RETRACTED ARTICLE: Surface modification of aramid fibers with novel chemical approach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

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。     

表面处理对可生物降解黄麻/PLA复合材料结构和性能的影响

采用注塑成型法制备了生物降解黄麻短纤维增强PLA复合材料,通过力学性能测试及SEM,探讨了碱处理、碱和硅烷偶联剂KH550同时处理对复合材料结构和性能的影响。结果表明:两种处理方法均能够增加黄麻纤维的表面粗糙度,但碱和偶联剂KH550同时处理的效果要优于碱处理,且KH550改善了黄麻短纤维与PLA树脂之间的界面黏结性能提,高了黄麻/PLA复合材料的拉伸强度和弯曲强度。     

硅烷偶联剂改性芳纶的性能测试

采用硅烷偶联剂对芳纶进行改性,然后用傅里叶红外光谱仪、单一纤维接触角测试仪和X射线衍射仪对改性前后的芳纶进行测试、观察并分析。结果显示:红外光谱分析表明芳纶的改性发生在纤维的表面,并没有对纤维大分子产生明显破坏;接触角测试表明改性后芳纶的接触角变小,说明KH550硅烷偶联剂可改善芳纶的亲水性;X射线衍射测试表明芳纶结晶度有所下降,可以更好地与树脂黏结。     

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.     

Application of the microbond technique. IV. Improved fiber–matrix adhesion by RF plasma treatment of organic fibers

The microbond technique is a modification of the single-fiber pullout test for measuring interfacial shear strength. Briefly, a cured microdroplet of material is debonded in shear from a single fiber. Ultra-high modulus polyethylene (Spectra) fibers and aramid fibers (Kevlar) were treated using a radio frequency plasma in order to increase the interfacial bond between the fibers and an epoxy resin. The treated fiber surface was subsequently analyzed by X-ray photoelectron spectroscopy (XPS). Plasma treatment resulted in an increased concentration of oxygen containing functionalities on the fiber surface. The interfacial shear strength as determined by the microbond test increased by 118% for the Spectra fibers and by 45% for the Kevlar fibers with the same epoxy resin. Scanning electron microscopy indicated little change of the surface topography of either fiber following plasma treatment. Effects of friction and surface composition of the plasma-treated fibers is discussed. © 1993 John Wiley & Sons, Inc.     

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     

The effect of atmospheric‐pressure air plasma discharge power on adhesive properties of aramid fibers

After exposure to the atmospheric‐pressure air plasma at different discharge powers, the adhesion characteristics of Twaron aramid fibers were investigated. For the 12 s‐300 W plasma treatment, the interlaminar shear strength of Twaron fiber reinforced thermoplastic poly(phthalazinone ether sulfone ketone) was increased from 46.0 to 61.7 MPa by 34.1%, and the diffusion of water molecule into the resulting composites was proved to be effectively prevented. These results showed that surface adhesive properties of the plasma‐treated aramid fibers were improved. At the power level of 300 W, X‐ray photoelectron spectroscopy analysis revealed the increases in concentrations of oxygen and nitrogen polar groups on the fiber surface, and atomic force microscopy observations led to the conclusion that the fiber surface morphology was changed and the surface roughness was greatly increased. These new polar and irregular surface structures accounted for the better adhesion between the fiber and the matrix, while due to the reasonability of this discharge power level applied to the surface modification, the measured fiber tensile strength only decreased by 2.0%. POLYM. COMPOS., 37:620–626, 2016. © 2014 Society of Plastics Engineers     

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.     

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。     

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 modification of aramid fibers with γ‐ray radiation for improving interfacial bonding strength with epoxy resin

Co⁶⁰ γ‐ray radiation as a simple and convenient method for surface modification of Armos aramid fibers was introduced in this article. Two kinds of gas mediums, N₂ and air, were chosen to modify aramid fiber surface by γ‐ray irradiation. After fiber surface treatment, the interlaminar shear strength values of aramid/epoxy composites were enhanced by about 17.7 and 15.8%, respectively. Surface elements of aramid fibers were determined by XPS, the analysis of which showed that the ratio of oxygen/carbon was increased. The crystalline state of aramid fibers was determined by X‐ray diffraction instrument. The surface topography of fibers was analyzed by atomic force microscopy and scanning electron microscope. The degree of surface roughness and the wettability of fiber surface were both enhanced by γ‐ray radiation. The results indicated that γ‐ray irradiation technique, which is a suitable way of batch process for industrialization, can significantly improve the surface properties of aramid fibers reinforced epoxy resin matrix composites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

A new coupling agent for aramid fibers

Various compounds were used for the surface treatment of aramid fibers in order to promote adhesion to polymeric matrices. The improvement of adhesive bond could be based either on the roughness of fiber surface or on chemical modification introduced by grafting. The compounds used are more or less reactive to the secondary amide groups, present on the aramid chain. Thus, the fibers were impregnated with acetic acid anhydride, sulfuric acid–acrylamide, and methacryloyl chloride. The effect of such treatment was first evaluated by optical microscopy and infrared analysis. Tensile measurements were also carried out in order to define any changes of strength and modulus. Finally, tensile specimens were prepared using unsaturated polyester reinforced with aramid fibers and the effect of chemical treatment on the tensile strength was determined. From the above study, methacryloyl chloride was proved an effective coupling agent with possible grafting to aramid fibers.     

Atomistic simulations of functionalization of aramid fiber-epoxy nanocomposite

Owing to its high degree of crystallinity and orientation, the surface of aramid fiber is smooth, causing its low bonding strength with polymer matrix. This has restricted the application of aramid fiber in reinforced polymer materials. Effective methods are by introducing functional groups through surface modification and by increasing its surface roughness thereby greatly improving its bonding strength with the polymer. In this work, molecular dynamics (MD) simulation study fiber functionalized with hydroxyl (OH), carboxyl (COOH), and the silane coupling agent as nanofillers for polymer nanocomposites. The interfacial characteristics and the mechanical behavior of polymer nanocomposites are investigated. The results show that the functionalization can enhance the interfacial shear stress and tensile strength. The functional group not only provides a stronger interface, but also provides additional mechanical interlocking effect, which effectively improves load-bearing transmission capacity. The analysis of the micro-mechanism from the energy level also provides new insights for the functionalized design of nanocomposites.     

Argon low‐temperature plasma modification of chopped aramid fiber and its effect on paper performance of aramid sheets

Chopped aramid fiber was modified by an argon low‐temperature plasma treatment to enhance the interfacial strength of aramid paper. The water contact angle of the aramid fiber and the tensile strength, tearing strength, and evenness of the aramid sheets were investigated under different conditions, and the parameters of the argon low‐temperature plasma modification, like gas pressure, discharge power, and discharge time, were optimized. The chemical structure and surface morphology of the fiber after plasma modification were characterized by X‐ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy. The strengthening mechanism of aramid paper by low‐temperature plasma modification was also studied. It was found that the argon low‐temperature plasma treatment introduced some new polar groups onto the fiber surface and increased the fiber surface wettability and roughness. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45215.     

Moisture absorption properties of wood‐fiber‐reinforced recycled polypropylene matrix composites

To reduce the moisture absorption of wood‐fiber‐reinforced recycled plastic composites (WRPCs), a coupling agent (KH550), methyl methacrylate (MMA), and maleic anhydride (MA) were used to modify the wood fibers. The surface‐treated wood fibers were mixed with recycled polypropylene and processing agents to fabricate the WRPCs. The mechanical properties and moisture absorption behavior of the WRPCs were determined. The results showed that the three surface treatment methods could effectively reduce the moisture absorption and thickness swelling of WRPCs. In Comparison to the properties of untreated wood‐fiber‐reinforced WRPCs, the moisture absorption ratio of WRPCs with wood fibers treated by MMA, KH550, and MA was reduced by 31.4%, 49.8%, and 38.2%, respectively, and the tensile strength was increased by 22.1%, 26.3%, and 4.2%, respectively. The impact toughness of the WRPCs was increased by 36.2% KH550 treatment and 19.2% for MMA treatment but was decreased by 4.2% for MA treatment. Coupling treatment of the wood fibers was the best way to reduce the moisture absorption of WRPCs, and this kind of WRPC possessed the best comprehensive properties. J. VINYL ADDIT. TECHNOL., 2010. © 2009 Society of Plastics Engineers     

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.     

硅烷偶联剂改性芳纶工艺研究

采用KH550硅烷偶联剂处理芳纶,将处理温度、时间、硅烷偶联剂的质量分数作为3个因素进行分析,通过单因素分析法确定每个因素对处理前后芳纶与树脂的界面剪切强度的影响,结合扫描电镜观察处理前后纤维的表面结构变化,得到最佳处理的工艺为:处理时间9 h、温度45℃、硅烷偶联剂的质量分数为25%。     

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。     

剑麻纤维的溶胶–凝胶技术改性

通过溶胶–凝胶技术以正硅酸乙酯作为溶胶前驱体对剑麻纤维进行改性,采用傅里叶变换红外光谱(FTIR)、热重(TG)分析、X射线光电子能谱(XPS)分析以及单根纤维拉伸性能测试对改性剑麻纤维进行表征。FTIR和XPS测试结果表明,SiO_2凝胶成功引入剑麻纤维中;TG分析结果表明,经过溶胶–凝胶技术改性后,剑麻纤维的起始热分解温度变化很小,仅提高约0.5℃,但失重率明显降低;拉伸性能测试结果表明,溶胶–凝胶技术改性剑麻纤维的拉伸强度高于未改性的纤维,且剑麻纤维的吸湿率越高,单根纤维的拉伸强度越高,当纤维吸湿率为22.7%时,其拉伸强度较未改性纤维提高了29.21%,较KH550改性纤维提高了7.84%。