Photoemission study of fluorination atmospheric pressure plasma processes on EPDM: Influence of the carrier and fluorinating gas

Fluorination plasma treatments at atmospheric pressure were used to modify the surface composition of EPDM elastomer. In this study, two different precursors (CF₄ and SF₆) and two carrier gases (He and Ar) were used for the surface modification of EPDM elastomer. The surface modifications were studied by means of X-ray photoelectron spectroscopy. We have observed a strong influence of the gas selection on the extent of the surface modification induced with these treatments. In general terms, the use of CF₄ generates a higher concentration of fluorine in the elastomer surface. On the other hand, the use of He as carrier gas also increases the effectiveness of the modification process. The fluorine uptake varies between 2 and 13%, although the formation of fluorine-containing functional groups was detected when the amount of fluorine on the surface exceeded 7%. After all treatments, an important oxygen uptake was observed, with amounts three or four times higher than the untreated elastomer.     

Changes in Properties of Dielectric Barrier Discharge Plasma Jets for Different Gases and for Insulating and Conducting Transfer Plates

Dielectric barrier discharge (DBD) plasma jets have been studied extensively in recent years because of its wide range of applications. DBD plasmas can be produced using many different gases and can be applied to a broad variety of surfaces and substrates. This work provides comparisons of DBD plasmas generated using argon (Ar), helium (He), and nitrogen (N₂), as well as their mixtures with water vapor in order to know how some plasma properties are affected by the use of different gases. All plasmas were studied in two different conditions: using a transfer plate made of a conductive material and using a transfer plate made of an insulating one. It was observed that the process of Penning ionization of nitrogen molecules by direct collisions with metastable atoms and molecules is evident and significant only in plasmas that use He as the working gas, which means that He atoms in metastable states have greater ability to transfer energy to molecules of nitrogen in the plasma. The collisions of metastable He with N₂ molecules determine the vibrational temperature (T _vib) values in He plasmas, while in Ar and N₂ plasmas, the T _vib values are determined mainly by collisions of electrons with N₂ molecules. It was noticed that the use of an insulating or a conducting transfer plate as the sample holder affects the results of adhesion between poly(dimethylsiloxane) samples, and it is mainly due to the differences in the plasma power, with a higher plasma power leading to better adhesion.     

The effect of fluorine-based plasma treatment on morphology and chemical surface composition of biocompatible silicone elastomer

X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) have been used to investigate the effect of reactive ion etching (RIE) on poly(methylhydrogensiloxane-co-dimethylsiloxane) surface in fluorine-based plasmas. Polysiloxane layers supported on the standard silicon wafers were etched using SF₆ + O₂ or CF₄ + O₂ plasmas. SEM studies show that the polysiloxane morphology depends on plasma chemical composition strongly. Presence of a columnar layer likely covered with a fluorine rich compound was found on the elastomer surface after the CF₄ + O₂ plasma exposure. After the SF₆ + O₂ or CF₄ + O₂ plasma treatment the polysiloxane surface enriches with fluorine or with fluorine and aluminum, respectively. Different morphologies and surface chemical compositions of the silicone elastomer etched in both plasmas indicate different etching mechanisms.     

The viscosity and diffusion coefficients of eighteen binary gaseous systems

The paper reports accurate measurements of the viscosity of the eighteen binary gaseous systems: CF₄ with He, Ne, Ar, N₂, CO₂, CH₄; SF₆ with He, Ne, Ar, N₂, CO₂, CH₄, CF₄ and O₂ with He, Ne, CO₂, CF₄, SF₆. The measurements were performed in a high-precision oscillating-disk viscometer at atmospheric pressure and in the temperature range 25–200°C for the systems containing CH₄ or SF₆ and in the temperature range 25–400°C for the remainder. The reported viscosities are believed to be accurate to within ±0.1% at room temperature and to within ±0.2% at 400°C.It is shown that the data conform to the extended law of corresponding states developed by Kestin, Ro and Wakeham despite the complexity of some of the component gases. The standard deviation between the experimental values and those calculated from the law of corresponding states is only 0.3% which is commensurate with the uncertainty in the experimental results.Binary diffusion coefficients derived from the mixture viscosity data are also presented; they have an estimated uncertainty of ±2%.     

Data and modeling of negative ion transport in gases of interest for production of integrated circuits and nanotechnologies

We review techniques to prepare, evaluate and apply sets of cross section and transport data for negative ions that are required for the modeling of collisional non-equilibrium plasmas used for processing of microelectronic circuits. We collect and discuss the transport coefficients and cross section sets.We have compiled data for negative ions in CF₄ and CF₄-related negative ions in rare gases. In addition, we consider data for F⁻ and CF₃⁻ in rare gases. Furthermore, we analyze the cross sections of halogen negative ions in rare gases and other molecules. This is followed by the data for SF₆ related ions in SF₆ and in rare gases. The cross section for scattering of O⁻ in O₂ has been derived from the transport data and used to make calculations of the transport properties. Finally we give a brief discussion of the availability of the data for H⁻ ions in H₂. We have derived cross sections in several cases but the basic aim is to show the basic features of transport coefficients. In particular we discuss the need to represent properly some details such as the non-conservative nature of transport coefficients and the anisotropy of diffusion. Application of approximate theories and representations of cross sections are also discussed.     

Modification of surface properties of polyamide 6 films with atmospheric pressure plasma

To investigate the effect of the different plasma gases treatment on the surface modification of atmospheric pressure plasma, polyamide 6 films were treated using pure helium (He), He/O₂ and He/CF₄, respectively. Atomic force microscopy (AFM) showed rougher surface, while X-ray photoelectron spectroscopy (XPS) revealed increased oxygen and fluorine contents after the plasma treatments. The plasma treated samples had lower water contact angles and higher T-peel strength than that of the control. The addition of small amount of O₂ or CF₄ to He plasma increases the effectiveness of the plasma treatment in polymer surface modification in terms of surface roughness, surface hydrophilic groups, etching rate, water contact angle and bonding strength.     

The formation of an intense secondary pulsed molecular beam and obtaining accelerated molecules and radicals in it

A method for obtaining an intense secondary pulsed molecular beam is described. The kinetic energy of molecules in the beam can be controlled by vibrational excitation of the molecules in the source under high-power IR laser radiation. A compression shock (shock wave) is used as a source of secondary beams. The shock wave is formed in interaction between an intense pulsed supersonic molecular beam (or flow) and a solid surface. The characteristics of the secondary beam were studied. Its intensity and the degree of gas cooling in it were comparable with the corresponding characteristics of the unperturbed primary beam. Vibrational excitation of molecules in the shock wave and subsequent vibrational-translational relaxation, which occurs when a gas is expanded in a vacuum, allow the kinetic energy of molecules in the secondary beam to be substantially increased. Intense [≥10²⁰ molecules/(sr s)] beams of SF₆ and CF₃I molecules with kinetic energies approximately equal to 1.5 and 1.2 eV, respectively, were generated in the absence of carrier gases, and SF₆ molecular beams with kinetic energies approximately equal to 2.5 and 2.7 eV with He (SF₆/He=1/10) and H₂ (SF₆/H₂=1/10) as carrier gases, respectively, were obtained. The spectral and energy characteristics of acceleration of SF₆ molecules in the secondary beams were studied. The optimal conditions were found for obtaining high-energy molecules. The possibility of accelerating radicals in secondary molecular beams was demonstrated.     

Spectroscopic diagnostics of barrier discharge plasmas in mixtures of zinc diiodide with inert gases

The spectral characteristics of the emission of gas discharge atmospheric pressure plasmas in mixtures of zinc diiodide vapor with inert gases (He, Ne, Ar, Kr, and Xe) are investigated. The formation of a gas discharge plasma and the excitation of the components of a working mixture were performed in a high-frequency (with a repetition frequency of sinusoidal voltage pulses of 100 kHz) barrier discharge. The gas discharge emission was analyzed in the spectral range 200–900 nm with a resolution of 0.05 nm. Emission bands of ZnI(B-X) exciplex molecules and I₂* excimer molecules, lines of inert gases, and emission bands of XeI* exciplex molecules (in Xe-containing mixtures) were revealed. It is ascertained that the strongest emission of ZnI* molecules is observed in ZnI₂/He(Ne) mixtures. The regularities in the spectral characteristics of the gas discharge plasma emission are considered.     

Deposition and Etching of Thin Films by Means of Beam Plasma Discharge with Tube-Like Electron Beam

The efficiency of energy dissipation caused by the mechanism of turbulent plasma heating from a tube-like electron beam in a electronegative gas is measured calorimetrically. Amorphous Si-layers are deposited from a SiH₄/Ar discharge both on conducting and nonconducting substrates and are analyzed by means of Auger-spectrometry. The velocity and specific energy of etching of SiO₂-layers in a CF₄-plasma are determined. Measured etching velocities of tungsten surfaces biased differently against the space potential provide information on the mechanism of plasma etching in a SF₆-plasma. Simultaneously performed Langmuir-probe measurements permit predictions to be made on the properties of the etching plasma.     

The effects of surface terminal bonds and microstructure of SiO2 aerogel films on dry etching

The effects of microstructure and surface terminal bonds of SiO₂ aerogel films on dry etching were investigated using Ar, SF₆, and C₂F₆ plasma gases. With Ar plasma etching, physical effect of ion bombardment on porous film was found. In residue-free SF₆ plasma etching, reactive etchant transport and high-mass ion bombardment were observed. With C₂F₆ plasma etching, fluorocarbon residue layer was revealed to maintain surface morphology as acting a barrier to radical transport and ion bombardment. An etching of 450°C-annealed SiO₂ aerogel showed that a dense surface induced the decrease in reaction area, inhibition of etchant transport, and then uniform etching.     

一种新型大气压毛细管介质阻挡放电冷等离子体射流技术

介绍一种结构设计简单、操作运行方便的新型毫米量级大气压冷等离子体射流发生技术.这种射流可以在大气压条件下，利用多种工作气体(如Ar,He,N₂)，通过毛细管介质阻挡放电(DBD)的方式实现.使用频率为33kHz，峰值电压为1—12kV的双向脉冲电源，利用Ar,He,N₂等工作气体，在毛细管内形成了稳定的冷等离子体射流.放电区域的光辐射空间分布利用商用CCD摄像机记录，从中研究放电形态和空间分布，观察到了在DBD区域的流动气体放电和在毛细管出口处形成的等离子体射流 关键词： 冷等离子体射流 毛细管介质阻挡放电 射流射程 射流激发温度     

悬浮型微波共振探针在电负性容性耦合等离子体中电子密度的测量

本文首先利用悬浮型微波共振探针测量了Ar等离子体的电子密度,并与朗缪尔双探针的测量结果进行了比较,表明了微波共振探针在低密度等离子体测量的可行性.对40.68 MHz单射频容性耦合Ar/SF₆和SF₆/O₂等离子体的测量结果表明:电负性气体SF₆掺入Ar等离子体显著降低了等离子体电子密度,但随着增加SF₆的流量,电子密度表现为缓慢下降;而O₂掺入SF₆等离子体中,电子密度则随着O₂流量的增加表现为持续的下降.另外,40.68 MHz/13.56 MHz双频激发的SF₆/O₂容性耦合离子体的电子密度并不随低频功率的变化而变化.本文对上述的实验现象进行了初步的解释.     

A gas flow proportional counter for the Mössbauer study of surfaces between 100 K and 400 K

A gas flow proportional counter has been constructed for operation between 100K and 400K without the need for an evacuated cryostat. The detector is temperature controlled and may be used for detecting conversion electrons or X-rays. Six different gases, pure He, He/1%CH₄, He/5%CH₄, He/10%CH₄, He/5%Co, and Ar/5%CH₄ have been investigated in order to obtain maximum efficiency and reliability of operation. At room temperature and above, all gases are suitable. At low temperatures, He/5%Co is the most suitable for electron detection, For X-ray detection, Ar/5%CH₄ is suitable over the entire temperature range.     

Is the critical Reynolds number universal?

This paper is devoted to checking whether the critical Reynolds number is universal in identical conditions for the flow of different fluids. The laminar-turbulent transition in a circular pipe flow has been tested experimentally. The flows of inert gases (He, Ne, Ar, Kr, Xe), molecular gases (N₂, CO, CO₂, SF₆), and two similar liquids (H₂O, D₂O) have been tested. A considerable, up to 40%, difference in critical Reynolds numbers was observed. The possible reasons for nonuniversality of the critical Reynolds number are discussed.     

±100 kV气体轨道开关击穿特性

 研制了一种用于快Marx发生器的三电极场畸变结构的气体轨道开关,针对3种不同的绝缘介质N₂、干燥空气和SF₆/Ar混合气体开展了轨道开关的自击穿特性和触发特性研究。结果表明:轨道开关的自击穿电压与气压基本呈现线性关系,并且在相同实验条件下,相对于N₂和干燥空气,当绝缘介质为SF₆/Ar混合气体时,轨道开关具有工作电压范围宽、工作系数低、触发击穿延时短、抖动小的优点。采用数码相机拍摄了开关导通过程中形成的放电通道积分图像,初步研究了绝缘介质、电流大小等因素对开关形成多通道的影响。结果表明:提高触发电压、充电电压和放电电流及采用SF₆/Ar混合气体均能够有效增加放电通道数目。     

Rapid and enhanced functionalization of MWCNTs in a dielectric barrier discharge plasma in presence of diluted CO<Subscript>2</Subscript>

Multiwalled carbon nanotubes (MWCNTs) have been functionalized in dielectric barrier discharge (DBD) plasma in presence of a mixture of carbon dioxide and a diluent gas at room temperature and atmospheric pressure. He, Ar, and N₂ were examined as the diluent gases. Temperature-programmed desorption was used to investigate the influence of various plasma parameters and type of diluent gas as well as the amount of diluent in the plasma gas. It is found that the quantity of functional groups on the surface of MWCNTs is a maximum when He is used as diluent gas. It also passes through a maximum when He content is 60%. The presence of He improves the reactivity of the plasma, which leads to an increase in the quantity of functional groups. However, high percentages of He decrease the CO₂ content, which in turn decreases the number of functional groups. FTIR and Raman spectroscopy showed the presence of Oxygen-containing functional groups on MWCNTs surfaces.     

Functionalization of hydrogen-free diamond-like carbon films using open-air dielectric barrier discharge atmospheric plasma treatments

A dielectric barrier discharge (DBD) technique has been employed to produce uniform atmospheric plasmas of He and N₂ gas mixtures in open air in order to functionalize the surface of filtered-arc deposited hydrogen-free diamond-like carbon (DLC) films. XPS measurements were carried out on both untreated and He/N₂ DBD plasma-treated DLC surfaces. Chemical states of the C 1s and N 1s peaks were collected and used to characterize the surface bonds. Contact angle measurements were also used to record the short- and long-term variations in wettability of treated and untreated DLC. In addition, cell viability tests were performed to determine the influence of various He/N₂ atmospheric plasma treatments on the attachment of osteoblast MC3T3 cells. Current evidence shows the feasibility of atmospheric plasmas in producing long-lasting variations in the surface bonding and surface energy of hydrogen-free DLC and consequently the potential for this technique in the functionalization of DLC-coated devices.     

Shielding gas influences on laser weldability of tailored blanks of advanced automotive steels

The effects of shielding gas types and flow rates on CO₂ laser weldability of DP600/TRIP700 steel sheets were studied in this work. The evaluated shielding gases were helium (He), argon (Ar) and different mixtures of He and Ar. Weld penetration, tensile strength and formability (Erichsen test) of laser welds were found to be strongly dependent upon the shielding gas types. The ability of shielding gas in removing plasma plume and thus increasing weld penetration is believed to be closely related to ionization potential and atomic weight which determine the period of plasma formation and disappearance. It was found that the higher helium shielding gas flow rate, the deeper weld penetration and the lower weld width.     

Superheat turbulence in gas discharged plasma

The influence of the electron concentration and temperature fluctuations on local thermodynamic equilibrium (LTE) in a gas-discharge plasma due to superheat turbulence development is analyzed. Data for the noble-gas atmospheric plasmas Ar and He (T=6-18 kK) and air ( T=4-9 kK) are given. It is shown that superheat turbulence causes deviation from LTE when parameter-space gradients are absent. As a result, the influence of superheat turbulence for weakly radiative gases (He, H₂) is considerably greater than for strong radiative gases (Ar, Xe, etc). The artificial excitement of superheat turbulence in plasma without any current by means of external electric field fluctuations is demonstrated     

Mass spectrometry of arcs in SF6 circuit breakers

Today, SF₆ is used to a great extent as insulating and arc-quenching medium in high-voltage gas-blast circuit breakers. The arcing in SF₆ during current interruption forms decomposition products. These can influence the arc-quenching properties of the circuit breaker. Furthermore, they can cause corrosion of the circuit breaker housing. In this comprehensive study we present results obtained for the first time from a direct mass spectrometric investigation of the exhaust gases of a high pressure SF₆ arc in a model circuit breaker. Our mass spectrometric system consists of a time-of-flight mass spectrometer (TOFMS) equipped with a molecular beam sampling systems. This device allows us to measure mass spectra of high pressure sources with a time resolution of up to 10,000 spectra per second. We have determined the formation rate of the most abundant decomposition products in a SF₆ arc at 1 bar. These products are SF₄, CF₄, WF₆, SOF₂, SO₂, CS₂ S₂F₂ and HF. The fast detection time inherent to our system permits also the determination of the formation of SF₄, which is 0.45–0.50 Vol. %/(kJ/1SF₆). In addition, we have studied the influence of water and oxygen impurities which are responsible for the production of highly corrosive HF. Finally, we have considered the influence of the thermal degradation of teflon (P.T.F.E.), which is used as nozzle and insulating material in circuit breakers. On this occasion we have demonstrated that CF₄, which exhibits dielectric properties similar to SF₆, is the main decomposition product formed from teflon. However, we have found that besides CF₄ also excess carbon is formed, which is deposited on insulators of the model circuit breaker.Our time-resolved mass spectra reveal that the CF₄ production from teflon is delayed by a few milliseconds with respect to the SF₆ dissociation in the arc. This delay can influence the interrupting process of the circuit breaker by changing the plasma composition during the arcing period. Although our experiments have been performed on a model circuit breaker we claim that the results presented in this study can be applied to real circuit breakers, since the arc current density and the energy dissipated per liter SF₆ are of the same order of magnitude in both devices.