Alignment of carbon nanotubes and reinforcing effects in nylon-6 polymer composite fibers

Alignment of pristine carbon nanotubes (P-CNTs) and fluorinated carbon nanotubes (F-CNTs) in nylon-6 polymer composite fibers (PCFs) has been achieved using a single-screw extrusion method. CNTs have been used as filler reinforcements to enhance the mechanical and thermal properties of nylon-6 composite fibers. The composites were fabricated by dry mixing nylon-6 polymer powder with the CNTs as the first step, then followed by the melt extrusion process of fiber materials in a single-screw extruder. The extruded fibers were stretched to their maxima and stabilized using a godet set-up. Finally, fibers were wound on a Wayne filament winder machine and tested for their tensile and thermal properties. The tests have shown a remarkable change in mechanical and thermal properties of nylon-6 polymer fibers with the addition of 0.5?wt% F-CNTs and 1.0?wt% of P-CNTs. To draw a comparison between the improvements achieved, the same process has been repeated with neat nylon-6 polymer. As a result, tensile strength has been increased by 230% for PCFs made with 0.5% F-CNTs and 1% P-CNTs as additives. These fibers have been further characterized by DSC, Raman spectroscopy and SEM which confirm the alignment of CNTs and interfacial bonding to nylon-6 polymer matrix.     

Effect of electrophoretically deposited carbon nanotubes on the interface of carbon fiber reinforced epoxy composite

The interface between reinforcing fiber and matrix is a crucial element in composite performance. Homogeneous and interconnected carbon nanotubes (CNTs) were deposited onto the surface of carbon fibers to produce multiscale reinforcement by electrophoretic deposition (EPD). Single fiber tensile tests showed that the tensile strength and Weibull modulus of the resulting multiscale materials were increased by 16 and 41%, respectively. Compared with as-received carbon fibers, CNTs-deposited carbon fibers provided the decreased surface energy by 20% and the increased adhesion work by 22% using modified Wilhelmy method. Results from single fiber pull-out testing showed that a significant improvement (up to 68.8%) of interfacial shear strength was obtained for the composites containing by CNTs/Carbon fiber multiscale reinforcement. All results strongly suggest that EPD process can provide a feasible platform for improving interface properties of advanced composites.     

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.     

碳纳米管加入方式对碳纤维/环氧树脂复合材料层间性能的影响

针对碳纤维/环氧树脂预浸料,对比了直接在树脂中加入碳纳米管(CNTs)后制备预浸料以及将CNTs喷涂在预浸料表面2种CNTs加入方式对CNTs-碳纤维/环氧树脂复合材料层合板I型与II型层间断裂韧性及层间剪切强度的影响。通过对树脂黏度、固化反应以及玻璃化转变温度的考察,分析了CNTs含量对树脂性能的影响,考察了添加方法对CNTs长度与形态的影响。分析了2种CNTs加入方式对CNTs-碳纤维/环氧树脂层合板断裂韧性及层间剪切强度的改善效果与作用规律。结果表明:CNTs的加入使树脂的黏度提高,固化反应程度下降;2种分散方法对CNTs的长度与形态无明显影响;直接在树脂中加入CNTs对CNTs-碳纤维/环氧树脂复合材料I型与II型层间断裂韧性的提高效果低于在碳纤维/环氧树脂预浸料表面喷涂CNTs的方式,后者的CNTs利用率较高;由于CNTs团聚及对树脂固化反应的影响,CNTs含量过高会使得其对CNTs-碳纤维/环氧树脂层合板的增韧效果下降。     

氧化石墨烯改性玄武岩纤维及其增强环氧树脂复合材料性能

为了改善玄武岩纤维/环氧树脂复合材料的界面性能,通过偶联剂对氧化石墨烯进行改性,并将改性后的氧化石墨烯引入到上浆剂中对玄武岩纤维进行表面涂覆改性,同时制备了氧化石墨烯-玄武岩纤维/环氧树脂复合材料.采用FTIR表征了氧化石墨烯的改性效果;运用SEM分析了改性上浆剂处理对玄武岩纤维表面及复合材料断口形貌的影响和作用机制.结果表明:偶联剂成功接枝到氧化石墨烯表面;玄武岩纤维经氧化石墨烯改性的上浆剂处理后,表面粗糙度及活性官能团含量增加,氧化石墨烯-玄武岩纤维/环氧树脂界面处的机械齿合作用及化学键合作用增强,界面黏结强度得到改善,玄武岩纤维的断裂强力提高了30.8%,氧化石墨烯-玄武岩纤维/环氧树脂复合材料的层间剪切强度提高了10.6%.     

Process and mechanical properties of carbon/carbon–silicon carbide composite reinforced with carbon nanotubes grown in situ

A hierarchical C_f/C–SiC composite was fabricated via in situ growth of carbon nanotubes (CNTs) on fiber cloths following polymer impregnation and pyrolysis process. The effects of CNTs grown in situ on mechanical properties of the composite, such as flexural strength, fracture toughness, crack propagation behavior and interfacial bonding strength, were evaluated. Fiber push-out test showed that the interfacial bonding strength between fiber and matrix was enhanced by CNTs grown in situ. The propagation of cracks into and in fiber bundles was impeded, which results in decreased crack density and a “pull-out of fiber bundle” failure mode. The flexural strength was increased while the fracture toughness was not improved significantly due to the decreased crack density and few interfacial debonding between fiber and matrix, although the local toughness can be improved by the pull-out of CNTs.     

Interfacially reinforced methylphenylsilicone resin composites by chemically grafting multiwall carbon nanotubes onto carbon fibers

Both silane and multiwall carbon nanotubes (CNTs) were grafted successfully onto carbon fibers (CFs) to enhance the interfacial strength of CFs reinforced methylphenylsilicone resin (MPSR) composites. The microstructure, interfacial properties, impact toughness and heat resistance of CFs before and after modification were investigated. Experimental results revealed that CNTs were grafted uniformly onto CFs using 3-aminopropyltriethoxysilane (APS) as the bridging agent. The wettability and surface energy of the obtained hybrid fiber (CF-APS-CNT) were increased obviously in comparison with those of the untreated-CF. The CF-APS-CNT composites showed simultaneously remarkable enhancement in interlaminar shear strength (ILSS) and impact toughness. Moreover, the interfacial reinforcing and toughening mechanisms were also discussed. In addition, Thermogravimetric analysis and thermal oxygen aging experiments indicated a remarkable improvement in the thermal stability and heat oxidation resistance of composites by the introduction of APS and CNTs. We believe the facile and effective method may provide a novel interface design strategy for developing multifunctional fibers.     

化学处理和吸湿水对剑麻纤维及其与树脂界面性能的影响

使用KMnO₄、NaOH、阻燃剂、硅烷对剑麻纤维进行表面处理。采用单丝拉伸和微脱粘方法分别测试了剑麻纤维的拉伸性能及其与改性丙烯酸酯、环氧树脂的界面性能,考察了吸湿水对剑麻纤维表面形貌、拉伸性能及其与树脂界面粘结的影响,分析了相应的破坏模式。结果表明,经过表面化学处理后剑麻纤维的拉伸强度和模量均有不同程度的下降,其中经KMnO₄和硅烷处理后,纤维拉伸强度下降了44%,经NaOH处理后其拉伸强度降低了27%,阻燃剂处理对剑麻性能的影响不明显。表面化学处理还会降低剑麻纤维与改性丙烯酸酯的界面粘结强度,其下降的幅度与纤维拉伸强度下降程度不一致,阻燃剂处理的剑麻/改性丙烯酸酯的界面强度最低,仅为2.0 MPa,较未处理剑麻纤维复合体系下降了80%。经硅烷处理后,剑麻纤维的吸水率下降,吸水后其拉伸性能保留率高于未处理剑麻纤维。湿态条件下未处理剑麻纤维与环氧树脂的界面强度为6.6 MPa,高于硅烷处理剑麻/环氧树脂的界面强度,其断口形貌表明硅烷处理可导致微纤之间的弱粘结,从而降低了剑麻纤维自身及其与树脂的界面性能。     

连续石墨纤维增强铝基复合材料准静态拉伸损伤演化与断裂力学行为

针对连续石墨纤维增强铝基(CF/Al)复合材料,采用三种纤维排布方式的代表体积单元(RVE)建立了其细观力学有限元模型,采用准静态拉伸试验与数值模拟结合的方法,研究了其在轴向拉伸载荷下的渐进损伤与断裂力学行为。结果表明,采用基体合金和纤维原位力学性能建立的细观力学有限元模型,对轴向拉伸弹性模量和极限强度的计算结果与实验结果吻合良好,而断裂应变计算值较实验结果偏低。轴向拉伸变形中首先出现界面和基体合金损伤现象,随应变增加界面发生失效并诱发基体合金的局部失效,最后复合材料因纤维发生失效而破坏,从而出现界面脱粘后纤维拔出与基体合金撕裂共存的微观形貌。细观力学有限元分析结果表明,在复合材料制备后纤维性能衰减而强度较低条件下,改变界面强度和刚度对复合材料轴向拉伸弹塑性力学行为的影响较小,复合材料中纤维强度水平是决定该复合材料轴向拉伸力学性能的主要因素。     

Failure analysis and the optimal toughness design of carbon nanotube-reinforced composites

The combined analysis of the fracture toughness enhancement of carbon nanotube (CNT)-reinforced composites is herein carried out on the basis of atomistic simulation, shear-lag theory and facture mechanics. It is found that neither longer reinforced CNTs nor stronger CNT/matrix interfaces can definitely lead to the better fracture toughness of these composites. In contrast, the optimal interfacial chemical bond density and the optimal CNT length are those making the failure mode just in the transition from CNT pull-out to CNT break. To verify our theory, an atomic/continuum finite element method (FEM) is applied to investigate the fracture behavior of CNT-reinforced composites with different interfacial chemical bond densities. Our analysis shows that the optimal interfacial chemical bond density for (6,6) CNTs is about 5–10% and that increasing the CNT length beyond 100 nm does not further improve fracture toughness, but can easily lead to the self-folding and clustering of the CNTs. The proposed theoretical model is also applicable to short fiber-reinforced composites.     

不同界面SiC/SiC复合材料的断裂行为研究

碳化硅纤维增强碳化硅复合材料(SiC/SiC)是极具前景的高温结构材料。通过先驱体浸渍裂解(PIP)工艺分别制备了PyC界面和CNTs界面SiC/SiC复合材料, 对两种SiC/SiC复合材料的整体力学性能以及界面剪切强度等进行了测试表征, 并对材料中裂纹的产生与扩展进行了原位观测。结果表明, 两种界面SiC/SiC复合材料弯曲强度相近, 但PyC界面SiC/SiC复合材料的断裂韧性约为CNTs界面SiC/SiC复合材料的两倍。在PyC界面SiC/SiC复合材料中, 裂纹沿纤维-基体界面扩展, PyC涂层能够偏转或阻止裂纹, 材料呈现伪塑性断裂特征; 而在CNTs界面SiC/SiC复合材料中, 裂纹在扩展路径上遇到界面并不偏转, 初始裂纹最终发展为主裂纹, 材料呈现脆性断裂模式。     

Effect of interfacial adhesion and statistical fiber strength on tensile strength of unidirectional glass fiber/epoxy composites. Part I: experiment results

The effects of fiber surface treatment on ultimate tensile strength (UTS) of unidirectional (UD) epoxy resin matrix composites are examined experimentally. The interfacial shear strength (IFSS) and statistical fiber strength are significantly altered by five different kinds of surface treatments, which are: (a) unsized and untreated; (b) γ-glycidoxypropyltrimethoxysilane (γ-GPS); (c) γ-methacryloxypropyltrimethoxysilane (γ-MPS); (d) mixture of γ-aminoxypropyltrimethoxysilane (γ-APS), film former (urethane) and lubricant (paraffin); and (e) urethane-sized. The maximum UTS is obtained for the relatively strong interfacial adhesion (glass/γ-MPS/epoxy) but not for the strongest interfacial adhesion (glass/γ-GPS/epoxy). The governing micro-damage mode around a broken fiber and the interface region is matrix cracking for γ-GPS treated fibers, and a combination of interfacial debonding and matrix cracking for γ-MPS treated fibers. The micro-damage mode related to the interfacial adhesion strongly affects the fracture process, and thus the UTS of UD composites. The results also indicate that the interfacial adhesion can be optimized for effective utilization of fiber strength for fiber composites. A parameter called “efficiency ratio” of fiber strength in UD composites is proposed to examine and distinguish different effects of IFSS and fiber strength on the UTS of UD composites. The experimental results show that improved UTS of UD composites due to surface treatments mainly result from the increase in fiber strength but not from the modified interface.     

炭纤维特性与炭纤维/环氧树脂界面断裂能关联分析

采用基于WND(Wagner-Nairn-Detassis)能量模型的单丝断裂法,测试了5种国产炭纤维、2种国外炭纤维与航空结构用环氧树脂复合体系的界面断裂能,通过SEM,AFM,IR以及XPS等手段分析了7种炭纤维的表面物理化学特性,并研究了炭纤维特性与界面断裂能的关联。结果表明:对于所研究的炭纤维/环氧树脂体系,去除炭纤维表面上浆剂后界面断裂能下降,说明上浆剂可以在一定程度上提高界面的韧性。此外,实验范围内,纤维拉伸强度较高时,测得的界面断裂能较高,炭纤维表面粗糙度较高时,测得界面断裂能较高,说明纤维拉伸性能和表面粗糙度对界面韧性有重要影响,而与这两种因素相比,上浆剂的种类影响相对较小。研究结果为高性能国产炭纤维的研发和炭纤维/树脂匹配性的评价提供了重要的实验数据。     

稀土Ce接枝碳纳米管-碳纤维多尺度增强体对环氧树脂基复合材料界面性能的影响

将马来酰亚胺官能化的多壁碳纳米管(CNTs)和碳纤维(CF)混合并通过CeCl₃处理,得到CNTs-CF多尺度增强体,采用FTIR、XPS、SEM对增强体的表面物理化学状态进行表征;以环氧树脂(EP)为基体,通过模压法制备CNTs-CF/EP复合材料,对其力学性能和断口形貌进行分析,探讨CNTs-CF多尺度增强体对CNTs-CF/EP复合材料界面性能的影响。结果表明:通过Ce的桥接作用,可以将改性后的CNTs化学接枝在CF表面,以同时解决CF与树脂基体间界面结合弱及CNTs不易分散的问题,有效改善了增强体与基体间的界面性能。因此CNTs-CF/EP复合材料的拉伸强度和杨氏模量较CF/EP复合材料分别提高了36.76%和71.57%;较CeCl₃改性CF(RECF)/EP复合材料分别提高了24.79%和52.17%。采用稀土Ce的化学接枝法成功制备出CNTs-CF多尺度增强体,为获得高级轻质树脂基复合材料提供了一种环境友好的新方法。      

不同物相电沉积CNTs对C/SiC复合材料力学性能的影响

采用电沉积法与化学气相渗透(CVI)法将碳纳米管(CNTs)分别引入到碳纤维表面和SiC基体中,制得了不同物相电沉积CNTs的C/SiC复合材料(CNTs-C)/SiC和C/(CNTs-SiC)。研究了CNTs沉积物相对C/SiC复合材料力学性能的影响,分析了不同CNTs沉积物相的C/SiC复合材料的拉伸强度及断裂机制。结果表明:相较于未加CNTs的C/SiC复合材料,CNTs沉积到碳纤维表面的(CNTs-C)/SiC复合材料的拉伸强度提高了67.3%,断裂功提高了107.2%;而将CNTs引入到SiC基体中的C/(CNTs-SiC)复合材料的断裂功有所降低,拉伸强度也仅提高了6.9%,CNTs没有表现出明显的增强增韧效果;C/(CNTs-SiC)复合材料与传统的C/SiC复合材料有相似的断裂形貌特征,断裂拔出机制类似,主要为纤维增强增韧,CNTs的作用不明显。     

Fracture behavior of carbon nanotube/carbon microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance composite delamination resistance, and possibly improve toughness. In the present study, aligned CNTs were grown upon carbon fabric via chemical vapor deposition. Continuously monitored single-fiber composite fragmentation tests were performed on pristine and CNT-grafted fibers embedded in epoxy, and single-laminate compact-tension specimens were tested for fracture behavior. A significant increase (up to 20 %) was observed in the interfacial adhesion, at the cost of a decrease in the fiber tensile strength. As a result, the maximum load of the composite was decreased, but its residual load-bearing capacity more than doubled. The likely sources of these effects are discussed, as well as their implications.     

Interfacial load transfer in carbon nanotube/ceramic microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance the composite delamination resistance, and possibly improve its toughness and any matrix-dominated elastic property as well. In the present work aligned CNTs were grown upon ceramic fibers (silica and alumina) by chemical vapor deposition (CVD) at temperatures of 650 °C and 750 °C. Continuously-monitored single fiber composite (SFC) fragmentation tests were performed on pristine as well as on CNT-grown fibers embedded in epoxy. The critical fragment length, fiber tensile strength at critical length, and interfacial shear strength were evaluated. Significant increases (up to 50%) are observed in the fiber tensile strength and in the interfacial adhesion (which was sometimes doubled) with all fiber types upon which CNTs are CVD-grown at 750 °C. We discuss the likely sources of these improvements as well as their implications.     

Application of continuously-monitored single fiber fragmentation tests to carbon nanotube/carbon microfiber hybrid composites

To assess the effect of carbon nanotube (CNT) grafting on interfacial stress transfer in fiber composites, CNTs were grown upon individual carbon T-300 fibers by chemical vapor deposition. Continuously-monitored single fiber composite (SFC) fragmentation tests were performed on both pristine and CNT-decorated fibers embedded in epoxy. The critical fragment length, fiber tensile strength at critical length, and interfacial shear strength were evaluated. Despite the fiber strength degradation resulting from the harsh CNT growth conditions, the CNT-modified fibers lead to a twofold increase in interfacial shear strength which correlates with the nearly threefold increase in apparent fiber diameter resulting from CNT grafting. These observations corroborate recently published studies with other CNT-grafted fibers. An analysis of the relative contributions to the interfacial strength of the fiber diameter and strength due to surface treatment is presented. It is concluded that the common view whereby an experimentally observed shorter average fragment length leads to a stronger interfacial adhesion is not necessarily correct, if the treatment has changed the fiber tensile strength or its diameter.     

黄泛区粉土-玻璃纤维增强聚合物复合材料布界面摩擦特性试验

玻璃纤维增强聚合物复合材料（GFRP）强度高、耐热性好、抗碱性腐蚀能力较强,目前已广泛的应用于土木工程领域中。为了研究黄泛区粉土和GFRP布之间的界面摩擦特性,利用TZY-1型土工合成材料综合测定仪开展了直剪摩擦试验研究,分析了含水率、压实度和法向应力对界面摩擦特性的影响。结果表明,黄泛区粉土和GFRP布的界面摩擦强度随着压实度的增大而增大;界面摩擦强度在土体的含水率最优时达到最大,超过最优含水率后会下降;界面抗剪力随着法向应力的增大而增大,摩擦系数随着法向应力的增大而降低。      

考虑界面效应的GFRP复合材料蠕变模型

建立了包含界面的玻璃纤维增强树脂复合材料(GFRP)蠕变混合率单胞模型,对GFRP的蠕变性能进行分析;并与GFRP在应力水平为初始弯曲强度的20%所对应的载荷下的弯曲蠕变实验结果进行对比。分析了界面模量、界面厚度、纤维连续性与形态以及位向等因素对复合材料蠕变性能的影响。结果表明:相较于不考虑界面效应的混合率模型,本模型具有更高的准确性,与实验结果更为吻合;界面模量反应了纤维与基体的结合程度,对复合材料的蠕变性能产生影响,其蠕变柔量随着界面模量的增大而减小;界面厚度的增大会导致复合材料的蠕变柔量略微增大;相较于连续纤维增强树脂复合材料,短切纤维毡增强树脂复合材料的蠕变性能更易受到界面效应的影响;纤维方向对复合材料蠕变性能有显著影响,随着纤维方向角的增大,复合材料蠕变柔量增大,但当纤维方向角达到60°后,纤维已基本失去载荷传递和增强能力,复合材料蠕变柔量不再继续随着纤维方向角的增大而增大。