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1.
A technique is described for producing a thick interlayer composite material composed of an epoxy resin as the matrix and an acrylic-coated fiberglass filler. Through the use of electrostatic forces, the fibers are encapsulated with a controlled, uniform layer(s) of the rubbery acrylic polymer. This coating is then crosslinked. These fibers are subsequently placed into the epoxy matrix, whereby the interfacial properties of the composite become modified. Rapid diffusion of the resin and curing agent results in an interpenetrating network being formed at the glass-epoxy interface. The placement of a uniform latex coating on the fiberglass surface results in improvements in the mechanical properties of the composite. Increases in damping, impact strength, and tensile properties are described. 相似文献
2.
The curing of an epoxy prepolymer based on the diglycidyl ether of bisphenol A (DGEBA) with dicyandiamide (DDA) as the hardener and imidazole as the catalyst agent was analyzed using microdielectrometry, differential scanning calorimetry, viscosity measurements, and insolubles in THF for gel-point detection. Interpreting dielectric data with respect to chemorheology continues to be the subject of scientific discussion. The focus of this issue is to give an industrial point of view on the collected on-line dielectric measurements during an epoxy/fiber glass composite cure. Hence, isothermal polymerizations of DGEBA/DDA/imidazole resin were examined and dielectric properties such as ionic conductivity were related to the cure kinetics by conversion through an experimentally established equation. This mathematical model was used to predict reaction advancement of epoxy processing under nonisothermal cure conditions. This model is shown to be able to forecast both isothermal and nonisothermal cure data of unaged resin. According to these results, cure monitoring was carried out on prepregs. Whereas some deviations of the law were observed at the time of the last stage of the cure, good correlation was obtained for the reaction rate during the in-mold process curing time. 相似文献
3.
The cure behaviour of two resin formulations (with high and low curing agent content respectively) of an epoxy resin system, used as matrix for carbon fibre composites, was studied through calorimetric analysis. The aim of this work is to investigate the kinetics of this specific epoxy system in order to be able to choose a proper set of processing parameters which will give good composite material properties. The shape of the conversion curves gives evidence of the differences in the cure kinetics of the two systems. Furthermore, the values of the activation energies were determined both for formulation in the conversion range where vitrification occurs, following a phenomenological approach. These values give an indication of the differences in the curing mechanisms, when varying the content of curing agent. In particular, for both systems, the same reaction represents the onset of the cure process, ie the autocatalytic epoxy ring opening through addition reaction to the primary amine. This reaction dominates the entire cure process of the epoxy formulation at high curing agent content. Conversely, in the formulations with a low curing agent content, after depletion of the primary amines, different reactions may take place (with secondary amines and hydroxyl groups), depending on the cure temperature and the resin viscosity. © 1999 Society of Chemical Industry 相似文献
4.
Patrick F. Mensah Michael A. Stubblefield Su-Seng Pang Doug Wingard 《Polymer Engineering and Science》1999,39(4):778-788
Thermal characterization of a fiberglass/epoxy prepreg fabric used as the bonding material to join composite-to-composite pipes by curing has been investigated. The prepreg material and composite pipes have temperature dependent thermal properties. Thus the resulting boundary value equations are nonlinear and analytical solutions cannot be easily obtained. Finite difference modeling (FDM) and numerical computational techniques were used to solve the one-dimensional heat conduction with chemical kinetics in the thermosetting material. Temperature distributions and degree of cure within the composite pipe joint are predicted. A Differential Scanning Calorimeter (DSC) in both isothermal and dynamic modes was used to characterize the curing kinetic properties of the prepreg. The result of this characterization is necessary for optimizing the curing process to produce a superior heat activated coupled joint. In addition, to assess the effects of induced thermal stress in the joint, the temperature profile is needed. The methodology employed in this analysis compares favorably with data from experimentation. 相似文献
5.
An accurate kinetics model is essential for understanding the curing mechanism and predicting the end properties of polymer materials. Graphite/epoxy AS4/8552 prepreg is a recent high‐performance thermosetting composite modified with thermoplastic, which is being used in the manufacture of aircraft and military structures. The isothermal cures of this system along with another thermoplastic toughened high‐performance prepreg, the T800H/3900‐2 system, were investigated by real‐time Fourier transform infrared (FTIR) spectroscopy. The cure rate was quantitatively analyzed based on the concentration profiles of both the epoxy and primary amine groups. Three autocatalytic models were used to determine kinetics parameters for both composite systems. The model which utilizes an empirical term, the final relative conversion (at different isothermal curing temperatures), describes the experimental data of both systems more satisfactorily than the model which applies a diffusion factor. The modeling results suggest that the curing of epoxy within both prepregs can be assumed to be a second order process. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008 相似文献
6.
The sequential heat release (SHR) taking place in dual‐curing systems can facilitate thermal management and control of conversion and temperature gradients during processing of thick composite parts, hence reducing the appearance of internal stresses that compromise the quality of processed parts. This concept is demonstrated in this work by means of numerical simulation of conversion and temperature profiles during processing of an off‐stoichiometric thiol–epoxy dual‐curable system. The simulated processing scenario is the curing stage during resin transfer moulding processing (i.e. after injection or infusion), assuming one‐dimensional heat transfer across the thickness of the composite part. The kinetics of both polymerization stages of the dual‐curing system and thermophysical properties needed for the simulations have been determined using thermal analysis techniques and suitable phenomenological models. The simulations show that SHR makes it possible to reach a stable and uniform intermediate material after completion of the first polymerization process, and enables a better control of the subsequent crosslinking taking place during the second polymerization process due to the lower remaining exothermicity. A simple optimization of curing cycles for composite parts of different thickness has been performed on the basis of quality–time criteria, producing results that are very close to the Pareto‐optimal front obtained by genetic algorithm optimization procedures. © 2018 Society of Chemical Industry 相似文献
7.
A manufacturing process is described that builds complex composite parts using a layered building process in which each layer of pre‐preg composite is laid and cured as the build progresses. In order to employ on‐line curing without molds, resin technologies that provide fast curing at room temperature—ultraviolet curable and epoxy/polyamide—were investigated. UV‐curable resins were tested for their ability to “shadow” cure by exposing carbon fiber composites to ultraviolet light to determine if the cure propagated from areas directly exposed to areas under fibers. Though ultraviolet curing showed advantages in cure time and low volatile production, very minimal “shadow” curing was achieved. A low temperature curing epoxy/polyamide mixture was tested for the effects of cure temperature, cure time, and mix ratio on the final degree of cure (%DOC) and glass transition temperature (Tg). Layers were made using different resin mixtures, partially cured, and used to build layered parts to determine curing characteristics during the lay‐up process. In the epoxy/polyamide mixtures, mix ratio had little effect on the reaction rate but did affect the Tg. A kinetic model was established for the resin epoxy/polyamide system for optimizing processing conditions during fabrication. However, the model failed to correctly predict the fabrication. The reaction of the material was different during the fabrication process than during the isothermal cure due to the presence of oxygen. During the build process, the degree of cure in each layer increased significantly over the prestaged degree of cure in less time than theoretically predicted. However, the final resin properties, such as Tg, were still below the specifications for high performance parts. 相似文献
8.
An epoxy and carbon fiber composite has been used to produce a light-weight rocket case for the Space Shuttle. A kinetic model is developed which can predict the extent of epoxy conversion during the winding and curing of the case. The model accounts for both chemical and physical kinetics. In the model, chemical kinetics occur exclusively up to the time the transition temperature equals the reaction temperature. At this point the resin begins to solidify and the rate of this process limits the rate of epoxy conversion. A comparison of predicted and actual epoxy conversion is presented for isothermal and temperature-programmed cure schedules. 相似文献
9.
为了深入了解某新型高温固化T800/环氧树脂预浸料的固化行为,借助差示扫描量热仪(DSC),采用非等温DSC法研究了T800/环氧树脂预浸料的固化反应过程。基于唯象模型,系统研究了该预浸料的固化反应特征温度及固化动力学参数,确定该预浸料中环氧树脂的固化反应动力学模型为自催化模型。采用等转化率法,分析了预浸料中环氧树脂的反应活化能随固化度的变化情况,结果表明在整个固化反应过程中,树脂固化反应活化能变化较大,传统模型法基于全固化过程活化能不变的假设无法准确描述该固化反应。采用变活化能自催化模型,利用粒子群全局优化算法,得到了T800/环氧树脂预浸料的固化动力学方程,结果表明该模型能较好地描述实验现象,可为进一步研究该预浸料的热力学性能及其成型过程中的质量控制提供理论基础。 相似文献
10.
The commercial epoxy prepreg SPX 8800, containing diglycidyl ether of bisphenol A, dicyanodiamide, diuron, and reinforcing glass fibers, was isothermally cured at different temperatures from 75 to 110°C and monitored via in situ near‐infrared Fourier transform spectroscopy. Two cure conditions were investigated: curing the epoxy prepreg directly (condition 1) and curing the epoxy prepreg between two glass plates (condition 2). Under both curing conditions, the epoxy group could not reach 100% conversion with curing at low temperatures (75–80°C) for 24 h. A comparison of the changes in the epoxy, primary amine, and hydroxyl groups during the curing showed that the samples cured under condition 2 had lower initial epoxy conversion rates than those cured under condition 1 and that more primary amine–epoxy addition occurred under condition 2. In addition, the activation energy under cure condition 2 (104–97 kJ/mol) was higher than that under condition 1 (93–86 kJ/mol), but a lower glass‐transition temperature of the cured samples was observed via differential scanning calorimetry. The moisture in the prepreg was assumed to account for the different reaction kinetics observed and to have led to different reaction mechanisms. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2295–2305, 2003 相似文献
11.
12.
The curing process of an epoxy–urethane copolymer in a heated mold was studied. The epoxy resin (DGEBA, Araldyt GY9527; Ciba Geigy), was coreacted with a urethane prepolymer (PU, Desmocap 12; Bayer) through an amine that acted as crosslinking agent (mixture of cycloaliphatic amines; Distraltec). The study focused on the effect of the curing condition and PU concentration on time–temperature profiles measured in the mold and the consequent final morphologies obtained. As the PU concentration increases, the maximum temperature reached in the mold decreases as a result of the dilution effect of the elastomer on reaction heat, whereas the Tg of the piece also decreases. Phase separation is a function of conversion and temperature reached in the curing part and was analyzed using experimental data and a mathematical model that predicts temperature and conversion throughout the thickness of the mold. Scanning electron microscopy and atomic force microscopy were used to determine the characteristics of the dispersed phase for the different formulations and conditions of curing. It was shown that the size of the dispersed phase increased with the initial PU concentration, whereas there were practically no differences in the separated phase as a function of position or temperature of curing (in the range of 70 to 100°C studied). The superposition of the phase diagrams with the conversion–temperature trajectories during cure provided an explanation of the morphologies generated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 889–900, 2001 相似文献
13.
In conventional processing, thermal gradients cause differential curing of thick laminates and undesirable outside‐in solidification. To reduce thermal gradients, thick laminates are processed at lower cure temperatures and heated with slow heating rates, resulting in excessive cure times. Microwaves can transmit energy volumetrically and instantaneously through direct interaction of materials with applied electromagnetic fields. The more efficient energy transfer of microwaves can alleviate the problems associated with differential curing, and the preferred inside‐out solidification can be obtained. In this work, both microwave curing and thermal curing of 24.5 mm (1 inch) thick‐section glass/epoxy laminates are investigated through the development of a numerical process simulation and conducting experiments in processing thick laminates in a conventional autoclave and a microwave furnace. Outside‐in curing of the autoclave‐processed laminate resulted in visible matrix cracks, while cracks were not visible in the microwave‐processed laminate. Both numerical and experimental results show that volumetric heating due to microwaves promotes an inside‐out cure and can dramatically reduce the overall processing time. 相似文献
14.
The cure kinetics of an epoxy resin used for the preparation of advanced polymeric composite structures was studied by isothermal differential scanning calorimetry (DSC). A series of isothermal DSC runs provided information about the kinetics of cure over a wide temperature range. According to the heat evolution behavior during the curing process, several influencing factors of isothermal curing reactions were evaluated. The results showed that the isothermal kinetic reaction of this epoxy resin followed an autocatalytic kinetic mechanism. In the latter reaction stage, the curing reaction became controlled mainly by diffusion. Cure rate was then modeled using a modified Kamal autocatalytic model that accounts for the shift from a chemically controlled reaction to a diffusion‐controlled reaction. The model parameters were determined by a nonlinear multiple regression method. Copyright © 2004 Society of Chemical Industry 相似文献
15.
C. Dispenza G. Spadaro J. T. Carter P. T. McGrail 《Polymer Engineering and Science》2001,41(9):1486-1496
A high molecular weight acrylonitrile/butadiene/methacrylic acid (Nipol 1472) rubber is chosen to control processability and mechanical properties of a TGDDM (tetra glycidyl diphenyl methane) based epoxy resin formulation for aerospace composite applications. The physical blend of rubber and epoxy resin, achieved by dissolution of all the components in a common solvent, forms a heterogeneous system after solvent removal and presents coarse phase separation during cure that impairs any practical relevance of this material. A marked improvement of rubberepoxy miscibility is achieved by reactive blending (‘pre‐reaction’) the epoxy oligomer with the functional groups present in the rubber. The epoxy‐rubber ‘adduct’ so obtained appears as a homogeneous system at room temperature and also after compounding with the curing agent. Depending on the nature and extent of interactions developed between the rubber and the epoxy resin during ‘pre‐reaction,’ materials with different resin flow characteristics, distinctive morphologies and mechanical properties after curing were obtained. The effect of ‘pre‐reaction’ on the resin cure reaction kinetics has been also investigated. 相似文献
16.
《国际聚合物材料杂志》2012,61(2):101-113
The isothermal curing kinetics of nanocomposite of o-cresol-formaldehyde epoxy resin (o-CFER), 3-methyl-tetrahydrophthalic anhydride (MeTHPA) with organic montmorillonite (O-MMT) were investigated by means of X-ray diffraction (XRD) and differential scanning calorimetry (DSC) using N,N-dimethyl-benzylamine as a curing accelerant. The XRD result indicates that an exfoliated O-MMT nanocomposite was obtained. The analysis of DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, which could be well described by the Kamal model. In the later stages, the reaction is mainly controlled by diffusion and a diffusion factor, f(α), was introduced into Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversion. The thermal degradation kinetics of this composite were investigated by thermogravimetric analysis (TGA), which revealed that with increasing O-MMT content, TG curves shift to higher temperature. 相似文献
17.
Minyoung Kim Wonho Kim Youngson Choe Joung‐Man Park In‐Seo Park 《Polymer International》2002,51(12):1353-1360
The cure kinetics of blends of epoxy (diglycidyl ether of bisphenol A)/anhydride (nadic methyl anhydride) resin with polyetherimide (PEI) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction parameters such as activation energy and reaction constants. By increasing the amount of PEI in the blends, the final cure conversion was decreased. Lower values of final cure conversions in the epoxy/PEI blends indicate that PEI hinders the cure reaction between the epoxy and the curing agent. The value of the reaction order, m, for the initial autocatalytic reaction was not affected by blending PEI with epoxy resin, and the value was approximately 1.0. The value of n for the nth order component in the autocatalytic analysis was increased by increasing the amount of PEI in the blends, and the value increased from 1.6 to 4.0. A diffusion‐controlled reaction was observed as the cure conversion increased and the rate equation was successfully analyzed by incorporating the diffusion control term for the epoxy/anhydride/PEI blends. Complete miscibility was observed in the uncured blends of epoxy/PEI at elevated temperatures up to 120 °C, but phase separations occurred in the early stages of the curing process. © 2002 Society of Chemical Industry 相似文献
18.
The cure kinetics and glass transition development of a commercially available epoxy/carbon fiber prepreg system, DMS 2224 (Hexel F584), was investigated by isothermal and dynamic‐heating experiments. The curing kinetics of the model prepreg system exhibited a limited degree of cure as a function of isothermal curing temperatures seemingly due to the rate‐determining diffusion of growing polymer chains. Incorporating the obtained maximum degree of cure to the kinetic model development, the developed kinetic equation accurately described both isothermal and dynamic‐heating behavior of the model prepreg system. The glass transition temperature was also described by a modified DiBeneditto equation as a function of degree of cure. Finally, the equivalent processing time (EPT) was used to investigate the development of glass transition temperature for various curing conditions envisioning the internal stress buildup during curing and cooling stages of epoxy‐based composite processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 144–154, 2002; DOI 10.1002/app.10282 相似文献
19.
Donghyon Kim Jung-ok Beak Youngson Choe Wonho Kim 《Korean Journal of Chemical Engineering》2005,22(5):755-761
The cure kinetics of blends of epoxy resin (4,4’-tetraglycidyl diaminodiphenyl methane; TGDDM)/curing agent (diaminodiphenyl
sulfone; DDS) with ATPEI (amine terminated poly-etherimide) -CTBN (carboxyl terminated poly (butadiene-co-acrylonitrile))
block copolymer (AB type) were studied using differential scanning calorimetry under isothermal conditions to determine the
reaction kinetic parameters such as activation energy and reaction constants. Final cure conversion decreased with increasing
amount of AB in the blends. A diffusion controlled reaction was observed as the cure conversion increased, and the curing
reaction was successfully analyzed by incorporating the diffusion control term in the rate equation for the epoxy/DDS/AB blends.
The fracture toughness was improved to about 350% compared to that of the unmodified resin at 30% of AB block copolymer. This
is attributed to the formation of co-continuous morphology between the epoxy phase and AB block copolymer phase. By increasing
the amount of AB, the modulus of the cured blends decreased, which was due to the presence of CTBN rubbery phases. 相似文献
20.
Cure monitoring of epoxy films by heatable in situ FTIR analysis: correlation to composite parts
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The curing mechanism of an epoxy film containing dicyandiamide (DICY) and an epoxy formulation based on diglycidyl ether of Bisphenol A (DGEBA) polymer was studied as a function of various temperature programs. The investigation was performed in situ, using a thin film of the epoxy mixture on a silicon wafer substrate in a heatable transmission tool of a FTIR spectrometer. Based on these model‐curing experiments, a major curing mechanism was proposed, taking into account the appearance, the decrease, and the development of characteristic bands at various temperatures. The conclusions of the model curing were correlated to FTIR measurements on a real, 50‐mm‐thick glass fiber reinforced component composite part from a technical process. It could be shown that characteristic bands that develop at curing temperatures above 150°C appear especially in the center of the thick sample. From the chemical or molecular point of view, this demonstrates the established technician's understanding that temperature control inside a large‐scale fiber composite of, for example, aircraft, wind‐turbine, automotive applications component is of major importance. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39832. 相似文献