Effects of facile amine‐functionalization on the physical properties of epoxy/graphene nanoplatelets nanocomposites

Graphene nanoplatelets (GNPs) have excellent thermal, electrical, and mechanical properties. The incorporation of GNPs into a polymer can remarkably enhance the thermal and mechanical properties of the polymer especially when GNPs are well dispersed in the polymer matrix with strong interfacial bonding. Therefore, in this study, GNPs were amine‐functionalized by covalently bonding 4,4′‐methylene dianiline onto their surfaces via a facile synthetic route. The amine‐functionalization was confirmed by FTIR spectroscopy and TGA. Epoxy/GNPs nanocomposites were prepared and their curing behavior, thermomechanical properties and impact strength were investigated. The amine‐functionalization increased curing rate, storage modulus, thermal dimensional stability, and impact strength of the nanocomposites. The SEM images for the fracture surface of the nanocomposite with amine‐functionalized GNPs showed a smooth and ductile failure‐like surface, resulted from the improved interfacial bonding between GNPs and the epoxy matrix. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42269.     

RETRACTED ARTICLE: Surface modification of aramid fibers with novel chemical approach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

Epoxy resin nanocomposites reinforced with ionized liquid stabilized carbon nanotubes

Epoxy resin nanocomposites reinforced with three different ionic liquid functionalized carbon nanotubes (f-CNTs) were fabricated by an in situpolymerization method. The influence of the anions on the curing process was studied through differential scanning calorimetry (DSC) and normalized Fourier transform infrared (FTIR) spectroscopy. The composition of the nanocomposites was analyzed by X-ray photoelectron spectroscopy. Two different mechanisms are proposed to explain the curing process of the neat epoxy and its composites. The electric conductivity and mechanical properties of the nanocomposites are also reported. The tensile strength was increased dramatically due to the insertion of f-CNTs. Scanning electron microsopy fracture surface analysis indicates a strong interfacial bonding between the carbon nanotubes and the polymer matrix.     

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。     

Improving Interfacial and Compressive Properties of Aramid by Synchronously Grafting and Crosslinking

Improving compressive strength of aramid and its adhesion to resin is of great significance for its application in reinforcing materials. In this study, a novel method for improving interfacial and compressive properties of aramid fiber is presented. α,α′‐Dichloro‐p‐xylene (DCX) is utilized as an external crosslinker to modify aramid fiber containing benzimidazole units during the post swelling process. Chloromethyl groups from DCX can react with benzimidazole moieties of the aramid fiber. The reaction can be regarded as crosslinking inside the fiber and grafting on the surface. By controlling the swelling effect of the solvent during modification, bulk crosslinking degree and surface grafting density can be adjusted. Therefore, intermolecular interaction and surface polarity of the aramid fiber can be improved simultaneously. After modification, the compressive strength of the fiber can be enhanced by nearly 100% and interfacial shear strength increases by 37%, while excellent mechanical properties are maintained. Therefore, comprehensive performance of aramid fiber can be improved significantly by synchronously crosslinking and grafting.     

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     

芳纶纤维等离子体接枝改性处理研究

采用等离子体接枝对芳纶纤维表面进行改性处理,采用XPS、浸润性、界面剪切强度对等离子体接枝处理前后的表面组成、复合材料界面粘接性能等进行了研究,结果表明:等离子体接枝处理可以有效地提高芳纶纤维表面的极性官能团,增加与基体树脂-环氧树脂的浸润性,进而提高芳纶/环氧复合材料的界面粘接强度.     

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.     

Enhanced interfacial adhesion of aramid fiber reinforced rubber composites through bio-inspired surface modification and aramid nanofiber coating

In order to improve the interfacial adhesion between aramid fiber (AF) and rubber matrix, a simple and facile method of aramid nanofiber (ANF) coating is demonstrated in this article. Tannic acid (TA) and polyethyleneimine (PEI) are polymerized in an alkaline solution to form a thin TA/PEI (TP) layer that is deposited on the surface of AF to introduce functional groups such as hydroxyl and amino groups. Then, the ANF coating is utilized to construct nanostructures on the surface of AF to improve the interfacial adhesion between the fiber and the rubber. Through hydrogen bonding and/or π-π stacking between the TP layer and the ANF, the ANF coating is firmly attached to the surface of AF. Compared with the untreated fiber, the interfacial adhesion of AF coated with ANF after 1, 3, 5, 7, 9 deposition cycles is increased by 27.8%, 29.1%, 31.5%, 43.1%, and 30.3%, and the mechanical properties of the fibers remain almost unchanged. This method shows its advantages of simple, facile, and time-effective, which is of great significance for industrial applications.     

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。     

The Study of Reactive Functional Groups in Adhesive Bonding at the Aramid-Epoxy Interface

In polymeric composites, reactive functional groups on the fiber surface are assumed to enhance the mechanical strength of the fiber-matrix interface greatly by forming covalent bonds with the matrix. To test this assumption, we sought to promote covalent bonding at the aramid fiber-epoxy matrix interface by attaching flexible reactive pendent groups to the fiber surface. Other factors that could affect interfacial adhesion were kept constant, i.e., surface energy and surface topography. Quantitative analysis showed a pendent group attachment level of 1.5 to 4.5 groups per 100 Ų of fiber surface, a level that agrees well with the theoretical amount. Surprisingly, in adhesive performance tests, the presence of these reactive pendent groups did not improve the fiber-matrix interface strength. Specific chemical tests for covalent bond formation between the terminal amine of the pendent group and the epoxy molecule showed that covalent bonding did not occur, thus explaining the unexpected lack of improvement in adhesive performance.     

Influence of Fiber Characteristics and Manufacturing Process on the Structure and Properties of Aramid Paper

The influence of fiber characteristics and calendering on the structure and properties of aramid paper was investigated. Laboratory aramid handsheets were prepared, and the structure and properties of them were investigated by Field Emission Scanning Electron Microscopy (FESEM), Dynamic Mechanical Analysis (DMA), X-ray Diffractometer (XRD) and strength test. A comparison with commerical Nomex papers showed that overdrawn fibers with high initial modulus and film-like fibrids were helpful for improving the interface bonding and mechanical strength of aramid paper. Hot calendering improved the crystallinity, storage modulus and interface bonding of aramid materials, thereby greatly improving the mechanical strength of aramid paper.     

Synthesis and characterization of multiwalled carbon nanotubes‐polymethyl methacrylate composites prepared by in situ polymerization method

Multiwalled carbon nanotubes‐polymethyl methacrylate composites (MWCNT‐PMMA) were prepared by an in situ polymerization method. The effect of nanotube content and their surface functionalization on the mechanical properties of the resulting nanocomposites was investigated. The use of only 1.8 wt% functionalized tubes improved flexural modulus by about 43% and flexural strength by about 60%. In situ polymerization using functionalized tubes improved interfacial bonding strength due to a chemical interaction between carbon nanotubes and the growing PMMA, which resulted in improved load transfer mechanism. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

The effects of transcrystalline interphase in advanced polymer composites

Surface-induced transcrystallization in fibers has been reported in some advanced polymer composites. It is believed that transcrystalline interphase may affect stress transfer efficiency between the reinforcing fiber and the matrix. In this study, attempts were made to examine the effects of transcrystallinity on composite performance, particularly on fiber-matrix interfacial bond strength, and to investigate possible attributes of transcrystallization. Three polymer resins, poly(etherketoneketone) (PEKK), poly(etheretherketone) (PEEK), and poly(phenylenesulfide) (PPS), and four types of fiber, polyacrylonitrile (PAN)-based AU-4 (untreated AS-4) carbon, pitch-based carbon, poly (p-phenylene terephthalamide) (PPDT) aramid, and E-glass were used. It was found that PPDT aramid and pitch-based carbon fibers induce a transcrystalline interphase in all three polymers because of an epitaxial effect. Under certain conditions, transcrystallization was also observed in PAN-based carbon and E-glass fibers, which may be partially attributed to the thermal conductivity mismatch between the fiber and the matrix. Plasma treatment on fiber surface showed a negligible effect on inducing transcrystallization, whereas solution-coating of PPDT on the fiber surface showed a positive effect. The Microdebonding test, which measures the interfacial bond strength between the fiber and the matrix, consistently showed more than 40% increments for various single filament systems with transcrystalline interphase versus without. However, the effects of transcrystallinity on the interfacial bond strength appeared to decrease as the fiber content increased in composites.     

低温等离子体改性芳纶1414的研究

对芳纶1414进行低温等离子体表面改性以改善其构成复合材料时的界面黏结性能。设计正交试验,得到低温等离子体处理芳纶1414的最佳条件为放电功率100 W,处理时间300 s,放电压强20 Pa。采用电子单纤维强力机、纤维摩擦因数测定仪、纤维接触角测量仪、扫描电子显微镜和傅里叶变换红外光谱仪对改性前后的芳纶1414进行性能表征。结果表明:经过低温等离子体改性的芳纶1414的断裂强力较原样下降了6.3%,静摩擦因数上升了15.7%,表面接触角减小了36.8%,纤维表面出现微小均匀的凹槽,增大了比表面积,引入了自由基团,增大了表面反应活性,从而改善了与树脂基体复合时的黏结强度。     

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。     

杂环芳纶表面ZnO纳米界面相的构筑及其界面强化作用

为了改善杂环芳纶(F3)与环氧树脂黏结性差以及不耐紫外辐射的缺点,首先对纤维进行功能化预处理,然后通过溶胶-凝胶法和水热法分别在芳纶表面生长了氧化锌纳米颗粒和氧化锌纳米线界面层。采用X成、形貌、与环氧树脂的黏结性以及抗紫外性能进行了研究。结果表明:纳米颗粒状和纳米线形态的ZnO纳米界面相能够显著提高纤维与树脂基体的黏结性能,与未处理的纤维相比,单纤维复合材料的界面剪切强度分别提高了14.1%和27.0%;同时ZnO的破坏,经过168 h紫外辐射试验后,纤维强度保持率从79.1%提高到96.7%。     

表面处理对Kevlar纤维复合材料界面结合强度的影响

为改善芳纶纤维增强树脂基复合材料的界面结合强度,用化学处理法对Kevlar-29纤维进行表面处理,并用傅里叶变换红外光谱和扫描电镜等方法对表面接枝进行鉴定,用单丝拔出试验表征芳纶纤维增强树脂基复合材料的界面结合强度。实验结果表明,纤维经过表面改性后,在单丝断裂强度降低不大的情况下,界面剪切强度显著提高。     

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.     

Covalent addition of diethyltoluenediamines onto carbon nanotubes for composite application

Diethyltoluenediamines (DETDA) was grafted to single‐walled carbon nanotubes (SWNTs) through diazonium‐based addition for improving dispersion and interfacial bonding in SWNT/epoxy nanocomposites. Characterization results of Fourier Transformed Infrared spectroscopy and Raman spectroscopy validated covalent bonding between DETDA and carbon nanotubes. The degree of functionalization was about 4% based on thermo‐gravimetric analysis. Interfacial bonding strength was computed in the presence of chemical bonding and the computation results indicated that the interfacial shear strength in the presence of functionalized carbon nanotubes was significantly enhanced. The experimental test revealed that the tensile strength of nanocomposites was enhanced about 23% and Young's modulus about 25%, with 0.5 wt% loading of functionalized‐nanotubes. These considerable improvements further verified the load‐transfer enhancement in the functionalized‐SWNTs/epoxy nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers