Surface Modification of Para-Aramid Fiber by Direct Fluorination and its Effect on the Interface of Aramid/Epoxy Composites

Surface modification of a para-aramid fiber (DAFIII) was performed by direct fluorination. The properties of treated and untreated fibers were characterized and compared in detail by mechanical testing, Fourier transform infrared (FTIR) spectroscopy characterization, X-ray photoelectron spectroscopy (XPS) analysis and static contact angle measurements. The results showed that little damage of the fiber occurred after direct fluorine treatment, and the content of polar groups on the fibers surfaces were increased significantly, which resulted in a lower value of contact angle. The interlaminar shear strength (ILSS) of DAFIII fiber/epoxy composites and the tensile strength of NOL-ring specimens increased by 33% and 12%, increasing to 56.2 MPa and 2340 MPa, respectively, which indicated that the interfacial adhesion between the matrix and the aramid fiber was improved significantly by the fluorination treatment. Further tests showed that the durability of the direct fluorination treatment on the aramid fiber was also satisfactory.     

Interfacial interaction in carbon fiber/thermoplastic composites

This work was undertaken in order to increase the understanding of the mechanism responsible for fiber/matrix interaction in carbon fiber/thermoplastic composite. From results of previous study on carbon fiber/PEEK composite, which suggested that the formation of the fiber/ matrix interaction was primarily related to a chemisorption mechanism, a study was done of the conditions required to obtain efficient fiber/matrix interaction in PA-12 and PP/carbon fiber composites. The interest in studying carbon fiber composite based on PP and PA-12 was that these two matrices are very different in terms of reactivity, polyamide having many more reactive groups than polypropylene. As expected, due to the non-reactive chemical structure of the polypropylene, fiber/matrix interaction in carbon fiber/PP composite occurred only when the matrix was thermally degraded, i.e. when the composite was molded at high temperature or under long residence time at the melt temperature. For the carbon fiber/PA-12 composite, strong fiber/matrix interaction occurred readily at relatively low molding temperature, i.e. well before thermal degradation of the matrix. It was also found that the short beam shear strength in these composites seems to evolve with molding temperature, and a maximum interfacial strength was observed at a molding temperature corresponding to the thermal degradation of the matrix. This indicates that although matrix degradation often results in strong reduction in the composite performance, some matrix degradation can be beneficial in terms of interfacial mechanical properties. Finally, this work demonstrated that while the formation of fiber/matrix interaction seems to be primarily related to a chemisorption mechanism, the contribution of interphase crystallinity to the interfacial strength is not negligible. In fact, interfacial crystallinity was found to be essential to ensure optimum interfacial strength.     

Influence of γ-ray radiation grafting on interfacial properties of aramid fibers and epoxy resin composites

This research used Co⁶⁰ γ-ray radiation to modify Armos fibers in 1,2-epoxy-3-chloropropane. After the treatment, the interlaminar shear strength (ILSS) values of aramid/epoxy composites were improved by about 20%. Surface elements of Armos fibers were determined by XPS analysis, which indicated that the oxygen/carbon ratio was increased. The surface of the fibers treated was rougher than that of the untreated fibers when examined by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Fourier transform infrared (FT-IR) spectra confirmed that the epoxy group was grafted onto the fibers. The wettability of the fibers' surface was also enhanced by the treatment. Nanoindentation technique analysis showed that the nanohardnesses of the various phases (the fiber, the interface and the matrix) in the composite, whose fibers were treated, were correspondingly higher than those in the composite, whose fibers were untreated. The results indicate that γ-ray irradiation grafting technique, which is a suitable batch process for industrialization, can modify the physicochemical properties of Armos fibers and improve the interfacial adhesion of its composite.     

Comparison of the Mechanical Properties and the Ballistic Behavior in Heracron®/Phenol Composite after Plasma Treatment

In this study, aramid, Heracron^®, which was purchased from Kolon Inc., Korea, and phenol composites were prepared by plasma treatment and the influence of this plasma treatment on their mechanical properties and ballistic behavior were ascertained. By measurement of water contact angle and XPS analysis, we find that the plasma treatment may help the incorporation of functional oxygen groups on the surface of the Heracron^® fabrics. Additionally, the surface roughness of Heracron^® fiber may be proportional to the plasma treatment times. By SEM and mechanical tests, it was shown that plasma-treated Heracron^®/phenol composites exhibited higher mechanical properties compared with plasma-untreated Heracron^®/phenol composites. Based on this finding, we can conclude that plasma-treatment can promote the interfacial adhesion between Heracron^® and phenol, resulting in the superior mechanical properties of their composites. However, the ballistic behavior conflicted with the mechanical properties. That is to say, a helmet, manufactured from the plasma-treated Heracron^®/phenol composites, exhibited lower ballistic properties than that of the plasma-untreated Heracron^®/phenol composites. As a result, we demonstrated that for ballistic application, somewhat weak fiber–matrix adhesion leads to the improved ballistic behavior. However, it becomes apparent that the optimum strength condition for the composite interphase depends on the particular application, thus increased fiber–matrix adhesion may be more appropriate.     

Interface and its effect on the interlaminate shear strength of novel glass fiber/hyperbranched polysiloxane modified maleimide-triazine resin composites

Interface is the key topic of developing advanced fiber reinforced polymeric composites. Novel advanced glass woven fabric (GF) reinforced composites, coded as GF/mBT, were prepared, of which the matrix resin was hyperbranched polysiloxane (HBPSi) modified maleimide-triazine (mBT) resin. The influence of the composition of the matrix on the interfacial nature of the GF/mBT composites were studied and compared with that of the composite based on GF and BT resin using contact angle, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), and dielectric properties over wide frequency and temperature ranges. Results show that the interfacial nature of the composites is dependent on the chemistries of the matrices, mBT matrices have better interfacial adhesion with GF than BT resin owing to the formation of chemical and hydrogen bonds between mBT resin and GF; while in the case of mBT resins, the content of HBPSi also plays an important role on the interfacial feature and thus the macro-performance. Specifically, with increasing the content of HBPSi in the matrix, the interlaminate shear strength of corresponding composites significantly improves, demonstrating that better interfacial adhesion guarantees outstanding integrated properties of the resultant composites.     

The effect of surface treatment of carbon fiber on the flexural property of thermoplastic polyimide composite

Rare earth solution (RES) surface modification and air-oxidation methods were used to improve the interfacial adhesion of the carbon fiber reinforced polyimide (CF/PI) composite. The flexural property of the PI composites reinforced by the carbon fibers treated with different surface modification methods was comparatively investigated. Results showed that the flexural strength of CF/PI composite was improved after RES treatment. The improvement of impact and flexural property of the CF/PI composite was mainly due to the improvement in interfacial adhesion after RES treatment. X-ray photoelectron spectroscopy (XPS) study of carbon fiber surface showed that the oxygen concentration was obviously increased after RES treatment. The increase in the amount of organic functional groups increased the interfacial adhesion between CF and PI matrix.     

Effect of chemical modifications of the pineapple leaf fiber surfaces on the interfacial and mechanical properties of laminated biocomposites

Natural fiber reinforced renewable resource based laminated composites were prepared from biodegradable poly(lactic acid) (PLA) and untreated or surface-treated pineapple leaf fibers (PALF) by compression molding using the film stacking method. The objective of this study was to determine the effects of surface treatment of PALF on the performance of the fiber-reinforced composites. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) were used to aid in the analysis. The mechanical properties of the PLA laminated composites were improved significantly after chemical treatment. It was found that both silane- and alkali-treated fiber reinforced composites offered superior mechanical properties compared to untreated fiber reinforced composites. The effects of temperature on the viscoelastic properties of composites were studied by dynamic mechanical analysis (DMA). From the DMA results, incorporation of the PALF fibers resulted in a considerable increase of the storage modulus (stiffness) values. The heat defection temperature (HDT) of the PALF fiber reinforced PLA laminated composites was significantly higher than the HDT of the neat PLA resin. The differential scanning calorimeter (DSC) results suggest that surface treatment of PALF affects the crystallization properties of the PLA matrix. Additionally, scanning electron microscopy (SEM) was used to investigate the distribution of PLA within the fiber network. SEM photographs of fiber surface and fracture surfaces of composites clearly indicated the extent of fiber–matrix interface adhesion. It was found that the interfacial properties between the reinforcing PALF fibers and the surrounding matrix of the laminated composite are very important to the performance of the composite materials and PALF fibers are good candidates for the reinforcement fiber of high performance laminated biodegradable biocomposites.     

Phase Structure of Polyamide 6/Poly(styrene-co-acrylonitrile) and Poly(styrene-b-(ethylene-co-butylene)-b-styrene) or Poly(maleated Styrene/Ethylene-co-Butylene/Styrene) Ternary Blends

Two sets of ternary blends; polyamide 6/poly(styrene-co-acrylonitrile)/poly(styrene-b-(ethylene-co-butylene)-b-styrene) (PA6/SAN/SEBS) and polyamide 6/poly(styrene-co-acrylonitrile)/poly(maleated styrene/ethylene-co-butylene/styrene) (PA6/SAN/SEBS-g-MA), based on 70 wt% of matrix and 30 wt% of the dispersed phases at various concentrations of the minor components, were prepared via melt blending. Morphologies of the ternary systems were studied using scanning electron microscopy (SEM) and compared with the predictions of the spreading coefficient (SC), minimum relative interfacial energy (RIE), and dynamic interfacial energy (DIE) phenomenological models. The effects of different reported surface tensions of the used polymers and different protocols of the core-shell ratio calculation on the prediction of the models were investigated. The core-shell structure for PA6/SAN/SEBS system and two separate minor phases for PA6/SAN/SEBS-g-MA were observed at all of the compositions. The results indicated that the most important parameter for the accurate prediction of the models is the accurate calculation of the interfacial tension of the used polymers, in both the static and dynamic conditions.     

Effect of fiber surface treatments on the fiber–matrix interaction in banana fiber reinforced polyester composites

Cellulosic fibers have been used as cost-cutting fillers in plastic industry. Among the various factors, the final performance of the composite materials depends to a large extent on the adhesion between the polymer matrix and the reinforcement and therefore on the quality of the interface. To achieve optimum performance of the end product, sufficient interaction between the matrix resin and the cellulosic material is desired. This is often achieved by surface modification of the resin or the filler. Banana fiber, the cellulosic fibers obtained from the pseudo-stem of banana plant (Musa sepientum) is a bast fiber with relatively good mechanical properties. The fiber surface was modified chemically to bring about improved interfacial interaction between the fiber and the polyester matrix. Various silanes and alkali were used to modify the fiber surface. Modified surfaces were characterized by SEM and FTIR. The polarity parameters of the chemically modified fibers were investigated using the solvatochromic technique. The results were further confirmed by electrokinetic measurements. Chemical modification was found to have a profound effect on the fiber–matrix interactions. The improved fiber–matrix interaction is evident from the enhanced tensile and flexural properties. The lower impact properties of the treated composites compared to the untreated composites further point to the improved fiber–matrix adhesion. In order to know more about the fiber–matrix adhesion, fractured surfaces of the failed composites where further investigated by SEM. Of the various chemical treatments, simple alkali treatment with NaOH of 1% concentration was found to be the most effective. The fiber–matrix interactions were found to be dependent on the polarity of the modified fiber surface.     

Influences of interfacial adhesion on gas barrier property of functionalized graphene oxide/ultra-high-molecular-weight polyethylene composites with segregated structure

The segregated graphene oxide(GO)/ultra-high-molecular-weight polyethylene (UHMWPE) composite films with various interfacial adhesion property were prepared by mechanical blending method from UHMWPE, GO, dodecyl amine (DA) functionalized graphene oxide(DA–GO) or uniform DA–GO/high density polyethylene (DA–GO/HDPE) powder. The results of XRD and XPS indicated that DA chain was successfully grafted onto GO sheets via a chemical method, which enhanced the interfacial adhesion between UHMWPE particles and GO sheets. The characterizations of POM and SEM proved that good segregated structure was only obtained in DA–GO/UHMWPE or DA–GO/HDPE/UHMWPE composite. Strong interfacial adhesion between fillers and matrix exhibits positive effect on gas barrier property. Compared to the GO/UHMWPE composite film, dramatic decrease in O₂ permeability coefficient by 42.2 and 48.1%, from 15.4 × 10^?14 to 8.9 × 10^?14 and 8.0 × 10^?14 cm³ cm cm^?2 s^?1 Pa^?1, is achieved upon the addition of only 0.5 wt% fillers, respectively. The DSC results demonstrated that the enhanced gas barrier performance was ascribed to the strong interfacial adhesion between DA–GO/HDPE and UHWMPE matrix, rather than the crystallinity of UHWMPE matrix. Additionally, the decrease in UHMWPE particle size might be conducive to improving the gas barrier property of composite films due to the formation of more isolation layers perpendicular to the film plane.     

Modification of nano-kenaf surface with maleic anhydride grafted polypropylene upon improved mechanical properties of polypropylene composite

The surface of nano-kenaf fiber is modified with maleic anhydride grafted polypropylene (MA-g-PP) and added into PP and the mechanical properties and the flow property of the composite are investigated. The addition of MA-g-PP in nano-kenaf/PP composite increases the tensile strength, the elongation%, and the impact strength (I.S.), while it decreases the flow property (melt flow index) compared to without MA-g-PP composite (nano-kenaf/PP). The scanning electron microscope photograph shows it also increases interfacial adhesion between nano-kenaf and PP matrix. Regardless of MA-g-PP, nano-kenaf fibers shows better adhesion with PP compared to micron-kenaf fibers. Addition of MA-g-PP further improved interfacial adhesion between nano-kenaf surface and PP matrix compared to without MA-g-PP nano-kenaf compound. The addition of MA-g-PP apparently improves the interfacial adhesion between nano-kenaf surface and PP by formation of 3-dimensional network structure.     

Cellulose-based biocomposites: comparison of different multiphasic systems

Biocomposites (biodegradable composites) are obtained by blending biodegradable polymers and fillers. Since the main components are biodegradable, the composite as a whole is also expected to be biodegradable. This paper presents various biocomposites that have been elaborated with cellulose or lignocellulose fibers from diverse sources, with different lignin contents. This paper is targeted on the analysis of 'fiber–matrix' interactions of two types of biocomposites based on agropolymer (plasticized wheat starch) and biopolyester (polybutylene adipate-co-terephthalate), named APB and BPB, respectively. Processing and main properties of both biocomposites are shown and compared. Polyolefin-based composite (PPC), which is known to present very poor 'fiber–matrix' interactions, is used as a reference. Through the Young's modulus, mechanical properties have shown that the reinforcement, by increasing fiber content, is much more significant for APB compared to BPB. The evolution of chains mobility, evidenced through shift of T _g values, according to the increase in fiber content and thence in interfacial area, have shown that the fiber–matrix interactions are higher for APB. BPB presents intermediate values, higher than PPC ones. These results are in agreement with the analysis of the composite morphologies performed by SEM on cryogenic fractures. Finally, by determining the theoretical works of adhesion and the interfacial tensions from contact angle measurements, it is shown that these parameters are partially able to predict the level of interaction between the fibers and the matrix. We could show that the perspectives of such work seem to be of importance to tailor new materials with a controlled end-use.     

Effects of γ-ray radiation grafting on aramid fibers and its composites

Armos fiber was modified by Co⁶⁰ γ-ray radiation in the different concentrations’ mixtures of phenol-formaldehyde and ethanol. Interlaminar shear strength (ILSS) was examined to characterize the effects of the treatment upon the interfacial bonding properties of Armos fibers/epoxy resin composites. The results showed that the ILSS of the composite, whose fibers were treated by 500 kGy radiation in 1.5 wt% PF, was improved by 25.4%. Nanoindentation technique analysis showed that the nanohardnesses of the various phases (the fiber, the interface and the matrix) in the composite, whose fibers were treated, were correspondingly higher than those in the composite, whose fibers were untreated. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FT-IR) spectrum confirmed the increase in the polar groups at the fibers’ surface. Atomic force microscopy (AFM) results revealed that the surface of the fibers treated was rougher than that of the fibers untreated. The wettability of the fibers’ surface was also enhanced by the treatment. The conclusion that γ-ray irradiation grafting significantly improved the surface properties of Armos fibers could be drawn.     

A Fluoropolymer Coating on Carbon Fibers Improves Their Adhesive Interaction with PTFE Matrix

Carbon fibers were treated in a HF glow discharge in tetrafluoroethylene and octafluorocyclobutane in order to improve their adhesion to poly(tetrafluoroethylene) matrix. As the result of the plasma treatment, a thin (20–140 nm) fluoropolymer coating was deposited onto the fiber surface. The structure of this coating was studied by means of IR spectroscopy, XPS, AFM and SEM techniques. The coating material appeared to be similar to PTFE in its chemical composition but distinguished by branched, partially crosslinked, amorphous structure and included unsaturated chemical bonds. The coating thickness of 70 nm was sufficient to effectively screen the field of molecular forces of the initial substrate, thus, decreasing the surface energy of the fibers and improving their compatibility with the PTFE matrix. The adhesive strength in the PTFE–carbon fiber systems, measured by means of the microbond test, more than doubled upon the plasma treatment (the local interfacial shear strength increased from 10.7 to 29.7 MPa, apparent IFSS from 4.3 to 7.8 MPa), and the interfacial frictional stress increased by 70%. The new composite material consisting of 20% short coated carbon fibers in the PTFE matrix showed better mechanical, thermal and tribological characteristics as compared with the composite reinforced with untreated fibers.     

Cellulose-Based Natural Fiber Topography and the Interfacial Shear Strength of Henequen/Unsaturated Polyester Composites: Influence of Water and Alkali Treatments

In the present work, the effect of surface treatment methods on the henequen fiber topography and how the surface treatment influences the interfacial shear strength of henequen/unsaturated polyester composites were studied. Two different surface treatment methods were used: soaking method and ultrasonic method. Two different treatment media were used: normal tap water and sodium hydroxide. The result showed that the topography of henequen fiber surfaces was greatly changed, strongly depending on the treatment method and media used. It was demonstrated from the single fiber microbonding test result that the interfacial shear strength (IFSS) between the natural fibers and the matrix of henequen/unsaturated polyester composites was significantly improved by the surface treatments of henequen prior to composite preparation. The topological and interfacial results were quite consistent with each other.     

Influence of Fiber Surface Treatment on Mechanical Properties of CF/PET Composites

Carbon fiber (CF) / poly (ethylene terephthalate) (PET) composites were prepared with various contents (2–15wt%) of short carbon fibers. To investigate the effect of surface treatment of the CF on the mechanical properties of the composites, three specimens were prepared; those with short carbon fibers (called SCF), short carbon fibers oxidized with nitric acid (called NASCF) and the fibers oxidized with nitric acid and treated with silane coupling agent (called SCSCF). Flexural, tensile and impact tests were performed to observe mechanical behavior of the specimens. The morphology of the specimens was also studied with a scanning electron microscope (SEM). SCSCF composite had better mechanical properties than the other composites with the same content of carbon fibers since the coupling agent resulted in better interfacial adhesion between the fiber and the matrix.     

Short sisal fiber reinforced polypropylene composites: the role of interface modification on ultimate properties

Sisal fibers have been used for the reinforcement of polypropylene matrix. The compatibilization between the hydrophilic cellulose fiber and hydrophobic PP has been achieved through treatment of cellulose fibers with sodium hydroxide, isocyanates, maleic anhydride modified polypropylene (MAPP), benzyl chloride and by using permanganate. Various fiber treatments enhanced the tensile properties of the composites considerably, but to varying degrees. The SEM photomicrographs of fracture surfaces of the treated composites clearly indicated the extent of fiber–matrix interface adhesion, fiber pullout and fiber surface topography. Surface fibrillation is found to occur during alkali treatment which improves interfacial adhesion between the fiber and PP matrix. The grafting of the fibers by MAPP enhances the tensile strength of the resulting composite. It has been found that the urethane derivative of polypropylene glycol and cardanol treatments reduced the hydrophilic nature of sisal fiber and thereby enhanced the tensile properties of the sisal–PP composites, as evident from the SEM photomicrographs of the fracture surface. The IR spectrum of the urethane derivative of polypropylene glycol gave evidence for the existence of a urethane linkage. Benzoylation of the fiber improves the adhesion of the fiber to the PP matrix. The benzoylated fiber was analyzed by IR spectroscopy. Experimental results indicated a better compatibility between benzoylated fiber and PP. The observed enhancement in tensile properties of permanganate-treated composites at a low concentration is due to the permanganate-induced grafting of PP on to sisal fibers. Among the various treatments, MAPP treatment gave superior mechanical properties. Finally, experimental results of the mechanical properties of the composite have been compared with theoretical predictions.     

Influence of material processing and interface on the fiber fragmentation process in titanium matrix composites

The objective of this work is to study the effect of composite processing conditions on the nature of the fiber–matrix interface in titanium matrix composites and the resulting fragmentation behavior of the fiber. Titanium matrix, single fiber composites (SFCs) were fabricated by diffusion bonding and tensile tested along the fiber axis to determine their interfacial load transfer characteristics and the resulting fiber fragmentation behavior. Two different titanium alloys, Ti-6Al-4V (wt%) and Ti-14Al-21Nb (wt%), were used as matrix material with SiC (SCS-6) fibers as reinforcement. The tensile tests were conducted at ambient temperature and were continuously monitored by acoustic emission. It was observed that the Ti-6Al-4V/SCS-6 composite system exhibited a greater degree of fiber–matrix interfacial reaction, as well as a rougher interface, compared to Ti-14Al-21Nb/SCS-6 composites. Acoustic emissions during tensile testing showed that most of the fiber fractures in Ti-6Al-4V/SCS-6 occurred at strains below ～5% and the fragmentation ceased at ～10% strain corresponding to specimen necking. In contrast, the Ti-14Al-21Nb/SCS-6 composite deformed without necking and fiber fractures occurred throughout the plastic range until final fracture of the specimen at about 12% strain. The markedly different fragmentation characteristics of these two composites were attributed to differences in the fiber–matrix interfacial regions and matrix deformation behavior.     

Friction and wear of rare earths modified carbon fibers filled PTFE composite under dry sliding condition

Carbon fibers (CF) were surface treated with air-oxidation and rare earths (RE), respectively. The friction and wear properties of polytetrafluoroethylene (PTFE) composites filled with differently surface treated carbon fibers, sliding against GCr15 steel under dry sliding condition, were investigated on a block-on-ring M-2000 tribometer. Experimental results revealed that RE treatment largely reduced the friction and wear of CF reinforced PTFE (CF/PTFE) composites. The RE treated composite exhibited the lowest friction and wear under dry sliding. Scanning electron microscopy (SEM) investigation of worn surfaces and transfer films of CF/PTFE composites showed that RE treated CF/PTFE composites had the smoothest worn surface under given load and sliding speed, and a continuous and uniform transfer film formed on the counterface. X-ray photoelectron spectroscopy (XPS) study of carbon fiber surface showed that the oxygen concentration was obviously increased after RE treatment, and more carboxyl groups were introduced onto CF surfaces after RE treatment. The increase in the amount of oxygen-containing groups increased the interfacial adhesion between CF and PTFE matrix, and accordingly increased the tribological properties of the composite.     

Surface and interfacial morphologies of PAN-CVI carbon–carbon composite

Scanning electron microscopy (SEM), polarized light microscopy (PLM), and transmission electron microscopy (TEM) techniques have been used to characterize the normal surface and flank surface microstructure of a polyacrylonitrile (PAN)-based carbon fiber reinforced chemical vapor infiltrated (CVI) matrix carbon–carbon composite. Optical and SEM results indicate that the CVI deposit consists of two structures: an isotropic phase is present in the fiber bundle-bundle junctions and a second highly oriented lamellar structure is present in the intrabundle matrix. TEM shows that matrix platelets are highly parallel to the fiber axis and the crystallites of the matrix near the fiber surface exhibit better alignment than those farther away from fibers.