氧化石墨烯/环氧树脂复合材料非等温固化动力学
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摘要
通过液相共混法制备了氧化石墨烯/环氧树脂(GO/EP)复合材料,利用非等温结晶动力学,探讨了氧化石墨烯对环氧树脂体系非等温固化行为的影响,分析了环氧树脂和氧化石墨烯/环氧树脂在不同升温速率下的固化过程。结果表明,纯环氧树脂体系比氧化石墨烯/环氧树脂复合体系的固化表观活化能高,即氧化石墨烯对环氧树脂的固化具有促进作用。利用Kissinger方程、Flynn-Wall-Ozawa方程和Friedman-Reich-Levi方程分别求得的环氧树脂体系的固化表观活化能比氧化石墨烯/环氧树脂复合体系高3. 11、5. 56、5. 86 k J/mol。说明Kissinger、Flynn-Wall-Ozawa和Friedman-Reich-Levi方程均能较好地描述环氧树脂和氧化石墨烯/环氧树脂的固化过程。通过外延法求解的环氧树脂和氧化石墨烯/环氧树脂的理论凝胶温度分别为95. 171和90. 981℃,理论固化温度分别为41. 949和41. 343℃。
Graphene oxide/epoxy resin composite was prepared by liquid phase blending. The effect of graphene oxide on the non-isothermal curing behavior of epoxy resin system was investigated by non-isothermal crystallization kinetics,and the curing process of epoxy resin and graphene oxide/epoxy resin at different heating rates were analyzed. The results showed that the apparent activation energy of the pure epoxy resin system was higher than that of the graphene oxide/epoxy resin composite system,namely,the oxygen fossils could promote the curing of epoxy resin. By using Kissinger equation,Flynn-Wall-Ozawa equation and Friedman-Reich-Levi equation,the apparent activation energy of epoxy resin system was higher than that of graphene oxide/epoxy resin composite system,which was 3. 11,5. 56,5. 86 k J/mol respectively. It showed that Kissinger,Flynn-Wall-Ozawa and Friedman-Reich-Levi equations could well describe the curing process of epoxy resin and graphene oxide/epoxy resin. The theoretical gel temperatures of epoxy resin and graphene oxide/epoxy resin were 95. 171 ℃ and90. 981 ℃ by epitaxial method,and the theoretical curing temperatures were 41. 949 ℃ and 41. 343 ℃,respectively.
Graphene oxide/epoxy resin composite was prepared by liquid phase blending. The effect of graphene oxide on the non-isothermal curing behavior of epoxy resin system was investigated by non-isothermal crystallization kinetics,and the curing process of epoxy resin and graphene oxide/epoxy resin at different heating rates were analyzed. The results showed that the apparent activation energy of the pure epoxy resin system was higher than that of the graphene oxide/epoxy resin composite system,namely,the oxygen fossils could promote the curing of epoxy resin. By using Kissinger equation,Flynn-Wall-Ozawa equation and Friedman-Reich-Levi equation,the apparent activation energy of epoxy resin system was higher than that of graphene oxide/epoxy resin composite system,which was 3. 11,5. 56,5. 86 k J/mol respectively. It showed that Kissinger,Flynn-Wall-Ozawa and Friedman-Reich-Levi equations could well describe the curing process of epoxy resin and graphene oxide/epoxy resin. The theoretical gel temperatures of epoxy resin and graphene oxide/epoxy resin were 95. 171 ℃ and90. 981 ℃ by epitaxial method,and the theoretical curing temperatures were 41. 949 ℃ and 41. 343 ℃,respectively.
引文
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[2]王伟.环氧树脂固化技术及其固化剂研究进展[J].热固性树脂,2001,16(3):29-32.
[3]李丽娟,罗兰. 2016—2017年国外环氧树脂应用进展[J].热固性树脂,2018,33(3):49-55.
[4]刘明.室温固化湿法缠绕用环氧树脂体系研究[J].热固性树脂,2017,32(3):57-60.
[5] SHIU S,TSAI J. Characterizing thermal and mechanical properties of graphene/epoxy nanocomposites[J]. Composites Part B:Engineering,2014,56:691-697.
[6] CHANG K,HSU M,LU H,et al. Room-temperature cured hydrophobic epoxy/graphene composites as corrosion inhibitor for cold-rolled steel[J]. Carbon,2014,66:144-153.
[7] MENG Q,WU H,ZHAO Z,et al. Free-standing,flexible,electrically conductive epoxy/graphene composite films[J]. Composites Part A:Applied Science and Manufacturing,2017,92:42-50.
[8] ALLAOUI A,EL BOUNIA N. How carbon nanotubes affect the cure kinetics and glass transition temperature of their epoxy composites?—a review[J]. e XPRESS Polymer Letters,2009,3(9):588-594.
[9] ABDALLA M,DEAN D,ROBINSON P,et al. Cure behavior of epoxy/MWCNT nanocomposites:the effect of nanotube surface modification[J]. Polymer,2008,49(15):3310-3317.
[10] ZHOU T,WANG X,LIU X,et al. Influence of multi-walled carbon nanotubes on the cure behavior of epoxy-imidazole system[J].Carbon,2009,47(4):1112-1118.
[11] ZHOU T,WANG X,WANG T. Cure reaction of multi-walled carbon nanotubes/diglycidyl ether of bisphenol A/2-ethyl-4-methylimidazole(MWCNTs/DGEBA/EMI-2,4)nanocomposites:effect of carboxylic functionalization of MWCNTs[J]. Polymer International,2009,58(4):445-452.
[12] ZHOU T,WANG X,LIU X H,et al. Effect of silane treatment of carboxylic-functionalized multi-walled carbon nanotubes on the thermal properties of epoxy nanocomposites[J]. e XPRESS Polymer Letters,2010,4(4):217-226.
[13] FLYNN J H,WALL L A. General treatment of the thermogravimetry of polymers[J]. Journal of Research of the National Bureau of Standards,1966,70A(6):487-523.
[14] KISSINGER H E. Reaction kinetics in differential thermal analysis[J]. Analytical Chemistry,1957,29(11):1702-1706.
[15] OZAWA T. Kinetic analysis of derivative curves in thermal analysis[J]. Journal of Thermal Analysis and Calorimetry,1970,2(3):301-324.