Curing of epoxy resin contaminated with water

Epoxy resins used for reinforcement of bridges and buildings are explored in the light of both curing rates and mechanical properties when resins are contaminated with water in outdoor construction. The developed resin is composed of a conventional resin of bisphenol A diglycidyl ether and a hardener with a polyoxipropyldiamine base. Curing rates were obtained by time variation of the near infrared absorbance of amine groups in the hardener at various water contents. They obeyed the second‐order reaction law with respect to the hardener, of which the activation energy was 70 kJ mol⁻¹. Water increased the reaction rate. Mechanical properties such as ultimate tensile strength, adhesive shear stress, and flexural strength were measured at various water contents for the developed epoxy resin and the commercially available low‐temperature epoxy resin. The developed cured resin shows not only higher mechanical strengths but also much less deterioration by water than the conventional cured resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 214–220, 2001     

Influence of aliphatic amine epoxy hardener on the adhesive properties of blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with epoxy resin

The adhesive properties have been investigated in blends of mono‐carboxyl‐terminated poly(2‐ethylhexyl acrylate‐co‐methyl methacrylate) with diglycidyl ether of bisphenol A and three different aliphatic amine epoxy hardener. The adhesives properties are evaluated in steel alloy substrate using single‐lap shear test. The copolymers are initially miscible in the stoichiometric blends of epoxy resin and hardener at room temperature. Phase separation is noted in the course of the polymerization reaction. Different morphologies are obtained according to the amine epoxy hardener. The most effective adhesive for steel–steel joints in single‐lap shear test is the blends using 1‐(2‐aminoethyl)piperazine (AEP) as hardener. This system shows the biggest lap shear strength. However, the modified adhesives show a reduction in the mechanical resistance. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Heterocyclic‐based epoxy‐terminated structural adhesive. II. Curing,adhesive strength,and thermal stability

We studied the curing behavior of heterocyclic‐based epoxy‐terminated resins using diaminodiphenyl ether, diaminodiphenyl sulfone, benzophenone tetracarboxylicdianhydride, and the commercial hardener of Ciba‐Geigy's two‐pack Araldite as curing agents. The adhesive strength of the adhesives was measured by various ASTM methods such as lap‐shear, peel, and cohesive tests on metal–metal, wood–wood, and wood–metal interfaces. All of these results were compared with those of an epoxy resin prepared from bisphenol‐A and epichlorohydrin resin with an epoxy equivalent value of 0.519. The thermal stability of both the virgin resin and its cured form was also studied by thermogravimetric analysis. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3520–3526, 2002     

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。     

Bonding properties of epoxy resins containing two mesogenic groups

Liquid‐crystalline epoxy resins, with introduced aliphatic chains between two mesogenic groups, were synthesized and their adhesive bonding properties were compared to those of the bisphenol‐A–type epoxy resin and the liquid‐crystalline epoxy resin, previously reported. The bonding strength of the former resin system was higher than that of the two later systems. We suggest that the high bonding strength of the twin mesogenic epoxy resins, cured with an aromatic amine, was attributable to the large plastic deformation of the adhesive layer in the fracturing process. We also investigated the effects of the aliphatic chain length in the twin mesogenic epoxy resin on their dynamic mechanical and bonding properties. The bonding strength of the cured twin mesogenic epoxy resins increased with an increase in the aliphatic chain length. We suggest that the high bonding strength of the system introduced by the long aliphatic chain was attributable to the large plastic deformation of the adhesive layer because of the higher network mobility. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3721–3729, 2004     

环氧胶体型缩聚理论

本文提出了环氧胶的体型缩聚理论,计算了固化剂理论用量和最佳用量,解释了粘接抗拉强度-固化剂用量曲线上出现双峰等现象,并预言了一系列结论.该理论可解释固化剂取最佳用量时固化产物良好的强度和韧性.该理论可望推广至用固化剂固化的其它类型的热固性树脂体系.     

Synthesis of curing agent for epoxy resin based on halogenophosphazene

Epoxy resins are, due to their excellent properties (such as chemical resistance, dimensional stability, and heat resistence), widely used in practice. The basic principle of curing epoxy resins with a hardener containing multiple amino groups is the crosslinking reaction between active hydrogen atoms in the hardener and the oxirane groups in the epoxy resin. This study deals with the synthesis and characterization of hexachloro‐cyclo‐triphosphazene derivative and its subsequent use for curing epoxy resins. The new hardener was prepared from hexachloro‐cyclo‐triphosphazene by nucleophilic substitution with isophorone diamine and its curing capability was compared with original isophorone diamine. The prepared derivative hexaisophorone diamino‐cyclo‐triphosphazene (HICTP) provided advantages over conventional curing system, as it improved mechanical properties as well as the flame resistance. Testing of the cured epoxy resin during burning was carried out using dual cone calorimeter, which enables more extensive monitoring of parameters in comparison with testing using oxygen index that has been used in many publications. The epoxy resin cured with the prepared phosphorus containing HICTP exhibits lower values for total heat release, amount of smoke released and oxygen consumed, which may cause a slower flame spread. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42917.     

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。     

Strength and Durability of Epoxy-Aluminum Joints

The adhesive strength and durability of adhesively-bonded aluminum joints in wet environments was analyzed. A2024-T4 alloy was subjected to two different surface treatments based on etching with chromic-sulfuric acid (FPL) and with sulfuric acid-ferric sulfate (P2). Small differences were observed in the lap shear strength as a function of the applied surface treatment. However, durability in humid environments was higher for the joints whose adherends were treated with P2.

Although the amount of water absorbed by the epoxy adhesive is lower in saline environments, the effects on the glass transition temperature of the epoxy adhesive and on the lap shear strength of the joints are more marked than the effects caused by aging with distilled water.

Finally, a new epoxy adhesive with a siloxanic hardener was tested, obtaining good mechanical properties, high glass transition temperature, moderate values of lap shear strength, and high durability in wet environments.     

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。()     

Toughened cycloaliphatic epoxy resin for demanding thermal applications and surface coatings

An epoxy resin based on nonglycidyl ether and varying content of carboxyl‐terminated (poly)butadiene acrylonitrile copolymer was cured using an aromatic amine hardener. The ultimate aim of the study was to modify the brittle epoxy matrix by the liquid rubber to improve toughness characteristics. Fourier transform infrared spectroscopic analysis of the modified was performed to understand the structural transformations taking place during the uncured and cured stage of the modified systems. The decreasing trend in exothermal heat of reaction with increasing rubber content in the epoxy resin can be explained by the fact that the increase of carboxyl‐terminated butadiene acrylonitrile copolymer (CTBN) modifier might induce a high reactivity of the end groups with the epoxide ring and resulting shorter curing times and, hence, the faster curing process than the unmodified resin. Tensile strength, impact strength, and elongation‐at‐break behaviors of neat as well as modified networks have been studied to observe the effect of rubber modification. Blends sample exhibits better properties as compared to pure epoxy resin in terms of increase in impact strength and elongation‐at‐break of the casting and gloss, scratch hardness, adhesion, and flexibility of the film. The improvement in these properties indicate that the rubber‐modified resin would be more durable than the epoxy based on di glycidyl ether of bis‐phenol‐A and other epoxies. The films of coating based on epoxy with 15 wt % CTBN offered the maximum resistance toward different concentrations of acids, alkalies, and solvents as compared to the cured films of other blend samples. The thermal stability of the cycloaliphatic‐based epoxy resin was increased with the addition of 15 wt % CTBN in epoxy matrix. Cycloaliphatic‐based epoxy network modified with CTBN displayed two phase separated morphology with dispersed rubber globules in the matrix resin, i.e., they revealed the presence of two phase morphological features. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Epoxy–lignin polyblends: Correlation between polymer interaction and curing temperature

A bisphenol A–polyamine hardener based epoxy adhesive (EP) was modified by polyblending with Kraft lignin (L). EP–L polyblends with an L content up to 40% by weight were cured at room temperature or above their glass transition temperature (T_g). Previous data have shown that the thermal and viscoelastic properties, as well as adhesive performance of the EP–L polyblends, are influenced by the curing temperature and by the L content in thermally cured polyblends. A reasonable explanation for the different behavior of EP–L polyblends as function of the curing temperature and their L content could be the enhanced degree of bonding between L and the EP network taking place at elevated temperature. This bonding was specifically considered to take place between L and possible unreacted amine groups of the hardener. Characterization of the EP–L polyblends was performed to search for evidence of irreversible chemical bonding between L and the EP network in thermally cured EP–L polyblends. FTIR studies, L extractibility from the crosslinked, polyblends, and quantitative data concerning the reactivity of L toward the polyamine hardener are discussed.     

One‐component epoxy resin with imine as water‐initiated latent hardener: Improvement of the mechanical and adhesive properties by the addition of methacrylate copolymer

The effect of addition of methacrylate polymer into a one‐component epoxy resin, containing Epikote 828 and diimine as a water‐initiated hardener, was examined. Although the cured epoxy resin in the presence of methyl methacrylate–butyl acrylate (MMA–BA) copolymer was very brittle, the resin containing MMA–BA–[γ‐(methacryloxy)propyl]trimethoxysilane (TMSMA) copolymer showed good mechanical and adhesive properties. The adhesive strength of the cured epoxy resin containing MMA–BA–TMSMA copolymer was much higher than that without its polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1943–1949, 2005     

Improvement of adhesive bonding of grit-blasted steel substrates by using diluted resin as a primer

This study reveals the micro-structural details on the metal substrate surface prepared by grit blasting, and then proposes a simple resin pre-coating method aiming at full wetting of the substrate surface for stronger adhesive bonding. The resin pre-coating solution consisting of around 90% acetone and around 10% resin without hardener is used as a primer, which can be sprayed or blushed onto the grit-blasted metal substrate. The acetone solution can carry resin deep into micro-cavities created by grit blasting and effectively coat and wet micro-debris so that micro-voids or gaps between the adhesive joint and metal substrate can be removed. Since the resin pre-coating does not contain hardener and remains wet, the wettability of the substrate is also improved. The normal epoxy adhesive with hardener can then be applied onto the substrate surface. Despite having the primer-like function, the proposed resin pre-coating method still maintains the simplicity of one epoxy resin system. Based on the current study, a resin and acetone solution without hardener does not seem to have adverse effects on the final bonding strengths of adhesive joints, although acetone is known to have detrimental effects on resin and hardener adhesive systems. Four different surface conditions are examined, each having 14 specimens: (1) Grit-Blasted (GB) surface, (2) GB-surface with ultrasonic cleaning, (3) GB-surface with resin Pre-Coating (PC) only, and (4) GB-surface with both ultrasonic cleaning and PC. 25% improvement in the shear strength has been achieved by the resin pre-coating method, even without ultrasonic cleaning, in comparison with 8% improvement after ultrasonic cleaning. These results show GB-surface with PC is beneficial to adhesive bonding, which can be adopted for structural applications even if thorough substrate surface cleaning on site is not possible. The improved wettability of metal substrates after resin pre-coating contributes to the maximum possible utilization of the contact areas over the roughened substrate surfaces and thus leads to the enhanced adhesive bond strength.     

Tough hyperbranched epoxy/poly(amido‐amine) modified bentonite thermosetting nanocomposites

A tough and highly flexible hyperbranched epoxy and poly(amido‐amine) modified bentonite based thermosetting nanocomposite was demonstrated. The FTIR, XRD, and TGA analyses confirmed the modification of bentonite. The formation of partially exfoliated structure of the nanocomposite with good physicochemical interactions among the hyperbranched epoxy, poly(amido‐amine) hardener and modified clay was investigated by the FTIR, XRD, SEM, and TEM analyses. Significant improvements of 750% toughness, 300% elongation at break, 50% tensile strength, 300% modulus, and 250% adhesive strength of the pristine epoxy were achieved by the formation of nanocomposites with 3 wt % of modified clay. The experimental modulus values of the nanocomposites were compared with three theoretical models to account the interactions between filler and matrix. Thus, the studied epoxy nanocomposite has great potential to be used as an advanced epoxy thermoset. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40327.     

Photoinduced cationic frontal polymerization of epoxy–carbon fibre composites

UV‐activated frontal polymerization was exploited for the preparation of epoxy–carbon fibre composites. The curing process was investigated showing the frontal behaviour, and the final properties of UV‐cured composites were compared with those of the same composites obtained by thermal curing in the presence of amine as hardener. The best curing formulations were designed, defining the photoinitiator‐to‐thermal initiator ratio, which was 1.5:1.5. It was observed that the presence of the carbon fibres induced an acceleration of the front velocity. By comparing the thermomechanical properties of the thermally cured composite and the same composite crosslinked using the frontal process, we could observe that the latter showed higher T_g value and lower σ_f. This was attributed to the formation of a different polymeric network structure. © 2019 Society of Chemical Industry     

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.     

Epoxidized natural rubber/epoxy blends: Phase morphology and thermomechanical properties

Epoxidized natural rubbers (ENRs) were prepared. ENRs with different concentrations of up to 20 wt % were used as modifiers for epoxy resin. The epoxy monomer was cured with nadic methyl anhydride as a hardener in the presence of N,N‐dimethyl benzyl amine as an accelerator. The addition of ENR to an anhydride hardener/epoxy monomer mixture gave rise to the formation of a phase‐separated structure consisting of rubber domains dispersed in the epoxy‐rich phase. The particle size increased with increasing ENR content. The phase separation was investigated by scanning electron microscopy and dynamic mechanical analysis. The viscoelastic behavior of the liquid‐rubber‐modified epoxy resin was also evaluated with dynamic mechanical analysis. The storage moduli, loss moduli, and tan δ values were determined for the blends of the epoxy resin with ENR. The effect of the addition of rubber on the glass‐transition temperature of the epoxy matrix was followed. The thermal stability of the ENR‐modified epoxy resin was studied with thermogravimetric analysis. Parameters such as the onset of degradation, maximum degradation temperature, and final degradation were not affected by the addition of ENR. The mechanical properties of the liquid‐natural‐rubber‐modified epoxy resin were measured in terms of the fracture toughness and impact strength. The maximum impact strength and fracture toughness were observed with 10 wt % ENR modified epoxy blends. Various toughening mechanisms responsible for the enhancement in toughness of the diglycidyl ether of the bisphenol A/ENR blends were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39906.     

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...