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。     

碳纤维三维立体织物中纤维表面改性的均一化研究

采用阳极氧化法对碳纤维三维织物进行了表面处理。通过复合材料的界面强度、抗冲击性能和抗压性能,研究了阳极氧化处理工艺参数对碳纤维三维织物复合材料性能的影响。实验结果表明该方法不仅能对三维织物表层的碳纤维进行表面改性, 而且能深入织物内部, 实现对碳纤维三维织物的均一化处理, 从而使碳纤维三维织物/酚醛复合材料的界面强度均得到大幅度提高, 复合材的整体性能得到改善。      

Enhancing both strength and toughness of carbon/carbon composites by heat-treated interface modification

A simple method to increase both strength and toughness of carbon/carbon (C/C) composites is presented. This method is based on the heat treatment of the pre-deposited thin carbon coating, leading to the formation of more orderly pyrolytic carbon (PyC) as a functional interlayer between fiber and matrix that could optimize the interfacial sliding strength in C/C composites. Effects of such a heat-treated PyC layers on the microstructure, tensile strength and fracture behavior of unidirectional C/C composites were investigated. Results showed that although the in-situ fiber strength was deteriorated after the introduction of interfacial layer, tensile strength of the specimen was greatly improved by 38.5% compared with pure C/C composites without any treatment. The interfacial sliding stress sharply decreased, which was interpreted from finite element analysis and verified by Raman spectra. Therefore, the fracture behavior was changed from brittle fracture to multiple-matrix cracking induced non-linear mechanical behavior. Finally, the ultimate strength can be predicted by different models according to the interfacial sliding stress. Our research would provide a meaningful way to improve both strength and toughness of C/C composites.     

甲基丙烯酰氧基倍半硅氧烷改性碳纤维/聚芳基乙炔复合材料界面性能

利用微脱粘法、三点弯曲法、扫描电镜（SEM）、力调制模式原子力显微镜（AFM）和动态力学热分析（DMTA）研究了甲基丙烯酰氧基倍半硅氧烷（Methacryl-POSS）涂层改性前后的碳纤维增强的聚芳基乙炔（PAA）复合材料的界面性能。用Wilhelmy法研究了处理前后的碳纤维与PAA树脂的浸润性。结果表明: POSS涂层处理后的碳纤维表面粗糙度增大,与PAA树脂的浸润性提高;复合材料的界面剪切强度提高了36%,层间剪切强度提高了50%。DMTA图谱表明, POSS涂层改性后,复合材料的玻璃化转变温度提高了12℃,损耗因子降低了53%,表明复合材料的界面粘接性能得到大幅度的改善。      

Optimum dispersion conditions and interfacial modification of carbon fiber and CNT–phenolic composites by atmospheric pressure plasma treatment

Electric resistance measurements were used to determine the optimal dispersion conditions for carbon nanotubes (CNTs) in phenolic resins. Plasma treatment is frequently used to modify carbon fiber surfaces to improve adhesion of the fibers to matrices. Such treatment might also influence carbon fiber tensile strength. In order to determine the effect of atmospheric pressure plasma treatment on carbon fiber tensile strength and interfacial bonding strength, change in tensile strength of the fiber was studied at different gage lengths before and after the plasma treatment. The wettability of carbon fibers was improved significantly after only 10 s of plasma treatment. Such plasma treatment resulted in a decrease in the advancing contact angle from 65° to 28°. Surface energies of carbon fiber and CNT–phenolic composites were measured using the Wilhelmy plate technique, indicating that the work of adhesion between plasma treated carbon fibers and CNT–phenolic composites was higher than it before plasma modification. The interfacial shear strength (IFSS) and apparent modulus were also increased by plasma treatment of the carbon fibers.     

低密度纤维增强纳米孔树脂基复合材料的断裂机制

纤维增强纳米孔树脂基复合材料(IPC)是一类轻质高效防隔热一体化耐烧蚀材料,具有典型的非均质结构特征。在外加载荷下,内部的纳米孔隙将会衍生出微裂纹。裂纹的萌生、聚合和扩展对复合材料的强度、刚度、变形性等力学性能有着重要的影响。本文分别以石英纤维针刺网胎(NQF)、石英纤维针刺网胎/纤维布(NQCF)为增强体,制备得到不同纤维结构增强的纳米孔酚醛树脂(NPR)基复合材料(NQF/NPR、NQCF/NPR),对比研究了材料拉伸强度、拉伸模量、断裂伸长率及拉伸疲劳性能,并采用CT原位拉伸装置表征了拉伸过程中复合材料的微观结构演变。结果表明：纤维布的引入极大提高了复合材料的力学性能,并且微裂纹首先在针刺区域边缘的树脂基体中出现。在裂纹扩展过程中,纤维结构对树脂基体的损伤起到了不同程度的阻碍作用。最后结合有限元法建立了NPR及纤维布的有限元模型,分析了不同尺度下材料的断裂机制。     

Adhesion and friction behavior between fluorinated carbon fibers and poly (vinylidene fluoride)

The potential use of fluorinated, polyacrylonirtile-based, high strength carbon fibers as reinforcement for a fluorocarbon polymer, namely poly (vinylidene fluoride) (PVDF), was investigated by means of the single fiber pull-out test. The apparent interfacial shear strength as a measure of practical adhesion was determined and the fracture and friction behavior of the model composites characterized.It was shown that the fracture behavior of the model composites is predominately brittle in nearly all cases. Fluorination of carbon fibers has a positive impact on the adhesive strength to PVDF. The apparent interfacial shear strength increases with increasing degree of fiber surface fluorination and becomes maximal at a degree of fiber fluorination (F/C-ratio) of around 0.8, determined by ESCA, which is close to that of PVDF. This result points to the fact that the increased practical adhesion is due to a physical compatibilization between the fluorinated fibers and the surrounding PVDF matrix. It was found that, even though the interfacial shear strength increases with increasing degree of fiber surface fluorination, the friction between fluorinated carbon fibers and the surrounding PVDF decreases.     

阳极氧化对高聚物基碳纤维复合材料界面性能的影响

采用阳极氧化法对Ｔ－３００高强度碳纤维和Ｍ－４０高模量碳纤维进行了表面处理。发现该方法能剥除Ｔ－３００碳纤维表面的高涂层，涂覆耐热涂层后可提高Ｔ－３００／聚酰亚胺复合材料界面的抗热氧化性能，并且可使基体改性的珠Ｍ－４０／酚醛环氧复合材料界面强度和冲击强度同时获得提高。     

酚醛树脂表面处理剂对炭纤维增强环氧树脂复合材料界面强度的影响

采用酚醛树脂作为炭纤维表面处理剂, 可以显著提高多种炭纤维和环氧树脂界面强度。通过XPS、AFM、SEM和层间剪切强度等方法, 研究了不同浓度的酚醛树脂表面处理剂对炭纤维增强环氧树脂复合材料层间剪切强度、炭纤维表面元素和化学键组成的影响, 以及炭纤维增强环氧树脂复合材料断面微观形貌的变化。XPS和AFM分析结果表明酚醛树脂和炭纤维表面发生了化学反应, 而且酚醛树脂处理剂浓度越高, 和炭纤维表面发生反应的基团也越多, 表面越光滑平整, SEM和层间剪切强度研究表明酚醛树脂处理后的复合材料界面粘结性能得到很大的改善, 而且界面粘结性能强烈依靠处理剂浓度。      

单丝断裂双树脂法研究碳纤维/环氧树脂界面粘结性能

建立了单丝断裂双树脂体系法, 利用外层树脂的韧性使包埋于内层脆性树脂中的纤维单丝断裂达到饱和, 解决了断裂伸长率较低的树脂基体采用传统的单丝断裂法无法测得界面剪切强度的问题。分别采用界面剪切强度和界面断裂能作为表征参量, 考察了干态及湿热条件下两种T300级和两种T800级碳纤维/环氧树脂的界面性能, 并与单丝断裂单树脂体系的界面性能进行比较。结果表明: 单丝断裂双树脂体系与单树脂体系在表征碳纤维/环氧树脂的界面性能上定性规律一致; 双树脂体系界面断裂能和界面剪切强度均可评价界面的耐湿热性能, 且二者得到的变化规律一致; 湿热处理后界面粘结性能均呈下降趋势, 国外碳纤维体系的界面耐湿热性能明显优于国产碳纤维体系。     

聚合物涂层对高模量碳纤维表面性能的影响

为改善碳纤维表面性能以及碳纤维/树脂复合材料的界面性能,对PAN基高模量碳纤维（HMCF）表面进行聚合物涂层处理。研究了不同潜伏性固化剂含量的聚合物涂层对HMCF表面以及碳纤维/树脂复合材料的界面性能的影响。IR分析表明,聚合物涂层与纤维或树脂基体发生了化学反应。扫描电镜和动态机械热分析的结果也说明,聚合物涂层能够提高...     

Silicon carbide (NicalonTM) fibre-reinforced borosilicate glass composites: mechanical properties

The objective of this study was to assess the applicability of an extrinsic carbon coating to tailor the interface in a unidirectional NicalonTM–borosilicate glass composite for maximum strength. Three unidirectional NicalonTM fibre-reinforced borosilicate glass composites were fabricated with different interfaces by using (1) uncoated (2) 25 nm thick carbon-coated and (3) 140 nm thick carbon coated Nicalon fibres. The tensile behaviours of the three systems differed significantly. Damage developments during tensile loading were recorded by a replica technique. Fibre–matrix interfacial frictional stresses were measured. A shear lag model was used to quantitatively relate the interfacial properties, damage and elastic modulus. Tensile specimen design was varied to obtain desirable failure mode. Tensile strengths of NicalonTM fibres in all three types of composites were measured by the fracture mirror method. Weibull analysis of the fibre strength data was performed. Fibre strength data obtained from the fracture mirror method were compared with strength data obtained by single fibre tensile testing of as-received fibres and fibres extracted from the composites. The fibre strength data were used in various composite strength models to predict strengths. Nicalon–borosilicate glass composites with ultimate tensile strength values as high as 585 MPa were produced using extrinsic carbon coatings on the fibres. Fibre strength measurements indicated fibre strength degradation during processing. Fracture mirror analysis gave higher fibre strengths than extracted single fibre tensile testing for all three types of composites. The fibre bundle model gave reasonable composite ultimate tensile strength predictions using fracture mirror based fibre strength data. Characterization and analysis suggest that the full reinforcing potential of the fibres was not realized and the composite strength can be further increased by optimizing the fibre coating thickness and processing parameters. The use of microcrack density measurements, indentation–frictional stress measurements and shear lag modelling have been demonstrated for assessing whether the full reinforcing and toughening potential of the fibres has been realized. This revised version was published online in November 2006 with corrections to the Cover Date.     

电热作用对碳纤维/树脂复合材料界面应力的影响电热作用对碳纤维/树脂复合材料界面应力的影响

碳纤维/树脂复合材料广泛应用于民用航空器结构中,在服役期间会受到复杂环境（湿热、腐蚀、复杂应力和电热作用等）的作用,低强度电流对碳纤维/树脂复合材料的影响受到的关注较少。以碳纤维/树脂复合材料为研究对象,根据碳纤维的温敏效应和通电时的电阻变化规律,计算出碳纤维单丝/环氧树脂复合试样的界面温度范围,之后采用拉曼光谱测试和单丝断裂实验研究了低强度电流对单丝复合体系界面应力和界面剪切强度的影响。结果表明:随着电流强度的提高,单丝复合体系的界面温度随之升高,电流为8 mA时,界面温度高达约200℃。随着电流强度的增大,单丝复合体系的界面压缩应力表现为先增大后减小的趋势,电流高于7 mA后,界面处树脂出现烧蚀降解破坏;单丝断裂实验结果表明随着电流强度增大,单丝复合体系的界面剪切强度呈现先升后降的趋势,在6 mA时界面剪切强度达到最大值62.39 MPa,而8 mA时界面剪切强度仅为34.95 MPa。      

苎麻纤维增强原位阴离子聚合尼龙6复合材料的制备及性能研究

以己内酰胺为单体,经热处理的苎麻纤维(RF)为增强材料,采用真空辅助树脂传递模塑成型工艺(VARTM)成功制备了苎麻纤维增强原位阴离子聚合尼龙6(APA6)复合材料.主要研究了热处理前后苎麻纤维表面官能团、结晶性能、力学性能和微观形貌的变化,并对复合材料的冲击断面、力学性能和热性能进行了考察.研究表明:当热处理温度为280℃时,苎麻纤维表面的羟基数量显著减少,结晶度略有降低,拉伸强度和模量有所下降,但苎麻纤维的形貌未有明显变化.RF/APA6复合材料中苎麻纤维与树脂的界面结合良好,与APA6相比,复合材料的拉伸强度略有提高,拉伸模量和弯曲性能得到明显提升,同时热稳定性显著提高.     

碳纤维-玻璃纤维层内混杂单向增强环氧树脂复合材料拉伸性能

采用不同混杂比的碳纤维-玻璃纤维层内经向混编单轴向织物制备了混杂纤维增强环氧树脂复合材料, 研究了不同混杂结构和不同混杂比的碳纤维-玻璃纤维/环氧树脂复合材料拉伸性能的变化及破坏形式。0°拉伸结果表明:同种混杂织物的不同混杂结构中, 碳纤维相对集中的完全对齐结构强度最高, 不同混杂比织物的完全对齐结构强度相当;碳纤维-玻璃纤维/环氧树脂复合材料的模量遵循混合定律。90°拉伸结果表明:纤维与树脂间的界面结合强度为碳纤维/树脂>玻璃纤维/树脂, 碳纤维-玻璃纤维/环氧树脂复合材料的强度、模量与材料厚度方向上界面的不同形式(单一或交替界面、碳纤维或玻璃纤维的分布位置等)有关, 与碳纤维的含量基本无关。      

羟基硅油改性酚醛树脂基碳纤维复合材料特性研究

利用FT-IR、SEM、拉伸试验等测试方法分析了羟基硅油改性酚醛树脂基碳纤维复合材料机理，并对羟基硅油改性酚醛树脂基碳纤维复合材料特性进行了研究。实验结果表明：羟基硅油能有效改善界面结合状态，提高酚醛树脂基碳纤维复合材料的拉伸强度，为合理调整原料配比，控制生产工艺参数，获得综合性能优异的复合材料奠定了基础。     

弹道防护用超高分子量聚乙烯纤维增强热塑性树脂基复合材料的拉伸力学行为

以弹道防护用超高分子量聚乙烯(Ultra-high molecular weight polyethylene,UHMWPE)纤维增强热塑性树脂基复合材料作为研究对象,通过热压工艺制备单向正交结构的复合材料层压板。基于自主设计的拉伸试验装置,开展UHMWPE纤维增强热塑性树脂基复合材料在宏观尺度和准细观尺度上的面内拉伸试验,研究其面内拉伸力学性能及失效模式。研究结果显示：弹道防护用UHMWPE纤维增强热塑性树脂基复合材料在准细观尺度上的面内拉伸力学性能是其本征性能;随着偏轴角度的增加,拉伸断裂强度呈现指数型下降,这是由于失效模式由纤维的拉伸断裂破坏转变为纤维-树脂基体的界面破坏;此外,其在宏观尺度上的拉伸破坏强度比在准细观尺度上的拉伸断裂强度降低了50.52%,这是由于宏观尺度上的面内拉伸力学响应是其面内拉伸变形和层间分层破坏的耦合结果,即层压板的叠层效应。     

改性酚醛树脂处理剂对石英纤维增强芳基乙炔复合材料性能的影响

采用改性酚醛树脂作为石英纤维表面处理剂来提高石英纤维增强芳基乙炔复合材料(SF/PAA)界面性能。通过性能测试,研究处理剂对力学性能和介电性能的影响。通过XPS和SEM分析方法,研究了酚醛树脂表面处理剂对复合材料界面官能团变化和微观形貌的影响。性能测试结果表明改性酚醛树脂处理剂可以显著提高PAA复合材料的力学性能和介电性能。XPS分析结果表明酚醛树脂处理后的石英纤维表面与酚醛树脂发生了化学反应,SEM研究表明酚醛树脂处理后的复合材料界面粘结性能得到显著提高。     

Surface structures of PAN-based carbon fibers and their influences on the interface formation and mechanical properties of carbon-carbon composites

Defects and microvoids in the surface region not only influenced the tensile strength and strain of carbon fibers but also affected the interface formation with pyrocarbon. The interface formation in carbon-carbon composites was closely correlated to rearrangement of carbon atoms and the evolution of surface structure of carbon fiber. Half-open elliptic microvoids or edge planes at the fiber surface were beneficial to the mechanical interlocking as well as chemical bonding with pyrocarbon, contributing to a compatible interface with high interlaminar shear strength of the composites. The closed microvoids in the surface region of carbon fiber would hardly open up to bond with pyrocarbon, which brought negative effects to the mechanical properties of composites. Carbon fiber without obvious microvoids or surface defects tended to have better tensile strain but form weak interface with pyrocarbon, leading to a better pseudo-ductility and ability to absorb more fracture energy under load.     

Interfacial properties and impact toughness of methylphenylsilicone resin composites by chemically grafting POSS and tetraethylenepentamine onto carbon fibers

Octaglycidyl polyhedral oligomeric silsesquioxane (gly-POSS) was successfully grafted on carbon fibers (CFs) surface to enhance interfacial properties and impact toughness of CFs reinforced methylphenylsilicone resin (MPSR) composites. After gly-POSS modification, POSS grafted CF (CF-POSS) with many epoxy functional groups was modified with tetraethylenepentamine (TEPA) to further enhance the interfacial strength. Atomic force microscopy (AFM) images showed that POSS and TEPA were grafted onto CFs surface uniformly and the surface roughness enhanced obviously. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed the chemical bonding nature between CFs and POSS, as well as between POSS and TEPA. POSS and TEPA modification could increase the fiber polarity, wettability and surface energy significantly. The interlaminar shear strength (ILSS) and impact toughness of composites showed a dramatic improvement, especially for grafting with POSS and further with TEPA (CF-POSS-TEPA). Additionally, the reinforcing and toughening mechanisms were also analyzed. Meanwhile, single fiber tensile strength (TS) had no decrease after modification.