激光对碳纤维及碳纤维/环氧树脂复合材料性能影响
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摘要
采用高能激光束对聚丙烯腈(PAN)基碳纤维进行表面改性。利用SEM、EDS、FTIR、XRD、万能试验机等表征手段,对改性前后碳纤维微观形态、成分变化、物相结构、力学性能进行表征,系统地研究了激光束对碳纤维微观组织变化、性能变化等的影响规律,探索激光束对碳纤维的作用机制。结果表明,碳纤维经激光表面改性后,其表面的粗糙度和比表面积增加,碳纤维的浸润性得到提升,且激光束的功率越高、扫描速度越低,碳纤维浸润性越好。改性后的碳纤维化学成分、微观结构及官能团种类没有改变;改性后的碳纤维官能团种类没有改变,说明激光改性过程主要以物理过程为主;激光改性没有改变碳纤维的微观结构,改性后微晶尺寸略有减小,有利于改善碳纤维与环氧树脂的界面黏结性能。激光表面改性碳纤维/环氧树脂复合材料的拉伸强度和冲击强度均有不同程度的提高,当碳纤维质量分数为0.2wt%、激光改性功率为150W时,碳纤维/环氧树脂复合材料的拉伸强度提高了59%,冲击强度提高了52%。
The surface of polyacrylonitrile(PAN)-based carbon fibre was modified by high energy laser beam.SEM,EDS,FTIR,XRD,and tensile testing machine were used to characterize the morphology,change of composition,phase structure,and mechanical properties of carbon fibre before and after modification.The effect of laser beam on changes of carbon fibre microstructure was systematically studied to explore the mechanisms of laser beam on carbon fibre.The results show that surface roughness,specific surface area and infiltration of carbon fibre are improved after laser surface modification.When the power is higher,scanning speed becomes lower,carbon fibre wettability exhibits better.There are no changes in chemical composition,microstructure and type of functional groups of the modified carbon fibre.The type of functional group of modified carbon fibre is not changed,which indicates that process of laser modification is mainly based on physical process.The laser modification does not change the microstructure of carbon fiber.A slight decrease in microcrystalline size is beneficial to improve to the interfacial adhesion properties between carbon fiber and epoxy resin.The tensile strength,impact strength of modified carbon fibre/epoxy resin composites are also improved.When the mass fraction of carbon fibre is 0.2 wt%and modified power is 150 W,the tensile strength of carbon fibre/epoxy resin composite increases by 59%,and the impact strength increases by 52%.
The surface of polyacrylonitrile(PAN)-based carbon fibre was modified by high energy laser beam.SEM,EDS,FTIR,XRD,and tensile testing machine were used to characterize the morphology,change of composition,phase structure,and mechanical properties of carbon fibre before and after modification.The effect of laser beam on changes of carbon fibre microstructure was systematically studied to explore the mechanisms of laser beam on carbon fibre.The results show that surface roughness,specific surface area and infiltration of carbon fibre are improved after laser surface modification.When the power is higher,scanning speed becomes lower,carbon fibre wettability exhibits better.There are no changes in chemical composition,microstructure and type of functional groups of the modified carbon fibre.The type of functional group of modified carbon fibre is not changed,which indicates that process of laser modification is mainly based on physical process.The laser modification does not change the microstructure of carbon fiber.A slight decrease in microcrystalline size is beneficial to improve to the interfacial adhesion properties between carbon fiber and epoxy resin.The tensile strength,impact strength of modified carbon fibre/epoxy resin composites are also improved.When the mass fraction of carbon fibre is 0.2 wt%and modified power is 150 W,the tensile strength of carbon fibre/epoxy resin composite increases by 59%,and the impact strength increases by 52%.
引文
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[24]刘丹丹,王宜,胡健,等.PBO纤维表面等离子改性及界面性能[J].华南理工大学学报(自然科学版),2006,34(3):10-14.LIU D D,WANG Y,HU J,et al.Plasma modification on PBO fiber surface and interfacial properties of PBO fiber[J].Journal of South China University of Technology(Natural Science Edition),2006,34(3):10-14(in Chinese).
[25]水兴瑶,刘猛,朱曜峰,等.水性上浆剂对碳纤维表面及碳纤维/环氧树脂复合材料界面性能的影响[J].复合材料学报,2017,34(6):1237-1244.SHUI X Y,LIU M,ZHU Y F,et al.Effect of waterborne sizing agent on carbon fiber surface and properties of carbon fiber/epoxy composites interface[J].Acta Materiae Compositae Sinica,2017,34(6):1237-1244(in Chinese).
[26]中国国家标准化管理委员会.碳纤维复丝拉伸性能试验方法:GB/T 3362-2005[S].北京:中国标准出版社,2005.Standardization Administration of the People's Republic of China.Test methods for tensile properties of carbon fiber multifilament:GB/T 3362-2005[S].Beijing:China Standards Press,2005(in Chinese).
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[28]徐永新,顾轶卓,马全胜,等.几种国产高模碳纤维特性实验分析[J].复合材料学报,2016,33(9):1905-1914.XU Y X,GU Y Z,MA Q S,et al.Experimental analysis of properties of several domestic high-modulus carbon fibers[J].Acta Materiae Compositae Sinica,2016,33(9):1905-1914(in Chinese).
[29]郭云霞,刘杰,梁节英.电化学改性对PAN基碳纤维表面状态的影响[J].复合材料学报,2005,22(3):49-54.GUO Y X,LIU J,LIANG J Y.Effect of electrochemical modification on the surface state of PAN-based carbon fibers[J].Acta Materiae Compositae Sinica,2005,22(3):49-54(in Chinese).
[30]成荣,蒋世春,安立佳.环氧树脂在碳纤维表面的浸润行为[J].高分子学报,2009(4):352-357.CHENG R,JIANG S C,AN L J.Wettability of epoxy resin on carbon fiber[J].Acta Polymerica Sinica,2009(4):352-357(in Chinese).
[2]LINDSAY B,ABEL M L,WATTS J F.A study of electrochemically treated PAN based carbon fibres by IGC and XPS[J].Carbon,2007,45(12):2433-2444.
[3]CHOI M H,JEON B H,CHUNG I J.The effect of coupling agent on electrical and mechanical properties of carbon fiber/phenolic resin composites[J].Polymer,2000,41(9):3243-3252.
[4]HARRWELL M G.Investigation of bond strength and failure mode between SiC-coated mesophase ribbon fiber and an epoxy matrix[J].Carbon,2000,38:1111-1121.
[5]GUO J H.Effect of electrophoretically deposited carbon nanotubes on the interface of carbon fiber reinforced epoxy composite[J].Journal of Materials Science,2012,47(6):2831-2836.
[6]WANG B,DUAN Y,ZHANG J,et al.Microwave radiation effects on carbon fibres interfacial performance[J].Composites Part B:Engineering,2016,99:398-406.
[7]王源升,朱珊珊,姚树人,等.碳纤维表面改性及对其复合材料性能的影响[J].高分子材料科学与工程,2014,30(2):16-20.WANG Y S,ZHU S S,YAO S R,et al.Surface modification of carbon fiber and its effect on the performance of composite materials[J].Polymer Materials Science&Engineering,2014,30(2):16-20(in Chinese).
[8]贾玲,周丽绘,薛志云,等.碳纤维表面等离子接枝及对碳纤维/PAA复合材料ILSS的影响[J].复合材料学报,2004,21(4):45-49JIA L,ZHOU L H,XUE Z Y,et al.Surface of carbon fiber grafted by plasma technology and its influence on the C/PAAcomposite[J].Acta Materiae Compositae Sinica,2004,21(4):45-49(in Chinese).
[9]ZHAO F,HUANG Y.Improved interfacial properties of carbon fiber/epoxy composites through grafting polyhedral oligomeric silsesquioxane on carbon fiber surface[J].Materials Letters,2010,64(24):2742-2744.
[10]YAO X,JIANG J,XU C.Improved interfacial properties of carbon fiber/epoxy composites through grafting polyhedral oligomeric silsesquioxane on carbon fiber surface[J].Fibers&Polymers,2017,18(7):1323-1329.
[11]TANG X,YU B,HANSEN R V,et al.Grafting low contents of branched polyethylenimine onto carbon fibers to effectively improve their interfacial shear strength with an epoxy matrix[J].Advanced Materials Interfaces,2015,2(12):1-5.
[12]MAO L,WANG Y,ZANG Z,et al.Amino-functionalization of carbon fibers through electron-beam irradiation technique[J].Journal of Applied Polymer Science,2014,131(10):376-418.
[13]ZHANG H X,LI W.Plasma-grafting polymerization on carbon fibers and its effect on their composite properties[J]Applied Surface Science,2015,356:492-498.
[14]TIWARI S.Polyetherimide composites with Gamma irradiated carbon fabric:Studies on abrasive wear[J].Wear,2011,270(9-10):688-694.
[15]倪新亮,金凡亚,沈丽如,等.等离子体处理碳纤维/树脂复合材料[J].复合材料学报,2015,32(3):721-727.NI X L,JIN F Y,SHEN L R,et al.Carbon fiber/resin composites treated by plasma[J].Acta Materiae Compositae Sinica,2015,32(3):721-727(in Chinese).
[16]张运海.聚合物材料表面激光改性与刻蚀研究[D].济南:山东师范大学,2005.ZHANG Y H.Surface modification and etching of polymer by excimer laser irradiation[D].Ji'nan:Shandong Normal University,2005(in Chinese).
[17]WIENER J,SHAHIDI S.Morphological and mechanical changes of glass fibers mat by CO2laser[J].Journal of the Textile Institute,2014,105(2):187-195.
[18]赵玉飞,袁剑民,费又庆.碳纤维网络增强环氧树脂基复合材料的制备与表征[J].复合材料学报,2015,32(6):1611-1617.ZHAO Y F,YUAN J M,FEI Y Q.Fabrication and characterization of carbon fiber network reinforced epoxy matrix composites[J].Acta Materiae Compositae Sinica,2015,32(6):1611-1617(in Chinese).
[19]罗云.纤维表面处理及增强环氧树脂复合材料的研究[D].长沙:湖南大学,2016.LUO Y.Study on fiber surface treatment and reinforced epoxy resin composites[D].Changsha:Hu'nan University,2016(in Chinese).
[20]SONG B,BISMARCK A,TAHHAN R,et al.A generalized drop length-height method for determination of contact angle in drop-on-fiber systems[J].Journal of Colloid&Interface Science,1998,197(1):68-77.
[21]WU X F,DZENIS Y A.Droplet on a fiber:Geometrical shape and contact angle[J].Acta Mechanica,2006,185(3-4):215-225.
[22]钟新辉,余英丰,詹国柱,等.一种纤维接触角在线测量方法与装置.中国,200810034892.1[P].2008-08-20.ZHONG X H,YU Y F,ZHAN G Z,et al.A method and device for on-line measurement of fiber contact angle.China,200810034892.1[P].2008-08-20(in Chinese).
[23]王宜,胡健,张英东,等.液滴形状法测量纤维接触角的研究[J].合成纤维工业,2004,27(2):12-14.WANG Y,HU J,ZHANG Y D,et al.Study on droplet profile method for determination of contact angle in drop-on-fiber systems[J].China Synthetic Fiber Industry,2004,27(2):12-14(in Chinese).
[24]刘丹丹,王宜,胡健,等.PBO纤维表面等离子改性及界面性能[J].华南理工大学学报(自然科学版),2006,34(3):10-14.LIU D D,WANG Y,HU J,et al.Plasma modification on PBO fiber surface and interfacial properties of PBO fiber[J].Journal of South China University of Technology(Natural Science Edition),2006,34(3):10-14(in Chinese).
[25]水兴瑶,刘猛,朱曜峰,等.水性上浆剂对碳纤维表面及碳纤维/环氧树脂复合材料界面性能的影响[J].复合材料学报,2017,34(6):1237-1244.SHUI X Y,LIU M,ZHU Y F,et al.Effect of waterborne sizing agent on carbon fiber surface and properties of carbon fiber/epoxy composites interface[J].Acta Materiae Compositae Sinica,2017,34(6):1237-1244(in Chinese).
[26]中国国家标准化管理委员会.碳纤维复丝拉伸性能试验方法:GB/T 3362-2005[S].北京:中国标准出版社,2005.Standardization Administration of the People's Republic of China.Test methods for tensile properties of carbon fiber multifilament:GB/T 3362-2005[S].Beijing:China Standards Press,2005(in Chinese).
[27]中国国家标准化管理委员会.树脂浇铸体性能试验方法:GB/T 2567-2008[S].北京:中国标准出版社,2009.Standardization Administration of the People's Republic of China.Test methods for properties of resin casting boby:GB/T 2567-2008[S].Beijing:China Standards Press,2009(in Chinese).
[28]徐永新,顾轶卓,马全胜,等.几种国产高模碳纤维特性实验分析[J].复合材料学报,2016,33(9):1905-1914.XU Y X,GU Y Z,MA Q S,et al.Experimental analysis of properties of several domestic high-modulus carbon fibers[J].Acta Materiae Compositae Sinica,2016,33(9):1905-1914(in Chinese).
[29]郭云霞,刘杰,梁节英.电化学改性对PAN基碳纤维表面状态的影响[J].复合材料学报,2005,22(3):49-54.GUO Y X,LIU J,LIANG J Y.Effect of electrochemical modification on the surface state of PAN-based carbon fibers[J].Acta Materiae Compositae Sinica,2005,22(3):49-54(in Chinese).
[30]成荣,蒋世春,安立佳.环氧树脂在碳纤维表面的浸润行为[J].高分子学报,2009(4):352-357.CHENG R,JIANG S C,AN L J.Wettability of epoxy resin on carbon fiber[J].Acta Polymerica Sinica,2009(4):352-357(in Chinese).