碳纳米材料在碳纤维上浆剂中的应用

简述了碳纤维上浆剂的分类及作用,重点介绍了碳纳米材料在碳纤维上浆剂中的应用,包括碳纤维上浆剂中碳纳米材料对上浆剂稳定性、碳纤维表面特性及碳纤维复合材料界面性能的作用。碳纤维上浆剂可分为溶剂型、乳液型、水溶性上浆剂,采用上浆法可以通过碳纤维上浆工序直接将碳纳米材料引入碳纤维表面。通过对上浆剂中的碳纳米材料进行改性,引入带同种电荷的官能团,可降低上浆剂乳胶粒子的团聚,提高上浆剂的稳定性,增加碳纤维表面粗糙度和改变碳纤维表面化学组成,增强碳纤维复合材料界面的物理锚定作用与化学键合作用,提高碳纤维复合材料的界面性能。指出通过化学键将改性碳纳米材料接枝到上浆剂主浆料分子上,可以缓解碳纳米材料的团聚,使碳纳米材料更均匀地包裹在碳纤维表面,进一步改善碳纤维表面特性和复合材料界面性能,这是未来碳纳米材料上浆剂研究的重要方向之一。     

连续玄武岩纤维改性方法的研究

简介了连续玄武岩纤维的性能与应用,重点阐述了偶联剂处理法、酸碱处理法、表面涂层法和低温等离子处理法4种常用的对连续玄武岩纤维改性研究方法的研究情况。表明无论采用偶联剂、酸碱、表面涂层和低温等离子处理法,都能有效改善纤维的表面性能,提高纤维与其它材质间的粘接性。指出对连续玄武岩纤维界面性质的基础研究深度不够,是限制连续玄武岩纤维界面改性方法开发和完善的主要原因。     

碳纤维/聚芳基乙炔复合材料界面改性方法的研究

为了改善碳纤维/聚芳基乙炔复合材料的界面性能,采用表面氧化、表面接枝、偶联剂、表面涂层等方法对碳纤维进行表面处理,探讨了各种方法对非极性聚芳基乙炔树脂基复合材料的界面改性效果。研究表明,纤维表面氧化处理后有利于碳纤维/聚芳基乙炔复合材料界面性能的改善,在此基础上通过表面接枝及表面偶联剂处理在纤维表面引入可与基体树脂发生反应的基团,可以达到非极性树脂基复合材料界面改性的目的。极性的高碳酚醛树脂可以更好地浸润氧化后的纤维表面,并且与聚芳基乙炔树脂在结构上相似,因此作为涂层处理纤维表面后可以明显提高材料的界面性能,该方法适于进行3D织物的改性处理,是较为理想的处理方案。     

苯并噁嗪树脂基复合材料的制备及性能表征

本文采用氧等离子体对碳纤维表面进行活化,后用偶联剂接枝的方法对碳纤维表面进行处理。按照GB3357-82和GB3356-82,对复合材料层间剪切强度和弯曲强度进行测试并研究等离子体处理及偶联剂接枝对碳纤维/苯并噁嗪(Polybenzoxazine,PBOZ)复合材料界面粘接性的影响。通过XPS,SEM对碳纤维表面及复合材料断裂面形貌进行测试,分析界面粘接机制。研究表明,氧等离子体处理使碳纤维表面粗糙度和活性含氧基团含量增加,增加了纤维与树脂之间的粘接性;氧等离子体处理后再进行偶联剂接枝,碳纤维表面的含氧官能团增加,浸润性得到改善,提高了碳纤维/PBOZ复合材料界面粘接性能。     

椰壳纤维/PBS可降解复合材料的研究

采用碱溶液和偶联剂对椰壳纤维进行表面处理,用转矩流变仪的密炼装置,制备未进行表面处理的不同纤维含量的椰壳纤维/PBS(聚丁二酸丁二醇酯)复合材料和经表面处理的不同纤维含量的椰壳纤维/PBS复合材料。重点研究了椰壳纤维和偶联剂含量对复合材料力学性能的影响。结果表明,椰壳纤维含量和偶联剂含量对复合材料的力学性能影响最大。当椰壳纤维含量为45%时,复合材料的力学性能最好,其拉伸强度、弯曲强度和冲击强度分别为38.59 MPa、52.43 MPa、10.45 k J/m2;偶联剂含量对冲击强度影响不大,但氢氧化钠浓度对冲击强度有一定影响。随着椰壳纤维含量的增加,材料的力学性能相应提高;偶联剂含量增加,纤维-树脂的界面黏结性能提高,材料的力学性能随之提高。扫描电子显微镜(SEM)图片显示,碱处理和偶联剂很好地改善了纤维-树脂的界面黏结性能。     

低温等离子处理对玄武岩纤维表面及复合材料性能的影响

对玄武岩纤维表面进行低温等离子处理,研究了低温等离子处理纤维对其表面性能、偶联剂吸附量及纤维增强树脂层间胶合强度和力学性能的影响。结果表明,纤维表面经低温等离子处理后,玄武岩纤维表面接触角由未处理时的132.23°降为75.22°,润湿性大大改善;纤维表面偶联剂吸附量在低温等离子处理10遍时达到最大;低温等离子及偶联剂处理纤维表面,处理10遍时,玄武岩纤维增强环氧树脂(BFRP)的拉伸性能、弯曲性能达到最优,而其剪切强度在处理2到10遍范围增加较快,10遍以后几乎不变。     

苎麻纤维增强聚丙烯复合材料的性能研究

用偶联剂对苎麻纤维进行改性处理,研究了偶联剂处理浓度及苎麻用量对聚丙烯/苎麻增强复合材料力学性能的影响。结果表明:随着苎麻纤维用量的增加,复合材料的拉伸强度和弯曲强度都随之提高,其中经偶联剂处理复合材料的力学性能提高幅度较大;偶联剂处理浓度为1%时,材料的拉伸强度最高。SEM观察发现:未经处理的苎麻纤维表面较光滑,而经偶联剂处理的苎麻纤维表面较粗糙,并黏附了聚丙烯基体,说明偶联剂的添加改善了复合体系的界面相容性,界面结合力提高。     

乳化剂对耐高温热塑性水分散乳液上浆剂性能的影响

在本项工作中,选用不同的表面活性剂,通过乳液/溶剂蒸发法制备杂萘联苯共聚芳醚砜(PPBES)水分散乳液上浆剂,以改善高性能热塑性复合材料中碳纤维与PPBES树脂之间的界面相容性。为获得最佳上浆效果,研究了PPBES浓度、表面活性剂种类及浓度对上浆剂平均粒径的影响;通过扫描电子显微镜(SEM)对上浆剂的成膜能力进行了分析,并研究了上浆处理对碳纤维性能的影响,结果表明:上浆后碳纤维制备的CFs/PPBES复合材料弯曲强度高达1781 MPa,相对于未上浆CFs制备的复合材料弯曲强度提高了15.6%,界面剪切强度提升了5.0%。     

碳纤维用水性乳液上浆剂的研究现状

简述了碳纤维用水性乳液上浆剂的制备、应用和性能表征手段的研究现状。介绍了相似相容和界面层理论在上浆剂主剂树脂选择方面的应用,说明了乳化剂、固化剂和纳米材料等原料的添加对上浆剂性能的影响,阐述了上浆剂乳液制备中自乳化法和相转乳化法的选择方法,以及表面处理和上浆处理工艺及工艺参数的优化方法。总结了应用于上浆剂乳液、上浆纤维和相应复合材料的表征手段,并解释了表征数据对上浆剂制备的指导意义。     

纳米SiO_2改性玄武岩纤维涂层浆料的制备及应用

经KH550改性的纳米SiO2粒子(150 nm),能够稳定分散在玄武岩纤维涂层浆料中,对浆料的粒径及表面张力影响不大。玄武岩纤维表面经改性纳米SiO2改性后,有效地改善了纤维表面粗糙度,使断裂强力提高18.75%,层间剪切强度提高18.76%。纳米SiO2改性的玄武岩连续纤维及其复合材料断面SEM分析表明,玄武岩连续纤维表面均匀涂覆一层纳米SiO2颗粒,使玄武岩连续纤维与环氧树脂的界面相容性大大提高,复合材料断面非常整齐。改性纳米SiO2在玄武岩纤维及环氧树脂之间起桥梁作用。     

Mechanical properties of carbon fiber composites modified with nano-SiO2 in the interphase

The performance of carbon fibers-reinforced composites is dependent to a great extent on the properties of fiber–matrix interface. To improve the interfacial properties in carbon fibers/epoxy composites, nano-SiO₂ particles were introduced to the surface of carbon fibers by sizing treatment. Atomic force microscope (AFM) results showed that nano-SiO₂ particles had been introduced on the surface of carbon fibers and increase the surface roughness of carbon fibers. X-ray photoelectron spectroscopy (XPS) showed that nano-SiO₂ particles increased the content of oxygen-containing groups on carbon fibers surface. Single fiber pull-out test (IFSS) and short-beam bending test (ILSS) results showed that the IFSS and ILSS of carbon fibers/epoxy composites could obtain 30.8 and 10.6% improvement compared with the composites without nano-SiO₂, respectively, when the nano-SiO₂ content was 1 wt % in sizing agents. Impact test of carbon fibers/epoxy composites treated by nano-SiO₂ containing sizing showed higher absorption energy than that of carbon fibers/epoxy composites treated by sizing agent without nano-SiO₂. Scanning electron microscopy (SEM) of impact fracture surface showed that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂-modified sizing treatment. Dynamic mechanical thermal analysis (DMTA) showed that the introduction of nano-SiO₂ to carbon fibers surface effectively improved the storage modulus of carbon fibers/epoxy.     

Reaction of carbon fiber sizing and its influence on the interphase region of composites

What might happen with the interphase region of composite if the sizing agent cannot afford the attack of processing temperature and firstly reacted before its combination with the resin, is rarely reported. On the basis of this, herein, effects of sizing reaction on the interphase region of composite were investigated, as well as on the carbon fiber surface properties. It showed that the interfacial shear strength of carbon fiber/epoxy composite was improved after the sizing reaction. The interphase modulus was also increased with a thinner gradient distance. Further analysis indicated that the fiber surface roughness increased, the fiber wettability with the resin lowered, and the chemical reactions between sizing agent and resin reduced after 200°C/2 h treatment on carbon fiber. These results explained the change of the interphase region, which are meaningful for sizing optimization. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41917.     

Interfacial improvement of carbon fiber/epoxy composites using a simple process for depositing commercially functionalized carbon nanotubes on the fibers

An aqueous suspension deposition method was used to coat the sized carbon fibers T700SC and T300B with commercially carboxylic acid-functionalized and hydroxyl-functionalized carbon nanotubes (CNTs). The CNTs on the fiber surfaces were expected to improve the interfacial strength between the fibers and the epoxy. The factors affecting the deposition, especially the fiber sizing, were studied. According to single fiber-composite fragmentation tests, the deposition process results in improved fiber/matrix interfacial adhesion. Using carboxylic acid-functionalized CNTs, the interfacial shear strength was increased 43% for the T700SC composite and 12% for the T300B composite. The relationship between surface functional groups of the CNTs and the interfacial improvement was discussed. The interfacial reinforcing mechanism was explored by analyzing the surface morphology of the carbon fibers, the wettability between the carbon fibers and the epoxy resin, the chemical bonding between the fiber sizing and the CNTs, and fractographic observation of cross-sections of the composites. Results indicate that interfacial friction, chemical bonding and resin toughening are responsible for the interfacial improvement of nanostructured carbon fiber/epoxy composites. The mechanical properties of the CNT-deposited composite laminate were further measured to confirm the effectiveness of this strategy.     

Effect of sizing on interfacial adhesion of commercial high strength carbon fiber‐reinforced resin composites

The influence of sizing agent on interfacial shear strength (IFSS) of carbon fiber/epoxy (CF/EP) and carbon fiber/bismaleimide (CF/BMI) was investigated. Since sizing agent can alter physicochemical properties of CF surface, possible affecting factors, including sizing reactivity, chemical reactions between sizing and resin, wettability of fiber with resin, fiber surface roughness, and chemical composition of fiber surface, were discussed. It is found that contact angle of fiber with resin and sufficient chemical reactions between sizing and resin reveal strong correlation with the interfacial adhesion of CF/EP and CF/BMI, while the effect of surface roughness and the amount of oxygen on the fiber surface are relatively weak. Due to EP type of the composition, the sizing agent tends to improve the wettability of CF with EP, while goes against for the fiber with BMI. POLYM. COMPOS., 254–261, 2016. © 2014 Society of Plastics Engineers     

Application of sustainable treatments to fiber surface for performance improvement of elastomeric polyurethane reinforced with basalt fiber

In order to overcome compatibility leakage between composite phases, which is a significant challenge in multidimensional composite applications, it is crucial to optimize the chemical nature of additives. The surface of basalt fiber (BF) was chemically enriched via biobased epoxy resin sizing and functional silanization process to improve its interfacial adhesion to the ecograde elastomeric polyurethane (EPU) matrix. The surface properties of BF were examined with the help of scanning electron microscopy X-ray spectroscopy (SEM/EDX) and Fourier-transformed infrared spectroscopy (FTIR) analyses. Impacts of surface modifications were compared based on mechanical, morphological, thermomechanical, and melt-flow behaviors of composites involving pristine and modified BF. Findings revealed that surface-modified BF inclusions improved the tensile strength and Shore-hardness values of composites. Tensile strength of EPU raised from 27.1 to 37.1 MPa after compounding with epoxy-sized BF. Additionally, the resin-coated BF incorporation exhibited a two-fold increase in the tensile modulus of EPU. Thermomechanical response of EPU exhibited an increasing trend by BF inclusions regardless of treatment type. Glass transition temperature of EPU shifted to 5 units higher value with modified BF loadings. SEM investigations confirmed the increased interfacial interaction between the EPU matrix and surface-sized BF. The chemically enriched surface of BF improves composite performance by improving adhesion at the EPU-BF interface. The results of this study confirmed that enhanced interfacial adhesion led to performance improvements for BF-loaded EPU composites.     

Nanoscale toughening of carbon fiber‐reinforced epoxy composites through different surface treatments

Interests in improving poor interfacial adhesion in carbon fiber‐reinforced polymer (CFRP) composites has always been a hotspot. In this work, four physicochemical surface treatments for enhancing fiber/matrix adhesion are conducted on carbon fibers (CFs) including acid oxidation, sizing coating, silane coupling, and graphene oxide (GO) deposition. The surface characteristics of CFs are investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, scanning electron microscopy, interfacial shear strength, and interlaminar shear strength. The results showed that GO deposition can remarkably promote fiber/matrix bonding due to improved surface reactivity and irregularity. In comparison, epoxy sizing and acid oxidation afford enhancement of IFSS owing to effective molecular chemical contact and interlocking forces between the fiber and the matrix. Besides, limited covalent bonds between silane coupling and epoxy matrix cannot make up for the negative effects of excessive smoothness of modified CFs, endowing them inferior mechanical properties. Based on these results, three micro‐strengthening mechanisms are proposed to broadly categorize the interphase micro‐configuration of CFRP composite, namely, “Etching” “Coating”, and “Grafting” modifications, demonstrating that proper treatments should be chosen for combining optimum interfacial properties in CFRP composites. POLYM. ENG. SCI., 59:625–632, 2019. © 2018 Society of Plastics Engineers     

激光改性玄武岩纤维性能研究

采用高能激光束对玄武岩纤维进行表面改性,并制备玄武岩纤维/环氧树脂复合材料。利用扫描电镜、原子力显微镜、X射线衍射等手段,表征改性前后玄武岩纤维的微观形态、物相结构,系统研究了激光对纤维的微观组织变化、性能等影响规律,并测试了玄武岩纤维/环氧树脂复合材料的力学性能。研究结果表明,随着激光功率的增加,玄武岩纤维表面缺陷深度和缺陷面积增加。当激光功率由0 W提高至120 W时,表面缺陷最大深度由9 nm增加至180 nm,表面缺陷的分布范围由3.5~6.5 nm增加至90~120 nm,表面粗糙度由1.41 nm增加至24.70 nm。激光改性后,玄武岩纤维单丝拉伸性能降低,由于激光对纤维的辐射作用,玄武岩纤维的表面缺陷深度与拉伸强度的关系不符合经典理论。激光改性前后,玄武岩纤维XRD谱峰位基本一致,表面所含元素的种类没有发生变化。激光改性使玄武岩纤维/环氧树脂复合材料的力学性能有所改善,随着激光功率的增加,复合材料的拉伸强度和冲击强度呈先升高后降低的趋势。     

Interfacial studies on the surface modified aramid fiber reinforced epoxy composites

In this work, solutions of rare earth modifier (RES) and epoxy chloropropane (ECP) grafting modification method were used for the surface treatment of aramid fiber. The effect of chemical treatment on aramid fiber has been studied in a composite system. The surface characteristics of aramid fibers were characterized by Fourier transform infrared spectroscopy (FTIR). The interfacial properties of aramid/epoxy composites were investigated by means of the single fiber pull‐out tests. The mechanical properties of the aramid/epoxy composites were studied by interlaminar shear strength (ILSS). As a result, it was found that RES surface treatment is superior to ECP grafting treatment in promoting the interfacial adhesion between aramid fiber and epoxy matrix, resulting in the improved mechanical properties of the composites. Meanwhile, the tensile strengths of single fibers were almost not affected by RES treatment. This was probably due to the presence of reactive functional groups on the aramid fiber surface, leading to an increment of interfacial binding force between fibers and matrix in a composite system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4165–4170, 2006     

石墨烯改性对环氧树脂/碳纤维复丝拉伸性能的影响

采用直接分散法和上浆剂法分别制备了环氧树脂/碳纤维复丝,通过红外光谱、分光光度法等分析方法对处理的石墨烯的表面官能团及表面形貌进行表征,借助扫描电子显微镜对碳纤维表面进行微观形貌观察,研究了石墨烯改性对环氧树脂/碳纤维复丝界面性能的影响。结果表明:石墨烯表面成功地接枝了硅烷偶联剂KH-560;接枝硅烷偶联剂KH-560的石墨烯的环氧树脂/碳纤维复丝的拉伸性能优于未经改性的石墨烯的复丝;上浆法制得的环氧树脂/碳纤维复丝的拉伸性能优于分散法制得的复丝的拉伸性能;上浆剂法制备的石墨烯改性的环氧树脂/碳纤维复丝的断裂强力比未经过改性的未上浆的复丝的提高了48.6%,拉伸强度提高了30.4%,断裂伸长率提高了90.9%。     

Studies on surface energetics of glass fabrics in an unsaturated polyester matrix system: Effect of sizing treatment on glass fabrics

The surfaces of glass fibers were sized by polyvinyl alcohol (PVA), polyester, and epoxy resin types in order to improve the mechanical interfacial properties of fibers in the unsaturated polyester matrix. The surface energetics of the glass fibers sized were investigated in terms of contact angle measurements using the wicking method based on the Washburn equation, with deionized water and diiodomethane as the wetting liquids. In addition, the mechanical behaviors of the composites were studied in the context of the interlaminar shear strength (ILSS), critical stress intensity factor (K_IC), and flexural measurements. Different evolutions of the London dispersive and specific (or polar) components of the surface free energy of glass fibers were observed after different sizing treatments. The experimental result of the total surface free energies calculated from the sum of their two components showed the highest value in the epoxy‐sized glass fibers. From the measurements of mechanical properties of composites, it was observed that the sizing treatment on fibers could improve the fiber–matrix interfacial adhesion, resulting in improved final mechanical behaviors, a result of the effect of the enhanced total surface free energy of glass fibers in a composite system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1439–1445, 2001