原位计算水分在碳/碳复合材料粘接接头的扩散系数和扩散动力学

利用X射线能谱分析 (EDX)计算出粘接层胶粘剂水分含量的增加 ,从而计算出胶粘剂粘接碳 碳复合材料湿热老化后的扩散系数和扩散动力学 ,该方法不用将仅 0 1mm厚的胶粘剂从被粘材料表面除去再进行分析 ,因此相对简单 ,与元素分析测试方法相比误差较小 .比较了碳 碳复合材料表面不同处理方法粘接接头的水分扩散系数和扩散动力学 ,表明碳 碳复合材料经偶联剂处理的耐久性能要好于化学氧化和砂纸打磨处理 .     

Preparation and characterization of functionalized graphene oxide/carbon fiber/epoxy nanocomposites

Graphene oxide (GO) was functionalized using three different diamines, namely ethylenediamine (EDA), 4,4′-diaminodiphenyl sulfone (DDS) and p-phenylenediamine (PPD) to reinforce an epoxy adhesive, with the aim of improving the bonding strength of carbon fiber/epoxy composite. The chemical structure of the functionalized GO (FGO) nanosheets was characterized by elemental analysis, FT-IR and XRD. Hand lay-up, as a simple method, was applied for 3-ply composite fabrication. In the sample preparation, the fiber-to-resin ratio of 40:60 (w:w) and fiber orientations of 0°, 90°, and 0° were used. The GO and FGO nanoparticles were first dispersed in the epoxy resin, and then the GO and FGO reinforced epoxy (GO- or FGO-epoxy) were directly introduced into the carbon fiber layers to improve the mechanical properties. The GO and FGO contents varied in the range of 0.1–0.5 wt%. Results showed that the mechanical properties, in terms of tensile and flexural properties, were mainly dependent on the type of GO functionalization followed by the percentage of modified GO. As a result, both the tensile and flexural strengths are effectively enhanced by the FGOs addition. The tensile and flexural moduli are also increased by the FGO filling in the epoxy resin due to the excellent elastic modulus of FGO. The optimal FGO content for effectively improving the overall composite mechanical performance was found to be 0.3 wt%. Scanning electron microscopy (SEM) revealed that the failure mechanism of carbon fibers pulled out from the epoxy matrix contributed to the enhancement of the mechanical performance of the epoxy. These results show that diamine FGOs can strengthen the interfacial bonding between the carbon fibers and the epoxy adhesive.     

碳纳米管及碳纤维增强环氧树脂复合材料研究进展

碳纳米管与碳纤维具有优异的力学、电学等性能,广泛用做复合材料增强体,但目前碳纳米管/碳纤维/环氧树脂复合材料的研究具有一定的局限性,只考虑了两相材料间的作用,即仅对单一相进行处理而忽略了另一相的改性。本文从碳纳米管/碳纤维协同增强环氧树脂基体复合材料的思路入手,结合自己的研究成果,综述了国内外相关研究进展。从研究结果可以看出,将三相材料之间完全有效地联系起来,发挥三者间的协同效应,复合材料的性能可以发生质的飞跃。     

亚临界水介质回收酸酐固化环氧树脂/碳纤维复合材料

研究了不同添加剂对碳纤维增强酸酐固化环氧树脂复合材料在亚临界水中降解的影响,通过IR、GC-MS等分析,确定了环氧树脂的分解机理主要为酯键的断裂。 结果表明,KOH与苯酚对酸酐固化环氧树脂的分解没有协同效应,碱性物质更有利于酯键的断裂。 甲基四氢邻苯二甲酸酐固化的环氧树脂增强碳纤维复合材料在反应温度为250 ℃、反应时间为60 min、KOH浓度为0.2 mol/L时可完全分解,回收碳纤维的拉伸强度和表面形貌未受影响。     

Epoxy‐based composite adhesives: Effect of hybrid fillers on thermal conductivity,rheology, and lap shear strength

Thermal management is an important parameter in an electronic packaging application. In this work, three different types of fillers such as natural graphite powder (Gr) of 50‐μm particle size, boron nitride powder (h‐BN) of 1‐μm size, and silver flakes (Ag) of 10‐μm particle size were used for thermal conductivity enhancement of neat epoxy resin. The thermal properties, rheology, and lap shear strength of the neat epoxy and its composite were investigated. The analysis showed that the loading of different wt% of Gr‐based fillers can effectively increase the thermal conductivity of the epoxy resin. It has also been observed that the thermal conductivity of the hybrid filler (Gr/h‐BN/Ag) reinforced epoxy adhesive composite increased six times greater than that of neat epoxy resin composite. Further, the viscosity of hybrid filler reinforced epoxy resin was found to be increased as compared with its virgin counterpart. The adhesive composite with optimized filler content was then subsequently subjected to determine single lap shear strength. The degree of filler dispersion and alignment in the matrix were determined by scanning electron microscopy (SEM) analysis.     

原位合成纳米SiO2增强阴离子聚酯型上浆剂及其对碳纤维复合材料层间剪切强度的影响

采用溶胶-凝胶法, 在侧链带有羧基的线性不饱和聚酯中加入正硅酸乙酯(TEOS), 使TEOS在酸性条件下发生水解反应, 原位合成纳米SiO₂增强阴离子型聚酯乳液(SEAPE). 利用傅里叶变换红外光谱(FTIR)仪、 激光粒度分析仪和冷冻扫描电子显微镜(Cryo-SEM)对SEAPE进行分析与表征. 将SEAPE与聚乙二醇单油酸酯润滑剂、 非离子型表面活性剂FC-4430及抗氧剂1010进行复配, 原位制备纳米SiO₂增强阴离子型聚酯乳液上浆剂(SEAPEs), 用扫描电子显微镜(SEM)、 视频动态接触角测量仪、 X射线能谱(EDS)仪和纤维强力仪对SEAPEs上浆后碳纤维的表面形貌、 表面能、 碳纤维(CF)表面元素及碳纤维增强不饱和聚酯(UPR)复合材料(CF/UPR)的层间剪切强度(ILSS)进行测试与表征. 结果表明, 当TEOS添加质量分数为5%时, SEAPEs上浆后的碳纤维有效增强了其与UPR的结合强度, CF/UPR复合材料的ILSS达到40.03 MPa, 与市售环氧树脂型上浆剂上浆后碳纤维增强UPR复合材料相比, ILSS提高90.1%. SEAPEs中原位生成的纳米SiO₂分散均匀, 乳液储存稳定, 上浆后SiO₂均匀吸附在碳纤维表面, 增加碳纤维表面能, 改善碳纤维与树脂间的浸润性, 可有效提高碳纤维增强不饱和聚酯树脂复合材料的ILSS.     

Procedures conditioning the absorption/desorption behavior of cold‐cured epoxy resins

The absorption/desorption behavior of a commercial cold‐cured bisphenolic epoxy resin, subjected to different treatments prior to exposure to water, was analyzed. The epoxy system has been already used as both matrix and adhesive for the manufacture and application, respectively, of fiber reinforced polymers composites employed for rehabilitation procedures. The effects of different curing, conditioning, and storing conditions on the water absorption/desorption process taking place in the cured resin were evaluated. The different conditioning procedures used to dry the specimens before their exposure to water caused a different extent of physical aging and of curing on each system, influencing the amount and the rate of diffusion of the water molecules inside the specimens. Moreover, if the specimens are subjected to thermohygrometric cycles prior to immersion in water, the rate of diffusion and the amount of water also depends on the presence of water molecules inside the cured resins not easy to remove by any drying treatment. During all the hygrometric treatments performed, a deaging process took place. The kinetic of this deaging process for the not‐fully cured systems depends on the additional crosslinking taking place in the samples. The different procedures used to condition the specimens also affect the variations in glass transition temperature (T_g) of the cured systems during and after immersion in water. Finally, the different drying procedures employed proved to be not equally appropriate for cold‐cured epoxy resins. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1320–1336, 2008     

Effect of carbon fiber surface functionality on the moisture absorption behavior of carbon fiber/epoxy resin composites

Polyacrylonitrile (PAN)‐based carbon fibers were electrochemically oxidized in aqueous ammonium bicarbonate with increasing current density. The electrochemical treatment led to significant changes of surface physical properties and chemical structures. The oxidized fibers showed much cleaner surfaces and increased levels of oxygen functionalities. However, it was found that there was no correlation between surface roughness and the fiber/resin bond strength, i.e. mechanical interlocking did not play a major role in fiber/resin adhesion. Increases in surface chemical functionality resulted in improved fiber/resin bonding and increased interlaminar shear strength (ILSS) of carbon fiber reinforced epoxy composites. The relationship between fiber surface functionality and the hydrothermal aging behavior of carbon fiber/epoxy composites was investigated. The existence of free volume resulted from poor wetting of carbon fibers by the epoxy matrix and the interfacial chemical structure were the governing factors in the moisture absorption process of carbon fiber/epoxy composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of low current density electrochemical oxidation on the properties of carbon fiber‐reinforced epoxy resin composites

Changes in surface physicochemical structures of polyacrylonitrile‐based carbon fibers resulted from low current density electrochemical oxidation were monitored by scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The relationship between the interlaminar shear strength (ILSS) values of carbon fiber‐reinforced polymers (CFRPs) and carbon fiber surface chemistry including elemental ratios and the relative content of oxygen‐containing functional groups were researched. SEM results revealed that the electrochemical oxidation got rid of surface contaminants generated during the production process. XPS analysis showed that the relative contents of oxygen and nitrogen increased by 446% and 202%, respectively, after the electrochemical oxidation. Carbon fiber surface chemistry was of paramount importance to the interfacial properties of CFRPs. The higher the carbon fiber surface activity, the better the interfacial bonding was, and an increase in the acidic‐group contents was responsible for a higher ILSS value. However, when the current density increased to 1.0 A/m², the interfacial bonding between carbon fiber and the epoxy resin became weak which led to the decline in ILSS values. Copyright © 2012 John Wiley & Sons, Ltd.     

Aligned electrospun cellulose fibers reinforced epoxy resin composite films with high visible light transmittance

Uniaxially oriented cellulose nanofibers were fabricated by electrospinning on a rotating cylinder collector. The fiber angular standard deviation (a parameter of fiber orientation) of the mats was varied from 65.6 to 26.2^o by adjusting the rotational speed of the collector. Optically transparent epoxy resin composite films reinforced with the electrospun cellulose nanofibrous mats were then prepared by the solution impregnation method. The fiber content in the composite films was in the range of 5–30 wt%. Scanning electron microscopy studies showed that epoxy resin infiltrated and completely filled the pores in the mats. Indistinct epoxy/fiber interfaces, epoxy beads adhering on the fiber surfaces, and torn fiber remnants were found on the fractured composite film surfaces, indicating that the epoxy resin and cellulose fibers formed good interfacial adherence through hydrogen-bonding interaction. In the visible light range, the light transmittance was 88–92% for composite films with fiber loadings of 16–32 wt%. Compared to the composite films reinforced with 20 wt% randomly oriented fibers, the mechanical strength and Young’s modulus of the composite films reinforced with same amount of aligned fibers increased by 71 and 61%, respectively. Dynamical mechanical analysis showed that the storage moduli of the composite films were greatly reinforced in the temperature above the glass transition temperature of the epoxy resin matrix.     

Mechanical properties of UV‐curable carbon fiber‐reinforced polymer composite patch: Repair evaluation of damaged aluminum alloy

Epoxy resin composite patches reinforced by carbon fiber were prepared through ultraviolet (UV)–curing method, and the damaged aluminum alloy plates are rapidly repaired by means of adhesively bonding method. Mechanical properties of the composite patches and damaged aluminum alloy plates before and after repair were studied by experiment and numerical simulation. Results indicated that the tensile properties of carbon fiber/epoxy resin composite patches presented the tendency of first increase and then decrease with the increase of layer numbers of reinforced fiber. The composite patches with two layers fiber showed the best tensile properties, and the tensile strength and modulus reached 1.13 GPa and 27.79 GPa, respectively. However, the bending strength of composite patches decreased with the increase of layer numbers. Results of performance evaluation on the mechanical properties of damaged aluminum alloy plates repaired by the two layers carbon fiber/epoxy resin composite patches showed that the repair efficiency of tensile and bending properties of the repaired aluminum alloys reached more than 83% and 160%, respectively, compared with the undamaged aluminum alloys. Besides, results of numerical simulation showed that the stress intensity factor (SIF) of the crack tip on repaired aluminum alloy plates decreased significantly in comparison with the unrepaired aluminum alloy plates, which further revealing the reinforced mechanism of composite patches on the bending properties of repaired aluminum alloy plates.     

Chemical recycling of carbon fibre reinforced epoxy resin composites in subcritical water: Synergistic effect of phenol and KOH on the decomposition efficiency

The combination of phenol and potassium hydroxide (KOH) was used to chemically recycle carbon fibre reinforced epoxy resin cured with 4,4′-diaminodiphenylmethane in subcritical water. This combination had a synergistic effect on decomposing this kind of epoxy resin. The main decomposition products from the epoxy resin were identified by means of GC-MS, and a possible free-radical reaction mechanism for the decomposition of epoxy resin is proposed. The recovered carbon fibres were characterized using single fibre tensile tests, scanning electron microscopy and X-ray photoelectron spectroscopy. Compared to virgin carbon fibres after sizing removal, the surface compositions of the recovered carbon fibres had little change and the tensile strength of the recovered carbon fibres was well retained.     

Friction and wear properties of combined surface modified carbon fabric reinforced phenolic composites

Carbon fabric (CF) was surface treated with silane-coupling agent modification, HNO₃ oxidation, combined surface treatment, respectively. The friction and wear properties of the carbon fabric reinforced phenolic composites (CFP), sliding against GCr15 steel rings, were investigated on an M-2000 model ring-on-block test rig. Experimental results revealed that combined surface treatment largely reduced the friction and wear of the CFP composites. Scanning electron microscope (SEM) investigation of the worn surfaces of the CFP composites showed that combined surface modified CFP composite had the strongest interfacial adhesion and the smoothest worn surface under given load and sliding rate. SEM and X-ray photoelectron spectroscopy (XPS) study of carbon fiber surface showed that the fiber surface became rougher and the oxygen concentration increased greatly after combined surface treatment, which improved the adhesion between the fiber and the phenolic resin matrix and hence to improve the friction-reduction and anti-wear properties of the CFP composite.     

Preparation,Characterization, and Evaluation of the Anticorrosion Performance of Submicron/Nanocarbon from Jute Sticks

Jute stick, one of the most commonly and abundantly available agricultural waste product, was converted to a value-added submicron/nano jute carbon by using pyrolysis and high-energy ball milling techniques. The submicron/nano jute carbon was characterized using FE-SEM, TEM, EDS, XRD, XPS and Raman spectroscopy. The anticorrosive performance of the submicron/nano jute carbon was investigated through electrochemical impedance spectroscopy (EIS), potentiodynamic polarization (PDP) and salt spray techniques, on mild steel plates coated with a mixture of epoxy resin and the submicron/nano jute carbon. The electrochemical impedance of the steel coated with the composite coating was two orders of magnitudes higher than that of the specimen coated with neat epoxy. Consequently, the corrosion rate of specimens coated with composite coating was 13–20 times higher than that of steel coated with neat epoxy coating. The salt spray results also indicate an improvement in the corrosion resistance performance of the composite coating compared to the neat epoxy. The uniform distribution of the submicron/nano jute carbon particles in the epoxy resin improved the denseness of the composite coating by acting as a barrier against the diffusion of chloride, moisture, and oxygen, thus, improving the corrosion resistance of the developed coating.     

The dynamic mechanical behavior of random-in-plane short fiber-reinforced epoxy resin composites

In the present paper, the dynamic mechanical properties of random-in-plane short fiber-reinforced epoxy resin composites were studied by using a rheometrics solids analyzer. The three-point bend testing of the four composites (glass fiber/913 epoxy resin, glass fiber/924 epoxy resin, carbon fiber/913 epoxy resin and carbon fiber/924 epoxy resin) was carried out over temperatures from −100°C to 200°C at a frequency of 10 Hz and strain 0.05%. The composites based on 924 epoxy resin, which has been designed specially for high temperature applications, have less energy loss than the 913 epoxy resinbased composites. For the same resin, the carbon fiber-reinforced composites have less energy loss than the glass fiber-reinforced composites. All the composites have less energy loss than their corresponding matrices; the greater the fiber content, the lower the energy loss. The beta transition of 913 epoxy resin has been shifted to a higher temperature after being reinforced. It was shifted from −50°C to −30°C after being reinforced with glass fiber and made a diffuse shoulder-like peak commencing at −30°C after being reinforced with carbon fiber. The 924 epoxy resin has undergone the same change in beta transition as the 913 resin, though to a smaller extent. The phenomenon suggested that interactions between the macromolecules of the epoxy resins and the molecules along the fiber's surface.     

ELECTRODEPOSITION OF POLYMERS ON CARBON FIBERS

Styrene-co-maleic anhydride, vinyl acetate-co-maleic anhydride, methyl methacrylate-co-maleic anhydride copolymers were deposited on the surface of carbon fibers by an electrodcposition technique. The anion-free radical mechanism of this process and the physical adhesion to the surface were preliminarily confirmed. The adhesion at fiber-resin matrix interface in carbon fiber reinforced plastics was improved by the electrodeposited polymer interlayer and the shear failure occurred mainly in the matrix. Interlaminar shear strength of the unidirectional carbon fiber reinforced epoxy composite is increased from about 600 kg/cm~2 to 1000 kg/cm~2 by electrodeposition of polymers and the strength loss of the composite which has been immersed in boiling water for 100 hrs is decreased.     

Effects of surface synergy for the dispersion of short carbon fibers sized by adipic acid modified epoxy resin potassium

The carbon fiber (CF) surface plays a critical role in the performance of CF composite materials. Adipic acid modified epoxy resin potassium (AAEK) prepared with epoxy resin and adipic acid, and KOH was employed as the CF sizing agent. Then, series of surface properties of AAEK‐treated carbon fiber (CF‐AAEK) including surface charge, morphology, and groups were characterized by using Faraday cup, friction coefficient gauge, atomic force microscopy, X‐ray photoelectron spectroscopy, and thermogravimetry. The results indicated that the dispersion coefficient of CF‐AAEK was increased by 1.72 times and there were synergistic effects for the dispersion of short CFs during the sizing treatment process with AAEK. In addition, the flexural strength of treated short CF composite proved to increase by 168%, which evaluated that the better CF dispersion in the matrix was a critical factor for the mechanical property improvement of short CF‐AAEK/epoxy resin composites.     

Surface molecular characterisation of different epoxy resin composites subjected to UV accelerated degradation using XPS and ToF-SIMS

Epoxy resin composites reinforced with E-glass (E), 3D glass (3D) and carbon fibre (CF) were subjected to an intense UV and high temperature accelerated degradation environment. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to provide a molecular characterisation of the surface of the degraded composites. The response at the surface of the epoxy resin composites to oxidative degradation is influenced by the composite reinforcement type and characteristics. XPS results indicate that 3D resin composites exhibit more surface oxidation as a result of the accelerated degradation in comparison with E and CF composites. Principal components analysis (PCA) of the ToF-SIMS positive ion spectra showed that E and 3D resin composites suffered chain scission while CF composites suffered chain scission and cross-linking reactions as a result of the intense UV exposure. The extent of the surface oxidation, cross-linking/condensation reaction and loss of low molecular weight (lower than C₄H_x) aliphatic hydrocarbons may be indicated using PCA of both the ToF-SIMS positive and negative ion spectra. PCA also provides insight for proposing epoxy resin chain scission and oxidation reaction mechanisms.     

Analysis and Protection of One Thousand Hand Buddha in Dazu Stone Sculptures

The components of the rock, the pigments, the gold foils and the adhesive of One Thousand Hand Buddha in Dazu stone sculptures, Chongqing, China, have been analyzed by X-ray diffraction (XRD), X-ray fluorescence (XRF), infrared spectroscopy (IR), energy dispersive X-ray analysis (EDX) and fiber optics reflectance spectroscopy (FORS). Furthermore, the weathering and degeneration of One Thousand Hand Buddha have been discussed and the protective methods have been provided. In this work some useful information to study on conservation of stone relics is given.     

Enhancement of water barrier properties and tribological performance of hybrid glass fiber/epoxy composites with inclusions of carbon and silica nanoparticles

Water barrier properties and tribological performance (hardness and wear behavior) of new hybrid nanocomposites under dry and wet conditions were investigated. The new fabricated hybrid nanocomposite laminates consist of epoxy reinforced with woven and nonwoven tissue glass fibers and two different types of nanoparticles, silica (SiO₂) and carbon black nanoparticles (C). These nanoparticles were incorporated into epoxy resin as a single nanoparticle (either SiO₂ or C) or combining SiO₂ and C nanoparticles simultaneously with different weight fractions. The results showed that addition of carbon nanoparticles with 0.5 and 1 wt% resulted in maximum reduction in water uptake by 28.55% and 21.66%, respectively, as compared with neat glass fiber reinforced epoxy composites. Addition of all studied types and contents of nanoparticles improves hardness in dry and wet conditions over unfilled fiber composites. Under dry conditions, maximum reduction of 47.26% in weight loss was obtained with specimens containing 1 wt% carbon nanoparticles; however, in wet conditions, weight loss was reduced by 17.525% for specimens containing 0.5 wt% carbon nanoparticles as compared with unfilled fiber composites. Diffusion coefficients for different types of the hybrid nanocomposites were computed using Fickian and Langmuir models of diffusion. Copyright © 2017 John Wiley & Sons, Ltd.