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1.
Parnia Navabpour Alan Nesbitt B. Degamber G. Fernando Tim Mann Richard Day 《应用聚合物科学杂志》2006,99(6):3658-3668
The cure of a commercial epoxy resin system, RTM6, was investigated using a conventional differential scanning calorimeter and a microwave‐heated calorimeter. Two curing methods, dynamic and isothermal, were carried out and the degree of cure and the reaction rates were compared. Several kinetics models ranging from a simple nth order model to more complicated models comprising nth order and autocatalytic kinetics models were used to describe the curing processes. The results showed that the resin cured isothermally showed similar cure times and final degree of cure using both conventional and microwave heating methods, suggesting similar curing mechanisms using both heating methods. The dynamic curing data were, however, different using two heating methods, possibly suggesting different curing mechanisms. Near‐infrared spectroscopy showed that in the dynamic curing of RTM6 using microwave heating, the epoxy‐amine reaction proceeded more rapidly than did the epoxy‐hydroxyl reaction. This was not the case during conventional curing of this resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3658–3668, 2006 相似文献
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The effect of wood flour on the cure kinetics of commercial phenol‐formaldehyde resins used as oriented strandboard face and core adhesives was studied using differential scanning calorimetry. The wood flour did not change the cure mechanism of the face resin, but lowered its cure temperature and activation energy and increased its cure reaction order. For the core resin (CR), the wood flour lowered the onset cure temperature, and caused separation of the addition and condensation reactions involved in curing of CR. Compared with neat CR, the addition reaction of CR/wood mixture also followed an nth‐order reaction mechanism but with a lower reaction order, while the condensation was changed from an autocatalytic reaction to an nth‐order one. The addition reaction happened at temperatures lower than 90°C, and the condensation reaction was dominant at temperatures higher than 110°C. The proposed models fitted the experimental data well. Relationships among cure reaction conversion (cure degree), cure temperature, and cure time were predicted. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:3774–3781, 2006 相似文献
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The effect of zinc borate (ZB) on the cure kinetics of commercial phenol–formaldehyde oriented strandboard adhesives was studied using differential scanning calorimetry. ZB caused a separation of the addition and condensation reactions for both face and core resin (CR) systems with lowered cure temperature for the addition reaction. For the face resin, ZB did not change its nth‐order curing mechanism, but retarded the whole cure reactions, and increased the reaction order and the activation energy. Compared with neat CR, the addition reaction of the CR/ZB mixture, which occurred at temperatures lower than 60°C, also followed an nth‐order reaction mechanism. The condensation reaction of the mixture was changed from an autocatalytic reaction to an nth‐order one with the reaction order of about 1. The proposed models fitted the experimental data well. Relationships among cure reaction conversion (i.e., cure degree), cure temperature, and cure time were predicted for various resin/ZB systems. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3886–3894, 2006 相似文献
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The curing behavior of polydimethylsiloxane‐modified allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (PDMS‐modified AN/BDM) was investigated by using Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry. The results of FTIR confirmed that the curing reactions of the PDMS‐modified AN/BDM resins, including “Ene” reaction and Diels–Alder reaction between allyl groups and maleimide groups, should be similar to those of the parent allylated novolac/4,4′‐bismaleimidodiphenylmethane (AN/BDM) resin. The results of dynamic DSC showed that the total curing enthalpy of the PDMS‐modified AN/BDM resins was lower than that of the parent resin. Incorporation of polydimethylsiloxane (PDMS) into the backbone of the allylated novolac (AN) resin favored the Claisen rearrangement reaction of allyl groups. The isothermal DSC method was used to study the kinetics of the curing process. The experimental data for the parent AN/BDM resin and the PDMS‐modified AN/BDM resins exhibited an nth‐order behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
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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
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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
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The kinetics of curing for a modified bismaleimide (BMI) resin was investigated to ascertain a suitable cure model for the material. The resin system used in this study was composed of 4,4′‐bismaleimidodiphenylmethane (BMIM) and 0,0′‐diallyl bisphenol A (DABPA, DABA). The BMIM was the base monomer and the DABPA was the modified agent. A series of isothermal DSC runs provided information about the kinetics of cure in the temperature range 170–220°C. Regardless of the different temperatures, the shape of the conversion curves was similar, and this modified BMI resin system underwent an nth‐order cure reaction. Kinetic parameters of this BMI resin system, including the reaction model, activation energy, and frequency factor, were calculated. From the experimental data, it was found that the cure kinetics of this resin system can be characterized by a first‐order kinetic model. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3338–3342, 2004 相似文献
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The curing reaction of bisphenol‐A epoxy resin (BPAER) with boron‐containing phenol–formaldehyde resin (BPFR) was studied by isothermal and dynamic differential scanning calorimetry (DSC). The kinetic reaction mechanism in the isothermal reaction of BPAER‐BPFR was shown to follow autocatalytic kinetics. The activation energy in the dynamic cure reaction was derived. The influence of the composition of BPAER and BPFR on the reaction was evaluated. In addition, the glass transition temperatures (Tgs) were measured for the BPAER‐BPFR samples cured partially at isothermal temperatures. With the curing conditions varying, different glass transition behaviors were observed. By monitoring the variation in these Tgs, the curing process and the thermal property of BPAER–BPFR are clearly illustrated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1054–1061, 2000 相似文献
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Phenol–formaldehyde (PF) resins have been the subject of many model‐fitting cure kinetic studies, yet the best model for predicting PF dynamic and isothermal cure has not been established. The objective of this research is to compare and contrast several commonly used kinetic models for predicting degree of cure and cure rate of PF resins. Toward this objective, the nth‐order Borchardt–Daniels (nth‐BD), ASTM E698 (E698), autocatalytic Borchardt–Daniels (Auto‐BD), and modified autocatalytic methods (M‐Auto) are evaluated on two commercial PF resins containing different molecular weight distributions and thus cure behaviors. The nth‐BD, E698, and M‐Auto methods all produce comparable values of activation energies, while Auto‐BD method yields aberrant values. For dynamic cure prediction, all models fail to predict reaction rate, while degree of cure is reasonably well predicted with all three methods. As a whole, the nth‐BD method best predicts degree of cure for both resins as assessed by mean squared error of prediction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007 相似文献
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A new isothermally based, cure kinetic model for the prepreg was presented using an industrially supplied prepreg rather than pure resin. The matrix resin was bismaleimide (BMI) resins, and the reinforcement was carbon fiber T700–12S. The BMI prepreg was measured from 170 to 220°C by isothermal DSC. The isothermal cure reaction heat increases with the increment of cure temperature. The DSC data were analyzed by the proposed nth‐order reaction model. An increase in reaction rate was observed at higher temperature in both neat and prepreg. After reaching the peak value, the reaction rate dropped off faster in prepreg, resulting in a lower average value of the ultimate heat of reaction. It was suggested the presence of carbon fiber had an effect on the cure kinetics as a heat sink. The carbon fibers imposed restrictions on the molecular mobility of the reactive species and did not change the cure mechanism. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2238–2241, 2005 相似文献
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Fast curing epoxy resins were prepared by the reactions of diglycidyl ether of bisphenol A with isophorone diamine (IPD) and N-(3-aminopropyl)-imidazole (API), and their curing kinetics and mechanical properties influenced by IPD content were also investigated. The analysis of curing kinetics was based on the nonisothermal differential scanning calorimetry (DSC) data with the typical Kissinger, Ozawa, and Flynn–Wall–Ozawa models, respectively. The glass-transition temperature was also measured by the same technique. Additionally, the mechanical properties including flexural, impact, and tensile performances were tested, and the curing time was estimated by isothermal DSC. The degree of cure (α) dependency of activation energy (Ea ) revealed the complexity of curing reaction. Detailed analysis of the curing kinetics at the molecular level indicated that the dependence of Ea on the α was a combined effect of addition reaction, autocatalytic reaction, viscosity, and steric hindrance. From the nonisothermal curves, the curing reaction mechanism could be proposed according to the increasingly obvious low temperature peaks generated by the addition reaction of epoxy group with the primary amines in API and IPD molecules. Using the preferred resin formulation, the resin system could be cured within 10 min at 120 °C with a relatively good mechanical performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47950. 相似文献
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Bisphenol‐A glycidyl ether epoxy resin was modified using reactive poly(ethylene glycol) (PEO). Dynamic mechanical analysis showed that introducing PEO chains into the structure of the epoxy resin increased the mobility of the molecular segments of the epoxy network. Impact strength was improved with the addition of PEO at both room (RT) and cryogenic (CT, 77 K) temperature. The curing kinetics of the modified epoxy resin with polyoxypropylene diamines was examined by differential scanning calorimetry (DSC). Curing kinetic parameters were determined from nonisothermal DSC curves. Kinetic analysis suggested that the two‐parameter autocatalytic model suitably describes the kinetics of the curing reaction. Increasing the reactive PEO content decreased the heat flow of curing with little effect on activation energy (Ea), pre‐exponential factor (A), or reaction order (m and n). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012 相似文献
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Wood liquefaction was conducted at a 2/1 phenol/wood ratio in two different reactors: (1) an atmospheric three‐necked flask reactor and (2) a sealed Parr reactor. The liquefied wood mixture (liquefied wood, unreacted phenol, and wood residue) was further condensed with formaldehyde under acidic conditions to synthesize two novolac‐type liquefied wood/phenol/formaldehyde (LWPF) resins: LWPF1 (the atmospheric reactor) and LWPF2 (the sealed reactor). The LWPF1 resin had a higher solid content and higher molecular weight than the LWPF2 resin. The cure kinetic mechanisms of the LWPF resins were investigated with dynamic and isothermal differential scanning calorimetry (DSC). The isothermal DSC data indicated that the cure reactions of both resins followed an autocatalytic mechanism. The activation energies of the liquefied wood resins were close to that of a reported lignin–phenol–formaldehyde resin but were higher than that of a typical phenol formaldehyde resin. The two liquefied wood resins followed similar cure kinetics; however, the LWPF1 resin had a higher activation energy for rate constant k1 and a lower activation energy for rate constant k2 than LWPF2. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 相似文献
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The curing kinetics and the resulting viscosity change of a two‐part epoxy/amine resin during the mold‐filling process of resin‐transfer molding (RTM) of composites was investigated. The curing kinetics of the epoxy/amine resin was analyzed in both the dynamic and the isothermal modes with differential scanning calorimetry (DSC). The dynamic viscosity of the resin at the same temperature as in the mold‐filling process was measured. The curing kinetics of the resin was described by a modified Kamal kinetic model, accounting for the autocatalytic and the diffusion‐control effect. An empirical model correlated the resin viscosity with temperature and the degree of cure was obtained. Predictions of the rate of reaction and the resulting viscosity change by the modified Kamal model and by the empirical model agreed well with the experimental data, respectively, over the temperature range 50–80°C and up to the degree of cure α = 0.4, which are suitable for the mold‐filling stage in the RTM process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2139–2148, 2000 相似文献
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The kinetics of the curing reaction for a system of o‐cresol formaldehyde epoxy resin (o‐CFER) with 4,4′‐diaminodiphenyl ether (DDE) as a curing agent were investigated with differential scanning calorimetry (DSC). An analysis of the DSC data indicated that an autocatalytic behavior appeared in the first stages of the cure for the system, and this could be well described by the model proposed by Kamal, which includes two rate constants and two reaction orders (m and n). The overall reaction order (m + n) was 2.7–3.1, and the activation energies were 66.79 and 49.29 kJ mol?1, respectively. In the later stages, a crosslinked network was formed, and the reaction was mainly controlled by diffusion. For a more precise consideration of the diffusion effect, a diffusion factor was added to Kamal's equation. In this way, the curing kinetics were predicted well over the entire range of conversions, covering both the previtrification and postvitrification stages. The glass‐transition temperatures of the o‐CFER/DDE samples were determined via torsional braid analysis. The results showed that the glass‐transition temperatures increased with the curing temperature and conversion up to a constant value of approximately 370 K. The thermal degradation kinetics of the system were investigated with thermogravimetric analysis, which revealed two decomposition steps. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 182–188, 2004 相似文献
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The cure kinetics of a high performance PR500 epoxy resin in the temperature range of 160–197°C for the resin transfer molding (RTM) process have been investigated. The thermal analysis of the curing kinetics of PR500 resin was carried out by differential scanning calorimetry (DSC), with the ultimate heat of reaction measured in the dynamic mode and the rate of cure reaction and the degree of cure being determined under isothermal conditions. A modified Kamal's kinetic model was adapted to describe the autocatalytic and diffusion‐controlled curing behavior of the resin. A reasonable agreement between the experimental data and the kinetic model has been obtained over the whole processing temperature range, including the mold filling and the final curing stages of the RTM process. 相似文献
19.
The aim of the study is to determine the optimum cure temperatures and kinetics for two different epoxy resin systems without using solvent. Two resin systems consist of EPIKOTE 828® epoxy resin–EPIKURE® 3090 polyamidoamine curing agent and DURATEK® KLM 606A epoxy resin–DURATEK® KLM 606B polyamide curing agent. The ratio of resin to curing agent was kept as 1:1 for both the systems. Curing temperatures of both the systems were determined and kinetic parameters were calculated with respect to the experimental results following nth‐order kinetics. Then, a series of isothermal temperatures was applied to the resin systems in order to assess the cure process in terms of conversion, time, and temperature by using differential scanning calorimeter (DSC). The test results of both systems show that the rate of degree of cure for EPIKOTE 828® epoxy resin–EPIKURE® 3090 polyamidoamine curing agent system is approximately 10 times higher than that of DURATEK® KLM 606A epoxy resin–DURATEK® KLM 606B polyamide curing agent system at 230°C. POLYM. COMPOS., 28:762–770, 2007. © 2007 Society of Plastics Engineers 相似文献
20.
Eva C. Vázquez Francisco Fraga J. M. Martínez‐Ageitos José Vázquez Tato 《应用聚合物科学杂志》2013,130(6):3972-3978
The curing reaction of a system consisting of a diglycidyl ether of bisphenol‐A (n = 0) and hemin (a protoporphyrin IX containing an iron ion and an additional chloride ligand) was studied with a differential scanning calorimeter. A maximum value of ?488.3 ± 8.4 J g?1 was obtained for the enthalpy of the reaction. The kinetics of the process was studied by the isothermal method, observing that it obeys to Kamal's model, with an overall reaction order equal to 3. From the dependence of the kinetic constant with temperature, the activation energy, activation enthalpy, and activation entropy were determined. The ratio of the kinetic constants associated to the autocatalytic and nth order terms of the reaction rate, together with the thermodynamic activation parameters suggest a trend to the autocatalytic path mechanism with increasing temperatures. This study demonstrates that macrocycles can be used as cross‐linking agents for curing epoxy resins and that when metallomacrocycles are used, metal ions can be introduced into the network structure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3972–3978, 2013 相似文献