环氧树脂高低温弹性模量的分子模拟和实验研究

玻璃钢/复合材料 ›› 2016, Vol. 0 ›› Issue (8): 33-37.

环氧树脂高低温弹性模量的分子模拟和实验研究

李浩, 张清杰, 高亮, 张文卿

北京化工大学有机无机复合材料国家重点实验室,北京100029

收稿日期:2016-03-18 出版日期:2016-08-28 发布日期:2016-08-28
通讯作者: 隋刚,男,教授,主要从事复合材料方面的研究,suigang@mail.buct.edu.cn。
作者简介:李浩(1990-),男,硕士,主要从事复合材料及分子模拟方面的研究。

MOLECULAR SIMULATION AND EXPERIMENTAL ANALYSIS ON ELASTIC MODULUS OF EPOXY RESIN AT HIGH-LOW TEMPERATURE

LI Hao, ZHANG Qing-jie, GAO Liang, ZHANG Wen-qing

State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China

Received:2016-03-18 Online:2016-08-28 Published:2016-08-28

摘要/Abstract

摘要： 环氧-胺树脂体系的力学性能与温度的关系受到研究人员的广泛关注。通过计算机分子模拟构建了DDM/DGEBA和DDS/DGEBA的交联结构模型,利用密度-温度曲线确定了各树脂体系的玻璃化转变温度(T_g),然后预测了两组环氧树脂体系从高温(420K)到低温环境(100K)范围内的弹性模量,并与实验结果进行比较分析。利用分子模拟分析模量的变化与树脂体系的内聚能密度(CED)以及自由体积等微观结构参数的关系。分子模拟结果表明两种树脂体系的弹性模量都随着温度下降而增大,与实验结果较为一致,这主要是由于树脂体系的自由体积分数随着温度的降低而降低,而CED随着温度的降低而增大引起的。

关键词: 环氧树脂, 分子模拟, 高低温弹性模量, 微观结构

Abstract: The relationship between mechanical properties of epoxy resin-amine system and temperature has attracted extensive attention. In this paper, two crosslinking unit cells of DDM/DGEBA and DDS/DGEBA were established by using molecular dynamic (MD) simulation. On the basis of simulation analysis of glass transition temperature (T_g) obtained from density-temperature curves, the elastic modulus from high temperature (420 K) to cryogenic temperature (100 K) of two systems were investigated by using MD simulation and experimental methods. Furthermore, the relationship between modulus and a serious of microstructure, i.e. cohesive energy density (CED) and free volume of epoxy resin-amine system on the change of elastic modulus were investigated. Both MD results and experimental results showed that the elastic modulus of two epoxy resin systems increased as the temperature decreasing, which was attributed to the decrease of CED as well as the increase of free volume fraction as temperature decreasing.

Key words: epoxy resin, molecular simulation, high-low temperature elastic modulus, microstructure

中图分类号:

TB332

李浩, 张清杰, 高亮, 张文卿. 环氧树脂高低温弹性模量的分子模拟和实验研究[J]. 玻璃钢/复合材料, 2016, 0(8): 33-37.

LI Hao, ZHANG Qing-jie, GAO Liang, ZHANG Wen-qing. MOLECULAR SIMULATION AND EXPERIMENTAL ANALYSIS ON ELASTIC MODULUS OF EPOXY RESIN AT HIGH-LOW TEMPERATURE[J]. Fiber Reinforced Plastics/Composites, 2016, 0(8): 33-37.

参考文献

[1] 郑国栋, 张清杰, 邓火英, 等. 不同官能化碳纳米管对MWCNTs-碳纤维/环氧树脂复合材料力学性能的影响[J]. 复合材料学报, 2015, 32(3): 640-648.
[2] 汪准, 邓京兰, 王继辉, 等. 纤维缠绕复合材料石油套管结构设计与优化[J]. 玻璃钢/复合材料, 2015(5): 5-10.
[3] 贾智源, 宋秋香, 王海珍, 等. 碳纤维真空灌注成型用环氧树脂的流变特性分析[J]. 玻璃钢/复合材料, 2013(7): 7-10.
[4] 牟书香, 贾智源. 碳纤维增强环氧树脂复合材料的液体成型及其性能研究[J]. 玻璃钢/复合材料, 2013(6): 16-20.
[5] 许丹, 隋刚, 杨青, 等. 石墨烯微片表面接枝PMMA及其环氧树脂复合材料性能[J]. 复合材料学报, 2014, 31(2): 368-374.
[6] 何自强, 张惠玲. 环氧树脂/对甲基苯基双胍固化反应动力学研究[J]. 玻璃钢/复合材料, 2015(12): 53-59.
[7] Zhang Q. Influence of matrix modulus on the mechanical and interfacial properties of carbon fiber filament wound composites[J]. Rsc Advances, 2015, 5(32): 25208-25214.
[8] 沈小军, 孟令轩, 付绍云. 石墨烯-多壁碳纳米管协同增强环氧树脂复合材料的低温力学性能[J]. 复合材料学报, 2015, 32(1): 21-26.
[9] Feng Q P, Liu Y, Deng Y H, et al. Enhanced cryogenic interfacial normal bond property between carbon fibers and epoxy matrix by carbon nanotubes[J]. Composites Science & Technology, 2014, 104:59-65.
[10] Li F, Hua Y, Qu C B, et al. Greatly enhanced cryogenic mechanical properties of short carbon fiber/polyethersulphone composites by graphene oxide coating[J]. Composites Part A Applied Science & Manufacturing, 2016.
[11] Ionita M. Multiscale molecular modeling of SWCNTs/epoxy resin composites mechanical behaviour[J]. Composites Part B Engineering, 2012, 43(43):3491-3496.
[12] Gavrilov A A, Komarov P V, Khalatur P G. Thermal Properties and Topology of Epoxy Networks: A Multiscale Simulation Methodology[J]. Macromolecules, 2015, 48(1):206-212.
[13] Khare K S, Khabaz F, Khare R. Effect of carbon nanotube functionalization on mechanical and thermal properties of cross-linked epoxy-carbon nanotube nanocomposites: role of strengthening the interfacial interactions[J]. ACS applied materials & interfaces, 2014, 6(9): 6098-6110.
[14] Li C, Medvedev G A, Lee E W, et al. Molecular dynamics simulations and experimental studies of the thermomechanical response of an epoxy thermoset polymer[J]. Polymer, 2012, 53(19): 4222-4230.
[15] Yang Q, Yang X P, Li X D, et al. The curing and thermal transition behavior of epoxy resin: a molecular simulation and experimental study[J]. RSC Advances, 2013, 3(20): 7452-7459.
[16] Shokuhfar A, Arab B. The effect of cross linking density on the mechanical properties and structure of the epoxy polymers: molecular dynamics simulation[J]. Journal of molecular modeling, 2013, 19(9): 3719-3731.
[17] Yang Q, Li X, Shi L, et al. The thermal characteristics of epoxy resin: Design and predict by using molecular simulation method[J]. Polymer, 2013, 54(23): 6447-6454.
[18] Masoumi S, Arab B, Valipour H. A study of thermo-mechanical properties of the cross-linked epoxy: An atomistic simulation[J]. Polymer, 2015, 70: 351-360.
[19] 杨青. 环氧树脂交联结构模拟及具有模量过渡层结构的碳纤维复合材料性能研究[D]. 北京: 北京化工大学, 2014.