磷酸处理芳纶纤维的缠绕环氧树脂基体

在用磷酸(PA)溶液处理芳纶纤维的基础上, 系统研究了适用于制备高性能芳纶纤维增强复合材料的缠绕环氧树脂基体, 测试了复合材料的力学性能和热机械性能, 讨论了树脂基体对芳纶纤维增强复合材料界面性能的影响。结果表明: 经过磷酸溶液处理的芳纶纤维表面存在一定量的极性官能团, 与缩水甘油酯类环氧树脂有良好的界面相容性; 经过优化的树脂体系其芳纶纤维增强复合材料的NOL环(Naval Ordnance Laboratory Ring)纤维强度转化率达到95％, 层间剪切强度(ILSS)达到79MPa, 界面剪切强度(IFSS)达到76MPa, 具有较好的界面性能。      

芳纶纤维复合材料界面粘结性能研究

为了改善芳纶纤维复合材料的界面粘结性能,从自制树脂基体入手,针对芳纶纤维的结构特点,合成了一种新型树脂(AFR)作为基体,制备了芳纶/AFR复合材料.通过宏观力学、微观力学以及接触角测试等方法研究了AFR树脂与芳纶纤维之间的界面粘结性能.结果表明:AFR树脂对芳纶纤维的浸润性好,单丝拔出强度高,复合材料的横向拉伸强度及层间剪切强度高,这说明芳纶纤维与AFR树脂之间具有良好的界面粘结性能.     

LiCl处理对芳纶纤维表面结构与性能的影响

为提高芳纶纤维与复合材料基体间的界面强度,首先,使用LiCl乙醇溶液处理芳纶纤维一定时间;然后,对LiCl处理芳纶纤维表面的化学组成、微观形貌、单丝拉伸强度及芳纶纤维/环氧树脂复合材料的界面性能等进行了测试分析。结果表明:使用LiCl乙醇溶液处理芳纶纤维后,芳纶纤维表面的含氮官能团含量增加;处理后,芳纶纤维表面有刻蚀出的沟槽,表面粗糙度增大,进而改善了芳纶纤维与环氧树脂基体的界面粘接性能,使芳纶纤维/环氧树脂复合材料的层间剪切强度由处理前的21.75 MPa提升到37.98 MPa;最佳处理时间为3~4 h,而处理时间过长会导致芳纶纤维的单丝拉伸强度及复合材料的层间剪切强度下降。所得结论证实使用LiCl处理芳纶纤维是一种有效的表面改性方法。      

γ-射线辐照Armos纤维对AFRC界面性能的影响

为改善Armos纤维和环氧树脂间的界面结合性能,采用对环氧树脂/丙酮溶液浸泡的Armos纤维进行γ-射线辐照改性处理,探索辐照剂量对其芳纶纤维增强复合材料(AFRC)界面性能的影响.研究结果表明:在辐照剂量200～1000kGy,AFRC的层间剪切强度(ILSS)和界面剪切强度(IFSS)均增加,且500kGy界面强度较未处理的提高幅度最大;经γ-射线辐照处理的芳纶纤维,表面氧含量有大幅度提高,使得纤维表面活性增大;辐照处理后纤维表面较未处理的纤维表面粗糙度有所增加;纳米硬度仪测试AFRC横断面纤维、界面和基体的纳米硬度,表明辐照可以提高复合材料的硬度.     

芳纶纤维表面分析及其对双马来酰亚胺树脂复合材料界面性能的影响

采用反气相色谱和扫描电子显微镜测试分析了芳纶纤维的表面性能,结果发现K1和K2两种芳纶纤维的表面均比较光滑,总表面能基本相当,但极性表面能和色散表面能分量存在较大差异。层间剪切强度测试表明K2/5405复合材料的界面强度高于K1/5405复合材料,断口形貌分别呈现出不同的基体破坏和界面破坏模式。利用Good-Girifalco相互作用参数分析纤维和树脂的表面能与复合材料界面性能的关系,结果发现复合材料中两相间的相互作用参数增大,匹配性提高,界面性能亦有所提高。     

CaCl1和多巴胺处理对芳纶纤维表面结构与性能的影响

采用氯化钙(CaCl2)乙醇溶液和多巴胺水溶液浸渍法对芳纶纤维表面进行改性处理,对改性后芳纶纤维表面的化学结构、微观形貌、表面粗糙度、单丝拉伸强度和芳纶纤维/环氧树脂复合材料的界面性能等进行了测试分析.结果表明,采用CaCl2乙醇溶液处理芳纶纤维后,芳纶纤维表面有刻蚀出的沟槽,表面粗糙度增大,芳纶纤维/环氧树脂复合材料的层间剪切强度明显提高,同时由于纤维结构受到破坏,单丝拉伸强度下降了11.12％;采用多巴胺水溶液处理时,芳纶纤维表面沉积了聚多巴胺涂层,表面粗糙度增大,芳纶纤维/环氧树脂复合材料的层间剪切强度进一步提高,纤维结构几乎不受影响,单丝拉伸强度降幅较小;采用CaCl2乙醇溶液和多巴胺水溶液先后处理芳纶纤维后,纤维表面的聚多巴胺涂层更致密,复合材料的层间剪切强度达到最大值,同时改性后的纤维具有一定的抗紫外性能,此方法改性效果最优.     

芳纶纤维的磷酸表面处理及其树脂基复合材料界面性能

采取不同浓度的磷酸水溶液对芳纶纤维进行表面处理, 并对不同处理条件下芳纶纤维的单丝强度、表面性质及其环氧树脂复合材料的界面性能进行了分析和测试。结果表明: 20 wt %磷酸溶液处理的芳纶纤维, 纤维表面含氧官能团含量最高; 继续提高磷酸溶液的浓度, 含氧官能团含量下降, 纤维表面趋于平整, 单丝强度上升。用20 wt %磷酸溶液处理芳纶纤维, 纤维/ 环氧树脂基复合材料的层间剪切强度达到62 MPa , 界面剪切强度提高18 % , 是一种简单有效的表面处理方法。纤维表面粗糙度和纤维表面含氧官能团的数量是影响芳纶纤维/ 环氧树脂复合材料界面结合性能的关键因素。      

CaCl_2和多巴胺处理对芳纶纤维表面结构与性能的影响

采用氯化钙(CaCl_2)乙醇溶液和多巴胺水溶液浸渍法对芳纶纤维表面进行改性处理,对改性后芳纶纤维表面的化学结构、微观形貌、表面粗糙度、单丝拉伸强度和芳纶纤维/环氧树脂复合材料的界面性能等进行了测试分析。结果表明,采用CaCl_2乙醇溶液处理芳纶纤维后,芳纶纤维表面有刻蚀出的沟槽,表面粗糙度增大,芳纶纤维/环氧树脂复合材料的层间剪切强度明显提高,同时由于纤维结构受到破坏,单丝拉伸强度下降了11.12%;采用多巴胺水溶液处理时,芳纶纤维表面沉积了聚多巴胺涂层,表面粗糙度增大,芳纶纤维/环氧树脂复合材料的层间剪切强度进一步提高,纤维结构几乎不受影响,单丝拉伸强度降幅较小;采用CaCl_2乙醇溶液和多巴胺水溶液先后处理芳纶纤维后,纤维表面的聚多巴胺涂层更致密,复合材料的层间剪切强度达到最大值,同时改性后的纤维具有一定的抗紫外性能,此方法改性效果最优。     

纤维增强树脂基复合材料防弹性能影响因素及破坏机制

以超高分子量聚乙烯(Ultra High Molecular Weight Polyethylene,UHMWPE)纤维、S-玻璃纤维、芳纶1414纤维和杂环芳纶纤维增强聚烯烃(Polyolefin,PO)和水性聚氨酯(Waterborne Polyurethane,WPU)树脂,采用热压工艺制备正交单向无纬(UD)结构复合材料装甲板;通过装甲板弹道极限速度测试,研究了纤维增强树脂基复合材料装甲板防弹性能的影响因素;通过体视显微镜观察装甲板侵彻破坏形貌,分析了纤维增强树脂基复合材料的破坏机制。结果表明:UHMWPE纤维增强PO树脂基复合材料的防弹性能与UHMWPE纤维的强度和模量呈正相关,但纤维模量对复合材料防弹性能的影响随着纤维模量的增大而逐渐变弱;在WPU树脂体系下,四种纤维的防弹性能由高到低依次是UHMWPE纤维、杂环芳纶纤维、芳纶1414纤维、S-玻璃纤维;纤维增强树脂基复合材料装甲板中纤维破坏方式有迎弹面纤维被剪切冲塞、中部被纤维拉伸变形后剪切、背弹面纤维被拉伸断裂,中部纤维拉伸变形是消耗子弹动能的主要方式。     

连续纤维增强PPESK树脂基复合材料的界面性能

用SEM观察了复合材料的微观断面结构,用横向拉伸强度和层间剪切强度表征玻璃纤维(GF)、T700碳纤维(CF)、芳纶纤维(F-12)增强PPESK树脂基复合材料的界面性能,研究了界面性能对三种复合材料耐湿热性能的影响.结果表明,T700/PPESK和F-12/PPESK复合材料的界面粘接性能均优于GF/PPESK复合体系.三种纤维复合材料的破坏机理不同:玻璃纤维发生纤维与树脂的界面脱粘破坏,碳纤维复合材料在破坏时,树脂与纤维并没有完全脱粘,破坏发生在树脂内;而芳纶纤维复合材料的破坏总伴随着纤维本身横向的撕裂破坏.三种复合材料体系均具有较低的吸湿率和良好的耐湿热性能,T700/PPESK复合材料在湿热条件下的性能保持率最高.     

Plasma surface modification of advanced organic fibres: Part V Effects on the mechanical properties of aramid/phenolic composites

Aramid fibres have been treated in ammonia and oxygen plasma to enhance adhesion to resole phenolic resins. The plasma treatments resulted in significant improvements in interlaminar shear strength (ILSS) and flexural strength of composites made from these materials. Composites containing aramid fibres with epoxide groups reacted on to the ammonia plasma-treated fibre surface also showed further improvements in ILSS and flexural strength. Scanning electron and optical microscopic observations were used to examine the microscopic basis for these results, which have been compared with those obtained previously for aramid/epoxy and aramid/vinyl ester composites. For composites containing oxygen and ammonia plasma-treated fibres, the enhanced ILSS and flexural strength are attributed to improved wetting of the surface-treated aramid fibres by the phenolic resin. However, for those containing fibres with reacted epoxide groups on the ammonia plasma-treated fibre surfaces, the enhanced composite properties may be due to covalent chemical interfacial bonding between the epoxide groups and the phenolic resin. Effects of catalyst levels and cure cycle on the ILSS of composites laminated with untreated fabric has also been examined and optimum values have been determined. The catalyst concentration has an influence on the phase-separated water domain density in the matrix which in turn, affects the available fibre/matrix bonding area and hence the composite ILSS and flexural strength. This revised version was published online in November 2006 with corrections to the Cover Date.     

双键超支化聚硅氧烷在芳纶纤维表面的原位生长

以显著提升芳纶纤维与橡胶基体之间的界面结合强度为目标,本文开发了一种在芳纶纤维表面原位生长碳碳双键超支化聚硅氧烷的策略:首先借助多巴胺的仿生修饰建立初始层,接着采用迈克尔加成反应接枝氨基硅烷偶联剂创建中间层,最后通过脱水缩合反应实现原位生长。改性前后的芳纶纤维表面形貌和化学结构采用扫描电镜、傅里叶变换红外线光谱分析仪、X射线光电子能谱分析仪及热失重分析仪进行了测试表征。由芳纶纤维增强橡胶基复合材料的H-抽出力测试结果可得,本文采用的改性方法能够提升约66.4%的界面结合强度,其原因主要可以归结为表面粗糙度的提升及纤维束与橡胶共硫化的实现。对比分析发现,聚多巴胺初始层的采用使本改性方法具有较高的普适性和工业应用潜力。      

提高芳纶及其与X4502基体体系界面的耐湿热性研究

以多环氧基化合物(Ag-80)和烯丙基化合物(3-氯丙烯)分别处理芳纶(Kevlar49)表面,可显着提高芳纶及其与X4502基体体系界面粘结的耐湿热性。     

Fabrication and mechanical properties of aramid/nylon plain knitted composites

The presence of fibre/matrix interfaces strongly influences the overall mechanical properties of composites. In order to produce fully recyclable fiber reinforced composites with improved adhesion properties, polyethylene and polypropylene materials were previously used as single-polymer composite materials. In this paper, another breed of single-polymer composite material has been defined as the ‘one-unity’ composite. Polyamide materials were chosen and combined with aramid fibre in an attempt to achieve better interfacial bonding. Weft-knitting technique was used to produce textile reinforcements for aramid/nylon composite processing. Aramid/epoxy knitted composites were also fabricated to compare them with aramid/nylon thermoplastic composites. Mechanical properties of aramid/nylon and aramid/epoxy composites and their relationships to the fibre/matrix interfacial adhesion and interactions have been investigated. With the increase in processing time, tensile modulus and strength of aramid/nylon composites have increased and decreased, respectively. Furthermore, scanning electron microscopic observations clearly indicated that longer molding time has resulted in stronger adhesion property between fiber and matrix. Aramid/nylon knitted composites have revealed comparable strength property in the course direction, albeit they have inferior tensile strength in the wale direction when compared to that in aramid/epoxy composites. In aramid/nylon knitted composites, while tensile modulus exhibited an increasing trend, there were clear drops in tensile strengths with longer molding time. This indicates that there could be an optimum molding condition at which maximum tensile properties can be obtained. Aramid/nylon knitted composites exhibited relatively better interfacial bonding properties than Aramid/epoxy composites, which suffered fibre/matrix debonding.     

The interfacial properties of aramid/epoxy model composites

Many attempts have been made to measure, evaluate and improve the level of interfacial adhesion in aramid/epoxy composites. Different surface treatments have been developed in order to promote chemical bonding between the fibre and the matrix but it is found that most of the surface treatments developed have shown little or no improvement in the level of interfacial adhesion. The interfacial properties of a model composite are often determined by measuring the interfacial shear strength using micromechanical test methods that employ different loading configurations. However, the values of interfacial shear strength determined using different test methods are found to be dependent upon the variation of localized stress in the samples due to the different loading configurations and often give different results. Using Raman spectroscopy it is shown that the strain-dependent shift of the 1610 cm^–1 aramid Raman band can be used to determine the point-to-point variation of axial fibre strain along aramid fibres embedded in epoxy resin matrices from which the interfacial properties can be derived. The interfacial properties of aramid/epoxy model composites have been determined using Raman spectroscopy where the properties of the fibre, including different surface treatments, and the matrix have been changed systematically. The results are reviewed here and compared to those obtained using conventional micromechanical test methods. It is also demonstrated that the Raman technique can be used to characterize the interfacial properties of aramid/epoxy model composites deformed using different micromechanical test methods. In this way the interfacial properties can be determined at different loading levels enabling the progressive failure of the fibre/matrix interface to be monitored and defined accurately.     

超临界二氧化碳对芳纶纤维的表面改性

针对芳纶纤维与树脂基体界面性能差及纤维原纤化的问题,采用超临界二氧化碳分散环氧树脂对芳纶纤维进行表面改性,研究超临界二氧化碳处理对芳纶纤维结构及性能的影响。结果表明超临界二氧化碳改性处理能够提高环氧树脂对芳纶纤维的浸润效果,利用超临界二氧化碳分散环氧树脂对芳纶纤维进行处理,可以在一定程度上提高芳纶纤维的性能并改善芳纶增强树脂基复合材料的界面性能。超临界二氧化碳处理能够提高芳纶纤维表面粗糙度及比表面积,且芳纶纤维性能不受影响。     

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.     

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。     

具有液晶性能的改性芳纶的合成

利用界面聚合法对间位芳纶进行表面接枝改性,制备出新型具有液晶性能的芳纶。采用傅立叶转换红外光谱(FT-IR)对芳纶表面结构进行表征。由扫描电子显微镜(SEM)照片可以看出,改性后的芳纶表面变得粗糙,改性后纤维直径约为20μm。利用差示扫描量热法(DSC)对改性后纤维进行热性能分析,结果表明纤维具有液晶性能,在升、降温过程中的介晶相范围分别为192℃~237℃和147℃~209℃。接枝改性后的芳纶可以增加纤维与基体间的界面粘合性,提高复合材料的力学性能。     

Control of interfacial adhesion in continuous carbon and kevlar fiber reinforced polymer composites

Carbon fiber surfaces were treated by cold plasmas of oxygen, nitrogen, argon, ammonia, and propylene. A two-component bismaleimide, an epoxy, and a model thermoplastic resin polypropylene were used as the matrices for composites. The effectiveness of various plasmas in improving the interfacial adhesion between carbon fibers and matrix resins was demonstrated. Predominant adhesion promotion mechanisms as influenced by various plasma treatments were determined. Oxygen and argon plasmas were found to promote mechanical keying by increasing the level of fiber surface roughness and porosity. The wettability of carbon fiber surface by the matrix resin was also enhanced by oxygen plasmas and argon plasmas (to a lesser extent), as evidenced by the increased total surface energies and their polar components. These surface energy increases are mainly due to the various oxygen-containing functional groups observed on the oxygen plasma-treated surface. For the cases of ammonia and combined ammonia/argon plasma treatments, possible chemical bonding between bismaleimide and the plasma-deposited amine groups is one important promoter of interfacial bonding. In these cases increased wettability was also observed. Ammonia and ammonia/argon plasmas appear to be the more appropriate treatments for carbon-fiber/thermoset resin composites considering that they generally do not induce any appreciable reduction in fiber strength. In contrast, excessively prolonged exposure of carbon fibers to oxygen, nitrogen or argon plasma could lead to a significant reduction in fiber strength. The plasma-polymerized polypropylene deposited on the fiber surface was capable of improving the compatibility and adhesion between the fiber and the polypropylene matrix.