The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO_(2) thin film

The effects of radio frequency(RF)atmospheric pressure(AP)He/H_(2)plasma and thermal treatment on the hydrogenation of TiO_(2)thin films were investigated and compared in this work.The color of the original TiO_(2)film changes from white to black after being hydrogenated in He/H_(2)plasma at160 W(gas temperature~381℃)within 5 min,while the color of the thermally treated TiO_(2)film did not change significantly even in pure H_(2)or He/H_(2)atmosphere with higher temperature(470℃)and longer time(30 min).This indicated that a more effective hydrogenation reaction happened through RF AP He/H_(2)plasma treatment than through pure H_(2)or He/H_(2)thermal treatment.The color change of TiO_(2)film was measured based on the Commission Internationale d’Eclairage L*a*b*color space system.Hydrogenated TiO_(2)film displayed improved visible light absorption with increased plasma power.The morphology of the cauliflower-like nanoparticles of the TiO_(2)film surface remained unchanged after plasma processing.X-ray photoelectron spectroscopy results showed that the contents of Ti3+species and Ti-OH bonds in the plasma-hydrogenated black TiO_(2)increased compared with those in the thermally treated TiO_(2).X-ray diffraction(XRD)patterns and Raman spectra indicated that plasma would destroy the crystal structure of the TiO_(2)surface layer,while thermal annealing would increase the overall crystallinity.The different trends of XRD and Raman spectra results suggested that plasma modification on the TiO_(2)surface layer is more drastic than on its inner layer,which was also consistent with transmission electron microscopy results.Optical emission spectra results suggest that numerous active species were generated during RF AP He/H_(2)plasma processing,while there were no peaks detected from thermal processing.A possible mechanism for the TiO_(2)hydrogenation process by plasma has been proposed.Numerous active species were generated in the bulk plasma region,accelerated in the sheath region,and bumped toward the TiO_(2)film,which will react with the TiO_(2)surface to form OVs and disordered layers.This leads to the tailoring of the band gap of black TiO_(2)and causes its light absorption to extend into the visible region.

INTRODUCTION OF NEW ANTICORROSIVE DESIGN FOR REACTORS EXPOSED TO HIGH TEMPERATURE AND HIGH PRESSURE HYDROGEN

This paper integrates the characteristic of structure design and manufacture and maintenance for Chinese flat steel band wound pressure vessel(UCWPV) with the problems existing in current in service high temperature and pressure vessel exposed to hydrogen. In view of economy and safety it is suggested that it be practicable for UCWPV to act as reactors for platreating, hydrogenating, and catforming. UCWPV has not only potential advantages, but also removes shortages present in in-service reactors for hydrogen.

Public debate on metallic hydrogen to boost high pressure research

Instead of praises from colleagues,the claim of observation of metallic hydrogen at 495 GPa by Dias and Silvera met much skepticism,and grew into a public debate at the International Conference on High-Pressure Science and Technology,AIRAPT26.We briefly review this debate,and extend the topic to show that this disputation could be an opportunity to benefit the whole high pressure community.

Comparative study on pressure swing adsorption system for industrial hydrogen and fuel cell hydrogen

In order to improve the design of PSA system for fuel cell hydrogen production,a non-isothermal model of eight-bed PSA hydrogen process with five-component(H_(2)/N_(2)/CH_(4)/CO/CO_(2)=74.59%/0.01%/4.2%/2.5%/18.7%(vol))four-stage pressure equalization was developed in this article.The model adopts a composite adsorption bed of activated carbon and zeolite 5 A.In this article,pressure variation,temperature field and separation performance are stimulated,and also effect of providing purge(PP)differential pressure and the ratio of activated carbon to zeolite 5 A on separation performance in the process of producing industrial hydrogen(CO content in hydrogen is 10μl·L^(-1))and fuel cell hydrogen(CO content is 0.2μl·L^(-1))are compared.The results show that Run 3,when the CO content in hydrogen is 10μl·L^(-1),the hydrogen recovery is 89.8%,and the average flow rate of feed gas is 0.529 mol·s^(-1);When the CO content in hydrogen is 0.2μl·L^(-1),the hydrogen recovery is 85.2%,and the average flow rate of feed gas is 0.43 mol·s^(-1).With the increase of PP differential pressure,hydrogen recovery first increases and then decreases,reaching the maximum when PP differential pressure is 0.263 MPa;With the decrease of the ratio of activated carbon to zeolite 5 A,the hydrogen recovery increases gradually.When the CO content in hydrogen is 0.2μl·L^(-1) the hydrogen recovery increases more obviously,from 83.96%to 86.37%,until the ratio of activated carbon to zeolite 5 A decreases to 1.At the end of PP step,no large amount of CO_(2) in gas or solid phase enters the zeolite 5 A adsorption bed,while when the CO content in hydrogen is 10μl·L^(-1),and the ratio of carbon to zeolite 5 A is less than 1.4,more CO_(2) will enter the zeolite 5 A bed.

A new dynamic method for measuring hydrogen partial pressure in molten aluminum alloy

Hydrogen partial pressure is an important parameter to calculate hydrogen concentration levels in molten aluminum alloy. A new dynamic method for measuring hydrogen partial pressure in molten aluminum alloy is studied. Dynamic and rapid measurement is realized through changing the volume of the vacuum chamber and calculating the pressure difference ΔP between the theoretical and measured pressures in the vacuum chamber. Positive ΔP indicates hydrogen transmits from melt to vacuum chamber and negative ΔP means the reverse. When ΔP is equal to zero, hydrogen transmitted from both sides reached a state of dynamical equilibrium and the pressure in the vacuum chamber is equal to the hydrogen partial pressure in the molten aluminum alloy. Compared with other existing measuring methods, the new method can significantly shorten the testing time and reduce measuring cost.

Pressure dissociation of dense hydrogen

The self-consistent fluid variational model （SFVM） has been used to describe the pressure dissociation of dense hydrogen at high temperatures. This paper focuses on a mixture of hydrogen atoms and molecules and is devoted to the study of the phenomenon of pressure dissociation at finite temperatures. The equation of state and dissociation degree have been calculated from the free energy functions in the range of temperature 2000-10,000K and density 0.02-1.0g/cm^3, which can be compared with other approaches and experiments. The pressure dissociation is found to occur in higher density range, while temperature dissociation is a more gradual effect.

The interaction of an atmospheric pressure plasma jet using argon or argon plus hydrogen peroxide vapour addition with bacillus subtilis

This paper reports that an atmospheric pressure dielectric barrier discharge plasma jet, which uses argon or argon ＋ hydrogen peroxide vapour as the working gas, is designed to sterilize the bacillus subtilis. Compared with the pure argon plasma, the bacterial inactivation efficacy has a significant improvement when hydrogen peroxide vapour is added into the plasma jet. In order to determine which factors play the main role in inactivation, several methods are used, such as determination of optical emission spectra, high temperature dry air treatment, protein leakage quantification, and scanning electron microscope. These results indicate that the possible inactivation mechanisms are the synergistic actions of chemically active species and charged species.

Simultaneous Effects of Hydrostatic Pressure and Conduction Band Non-parabolicity on Binding Energies and Diamagnetic Susceptibility of a Hydrogenic Impurity in Spherical Quantum Dots

Simultaneous effects of conduction band non-parabolicity and hydrostatic pressure on the binding energies of 1S, 2S, and 2P states along with diamagnetic susceptibility of an on-center hydrogenic impurity confined in typical GaAs/Alx- Ga1-x As spherical quantum dots are theoretically investigated using the matrix diagonalization method. In this regard, the effect of band non-parabolieity has been performed using the Luttinger-Kohn effective mass equation. The binding energies and the diamagnetic susceptibility of the hydrogenic impurity are computed as a function of the dot radius and different values of the pressure in the presence of conduction band non-parabolicity effect. The results we arrived at are as follows： the incorporation of the band edge non-parabolicity increases the binding energies and decreases the absolute value of the diamagnetic susceptibility for a given pressure and radius; the binding energies increase and the magnitude of the diamagnetic susceptibility reduces with increasing pressure.

Hydrogen Purification Performance of Pressure Swing Adsorption Based on Cu-BTC/zeolite 5A Layered Bed

A pressure swing adsorption (PSA) hydrogen purification model for the four-component gas (H_(2)/CO_(2)/CH_(4)/CO=73/16/8/3 mol%) in a layered bed packed with Cu-BTC and zeolite 5A was established to achieve better hydrogen purification performance.By comparing its simulation results with the experimental data,the adsorption isotherm model was validated and could be used to accurately describe the adsorption process of the gas mixture on the two adsorbents.The breakthrough curves of the mixed gas on the layered bed were studied to verify the correctness of the established simulation models.Based on the validated model,the performance of the PSA system based on the layered bed was carried out,including the hydrogen purity and recovery.The simulation results show that the hydrogen purification system based on the layered bed model can achieve hydrogen purity of 95.469% and hydrogen recovery of 83.219%.Moreover,a parametric study was carried out and its results show that reductions in feed flow rate and adsorption time result in an increase in hydrogen purity and a decrease in hydrogen recovery.A longer equalization time between the two adsorption beds can simultaneously increase the hydrogen purity and recovery.

Growth and annealing study of hydrogen-doped single diamond crystals under high pressure and high temperature

A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric（2850 cm-1） and sp 3 CH 2-antisymmetric vibrations（2920 cm-1）.The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.

Numerical Simulation of Turbulent Diffusion Flames of a Biogas Enriched with Hydrogen

Any biogas produced by the anaerobic fermentation of organic materials has the advantage of being an environmentally friendly biofuel.Nevertheless,the relatively low calorific value of such gases makes their effective utilization in practical applications relatively difficult.The present study considers the addition of hydrogen as a potential solution to mitigate this issue.In particular,the properties of turbulent diffusion jet flames and the related pollutant emissions are investigated numerically for different operating pressures.The related numerical simulations are conducted by solving the RANS equations in the frame of the Reynolds Stress Model in combination with the flamelet approach.Radiation effects are also taken into account and the combustion kinetics are described via the GRI-Mech 3.0 reaction model.The considered hydrogen fuel enrichment spans the range from 0%to 50%in terms of volume.Pressure varies between 1 and 10 atm.The results show that both hydrogen addition and pressure increase lead to an improvement in terms of mixing quality and have a significant effect on flame temperature and height.They also reduce CO_(2) emissions but increase NOx production.Prompt NO is shown to be the predominant NO formation mechanism.

Development of CONTHAC-3D and hydrogen distribution analysis of HPR1000

An in-house code,CONTHAC-3D,was developed to calculate and analyze thermal-hydraulic phenomena in containments during severe accidents.CONTHAC-3D is a three-dimensional computational fluid dynamics code that can be applied to predict gas flow,diffusion,and steam condensation in a containment during a severe hypothetical accident,as well as to obtain an estimate of the local hydrogen concentration in various zones of the containment.CONTHAC-3D was developed using multiple models to simulate the features of the proprietary systems and equipment of HPR1000 and ACP100,such as the passive cooling system,passive autocatalytic recombiners and the passive air cooling system.To validate CONTHAC-3D,a GX6 test was performed at the Battelle Model Containment facility.The hydrogen concentration and temperature monitored by the GX6 test are accurately predicted by CONTHAC-3D.Subsequently,the hydrogen distribution in the HPR1000 containment during a severe accident was studied.The results show that the hydrogen removal rates calculated using CONTHAC-3D for different types of PARs agree well with the theoretical values,with an error of less than 1%.As the accident progresses,the hydrogen concentration in the lower compartment becomes higher than that in the large space,which implies that the lower compartment has a higher hydrogen risk than the dome and large space at a later stage of the accident.The amount of hydrogen removed by the PARs placed on the floor of the compartment is small;therefore,raising the installation height of these recombiners appropriately is recommended.However,we do not recommend installing all autocatalytic recombiners at high positions.The study findings in regard to the hydrogen distribution in the HPR1000 containment indicate that CONTHAC-3D can be applied to the study of hydrogen risk containment.

Hydrogen Permeation Characteristics of Pd-CuMembrane in Plasma Membrane Reactor

Hydrogen is an alternative energy source that has the potential to replace fossil fuels.One of the hydrogen applications is as a material for Polymer Electrolyte Membrane Fuel Cells(PEMFC)in fuel cell vehicles.High-purity hydrogen can be obtained using a hydrogen separation membrane to prevent unwanted contaminants from potentially harming the PEMFC components.In this study,we fabricated a plasma membrane reactor and investigated the permeation performance of a hydrogen separation membrane in a plasma membrane reactor utilizing atmospheric pressure plasma.The result showed the hydrogen permeation rate increasing with time as reactor temperature is increased through joule heating.By decreasing the gap length of the reactor from 2 to 1 mm,the hydrogen permeation rate increases by up to 40%.The hydrogen permeation rate increases by 30%when pressure is applied to the plasma membrane reactor by up to 100 kPa.

HYDROGEN DISTRIBUTION AND DIFFUSION BEHAVIOUR IN HIGH PRESSURE HYDROGEN CHARGED AUSTENITIC STEEL BY IMMA

The hydrogen distribution curve along cross-section of high pressure hydrogen charged spec- imens of 21Cr-7Ni-9Mn-N austenitic steel was obtained quantitatively by IMMA(Ion Microprobe Mass Analyzer).Thus the hydrogen solubility and diffusivity may be measured, and the hydrogen permeability and other parameters may be calculated indirectly.The hydrogen distribution in specimens either long-term aged in air or in electron beam weld seam after high pressure hydrogen charging was also examined.

INVESTIGATION OF INFLUENCE OF HYDROGEN ATTACK ONFATIGUE PROPERTIES OF PRESSURE VESSEL STEELS

Influence of hydrogen attack on mechanical and fatigue properties of 1020, 15CrMo and 2.25Cr-1Mo steels has been studied, which were exposed to gaseous hydrogen at pressure of 18MPa and 300-480℃ for up to 480h. The results of fatigue test showed that hydrogen attack (HA) resulted in an obvious change in fatigue properties of 1020 and 15CrMo steels, however, 2.25Cr-1Mo steel showed a lower susceptibility to hydrogen attack due to the addition of Cr and Mo. Fatigue crack behaviour for 1020 steel is attributed to hydrogen attack damage and the crack closure induced by the rough cracking surface, which lead to a valley on △Kth～HA% plot. The change in the fatigue behaviour of 15CrMo steel is possibly caused by severe surface decarburization.

Direct Production of High Pressure Hydrogen at Great Rate from Glycerol/Water/Metal Mixture

One of the key issues facing the global society today is to find renewable and sustainable energy sources. Hydrogen has gained much attention in recent years since it is one of fuels for fuel cells. It emits no carbon dioxide when it is used and so on. In this study, a great rate production of high pressure hydrogen rich gas from glycerol/water/metal mixtures was developed since glycerol has become one of the enormous industrial by-products, especially from biodiesel processing plants. It was found that cobalt was the optimum metal additive among tested metals of aluminum, cobalt, magnesium and nickel in terms of a hydrogen producing rate, a hydrogen partial pressure and a conversion ratio from 50 mol% glycerol/water mixtures under an operating temperature of 723 K. Concretely, hydrogen rich gas with concentration about 64%H2 and high partial pressure about 4 MPaN,H2 could be produced at the great producing rate of 42.9 LN,H2 dm-2min-1 and high conversion ratio about 60%H2. All the produced hydrogen rich gases from glycerol/water/metal mixtures were by no means inferior to pure hydrogen as a fuel for the polymer elec-trolyte fuel cell.

The Effect of Discharge Power on the Atmospheric Pressure Non-equilibrium Ar/O_2/TiCl_4 Plasma Deposition of TiO_2 Film

Deposition of TiO2 film from atmospheric pressure non- equilibrium Ar/O2/TiCl4 plasma was done to study the effect of discharge power during the film deposition process in this paper. TiO2 films with kinds of morphologies and controlled crystallization were deposited from mixtures of TiCl4 and O2 on quartz substrate by one step process. Scanning electron microscope （SEM） and transmission electron microscope （TEM） were used to analyze the morphology and crystallization of the deposited TiO2 films. It was found that the discharge power played a key role in the morphology and crystallization of the deposited TiO2 film whether the flow of TiCl4was large or small. When the flow of TiCl4 was large, the deposited TiO2 film was amorphous particles at low discharge power and was multi-crystalline at high discharge power. When the flow of TiCl4 was small, the deposited TiO2 film became more compact and the crystallization was enhanced as the discharge power increased. The dependence of the discharge current and the applied voltage with the discharge power indicated that it was a glow discharge. The gas temperature which increases with the discharge power is one of the main causes that affect the morphology and crystallization of the deposited film.

Growth and annealing study of hydrogen-doped single diamond crystals under high pressure and high temperature

A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric(2850 cm-1) and sp 3 CH 2-antisymmetric vibrations(2920 cm-1).The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.

Effects of Hydrogen Charging Time and Pressure on the Hydrogen Embrittlement Susceptibility of X52 Pipeline Steel Material

The effects of hydrogen charging time and pressure on the hydrogen embrittlement(HE)susceptibility of X52 pipeline steel material are studied by slow strain rate tensile tests.The fracture morphologies of the specimens are observed by scanning electron microscopy.The HE susceptibility of the X52 pipeline steel material increases with an increase in both hydrogen charging time and hydrogen pressure.At a charging time of 96 h,the HE susceptibility index reaches 45.86%,approximately 3.6 times that at a charging time of 0 h.Similarly,a charging pressure of 4 MPa results in a HE susceptibility index of 31.61%,approximately 2.5 times higher than that at a charging pressure of 0.3 MPa.

Indium recovery from zinc oxide flue dust by oxidative pressure leaching

Indium was recovered from zinc oxide flue dust(ZOFD)with sulfuric acid by oxidative pressure leaching in an autoclave, and the effects of different technological conditions on indium leaching were studied.Potassium permanganate and hydrogen peroxide were used as oxidants.The atmospheric pressure leaching experiments were also carried out.The experimental results show that the leaching rate of indium can be effectively improved by oxidative pressure leaching.The optimum conditions of pressure leaching are determined as sulfuric 5.10 mol/L acid,leaching time 150 min,temperature 90℃,and the H2O2 dosage of 0.5 mL/g or 2.5%KMnO4.The leaching rate of indium is more than 90%,which is increased by 13%compared with that of atmospheric pressure leaching process without oxidant under the optimum conditions.