碳纤维电沉积处理对其复合材料结构与性能的影响

为了(1)研究共聚物在碳纤维表面的电沉积处理对复合材料剪切强度的改善;(2)寻找适用于工业生产的电沉积条件;(3)探求聚合物在碳纤维表面的电沉积机理;(4)分析电沉积对复合材料破坏模式的影响,本工作分别以苯乙烯-马来酸酐、醋酸乙烯酯-马来酸酐和甲基丙烯酸甲酯-马来酸酐共聚物的钱盐水溶液作为电沉积液, 取纤维前处理、电沉积电流密度和沉积时间三个因子, 各选三个水平排成拉丁方来优选处理条件。     

甲基磺酸对PBO纤维的表面改性

采用甲基磺酸(MSA)溶液对PBO纤维表面进行化学改性,用单丝拔出试验测定了改性前后PBO纤维与环氧树脂基体的界面剪切强度,并通过扫描电镜(SEM)、X-射线光电子能谱(XPS)、接触角分别对处理前后纤维的表面形貌、表面组成以及表面自由能进行了表征.研究结果表明:在甲基磺酸质量分数为60%的溶液中,60℃下处理6 h的PBO纤维与环氧树脂基体的界面剪切强度比未处理的提高了81%,并且纤维表面O元素的质量分数增加了13.3%,表面自由能增加了17.3%.当溶液中甲基磺酸的质量分数、处理时间和处理温度进一步提高时,PBO纤维的皮层将遭受破坏,导致界面剪切强度下降.     

多聚磷酸/乙酸体系对PBO纤维表面改性的研究

采用多聚磷酸/乙酸体系并结合偶联剂处理方法对PBO纤维表面进行化学改性,采用扫描电镜和液滴形状法对处理前后纤维表面形态结构和纤维表面亲水性进行了表征,通过单丝拔出试验测定了改性前后PBO纤维与环氧树脂基体的界面剪切强度。利用X光电子能谱和热重分析等方法对纤维表面元素组成和热稳定性进行了分析。研究发现,多聚磷酸/乙酸体系偶联剂的方法改性后PBO纤维表面亲水性明显增强,与水的接触角从大于90°下降到42.8,°PBO纤维/环氧树脂的界面剪切强度较未处理样品提高了45%。     

高性能纤维表面改性及其双马树脂基复合材料界面

采用电感耦合射频等离子体(ICP)和介质阻挡放电(DBD)低温等离子体对高性能连续纤维表面进行改性,分别采用X光电子能谱(XPS)、原子力显微镜(AFM)和动态接触角测定仪(DCA)等分析测试手段系统地研究了等离子体处理时间、放电功率、放电气压等对连续碳纤维、聚苯并二噁唑(PBO)纤维改性处理前后,纤维表面状态、表面组成、表面形貌、浸润性能的变化规律以及经等离子体处理前后纤维增强双马树脂基复合材料界面结构与性能的影响关系及变化规律、复合材料界面粘结和破坏机理.研究结果表明,经过等离子体处理后,纤维表面接枝上了大量的含羧基、羟基等极性官能团,表面粗糙度增加,表面自由能增加,纤维浸润性能得到明显改善,导致纤维与双马树脂基体界面层间剪切强度(ILSS)明显提高,复合材料的破坏模式由未处理的界面脱粘破坏转变为等离子体处理后的树脂基体破坏.最后,对纤维表面时效性及其对纤维增强双马树脂基复合材料界面性能的影响关系也进行了论述.     

氨基硅烷/马来酸酐接枝聚丙烯界面化学反应的研究

利用溶剂萃取与红外光谱（IR）、光电子能谱（XPS）技术研究了化学键接在玻璃纤维表面的硅烷偶联剂与接枝聚丙烯间的界面化学反应。结果表明：溶剂萃取可以除去玻璃纤维/树脂界面区物理结合的聚合物基体,减少基体信号的影响,在此基础上,利用IR、XPS可以直接证明氨基硅烷（APS）与马来酸酐接枝聚丙烯（MA-g-PP）间发生了界面化学反应,生成了含酰胺基的反应产物。进一步对不同化学状态的N1s的XPS定量分析发现,尽管APS在玻纤表面以开环直链和以氢键结合的环状两种结构形式存在,但在界面上主要是无环开链结构中的氨基与酸酐发生反应。     

氧化石墨烯接枝碳纤维新型增强体的制备与表征

利用“Grafting-to”化学修饰法制备氧化石墨烯接枝国产碳纤维新型增强体。利用红外光谱、X射线光电子能谱和原子力显微镜对样品的官能团和表面形貌进行表征;利用接触角测量、单丝拉伸方法研究了接枝前后纤维单丝的润湿性能及拉伸强度,并通过微脱粘法分析了其复合材料的界面剪切强度。结果表明：氧化石墨烯的接枝修饰使国产碳纤维表面粗糙度提高了166%,表面能提高了46.3%,拉伸强度提高了7.8%,复合材料的界面剪切强度提高了111.7%。     

高亲水性环氧树脂的制备及对碳纤维的表面处理

在三乙胺催化下,以己二酸和环氧树脂制备了己二酸改性环氧树脂(AAEP),通过考察反应温度等因素对己二酸转化率和AAEP环氧值的影响,得到了AAEP合成的最佳条件.用傅里叶变换红外光谱和核磁共振对AAEP进行了表征.用KOH中和AAEP得到己二酸改性环氧树脂钾盐(AAEPK),测试了AAEPK乳液的性质和AAEPK处理后碳纤维的分散性,并通过场发射扫描电子显微镜和X射线光电子能谱对碳纤维的表面形貌和基团进行了研究.结果表明,AAEPK具有高亲水性,适用于碳纤维处理剂,当AAEPK的浓度和吸附量分别为1.0%(质量分数)和3.0 mg/g时,处理剂可在纤维表面均匀分布,使得碳纤维在树脂基体中的分散性得到改善.研究了处理剂对碳纤维/环氧树脂复合材料弯曲和剪切性能的影响,发现处理后碳纤维短丝/环氧树脂复合材料的弯曲强度和碳纤维布/环氧树脂复合材料的层间剪切强度较未处理的试样分别增加了168%和113%,说明AAEPK处理后碳纤维在基体中分散性和黏结性的提高是碳纤维/环氧树脂复合材料力学性能提高的主要原因.     

碳纤维的表面处理及其特性

碳纤维复合材料是一种低密度、高比强度、高比刚度,耐热、耐烧融的新材料。从七十年代初问世以来,已经得到了广泛的研究和应用,至今,仍处于迅速发展阶段中。作为结构材料使用,在复合材料的特性中,层间剪切强度是重要的。就一种树脂(聚酯、环氧、聚酰胺等)和特定碳纤维所制成的复合材料而言,其层间剪切强度主要取决于树脂与纤维两相间的粘结性能。碳纤维表面处理的根本目的,则在于改善两相间的粘结,以提高碳纤维复合材料的层间剪切强发。本文着重介绍若干表面处理方法和有关碳纤维表面特性及其对复合材料性能的影响。     

碳纤维表面改性研究进展

碳纤维因其优异的综合性能常被用作树脂基体的增强材料.然而由于碳纤维与树脂基体之间的界面结合性能较差,其增强的复合材料的力学性能往往与理论值相差甚远,因此必须对碳纤维进行表面改性,以提高其与聚合物基体的界面粘结性能.本文作者综述了国内外关于碳纤维表面改性技术的研究进展,概述了涂层法、氧化法、高能辐射法等改性方法对碳纤维增强复合材料界面强度的改性效果.     

多巴胺表面改性碳纤维对PVDF/CF复合材料性能的影响

对碳纤维(CF)进行去浆处理,再利用多巴胺对CF改性,得到多巴胺改性CF(DARCF),添加马来酸酐接枝聚偏氟乙烯(PVDF-g-MAH),制备了DARCF增强PVDF-g-MAH复合材料(PVDF-g-MAH/DARCF)。采用原子力显微镜(AFM)、X射线光电子能谱(XPS)和傅里叶变换红外光谱(FT-IR)对CF表面的粗糙度、结构和官能团进行表征。采用扫描电镜(SEM)、界面接触角测试和力学性能测试对复合材料的界面、力学性能进行测试。结果表明:改性之后,DARCF表面粗糙度增加,与树脂的界面结合强度提高,PVDF-g-MAH/DARCF的弯曲强度和模量比未改性的PVDF/CF分别提高了71.3%和36.9%。     

ELECTRODEPOSITION OF POLYMERS ON CARBON FIBERS

Styrene-co-maleic anhydride, vinyl acetate-co-maleic anhydride, methyl methacrylate-co-maleic anhydride copolymers were deposited on the surface of carbon fibers by an electrodcposition technique. The anion-free radical mechanism of this process and the physical adhesion to the surface were preliminarily confirmed. The adhesion at fiber-resin matrix interface in carbon fiber reinforced plastics was improved by the electrodeposited polymer interlayer and the shear failure occurred mainly in the matrix. Interlaminar shear strength of the unidirectional carbon fiber reinforced epoxy composite is increased from about 600 kg/cm~2 to 1000 kg/cm~2 by electrodeposition of polymers and the strength loss of the composite which has been immersed in boiling water for 100 hrs is decreased.     

Strength and toughness of carbon fibers reinforced rigid polyurethane composites by adsorbing tannic acid and refining Ni grains on carbon fibers surface

In this article, short carbon fibers (CFs) reinforced rigid polyurethane (RPU) composites were prepared with the aim of improving both strength and toughness. A tannic acid (TA)‐nickel (Ni) composite coating was spontaneously co‐deposited onto CFs surface by a one‐step electrodeposition method to strengthen the interface bonding of the composites. The satisfactory mechanical properties of the composites were mainly attributed to the superior interfacial adhesion. On the one hand, TA could play a role in refining Ni grain during electrodeposition. On the other hand, the hydroxyl groups attached to composite coating, which were introduced by TA, could react with the RPU matrix to form chemical bonds. When the composites were under stress, the chemical bonds could effectively transfer the stress from matrix to the interface, while the refined Ni crystals could greatly increase the stress transfer path, and thus improve the strength and toughness of the material. Compared with pure RPU, the tensile strength, bending strength,interlaminar shear strength, and impact strength of TA‐Ni‐coated CFs/RPU composites were improved by 14.8%, 83.1%, 28.7%, and 121.4%, respectively.     

Improved thermo-oxidative stability of three-dimensional and four-directional braided carbon fiber/epoxy hierarchical composites using graphene-reinforced gradient interface layer

In order to improve the thermo-oxidative stability of three-dimensional and four-directional braided carbon fiber/epoxy composites, we introduced a gradient interphase reinforced by graphene nanoplatelets (GN) between the carbon fiber and the matrix, with a liquid phase deposition strategy. Both the interlaminar shear strength and the flexural strength of the composites were improved after thermo-oxidative aging at 140 °C for various durations (up to 1200 h). The interfacial reinforcing mechanisms are explored by analyzing the structure of the interfacial phase, thermal conductivity, weight loss, surface topography, fiber/matrix interfacial morphology and thermomechanical properties of the composites. Results indicate that the GN-reinforced gradient interphase provides an effective shield against interface oxidation, assists in thermal stress transfer, and restricts the movement of the different phases of materials at the composite interface.     

The improvement in interfacial shear strength of wood fiber/epoxy composite by sizing with epoxy sizing agent containing MWCNTs

This paper discloses a feasible and high efficient strategy for wood fiber treatment to introducing multi‐wall carbon nanotubes (MWCNTs) to the surface of wood fibers for the aim of improving the interfacial shear strength of wood fiber/epoxy composite. Briefly, a layer of MWCNT was deposited on wood fibers through sizing wood fibers with epoxy sizing agent containing amine‐treated MWCNTs (MWCNT‐PEI). The surface functional groups, morphology, wettability, and interphase properties of MWCNTs on the surface of wood fiber were studied. The remarkable enhancements were achieved in interfacial shear strength of reinforced composites by dipping wood fiber in MWCNTCOOH suspension and wood fiber sizing containing MWCNT‐PEI.     

Interfacial adhesion and microfailure modes of electrodeposited carbon fiber/epoxy-PEI composites by microdroplet and surface wettability tests

Interfacial properties and microfailure modes of electrodeposition (ED)-treated carbon fiber-reinforced polyetherimide (PEI) toughened epoxy composite were investigated using microdroplet test and the measurement of surface wettability. ED was performed to improve the interfacial shear strength (IFSS). As PEI content increased, IFSS increased due to enhanced toughness and plastic deformation of PEI. In the untreated case, IFSS increased with adding PEI content, and the IFSS of the pure PEI matrix showed the highest. On the other hand, for the ED-treated case IFSS increased with PEI content with rather low improvement rate. In the untreated case, neat epoxy resin appeared brittle microfailure mode, whereas the pure PEI matrix exhibited a more likely ductile microfailure mode. In the ED-treated case, neat epoxy exhibited a more ductile fracture than that of the untreated case. Critical surface tension and polar surface free energy of ED-treated carbon fiber was higher than those of the untreated fiber. The work of adhesion between fiber and matrix was not directly proportional to IFSS for both the untreated and ED-treated cases. The matrix toughness might contribute to IFSS more likely than the surface wettability. Interfacial properties of the epoxy-PEI composite can be affected efficiently by both the control of matrix toughness and ED treatment.     

亚临界水介质回收酸酐固化环氧树脂/碳纤维复合材料

研究了不同添加剂对碳纤维增强酸酐固化环氧树脂复合材料在亚临界水中降解的影响,通过IR、GC-MS等分析,确定了环氧树脂的分解机理主要为酯键的断裂。 结果表明,KOH与苯酚对酸酐固化环氧树脂的分解没有协同效应,碱性物质更有利于酯键的断裂。 甲基四氢邻苯二甲酸酐固化的环氧树脂增强碳纤维复合材料在反应温度为250 ℃、反应时间为60 min、KOH浓度为0.2 mol/L时可完全分解,回收碳纤维的拉伸强度和表面形貌未受影响。     

原位合成纳米SiO2增强阴离子聚酯型上浆剂及其对碳纤维复合材料层间剪切强度的影响

采用溶胶-凝胶法, 在侧链带有羧基的线性不饱和聚酯中加入正硅酸乙酯(TEOS), 使TEOS在酸性条件下发生水解反应, 原位合成纳米SiO₂增强阴离子型聚酯乳液(SEAPE). 利用傅里叶变换红外光谱(FTIR)仪、 激光粒度分析仪和冷冻扫描电子显微镜(Cryo-SEM)对SEAPE进行分析与表征. 将SEAPE与聚乙二醇单油酸酯润滑剂、 非离子型表面活性剂FC-4430及抗氧剂1010进行复配, 原位制备纳米SiO₂增强阴离子型聚酯乳液上浆剂(SEAPEs), 用扫描电子显微镜(SEM)、 视频动态接触角测量仪、 X射线能谱(EDS)仪和纤维强力仪对SEAPEs上浆后碳纤维的表面形貌、 表面能、 碳纤维(CF)表面元素及碳纤维增强不饱和聚酯(UPR)复合材料(CF/UPR)的层间剪切强度(ILSS)进行测试与表征. 结果表明, 当TEOS添加质量分数为5%时, SEAPEs上浆后的碳纤维有效增强了其与UPR的结合强度, CF/UPR复合材料的ILSS达到40.03 MPa, 与市售环氧树脂型上浆剂上浆后碳纤维增强UPR复合材料相比, ILSS提高90.1%. SEAPEs中原位生成的纳米SiO₂分散均匀, 乳液储存稳定, 上浆后SiO₂均匀吸附在碳纤维表面, 增加碳纤维表面能, 改善碳纤维与树脂间的浸润性, 可有效提高碳纤维增强不饱和聚酯树脂复合材料的ILSS.     

Interfacial studies on the ozone and air‐oxidation‐modified carbon fiber reinforced PEEK composites

In this work, ozone modification method and air‐oxidationwere used for the surface treatment of polyacrylonitrile(PAN)‐based carbon fiber. The surface characteristics of carbon fibers were characterized by XPS. The interfacial properties of carbon fiber‐reinforced (polyetheretherketone) PEEK (CF/PEEK) composites were investigated by means of the single fiber pull‐out tests. As a result, it was found that IFSS (interfacial shear strength) values of the composites with ozone‐treated carbon fiber are increased by 60% compared to that without treatment. XPS results show that ozone treatment increases the amount of carboxyl groups on carbon fiber surface, thus the interfacial adhesion between carbon fiber and PEEK matrix is effectively promoted. The effect of surface treatment of carbon fibers on the tribological properties of CF/PEEKcomposites was comparativelyinvestigated. Experimental results revealed that surface treatment can effectively improve the interfacial adhesion between carbon fiber and PEEK matrix. Thus the wear resistance was significantly improved. Copyright © 2009 John Wiley & Sons, Ltd.     

The interfacial feature of thermoplastic polystyrene composite filled with nitric acid oxidized carbon fiber

The quality of interfacial interaction is dictated by the surface chemistry of the carbon fibers and the composition of the matrix. The composition of polystyrene was modified by the addition of maleic anhydride (MAH) grafted polystyrene. The surface properties of the various matrix formulations were characterized by contact angle. Carbon fibers were modified by oxidation in nitric acid. The surface composition of the carbon fibers was characterized. The interaction between modified polystyrene and the carbon fibers was studied by single fiber pull‐out tests. The best adhesion behavior was achieved between polystyrene containing grafted MAH and nitric acid oxidation carbon fibers. The addition of MAH‐grafted polystyrene to the unmodified polystyrene caused the interfacial shear strength (IFSS) to increase. The IFSS of this fiber‐matrix combination allowed for the full utilization of the tensile strength of polystyrene. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of carbon fiber surface functionality on the moisture absorption behavior of carbon fiber/epoxy resin composites

Polyacrylonitrile (PAN)‐based carbon fibers were electrochemically oxidized in aqueous ammonium bicarbonate with increasing current density. The electrochemical treatment led to significant changes of surface physical properties and chemical structures. The oxidized fibers showed much cleaner surfaces and increased levels of oxygen functionalities. However, it was found that there was no correlation between surface roughness and the fiber/resin bond strength, i.e. mechanical interlocking did not play a major role in fiber/resin adhesion. Increases in surface chemical functionality resulted in improved fiber/resin bonding and increased interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composites. The relationship between fiber surface functionality and the hydrothermal aging behavior of carbon fiber/epoxy composites was investigated. The existence of free volume resulted from poor wetting of carbon fibers by the epoxy matrix and the interfacial chemical structure were the governing factors in the moisture absorption process of carbon fiber/epoxy composites. Copyright © 2016 John Wiley & Sons, Ltd.