Evaluation of fiber surfaces treatment and sizing on the shear and transverse tensile strengths of carbon fiber-reinforced thermoset and thermoplastic matrix composites

The mechanical performance of advanced composite materials depends to a large extent on the adhesion between the fiber and matrix. This is especially true for maximizing the strength of unidirectional composites in off-axis directions. The materials of interest in this study were PAN-based carbon fibers (XA and A4) used in combination with a thermoset (EPON 828 epoxy) and a thermoplastic (liquid crystal poymer) matrix. The effect of surface treatment and sizing were evaluated by measuring the short-beam shear (SBS) and transverse flexural (TF) tensile strengths of unidirectional composites. Results indicated that fiber surface treatment improves the shear and trasverse tensile strengths for both thermosetting and thermoplastic matrix/carbon fiber-reinforced unidirectional composites. A small additional improvement in strengths was observed as the result of sizing treated fibers for the epoxy composites. Scanning electron microscope photomicrographs were used to determine the location of composite failure, relative to the fiber-matrix interface. Finally, the epoxy composites SBS and TF strengths appear to be limited to the maximum transeverse tensile strength of the epoxy matrix, while the thermoplastic composite SBS and TF strengths are limited by the LCP matrix shear and transverse tensile strengths, respectively.     

表面处理对玻纤/碳纤增强橡胶基密封复合材料性能的影响

采用压延成张工艺制备碳纤维和玻璃纤维混杂增强非石棉橡胶基密封复合材料(NAFC),以横向抗拉强度作为表征混杂增强橡胶基密封材料中纤维与橡胶界面粘结性能的指标.通过扫描电镜(SEM)对材料横向拉伸试样断口进行形貌分析,及对材料的耐油、耐酸、耐碱性能进行测试,探讨了不同表面处理工艺对纤维与基体界面粘结效果的影响.研究结果表明,对玻璃纤维采用偶联剂KH-550浸渍后涂覆环氧树脂涂层,对碳纤维在空气氧化后涂覆环氧树脂涂层,可有效增强纤维、基体的界面粘结,所制得的混杂纤维增强复合材料具有较好的机械性能和耐介质性能.     

Development and evaluation of surface treatments to enhance the fiber-matrix adhesion in PAN-based carbon fiber/liquid crystal polymer composites. Part I: Coupling agent and amine surface treatments

Several surface treatments, using both commercially available coupling agents and reagents containing multiple amines, were applied to commingled continuous as-received AS4 carbon reinforcing fiber/liquid crystal polymer (LCP) matrix fibers. Unidirectional composites (normally 60 vol% carbon fiber) were prepared from as-received and treated commingled fibers and characterized. To estimate the effect the effect of the treatments on fiber-matrix adhesion, short beam shear (SBS) tests were conducted, the failure surfaces were examined, and spectroscopic studies wee performed. The mean SBS strength of the as-received unidirectional AS4 carbon fiber/LCP matrix composite system was 49 MPa. The best coupling agent and amine treatments yielded increases in composite shear strength of ∼ 10 to 20%, relative to the as-received AS4/LCP system. For the amine treatments, ESCA and FTIR analyses suggested of both the carbon and LCP fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers may have caused the increased adhesion. Moreover, SEM analysis of the failure surfaces of SBS specimens from composites prepared with the treated fibers (both with coupling agents and amines) showed that strong fiber-matrix adhesion was present. That is, failure occurred in the LCP matrix material.     

Stress-Strain and stress relaxation in oxidated short carbon fiber-thermoplastic elastomer composites

Stress-strain and stress relaxation properties are studied in composites consisting of a thermoplastic elastomer butadiene styrene copolymer (SBS) matrix and oxidated carbon fiber. The results obtained from samples at different degrees of oxidation are contrasted with those obtained from SBS filled with commercial carbon fiber. Carbon fiber oxidation with nitric acid gives rise to an increase in functional surface groups, which in turn enhance the capacity in the fiber to interact with the matrix. In the experimental composites, the increase in fiber-matrix interactions translates into proportionally greater strain necessary to reach the yield point, as well as into an increase in stress at the yield point. In addition, at initial strain below the strain at yield point, a slower stress relaxation rate is observed in oxidated fiber composites, as compared with those recorded for the matrix filled with commercial fiber. In the oxidated fiber composites, stress relaxation occurs in three stages, the first two of which may be associated to the fiber-matrix interface. © 1996 John Wiley & Sons, Inc.     

化学气相渗C／SiC材料结构与性能的研究

采用碳布层叠然后用化学气相渗方法制备了Ｃ／ＳｉＣ复合材料，这种材料纤维与基体间的界面是决策材料力学行为的重要因素，带有热解碳作为界面层的Ｃ／ＳｉＣ材料，在断裂进表现出大范围的脱粘，纤维与周围的基体不同发生断裂，有大量的纤维拨出，断口类似毛刷，无界央层材料表现为脆性平面断口，裂纹直接通过纤维和基体向前扩展，没有发生脱粘。     

Effect of Oxidation Heat Treatments on the Mechanical Behavior of a Si-C-O-Fiber-Reinforced Magnesium Aluminosilicate

Oxidized magnesium aluminosilicate composites reinforced with Si-C-O (Nicalon) fiber have been found to retain their as-received flexural strength. The elastic moduli of the oxidized composites exhibited an increase for samples oxidized at 1000°C and a decrease at higher temperatures. Densification of the matrix may increase the elastic modulus of composites oxidized at 1000°C, whereas cracks in the matrix and at the fiber-matrix interfaces may be responsible for the low elastic moduli of composites oxidized at higher temperatures. The interfacial friction stresses were high at or near the edges and low in the interior of the oxidized samples. As a result, the oxidized composites failed by fiber fracture on the surface, followed by delamination and fiber pullout in the interior.     

Poly(glycolic acid) fiber-reinforced bioabsorbable composites with improved interfacial properties

Bioabsorbable composites, designed for use as rigid tissue scaffolds, were fabricated by reinforcing free radically cured poly(D,L-lactide) fumarate matrices with absorbable poly(glycolic acid) fibers. To investigate the benefits of an improved fiber/matrix interphase, fiber pretreatments were employed including surface-etching by exposure to mild acidic conditions and incorporation of 3-methacryloxypropyltrimethoxysilane as a coupling agent. SEM of composite fracture surfaces showed that fiber pretreatment yielded improved wetting and encapsulation of the fibers by the matrix resin. The composites fabricated with poly(glycolic acid) fibers which were acid-etched and pretreated with the coupling agent showed an average 41% increase in tensile strength; a representative sample displayed an increase from 73.9 MPa to 105.5 MPa, compared to the composite made from untreated fibers.     

The Effect of Nitric Acid Oxidization Treatment on the Interface of Carbon Fiber-Reinforced Thermoplastic Polystyrene Composite

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 characterised 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 to increase. The apparent interfacial shear strength of this fiber-matrix combination allowed for the utilisation of 100% of the yield tensile strength of polystyrene.     

Polyethylene fibers-polyethylene matrix composites: Preparation and physical properties

Drawing on the difference in melting points of UHMPE fiber (150°C) and HDPE matrix (130°C), single-polymer composites were fabricated under various processing conditions. Because of the chemical similarity of the composite components, good bonding at the fiber-matrix interface could be expected. The matrix, the fiber, and unidirectional composite laminae were studied using TMA and DSC analyses, a hot-stage crystallization unit attached to a polarizing microscope, and an universal tensile testing machine. The TMA showed negative thermal expansion of the fiber over the complete temperature range of the experiment. Three regimes of contraction according to the values of the thermal expansion coefficient were detected. DSC analyses of either the fiber or the composite specimens did not show any appreciable changes after various thermal treatments. They also showed no evidence of fiber relaxation during manufacture, probably because of the pressure-related transverse constraint. The tensile strength and modulus values of the composite appeared to be fairly high and close to those reported for other composites reinforced with polyethylene (PE) fibers. An apparent maximum on the temperature dependencies of tensile properties was observed. A study of the matrix microstructure did not give any proof of transcrystalline growth at the fiber-matrix interface even for chemical or plasma surface-treated fibers. © 1993 John Wiley & Sons, Inc.     

Ionic interphase of glass fiber/polyamide 6,6 composites

Interfacial polymerization to polyamide 6, 6 followed by introduction of ionic groups was performed on the surface of short glass fibers. The ionic interphase-modified fibers were used with poly(ethylene-co-methacrylic acid) (DuPont Surlyn) to prepare composites with specific fiber-matrix interactions. Fiber treatment increased composite tensile and bending properties. An increase in the average fiber length was observed, which was attributed to a decrease in the fiber attrition during mixing. The effect of increasing temperature on the composite mechanical properties was studied. Different behavior was observed before and after the glass transition temperature, T_g, of the matrix. The dynamic mechanical measurements showed an increase in the T_g of the matrix after the treatments, which is attributed to a decrease in chain mobility at the interface resulting from increased interactions of the treated fiber surface with the polymer. Scanning electron microscopy of fractured composites after tensile tests revealed a smooth fiber surface with no polymer at the surface for the untreated composites. Adhered polymer was clearly observed on the surface of treated fibers, indicating better fiber wetting by the matrix. This improved adhesion was attributed to the grafted nylon molecules at the glass fiber surface.     

Surface modification of ultra-high molecular weight polyethylene fibers by γ-radiation-induced grafting

A technique for grafting acrylic polymers on the surface of ultra-high molecular weight polyethylene (UHMWPE) fibers utilizing ⁶⁰Co gamma radiation at low dose rates and low total dose has been developed. Unlike some of the more prevalent surface modification schemes, this technique achieves surface grafting with complete retention of the exceptional UHMWPE fiber mechanical properties. In particular, poly(butyl acrylate) and poly(cyclohexyl methacrylate) were successfully grafted onto UHMWPE fibers with no loss in tensile properties. The surface and tensile properties of the fibers were evaluated using Fourier transform infrared/photoacoustic spectroscopy (FTIR/PAS), X-ray photoelectron spectroscopy (XPS), and tensile tests. The reinforcement efficiency of untreated, polymer-grafted, and plasma-treated UHMWPE fibers in polystyrene and a poly(styrene-co-butyl acrylate-co-cyclohexyl methacrylate) statistical terpolymer was characterized using mechanical tensile tests. The thermoplastic matrix composites were prepared with 4 wt% discontinuous (10 mm), randomly distributed UHMWPE fibers. An approximate 30% increase in composite strength and modulus was observed for poly(cyclohexyl methacrylate)-grafted fibers in the terpolymer and polystyrene matrices. A comparable improvement was realized with the plasma-treated fibers. On the other hand, poly(butyl acrylate) grafts induced void formation, i.e. energy dissipation through plastic deformation and volume expansion at the fiber/matrix interface in terpolymer composites. The latter resulted in a 75% increase in the elongation to failure. The effect of polymer grafts on fiber/matrix adhesion is discussed in terms of the graft and matrix chain interactions and solubility, graft chain mobility, and fracture surface characteristics as determined by scanning electron microscopy (SEM).     

Mechanical and microwave dielectric properties of SiCf/SiC composites with BN interphase prepared by dip-coating process

The BN interphase of SiC fiber-reinforced SiC matrix (SiCf/SiC) composites was fabricated by dip-coating process with boric acid and urea as precursor. The results show that the tensile strength of SiC fiber decreases about 30% after BN coating treatment, but the BN coating has little influence on the electrical resistivity of SiC fiber. Compared with the as-received SiCf/SiC composites, the SiCf/SiC composites with BN interphase exhibit a toughened fracture behavior, and the flexural strength is about 2 times that of the as-received SiCf/SiC composites. From the microstructural analysis, it can be confirmed that the BN interphase plays a key part in weakening interfacial bonding, which can improve the mechanical properties of SiCf/SiC composites remarkably. Owing to the close dielectric properties between SiC and BN, the complex permittivity of SiCf/SiC composites with and without the BN interphase is similar.     

Effect of Interfacial Shear Strength on Crack-Fiber Interaction Behavior in Ceramic Matrix Composites

Zircon matrix composites uniaxially reinforced with SiC fibers were fabricated with different interfacial properties by changing the fiber coatings. The phenomenon of crack interaction with fibers and/or fiber coatings and its dependence on the interfacial properties were studied using a microindentation technique. The influence of the fiber orientation relative to the crack extension direction on the crack-fiber interaction was also investigated. Crack deflection was observed at the fiber-matrix interface in composites having low interfacial shear strength, and the crack deflection was mostly single-sided, but double-sided deflection was also observed. Crack penetration into the fiber occurred in composites with high values of the interfacial shear strength. These observations were in general agreement with the theoretical predictions of the crack deflection behavior based on the bimaterial interfaces in ceramic composites, but additional observations were made on crack deflection at multiple fiber-matrix interfaces.     

Banana fiber reinforced low-density polyethylene composites: effect of chemical treatment and compatibilizer addition

In this study, an attempt has been made to utilize banana fiber (a natural fiber from agricultural waste) as reinforcement for low-density polyethylene (LDPE) to develop environmental friendly composite materials. LDPE/banana fiber composites were fabricated at different fiber loadings (10, 15, 20, 25, and 30 wt %) using compression molding technique. The composite with the composition of 25 wt % banana fiber was observed to be optimum on the basis of biodegradability and mechanical properties. Further, the effect of banana fiber surface treatment (alkali and acrylic acid) on the mechanical properties, morphology and water absorption behavior of the LDPE/banana fiber composites in the absence and presence of compatibilizer (maleic anhydride grafted LDPE, MA-g-LDPE) was comparatively studied. The alkali and acrylic acid treatment of the banana fibers led to enhanced mechanical properties and water resistance property of the composites, and these properties got further improved by the addition of the compatibilizer. The addition of compatibilizer to the acrylic acid treated banana fiber composites showed the most effective improvement in the flexural and impact strength and also, exhibited a reduction in the water absorption capacity. However, the tensile strength of the compatibilized composites with treated fibers resulted in slightly lower values than those with untreated fibers, because of the degradation of fibers by chemical attack as was evidenced by scanning electron microscopy (SEM) micrographs. SEM studies carried out on the tensile fractured surface of the specimens showed improved fiber-matrix interaction on the addition of compatibilizer.     

Short sisal fiber reinforced styrene-butadiene rubber composites

Styrene-butadiene rubber (SBR) composites were prepared by incorporating short sisal fibers of different lengths and concentrations into the SBR matrix in a mixing mill according to a base formulation. The curing characteristics of the mixes were studied and the samples were vulcanized at 150°C. The properties of the vulcanizates such as stress-strain behavior, tensile strength, modulus, shore-A hardness, and resilience were studied. Both the cured and uncured properties showed a remarkable anisotropy. It has been found that aspect ratio in the range of 20–60 is effective for sufficient reinforcement. The mechanical properties were found to increase along and across the grain direction with the addition of fibers. The effects of fiber length, orientation, loading, type of bonding agent, and fiber-matrix interaction on the properties of the composites were evaluated. The extent of fiber orientation was estimated from green strength measurements. The adhesion between the fiber and the rubber was enhanced by the addition of a dry bonding system consisting of resorcinol and hexamethylene tetramine. The bonding agent provided shorter curing time and enhanced mechanical properties. The tensile fracture surfaces of the samples have been examined by scanning electron microscopy (SEM) to analyze the fiber surface morphology, orientation, fiber pull-out, and fiber-matrix interfacial adhesion. Finally, anisotropic swelling studies were carried out to analyze the fiber-matrix interaction and fiber orientation. © 1995 John Wiley & Sons, Inc.     

Plasma surface modification of carbon fibers: a review

The properties of the fiber/matrix interface in carbon fiber-reinforced composites play a dominant role in governing the overall performance of the composite materials. Understanding the surface characteristics of carbon fibers is a requirement for optimizing the fiber-matrix interfacial bond and for modifying fiber surfaces properly. Therefore, a variety of techniques for the surface treatment of carbon fibers have been developed to improve fiber-matrix adhesion as well as to enhance the processability and handling of these fibers. Many research groups have studied the effects of plasma treatments, correlating changes in surface chemistry with the interfacial shear strength. This article reviews the recent developments relative to the plasma surface modification of carbon fibers.     

Mechanical properties and morphology of polypropylene composites. III. Short glass fiber reinforced elastomer modified polypropylene

The impact strength and rigidity of polypropylene composites can be significantly improved by application of short glass fibers instead of mineral fillers in elastomer-modified polypropylene. The properties of such composites are strongly dependent on the adhesive forces at the fiber-matrix interface. Poor adhesion results in interfacial fracture solely by fiber-matrix debonding, as evidenced by scanning electron microscopy on the fracture surfaces. This is accompanied by relatively low impact strengths. By contrast, increased adhesion leads to fracture not only by fiber-matrix debonding, but also by crack propagation through the elastomeric phase at the fiber surface. This mechanism is thought to be responsible for a remarkable increase of the impact strength. Appropriate compositions of polypropylene, glass fiber, and elastomer resulted in composite properties similar to, or even better than, those of a typical acrylonitrile-butadiene-styrene copolymer. The lengths of the fibers recovered from the test specimens were somewhat smaller than the critical fiber lengths as calculated by simple shear lag theory. The properties of the present composites should thus be regarded as minima, rather than as potential maxima. This suggests that current composites may be suitable for engineering applications.     

New hybrid method for simultaneous improvement of tensile and impact properties of carbon fiber reinforced composites

For weight savings of automobiles to improve fuel efficiency, tensile and impact strengths of carbon fiber reinforced composites (CFRC) are important properties required for substitution of metallic or ceramic automotive parts by CFRC parts. Effect of surface treatments of carbon fiber (CF) such as plasma, nitric acid, and liquid nitrogen treatments on interfacial bonding and mechanical properties of CF reinforced thermoplastic composites was investigated and nitric acid treatment was the best method to improve the interfacial affinity between the used CF and thermoplastic polymer matrix since the treatment induced acidic functional groups on the surface and increased surface roughness simultaneously. A new hybrid fabrication method was suggested by applying a bi-component two-layer structure to the film insert molding to improve tensile and impact strengths of CFRC simultaneously. Compared with tensile and impact strengths of the base polymer, those of the new hybrid composites filled with rubber particles and CF were improved by about 41.3% and 105.7%, respectively. In particular, tensile and impact strengths of the composite specimen prepared by the hybrid fabrication method were improved by about 15.0% and 36.0%, respectively when compared with those of the composite specimen prepared by the conventional melt mixing.     

Interfacial properties of kevlar-49 fiber-reinforced thermoplastics

A single-filament pull-out test was used to study adhesion of Kevlar-49 fibers to thermoplastic polymers. The test involved pulling a partially embedded fiber out of a polymer film. Kevlar-49 fibers with three different surface treatments were used with five thermoplastic materials. The test resulted in the measurement of two properties, an interfacial bond strength and a frictional shear strength. The interfacial bond strength is an essential factor in determining the critical aspect ratio of discontinuous fibers in a composite. The frictional shear strength was found to correlate with the tensile strength of discontinuous fiber composites which fail by fiber pull-out. Scanning electron microscopy was used to examine the fiber pull-out specimens after testing. Observations of the fiber showed that the failure mode at the fiber–matrix interface was complex. The predominant failure mode was fracture at the interface (or in some weak boundary layer). In some cases, cohesive failure of the fiber surface was observed, with the result that strips of material were torn from the fiber surface.     

Damage tolerant oxide/oxide fiber laminate composites

Oxide-fiber/oxide-matrix composites were developed using non-infiltrated woven fiber layers between matrix-infiltrated fiber layers in order to achieve damage tolerant behavior. A fiber interface coating was not used. This technique enables damage tolerance in materials with strong fiber-matrix bonding and under oxidizing conditions. Fabrication of composites was carried out through a slurry infiltration technique. Slurries for fiber (Nextel™ 720, 3M) infiltration were prepared using a submicron α-Al₂O₃ powder coated with an amorphous SiO₂-layer through a sol–gel process. Hot-pressing was used to densify and bond the laminate layers together, followed by pressureless heat-treatment to allow mullite to form. Room temperature three-point bending tests were performed on as-received samples and on samples which underwent long-term annealing at high temperatures (1200–1300°C) in air. Subsequent examination revealed that due to the lack of a fiber interface coating, matrix-infiltrated fiber layers behaved in a quasi-monolithic manner with little or no crack deflection. Layers of non-infiltrated fibers, however, provided damage tolerance by deflecting cracks in the plane of the laminate and by serving as a mechanical bond between matrix-infiltrated layers. The laminate composites demonstrate reasonable room-temperature fracture strength both in the as-received state (88 MPa) and after exposure to 1300°C air for 200 h (72 MPa) along with extensive fracture deflection through the layers of non-infiltrated fiber. Composite properties, specifically fracture strength and damage tolerance, can be tailored by varying lay-up and processing parameters such as fiber-matrix ratio and type of fiber weave.