温度对CF/VE复合材料等温固化过程及其性能的影响

用DMTA和DSC扫描了碳纤维/乙烯基酯树脂复合材料在不同温度下的等温固化过程,然后再次用DSC扫描其后固化过程,用DMTA温度谱扫描其后固化前后的样条;制备碳纤维/乙烯基酯树脂复合材料浇注体,测试其力学性能。结果表明,等温固化温度低时固化过程中有相分离现象,后固化能使90℃下等温固化复合材料的层间剪切强度提高55.64%,而对120℃下等温固化复合材料的层间剪切强度作用不大。     

工艺因素对RTM成型聚酰亚胺复合材料性能的影响

采用低熔体粘度适用于液态成型的聚酰亚胺树脂研究了树脂传递模塑（RTM）工艺中树脂注射压力、注射流速、固化温度对碳纤维增强聚酰亚胺复合材料性能的影响，以确定最佳的成型工艺参数。结果表明，随着注射压力增大，复合材料的玻璃化转变温度下降，层间剪切强度提高，弯曲强度略有提升。随着注射流速增加，复合材料玻璃化转变温度不变，层间剪切强度和弯曲强度降低。随着固化温度升高，复合材料的玻璃化转变温度升高，但固化温度达到400℃时，层间剪切强度和弯曲强度明显降低。根据树脂工艺性，综合考虑复合材料内部质量、耐热性和力学性能，采用注射压力1.2 MPa，注射流速15 mL/min以及固化温度380℃的成型工艺较优。     

先进树脂基复合材料高压微波固化工艺实验研究

先进树脂基复合材料在航空航天领域应用广泛,采用高效率、低能耗的微波固化工艺以获得令人满意的固化质量的构件,已逐渐引起学者们的关注。将高压引入树脂基复合材料的固化过程中,通过缺陷分析、显微金相、力学性能检测等手段,对先进树脂基复合材料的高压微波固化质量进行实验研究。结果表明,高压微波固化能有效实现树脂基复合材料的固化,与传统热压罐工艺相比,高压微波固化工艺可获得低孔隙、少缺陷、纤维/树脂界面结合较好的固化质量,拉伸强度提高4.82%,层间剪切强度提高10.32%。研究结果为复合材料高压微波固化技术的推广与应用提供了实验数据支撑。     

弹性固化环氧树脂体系及其复合材料研究

制备了一种体育用品用弹性固化EP(环氧树脂)体系,并着重探讨了其与碳纤维制成的复合材料的相关性能。研究结果表明:弹性固化EP体系的相对最佳固化温度为113.5~147.0℃,95~110℃时固化度超过90%;复合材料的横向拉伸强度60.00 MPa、拉伸弹性模量≥8.20 GPa、弯曲强度≥1.50 GPa、弯曲弹性模量110.00 GPa和层间剪切强度82.00 MPa,经98℃水煮48 h后,复合材料的弯曲性能和层间剪切强度与国内外同类产品(150℃固化40 min)的性能相当;纤维表面有树脂附着,并且有部分树脂浸润纤维,说明该弹性固化EP体系与碳纤维之间的浸润效果良好。     

碳纤维增强双马树脂基复合材料微波固化工艺及性能研究

针对改性双马树脂T700级预浸料微波固化成型工艺,研究了保温时间、加压方式、升温速率对复合材料力学性能的影响,获得了不同条件下的微波固化复合材料的性能数据和较优的成型工艺方案;对比研究了不同加热方式对复合材料力学性能的影响。研究表明,微波固化样件的压缩强度、弯曲强度、拉伸模量和150℃干态弯曲性能都达到了热压罐水平,而拉伸强度、层间剪切强度和150℃干态层剪性能低于热压罐水平。微波固化工艺加热均匀,相对于热压罐成型,固化周期缩短50%以上,能有效提升复合材料制造效率,降低能耗。     

快速固化环氧树脂/碳纤维复合材料的性能

利用差示扫描量热分析仪研究了一种快速固化环氧树脂体系的固化工艺参数,确定了以真空辅助树脂灌注工艺制备快速固化环氧树脂/碳纤维复合材料的成型方法,并与常规固化环氧树脂体系制备的碳纤维复合材料进行对比,采用傅里叶变换红外光谱仪对两种材料的树脂基体进行了分析,考察了两种复合材料的纤维含量、孔隙率及力学性能,最后通过扫描电子显微镜观察了快速固化树脂基体与碳纤维的界面结合性。结果表明,快速固化树脂在99℃下固化6 min后固化度可达96%,能够大幅缩减碳纤维复合材料的成型时间,以其制备的碳纤维复合材料拉伸强度比常规固化环氧树脂复合材料高11.20%,弯曲强度高16.92%,纵横剪切强度高7.44%,快速固化树脂与碳纤维界面结合性良好。     

上浆剂类型对碳纤维/乙烯基酯树脂复合材料性能影响

本文研究了乙烯基酯树脂固化工艺,并根据固化工艺制备出不同上浆剂的碳纤维/乙烯基酯树脂复合材料,并对复合材料进行了力学性能和热稳定性能测试,结果表明水性聚氨酯上浆剂碳纤维较水性环氧上浆剂碳纤维制备的碳纤维/乙烯基酯树脂复合材料拉伸强度提升了16%,弯曲强度提高10%,层间剪切强度提高19%,并采用扫描电镜(SEM)分析了两种上浆剂碳纤维制备的碳纤维/乙烯基酯树脂复合材料的层间剪切断面的表面形态,发现聚氨酯上浆剂的碳纤维能够与乙烯基酯树脂有更好的界面结合性能。     

低温固化工艺对环氧-氰酸酯树脂性能影响研究

主要研究了环氧-氰酸酯(EP-CE)树脂在三种低温固化工艺(80℃/96h、120℃/48h、100℃/12h+150℃/12h)条件下性能和结构的变化.结果表明:固化工艺对树脂固化度、玻璃化温度、高温剪切强度和介电损耗的影响比较明显.三种低温固化工艺树脂的固化度分别为78.74％、93.41％、96.38％,Tg分别...     

芳纶纤维复合材料基体(AFR-TE)的性能研究

为了改善芳纶纤维增强树脂基复合材料的界面粘结性能,本文从树脂基体入手,依据相似相容原理和芳纶的结构特点,合成出新型热固性树脂(AFR-TE)用作芳纶复合材料的基体.采用非等温DSC法研究了AFR-TE树脂体系的固化反应动力学,确定了合理的固化制度;测定了AFR-TE树脂浇铸体的力学性能和耐热性能;探讨了芳纶/AFR-TE复合材料的界面粘结性能.结果表明,AFR-TE树脂固化反应级数为一级;AFR-TE树脂浇铸体的热变形温度(123.5℃)比E-51环氧树脂提高了25％,AFR-TE树脂各项力学性能都优于E-51环氧树脂,韧性得到明显改善;芳纶纤维/AFR-TE树脂复合材料的层间剪切强度和横向拉伸强度为71.2MPa和30.2MPa,分别比芳纶/E-51环氧复合材料提高了22.8％和58.1％,这表明AFR-TE树脂对芳纶的界面粘结性明显优于环氧树脂.     

MMA对乙烯基酯树脂及其复合材料性能的影响

通过粘度分析和力学性能、阻燃性能测试,研究了以甲基丙烯酸甲酯(MMA)作活性稀释剂的乙烯基酯树脂的流变性能及其对复合材料性能的影响。结果表明:常温下MMA能有效降低乙烯基酯树脂的粘度,20~40℃下,添加量>30%时,树脂体系的粘度在450 mPa.s以内,可应用于RTM工艺;固化后该复合材料的拉伸、弯曲强度、抗冲击性能、层间剪切强度和阻燃性能优异,可应用于高性能阻燃型复合材料构件的制备。     

Rubber modified epoxy resin. I: Cure kinetics and chemorheology

The curing and vitrification effect during the reaction of ATBN modified epoxy resin was studied through the dynamic differential scanning calorimetry method and a new reaction kinetic equation containing generalized WLF equation was developed to describe the reaction rate at both glassy and rubbery state. An autocatalytic mechanism was found to describe adequately the cure kinetics of the rubber modified epoxy resin and the overall order of reaction was assumed to be 2. The kinetic parameters were determined from the DSC data through the Marquardt's multivariable nonlinear regression method and Runge–Kutta integration technique. The presence of rubber indicated minor effect on the cure kinetics of epoxy resin. The Arrhenius type viscosity function was employed to establish a relationship between viscosity data measured by RMS and chemical conversion calculated from the reaction kinetic equation.     

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。     

Cure kinetics of methacrylate-type resin that include cyclohexane moiety

Two methacrylate-type resin including cyclohexane moiety were synthesized and characterized. The curing characteristics of these resins were investigated according to the change of thermal initiator. An autocatalytic kinetic reaction occurs in these systems, and the kinetic parameters of all systems were reported in terms of generalized kinetic equation that considered the diffusion term. It can be shown that the reaction conversion rate of one methacrylate-type resin (NC-9110-MA) is faster than another resin (EHPE-3150-MA), regardless of the kinds of thermal initiator, which is attributed to the reaction rate constant increases of NC-9110-MA with lower activation energy compared with EHPE-3150-MA. It can be seen that the conversion reaction rate of these resin systems with BPO as thermal initiator at low temperature is higher than those with AIBN. A main factor of reaction conversion rate increase for the NC-9110-MA resin system is a reaction rate constant; however, that for the EHPE-3150-MA resin system is a total reaction order. These resin with BPO as thermal initiator represent a lower cure reaction activation energy and collision frequency factor than those with AIBN.     

A novel rapid cure epoxy resin with internal mold release

Mold preparation, material layup, and cure times for thermoset-based composites often limit their use in high-volume applications. As such, new rapid cure epoxy resins are being developed to achieve a complete cycle time within 3 min. In this research, calorimetry and rheometry are used to examine and model two novel rapid cure epoxy resin systems with internal mold release. The rapid cure epoxy resins followed an autocatalytic cure kinetic and William–Landel–Ferry diffusion model. The rapid cure epoxy resin was shown to achieve 94% cure in 2 min at 150°C. However, adding an additional 2.5 wt% internal mold release hindered the first step of the reaction, which delayed the second reaction step since the final degrees of cure were similar. Furthermore, the resin viscosity followed a modified William–Landel–Ferry equation and at 120°C could maintain a viscosity below 5 Pa s for 4.1 min. These models provided valuable insight into the range of processing conditions these novel resins could experience during impregnation and molding processes.     

MAP-POSS改性不饱和聚酯树脂的固化反应

为改进不饱和聚酯（UP）树脂的性能,用非等温差示扫描量热法（DSC）研究了甲基丙烯酰氧丙基笼形倍半硅氧烷（MAP-POSS）与通用UP树脂的共同化反应。UP、苯乙烯和MAP—POSS有较好的相容性,可共同固化,MAP-POSS可均匀分散在UP基体中形成原位纳米分子复合材料。测定了固化动力学参数,建立了固化反应动力学数学模型。     

Modelling of the chemo–rheological behavior of thermosetting polymer nanocomposites

Epoxy/amine/montmorillonite nanocomposite systems are studied in this article. Both a thermo−kinetic analysis (performed using a differential scanning calorimeter) and a chemorheological characterization were carried out. The comparison of DSC thermograms has shown that the addition the nanofiller does not change the mechanism of crosslinking from a qualitative standpoint, but the nanoreinforcement seemed to produce an evident hindrance on the molecular mobility, which in turn influences the cure reactions. As none of the kinetic models available in literature was able to describe the cure behavior of the aforementioned materials, a new phenomenological model is proposed in this work, which considers the activation energy of the networking process a function of the degree of cure (rising exponentially towards infinity when thesystem approaches vitrification). The effects of the presence of the clay on the chemorheology of the composites was resumed as follows: the viscosity of the nanocomposite was higher at any temperature, furthermore the composite viscosity showed an higher heating sensitivity before networking and gelation occurred at lower degrees of cure, thus determining a narrower shape of the chemoviscosity behavior. A modified version of the classical Williams–Landel–Ferry (WLF) equation that took into account the gelation and the effects of crosslinking was uses as chemorheological model. Once the characteristic parameters of both the neat resin and the nanocomposite were found, the chemoviscosity models were integrated using a numerical algorithm, to check their ability to foresee the behavior of the systems during a dynamic cure process. A very good correspondence between the results and the experimental data was obtained. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Cure kinetics of dicyanate matrix polymers

The cure kinetics of two dicyanate resins were investigated by differential scanning calorimetry under isothermal and nonisothermal conditions. An autocatalytic kinetic model was proposed and a set of general kinetic parameters was calculated from the isothermal experiments. Good agreement between experimental data and the kinetic model has been obtained under different processing conditions, which demonstrated the validity and the usefulness of the analytical procedure and of the kinetic expression employed. Consequently, in its current form, the modeling methodology is capable of describing the degree of cure during a typical processing cycle and has the potential for comparing different resin formulations as well as the manifestations of cure in property development. Specifically, in this work the modeling methodology was tested using two distinct dicyanate resin systems while the development of the cure was also observed through dielectric analysis (DEA).     

A kinetic model for free‐radical crosslinking co‐polymerization of styrene/vinylester resin

Vinylester resin is a major thermoset polymer used In low temperature composite manufacturing processes, such as the Seemann Composite Resin Infusion Molding Process (SCRIMP). In this study, the effect of temperature on the cure kinetics of vinylester resin in the range of 35 to 90°C was investigated using a differential scanning calorimeter (DSC) and a Fourier transform infrared spectrometer (FTIR). A mechanistic kinetic model was developed to simulate the reaction rate and conversion profiles of vinylester vinylene and styrene vinyl groups, as well as the total reaction action rate and conversion. Experimental results from DSC and FUR at different temperatures were compared with model predictions. The glass transition temperature of the vinylester resin cured at different temperatures was identified and used to monitor the final conversion change. A series of SCRIMP molding experiments were conducted. The developed kinetic model in conjunction with a heat transfer model was used to simulate the temperature and conversion changes inside the SCRIMP‐molded composites.     

Cure kinetics of neat and graphite-fiber-reinforced epoxy formulations

An investigation was carried out into the cure kinetics of neat and graphite fiber-reinforced epoxy formulation, composed of tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) resin and diaminodiphenyl sulfone (DDS) curing agent. Two experimental techniques were employed: isothermal differential scanning calorimetry (IDSC) and dynamic differential scanning calorimetry (DDSC). An autocatalytic mechanism with the overall reaction rate order of 2 was found to describe adequately the cure kinetics, of the neat resin and the composite. All kinetic parameters, including reaction rate constants, activation energies and preexponential factors, were calculated and reported. The presence of graphite fibers in the composite had only a very small initial effect on the kinetics of cure.     

Curing characteristics of epoxy resin systems that include a biphenyl moiety

The curing characteristics of epoxy resin systems that include a biphenyl moiety were investigated according to the change of curing agents. Their curing kinetics mainly depend on the type of hardener. An autocatalytic kinetic reaction occurs in epoxy resin systems with phenol novolac hardener, regardless of the kinds of epoxy resin and the epoxy resin systems using Xylok and DCPDP (dicyclopentadiene‐type phenol resin) curing agents following an nth‐order kinetic mechanism. The kinetic parameters of all epoxy resin systems were reported in terms of a generalized kinetic equation that considered the diffusion term. The fastest reaction conversion rate among the epoxy resin systems with a phenol novolac curing agent was obtained in the EOCN‐C epoxy resin system, and for systems with Xylok and DCPDP hardeners, the highest reaction rate values were obtained in NC‐3000P and EOCN‐C epoxy resin systems, respectively. The system constants in DiBenedetto's equation of each epoxy resin system with different curing agents were obtained, and their curing characteristics can be interpreted by the curing model using a curing agent as a spacer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1942–1952, 2002