增韧改性环氧树脂固化动力学研究及TTT图绘制

复合材料科学与工程 ›› 2020, Vol. 0 ›› Issue (10): 21-29.

增韧改性环氧树脂固化动力学研究及TTT图绘制

陶雷¹, 闵伟¹, 戚亮亮¹, 孙泽玉^2,3*

1.东华大学材料科学与工程学院,上海201620;
2.上海市轻质结构重点实验室,上海201620;
3.东华大学民用航空复合材料协同创新中心,上海201620

收稿日期:2020-06-15 出版日期:2020-10-28 发布日期:2020-10-28
通讯作者: 孙泽玉(1986-),男,工程师,博士,主要研究方向为复合材料及其结构设计,sunzeyu@dhu.edu.cn。
作者简介:陶雷(1992-),男,研究生,主要研究方向为环氧树脂增韧改性及复合材料。本文作者还有余木火^1,2。
基金资助:
上海市科学技术委员会(17511102801);中央高校基础研究基金(2232018A3-02)

STUDY ON CURING KINETICS OF TOUGHENED MODIFIED EPOXY RESIN AND DRAWING OF TTT DIAGRAM

TAO Lei¹, MIN Wei¹, QI Liang-liang¹, SUN Ze-yu^2,3*

1. College of Materials Science and Engineering, Donghua University, Shanghai 201620, China;
2. Shanghai Key Laboratory of Lightweight Structural Composites, Donghua University, Shanghai 201620, China;
3. Center for Civil Aviation Composites, Donghua University, Shanghai 201620, China

Received:2020-06-15 Online:2020-10-28 Published:2020-10-28

摘要/Abstract

摘要： 本研究采用小振幅振荡剪切法和差示扫描量热法(Differential Scanning Calorimetry,简称“DSC”)实验测量了增韧改性环氧树脂的凝胶化和玻璃化行为,建立了环氧树脂体系的时间-温度-转变图(Time-Temperature-Transformation,简称“TTT”)。对增韧改性环氧树脂体系进行DSC实验,并且利用唯象模型建立了树脂体系的固化动力学模型。利用等温DSC和动态DSC结合DiBenedetto方程研究树脂玻璃化转变温度与固化度之间的关系,并给出玻璃化转变温度T_g与时间t和温度T的数学关系。使用平板流变仪测试增韧改性树脂体系,并通过线性回归分析获得凝胶时间与温度之间的关系。绘制了基于增韧改性环氧树脂体系的TTT图,为环氧树脂及其预浸料的成型工艺提供理论指导,有利于提高生产效率。

关键词: 环氧树脂增韧, 固化动力学, 玻璃化转变温度, 凝胶点, TTT图, 复合材料

Abstract: In this study, the gelation and vitrification behavior of toughened modified epoxy resin were measured by small amplitude oscillatory shear method and differential scanning calorimetry, respectively, and the time-temperature-transition (TTT) diagram of the epoxy system was established. A dynamic differential scanning calorimetry (DSC) experiment was carried out on the toughened modified epoxy resin system, and a curing kinetic model was established using a phenomenological model. Using isothermal DSC and dynamic DSC combined with DiBenedetto equation to study the relationship between resin glass transition temperature and degree of curing, and gives the mathematical relationship between the glass transition temperature T_g and time t and temperature T. The gel time at different temperatures of the resin system was tested using a flat plate rheometer, and the relationship between the gel time and temperature was obtained by linear regression analysis. The TTT diagram based on the toughened modified epoxy resin system is drawn to provide theoretical guidance for the molding process of epoxy resin and its prepreg, which is conducive to improving manufacturing efficiency.

Key words: epoxy resin toughening, curing kinetics, glass transition temperature, gel point, TTT diagram, composites

中图分类号:

TB332

陶雷, 闵伟, 戚亮亮, 孙泽玉. 增韧改性环氧树脂固化动力学研究及TTT图绘制[J]. 复合材料科学与工程, 2020, 0(10): 21-29.

TAO Lei, MIN Wei, QI Liang-liang, SUN Ze-yu. STUDY ON CURING KINETICS OF TOUGHENED MODIFIED EPOXY RESIN AND DRAWING OF TTT DIAGRAM[J]. Composites Science and Engineering, 2020, 0(10): 21-29.

参考文献

[1] SUN Z, XIAO J, TAO L, et al. Preparation of high-performance carbon fiber-reinforced epoxy composites by compression resin transfer molding[J]. Materials, 2018, 12(1). DOI: 10.3390/ma12010013.
[2] PECORA M, PANNIER Y, LAFARIEFRENOT M C, et al. Effect of thermo-oxidation on the failure properties of an epoxy resin[J]. Polymer Testing, 2016, 209-217.
[3] 刘万双. 汽车轻量化用碳纤维复合材料国内外应用现状[J]. 纺织导报, 2016(5): 48-52.
[4] SUN Z, XU L, CHEN Z, et al. Enhancing the mechanical and thermal properties of epoxy resin via blending with thermoplastic polysulfone[J]. Polymers, 2019, 11(3). DOI: 10.3390/polym11030461.
[5] 刘天舒, 陈祥宝, 张宝艳. 5228高温固化环氧树脂体系的固化反应动力学研究[C]//第十三届全国复合材料学术会议. 2004.
[6] FRANCIS B. Cure kinetics of epoxy/thermoplastic blends[M]. Springer International Publishing, 2017.
[7] PASCAULT J P, WILLIAMS R J J. Thermosetting polymers[M]//Handbook of Polymer Synthesis, Characterization, and Processing. 2013.
[8] NU＇EZ L, FRAGA F, CASTRO A, et al. TTT cure diagram for an epoxy system diglycidyl ether of bisphenol A/1,2 diamine cyclohexane/calcium carbonate filler [J]. Polymer, 2001, 42(8): 3581-3587.
[9] TUNG C I M, DYNES P J. Relationship between viscoelastic properties and gelation in thermosetting systems[J]. Journal of Applied Polymer Science, 1982, 27(2): 569-574.
[10] ENNS J B, GILLHAM J K. Time-temperature-transformation (TTT) cure diagram: Modeling the cure behavior of thermosets[J]. Journal of Applied Polymer Science, 1983, 28(8): 2567-2591.
[11] CADENATO A, SALLA J M, RAMIS X, et al. Determination of gel and vitrification times of thermoset curing process by means of TMA, DMTA and DSC techniques-TTT diagram[J]. Journal of Thermal Analysis, 1997, 49(1): 269-279.
[12] GONIS J, SIMON G P, COOK W D. Cure properties of epoxies with varying chain length as studied by DSC[J]. Journal of Applied Polymer Science, 1999, 72(11): 1479-1488.
[13] YANG L F, YAO K D, KOH W. Kinetics analysis of the curing reaction of fast cure epoxy prepregs[J]. Journal of Applied Polymer Science, 1999, 73(8): 1501-1508.
[14] YANG R T, STEINBERG M. Reaction kinetics and differential thermal analysis[J]. Journal of Physical Chemistry, 1976, 80(9): 965-968.
[15] TANAKA N, IIJIMA T, FUKUDA W, et al. Synthesis and properties of interpenetrating polymer networks composed of epoxy resins and polysulphones with cross-linkable pendant vinylbenzyl groups[J]. Polymer International, 1997, 42(1): 95-106.
[16] DIBENEDETTO A T. Prediction of the glass transition temperature of polymers: A model based on the principle of corresponding states[J]. Journal of Polymer Science Part B Polymer Physics, 1987, 25(9): 1949-169.
[17] RAMIS X, CADENAT O A, MORANCHO J M, et al. Curing of a thermoset ting powder coating by means of DMTA, TMA and DSC[J]. Polymer, 2003, 44(7):2067-2079.