Adhesive Bonding of Clean and Oil-Contaminated Electrogalvanized Steel Substrates

The performance of two-part, amidoamine-cured epoxy adhesives on clean and oil-contaminated electrogalvanized steel (EGS) was studied using screening and lap shear tests. On exposure to boiling water, the cured epoxy adhesives with amidoamines having higher amine value delaminated from the clean and oil-contaminated EGS surfaces before those cured with amidoamines having low amine value. The results of X-ray photoelectron spectroscopy (XPS) showed that the adhesives cured with amidoamines having high amine value were unable to displace the oil from the EGS substrate. However, the durability and the strength of the adhesive bonds on the oiled EGS could be improved by adding proper amounts of silane or wetting agent to the adhesive. The preferential adsorption of amino curing agents occurred on the clean EGS surface, confirmed by XPS and reflection absorption infrared spectroscopy, and this decreased the durability of the bonds in boiling water. In addition, from XPS analyses of various specimens, different amounts of cured resins were detected in the adhesive/EGS interfacial regions which affecting the durability of the adhesive bonds. In addition, the amidoamine curing agents may form complexes on the EGS surface.     

Adhesive Bonding of Oil-Contaminated Steel Substrates

Durability of adhesive bonds formed by curing epoxies against oil-contaminated steel substrates using amidoamine curing agents was determined during exposure to boiling water. The most durable bonds were obtained using amidoamine curing agents with relatively low amine numbers and by blending silane coupling agents such as γ-glycidoxypropyltrimethoxysilane (γ-GPS) and N-(2-aminoethyl)-3-aminopropyltrimethoxy silane (AAMS) into the adhesives. When X-ray photoelectron spectroscopy (XPS) was used to characterize the failure surfaces of the adhesive joints after exposure to boiling water, it was determined that adhesives prepared using amidoamine curing agents with low amine numbers were able to displace the oil from the steel surface but adhesives prepared with amidoamine curing agents with high amine numbers were not. Results obtained from XPS also showed that the amino groups on the substrate fracture surfaces of joints prepared using curing agents with low amine numbers were protonated whereas the amino groups in the bulk adhesive were not, indicating that there was a chemical interaction between the curing agent and the hydrated surface of the substrate. It was also shown using infrared spectroscopy that the amidoamine curing agents formed salts with calcium compounds in the oil.     

Adhesive Bonding of Oil-Contaminated Steel Substrates

Durability of adhesive bonds formed by curing epoxies against oil-contaminated steel substrates using amidoamine curing agents was determined during exposure to boiling water. The most durable bonds were obtained using amidoamine curing agents with relatively low amine numbers and by blending silane coupling agents such as γ-glycidoxypropyltrimethoxysilane (γ-GPS) and N-(2-aminoethyl)-3-aminopropyltrimethoxy silane (AAMS) into the adhesives. When X-ray photoelectron spectroscopy (XPS) was used to characterize the failure surfaces of the adhesive joints after exposure to boiling water, it was determined that adhesives prepared using amidoamine curing agents with low amine numbers were able to displace the oil from the steel surface but adhesives prepared with amidoamine curing agents with high amine numbers were not. Results obtained from XPS also showed that the amino groups on the substrate fracture surfaces of joints prepared using curing agents with low amine numbers were protonated whereas the amino groups in the bulk adhesive were not, indicating that there was a chemical interaction between the curing agent and the hydrated surface of the substrate. It was also shown using infrared spectroscopy that the amidoamine curing agents formed salts with calcium compounds in the oil.     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

The Modification of Epoxy/Metal Interphases by Adsorbed Contaminants

The interfacial region formed between an epoxy/polyamide adhesive and three metallic substrates has been investigated using x-ray photoelectron spectroscopy. The effect of adsorbed contaminants on the interfacial region has also been studied. The substrates studied were cold-rolled steel, electrogalvanized steel and 2024 aluminum. A “ship-out” oil was used to contaminate the cold-rolled steel and electrogalvanized steel whereas an aerospace hydraulic fluid was used to contaminate the 2024 aluminum. Preferential adsorption of the curing agent by the substrates was observed, the effect being most marked in the case of the electrogalvanized steel substrates. The interaction between the galvanized steel and the 2024 aluminum and the curing agent was primarily via the free amines in the polyamide curing agent. In the case of cold-rolled steel the interaction occurred via the amide component. Cold-rolled steel and 2024 aluminum protonated the curing agents. No protonation was detected in the case of the electrogalvanized steel substrates due to the formation of a zinc/amine coordination compound involving the lone pairs of electrons on the nitrogen atoms. When the contaminated cold-rolled steel substrates were studied, the adhesive displaced the majority of the ship-out oil, but no protonation of the curing agent was observed. This indicated that some residual contaminant remained associated with the cold-rolled steel substrate. The majority of the ship-out oil was not displaced from the electrogalvanized steel because the strong preferential adsorption of the curing agent by the substrates created an adhesive layer enriched in epoxy. As the epoxy resin was incompatible with the oil, this epoxy-rich layer acted as a barrier, preventing the absorption of the oil by the bulk adhesive. In the case of the 2024 aluminum substrate, the level of preferential adsorption of the curing agent was decreased, but protonation of the nitrogen groups was still observed. These results indicated that the hydraulic fluid was displaced from the 2024 aluminum in some areas.     

The Modification of Epoxy/Metal Interphases by Adsorbed Contaminants

The interfacial region formed between an epoxy/polyamide adhesive and three metallic substrates has been investigated using x-ray photoelectron spectroscopy. The effect of adsorbed contaminants on the interfacial region has also been studied. The substrates studied were cold-rolled steel, electrogalvanized steel and 2024 aluminum. A “ship-out” oil was used to contaminate the cold-rolled steel and electrogalvanized steel whereas an aerospace hydraulic fluid was used to contaminate the 2024 aluminum. Preferential adsorption of the curing agent by the substrates was observed, the effect being most marked in the case of the electrogalvanized steel substrates. The interaction between the galvanized steel and the 2024 aluminum and the curing agent was primarily via the free amines in the polyamide curing agent. In the case of cold-rolled steel the interaction occurred via the amide component. Cold-rolled steel and 2024 aluminum protonated the curing agents. No protonation was detected in the case of the electrogalvanized steel substrates due to the formation of a zinc/amine coordination compound involving the lone pairs of electrons on the nitrogen atoms. When the contaminated cold-rolled steel substrates were studied, the adhesive displaced the majority of the ship-out oil, but no protonation of the curing agent was observed. This indicated that some residual contaminant remained associated with the cold-rolled steel substrate. The majority of the ship-out oil was not displaced from the electrogalvanized steel because the strong preferential adsorption of the curing agent by the substrates created an adhesive layer enriched in epoxy. As the epoxy resin was incompatible with the oil, this epoxy-rich layer acted as a barrier, preventing the absorption of the oil by the bulk adhesive. In the case of the 2024 aluminum substrate, the level of preferential adsorption of the curing agent was decreased, but protonation of the nitrogen groups was still observed. These results indicated that the hydraulic fluid was displaced from the 2024 aluminum in some areas.     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

几种胺类固化剂对环氧树脂固化行为及固化物性能的影响

固化剂结构对环氧树脂的固化行为和固化物性能具有重要影响,本文研究了聚醚胺(D-230)、异佛尔酮二胺(IPDA)和3,3'-二甲基-4,4'-二氨基-二环己基甲烷(DMDC) 3种胺类固化剂与实验室自制的低翻度环氧树脂A进行固化反应.通过薪度分析、红外(FTIR)光谱分析、DSC分析等手段研究了环氧树脂与固化剂反应程度...     

Structural Adhesive Bonds to Primers Electrodeposited on Steel

Adhesive bond strength and durability were investigated for steel substrates which had been cathodically electroprimed before bonding. Lap shear and torsional impact strengths of two model epoxy adhesives were evaluated. Very poor strengths and durability were found for one adhesive, which was cured with a mixture of three amine curing agents. Scanning electron microscopy and analysis of primer susceptibility to interaction with the curing agents suggested that, for the high concentrations of curing agent in the amine-cured adhesive, chemical and physical degradation of the primer occurred during cure at elevated temperature.

For the second adhesive, which was cured with a single imidazole catalyst, excellent strength and durability were obtained, with no evidence of primer degradation. Surprisingly, for this adhesive, strengths to primed steel were up to 88% higher than to cleaned (i.e., degreased) bare steel. The concurrent improvements in environmental durability over bare steel, as assessed by water immersion and salt spray accelerated exposures, were attributed to the more favourable surface energetics of the adhesive/primer interface.     

室温固化抗剥离耐温环氧胶粘剂

研究了一种室温固化,可在１２０℃下使用的环氧树脂胶粘剂。通过ＣＴＢＮ增韧改性,获得了较高的剥离强度和剪切强度,通过加入高官能度环氧树脂和改性芳胺及催化剂,使得该体系具有一定的耐温性和可室温固化性。     

固化剂对低温固化环氧建筑胶性能的影响

研究了6种不同固化体系在-12～0℃温度下的固化情况,探讨了不同固化剂对胶粘剂固化反应速度、压缩强度及钢一钢拉伸剪切强度的影响。试验结果表明,MS-0021固化剂各项性能优于其他固化剂,其压缩强度值为62．56MPa,钢－钢拉伸剪切强度值为1523MPa,可满足胶粘剂的冬季施工要求。     

Adhesive Properties of Epoxy Resin with Chromic Hardener

Cohesive and adhesive properties have been compared of epoxy resins crosslinked either with chromic‐based hardener or with conventional amine‐type hardener. Higher cohesive parameters, such as yield strength, Young's modulus and impact resistance were observed for the material cured with chromic hardener. The adhesive strength of metal‐metal joints (steel‐aluminium) has been also found to be higher for chromic hardener containing epoxy compared to conventional curing systems. The time dependencies of adhesive strength after thermal treatment at 140°C of the joints showed a higher thermal resistance of the epoxy with chromic hardener when compared to the amine cured resin.     

水下环氧树脂胶粘剂用水下固化剂的性能研究

目前可用于水下粘接的EP(环氧树脂)胶粘剂用水下固化剂种类不多,主要是一些憎水类改性胺固化剂(如810和301P等)。以不同种类的水下固化剂作为试验对象,着重探讨了水下固化剂的本体黏度、相应水下EP胶粘剂的某些性能(如水下凝胶时间、水下拉伸剪切强度及水下压缩强度等)。研究结果表明:水下EP胶粘剂的适宜凝胶时间为1h左右;水膜隔离胶粘剂/被粘物的界面问题只影响拉伸剪切强度,而不影响压缩剪切强度,故水下固化剂的憎水性良好时,相应EP胶粘剂的压缩强度相对较高,但其钢/钢拉伸剪切强度会受到一定的影响;810和301P具有一定的憎水性,并且相应EP胶粘剂的水下凝胶时间均为1h左右,故不同黏度的810和301P复配可制得综合性能更好的水下EP胶粘剂。     

Amidoamine: Synthesis,disparity in cure with epoxy resins between bulk and solvent systems,and structure–property relationships of its epoxy‐based coatings

Amidoamines are widely used as crosslinkers for epoxy resins in protective coatings on metal substrates; however, their cure chemistry is not well elaborated in the technical literature. During cure, the epoxy–amine and epoxy–amide NH reactions could be accompanied by epoxy–hydroxyl etherification, epoxy–epoxy homopolymerization, and reaction between hydroxyls and amide moiety to form in situ ester and amine. To understand the epoxy–amidoamine cure chemistry and correlate it with coating performance properties, amidoamines of known structure are required. Therefore, amidoamines were synthesized by reacting dimer fatty acids with diethylene triamine. When these amidoamines were cured with epoxy resins, discrepancies were observed between systems cured at ambient and thermal conditions. The presence of solvents were seen to greatly affect the rate of epoxy–amidoamine cure at ambient, and before and after vitrification. Near‐IR and mid‐IR spectroscopy studies indicated that side reactions occurred to some extent during cure. No reaction was noted between the amide NH moiety and the epoxide group below 150°C whereas ester formation was noted above 120°C. Solvent‐based clear epoxy–amidoamine coatings formulated at an epoxy:amine equivalent ratio 1.15 passed basic organic coatings evaluation tests. POLYM. ENG. SCI., 59:E69–E81, 2019. © 2018 Society of Plastics Engineers     

室温固化耐高温耐水胶粘剂的研制

采用酚醛环氧树脂F-51和环氧树脂CYD-128复合树脂、自制的羧基丁腈改性环氧树脂增韧剂和酚醛胺固化剂以及陶瓷耐热填充剂复配,研制出1种室温固化耐高温耐水胶粘剂。测试了不同固化剂,增韧剂,填充剂对胶粘剂粘接强度的影响并考察了胶粘剂的耐水性。结果表明,该胶A组分最佳配方为:CYD-12880g,F-5120g,羧基丁腈改性环氧树脂10g,轻质碳酸钙20g,陶瓷耐热填充剂1#40g,2#20g;B组分配方为:酚醛胺固化剂40g,轻质碳酸钙20g,陶瓷耐热填充剂1#35g,A与B质量比为2:1时,室温固化1d后的剪切强度达21.4MPa(室温),150℃剪切强度6.2MPa,水中浸泡30d后强度几乎无变化。该胶可长期在高温条件下使用,满足耐磨陶瓷粘接的技术要求。     

Novel imidazole derivatives with recoverable activity as latent curing agents for epoxy

A series of latent curing agents were developed by replacing the hydrogen atom on secondary amine in imidazole with methoxy polyethylene glycol maleate diesters via Michael addition reaction. Methoxy polyethylene glycol maleate diesters with different molecular weight also restrained the reactivity of tertiary amine in imidazole ring. The curing properties and pot-life of the modified imidazole/epoxy systems were measured by differential scanning calorimeter and rotational rheometer. The modified imidazole/epoxy system could be cured quickly at 175°C. The modified imidazole shows good latency. After stored for more than 1 month, viscosity of modified imidazole/epoxy system remains unchanged. The longer chain polyether had the better thermal latency these curing agents had. Compared with unmodified imidazole, the novel latent curing agents led to better impact strength for cured epoxy. However, the compatibility between epoxy and latent curing agent will get worse if the molecular weight of polyether unite is over 750.     

胺化酰亚胺固化的环氧树脂体系的特性及其固化机理

能热分解成异氰酸酯和叔胺的胺化酰亚胺是很好的潜伏性环氧树脂固化剂和环氧-酸酐体系的固化促进剂,它固化的环氧树脂有许多优异的性能,特别是高的韧性和粘接强度。由胺化酰亚胺热分解速度控制的、高温下相对慢的、独待的固化机理是韧性的起因。     

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