Catalytic grafting: A new technique for polymer/fiber composites. II. Plasma treated UHMPE fibers/polyethylene composites

In this paper, the catalytic grafting technique for preparation of polymer/fiber composites is extended to plasma treated ultra-high modulus polyethylene (UHMPE) fiber/high density polyethylene (HDPE) system. The OH groups introduced on the UHMPE fiber surface by oxygen plasma treatment were used to chemically anchor Ziegler-Natta catalyst which then was followed by ethylene polymerization on the fiber surface. The morphology and interfacial behavior, as well as the mechanical properties, of the HDPE composites reinforced by catalytic grafted or ungrafted UHMPE fibers were investigated by SEM, DSC, polarized light optical microscopy, and tensile testing. The experimental results show that the polyethylene grafted on the fibers acted as a transition layer between the reinforcing UHMPE fibers and a commercial HDPE matrix. The interfacial adhesion was also significantly improved. Compared with the composite reinforced by ungrafted UHMPE fibers, the composite reinforced by catalytic grafted UHMPE fibers exhibits much better mechanical properties.     

The influences of fiber feature and polymer melt index on mechanical properties of sugarcane fiber/polymer composites

The fiber characteristics (i.e., the fiber type, morphology, and dimension) and polymer melt flow index (MFI) significantly affected mechanical properties of sugarcane fiber/HDPE composites. The length and diameter of sugarcane fibers followed a lognormal distribution before and after compounding. The long fibers had a significant reduction in the dimension and aspect ratio during compounding. However, the short fibers had close values in these two properties before and after compounding. For the resultant sugarcane fiber/polymer composites, the HDPE resins with a low MFI value presented high tensile and impact strengths. Because of high sugar content, the pure rind fiber had a poor performance as filler in the HDPE resins with respect to the raw bagasse fiber and alkali‐extracted bagasse fiber. On the other hand, the aspect ratio was proportional to the mechanical performance of the fibers in the HDPE resins. As a result, the fibers with a large aspect ratio and low sucrose content improved the strength properties of the resultant composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5607–5619, 2006     

Polyethylene‐Palygorskite nanocomposite prepared via in situ coordinated polymerization

A polyethylene/palygorskite nano‐composite (IPC composite) was prepared via an in‐situ coordinated polymerization method, using TiCl₄ supported on palygorskite fibers as catalyst and alkyl aluminum as co‐catalyst. These composites were compared with those prepared by melt blending (MBC composites). It was found that in the IPC composites, nano‐size fibers of palygorskite were uniformly dispersed in the polyethylene matrix. In contrast, in the MBC composites, the palygorskite was dispersed as large clusters of fibers. Regarding the mechanical properties of the IPCs, the tensile modulus increased and the elongation at break decreased with increasing fiber content, while the tensile strength passed through a maximum. The tensile strength and elongation at break were much smaller for the MBC composites. The final degree of crystallinity of the IPC composites decreased with increasing palygorskite content. Regarding the kinetics of crystallization, the ratio between the degree of crystallinity at a given time and the final one was a universal function of time. It was found that large amouns of gel were present in the IPC composites and much smaller amountes in the MBC composites.     

Adhesion improvement in glass fiber reinforced polyethylene composite via admicellar polymerization

Admicellar polymerization (polymerization of monomer solubilized in adsorbed surfactant bilayers) has been used to form a thin film of polyethylene onto the surface of milled glass fibers using sodium dodecyl sulfate as the surfactant. The decrease in ethylene pressure was used to follow the solubilization and adsolubilization processes as well as the reaction processes. An increase in initiator (Na₂S₂O₈) to surfactant ratio gave thicker and more uniform coatings of polymer onto the glass fiber surface according to SEM micrographs. Although a substantial amount of ethylene polymerized in solution according to the pressure drop, the decrease in pressure attributed to admicelle polymerization corresponded to the amount of polymer formed on the glass fiber, indicating little, if any, solution polymer deposited on the fibers. The admicellar‐treated glass fiber was used to make composites with high‐density polyethylene. The composites showed an increase in tensile and flexural strength over composites made from as‐received glass fiber, indicating an improvement in the fiber‐matrix adhesion of the admicellar‐treated glass fiber.     

Preparation and characterization of functionalized low density polyethylene matrix biocomposites

The incorporation of cellulosic fibers into polyethylene matrices was studied in this work, by dispersion of fluff pulp from maritime pine in a hot polymer solution, followed by co‐precipitation of the solid components by cooling at room temperature. The above method was found suitable for proper wetting and dispersion of fibers in the polymeric matrix, as compared with melt compounding. Unmodified low density polyethylene [LDPE], modified LDPE with maleic anhydride grafted linear low density polyethylene [M‐LLDPE] and a copolymer of acrylic acid and n‐butyl acrylate polyethylene [(AA/n‐BA)‐LDPE], were used as matrices for the preparation of fiber reinforced composites. The thermal properties of these composites were determined using differential scanning calorimetry and thermogravimetric analysis. The incorporation of cellulosic fibers results in a decrease of the crystallinity of the polymer matrix, as they act as inert material. In addition, the appropriate tests were run in order to determine the density and tensile properties of the composite specimens prepared by compression molding, with filler content ranging from 10 to 40% (w/w). Composites based on modified LDPE showed improved mechanical properties. The Takayanagi model, applied to predict the Young's modulus of composites, was in very good agreement with the experimental data obtained in this work. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Catalytic grafting: A new technique for polymer–fiber composites I. Polyethylene–asbestos composites

In this work we present a new technique to prepare polyolefin-fiber composites. This technique is based on chemical anchoring of a catalyst on reinforcing agents containing OH groups on their surface and then conducting an olefin polymerization on the supported catalyst. This technique offers the possibility to approach the challenging problems encountered in polymer composites, namely, the reinforcement-matrix adhesion, the dispersion, and the wetting of the reinforcement by the resin. As a first part of a systematic research, we report on the procedure of fixation of titanium tetrachloride on the surface of asbestos fibers and the Ziegler-Natta polymerization of ethylene on the surface-modified fibers. The procedure as well as the structure and properties of the composite were investigated by means of FTIR, atomic absorption, SEM, solvent extraction, and tensile testing. The experimental results show that the Ziegler-Natta catalyst can be efficiently anchored on the surface of the fibers to conduct successful polymerization and to “synthesize” a new class of polymer composites.     

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.     

Recycled polypropylene reinforced with curaua fibers by extrusion

Curaua fibers were studied as reinforcing agents for postconsumer polypropylene. The composites were processed by extrusion. The composite properties were investigated by mechanical tests, thermal methods, melt flow index, surface morphology, and water uptake. The variables studied were as follows: fiber contents (10 to 40 wt %), fiber surface treatment, initial fiber length, and modification of the polypropylene matrix. The treatment of the fiber with 5 wt % NaOH aqueous solution did not improve fiber‐matrix adhesion and the composites using 20 wt % of untreated curaua fibers presented the better mechanical properties. Feeding the extruder with fibers having shorter lengths (0.01–0.4 mm) produced better fiber dispersion, improving the mechanical properties of the composites. Composites prepared using fibers without surface treatment with postconsumer polypropylene and with polypropylene modified with maleic anhydride showed mechanical properties and water uptake similar to composites using the same polymer reinforced with other lignocellulosic fibers. The extrusion process caused also partial fibrillation of the fibers, improving their aspect ratio. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Interfacial studies on the surface modified aramid fiber reinforced epoxy composites

In this work, solutions of rare earth modifier (RES) and epoxy chloropropane (ECP) grafting modification method were used for the surface treatment of aramid fiber. The effect of chemical treatment on aramid fiber has been studied in a composite system. The surface characteristics of aramid fibers were characterized by Fourier transform infrared spectroscopy (FTIR). The interfacial properties of aramid/epoxy composites were investigated by means of the single fiber pull‐out tests. The mechanical properties of the aramid/epoxy composites were studied by interlaminar shear strength (ILSS). As a result, it was found that RES surface treatment is superior to ECP grafting treatment in promoting the interfacial adhesion between aramid fiber and epoxy matrix, resulting in the improved mechanical properties of the composites. Meanwhile, the tensile strengths of single fibers were almost not affected by RES treatment. This was probably due to the presence of reactive functional groups on the aramid fiber surface, leading to an increment of interfacial binding force between fibers and matrix in a composite system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4165–4170, 2006     

Enzyme‐mediated surface modification of jute and its influence on the properties of jute/epoxy composites

Surface modification of jute fibers is necessary to improve the adhesion and interfacial compatibility between fibers and resin matrix before using fibers in polymer composites. In this study, dodecyl gallate (DG) was enzymatically grafted onto the jute fiber by laccase to endow the fiber with hydrophobicity. A hand lay‐up technique was then adopted to prepare jute/epoxy composites. Contact angle and wetting time measurements showed that the surface hydrophobicity of the jute fabric was increased after the enzymatic graft modification. The water absorption and thickness swelling of the DG‐grafted jute fabric/epoxy composite were lower than those of the other composites. The tensile and dynamic mechanical properties of the jute/epoxy composites were enhanced by the surface modification. Scanning electron microscopy images revealed stronger fiber–matrix adhesion in composites with modified fibers. Therefore, the enzymatic graft modification increased the fiber–matrix interface area. The fiber–matrix adhesion was enhanced, and the mechanical properties of the composites were improved. POLYM. COMPOS., 38:1327–1334, 2017. © 2015 Society of Plastics Engineers     

Interfacial evaluation of epoxy/carbon nanofiber nanocomposite reinforced with glycidyl methacrylate treated UHMWPE fiber

Interface interactions of fiber–matrix play a crucial role in final performance of polymer composites. Herein, in situ polymerization of glycidyl methacrylate (GMA) on the ultrahigh molecular weight polyethylene (UHMWPE) fibers surface was proposed for improving the surface activity and adhesion property of UHMWPE fibers towards carbon nanofibers (CNF)‐epoxy nanocomposites. Chemical treatment of UHMWPE fibers was characterized by FTIR, XPS analysis, SEM, and microdroplet tests, confirming that the grafting of poly (GMA) chains on the surface alongside a significant synergy in the interfacial properties. SEM evaluations also exhibited cohesive type of failure for the samples when both GMA‐treated UHMWPE fiber and CNF were used to reinforce epoxy matrix. Compared with unmodified composite, a ～319% increase in interfacial shear strength was observed for the samples reinforced with both 5 wt % GMA‐grafted UHMWPE and 0.5 wt % of CNF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43751.     

Production of leather-like composites using short leather fibers. II. Mechanical characterization

Leather-like composites were prepared by addition of chemically modified short leather fibers (SLF) into a plasticized polyvinyl chloride (pPVC) matrix. The fibers were subjected to chemical modification by emulsion polymerization to achieve good interfacial adhesion between SLF and the pPVC matrix. The SLF with chemical modification were obtained from three different reaction conditions where these SLF have different percentages of grafted and deposited PMMA polymer onto the fiber surface. The incorporation of the SLF into the thermoplastic matrix was carried out using a torque-rheometer and the composites obtained were molded by compression. Tensile and tear mechanical tests were performed on composite samples, and the morphology of the fractured surfaces was analyzed using scanning electron microscopy (SEM). The results show that the incorporation by grafting of polymethyl metacrylate (PMMA) onto the fibers produced a significant improvement of their interfacial adhesion to pPVC, promoting the compatibilization between the fiber surface and matrix. The findings are discussed and interpreted in terms of enhanced adhesion at phase boundaries. Overall, the results confirm that it is possible to produce modified leather composites based on a pPVC matrix, which exhibit relatively high tensile strength, tear resistance and flexibility. These composites are very suitable candidate materials for applications in the footwear industry.     

Influence of fiber wettability on the interfacial adhesion of continuous fiber‐reinforced PPESK composite

Interfacial adhesion between fiber and matrix has a strong influence on composite mechanical performance: better interfacial adhesion can enhance composite transverse properties, flexural properties, and interlaminar shear strength, and so on. To exploit the reinforcement potential of the fibers in advanced composite, it is necessary to reach a deeper understanding on the relation between fiber wettability and interfacial adhesion. In our experiment, we study the influence of fiber wettability on interfacial properties of fiber/PPESK composites by choosing three kinds of fibers with different wettabilities. The relation between fiber wettability and surface free energy was discussed, and the influence of fiber wettability on the interfacial property of fiber/PPESK composites was analyzed. Results indicate that higher surface free energy can enhance the wettability between fiber and matrix, and the humid resistance and interfacial adhesion can be improved at the same time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2544–2551, 2006     

废弃木粉与短切玻璃纤维组合增强聚丙烯的力学性能

用废弃木粉与短切玻璃纤维作为增强材料，制得了组合增强的聚丙烯复合材料，研究了制备工艺及设备、材料配方及界面改性方法等对材料力学性能的影响。结果表明，用单螺杆挤出机制备组合增强材料，可减少对玻璃纤维的损伤，保持较长的玻璃纤维，有利于其增强作用的发挥；随着玻璃纤维含量的增加，体系的力学性能提高，而木粉含量对材料力学性能的影响与玻璃纤维的含量相关；采用硅烷偶联剂对木粉进行表面处理，在基体中添加接枝极性基团的改性聚丙烯，可改善体系的界面结合，提高力学性能。     

Studies of the effect of fiber surface and matrix rheological properties on nonwoven reinforced elastomer composites

The influence of fiber type and fiber-surface properties on matrix flow behavior was investigated using structural reaction injection-molding (SRIM). The influence of fiber type, fiber-surface properties, and matrix type on strength properties in elastomeric composites reinforced with nonwoven fibrous structures was investigated using tensile tests on elastomer composite samples from SRIM and latex coagulation (LC) fabrication methods and the microbond strength method on individual fibers. The fibers used were PET, LLDPE, and p-aramid. Fibers were treated with epoxy, styrene, and isocyanate derivatives, which make the surface chemically reactive. Treatments were also made with NaOH and a copolymer of polyester and polyol ether, causing a change in the fiber surface energy. The matrix types were polyurethane elastomer and natural rubber. The results show that the surface treatments which produced a change in the surface energy influenced the flow rate of the matrix polymer during the composite fabrication process. The treatments resulted in chemically reactive fiber surfaces which improved the fiber-matrix bond strength without affecting the Young's modulus of the composite material. Good correlation was found between bond strength and surface energy including the dispersive component of surface energy in the case of polyurethane elastomer and surface-modified PET fibers. The age of the polyurethane matrix has a marked influence on the bond strength. The fiber volume fraction in composites has a strong influence on the Young's modulus of the elastomer composite. © 1995 John Wiley & Sons, Inc.     

Studies in Effect of Synthetic and Natural Microfibers on Properties of High-Density Polyethylene-Reinforced Composite

Natural fibers are now arising as one of the promising reinforcement components for fiber-reinforced polymer composites. A study has been conducted to optimize weight concentration of surface-treated and surface-untreated microfibers on the properties of high-density polyethylene composite. Polyethylene terephthalate and henequen microfibers in varying compositions, namely, 1, 3, 5, 8, 10, and 20?wt% were reinforced into high-density polyethylene matrix. These fibers were treated with coupling agent at 0.5?wt%. Vinyltrimethoxysilane-treated composite shows enhanced properties as compared to untreated microfiber composite. Rheological and morphological results reveal that addition of coupling agent improves dispersion and matrix fiber interactions.     

Effect of agave fiber surface treatment on the properties of polyethylene composites produced by dry‐blending and compression molding

In this work, the effect of natural fiber surface treatment with maleated polyethylene (MAPE) is presented to improve the mechanical properties of natural fiber composites (NFC). In particular, a simple dry blending technique was used to disperse natural fibers (agave) in a polymer matrix (linear low density polyethylene) and produce samples via compression molding. The effect of fiber content was also studied (0, 10, 20, 30, and 40 wt%) and the samples were characterized in terms of morphology, density, hardness, as well as mechanical (tensile, flexion, and impact) and thermal (DSC and TGA) properties. The results show that the simple dry‐blending method is efficient to produce homogeneous NFC and that surface treatment can substantially improve composite modulus (164%) and strength (121%). POLYM. COMPOS., 38:96–104, 2017. © 2015 Society of Plastics Engineers     

Composites of poly(lactic acid) with flax fibers modified by interstitial polymerization

Natural fiber composites were designed and optimized to achieve good mechanical properties and resistance to growth of living organisms. Composite materials were prepared from poly(lactic acid) (PLA) with flax fibers, which had been subjected to interstitial polymerization to replace the water in the cellulose fibers. Prior to the polymerization, the flax fibers were extracted with sodium hydroxide and acetone to remove lignin, pectin, and waxes from the cellulose. Differential scanning calorimetry was used to study the crystallization and melting of the composites compared to pure PLA. The surface wetting of the fibers and morphology of the composites were studied by scanning electron microscopy and optical microscopy. Mechanical properties were studied using dynamic mechanical analysis. The influence of the interstitial polymerization on the dynamic storage modulus was found to be significant. The composites of polymerization treated flax with acetone washed fibers had higher storage moduli than the unwashed fiber composites, which suggested that the adhesion between the flax fibers and the matrix was improved by the treatments. The composites were subjected to moist environmental conditions in order to test for development of mold and fungi, and the acetone washed polymerization treated flax composites were resistant to these growths. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3620–3629, 2006     

Pineapple leaf fiber reinforced thermoplastic composites: Effects of fiber length and fiber content on their characteristics

Pineapple leaf fiber (PALF) was used as a reinforcement in polyolefins. Polypropylene (PP) and low‐density polyethylene (LDPE) composites with different fiber lengths (long and short fibers) and fiber contents (0–25%) were prepared and characterized. The results showed that the tensile strength of the composites increased when the PALF contents were increased. It was observed that the composites containing long fiber PALF were stronger than the short fiber composites as determined by greater tensile strength. An SEM study on the tensile fractured surface confirmed the homogeneous dispersion of the long fibers in the polymer matrixes better than dispersion of the short fibers. The unidirectional arrangement of the long fibers provided good interfacial bonding between the PALF and polymer which was a crucial factor in achieving high strength composites. Reduction in crystallinity of the composites, as evident from XRD and DSC studies suggested that the reinforcing effect of PALF played an important role in enhancing their mechanical strength. From the rule of mixtures, the stress efficiency factors of the composite strength could be calculated. The stress efficiency factors of LDPE were greater than those of PP. This would possibly explain why the high modulus fiber (PALF) had better load transfers to the ductile matrix of LDPE than the brittle matrix of PP. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polypropylene/low density polyethylene blends with short glass fibers. II: Effect of compounding method on mechanical properties

Polypropylene/low density polyethylene blend matrices have been reinforced with short glass fibers in order to study their tensile, flexural, and impact behavior. Two-roll milling and twin-screw extrusion compounding methods were used to incorporate the fiber within the polymer matrices, and standard test samples were prepared by injection molding. The effects of matrix composition and fiber concentration on mechanical properties were investigated keeping in mind the matrix and fiber morphology, the latter being intimately dependent upon the compounding method employed.