RETRACTED ARTICLE: Surface modification of aramid fibers with novel chemical approach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

Temperature effect on graphene‐filled interface between glass–carbon hybrid fibers and epoxy resin characterized by fiber‐bundle pull‐out test

The overall mechanical performance of glass–carbon hybrid fibers reinforced epoxy composites depends heavily upon fiber–matrix interfacial properties and the service temperatures. Fiber‐bundle pull‐out tests of glass (GF) and/or carbon fiber (CF) reinforced epoxy composites were carried out at room and elevated temperatures. Graphene nanoplatelets were added in the interfacial region to investigate their influence on the interfacial shear strength (IFSS). Results show that IFSS of specimens with fiber‐bundle number ratio of GF:CF = 1:2 is the largest among the hybrid composites, and a positive hybridization effect is found at elevated temperatures. IFSS of all the specimens decreases with the increasing of test temperatures, while the toughness shows a contrary tendency. As verified by scanning electron microscopy observations, graphene nanoplatelets on fiber surface could enhance the IFSS of pure glass/carbon and hybrid fibers reinforced epoxy composites at higher temperatures significantly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46263.     

Evaluation of interfacial properties and microfailure mechanisms in single fiber‐reinforced epoxy composites at low temperature

In this preliminary study, micromechanical techniques were used to compare the interfacial properties of both carbon and glass fiber composites with two structurally different epoxy matrices (YD‐114 and YDF‐175) at ambient and relatively low temperatures (25°C and −10°C). Tensile modulus of elasticity for both epoxies was higher at lower temperature. Although both fibers exhibited more bimodality at lower temperature than at ambient temperature, glass fiber composites exhibited a statistically greater improvement in tensile strength. This may be attributed to differences in inherent flaws and rigidity. A decrement in stress was observed for YDF‐175 epoxy composites under cyclic loadings at both temperatures, which was attributed to lower interfacial shear strength (IFSS). In contrast to the IFSS of conventional YD‐114 epoxy composites, the IFSS of both the carbon and glass fibers/YDF‐175 epoxy composites studied was higher at the lower temperature. The microfailure pattern observed in microdroplet pullout tests was consistent with the other IFSS results. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

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     

Promoting the adhesion of high‐performance polymer fibers using functional plasma polymer coatings

Plasma‐copolymerized functional coatings of acrylic acid and 1,7‐octadiene were deposited onto high strength, high modulus, poly‐p‐phenylene benzobisoxazole (PBO) fibers. X‐ray photoelectron spectroscopy (XPS) with trifluoroethanol derivatization confirmed that the PBO fibers were covered completely with the plasma copolymer and that the coating contained a quantitative concentration of carboxylic acid groups. Microdebond single filament adhesion and interlaminar shear strength (ILSS) tests were used to evaluate the interfacial strength of epoxy resin composites containing these functionalized PBO fibers. Both the interfacial shear strength (IFSS) obtained from single filament tests, and the ILSS of high volume fraction composites were a function of the surface functionality of the fibers so that there was a good correlation between ILSS and IFSS data. The tensile strengths of single fibers with or without coating were comparable, demonstrating that the fiber surface was not damaged in the plasma‐coating procedure. Indeed, the statistical analysis showed that Weibull modulus was increased. Therefore, plasma‐polymerized coatings can be used to control the interfacial bond between PBO fibers and matrix resins and act as a protective size for preserving the mechanical properties of the fibers. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

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     

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     

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。     

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     

高能辐照对国产芳纶纤维/环氧复合材料界面性能影响

芳纶纤维因其表面惰性、光滑使其与树脂浸润性差,界面结合强度低。以环氧氯丙烷为介质1,采用60Coγ-射线辐照方法对国产芳纶纤维进行表面改性,以界面剪切强度（IFSS）和层间剪切强度（ILSS）表征芳纶/环氧复合材料界面结合性能。结果表明在400kGy辐照剂量下改性效果最好;经高能辐照处理的芳纶纤维表面能升高,并失去了原有的光滑表面,且纤维表面氧含量有大幅度提高,使得纤维表面活性增大。     

Effect of silane coupling agents on basalt fiber–epoxidized vegetable oil matrix composite materials analyzed by the single fiber fragmentation technique

The fiber–matrix interfacial shear strength (IFSS) of biobased epoxy composites reinforced with basalt fiber was investigated by the fragmentation method. Basalt fibers were modified with four different silanes, (3‐aminopropyl)trimethoxysilane, [3‐(2‐aminoethylamino)propyl]‐trimethoxysilane, trimethoxy[2‐(7‐oxabicyclo[4.1.0]hept‐3‐yl)ethyl]silane and (3‐glycidyloxypropyl)trimethoxysilane to improve the adhesion between the basalt fiber and the resin. The analysis of the fiber tensile strength results was performed in terms of statistical parameters. The tensile strength of silane‐treated basalt fiber is higher than the tensile strength of the untreated basalt fiber; this behavior may be due to flaw healing effect on the defected fiber surfaces. The IFSS results on the composites confirm that the interaction between the fiber modified with coupling agents and the bio‐based epoxy resin was much stronger than that with the untreated basalt fiber. POLYM. COMPOS., 36:1205–1212, 2015. © 2014 Society of Plastics Engineers     

Rigid‐rod polymeric fibers

This paper traces the historical development of high temperature resistant rigid‐rod polymers. Synthesis, fiber processing, structure, properties, and applications of poly(p‐phenylene benzobisoxazole) (PBO) fibers have been discussed. After nearly 20 years of development in the United States and Japan, PBO fiber was commercialized with the trade name Zylon® in 1998. Properties of this fiber have been compared with the properties of poly(ethylene terephthalate) (PET), thermotropic polyester (Vectran®), extended chain polyethylene (Spectra®), p‐aramid (Kevlar®), m‐aramid (Nomex®), aramid copolymer (Technora®), polyimide (PBI), steel, and the experimental high compressive strength rigid‐rod polymeric fiber (PIPD, M5). PBO is currently the highest tensile modulus, highest tensile strength, and most thermally stable commercial polymeric fiber. However, PBO has low axial compressive strength and poor resistance to ultraviolet and visible radiation. The fiber also looses tensile strength in hot and humid environment. In the coming decades, further improvements in tensile strength (10–20 GPa range), compressive strength, and radiation resistance are expected in polymeric fibers. Incorporation of carbon nanotubes is expected to result in the development of next generation high performance polymeric fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 100: 791–802, 2006     

Surface modification and physical properties of various UHMWPE‐fiber‐reinforced modified epoxy composites

Two surface modification methods—plasma surface treatment and chemical agent treatment—were used to investigate their effects on the surface properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE) fibers. In the analyses, performed using electron spectroscopy for chemical analysis, changes in weight, and scanning electron microscope observations, demonstrated that the two fiber‐surface‐modified composites formed between UHMWPE fiber and epoxy matrix exhibited improved interfacial adhesion and slight improvements in tensile strengths, but notable decreases in elongation, relative to those properties of the composites reinforced with the untreated UHMWPE fibers. In addition, three kinds of epoxy resins—neat DGEBA, polyurethane‐crosslinked DGEBA, and BHHBP‐DGEBA—were used as resin matrices to examine the tensile and elongation properties of their UHMWPE fiber‐reinforced composites. From stress/strain measurements and scanning electron microscope observations, the resin matrix improved the tensile strength apparently, but did not affect the elongation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 655–665, 2007     

Surface modification of aramid fibers via ammonia‐plasma treatment

In this article, aramid fibers III were surface modified using an ammonia‐plasma treatment to improve the adhesive performance and surface wettability. The surface properties of fibers before and after plasma treatment were investigated by X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, and water contact angle measurements. The interfacial shear strength of each aramid fibers III‐reinforced epoxy composites was studied by micro‐debonding test. The ammonia‐plasma treatment caused the significant chemical changes of aramid fibers III, introducing nitrogen‐containing polar functional groups, such as ? C? N? and ? CONH? , and improving their surface roughness, which contributed to the improvement of adhesive performance and surface wettability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40250.     

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。     

Improvement of the interfacial shear strength of poly(p‐phenylene benzobisoxazole) fiber/epoxy resin composite via a novel surface coating agent

Poly(p‐phenylene benzobisoxazole) (PBO) fiber with a smooth surface exhibits limited interfacial interaction with resin matrix. One of the effective strategies to improve the adhesion between the fiber and resin matrix is through surface modification of the fiber. In this study, we have proposed a novel surface treatment agent based on phosphoester cross‐linked castor oil (PCCO) for effective surface treatment of PBO fibers. The surface treatment agent was prepared by a simple cross‐linking reaction between hydroxy phosphorylated castor oil (PCO) and epoxy resin, with alcohol as the solvent at 65°C. Once the PBO fiber was treated with this agent, the interfacial adhesion between the PBO fiber and the epoxy resin could then be improved. Systematic analyses suggest that the surface treatment with (PCO + epoxy)/alcohol solution improves the interaction of the PBO fiber with the epoxy resin matrix. The PCCO coated onto the surface of PBO fiber acts as a coupling agent, improving the interfacial shear strength (IFSS) of the PBO fiber/epoxy resin composite. Results indicate a 156% increase in IFSS without compromising the mechanical properties of the fiber. POLYM. COMPOS., 37:1198–1205, 2016. © 2014 Society of Plastics Engineers     

Adhesive joints between carbon fiber and aluminum foam reinforced by surface‐treated aramid fibers

Short aramid fibers have been successfully used to reinforce the interface adhesive property between carbon fiber/epoxy composites and aluminum foam, and to form aramid‐fiber “composite adhesive joints.” In this study, to further improve the reinforcing effect of the aramid‐fiber‐reinforced adhesive joints, aramid fibers were ultrasonic treated to conduct different surface conditions. Critical energy release rate of the carbon fiber/aluminum foam sandwich beams with as‐received and treated interfacial aramid fibers were measured to study the influence of the surface treatment on aramid fibers. It was found that reinforcements in critical energy release rate were achieved for all samples with treated aramid fiber as measured under double cantilever beam condition. The interfacial characteristics of the short aramid fibers with different surface condition were investigated and discussed based on scanning electron microscopy observations. It is suggested that advanced bonding between aramid fibers and epoxy resin was conducted after surface treatment, and more energy was therefore absorbed through fiber bridging during crack opening and extension process. POLYM. COMPOS., 36:192–197, 2015. © 2014 Society of Plastics Engineers     

Mechanical properties of surface‐modified ultra‐high molecular weight polyethylene fiber reinforced natural rubber composites

The mechanical properties of ultra‐high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were determined, and the effects of fiber surface treatment and fiber mass fraction on the mechanical properties of the composites were investigated. Chromic acid was used to modify the UHMWPE fibers, and the results showed that the surface roughness and the oxygen‐containing groups on the surface of the fibers could be effectively increased. The NR matrix composites were prepared with as‐received and chromic acid treated UHMWPE fibers added 0–6 wt%. The treated UHMWPE fibers increased the elongation at break, tear strength, and hardness of the NR composites, especially the tensile stress at a given elongation, but reduced the tensile strength. The elongation at break increased markedly with increasing fiber mass fraction, attained maximum values at 3.0 wt%, and then decreased. The tear strength and hardness exhibited continuous increase with increasing the fiber content. Several microfibrillations between the fiber and NR matrix were observed from SEM images of the fractured surfaces of the treated UHMWPE fibers/NR composites, which meant that the interfacial adhesion strength was improved. POLYM. COMPOS., 38:1215–1220, 2017. © 2015 Society of Plastics Engineers     

The interfacial strength and fracture characteristics of ethanol and polymer modified carbon nanotube fibers in their epoxy composites

Carbon nanotube (CNT) fibers spun from CNT arrays were used as the reinforcement for epoxy composites, and the interfacial shear strength (IFSS) and fracture behavior were investigated by a single fiber fragmentation test. The IFSS between the CNT fiber and matrix strongly depended on the types of liquid introduced within the fiber. The IFSS of ethanol infiltrated CNT fiber/epoxy varied from 8.32 to 26.64 MPa among different spinning conditions. When long-molecule chain or cross-linked polymers were introduced, besides the increased fiber strength, the adhesion between the polymer modified fiber and the epoxy matrix was also significantly improved. Above all, the IFSS can be up to 120.32 MPa for a polyimide modified CNT fiber, one order of magnitude higher than that of ethanol infiltrated CNT fiber composites, and higher than those of typical carbon fiber/epoxy composites (e.g. 60–90 MPa). Moreover, the composite IFSS is proportional to the tensile strength and modulus of the CNT fiber, and decreases with increasing fiber diameter. The results demonstrate that the interfacial strength of the CNT fiber/epoxy can be significantly tuned by controlling the fiber structure and introducing polymer to optimize the tube–tube interactions within the fiber.     

Enzyme‐mediated surface modification of jute and its influence on the properties of jute/epoxy composites

Surface modification of jute fibers is necessary to improve the adhesion and interfacial compatibility between fibers and resin matrix before using fibers in polymer composites. In this study, dodecyl gallate (DG) was enzymatically grafted onto the jute fiber by laccase to endow the fiber with hydrophobicity. A hand lay‐up technique was then adopted to prepare jute/epoxy composites. Contact angle and wetting time measurements showed that the surface hydrophobicity of the jute fabric was increased after the enzymatic graft modification. The water absorption and thickness swelling of the DG‐grafted jute fabric/epoxy composite were lower than those of the other composites. The tensile and dynamic mechanical properties of the jute/epoxy composites were enhanced by the surface modification. Scanning electron microscopy images revealed stronger fiber–matrix adhesion in composites with modified fibers. Therefore, the enzymatic graft modification increased the fiber–matrix interface area. The fiber–matrix adhesion was enhanced, and the mechanical properties of the composites were improved. POLYM. COMPOS., 38:1327–1334, 2017. © 2015 Society of Plastics Engineers