Numerical and experimental study on the falling film flow characteristics with the effect of co-current gas flow in hydrogen liquefaction process

Liquid hydrogen storage and transportation is an effective method for large-scale transportation and utilization of hydrogen energy. Revealing the flow mechanism of cryogenic working fluid is the key to optimize heat exchanger structure and hydrogen liquefaction process(LH2). The methods of cryogenic visualization experiment, theoretical analysis and numerical simulation are conducted to study the falling film flow characteristics with the effect of co-current gas flow in LH2spiral wound heat exchanger.The results show that the flow rate of mixed refrigerant has a great influence on liquid film spreading process, falling film flow pattern and heat transfer performance. The liquid film of LH2mixed refrigerant with column flow pattern can not uniformly and completely cover the tube wall surface. As liquid flow rate increases, the falling film flow pattern evolves into sheet-column flow and sheet flow, and liquid film completely covers the surface of tube wall. With the increase of shear effect of gas-phase mixed refrigerant in the same direction, the liquid film gradually becomes unstable, and the flow pattern eventually evolves into a mist flow.

Preparation of a zeolite-palladium composite membrane for hydrogen separation:Influence of zeolite film on membrane stability

With the development of hydrogen energy,palladium-based membranes have been widely used in hydrogen separation and purification.However,the poor chemical stability of palladium composite membranes limits their commercial applications.In this study,a zeolite-palladium composite membrane with a sandwich-like structure was obtained by using a TS-1 zeolite film grown on the surface of palladium membrane.The membrane microstructure was characterized by SEM and EDX.The effects of the TS-1 film on the hydrogen permeability and stability of palladium composite membrane were investigated in details.Benefited from the protection of the TS-1 zeolite film,the stability of palladium composite membrane was enhanced.The results indicate that the TS-1-Pd composite membrane was stable after eight cycles of the temperature exchange cycles between 773 K and 623 K.Especially,the loss of hydrogen permeance for TS-1-Pd composite membrane was much smaller than that of the pure palladium membrane when the membrane was tested in the presence of C3H6atmosphere.It indicated that the TS-1-Pd composite membrane had better chemical stability in comparison with pure palladium membrane,owing to its sandwich-like structure.This work provides an efficient way for the deposition of zeolite film on palladium membrane to enhance the membrane stability.

Study on stability of hydrogenated amorphous silicon films

Hydrogenated amorphous silicon （a-Si：H） films with high and same order of magnitude photosensitivity （-10^5） but different stability were prepared by using microwave electron cyclotron resonance chemical vapour deposition system under the different deposition conditions. It was proposed that there was no direct correlation between the photosensitivity and the hydrogen content （CH） as well as H-Si bonding configurations, but for the stability, they were the critical factors. The experimental results indicated that higher substrate temperature, hydrogen dilution ratio and lower deposition rate played an important role in improving the microstructure of a-Si：H films. We used hydrogen elimination model to explain our experimental results.

Influence of Microwave Power on the Properties of Hydrogenated Diamond-Like Carbon Films Prepared by ECR Plasma Enhanced DC Magnetron Sputtering

Electron cyclotron resonance （ECR） plasma was applied to enhance the direct current magnetron sputtering to prepare hydrogenated diamond-like carbon （H-DLC） films. For different microwave powers, both argon and hydrogen gas are introduced separately as the ECR working gas to investigate the influence of microwave power on the microstructure and electrical property of the H-DLC films deposited on P-type silicon substrates. A series of characterization methods including the Raman spectrum and atomic force microscopy are used. Results show that, within a certain range, the increase in microwave power affects the properties of the thin films, namely the sp3 ratio, the hardness, the nanoparticle size and the resistivity all increase while the roughness decreases with the increase in microwave power. The maximum of resistivity amounts to 1.1×10^9 Ω.cm. At the same time it is found that the influence of microwave power on the properties of H-DLC films is more pronounced when argon gas is applied as the ECR working gas, compared to hydrogen gas.

Research on the optimum hydrogenated silicon thin films for application in solar cells

Hydrogenated silicon （Si：H） thin films for application in solar ceils were deposited by using very high frequency plasma enhanced chemical vapour deposition （VHF PECVD） at a substrate temperature of about 170 ℃, The electrical, structural, and optical properties of the films were investigated. The deposited films were then applied as i-layers for p-i-n single junction solar cells. The current-voltage （I - V） characteristics of the cells were measured before and after the light soaking. The results suggest that the films deposited near the transition region have an optimum properties for application in solar cells. The cell with an i-layer prepared near the transition region shows the best stable performance.

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.

Smooth Surface Morphology of Hydrogenated Amorphous Silicon Film Prepared by Plasma Enhanced Chemical Vapor Deposition

Influence of the parameters of plasma enhanced chemical vapor deposition （PECVD） on the surface morphology of hydrogenated amorphous silicon （α-Si：H） film was investigated. The root-mean-square （RMS） roughness of the film was measured by atomic force microscope （AFM） and the relevant results were analyzed using the surface smoothing mechanism of film deposition. It is shown that an α-Si：H film with smooth surface morphology can be obtained by increasing the PH3/N2 gas flow rate for 10% in a high frequency （HF） mode. For high power, however, the surface morphology of the film will deteriorate when the Sill4 gas flow rate increases. Furthermore, optimized parameters of PECVD for growing the film with smooth surface were obtained to be Sill4：25 sccm （standard cubic centimeters per minute）, At： 275 sccm, 10%PH3/N2：2 sccm, HF power： 15 W, pressure： 0.9 Torr and temperature： 350℃. In addition, for in thick fihn deposition on silicon substrate, a N20 and NH3 preprocessing method is proposed to suppress the formation of gas bubbles.

Electrochemical Hydrogen Charging on Corrosion Behavior of Ti-6Al-4V Alloy in Artificial Seawater

This study employs advanced electrochemical and surface characterization techniques to investigate the impact of electrochemical hydrogen charging on the corrosion behavior and surface film of the Ti-6Al-4V alloy.The findings revealed the formation ofγ-TiH andδ-TiH_(2) hydrides in the alloy after hydrogen charging.Prolonging hydrogen charging resulted in more significant degradation of the alloy microstructure,leading to deteriorated protectiveness of the surface film.This trend was further confirmed by the electrochemical measurements,which showed that the corrosion resistance of the alloy progressively worsened as the hydrogen charging time was increased.Consequently,this work provides valuable insights into the mechanisms underlying the corrosion of Ti-6Al-4V alloy under hydrogen charging conditions.

Characterization of doped hydrogenated nanocrystalline silicon films prepared by plasma enhanced chemical vapour deposition

The B- and P-doped hydrogenated nanocrystalline silicon films （nc-Si：H） are prepared by plasma-enhanced chemical vapour deposition （PECVD）. The microstructures of doped nc-Si＇H films are carefully and systematically characterized by using high resolution electron microscopy （HREM）, Raman scattering, x-ray diffraction （XRD）, Auger electron spectroscopy （AES）, and resonant nucleus reaction （RNR）. The results show that as the doping concentration of PH3 increases, the average grain size （d） tends to decrease and the crystalline volume percentage （Xc） increases simultaneously. For the B-doped samples, as the doping concentration of B2H6 increases, no obvious change in the value of d is observed, but the value of Xc is found to decrease. This is especially apparent in the case of heavy B2H6 doped samples, where the films change from nanocrystalline to amorphous.

Room Temperature Growth of Hydrogenated Amorphous Silicon Films by Dielectric Barrier Discharge Enhanced CVD

Hydrogenated amorphous silicon （a-Si： H） films were deposited on Si （100） and glass substrates by dielectric barrier discharge enhanced chemical vapour deposition （DBD-CVD） in （SiH4＋H2） atmosphere at room temperature. Results of the thickness measurement, SEM （scanning electron microscope）, Raman, and FTIR （Fourier transform infrared spectroscopy） show that with the increase in the applied peak voltage, the deposition rate and network order of the films increase, and the hydrogen bonding configurations mainly in di-hydrogen （Si-H2） and poly hydrogen （SiH2）n are introduced into the films. The UV-visible transmission spectra show that with the decrease in SiH4/ （SiHn＋H2） the thin films＇ band gap shifts from 1.92 eV to 2.17 eV. These experimental results are in agreement with the theoretic analysis of the DBD discharge. The deposition of a-Si： H films by the DBD-CVD method as reported here for the first time is attractive because it allows fast deposition of a-Si： H films on large-area low-melting-point substrates and requires only a low cost of production without additional heating or pumping equipment.

SUBSTRATE EFFECT ON HYDROGENATED MICROCRYSTALLINE SILICON FILMS DEPOSITED WITH VHF-PECVD TECHNIQUE

Raman spectra and scanning electron microscope （SEM） techniques were used to determine the structural properties of microcrb＇stalline silicon （μc-Si：H） films deposited on different substrates with the very high frequency plasma-enhanced chemical vapor deposition （VHF-PECVD） technique. Using the Raman spectra, the values of crystalline volume fraction Xc and average grain size d are 86%, 12.3nm; 65%, 5.45nm; and 38%, 4.05nm, for single crystalline silicon wafer, coming 7059 glass, and general optical glass substrates, respectively. The SEM images further demonstrate the substrate effect on the film surface roughness. For the single crystalline silicon wafer and Coming 7059 glass, the surfaces of the μc-Si：H films are fairly smooth because of the homogenous growth or h＇ttle lattice mismatch. But for general optical glass, the surface of the μ-Si： H film is very rough, thus the growing surface roughness affects the crystallization process and determines the average grain size of the deposited material. Moreover, with the measurements of thickness, photo and dark conductivity, photosensitivity and activation energy, the substrate effect on the deposition rate, optical and electrical properties of the μc-Si：H thin films have also been investigated. On the basis of the above results, it can be concluded that the substrates affect the initial growing layers acting as a seed for the formation of a crystalline-like material and then the deposition rates, optical and electrical properties are also strongly influenced, hence, deposition parameter optimization is the key method that can be used to obtain a good initial growing layer, to realize the deposition of μc-Si：H films with device-grade quality on cheap substrates such as general glass.

Effects of ratio of hydrogen flow on microstructure of hydrogenated microcrystalline silicon films deposited by magnetron sputtering at 100 ℃

Hydrogenated microcrystalline silicon(μc-Si:H)films were prepared on glass and silicon substrates by radio frequency magnetron sputtering at 100°C using a mixture of argon(Ar)and hydrogen(H2)gasses as precursor gas.The effects of the ratio of hydrogen flow(H2/(Ar+H2)%)on the microstructure were evaluated.Results show that the microstructure,bonding structure,and surface morphology of theμc-Si:H films can be tailored based on the ratio of hydrogen flow.An amorphous to crystalline phase transition occurred when the ratio of hydrogen flow increased up to 50%.The crystallinity increased and tended to stabilize with the increase in ratio of hydrogen flow from 40%to 70%.The surface roughness of thin films increased,and total hydrogen content decreased as the ratio of hydrogen flow increased.Allμc-Si:H films have a preferred(111)orientation,independent of the ratio of hydrogen flow.And theμc-Si:H films had a dense structure,which shows their excellent resistance to post-oxidation.

Tribological behaviors of hydrogenated diamond-like carbon films in different testing environments

Hydrogenated diamond-like carbon (DLC) films were deposited on Si substrate using plasma enhanced chemical vapor deposition(PECVD) technique with CH4 plus H2 as the feedstock. The tribological properties of the hydrogenated DLC films were measured on a ball-on-disk tribometer in different testing environments (humid air,dry air, dry O2, dry Ar and dry N2 ) sliding against Si3 N4 balls. The friction surfaces of the films and Si3 N4 balls were observed on a scanning electron microscope (SEM) and investigated by X-ray photoelectron spectroscopy (XPS). The results show that the tribological properties of the hydrogenated DLC films are strongly dependent on the testing environments. In dry Ar and dry N2 environments, the hydrogenated DLC films provide a superlow friction coefficient of about 0. 008 -0.01 and excellent wear resistance (wear life of above 56 km). In dry air and dry O2, the friction coefficient is increased to 0. 025 - 0.04 and the wear life is decreased to about 30 km. When sliding in moist air, the friction coefficient of the films is further increased to 0. 08 and the wear life is decreased to 10. 4 km. SEM and XPS analyses show that the tribological behaviors appear to rely on the transferred carbon-rich layer processes on the Si3 N4 balls and on the friction-induced oxidation of the films controlled by the nature of the testing environments.

New Numerical Method to Calculate the True Optical Absorption of Hydrogenated Nanocrystalline Silicon Thin Films

The enhanced optical absorption measured by Constant Photocurrent Method (CPM) of hydrogenated nanocrystalline silicon thin films is due mainly to bulk and/or surface light scattering effects. A new numerical method is presented to calculate both true optical absorption and scattering coefficient from CPM absorption spectra of nanotextured nano-crystalline silicon films. Bulk and surface light scattering contributions can be unified through the correlation obtained between the scattering coefficient and surface roughness obtained using our method.

Effect of Chromium on Structure and Tribological Properties of Hydrogenated Cr/a-C:H Films Prepared via a Reactive Magnetron Sputtering System

Hydrogenated Cr-incorporated carbon films （Cr/a-C：H） are deposited successfully by using a dc reactive mag- netron sputtering system. The structure and mechanical properties of the as-deposited Cr/a-C：H films are characterized systematically by field-emission scanning electron microscope, x-ray diffraction, Raman spectra, nanoindentation and scratch. It is shown that optimal Cr metal forms nanocrystalline carbide to improve the hardness, toughness and adhesion strength in the amorphous carbon matrix, which possesses relatively higher nano-hardness of 15. 7 CPa, elastic modulus of 126.8 GPa and best adhesion strength with critical load （Lc） of 36 N for the Cr/a-C：H film deposited at CH4 flow rate of 20sccm. The friction and wear behaviors of as-deposited Cr/a-C：H films are evaluated under both the ambient air and deionized water conditions. The results reveal that it can achieve superior low friction and anti-wear performance for the Cr/a-C：H film deposited at CH4 flow rate of 20sccm under the ambient air condition, and the friction coetllcient and wear rate tested in deionized water condition are relatively lower compared with those tested under the ambient air condition for each film. Superior combination of mechanical and tribological properties for the Cr/a-C：H film should be a good candidate for engineering applications.

An overview of progress in Mg-based hydrogen storage films

Mg-based hydrogen storage materials are considered to be one of the most promising solid-state hydrogen storage materials due to their large hydrogen storage capacity and low cost. However, slow hydrogen absorption/desorption rate and excessive hydrogen absorption/desorption temperature limit the application of Mg-based hydrogen storage materials.The present paper reviews the advances in the research of Mg-based hydrogen storage film in recent years, including the advantage of the film, the function theory of fabricating method and its functional theory, and the influencing factors in the technological process. The research status worldwide is introduced in detail. By comparing pure Mg, Pd-caped Mg, nonpalladium capped Mg, and Mg alloy hydrogen storage films, an ideal tendency for producing Mg-based film is pointed out,for example, looking for a cheap metal element to replace the high-priced Pd, compositing Mg film with other hydrogen storage alloy of catalytic elements, and so on.

Review of Alloy Membranes/Films for Hydrogen Separation or Purification

Hydrogen separation and purification are two important chemical processes in the extensive application of hydrogen energy. Membrane technology has opened up a potential solution to the problems of separation and purification in an energy effective way. Membranes of adequate hydrogen permeability, good thermal and mechanical stability are the key to successful application of membrane technology in hydrogen separation and purification. In this paper, the relative parameters concerning hydrogen permeability, the development of different types of membranes namely: palladium composite membranes; V-based alloy membranes, specific functionality embraced alloy membranes, metal hydride (MH) thin films and fabrications, were reviewed and discussed. Pd-free membranes are found to be the ideal alternatives. Suitable MH thin films with mono- or multi-layer microstructures produced by novel fabrication techniques, is likely to be the promising candidates due to possessing properties distinct from those of bulk materials in membrane form.

Electro-Deposition of Ni-La Film in Urea-NaBr Melt and Its Hydrogen Evolution Properties

The Ni-La alloy was electro-deposited in urea-NaBr melt. The codeposition behavior and effect of the cathodic current density on the coating composition were examined. As a result, lanthanum codeposited with nickel to form Ni-La alloy under the inducement effect of nickel. With the increase of the cathodic current density, the content of lanthanum of the deposit rose at first, then decreased, and reached the maximal value (10.3%(atom fraction)) at the current density 15 mA·cm-2. The crystallization behavior of Ni89.7La10.3 coating was investigated by means of differential scanning calorimetry and X-ray diffraction. The structure of Ni89.7La10.3 as-plated coating was amorphous phase. The amorphous phase was converted into center cubic close packed Ni-La (Fm3m) solid solution at 469.8 ℃. The electro-catalytic activity of hydrogen evolution of Ni89.7La10.3 coating was studied using electrochemical experiments, the results showed that the electro-catalytic activity of hydrogen evolution of Ni89.7La10.3 coating was better than that of nickel.

Improved electrochemical hydrogen storage properties of Mg-Y thin films as a function of substrate temperature

Pd-capped Mg78Y22 thin films have been prepared by direct current magnetron co-sputtering system at different substrate temperatures and their electrochemical hydrogen storage properties have been investigated.It is found that rising substrate temperature to 60 ℃ can coarsen the surface of thin film,thus facilitating the diffusion of hydrogen atoms and then enhancing its discharge capacity to 1725 mAh·g-1.Simultaneously,the cyclic stability is effectively improved due to the increased adhesion force between film and substrate as a function of temperature.In addition,the specimen exhibits a very long and flat discharge plateau at about —0.67 V,at which nearly 60%of capacity is maintained.The property is favorable for the application in metal hydride/nickel secondary batteries.The results indicate that rising optimal substrate temperature has a beneficial effect on the electrochemical hydrogen storage of Mg-Y thin films.

Carbon film encapsulated Fe_2O_3: An efficient catalyst for hydrogenation of nitroarenes

Iron catalysis has attracted a wealth of interdependent research for its abundance,low price,and nontoxicity.Herein,a convenient and stable iron oxide(Fe2O3)‐based catalyst,in which active Fe2O3nanoparticles(NPs)were embedded into carbon films,was prepared via the pyrolysis of iron‐polyaniline complexes on carbon particles.The obtained catalyst shows a large surface area,uniform pore channel distribution,with the Fe2O3NPs homogeneously dispersed across the hybrid material.Scanning electron microscopy,Raman spectroscopy and X‐ray diffraction analyses of the catalyst prepared at900°C(Fe2O3@G‐C‐900)and an acid‐pretreated commercial activated carbon confirmed that additional carbon materials formed on the pristine carbon particles.Observation of high‐resolution transmission electron microscopy images also revealed that the Fe2O3NPs in the hybrid were encapsulated by a thin carbon film.The Fe2O3@G‐C‐900composite was highly active and stable for the direct selective hydrogenation of nitroarenes to anilines under mild conditions,where previously noble metals were required.The synthetic strategy and the structure of the iron oxide‐based composite may lead to the advancement of cost‐effective and sustainable industrial processes.