Cold remote nitrogen plasma polymerization from 1.1.3.3-tetramethyldisiloxane–oxygen mixture

Cold remote nitrogen plasma (CRNP) selectively reacts with silane-terminated organosiloxane compounds such as 1.1.3.3-tetramethyldisiloxane to give polymeric layers. Deposition rate measurements, FT-IR and Raman spectroscopy were performed. The chemical composition of the deposited film is closely dependent on the reactive gas composition and its flowing conditions. An original effect of dioxygen addition in the nonionic reactive media is pointed out: dioxygen addition leads to a fast and highly hydrocarbonated polymer formation with a nitrogen fixation in a silazane structure. Polymerization is described by a model where ?Si? O^· type of radicals are the critical reactant. A global mechanism is proposed involving active species of the CRNP in initiation step of hydrogen abstraction and the nitrogen triplet state molecule N₂(A³Σ) in methyl abstraction on ?Si^· type of free radical. Dioxygen adjunction appears to limit the methyl abstraction steps. The efficient direct oxygen reaction on free radicals leads to an increase of the ?Si? O^· radical density and, consequently of the average length of the growing polymeric fragments. Nitrogen fixation, involving oxygenated species, is discussed. Under defined conditions, a highly hydrophobic polymeric film is obtained with a volumic mass of 1.34g/cm³ and a deposition rate of about 12 mg/cm² h corresponding to a growth rate of 200 Å/s. © 1994 John Wiley & Sons, Inc.     

Pervaporation of water–ethanol mixtures through plasma graft polymerization of polar monomer onto crosslinked polyurethane membrane

To improve the pervaporation performance, the plasma post-graft polymerization of 2,3-epoxypropylmethacrylate (EPMA) onto the crosslinking polyurethane (CPU) membrane, EPMA-g-CPU, was synthesized in this study. The crosslinking between soft–soft hydroxyl-terminated polybutadiene (HTPB) segments were prepared by the introduction of benzoyl peroxide to the HTPB-based PU membrane. The effect of plasma treatment time and plasma supply power on the grafting yield was discussed. The optimum plasma treatment conditions were 10 W supply power and 120 s treatment time. The surface properties of the EPMA-g-CPU membrane were characterized by Fourier transform infrared spectroscopy, electron spectroscopy for chemical analysis, and a contact angle meter. A separation factor of 97 and a 240 g m⁻² h⁻¹ permeation rate through the EPMA-g-CPU membrane with a 4.81 mg/cm² grafting yield for a 90 wt % feed ethanol concentration were obtained. Compared with ungrafted CPU membrane, the EPMA-g-CPU membrane effectively improved the pervaporation performances. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1789–1797, 1998     

Core–shell polypyrrole nanoparticles obtained by atmospheric pressure plasma polymerization

Polypyrrole hollow nanoparticles were prepared by atmospheric pressure plasma polymerization. The structure of the nanoparticles was studied using Fourier transform infrared and X‐ray photoelectron spectroscopies, thermogravimetric analysis, scanning and transmission electron microscopies and atomic force microscopy. In contrast to low‐pressure plasma polymerization of pyrrole, which can produce films and solid nanoparticles, we obtained two types of hollow nanoparticles: a fraction with single spherical core and another with a core composed of small bubbles. Thermal characterization allowed us to determine that the nanoparticles are composed of highly crosslinked polymer. A mechanism that explains the formation of both types of hollow nanoparticles as well as solid nanoparticles is proposed. Chemical characterization shows that, in addition to the expected chemical structures due to pyrrole polymerization, the high energy of the plasma at atmospheric pressure produces intense dehydrogenation and oxidation processes. The fluorescence spectrum of the nanoparticles, however, shows a peak at 482 nm indicating that some degree of π‐conjugation is present in the material. © 2014 Society of Chemical Industry     

Modification of vitrinite coals in a low-temperature oxygen plasma

Transformations in the organic matter of vitrinites in coals of various ranks as a result of their interaction with oxygen activated in an RF field were characterized using IR spectroscopy and solvent extraction.     

Modification of Mongolian coals using a low-temperature oxygen plasma

The results of a study of the effect of the treatment of coals from the Khar Tarvagatai, Nuurst Khotgor, and Khushuut deposits of Mongolia in a low-temperature oxygen plasma are presented in this article.     

Modification of surface wettability of sodium ionomer sheets via atmospheric plasma treatment

In this study, atmospheric plasma treatment has been used to modify the wetting properties of ethylene‐methacrylic acid sodium ionomer. The effects of the plasma treatment on surface properties of this ionomer have been followed by contact angle measurements, Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and atomic force microscopy (AFM). With the use of these techniques, the overall effects on activation–functionalization and surface topography changes have been determined in terms of the processing parameters of the atmospheric plasma treatment (rate and distance). The obtained results show a remarkable increase of the wetting properties and optimum balanced behavior is obtained for atmospheric plasma treatment with a rate of 100 mm/s and a distance of 6 mm; in this case, surface free energy is increased from 33 mJ/m² (untreated ionomer) up to 62 mJ/m², maintaining good transparency. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Modification of polyethylene surface using plasma polymerization of silane

In the present study plasma polymerization of tetraethylorthosilicate and hexamethyldisiloxane was carried out on polyethylene film with an aim of enhancing barrier properties. The glow discharge was obtained at 0.2 mbar using 13.56 MHz radio frequency source capable of giving power out put up to 100 W. The monomer vapors were passed in the system at the rate of 15 SCCM. The extent of deposition was determined from the weight gain study and the morphology was studied using SEM. Films were further characterized by surface energy measurement, ATR‐FTIR and ESCA analysis. Since PE is widely used for packaging and in this process a thin layer of glass‐like transparent SiOx was deposited, therefore it was thought necessary to study permeability to water vapors. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Modification of coal tar in low-temperature oxygen plasma

Oxidative modification of coal tar by activated components of low-temperature plasma is considered. Such modification of tar is accompanied by polarization and polycondensation processes, with consequent increase in thermostability of the product.     

Modification of polyethylene–octene elastomer by silica through a sol–gel process

In this study, tetraethoxysilane (TEOS) and a metallocene polyethylene–octene elastomer (POE) were chosen as the ceramic precursor and the continuous phase, respectively, for the preparation of new hybrids by an in situ sol–gel process. To obtain a better hybrid, a maleic anhydride‐grafted polyethylene–octene elastomer (POE‐g‐MAH), used as the continuous phase, was also investigated. Characterizations of POE‐g‐MAH/SiO₂ and POE/SiO₂ hybrids were performed by Fourier transform infrared (FTIR) and ²⁹Si solid‐state nuclear magnetic resonance (NMR) spectrometers, a differential scanning calorimeter (DSC), a thermogravimetry analyzer, and an Instron mechanical tester. The results showed that the POE‐g‐MAH/SiO₂ hybrid could improve the properties of the POE/SiO₂ hybrid because the interfacial force between the polymer matrix and the silica network was changed from hydrogen bonds into covalent Si? O? C bonds through dehydration of hydroxy groups in POE‐g‐MAH with residual silanol groups in the silica network. The existence of covalent Si? O? C bonds was proved by FTIR spectra. For the POE/SiO₂ and POE‐g‐MAH/SiO₂ hybrids, maximum values of the tensile strength and the glass transition temperature were found at 9 wt % SiO₂ since a limited content of silica might be linked with the polymer chains through the covalent bond. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 966–972, 2003     

Drag reduction by polymer–polymer mixtures

An extensive study on the turbulent drag reduction caused by the various mixtures of polyacrylamide, purified guargum, xanthangum, and their graft copolymers has been conducted at low concentrations and Re = 14,000 using a turbulent flow rheometer. It has been found in most of the cases that the drag reduction caused by mixtures shows a positive deviation from the linearly additive straight line. This effect is more prominent when the drag reduction caused by both the constituents differ appreciably. In most of the cases, the drag reduction caused by the mixtures is higher than the DR caused by either of the constituent polymers; however, the drag reduction caused by the mixture is less than the sum of the drag reduction caused by both the constituents at their respective concentration in the mixture. It has also been noticed that there is no evidence of synergism in these mixtures at low concentrations.     

Modification of kaolinite by surface polymerization

Kaolinite filler surfaces were modified by both surface adsorption and surface reaction. Their subsequent wetting and adhesion properties were determined by measurement of the contact angle of the powders by the Washburn technique using three probe liquids that spanned molecular polarity. Surface modification by adsorption utilized the kaolinite surface acidity to polymerize styrene. Surface reaction involved reaction of kaolinite hydroxyl groups with aryl diisocyanates and subsequent termination with a series of alcohols of increasing complexity. It was shown that kaolinite surfaces could be modified to produce surfaces of controlled hydrophobicity that could exceed that of conventionally silanated kaolinite. The ability of phases to spread and wet these filler surfaces was analysed in terms of the thermodynamic functions—spreading coefficient S₁₂ and spreading pressure π_e.     

Structural defects created on natural graphite surface by slight treatment of oxygen plasma: – STM observations –

The creation of structural defects on natural graphite surfaces by slight treatment of oxygen plasma was studied by scanning tunneling microscopy (STM) at nanoscopic scale. Most of the defects were vacancies with the depth of one or two layers, while the mean number of defects per μm² of graphite surface and the mean area of defects increased with the increase in input power, time and temperature of the irradiation. After very slight treatment at room temperature, single carbon atom vacancies were obtained on graphite surfaces with a percentage more than 50%, though some large vacancies were formed. After slight irradiation at a high temperature (400°C), an agglomeration of defects occurred (the mean area increases whereas the defect density decreases), while the defects once formed were difficult to be annealed by heating at high temperatures up to 400°C in vacuum. The present work showed the possibility to control the modification of natural graphite surfaces for further applications by changing the condition of oxygen plasma treatment.     

Modification of styrene–divinylbenzene copolymer by anchoring ferric–dipyridylamine complex

Polystyrene–divinylbenzene (PS–DVB) copolymer was modified by anchoring dipyridylamine (DPA) on it followed by complexation with Fe(III). Under the experimental conditions followed, 9% incorporation of Fe(III) was achieved. PS–DVB–DPA and PS–DVB–DPA–Fe(III) were characterized by IR spectra. Diffuse reflectance spectra for PS–DVB–DPA–Fe(III) and DPA–Fe(III) revealed λ_max at ～ 360 and ～ 310, respectively. This difference could be due to a difference in the nature of the coordinating moieties complexing with Fe(III) in these two systems. Scanning electron micrographs of PS–DVB, PS–DVB–DPA–Fe(III), and heat-treated PS–DVB–DPA–Fe(III) revealed some typical surface features. Thermal stability varied in the order PS–DVB–DPA–Fe(III) > PS–DVB–DPA ?PS–DVB, and DTA showed characteristic exotherms. © 1992 John Wiley & Sons, Inc.     

Pervaporation membranes for ethanol–water mixture prepared by plasma polymerization. III. Perfluorocarbon membranes

Pervaporation membranes for the ethanol–water mixture were prepared by plasma polymerization of tetrafluoroethylene, perfluoropropane, and perfluoropropylene onto porous substrates. The influence of the monomers on the elemental ratio (F/C) of the polymer depositions by X-ray photoelectron spectroscopy was rather small compared with that of the W/FM parameter (W = wattage for plasma excitation, FM = mass flow rate of a monomer). The optical emission spectroscopy indicated the similarity of gaseous species formed in the plasmas. The membranes were found ethanol-permselective, showing separation coefficients (α_EtOH) around 4–7 and a wide range of permeation rates (J), 10–10^?2 kg/m² h, for the 4.8 wt % ethanol solution at 40°C. The α_EtOH of the membranes with thicker depositions could be correlated to the F/C ratios as a measure of membrane hydrophobicity. It was thought that, by making a plot α_EtOH against J values for the perfluorocarbon membranes, they could be classified into three groups on thickness of deposition. The ethanol-separation mechanisms for each group, which may contain four kinds of mass transfer schemes, i.e., distillation through larger pores, flow of sorption layer at the liquid–membrane interface, and diffusions through deposition or substrate, were also discussed.     

Styrene–butadiene–styrene/montmorillonite nanocomposites synthesized by anionic polymerization

We successfully synthesized an exfoliated styrene–butadiene–styrene triblock copolymer (SBS)/montmorillonite nanocomposite by anionic polymerization. Gel permeation chromatography showed that the introduction of organophilic montmorillonite (OMMT) resulted in a small high‐molecular‐weight fraction of SBS in the composites, leading to a slight increase in the weight‐average and number‐average molecular weights as well as the polydispersity index. The results from ¹H‐NMR revealed that the introduction of OMMT almost did not affect the microstructure of the copolymer when the OMMT concentration was lower than 4 wt %. Transmission electron microscopy and X‐ray diffraction showed a completely exfoliated nanocomposite, in which both polystyrene and polybutadiene blocks entered the OMMT galleries, leading to the dispersion of OMMT layers on a nanoscale. The exfoliated nanocomposite exhibited higher thermal stability, glass‐transition temperature, elongation at break, and storage modulus than pure SBS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Modification of polyester fabric properties by surfactant‐aided surface polymerization

Poly(methyl methacrylate) (PMMA) was applied to polyester fabric using a surface analog of emulsion polymerization. The admicellar polymerization was carried out using 1.5 mM dodecylbenzenesulfonic acid (DBSA) at pH 4 with 0.15M NaCl, 1 : 8 DBSA:monomer, and 1 : 10 initiator:monomer molar ratio. The PMMA film, which was formed, was characterized by SEM and FTIR. Hydrolysis of the PMMA film on polyester fabric was carried out to introduce carboxylic acid groups to the polyester surface to increase its hydrophilicity. The results show that a PMMA thin film was successfully formed on the polyester fabric. The water contact angle of the PMMA‐coated polyester fabric after hydrolysis by 10M H₂SO₄ for 5 h was reduced from 117.3° to 0° and there was a significant increase in the moisture‐regain value of the treated fabric. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4059–4064, 2007     

Control of molecular weight distribution in propylene polymerization with Ziegler–Natta/metallocene catalyst mixtures

Propylene polymerization was investigated with a sequential addition of Ziegler–Natta and metallocene catalysts. From the fact that the molecular weights of polypropylene (PP) produced with Ziegler–Natta and with metallocene catalysts differ, it was possible to control the molecular weight distribution (MWD) of PP with a sequential addition of methylaluminoxane and rac-ethylenebis(indenyl)zirconium dichloride followed by triethylaluminum and magnesium dichloride-supported titanium tetrachloride catalyst. The obtained PP exhibited a wide MWD curve with shoulder peak. The position and height of each peak was controlled with the variation of polymerization time for each catalyst as well as the amount of each catalyst. The MWD of PP prepared with sequential addition of catalysts was much wider than that of PP obtained from each catalyst. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2213–2222, 1998     

Preparation of polydimethylsiloxane nanolatices by emulsion polymerization in a water–aminoethanol system

Stable and translucent polydimethylsiloxane nanolatices in a water–aminoethanol (AE) system were prepared by the emulsion polymerization of octamethylcyclotetrasiloxane (D₄) with nonionic polyoxyethylene alcohol ethers and polyoxyethylene aryl ether as surfactants and with KOH as an initiator. The effects of the AE concentration on the emulsion polymerization rate (R_p) of D₄ and the physical properties of the resultant nanolatices were investigated. Increasing the AE concentration in the reaction mixture dramatically increased the emulsion R_p value of D₄, and the kinetics of the D₄ emulsion polymerization in this system were consistent with the Morgan–Kaler theory of microemulsion polymerization. When the AE concentration in the emulsion increased, the transparency value of the resultant emulsion increased, and the size of the droplets in the resultant nanolatices decreased. In addition, the molecular weight of the polysiloxane in the resultant emulsion also increased with the increase in the AE concentration in the reaction mixture. A nanolatex prepared by the emulsion polymerization of 0.98M D₄ with 185 g/L AE had a transparency value of 80.9% and a mean diameter of 59.5 nm. The morphology of polysiloxane nanolatices cured with (N,N‐diethylaminomethyl)‐triethoxysilane was observed with transmission electron microscopy, and the size of the globular particles was consistent with that obtained by dynamic light scattering. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 347–352, 2005