Effect of side‐chain length of succinic anhydride on coefficient of thermal expansion behavior of epoxy resins

The effect of an alkenyl side‐chain of succinic anhydride (SA) on the thermal behavior and the coefficient of thermal expansion (CTE) of diglycidylether of bisphenol A (DGEBA) epoxy resins was studied. The number of carbons in the side‐chain of SA was varied from 6 to 14 and N,N‐Dimethylbenzylamine was used as an accelerator. As a result, the reactivity of SA with epoxide groups was decreased on increasing the length of the alkenyl side‐chain of SA. The thermal stabilities of cured DGEBA/SA samples were approximately constant with varying alkenyl side‐chain of SA. Also, the CTE of the systems was increased as the length of the alkenyl side‐chain of SA increased. This could be attributed to the increased motion of the chain segments in the epoxy network structure induced by the longer alkenyl side‐chain of SA. The effect of amount anhydride, thermoplastics, and fillers on the CTE of the epoxy resins was also discussed. Copyright © 2006 Society of Chemical Industry     

Effect of network structure on thermal and mechanical properties of biphenol-type epoxy resins cured with phenols

In the biphenol-type epoxy resin cured with catechol novolac (CN), a very weak glass transition and, thus, a very high rubbery modulus were observed. On the other hand, the glass transition was clearly observed in the system cured with phenol novolac (PN). This means that the micro-Brownian motion of network chains is highly suppressed in the system cured with CN. The reason for this suppression of the chain motion in the CN-cured system has been pursued from the viewpoint of the conformation of network chains. The disappearance of the glass transition in the biphenol-type resin depends on the formation of the active hydrogens in the curing agents. Thus, it was suggested that the suppression of the micro-Brownian motion is due to the orientation of the biphenyl groups in the network. Moreover, it has been shown that the mechanical and bonding strength at high temperature is considerably improved by the suppression of the network chain motion in the CN-cured biphenol resin system. © 1995 John wiley & Sons, Inc.     

Thermal modification of amine cured epoxy resins - thermal and mechanical studies

Mechanical test data are reported on lap joints and tensile test specimens which have been subjected to a defined post cure cycle. The mechanical properties exhibited an apparently systematic variation with temperature. Inspection of the resins indicated that chemical modification does not appear to occur to a significant extent below 433K. The change in the strength of the joints tensile test samples are discussed in terms of the relative importance of physical and chemical changes on the mechanical properties. It is evident that in the presence of oxygen considerable chemical modification can occur and this is observed both in terms of a change in colour of the resin and the appearance of voids.     

环氧树脂／酸酐固化体系的固化动力学及耐热性研究

通过不同升温速率下的DSC研究了环氧树脂/酸酐固化体系的固化动力学.利用DSC、DMA和TGA研究了固化体系的耐热性能.通过分析确定了体系的固化工艺,采用Kissinger、Ozawa法计算出固化体系的表观活化能.其均值为62.00 kJ/mol,结合Crane公式求出反应级数为0.92.采用DSC法测得玻璃化转变温度Tg=183℃.采用DMA法测得玻璃化转变温度Tg=182℃.热失重曲线表明,固化体系的起始分解温度为350℃.     

Correlations between dynamic mechanical properties and nodular morphology of cured epoxy resins

Various epoxy resin formulations, based on the diglycidyl ether of bisphenol A (DGEBA) and cured with diethylene triamine (DETA) were studied. Dynamic mechanical measurements were used to characterize changes in mechanical properties as a function of temperature. The morphology of the cured resins was investigated by transmission electron microscopy. Correlations between dynamic mechanical properties and morphology were described and discussed by applying the concept of inhomogeneous (nodular) thermoset morphology. The elastic storage modulus in the glassy state was determined primarily by the internodular matrix, whereas the glass transition of cured resins depended upon the intranodular crosslink density.     

Synthesis of epoxy resins from alcohol‐liquefied wood and the mechanical properties of the cured resins

New wood‐based epoxy resins were synthesized from alcohol‐liquefied wood. Wood was first liquefied by the reaction with polyethylene glycol and glycerin. The alcohol‐liquefied wood with plenty of hydroxyl groups were precursors for synthesizing the wood‐based epoxy resins. Namely, the alcoholic OH groups of the liquefied wood reacted with epichlorohydrin under alkali condition with a phase transfer catalyst, so that the epoxy groups were put in the liquefied wood. The wood‐based epoxy resins and the alcohol‐based epoxy resins as reference materials were cured with polyamide amine. The glass transition temperature (Tg), the tensile strength, and the modulus of elasticity of the wood‐based epoxy resin were higher than those of the alcohol‐based epoxy resin. Also, the shear adhesive strength of the wood‐based epoxy resin to steel plates was higher than those of the alcohol‐based epoxy resins, which was equivalent to the level of petroleum‐based bisphenol‐A type epoxy resins. The higher Tg of the wood‐based epoxy resin than that of the alcohol‐based epoxy resin is one of the evidences that the wood‐derived molecules were chemically incorporated into the network structures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fracture and mechanical properties of epoxy resins and rubber-modified epoxy resins

Fracture and mechanical property data on a wide range of epoxy resin systems are presented. The extent to which toughening can be induced by heterophase rubber inclusions depends more on the curing agent used than on the resin component. The greatest improvements in toughness were obtained by rubber modification of epoxy resins cured with an anhydride. A preformed ABS polymer can be used to toughen many epoxy resin systems. With one major exception (where a large improvement was found) only small changes in tensile properties occur when small amounts of rubber are present.     

TGA-FTIR研究环氧/酸酐固化物热降解行为

采用TGA-FTIR联用技术在高纯氮气保护下实时研究了环氧树脂酸酐固化物热降解过程和气相产物。TG和DTG曲线表明,环氧树脂酸酐固化物存在着2个热失重阶段,最大热失重速率峰值温度分别在163℃和389℃,其失重温度范围分别在100~210℃和260~570℃。FTIR谱图表明第一失重阶段主要是体系中所含的水分挥发和/或伯醇脱水及一些小分子物质挥发过程。CO和酮类物质分别产生于280℃和305℃,并一直持续到本实验结束;酸酐类物质在455℃以下时吸收峰的强度很微弱,此后逐步增强。此外,环氧树脂酸酐固化物热降解气相挥发物还有各种碳氢混合物。     

Preparation and cured properties of novel cycloaliphatic epoxy resins

Preparation and characterization of novel cycloaliphatic epoxy resins, which are derived from octadienyl compounds, were studied. From a model peracetic acid epoxidation reaction using 2,7-octadienyl acetate-1, the structure of the liquid resins is estimated to be mainly terminal epoxides and some amount of inner epoxide depending on the epoxide content. The epoxy resins offer lower toxicity and lower vapor pressure. The reactivity of the resin with acid anhydrides is moderate but faster than that of traditional cyclohexane epoxide-type resins and slower than that of the glycidyl ester-type resins. This reactivity was also examined using model compounds. The heat deflection temperature of the hexahydro-phthalic anhydride-cured resins is shown to be directly proportional to the number of epoxy groups in the molecules. The flexural strength of the cured resins is nearly equivalent to that of the commercial resins, although the flexural elongation of the resins is larger than that of the rigid cyclohexane epoxide-type resins. The thermal stability of the cured resins is comparable to typical rigid cycloaliphatic resins; furthermore, high water resistance of the cured resins is suggested to be attributed to the hydrophobic character of the C₈ chain by cross-linking. © 1993 John Wiley & Sons, Inc.     

Toughened epoxy-liquid polybutadiene networks cured with anhydride with outstanding thermal and mechanical properties

Toughened epoxy systems cured with anhydride-based hardener were successfully prepared by incorporating nonpolar liquid polybutadiene (PB) previously functionalized with isocyanate groups (PBNCO). The NCO groups in PBNCO react with the hydroxyl and/or epoxy groups of the matrix forming a ER-PB-ER triblock copolymer. The block copolymer is evidenced by transmission electron microscopy (TEM). In fact the modified epoxy resin (ER) networks presented domains with cocontinuous-like morphology, composed by PB and ER phases in nanomeric dimensions. The effect of PBNCO on the curing process of ER was studied by rheometry. Also the resulting networks were characterized by mechanical and dynamic mechanical properties, differential scanning calorimetry, and TEM. By adding an amount of rubber as high as 20 phr, a great improvement of toughness (around 140%) and impact resistance as well as a good transparency were achieved without significantly affecting the modulus and stiffness. Also the glass transition temperature (Tg) increased around 10°C with the presence of 5 phr of PBNCO. Even with the addition of 20 phr of rubber, the Tg of the system was superior than that found for the neat epoxy network. The outstanding physic-mechanical performance is attributed to the peculiar morphology.     

Modeling the effect of the curing conversion on the dynamic viscosity of epoxy resins cured by an anhydride curing agent

Nanocomposites of poly(vinyl alcohol) (PVA) with Mg‐Al layered double hydroxides (LDHs) were prepared with different compositions, viz., 2, 4, 6, and 8 wt %, of LDH, by solution‐intercalation method. The effect of LDH contents on thermal, physicomechanical, and morphological property of PVA films were investigated. Differential scanning calorimetric analysis reveals that LDH layers promote a new crystalline phase for PVA. The tensile analysis of PVA/LDH nanocomposites indicates reduction in tensile strength and modulus with change in LDH concentration and moisture. The microstructure analysis by optical microscopy and scanning electron microscopy demonstrates exfoliation and dispersion of LDHs in the PVA matrix in a disorderly fashion. The primary focus of the present investigation is to explore the potential of LDHs as nanofiller in a polyhydroxy polymer without surface modification. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Physical properties and shrinkage of epoxy resins cured with lactams

In order to reduce the shrinkage of epoxy resin during the curing process, lactam is incorporated into epoxy in a copolymerization reaction. In this study, various amounts of lactams and BF₃-MEA were added to epoxy, and the volume shrinkage of polymerization was investigated. It was found that shrinkage decreases with the increase of the lactam content and with the lactam ring size as well. Infrared spectroscopic analysis, scanning electronic microscopic analysis, and mechanical tests were used to investigate the structure and properties of the copolymers. The results show that the incorporation of caprolactam leads to an increase in tensile strength and elongation, but the Izod impact strength is not improved.     

Curing behavior,thermal, and mechanical properties of epoxy resins cured with a novel liquid crystalline dicarboxylic acid curing agent

A novel di‐carboxylic acid curing agent (DACA) was successfully synthesized and cured with three different epoxy resins: glycidyl end‐capped poly(bisphenol‐A‐co‐epichlorohydrin) (pDGEBA, M_n = 377), N,N‐diglycidyl‐4‐glycidyloxyaniline (TGAP), and 4,4′‐methylenebis(N,N‐diglycidylaniline) (TGDDM). The cured epoxy exhibited excellent thermal stability, which was indicated by high initial degradation temperature (T_id) and char yield. The T_id values of cured epoxy were in the range of 327–338°C, and the char yields increased with increasing epoxy functionality. The char yields of cured DACA/pDGEPA, DACA/TGAP, and DACA/TGDDM samples were 21.1, 60.4, and 66.9%, respectively. In addition, the cured epoxy samples also showed low coefficients of thermal expansion and high storage moduli (E′), which were around 60 ppm/°C and 2800 MPa, respectively. The failure surfaces were ductile and rough, so the cured epoxy samples are expected to have high fracture toughness and impact strength. POLYM. ENG. SCI., 54:695–703, 2014. © 2013 Society of Plastics Engineers     

Thermoplastic‐modified epoxy resins cured with different functionalities amine mixtures: Morphology,thermal behavior,and mechanical properties

Epoxy matrices inherent brittleness and poor crack resistance make necessary some form of toughening. In this work, to improve their fracture toughness and ductility epoxy matrices were modified by changing its architecture and by the addition of a third component. The matrices architecture were modified by stoichiometrically reacting a bifunctional epoxy resin with different functionalities amine mixtures, one of which being a monoamine that plays the role of chain extender. In the modification by the addition of a third component, poly(methyl methacrylate) (PMMA) was selected as modifier. PMMA is initially miscible with epoxy/amine systems but can phase separate during curing. The kinetics and miscibility of these systems were studied previously. At constant curing conditions, materials from completely opaque (phase separated) to transparent (miscible) can be obtained with the increase in monoamine content. In this work, the effects of the modifier content and of the monoamine : diamine ratio in stoichiometric epoxy/amine mixtures on the resultant morphologies as well as on their thermal and mechanical properties was studied.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Correlation between nodular morphology and fracture properties of cured epoxy resins

Various bulk epoxy resin formulations, based on diglycidyl ether of bisphenol A (DGEBA) and cured with diethylene triamine (DETA) were studied. Methods of linear elastic fracture mechanics were employed and all systems were characterized by the corresponding values of the critical strain energy release rate for crack initiation and crack arrest. Fracture morphology was studied by scanning electron microscopy and transmission electron microscopy of carbon—platinum surface replicas. An apparent correlation between morphology and ultimate mechanical properties has been found. All fracture surfaces are shown to be characterized by distinct nodular morphology. Nodules, ranging in size from 15–45 nm, represent the sites of higher crosslink density in an inhomogeneous network structure. Fracture surfaces were further characterized by three crack propagation zones. A smooth, brittle fracture zone was preceded and followed by crack initiation and crack arrest zones, respectively. An apparent plastic flow was confined to the initiation and arrest regions. No crazing phenomenon was seen in the initiation zone; instead a step-like fracture was observed, typified by the ‘flow’ of internodular matrix during step formation. Local plastic deformation in the initiation zone and the corresponding value of critical strain energy release rate, G_Ic, were correlated with the nodular morphology. The size of nodules was found to vary with the curing agent concentration, thus allowing us to establish a fundamental correlation between the nodular morphology and the ultimate mechanical properties of epoxy resins.     

The effect of mesogenic length on the curing behavior and properties of liquid crystalline epoxy resins

The effect of mesogenic structure on the properties of liquid crystalline epoxy (LCE) resins was investigated. The mesogenic lenght of the LCE was changed by changing the length of the rigid rod unit of LCE and it was correlated with the curing behavior and thermomechanical properties of LCE resins. The curing of LCE resins was accelerated in the LCE with LC phase during curing and storage modulus and glass transition temperature of LCE thermosets were high in the epoxy networks with long mesogenic group. In addition, the LC phase of LCE was stable for LCE with long mesogenic group and it was maintained until decomposition.     

Investigation on the effect of the presence of hyperbranched polymers on thermal and mechanical properties of an epoxy UV‐cured system

The use of hydroxyl‐functionalized hyperbranched polymers (HBPs) (Boltorn^® H20, H30 and H40) was investigated with respect to a UV‐cured epoxy system. Their presence induced an increase of the final epoxy conversion, which was interpreted on the basis of a chain‐transfer reaction. A decrease of the T_g values in the photocured films was observed when the amount of HBP additive in the photocurable formulation was increased. When the amount of HBP in the photocurable resin was increased, the density of photocured films increased, indicating a decrease on the free volume. Moreover, a clear increase in toughness was observed and attributed to the plasticization effect induced by the presence of HBP. This effect is particularly interesting for epoxy thermosets, which are characterized by good mechanical properties, although they are brittle and fragile. By increasing the toughness properties of these photocured resins it may be possible to broad their applications. Copyright © 2005 Society of Chemical Industry     

Studies on epoxy resins cured by cationic latent thermal catalyst at elevated temperature

In this work, the effect of the catalyst content was investigated in terms of the thermal and mechanical properties of epoxy resins at elevated temperature. A synthesized cationic latent thermal catalyst, N‐benzylpyrazinium hexafluoroantimonate (BPH), was used to cure epoxy resins. The content of catalyst added was 0.5, 1, 2, 3 and 5 wt% and the heating time was varied from 0 to 1024 h. As a result, the mechanical properties, including flexural strength, elastic modulus in flexure and impact strength, as well as thermal‐oxidative resistance, showed a maximum value in the presence of 1 wt% BPH. With increasing elapsed time, up to 4 h, the thermal and mechanical properties of the specimens were improved. These results show that the internal structure of the epoxy system was stabilized, and post‐curing for a longer period of time, resulted in improved thermal and mechanical behaviour of the cast specimens. Copyright © 2004 Society of Chemical Industry     

Frontal curing of epoxy resins: Comparison of mechanical and thermal properties to batch-cured materials

The epoxy resin diglycidyl ether of bisphenol F (DGEBF) was cured by the aliphatic amine curing agent Epicure 3371 in a stoichiometric ratio both frontally and in a batch-cure schedule. Glass transition temperatures (T_g) were determined using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). DMA also was used for studying the storage modulus (E′) and tan delta (tan δ) of the cured samples. Tensile properties of epoxy samples were tested according to ASTM D638M-93. The properties of the frontally cured epoxy resin were found to be very close to that of batch-cured epoxy resin. Velocity of cure-front propagation was measured for both neat and filled epoxy. Rubber particles (ground tires) were used as a filler. The maximum percentage of filler in the epoxy resin allowing propagation was 30%. Because of convection, only descending fronts would propagate. Advantages and disadvantages of frontal curing of epoxy resins are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1209–1216, 1997     

Intermolecular force and thermal properties of the sulfonyl epoxy blends cured with DGEBA epoxy

The sulfonyl epoxy monomer (SEP) was synthesized and further to blend with the diglycidyl ether of bisphenol A (DGEBA). The glass transition temperature (T_g) of the SEP/DGEBA blended materials increased from 103.7 to 163.8°C. The cross‐linking density and polymer chain self‐association intra‐molecular action affected more than that the polymer–polymer intermolecular action (hydrogen bonding) in the SEP blended with the DGEBA materials. The excess stabilization energy in the overall stabilization was only 0.00145% (14.5 ppm), which indicated that the polymer‐polymer intermolecular action was weak. The thermal degradation of the SEP segments could form various sulfate derivatives at lower temperature and analyzed by the TGA/GC/Mass. The sulfate derivatives could generate the thermal stable chars, which provided the “shielding effect” and antioxidation property. Additionally, these chars could also improve the protective effect and inhibit the thermal‐oxidation decomposition under the air atmosphere. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010