Curing kinetics and viscosity change of a two‐part epoxy resin during mold filling in resin‐transfer molding process

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     

Cure kinetics of epoxy resin used for advanced composites

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     

Resin‐transfer molding of natural fiber–reinforced plastic. I. Kinetic study of an unsaturated polyester resin containing an inhibitor and various promoters

In this study an autocatalytic model was used to describe the cure of a polyester system containing various promoters and an inhibitor. The effect of the initiator concentration was investigated. Isothermal DSC measurements were used to determine the kinetic parameters for the curing reaction. The rate of curing increased with increasing initiator concentration. The parameters were found to be temperature dependent. The nonlinear regression analysis showed that by fixing one parameter at a constant value the temperature dependency of the other parameters was described by simple relationships. The model was then compared to the experimental data. The reaction rate could be predicted fairly well in a wide range of temperatures. These results will be used to model the cure of this resin in a resin transfer‐molding (RTM) process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2553–2561, 2003     

Study of the effect of BDMA catalyst in the epoxy novolac curing process by isothermal DSC

Epoxy novolac/anhydride cure kinetics has been studied by differential scanning calorimetry under isothermal conditions. The system used in this study was an epoxy novolac resin (DEN431), with nadic methyl anhydride as hardener and benzyldimethylamine as accelerator. Kinetic parameters including the reaction order, activation energy and kinetic rate constants, were investigated. The cure reaction was described with the catalyst concentration, and a normalized kinetic model developed for it. It is shown that the cure reaction is dependent on the cure temperature and catalyst concentration, and that it proceeds through an autocatalytic kinetic mechanism. The curing kinetic constants and the cure activation energies were obtained using the Arrhenius kinetic model. A suggested kinetic model with a diffusion term was successfully used to describe and predict the cure kinetics of epoxy novolac resin compositions as a function of the catalyst content and temperature. Copyright © 2003 Society of Chemical Industry     

基于变活化能模型的T800/环氧树脂预浸料固化反应动力学研究

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。     

Comparison of the curing kinetics of the RTM6 epoxy resin system using differential scanning calorimetry and a microwave‐heated calorimeter

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     

Modeling the curing kinetics for a modified bismaleimide resin using isothermal DSC

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     

Curing kinetics of medium reactive unsaturated polyester resin used for liquid composite molding process

The cure kinetics of medium reactivity unsaturated polyester resin formulated for Liquid Composite Molding process simulation was studied by Differential Scanning Calorimetry (DSC) under isothermal conditions over a specific range of temperature. For isothermal curing reactions performed at 100, 110, and 120°C, several influencing factors were evaluated using the heat evolution behavior of curing process. We propose two‐ and three‐parameter kinetic models to describe the cure kinetics of thermoset resins. Comparisons of the model solutions with our experimental data showed that the three‐parameter model was the lowest parameter model capable of capturing both the degree of cure and the curing rate qualitatively and quantitatively. The model parameters were evaluated by a non‐linear multiple regression method and the temperature dependence of the kinetic rate constants thus obtained has been determined by fitting to the Arrhenius equation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Modelling the cure of a commercial epoxy resin for applications in resin transfer moulding

An analytical procedure has been developed for modelling the kinetics of the cure process of a commercial epoxy resin for resin transfer moulding (RTM) applications, using differential scanning calorimetry (DSC) in the isothermal and dynamic modes to obtain the experimental database. The overall reaction rate of the epoxide groups with amines was determined and fitted by an autocatalytic kinetic model. An improvement of the model to allow for diffusion limitation effects results in a good agreement between experimentally determined and predicted reaction rates. A non-linear least squares regression analysis method based on Marquardt's algorithm was used to fit the DSC reaction rate data with an appropriate model and to evaluate the activation energies and the reaction orders for this particular resin system. The Di Benedetto equation was utilised to establish the relationship between conversion and glass transition temperature (T_g), required to develop the diffusion-dominated part of the model.     

Modeling the chemorheological behavior of epoxy/liquid aromatic diamine for resin transfer molding applications

The analysis of the chemorheological behavior of an epoxy prepolymer based on a diglycidylether of bisphenol‐A (DGEBA) with a liquid aromatic diamine (DETDA 80) as a hardener was performed by combining the data obtained from Differential Scanning Calorimetry (DSC) with rheological measurements. The kinetics of the crosslinking reaction was analyzed at conventional injection temperatures varying from 100 to 150°C as experienced during a Resin Transfer Molding (RTM) process. A phenomenological kinetic model able to describe the cure behavior of the DGEBA/DETDA 80 system during processing is proposed. Rheological properties of this low reactive epoxy system were also measured to follow the cure evolution at the same temperatures as the mold‐filling process. An empirical model correlating the resin viscosity with temperature and the extent of reaction was obtained to carry out later a simulation of the RTM process and to prepare advanced composites. Predictions of the viscosity changes were found to be in good agreement with the experimental data at low extents of cure, i.e., in the period of time required for the mold‐filling stage in RTM process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4228–4237, 2006     

最概然Malek法分析TDE 85/MeNA环氧树脂体系固化机理

 采用非等温DSC法对三官能团环氧树脂TDE 85与甲基纳迪克酸酐（MeNA）固化体系进行了放热特性分析,升 温速率分别为5k/min、10k/min、15k/min、20k/min、25k/min及35k/min。在此基础上重点提出最概然Malek Flynn Wall Ozawa分析法,对其固化反应机理进行固化动力学参数分析,建立了能够正确描述固化反应过程的机 理模型。该方法求得固化体系反应表观活化能为E=67.05kJ/mol,表观指前因子为A=5.05×109s 1,反应机理函数 为f(a)=22.24(1-a)1.76。最后通过实验数据对最概然Malek Flynn Wall Ozawa分析法进行验证,证明该方法 能够精确的描述固化反应过程和机理特征。     

聚酯树脂粉末涂料的固化行为

用差示扫描量热法(DSC)对固态条件下聚酯/TGIC(triglycidyl isocyanurate)体系的非等温固化反应动力学进行了研究。根据DSC和热重（TG）的分析结果,对聚酯粉末的固化过程及热稳定性进行了探讨,通过温度-升温速率图外推法确定了该体系的凝胶温度、固化温度和后固化温度分别为113、146和195℃。采用Kissinger方程、Doyle-Ozawa方程和Crane方程对DSC数据进行分析,得到了固化反应的平均表观活化能65.71 kJ·mol^-1,频率因子8.50×106 min^-1、反应级数0.95,建立了该树脂体系的固化动力学模型。讨论了固化反应速率、固化度、固化温度与时间等关系的变化规律及影响因素,为优化铝型材用粉末涂料聚酯体系的固化工艺提供了理论基础。     

Curing cycle modification for RTM6 to reduce hydrostatic residual tensile stress in 3D woven composites

Triaxial residual tensile stresses resulting after cooling a 3D woven composite from the curing temperature cause cracking in the resin pockets for weave architectures that have high through‐the‐thickness constraint. We show how curing cycle modifications can reduce the hydrostatic tensile stress generated by thermal mismatch during cooling of Hexcel RTM6 epoxy resin constrained in a quartz tube which simulates extreme constraint in a composite. The modified curing schedule consists of a high temperature cure to just before the glass transition, a lower temperature hold that takes the resin through the glass transition thereby freezing in the zero stress state, followed by high temperature cure to bring the resin to full conversion. We show that this process is sensitive to heating rates and can reduce the zero stress state of non‐toughened RTM6 resin to a temperature similar to a commercial rubber‐toughened resin, Cycom PR520. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43373.     

A cure-rate model for the shuttle filament-wound case

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.     

A chemorheological model for the cure of unsaturated polyester resin

A chemorheological model is developed, using the free volume concept, for the prediction of viscosity during the cure of unsaturated polyester resin. We have incorporated into the development of the chemorheological model a mechanistic kinetic model of curing kinetics that predicts the degree of cure as a function of cure time. The mechanistic kinetic model uses an approach of free-radical polymerization that takes into account diffusion-controlled curing reactions, In order to test the usefulness of the chemorheological model developed, we have conducted cure experiments and measured viscosities of partially cured resin samples, using a general-purpose unsaturated polyester resin. Specifically, the following measurements were taken: (1) the quantity of ethylenic double bonds in the resin system before and after the cure reaction by infrared spectroscopy, (2) the glass transition temperature by differential scanning calorimetry (DSC) and (3) the viscosity as a function of shear rate, at several temperatures, using a cone-and-plate rheometer. It is concluded that the chemorheological model developed is very useful for predicting the variation of viscosity during the cure of unsaturated polyester resin.     

Cure modelling of polyester thermosets in a glass mould

The curing of unsaturated polyester was studied experimentally and using a model of the process. The kinetic parameters were calculated from the heat flow–time curves obtained by differential scanning calorimetry (Mettler Toledo DSC 823), operating in a non-isothermal mode. The temperature–time histories were studied in a cylindrical glass mould. A potential use of glass as a mould for polymer curing is found in the production of optical sensors. Here, glass was selected as a mould material because it is UV transparent, chemically inert and easy to clean. The thermal properties of glass moulds coupled with the intrinsic curing kinetics are of a significant interest in such investigations. Taking into account the heat transferred by the convection from the air to the mould surface and the conduction through the mould wall and resin, as well as the kinetics of the heat generated in the cure reaction, a numerical model has been constructed. The contributions to the rise in temperature from the heat conduction and chemical reaction are different in different parts of the composite, which can explain the temperature–time histories. The introduction of a carbonate based filler reduced the amount of heat released in the composite and, as a result, lowered the temperatures through the resin. A good agreement between experimental data and the predicted mathematical model of the curing process in the mould has been observed.     

Correlation analysis of epoxy/amine resin cure,structure and chemorheological behavior in RTM processes

At the reactive mould‐filling stage in resin transfer moulding (RTM) processes, the correlation analysis of epoxy/amine resin cure, structure and chemorheological behavior plays a key role in the optimum control of RTM processes. A new methodology used to simulate the reactive resin flow in RTM processes with edge effect is presented in this article. The recursive approach and the branching theory are used to describe the evolution of molecular structure and resin viscosity, respectively. And then the resin flow process is simulated by means of a semi‐implicit iterative calculation method and the finite volume method. The results reveal the proposed resin cure‐structure‐viscosity model provides excellent agreement with the experimental viscosity data during the RTM filling process. It is also observed that the curing reaction causes the inhomogeneous distribution of resin conversion and resin molecular weight in the mould cavity, which will result in the spatially structural and performance inhomogeneities in the finished products. With the injection temperature or the edge width increasing, the discrepancy of resin conversion and resin molecular weight in the mould cavity is more evident. This study is helpful for understanding the complicated relationship among the processing variables, resin structures, and properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

低温固化改性BMI树脂基体动力学研究

采用催化剂、3,3′-二烯丙基双酚A(DP)和多官能团单体C改性4,4′-二氨基二苯甲烷双马来酰亚胺(BMI)树脂,制取低温固化、高温性能优良的改性BMI树脂。采用差示扫描量热法(DSC)研究了改性BMI树脂的固化反应动力学,计算了固化反应体系的动力学参数,进而提出了该改性BMI树脂固化成型过程的动力学模型,并结合傅里叶红外光谱(FT-IR)对反应机理进行了探讨。研究结果表明,催化剂对固化反应的进行有重要的促进作用,改性BMI树脂的固化温度由259℃降为178℃;烯丙基与马来酰亚胺基的"ene"反应非常显著,且改性剂C与DP的"ene"反应历程相似;改性BMI树脂的固化工艺确定为120℃×6h+140℃×2h+160℃×2h+180℃×2h,后处理工艺为200℃×6h。     

Material systems for rapid manufacture of composite structures

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 (T_g). 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 T_g. 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 T_g, were still below the specifications for high performance parts.     

Cure kinetics of epoxy formulations of the type used in advanced composites

An analysis of the cure kinetics of three different formulations composed of tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) epoxy resin and diaminodiphenyl sulfone (DDS) was performed. A series of isothermal tests was run, and the experimentally obtained results were checked against the proposed kinetic model. An autocatalyzed mechanism with the overall reaction order of 2 was found to adequately describe the cure kinetics. An increase in reaction rate was observed at higher temperature and higher DDS concentration. For a given formulation, the extent of reaction corresponding to the maximum reaction rate was independent of temperature. A secondary exotherm was detected, particularly in formulations with low DDS concentration, at approximately 40% conversion. At that point, the rate of primary amine–epoxide reaction decreases, and other reactions dominate the curing process. Such a mechanism is likely to cause a formation of an inhomogeneous thermoset morphology.