DBD coupled with MnOx/γ-Al2O3 catalysts for the degradation of chlorobenzene

This paper investigates the degradation of chlorobenzene by dielectric barrier discharge(DBD)coupled with MnOx/γ-Al2O3 catalysts.MnOx/γ-Al2O3 catalysts were prepared using the impregnation method and were characterized in detail by N2 adsorption/desorption,x-ray diffraction and x-ray photoelectron spectroscopy.Compared with the single DBD reactor,the coupled reactor has a better performance on the removal rate of chlorobenzene,the selectivity of COx,and the inhibition of ozone production,especially at low discharge voltages.The degradation rate of chlorobenzene and selectivity of COx can reach 96.3%and 53.0%,respectively,at the specific energy density of 1350 J l-1.Moreover,the ozone concentration produced by the discharge is significantly reduced because the MnOx/Al2O3 catalysts contribute to the decomposition of ozone to form oxygen atoms for the oxidation of chlorobenzene.In addition,based on analysis of the byproducts,the decomposition mechanism of chlorobenzene in the coupled reactor is also discussed.     

Decomposition of a gas mixture of four n-alkanes using a DBD reactor

This study investigates the decomposition of a gas mixture of four n-alkanes (n-heptane, n-octane, n-nonane, and n-decane) using a dielectric barrier discharge reactor. We show that the conversion of n-alkanes increased from 7.2% (C₇H₁₆), 9.7% (C₈H₁₈), 8.4% (C₉H₂₀), and 10.5% (C₁₀H₂₂) to 23.8% (C₇H₁₆), 25.0% (C₈H₁₈), 27.9% (C₉H₂₀), and 32.1% (C₁₀H₂₂) when the energy density increased from 84 J l⁻¹ to 324 J l⁻¹. The conversion of n-alkanes when using the gas mixture is close to that found when using a single n-alkane. The influences of reaction temperature and O₂ concentration are also investigated, and the activation energies for the decomposition of each alkane are given.     

DBD plasma assisted atomic layer deposition alumina barrier layer on self-degradation polylactic acid film surface

In this work, the plastic of polylatic acid(PLA) film is coated by alumina(Al_2O_3)through dielectric barrier discharge plasma assisted atomic layer deposition(DBD PA-ALD) for the proposal of the barrier property enhancement. The influence of ALD Al_2O_3 thickness on properties of barrier, mechanical, optical and degradation is investigated in detail. It is obtained that the growth rate of Al_2O_3 in DBD PA-ALD is as quick as 0.12 nm/cycle. After coated～40 nm Al_2O_3, the water vapor transmission rate of PLA is reduced by two orders of magnitude.Additionally, it is noticed that the tension strength of the coated film is improved slightly,whereas the light transmission rate is decreased with the increase of Al_2O_3 thickness. The degradation test shows that Al_2O_3 coating almost does not affect the self-degradation rate of PLA film.     

Formation mechanism of Al_2O_3/MoS_2 nanocomposite coating by plasma electrolytic oxidation(PEO)

In this study, an Al_2O_3/MoS_2 nanocomposite coating was created on an aluminum 1050 substrate using the plasma electrolytic oxidation method. The zeta potential measurements showed that small MoS_2 particles have negative potential and move toward the anode electrode.The nanoparticles of MoS_2 were found to have a zeta potential of-25 mV, which prevents suspension in the solution. Thus, to produce an Al_2O_3/MoS_2 nanocomposite, one has to use the microparticles of MoS_2. The X-ray diffraction analyses showed that the produced coatings contained α-Al_2O_3, γ-Al_2O_3, and MoS_2, and that the size of MoS_2 particles can be reduced to 30 nm. It was observed that prolonged suspension in the electrolyte results in an enhanced formation of an Al_2O_3/MoS_2 nanocomposite. Using the results, it was hypothesized that the mechanism of the formation of the Al_2O_3/MoS_2 nanocomposite coating on the aluminum 1050 substrate is based on electrical energy discharge.     

α/γ相比率调控对超音速等离子喷涂Al2O3阻氚涂层微结构及性能的影响

采用超音速等离子喷涂技术在中国低活化马氏体钢表面制备不同α/γ相比率的Al₂O₃阻氚涂层,研究了α/γ相比率调控对Al₂O₃涂层微观结构、力学性能和耐电化学腐蚀性能的影响。利用掠入射X射线衍射（GIXRD）和扫描电子显微镜（SEM）表征Al₂O₃涂层的微观结构、粘结拉伸试验法和纳米压痕仪表征涂层的力学性能、动电位极化曲线法测试涂层的耐电化学腐蚀性能。研究结果显示：通过调控特征喷涂参数（CPSP）,Al₂O₃涂层中α相含量从78.6%至24.4%可控调节,且孔隙率从2.8%降低至1.5%;α相含量为78.6%的Al₂O₃涂层硬度为(11.500±0.575) GPa,约为高γ相含量(75.6%)涂层的2倍;且高α相含量(78.6%)涂层的腐蚀电流密度较高γ相含量(75.6%)涂层的腐蚀电流密度低1个数量级。以上结果表明,高α相含量(78.6%)的Al₂O₃涂层具有更优异的力学性能、耐电化学腐蚀性能以及耐Cl^-扩散穿透能力,具有应用于聚变堆结构材料表面阻氚涂层的潜能。     

基于铌酸银的耐高温放射性碘吸附剂的制备及性能

通过机械混合法制备了一种基于铌酸银(AgNbO_3)的耐高温放射性碘吸附剂(AgNbO_3/Al_2O_3)。和常规载银吸附剂(Ag/Al_2O_3)相比,AgNbO_3/Al_2O_3吸附剂的吸附性能更为稳定;特别是在650℃以上时,其对放射性碘的去污因子远高于常规载银吸附剂。表征测试结果表明,该吸附剂结构稳定性良好,可耐受较长时间的高温。热重测试和高温脱附试验等结果表明,碘化银在AgNbO_3/Al_2O_3吸附剂表面稳定性的提高是该吸附剂在高温时吸附性能更佳的主要原因,其将来有望用于核事故中的应急处置。     

Enhancing toluene removal in a plasma photocatalytic system through a black TiO_2 photocatalyst

An efficient toluene removal in air using a plasma photocatalytic system(PPS) not only needs favorable surface reactions over photocatalysts under the action of plasma,but also requires the photocatalysts to efficiently absorb light emitted from the discharge for driving the photocatalytic reactions. We report here that the PPS constructed by integrating a black titania(B-TiO_2)photocatalyst with a dielectric barrier discharge(DBD) can effectively remove toluene with above 70% CO_2 selectivity and remarkably reduced the concentration of secondary pollutants of ozone and nitrogen oxides at a specific energy input of 1500 J·l~(-1),while exhibiting good stability. Photocatalyst characterizations suggest that the B-TiO_2 provides a high concentration of oxygen vacancies for the surface oxidation of toluene in DBD,and efficiently absorbs ultraviolet–visible light emitted from the discharge to induce plasma photocatalytic oxidation of toluene. The presence of B-TiO_2 in the plasma region also results in a high discharge efficiency,facilitating the generation of large numbers of reactive species and thus the oxidation of toluene towards CO_2. The greatly enhanced performance of the PPS integrated with B-TiO_2 in toluene removal offers a promising approach to efficiently remove refractory volatile organic compounds from air at low temperatures.     

Numerical investigation on the effect of gas parameters on ozone generation in pulsed dielectric barrier discharge

Pulsed dielectric barrier discharge is a promising technology for ozone generation and is drawing increasing interest. To overcome the drawback of experimental investigation, a kinetic model is applied to numerically investigate the effect of gas parameters including inlet gas temperature, gas pressure, and gas flow rate on ozone generation using pulsed dielectric barrier discharge. The results show that ozone concentration and ozone yield increase with decreasing inlet gas temperature, gas pressure, and gas flow rate. The highest ozone concentration and ozone yield in oxygen are about 1.8 and 2.5 times higher than those in air, respectively. A very interesting phenomenon is observed: the peak ozone yield occurs at a lower ozone concentration when the inlet gas temperature and gas pressure are higher because of the increasing average gas temperature in the discharge gap as well as the decreasing reduced electric field and electron density in the microdischarge channel. Furthermore, the sensitivity and rate of production analysis based on the specific input energy (SIE) for the four most important species O₃, O, O(1D), and O₂(b¹∑) are executed to quantitatively understand the effects of every reaction on them, and to determine the contribution of individual reactions to their net production or destruction rates. A reasonable increase in SIE is beneficial to ozone generation. However, excessively high SIE is not favorable for ozone production.     

Atomic mixing at metal–oxide interfaces by high energy heavy ions

We study the atomic mixing at metal (Bi or Au)/oxide (SiO₂ or Al₂O₃) interfaces under 150–200 MeV heavy ion irradiation. Irradiation-induced interface mixing state is examined by means of Rutherford backscattering spectrometry (RBS). For Bi/Al₂O₃ interfaces, the heavy ion irradiations induce a strong atomic mixing and the amount of the mixing increases with increasing the electronic stopping power for heavy ions. By comparing the results with that for 3 MeV Si ion irradiation, we conclude that the strong atomic mixing observed at Bi/Al₂O₃ interfaces is attributed to the high-density electronic excitation. On the other hand, for other interfaces (Bi/SiO₂, Au/Al₂O₃ and Au/SiO₂), atomic mixing is rarely observed after the irradiation. The dependence of atomic mixing on combinations of irradiating ions and interface-forming materials is discussed.     

Al_2O_3纯化闪烁液过程中的放射性污染

Al_2O_3可用于纯化闪烁液,但在纯化过程中有可能引入放射性污染。本工作对Al_2O_3纯化闪烁液过程中氡及Al_2O_3本身放射性对闪烁液的污染问题进行了研究。研究结果表明:通过Al_2O_3与闪烁液的混合澄清实验,发现若有细小Al_2O_3颗粒悬浮于闪烁液中会对闪烁液产生污染。但经过滤实验,发现过滤纯化闪烁液过程中的放射性污染主要来源于环境空气中氡的溶解,Al_2O_3过滤柱能阻挡绝大部分Al_2O_3中的放射性核素随着极细颗粒进入闪烁液。排除氡的影响后,在标准偏差范围内,未过滤与经Al_2O_3过滤后的闪烁液的放射性计数率无明显变化,说明Al_2O_3样品中的放射性对闪烁液的影响已低于液闪的探测灵敏度。     

Plasma-catalytic degradation of tetracycline hydrochloride over Mn/γ-Al2O3 catalysts in a dielectric barrier discharge reactor

A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series ofMn/γ-Al₂O₃ catalysts prepared by the incipient wetness impregnation method. The combination of plasma and theMn/γ-Al₂O₃ catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone, with the 10%Mn/γ-Al₂O₃ catalyst exhibiting the best tetracycline hydrochloride degradation efficiency. A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W, with only 69.7% by a single plasma process. The highest energy yield of the plasma-catalytic process is 91.7 gkWh⁻¹. Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.     

阻氚用Fe-Al渗铝层表面稳态相Al2O3膜生长机理研究

为阐释Fe-Al渗铝层表面暂态相Al₂O₃膜向稳态相α-Al₂O₃膜的转变机理,探索稳态相α-Al₂O₃膜制备的氧化工艺参数范围,采用掠入射角X射线衍射仪、辉光放电光谱仪、聚焦离子束、透射电镜等,结合热重分析对CLAM钢基体Fe-Al渗铝层在940～980 ℃、1 Pa～20 kPa参数下的氧化生长行为进行了深入表征与机理分析。研究结果表明,在1 Pa～20 kPa氧分压范围内Al₂O₃膜生长初期反应速率常数随着氧分压的升高而增大,而后期反应速率常数反而随之下降;采用掠入射角X射线衍射仪对3～180 min氧化不同时期表面Al₂O₃膜的相结构进行了掠入射角分析,推测Al2O3膜的生长经历了从氧化初期形成暂态相γ-Al₂O₃（15 min）→过渡态相α-（Al_0.948Cr_0.052）₂O₃（30 min）→稳态相α-Al₂O₃（120～180 min）的演变过程,最短相转变时间约60～90 min,连续Al₂O₃膜厚度约2 000 nm;同时,结合聚焦离子束对30、120 min形成的Al₂O₃膜表面进行了精确定向切割制样,并采用透射电镜选区电子衍射分析验证了相转变前Al₂O₃膜结构为过渡态相α-（Al_0.948Cr_0.052）₂O₃（113）,转变后为稳态相α-Al₂O₃（113）,证实了Cr作为第三组元促进暂态相向稳态相α-Al₂O₃的转变规律。     

Investigation of Stable Al2O3 Scale on Fe-Al Aluminized Coating for Tritium Barrier

It is well known that α-Al₂O₃ phase has stablility performance, high permeation reduction factor and good resistance performance in liquid LiPb, which is considered as the reference tritium barrier coating in future fusion reactor. In order to study the formation mechanism of stable α-Al₂O₃ scales on fusion structure material, the oxidation behavior of Fe-Al aluminized coating on China Low Activated Martensitic （CLAM） steel was investigated under the oxygen partial pressure from 1 Pa to 20 kPa at the temperature of 940-980 ℃. The Al₂O₃ scales were analyzed by thermogravimetric analysis meter, grazing angle X-ray diffractometer, glow discharge spectrometer, focused ion beam and transmission electron microscope. A single continuous Al₂O₃ scales with the maximum thickness of about 2 000 nm was formed on the diffusion Fe-Al aluminized layer. Thermogravimetric analysis results show that the higher oxidation rate constant is achieved while increasing the oxygen partial pressure, and then oxidation rate constant decreases. The phase transformation of Al₂O₃ scales on the surface of Fe-Al aluminized coating was studied during different oxidation time ranges from 3 min to 180 min. The metastable γ-Al₂O₃ and α-（Al0.948Cr0.052）₂O₃ phases is formed in the earlier oxidation process and finally transformed to stable α-Al₂O₃ phase. The features of the transient α-（Al0.948Cr0.052）₂O₃（113） and α-Al₂O₃（113） were detected by GXRD and then confirmed by focused ion beam and transmission electron microscope.     

Fe-Al/Al2O3涂层表面氧化膜的掠入射X射线衍射研究

本文采用掠入射X射线衍射（GXRD）α-2θ扫描模式,进行了掠入射角α为0.1°～5°范围内Fe-Al/Al₂O₃阻氚涂层表面氧化膜的X射线衍射实验。结果表明,随α的增加,表面氧化膜中Al₂O₃相与Fe₃Al相对应的衍射峰强度绝对值增强;α的增加加深了分析区域的深度,引起Al₂O₃相的相对含量下降,导致Al₂O₃相对衍射峰强度降低。对Fe-Al/ Al₂O₃涂层表面氧化膜的掠入射X射线衍射而言,较佳的掠入射角是0.25°,此时对应Al₂O₃相的衍射峰相对强度最高。经比对PDF卡片,表面氧化膜相结构为暂态γ-Al₂O₃（200）。在此基础上建立了GXRD分析Fe-Al/ Al₂O₃涂层表面亚微米氧化膜的相结构组成的快速无损检测方法。     

Analysis of the critical active species for methylene blue decoloration in a dielectric barrier discharge plasma system

In the paper, a hybrid gas–liquid dielectric barrier discharge (DBD) plasma system was set up to treat a methylene blue (MB) solution. The effects of the change of the carrier gas, the gas bubbling rate and different kinds of scavenger addition, including sodium carbonate (Na₂CO₃), para benzoquinone (p-BQ), triethylenediamine and sodium dihydrogen phosphate (NaH₂PO₄), on the MB decoloration were reviewed to clarify the critical active species for the dye decoloration in the DBD plasma system. The obtained results show that higher decoloration of the MB solution could be achieved when O₂ was used as the carrier gas, which could be 100% after 20 min discharge treatment, and the result confirmed the crucial effect of O₃ in the MB decoloration. Based on the experiments of the scavenger addition, it could be concluded that O₂⁻ and ¹O₂ were two other important reactive oxygen species (ROS) for the MB decoloration. The results of the higher chemical oxygen demand removal and faster disappearance of the characteristic peak of the MB from the UV–vis analysis under O₂ bubbling conditions also proved the critical effect of the ROS formed by O₂ on the MB decoloration.     

Plasma propagation in single-particle packed dielectric barrier discharges: joint effects of particle shape and discharge gap

In this work, a single Al₂O₃ particle packed dielectric barrier discharge (DBD) reactor with adjustable discharge gap is built, and the influences of the particle shape (ball and column) and the residual gap between the top electrode and particle on the electrical and optical characteristics of plasma are studied. Our research confirms that streamer discharge and surface discharge are the two main discharge patterns in the single-particle packed DBD reactor. The strong electric field distortion at the top of the ball or column caused by the dielectric polarization effect is an important reason for the formation of streamer discharge. The length of streamer discharge is proportional to the size of the residual gap, but the number of discharge times of a single voltage cycle shows an opposite trend. Compared to the column, a smooth spherical surface is more conducive to the formation of large and uniform surface discharges. The surface discharge area and the discharge intensity reach a maximum when the gap is equal to the diameter of the ball. All in all, the results of this study will provide important theoretical support for the establishment of the synergistic characteristics of discharge and catalysis in plasma catalysis.     

Melting behaviour of oxide systems for heterogeneous transmutation of actinides. II. The system MgO–Al2O3–PuO2

Isothermal sections of the phase diagram of the system MgO–Al₂O₃–PuO₂ at various temperatures were calculated using sublattice models. The results show that below 2133 K no liquid occurs in the system. Above 2133 K liquid starts to form at the Al₂O₃–PuO₂ side. The phase diagram of the pseudo-binary system PuO₂–MgAl₂O₄ was also obtained from an isopleth T–x calculation.     

Na_2O/Al_2O_3摩尔比对模拟高放废液硼硅酸盐玻璃固化体结构和性能的影响

研究了Na2O/Al2O3摩尔比(n)对模拟高放废液硼硅酸盐玻璃固化体结构和性能的影响。利用红外光谱分析了不同Na2O/Al2O3摩尔比时硼硅酸盐玻璃固化体的结构变化,并用溶解速率法(DR)和全谱直读等离子发射光谱(ICP-OES)表征了所制备出固化体的化学稳定性。结果表明:在研究组分范围内,当n1.0时,硼硅酸盐玻璃固化体结构中Al以[AlO4]四面体的形式存在,但[BO3]三角体的量较大;随着Na2O/Al2O3摩尔比的增加(n=1.0),固化体结构中[BO3]三角体向[BO4]四面体转变,Al仍以[AlO4]四面体的形式存在,固化体结构稳定性增加;Na2O/Al2O3摩尔比继续增加(n=1.5或2.0),固化体成分中由于Al含量已很少而使[AlO4]含量过少,对固化体结构网络致密性的影响起主要作用,且此时成分中存在过多的碱金属离子在结构中起断网作用,玻璃固化体网络结构变疏松。在Na2O/Al2O3摩尔比为1.0时,玻璃固化体有相对较佳的结构稳定性和化学稳定性,浸泡56d后的失重速率为10-9 g/(cm2·min)数量级,且浸出液中各浸出离子的平均浓度最低。     

Enthalpies of formation of U-, Th-, Ce-brannerite: implications for plutonium immobilization

Brannerite, ideally MTi₂O₆, (M=actinides, lanthanides and Ca) occurs in titanate-based ceramics proposed for the immobilization of plutonium. Standard enthalpies of formation, ΔH⁰_f at 298 K, for three brannerite compositions (kJ/mol): CeTi₂O₆ (−2948.8 ± 4.3), U_0.97Ti_2.03O₆ (−2977.9 ± 3.5) and ThTi₂O₆ (−3096.5 ± 4.3) were determined by high temperature oxide melt drop solution calorimetry at 975 K using 3Na₂O · 4MoO₃ solvent. The enthalpies of formation were also calculated from an oxide phase assemblage (ΔH⁰_f-ox at 298 K): MO₂ + 2TiO₂=MTi₂O₆. Only UTi₂O₆ is energetically stable with respect to an oxide assemblage: U_0.97Ti_2.03O₆ (ΔH⁰_f-ox=−7.7±2.8 kJ/mol). Both CeTi₂O₆ and ThTi₂O₆ are higher in enthalpy with respect to their oxide assemblages with (ΔH⁰_f-ox=+29.4±3.6 kJ/mol) and (ΔH⁰_f-ox=+19.4±1.6 kJ/mol) respectively. Thus, Ce- and Th-brannerite are entropy stabilized and are thermodynamically stable only at high temperature.     

Activated persulfate by DBD plasma and activated carbon for the degradation of acid orange Ⅱ

In this study, the effect of activated peroxydisulfate(PDS) by dielectric barrier discharge(DBD) plasma and activated carbon(HGAC) on the removal of acid orange Ⅱ(AOⅡ) was investigated. The effects of applied voltage, PDS dosage, HGAC dosage, initial pH value, and inorganic anions on the removal rate of AOⅡ were discussed. The main free radicals degrading azo dyes during the experiment were also studied. Experimental results show that the removal rate of AOⅡ in DBD/HGAC/PDS synergistic system is much higher than that in the single system. With the applied voltage of 16 kV, HGAC dosage of 1 g l-1, PDS and AOⅡ molar ratio of 200:1, initial pH value of 5.4 and concentration of AOⅡ solution of 20 mg l-1, the removal rate of AOⅡ reached 97.6% in DBD/HGAC/PDS process after 28 min of reaction.Acidic and neutral conditions are beneficial for AOⅡ removal. Sulfate and hydroxyl radicals play an important role in the removal of AOⅡ. Inorganic anions are not conducive to the removal of AOⅡ.