Selected aspects of epoxy adhesive compositions curing process

The paper focuses on selected parameters of curing process – temperature and time. The tests aimed at evaluating the impact of short-term thermal recuring on 1050A and 2017A aluminium alloy sheet adhesive joints strength. Joints were formed with two different adhesives, the main component of which was in both cases epoxy resin Epidian 53 and two different cure agents – poliamineamide C (PAC) and triethylenetetraamine (PF) curing agents. Curing conditions – first curing time, recuring time and recuring temperature – were modified for each of the four tests conducted. For the sake of comparative analysis, adhesive joints were subjected to a single-stage cure cycle at ambient temperature. A two-stage cure cycle of both Epidian 53 compositions at 80?°C for 1 and 2?h produces a material of different mechanical properties than the same material which submits a single-stage cure cycle at ambient temperature, as well as at 60?°C for 30?min. Simultaneously, Epidian 53/PF/100:50 composition proves to produce higher joint strength after recuring than Epidian 53/PAC/100:80; the strength of a joint formed with the former composition increases up to 50% when compared with joints subjected to a single-stage cure cycle. Moreover, tests show that recuring of the adhesive joint formed with both compositions at 60?°C for 30?min does not have a considerable influence on either 1050A or 2017A aluminium adhesive joint strength.     

Effects of moisture and temperature ageing on reliability of interfacial adhesion with black copper oxide substrate

The reliability of adhesion performance of bare Cu, as-deposited and surface-hardened black oxide coatings on Cu substrates was studied. The interfacial adhesion with a polyimide adhesive tape and an epoxy moulding compound was measured using the button shear and tape peel tests after hygrothermal ageing in an autoclave, high temperature ageing and thermal cycles. Moisture adsorption and desorption studies at different aging times suggested that the black oxide coating was effective in reducing the moisture adsorption. The bond strengths for all substrates remained almost unchanged after thermal ageing at 150°C for 8 h. Thermal cycling between ?50°C and 150°C for 500 cycles reduced by about 20% the button shear strength of the as-deposited black oxide substrate, but it did change much the bonding performance of the bare Cu substrate. Hygrothermal ageing at 121°C/100% RH in an autoclave was most detrimental to adhesion performance because of the combined effect of elevated temperature and high humidity. The reduction in button shear strength after the initial ageing for 48 h was 50–67%, depending on the type of coating. In all accelerated ageing tests, the residual interfacial bond strengths were consistently much higher for the black-oxide-coated substrates than the bare Cu surface, confirming a higher reliability of black oxide coating. Fracture surfaces analysis of tape-peeled bare copper substrates after 500 cycles of thermal loading revealed a transition in failure mechanism from interfacial to cohesive failure. In contrast, the failure mechanism remained unchanged for black-oxide-coated substrates. The observations made from the button shear and tape peel tests were generally different because of the different fracture modes involved.     

Study on benzoxazine-based film adhesive and its adhesion properties with CFPR composites

In this paper, a benzoxazine-based (BZ) adhesive with high temperature resistant was developed by blending benzoxazine monomer and tetrafonctional epoxy monomer as matrix modifier and polyetherimide as toughening agent. The results show that benzoxazine-based film adhesive could be cured at 190 °C, and the cured film adhesive exhibited high temperature resistance and a high glass transition temperature of 224 °C. The 5% weight loss temperature in air was 400 °C and the char yield in nitrogen at 800 °C was 48%. The cured film adhesive has good ablation resistance. The fabricated benzoxazine-based film adhesive has high adhesion reliability, with single-lap shear strength of 23.20, 28.36 and 20.04 MPa at room temperature, 140 and 175 °C respectively. The curing process of the film adhesive matches well with that of carbon fiber reinforced BZ prepreg and the film adhesive has stable adhesion properties. Its biggest advantage is that, during storage and transportation, there is no need of refrigeration. After 60 days of storage for benzoxazine-based film adhesive at room temperature, its process performance and adhesion properties remain unchanged. It is expected that the benzoxazine-based film adhesive can be used in aerospace, high-speed rail and other applications.     

环氧大豆油低聚物增韧环氧树脂胶粘剂

合成了三种环氧大豆油低聚物作为室温和高温固化环氧树脂增韧剂,对其增韧环氧体系的粘接性能和力学性能进行了考察。试验结果表明,环氧树脂低聚物对固化体系的初期粘度等性能没有影响,对固化体系粘接性能和力学性能等有较大影响。与未改性的环氧树脂相比,由顺丁烯二酸酐扩链的环氧大豆油低聚物改性的环氧树脂剪切强度提高了56.64%。     

Adhesion improvement of epoxy resin/copper lead frame j oints by azole compounds

The adhesion strength of epoxy resin/copper joints is often very poor, due to the naturally formed copper oxide having a low mechanical strength. To improve the adhesion strength of epoxy resin/copper lead frame joints, copper lead frames were treated with azole compounds as adhesion promoters. The azole compounds used were benzotriazole (BTA), benzotriazole-5-carboxylic acid (CBTA), 8-azaadenine, imidazole, 2-methyl imidazole, urocanic acid, adenine, benzimidazole, and polybenzimidazole (PBI). The dependence of the adhesion strength of epoxy resin/azole-treated copper joints on the structure of the azole compound, the azole treatment time, and the azole treatment temperature was investigated. The surface coverage of azole-treated copper was examined by contact angle measurements, a surface defect test, optical microscopy, and scanning electron microscopy (SEM), and the locus of failure was studied by X-ray photoelectron spectroscopy (XPS). Triazole compounds such as CBTA and 8-azaadenine showed excellent adhesion strength; imidazole-based azole compounds did not improve the adhesion strength. However, the adhesion strength of CBTA- and 8-azaadenine-treated joints decreased with increasing treatment time, since thick porous Cu-azole complexes had a weaker mechanical strength when formed. The polymeric azole compound PBI showed the highest adhesion strength, 785 N/m, because of complete coverage of the copper surface. The thermal stability of azole compounds and epoxy resin/azole-treated copper joints was also investigated. CBTA and 8-azaadenine did not decompose up to 250°C, while PBI was stable up to 500°C in an air atmosphere.     

Blends of poly(ethylene terephthalate) and epoxy as matrix material for continuous fibre reinforced composites

Abstract

The morphology and mechanical properties of poly(ethylene terephthalate) (PET)–epoxy blends and the application of these blends in continuous glass fibre reinforced composites have been investigated. Epoxy resin was applied as a reactive solvent for PET to obtain homogeneous solutions with a substantially decreased melt viscosity. The epoxy resin in these solutions was cured using an amine hardener according to two different schedules. In the first, high temperature curing at 260°C preceded low temperature crystallisation of the PET at 180°C. In the second, the PET was allowed to crystallise prior to low temperature curing at 180°C. After cure, all blends revealed a phase separated morphology of dispersed epoxy in a continuous PET matrix. The flexural strength and failure strain of all cured blends showed an increase with increasing epoxy content, whereas the high temperature cured blends exhibited overall lower flexural properties than those cured at the lower temperature. Microstructural analysis and flexural properties of continuous glass fibre reinforced PET–epoxy laminates showed that the composites obtained had a low void content. These PET–epoxy laminates had increased inplane shear strength in comparison with unmodified PET based laminates, indicating considerably increased fibre–matrix adhesion.     

Fabrication and evaluation of structural film adhesive using oxazolidinone modified novolac epoxy resin

Epoxy film adhesives are of prime importance for the fabrication of lightweight honeycomb structures for aerospace industries. This work involves the synthesis of oxazolidinone modified epoxy novolac resin (EPN-OXA) via the reaction of EPN and toluene diisocyanate. EPN-OXA was characterized by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, gel permeation chromatography, and epoxy equivalent weight. EPN-OXA was blended with solid epoxy resin, polyethersulfone (PES) toughened liquid epoxy resin, dicyandiamide, and aluminum powder to fabricate a film adhesive curing at 170–180 °C. Effect of additives and curative on the adhesive property was studied to optimize the composition. Effect of PES on the optimized composition was studied in detail. The best composition exhibited lap shear strength of 370 ± 10 kgf cm⁻² at 25 °C and the strength was retained to 75% at −196 °C and 52% at 120 °C. PES significantly enhanced the interfacial strength at different temperatures (~1.6-fold at −196 and 25 °C and ~1.8-fold at 120 °C). It also improved tensile strength and fracture toughness by 1.4- and 2-fold, respectively. The toughening effect of PES was further confirmed by scanning electron microscopy images. PES marginally reduced the glass-transition temperature and it exhibited no effect on thermal stability. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47520.     

Copper particles/epoxy resin thermosetting conductive adhesive using polyamide resin as curing agent

Thermosetting conductive adhesive (TCA) comprised of epoxy resin E‐51 as matrix, Cu microparticles and nanoparticles modified by silane coupling KH550 as conductive fillers, polyamide resin with low molecular weight as curing agent, and some other additives. It was reported creatively a new liquid curing agent, which solved successfully some difficult problems during preparation of TCA, such as limit of quantity of conductive fillers. Therefore, application of this liquid curing agent decreased greatly the resistivity of TCA under the condition of keeping enough adhesion strength. Antioxidized and mixed Cu particles were developed as conductive fillers in place of expensive Ag. The results showed that optimum conditions of conductive adhesive composed of 16 wt % of epoxy resin E‐51, 8 wt % polyamide resin, 65 wt % of Cu microparticles and nanoparticles, 1.3 wt % of silane coupling agent, and 9 wt % of other additives with curing time for 4 h at 60°C. The adhesion strength reached 16.7 MPa and the bulk resistivity was lower than 3.7 × 10^?4 Ω cm. The variation of bulk resistivity was less than 15% at high temperature (100°C). © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

新型有机硅多元胺环氧树脂固化剂结构与性能

评价了3种有机硅多元胺APS、SFA和PSPA分别固化环氧树脂E51(DGEBA)时,固化物的力学性能和粘接强度,并与常见脂肪胺类固化剂[乙二胺、己二胺、聚醚胺(D-230)]作了对比。固化物基体力学和热性能测试表明,有机硅多元胺环氧固化物表现出较佳的冲击强度、弯曲强度和热稳定性。有机硅多元胺/环氧树脂胶粘剂的铁片粘接强度以及耐水性明显高于脂肪胺/环氧胶粘剂体系,其中含苯基有机硅多元胺作为固化剂时粘接强度最高,达到14.8 MPa。()     

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.     

Surface Modification of a Photo-Definable Epoxy Resin with Polydopamine to Improve Adhesion with Electroless Deposited Copper

Abstract

This paper describes the influence of polydopamine surface modifications on the adhesion strength of electroless deposited copper on roughened epoxy resin substrates. The surfaces are characterized with XPS and ToF-S-SIMS. Next, a thorough investigation of the copper–epoxy interface is performed using SEM. Both the polydopamine modification and the variation of the electroless plating bath temperature lead to new insights into the different contributions of chemical and physical adhesion to the overall adhesion strength.     

聚氨酯改性环氧树脂胶粘剂的制备及性能研究

由端-NCO基聚氨酯(PU)预聚物与环氧树脂反应,制备了PU接枝改性环氧树脂。着重探讨了PU预聚物的含量、活性稀释剂的含量和异氰酸酯结构等因素,对改性环氧树脂的粘度和粘接性能的影响。实验结果表明,该改性环氧树脂的粘度随着PU预聚物含量的增加而逐渐增大,随着活性稀释剂含量的增加而逐渐降低,而且在相同的条件下,用不同的二异氰酸酯改性环氧树脂的粘度大小次序为:IPDI型>MDI型>TDI型;该改性环氧树脂在PU预聚物含量为20%时,对铝片/铝片的剪切强度最大(7.82 MPa);在PU预聚物含量为10%时,对铁片/铁片的剪切强度最大(11.70 MPa),而且TDI型和IPDI型改性环氧树脂的粘接性能明显好于MDI型改性环氧树脂。     

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     

可固化性环氧-丙烯酸酯聚合物压敏胶的研究

在丙烯酸酯类单体的乳液聚合过程中加入环氧树脂,可以制得可固化性乳液压敏胶.研究了环氧树脂含量、聚合物的玻璃化温度、聚合工艺等因素对压敏胶主要性能的影响,并通过对交联度的测量,确认了环氧树脂参与聚合交联的事实.实验得出:采用核-壳聚合工艺、当环氧树脂的含量为30%(wt)、共聚物玻璃化温度为243.15K时,制得的可固化性乳液压敏胶的初黏力为9号球,固化后对铝合金的粘接强度可达10MPa.     

Characterization of a rigid silicone resin

Silicone resins have been used as binders for ceramic frit coatings and can withstand temperatures of 650°C to 1260°C. Conceptually, silicone resins can potentially be used as matrices for high temperature fiber‐reinforced composites. The mechanical and thermal properties of a commercially available silicone resin, Dow Corning® 6‐2230, were characterized. Neat 6‐2230 resin was found to have inferior room temperature mechanical properties such as flexural, tensile and fracture properties when compared to epoxy. The room temperature flexural properties and short beam shear strength of the silicone/glass composites were also found to be lower than those of epoxy/glass composite with similar glass content. However, the silicone resin had better elevated temperature properties. At an elevated temperature of 316°C, the retentions of flexural modulus and strength were 80% and 40% respectively of room temperature values; these were superior to those of phenolic/glass. Unlike the carbon‐based resins, the drop in flexural properties of the silicon/glass laminates with temperature leveled off with increase in temperature beyond 250°C. The resin weight loss at 316°C in 100 cm³/min of flowing air was small compared to other carbon‐based resins such as PMR‐15 and LaRC TPI. Only Avimid‐N appeared comparable to Dow Corning® 6‐2230.     

Improvement of adhesion and electrical properties of reworkable thermoplastic conductive adhesives

The adhesion and electrical properties of a PAE-2-based isotropically conductive adhesive (ICA) material were investigated. PAE-2 (thermoplastic polymer)-based ICAs, as well as a commercial epoxy-based ICA, showed dramatic reduction in adhesion to a NiAu surface after the 85°C/85% RH aging test, while the adhesion to a SnPb surface did not change much. To improve the adhesion strength of PAE-2 to a Ni:Au surface after the humidity aging test, coupling agents and epoxy blends were used. The formulation with a higher amount of epoxy showed a higher adhesion strength. The combined use of epoxy blending and coupling agents was effective in increasing the adhesion strength of PAE-2 before aging and also in maintaining adhesion at a 50% level after humidity aging. However, its adhesion strength to NiAu was reduced to less than 50% after 85°C/85% RH aging. PAE-2-based ICAs showed excellent reworkability.     

Adhesive and thermal characteristics of maleimide-functional novolac resins

A novel, addition-curable maleimide-functional novolac phenolic resin was evaluated for adhesive properties such as lap shear strength and T-peel strength using aluminium adherends, when thermally self-cured and cocured with epoxy resins. The adhesive properties of the self-cured resin, although inferior at ambient temperature, improved at high temperature and were found to depend on the cure conditions. When cocured with epoxy resin, the adhesive properties improved significantly and showed a strong dependence on the nature of the epoxy resin used, on the stoichiometry of the reactants, on the concentration of imide groups in the phenolic resin, and on the extent of polymerization of the maleimide groups. Optimum adhesive properties were obtained for novolac resins with a moderate concentration of maleimide groups, taken on a 1 : 1 hydroxyl–epoxy stoichiometry with a novolac epoxy resin. In comparison to the conventional novolac, the imide–novolac contributed to improved adhesion and better adhesive property retention at higher temperature when cured with the novolac–epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 695–705, 1999     

改性胺催化固化环氧树脂的研究

研究将脂肪胺预先与酮类形成酮亚胺后催化固化环氧树脂的一些力学性能。实验表明，酮亚胺作环氧树脂固化剂配制时反应温和不易爆聚，并且起始黏度低．渗透性好，固结体压缩强度和粘接强度高，韧性好，破坏时的压缩形变可达20％以上。酮亚胺改性后掺入催化剂C1促进环氧树脂的固化，固结体强度大大提高，压缩强度达130MPa，粘接铁片的拉伸剪切强度为16．1MPa。     

Durability of Aluminium Adhesive Joints Bonded with a Homopolymerised Epoxy Resin

The durability of epoxy-aluminium joints that use a homopolymerised epoxy resin was studied, and the effects of relative humidity, temperature, and salt concentration were analysed. The adhesive properties were measured by lap-shear tests, and the water uptake of the epoxy resin was determined by gravimetric measurements. Ageing and degradation effects on the epoxy resin and on the aluminium substrates were also analysed.

The homopolymerised epoxy resin absorbs little water (1.5 wt%) because of its nonpolar network structure. The water uptake is enhanced by increasing relative humidity and temperature; however, the joint strength remains constant because of epoxy plasticization. A saline environment is damaging to the adhesive joints, because of metal corrosion, but was not significantly harmful to the epoxy resin, because of a lower diffusion coefficient of salt water. The T_g decrease of the epoxy adhesive due to water absorption depends only on the amount of absorbed water and is independent of the hydrothermal ageing conditions.     

Moisture and temperature degradation of double cantilever beam adhesive joints

In this work, the double cantilever beam (DCB) test is analysed in order to evaluate the combined effect of temperature and moisture on the mode I fracture toughness of adhesives used in the automotive industry. Very few studies focus on the combined effect of temperature and moisture on the mechanical behaviour of adhesive joints. To the authors’ knowledge, the simultaneous effect of these conditions on the fracture toughness of adhesive joints has never been determined. Specimens using two different adhesives for the automotive industry were subjected to two different ageing environments (immersion in distilled water and under 75% of relative humidity). Once they were fully degraded, they were tested at three different temperatures (?40, 23 and 80 °C), which covers the range of temperature an adhesive for the automotive industry is required to withstand. The aim is to improve the long term mechanical behaviour prediction of adhesive joints. The DCB substrates were made of a high strength aluminium alloy to avoid plastic deformation during test. The substrates received a phosphoric acid anodisation to improve their long term adhesion to the adhesive. Results show that even though a phosphoric acid anodization was applied to the adherends, when the aged specimens were tested at room temperature and at 80 °C, they suffered interfacial rupture. At ?40 °C, however, cohesive rupture was observed and the fracture toughness of the aged specimens was higher.