氧化石墨烯改性高温环氧树脂基碳纤维复合材料的热性能与力学性能
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摘要
采用湿法预浸技术和模压工艺制备了氧化石墨烯(GO)改性碳纤维/环氧树脂(CF/E54-DDS)复合材料,利用差示扫描量热(DSC)分析、动态热机械分析(DMTA)、超声波C扫描等研究了GO对复合材料的热固化性能、凝胶工艺性能、动态热机械性能以及抗冲击损伤性能的影响.结果表明:GO结构中的羟基和羧基会促进改性树脂体系的固化反应,加快GO/E54-DDS的固化反应进程.在GO添加量(质量分数)小于0.5%时,GO的活性基团可增加改性树脂体系的交联密度,从而提高复合材料的玻璃化转变温度;但GO添加量大于0.8%时,会因DDS在固化网络结构中比例的大幅下降,反而降低复合材料的玻璃化转变温度.微观形貌分析显示GO/CF/E54-DDS预浸料比CF/E54-DDS预浸料表现出更好的浸润效果.CF/E54-DDS复合材料被破坏后CF表面光洁,破坏主要发生在CF与树脂基体的界面;而GO/CF/E54-DDS复合材料被破坏后,CF表面紧密黏附着GO/E54-DDS固化物,破坏主要发生在CF织物层间的GO/E54-DDS区域.冲击后压缩强度测试表明GO的存在提高了GO/CF/E54-DDS复合材料抵抗横向裂纹和纵向裂纹扩展的能力,减小了复合材料的损伤投影面积和裂纹凹坑深度,提高了冲击后压缩强度.
Graphene oxide(GO)modified carbon fiber/epoxy(CF/E54-DDS)composites were prepared by wet prepreg technology and molding process.And the effects of GO on the thermal curing property,gelation process,dynamic thermal mechanical property and anti-impact damage property of the composites were tested with differential scanning calorimetry(DSC)analysis,dynamic mechanical thermal analysis(DMTA),ultrasonic C scanning and so on.Results showed that hydroxyl groups and carboxyl groups of GO could promote the curing reaction of the modified resin system,and accelerate the process of curing reaction of GO/E54-DDS.When the additive amount(by mass)of GO was less than 0.5%,the active group of GO could increase the crosslinking density of the modified system and improve the glass transition temperature(Tg)of the composites.However,when the additive amount of GO was greater than 0.8%,it would decrease the proportion of DDS in the structure of the solidified network,while the Tgof the composites decreased.Micromorphological analysis showed that GO/CF/E54-DDS prepreg had better infiltration effect than CF/E54-DDS,and the failure of the CF/E54-DDS composites mainly occurred along the interfaces between the CF and the resin matrix,and the CF had a smooth surface.In contrast,the failure of the GO/CF/E54-DDS mainly occurred in the interlaminar GO/E54-DDS region benefited by the close adhering of cured GO/E54-DDS onto the CF surfaces,indicating effectively improved interfacial property of the GO/CF/E54-DDS hybrid composites.Compression strength after impact(CAI)test indicated that GO enhanced the ability of GO/CF/E54-DDS composites to resist transverse crack and longitudinal crack growth,so that damage projection area and crack pit depth decreased,and the CAI improved.
Graphene oxide(GO)modified carbon fiber/epoxy(CF/E54-DDS)composites were prepared by wet prepreg technology and molding process.And the effects of GO on the thermal curing property,gelation process,dynamic thermal mechanical property and anti-impact damage property of the composites were tested with differential scanning calorimetry(DSC)analysis,dynamic mechanical thermal analysis(DMTA),ultrasonic C scanning and so on.Results showed that hydroxyl groups and carboxyl groups of GO could promote the curing reaction of the modified resin system,and accelerate the process of curing reaction of GO/E54-DDS.When the additive amount(by mass)of GO was less than 0.5%,the active group of GO could increase the crosslinking density of the modified system and improve the glass transition temperature(Tg)of the composites.However,when the additive amount of GO was greater than 0.8%,it would decrease the proportion of DDS in the structure of the solidified network,while the Tgof the composites decreased.Micromorphological analysis showed that GO/CF/E54-DDS prepreg had better infiltration effect than CF/E54-DDS,and the failure of the CF/E54-DDS composites mainly occurred along the interfaces between the CF and the resin matrix,and the CF had a smooth surface.In contrast,the failure of the GO/CF/E54-DDS mainly occurred in the interlaminar GO/E54-DDS region benefited by the close adhering of cured GO/E54-DDS onto the CF surfaces,indicating effectively improved interfacial property of the GO/CF/E54-DDS hybrid composites.Compression strength after impact(CAI)test indicated that GO enhanced the ability of GO/CF/E54-DDS composites to resist transverse crack and longitudinal crack growth,so that damage projection area and crack pit depth decreased,and the CAI improved.
引文
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[2] DU J H,CHENG H M.The fabrication,properties,and uses of graphene/polymer composites[J].Macromolecular Chemistry and Physics,2012,213(10/11):1060-1077.
[3] CAI W,PINER R D,STADERMANN F J,et al.Synthesis and solid-state NMR structural characterization of 13 Clabeled graphite oxide[J].Science,2008,321(5897):1815-1817.
[4] STANKOVICH S,DIKIN D A,PINER R D,et al.Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide[J].Carbon,2007,45(7):1558-1565.
[5] WANG S,CHIA P J,CHUA L L,et al.Band-like transport in surface-functionalized highly solution-processable graphene nanosheets[J].Advanced Materials,2010,20(18):3440-3446.
[6] SHAH R,KAUSAR A,MUHAMMAD B,et al.Progression from graphene and graphene oxide to high performance polymer-based nanocomposite:a review[J].Polymer-Plastics Techndogy and Engineering,2015,54(2):173-183.
[7] WAN Y J,TANG L C,GONG L X,et al.Grafting of epoxy chains onto graphene oxide for epoxy composites with improved mechanical and thermal properties[J].Carbon,2014,69:467-480.
[8] WANG T Y,TSAI J L.Investigating thermal conductivities of functionalized graphene and graphene/epoxy nanocomposites[J].Computational Materials Science,2016,122:272-280.
[9]周宏,朴明昕,李芹,等.氧化石墨烯纳米片/环氧树脂复合材料的制备与性能[J].复合材料学报,2015,32(5):1309-1315.
[10] ZHOU T L,NAGAO S,SUGAHARA T,et al.Facile identification of the critical content of multi-layer graphene oxide for epoxy composite with optimal thermal properties[J].RSC Advances,2015,5(26):20376-20385.
[11] PATHAK A K,BORAH M,GUPTA A,et al.Improved mechanical properties of carbon fiber/graphene oxideepoxy hybrid composites[J].Composites Science and Technology,2016,135:28-38.
[12] LI Y,ZHAO Y,SUN J M,et al.Mechanical and electromagnetic interference shielding properties of carbon fiber/graphene nanosheets/epoxy composite[J].Polymer Composites,2016,37(8):2494-2502.
[13] WATSON G,STAROST K,BARI P,et al.Tensile and flexural properties of hybrid graphene oxide/epoxy carbon fibre reinforced composites[C]∥3rd International Conference on Structural Nano Composites.[S.l.]:IOP Publishing,2017:012009.doi:10.1088/1757-899X/195/1/012009.
[14] KOSTAGIANNAKOPOULOU C,LOUTAS T H,SOTIRIADIS G,et al.On the interlaminar fracture toughness of carbon fiber composites enhanced with graphene nano-species[J].Composites Science&Technology,2015,118:217-225.
[15] ADAK N,CHHETRI S,MURMU N,et al.Effect of thermally reduced graphene oxide on mechanical properties of woven carbon fiber/epoxy composite[C]∥NCPCM 2017.[S.l.]:IOP Publishing,2018:012015.doi:10.1088/1757-899X/338/1/012015.
[16] HUMMERS W S,JR,OFFEMAN R E.Preparation of graphitic oxide[J].Journal of the American Chemical Society,1958,80(6):1339.
[17] American Society for Testing and Materials.Standard test method for glass transition temperature(DMA Tg)of polymer matrix composites by dynamic mechanical analysis(DMA):ASTM D 7028-07e1[S].Philadelphia:AmericanSocietyforTestingandMaterials International,2007.
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[19]李桂林.环氧树脂与环氧涂料[M].北京:化学工业出版社,2003:126-129.
[20]陈平,刘胜平,王德中.环氧树脂及其应用[M].北京:化学工业出版社,2014:52-54.
[21]孙曼灵.环氧树脂应用原理与技术[M].北京:机械工业出版社,2002:115-117.
[22] WANG X,JIN J,SONG M,et al.Effect of graphene oxide sheet size on the curing kinetics and thermal stability of epoxy resins[J].Materials Research Express,2016,3(10):105303.
[23] RYU S H,SIN J H,SHANMUGHARAJ A M.Study on the effect of hexamethylene diamine functionalized graphene oxide on the curing kinetics of epoxy nanocomposites[J].European Polymer Journal,2014,52(1):88-97.
[24]胡玉明,吴良义.固化剂[M].北京:化学工业出版社,2004:9-14.
[25] QIU S L,WANG C S,WANG Y T,et al.Effects of graphene oxides on the cure behaviors of a tetrafunctional epoxy resin[J].Express Polymer Letters,2011,5(9):809-818.
[26]仇士龙,王玉婷,王成双,等.环氧树脂/氧化石墨纳米复合物的等温固化行为研究[J].高分子学报,2012(1):25-32.
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[29] BORTZ D R,HERAS E G,MARTIN-GULLON I.Impressive fatigue life and fracture toughness improvements in graphene oxide/epoxy composites[J].Macromolecules,2012,45(1):238-245.
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[31]陈淙洁,张明,王春红,等.四种碳纤维表面理化特性研究[J].玻璃钢/复合材料,2012(增1):73-80.
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