Influence of complexing treatment and epoxy resin coating on the properties of aramid fiber reinforced natural rubber

In this work, natural rubber/aramid fiber (NR/AF) composites were prepared with master batch method. AF was modified by using epoxy resin (EP) and accelerator 2‐ethyl‐4‐methylimidazole (2E4MZ) through surface coating on the basis of the complexing treatment with CaCl₂ solution. Hydroxyl‐terminated liquid isoprene rubber (LIR) was regarded as a compatibilizer between EP and NR. It is found that the crystallinity on AF surface is decreased by complexing reaction with CaCl₂ solution. Swelling and mechanical properties of the vulcanized composites, such as swelling degree, tensile and tear strength, tensile modulus at 300% elongation, are measured, and the tensile fracture morphology and dynamic mechanical analysis of the composites are investigated. The results show that the mechanical properties of composites with modified fibers are improved obviously and interfacial adhesion between matrix and the fiber is enhanced, especially for the AF coated with EP and imidazole. The best comprehensive mechanical properties of the composites are obtained with using CaCl₂‐EP/2E4MZ system when the ratio of m(EP)/m(AF) is 3%. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42122.     

空气等离子体处理芳纶纤维及其与天然橡胶/乳聚丁苯橡胶的黏合性能

考察了空气等离子体处理对芳纶纤维表面结构形态的影响,研究了空气等离子体和间苯二酚-甲醛-胶乳(RFL)浸胶处理芳纶纤维与天然橡胶(NR)/乳聚丁苯橡胶(ESBR)的黏合性能,并对经处理的芳纶纤维与NR/ESBR体系的界面层作了动态力学分析。结果表明,芳纶纤维经空气等离子体处理后,表面粗糙度增大,表面积增加,结晶度减小,但处理功率过大、处理时间过长时,芳纶纤维的表面又变得比较光滑、结晶度又呈增大趋势。随着等离子体处理时间的延长,芳纶纤维与NR/ESBR的黏合性能增强,但处理时间过长时,芳纶纤维与NR/ESBR的黏合性能下降;等离子体处理芳纶纤维经RFL进一步浸胶处理后,芳纶纤维与NR/ESBR的黏合性能大幅度提高。芳纶纤维与NR/ESBR的界面存在介于高模量芳纶纤维和低模量橡胶之间的过渡层。     

Aramid nanofiber reinforced nitrile rubber assisted by cellulose nanocrystals

A fiber-reinforced rubber composite was prepared by mixing aramid nanofibers (ANF) suspension and nitrile rubber (NBR) latex. The effects of ANF content and corresponding surface modification on the microstructure, vulcanization performance, processing and mechanical properties of composite materials, were systematically investigated. We found that, compared with commonly used short-cut aramid fibers, ANF fillers tend to form a stronger filling network within NBR matrix, resulting in a pronounced Payne effect. By improving the interfacial adhesion via dopamine (DA) coating onto ANF surface, the tensile strength can be further enhanced as expected. Besides, to eliminate the detriment of mechanical performance due to residual sodium polyacrylate in the course of flocculation, cellulose nanocrystal (CNC) was adopted to serve as a thickener during solution mixing. The incorporation of CNC can significantly improve the mechanical properties, which identifies a synergistic reinforcement effect arising from the cooperation of two types of fillers.     

Construction of an in situ interfacial layer for aramid fiber reinforced styrene butadiene rubber composites

In this work, the in situ interface layer composite was prepared by using the coating agent dispersion. Aramid fiber (AF) was modified with lithium chloride aqueous solution, and then coated with the blends of a low-molecular weight maleated polybutadiene liquid rubber (MLPB), the epoxy resin (E51), and 2-ethyl-4-methylimidazole (2E4MZ). The in situ interface layer was formed via the reaction of epoxy group with anhydride group in the presence of the accelerator 2E4MZ and covulcanization of MLPB with styrene butadiene rubber (SBR) in the process of preparing vulcanized AF reinforced SBR. It can be seen from analysis of scanning electronic microscopy, attenuated total reflection Fourier transform infrared, and thermogravimetric analysis that the in situ interfacial layer was a uniform and dense interfacial layer on the fiber surface and was not be destroyed during processing. The results of the dynamic mechanical analysis and mechanical properties showed that the in situ interface layer formed in processing had higher flexibility and better integrity than the interface layer prepared before processing, which is favorable for stress relaxation, and the in situ interface layer imparts better tensile strength and tear strength to the composite. The 100% modulus of composites with in situ interface layers was 14.6% higher than that of composites prepared without uncoated AF.     

Synthesis and characterization of the novel meta‐modified aramid fibers with liquid crystalline properties

To improve the interfacial adhesion between the meta‐aramid fibers and the matrix, the new method of interfacial polymerization was used to complete the aramid's surface modification. Two new kinds of grafted fibers which had liquid crystalline properties were prepared. The structure and properties of the aramid fibers before and after modification were characterized by scanning electron microscope (SEM), Fourier transform infrared, differential scanning calorimetry, and polarizing optical microscope. The surface of grafted aramid fibers was very rough. The range of liquid crystalline phase of the grafted fibers AF‐1 and AF‐2 on the cooling scan, respectively, is from 147 to 209°C and from 163 to 221°C. It was novel that the grafted fibers with rigid‐rod structure had typical nematic texture. The grafted aramid fibers as the ideal substitute material of asbestos were used as reinforcing fibers in nitrile butadiene rubber (NBR) matrix. Combining with NBR, the composites reinforced with the unmodified and grafted aramid fibers were synthesized. The micrographs of the composites' fractured surface were studied by SEM. The mechanical properties of the grafted fibers/NBR composites were superior to the unmodified fibers/NBR composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

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.     

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     

芳纶表面改性研究进展

简单回顾了芳纶的发展历史,阐述了表面涂层法、化学改性、物理改性等几种芳纶表面改性方法的研究现状,同时介绍了3种常用来表征纤维复合材料界面结合强度的方法,最后指出芳纶表面改性技术的发展方向。     

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.     

Adhesion of RFL-coated aramid fibres to elastomers: The role of elastomer–latex compatibility

The performance of fibre-reinforced composites is strongly dependent on the nature and the strength of the fibre–matrix interface. Good interfacial bonding is required to ensure load transfer from matrix to reinforcing fibres. For rubber-reinforced composites, resorcinol formaldehyde latex (RFL) is known as a fibre surface coating which is able to provide good adhesion between rubber and fibres. In the present study, aramid fibres are investigated, because of their significantly higher modulus and strength, compared to other commercial fibres. Their adhesion after being coated with RFL, in compounds based on natural rubber (NR) and in NR blended with a small amount of styrene butadiene rubber (SBR) is investigated. It is shown that though having very similar tensile properties, the latter compound has much better adhesion to RFL which is also less sensitive to RFL ageing, compared to the pure NR compound. It is argued that an interphase region is formed between RFL and the elastomer, which is stronger for the compound containing SBR due to its enhanced compatibility with the latex part of the RFL.     

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     

Adhesion of RFL-coated aramid fibres to sulphur- and peroxide-cured elastomers

The performance of fibre-reinforced composites is strongly dependent on the nature and the strength of the fibre–matrix interface. Good interfacial bonding is required to ensure load transfer from matrix to reinforcing fibres. For rubber-reinforced composites, resorcinol formaldehyde latex (RFL) is known as a fibre surface coating which is able to provide good adhesion between rubber and fibres. But the performance of this substance in many cases can be largely affected due to exposure of the coated fibres to air and light. Moreover, most data available in the literature concern sulphur-cured elastomers only. In the present study, aramid fibres are investigated, because of their significantly higher modulus and strength compared to other commercial fibres. The adhesion of these fibres in compounds based on sulphur-cured natural rubber and peroxide-cured ethylene propylene diene rubber is investigated after being coated with RFL which is the most common adhesive coating for various sort of fibres, including aramid. The effect of physical interaction between fibres and rubbers is shown to be minor, and the effect of ageing of RFL on its ability to bond with rubbers using peroxide and sulphur curing systems are shown. As a result of ageing, ozone is able to decrease the double bonds of the latex part of the RFL, which negatively affects the RFL–rubber adhesion in sulphur-cured systems, while it has almost no effect in peroxide-cured systems. It is also discussed that, unlike in sulphur vulcanization in which bonding happens just between the latex in the RFL and rubber, peroxide is able to generate bonds between elastomer and the resin structure of the RFL-coating.     

芳香族聚酰胺纤维增强丁腈橡胶垫片材料

研究了纤维含量、粘合处理方法、混炼胶薄通知出片因素对芳香族聚酰胺短纤维增强ＮＢＲ性能的影响。结果表明，芳香族聚酰胺短纤维的加入明显的ＮＢＲ的拉伸强度、撕裂强度和溶胀性能。密封性能测试结果表明，该材料可以代替石棉增强ＮＢＲ制作垫片，产品性能符合ＧＢ５３９－８３指标。     

磷酸酯偶联剂改性芳纶纤维增强聚丙烯复合材料的性能研究

采用磷酸酯偶联剂对芳纶纤维表面进行接枝改性,研究了实验条件和纤维含量对芳纶纤维增强聚丙烯(PP)复合材料力学性能的影响,并用电子扫描显微镜观察了PP复合材料的微观形态结构。结果表明:磷酸酯偶联剂成功接枝到芳纶纤维表面上,使芳纶纤维和PP的界面黏结性能得以明显改善。芳纶纤维可以显著地提高PP复合材料的力学性能当,其含量为20%时复,合材料的综合性能最优。     

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     

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.     

热空气老化对芳纶/橡胶复合体系粘合性的影响研究

研究了热空气老化对芳纶／橡胶复合体系粘合性的影响，通过对H抽出力一位移曲线特征值分析考察，发现芳纶经一定条件的空气等离子体处理再结合浸胶处理，与橡胶形成的粘合体系有较好的耐热空气老化能力和抵抗粘合破坏的能力，综合性能良好。     

芳纶纤维增强天然橡胶性能的研究

以磷酸、环氧树脂预处理芳纶,用端羟基液体橡胶和母炼胶法增强界面粘合,预分散纤维,进行NR的混炼和硫化,在混炼胶中纤维含量不变的前提下,采用均匀设计试验研究了母炼胶中芳纶纤维（AF）和液体橡胶（LIR）含量对硫化胶力学性能的影响。结果表明,母炼胶中AF和LIR的含量可通过改变复合材料中纤维的长度、纤维的分散性及界面的粘接对硫化天然橡胶的力学性能产生影响。通过光学显微镜、电子显微镜和动态力学性能检测,分析了纤维在混炼胶和硫化胶中的长度和形态对材料性能的影响。     

芳纶浆粕预处理及在橡胶中的应用研究进展

综述了芳纶浆粕在使用过程中存在的问题及目前的预处理方法,包括表面改性处理和预分散处理方法。其中芳纶浆粕的表面改性处理可以采用超声波法、接枝改性、偶联改性、聚合物涂层改性等,预分散处理可以通过浆粕母胶法、粉体隔离法等。同时综述了芳纶浆粕在橡胶中的应用,主要集中在密封橡胶、隔热橡胶以及承载橡胶中。     

芳纶浆粕纤维对CR基质补强特性的研究

对比研究未处理芳纶浆粕和芳纶浆粕预分散体以及不同品种芳纶浆粕纤维补强CR复合材料的微观结构形态及芳纶浆粕纤维对CR基质的补强特性。结果表明,芳纶浆粕对基质橡胶补强潜力的发挥取决于超细纤维在基质橡胶中的分散均匀性、伸展性和取向性,芳纶浆粕纤维对基质橡胶在常温和高温下都具有很高的模量补强效率。