The effect of fiber-matrix stress transfer on the strength of fiber-reinforced composite materials

A model for the mechanism of tensile failure in oriented fiber composites based on random fragmentation of the reinforcing fibers biased by stress concentrations at fracture sites has been developed. Single-fiber composites and composite strands of 34 to 36 volume percent fiber were prepared from an epoxy resin reinforced with Hercules AS4, HMS4, and IM6G carbon fibers. Fiber strength distributions and single-fiber composite fragmentation data were used to calculate theoretical composite tensile strengths, which were then compared with experimental values. The fractures in single-fiber composites were observed in situ under cross-polarized light, and the mechanisms of interfacial failure were discussed.     

The influence of crystallinity on interfacial properties of carbon and SiC two‐fiber/polyetheretherketone (PEEK) composites

The influence of the degree of crystallinity on interfacial properties in carbon and SiC two‐fiber reinforced poly(etheretherketone) (PEEK) composites was investigated by the two‐fiber fragmentation test. This method provides a direct comparison of the same matrix conditions. The tensile strength of the PEEK matrix and the interfacial shear strength (IFSS) of carbon or SiC fiber/PEEK exhibited the maximum values at around 30% crystallinity, and then showed a decline. The tensile modulus increased continuously with an increase in the degree of crystallinity. Spherulite sizes in the PEEK matrix became larger as the cooling time from the crystallization temperature increased. Transcrystallinity of carbon fiber/PEEK was developed easily and more densely than with SiC fiber/PEEK. This might have occurred because the unit cell dimensions of the crystallite in the fiber axis direction on the carbon surface was more suitable for making nucleation sites. The IFSS of carbon fiber/PEEK was significantly higher than that of SiC fiber/PEEK because it formed transcrystallinity of IFSS more favorably.     

The effects of transcrystalline interphase in advanced polymer composites

Surface-induced transcrystallization in fibers has been reported in some advanced polymer composites. It is believed that transcrystalline interphase may affect stress transfer efficiency between the reinforcing fiber and the matrix. In this study, attempts were made to examine the effects of transcrystallinity on composite performance, particularly on fiber-matrix interfacial bond strength, and to investigate possible attributes of transcrystallization. Three polymer resins, poly(etherketoneketone) (PEKK), poly(etheretherketone) (PEEK), and poly(phenylenesulfide) (PPS), and four types of fiber, polyacrylonitrile (PAN)-based AU-4 (untreated AS-4) carbon, pitch-based carbon, poly (p-phenylene terephthalamide) (PPDT) aramid, and E-glass were used. It was found that PPDT aramid and pitch-based carbon fibers induce a transcrystalline interphase in all three polymers because of an epitaxial effect. Under certain conditions, transcrystallization was also observed in PAN-based carbon and E-glass fibers, which may be partially attributed to the thermal conductivity mismatch between the fiber and the matrix. Plasma treatment on fiber surface showed a negligible effect on inducing transcrystallization, whereas solution-coating of PPDT on the fiber surface showed a positive effect. The Microdebonding test, which measures the interfacial bond strength between the fiber and the matrix, consistently showed more than 40% increments for various single filament systems with transcrystalline interphase versus without. However, the effects of transcrystallinity on the interfacial bond strength appeared to decrease as the fiber content increased in composites.     

Fiber/Matrix load transfer in cyanate resin carbon fiber systems

Comparative single fiber fragmentation test measurements are used to charcterize cynate and epoxy resin interface load transfer with high modulus (HMS4) and high strength (AS4) carbon fibers. The HMS4 fiber forms a weak interface with a fiber controlled failure mode, and the AS4 fiber forms a strong interface with the resin properties, apparently determining the level of load transfer. The resin properties examined are critical surface energy for wetting, cure shrinkage, thermal shrinkage, and mechanical modulus and strength. The cynate and epoxy resins display no significant difference in critical surface energy. Cure shrinkage has a negligible effect on load transfer. The compressive force from thermal shrinkage is significant, but the larger Tg to testing temperature range of the cyanate resin is offset by the larger thermal expansion coefficient of the epoxy, resulting in a near equal compressive force for the two resins. There is little difference in modulus between the two resins but a significant difference in shear strength. This difference is reflected in the larger load transfer measurement for the cyanate resin. A comparison of simple one-dimensional elastic and plastic models for the fiber fragmentation experiment resulted in better conformity with the plastic model. This would indicate that interfacial failure occurs by plastic deformation of the resin for the systems of this study.     

Effects of thermal history on mechanical behavior of PEEK and its short-fiber composites

The effect of crystallinity differences induced by mold wall temperature and annealing on mechanical behavior is evaluated for poly(etheretherketone) (PEEK) resin and its composites. The systems investigated were neat PEEK, glass fiber (GF) reinforced PEEK, and carbon fiber (CF) reinforced PEEK. Both composite systems were reinforced with 10, 20, and 30 wt% fiber. The degree of crystallinity (X_c) of PEEK was found to increase by processing at higher mold temperatures, by annealing, and by fiber length reductions, which appears to indicate the ability of short fibers to nucleate the crystallization of PEEK under favorable thermal conditions. Improvements in Young's modulus and strength together with ductility reductions are generally obtained as crystallinity increases in both neat PEEK and its composites. The contribution of crystallinity to mechanical behavior is significant only for neat PEEK and PEEK reinforced by 10% fiber. SEM micrographs reveal that this is due to a change in failure mode. When PEEK is reinforced by carbon fibers or by 20–30% glass fibers, a macroscopic brittle mode of failure is observed irrespective of matrix crystallinity, and mechanical behavior is principally determined by the nature and content of the reinforcing fibers.     

Transcrystallinity in aramid and carbon fiber reinforced nylon 66: determining the lamellar orientation by synchrotron X-ray micro diffraction

This paper presents the structural details of nylon 66 transcrystallinity induced by aramid (kevlar 29, 49 and 149) and carbon (pitch based) fibers, as determined by high spatial resolution X-ray diffraction. Using stepwise scanning, the orientation of the lamellae in the transcrystalline layer was measured as a function of distance from the fiber. The main observation is that this orientation is distinct for each system and almost independent of distance from the fiber. Of particular interest is the bi-layered transcrystallinity formed on a surface treated kevlar 49 fiber, in which the lamellar a^* axis is nearly perpendicular and at an angle of ∼12° to the fiber in the outer and inner layer, respectively. The crystallographic analysis generates grids of oriented lamellae with respect to the fiber axis.     

Effects of sorbed caprolactam on the crystallinity,morphology, and deformation behavior of polyetheretherketone and poly(phenylene sulfide)

Studies on the high temperature sorption of caprolactam by polymer resins and their composites have been conducted. The systems investigated were glass fiber reinforced (GFR) poly(phenylene sulfide) (PPS), polyetheretherketone (PEEK) neat resin, GFR PEEK and carbon fiber reinforced (CFR) PEEK. To measure changes of caprolactam sorption, melting behavior, mechanical properties, and fracture surface morphology were determined. Absorption of caprolactam by the PEEK composites was 30 to 40 percent less than by the neat resin. This is attributed to the fibers, which acted to constrain the matrix and thus limit its swellability. Reductions in melt temperature, percent crystallinity, ultimate tensile strength, and modulus were observed following exposure to the chemical environment. The loss of strength and stiffness was a consequence of the degradation of the matrix/fiber interface by the sorbed caprolactam.     

Evaluation of Fracture Surfaces in Carbon Fiber/Epoxy Composites

We have investigated carbon fiber/resin debonding mechanisms using wetting force scanning to examine the fracture surfaces. The wettability of the site of a resin microdroplet (50-150 μm long) on a fiber after debonding is compared with that of the original fiber surface by scanning along the fiber with an appropriate probe liquid. For an HMS/Epon828 system, debonding seems to involve removal of a layer of carbon fiber, while for an AS4/Epon828 system, there is evidence for adhesive failure as well as cohesive failures in both fiber and resin. These contrasting failure mechanisms are consistent with the morphological structures of the carbon fibers studied.     

Influence of the addition of lubricant on the properties of poly(ether ether ketone) fibers

A high‐temperature lubricant genioplast pellets (GPPS) was used in order to improve the processing behavior of poly(ether ether ketone) (PEEK) resin and high‐performance PEEK fibers were produced by melt‐spinning. The rheological properties of spinning material, morphology, mechanical, and thermal properties of PEEK fibers were characterized by using a polymer capillary rheometer, scanning electron microscopy, single fiber electronic tensile strength tester, wide‐angle X‐ray diffraction and thermal gravimetric analyzer, respectively. The results indicated that the introduction of lubricant GPPS decreased the melting viscosity of PEEK resin and improved spinnability of PEEK resin without sacrificing its thermal properties. The filaments are cylindrical with smooth surface and uniform diameter. The optimized content of GPPS was determined to be 1.0 wt% by balancing the decreased torque and changes of the mechanical properties. The strength and modulus of PEEK fibers were 420 MPa and 3.6 GPa, respectively. This should be due to the improvement in spinnability, followed by the enhancements in the orientation and crystallization of PEEK fibers in the process of drawing and annealing. POLYM. ENG. SCI., 53:2254–2260, 2013. © 2013 Society of Plastics Engineers     

Preparation and characterization of high‐performance poly(ether ether ketone) fibers with improved spinnability based on thermotropic liquid crystalline poly(aryl ether ketone) copolymer

High‐performance poly(ether ether ketone) (PEEK) fibers were prepared by melt‐spinning in the presence of thermotropic liquid crystalline poly(aryl ether ketone) copolymer (FPAEKLCP). The rheological and mechanical properties, birefringence, orientation, and crystallization of the resulting PEEK/FPAEKLCP fibers were characterized by using a melt flow indexer, capillary rheometer, single fiber electronic tensile strength tester, polarized light microscopy (PLM), and wide‐angle X‐ray diffraction (WAXD), respectively. The results indicate that the melt viscosity of PEEK significantly reduced by introducing FPAEKLCP, followed by the improvements in the spinnability and the quality of as‐spun fibers. The tensile properties of PEEK/FPAEKLCP fibers mainly depend on the content of FPAEKLCP, drawing temperature, drawing ratio, and annealing processes. Moreover, the tensile strength and modulus of PEEK/FPAEKLCP fibers are obviously higher than those of neat PEEK fibers under the same processing conditions. This should be attributed to an enhancement in the orientation and crystallization of PEEK compounded with FPAEKLCP. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1406‐1414, 2013     

Effect of SiO2 nanoparticles-decorated SCF on mechanical and tribological properties of cenosphere/SCF/PEEK composites

A silicon oxide (SiO₂) nanoparticles-decorated short carbon fiber (SCF) hybrid (SCF-SiO₂) was designed to improve the weak interfacial bonding between fibers and matrix. Nano-SiO₂ was grafted onto carbon fibers by introducing amino group and epoxy group on the surface of carbon fibers and SiO₂, respectively. The chemical composition of SCF-SiO₂ was analyzed by Fourier transform infrared spectrometer and energy-dispersive spectrometry, the microstructure of SCF-SiO₂ were investigated by scanning electron microscope, and then the hybrid filler was introduced into Poly(ether ether ketone) (PEEK). Due to the strong interfacial interaction between filler and matrix, the mechanical and tribological properties of SCF-SiO₂/PEEK composites were significantly better than SCF/PEEK composites. In order to further improve the tribological properties of the composites, micrometer-sized cenosphere (CS) particles were introduced into the aforementioned system to prepare multicomponent composites. The test results of friction and wear indicate that the CS/SCF-SiO₂/PEEK composites have the optimal tribological properties. Compared with pure PEEK, the friction coefficient of CS/SCF-SiO₂/PEEK composites under 200 N load decreases by 56.4% and the specific wear rate decreases by 87.4%. Meanwhile, the thermal decomposition temperature of CS/SCF-SiO₂/PEEK composites is increased by 40 °C compared to pure PEEK. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48749.     

Improvement of interfacial interactions in CF/PEEK composites by an s-PSF/graphene oxide compound sizing agent

The interfacial interactions of carbon fiber (CF)-reinforced polymer composites is a key factor affecting the overall performance of the material. In this work, we prepared a sulfonated poly(ether sulfone)–graphene oxide mixed sizing agent to modify the interface of CF/PEEK composites and improve the interfacial properties between the PEEK matrix and CF. Results showed that the mechanical and interfacial properties of CF/PEEK composites are improved by the sizing agent. Specifically, the flexural strength, flexural modulus and interlaminar shear strength of the materials reached 847.29 MPa, 63.77 GPa, and 73.17 MPa, respectively. Scanning electron microscopy confirmed markedly improved adhesion between the resin matrix and fibers. This work provides a simple and effective method for the preparation of high-performance CF/PEEK composites, which can improve the performance of composites without degrading the mechanical property of pristine CF.     

Crystallization and fiber/matrix interaction during the molding of PEEK/carbon composites

The objective of this work was to investigate the effects of molding conditions (molding temperature, residence time at melt temperature, and cooling rate) on the crystallization behavior and the fiber/matrix interaction in PEEK/carbon composites made from both prepreg and commingled forms. In order to investigate the crystallization behavior of the PEEK matrix, the molding process was simulated by differential scanning calorimetric analysis, DSC. The results show that the prepreg and commingled systems do not have the same matrix morphology; prepreg tape was found to be at its maximum of crystallinity, whereas the commingled system was found to be only partially crystalline. The results show that processing must be carried out at a temperature sufficiently high to destroy the previous thermal history of the PEEK matrix; this is an essential requirement to produce efficient fiber/matrix adhesion in the commingled fabric system. Optical microscopic observations also suggest that matrix morphology near the fibers is dependent on the melting conditions; a well-defined transcrystalline structure at the interface is observed only when the melt temperature is sufficiently high. However, the high temperature of molding can easily result in degradation of the PEEK matrix such as chain scission and crosslinking reactions. Thermal degradation of the matrix during processing is found to affect the crystallization behavior of the composites, the fiber/matrix adhesion, and the matrix properties. This effect is more important in the case of a commingled system containing sized carbon fibers because the sizing agent decomposes in the molding temperature range of PEEK/carbon composites. This produces a decrease of the matrix crystallinity and an elimination of the nucleating ability of the carbon fibers. A transition between cohesive and adhesive fracture is observed when the cooling rate increases from 30°C/min to 71°C/min for the composite made from the commingled fabric. This critical cooling rate is found to closely correspond to a change in the mechanism of crystallization of the PEEK matrix.     

Compressive Fiber Fragmentation in Carbon/Polypropylene Composites: Effects of Residual Thermal Stresses and Transcrystallinity

The effects of fiber volume fraction and transcrystallinity in single fiber composites, on the phenomenon of compressive fiber fragmentation due to residual thermal stresses, are studied. A concentric cylinder model is used, jointly with experimental data, to predict the Weibull shape parameter of the compressive strength distribution of pitch-based high and medium modulus (HM and MM) carbon fibers, with isotactic polypropylene as the semi-crystalline embedding matrix. A severe effect of the fiber content on the thermal residual stress in the fiber and, thus, on the fiber break density, is predicted and experimentally confirmed. The effect of the presence of isothermally grown polypropylene transcrystalline interlayers (using pitch-based HM carbon fibers as a substrate) on the compressive stresses induced upon subsequent quenching is investigated, both experimentally and theoretically. Cooling rate results are also presented. The thermoelastic constants of the interlayer are predicted to have a severe effect on the residual stresses generated in the fiber, the interphase, and the matrix. There is therefore, a definite need for direct experimental measurements of these constants.     

High performance thermoplastic composites: Study on the mechanical,thermal, and electrical resistivity properties of carbon fiber‐reinforced polyetheretherketone and polyethersulphone

High temperature processing thermoplastic polymers, polyetheretherketone (PEEK) and polyethersulphone (PES), were melt blended with carbon fibers (CFs) to make composites. These composites were investigated for their mechanical, thermal, and electrical properties. Mechanical properties that are expressed in terms of storage modulus, loss, and damping were enhanced with the addition of CFs. Thermal properties were determined by DSC and TGA. These methods help to understand the effects of fiber content and fiber–matrix adhesion in the composites. Composites were also tested for their electrical and thermal conductivity because CFs leave the composites thermally and electrically conductive. CFs enhanced the crystallinity of the PEEK appreciably that in turn influenced thermal conductivity, electrical resistivity, and the stiffness of PEEK/CF (composites of PEEK with CFs). PES/CF (composites of PES with CF) shows a different behavior due to the amorphous nature of PES. The work involves one filler and two different matrices, and so it provides an interesting comparison of how matrix morphology can influence the properties of composites. POLYM. COMPOS. 28:785–796, 2007. © 2007 Society of Plastics Engineers.     

Effects of fibers and nanoparticles reinforcements on the mechanical and biological properties of hybrid composite polyetheretherketone/short carbon fiber/Nano‐SiO2

Polyetheretherketone (PEEK) composites reinforced with short carbon fibers (SCFs) (20 vol%) and nano‐SiO₂ (1, 1.5, and 2 wt%) particles were prepared by incorporating nanoparticles into PEEK/SCF composites using the internal mixer. In the development of biomaterial, both mechanical and biological characteristics must be considered. Thus, the effects of nanoparticles on the mechanical and biological properties of the PEEK/SCF composites were studied. To evaluate the mechanical properties of this biomaterial, nanoindentation method and tensile test were used. Results showed that by increasing the weight percentage of nano‐SiO₂, the elastic modulus, hardness, and tensile energies were increased. In vitro biological evaluations of the samples were done by performing cytotoxicity (3‐[4,5‐dimethylthiazol‐2‐yl]‐2,5‐iphenyltetrazolium bromide assay) and cell adhesion assays. Cell–material interaction with the surface of the composite was examined by scanning electron microscopy (SEM). In all of the tests, osteoblast cells were used. Results of biological tests showed that the samples are biocompatible and they have no toxicity. Also, Adhered cells presented a normal morphology by SEM and many of the cells were observed to be undergoing cell division. POLYM. COMPOS., 34:1960–1968, 2013. © 2013 Society of Plastics Engineers     

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.     

Crystallization of fiber-reinforced poly(phenylene sulfide) composites. I. Experimental studies of crystallization rates and morphology

The isothermal crystallization from the melt of unreinforced poly(phenylene sulfide) (PPS) and of model carbon, aramid, and glass-fiber-reinforced PPS composites was studied by differential scanning calorimetry and optical microscopy. Crystallization was studied as a function of temperature, and the fiber contents in the composites were varied over a wide range. The results indicate that the influence of fibers on PPS crystallization is not only fiber specific, but also strongly dependent on the surface treatment (size). In general, fiber-reinforced systems crystallized faster than unreinforced (PPS), and the degree of crystallinity was less under comparable crystallization conditions. It was also observed that the rate of crystallization was enhanced in those systems which exhibited transcrystallinity in thin PPS film/single fiber composites as compared to those systems which did not exhibit transcrystallinity. Furthermore, the degree of crystallinity showed a nonlinear crystallization temperature dependence for those systems that exhibited transcrystallinity.     

熔纺工艺对PEEK初生丝性能的影响

选用国产ＰＥＥＫ树脂，系统研究了熔纺温度、热甬道温度及初始拉伸比对初生丝取向和拉伸性能的影响。结果表明，纺丝甬道在室温条件下纺制的ＰＥＥＫ初生丝有一定程度的分子取向，熔纺温度越低，初始拉伸比越大，取向越明显；有热甬道条件下，甬道温度越高，取向程度越低，当温度高于２６０℃时，所得初生丝基本无取向。初生丝取向度越低，拉伸性能越好。     

Ionic liquid assisted polyetheretherketone-multiwalled carbon nanotubes nanocomposites: An environmentally friendly approach

Reinforcement of PEEK by nanoparticles such as multiwalled carbon nanotubes (MWCNTs), is a promising technique to prepare PEEK nanocomposites with improved properties for promising biomedical applications. However, proper dispersion of MWCNTs in the polymer matrices is a primary processing challenge. The present study reports a novel and environmentally beneficial approach for homogeneous dispersion of MWCNT in PEEK by using ionic liquid (IL) 1-ethyl-3-methylimidazolium hydrogen sulfate ([EMIM][HSO₄]). Neat PEEK, PEEK-MWCNTs (using conventional organic solvent dimethylformamide), and PEEK-MWCNTs-IL (using [EMIM][HSO₄]) nanocomposites were fabricated via melt-compounding and compression molding techniques. The fabricated composites were characterized for morphological, thermal, and mechanical properties and compared to those of neat PEEK and PEEK-MWCNTs. Ionic liquid provoked proficient dispersion of the MWCNTs in PEEK, as confirmed by FESEM and optical micrographs. The thermal stability of PEEK-MWCNTs-IL composite was significantly superior to that of the neat PEEK and PEEK-MWCNTs. Analysis of tensile strength and nanoindentation depicted that the modulus of elasticity of PEEK-MWNCTs-IL was significantly increased by 76% as compared to that of neat PEEK. We believe that the present work could provide a new and green platform for the manufacturing of PEEK nanocomposites with enhanced dispersion of nanofillers for biomedical applications.