Improvement of interfacial properties of carbon fiber‐reinforced poly(phthalazinone ether ketone) composites by introducing carbon nanotube to the interphase

This article aims to improve interfacial properties of carbon fiber‐reinforced poly(phthalazinone ether ketone) (PPEK) composites by means of preparing carbon nanotube (CNT)/carbon fiber hybrid fiber. XPS was used to characterize the chemical structure of unsized carbon fiber and SEM was used to observe the surface topography of carbon fibers. Specific area measurement, dynamic contact angle, and interfacial shear strength (IFSS) testing were performed to examine the effect of CNT on the interfacial properties of carbon fiber/PPEK composites. By the introduction of CNT to the interphase of carbon fiber‐reinforced PPEK composites, an enhancement of IFSS by 55.52% was achieved. Meanwhile, the interfacial fracture topography was also observed and the reinforcing mechanism was discussed. POLYM. COMPOS., 36:26–33, 2015. © 2014 Society of Plastics Engineers     

Effects of electrophoretically deposited carbon nanofibers on the interface of single carbon fibers embedded in epoxy matrix

Electrophoretic deposition (EPD) was used to deposit carboxylic acid-functionalized carbon nanofibers (O-CNFs) on the surface of single carbon fibers. Using the single fiber fragmentation technique and Weibull analysis, interfacial shear strength (IFSS) was estimated for different fiber surface treatments. Samples for sized, unsized, O-CNF deposited sized, and O-CNF deposited unsized carbon fibers were tested. Additionally, the effects of EPD were investigated by testing sized and unsized carbon fiber samples exposed to an electric field in water. Removal of the fiber sizing decreased IFSS by approximately 27%, but addition of O-CNFs to the unsized fiber surface led to an increase of 15% compared to the sized base fiber. The O-CNF deposited sized fibers provided IFSS increases of 207.6% and 66.9% for 1 and 5 min deposition durations, respectively. The surface morphology of all samples was characterized, and those containing homogeneous deposition of closely bound O-CNFs provided the highest IFSS values. Exposing sized fibers to the electric field for 1 min led to an IFSS increase of 79%, while unsized fibers undergoing the same treatment provided increases of 7.7% and 46% compared to the base sized fiber and unsized fiber samples, respectively.     

Effect of polyurethane sizing on carbon fibers surface and interfacial adhesion of fiber/polyamide 6 composites

Commercial epoxy sized carbon fibers (CFs) or unsized CFs have poor interfacial adhesion with polyamide 6 (PA6). Here, CFs are coated with polyurethane (PU) and their surface properties in terms of surface chemistry, contact angle, roughness, and morphology, are investigated. The results of Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy demonstrate PU sizing evidently increases the quantity of polar functional groups on the CFs surface. The surface energy of the PU sized fiber is calculated according to the Owens–Wendt method. Compared with unsized fibers, the contact angle of PU sized fibers is decreased while their total surface energy is increased, indicating superior wettability. Moreover, transverse fiber bundle tests are performed to determine the interfacial adhesion between the CFs and PA6 matrix. The transverse fiber bundle strength of unsized CF is measured to be 12.57 MPa. For PU sized CFs processed with sizing concentration of 1.2%, this value is increased to 24.35 MPa, showing an increase of more than 90%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46111.     

Development of multiwalled‐carbon‐nanotube‐welded carbon fibers and evaluation of the interfacial strength in epoxy composites

Multiwalled carbon nanotube (MWCNT)‐welded carbon fibers (CFs) were prepared by a three‐step process, which included polyacrylonitrile (PAN) coating, MWCNT absorption, and heat treatment. The structure of these materials was characterized by scanning electron microscopy, Fourier‐transform infrared spectroscopy, and Raman spectroscopy. The MWCNTs were uniformly assembled on the surface of the PAN‐coated CFs and welded by a PAN‐based carbon layer after heat treatment. The contact angle of the MWCNT‐welded CFs in the epoxy resins was 41.70°; this was 22.35% smaller than that of the unsized CFs. The interfacial shear strength (IFSS) of the MWCNT‐welded CF–epoxy composite was 83.15 MPa; this was 28.89% higher than that of the unsized CF–epoxy composite. The increase in the IFSS was attributed to the enhancement of adhesions between the CFs and polymer matrix through the welding of the MWCNTs on the CFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45027.     

Interfacial shear strength in carbon fiber‐reinforced poly(phthalazinone ether ketone) composites

We studied interfacial shear strength (IFSS) in carbon fiber (CF)‐reinforced poly (phthalazinone ether ketone) (PPEK) composites system, with emphasis on the influence of forming temperature of composite and sizing agent on CFs. To obtain apparent IFSS of CF‐reinforced PPEK composites shaped at various forming temperatures ranged from 20 up to 370°C, microbond test was carried out at single‐fiber composites. Results of microbond test showed that apparent IFSS was directly proportional to the difference between the matrix solidification temperature (forming temperature) and the test temperature and approximately 80% of the apparent IFSS in CF/PPEK composite system was attributed to residual radial compressive stress at the fiber/matrix interface. By sizing CF with sizing agent, the wettability of the fiber by the matrix was improved and the final apparent IFSS was also improved. POLYM. COMPOS., 34:1921–1926, 2013. © 2013 Society of Plastics Engineers     

微脱黏法在碳纤维/环氧树脂界面性能评价中的应用

利用微脱黏法测定碳纤维/环氧树脂复合材料的界面剪切强度,并分析了造成测试结果分散的影响因素.结果表明:在脱黏过程中,最大脱黏力随碳纤维埋人环氧树脂内长度的增加而线性递增,当埋人长度超过一定值后最大脱黏力趋于稳定:碳纤维与环氧树脂间的接触角对复合材料界面剪切强度有一定影响,接触角越大,界面剪切强度越高;测试结果的分散性与树脂微球的半月板区域、钳口区等因素有关;未经表面处理的碳纤维增强环氧树脂复合材料的界面剪切强度仪为39.4 MPa,低于处理后的复合材料(60.6 MPa).     

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.     

Physical and chemical properties of polypyrrole–carbon fiber interphases formed by aqueous electrosynthesis

The properties of carbon fibers modified by aqueous electrochemical synthesis of pyrrole has been determined by using the dynamic contact angle analyzer (DCA), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). Electrochemical process parameters such as the initial pyrrole concentration, electrolyte concentration, applied voltage, electrolyte type, and reaction time were systematically varied, and their impact on the polypyrrole–carbon fiber interphases surface free energy and morphology was ascertained. The surface free energies of the polypyrrole–carbon fiber interphases were obtained by using single fiber filaments. SEM analysis of the interphases revealed several distinct surface structures, including smooth, porous, granular, microspheroidal, and leafoidal morphologies. The noncoated but commercially surface oxidized carbon fibers have smooth surface morphology with occasional longitudinal striations. FTIR analysis of the polypyrrole interphases confirmed that the counterions derived from the electrolytes were incorporated into the film. The surface free energies of the electrochemically formed polypyrrole–carbon fiber interphases equivalent to 60–75 dynes/cm, was determined to be up to 40% higher than that for the surface oxidized but unsized carbon fibers equivalent to 50 dynes/cm. This improvement in the surface free energies of the polypyrrole–carbon fiber interphases suggests easy wettability by polymer matrices such as epoxy resin, γ ˜ 47 dynes/cm and, polyimide matrix, γ ˜ 45 dynes/cm. © 1996 John Wiley & Sons, Inc.     

Effect of surface treatment of ramie fiber on the interfacial adhesion of ramie/acetylated epoxidized soybean oil (AESO) green composite

Recently, many researchers have attempted to convert soybean oil into useful polymers. One of the ways to make soybean oil into a matrix of green composites is to modify its triglyceride structure to obtain the acrylated epoxidized soybean oil (AESO) through epoxidization and acrylation. In this study, the effects of ramie fiber surface treatments such as acetylation, silane, and peroxide treatments on the chemical, morphological, and interfacial adhesion properties of a ramie/AESO green composite were studied. Surface-treated fibers were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and dynamic contact angle analysis. The crystallinity and thermal stability of chemically treated fibers were investigated by wide angle X-ray diffraction and thermogravimetric analyzer. It was demonstrated that surface treatments lead to several morphological changes, including the formation of micro-cracks and removal of impurities by acetylation and peroxide treatment as well as surface smoothing by silane treatment. Surface energy of acetylated fiber decreased with treatment time and showed the lowest value for silane treated fiber. The interfacial shear strength (IFSS) of a fiber/AESO composite was investigated through the microbond test. The IFSS of silane treated ramie was higher than that of others. The result indicates that silane treated fibers improve the interfacial property, which is the most important characteristic for the end use of green composites.     

Influence of temperature and relative humidity on aging of atmospheric plasma jet treatment effect on ultrahigh-modulus polyethylene fibers

The aging effects of atmospheric pressure plasma treated fiber surfaces are important for storage and processing of the fibers. One of the high-performance fibers, ultrahigh modulus polyethylene (UHMPE) fiber, was chosen as a model system to investigate the aging process of atmospheric pressure plasma jet (APPJ) treated fibers surfaces 0, 7, 15 and 30 days after initial plasma treatment. The fiber was first plasma-treated and then stored at temperatures varying from ?80 to 80°C on the same relative humidity (RH, 0%) and on RH of 0%, 65% and 100% at the same temperature of 20°C. Immediately after the plasma treatment, scanning electron microscope (SEM) showed the roughened fiber surface. X-ray photoelectron spectroscopy analysis showed changed surface chemical compositions. Contact-angle measurement showed increased surface wettability and microbond test showed an increase in IFSS. With increasing relative humidity or decreasing temperature, the IFSS value decreased and the contact angle increased more slowly. However, after 30 days, the IFSS values and contact angles reached a similar level for all groups. Moisture showed no effect on the single fiber tensile strengths during aging. The reasons for the observed aging behavior could be that decreasing temperature or increasing relative humidity hindered the surface rearrangement of polymer chains after plasma treatment.     

A Novel Route to Modify the Interface of Glass Fiber-Reinforced Epoxy Resin Composite via Bacterial Cellulose

A simple and novel method to modify the surface of glass material with Acetobacter xylinum bacteria to deposit bacterial cellulose (BC) around glass material during the process of fermentation was described. The modified glass material with more hydrophobic and rougher surface was characterized by FTIR, SEM, XPS, peeling experiments, and water/air contact angle. It was found that heat treatment at 140 ～ 150°C was able to improve the interaction between BC and glass material owing to the increase in chemical bonds between them. The biological modified glass fibers were compounded with epoxy resin. The influence of incubation time and high temperature on the interfacial shear strength (IFSS) between glass fibers and epoxy resin was identified by Microbond Test. The strongest IFSS could be obtained with incubation time of 1 hour and temperature of 140°C, which then offers a biological approach to improve the interface of silicates materials and resin matrix.     

Effect of PEKK oligomers sizing on the dynamic mechanical behavior of poly(ether ketone ketone)/carbon fiber composites

Poly(ether ketone ketone) (PEKK)/unidirectional carbon fiber (CF) composites have a poor interface. Accordingly, PEKK oligomer (PEKKo) sizing with a chemical compatibility with PEKK is proposed for promoting interfacial interactions in order to enhance mechanical performances. The thermal stability until 500 °C has been shown by thermogravimetric analysis (TGA). In order to compare static and dynamic sizing methods, “lab sizing” and “pilot sizing” were carried out. Scanning electron microscopy images of freeze fractures of PEKK/unsized CF, PEKK/PEKKo lab-sized CF and PEKK/PEKKo pilot-sized CF show that the PEKKo sizing causes an improvement of fiber/PEKK interactions, regardless of the sizing method. Indeed, in both cases, there is a continuity of matter at the interface while we observe a poor wetting of CF by matrix in PEKK/unsized CF. Dynamic mechanical relaxations in shear were analyzed as a function of temperature. The increase of storage modulus upon sizing is observed for both methods but it is more important for PEKKo pilot sizing. In the same way, the mechanical energy loss increases, it reflects the optimization of stress transfer between matrix and fibers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48818.     

Surface energetics of carbon fibers and its effects on the mechanical performance of CF/EP composites

To exploit the reinforcement potential of the fibers in advanced composites, it is necessary to reach a deeper understanding on the interrelations between fiber surface chemical and energetic characteristics, wetting properties, and mechanical performance. In this study CF/EP was chosen as a model thermoset composite material, whereby a hot-curing epoxy (EP) system served as the matrix. The fibers selected were PAN-based high-tenacity carbon fibers (CF) of varying surface treatment level and/or coating. Surface free energies for the carbon fibers were determined by dynamic contact angle measurements in a variety of test liquids of known polar and dispersive surface tension utilizing a micro-Wilhelmy wetting balance and following the methods proposed by Zisman and Owens and Wendt, respectively. Surface treatment resulted in an increase of the polar fraction of the fiber surface free energy, whereas its dispersive part remained unaffected. The interfacial shear strength (IFSS) as determined in the microdroplet pull-off test was enhanced both by intensification of the surface treatment and sizing the CF with an EP component. A linear relationship between IFSS and the polar fraction of the fiber surface free energy γ^p_s was found. Further attempts were made to find correlations between surface free energy of the CF and laminate strengths measured in shear and transverse tension. © 1996 John Wiley & Sons, Inc.     

阳极氧化及上浆过程中PAN基碳纤维表面形态结构的演变

采用阳极氧化法对PAN基碳纤维的表面进行改性,然后使用上浆剂对纤维表面进行上浆处理。使用扫描电镜、原子力显微镜、X射线光电子能谱仪等分析了处理过程中碳纤维表面形态结构的变化,研究了阳极氧化及上浆处理对碳纤维的拉伸强度及其与环氧树脂间界面剪切强度(IFSS)的影响。结果表明:阳极氧化处理后,碳纤维表面平均粗糙度从48.0 nm增大到90.5 nm,而上浆后碳纤维平均粗糙度下降到32.3nm;经阳极氧化处理后,碳纤维表面碳(C)元素含量降低,氧(O)、氮(N)元素含量增加,—OH基团含量由14.43%增加到39.32%,而上浆后纤维表面—OH基团含量变化不大;在阳极氧化过程中随着氧化程度的提高,碳纤维的拉伸强度逐渐降低,但其IFSS逐渐升高;上浆对碳纤维拉伸强度影响不大,但上浆剂中较高的活性基团使得其IFSS进一步提高。     

Mechanical properties and mechanism of the degradation process of 316°C isothermally aged graphite fiber/PMR-15 composites

A series of graphite fiber/PMR-15 polyimide composites, isothermally aged at 316°C in flowing air (100 cc/min) for time periods up to 2000 h, were investigated for mechanical property changes, fiber/resin interface changes, overall dimensional changes, and weight loss. The mechanism of the degradation process is suggested based on shear and flexural property measurements at room temperature and 316°C, optical micrographs of composite cross sections, and SEM analysis of fractured surfaces. The fiber materials investigated in composite form were Celion 6000 unsized and epoxy sized. G40-700 unsized and epoxy sized, and T40R and IM6 both unsized.     

Surface modification of ultra-high strength polyethylene fibers for enhanced adhesion to epoxy resins using intense pulsed high-power ion beam

The effects of intense pulsed high power ion beam (HPIB) treatment of ultra-high strength polyethylene (UHSPE) fibers on the fiber/epoxy resin interface strength were studied. For this study, argon ions were used to treat Spectra? 1000 (UHSPE) fibers in vacuum. Chemical and topographical changes of the fiber surfaces were characterized using Fourier transform infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), dynamic wettability measurements, and scanning electron microscopy (SEM). The fiber/epoxy resin interfacial shear strength (IFSS) was evaluated by the single fiber pull-out test. The FTIR-ATR and XPS data indicate that oxygen was incorporated onto the fiber surface as a result of the HPIB treatment. The wettability data indicate that the fibers became more polar after HPIB treatment and also more wettable. Although the total surface energy increased only slightly after treatment, the dispersive component decreased significantly while the acid-base component increased by a similar amount. SEM photomicrographs revealed that the surface roughness of the fibers increased following the HPIB treatment. The single fiber pull-out test results indicate that HPIB treatment significantly improved the IFSS of UHSPE fibers with epoxy resin. This enhancement in IFSS is attributed to increased roughness of the fiber surface resulting in mechanical bonding and in increased interface area, increased polar nature and wettability, and an improvement in the acid-base component of the surface energy after the HPIB treatment.     

Effect of sizing on interfacial adhesion of commercial high strength carbon fiber‐reinforced resin composites

The influence of sizing agent on interfacial shear strength (IFSS) of carbon fiber/epoxy (CF/EP) and carbon fiber/bismaleimide (CF/BMI) was investigated. Since sizing agent can alter physicochemical properties of CF surface, possible affecting factors, including sizing reactivity, chemical reactions between sizing and resin, wettability of fiber with resin, fiber surface roughness, and chemical composition of fiber surface, were discussed. It is found that contact angle of fiber with resin and sufficient chemical reactions between sizing and resin reveal strong correlation with the interfacial adhesion of CF/EP and CF/BMI, while the effect of surface roughness and the amount of oxygen on the fiber surface are relatively weak. Due to EP type of the composition, the sizing agent tends to improve the wettability of CF with EP, while goes against for the fiber with BMI. POLYM. COMPOS., 254–261, 2016. © 2014 Society of Plastics Engineers     

Interfacial stress transfer in nylon‐6/E‐Glass microcomposites: Effect of temperature and strain rate

In this study, the interfacial properties between E‐glass fibers with different commercial sizings have been investigated on model composites with a nylon‐6 matrix. In particular, the fiber critical length was measured by means of the single‐fiber fragmentation test over a wide range of temperatures (from 25 to 175°C) and strain rates (from 0.0008 to 4 min⁻¹). The general trend observed is that the fiber critical aspect ratio increases as the temperature increases and it decreases as strain rate is increased. The fiber critical aspect ratio for unsized fibers resulted to be reasonably well linearly related to the square root of the fiber to matrix modulus ratio. This results is in accordance with the Cox's shear‐lag theoretical model and the Termonia's numerical simulations. Sized fibers display an higher deviation from the theoretical prevision probably because of the presence of interphases whose properties are different from the bulk matrix. As a consequence, the interfacial shear strength values resulted to be dependent on the fiber sizing. In particular, the fibers coated with an epoxy sizing showed a superior thermal stability of the fiber matrix‐interface with respect to the unsized or nylon compatible sized fibers.     

Surface modification of ultra high modulus polyethylene fibers by an atmospheric pressure plasma jet

To improve their adhesion properties, ultra high modulus polyethylene (UHMPE) fibers were treated by an atmospheric pressure helium plasma jet (APPJ), which was operated at radio frequency (13.56 MHz). The surface properties of the fibers were investigated by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and contact angle measurement. The surface dyeability improvement after plasma treatments was investigated using laser scanning confocal microscopy (LSCM). The adhesion strengths of the fibers with epoxy were evaluated by microbond tests. In addition, the influence of operational parameters of the plasma treatment including power input and treatment temperature was studied. XPS analysis showed a significant increase in the surface oxygen content. LSCM results showed that the plasma treatments greatly increased fluorescence dye concentrations on the surface and higher diffusion rate to the fiber center. The tensile strength of UHMPE fiber either remained unchanged or decreased by 10–13.6% after plasma treatment. The contact angle exhibited a characteristic increase in wettability, due to the polar groups introduced by plasma treatment. The microbond test showed that the interfacial shear strengths (IFSS) increase significantly (57–139%) after plasma treatment for all groups and the optimum activation is obtained at 100°C and 5 W power input. SEM analysis showed roughened surfaces after the plasma treatments. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Mechanical properties of carbon fiber composites modified with nano-SiO2 in the interphase

The performance of carbon fibers-reinforced composites is dependent to a great extent on the properties of fiber–matrix interface. To improve the interfacial properties in carbon fibers/epoxy composites, nano-SiO₂ particles were introduced to the surface of carbon fibers by sizing treatment. Atomic force microscope (AFM) results showed that nano-SiO₂ particles had been introduced on the surface of carbon fibers and increase the surface roughness of carbon fibers. X-ray photoelectron spectroscopy (XPS) showed that nano-SiO₂ particles increased the content of oxygen-containing groups on carbon fibers surface. Single fiber pull-out test (IFSS) and short-beam bending test (ILSS) results showed that the IFSS and ILSS of carbon fibers/epoxy composites could obtain 30.8 and 10.6% improvement compared with the composites without nano-SiO₂, respectively, when the nano-SiO₂ content was 1 wt % in sizing agents. Impact test of carbon fibers/epoxy composites treated by nano-SiO₂ containing sizing showed higher absorption energy than that of carbon fibers/epoxy composites treated by sizing agent without nano-SiO₂. Scanning electron microscopy (SEM) of impact fracture surface showed that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂-modified sizing treatment. Dynamic mechanical thermal analysis (DMTA) showed that the introduction of nano-SiO₂ to carbon fibers surface effectively improved the storage modulus of carbon fibers/epoxy.