Investigation of the nanoscale mechanical properties of carbon fiber/epoxy resin interphase. I. analysis of fiber‐stiffening effect during the nanoindentation process based on numerical simulation

The interphase in fiber reinforced polymer composites is a narrow region around the fiber with the thickness in nanoscale, and its properties have a significant effect on the composite mechanical properties. Nanoindentation method was widely accepted for the measurement of the interphase properites. Different from the homogenous material, the modulus diffence between fiber and matrix is very obvious, it is difficult to get the intrinsic properties of the interphase just depending on the experimental data due to the fiber‐stiffening effect. A numerical method is developed to simulate the nanoindentation process, to understand the fiber‐stiffening effect during the nanoindentation process in the carbon fiber/epoxy composites. The predicted results reveal that the fiber impacts the indentation response in the vicinity region of the fiber. When the indent contacts the fiber, there will be a mutation in the load–displacement curve, and the fiber‐stiffening effect is obvious, which is less affected by the thickness and modulus of the interphase and the resin matrix modulus. If the interphase thickness is smaller than the distance of indent contacting the fiber, it is nearly impossible to get the intrinsic modulus of the interphase due to the effect of fiber. On the other hand, if the interphase thickness is larger than that, in the near region about 100 nm away the indent contacting the fiber, the indentation response can reflect the difference of the interphase modulus. The gradient of the curve, that is, the indentation force varying with the distance from the fiber surface, decreases with the increase in the interphase modulus. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

A kinetics model for interphase formation in thermosetting matrix composites

During the cure of thermosetting polymer composites, the presence of reinforcing fibers significantly alters the resin composition in the vicinity of the fiber surface via several microscale processes, forming an interphase region with different chemical and physical properties from the bulk resin. The interphase composition is an important parameter that determines the micromechanical properties of the composite. Interphase development during processing is a result of the mass‐transport processes of adsorption, desorption, and diffusion near the fiber surface, which are accompanied by simultaneous cure reactions between the resin components. Due to complexities of the molecular‐level mechanisms near the fiber surface, few studies have been carried out on the prediction of the interphase evolution as function of the process parameters. To address this void, a kinetics model was developed in this study to describe the coupled mass‐transfer and reaction processes leading to interphase formation. The parameters of the model were determined for an aluminum fiber/diglycidyl ether of bisphenol‐A/bis(p‐aminocyclohexyl)methane resin system from available experimental data in the literature. Parametric studies are presented to show the effects of different governing mechanisms on the formation of the interphase region for a general fiber–resin system. The interphase structure obtained from the model may be used as input data for the prediction of the overall composite properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3220–3236, 2003     

Nanoscale characterization of interphase properties in maleated polypropylene‐treated natural fiber‐reinforced polymer composites

Contact resonance force microscopy has been used to evaluate the effect of maleated polypropylene (MAPP) concentration on interphase thickness as well as the spatial distribution of mechanical properties within the interphase of cellulose fiber‐reinforced polypropylene composites. The average interphase thickness values ranged from 25 nm to 104 nm for different concentrations of MAPP. The interphase region showed a gradient in the elastic modulus, with a gradual decrease in modulus from fiber to matrix. The interphase region in the specimen containing 0% MAPP showed a narrow interphase with steep gradient in modulus from fiber to matrix, whereas the use of MAPP significantly increased the interphase thickness which resulted in a more gradual change in modulus from fiber to matrix. POLYM. ENG. SCI., 2013. © Society of Plastics Engineers     

Effect of an epoxy‐based bonding agent on the cure characteristics and mechanical properties of short‐nylon‐fiber‐reinforced acrylonitrile–butadiene rubber composites

The cure characteristics and mechanical properties of short‐nylon‐fiber‐reinforced acrylonitrile–butadiene rubber composites with and without an epoxy resin as a bonding agent were studied. The epoxy resin was a good interfacial‐bonding agent for this composite system. The minimum torque showed a marginal increase with the resin concentration. The maximum–minimum torque showed only a marginal change with the resin. The scorch time decreased with the fiber concentration and resin content. The tensile strength and abrasion resistance were improved and the tear resistance and resilience were reduced with the resin concentration. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 532–539, 2006     

Micromechanical analysis of long fiber‐reinforced composites with nanoparticle incorporation into the interphase region

The influence of the distribution type, Young's modulus, and volume fraction of the nanoparticles within the interphase region on the mechanical behavior of long fiber‐reinforced composites with epoxy resin matrix under transverse tensile loading is investigated in this article. An infinite material containing unidirectional long fiber and periodic distribution of elastic, spherical nanoparticles was modeled using a unit cell approach. A stiffness degradation technique has been used to simulate the damage and crack progress of the matrix subjected to mechanical loading. A series of computational experiments performed to study the influence of the nanoparticle indicate that the mechanical properties, nanoparticle‐fiber distance, and volume fraction of nanoparticle have a significant effect on both the stiffness and strength properties of these composite materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41573.     

Characterizing elastic properties of carbon nanotube‐based composites by using an equivalent fiber

Effective elastic properties for carbon nanotube (CNT)‐reinforced composites are obtained through a variety of micromechanics techniques. An embedded CNT in a polymer matrix and its surrounding interphase is replaced with an equivalent fiber for predicting the mechanical properties of the CNT/polymer composite. Formulas to extract the effective material constants from solutions for the representative volume element under three loading cases are derived based on the elasticity theory. The effects of an interphase layer between the nanotubes and the polymer matrix as result of effective interphase layer are also investigated. Furthermore, this research is aimed at characterizing the elastic properties of CNTs‐reinforced composites using Eshelby–Mori–Tanaka approach based on an equivalent fiber. The variations of mechanical properties with tube radius, interphase thickness, and degree of aggregation are investigated. It is shown that the presence of aggregates has stronger impact than the interphase thickness on the effective modulus of the composite. This is because aggregates have significantly lower modulus than individual CNTs. POLYM. COMPOS., 2013 © 2013 Society of Plastics Engineers     

Curing characteristics and mechanical properties of alkali‐treated grass‐fiber‐filled natural rubber composites and effects of bonding agent

To improve adhesion between fiber and matrix, natural rubber was reinforced with a special type of alkali‐treated grass fiber (Cyperus Tegetum Rox b). The cure characteristics and mechanical properties of grass‐fiber‐filled natural rubber composites with different mesh sizes were studied with various fiber loadings. Increasing the amount of fibers resulted in the composites having reduced tensile strength but increased modulus. The better mechanical properties of the 400‐mesh grass‐fiber‐filled natural rubber composite showed that the rubber/fiber interface was improved by the addition of resorcinol formaldehyde latex (RFL) as bonding agent for this particular formulation. The optimum cure time decreased with increases in fiber loading, but there was no appreciable change in scorch time. Although the optimum cure time of vulcanizates having RFL‐treated fibers was higher than that of the other vulcanizates, it decreased with fiber loading in the presence of RFL as the bonding agent. But this value was lower than that of the rubber composite without RFL. Investigation of equilibrium swelling in a hydrocarbon solvent was also carried out. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3151–3160, 2006     

Stress‐initiated void formation during cure of a three‐dimensionally constrained thermoset resin

During cure of epoxy resins, polymerization induces an increase in mechanical properties, which is accompanied by a volumetric shrinkage. When the resin is cured in a constrained mold to which it adheres, tensile stresses will hence develop, which may exceed the stremgth of the resin at a given curing stage. Voids will then form. The origin and governing parameters of void formation are studied using an epoxy resin cured in a three‐dimensionally constrained glass mold following isothermal cure cycles. Two types of voids are shown to appear during cure, one early in the process and a second around the gelation point. A viscoelastic analysis of the material stress state over the whole range of cure is performed. Both the viscoelastic modulus obtained from a time‐cure‐temperature superposition and the volumetric shrinkage, which was continuously measured by density change, are taken into account. A value for the critical internal stress at void initiation is thus proposed. This criterion can be used to provide guidelines for tailoring the material properties toward an increase of the critical stress for void initiation. Also, since during theprocessing of composite materials, cases may arise where the resin cures within the interstices left between consolidated fibres that do not move, this critical stress failure criterion can be of use in the eastablishment of a process window providing guidelines for the production of void free composites.     

Influence of epoxy sizing of carbon‐fiber on the properties of carbon fiber/cyanate ester composites

The high modulus carbon fiber (M40J) sized by epoxy resin E51 and E20 reinforced bisphenol A dicyanate (2,2′‐bis(4‐cyanatophenyl) isopropylidene resin composite was prepared in order to investigate the influence of epoxy sizing of the fiber on the properties of the composite. Differential scanning calorimetry (DSC) and fourier transforms infrared (FTIR) analysis showed that epoxy resin have catalytic effect on cure reaction of cyanate ester. Mechanical properties of the composite revealed that M40J fiber sized by epoxy resin could improve the flexural strength and interlaminar shear strength of M40J/bisphenol A dicyanate composites. The micro‐morphology of the composite fractures was studied by means of scanning electron microscopy (SEM). Reduced flaws were observed in the M40J‐bisphenol A dicyanate interface when the sized fiber was used. Water absorption of the composites was also investigated. It was found that the water absorption descended at the initial boiling stage (12 h). POLYM. COMPOS, 27: 591–598, 2006. © 2006 Society of Plastics Engineers     

Use of an epoxidized oil‐based resin as matrix in vegetable fibers‐reinforced composites

Hemp fibers were used as natural reinforcement in composites of thermosetting vegetal oil based resin. Boards with fibers content from 0 to 65 vol % were produced by hot pressing. The mechanical properties were investigated with flexural testing. The effect of effect has been observed on both modulus and strength, indicating a good fiber–matrix interfacial adhesion, which was confirmed by means of scanning electron microscopy observations. Dynamic mechanical analysis also showed an important reinforcement effect in the polymer rubbery region, where at 180°C the storage modulus increased from 17 MPa for the neat resin to 850 MPa for 65 vol % fiber content composites. It also revealed an glass transition temperature decrease when fiber amount in the composite increased. Additional experiments based on differential scanning calorimetry show a weakly accelerated cure when fibers content increases, which usually lead to a lower T_g. But, this phenomenon alone cannot explain the observed T_g change. Contact angle on hemp evolution with time for the resin components show that anhydride is totally absorbed after a few seconds, whereas contact angle of epoxydized oil decreases slowly. This indicates probably a preferential anhydride absorption that leads to a lower amount of anhydride in the matrix and as a consequence to a reduced T_g. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4037–4043, 2006     

Monitoring the reaction progress of a high‐performance phenylethynyl‐terminated poly(etherlmide). Part II: Advancement of glass transition temperature

The cure schedule for carbon fiber‐reinforced, phenylethynyl‐terminated Ultem™ (GE Plastics) composites was studied in an attempt to optimize the resultant glass transition temperature, T_g. Reaction progress and possible matrix degradation were monitored via the T_g. On the basis of previous research, matrix degradation induced T_g reduction was expected for increases in cure time or temperature beyond approximately 70 minutes at 350°C. Using the central composite design (CCD) of experiment technique, composite panels, neat resin, and polymer powder‐coated tow (towpreg) were cured following various cure schedules to allow for the measurement of the glass transition temperatures resulting fronm cure time and temperature variations. The towpreg and neat resin specimens were cured in a differential scanning calorimeter. The glass transition temperatures of all specimens were measured via differential scanning calorimetry; the composite glass transition temperatures were also measured with dynamic mechanical thermal analysis. The composite panels and towpreg specimens showed similar trends in T_g response to cure schedule variations. Composite and towpreg glass transition temperatures increased to a plateau with increasing cure time and temperature, whereas, the neat resin showed an optimal T_g followed by T_g reduction with increasing cure time and temperature. The optimal neat resin T_g occurred within a cure time and temperature significantly below that required to maximize the composite and towpreg glass transition temperatures.     

Effect of initial cure time on toughness of geopolymer matrix composites

The toughness of geopolymer matrix composites (GMC) has been identified as a limiting factor to their use in structural applications. Advanced ceramic matrix composites (CMC), which also are limited by brittle behavior, have shown gains in toughness through careful tailoring of the interface between fiber and matrix. This can create various crack dissipating mechanisms and prevent premature composite failure. Such interface modification has already been applied to a fiber reinforced geopolymer and while the resulting composite showed a reduction in brittle behavior, the modified interface produced an unacceptable loss in modulus without any other well-defined quantitative gains. Information gathered from other studies suggests the large decrease in modulus observed in the GMCs with the weakened interface may have been the result of poor matrix properties stemming from an inadequate cure. Therefore, this current study explores the effects of initial cure time on composite performance by measuring the mechanical properties GMCs with a modified interface. GMCs containing unidirectional Nextel 610 fiber were cured under two different sets of process conditions to better understand the influence of matrix properties. Additionally, specimens consisted of cleaned and carbon coated fiber surfaces, in an attempt to evaluate extremes of interfacial strength. Mechanical properties were then evaluated for comparison to determine if improved geopolymer matrix properties would allow a weakened interface to yield performance gains more in keeping with expectations based on CMC's. The results of the study indicate that specimens with carbon coating benefited from the longer initial cure time. The average increase in flexural modulus and strength over samples with one hour initial cure time was ~65% and ~170% respectively. Stress-strain behavior of the carbon-coated specimens with an extended cure time also indicated a greater degree of damage tolerance as compared to those without interphase.     

Characterization of the interphase in carbon fiber/polymer composites using a nanoscale dynamic mechanical imaging technique

The interphase of fiber reinforced polymer composites is a narrow region around the fiber, and the mechanical performance of a composite strongly depends on the properties of the interphase. The interphase of carbon fiber reinforced polymer composites (CFRPs) is difficult to quantitatively characterize because of its nanometer dimension. To solve this problem, we present a nanomechanical imaging technique for mapping the dynamic mechanical property around the interphase region in CFRPs, and for providing nanoscale information of the interfacial dimension. The experimental results show that this method can determine the width and topography of the interphase with nanoscale lateral resolution, based on the storage modulus profile on the cross section of the composite. The average interphase thicknesses of a T300 carbon fiber/epoxy resin composite and a T700 carbon fiber/bismaleimide resin composite are 118 nm and 163 nm, respectively, and the size of interphase is uneven in width and “river-like”, which is consistent with the surface topography of the carbon fibers. Furthermore, the effect of water-aging on the interphase of the T300/epoxy composite was analyzed using the in situ imaging technique. An increase in the interphase width and interface debonding were revealed, implying a degradation in the interphase region.     

碳纤维湿法缠绕用环氧树脂基体研究

以TDE-85树脂和AFG-90树脂为主体树脂,混合芳香胺为固化剂,研究了一种适合于碳纤维复合材料湿法缠绕成型的树脂配方。结果表明,该树脂的黏度低(＜550 mPa·s)、适用期长,其浇铸体具有优异的力学性能,其拉伸强度为107 MPa,拉伸模量为4．09 GPa,弯曲强度为161 MPa,弯曲模量为3．88 GPa,断裂伸长率超过6%。用其制备的T-700碳纤维缠绕复合材料界面粘接好,NOL环层间剪切强度达到66．8 MPa,拉伸强度达到2．44 GPa。     

The effect of fiber concentration on mechanical and thermal properties of fiber‐reinforced polypropylene composites

A novel composite material consisting of polypropylene (PP) fibers in a random poly(propylene‐co‐ethylene) (PPE) matrix was prepared and its properties were evaluated. The thermal and mechanical properties of PP–PPE composites were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC) with reference to the fiber concentration. Although, by increasing PP fiber concentration in PPE, no significant difference was found in melting and crystallization temperatures of the PPE, the storage, and the tensile and flexural modulus of the composites increased linearly with fiber concentrations up to 50%, 1.5, 1.0, 1.3 GPa, respectively, which was approximately four times higher than that for the pure PPE. There is a shift in glass transition temperature of the composite with increasing fiber concentration in the composite and the damping peak became flatter, which indicates the effectiveness of fiber–matrix interaction. A higher concentration of long fibers (>50% w/w) resulted in fiber packing problems, difficulty in dispersion, and an increase in void content, which led to a reduction in modulus. Cox–Krenchel and Haplin–Tsai equations were used to predict tensile modulus of random fiber‐reinforced composites. A Cole–Cole analysis was performed to understand the phase behavior of the composites. A master curve was constructed based on time–temperature superposition (TTS) by using data over the temperature range from −50 to 90°C, which allowed for the prediction of very long and short time behavior of the composite. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2260–2272, 2005     

Enhanced microwave‐absorbing property of precursor infiltration and pyrolysis derived SiCf/SiC composites at X band: Role of carbon‐rich interphase

Ceramic matrix composites (CMCs) can be microwave‐absorbent when endowing the composite constituents with proper dielectric properties. In this work, we report a new method to enhance the microwave‐absorbing property of CMCs by in situ fabrication of a carbon‐rich interphase at the fiber/matrix interface. This was achieved in a SiC fiber reinforced SiC matrix (SiCf/SiC) composite fabricated by precursor infiltration and pyrolysis (PIP). We found that as the PIP temperature increased from 800 to 1000°C, the microwave‐absorbing property of the SiCf/SiC composite was significantly enhanced at X band, which also surpassed those of the SiC fiber and monolithic SiC ceramic fabricated at the same temperature. The dominant mechanism was studied by decoupling the effect of individual SiC fibers, SiC matrix, and fiber/matrix interface. The results showed that the SiC fiber and SiC matrix were barely microwave‐absorbent, due to their low dielectric losses. The microwave‐absorbing mechanism was finally ascribed to the fiber/matrix interface, which was carbon‐rich, containing Si and O elements. The interphase showed a conductivity that was superior to that of the fiber and the matrix, and mainly dominated the dielectric property of the overall composite. The results highlight the role of carbon‐rich interphase on the microwave‐absorbing property of CMCs.     

Wood‐fiber‐reinforced poly(lactic acid) composites: Evaluation of the physicomechanical and morphological properties

This article presents the results of a study of the processing and physicomechanical properties of environmentally friendly wood‐fiber‐reinforced poly(lactic acid) composites that were produced with a microcompounding molding system. Wood‐fiber‐reinforced polypropylene composites were also processed under similar conditions and were compared to wood‐fiber‐reinforced poly(lactic acid) composites. The mechanical, thermomechanical, and morphological properties of these composites were studied. In terms of the mechanical properties, the wood‐fiber‐reinforced poly(lactic acid) composites were comparable to conventional polypropylene‐based thermoplastic composites. The mechanical properties of the wood‐fiber‐reinforced poly(lactic acid) composites were significantly higher than those of the virgin resin. The flexural modulus (8.9 GPa) of the wood‐fiber‐reinforced poly(lactic acid) composite (30 wt % fiber) was comparable to that of traditional (i.e., wood‐fiber‐reinforced polypropylene) composites (3.4 GPa). The incorporation of the wood fibers into poly(lactic acid) resulted in a considerable increase in the storage modulus (stiffness) of the resin. The addition of the maleated polypropylene coupling agent improved the mechanical properties of the composites. Microstructure studies using scanning electron microscopy indicated significant interfacial bonding between the matrix and the wood fibers. The specific performance evidenced by the wood‐fiber‐reinforced poly(lactic acid) composites may hint at potential applications in, for example, the automotive and packaging industries. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4856–4869, 2006     

Relationship Between Interphase Composition, Material Properties, and Residual Thermal Stresses in Composite Materials

A methodology for predicting the formation and influence of interphase regions in composite materials is illustrated through an investigation of the relationship of sizing-induced interphase regions to the development of residual thermal stresses in a carbon fiber epoxy-amine composite. Fiber surface and sizing induced concentration gradients in the epoxy-amine system were predicted. Material property data was measured for bulk epoxy-amine systems corresponding to the predicted interphase concentrations and the properties mapped into property profiles in the vicinity of the fiber surface. Micromechanical models were used to predict residual thermal stresses for carbon fiber epoxy-amine composites with these interphase properties. The analyses predict that the thermal stress state is significantly affected by modulus variations in the interphase region. The variations in the properties of the interphase material can be affected through processing conditions and/or material selections.     

Relationship Between Interphase Composition,Material Properties,and Residual Thermal Stresses in Composite Materials

A methodology for predicting the formation and influence of interphase regions in composite materials is illustrated through an investigation of the relationship of sizing-induced interphase regions to the development of residual thermal stresses in a carbon fiber epoxy-amine composite. Fiber surface and sizing induced concentration gradients in the epoxy-amine system were predicted. Material property data was measured for bulk epoxy-amine systems corresponding to the predicted interphase concentrations and the properties mapped into property profiles in the vicinity of the fiber surface. Micromechanical models were used to predict residual thermal stresses for carbon fiber epoxy-amine composites with these interphase properties. The analyses predict that the thermal stress state is significantly affected by modulus variations in the interphase region. The variations in the properties of the interphase material can be affected through processing conditions and/or material selections.