Electrical and Optical Diagnostics of Dielectric Barrier Discharges (DBD) in He and N2 for Polymer Treatment

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.     

Concentration Dependence of VOC Decomposition by Dielectric Barrier Discharges

A comparative study of the decomposition of Volatile Organic Compounds (VOCs: Vinyl Chloride (VC), Ethyl Acetate (EA), Toluene (T), Acetone (A)) in dielectric barrier discharges (DBD) in zero and humidified air at atmospheric pressure was performed. Small scale tubular-flow with pulse excitation and large scale planar-flow with sinusoidal excitation were used to determine the removal efficiency in dependence on inlet concentration S₀ and air humidity. According to the destruction law S=S₀ exp(–E/), where E is the plasma energy density, linear functions were found for the -parameters with respect to S₀ containing an absolute term ₀. By modeling the reaction kinetics it was possible to discriminate active species responsible for the decomposition. Ozone was confirmed to be involved in VC decomposition in zero air whereas OH radicals were best suited to explain the absolute efficiency of EA and toluene destruction in humid air. Their decomposition in zero air however, as well as the degradation of acetone cannot be explained in a similar way.     

A New Approach to Metal Surface Nitriding Using Dielectric Barrier Discharge at Atmospheric Pressure

A new approach to metal surface nitriding using dielectric barrier discharge (DBD) plasma at atmospheric pressure is presented in this paper. Results of the study show that the plasma nitriding at atmospheric pressure using DBDs is realizable. Harder and thicker compound layer and diffusion layer on the treated surface has been formed in shorter treatment time comparing with the conventional vacuum plasma nitriding, Increasing the applied voltage will facilitate the formation of a thicker nitrided layer using the DBD. The nitrided layer acquired by this new approach is mainly composed of ɛ phase and γ′ phase, and the crystal grains of the ɛ phase is fine and has high dislocations density.     

Surface Functionalization at Atmospheric Pressure by DBD-Based Pulsed Plasma Polymerization

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.     

Comparison Between Air Filamentary and Helium Glow Dielectric Barrier Discharges for the Polypropylene Surface Treatment

Recently, a glow like dielectric controlled barrier discharge (GDBD) working at atmospheric pressure has been observed. Such a discharge could replace a filamentary dielectric controlled barrier discharge (FDBD) used in corona treatment systems to improve the wettability or the adhesion of polymers. So it is of interest to compare these two types of discharges and their respective effect on a polymer surface. This is the aim of an extensive study we have undertaken. The first step presented here is the comparison of a filamentary discharge in air with a glow discharge in helium. Helium is the most appropriate gas to realize a glow discharge at atmospheric pressure. Air is the usual atmosphere for a corona treatment. The plasma was characterized by emission spectroscopy and current measurements. The surface transformations were indicated by the water contact angle, the leakage current measurement and the X-ray photoelectron spectroscopy. Results show that the helium GDBD is better than air FDBD to increase polypropylene wettability without decreasing the bulk electrical properties below a certain level. Contact angle scattering as well as leakage current measurements confirm that the GDBD clearly results in more reproducible and homogeneous treatment than the FDBD.     

Abatement of Gas-phase p-Xylene via Dielectric Barrier Discharges

The effectiveness of applying dielectric barrier discharges (DBDs) to remove p-xylene from gas streams was experimentally investigated in this study. Parameters investigated include applied voltage, gas flow rate, gas temperature and gas composition. Experimental results indicate that as high as 100% p-xylene removal efficiency is achieved for the gas stream containing low p-xylene concentration of 26 ppmv. Removal efficiency of p-xylene achieved with DBDs increases with increasing applied voltage. However, energy consumption is also increased with increasing applied voltage. The best energy efficiency of 7.1 g/kWh is achieved for the gas streams containing 500 ppmv p-xylene, 5% O₂, 1.6% H₂O_(g), and balanced N₂ at the applied voltage of 18 kV. Product analysis indicates that around 70 or 95% of the carbons in p-xylene molecules are transformed into carbon dioxide for the gas streams without or with water vapor, respectively.     

Treatment of Soot by Dielectric Barrier Discharges and Ozone

The results of the presented special treatment method indicate a soot decomposition mechanism due to long-living species like ozone and a multistage process between diesel soot and ozone. Measurements inside a dielectric barrier discharge (DBD) and measurements with ozone externally generated show a strong dependence of the decomposition rate on the temperature. In addition the temperature dependence of the lifetime of ozone up to 180°C and the oxidation of carbonmonoxide to carbondioxide were investigated.     

Oxidative Conversion of PFC via Plasma Processing with Dielectric Barrier Discharges

Perfluorocompounds (PFCs) have been extensively used as plasma etching andchemical vapor deposition (CVD) gases for semiconductor manufacturingprocesses. PFCs have significant effects on the global warming and havevery long atmospheric lifetimes. Laboratory-scale experiments were performedto evaluate the effectiveness of CF4 conversion by using dielectric barrierdischarges (DBD). The results of this study revealed that the removalefficiency of CF₄ increased with application of higher voltage, gas residence time, oxygen content, and frequency. Combined plasma catalysis(CPC) is an innovative way for abatement of PFC and experimental results indicated that combining plasma with catalysts could effectively remove CF4. Products were analyzed by Fourier transform–infrared spectroscopy (FT–IR) and the major products of the CF4 processing with DBD were CO2, COF2, and CO, when O was included in the discharge process. Preliminary results indicated that as high as 65.9% of CF4 was decomposed with CPC operated at 15 kV, 240 Hz for the gas stream containing 300 ppmv CF₄,20% by volume O₂, and 40% by volume Ar, with N₂ as thecarrier gas.     

Sterilization of Polymer Foils with Dielectric Barrier Discharges at Atmospheric Pressure

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.     

Methane Conversion Using Dielectric Barrier Discharge：Comparison with Thermal Process and Catalyst Effects

The direct conversion of methane using a dielectric barrier discharge has been experimentally studied. Experiments with different values of flow rates and discharge voltages have been performed to investigate the effects on the conversion and reaction products both qualitatively and quantitatively. Experimental results indicate that the maximum conversion of methane has been 80% at an input flow rate of 5 ml/min and a discharge voltage of 4 kV. Experimental results also show that the optimum condition has occurred at a high discharge voltage and higher input flow rate. In terms of product distribution, a higher flow rate or shorter residence time can increase the selectivity for higher hydrocarbons. No hydrocarbon product was detected using the thermal method, except hydrogen and carbon. Increasing selectivity for ethane was found when Pt and Ru catalysts presented in the plasma reaction. Hydrogenation of acetylene in the catalyst surface could have been the reason for this phenomenon as the selectivity for acetylene in the products was decreasing.     

Decomposition of CO2 Using Pulsed Corona Discharges Combined with Catalyst

The combination of pulsed corona discharges and catalyst was examined for decomposition of pure carbon dioxide in a corona reactor packed with porous -Al₂O₃ pellets. The decomposition of CO₂ was greatly enhanced by packing -Al₂O₃. In the presence of -Al₂O₃, the conversion of CO₂, yield of CO reach 23 and 15%, respectively. The CO₂ conversion increases with increasing applied voltage and decreasing gas flow rate. The maximum energy efficiency for decomposition of CO₂ reaches 318.7 g/kW hr. It was found that high surface area of -Al₂O₃ and strong adsorption capacity of CO₂ on -Al₂O₃ play an important role in CO₂ decomposition under corona discharges. At the same time, the presence of -Al₂O₃ suppresses the reaction of CO and O.     

高频介质阻挡放电烟气脱硫研究

采用高频介质阻挡放电的方式产生低温等离子体,研究在不加入NH₃的情况下流动态SO₂的去除情况.实验表明,在输入电压为12 kV,SO₂浓度为5400 mg/m³,气体流量为0.36 m³/h,相对湿度为55%时,脱硫率可达到70%以上;水气的存在对SO₂的去除有较大的促进作用,升高电压和增加O₂量对脱硫率的促进作用有限.对实验结果进行了解释,并提出了反应机理.     

Gas-Phase Removal of Acetaldehyde via Packed-Bed Dielectric Barrier Discharge Reactor

The effectiveness of applying packed-bed dielectric barrier discharge(PBDBD) technology for removing acetaldehyde from gas streams wasinvestigated. Operating parameters examined in this study include appliedvoltage, oxygen content, and gas-flow rate. Experimental results indicatethat the destruction efficiency of acetaldehyde predominantly depends onthe applied voltage. Removal of 99% of acetaldehyde has been achieved forgas streams containing 1000 ppmv acetaldehyde, 5% oxygen, with nitrogen asthe carrier gas. The oxygen content in the gas stream plays an importantrole in removing acetaldehyde within PBDBD. A higher CH3CHO removalefficiency is achieved for the gas stream containing less oxygen, since itwill dissipate energy due to its electronegative property. Carbon dioxideis the major end product, which is less hazardous to the environment and tohuman health. However, undesirable products, e.g., NO₂ and N₂O,CH₃OC₂H₅, CH₃COOH, CH₃NO₂,HCN, CH₃NO₃, and CH₃OH, are detected as well.     

The Role of Dielectric Barrier Discharge Atmosphere and Physics on Polypropylene Surface Treatment

Dielectric barrier discharge (DBD) is the discharge involved in corona treatment, widely used in industry to increase the wettability or the adhesion of polymer films or fibers. Usually DBD's are filamentary discharges but recently a homogeneous glow DBD has been obtained. The aim of this paper is to compare polypropylene surface transformations realized with filamentary and glow DBD in different atmospheres (He, N₂, N₂ + O₂ mixtures) and to determine the relative influence of both the discharge regime and the gas nature, on the polypropylene surface transformations. From wettability and XPS results it is shown that the discharge regime can have a significant effect on the surface transformations, because it changes both the ratio of electrons to gas metastables, and the space distribution of the plasma active species. This last parameter is important at atmospheric pressure because the mean free paths are short (m). These two points explain why in He, polypropylene wettability increase is greater by a glow DBD than by a filamentary DBD. In N₂, no significant effect of the discharge regime is observed because electrons and metastables lead to the same active species throughout the gas bulk. The specificity of a DBD in N₂ atmosphere compared to an atmosphere containing oxygen is that it allows very extensive surface transformations and a greater increase of the polypropylene surface wettability. Indeed, even in low concentration and independently of the discharge regime, when O₂ is present in the plasma gas, it controls the surface chemistry and degradation occurs.     

Multi-Hollow Surface Dielectric Barrier Discharge for Bacterial Biofilm Decontamination

The plasma-activated gas is capable of decontaminating surfaces of different materials in remote distances. The effect of plasma-activated water vapor on Staphylococcus epidermidis, methicillin-resistant Staphylococcus aureus, Pseudomonas aeruginosa, and Escherichia coli biofilm contamination was investigated on the polypropylene nonwoven textile surface. The robust and technically simple multi-hollow surface dielectric barrier discharge was used as a low-temperature atmospheric plasma source to activate the water-based medium. The germicidal efficiency of short and long-time exposure to plasma-activated water vapor was evaluated by standard microbiological cultivation and fluorescence analysis using a fluorescence multiwell plate reader. The test was repeated in different distances of the contaminated polypropylene nonwoven sample from the surface of the plasma source. The detection of reactive species in plasma-activated gas flow and condensed activated vapor, and thermal and electrical properties of the used plasma source, were measured. The bacterial biofilm decontamination efficiency increased with the exposure time and the plasma source power input. The log reduction of viable biofilm units decreased with the increasing distance from the dielectric surface.     

Deposition of Ethylene-Hexafluoropropene Gradient Plasma-Copolymer Using Dielectric Barrier Discharge Reactor at Atmospheric Pressure: Application to Release Coatings on Pressure-Sensitive Tape

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.     

Study of SO2 Removal Using Non-thermal Plasma Induced by Dielectric Barrier Discharge (DBD)

Dielectric Barrier Discharge (DBD) non-thermal plasma reactors built with three different dielectric materials for SO₂ removal were studied. The discharge characteristics of the three dielectrics, namely glass, Teflon, and glass fiber-based epoxy resin, were analyzed using Lissajous figures. From the Lissajous figures, the transition charge and energy deposition for each dielectric material were determined. When both the discharge characteristics and mechanical processability were considered, glass fiber-based epoxy resin was regarded as the best dielectric barrier among the three for DBD plasma reactors. A multi-cell DBD reactor built with glass fiber-based epoxy resin was used for treating air stream containing SO₂. SO₂ % removal decreased with increasing initial SO₂ concentration in a biphasic fashion. SO₂ removal was greatly improved by adding NH₃ into the air stream. Raising the relative humidity of the air stream also helped SO₂ removal. A SEM (scanning electron microscope) test illustrated some changes in surface morphology of Teflon and glass fiber-based epoxy resin.     

介质阻挡放电脱除甲醛的化学动力学模拟

对大气压介质阻挡放电脱除甲醛进行了化学动力学模拟, 建立了时空平均化的模型, 并对相关的结果进行了实验验证. 分析了各主要物种的浓度随放电时间的变化, 在模拟空气气氛下, HCHO主要由O·和OH·自由基脱除, 其中, OH·自由基的作用更为突出. 强调了氮分子的第一电子激发态N2(A3∑+u)的作用, 它与O2、H2O 分子的碰撞增加了O·和OH·自由基的浓度,在氮气气氛中, N2(A3∑+u)态是使HCHO脱除的主要物种.讨论了HCHO初始浓度、气体流量对HCHO 脱除比能耗和产物中CO2/CO 摩尔比值的影响, HCHO 初始浓度较高时, 甲醛脱除的比能耗较低, 在输入能量密度<60 J·L-1, HCHO 初始浓度较低时, 产物中nCO2 /nCO值较高.     

A Study of Two-Dimensional Microdischarge Pattern Formation in Dielectric Barrier Discharges

Although microdischarges in dielectric-barrier discharges (DBDs) have been studied for the past century, their mutual interaction was explained only recently. This interaction is responsible for the formation of microdischarge patterns reminiscent of two-dimensional crystals. Depending on the application, microdischarge patterns may have a significant influence on DBD performance, particularly when spatial uniformity is desired. This paper presents the results of study of regular microdischarge pattern formation in DBD in air at atmospheric pressure. Experimental images of DBD (Lichtenberg figures) were obtained using photostimulable phosphors. A new method for analysis of microdischarge patterns that allow measuring the degree of pattern regularity was developed. Simulated and experimental patterns were compared using the newly developed method and comparison indicates the presence of interaction between microdischarges. Analysis of microdischarge patterns shows that regularity of the patterns increases with the number of excitation cycles used to produce the pattern.     

甲烷参与下催化剂填充型介质阻挡放电等离子体脱除NOx

 将In/HZSM-5催化剂填充于介质阻挡放电反应器中,考察了甲烷参与下NOx的脱除及其脱除产物. 结果表明,在200～350 ℃间,等离子体与催化剂共同作用时NOx的转化率明显高于等离子体或催化剂单独作用时NOx的转化率. 在0.03%NO-0.05%CH4-2%O2-97.92%N2,空速7200 h-1和300 ℃的条件下,单纯等离子体、单纯催化剂和二者共同作用下NOx的转化率分别为24%,25%和65%. 甲烷参与下等离子体和催化剂共同作用时,在催化剂表面没有硝酸盐或亚硝酸盐生成,仅有少量副产物N2O生成. 由此可以推断,NOx脱除的主要产物为N2. 低于300 ℃时,NOx的脱除以分解途径为主,甲烷的作用主要是抑制放电条件下NOx生成的副反应; 在300～350 ℃间,甲烷作为还原剂被等离子体和催化剂协同活化,NOx的脱除以还原途径为主. 采用催化剂填充型介质阻挡放电反应器,可在非常宽的温度区间实现NOx的脱除.