Showing papers in "Plasmas and Polymers in 2000"

Sterilization by Low-Pressure Plasma: The Role of Vacuum-Ultraviolet Radiation

Abstract: Low-pressure plasma is a promising method for destroying microorganisms, an alternative to “conventional” methods, which have numerous drawbacks. Several plasma-based sterilization technologies are presently under development, even though the exact role of the various plasma constituents, for example ultraviolet radiation, on the sterilization mechanism is still unknown and subject to controversy. In this study, we first report high sporicidal activity of a microwave (MW) plasma compared to its radio-frequency (RF) counterpart, which we believe to be due to the higher concentration of reactive particles in the former plasma. We then report a relatively low sporicidal efficacy of vacuum ultraviolet (VUV) radiation (between 115 and 170 nm) emitted by an hydrogen MW plasma, in spite of the high effectiveness of these photons to break chemical bonds. We discuss these results in terms of etching (ablation), which we have observed for both synthetic polymers and spores, and in terms of other possible mechanisms proposed in the literature. The sporicidal effectiveness of VUV/UV radiation appears to vary markedly with wavelength and intensity, on account of spore structure and molecular absorption.

Thin films deposition from hexamethyldisiloxane and hexamethyldisilazane under Dielectric-Barrier discharge (DBD) conditions

Abstract: Hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDSN) were used as organosilicon reagents for PE-CVD of thin films under filamentary barrier-discharge conditions at atmospheric pressure. Efficient discharges were obtained in the region of moderate frequencies (5 kHz). The following mixtures of organosilicon reagents with carrier gas and oxidants or ammonia were investigated: HMDSO+Ar, HMDSO+N2, HMDSO+O2+Ar, HMDSO+N2O+Ar, and HMDSN+NH3+N2. Under such conditions HMDSO was converted to produce thin films (10–1000 nm) of silicon oxide, generally containing admixtures of residual “organic” content (Si—CHn and Si—H groups). The films deposited from HMDSN+NH3+N2 contained silicon, nitrogen and oxygen.

Electrical and optical diagnostics of dielectric barrier discharges (DBD) in He and N2 for polymer treatment

Abstract: Synchronous, real-time optical and electrical diagnostics have been carried out on dielectric barrier discharges in flowing gases (air, He, N2) at atmospheric pressure A true “Atmospheric Pressure Glow Discharge” (APGD) is observed in N2 when O2 and H2 concentrations are below ≈500 ppm and 2500 ppm,respectively, and the APGD regime can be beneficially modified by suitably chosen dielectric coatings X-ray photoelectron spectroscopy (XPS) analyses of some APGD-treated polymer surfaces are presented

Surface functionalization at atmospheric pressure by DBD-based pulsed plasma polymerization

Abstract: Dielectric barrier discharge (DBD)-based plasma deposition at atmospheric pressure, using glycidyl methacrylate (GMA, methacrylic acid-[2,3-epoxy-propyl ester]) as a prototype precursor was investigated in order to evaluate the applicability of dielectric barrier discharges to obtain plasma polymers with a high degree of structural retention of the starting precursor. Using pulsed excitation of the discharge, up to about 90% of the epoxy groups of GMA can be retained in plasma polymers obtainableat deposition rates in the order of 3–5nm/s. Preliminary investigations of the mechanism of film formation under pulsed plasma conditions indicate that the reaction of intact monomer molecules withsurface radicals generated during the pulses play a prominent role.

Plasma-deposition of Ag-containing polyethyleneoxide-like coatings

Abstract: Ag-containing polyethyleneoxide (PEO)-like thin films have been deposited in Radio Frequency Glow Discharges fed with vapors of diethyleneglycol-dimethylether and argon. Proper experimental conditions have been utilized in order to fragment the monomer in the glow and, at the same time, sputter Ag from the silver RF cathode of the reactor, in a way that polyethyleneoxide(PEO)-like coatings with embedded Ag clusters have been deposited at the ground electrode. The compostion of the coatings has been investigated by means of different techniques; the plasma process has been investigated by means of Actinometric Optical Emission Spectroscopy. A correlation has been found between the amount of silver embedded in the coatings and that sputtered in the discharge, monitored by actinometry, that could eventually be utilized to control in situ the deposition process.

A Surface Masking Technique for the Determination of Plasma Polymer Film Thickness by AFM

Abstract: A method for the determination of coating film thicknesses at nanometer resolution based on surface masking and atomic force microscopy (AFM) is described. A polymeric mask is used to cover part of a substrate during the deposition of thin polymeric coatings by plasma polymerization, allowing the production of well defined polymer steps of heights of a few tens of nanometers. Tapping mode AFM has been employed to analyze the topography of these steps at high resolution. This method has also allowed accurate measurement of the kinetics of the deposition of plasma polymer films over a range of exposure times. XPS analysis of different substrate surfaces following mask removal found barely detectable residues, suggesting that the underlying surface chemistry remains unchanged, and accessible for further modification. In combination with quartz crystal microgravimetry, the method has been applied to the measurement of the density of plasma polymer coatings in the thickness range 4–50 nm.

Synthesis of Organic Compounds from Mixtures of Methane with Carbon Dioxide in Dielectric-Barrier Discharges at Atmospheric Pressure

Abstract: The entire range of gas phase reaction products, depending on the composition of initial binary mixtures of methane and carbon dioxide in dielectric barrier discharges, has been determined (saturated as well as unsaturated hydrocarbons and oxygenated organic compounds) The macro-kinetics of the basic chemical pathways of the system under consideration has been investigated This system is found to display a strong feedback effect (positive or negative, depending on the initial state of the surfaces, as well as the chemical composition of the feed-gas mixture) It is demonstrated that these properties undergo significant changes during operation, due to surface modification processes (polymer film deposition, its oxidation or reduction) They are found to exert a considerable influence on the chemical efficiency of the discharge (for example, on the absolute and relative chemical yields of the reaction products), the Lissajous figures appear to be a sensitive tool to monitor the operation conditions of the discharge

Silane-based coatings on polypropylene, deposited by atmospheric pressure glow discharge plasmas

Abstract: The aim of this paper is to show the possibility to synthesize silicon-based deposits on a polypropylene substrate, using a glow dielectric barrier discharge at atmospheric pressure, and to correlate the gas phase behavior with the properties of the thin film deposits. The discharge is generated in a mixture of nitrous oxide and silane, diluted in nitrogen. The influence of the [N2O]/[SiH4] ratio on the layer characteristics is mainly studied. Deposits are analyzed by XPS, SSIMS, AFM and wetting angle measurements. The discharges are also characterized by their optical emission spectra. Measurements are made as a function of the distance from the gas inlet, and they allow one to correlate these spectra with the film thickness and its chemical composition. Finally, chemical kinetics of the reactive gas decomposition reactions are proposed.

Modification of polyimide in barrier discharge air-plasmas : Chemical and morphological effects

Abstract: Chemical and physical modifications of polyimide (PI) surfaces caused by an air plasma have been studied. The plasma-induced surface changes of PI were investigated by using a local dielectric barrier discharge (DBD) in air at atmospheric pressure and room temperature as a function of the plasma exposure time and plasma power, while the excitation frequency was kept constant at about 130 kHz. The first results obtained in this work suggest that DBDs operating in air at atmospheric pressure can be an efficient alternative plasma source for surface treatment of polymers: a short time air plasma treatment of few seconds leads to chemical and physical changes including the rise of wettability, surface oxidation, and enhancement of surface roughness. Therefore, this simple kind of dry surface treatment seems to be an effective, low cost method for production of well-adhering subsequent layers such as metal films, paints, glues, etc. on DBD pretreated polymers.

Cleaning of Silicon and Steel Surfaces Using Dielectric Barrier Discharges

Abstract: The plasma-activated removal of oil from contaminated silicon substrates and galvanized steel sheets has been performed using dielectric barrier discharges (DBD) at atmospheric pressure. Removal rates were determined by ellipsometric measurement of the oil film thickness, using polished silicon as substrates. With galvanized steel sheets, qualitative and quantitative investigations were done using fluorescence microscopic characterization of theplasma-treated surfaces. Both the ellipsometric and the fluorescence microscopic measurements yield the dependence of the removal rate on treatment parameterssuch as plasma–gas composition and gas flow. The film thickness measurements were calibrated using quantitative IR spectroscopic measurements. It could be shown that the removal rate increases with increasing oxygen content in the process gas, static removal rates of 0.6 nm/s and 7 nm/s being obtainedin pure nitrogen and in pure oxygen, respectively. Fluorescence microscopic investigations showed that oil can be removed even from grooves in the galvanized steel sheets.

ESR Study of the plasma polymerizations of trimethylsilane and methane

Abstract: Electron Spin Resonance (ESR) was used to study, at the molecular level, the plasma polymerization of trimethylsilane (TMS) and methane. Direct ESR analysis of the plasma coated Al substrate required the use of a novel ESR technique. TMS plasma deposit on Al showed a single broad resonance line near g = 2.003. The signal was stable in vacuum and decayed on exposure to air, with a significant fraction persisting for days. Results show that this signal arises from silicon dangling bonds. Identical TMS signals were observed from films prepared by the DC cathodic or the AF glow discharge method but their decay rates were different. In contrast, the deposition of methane produced two distinct types of carbon-based signals depending upon the method of deposition. TMS or CH4 films deposited by the DC cathodic method showed slow signals decay and high refractive indices value. While the use of Al as the substrate showed plasma-coating radicals, only substrate radicals were observed when PE was used as the substrate. The nature of radicals formed depends not only on the deposition method used but also on the substrate type.

Surface Modification of Poly(tetrafluoroethylene) Films by Plasma Pre-Activation and Plasma Polymerization of Glycidyl Methacrylate

Abstract: Surface modification of poly(tetrafuoroethylene) (PTFE) film by plasma polymerzation and deposition of glycidyl methacrylate (GMA), in the presence and absence of Ar or O2 plasma pre-activation, was carried out to enhance the adhesion with polyimides (PI) film in the presence of an epoxy adhesive. For deposition carried out at low RF power, a high epoxide concentration was preserved in the plasma-polymerized GMA (pp-GMA) layer on PTFE (pp-GMA-PTFE). However, high adhesion strength of the PI/pp-GMA-PTFE laminate was obtained only in the presence of O2 plasma pre-activation of the PTFE substrates prior to plasma polymerization and deposition of GMA. In the absence of any plasma pre-activation or in the presence of Ar plasma pre-activation, the deposited pp-GMA layer on the PTFE surface could be readily removed by solvent extraction. The adhesion enhancement of the PI/pp-GMA-PTFE laminates in the presence of O2 plasma pre-activation was attributed to the preservation of the epoxide functional groups in the pp-GMA layer, the curing of the GMA chains into the matrix of the epoxy adhesive, and the covalent bonding of the pp-GMA layer on the PTFE surface.

Plasma polymers applied to chemical sensing

Abstract: The paper describes attempts to apply plasma polymers to the development of chemical sensors. The plasma polymers were used as membranes to coat conventional conducting polymer sensors, as stand-alone chemiresistive sensors and as absorbent coatings on quartz crystal microbalances. The plasma polymers were derived from combinations of pyrrole and three silicon containing monomers. In the chemiresistive sensors, conductivity was induced in the polymer matrix by doping with iodine. The paper describes the experimental polymerization conditions, the physical characteristics of the polymers, and the application of the different polymers to sensing common volatile analytes.

Influence of vapor phase pretreatments of epoxy surfaces on the nucleation of MOCVD copper thin films

Abstract: Vapor phase pretreatments of epoxy composite material reinforced with carbon fibers were carried out prior to the growth of Cu thin films by metal-organic chemical vapor deposition (MOCVD) using Cu (hfa)(COD) as copper precursor. These dry surface oxidation processes include H2O/UV, O2/UV and O2/Plasma treatments. Oxygen plasma method is the most efficient to oxidize the surface and it has the greatest effect to improve the wettability of epoxy samples. As a consequence, the higher hydrophilicity of the plasma-modified epoxy surface induces a higher nucleation density in the Cu film. Furthermore, this treatment reduces drastically the induction period observed for the growth of the metal. Even though the O2/UV pretreatment incorporates almost the same amount of oxygen in the epoxy surface than the plasma treatment, the functional groups are different, as revealed by XPS analyses, and the surface is less hydrophilic. Correlations between oxidation, wettability and nucleation density of the Cu films are discussed.

Surface Modification of Polyester Monofilaments by Atmospheric-Pressure Nitrogen Plasma

Abstract: Polyester monofilaments were treated by a pulsed surface electrical discharge in nitrogen at atmospheric pressure, to increase their adhesion to an epoxy resin matrix. The treatment resulted in an eight-fold increase in adhesive strength, without any change in mechanical properties of the monofilaments. It is concluded that polar group interactions, rather than increased surface area, are responsible for the improved adhesive strength.

Industrial-Scale Process Control by Means of Electrostatics Probes

Abstract: We performed a series of measurements by means of the triple probe technique during plasma deposition of polymer films on large volume plastic containers. Based on the measured data, the process stability and process homogeneity were determined. The process stability was better than 5% and process reproducibility was about 6%. An inhomogeneity of the plasma density correlated to the barrier efficiency of the film deposited at different positions on the container. An increase in the power losses were found after changes in the electrical configuration of the deposition set-up. The quotient of electron density ne and product of molar mass of the working gas M and its flow F is proposed as invariant instead the Yasuda's parameter W/MF for characterization of large-scale industrial plasma polymerization process.