Studies on surface modification of UHMWPE fibers via UV initiated grafting

In this research, the surface of ultra high molecular weight polyethylene (UHMWPE) fiber was modified by high energy ultraviolet (UV) initiated grafting reactions and acrylamide groups were grafted onto UHMWPE chains. The initiating and grafting mechanism of the reactions was studied. Some important factors influencing the grafting effect, e.g. crystallinity of UHMWPE fiber, concentration of the initiating reagent, grafting time and the concentration of grafting monomer (acrylamide) were discussed. Fourier transform infrared (FTIR) was used to manifest the mechanism of the grafting reaction. Scanning electron microscopy (SEM) was used to show the morphology changing of the fiber surface. Single fiber pull-out strength and ILSS tests of the composite showed that acrylamide grafted onto the surface of the fiber could improve the interfacial adhesion between treated fibers and matrices.     

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.     

Surface Modification of Ultrahigh-molecular-weight Polyethylene Fibers with Coupling Agent during Extraction Process

Ultrahigh molecular weight polyethylene (UHMWPE) fibers were treated with a coupling agent following the extraction of gel fibers, resulting in modified fibers after subsequent ultra-drawing. The structure and morphology of the modified UHMWPE fibers were characterized and their surface wetting, interfacial adhesion, and mechanical properties were investigated. It was found that the coupling agent was absorbed into the UHMWPE fiber and trapped on the fiber surface. Compared with unmodified UHMWPE fibers, the modified fibers had smaller contact angle, higher crystallinity, and smaller crystal size. The interfacial adhesion and mechanical properties of UHMWPE fibers were significantly improved with increasing coupling agent concentration and gradually reached a plateau value. After treatment with 1.5 wt% solution of a silane coupling agent (γ -aminopropyl triethoxysilane, SCA-KH-550), the interfacial shear strength of the UHMWPE-fiber/epoxy composites was increased by 108% and the tensile strength and modulus of modified UHMWPE fibers were increased by 11% and 37% respectively.     

The effect of surface modification on the properties of sisal fiber and improvement of interfacial adhesion in sisal/starch composites induced by starch nanocrystals

A facile approach was utilized to introduce starch nanocrystals (SNCs) onto sisal fiber (SF) to improve the interfacial adhesion between SF and starch. For this, fibers were treated with alkali and then subjected to cold plasma treatment to increase the accessibility with SNCs, which was confirmed through X-ray photoelectron spectroscopy (XPS). It was found that due to the influence of cold plasma treatment, new functional groups were introduced onto SF. The surface characteristics of SF were examined by Fourier transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM). The observed results suggested that SNCs were successfully distributed onto SF. Tensile strength and interfacial shear strength of fibers treated under different conditions were calculated and compared through a two-parameter Weibull model. The highest interfacial shear strength of 3.05 MPa was obtained by Alkali-300 W-SNCs, which indicated an increase of 80.6% than untreated SF. It has also been proved that the starch nanocrystals produced hydrogen bonding and physical interlocking between sisal fiber and starch. Notably, the outcome of this investigation indicates that SNCs may be applied for the fabrication of high performance, environmentally friendly sisal/starch composites for a range of technological applications.     

Improving the interfacial strength of PMMA resin composites by chemically grafting graphene oxide on UHMWPE fiber

Controlling interfacial microstructure and interactions between (ultra high molecular weight polyethylene) UHMWPE fiber and matrix is of crucial importance for the fabrication of advanced polymer composites. In this paper, (UHMWPE fiber-g-graphene oxide [GO]) was prepared. GO nanoparticles distributed onto the ?ber surface uniformly, which could increase surface polarity and roughness. Increases of interlaminar shear strength (ILSS) and interfacial shear strength (IFSS) of UHMWPE fiber-g-GO composites were achieved. These enhancements can be attributed to the existent of GO interface with providing chemical bonding and strong mechanical interlocking between the ?ber and matrix. Moreover, impact resistance of UHMWPE fiber-g-GO composites was enhanced.     

Preparation of Ultrahigh Molecular Weight Polyethylene/WS2 Composites for Bulletproof Materials and Study on Their Bulletproof Mechanism

Ultrahigh molecular weight polyethylene (UHMWPE)/WS₂ nanoparticle fibers were prepared by adding inorganic fullerene-like (IF) WS₂ nanoparticles treated by a coupling agent to the precursor solution of UHMWPE. The influence of WS₂ nanoparticles on the microstructure and properties of UHMWPE fibers were characterized by the scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and mechanical property measurements. The bulletproof performance of the UHMWPE/WS₂ composite was tested by a bullet-shock test, and the bulletproof mechanism of the UHMWPE/WS₂ composite was preliminarily studied. The results showed that WS₂ nanoparticles could be uniformly dispersed in the UHMWPE fiber. After incorporating of WS₂ nanoparticles, the UHMWPE fibers became stiffer and tougher than the pristine ones. In particular, the modulus of the fibers increased from 1203 to 1326 cN/dtex. The introduction of IF-WS₂ nanoparticles led to significantly improved bulletproof performance of UHMWPE fibers.     

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.     

Benzothiazole sulfide compatibilized polypropylene/halloysite nanotubes composites

Clay-philic benzothiazole sulfide, capable of donating electrons, is grafted onto polypropylene (PP) backbones when N-cyclohexyl-2-benzothiazole sulfonamide (CBS), a commonly used accelerator in the tire industry, is included in the processing of PP/halloysite nanotubes (HNTs) composites. CBS decomposes at elevated temperature and yields benzothiazole sulfide radicals, which react with the PP polymeric free radicals generated during the processing of the composites. On the other hand, the benzothiazole group of CBS is reactive to HNTs via electron transferring. The compatibilization between HNTs and PP is thus realized via interfacial grafting and electron transferring mechanism. The interfacial interactions in the compatibilized systems were fully characterized. Compared with the control sample, the dispersion of HNTs and the interfacial bonding are enhanced substantially in the compatibilized composites. The significantly improved mechanical properties and thermal properties of benzothiazole sulfide compatibilized PP/HNTs composites are correlated to the enhanced interfacial property. The present work demonstrates a novel interfacial design via interfacial grafting/electron transferring for the compatibilization of PP/clay composites.     

Enhanced mechanical properties of bamboo fiber/HDPE composites by grafting poly(amido amine) onto fiber surface

The mechanical properties of bamboo fiber composites depend on the interfacial strength between fiber and high-density polyethylene (HDPE) matrix. Different poly (amido amine) (PAMAM) dendrimers were grafted onto bamboo fiber to improve the interfacial strength of the resulting composites. The surface morphology of the resulting materials was characterized by scanning electron microscopy and atomic force microscope. Surface characteristic the bamboo fiber surface were examined by X-ray photoelectron spectroscopy and Fourier transform infrared (FT-IR). The characterization results revealed that PAMAM were chemically grafted onto the surface of bamboo fiber.     

Surface modification of magnetic metal nanoparticles through irradiation graft polymerization

To tailor the interfacial interaction in magnetic metal nanoparticles filled polymer composites, the surfaces of iron, cobalt and nickel nanoparticles were grafted by irradiation polymerization. In the current report, effects of grafting conditions, including irradiation atmosphere, irradiation dose and monomer concentration, on the grafting reaction are presented. The interaction between the nanoparticles and the grafted polymer was studied by thermal analysis and X-ray photoelectron spectrometry. It was found that there is a strong interfacial interaction in the form of electrostatic bonding in the polymer-grafted nanoparticles. The dispersibility of the modified nanoparticles in chloroform was significantly improved due to the increased hydrophobicity.     

Radical graft polymerization from carbon whisker initiated by peroxyester groups introduced onto the surface

The radical graft polymerization of vinyl monomers onto carbon whiskers, i.e. vapor grown carbon fibers, initiated by tert-butyl peroxyester groups that are introduced onto the surface was investigated. The introduction of tert-butyl peroxyester groups onto the carbon whisker surface was achieved by the reaction of acyl chloride groups on the surface with tert-butyl hydroperoxide. The carbon whisker having acyl chloride groups was prepared by the following three methods: (1) reaction of surface carboxyl groups with thionyl chloride, (2) reaction of surface phenolic hydroxyl groups with succinyl dichloride, and (3) reaction of surface phenolic hydroxyl groups with phthaloyl dichloride. The carbon whiskers having tert-butyl peroxyester groups prepared from these three methods were abbreviated as CW-POE 1, 2, and 3, respectively. The peroxyester group content of CW-POE 1, 2, and 3 was determined to be 0.06, 0.05, and 0.17 mmol/g, respectively. It was found that the radical polymerization of vinyl monomers such as methyl methacrylate, styrene, and N-vinylcarbazole was successfully initiated in the presence of CW-POE 2 and 3, and the corresponding polymers were grafted onto the surface. However, CW-POE 1 failed to initiate the radical graft polymerization, because surface phenyl radicals formed by the thermal decomposition of the tert-butyl peroxyester groups are stabilized by the aromatic rings of the carbon whisker surface.     

Superhydrophobicity of silica nanoparticles modified with polystyrene

Polystyrene/silica nanoparticles were prepared by radical polymerization of silica nanoparticles possessing vinyl groups and styrene with benzoyl peroxide. The resulting vinyl silica nanoparticles, polystyrene/silica nanoparticles were characterized by means of Fourier transformation infrared spectroscopy, scanning electron microscopy and UV-vis absorption spectroscopy. The results indicated that polystyrene had been successfully grafted onto vinyl silica nanoparticles via covalent bond. The morphological structure of polystyrene/silica nanoparticles film, investigated by scanning electron microscopy, showed a characteristic rough structure. Surface wetting properties of the polystyrene/silica nanoparticles film were evaluated by measuring water contact angle and the sliding angle using a contact angle goniometer, which were measured to be 159° and 2°, respectively. The excellent superhydrophobic property enlarges potential applications of the superhydrophobic surfaces.     

Influence of ethylene glycol pretreatment on effectiveness of atmospheric pressure plasma treatment of polyethylene fibers

For atmospheric pressure plasma treatments, the results of plasma treatments may be influenced by liquids adsorbed into the substrate. This paper studies the influence of ethylene glycol (EG) pretreatment on the effectiveness of atmospheric plasma jet (APPJ) treatment of ultrahigh molecular weight polyethylene (UHMWPE) fibers with 0.31% and 0.42% weight gain after soaked in EG/water solution with concentration of 0.15 and 0.3 mol/l for 24 h, respectively. Scanning electron microscopy (SEM) shows that the surface of fibers pretreated with EG/water solution does not have observable difference from that of the control group. The X-ray photoelectron spectroscopy (XPS) results show that the oxygen concentration on the surface of EG-pretreated fibers is increased less than the plasma directly treated fibers. The interfacial shear strength (IFSS) of plasma directly treated fibers to epoxy is increased almost 3 times compared with the control group while that of EG-pretreated fibers to epoxy does not change except for the fibers pretreated with lower EG concentration and longer plasma treatment time. EG pretreatment reduces the water contact angle of UHMWPE fibers. In conclusion, EG pretreatment can hamper the effect of plasma treatment of UHMWPE fibers and therefore longer plasma treatment duration is required for fibers pretreated with EG.     

Hydrophilic modification of microporous polysulfone membrane via surface-initiated atom transfer radical polymerization of acrylamide

Polyacrylamide (PAM) brushes were grafted from chloromethylated polysulfone (CMPSF) membrane surface by surface-initiated atom transfer radical polymerization (SI-ATRP) to improve the membrane's hydrophilic property. In order to anchor the initiator onto polysulfone (PSF) membrane surface, CMPSF was used to prepare the microporous membrane by phase-inversion process. Attachment of the PAM chains on membrane surface was confirmed by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The grafted density of PAM was calculated to be 0.08 chains nm⁻². Field emission scanning electron microscopy (FESEM) and atomic force microscope (AFM) were used to characterize the surface morphology of the CMPSF membrane and modified membrane. The number-average molecular weight (M_n) of PAM linearly increased with the polymerization time, while the static water contact angle (θ) of the membrane grafted with PAM linearly decreased. This indicated the hydrophilic property of the membrane was linearly correlated with the chain length of graft polymer. Therefore linear control of PSF membrane's hydrophilic property was realized through adjusting polymerization time.     

Synthesis and Characterization of Methylacrylic Acid and Butyl Acrylate Grafted onto Ethylene-Propylene-Diene Terpolymer

A multi-component polymer of methacrylic acid (MAA) and butyl acrylate (BA) grafted onto ethylene-propylene-diene (EPDM) terpolymer was synthesized in toluene using benzoyl peroxide (BPO) as initiator. The effect of EPDM/MAA-BA ratio and MAA/BA ratio on the grafting ratio of polymerization was investigated. The products were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), surface energy, inherent viscosity, and atomic force microscopy (AFM). The results showed that the MAA and BA monomers were successfully grafted onto EPDM. Furthermore, after being grafted, the polarity of the surface of the EPDM-g-MAA-BA increased with increasing grafting ratio, and the morphology of its surface became more smooth.     

Radical grafting from carbon fiber surface: graft polymerization of vinyl monomers initiated by azo groups introduced onto the surface

This paper describes the radical graft polymerizations of vinyl monomers from carbon fiber surface initiated by azo groups introduced onto the fiber surface. The carbon fiber used in this experiment was the polyacrylonitrile type. The introduction of azo groups onto the carbon fiber surface was achieved by the reaction of 4,4'-azobis (4-cyanopentanoic acid) with isocyanate groups which were previously attached onto the surface by the treatment of the fiber with tolylene 2,4-diisocyanate. The amount of surface azo groups introduced onto nitric acid-treated carbon fiber was determined to be 0.60 x 10^-5 mol 9^-1 by nitrogen analysis. The radical graft polymerization of methyl methacrylate (MMA) was tried. Though the thermal polymerization of MMA proceeded slightly in the absence or in the presence of untreated carbon fiber, the rate of the polymerization was considerably low. In contrast, the graft polymerization of MMA was initiated in the presence of the carbon fiber having surface azo groups, and part of resultant poly(MMA) grafted onto the surface. The percentage of grafting increased with an increase in polymerization time and reached 42.8% after 24 h. The graft polymerizations of other monomers, such as styrene, vinyl acetate, and acrylic acid, were also initiated by the surface azo groups attached onto the carbon fiber, and the corresponding polymer effectively grafted onto the surface.     

Surface modification of UHMWPE with γ-ray radiation for improving interfacial bonding strength with bone cement (II)

The surface of ultra high molecular weight polyethylene (UHMWPE) was exposed to γ-ray for improving bonding strength to polymethylmethacrylate (PMMA) bone cement. Two types of irradiation methods, pre-irradiation and syn-irradiation, were engaged in this study. The intensity of irradiation was 5–30 kGy for pre-irradiation, and 1–3 kGy for syn-irradiation. The grafting process was performed in a glass ampule filled with methanol, MMA monomer (60 v%), FeSO₄ · 7H₂O (1.5 × 10⁻⁴ M) and H₂SO₄ (0.1 M). The graft rate of each specimen was measured with time variation. The grafting effect of the acrylates on to the UHMWPE surface was investigated by mechanical test for bonding strength. Pre-irradiation method showed thinner coverage PMMA graft on the surface of the UHMWPE and higher bonding strength than syn-irradiation method. The interfacial bonding strength between UHMWPE and PMMA bone cement was considerably improved by γ-ray irradiation method. For medical application, the pre-irradiation method might be recommended, because the PMMA could be grafted as optimized thickness to the UHMWPE surface.     

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.     

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.     

Grafting of polymers onto graphene oxide by cationic and anionic polymerization initiated by the surface-initiating groups

The grafting of polymers onto graphene oxide (GO) was achieved by two process: (1) cationic polymerization initiated by carboxyl (COOH) groups on GO and (2) anionic alternating copolymerization of epoxides with cyclic acid anhydrides initiated by potassium carboxylate (COOK) groups on GO. The cationic polymerizations of isobutyl vinyl ether and N-vinylcarbazole were successfully initiated by COOH groups on GO to give the corresponding polymer-grafted GO. The cationic polymerization was considered to be initiated by proton addition from COOH groups to monomer and propagation of polymer cation proceeds with carboxylate anion as a counter ion. It was found that the corresponding polymer was successfully grafted onto GO based on the termination reaction of growing polymer cation and surface counter carboxylate anion. On the other hand, the anionic ring-opening alternating copolymerization of epoxide and cyclic acid anhydrides were also initiated by COOK groups on GO, which were previously introduced onto GO by the neutralization of COOH groups with KOH. During the anionic ring-opening copolymerization of styrene oxide (SO) with phthalic anhydride (PAn) and maleic anhydride (MAn), the corresponding polyesters, poly(SO-alt-PAn) and poly(SO-alt-MAn), were successfully grafted onto GO, based on the propagation of the polyesters from COOK groups. The grafting of polymers onto GO during the above cationic and anionic polymerizations was confirmed by thermal decomposition gas chromatogram/mass spectrum. The untreated GO in THF was immediately precipitated within 15 min. On the contrary, these polymer-grafted GOs gave stable dispersions in THF and no precipitation of polymer-grafted GOs was observed even after one week.