碳纤维/乙烯基酯树脂拉挤复合材料界面性能研究

对PAN基碳纤维在线热氧化表面处理,分析了处理前后碳纤维的表面形貌,通过拉挤成型工艺制备出碳纤维/乙烯基酯树脂复合材料。对拉挤复合材料的微观结构观察以及力学性能测试表明:碳纤维经表面处理后表面粗糙度增加,与乙烯基酯树脂的界面粘结性明显改善,复合材料的力学性能尤其是层间剪切强度得到显著提高。对不同界面性能的碳纤维复合材料进行动态热机械分析(DMTA),认为界面性能的改善可降低损耗模量,提高复合材料的耐疲劳性能。     

碳纤维复合材料界面结构的形貌与尺寸的表征

为了准确测定碳纤维增强树脂基复合材料界面结构的形貌和尺寸, 本文中介绍了一种原位纳米力学动态模量成像技术, 并采用该方法对碳纤维增强热固性树脂基复合材料进行了测试, 对该技术在界面结构测试上的参数设置、 数据处理方法以及适用性等方面进行了分析。研究表明, 该方法的横向分辨率可以达到纳米尺度, 适于测量界面尺寸在纳米级别的碳纤维复合材料界面形貌与尺寸。对于碳纤维/环氧树脂和碳纤维/双马树脂体系, 界面区的储能模量呈梯度变化, 根据储能模量成像图的统计分析可得到界面的形貌和厚度。所得界面平均厚度在100nm左右, 横截面上界面形貌呈不均匀的“河流状”, 并与碳纤维表面形貌相似。      

Influence of cold remote nitrogen oxygen plasma treatment on carbon fabric and its composites with specialty polymers

The parameters controlling performance of a fiber-reinforced polymer composite are type of matrix and fibers, their amount, aspect ratio, fiber orientation with respect to loading direction, fiber–matrix interface, and processing technique. In the case of carbon fiber reinforcement, fiber–matrix interface has always been a serious concern, because of chemical inertness of carbon fibers toward matrix and hence efforts are continued to enhance the fiber–matrix adhesion. A recent technique of cold remote nitrogen oxygen plasma was employed for surface treatment of carbon fabric (CF) to enhance its chemical reactivity and mechanical interaction toward matrix material. Untreated and plasma treated CF were used as bidirectional reinforcement for developing high performance composites with various specialty polymer matrices such as Polyetherimide, Polyethersulfone, and Polyetheretherketone. Treated CF reinforced composites showed appreciable improvement in most of the mechanical properties, which varied with type of plasma, its dozing and matrix used. X-ray Photoelectron Spectroscopy confirmed improvement in O/C and N/C ratio indicating inclusion of Oxygen and Nitrogen on the surfaces of fibers due to plasma treatment, which was responsible for enhanced adhesion. Similarly, Fourier Transform Infrared–Attenuated Total Reflectance Spectroscopy indicated presence of ether, carboxylic, and carbonyl functional groups on the plasma-treated surface of fibers. Raman spectroscopy indicated slight distortion in graphitic structure of treated CF. Scanning Electron Microscopy also indicated changes in the topography of treated CF, indicating enhanced mechanical interlocking with matrix.     

国产T800碳纤维用氰酸酯树脂开发及其复合材料性能

基于飞行器减重对耐高温结构复合材料的应用背景,为了拓展国产T800碳纤维增强氰酸酯复合材料体系的应用,通过对国产T800碳纤维表面上浆剂的分析,开展适于国产T800碳纤维的氰酸酯树脂基体配方设计,研究国产T800碳纤维/氰酸酯复合材料的力学性能和耐热性能,分析树脂基体对复合材料界面性能的影响。结果表明:国产T800碳纤维表面上浆剂中含有环氧基团。配方优化后的氰酸酯树脂与国产T800碳纤维复合后,复合材料的室温-湿态力学性能保持率大于74.8%,200℃力学性能保持率大于57%,玻璃化转变温度为226℃,具有优异的热机械性能和界面性能。     

Investigation of structure,mechanical and tribological properties of short carbon fiber reinforced UHMWPE-matrix composites

Structural, mechanical and tribological properties of composite materials based on ultra-high molecular weight polyethylene reinforced with carbon fibers were investigated. The effect of surface modification of carbon fibers on the interaction at the fiber–matrix interface in UHMWPE based composites was studied. It was found that the thermal oxidation of carbon fibers by air oxygen at 500 °C can significantly enhance the interfacial interaction between the polymer matrix and carbon fibers. This allowed us to form composite materials with improved mechanical and tribological properties.     

短切碳纤维表面处理对木粉/高密度聚乙烯复合材料性能的影响

木粉（WF）填充增强高密度聚乙烯（HDPE）复合材料具有良好的环境效益,少量引入短切碳纤维（SCF）可进一步提高其力学性能。为改善SCF与WF/HDPE复合材料中塑料基体的界面结合,提高SCF在WF/HDPE复合材料中的增强作用,采用气相、液相及气液双效氧化3种表面处理方式处理SCF,通过挤出工艺制备短切碳纤维增强木粉/高密度聚乙烯复合材料（SCF-WF/HDPE）,探讨了不同处理方法对SCF-WF/HDPE复合材料性能的影响。SEM观察显示,表面处理增大了SCF的表面粗糙度,可提高其与基体的界面结合;动态力学性能分析证实碳纤维提高了存储模量。测试结果表明：表面处理过的短切碳纤维可使SCF-WF/HDPE复合材料的力学性能、热力学性能和蠕变性能均得到显著提高,其中气相表面处理的效果最好。对比WF/HDPE复合材料,SCF-WF/HDPE的拉伸强度提高了34.5%,弯曲强度提高了23%,冲击强度提高了54.7%。     

Carbon and glass hierarchical fibers: Influence of carbon nanotubes on tensile,flexural and impact properties of short fiber reinforced composites

Dense carbon nanotubes (CNTs) were grown uniformly on the surface of carbon fibers and glass fibers to create hierarchical fibers by use of floating catalyst chemical vapor deposition. Morphologies of the CNTs were investigated using scanning electronic microscope (SEM) and transmission electron microscope (TEM). Larger diameter dimension and distinct growing mechanism of nanotubes on glass fiber were revealed. Short carbon and glass fiber reinforced polypropylene composites were fabricated using the hierarchical fibers and compared with composites made using neat fibers. Tensile, flexural and impact properties of the composites were measured, which showed evident enhancement in all mechanical properties compared to neat short fiber composites. SEM micrographs of composite fracture surface demonstrated improved adhesion between CNT-coated fiber and the matrix. The enhanced mechanical properties of short fiber composites was attributed to the synergistic effects of CNTs in improving fiber–matrix interfacial properties as well as the CNTs acting as supplemental reinforcement in short fiber-composites.     

Comparison of chemical vapor deposition and chemical grafting for improving the mechanical properties of carbon fiber/epoxy composites with multi-wall carbon nanotubes

By engineering the fiber/matrix interface, the properties of the composite can be changed significantly. In this work, we increased the effective surface area of the fiber/matrix interface, to facilitate additional stress transfer between fibers and matrix, by grafting carbon nanotubes on to carbon fibers (in the form of carbon fabric) by two different methods: (1) chemical vapor deposition (CVD) method and (2) a purely chemical method. With the CVD process, carbon nanotubes (CNT) were directly grown on carbon fiber substrate using chemical vapors. For the chemical method, CNT with carboxyl groups were grafted on functionalized carbon fiber via a chemical reaction. The morphology of CNT/carbon fibers was examined by scanning electron microscope (SEM) which revealed uniform coverage of carbon fibers with CNT in both of CVD method and chemical grafting method. CNT-grafted woven carbon fibers were used to make carbon/epoxy composites, and their mechanical properties were measured using three-point bending and tension tests which showed that those with CNT-grafted carbon fiber reinforcements using the CVD process has 11 % higher tensile strength compared to those containing carbon fibers modified with the chemical method. Also, composites with CNT-grafted carbon fibers with chemical method showed 20 % higher tensile strength compared to composites with unmodified carbon fibers. The results of tensile test revealed that both CVD and chemical grafting could significantly improve the mechanical properties of the carbon fiber composites.     

Permeability and mechanical properties of plant fiber reinforced hybrid composites

Plant fibers with small diameter generally possess high mechanical properties, while their permeability was relatively low compared to those with large diameter. By hybridizing these two kinds of plant fibers, a composite with both high permeability and good mechanical properties can be achieved. Here, permeability of jute/ramie and ramie fabrics were compared, regarding the flow rate of a vinyl ester resin during the Vacuum-Assisted Resin Transfer Molding process; and mechanical properties of their composites were addressed thereafter. The faster flow rates of vinyl ester resin proved that jute/ramie fabrics were more permeable than pure ramie fabrics resulting from larger flow space and the greater capillary effect of jute fabrics. Both tensile strength and Charpy impact strength of the hybrid composites dropped slightly after hybridization due to the lower properties of jute than of ramie fiber as the properties of fiber dominated the failure mode. However, interlaminar shear strength remained, since the middle layer was far from the weak jute–ramie interface. The results implicated a method to improve the permeability of plant fiber reinforcement when manufacturing efficiency is considered in industrial application.     

Special manufacturing and characteristics of basalt fiber reinforced hybrid polypropylene composites: Mechanical properties and acoustic emission study

Basalt fiber reinforced, polypropylene matrix hybrid composites were manufactured in the process of carding, needle-punching and pressing. Hemp, glass and carbon fibers were applied besides basalt fiber in these composites. In order to achieve a sufficient interfacial adhesion, the fibers were treated with the reaction mixture of maleic acid anhydride and sunflower oil. The hybrid effect in these composites was examined as a function of fiber content and fiber combination. The strength properties of hybrid composites improved owing to surface treatment and this was proven by mechanical tests and microscopic analysis, as well. Acoustic emission methods revealed that there is a correlation between the physical parameters of sound waves that occurred during failure and the mechanical properties.     

碳纤维改性对不饱和聚酯自修复复合材料性能的影响

采用H_2O_2和浓HNO_3对碳纤维(CF)表面分别进行氧化处理,得到氧化碳纤维(OCF1和OCF2),采用硅烷偶联剂γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)对OCF1进行接枝处理,得到接枝改性碳纤维(KCF),将改性前后CF应用于不饱和聚酯(UP)自修复复合材料中,分析比较了不同改性剂及改性方法对碳纤维/不饱和聚酯(CF/UP)自修复复合材料性能的影响。利用FTIR、XPS、SEM表征CF与CF/UP自修复复合材料的化学结构与形貌,通过TGA、万能拉力试验机、悬臂梁冲击仪、邵氏硬度计等对复合材料的热稳定性、力学性能及自修复效率进行测试。结果表明:氧化、接枝反应均可增加CF表面的粗糙度和活性官能团含量,从而改善CF与UP基体的界面相容性。其中OCF1/UP自修复复合材料的综合力学性能比OCF2/UP自修复复合材料好,KCF/UP自修复复合材料的力学性能在三者之中最佳,其自修复效率最高,可达67.03%。     

Effect of crystal morphology transition of polypropylene on interfacial properties of carbon fiber-reinforced composites through AlOOH surface treatment

Carbon fiber reinforced thermoplastics (CFRTPs) have many advantages, such as short processing cycle times, recyclability and design flexibility. However, CFRTPs have weak interfacial properties due to the non-polarity of carbon fibers. In this study, AlOOH surface treatment was applied on carbon fibers to improve the interfacial properties between the fiber and the matrix. The effect of the surface treatment on the crystal morphology of isotactic polypropylene (i-PP) at the interface was investigated by polarized optical microscopy (POM). The mechanical properties of fabricated CFRTPs were evaluated by measuring the interlaminar shear strength (ILSS). The ILSS of the AlOOH treated specimens after epoxy desizing increased by 106.8% compared with that of the untreated specimens.     

Effects of emulsion sizing with nano-SiO<Subscript>2</Subscript> on interfacial properties of carbon fibers/epoxy composites

Nano-SiO₂ particles were used to modify epoxy emulsion sizing of carbon fibers to improve the interfacial properties of carbon fibers reinforced epoxy composites. The mechanical interfacial strength between fibers and matrix was investigated by the single fiber fragmentation test and the 3-point short beam shear test, respectively. Dynamic contact angle analysis (DCAA), X-ray photoelectron spectrometry (XPS) and atomic force microscopy (AFM) were performed on the carbon fibers with unmodified sizing and nano-SiO₂ modified sizing. The results indicated that modified sizing with nano-SiO₂ slightly increased the surface energy, the hydroxyl functional group and the surface roughness of carbon fibers compared to unmodified sizing, so that the interfacial shear strength (IFSS) of the single fiber composites and the interlaminar shear strength (ILSS) of composites were enhanced. SEM images of fracture sections of composites proved powerfully that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂ modified emulsion sizing treatment.     

Damping,tensile, and impact properties of superelastic shape memory alloy (SMA) fiber-reinforced polymer composites

The potential of superelastic shape memory alloy (SMA) fibers to enhance the damping capacity and toughness of a thermoset polymer matrix was evaluated. A single-fiber winder was designed and built to manufacture a pre-form consisting of 102 μm diameter SMA fibers aligned parallel to each other. This pre-form was loaded to varying amounts of pre-strain and impregnated with vinyl ester to manufacture SMA fiber composites with 20% fiber volume fraction. The composites were tested using a Differential Scanning Calorimeter (DSC) and a Dynamic Mechanical Analysis (DMA), to evaluate the improvement in damping capacity of the polymer matrix due to the SMA fibers. Tensile and instrumented impact testing were carried out to evaluate improvements in mechanical properties and toughness of the composites. Appreciable improvement was observed in damping, tensile, and impact properties of the polymer matrix due to reinforcement with superelastic SMA fibers, highlighting the advantages of their use in polymer composites.     

Mechanical properties of basalt fibers and their adhesion to polypropylene matrices

This work is aimed to study the mechanical properties of basalt fibers, and their adhesion to polypropylene (PP) matrices. Single filament tensile tests were used to calculate the strength of different types of fibers, characterized by different providers and surface treatment. Single fiber fragmentation tests (SFFT) were used to calculate the critical length of the fibers, in a homopolymer PP matrix and in a maleic anhydride modified PP matrix. It was shown that the tensile strength of the fibers is not significantly influenced by the origin or the surface treatment. Only fibers without any sizing show very reduced mechanical properties. On the other hand, the tensile strength was shown to be severely dependent on the filament length. Weibull theory was used in order to calculate the fitting parameters σ₀ and β, which were necessary in order to extrapolate the tensile strength to the critical length determined by SFFT. This allowed calculating the adhesion properties of the basalt fibers. It was shown that fiber–matrix adhesion is dependent on both the presence of sizing on the fiber surface, as well as on the modification of the matrix.     

Electrophoretic deposition of aramid nanofibers on carbon fibers for highly enhanced interfacial adhesion at low content

Here, an anodic electrophoretic deposition was adopted to facilitate the large-scale uniform coating of nano-fillers onto carbon fibers to enhance the interfacial properties between carbon fibers and epoxy matrix. As interface–reinforcing materials, aramid nanofibers were introduced because of their superior mechanical properties and epoxy matrix-friendly functional groups. Furthermore, aramid nanofibers can be readily coated on carbon fibers via electrophoretic deposition because they are negatively-charged in solution with high electrical mobility. Finally, aramid nanofiber-coated carbon fibers showed significantly improved interfacial properties such as higher surface free energy and interfacial shear strengths (39.7% and 34.9% increases, respectively) than those of a pristine carbon fiber despite a very small amount of embedding (0.025 wt% of aramid nanofibers in a carbon fiber), and the short beam strength of the laminated composite prepared with the aramid nanofiber-coated carbon fibers was also improved by 17.0% compared to a non-modified composite.     

A study of the mechanical properties of short natural-fiber reinforced composites

The degree of fiber–matrix adhesion and its effect on the mechanical reinforcement of short henequen fibers and a polyethylene matrix was studied. The surface treatments were: an alkali treatment, a silane coupling agent and the pre-impregnation process of the HDPE/xylene solution. The presence of Si–O–cellulose and Si–O–Si bonds on the lignocellulosic surface confirmed that the silane coupling agent was efficiently held on the fibres surface through both condensation with cellulose hydroxyl groups and self-condensation between silanol groups.

The fiber–matrix interface shear strength (IFSS) was used as an indicator of the fiber–matrix adhesion improvement, and also to determine a suitable value of fiber length in order to process the composite with relative ease. It was noticed that the IFSS observed for the different fiber surface treatments increased and such interface strength almost doubled only by changing the mechanical interaction and the chemical interactions between fiber and matrix.

HDPE-henequen fiber composite materials were prepared with a 20% v/v fiber content and the tensile, flexural and shear properties were studied. The comparison of tensile properties of the composites showed that the silane treatment and the matrix-resin pre-impregnation process of the fiber produced a significant increase in tensile strength, while the tensile modulus remained relatively unaffected. The increase in tensile strength was only possible when the henequen fibers were treated first with an alkaline solution. It was also shown that the silane treatment produced a significant increase in flexural strength while the flexural modulus also remained relatively unaffected. The shear properties of the composites also increased significantly, but, only when the henequen fibers were treated with the silane coupling agent. Scanning electron microscopy (SEM) studies of the composites failure surfaces also indicated that there is an improved adhesion between fiber and matrix. Examination of the failure surfaces also indicated differences in the interfacial failure mode. With increasing fiber–matrix adhesion the failure mode changed from interfacial failure and considerable fiber pull-out from the matrix for the untreated fiber to matrix yielding and fiber and matrix tearing for the alkaline, matrix-resin pre-impregnation and silane treated fibers.     

A biodegradable composite material based on polyhydroxybutyrate (PHB) and carnauba fibers

In this investigation, carnauba fibers obtained from the leaves of the carnauba palm tree were chemically modified and their potential for the development of a biodegradable composite was evaluated. Fiber treatments to improve interfacial bonding were carried out by alkali, peroxide, potassium permanganate and acetylation. Biodegradable composites were prepared using carnauba fibers and polyhydroxybutyrate (PHB) as matrix. Mechanical properties of the composites prepared with 10 wt.% of short carnauba fibers were investigated and related to fiber treatment. According to the results, the tensile strength of the composites made from peroxide treated fibers was superior to those using untreated fibers or any other fiber treatment. SEM observations on the fracture surface of the composites suggest improved fiber–matrix adhesion after peroxide treatment. This surface modification of the fibers was found to contribute to the enhancement of the mechanical properties of the composites, even though the tensile strength of the fibers was slightly reduced. Dynamic mechanical thermal analyses suggested improvement in storage modulus of the composites reinforced with carnauba fibers at higher temperatures as compared to the neat polymer.     

电子束固化树脂基复合材料中碳纤维表面改性研究

利用阳极氧化方法和偶联剂对碳纤维表面的物理和化学性质进行改性，采用原子力显微镜（AFM）和X射线光电子能谱（XPS）分析了碳纤维表面改性前后的形貌和化学成分的变化，利用Keaelble法计算了碳纤维的表面能。研究结果表明，阳极氧化改性的碳纤维表面粗糙度增加，表面活性；表面活性官能闭增多，表面能中极性成分增加明显，碳纤维表面引入的活性氮和化学吸附的碱性物质使电子束固化复合材料界面处的引发剂中毒，复合材料界面性能减弱，与电子束固化工艺相匹配的偶联剂在碳纤维与树脂基体之间形成化学桥，使电子束固化复合材料界面性能得到明显提高。     

电子束固化复合材料界面

电子束固化复合材料界面粘结性能较低是急待解决的问题。利用阳极氧化技术和偶联剂涂层对碳纤维表面进行处理。处理前后的碳纤维表面性能利用SEM、XPS和接触角测试方法进行分析,通过层间剪切强度表征电子束固化复合材料界面粘结性能,并且与热固化复合材料进行对比。结果表明: 当碳纤维在酸性电解液中进行阳极氧化时,有利于提高电子束固化复合材料界面粘合性能,在碱性电解液中进行阳极氧化时, 则导致较低界面粘接性能。阳极氧化与偶联剂双重增效作用能够提高电子束固化复合材料界面粘合性能。