聚合物在碳纤维表面的电沉积

用电沉积方法将苯乙烯-马来酸酐、乙酸乙烯酯-马来酸酐、甲基丙烯酸甲酯-马来酸酐共聚物沉积于碳纤维表面。通过实验初步证实了此过程的负离子-自由基机理,以及沉积层在纤维表面的物理粘附。由于电沉积的聚合物中间层改善了碳纤维增强塑料中纤维-基体树脂间的界面粘接作用,使原来的剪切破坏基本上发生于界面的情况转变成发生于基体本身为主。并将单向碳纤维增强环氧树脂复合材料的层间剪切强度,由原来的600kg/cm~2左右提高到1000kg/cm~2以上,经沸水浸泡100小时后的强度损失也减少了。     

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.     

Interfacial adhesion and microfailure modes of electrodeposited carbon fiber/epoxy-PEI composites by microdroplet and surface wettability tests

Interfacial properties and microfailure modes of electrodeposition (ED)-treated carbon fiber-reinforced polyetherimide (PEI) toughened epoxy composite were investigated using microdroplet test and the measurement of surface wettability. ED was performed to improve the interfacial shear strength (IFSS). As PEI content increased, IFSS increased due to enhanced toughness and plastic deformation of PEI. In the untreated case, IFSS increased with adding PEI content, and the IFSS of the pure PEI matrix showed the highest. On the other hand, for the ED-treated case IFSS increased with PEI content with rather low improvement rate. In the untreated case, neat epoxy resin appeared brittle microfailure mode, whereas the pure PEI matrix exhibited a more likely ductile microfailure mode. In the ED-treated case, neat epoxy exhibited a more ductile fracture than that of the untreated case. Critical surface tension and polar surface free energy of ED-treated carbon fiber was higher than those of the untreated fiber. The work of adhesion between fiber and matrix was not directly proportional to IFSS for both the untreated and ED-treated cases. The matrix toughness might contribute to IFSS more likely than the surface wettability. Interfacial properties of the epoxy-PEI composite can be affected efficiently by both the control of matrix toughness and ED treatment.     

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。     

The improvement in interfacial shear strength of wood fiber/epoxy composite by sizing with epoxy sizing agent containing MWCNTs

This paper discloses a feasible and high efficient strategy for wood fiber treatment to introducing multi‐wall carbon nanotubes (MWCNTs) to the surface of wood fibers for the aim of improving the interfacial shear strength of wood fiber/epoxy composite. Briefly, a layer of MWCNT was deposited on wood fibers through sizing wood fibers with epoxy sizing agent containing amine‐treated MWCNTs (MWCNT‐PEI). The surface functional groups, morphology, wettability, and interphase properties of MWCNTs on the surface of wood fiber were studied. The remarkable enhancements were achieved in interfacial shear strength of reinforced composites by dipping wood fiber in MWCNTCOOH suspension and wood fiber sizing containing MWCNT‐PEI.     

Improved thermo-oxidative stability of three-dimensional and four-directional braided carbon fiber/epoxy hierarchical composites using graphene-reinforced gradient interface layer

In order to improve the thermo-oxidative stability of three-dimensional and four-directional braided carbon fiber/epoxy composites, we introduced a gradient interphase reinforced by graphene nanoplatelets (GN) between the carbon fiber and the matrix, with a liquid phase deposition strategy. Both the interlaminar shear strength and the flexural strength of the composites were improved after thermo-oxidative aging at 140 °C for various durations (up to 1200 h). The interfacial reinforcing mechanisms are explored by analyzing the structure of the interfacial phase, thermal conductivity, weight loss, surface topography, fiber/matrix interfacial morphology and thermomechanical properties of the composites. Results indicate that the GN-reinforced gradient interphase provides an effective shield against interface oxidation, assists in thermal stress transfer, and restricts the movement of the different phases of materials at the composite interface.     

The crosslinking of epoxy resins at interfaces. III. At a carbonized polyacrylonitrile surface

The crosslinking chemistry of an anhydride-cured epoxy resin, in the first 200–400 nm adjacent to a carbonized polyacrylonitrile (PAN) surface (a model for the surface of a carbon fiber), is significantly affected by the humidity history of that surface. Prior humid aging of the carbonized PAN surface increases the subsequent rate of consumption of anhydride curing agent, and decreases the yield of ester crosslinked products. The crosslinking chemistry of an amine-cured epoxy resin appears unchanged by the presence of the carbonized surface. Dynamic mechanical analysis (DMA) of unidirectional composites made from carbon fibers and the above epoxy resin matrices shows that the damping characteristics of composites made with an epoxy–anhydride matrix are sensitive to the preconditioning history of the carbon fibers, while composites made with an epoxy–amine matrix are unaffected by the preconditioning history of the fibers. Partial removal of the carbon fiber surface coating by dichloromethane extraction does not change the sensitivity of the composites to fiber preconditioning history. These results are rationalized on the basis of the effect moisture adsorbed by the carbonized PAN and by the carbon fiber has on the epoxy resin crosslinking processes.     

Increased interfacial adhesion between carbon fiber and poly(vinylidene fluoride) by an aqueous sizing agent

The adhesion behavior of poly(vinylidene fluoride) (PVDF) to carbon fiber (CF) has always been a huge challenge, on account of the inertness nature of PVDF and the lack of reactive functional groups. In this work, a novel maleic anhydride grafted PVDF (MPVDF) aqueous sizing agent was prepared to modify the interface between CF and PVDF matrix. The surface properties of desized, MPVDF‐sized, and PVDF‐sized carbon fibers were characterized by the scanning electron microscopy, X‐ray photoelectron spectroscopy, atomic force microscopy, and dynamic contact angle analysis test. The results demonstrated that the surface roughness increased from 39 to 55 nm, and surface energy increased from 40 to 74 mN m^?1 after MPVDF sizing treatment. The content of activated carbon atoms increased from 31.0% to 48.4%. Subsequently, the interlaminar shear strength was examined, for which was a critical indicator of the interfacial adhesion between CF and matrix. Compared with the desized CF, the value of interlaminar shear strength increased from 14.8 MPa to 25.5 MPa improved by 72% because of the improved H‐bonding formation, surface roughness, and wettability for MPVDF‐sized CF. In addition, the flexural strength and modulus were also improved by 47% and 74%, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Interfacial studies on the ozone and air‐oxidation‐modified carbon fiber reinforced PEEK composites

In this work, ozone modification method and air‐oxidationwere used for the surface treatment of polyacrylonitrile(PAN)‐based carbon fiber. The surface characteristics of carbon fibers were characterized by XPS. The interfacial properties of carbon fiber‐reinforced (polyetheretherketone) PEEK (CF/PEEK) composites were investigated by means of the single fiber pull‐out tests. As a result, it was found that IFSS (interfacial shear strength) values of the composites with ozone‐treated carbon fiber are increased by 60% compared to that without treatment. XPS results show that ozone treatment increases the amount of carboxyl groups on carbon fiber surface, thus the interfacial adhesion between carbon fiber and PEEK matrix is effectively promoted. The effect of surface treatment of carbon fibers on the tribological properties of CF/PEEKcomposites was comparativelyinvestigated. Experimental results revealed that surface treatment can effectively improve the interfacial adhesion between carbon fiber and PEEK matrix. Thus the wear resistance was significantly improved. Copyright © 2009 John Wiley & Sons, Ltd.     

Influence of surface properties of graphene oxide/carbon fiber hybrid fiber by oxidative treatments combined with electrophoretic deposition

An effective way to prepare graphene oxide/carbon fiber hybrid fiber was proposed by the treatment with hydrogen peroxide and concentrated nitric acid combined with electrophoretic deposition process. Surface functional group, surface roughness, and surface morphologies of carbon fibers were examined by Fourier transform infrared spectrometer, atomic force microscopy, and scanning electron microscopy. Results showed that a uniform and thick graphene oxide films were constructed on the surface of carbon fiber. Deposition density increased by introduction of pretreatment of the carbon fiber in the electrophoretic deposition process has been shown as a possible method. Dynamic contact angle analysis results indicated that the deposition of graphene oxide significantly improved surface free energy of carbon fiber by increasing surface area and polar groups. The introduction of graphene oxide in the carbon fiber‐reinforced epoxy composites results in a 55.6% enhancement in the interfacial shear strength and confirms the remarkable improvement in the interfacial adhesion strength of the composites, and the fracture mechanism was also analyzed. Copyright © 2016 John Wiley & Sons, Ltd.     

Improvement of interfacial adhesion for plasma‐treated aramid fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite and fiber surface aging effects

Interfacial adhesion between the fiber and the matrix in a composite is a primary factor for stress transfer from the matrix to the fiber. In this study, oxygen plasma treatment method was applied to modify the fiber surface for improving interfacial adhesion of aramid fiber‐reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite. Composite interfacial adhesion properties were determined by interlaminar shear strength (ILSS) using a short‐beam bending test. The composite interfacial adhesion mechanism was discussed by SEM. The changes of chemical composition and wettability for plasma‐treated fiber surfaces stored in air as long as 10 days were investigated by XPS and dynamic contact angle analysis (DCAA), respectively. Results indicated that oxygen plasma treatment was an effective method for improving interfacial adhesion; plasma‐treated fiber surface suffered aging effects during storage in air. Copyright © 2008 John Wiley & Sons, Ltd.     

Flexural properties of fiber‐reinforced polypropylene composites with and without a transcrystalline layer

The flexural properties of isotactic polypropylene (PP) matrix composites reinforced with 5–30 vol% of unidirectional pitch‐based carbon, polyacrylonitrile (PAN)‐based carbon, e‐glass or aramid fibers were measured using both static and dynamic test methods. Previous research has shown that these pitch‐based carbon and aramid fibers are capable of densely nucleating PP crystals at the fiber surface, leading to the growth of an oriented interphase termed a “transcrystalline layer” (TCL), while the e‐glass and PAN‐based carbon fibers show no nucleating ability. The PP matrices examined included unmodified homopolymers, nucleated homopolymers and PP grafted with maleic anhydride (MA). The composites based on the unmodified PP homopolymers all exhibited poor fiber/matrix adhesion, regardless of fiber type and presence or absence of a TCL. The addition of nucleating agent to the PP matrix had no measurable effect on either the amount of TCL material in pitch‐based carbon‐fiber‐reinforced composites, as measured by wide‐angle X‐ray scattering, WAXS, or the static flexural properties of the composites reinforced with either type of carbon fiber. However, MA grafting reduced the transcrystalline fraction of the matrix in pitch‐based carbon‐fiber‐reinforced composites; at the highest level of MA grafting, the TCL was completely suppressed. In addition, high levels of MA grafting improved the transverse flexural modulus of the composites containing both types of carbon fibers, and reduced the extent of fiber pull‐out, indicating an improvement in fiber/matrix adhesion. Copyright © 1999 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.     

The interfacial feature of thermoplastic polystyrene composite filled with nitric acid oxidized carbon fiber

The quality of interfacial interaction is dictated by the surface chemistry of the carbon fibers and the composition of the matrix. The composition of polystyrene was modified by the addition of maleic anhydride (MAH) grafted polystyrene. The surface properties of the various matrix formulations were characterized by contact angle. Carbon fibers were modified by oxidation in nitric acid. The surface composition of the carbon fibers was characterized. The interaction between modified polystyrene and the carbon fibers was studied by single fiber pull‐out tests. The best adhesion behavior was achieved between polystyrene containing grafted MAH and nitric acid oxidation carbon fibers. The addition of MAH‐grafted polystyrene to the unmodified polystyrene caused the interfacial shear strength (IFSS) to increase. The IFSS of this fiber‐matrix combination allowed for the full utilization of the tensile strength of polystyrene. Copyright © 2009 John Wiley & Sons, Ltd.     

Studies on PAN-based carbon fibers irradiated by Ar+ ion beams

In this work, the effects of Ar+ ion beam irradiation on carbon fibers were studied using tensile and surface analytical techniques. The single-fiber pull-out test was executed in order to characterize the fiber/epoxy matrix interfacial adhesion. The Ar+ ion beam was irradiated using an ion-assisted reaction (IAR) method in reactive gas conditions under an oxygen environment with 1 x 10(16) ions/cm(2) Ar+ ion dose (ID), 6 sccm blown gas flow rate, and different ion beam energy intensities. From the experimental results, both the interfacial shear strength (IFSS) and fracture toughness (Gi) were found to increase with increasing Ar+ ion irradiation intensity. This was probably due to the fact that Ar+ ion beam irradiation on carbon fibers was effective in altering their surface physical chemistry and structural morphology, resulting in improved interfacial adhesion in the fiber/epoxy matrix. The reliability of single-fiber pull-out test data could be improved by statistical analysis using the Weibull distribution, which served to predict the variation of the mechanical interfacial properties in a composite system.     

Interfacial Aspects of Electrodeposited Conductive Fibers/Epoxy Composites using Electro-Micromechanical Technique and Nondestructive Evaluation

Interfacial adhesion and nondestructive behavior of the electrodeposited (ED) carbon fiber reinforced composites were evaluated using the electro-micromechanical technique and acoustic emission (AE). Interfacial shear strength (IFSS) of the ED carbon fiber/epoxy composites was higher than that of the untreated case. This might be expected because of the possible chemical and hydrogen bonding based on an electrically adsorbed polymeric interlayer. Logarithmic electrical resistivity of the untreated single-carbon fiber composite increased suddenly to infinity when the fiber fracture occurred, whereas that of the ED composite increased relatively broadly up to infinity. This may be due to the retarded fracture time as a result of the enhanced IFSS. In single- and 10-carbon fiber composites, the number of AE signals coming from the interlayer failure of the ED carbon fiber composite was much larger than that of the untreated composite. As the number of each first fiber fracture increased in the 10-carbon fiber composite, the electrical resistivity increased stepwise, and the slope of logarithmic electrical resistance increased. In the three-graphite filament composite with a narrow 1 time inter-filament distance, the total numbers of the filament fracture and the IFSS were smaller than those of the wider 5 times case. This might be because the interacting fracture energy caused by a filament break could affect the adjacent filaments. Copyright 2001 Academic Press.     

Improvement of PBO fiber surface and PBO/PPESK composite interface properties with air DBD plasma treatment

The interface of fibrous composites is a key factor to the whole properties of the composites. In this study, the effects of air dielectric barrier discharge (DBD) plasma discharge power density on surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fiber and the interfacial adhesion of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated by several characterization methods, including XPS, SEM, signal fiber tensile strength, interlaminar shear strength, and water absorption. After the air DBD plasma treatment at a power density of 41.4 W/cm³, XPS analysis showed that some polar functional groups were introduced on the PBO fiber surface, especially the emergence of a new oxygen‐containing group (?O–C = O group). SEM observations revealed that the air DBD plasma treatment had a great influence on surface morphologies of the PBO fiber, while the signal fiber tensile strength results showed only a small decline of 5.9% for the plasma‐treated fiber. Meanwhile, interlaminar shear strength value of PBO/PPESK composite was increased to 44.71 MPa by 34.5% and water absorption of the composite decreased from 0.46% for the untreated specimen to 0.27%. The results showed that the air DBD plasma treatment can effectively improve the properties of the PBO fiber surface and the PBO/PPESK composite interface. Results obtained from the above analyses also showed that both the fiber surface and the composite interface performance would be reduced when an undue plasma discharge power density was applied. Copyright © 2011 John Wiley & Sons, Ltd.     

New additives in glass reinforced polyolefins

Poly(butyl acrylate)-g-poly(4-vinylpyridine) graft copolymer and polypropylene modified with maleic anhydride or poly(maleic anhydride) have been prepared and characterised. These products have been tested as coupling agents in glass reinforced polyolefins. The adhesion of glass fiber or glass filler to polyolefin has been evaluated by “Single fiber composite” method or studying the volume variation under tensile strength. The results indicate that all the prepared additives improve the adhesion between olefin matrix and glass filler or fiber.     

Influence of coupling agent chain lengths on interfacial performances of carbon fiber and polyarylacetylene resin composites

The influence of chain lengths on interfacial performances of carbon fiber/polyarylacetylene composites was studied. For this purpose, four coupling agents, methyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane and dodecyltrimethoxysilane, were grafted onto fiber surface to obtain different chain lengths. The resulting carbon fiber surface was characterized by XPS and dynamic contact angle test. Interfacial adhesion in the resulting fiber reinforced polyarylacetylene resin composites was also evaluated by fracture morphology analysis and interfacial shear strength test. It was found that the interfacial adhesion in composites greatly increased with chain lengths on fiber surface. The improvement of interfacial adhesion was attributed to the interaction between the chain of coupling agents on fiber surface and that of polyarylacetylene resin at the interface. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of Silane Coupling Agent and Compatibilizer on Properties of Short Rossells Fiber/Poly(propylene) Composites

Rossells fiber reinforced polypropylene composites were prepared by melt mixing. The fiber content was 20 wt%. Octadecyltrimethoxysilane (OTMS) and maleic anhydride grafted polypropylene (MAPP) were used to improve the adhesion between poly(propylene) (PP) and the fiber. The mechanical, rheological, and morphological properties, and heat distortion temperature (HDT) of the composites were investigated. Tensile strength, impact strength, flexural strength and HDT of MAPP modified PP composites increased with an increase in MAPP content. However, no remarkable effect of MAPP content on the Young's modulus of the composites was found. OTMS resulted in small decreases of tensile strength and Young's modulus, and increase in impact strength. Scanning electron micrographs revealed that MAPP enhanced surface adhesion between the fiber surface and PP matrix.