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.     

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.     

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.     

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.     

电子能量对沿面介质阻挡放电等离子体化学产物的影响

基于光电倍增管研制了一套无触发信号的双通道光学探测系统, 并组装了测试样机, 实现了对沿面介质阻挡放电(SDBD)等离子体约化电场的测量, 进而通过BOLSIG+软件获得了电子能量. 采用原位紫外吸收光谱和傅里叶变换红外光谱, 研究了SDBD等离子体在不同电压和频率下的化学产物的浓度变化, 并结合空气等离子体化学反应揭示了产物相互作用的微观机理. 结果表明, 电子能量能够改变电子碰撞反应的速率系数, 调控化学反应的源头活性粒子的浓度, 进而影响到化学产物的生成和猝灭.     

低温等离子体转化NO/O2/N2气氛中NO的实验研究

通过建立低温等离子体实验系统, 研究了介质阻挡放电型低温等离子体反应器作用于NO/O2/N2混合气体系时, NO, O2初始浓度对NO的转化效率的影响以及NOx, O3浓度随能量密度的变化关系. 低温等离子体作用于NO/O2/N2混合气体系时, NO同时发生氧化还原反应, 氧化反应占主导地位, 大部分NO转化为NO2; NO转化率随O2, NO初始浓度增大而降低, 能量密度在450～600 J/L时转化率较高; 产生的O3浓度随能量密度的增大呈先增后减的趋势.     

催化增强化学蒸气沉积法在聚酰亚胺上沉积钯-铂合金薄层

以N₂，O₂作载气，通过催化增强化学蒸气沉积(CECVD)分别制得在聚酰亚胺上的金属铂、钯及其合金薄层。铂、钯配合物的共同沉积可生成Pt-Pd合金薄膜。在Pd-Pt合金的沉积过程中，Pd/Pt的原子数比率随共同沉积的条件改变而变化。O₂为载气、300 ℃条件下,用Pd(η³-allyl)(hfac)和Pt(COD)Me₂作前驱体共沉积制备Pd-Pt合金，得到含Pd 37.2%，Pt 62.8%且不     

Surface modification of acrylate intraocular lenses with dielectric barrier discharge plasma at atmospheric pressure

Surface modification with dielectric barrier discharge (DBD) plasma was carried out at atmospheric pressure (argon as the discharge gas) to improve the biocompatibility of hydrophobic acrylate intraocular lens (IOL). Changes of the plasma-treated IOL surface in chemical composition, morphology and hydrophilicity were comprehensively evaluated by X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and water contact angle (WCA) measurements. The surface biocompatibility of the untreated and plasma-treated IOLs was compared with the adhesion behavior of platelets, macrophages and lens epithelial cells (LECs) in vitro. After DBD plasma treatment, the hydrophilicity of the IOL surface was obviously improved. The changes in WCA with treatment extension may be attributed to both the introduction of oxygen or/and nitrogen-containing polar groups and the increase of surface roughness induced by plasma etching effect. The existence of low molecular weight oxidized material (LMWOM) was proved on the plasmatreated IOL which was caused by the chain scission effect of the plasma treatment. The plasma-treated IOLs resisted the adhesion of platelets and macrophages significantly. The LECs spreading and proliferation were postponed on the IOLs plasma-treated for more than 180 s, with a well maintained epithelial phenotype of LECs. The IOL biocompatibility was improved after the DBD plasma treatment. We speculate that slighter foreign-body reaction and later incidence of anterior capsule opacification (ACO) may be expected after implantation of the argon DBD plasma-treated IOL. Supported by the Zhejiang Natural Science Foundation of China (Grant No. 2004C23003)     

Oxidation of Styrene in a Silent Discharge Plasma

A silent discharge plasma reactor has been developed to study the oxidation of styrene vapor in argon/oxygen mixtures. A number of analytical techniques were employed to determine the destruction efficiency and to characterize the intermediate products. The destruction efficiency was measured as a function of initial styrene concentration, temperature, and energy density of the plasma. The formation of solid products was observed in most experiments. At low temperature (100°C), the solid deposit was polymeric in nature, while at high temperature (300°C) the solid appeared to be amorphous carbon. A combination of high temperature and high energy density resulted in high destruction efficiency and minimal production of solid films. The destruction efficiency vs. energy density is shown to be more complex than a simple model predicting exponential behavior. Several reasons for the discrepancy are suggested. The e-folding energy density for the destruction of styrene is compared to literature values for other organic compounds, measured using similar types of plasma reactors.     

不同组分过渡金属氧化物催化剂对介质阻挡放电固氮的影响机制

为了促进介质阻挡放电(DBD)协同催化固氮效果, 制备了不同组分Mn/Co/W元素的单一型、 二元和三元复合型负载催化剂, 并将催化剂置入DBD气隙中进行等离子体协同催化固氮反应. 通过X射线衍射(XRD)、 扫描电子显微镜(SEM)和X射线能谱(EDS)表征了催化剂的性质, 并采用紫外分光光度法测定了液相中的总氮浓度. 结果表明, 填充催化剂实验组比未填充催化剂组的总氮浓度明显提升. 采用傅里叶变换红外光谱仪对有/无催化剂填充两种情况下DBD的气相产物进行了检测, 结果表明, 填充催化剂能促进空间内NO₂和N₂O₅的生成. 通过DBD气相链式反应和催化原理揭示了总氮浓度得以提升的原因, 是由于催化剂在等离子协同过程中提供了大量的氧空位, 使得NO _x 充分氧化. 多元复合型催化剂能在单一型的基础上, 通过金属元素价态的变换和能量的传递进一步促进固氮效果, 三元复合型催化剂Mn₃WCo/γ-Al₂O₃在电压为22 kV时的固氮最高总氮浓度为119.13 mg/L, 较未填充催化剂组的最大值提升了71.61%, 能耗降低了21.70%.     

Plasma-Catalytic Decomposition of Phenols in Atmospheric Pressure Dielectric Barrier Discharge

This study investigated the processes for the destruction of phenol and its derivatives (resorcin and pyrocatechol) in aqueous solutions under the action of an oxygen dielectric barrier discharge (DBD) at atmospheric pressure in the presence or absence of catalysts in the plasma zone. It was shown that the DBD had a high decomposition efficiency for phenol and its derivatives (up to 99%). Phenol was the most stable and pyrocatechol was the least. In a plasma-catalytic hybrid process, the effective rate constants for phenol, resorcin and pyrocatechol decomposition were 11, 4 and 2.5 times higher, respectively, than those for the DBD treatment without catalysts. The process also resulted in a 1.4, 1.6 and 1.2 times higher rate of carboxylic acid formation for phenol, resorcin and pyrocatechol, respectively. The fractional conversion into the respective carboxylic acids reached 56% for phenol and 68% for resorcin and pyrocatechol.     

甲烷二氧化碳介质阻挡放电转化产物分布研究

针对介质阻挡放电甲烷二氧化碳转化实验,分析了反应的产物分布,探讨了进料组成和反应器结构对反应的影响.反应产物包括:高H2/CO摩尔比的合成气、气态烃、高辛烷值的汽油组分、醇和酸等含氧有机物.对所述电极结构,产物的选择性随碳数增加而降低;高的甲烷进料浓度有利于烃的生成,对醇和酸的最佳甲烷进料体积分数范围在67.4％～75.1％;放电间隙越小,原料转化率和烃、酸的选择性越大,大的放电间隙对醇的生成有利.     

Cleaning of Silicon and Steel Surfaces Using Dielectric Barrier Discharges

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.     

介质阻挡放电与 CuZSM-5 结合方式对脱除 NOx 的影响

 研究了介质阻挡放电 (DBD) 与 CuZSM-5 结合方式, 即 DBD 和 CuZSM-5 两段分置 (两段法) 或将 CuZSM-5 放入 DBD 区 (一段法), 对脱除氮氧化物的影响. 结果表明, 在 NO/N2 或 NO/C2H4/N2 无氧体系中, DBD 与 CuZSM-5 结合产生的协同效应很小; 在 NO/O2/N2 富氧体系中, DBD 与 CuZSM-5 结合导致氮氧化物转化率下降; 而在 NO/C2H4/O2 /N2 富氧体系中, 在 250 ºC, 空速 12 000 h1, 输入放电能量密度 (Ein) 155 J/L 的条件下, 单纯催化、单纯等离子体放电、一段法和两段法时氮氧化物转化率分别为 39%, 1.5%, 79% 和 52%. 两段法产生了中等程度的协同效应, 主要是第一段等离子体放电产生新稳态物种 (如 NO2, CO 和 CO2 等) 起作用; 而一段法产生的协同效应较大, 主要是由于等离子体放电产生的新稳态物种和激发态短寿命物种 (如 N2*, NO*, CH 和 CN 等) 共同起作用.     

Partial Oxidation of Methane to Methanol with Oxygen or Air in a Nonequilibrium Discharge Plasma

The partial oxidation of methane to methanol with oxygen or air was investigated experimentally and theoretically in a dielectric-barrier discharge (DBD). The predominant parameters of specific electric energy, oxygen content, flow rate, temperature, and gas pressure were determined in CH ₄ /O ₂ and CH ₄ /air mixtures. Optimum selectivities toward methanol formation were found at an oxygen concentration of about 15% in both feed gas mixtures. Low specific energy favors the selectivity toward methanol and suppresses the formation of carbon oxides. The experiments indicate that high methanol selectivities can be obtained at high methane conversion. The highest methanol yield of 3% and the highest methanol selectivity of about 30% were achieved in CH ₄ /O ₂ mixtures. In CH ₄ /air mixtures, as high as 2% methanol yield was also obtained. In addition, other useful products, like ethylene, ethane, propane, and ethanol, were detected. Experiment and numerical simulations show that the formation of H ₂ O and CO has a strong negative influence on methanol formation.     

Modification of porous silica particles with poly(acrylic acid)

The surface of porous silica particles was modified with poly(acrylic acid) by reacting the carboxyl groups on poly(acrylic acid) with the amino groups of pregrafted aminopropyltriethoxysilane (APS). The chemical modifications by APS and polymer were characterized by infrared spectroscopy and the amount of APS and poly(acrylic acid) grafted to the surface were determined by thermal gravimetric analyses. The wettability of the modified silica particles, based on the rate of water penetration, was pH‐dependent with PAA; at pH 1.5 the wettability increased but at pH 5.5 it decreased dramatically. The pore size and size distribution of the silica particles decreased with APS and polymer grafting. Copyright © 2000 John Wiley & Sons, Ltd.     

Comparison of the Plasma Temperature and Electron Number Density of the Pulsed Electrolyte Cathode Atmospheric Pressure Discharge and the Direct Current Solution Cathode Glow Discharge

A novel-pulsed electrolyte cathode atmospheric pressure discharge (pulsed-ECAD) plasma source driven by an alternating current (AC) power supply coupled with a high-voltage diode was generated under normal atmospheric pressure between a metal electrode and a small-sized flowing liquid cathode. The spatial distributions of the excitation, vibrational, and rotational plasma temperatures of the pulsed-ECAD were investigated. The electron excitation temperature of H T_exc(H), vibrational temperature of N₂ T_vib(N₂), and rotational temperature of OH T_rot(OH) were from 4900?±?36 to 6800?±?108 K, from 4600?±?86 to 5800?±?100 K, and from 1050?±?20 to 1140?±?10 K, respectively. The temperature characteristics of the dc solution cathode glow discharge (dc-SCGD) were also studied for the comparison with the pulsed-ECAD. The effects of operating parameters, including the discharge voltage and discharge frequency, on the plasma temperatures were investigated. The electron number densities determined in the discharge system and dc-SCGD were 3.8–18.9?×?10¹⁴?cm^–3 and 2.6?×?10¹⁴ to 17.2?×?10¹⁴?cm^–3, respectively.     

Chemical Modification of Tryptophan Residues in Pullulanase

Tryptophan（Trp）residues in pullulanase have been chemically modified with N-bromossuccinimide（NBS）. The results of ultraviolet spectra indicated that there are 18 Trp residues in pullulanase and nine of them are located on the surface of the enzyme. Three of these Trp residues are none-essential residues which showed the fastest reaction speed by Zhou＇s plot. Two of the seven relative faster reacting residues are essential for the activity of the enzyme. The other eight are none-reactive residues with lowest reaction speed.     

人纤维蛋白溶酶原中色氨酸残基的化学修饰

以Ｎ－溴代琥珀酰亚胺为修饰剂，对人纤维蛋白溶酶原（ＨＰｇ）中色氨酸（Ｔｒｐ）残基的分布及其与酶活力的关系进行了研究，发现每个ＨＰｇ分子有１９个Ｔｒｐ残基，５个位于分子表面：有２个是快反应残基，其中１个是活性必需的氨基酸，酶被修饰后其荧光光谱及圆二色谱发生了变化。     

Surface Modification of Textile Fibers and Cords by Plasma Polymerization

In this paper we report on the treatment of industrial fibers and cords by means of plasma polymerization techniques. Coatings of plasma-polymerized pyrrole or acetylene were deposited on aramid fibers, aramid cords and polyester cords. The equipment was a custom-built semi-continuous reactor operated on a pulsed DC glow discharge. The fibers and cords were tested for adhesion to various polymers such as tire cord skim stock rubber compounds and epoxy adhesives. Standard industrial pull-out force adhesion measurement techniques were used. The deposition conditions of the plasma polymer films were varied within wide limits. It was found that, in general, films deposited under low-power and high-pressure conditions performed better than films prepared under high-power and low-pressure conditions. For some systems pulsing of the discharge power improved the performance further. For all systems studied, the optimized plasma polymer surface modification outperformed current industrial standards. The plasma-polymerized coatings were characterized by various techniques and the excellent performance results are explained in a tentative model based on the molecular structure of the films. This structure was found to be strongly dependent on the discharge conditions.