Iop Publishing Journal of Physics D: Applied Physics (original) (raw)
2007
https://doi.org/10.1088/0022-3727/40/22/016
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Abstract
Continuous processing of polymers in repetitively pulsed atmospheric pressure discharges with moving surfaces and gas flow
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Journal of Applied Polymer Science, 1999
Modification of polyolefin surfaces is often necessary to achieve improved printability, lamination, etc. Although corona discharge and flame treatments can produce the higher surface energy needed for these applications, the properties of the resulting surfaces are not always optimal. Atmospheric pressure plasma is a surface modification technique that is similar to corona discharge treatment, but with more control, greater uniformity, and higher efficiency. Using an atmospheric pressure plasma unit with a dielectric barrier discharge generated using an asymmetric pulse voltage, the effects of different gases, powers, and linespeeds on polyethylene surface treatment were studied. Our results show that atmospheric pressure plasma can be used to achieve higher long-term wettability, higher surface oxygen and nitrogen, and a greater range of surface chemistries with better robustness versus standard corona treatment. Atomic force microscopy results suggest significant differences in the mechanism of surface functionalization versus etching and ablation depending on the gases used.
Atmospheric-Pressure Dielectric Barrier Discharge for Surface Processing of Polymer Films and Fibers
IEEE Transactions on Plasma Science, 2000
Recently atmospheric pressure dielectric barrier discharge (APDBD) plays an important role in chemical, industrial and biological applications. It has been used for ozone synthesis, hydrogen production from natural gas, surface treatment including textile and polymer treatment, yeast and bacterial inactivation. The physics and mechanism of atmospheric pressure dielectric barrier discharge will be reviewed. Coaxial and planar DBD have been constructed for ozone production, textile treatment and yeast sterilization. Oxygen has been used as working gas for ozone production, while oxygen and argon will be used for yeast inactivation.
European Physical Journal-applied Physics, 2002
This paper is the third of a trilogy [16, 75] devoted to polystyrene thin film treatment under DC pulsed discharges conditions. In order to study the wettability variations (∆θ/θi) of the surface, N2-Ar or O2-Ar mixtures are used. The experimental conditions are close to the best running conditions deduced from [16, 75]. The pressure is varied from 1 mbar to 10 mbar and the mixture proportion from 0% to 100%. The importance of metastable states is pointed out. Reaction processes in the plasma and on the polystyrene surface are proposed in order to explain the surface activation and the formation of chemical bonds with nitrogen or oxygen. The best running conditions are reached when the generator frequency equals 500 Hz for a pressure about 4 mbar in nitrogen and 10 mbar in oxygen, whatever the gas mixture composition is. The wettability is better with oxygen than with nitrogen and the best value is reached for a duration time shorter in oxygen than in nitrogen. The minimum of treatment time necessary to reach the ∆θ/θi plateau value depends on the mixture composition.
Evaluation of a reel-to-reel atmospheric plasma system for the treatment of polymers
Surfaces and Interfaces, 2017
Plasma treatments are widely used to enhance the surface energy of polymers prior to bonding or the application of functional coatings. This study investigates the performance of a linear atmospheric pressure plasma source for the reel-to-reel treatment of polymer webs. The continuous argon plasma treatments were carried out on 15 cm diameter polyethylene terephthalate (PET) web substrates using the linear plasma source (Plamax), operating at 13.56 MHz. The study investigated how the processing parameters influenced the effectiveness of the plasma treatment in enhancing both the polymer web's water contact angle (WCA) and surface energy (SE). Based on these measurements the plasma treatment was found to yield a homogeneous level of activation across the 15 cm web, using a treatment speed of 0.9 m/min. The plasma discharge was monitored using both thermal imaging and optical emission spectroscopy (OES). The latter demonstrated how the oxygen species which diffuse into the argon plasma due to air ingress, were directly correlated with the level of polymer activation.
Cold Atmospheric Pressure Plasma Jet for the Improvement of Wettability of Polypropylene
International Journal of Polymer Science, 2020
This paper reports the generation of cold plasma jet working under atmospheric pressure condition, for surface treatment of polymeric films. The discharge has been characterized by electrical and optical methods. The electrical property of the discharge has been studied by taking current-voltage wave forms using voltage and current probes. The production of argon plasma jet is done in atmospheric conditions which are relatively much cheaper, convenient, and safer to use. The atmospheric pressure plasma jet sustained in pure argon has been used to improve wettability of polypropylene (PP). Cold atmospheric pressure plasma jet (CAPPJ) has been generated by a high-voltage power supply (5.5 kV, 0-20 kV) at an operating frequency of 20 kHz. The surface properties of the controls and plasma-treated PP samples were characterized by contact angle measurement, surface free energy measurement, scanning electron microscopy, and the Fourier transform-infrared spectroscopy analysis.
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Plasma polymer films were deposited from an argon and acetylene mixture by plasma enhanced chemical vapor deposition in pulsed r.f. discharges. The discharge on-time varied from 50 to 150 ms and the off-time was kept constant at 1900 ms. The kinetics of the film growth was studied by in situ reflectance measurements. The films were further investigated ex situ by spectroscopic ellipsometry, atomic force microscopy, scanning and transmission electron microscopes. Damages in the films caused by residual stress were investigated with an optical microscope. The hydrogen content and film densities were measured by nuclear resonance reaction analyses. Some film properties namely the residual stress, deposition rate, optical properties and surface roughness were significantly influenced by the duration of the discharge pulses. We found refractive indices of the films in the visible in the range 1.60-1.73. The hydrogen-to-carbon ratio in the films and the film density were approximately 3:2 and 0.6 gycm , respectively.
Distribution of inception times in repetitive pulsed discharges in synthetic air
Plasma Sources Science and Technology
Knowing which processes and species are responsible for discharge inception is important for being able to speed up, delay, or completely avoid it. We study discharge inception in 500 mbar synthetic air by applying 10 ms long 17 kV pulses with a repetition frequency of 2 Hz to a pin-to-plate electrode geometry with a gap length of 6 cm. We record inception times for hundreds of pulses by measuring the time delay between the rising edge of the high-voltage (HV) pulse and the signal from a photo-multiplier tube. Three characteristic time scales for inception are observed: (1) 20 ns, (2) 25 μs, and (3) 125 μs. To investigate the underlying processes, we apply a low-voltage (LV) pulse in between the HV pulses. These LV pulses can speed up or delay discharge inception, and our results suggest that the three time scales correspond to: (1) free electrons or electron detachment from negative ions close to the electrode, (2) a process that liberates electrons from (quasi)-neutrals, and (3) t...
Study of a Conical Plasma Jet with a Cloth-Covered Nozzle for Polymer Treatment
Polymers
Although atmospheric pressure plasma jets (APPJs) have been widely employed for materials modification, they have some drawbacks, such as the small treatment area (couple of cm2). To overcome this limitation, a funnel-like APPJ with a wide exit has been proposed. In this work, a gas-permeable cotton cloth covered the nozzle of the device to improve the gas flow dynamics and increase its range of operation. The funnel jet was flushed with Ar, and the plasma was ignited in a wide range of gas flow rates and the gap distances between the exit nozzle and the sample holder. The device characterization included electric measurements and optical emission spectroscopy (OES). To evaluate the size of the treatment and the degree of surface modification, large samples of high-density polyethylene (PE) were exposed to plasma for 5 min. Afterward, the samples were analyzed via water contact angle WCA measurements, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). It...
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Plasmas and atom beam activation of the surface of polymers
Journal of Physics D-applied Physics, 2008
Wetting properties of polyethylene terephthalate (PET) and low-density polyethylene polymers have been investigated after treatment with a microwave (MW) plasma discharge at low pressure and a dielectric barrier discharge at atmospheric pressure. Experiments have also been carried out in situ with an atom source installed in an x-ray photoemission spectrometer (XPS). The water contact angle measured on both polymers experienced a significant decrease after activation, but a progressive recovery up to different values after ageing. Standard chemical analysis by XPS showed that the plasma and oxygen beam treatments produced an increase in the concentration of -C(O) x functional groups at the outermost surface layers of the treated polymers. Besides, the oxygen distribution between the topmost surface layer and the bulk has been obtained by non-destructive XPS peak shape analysis. Atomic force microscopy analysis of the surface topography showed that, except for PET treated with the MW plasma and the atom beam, the surface roughness increased after the plasma treatments. Wetting angle variations, oxygen content and distribution, surface roughness and evolution of these properties with time are comparatively discussed by taking into account the basic processes that each type of activation procedure induces in the outmost surface layers of the treated polymers.
Plasma Processes and Polymers, 2014
The atmospheric pressure plasma deposition of hydroxyl functionalized hydrocarbon films is reported in this work, with a reactor fed with water aerosol and ethylene. The effects of power and feed flow rates onto film chemistry have been investigated. Coatings produced with this approach can find application in the biomedical field, among others, as platforms for cell adhesion and proliferation. Results show that operating at 4 kHz provides a much higher amount of hydroxyl group in the coating compared with samples obtained at 11 kHz. After water immersion, the stability of the films and their amount of hydroxyl groups remain high. A simplified deposition mechanism is proposed.
The European Physical Journal Applied Physics
The aim of this paper is to quantify the effects of dielectric barrier discharge (DBD) exposure on the physico-chemical and tribo-electric properties of polymers. The study was conducted in atmospheric air on polypropylene, polyethylene and polyvinyl-chloride. These three types of polymers are widely used in industry. The polymers were characterized by means of an optical profilometer, a fourier-transform infrared (FTIR) spectrometer and an electric charge measurement system. The latter is composed of a Faraday pail connected to an electrometer. The profilometer analyses showed that the DBD plasma treatment has increased the surface roughness of the three polymers. FTIR revealed that oxygen atoms and polar groups were grafted on their surfaces, thereby conferring them a hydrophilic character. The short (2 sec) DBD plasma treatment has considerably improved the electrostatic charge acquired by the polymers during electrostatic tribo-charging, while longer exposures conferred the poly...
Interaction of multiple atmospheric-pressure micro-plasma jets in small arrays: He/O2into humid air
Plasma Sources Science and Technology, 2014
Arrays of atmospheric-pressure plasma jets are being considered as a means to increase the area being treated in surface modification and in plasma medicine in particular. A unique challenge of scaling plasma jet arrays is that individual plasma jets in an array tend to interact with each other, which can lead to quenching of some individual jets. To investigate these potential interactions, a computational study of one-, two-and three-tube arrays of micro-plasma jet arrays was performed. An atmospheric-pressure He/O 2 = 99.8/0.2 mixture was flowed through the tubes into humid room air. We found that the jets interact through electrostatic, hydrodynamic and photolytic means. The hydrodynamic interactions result from the merging of individual He channels emerging from individual tubes as air diffuses into the extended gas jets. Ionization waves (IWs) or plasma bullets, which form the jets on the boundaries of an array, encounter higher mole fractions of air earlier compared with the center jet and so are slower or are quenched earlier. The close proximity of the jets produces electrostatic repulsion, which affects the trajectories of the IWs. If the jets are close enough, photoionizing radiation from their neighbors is an additional form of interaction. These interactions are sensitive to the spacing of the jets.
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Surface and Coatings Technology, 2010
A micro-cavity discharge array (2500 cavities of 50 µm 2 size) was operated in neon at atmospheric pressure to modify polystyrene (PS), fluorinated ethylene-propylene co-polymer (FEP) and polytetrafluoroethylene (PTFE) polymer surfaces and, with the injection of a polymerisable monomer (acrylic acid), to deposit patterned, thin polymeric coatings. The aim of this study was to investigate the utility of these microdischarge sources in the surface treatment of polymers and for the patterned deposition of polymeric material. The influence of the driving frequency, treatment time and sample-array distance on polymer surface treatment was investigated. X-ray photoelectron spectroscopy (XPS) was used to explore the surface chemistry of the treated polymer surfaces and of the polymer deposits. It was found that increasing the micro-cavity discharge source driving frequency and/or treatment time and decreasing the sample-array distance all led to a significant decrease in surface energy as determined by water contact angle measurements. For a period of time, post treatment surface hydrophilicity degraded due to the well known "ageing effect" but stabilized after two days. Finally, it was demonstrated that the device could be used for the localized, array sized, deposition of acrylic acid. High resolution XPS analysis of the deposit registered a C 1s spectra typical of poly(acrylic acid) with a prominent peak centred at approximately 289.3 eV indicating a relatively high level retention of the original monomer functionality. These results demonstrate that microcavity discharges, operated at or near atmospheric pressure, can be used to both modify and locally deposit polymeric material.
Characterization of atmospheric pressure discharges
The interest towards atmospheric pressure discharges for plasma processing of materials is continuosly growing because of their technological advanteges respect to low pressure discharges. The development of new plasma source design and their application to processes of surface modification and functionalization of materials is actively pursued also in the plasma physics community. On the contrary, research aimed to the development of suitable diagnostics and process control tools is not so advanced and investigated. Indeed diagnostics of atmospheric pressure plasmas are very demanding because of the short temporal and the small spatial scales involved in the plasma state and in the different discharge regimes. Indeed such plasmas are often made up of intermittent and higly localized structures like stremers or microdischarges. We will presents results concerning the diagnostics of dielectric barrier discharges (DBD) operated in a streamer regime in a controlled high pressure gas mi...
We present a set-up consisting of parallel plate dielectric barrier discharge (DBD) and a dedicated electronic circuit. Using the dedicated electronic circuit a uniform glow-like discharge is generated in a process gas consisting of 20 % nitrogen in argon at a driving frequency of 380 kHz. The discharge is characterized by means of IV-measurements and CCD images. The discharge is used for surface treatment of polypropylene (PP). The set-up is configured in such a way that the treated PP also serves as the dielectric barrier of the DBD. The PP can be transported across the electrodes in a roll-to-roll process. The treated surface is characterized by means of contact angle measurements. The water contact angle of PP decreases from 100° to a saturated value of 30° within half a second of plasma treatment time. This decrease in water contact angle corresponds to an increase of the surface energy from 30 mJ/m 2 to 65 mJ/m 2 , which is entirely due to an increase in the polar component of...
Characterization of pulsed discharge plasma at atmospheric pressure
Surface and Coatings Technology, 2007
Experiments are performed to improve a pulsed corona discharge system for methane destruction at atmospheric pressure. The corona discharge is energized by 6-12 µs wide voltage pulses (0.3-7 kV) at a repetition frequency of 1.050 kHz. The characteristic of methane destruction is observed by a mass spectrometer. We have found that methane destruction depends on the parameters such as: pulse width, input pulse voltage, repetition frequency, discharge current and discharge time. The effects of argon gas on methane destruction were also observed. The structural geometry of the soot, resulting from discharge process, is observed by transmission electron microscope. The main aim of this study is to show that the discharge could help as for the production of hydrogen and carbon nanotubes.
Surface modification of polyethylene and polypropylene in atmospheric pressure glow discharge
Journal of Physics D: Applied Physics, 2005
An atmospheric pressure glow discharge (APGD) was used for surface modification of polyethylene (PE) and polypropylene (PP). The discharge was generated between two planar metal electrodes, with the top electrode covered by a glass and the bottom electrode covered by the treated polymer sample. The discharge burned in pure nitrogen or in nitrogen-hydrogen or nitrogen-ammonia mixtures. The surface properties of both treated and untreated polymers were characterized by scanning electron microscopy, atomic force microscopy, surface free energy measurements and x-ray photoelectron spectroscopy. The influence of treatment time and power input to the discharge on the surface properties of the polymers was studied. The ageing of the treated samples was investigated as well. The surface of polymers treated in an APGD was homogeneous and it had less roughness in comparison with polymer surfaces treated in a filamentary discharge. The surface free energy of treated PE obtained under optimum conditions was 54 mJ m −2 and the corresponding contact angle of water was 40˚; the surface free energy of treated PP obtained under optimum conditions was 53 mJ m −2 and the contact angle of water 42˚. The maximum decrease in the surface free energy during the ageing was about 10%.
The Transition Between Different Discharge Regimes in Atmospheric Pressure Air Barrier Discharge
Contributions to Plasma Physics, 2007
Key words APG in air, diffuse barrier discharge, OAUGDP. PACS 52.80. Hc, 52.50.Dg In our previous work [1], we have demonstrated the possibility of observing the transition from a filamentary dielectric barrier discharge operation regime into the diffuse barrier discharge regime in air at atmospheric pressure. This work presents our attempt to reproduce the transition conditions in newly constructed transparent discharge reactor. The role of appropriate power supply and dielectric barrier to stabilize the discharge in a Townsend-to-glow discharge region is investigated and discussed. Unlike operating in nitrogen, a streamer mechanism is involved in the formation of the uniform air plasma. Nevertheless the electrical current waveform of a diffuse streamer pulse differs from the filamentary streamer pulse, as the diffuse mode pulse exhibits an extended tail part.
Polymers
A conical-shaped atmospheric pressure plasma jet (CS-APPJ) was developed to overcome a standard limitation of APPJs, which is their small treatment area. The CS-APPJs increase the treatment area but use the same gas flow. In the present work, polypropylene samples were treated by CS-APPJ and characterized by scanning electron microscope (SEM), the contact angle, Fourier-transformed infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). It was observed that the treatment co-occurs on the face directly in contact with the plasma and on the opposite face (OF) of the samples, i.e., no contact. However, the treatment changed the chemical composition on each side; the OF is rougher than the direct contact face (DCF), probably due to the oxygen groups in excess at the DCF and nitrogen in quantity at the OF. Although simultaneous treatment of both sides of the sample occurs for most atmospheric plasma treatments, this phenomenon is not explored in the literature.
Plasma polymerization in a microcapillary using an atmospheric pressure dielectric barrier discharge
2013
Atmospheric pressure plasma deposition is a beneficial technology due to its low cost and flexibility in terms of its operation and integration for in-line processing. This paper presents the use of an atmospheric pressure dielectric barrier discharge (DBD) to deposit an amine functional polymer film onto the inner surface of a glass microcapillary. A micro discharge was generated in a DBD chip made from a rectangular borosilicate glass capillary using externally attached parallel plate electrodes. A new microplasma configuration which consists of a perforated high voltage electrode and a ground electrode with large surface area is implemented to sustain a stable glow discharge at atmospheric pressure and a temperature of 35°C. Polymerization was performed using a laboratory made plasma source working at a frequency of 8 kHz with 50% duty ratio of the inverter. The monomer precursors allylamine and ethylenediamine were selected to optimize the polymerization conditions at atmospheric pressure. The hydrophobicity and philicity of the deposited surface were controlled as functions of plasma power. The atmospheric pressure plasma polymerized (APPP) films were characterized using Fourier transform infrared (FTIR) spectroscopy, atomic force microscopy (AFM), plasma emission spectroscopy, contact angle measurements and growth rate analysis. An average growth rate of 1.18 μg s −1 for plasma polymerized ethylenediamine (PPEDA) and 1.91 μg s −1 for plasma polymerized allylamine (PPAA) was obtained at a discharge power of 15 W and 10 sccm of monomer flow rate. The film thickness of 0.9 μm for PPEDA and 2.1 μm for PPAA was determined using AFM for deposition time of 10 min. Polymerization results showed that the properties of APPP films can be controlled through optimization of parameters such as discharge power, treatment time and flow rates of the main gas and monomer vapors.
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