In this work it was investigated the effect of the exposure to different plasmas on the wettability of silicone samples. We have observed that oxygen. argon, and hydrogen glow discharges are quite effective in reducing the water contact angle of such polymer. However, indifferently to efficiency of the treatment, practically all the modified surfaces recovered great part of their original hydrophobicity. We have investigated this hydrophobic recovery using surface energy measurements and theoretical simulations based on the exponential decay of the population of polar groups on the surface. According to our results such recovery can be attributed to the decrease of polar species at the interface water–polymer surface.
The emission of UV light as well as chemical reaction in plasmas allow them to be used for decontamination of food packaging. Sterilization efficiency of different dielectric barrier discharge (DBD) setups at atmospheric pressure was investigated for spores of B. subtilis and A. niger sprayed onto PET foils. In normal DBDs the efficiency of spore reduction in different gases (nitrogen, argon, synthetic air) can be related to the UV spectra of these gases in the discharge. With special so-called cascaded dielectric barrier discharges (CDBDs) a fast reduction of viable cells by more than four orders of magnitude is possible within few seconds, even for UV resistant cells. The sealing properties of commonly used PE-PET-laminate can be maintained in CDBD which is not observed for single-gap DBD.
Diamond-like carbon (DLC) films were grown from radiofrequency plasmas of acetylene-argon mixtures, at different excitation powers, P . The effects of this parameter on the plasma potential, electron density, electron temperature, and plasma activity were investigated using a Langmuir probe. The mean electron temperature increased from about 0.5 to about 7.0 eV while the mean electron density decreased from about 1.2 × 10 9 to about 0.2 × 10 9 cm −3 as P was increased from 25 to 150 W. Both the plasma potential and the plasma activity were found to increase with increasing P . Through actinometric optical emission spectrometry, the relative concentrations of CH, [CH], and H, [H], in the discharge were mapped as a function of the applied power. A rise in [H] and a fall in [CH] with increasing P were observed and are discussed in relation to the plasma characteristics and the subimplantation model. The optical properties of the films were calculated from ultraviolet-visible spectroscopic data; the surface resistivity was measured by the two-point probe method. The optical gap, E G , and the surface resistivity, ρ s , fall with increasing P . E G and ρ s are in the ranges of about 2.0–1.3 eV and 10 14 –10 16 Ω/□, respectively. The plasma power also influences the film self-bias, V b , via a linear dependence, and the effect of V b on ion bombardment during growth is addressed together with variation in the relative densities of sp 2 and sp 3 bonds in the films as determined by Raman spectroscopy.
Pulsed corona discharges have been utilized for plasma polymerization in aqueous solution for the first time. Superabsorbent copolymers, i.e., poly(acrylamide-co-acrylic acid) hydrogels, were synthesized by aqueous solution polymerization using free radicals produced by pulsed corona discharges as initiator and N,N-methylene-bis-acrylamide as cross-linking agent. Acrylic acid contents in the monomers varied from 0% to 50%. The copolymers thus formed adsorbed 30–1100 g H2O/g of copolymer. The FTIR spectra of the copolymers are comparable with the published FTIR spectra of the corresponding copolymers synthesized by a conventional chemical method and by γ-ray technique.
To supply combustion engines or gasturbines with fuel gas obtained from biomass gasification, it is necessary to clean the fuel gas. Also the production of chemicals by processes such as Fisher-Tropsch requires a high gas quality. Especially heavy aromatic hydrocarbons (“tars”) must be removed. In this work, we give an overview of our investigations on tar removal by pulsed corona discharges as an alternative approach to catalytic or thermal tar cracking. Experimental results (at a gas temperature of 200°C) are reported for the removal of various model tar components in synthetic fuel gas. In order to identify the major reaction pathways, experiments were also done on tars in individual fuel gas components. The results show that tar removal by pulsed corona processing is possible. The process for tar removal is mainly via oxidation. Also termination reactions by CO play an important role.
The modifications induced on poly (ethylene terephthalate) (PET) by an excimer laser radiation or a low pressure plasma as well as their ability to improve Al–PET adhesion were investigated. For this purpose, surface roughness, chemical composition, surface wettability, and adhesion properties of PET were studied depending on the process parameters. Both treatments can significantly enhance the adhesion but the surface change responsible for the improvement was different for each pretreatment.
Surface corona discharge characteristics from single-stripped and multi-stripped electrodes on the surface of thin dielectric plates of different kinds of ceramics and polymers are presented. Experimental results are obtained with voltage pulses of microsecond and nanosecond duration and they show significant difference in the values of the inception voltage, the discharge structure and current impulse amplitude for different barrier materials. Analysis of calculated and experimental values of the inception voltage is given, and it shows that beside electrical characteristics such as the relative permittivity ε and the specific resistance of the barrier material, the surface properties of the barrier, its thickness and its structure play a significant role in the discharge appearance and development. Nanosecond applied voltage pulses give a more dense and uniform discharge structure than microsecond ones, other conditions being equal.
Surface of polypropylene (PP) film was modified in plasma of dichloromethane (CH2Cl2). The nature of surface modifications and formation of cross-linked layer due to plasma polymerization was studied by surface energy measurements and solubility test. Surface modification achieved by CH2Cl2 plasma was compared with the reported work on chloroform (CHCl3) and carbontetrachloride (CCl4) plasma modifications. Modified surface characterized by ATR-FTIR technique indicated formation of saturated and unsaturated cross-linked product. On the basis of relative intensity change of the specific bands, the site of attachment of chlorine on PP surface was investigated. Adhesive strength of modified film was measured by T-peel test method. Stability of modified surface was studied by measuring surface energy and peel strength after two months.
Trichloroethylene (TCE) and vinyl chloride (VC) removal by gas phase pulsed corona discharge was investigated with attention to energy efficiency and byproduct identification. Approximately 50–95% removal of TCE and vinyl chloride was observed, depending on the energy density applied to the gas. Water vapor reduced TCE removal in some experiments. Evidence was found for post-corona reactions leading to removal of vinyl chloride downstream of the plasma discharge, while significant post-corona removal of TCE was not observed. Removal efficiencies of 100–900 g/kW-hr in the case of 1000 ppm feed of TCE, and of 2–24 g/kW-hr for a 100 ppm feed of vinyl chloride were found. In the TCE experiments, the formation of dichloroacetyl chloride was observed, while an unknown byproduct was found with vinyl chloride. The addition of a platinum-rhodium coated electrode was found to reduce the post-corona removal of vinyl chloride at low energy density.
The comparison of corona-treated and flame-treated polypropylene (PP) films provides insight into the mechanism of these surface-oxidation processes. Atomic force microscopy (AFM), contact-angle measurements, and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize surface-treated biaxially oriented PP. While both processes oxidize the PP surface, corona treatment leads to the formation of water-soluble low-molecular-weight oxidized materials (LMWOM), while flame treatment does not. Computational modeling of the gas-phase chemistry in an air corona was performed using a zero-dimensional plasma-chemistry model. The modeling results indicate that the ratio of O to OH is much higher in a corona discharge than in a flame. Chain scission and the formation of LMWOM are associated with reactions involving O atoms. The higher ratios of O to OH in a corona are more conducive to LMWOM production. Surface-oxidized PP exhibits considerable thermodynamic contact-angle hysteresis that is primarily caused by microscopic chemical heterogeneity.
OH radicals play an essential role in various plasma-chemical processes aimed at the abatement of organic and inorganic pollutants from off-air flows. We report about the oxidation of carbon monoxide in nonthermal air and nitrogen plasmas in dependence on CO inlet concentration and flow humidity. Thereby the reaction CO + OH → CO2 + H served as a diagnostic tool for OH radical determination in the dielectric barrier discharge at atmospheric pressure. The results were numerically fitted to the equations of a kinetic model allowing the determination of the average OH production efficiency (GOH-value) and OH lifetime (TOH) in dependence on flow humidity. Finally,results on ethyl acetate abatement obtained under similar experimental conditions were modeled by OH radical decomposition.
Plasma-polymerized hexafluoropropene (PPHFP) film deposited using a dielectric barrier discharge reactor at atmospheric pressure had low enough adhesive strength, 22.2 Nm−1, for use as a release coating of pressure-sensitive adhesive tapes, but the bond strength between PPHFP film and a poly (ethylene terephthalate) (PET) substrate film was slightly weak: some part of the PPHFP deposits could be peeled from the PET substrate. Since the XPS results indicated that the bond strength between plasma-polymerized ethylene (PPE) film and PET substrate was strong enough, we tried to deposit PPE and plasma-polymerized ethylene - hexafluoropropene gradient plasma-copolymer between the PET substrate and the PPHFP film. This multi-layer film (MLF) had low enough adhesive strength, 36.6 Nm−1, for use as the release coating; this value was near that of a control sample, Teflon sheet, 21.6 Nm−1. Moreover, the bond strength between MLF and PET substrate became stronger than that between PPHFP and PET films.
This paper deals with the determination of by-products formed in plasmas fed with hexamethyldisiloxane (HMDSO), oxygen, and Ar. The gas effluent has been sampled by means of a cold trap and analyzed using gas chromatography-mass spectrometry. The results indicate that under the experimental conditions utilized, HMDSO is not activated by reactions with oxygen but mainly by electron collisions. Oxygen controls the overall chemistry of the plasma since it influences the quali-quantitative distribution of by-products. Many linear and cyclic oligomers have been observed and most of them contained one or more―Me2SiO― groups. The concentration of detected by-products, except trimethylsilylformate, decreases with O2 addition.
The surface modification of polyethylene (PE) by neutral nitrogen species ( ground and excited state N-2 as well as atomic N; modified nitrogen plasma treatment) has been compared to the effect of nitrogen ion bombardment using X-ray Photoelectron Spectroscopy (XPS) and contact angle measurements. XPS results indicate that a greater nitrogen concentration was grafted during the modified nitrogen plasma treatment of PE, an effect that was attributed to surface sputtering during ion beam modification. The distribution of nitrogen-containing functionalities was strongly dependent upon the treatment strategy; the modified nitrogen plasma treatment lead predominantly to imine groups being formed at the PE surface, while amine groups were the dominant species produced during ion beam modification. The presence of electron irradiation during the modified nitrogen plasma treatment of PE did not modify the rate of nitrogen incorporation or change the nature of N-containing functional groups produced but did lead to a systematic decrease in contact angle.
Acetonitrile and acrylonitrile were plasma polymerized on Polypropylene (PP) surface. Surface modifications were characterized by surface energy measurements and ATR-FTIR spectroscopy. Surface energy measurement showed incorporation of hydrophilic groups along with deposition of cross-linked network of plasma-polymerized product. ATR-FTIR analysis of modified films showed incorporation of conjugated imine and amine groups. Using change in the relative intensities of C—H stretch bands of polypropylene surface, site of attachment of hydrophilic group and most predominant surface chemical reaction could be inferred. Chemical nature of plasma polymerized product was studied using FTIR by KBr disc method. Adhesion test was performed on modified surface by peel test method. Surface energy and peel strength measurements were performed for the samples aged for 2 months in order to check the durability of surface modification.
Commercial polyvinylchloride (PVC) sheets were treated by plasma immersion ion implantation, PIII. Samples were immersed in argon glow discharges and biased with 25 kV negative pulses. Exposure time to the bombardment plasma changed from 900 to 10,800 s. Through contact angle measurements, the effect of the exposure time on the PVC wettability was investigated. Independent of t, all samples presented contact angles, θ, equal to zero after the treatment. However, in some cases, surface hydrophilization was not stable, as revealed by the temporal evolution of θ. Samples bombarded for shorter periods recovered partially or totally the hydrophobic character while the one exposed for the longest time stayed highly hydrophilic. These modifications are ascribed to the Cl loss and O incorporation as shown by XPS measurements. Furthermore, the mobility of surface polar groups and the variation in the cross-linking degree can also affect the PVC wettability.
A Far Cold Remote Nitrogen Plasma is used both to fluidize and to treat a polyethylene powder in order to increase its hydrophilic character. The evolution of the wettability of the powder as well as the one of its physical (density, particles size distribution, average diameter, shape factor, and BET surface area) and flow properties (angle of repose, angle of slide, and Hausner index) are determined versus various experimental conditions. It is shown that the plasma treatment efficiency is strongly dependant on the oxygen content of the nitrogen flow and on the velocity of fluidizing gas. Best wettability is obtained by the addition of 0.75% of O2 in the nitrogen plasma gas and with a high gas velocity. It is also evidenced that the flowability of the powder is slightly altered by the plasma treatment.
Octamethyltrisiloxane (OMTS), bis(trimethylsiloxy)methylsilane (BTMS), or 1,1,3,3-tetramethyldisiloxane (TMDS) mixed with oxygen and argon produced organosilicate glass (OSG) films having high methyl content under pulse plasma-enhanced chemical vapor deposition (PECVD). The hydrogen concentration in films deposited from OMTS, BTMS, and TMDS can exceed twice the maximum concentration in films grown from methylsilane precursors. However, the refractive indices and dielectric constants of the films grown from OMTS, BTMS, and TMDS were close to that of minimum values observed for the films grown from methylsilane precursors. This suggests that at high concentrations, methyl incorporation does not result in further reduction of film density. 29 Si nuclear magnetic resonance (NMR) resolves the complex differences in the structure of the OSG films that are not apparent from Fourier transform infrared spectroscopy (FTIR) and reveals that the stability of OSG materials is improved by eliminating M groups and favoring the incorporation of T groups. These films exhibit low dielectric constants in the range of 2.4–2.6.
Self-organization and dynamic processes of nano/micron-sized solid particles grown in low-temperature chemically active plasmas as well as the associated physico-chemical processes are reviewed. Three specific reactive plasma chemistries, namely, of silane (SiH4), acetylene (C2H2), and octafluorocyclobutane (c -C4F8) RF plasma discharges for plasma enhanced chemical vapor deposition of amorphous hydrogenated silicon, hydrogenated and fluorinated carbon films, are considered. It is shown that the particle growth mechanisms and specific self-organization processes in the complex reactive plasma systems are related to the chemical organization and size of the nanoparticles. Correlation between the nanoparticle origin and self-organization in the ionized gas phase and improved thin film properties is reported. Self-organization and dynamic phenomena in relevant reactive plasma environments are studied for equivalent model systems comprising inert buffer gas and mono-dispersed organic particulate powders. Growth kinetics and dynamic properties of the plasma-assembled nanoparticles can be critical for the process quality in microelectronics as well as a number of other industrial applications including production of fine metal or ceramic powders, nanoparticle-unit thin film deposition, nanostructuring of substrates, nucleating agents in polymer and plastics synthesis, drug delivery systems, inorganic additives for sunscreens and UV-absorbers, and several others. Several unique properties of the chemically active plasma-nanoparticle systems are discussed as well.
The polypropylene modification in CO2 plasma mainly contributes to degradation, functionalization, and cross-linking. The degradation, whose rate is depending on CO2 dissociation and oxygen atom formation, is a quite slow reaction and it is associated with surface topography alteration, especially of the amorphous phase of the polypropylene. The surface roughness increases with the treatment duration and the amorphous phase is more degraded than the crystallized part. The functionalization, corresponding to an increase of the surface energy (57.3 mJċ m− 2 in 30 s), and to an oxidation (23 oxygen at.%) with the appearance of alcohol, ketone, and acid functions is a much faster phenomenon. Cross-linking takes also place during this type of treatment and will reinforce the stability of the modified surface.
