Preparation and tribological properties of carbon fibre reinforced poly(vinylidene fluoride) composites

Abstract

The current study examines the tribological performance of poly(vinylidene fluoride) (PVDF) and carbon fibre reinforced poly(vinylidene fluoride) (CF/PVDF) under dry sliding condition. Different contents of carbon fibres (CFs) were employed as reinforcement. All filled and unfilled polyimide composites were tested against CGr15 ball and representative testing was performed. The effects of CF content on tribological properties of the composites were investigated. The worn surface morphologies of neat PVDF and its composites were examined by scanning electron microscopy and the wear mechanisms were discussed. Moreover, all filled PVDFs have superior tribological characteristics to unfilled PVDFs. The optimum wear reduction was obtained when the content of CF is 20 vol.-%.     

Wettability of Polymeric Solids by Aqueous Solutions of Anionic and Nonionic Surfactant Mixtures

Measurements of the surface tension (γ _LV) and advancing contact angle () on poly(tetrafluoroethylene) (PTFE) and poly(methyl methacrylate) (PMMA) were carried out for aqueous solutions of sodium decyl sulfate (SDS) and p-(1,1,3,3-tetramethylbutyl)phenoxypoly(ethylene glycol) (TX100) and their mixtures. The results obtained indicate that the values of the surface tension and contact angles of solutions of surfactants on PTFE and PMMA surfaces depend on the concentration and composition of the surfactant mixtures. Calculations based on the Lucassen-Reynders equation indicate that for single surfactants and their mixtures at a given concentration in the bulk phase the values of surface excess concentration of surfactants at water–air and PTFE–water interfaces are nearly the same, so the adsorption of the surfactants at water–air and PTFE–water interfaces should also be the same. However, the adsorption of TX100 and its mixtures with SDS at water–air interface is higher than that at PMMA–water interface, which is confirmed by the ratio of absolute values of molecular interaction parameters at these interfaces calculated on the basis of Rosen approach. If we take into account the hydration of the poly(ethylene oxide) chains of TX100 and acid and base parameters of the surface tension of water it appears that the PMMA surface is covered by the 'pure' water molecules from the solution or molecules connected with the chain of nonionic surfactant. On the other hand, the lack of SDS molecules at the PMMA–water interface may result from the formations of its micelles which are connected with the TX100 chain.     

Distribution of acrylic acid grafted chains introduced into polyethylene film by simultaneous radiation grafting with water and ethanol as solvents

The graft copolymerization of acrylic acid onto low‐density polyethylene films by simultaneous γ‐ray irradiation was carried out. The effect of water and ethanol as grafting solvents on the distribution of grafted poly (acrylic acid) in the low‐density polyethylene films was studied with optical microscopy observations of dyed and sliced samples and attenuated total reflection/Fourier infrared spectroscopy analysis. When no vigorous homopolymerization occurred, both polyethylene and poly(acrylic acid) existed in the grafted layer, and the thickness of the grafted layer and the poly(acrylic acid) concentration in the grafted layer increased with an increasing degree of grafting, regardless of the grafting conditions, the former increasing faster than the latter. In comparison with water as the solvent, in the absence of the inhibitor, homopolymerization could be suppressed to a certain degree in the ethanol solvent system, whereas in the presence of the inhibitor, obvious homopolymerization occurred at a lower monomer concentration, and both the degree of grafting and the thickness of the grafted layer were lower. Such differences could be explained by the chain transfer and the relatively low solubility of poly(acrylic acid) in ethanol. In addition, an experimental scheme using optical microscopy to observe the dyed and sliced polymers was optimized. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1570–1577, 2007     

Thermosensitive surface properties of polyethylene film with poly(N-isopropylacrylamide) chains prepared by corona discharge induced grafting

Polyethylene (PE) film was treated by corona discharge and then grafted with N-isopropylacrylamide (NIPAAm) for modification of the surface. The grafted amount was determined by gravimetry and the surface morphology was observed by using a scanning electron microscope. The surface analysis was carried out with a x-ray photoelectron spectroscopy and electron probe microanalysis. It was clarified that grafting was limited surface and there was no change of the surface morphology after grafting. The water absorption at various temperature under the absolute humidity (11.4 g/cm³) and the leakage of electrostatic charge from PE film were measured. PolyNIPAAm that was introduced onto PE surface has hydrophilic-hydrophobic transition properties at the 32°C in the atmospheric condition. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1773–1779, 1998     

Styrene‐assisted grafting of maleic anhydride onto polypropylene by reactive processing

The grafting of maleic anhydride (MA) onto polypropylene (PP) was performed in the presence of the electron‐donating monomer styrene (ST) according to a central composite experimental design, in which the initial MA and ST concentrations were varied. The grafting of MA onto PP in the absence of ST was also performed. All reactions were carried out in the molten state in a Haake rheometer. The amount of reacted MA and the extent of degradation in PP were determined by means of Fourier transform infrared spectroscopy and melt flow index (MFI) measurements, respectively. The results showed that the presence of ST in the reactive processing caused a reduction in MFI and an increase in the level of reacted MA when the initial MA concentration equaled the initial ST concentration. An increase in the initial MA concentration presented distinct behavior that depended on the ST content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparison of maleic anhydride grafting onto powder and granular polypropylene in the melt by reactive extrusion

The grafting of powder and granular polypropylene (PP) with maleic anhydride (MA) was investigated in a reactive extrusion process with dicumyl peroxide (DCP) as an initiator. The effects of the MA and DCP contents in the feed on grafting were investigated. Under the experimental conditions applied in this study, the grafted monomer unit content was varied from 0.023 to 0.5%. The MA grafting efficiency of powder PP was higher than that obtained for the granular form of PP. In general, the grafting degree first increased with the MA or DCP content in the feed, then reached a maximum value, and finally decreased because of several possible alternative reactions during the grafting. The grafting of powder PP was more successful because of better initial mixing and less diffusional resistance during the grafting. An increase in the MA content in the feed caused significant reductions in the melt‐flow index of the graft copolymers. The results obtained with Fourier transform infrared, differential scanning calorimetry, and X‐ray powder diffraction analyses indicated that the structure, macrotacticity, crystallinity, crystallization, and thermal behavior of PP changed with grafting and depended on the grafting degree. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3675–3684, 2004     

Ozone‐induced grafting of a sulfoammonium zwitterionic polymer onto low‐density polyethylene film for improving hemocompatibility

Ozone‐induced grafting was developed to improve the hemocompatibility of biomaterials based on low‐density polyethylene (LDPE). An LDPE film was activated with ozone and graft‐polymerized with N,N′‐dimethyl(methacryloylethyl)ammonium propane sulfonate (DMAPS). The existence of sulfobetaine structures on the grafted film was confirmed by X‐ray photoelectron spectroscopy and attenuated total reflection/Fourier transform infrared (ATR–FTIR). More DMAPS was grafted onto the LDPE film as the DMAPS concentration increased, as determined by ATR–FTIR. Static contact‐angle measurements indicated that the DMAPS‐grafted LDPE film had a significant increase in hydrophilicity. The blood compatibility of the grafted film was preliminarily evaluated with a platelet‐rich‐plasma (PRP) adhesion study. No platelet adhesion was observed on the grafted film incubated with PRP at 37°C for 180 min. This new sulfoammonium zwitterionic‐structure‐grafted biomaterial might have potential for biomedical applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3697–3703, 2006     

Double crosslinked polyetheretherketone-based polymer electrolyte membranes prepared by radiation and thermal crosslinking techniques

Novel one-step preparation of polymer electrolyte membranes without a membrane casting process is achieved by radiation crosslinking of a polyetheretherketone (PEEK) film to prevent dissolution and deformation of the original film in sulfonating solutions. The films crosslinked with doses more than 33 MGy can be effectively sulfonated in a chlorosulfonic solution, resulting in a crosslinked sulfonated PEEK (sPEEK) electrolyte membrane with high proton conductivity comparable to Nafion. Nevertheless, its water uptake was high for application in fuel cells. The thermal treatment was effective for further crosslinking of the membrane; as a result, the water uptake and methanol permeability of the double crosslinked sPEEK membranes drastically decreased, compensating for a slight decrease of proton conductivity. In addition, unlike the traditional cast sPEEK membrane showing the irreversible swelling in hot water, the double crosslinked sPEEK membranes exhibited excellent stability toward 100 °C hot water for more than 200 h without any decrease in proton conductivity, and had the mechanical and thermal properties superior to those of Nafion.     

Radiation‐induced grafting of glycidyl methacrylate onto high‐density polyethylene (HDPE) and radiation lamination of HDPE

Radiation‐induced grafting of glycidyl meth‐acrylate (GMA) onto high‐density polyethylene (HDPE) and the radiation lamination of HDPE by bulk grafting of GMA were reported. The effects of irradiation dose, monomer concentration, and atmosphere on grafting were investigated. The extent of grafting initially increased with irradiation dose and then remained almost constant. The extent of grafting was higher in 2M GMA than in 1M GMA at the same irradiation dose. The extent of grafting in nitrogen was higher than that in air. The grafted samples were characterized with FTIR spectrometry and thermogravimetric (TG) analysis. A carbonyl group was found on grafted HDPE samples, and the carbonyl index increased with the extent of grafting. TG analyses proved the existence of grafted materials on HDPE and the grafted GMA thermally decomposes at a temperature lower than that of HDPE. Strong adhesion could be obtained with radiation lamination of HDPE by bulk grafting of GMA. Benzophenone facilitates the grafting in a proper concentration range. The adhesion mechanism of the laminated samples was the entanglement of the grafted chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 772–779, 2005     

Copoly(styrene-divinylbenzene)-g-poly(maleic anhydride-styrene): Preparation through radiation induced grafting and application in organic synthesis

Poly(styrene-divinylbenzene beads, preirradiated in air, were graft-copolymerized with mixtures of maleic anhydride and styrene. A detailed study of grafting was made under various reaction parameters. The succinic anhydride residues of a sample of copoly(styrene-divinylbenzene)-g-poly(maleic anhydride-styrene) with 111% grafting were chemically transformed into N-hydroysuccinimide (Resin I) and N-bromosuccinimide (Resin II) residues. The esters derived from Resin I (analogous to the N-hydroxysuccinimide esters) were good acylating agents and their use was explored for the synthesis of peptides. Resin II was used for the bromination of benzylic substrates. The spent resins were found to be reusable without much loss to their capacity. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 847–852, 1997     

Functionalization of polypropylene film by radiation grafting of acryloyl chloride and subsequent esterification with Disperse Red 1

Polypropylene (PP) films were grafted with acryloyl chloride by γ‐irradiation, and the grafted films were reacted with an azo dye, Disperse Red 1. The films were characterized by X‐ray diffraction, scanning electron microscopy, atomic force microscopy, and differential scanning calorimetry. It was found that the grafting takes place first on the film surface, and with increase in the radiation dose the grafting penetrated inside of the film, decreasing the crystallinity of the PP film. The surface of the films was homogeneous, and a mesophase was observed for the film grafted with the dye through a polarized optical microscope. The dye underwent trans to cis photoreaction, whereby the red films became colorless by the irradiation of UV light at room temperature, although the color was recovered on standing, and more quickly when heated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 172–178, 2004     

Visualization of reactive and non-reactive mixing processes in a stirred tank using planar laser induced fluorescence (PLIF) technique

A comprehensive study on the liquid mixing with/without instantaneous reactions was conducted using planar laser induced fluorescence (PLIF) technique, where a novel reactive PLIF technique was adopted to quantitatively visualize the dynamic variation of the concentration of fluorescence dye due to signal quenching by a Fenton reaction. The factors (e.g., tracer injection direction, tracer injection position, impeller speed) influencing the reactive and non-reactive mixing processes were investigated, and the mixing performances were characterized by non-reactive mixing times (τ₉₅ and τ₉₉), and reactive mixing time (θ₉₉), respectively. The experimental results from the 2-D measurements of liquid mixing behavior emphasized the significance of the understanding on the spatio-temporal mixing patterns: not only did the tracer injection position affect the mixing performances in the stirred tank, but also the sampling position to monitor the mixing status would lead to a large difference in evaluating the mixing performance. For the stirred tank with fast reactions, the reactive mixing performance had a strong interplay with the non-reactive mixing.     

Preparation and swelling properties of glycoside-bearing hydrogels by gamma-ray radiation to glycoside-bearing polymer aqueous solutions

γ-Ray radiation on poly(glucosyloxyethyl methacrylate) [poly(GEMA)] and poly(glucosyloxyethyl acrylate) [poly(GEA)] aqueous solutions without any crosslinkers gives glycoside-bearing hydrogels in a high yield. The degree of the swelling ratios of each obtained hydrogel in water was decreased with an increase in the total radiation dose to each polymer solution. In order to clarify the formation mechanism of obtained poly(GEMA) hydrogel by γ-ray radiation, the swelling properties of each hydrogel were also compared with those of poly(GEA) under various conditions. Poly(GEMA) in an organic solvent, N,N-dimethylformamide and dimethylsulfoxide, was not gelled by γ-ray radiation, although poly(GEA) was gelled under these conditions. These results suggest that the radiation formation mechanism of the poly(GEMA) hydrogels is different from that of the poly(GEA) hydrogels. In addition, the radiolysis of water is necessary in order to form the hydrogels for poly(GEMA). Next, we predicted the radiation formation mechanism of the poly(GEMA) hydrogels by the crosslinking between the glucoside moieties in poly(GEMA). © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 965–972, 1998     

Controlled grafting of polymer brushes on poly(vinylidene fluoride) films by surface‐initiated atom transfer radical polymerization

Controlled grafting of well‐defined polymer brushes on the poly(vinylidene fluoride) (PVDF) films was carried out by the surface‐initiated atom transfer radical polymerization (ATRP). Surface‐initiators were immobilized on the PVDF films by surface hydroxylation and esterification of the hydroxyl groups covalently linked to the surface with 2‐bromoisobutyrate bromide. Homopolymer brushes of methyl methacrylate (MMA) and poly(ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the α‐bromoester‐functionalized PVDF surface. The chemical composition of the graft‐functionalized PVDF surfaces was characterized by X‐ray photoelectron spectroscopy (XPS) and attenuated total reflectance (ATR)–FTIR spectroscopy. Kinetics study revealed a linear increase in the graft concentration of PMMA and PEGMA with the reaction time, indicating that the chain growth from the surface was consistent with a “controlled” or “living” process. The “living” chain ends were used as the macroinitiator for the synthesis of diblock copolymer brushes. Water contact angles on PVDF films were reduced by surface grafting of PEGMA and MMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3704–3712, 2006     

Electrochemiluminescence of coumarin derivatives induced by injection of hot electrons into aqueous electrolyte solution

Hot electrons can be injected from conductor/insulator/electrolyte (C/I/E) junctions into an aqueous electrolyte solution by cathodic pulse-polarization of the electrode. Injected hot electrons induce electrogenerated chemiluminescence of various luminophores including coumarins in fully aqueous solutions. This is based on the tunnel emission of hot electrons into aqueous electrolyte solution, which can result in the generation of hydrated electrons as reducing mediators. These tunnel-emitted electrons allow also the production of highly oxidizing radicals from added precursors. This work shows that coumarin derivatives are suitable candidates as ECL labels for bioaffinity assays or other analytical applications in which detection is based on the ECL of pulse-polarized C/I/E tunnel-emission electrodes in fully aqueous solutions. The mechanisms of the ECL of coumarins are discussed and the analytical applicability of the ECL of three coumarin derivatives is studied.     

Influence of the process on phase separation induced by radical copolymerization of styrene and divinylbenzene in the presence of reactive polyurethane network precursors

Interpenetrating polymer systems based on crosslinked polyurethane (PU) and polystyrene (PS) were prepared at room temperature by a one‐shot (in situ) method, starting from an initial homogeneous mixture of reagents via noninterfering mechanisms. Both polymerizations were performed either simultaneously or one after the other. True simultaneity at every stages of the process is not possible. Despite the difference in refractive index of the components, hazy or optically clear films were obtained, thus indicating various levels of phase separation, also confirmed by glass transition temperature (T_g) measurements. The results suggest that controlling the chemistry and process (crosslink density, composition, and time sequence of events) of in situ interpenetrating network formation will give various morphologies, and hence properties, ranging from microphase separated materials to larger macrophase separated materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Grafting reactions onto poly(organophosphazenes). VI. Thermooxidative stabilization of poly[bis (4-benzylphenoxy)phosphazene] by grafting acrylate polymers containing HALS groups

Poly[bist 4-benzylphenoxy phosphazene] is heated at 200 C in air and the oxidation of the 4-diphenylmethane side substituent to phosphazene-supported benzophenone, benzhydrol, and hydroperoxides is observed. The thermo-oxidative stabilization of the polymer is obtained by light-induced grafting copolymerization of the acrylic acid 2.2.6.6-tetramethyl-piperidin-4-yl ester onto the polyphosphazene substrate. The HALS moieties grafted onto the polyphosphazene films prevent the oxidative modification of the substituents and preserve the polymer against thermal damage. This process, investigated by IR. UV, and EPR spectroscopy, is basically dependent on the amount of HALS groups grafted onto the polyphosphazene matrix and on the composition of the reaction medium used to carry out the grafting process. The comparison between the thermooxidative stabilization process and the corresponding photooxidative stabilization reaction is also discussed.Presented at the 1st Italian Workshop on Cyclo- and Poly(phosphazene) Materials. Lebruary 15–16, 1996, at the CNR Research Area in Padova, Italy.     

Temperature‐sensitive membranes prepared by the plasma‐induced graft polymerization of N‐Isopropylacrylamide into porous polyethylene membranes

A temperature‐responsive polymer, poly(N‐isopropylacrylamide) (PNIPAAm), was grafted onto porous polyethylene membranes by a plasma‐induced graft polymerization technique. A wide range of grafting was achieved through variations in the grafting conditions, including the postpolymerization temperature, time, monomer concentration, and graft‐reaction medium. The active species induced by plasma treatment was proven to be long‐living via a postpolymerization time of 95 h. Different solvent compositions, that is, water, methanol, benzene, and water/methanol, were used as reaction media, and water showed a much higher polymerization rate than the organic solvents. Based on the hydrophilicity of the active species, a mechanism explaining the solvent effect in plasma‐induced graft polymerization was examined. Characterizations by scanning electron microscopy, X‐ray photoelectron spectroscopy (XPS), and micro Fourier transform infrared showed that the grafted polymers were located on both the outer surface and inside pores of the membranes. The XPS analysis also confirmed that the polar amide groups tended to distribute more outward when grafted PNIPAAm was in its expanding state than when it was in its shrinking state. Water permeation experiments showed that the permeability of the grafted membranes varied dramatically with a slight temperature change in the vicinity of the lower critical solution temperature (LCST) of PNIPAAm. The effective pore radii of the grafted membranes above and below the LCST could be depicted by Hagen‐Poiseuille's law. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3180–3187, 2003     

Proton exchange membranes prepared by simultaneous radiation grafting of styrene onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films. II. Properties of sulfonated membranes

Proton exchange membranes were prepared by radiation‐induced grafting of styrene onto commercial poly(tetrafluoroethylene‐co‐hexafluoropropylene) films using a simultaneous irradiation technique followed by a sulfonation reaction. The resulting membranes were characterized by measuring their physicochemical properties such as water uptake, ion exchange capacity, hydration number, and proton conductivity as a function of the degree of grafting. The thermal properties (melting and glass transition temperatures) and thermal stability of the membrane were also investigated using differential scanning calorimetry and thermal gravimetric analysis, respectively. Membranes having degrees of grafting of 16% and above showed proton conductivity of the magnitude of 10⁻² Ω⁻¹ cm⁻¹ at room temperature, as well as thermal stability at up to 290°C under an oxygen atmosphere. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2443–2453, 2000     

Functionalization of poly(ester‐urethane) surface by radiation‐induced grafting of N‐isopropylacrylamide using conventional and reversible addition–fragmentation chain transfer‐mediated methods

The functionalization of poly(ester‐urethane) (PUR) surface was conducted using radiation‐induced grafting. A thermosensitive layer constructed from N‐isopropylacrylamide (NIPAAm) was introduced onto a polyurethane film and characterized using attenuated total reflection Fourier transform infrared and X‐ray photoelectron spectroscopies and contact angle measurements. Size exclusion chromatography was used to analyse the PUR‐graft‐PNIPAAm copolymers and homopolymers formed in solution. Additionally, reversible addition–fragmentation chain transfer (RAFT) polymerization was performed in order to obtain PNIPAAm‐grafted surfaces with well‐defined properties. Atomic force microscopy was used to evaluate the surfaces synthesized via conventional and RAFT‐mediated grafting methods. The results of various techniques confirmed the successful grafting of NIPAAm from PUR film. © 2015 Society of Chemical Industry