex PG1). The shear tests were performed under different temperatures and the timber samples had different moisture contents. A simple shear test tool was designed and was clamped into a universal testing machine for the shear test. The force and crosshead displacement values from the universal testing machine were used for evaluating the results. The environmental conditions of 20 °C and 5% timber moisture content resulted in the highest average shear strength obtained from the shear tests of the analysed joints (9.89 MPa), whereas the environmental conditions of 50 °C and 20% timber moisture content resulted in the lowest average shear strength (3.42 MPa). It was found that the joint strength is dependent on the environmental temperature and timber moisture content. Moreover, the shear specimen load-displacement behaviour at the environmental temperature of 50 °C was linear and nonlinear – depending on the timber moisture content. The most frequent failure type was timber failure. Additionally, a nonlinear contact finite element analysis was performed to demonstrate the additional shear specimen rotation due to the clearance between the shear specimen and shear tools. This impact was evaluated regarding the stress distribution in the bond line. The evaluated epoxy resin adhesive was proved to be suitable for timber-glass bonds.     

Internal stress analysis of epoxy adhesively-boned joints based on their thermomechanical properties at cryogenic temperature

Internal stress analysis is essential to structural design of materials applied in cryogenic engineering. In this contribution, thermomechanical properties including dynamic thermomechanical properties and thermal expansion behavior of four epoxy resins, namely the polyurethane modified epoxy resin (PUE), diglycidyl ether of bisphenol A (DGEBA), tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol (TGPAP) were studied by dynamic thermomechanical analysis. Internal stress of the epoxy layer in the bonded joint was calculated based on the thermomechanical properties. Meanwhile, the structure-cryogenic property relationship of epoxy resins were investigated. Results demonstrate that internal stress in the four epoxies bonded joints is 6 ~ 21 MPa at −150°C, and is positively correlated with the average thermal expansion coefficient (CTE) of epoxy resins. TGDDM and TGPAP showed higher retention of lap shear strength both at −196°C and after temperature cycling due to their lower CTE. Morphology of the fractured surface of bonded joints demonstrated that internal stress is responsible for the severe interface failure at −196°C. It reveals that selection of epoxy resins with low CTE is beneficial for designing high-performance epoxy adhesive systems served at cryogenic temperature.     

In situ synthesis of novel biomass lignin/silica based epoxy resin adhesive from renewable resources at different pHs

Novel biomass lignin/silica composites were prepared and isolated from rice husk renewable resources at different pHs. Selective precipitation was achieved by decreasing the solution pH from 9.5 to 1.5. When pH reached 3.5, the ratio of lignin and silica mostly achieved the maximum of 1:1. We selected lignin/silica composites as reactants to replace 20?wt% bisphenol A in preparing epoxy resin. The cured novel biomass function lignin/silica-based epoxy resin adhesive showed the highest adhesive strength up to 2.68?MPa, which displayed 123% of neat epoxy resin adhesive. In addition, lignin/silica composites were depolymerized through the hydrothermal method by NaOH as a catalyst, which was used as reactants to replace 35?wt% bisphenol A in the process of in situ synthesis of epoxy resin adhesive. At this point, the high epoxy value (1.42?wt%) and large adhesive strength (3.98?MPa) of lignin/silica-based epoxy resin adhesive were obtained, which adhesive strength was 183% of neat epoxy resin adhesive. The results demonstrated that depolymerized lignin/silica-based epoxy resin adhesive showed the higher epoxy value and the adhesive strength compared with neat epoxy resin adhesive and lignin/silica-based epoxy resin adhesive. Their function in epoxy matrix resulted in better processability.     

Epoxy resin cured by bisphenol A based benzoxazine

Bisphenol A based benzoxazine was prepared from bisphenol A, formaline, and aniline. This benzoxazine was used as a hardener of the epoxy resin. Curing behavior of the epoxy resin and the properties of the cured resin were investigated. Consequently, curing reaction proceeded without a curing accelerator. The molding compound showed good thermal stability under 150°C, which corresponded to the temperature in the cylinder of injection molding. Above 150°C, the curing reaction proceeded rapidly. The cured epoxy resin showed good heat resistance, water resistance, electrical insulation, and mechanical properties compared with the epoxy resin cured by the bisphenol A type novolac. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1903–1910, 1998     

Effect of a reactive interfacial agent on the properties of a nitrile-rubber-modified epoxy film adhesive

Reactive interfacial agents are often used to homogenise the morphology of immiscible polymer blends and to improve the level of adhesion between the phases to achieve enhanced properties. This paper demonstrates the ability of hydroxyl methyl bisphenol A (HMBPA) to function as a reactive interfacial agent (compartibilizer) in a nitrile-epoxy film adhesive made from nitrile rubber (NBR) and solid epoxy resin blend. The curing of the adhesive film was achieved at 170° C by adding dicyandiamide, a latent curing agent for epoxy resin, and rubber vulcanising agents. Hydroxyl methyl bisphenol A resins with different hydroxyl methyl content, synthesised by the base-catalysed reaction of bisphenol A and formaldehyde in various mole ratios, were used to compatibilize a blend of nitrile rubber (NBR) and epoxy resin 50/50wt/wt. The effect of addition of HMBPA on the morphology, adhesive, thermal, and mechanical properties of the adhesive film was investigated. The nitrile-epoxy adhesive films were characterised by measurements of adhesive joint strength, stress-strain properties, DSC, TGA, TMA, DMA, and SEM. Results revealed that significant improvement in joint strength occurred at low levels of HMBPA, and the optimum strength was obtained at about 15 wt% of HMBPA in the blend. The hydroxyl methyl content in HMBPA was found to influence the properties of the adhesive film. The concept of strengthening the interphase between NBR and epoxy through the coupling reactions of HMBPA was used for interpreting the results. The effect of addition of silica, alumina, and aluminium fillers on the properties of the nitrile-epoxy adhesive film was also studied, and a comparison of properties with and without HMBPA is presented.     

电机用单组分环氧树脂胶粘剂的研制

通过剪切强度和剥离强度测试研究了不同环氧树脂配比,不同增韧剂及促进剂对单组分电机胶性能的影响。结果表明,CYD-128环氧与双酚F环氧质量比为80∶20,纳米丁腈橡胶粒子VP-501为增韧剂,双氰胺作固化剂,咪唑为促进剂制得的单组分环氧胶25℃和150℃的剪切强度分别达到15.9 MPa,7.3 MPa,可用于电机的低碳钢与磁体的粘接。     

Durable adhesives for large laminated timber

Large laminated timber (LT) made of hardwood is widely used as the main constitutional element of goods such as furniture, pianos and doors. A high durability of LT is essential to these products. This study focused on finding as to what adhesives were acceptable as highly durable adhesives for LT. Twelve different adhesives such as resorcinol-formaldehyde resin, aqueous emulsion-type isocyanate resin, poly(vinyl acetate) emulsion, epoxy resin, etc. were used. The durability of LT, i.e., the percentage of delamination length of LT under tests such as humidity and temperature cycling tests, and outdoor tests, was discussed in relation to the adhesive shear strength of a lap joint (LJ). The results showed that the percentage of delamination length under both low ?20°C for 16 h and high-temperature 50°C for 8 h cycling tests (temperature-resistance) on LT indicated a strong trend with the adhesive shear strength of the LJ exposed to dry air at 100°C for 24 h. In addition, the percentage of delamination length under outdoor exposure test for three months (outdoor-resistance) of the LT showed a trend with the adhesive shear strength of the LJ exposed to dry air at 100°C for 24 h, as well as with the adhesive shear strength of the LJ immersed in water at 60°C for 3 h. These trends pointed out that the thermal stability of the adhesive from ?20°C for 16 h up to 50°C for 8 h was an important parameter in order to improve adhesive durability for the LT.     

Preparation of epoxy hardeners from waste rigid polyurethane foam and their application

Aliphatic amines were used as decomposer to decompose waste rigid polyurethane and polyisocyanurate foams, and the obtained decomposed products were directly used as curing agent of epoxy resin. Effects of the decomposing condition including amine type, foam–decomposer ratio, and reaction temperature on the decomposition reaction and properties of the decomposed products were investigated. Using amines with low molecular weight could enhance decomposition reaction rate and total amine number and lessen viscosity of the obtained decomposed products. Viscosity of the decomposed products decreased with increase of reaction temperature, but increased with increment of foam–decomposer ratio. Shear strength of adhesives consisting of decomposed products and epoxy resin was measured, and their thermal properties were analyzed. The adhesives could be cured completely over 60°C and their shear strength enhances with adding coupling agent in the adhesive system. The adhesives have good thermal stability and show satisfactory shear strength with more than 15, 15, 7, and 3 MPa at 25, 60, 100, and 150°C, respectively. The results demonstrate that the obtained adhesive systems can be used as structural adhesive. © 1995 John Wiley & Sons, Inc.     

Adhesive and flame resistance behavior of poly(arylene ether phosphine oxide) (PEPO) and PEPO‐modified epoxy resins

Poly(arylene ether phosphine oxide) (PEPO) with controlled molecular weights and amine end‐groups was synthesized, and used as an adhesive, a coating material for adherend or a modifier for diglycidyl ether of bisphenol A (DGEBA)‐based epoxy resins. Closely related poly(arylene ether sulfone) and commercial polyethersulfone, Udel® P‐1700, were also utilized for comparison purposes. Adhesive behavior was measured via single lap shear samples as a function of coated polymer type, test temperature (R.T. and 100°C), and aging condition in boiling distilled water or 5% salt water. Flame resistance of PEPO and PEPO‐modified epoxy resin was evaluated by TGA and a flame test. PEPO exhibited better adhesive properties than PES or Udel® P‐1700. PEPO coating on an Al adherend markedly improved adhesive property of PES and Udel® even at 100°C, and after aging study failure mode changed from adhesive to cohesive with the PEPO. Aminophenyl terminated PEPO‐modified epoxy resins also exhibited highly improved adhesive behavior and flame resistance, compared to control samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1198–1205, 2001     

有机硅硼改性环氧耐高温胶粘剂

采用自制有机硅硼树脂改性双酚A环氧树脂,配合AG-80环氧树脂,改性咪唑为固化剂,得到80～100℃固化的无溶剂耐高温胶粘剂。室温剪切强度大于15MPa,200℃剪切强度大于8Mpa,分析表明,该树脂体系具有优异的耐温性能。200℃／1000h老化具有较高的粘接强度,DSC分析表明,具有良好的热稳定性。扫描电镜分析表明,二元改性体系中存在均匀的“孔洞”结构和微分相,可以减小应力集中和阻止断裂发生,达到增韧效果。     

阻燃环氧树脂胶黏剂的研制

采用以KH-560硅烷偶联剂包覆三聚氰胺多聚磷酸酯（MPP）为阻燃剂,以环氧树脂E-44为基体,制备阻燃环氧树脂胶黏剂。通过对所制得胶黏剂进行剪切强度测试、热失重测试以及阻燃性能测试,研究了包覆阻燃剂对环氧树脂胶黏剂力学性能、热稳定性和阻燃性能的影响。结果表明,采用包覆处理MPP为阻燃剂制备的阻燃环氧树脂胶黏剂综合性能较好,其剪切强度为19．9MPa,氧指数为31．2。最佳配方为100份环氧树脂、30份阻燃剂、30份固化剂、温度为70℃。     

Accelerated-curing epoxy structural film adhesive for bonding lightweight honeycomb sandwich structures

Accelerating the curing of epoxy/aromatic amine adhesives and improving their toughness are challenges in heat-resistant epoxy structural adhesives. Herein, we report an epoxy/aromatic amine adhesive accelerated curing system with an oxo-centered trinuclear (chromium III) complex, which is toughened using a thermoplastic block copolymer (TPBC). The reaction characteristics, heat resistance, microstructure, and bonding properties of the accelerated epoxy adhesives were analyzed. The reaction peak temperature of the epoxy with 3% catalyst was 113.1°C, which was 113.6°C lower than that of epoxy without catalyst, and the modified epoxy resin demonstrated a potential for rapid curing at medium temperature. The glass transition temperature of the TPBC-toughened epoxy adhesive was 125°C after curing, indicating excellent thermal stability after medium temperature curing. The introduction of the TPBC increased the single-lap shear strength of the epoxy adhesive without reducing its heat resistance. The shear strength at room temperature and 120°C of the modified epoxy adhesive with 50 phr of TPBC was 25.2 and 10.9 MPa, respectively. Moreover, the epoxy film adhesive exhibited outstanding bonding properties when used in the bonding of lightweight honeycomb sandwich structures.     

双酚A型苯并二噁嗪树脂粘接性能研究

以环氧树脂(EP)、双马来酰亚胺(BDM)作为纯双酚A型苯并二噁嗪(BA-a)树脂的改性共聚单体,研究了不同改性BA-a体系的粘接性能和热稳定性能。结果表明:纯BA-a树脂与钢材之间的拉伸剪切强度为15.34 MPa,说明纯BA-a树脂具有作为胶粘剂的潜力;当m(BA-a)∶m(EP)∶m(BDM)=100∶60∶0或100∶27∶27时,改性BA-a体系的拉伸剪切强度为24.81 MPa或21.36 MPa,160℃时凝胶时间为150 min或20 min;改性BA-a体系的热稳定性能依次为BA-a/甲基四氢苯酐体系>BA-a/EP体系>BA-a/BDM体系>纯BA-a体系。