Toughening of Epoxy Resins with Thermoplastics: 3. An Investigation into the Effects of Composition on the Properties of Epoxy Resin Blends

Three different epoxy resins, based on the diglycidylether of bisphenol A (DGEBA), triglycidyl-p-aminophenol (TGPAP) and tetra-glycidyldiaminodiphenylmethane (TGDDM), which are di-, tri- and tetrafunctional, respectively, were mixed in varying proportions and cured with both 3,3′-diaminodiphenylsulphone and 4,4′-[1,4-phenylene(1-methylethylidene)]bis(2,6-dimethylbenzenamine) (EPON 1062-M from Shell). All the blends could be satisfactorily cured and gave homogeneous materials. The dynamic mechanical and fracture properties of the cured materials were measured. It was found that the glass transition temperature varied with composition systematically, whereas values of the strain energy release rate (G_1c) and the stress intensity factor (K_1c) showed relatively small variations with the blend composition. Toughened epoxy resins were prepared by adding a polyetherimide (PEI), in varying proportions, to the resin mixture. The ‘toughenabilities’ of different resins, or resin mixtures, were compared. This showed that the 75/25 TGPAP/DGEBA resin mixture was the most toughenable. Adding 20% of PEI led to a more than three-fold increase of the G_1c value. © of SCI.     

Toughening of epoxy resins by modified m-phenylene diamine having soft ether chain

A new soften curing agent for toughening epoxy resins was synthesized by m-phenylene diamine modified with epoxypropyl butyl ether. The curing processes of epoxy resin/modified m-phenylene diamine were traced by differential scanning calorimetry (DSC), then kinetic parameters, ΔE and n, were deduced. Fourier transform infrared (FTIR) analysis showed that the longer the reaction time was, the smaller the absorption peaks of epoxy group were. The results of the mechanical properties demonstrated that the impact property of the epoxy resin cured by modified m-phenylene diamine at the moderate temperature was better than that of cured by unmodified one because of the introduction of soft ether chain. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of brominated epoxy on epoxy/phenolic reactive blends

Innovative reactive blends containing epoxy and brominated epoxy (BE) incorporated with resole-type phenolic were studied with the aim to elucidate the curing kinetics and the final thermomechanical characteristics of this unique system. Curing kinetics was investigated by means of the activation energy determined using differential scanning calorimetry (DSC ) at various heating rates analyzed by the Arrhenius equation. Both DSC and Fourier transform infrared revealed that bromine elimination at elevated temperatures (above 220 °C) had lowered the activation energy in the case of BE containing phenolic blends. The thermomechanical properties showed that the addition of conventional epoxy to resole decreased its thermal properties and modulus compared to neat resole. Distinctively, BE/resole blends exhibited increased glass-transition temperature, compared to diglycidyl ether of bisphenol A/resole blends in combination with higher elongation and toughness compared to neat resole. It was concluded that BE/epoxy resin/phenolic reactive systems offer high T _g, mechanical properties and toughness and hence are applicable for structural adhesives and for matrices of polymer-fiber composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47172.     

Toughening of epoxy resins with aromatic polyesters

Polyesters, prepared by direct polycondensation from bisphenol A and aliphatic dicarboxylic acids [adipic acid (AD), suberic acid, sebacic acid (SE), and dodecanedioic acid], were used to improve the toughness of the diglycidyl ether of the bisphenol A/diaminodiphenyl methane epoxy system. Polyesters had the number average molecular weight (M_n) ranging from 4300 to 19,200 g/mole. The epoxy systems modified with the AD system (M_n = 6400 g/mole) and the SE system (M_n = 10,200 g/mole) showed phase separated structures with discrete domains of 0.2 μm, but other systems showed smooth fracture surfaces when observed by scanning electron microscopy. The modified epoxy systems except for the AD system and SE system showed two tan δ peaks corresponding to the α and β transitions of the epoxy resin. The modified epoxy systems showed maximum values of K_1c at around 10 wt % of polyester and maximum flexural properties at 5 wt % of polyester. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2464–2473, 2000     

Studies on isotactic poly(phenyl glycidyl ether)‐modified epoxy resins. II. Toughening of epoxy resins

A semicrystalline polymer, isotactic poly(phenyl glycidyl ether) (i‐PPGE) was used as a modifier for epoxy resin; 1,8‐Diamino‐p‐methane (MNDA) and 4,4′‐Diamino diphenyl sulfone (DDS) were used as curing agents. In the MNDA‐cured resins, the dispersed phase were spherical particles with diameters in the range of 0.5–1.0 μm when the resin was blended with 5 phr i‐PPGE. In the DDS‐cured resins, the particle size distribution of the dispersed phase was much wider. The difference was traced back to the reactivity of the curing agent and the different regimes used for curing. Through dynamic mechanical analysis, it was found that in the MNDA‐cured systems, i‐PPGE had a lower crystallinity than in the DDS‐cured system. In spite of the remarkable difference in the morphology and microstructure of the modified resins cured with these two curing agents, the toughening effects of i‐PPGE were similar for these resins. The critical stress intensity factor (K_IC) was increased by 54% and 53%, respectively, for the resins cured by DDS and by MNDA, blending with 5 phr of the toughner. i‐PPGE was comparable with the classical toughners carboxyl‐terminated butadiene‐acrylonitrile copolymers in effectiveness of toughening the epoxy resin. An advantage of i‐PPGE was that the modulus and the glass‐transition temperature of the resin were less affected. However, this modifier caused the flexural strength to decrease somewhat. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1223–1232, 2002; DOI 10.1002/app.10445     

Toughening of thermosets by the creation of residual compressive stresses

The toughening of thermosets through the creation of residual compressive stresses around microspheres was studied. Expandable, hollow microspheres containing gas with heating were used for the creation of residual compressive stresses. Microscopic compressive residual stresses in the vicinity of the crack tip were graphically analyzed and related to the macroscopic mechanical behavior for mode I fracture. The graphical analysis and experimental results confirmed that toughening was achieved mainly because of residual compressive stresses rather than a postcure effect. As expected, however, no toughening effect was found in mode III fracture. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4045–4051, 2006     

脂环族环氧树脂／双酚A环氧树脂共混改性研究

采用脂环族环氧树脂（EPL-4221）与双酚A型环氧树脂E-51共混,用酸酐固化剂和促进剂使其固化,研究脂环族环氧树脂的用量对共混树脂性能的影响及其规律性,包括冲击强度、弯曲强度、拉伸强度、维卡软化点温度、漆膜的粘附力、铅笔硬度、耐磨性以及拉伸剪切强度。结果表明,随脂环族环氧树脂用量的增加,共混树脂的综合性能先增加后降低,脂环族环氧树脂的质量分数为15％-20％时,具有最大值。     

On hybrid toughened DGEBA epoxy resins

Considerable improvements in the fracture resistance of epoxy resins have recently been achieved by adding either rubbery or rigid second phase dispersions, or both, to an epoxy matrix. These multiphase epoxy systems are particularly useful as high performance adhesives and as matrix materials in advanced composites. This paper describes the development of new toughened epoxy hybrids, which contain both rubbery and rigid dispersions. The latter dispersions were either zirconia particles, short alumina fibres or glassy-metal ribbons. Micromechanisms of toughening and failure processes in these new materials are identified and discussed in the light of microstructures.     

Effects of epoxy content on dynamic mechanical behaviour of PEI‐toughened dicyanate–novolac epoxy blends

By varying the cyanate/epoxy ratio, three polyetherimide(PEI)‐modified bisphenol A dicyanate–novolac epoxy resin blends with different epoxy contents were prepared. The effects of epoxy content on the dynamic mechanical behaviour of those blends were investigated by dynamic mechanical thermal analysis. The results showed that the glass transition temperature of the cyanate–epoxy network (T_g1) in the modified blend decreases with epoxy content. When the epoxy content increases, both the width of the glass transition of the cyanate–epoxy network and its peak density are depressed substantially. Although the tangent delta peak value of PEI is basically independent of epoxy content, the T_g of PEI (T_g2) decreases with epoxy content. T_g1 is independent of the PEI loading. When T_g1 is lower than T_g2, however, the T_g1 in the blend with revised phase structure is substantially lower than other blends. Copyright © 2004 Society of Chemical Industry     

Toughening of Diglycidyl Ether of Bisphenol-A Epoxy Resin Using Poly (Ether Ether Ketone) with Pendent Ditert-Butyl Groups

Poly(ether ether ketone) (PEEKDT), hydroxyl terminated poly(ether ether ketone) (PEEKDTOH) and fluorine terminated poly (ether ether ketone) (PEEKDTF) with pendent ditert-butyl groups were synthesized by the nucleophilic substitution reaction of 4,4′-difluorobenzophenone with 2,5-ditert-butylhydroquinone in N-methyl-2-pyrrolidone medium using anhydrous potassium carbonate as catalyst. Diglycidyl ether of bisphenol-A epoxy resin was blended with PEEKDT, PEEKDTOH, and PEEKDTF, and cured with 4,4′-diaminodiphenylsulfone (DDS). The polymers formed heterogeneous blends before curing, and upon curing the polymers got dispersed in the epoxy matrix. The mechanical properties of the cured blends were slightly lower than that of the unmodified resin. The fracture toughness increased with the addition of ditert-butyl PEEK into epoxy resin and the extent of improvement was dependent on the type of modifier used. Hydroxyl terminated polymers gave up to 40% increase in fracture toughness. The dynamic mechanical spectrum of the blends showed only a single T_g due to the proximity of the glass transition temperature of modified PEEK and DDS cured epoxy resin.     

Toughening of cycloaliphatic epoxy resin improved by reactive copolymers with flexible alkyl side chains

Reactive copolymers with flexible alkyl side chains were used as modifiers to improve the toughness of a cycloaliphatic epoxy resin. In this study, we used three types of copolymers with different alkyl chain length (C₄H₉, C₆H₁₃, and C₁₀H₂₁). As a result, the system with an added copolymer having the longest alkyl chain length (C₁₀H₂₁) formed a phase separation structure. The addition of this copolymer (C₁₀H₂₁) led to a 50% increase in the fracture toughness (K_IC) of the cured resin at the slight expense of its glass transition temperature. Scanning electron microscope observations in the vicinity of a crack tip after a compact tension test showed that cavitation of the dispersed phase occurred. The crack growth was inhibited and thus the toughness was improved due to the plastic deformation of the epoxy matrix followed by cavitation. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

New polythiourethane hardeners for epoxy resins

New mercaptan‐terminated polythiourethanes were synthesized from low‐molecular‐weight dimercaptan oligomers and diisocyanates. The characteristic bands in the FT‐IR spectra, and the specific peaks in the ¹H‐NMR spectra correlate rather well with the proposed structures of these polymers. Chemical analysis of the epoxy group conversion and swelling measurements were conducted in order to determine the crosslink densities of the cured epoxy resins. The curing characteristics and thermal behaviour of the formulated curing mixtures indicate that the epoxy/polythiourethane stoichiometry and thermal history during cure may greatly affect the curing mechanism and final properties of the epoxy networks. Mechanical studies indicated that the application of polythiourethane hardeners improves the flexibility with increasing tensile strength and impact toughness. The prepared polythiourethane hardeners have an acceptable odour and give a perfectly homogeneous system with the epoxy resins and have good storage stability with other coreactants such as diamines. Copyright © 2005 Society of Chemical Industry     

Cure kinetics of ternary blends of epoxy resins studied by nonisothermal DSC data

The curing kinetics of blends of diglycidyl ether of bisphenol A (DGEBA), cycloaliphatic epoxy resins, and carboxyl‐terminated butadiene‐acrylonitrile random copolymer (CTBN) in presence of 4,4′‐diamino diphenyl sulfone (DDS) as the curing agent was studied by nonisothermal differential scanning calorimetry (DSC) technique at different heating rates. The kinetic parameters of the curing process were determined by isoconversional method given by Malek for the kinetic analysis of the data obtained by the thermal treatment. A two‐parameter (m, n) autocatalytic model (Sestak‐Berggren equation) was found to be the most adequate selected to describe the cure kinetics of the studied epoxy resins. The values of E_a were found to be 88.6 kJ mol^?1 and 61.6 kJ mol^?1, respectively, for the studied two sample series. Nonisothermal DSC curves obtained using the experimental data show a good agreement with that theoretically calculated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Biolignin™ based epoxy resins

Wheat straw Biolignin? was used as a substitute of bisphenol‐A in epoxy resin. Synthesis was carried out in alkaline aqueous media using polyethyleneglycol diglycidyl ether (PEGDGE) as epoxide agent. Structural study of Biolignin? and PEGDGE was performed by solid‐state ¹³C NMR and gel permeation chromatography, respectively, before epoxy resin synthesis. Biolignin? based epoxy resins were obtained with different ratios of Biolignin? : PEGDGE and their structures were analyzed by solid‐state ¹³C NMR. The crosslinking of PEGDGE with Biolignin? was highlighted in this study. Properties of Biolignin? based epoxy resins were analyzed by differential scanning calorimetry and dynamic load thermomechanical analysis as well as compared with those of a bisphenol‐A epoxy‐amine resin. Depending on the epoxy resin formulation, results confirmed the high potential of Biolignin? as a biosourced polyphenol used in epoxy resin applications. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Aromatic amino acids as latent,bio-based curing agents and toughening agents for epoxy resins

In the realm of bio-based curing agents, recent investigations have focused on amino acids owing to their distinctive attributes. Nevertheless, the suitability of thermosets cured with aromatic amino acids as latent matrix materials for fiber-reinforced composites remains to be empirically established. Consequently, this study is oriented toward assessing the mechanical properties of diglycidyl ether of bisphenol A when cured with either L-tryptophan or L-tyrosine, in the presence of a latent, urea-based accelerator. The investigated properties include glass transition temperatures, tensile, flexural, compression, and fracture toughness properties. The predominant variations in the mechanical characteristics of these thermosets are confined to their Young's moduli and fracture toughness properties. This divergence is attributed to the greater presence of crystals in the L-tyrosine-cured thermoset, resulting in enhanced reinforcement and toughening effects compared to the L-tryptophan-cured thermoset.     

Fracture properties of epoxy/poly(styrene‐co‐allylalcohol) blends

The epoxy/polystyrene system is characterized by a poor adhesion between the constituent phases, which determines its mechanical properties. The adhesion can be improved via blends based on epoxy resin and random copolymers, poly(styrene‐co‐allylalcohol) (PS‐co‐PA). In this work, the influence of PS‐co‐PA content and the good adhesion between the phases on the tensile properties and the fracture toughness achieved through instrumented Charpy tests have been investigated. The tensile strength and the deformation at break showed an increase in the PS‐co‐PA content while the Young's modulus remained the same. The tensile fracture surfaces revealed that the improvement of these magnitudes was mainly due to a crack deflection mechanism. Also, the fracture toughness of the blends was superior to that of the pure epoxy resin. The main operating toughening mechanism was crack deflection. The fractographic analysis showed that ～ 80% of the particles were broken, and the crack tended to divert from its original path through the broken PS‐co‐PA particles. The remaining particles were detached from the epoxy resin, and the holes left suffered plastic deformation. Analytical models were used to predict successfully the toughness due to these mechanisms. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Fibre reinforced composites of multifunctional epoxy resins

Glass and carbon fibre reinforced epoxy composites were fabricated for N,N,N′,N′-tetraglycidyl-4,4′-diaminodiphenyl methane (TGDDM) and its formulated systems with tri- and di-functional reactive epoxy diluents using 30% diaminodiphenyl sulphone (DDS) as a curing agent. The epoxy laminates were evaluated for their physical, chemical and mechanical properties [at room (26°C) and high (100°C) temperatures]. A marginal increase (<20%) in the mechanical properties of CFRP was found compared with GFRP laminates. Incorporation of epoxy diluents altered the mechanical properties of the composites significantly. The incorporation of triglycidyl-4-aminophenol diluent to TGDDM systems resulted in an improvement in mechanical properties of about 2–6%.     

聚丙烯酸酯增韧改性环氧树脂的研究

以丙烯酸正丁酯(BA)、甲基丙烯酸甲酯(MMA)及甲基丙烯酸缩水甘油酯(GMA)为单体通过悬浮聚合反应合成了共聚物P(MMA-BA-GMA)简称(PMBG),采用傅里叶红外光谱仪、核磁共振波谱仪、凝胶渗透色谱仪对PMBG的结构与组成进行了表征。采用合成的PMBG对环氧树脂(DER663)/固化剂(HTP-305)体系进行增韧改性,研究了PMBG含量对体系力学性能和热性能的影响,并通过扫描电镜(SEM)对固化物断面的微观结构进行了分析。结果表明:PMBG改性后的环氧树脂冲击强度及断裂伸长率提高,当PMBG的质量分数为5%时,冲击强度显著提高,增韧改性效果最好,并且对体系的玻璃化转变温度(Tg)影响不大;共聚物在体系固化时发生微相分离,因而提高了环氧树脂的韧性。     

Structure and properties of epoxy resins modified with acrylic particles

The morphology and material properties of dicyandiamide (DICY)‐cured epoxy resins modified with acrylic particles consisting of a PBA (polybutyl acrylate) core and a PMMA (polymethyl methacrylate) shell and epoxy resins modified with acrylic rubber (PBA) particles alone were studied. It was found that the epoxy system modified with core/shell acrylic particles showed higher fracture toughness, indicating that the modification had a larger effect on improving the material properties of the epoxy resin. A characteristic shown by the core/shell acrylic particles is that they swell along with the epoxy resin under exposure to heat and gel before the latter cures. In this process, the epoxy resin penetrates the surface of the shell layer and a bond is formed between the epoxy matrix and the core/shell acrylic particles. This suggests that the epoxy matrix around the core/shell acrylic particles has the effect of increasing the level of energy absorption due to plastic deformation of the matrix. This is thought to explain why the epoxy resin modified with core/shell acrylic particles showed higher fracture toughness. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2955–2962, 1999     

Toughening of epoxy resins modified with polyetherester block copolymers: the influence of modifier molecular architecture on mechanical properties

Thermoplastic elastomers based on polyetheresters with polyoxytetramethylene soft segments and poly(hexamethyleneterephthalate) hard segments were used to toughen anhydride‐cured epoxy resins. The ratio between hard and soft segments and the crystallinity of the hard segments prepared by incorporating poly(hexamethyleneisophthalate) in the block copolymer were varied in order to examine the effect of the modifier's molecular architecture on morphology and mechanical properties of the resin, such as toughness, strength, and stiffness. The experimental data show that segmented polyetheresters are suitable toughening agents for epoxies. The compatibility between resin and toughener and also the mechanical properties of the modified resin depend on the ratio between the hard and soft segments. Epoxy resins blended with 10 wt % of the polyetherester exhibit an increase in toughness by 50–150%, while strength and modulus decrease by 20% or less. An optimal phase adhesion at levels between 70 and 85 wt % of soft segments in the modifier results in a maximum of toughness enhancement (by about 150%) of the resin accompanied with only a slight drop in strength and stiffness (by about 15%). The glass transition temperature is only slightly affected. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 623–634, 2000