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1.
We studied the effects of functional groups on the physicochemical properties, such as rheological behavior, thermal stability, glass‐transition temperature, and electrical and mechanical properties, of 4,4′‐diaminodiphenyl methane (DDM) cured methyl‐substituted and trifluoromethyl‐substituted difunctional epoxy resins [i.e., 2‐diglycidylether of toluene (DGET) and 2‐diglycidylether of benzotrifluoride (DGEBTF)]. The DGEBTF/DDM system showed higher thermal stability and lower dielectric constant values than the DGET/DDM system. The impact strength of the DGEBTF/DDM system was significantly higher than that of the DGET/DDM system. The increase in intermolecular interactions because of the increasing polarity of the fluorine in the epoxy backbone was probably the key to these results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1860–1864, 2005  相似文献   

2.
The aim of this study was to determine the effect of the ester carbon chain length of curing agents modified by epoxidized oleic esters on the toughness of cured epoxy resins. An amine‐terminated prepolymer (i.e., curing agent G) was synthesized from a bisphenol A type liquid epoxy resin and triethylene tetramine. The toughening curing agents (G1 and G2) were prepared by reactions of epoxidized oleic methyl ester and epoxidized oleic capryl ester, respectively, with curing agent G. Fourier transform infrared spectrometry was used to characterize the chemical structure of the curing agents. The effects of the carbon chain length of the oleic ester group in the curing agents on the toughness and other performances of the curing epoxy resins were investigated by analysis of the Izod impact strength, tensile strength, elongation at break, thermal properties, and morphology of the fracture surfaces of the samples. The results denote that the toughness of the cured epoxy resins increased with the introduction of oleic esters into the curing agents without a loss of mechanical properties and that the toughness and thermal stability of the materials increased with increasing ester carbon chain length. The toughness enhancement was attributed to the flexibility of the end carbon chains and ester carbon chains of the oleic esters in the toughening curing agents. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

3.
Epoxy resins are among the most versatile engineering structural materials. A wide variety of epoxy resins are commercially available, but most are brittle. Several approaches have been used to improve the toughness of epoxy resins, including the addition of fillers, rubber particles, thermoplastics, and their hybrids, as well as interpenetrating polymer networks (IPNs) of acrylic, polyurethane, and flexibilizers such as polyols. This last approach has not received much attention; none of them have been able to suitably increase resin toughness with out sacrificing tensile properties. Therefore, in an attempt to fill this gap, we experimented with newly synthesized hydroxy‐terminated silicon‐modified polyurethane (SiMPU) oligomers as toughening agents for epoxy resins. SiMPU oligomers were synthesized from dimethyl dichlorosilane, poly(ethylene glycol) (weight‐average molecular weight ~ 200), and toluene 2,4‐diisocyanate and characterized with IR, 1H‐NMR and 13C‐NMR, and gel permeation chromatography. The synthesized SiMPU oligomers, with different concentrations, formed IPNs within the epoxy resins (diglycidyl ether of bisphenol A). The resultant IPN products were cured with diaminodiphenyl sulfone, diaminodiphenyl ether, and a Ciba–Geigy hardener under various curing conditions. Various mechanical properties, including the lap‐shear, peel, and impact strength, were evaluated. The results showed that 15 phr SiMPU led to better impact strength of epoxy resins than the others without the deterioration of the tensile properties. The impact strength increased continuously and reached a maximum value (five times greater than that of the virgin resin) at a critical modifier concentration (20 phr). The critical stress intensity factor reached 3.0 MPa m1/2 (it was only 0.95 MPa m1/2 for the virgin resin). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1497–1506, 2003  相似文献   

4.
Physical properties of epoxy resins filled with microparticles are presented and discussed. Microparticles were synthesized in the form of micron‐sized, crosslinked spherical particles, with an excess of reactive amino groups on their outer surface, and subsequently blended with EPON828‐3,3′DDS in different weight percents (10 and 20 wt %). Differential scanning calorimetry and scanning electronic microscopy were applied to investigate microsphere properties such as morphology, shape, size, and size distribution. Electron spectroscopy for chemical analysis was applied on particles to relate surface composition and reactivity of microspheres. Rheological, dynamic–mechanical, and mechanical properties of the cured blends were analyzed and related to the pure resin and to the same resin modified with PES180. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2031–2044, 2004  相似文献   

5.
Diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin was modified using liquid carboxyl-terminated poly(butadiene-co-acrylonitrile) (CTBN) rubber. The liquid CTBN contents used ranged from 2.5 to 20 parts per hundred parts of resin (phr). Mechanical properties of the modified resins were evaluated and the microstructures of the fracture surfaces were examined using SEM technique. The changes in storage modulus and the glass transition temperature were also evaluated using dynamic mechanical analysis (DMA). The tribological tests were performed using a ball-on-disc tribometer. The worn surfaces and the ball counter-mates after tribological tests were investigated using optical microscope technique. The results revealed the influence of liquid CTBN content on mechanical and tribological properties, and also microstructure of the modified epoxy resins. Impact resistance increased whereas the storage modulus and the hardness decreased when the CTBN rubber was introduced to the epoxy network. The coefficient of friction of the CTBN-modified epoxy was lower than that of the neat epoxy. The CTBN content of lower than 10 phr was recommended for improving the wear resistance of epoxy resin. Changes in tribological properties of the CTBN-modified epoxy correspond well to those in mechanical changes, especially the toughness properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

6.
Two kinds of aliphatic epoxy curing agents containing ring structures were synthesized from rosin acid and isosorbide, respectively. They were cured with diglycidyl ether bisphenol A (DER331) and the ultimate propertied of the cured resins were investigated. For comparison, the petroleum‐based curing agent containing planar benzene ring was synthesized from terephthalic acid. The chemical structures of the synthesized curing agents were identified by Fourier transform‐infrared and H‐nuclear magnetic resonance. The ultimate properties of the cured epoxy resins were investigated by thermogravimetric analysis and dynamic mechanical analysis. Especially, the effects of ring structure on their shape memory properties were studied in terms of shape fixity, shape recovery, and shape recovery time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44219.  相似文献   

7.
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  相似文献   

8.
Toughening of epoxy resin by block copolymers containing an epoxy‐philic block and an epoxy‐phobic block is usually costly because of their complex preparation procedure. In this work, a novel, random epoxy‐amphiphilic copolymer (PHGEL), which combines an “epoxy‐philic” component and an “epoxy‐phobic” component, has been synthesized and evaluated as a potential toughening agent for a diglycidyl ether of bisphenol A–based epoxy thermoset (EP). The curing behavior of the EP/PHGEL system has been investigated, and the results show that the hydroxyl group on the PHGEL chain can slightly activate the curing reaction. The mechanical testing shows that the toughness of the epoxy resin is improved by 294% when 4 wt % of PHGEL is added. Simultaneously, the tensile strength, elongation at break, and glass‐transition temperature are also improved. In addition, the thermogravimetric analysis shows that PHGEL has no obvious effect on the thermal stability of the epoxy thermosets. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44863.  相似文献   

9.
Isothermal physical ageing below the glass‐transition temperature (Tg) of a high‐Tg thermosetting difunctional epoxy/tetrafunctional aromatic amine system was investigated at different ageing temperatures (Ta) and chemical conversions (monitored by the Tg) using the torsional braid analysis freely oscillating torsion pendulum technique. In the absence of chemical reaction during an isothermal ageing process, the rate of isothermal physical ageing passes through a minimum with increasing conversion. The minimum is related to the minimum in mechanical loss between the secondary relaxation in the glassy state (Tβ) and the glass‐transition relaxation (Tg) (the temperatures of both of which increase with increasing conversion). If isothermal ageing rates for all conversions (beyond gelation) would have been measured directly from temperatures below Tβ to above Tg, it is concluded that two maxima in isothermal ageing rate would have been observed corresponding to the two relaxation processes. There exists a superposition in isothermal ageing rate versus Tg ? Ta [by shifting horizontally (and vertically)], which implies that the ageing rate is independent of the details of the changing chemical structure attributed to cure. Controlling mechanisms during physical ageing are segmental mobility associated with the Tg region and more localized motion associated with the glassy‐state relaxation Tβ. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2665–2675, 2003  相似文献   

10.
Three cold‐cured epoxy resins, specifically designed as structural adhesives for rehabilitation or renewal applications of civil infrastructures and cultural heritage, were submitted to natural and artificial weathering. We evaluated the variations in the thermal and mechanical properties and color changes after an artificial treatment carried out at 70°C and 75% relative humidity and after natural weathering, performed in two areas of South Italy, both located adjacent to the Mediterranean Sea. The variations in properties due to both natural exposure and artificial weathering were qualitatively similar. However, the selected artificial weathering procedure appeared excessively severe compared to the weathering that occurred after outdoor exposure. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

11.
Toughened epoxy systems have found increasing applications in automotive, aerospace, and electronic packaging industries. The present article reported work done for elucidation of gelation and vitrification for various epoxy systems and their blends with dendritic hyperbranched polymers (HBPs) having epoxy and hydroxyl functionality. Gel time was found to increase with increasing functionality from diglycidyl ether of bisphenol A (DGEBA) to tetraglycidyl diaminodiphenyl methane (TGDDM). The vitrification point was clearly identified from rheological experiments for triglycidyl p‐amino phenol (TGAP) and TGDDM. In the case of DGEBA a clear display of vitrification was not observed. TGDDM underwent vitrification sooner than did TGAP. Hydroxyl‐functionalized HBP reduced the gel time of the blends because of the accelerating effect of –OH groups to the epoxy curing reaction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1604–1610, 2004  相似文献   

12.
The relationship between the postcuring conditions and the fracture toughness of a bisphenol A‐type epoxy resin cured with acid anhydride was investigated. The glass transition temperature and fragility parameter, derived from the thermo‐viscoelasticity, were used to characterize the epoxy resin postcured under various conditions. Relationship between these two parameters and the fracture toughness was then investigated, based on the fractography results of a microscopic roughness examination of a fractured surface. The values of the glass transition temperature and fragility greatly depended on the postcuring conditions. The glass transition temperature was approximately 400 K when the crosslinking reaction was saturated. The fragility was independent of the saturation of the reaction and varied between 50 and 180. The results of the fracture test and fractography examination showed that there was no direct correlation between the glass transition temperature, the fracture toughness, and the roughness. On the other hand, there was a correlation between the fragility, fracture toughness, and roughness when the glass transition temperature saturated (at 400 K). As the fragility decreased from 180 to 50, the fracture toughness increased from 0.6 to 1.1 MPa · m1/2 at the same glass transition temperature. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 10: 2266–2271, 2002  相似文献   

13.
The relationship between the postcuring conditions and fracture toughness on three silica particulate‐filled epoxy composites was investigated. The glass transition temperature, Tg, and the fragility parameter, m, derived from the thermo‐viscoelasticity, were used to characterize the composites, which were postcured under various conditions. The glass transition temperature and fragility both depended on both of the curing conditions and the volume fraction of silica particles. The glass transition temperature increased with the postcuring time and temperature, while the fragility generally decreased as the volume fraction increased. There was no direct correlation between the glass transition temperature and fragility. The fracture toughness depended on both the glass transition temperature and fragility. The composites with a high glass transition temperature and low fragility had high fracture toughness. These results indicate that the glass transition temperature and fragility are useful parameters for estimating the fracture toughness of the silica particulate‐filled epoxy composites. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2261–2265, 2002  相似文献   

14.
Amino-modified silica nanoparticles (SiO2─NH2) were first prepared by hydrolytic condensation of tetraethyl orthosilicate and 3-aminopropylmethyldiethoxysilane. Then, organic–inorganic hybrid particles (SiO2─SMA) were prepared by the amidation reaction between SiO2─NH2 and poly(styrene-alt-maleic anhydride) (SMA). Subsequently, SiO2─SMA particles were employed for modifying bisphenol-A epoxy/anhydride thermoset. Compared with pure cured epoxy, the modified epoxy thermosets with only 1 wt % of SiO2─SMA particles could achieve a simultaneous toughening and reinforcing performance. The tensile strength, impact strength, and fracture toughness of epoxy thermoset were increased by 14.1, 44.3, and 114.4%, respectively. Moreover, the modification also improved the thermal stability of epoxy thermosets, and the modulus and glass transition temperature of cured resin were not sacrificed. It can be attributed to the rigid structure of SiO2, as well as the anhydride and carboxyl groups onto the surface of SiO2─SMA particles participating in the epoxy curing reaction and effectively enhancing the crosslinking density of epoxy thermoset.  相似文献   

15.
Epoxy polymers, having good mechanical properties and thermal stability, are often used for engineering applications. Their properties can be further enhanced by the addition of iron oxide (Fe3O4) nanoparticles (NPs) as fillers to the resin. In this study, pristine Fe3O4 NPs were functionalized with polydopamine (PDA), (3-glycidoxypropyl)trimethoxysilane (GPTMS), and (3-aminopropyl)trimethoxysilane (APTES). X-ray diffraction and scanning electron microscopy (SEM) were used to study any changes in the crystal structure and size of the NPs while Fourier-Transform Infrared Spectroscopy (FTIR) and Thermogravimetric Analysis (TGA) were used to ensure the presence of functional groups on the surface. The mechanical properties of the Fe3O4-based nanocomposites generally improved except when reinforced with Fe3O4/PDA. The maximum improvement in tensile strength (∼34%) and fracture toughness (∼13%) were observed for pristine Fe3O4-based nanocomposites. Dynamic mechanical analysis (DMA) showed that the use of any of the treated NPs improved the material's initial storage modulus and had a substantial impact on its dissipation potential. Also, it was observed that the glass transition temperature measurements by DMA and differential scanning calorimetry were below that of pure epoxy. SEM of the cracked surfaces shows that the incorporation of any NPs leads to an enhancement in its thermal and mechanical properties.  相似文献   

16.
Urea-formaldehyde (UF) resin with excellent intrinsic flame retardancy, high strength, and low cost has been widely used as adhesives, coatings as well as molding compounds, and it is a challenge to prepare UF resin with combined properties of high toughness/strength and low formaldehyde emissions. In this work, glutaraldehyde was introduced into the synthesis system of UF resin to partially replace formaldehyde, and urea-glutaraldehyde-formaldehyde (UGF) copolycondensation resin was prepared. It was found that glutaraldehyde participated in additional/condensation reactions of UF resin, and the crosslinking reaction of UGF resin was hindered with higher curing activation energy than that of neat UF resin. Due to the controllable curing kinetics and introduction of long methylene chains, UGF resin presented relatively low crosslinking density, and under external force, it underwent distinct yielding before fracture and many yield folds appeared on the fractured surface, showing high toughness and strength. Compared with neat UF resin, the tensile strength, elongation at break, impact strength, and critical stress intensity factor (KIC) of UGF resin increased by 26%, 42.30%, 14.6%, and 30%, respectively. Meanwhile, the free formaldehyde emission for UGF resin decreased by 47.5%, meeting the requirement of E0 grade. Such developed eco-friendly UGF resin exhibited promising application potentials.  相似文献   

17.
A novel tetra‐functional epoxy monomer with mesogenic groups was synthesized and characterized by 1H‐NMR and FTIR. The synthesized epoxy monomer was cured with aromatic amine to improve the thermal property of epoxy/amine cured system. The glass transition temperature (Tg) and coefficient of thermal expansion (CTE) of the cured system were investigated by dynamic mechanical analysis and thermal mechanical analysis. The properties of the cured system were compared with the conventional bisphenol‐A type epoxy and mesogenic type epoxy system. The storage modulus of the tetra‐functional mesogenic epoxy cured systems showed the value of 0.96 GPa at 250 °C, and Tg‐less behavior was clearly observed. The cured system also showed a low CTE at temperatures above 150 °C without incorporation of inorganic components. These phenomena were achieved by suppression of the thermal motion of network chains by introduction of both mesogenic groups and branched structure to increase the cross linking density. The temperature dependency of the tensile property and thermal conductivity of the cured system was also investigated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46181.  相似文献   

18.
Effects of resin compositions in ternary systems of benzoxazine, epoxy, and phenolic novolac resins on processability, and thermomechanical properties of their carbon fiber‐reinforced composites are investigated. At suitable range of resin mass ratios, the ternary mixtures can provide a relatively wide processing window ranging from 50 to 200°C by maintaining their low A‐stage viscosity for a relatively long time which is crucial in the fiber preimpregnating process. Furthermore, relatively long shelf‐life of the ternary mixtures stored at room temperature (~ 30°C) up to 270 days is obtained with minimal effect on their processability. The optimum mass ratio of B : E : P was determined to be 3 : 6 : 2, i.e., BEP362 resin. Finally, the carbon fiber composite based on BEP362 was found to exhibit substantial enhancement in its mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

19.
A novel P? C? N bond containing azaphosphorine, 5‐(4‐hydroxy)anilinomethyl‐1,3‐di(4‐hydroxy)phenyl‐1,3,5‐diazaphosphorinane (ADDPP‐OH), which could be used as both a cocuring agent and a flame‐retarding agent for epoxy resins (EPs), was synthesized from tetrakis(hydroxymethyl)phosphonium sulfate and characterized by FTIR, 1H‐NMR, 13C‐NMR, 31P‐NMR, and so on. Compared with the pure EP, the ADDPP‐OH–EP composites showed increased decomposition temperatures and char yields. When the content of ADDPP‐OH was 10 wt %, the cured EP composite possessed a limiting oxygen index value of 33.7% and passed the V‐0 rating of the UL‐94 test. The mechanical properties of the ADDPP‐OH–EP composites was improved because of the increased crosslinking density. In addition, the morphology of the residual char indicated an intumescent and multiporous structure in the inner space and a compact and continual appearance in the outer layer; this was important in preventing the materials from burning further. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45721.  相似文献   

20.
The glass transition temperature (Tg) of epoxy thermosets is a critical material property that depends on the component chemistry, the final cross-link density, and processing conditions. This study incorporates dynamic mechanical analysis (DMA) testing with a torsion clamp geometry on a TA Instruments DHR-2 and differential scanning calorimetry (DSC) to characterize five different two-component epoxy-amine systems. Investigation of the Tg dependence on DMA frequency and heating shows that lowering the frequency from 1 to 0.01 Hz results in a Tg very similar to that measured using DSC, while a heating rate of 0.3°C/min using DMA gives a Tg comparable to the DSC measured value at 30°C/min. The DMA technique reveals secondary relaxation transitions and peak broadening in the tan(δ) plots of poorly mixed epoxy blends, quantified using full width at half maximum (FWHM) of tan(δ) peaks, and are indicative of a non-homogeneous cross-linked network and off-ratio blending, respectively. The increase in the FWHM due to poor mixing ranges from 8% to 96%. These parameters are easily measurable and quantifiable in DMA, but are not observed in DSC. The additional DMA insights are valuable for process development and failure analysis, and can improve the understanding of epoxies.  相似文献   

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