Treated aramid fibers as reinforcement in nonpolar matrices

Crosslinked polyethylene finds extensive use in applications where improved thermal resistance is required. Furthermore, reinforced and crosslinked polyethylene presents high strength at elevated temperatures, so that the field of applications of such materials is considerably enlarged. Aramid fibers seem to be a promising reinforcement for the above materials since they combine high modulus with thermal resistance and light weight. The development of an adequate adhesive bond between aramid fiber and polyethylene matrix is of course the main problem, taking into consideration that both polyethylene and aramid present reduced chemical affinity to other substances. Thus, fiber pretreatment was performed in order to insert unsaturated groups in the aramid chain. These groups could be, in turn, grafted in the polyethylene backbone during the crosslinking reaction. The aramid fibers were treated with methacryloyl chloride, and then dispersed under stirring in 2% aqueous sodium hydroxide containing 0.5% of a nonionic surfactant. After washing and drying, the fibers were dry blended with polyethylene powder containing 2 phr dicumyl peroxide. The mixture was melt-blended in a Brabender plasticorder and tensile specimens were prepared. Tensile measurements and microscopy on the fracture surface were carried out in order to evaluate changes introduced in the fiber by surface treatment.     

Mechanical properties of epoxies reinforced with chloride-treated aramid fibers

Surface treatment of aramid fibers by immersion in a solution of methacryloyl chloride in carbon tetrachloride was carried out, and the resulting material was examined by means of electron microscopy and chemical analysis in an attempt to record any changes in the morphology and nature of the surface. Mechanical testing of tensile, flexural, and interlaminar shear strength, as well as dynamic mechanical analysis (DMA), were performed in an attempt to explore the effect of this treatment on the strength of the fiber. In a subsequent stage, the performance of those fibers as reinforcement in composites of epoxy matrix was assessed. The aim of this study was to provide more information about the interactions between the chloride-treated aramid fibers and the epoxy resin and, more specifically, to compare the behavior of the epoxy matrix composites with those composed of unsaturated polyester, polyethylene, and polyurethane matrix, which were studied in the past. It was found that specimens containing chloride-treated aramids display better flexural properties, whereas their tensile strength is drastically reduced. Improved performance was also identified by the DMA experiments. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:–, 1997     

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     

RETRACTED ARTICLE: Surface modification of aramid fibers with novel chemical approach

Friedel–Crafts Reaction as a simple and convenient approach to the surface modification of aramid fiber was introduced in this paper. Epoxy chloropropane was chosen as the treatment reagent to modify aramid fibers surface via Graft reaction. After the modification, the interfacial properties of aramid/epoxy composites were investigated by the single fiber pull-out test (SFP), and the mechanical properties of aramid fibers were investigated by the tensile strength test. The results showed that the interfacial shear strength (IFSS) value of aramid/epoxy composites was enhanced by about 50%, and the tensile strength of aramid fibers had no obvious damage. The crystalline state of aramid fibers was determined by X-ray diffraction instrument (XRD), and the results showed that there were not any distinct crystal type varieties. The surface elements of aramid fibers were determined by X-ray photoelectron spectroscopy (XPS), the analysis of which showed that the oxygen/carbon ratio of aramid fiber surface increased obviously. The possible changes of the chemical structure of aramid fibers were investigated via Fourier transform infrared spectrum (FTIR), and the analysis of which showed that the epoxy functional groups were grafted into the molecule structure of aramid fibers. The surface morphology of aramid fibers was analyzed by Scanning electron microscope (SEM), and the SEM results showed that the physical structure of aramid fibers was not etched or damaged obviously. The surface energy of aramid fibers was investigated via the dynamic capillary method, and the results showed that the surface energy was enhanced by 31.5%, and then the wettability degree of aramid fiber surface was enhanced obviously too. All of the results indicated that this novel chemical modification approach not only can improve the interfacial bonding strength of aramid/epoxy composites remarkably, but also have no negative influence on the intrinsic tensile strength of aramid fibers.     

Surface modification of aramid fibers with CaCl2 treatment and secondary functionalization of silane coupling agents

Aramid fibers have excellent mechanical properties as the main reinforcing filler in high-performance composites. However, the adhesion properties between fibers and most polymer matrices were poor. In this study, aramid fiber (AF) was modified by KH550 through surface coating based on the treatment with CaCl₂ solution. The new surface treated with complexing agents could act as an active platform for secondary reactions for further modification. The surface morphology and composition of the treated aramid fibers were tested by scanning electron spectroscopy and X-ray photoelectron spectroscopy, the interlaminar shear strength and the tensile strength of aramid fiber-reinforced polymer (AFRP) of were evaluated. The results showed that the silane coupling agent KH550 was successfully grafted onto the surface of aramid fibers after treatment with CaCl₂. Interlayer shear strength is greatly improved and the tensile strength of AFRP through further grafting with KH550 on the surface treated with CaCl₂ was improved by 48.7%, compared with untreated aramid fiber. In the current scenario, this study is of immense importance because it validates the possibility of secondary modification after fiber complexation modification and useful modification methods, and provides a new direction for the modification of AF.     

左旋多巴胺处理对芳纶表面结构与性能的影响

利用L-3,4-二羟基苯丙氨酸(L-DOPA)的氧化自聚合,在杂环芳纶表面修饰聚L-3,4-二羟基苯丙氨酸(PDOPA)活性涂层来提高芳纶的表面活性及耐紫外辐照性能。结果表明:改性后芳纶表面粗糙度显著提高,同时,PDOPA涂层上大量的羧基、羟基等活性单元均有利于增强与环氧树脂的机械锁合力,改性后芳纶/环氧树脂复合材料的界面剪切强度提高了32.0%。此外,上述改性过程对杂环芳纶本身力学性能影响较小,纤维的拉伸强度保持率可以达到100%,基本实现了无损改性。同时,由于PDOPA的保护作用,改性后芳纶的耐紫外辐射性能显著提高;经过168 h紫外线辐照处理后,其拉伸强度保持率可达到92.5%,显著提升了杂环芳纶的耐紫外线辐照特性。     

Effect of rare earth elements surface treatment on tensile properties of aramid fiber‐reinforced epoxy composites

Solutions of rare earth modifier (RES) and epoxy chloropropane (ECP) grafting modification method were used for the surface treatment of aramid fiber. Tensile properties of both the aramid/epoxy composites and single fibers were tested. The effects of RES concentration on tensile properties of aramid/epoxy composites were investigated in detail to explore an optimum amount of rare earth elements in solution for modifying aramid fiber. The fracture surface morphologies of tensile specimens were observed and analyzed with the aid of SEM. The experimental results show that rare earth treatment is superior to ECP grafting treatment in promoting interfacial adhesion between the aramid fiber and epoxy matrix. Meanwhile, the tensile strengths of single fibers were almost not affected by RES treatment. The optimum performance is obtained when the content of rare earth elements is 0.5 wt %. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1037–1041, 2004     

芳纶表面化学改性技术研究现状

概述了芳纶表面化学改性的方法。从芳纶分子结构的特点出发,论述了芳纶表面化学刻蚀及化学接枝等化学改性技术的原理、特点和应用效果;详述了基于芳纶结构中苯环上的硝化还原反应、氯磺化反应和酰胺基上的水解反应、氢取代反应、金属化反应等的反应原理及应用效果。指出多种化学改性技术的交叉应用将成为芳纶表面化学改性的趋势。     

芳纶纤维/AFR树脂复合材料界面粘结性能的研究

为了改善芳纶纤维复合材料的界面粘结性能,合成了一种新型树脂(AFR)作为基体,以未经任何表面处理的芳纶纤维作增强材料,制备了芳纶纤维/AFR复合材料。采用测定表面能、接触角、层间剪切强度、横向拉伸性能和扫描电镜观察形貌等方法,从宏观和微观等方面研究了芳纶纤维/AFR复合材料的界面粘结性能。结果表明,AFR树脂与芳纶纤维有相近的表面能,AFR树脂溶液与芳纶纤维的接触角为42.8°,而环氧树脂(EP)与芳纶纤维的接触角为68°,说明AFR树脂对芳纶纤维的润湿性优于EP树脂;芳纶/AFR复合材料的层间剪切强度、横向拉伸强度和纵向拉伸强度分别为74.64MPa、25.34MPa和2256MPa,比芳纶/EP复合材料的相应强度分别提高了28.7%、32.5%和13.4%,其复合材料破坏面的形貌也说明芳纶纤维与AFR树脂之间的界面粘结性能较好。     

芳纶纤维增强树脂基复合材料的界面粘结性能研究

为了改善芳纶纤维增强树脂基复合材料的界面粘结性能,从树脂基体入手,依据相似相容原理和芳纶的结构特点,合成出新型热固性树脂(AFR–T)用作芳纶复合材料的基体,以未经表面处理的芳纶作增强材料,采用热压成型法制备了AFR–T/芳纶纤维复合材料,并通过测定溶度参数、接触角、线膨胀系数、层间剪切强度(ILSS)和横向拉伸强度等方法研究了复合材料的界面粘结性能。结果表明,AFR–T树脂浇注体与芳纶的溶度参数相近,AFR–T树脂溶液在芳纶纸表面的接触角为36.9°,小于环氧树脂(EP)溶液与芳纶纸的接触角(53.2°),说明AFR–T树脂对芳纶的浸润性优于EP;AFR–T/芳纶纤维复合材料的ILSS和横向拉伸强度为73.0 MPa和25.3 MPa,分别比EP/芳纶纤维复合材料提高了25.9%和32.5%,这表明AFR–T树脂与芳纶纤维之间的浸润性和界面粘结性能较好。     

超声处理对芳纶Ⅲ性能的影响研究

为了改善芳纶Ⅲ的表面状态,以二甲基乙酰胺(DMAc)为超声介质,对纤维进行超声处理,研究了超声处理速率和超声波功率对纤维性能的影响。结果表明:超声处理后,纤维的强度和模量随着超声波功率的增大而下降;超声波处理速率越慢,处理时间越长,纤维的强度和模量下降越明显,纤维表面沟壑越深,比表面积明显增大;纤维拔出强度随超声波功率和超声处理速率的增大而先增大再减小。     

Kevlar 49纤维与芳纶Ⅲ的结构与性能研究

借助傅立叶变换红外光谱仪、扫描电子显微镜、X射线光电子能谱仪和强力拉伸仪分析研究了Kevlar 49和芳纶Ⅲ的化学结构、表面特征及力学性能。结果表明:芳纶Ⅲ的红外谱图上多出了苯并咪唑环的吸收峰;芳纶Ⅲ的表面较粗糙,Kevlar 49表面较光滑,芳纶Ⅲ和Kevlar 49纤维表面的碳、氧元素均比化学式计算值有所增加,但氮元素含量下降;芳纶Ⅲ表面的极性基团种类比Kevlar 49多。芳纶Ⅲ的单纤维拉伸强度是Kevlar 49的1.5倍,断裂伸长率比Kevlar49提高了45%～65%;2种纤维的断裂方式均为劈裂断裂,具有皮芯结构,但芳纶Ⅲ分子间的作用力比Kevlar49纤维强。     

表面处理芳纶纤维在丁羟橡胶中的应用

为改进芳纶纤维的表面光滑、化学惰性强、与橡胶黏结性能差等缺点,用硅烷偶联剂KH-550对其表面进行改性处理.用电子能谱仪(ESCA)和扫描电镜(SEM)对改性后的纤维和丁羟橡胶表面进行了测试,结果表明:C元素的含量明显下降,N和O元素的含量提高,纤维表面活性提高.制得芳纤/丁羟橡胶复合材料的拉伸强度由未处理的2.58 MPa提高到处理后的3.22 MPa.处理后,由SEM得到芳纶纤维丁羟橡胶复合材料表面的丁羟橡胶量增加.在KH-550的质量分数为5%、处理时间为5 h的条件下,芳纶纤维的处理效果最佳.     

Surface ammonification of the mutual‐irradiated aramid fibers in 1,4‐dichlorobutane for improving interfacial properties with epoxy resin

The mutual irradiated aramid fibers in 1,4‐dichlorobutane was ammoniated by ammonia/alcohol solution, in an attempt to improve the interfacial properties between aramid fibers and epoxy matrix. Scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS), dynamic contact angle analysis (DCA), interfacial shear strength (IFSS), and single fiber tensile testing were carried out to investigate the functionalization process of aramid fibers and the interfacial properties of the composites. Experimental results showed that the fiber surface elements content changed obviously as well as the roughness through the radiation and chemical reaction. The surface energy and IFSS of aramid fibers increased distinctly after the ammonification, respectively. The amino groups generated by ammonification enhanced the interfacial adhesion of composites effectively by participating in the epoxy resin curing. Moreover, benefited by the appropriate radiation, the tensile strength of aramid fibers was not affected at all. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44924.     

Effects of atmospheric pressure helium/air plasma treatment on adhesion and mechanical properties of aramid fibers

In order to investigate the effect of atmospheric pressure plasmas on adhesion between aramid fibers and epoxy, aramid fibers were treated with atmospheric pressure helium/air for 15, 30 and 60 s on a capacitively-coupled device at a frequency of 5.0 kHz and He outlet pressure of 3.43 kPa. SEM analysis at 10 000× magnification showed no significant surface morphological change resulted from the plasma treatments. XPS analysis showed a decrease in carbon content and an increase in oxygen content. Deconvolution analysis of C1s, N1s and O1s peaks showed an increase in surface hydroxyl groups that can interact with epoxy resin. The microbond test showed that the plasma treatment for 60 s increased interfacial shear strength by 109% over that of the control (untreated). The atmospheric pressure plasma increased single fiber tensile strength by 16-26%.     

两种对位芳纶纤维本体性能的对比研究

采用SEM、AFM和红外光谱对F-12芳纶纤维和国产芳纶Ⅲ纤维表面微观形态以及纤维化学结构进行了测试分析;通过芳纶复丝性能测试考核了两种纤维本体的力学性能。结果表明:两种芳纶纤维结构和化学成分相似,都具有"皮-芯"结构,表面具有较多的微观缺陷,且F-12芳纶纤维表面比国产芳纶Ⅲ纤维表面粗糙;两种芳纶纤维都是全芳香族聚酰胺结构;F-12芳纶复丝拉伸强度和断裂伸长率比国产芳纶Ⅲ纤维分别高出33.6%和62.5%但,拉伸弹性模量比国产芳纶Ⅲ纤维低11.9%。     

Synergistic effect of hyperthermal atomic oxygen beam and vacuum ultraviolet radiation exposures on the mechanical degradation of high-modulus aramid fibers

The synergistic effect of atomic oxygen and vacuum ultraviolet (VUV) radiation exposures was investigated on the mechanical properties of high-modulus aramid fibers. Tensile tests were performed on single fibers. It was found that both tensile strength and Young's modulus decreased significantly due to the simultaneous exposures of atomic oxygen and vacuum ultraviolet radiation. In contrast, the surface of aramid fiber exposed to ultraviolet alone showed no change in tensile strength and Young's modulus. X-ray photoelectron spectroscopy showed that atomic oxygen exposure leads to oxidization and decomposition of amid groups, that only VUV exposure does not change the fiber surface, and that VUV exposure decreased oxidized components on the oxidized fiber surface exposed to atomic oxygen and ultraviolet simultaneously. Scanning electron microscopy revealed that the diameter of the fiber was not influenced so much by atomic oxygen and ultraviolet exposures, but the fiber surface became substantially rougher than the aramid fiber surface exposed to atomic oxygen alone.     

苎麻落麻的表面处理及其复合材料的性能研究

采用甲基丙烯酸甲酯、丙烯腈接枝,硅烷偶联剂(A-151)偶联,聚氯乙烯(PVC)包覆等方法对苎麻落麻纤维进行表面处理;测试了处理前后落麻纤维的吸水率、单丝强度及其与环氧树脂(EP)、酚醛树脂(PF)和不饱和聚酯(UP)等的接触角;观察了偶联和包覆后落麻纤维的表面状况;选取偶联和包覆后的落麻纤维制备了UP/落麻毡和PP/落麻纤维复合材料,测试了其拉伸和弯曲性能并观察了处理前后复合材料的拉伸断面形貌。结果表明,接枝、偶联和包覆不仅降低了落麻纤维的吸水速率。而且也降低了平衡吸水量;接枝对落麻纤维单丝强度影响最大,偶联次之,包覆最小;接枝、偶联和包覆均能大幅度改善落麻纤维与EP、PF和UP的浸润性;偶联和包覆后的落麻纤维表面都比处理前粗糙;偶联使UP/落麻毡复合材料的拉伸强度、拉伸弹性模量提高了21％,弯曲强度提高了34％,弯曲弹性模量提高了40％,包覆使PP/落麻纤维复合材料的拉伸、弯曲强度提高了20％左右。     

混杂比对交织芳纶碳纤维复合材料力学性能的影响

为了分析混杂比对层内混杂复合材料力学性能的影响,利用交织方式制备芳纶碳纤维混杂增强体织物,并通过交织物纬纱系统中芳纶与碳纤维的纱线配置比例调整碳纤维在增强体结构中的混杂比。采用真空辅助成型技术制备层内混杂结构的芳纶碳纤维混杂（ACFH）复合材料,并对复合材料的拉伸性能、弯曲性能和冲击性能进行测试。结果表明,增强体纬向系统中芳纶与碳纤维的不均质性对ACFC复合材料经方向上的拉伸强度起消极作用;混杂比的增加对ACFC复合材料的纬向拉伸破坏和弯曲损伤具有抑制作用;纬向上,ACFC复合材料的拉伸强度最高提高了近6倍,弯曲强度最小增加了4.04倍;芳纶与碳纤维混杂协同作用有利于ACFC复合材料的抗冲击性能改善,且混杂比存在最佳值。     

Effect of ultrasound on wettability between aramid fibers and epoxy resin

Good wetting of reinforced fiber by resin was a main factor in the improvement of the interface adhesion of their composites. Ultrasound with a frequency of 20 kHz was used to improve the wettability between aramid fibers and epoxy resin during the winding process of the composites. The effects of ultrasound on the viscosity and surface tension of epoxy resin and on the surface characteristics of aramid fibers were investigated. The wettability of aramid fibers and treated epoxy resin under different conditions and of aramid fibers and epoxy resin under ultrasonic online treatment were compared. The results indicated that the main action of ultrasound was to force epoxy resin to impregnate aramid fibers, in addition to the influence of ultrasound on the properties of epoxy resin and aramid fibers. The results of microdebond testing showed that the interfacial shear strength (IFSS) of aramid/epoxy composites could be 26% higher than that of untreated composites because of the improved wettability between aramid fibers and epoxy resin subjected to ultrasonic online treatment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006