Conversion of coalbed methane surrogate into hydrogen and graphene sheets using rotating gliding arc plasma

The use of atmospheric rotating gliding arc(RGA) plasma is proposed as a facile, scalable and catalyst-free approach to synthesizing hydrogen(H_2) and graphene sheets from coalbed methane(CBM). CH_4 is used as a CBM surrogate. Based on a previous investigation of discharge properties, product distribution and energy efficiency, the operating parameters such as CH_4 concentration, applied voltage and gas flow rate can effectively affect the CH_4 conversion rate,the selectivity of H_2 and the properties of solid generated carbon. Nevertheless, the basic properties of RGA plasma and its role in CH_4 conversion are scarcely mentioned. In the present work, a 3D RGA model, with a detailed nonequilibrium CH_4/Ar plasma chemistry, is developed to validate the previous experiments on CBM conversion, aiming in particular at the distribution of H_2 and other gas products. Our results demonstrate that the dynamics of RGA is derived from the joint effects of electron convection, electron migration and electron diffusion, and is prominently determined by the variation of the gas flow rate and applied voltage. Subsequently,a combined experimental and chemical kinetical simulation is performed to analyze the selectivity of gas products in an RGA reaction, taking into consideration the formation and loss pathways of crucial targeted substances(such as CH_4, C_2H_2, H_2 and H radicals) and corresponding contribution rates. Additionally, the effects of operating conditions on the properties of solid products are investigated by scanning electron microscopy(SEM) and Raman spectroscopy. The results show that increasing the applied voltage and decreasing CH_4 concentration will change the solid carbon from its initial spherical structure into folded multilayer graphene sheets, while the size of the graphene sheets is slightly affected by the change in gas flow rate.     

Removing of Mixed Coatings by Plasma Discharges

Next generation tokamaks offer the possibility of highly efficient energy generation from the fusion reaction of hydrogen isotopes. In tokamak operation, the core plasma interaction with the wall materials could produce tiles erosion. Redeposition of the eroded materials (C–W–Be) leads to an increase in the allowable tritium load if the coatings are not periodically removed. Amongst removal methods, plasma based techniques employing Ar, H₂ gas have been investigated. Plasma cleaning has been carried out on hydrogenated carbon and carbon–tungsten coatings. It has been shown that at a RF power density of 1.3 W/cm² (pressure of 1 Pa), the plasma cleaning was effective in removing the coatings. Details of further work in this research activity will be presented.     

Effect of methane content and the oscillating electric field between electrodes on atmospheric Ar/methane plasma jet and DLC coating deposition

In this work, the effects of the methane gas flow and the internal oscillating electric field between electrodes on radio-frequency(RF) atmospheric pressure argon/methane plasma jet and process of diamond-like carbon(DLC) film deposition have been investigated. Properties of RF atmospheric Ar/methane plasma jet such as active species density, length, electron temperature,appearance and ionization process of argon/methane plasma jet are changed due to the changing of methane flow content and electric field vector and its gradient. With increasing methane flow,the formation of C2 hydrocarbon and CH band content is decreased because injected electrical energy to a mixture of Ar/methane gases is insufficient to stabilize the ionization process of methane gas and the electrical-chemical reaction rate is decreased. With shortening the gas gap between two electrodes, electric field strength and its gradient are increased leading to more energy injection to the electron. Electrical-chemical reactions are strengthened leading to increasing the CH band content. These phenomena introduce the Ar/methane plasma jet in different modes causing to deposit the DLC film with different structures and properties. With using quartz glass and alumina ceramic as dielectric barriers tubes, RF atmospheric pressure Ar/methane plasma jet has been used to deposit DLC coating in different modes. Increasing methane content and shortening the gas gap leads to decreasing sp3 bonded content and the quality of the deposited film.     

Atmospheric Pressure Plasma Jet in Ar and O2/Ar Mixtures： Properties and High Performance for Surface Cleaning＊

An atmospheric pressure plasma jet generated in Ar and O2/Ar mixtures has been investigated by specially designed equipment with double power electrodes at 20~32 kHz, and their effects on the cleaning of surfaces have been studied. Properties of the jet discharge are studied by electrical diagnostics, including the waveform of discharge voltage, discharge current and the Q-V Lissajous figures. The optical emission spectroscopy is used to measure the plasma parameters, such as the excitation temperature and the gas temperature. It is found that the consumed power and the excitation temperature increase with increase of the discharge frequency. On the other hand, at the same discharge frequency, these parameters in O2/Ar mixture plasma are found to be much larger. The effect on surface cleaning is studied from the changes in the contact angle. For Ar plasma jet, the contact angle decreases with increase of the discharge frequency. For O2/Ar mixture plasma jet, the contact angle decreases with increase of discharge frequency up to 26 kHz, however, further increase of discharge frequency does not show further decrease in the contact angle. At the same discharge frequency, the contact angle after O2/Ar mixture plasma cleaning is found to be much lower compared to the case of pure Ar. From the results of quadrupole mass-spectrum analysis, we can identify more fragment molecules of CO and H2O in the emitted gases after O2/Ar plasma jet treatment compared with Ar plasma jet treatment, which are produced by the decomposition of surface organic contaminants during the cleaning process.     

Fischer-Tropsch Performance of an SiO2-Supported Co-Based Catalyst Prepared by Hydrogen Dielectric-Barrier Discharge Plasma

A silica-supported cobalt catalyst was prepared by hydrogen dielectric-barrier dis- charge （H2-DBD） plasma. Compared to thermal hydrogen reduction, H2-DBD plasma treatment can not only fully decompose the cobalt precursor but also partially reduce the cobalt oxides at lower temperature and with less time. The effect of the discharge atmosphere on the property of the plasma-prepared catalyst and the Fischer-Tropsch synthesis activity was studied. The re- sults indicate that H2-DBD plasma treatment is a promising alternative for preparing Co/SiO2 catalysts from the viewpoint of energy savings and efficiency.     

Preliminary results of optical emission spectroscopy by line ratio method in the RF negative ion source at ASIPP

Optical emission spectroscopy (OES) using the trace rare gases of Ar and Xe have been carried out in a radio frequency (RF) driven negative ion source at Institute of Plasma Physics, Chinese Academy of Science (ASIPP), in order to determine the electron temperature and density of the hydrogen plasma. The line-ratio methods based on population models are applied to describe the radiation process of the excited state particles and establish their relations with the plasma parameters. The spectral lines from the argon and xenon excited state atoms with the wavelength of 750.4 and 828.0 nm are used to calculate the electron temperature based on the corona model. The argon ions emission lines with the wavelength of 480 and 488 nm are selected to calculate the electron density based on the collisional radiative model. OES has given the preliminary results of the electron temperature and density by varying the discharge gas pressure and RF power. According to the experimental results, the typical plasma parameters is T_e ≈ 2–4 eV and n_e ≈ 1×10 ¹⁷– 8×10¹⁷ m⁻³ in front of plasma grid.     

加热去氩处理工艺对离子束混合沉积的C-SiC涂层阻氢性能的影响

利用Ar＋离子束混合技术在不锈钢基体上沉积C-SiC涂层，然后对部分样品进行加热去氩处理（400℃，30min），再用5keV氢离子源辐照样品。通过扫描电镜（SEM）的表面形貌观察、二次离子质谱仪（SIMS）的H与Ar元素深度分布和正离子质谱分析，研究去氩处理对氢离子辐照的C-SiC涂层的形貌和阻氢性能的影响。结果表明，经去氩处理，样品中不锈钢基体内的氢浓度降低了80%，显示出去氩处理的C-SiC涂层具有更高的阻氢性能。研究结果将为该技术应用于不锈钢基体上C-SiC涂层制备工艺的进一步改善提供依据。     

Plasma Radiofrequency Discharges as Cleaning Technique for the Removal of C–W Coatings

Erosion of materials by chemical and physical sputtering is one of the most concern of plasma wall interaction in tokamaks. In divertor ITER-like tokamaks, where carbon and tungsten are planned to be used, hydrogenated C–W mixed compounds are expected to form by erosion, transport and re-deposition processes. The selection of these materials as divertor components involves lifetime and safety issues due to tritium retention in carbon co-deposits. In this paper a cleaning technique based on RF (13.56 MHz) capacitively coupled H₂/Ar plasmas has been used to remove C–W mixed materials from test specimens. The dependence of the removal rate on the H₂/Ar ratio and on the plasma pressure has been investigated by X-ray photoelectron spectroscopy, atomic force microscopy, profilometry as regards the solid phase and by Langmuir probe and optical emission spectroscopy as regards the plasma phase. The best result has been obtained with a H₂/Ar ratio of 10/90 at a pressure of 1 Pa. An explanation based on a synergistic effect between physical sputtering due to energetic ions and chemical etching due to radicals, together with the pressure dependence of the ion energy distribution function, is given.     

Line identification of extreme ultraviolet(EUV) spectra from low-Z impurity ions in EAST tokamak plasmas

Extreme ultraviolet(EUV) spectra emitted from low-Z impurity ions in the wavelength range of10–500 ? were observed in Experimental Advanced Superconducting Tokamak(EAST)discharges. Several spectral lines from K-and L-shell partially ionized ions were successfully observed with sufficient spectral intensities and resolutions for helium, lithium, boron, carbon,oxygen, neon, silicon and argon using two fast-time-response EUV spectrometers of which the spectral intensities are absolutely calibrated based on the intensity comparison method between visible and EUV bremsstrahlung continua. The wavelength is carefully calibrated using wellknown spectra. The lithium, boron and silicon are individually introduced for the wall coating of the EAST vacuum vessel to suppress mainly the hydrogen and oxygen influxes from the vacuum wall, while the carbon and oxygen intrinsically exist in the plasma. The helium is frequently used as the working gas as well as the deuterium. The neon and argon are also often used for the radiation cooling of edge plasma to reduce the heat flux onto the divertor plate. The measured spectra were analyzed mainly based on the database of National Institute of Standards and Technology. As a result, spectral lines of He Ⅱ, Li Ⅱ–Ⅲ, B Ⅳ–Ⅴ, C Ⅲ–Ⅵ, O Ⅲ–Ⅷ, Ne Ⅱ–Ⅹ,Si Ⅴ–Ⅻ, and Ar Ⅹ–XVI are identified in EAST plasmas of which the central electron temperature and chord-averaged electron density range in T_(e0)=0.6–2.8 keV and n_e=(0.5–6.0)×10~(19) m~(-3), respectively. The wavelengths and transitions of EUV lines identified here are summarized and listed in a table for each impurity species as the database for EUV spectroscopy using fusion plasmas.     

OES diagnostic of radicals in 33MHz radio-frequency Ar/C_2H_5OH atmospheric pressure plasma jet

Ar/C_2H_5OH plasma jet is generated at atmospheric pressure by 33 MHz radio-frequency power source. This RF excitation frequencies which are higher than 13.56 MHz had rarely been used in atmospheric pressure plasma. The plasma characteristics of ethanol are investigated. The introduction of ethanol leads to the generation of four excited carbonaceous species C, CN, CH and C_2 in plasma, respectively. Optical emission intensities of four carbonaceous species were strengthened with ethanol content increasing in the range of 0-4600 ppm. The ethanol content increase results in all the Ar spectra lines decrease. The reason is that the electron temperature decreases when ethanol content is high. The emission intensity ratios of C/C_2, CN/C_2 and CH/C_2 decrease with the increase of ethanol content, showing that the relative amount of C_2 is increasing by increasing the ethanol flow. The emission intensity ratios of excited species did not change much with the increase of RF power in stable discharge mode.     

Plasma Syntheses of Carbon Nanotube-Supported Pt-Pd Nanoparticles

It is reported that the highly dispersed Pt nanoparticles on carbon nanotubes can be synthesized under mild conditions by in situ plasma treatment.The carbon nanotube was pretreated by O₂ plasma to transform into oxide carbon nanotubes（O-CNTs）,and then it was mixed with the precursors（the mixture of H₂ PtCl₆and PdCl₆）.After that,the O-CNTs and the precursors were simultaneously treated by H₂ plasma.The precursors were transformed into Pt-Pd nanoparticles（NPs）and the O-CNTs transformed into CNT.The synthesized CNT-based Pt-Pd nanoparticles were characterized by scanning electron microscopy,transmission electron microscopy,X-ray diffraction and X-ray photoelectron spectroscopy.All the analysis showed that the Pt-Pd nanoparticles were deposited on CNT as a form of face-centered cubical structure.     

Synthesis of vertical graphene nanowalls by cracking n-dodecane using RF inductively-coupled plasma-enhanced chemical vapor deposition

A facile and controllable one-step method to treat liquid hydrocarbons and synthesize vertical graphene nanowalls has been developed by using the technique of inductively-coupled plasma-enhanced chemical vapor deposition for plasma cracking of n-dodecane.Herein,the morphology and microstructure of solid carbon material and graphene nanowalls are characterized in terms of different operating conditions,i.e.input power,H2/Ar ratio,injection rate and reaction temperature.The results reveal that the optimal operating conditions were 500 W,5:10,30μl min^-1 and 800℃ for the input power,H2/Ar ratio,injection rate and reaction temperature,respectively.In addition,the degree of graphitization and the gaseous product are analyzed by Raman spectroscopy and gas chromatography detection.It can be calculated from the Raman spectrum that the relative intensity of ID/IG is approximately 1.55,and I2D/IG is approximately 0.48,indicating that the graphene prepared from n-dodecane has a rich defect structure and a high degree of graphitization.By calculating the mass loading and detecting the outlet gas,we find that the cracking rate of n-dodecane is only 6%-7%and that the gaseous products below C2 mainly include CH4,C2H2,C2H4,C2H6 and H2.Among them,the proportion of hydrogen in the outlet gas of n-dodecane cracking ranges from 1.3%-15.1%under different hydrogen flows.Based on our research,we propose a brand new perspective for both liquid hydrocarbon treatment and other value-added product syntheses.     

环境气氛对DEB吸氢性能的影响

考察了CO、O₂等杂质气体对DEB-Pd/C消氢剂吸氢性能的影响。实验结果表明,CO对DEB-Pd/C初期的吸氢性能影响较大,而O₂对DEB-Pd/C初期的吸氢性能影响较小。同时考察了贮存气氛及贮存时间对DEB-Pd/C吸氢性能的影响。实验结果表明,在氮气、空气环境下贮存1.5 a的消氢剂仍具有良好的消氢性能;当密闭体系中的氢含量为吸氢剂理论吸氢容量的50%时,仍能将氩、氢混合气中的残余氢量控制在10 ppm以下。室温、潮湿环境气氛下贫铀样品贮存气氛中的消氢实验结果也表明,DEB-Pd/C消氢剂能很好地控制密闭体系中的氢含量。     

过氧化氢湿法氧化模拟有机污物的研究

用过氧化氢湿法氧化处理有机污物,研究了过氧化氢的投加量和投加方式,催化剂以及pH值等对反应的影响。结果表明,为提高H2O2的利用率,H2O2应以间歇式投加,选取Fe^2 作催化剂,体系pH值为1～2。为保证反应快速启动和平稳进行,反应时将催化剂总投加量的1／3提前与要分解氧化的物质混合一段时间,剩余2／3在反应进行中连续定量滴加,并于反应结束前半小时投加完毕。正交试验表明,分解2．00g界面污物的最佳实验条件为：pII-1．10mL30％H2O2溶液,10mL 0．1mol／L Fe^2 溶液。反应结束时,反应釜底部的白色残余物经红外分析和元素分析表明主要是磷酸盐。H2O2湿法氧化能够有效分解TBP／OK,HDBP／OK溶液和界面物。     

Development of Sensors for On-Line Monitoring of Nonmetallic Impurities in Liquid Sodium

Sensors for on-line monitoring of hydrogen and carbon in sodium and hydrogen in argon cover gas circuits over sodium have been developed. The performance of these sensors in fast breeder test reactor (FBTR) and large sodium facilities is evaluated. A sensor for monitoring oxygen in sodium is under development. The in-sodium electrochemical hydrogen sensors are found to detect about 10 ppb increase in hydrogen concentration over a background of 50 ppb. The cover gas hydrogen monitoring sensor system is found to sense hydrogen down to 2 vppm in argon over sodium systems. Electrochemical carbon sensors are capable of detecting down to 1 ppm of carbon in sodium.     

Effect of Addition of Nitrogen to a Capacitively Radio-Frequency Hydrogen Discharge

A hybrid PIC/MC model is developed in this work for H2-xN2 capacitively coupled radio-frequency （CCRF） discharges in which we take into account 43 kinds of collisions reaction processes between charged particles （e-, H3＋, H＋, H＋, N＋, N＋） and ground-state molecules （H2, H＋ N2）. In addition, the mean energies and densities of electrons and ions （ 3, H＋, H＋）, and electric field distributions in the H2-N2 CCRF discharge are simulated by this model. Furthermore, the effects of addition of a variable percentage of nitrogen （0-30%） into the H2 discharge on the plasma processes and discharge characteristics are studied. It is shown that by increasing the percentage of nitrogen added to the system, the RF sheath thickness will narrow, the sheath electric field will be enhanced, and the mean energy of hydrogen ions impacting the electrodes will be increased. Because the electron impact ionization and dissociative ionization rates increase when N2 is added to the system, the electron mean density will increase while the electron mean energy and hydrogen ion density near the electrodes will decrease. This work aims to provide a theoretical basis for experimental studies and technological developments with regard to H2-N2 CCRF plasmas.     

小型氟盐冷却高温堆耦合布雷顿循环系统分析与研究

为满足小型氟盐冷却高温堆（FHR）能量转换需求,开发与之匹配的高效、紧凑、无水冷却动力转换系统,本文对比了超临界二氧化碳（SCO₂）、空气、氩气（Ar）、氮气（N₂）、氙气（Xe）5种气体工质在不同布雷顿循环构型中的热电转换效率、?效率、?损失分布。研究发现,SCO₂布雷顿循环相比其它工质循环具有最高的热电转换效率和?效率,且结构更为紧凑,易于小型化和模块化,与小型氟盐冷却高温堆耦合更具优势;进而对SCO₂布雷顿循环进行构型优化,得出匹配小型氟盐冷却高温堆的最佳循环构型方式,构成固有安全模块化小型氟盐冷却高温堆热电转换系统,为西部能源利用提供新研究思路。      

Cleaning of carbon-contaminated optics using O2/Ar plasma

Cleaning of carbon-contaminated beamline optics was studied by RF plasma discharge process using O2/At.Carbon-coated samples were prepared,and through their cleaning processes key parameters were determined,such as the optimal RF output power,mixing rates of O2/Ar,and chamber vacuum.Considerations were made against possible adverse effects in cleaning the beamline optics,such as comparing the roughness of samples before and after cleaning,and possible detrimental kinetic effects on cable insulation.Under the cleaning parameters to clean the beamline optics,the thickness of removed carbon film and the change in beamline photon flux were analyzed.     

Formation of Nano-Crystalline Phase in Hydrogenated Amorphous Silicon Thin Film by Plasma Focus Ion Beam Irradiation

A 3.3 kJ Mather type dense plasma focus device is used to generate a pulsed argon ion beam of 100 KeV in this work. Hydrogenated amorphous silicon (a-Si:H) film prepared by plasma enhanced chemical vapor deposition (PECVD) on c-Si substrate was irradiated with the argon ion beam produced by this dense plasma focus device. The effects of exposure to a single, 5 and 10 shots of dense plasma focus argon ion beam irradiation on the surface morphology, crystallinity and chemical bonding properties of the a-Si:H films were studied using Field Emission Scanning Electron Microscope (FESEM), X-ray Diffraction (XRD), Raman scattering and Fourier Transform Infrared (FTIR) spectroscopy, respectively. Formation of nano-crystalline silicon phase along with increase in structural order and hydrogen content in the film structure has been observed when the a-Si:H film was irradiated with a single shot of dense plasma focus argon ion beam. Exposure to 5 and 10 shots of the dense plasma focus argon ion beam irradiation reduced the hydrogen content resulting in a decrease in crystallinity and structural order in the film structure.     

Erosion research of CX-2002U carbon composites under low-temperature high-flux hydrogen plasma

The net erosion yield of CX-2002 U carbon fiber composites under high-flux low-temperature hydrogen plasma is investigated using a linear plasma device. It is found that the net erosion yield decreases rapidly first, and then tends to saturate with the increase of hydrogen–plasmaflux. When the temperature of the sample eroded by hydrogen plasma is above 300 °C, the hybridization of electrons outside the carbon atom would change. Then the carbon atoms combine with hydrogen atoms to form massive spherical nanoparticles of hydrocarbon compounds and deposit on the surface at the flux condition of 1.77?×?1022 m-2·s-1. Under the irradiation of hydrogen plasma loaded with negative bias, the surface morphology of the matrix carbon is changed dramatically. Moreover, the energy dependence of mass loss does not increase in proportion to the increase of hydrogen–plasma energy, but reaches a peak around 20 V negative bias voltage. Based on the analysis of different samples, it can be concluded that the enhancement of energy could make a contribution to chemical erosion and enlarge the size of pores existing on the surface.