Cure behavior of epoxy resin/MMT/DETA nanocomposite

The Flory's gelation theory, non-equilibrium thermodynamic fluctuation theory and Avrami equation have been used to predict the gel time t _g and the cure behavior of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposites at various temperatures and organo-montmorillonite loadings. The theoretical prediction is in good agreement with the experimental results obtained by dynamic torsional vibration method, and the results show that the addition of organo-montmorillonite reduces the gelation time t _gand increases the rate of curing reaction, the value of k, and half-time of cure after gelation point t_1/2 decreases with the increasing of cure temperature, and the value of n is ~2 at the lower temperatures (<60°C) and decreases to ~1.5 as the temperature increases, and the addition of organo-montmorillonite decreases the apparent activation energy of the cure reaction before gelation point, but has no apparent effect on the apparent activation energy of the cure reaction after gelation point. There is no special curing process required for the formation of epoxy resin/organo-montmorillonite/diethylenetriamine intercalated nanocomposite. This revised version was published online in July 2006 with corrections to the Cover Date.     

Tribological performance and thermal behavior of epoxy resin nanocomposites containing polyurethane and organoclay

A series of epoxy resin nanocomposites modified by polyurethane and organically modified montmorillonite was prepared by effectively dispersing the organically modified montmorillonite in interpenetrating polymer networks (IPNs) of epoxy and polyurethane via the sequential polymeric technique and in situ polymerization. The tribological performance of the resultant EP/PU nanocomposites was investigated by a pin‐on‐disc tester, and the results showed that adding polyurethane and organically modified clay to the EP matrix had a synergistic effect on improving tribological performance of EP/PU nanocomposites. The morphologies of the worn surface were studied by scanning electron microscopy (SEM) observations, and the results indicated that the mechanism of improving tribological performance of EP/PU nanocomposites was different from that of pure EP or pure EP/PU IPNs. The thermal behavior of these nanocomposites was also investigated by thermogravimeric analysis (TGA), and the results indicated that adding organically modified clay to the matrix remedied the deterioration of the thermal degradation temperature of the interpenetrating networks. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and characterization of microencapsulated LDHs with melamine‐formaldehyde resin and its flame retardant application in epoxy resin

Layered double hydroxides (LDHs) are emerging as a new and green high‐efficient flame retardant. But LDHs aggregate seriously because of their hydrophilicity, which affect deeply the mechanical and flame retardant properties of their composites. For the first time in this paper, microencapsulated LDHs (MCLDHs) with melamine‐formaldehyde (MF) resin were prepared by microencapsulation technology to enhance their compatibility and dispersion within epoxy resin (EP). The mechanical and flame retardant performances of EP/MCLDH composite were studied by comparing with EP/LDH composite. Results showed that the water contact angle of MCLDHs increased from 8.9° to 122.1°, which indicated good compatibility. The particle size of MCLDHs decreased sharply, and more than one‐third were up to submicron scale, which can be conducive to dispersion. Moreover, the tensile strength and elongation at break of EP/MCLDHs with different flame retardant contents were higher than those of EP/LDHs. And the addition of MCLDHs increased the glass transition temperature (Tg) of EP/MCLDHs, which meant a strong interfacial interaction. Besides, compared with EP/LDHs, the limiting oxygen index values of EP/MCLDHs were higher, and its peak of heat release rate and total heat release decreased by 16.3% and 5.5% respectively. EP/MCLDHs achieved from V‐1 to V‐0 rate with the increasing content of MCLDHs from 20% to 30%, while LDHs/EP never passed tests. In the process of heating, H₂O, CO₂, and NH₃ released from MCLDHs formed gaseous phase, and the remaining dense char layers and oxides produced condensed phase, which played an important role in inhibiting combustion.     

水性环氧树脂的研制及其固化性能研究

采用端甲氧基聚乙二醇、马来酸酐、E-44环氧树脂合成了反应型环氧树脂乳化剂MeO-PEG-Ma-E-44,以相反转乳化技术制备E-44水性环氧树脂,研究了工艺条件对其性能的影响。结果表明:酯化率达98.5%的MeO-PEG-Ma-E-44,用量为E-44的ω=16.5%-20%得到的水性环氧树脂乳液最稳定。DSC和TG分析结果表明:乳化前后的E-44环氧树脂都能室温条件2h内很好的固化,固化后热性能基本不变,分解温度约在380℃,热失重率89%,其玻璃转变温度有所降低,韧性有所提高,其它性能基本不受影响。     

Effects of organoclays on the thermal processing of pe/clay nanocomposites

Nanocomposites containing both polyethylene and montmorillonite clay organically modified with four different types of quaternary ammonium salts were obtained via direct melt intercalation. Thus, the main purpose of this work was to evaluate the effect of the organoclay on the thermal stability of polyethylene. The organoclays were characterized by XRD, FTIR, DSC and TG. The polyethylene/organoclay nanocomposites were studied by XRD, TEM, TG, besides an evaluation of their mechanical properties. The results showed that the salts were incorporated by intercalation between the layers of the organoclay and, apparently that the nanocomposites were more thermally stable than pure polyethylene.     

The dynamic mechanical behavior of random-in-plane short fiber-reinforced epoxy resin composites

In the present paper, the dynamic mechanical properties of random-in-plane short fiber-reinforced epoxy resin composites were studied by using a rheometrics solids analyzer. The three-point bend testing of the four composites (glass fiber/913 epoxy resin, glass fiber/924 epoxy resin, carbon fiber/913 epoxy resin and carbon fiber/924 epoxy resin) was carried out over temperatures from −100°C to 200°C at a frequency of 10 Hz and strain 0.05%. The composites based on 924 epoxy resin, which has been designed specially for high temperature applications, have less energy loss than the 913 epoxy resinbased composites. For the same resin, the carbon fiber-reinforced composites have less energy loss than the glass fiber-reinforced composites. All the composites have less energy loss than their corresponding matrices; the greater the fiber content, the lower the energy loss. The beta transition of 913 epoxy resin has been shifted to a higher temperature after being reinforced. It was shifted from −50°C to −30°C after being reinforced with glass fiber and made a diffuse shoulder-like peak commencing at −30°C after being reinforced with carbon fiber. The 924 epoxy resin has undergone the same change in beta transition as the 913 resin, though to a smaller extent. The phenomenon suggested that interactions between the macromolecules of the epoxy resins and the molecules along the fiber's surface.     

Graft interpenetrating polymer networks composed of epoxy resin and urethane acrylate resin

For enhancing the interpenetratoin and/or compatibility of the simultaneous interpenetrating networks (SINs) composed of epoxy resin (epoxy) and urethane acrylate resin (UAR), the graft epoxy consisting of different lengths of poly(oxypropylene) (PO) side chains were synthesized and characterized. It was found that the graft epoxy composed of short PO side chains [MW 480, epoxy-g-PO(480)] showed a compatible system while if consisting of longer PO grafts [MW 950, epoxy-g-PO(950)] exhibited a partial microphase separation morphology. DSC measurements as well as the SEM or TEM observation indicated that the interpenetration between the two phases for epoxy/UAR SINs including epoxy-g-PO(480) was improved appreciably due to the excellent miscibility between the PO grafts and PO segments existing in the graft epoxy and the UAR network, respectively. In this case, for SIN(80/20) containing 10 wt % of epoxy-g-PO(480) the tensile strength increases by a factor of 2.70 compared with that of pure epoxy network. However, the improvement of interpenetration and/or compatibility between the two networks as well as the mechanical properties for SINs composed of epoxy-g-PO(950) are limited resulting in the partial microphase separation of epoxy-g-PO(950) network's own self. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3568–3574, 1999     

Enthalpy relaxation in a partially cured epoxy resin

The enthalpy relaxation of a partially cured (70%) epoxy resin, derived from diglycidyl ether of bisphenol-A cured by methyl-tetrahydrophthalic anhydride with accelerator, has been investigated. The key parameters of the structural relaxation (the apparent activation energy Δh*, the nonlinearity parameter x, and the nonexponentiality parameter β) are compared with those of the fully cured epoxy resin. The aging rates, characterized by the dependences of the enthalpy loss and peak temperature on log(annealing time), are greater in the partially cured epoxy than they are in the fully cured resin at an equivalent aging temperature (T_a = T_g − 20°C). There is a significant reduction in Δh*, from 1100 kJ mol⁻¹ for the fully cured system to 615 kJ mol⁻¹, as the degree of cure is reduced. The parameter x determined by the peak-shift method appears essentially independent of the degree of cure (x = 0.41 ± 0.03 for the partially cured resin compared with 0.42 ± 0.03 obtained previously for the fully cured resin), and does not follow the usually observed correlation of increasing x as Δh* decreases. This invariability of the parameter x seems to indicate that it is determined essentially by the local chemical structure of the backbone chain, and rather little by the supramolecular structure. On the other hand, the estimated nonexponentiality parameter β lies between 0.3 and 0.456, which is significantly lower than in the fully cured epoxy (β ≅ 0.5), indicative of a broadening of the distribution of relaxation times as the degree of cross-linking is reduced. Like the parameter x, this also does not follow the usual correlation with Δh*. These results are discussed in the framework of strong and fragile behavior of glass-forming systems, but it is difficult to reconcile these results in any simple way with the concept of strength and fragility. © 1996 John Wiley & Sons, Inc.     

Study on curing reaction of epoxy resin modified with prepolymers containing spiro orthocarbonate

Prepolymers were prepared by the reaction of 3,9-dihydroxyethyl-3′9′-dibenzyl-1,5,7,11-tetraoxaspiro(5,5)undecane with 4,4′-diphenylmethane diisocyanate (MDI) and 1,6-hexa-methylene diisocyanate (HDI). The number-average molecular weights of the prepolymers can be controlled by changing the mole ratios of spiro compound and diisocyanates. Kinetic studies of the cure reaction for the epoxy resin system modified with or without prepolymers were followed by a HLX-1 dynamic torsional vibration apparatus. The results indicated that gel time (t_g) and activation energy (E_a) increased as the content of prepolymers in the epoxy resin system increased. A difference with the cure reaction of the pure epoxy resin, the second-order reaction for the epoxy resin modified with the prepolymers, was obtained. Rate constants (k) of the cure reaction are 0.231 min^?1 for the epoxy resin, and 0.312 min^?1 for the modified epoxy resin. The mechanism of the cure reaction was discussed. © 1995 John Wiley & Sons, Inc.     

The mechanical properties and tribological behavior of epoxy resin composites modified by different shape nanofillers

Mechanical properties and tribological behavior of epoxy resin (EP) and EP nanocomposites containing different shape nanofillers, such as spherical silica (SiO₂), layered organo‐modified montmorillonite (oMMT) and oMMT‐SiO₂ composites, were investigated. The SiO₂‐oMMT composites were prepared by in situ deposition method and coupling agent modification, and transmission electron microscopy (TEM) analysis shows that spherical SiO₂ is self‐assembled on the surface of oMMT, which forms a novel layered‐spherical nanostructure. The mechanical properties test results show that oMMT obviously improves the strength of EP and SiO₂ enhances its toughness, but oMMT‐SiO₂ exhibits a synergistic effect on toughening and reinforcing EP simultaneously. A pin‐on‐disc rig was used to test friction and wear loss of pure EP and EP nanocomposites. The tribological test results prove that these nanofillers with different shapes play different roles for improving the wear resistance of EP nanocomposites. Morphologies of the worn surfaces were studied further by scanning electron microscopy (SEM) observations, and it was clarified that the EP and EP nanocomposites undergo similar wear mechanisms. Copyright © 2006 John Wiley & Sons, Ltd.     

环氧树脂在热塑性树脂改性中的应用

本文综述了国内外有关利用环氧树脂改性热塑性树脂共混体系研究的最新进展。着重阐述了环氧树脂在热塑性树脂之间的增容作用,如尼龙6(PA6)合金体系,改性聚苯乙烯塑料(ABS)合金体系,以及聚对苯二甲酸丙二醇酯(PTT)合金体系等。同时,介绍了利用环氧树脂的反应活性提高无机填料在聚合物中分散性研究的情况,如二氧化硅纳米粒子在聚醚砜(PES)中,以及滑石粉在聚丙烯(PP)中分散性的提高。最后,简介了环氧树脂改性热塑性树脂提高热塑性树脂物理机械性能方面的研究方向和成果并展望了环氧树脂在热塑性树脂改性研究中的前景。     

液晶环氧p-PEPB的合成及改性双酚-A环氧树脂的研究

本文以对羟基苯甲酸乙酯、丙烯溴、对苯二酚等为原料合成了双4-环氧丙基醚苯甲酸对苯二酚酯液晶环氧树脂(p-PEPB).用IR、1HNMR、DSC、POM和XRD的对其进行了表征,结果表明该化合物为向列型液晶,其熔点为180℃,清晰点为250 ℃.研究了 p-PEPB/双酚-A环氧(BPAER)/4,4,-二氨基二苯醚(DDE)体系的非等温固化过程,得到了固化温度参数、表观活化能Ea及p-PEPB含量对Tg的影响,结果表明p-PEPB为5%可使BPAER的Tg提高14 ℃,固化过程服从Ozawa模型.     

Reaction of epoxy resin and hyperbranched polyacids

The condensation reaction between two different epoxy resins and a hyperbranched polyester (MAHP) [poly(allyloxy maleic acid‐co‐maleic anhydride)] was studied. We compared two kinds of diglycidyl ether bisphenol A type of epoxy resins with different molecular weights, that is, epoxy resin GY240 (M = 365 g/mol) and GT6064 (M = 1540 g/mol) in this reaction. The results showed a marked difference in their reaction pattern in terms of ability to form crosslinked polymer networks with MAHP. For the former low‐molecular‐weight epoxy resin, no crosslinking could be observed in good solvents such as THF or dioxane within the set of reaction conditions used in this study. Instead, polymers with epoxide functional degrees between 0.34 and 0.5 were formed. By contrast, the latter high‐molecular‐weight epoxy resin, GT6064, rapidly produced highly crosslinked materials with MAHP under the same reaction conditions. The spherical‐shape model of hyperbranched polymer was applied to explain this difference in reaction behavior. Hence, we have postulated that low‐molecular‐weight epoxy resins such as GY240 are unable to crosslink the comparatively much bigger spherically shaped MAHP molecules. However, using high‐molecular‐weight epoxy resins greatly enhances the probability of crosslinking in this system. Computer simulations verified the spherical shape and condensed bond density of MAHP in good solvents, and submicron particle analysis showed that the average MAHP particle size was 9 nm in THF. Furthermore, the epoxy‐functionalized polyesters were characterized by ¹H NMR and FTIR, and the molecular weights and molecular‐weight distributions were determined by size‐exclusion chromatography. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4457–4465, 2000     

The effect of annealing conditions on the intercalation and exfoliation of layered silicates in polymer nanocomposites

Layered silicate nanocomposites based on polyamide 6 and polypropylene have been prepared via static annealing experiments. The evolution of clay dispersion into the polymer matrices was monitored by wide angle X‐ray diffraction analysis and transmission electron microscopy. The results have evidenced that the polymer diffusion inside the organoclay galleries is spontaneous and have elucidated the mechanism of nanostructured system formation under static conditions. Indeed, the exfoliation mechanism turned to be a two‐step process consisting of polymer intercalation into the clay galleries and progressive layer delamination. Both steps have turned out to depend on thermodynamic and kinetic parameters. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Preparation of epoxy-acrylic latex based on bisphenol F epoxy resin

Bisphenol F based epoxy-acrylic latex with different amount of epoxy resin was successfully prepared by semi-continuous seeded emulsion polymerization. The resulting composite latexes had a narrow size distribution of about 105 nm in diameter. The DSC result showed that the epoxy resin and polyacrylate were grafting copolymerization. The FTIR spectra showed that the epoxy group had been introduced into the epoxy acrylic latex system, and the composite latex could be crosslinked with epoxy hardener at room temperature. The crosslinked composite latex film exhibited a high Tg compared to epoxy-acrylic latexes. The surface of the films with the epoxy resin was regular, and diffused into the polyacrylate phase in the epoxy-acrylic latexes films. Since the curing reactions occurred before latex particle coalescence stage, the surfaces of the cured epoxy-acrylate latex films had a number of interface particle. Compared with the acrylic latex, the thermal stability of the epoxy-acrylate latex was increased, and the stability of the cured film increased with increasing epoxy content.     

Synthesis and curing of liquid crystalline epoxy resin based on naphthalene mesogen

Aromatic liquid crystalline epoxy resin (LCE) based on naphthalene mesogen was synthesized and cured with aromatic diamines to prepare heat‐resistant LCE networks. Diaminodiphenylester (DDE) and diaminodiphenylsulfone (DDS) were used as curing agents. The curing reaction and liquid crystalline phase of LCE were monitored, and mechanical and thermal properties of cured LCE network were also investigated. Curing and postcuring peaks were observed in dynamic DSC thermogram. LCE network cured with DDE displayed liquid crystalline phase in the curing temperature range between 183 and 260°C, while that cured with DDS formed one between 182 and 230°C. Glass transition temperature of cured LCE network was above 240°C, and crosslinked network was thermally stable up to 330°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 419–425, 1999     

Effect of carbon fiber surface functionality on the moisture absorption behavior of carbon fiber/epoxy resin composites

Polyacrylonitrile (PAN)‐based carbon fibers were electrochemically oxidized in aqueous ammonium bicarbonate with increasing current density. The electrochemical treatment led to significant changes of surface physical properties and chemical structures. The oxidized fibers showed much cleaner surfaces and increased levels of oxygen functionalities. However, it was found that there was no correlation between surface roughness and the fiber/resin bond strength, i.e. mechanical interlocking did not play a major role in fiber/resin adhesion. Increases in surface chemical functionality resulted in improved fiber/resin bonding and increased interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composites. The relationship between fiber surface functionality and the hydrothermal aging behavior of carbon fiber/epoxy composites was investigated. The existence of free volume resulted from poor wetting of carbon fibers by the epoxy matrix and the interfacial chemical structure were the governing factors in the moisture absorption process of carbon fiber/epoxy composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Swelling behavior of organoclays in styrene and exfoliation in nanocomposites

Organoclays were prepared by cationic exchange of montmorillonite (MMT) with three commercial surfactants: octadecylamine (ODA), hexadecyltrimethylammonium bromide (HTAB), benzalkonium chloride (BAC), and an in-house synthesized surfactant, vinylbenzylalkyldimethylammonium chloride (VDAC). The swelling behaviors of organoclays in styrene were compared by wettability and rheology measurements. VDAC-MMT had the slowest capillary rise rate in styrene. The Washburn equation was found not suitable for the swellable organoclay powders. All organoclay-styrene and organoclay-toluene mixtures demonstrated yield stress. However, VDAC-MMT-styrene and VDAC-MMT-toluene mixtures showed significant higher yield stresses than the other organoclay mixtures. The wettability and rheology measurements indicate that VDAC-MMT bearing a styryl functional group has the strongest interaction with styrene monomer and toluene. In order to further evaluate the extent of swelling and the microstructure, polystyrene (PS)-clay nanocomposites were prepared by in situ polymerization. X-ray diffraction (XRD) and transmission electron microscopy (TEM) indicate that ODA and HTAB-MMT led to intercalated PS-clay nanocomposites, while VDAC-MMT formed exfoliated PS-clay nanocomposites.     

Thermotropic liquid crystalline polyester nanocomposites via in situ intercalation polycondensation

A thermotropic liquid crystalline polyester (TLCP)/organoclay nanocomposite was synthesized via in situ intercalation polycondensation of diethyl‐2,5‐dihexyloxyterephthalic acid and 4,4′‐biphenol in the presence of organically modified montmorillonite (MMT). The organoclay, C18‐MMT, was prepared by the ion exchange of Na⁺‐MMT with octadecylamine chloride (C18‐Cl^?). TLCP/C18‐MMT nanocomposites were prepared to examine the variations of the thermal properties, morphology, and liquid crystalline phases of the nanocomposites with clay content in the range of 0–7 wt%. It was found that the addition of only a small amount of organoclay was sufficient to improve the thermal behavior of the TLCP hybrids, with maximum enhancement being observed at 1 wt% C18‐MMT. Copyright © 2008 John Wiley & Sons, Ltd.     

Properties of epoxy systems with clay nanoparticles

Low molecular epoxy resin was mixed with different concentrations of montmorillonite clay with alkylamine-modified surface. The presence of the clay nanoparticles influences the gel time of the amine cured resin as well as the mechanical properties. Toughness and modulus, both in the glass and the rubberlike region, increase with clay concentration. An increasing amount of lower mobility phase with increased clay concentration was observed.