Alloying effects of Ru and W on hydrogen diffusivity during hydrogen permeation through Nb-based hydrogen permeable membranes

The hydrogen permeability have been measured for pure niobium and Nb-5 mol%X (X = Ru and W) alloys in order to investigate the alloying effects of ruthenium and tungsten on the hydrogen diffusivity during hydrogen permeation. The hydrogen diffusion coefficient during hydrogen permeation is estimated from a linear relationship between the normalized hydrogen flux, J·d, and the difference of hydrogen concentration, ΔC, between the inlet and the outlet sides of the membrane. It is found that the addition of ruthenium or tungsten into niobium increases the hydrogen diffusion coefficient during the hydrogen permeation. On the other hand, the activation energy for hydrogen diffusion in pure niobium under the practical permeation condition is much higher than the reported values measured for dilute hydrogen solid solutions. It is interesting that the activation energy for hydrogen diffusion is decreased by alloying of ruthenium or tungsten into niobium.     

Analysis of hydrogen diffusion coefficient during hydrogen permeation through pure niobium

The hydrogen solubility and the hydrogen permeability of pure niobium at high temperature are investigated in order to analyze the hydrogen diffusion coefficient during the hydrogen permeation. It is shown that the hydrogen dissolution reaction into niobium metal does not follow the Sieverts' law at the practical hydrogen permeation pressures. The hydrogen diffusion coefficient during the hydrogen permeation through pure niobium at high temperature is evaluated from the linear relationship between the normalized hydrogen flux, J·d, and the hydrogen concentration difference, ΔC. It is found that the hydrogen diffusion coefficient under the practical condition is much lower than the reported values measured for dilute hydrogen solid solutions. Surprisingly, the hydrogen diffusion is found to be faster in Pd–Ag alloy with fcc crystal structure than in pure niobium with bcc crystal structure at 773 K during the hydrogen permeation.     

Study of the plasma and heating effect on hydrogen permeation through Pd0.60-Cu0.40 membrane in a micro-channel plate reactor

The diffusion of hydrogen through palladium and palladium-copper alloys membrane have been provided the highest hydrogen selectivity and permeance. In this study the composite Pd_0.60-Cu_0.40 wt% membrane foil with thickness 20 μm was measured in the micro-channel plate reactor (MPR) with gap length 4.5 mm. The hydrogen permeation flux was measured at atmospheric feeding pressure for 100% H₂ concentration in the temperatures range of 423–573 K under heating only and plasma-heating experiments. The plasma firing high voltage source ranges of 10–18 kV are tested. The hydrogen permeation flux and hydrogen permeability have been calculated according to Fick's and Sieverts combining laws with power exponent n-value 0.5. It was found that the maximum hydrogen flux, hydrogen permeability and Permeation rate percent of the heating only experiment at MPR heating temperature of 573 K and flow rate 0.1 l/min. In the plasma heating experiment, it was observed that the maximum hydrogen flux, hydrogen permeability, and permeation rate percent at MPR heating temperature of 573 K and plasma firing voltage of 14 kV. Also, the hydrogen permeation rate percent decreased due to the hydrogen reverse reaction even though the plasma firing voltage increased to 16 kV and 18 kV. The results also reveal that the activation energy and Pre-exponential constant factor decreased with increasing the feeding H₂ flow rate while the linear regression R² decreased with increasing H₂ feeding flow rate that in the heating only experiment, in contrast, the plasma-heating experiment showed non-linearity values. A comparison between both experiments showed the hydrogen permeation flux of the plasma-heating experiment is higher than that obtained from the heating only experiment, additionally; the plasma effect increased at low hydrogen flow rates. In contrast, the energy efficiency of heating only experiment was higher than that obtained from the plasma-heating experiment due to the total energy consumption of plasma experiment is high.     

Hydrogen transport in solution-treated and pre-strained austenitic stainless steels and its role in hydrogen-enhanced fatigue crack growth

Hydrogen solubility and diffusion in Type 304, 316L and 310S austenitic stainless steels exposed to high-pressure hydrogen gas has been investigated. The effects of absorbed hydrogen and strain-induced martensite on fatigue crack growth behaviour of the former two steels have also been measured. In the pressure range 10–84 MPa, the hydrogen permeation of the stainless steels could be successfully quantified using Sieverts' law modified by using hydrogen fugacity and Fick's law. For the austenitic stainless steels, hydrogen diffusivity was enhanced with an increase in strain-induced martensite. The introduction of dislocation and other lattice defects by pre-straining increased the hydrogen concentration of the austenite, without affecting diffusivity. It has been shown that the coupled effect of strain-induced martensite and exposure to hydrogen increased the growth rate of fatigue cracks.     

Experimental analysis of plasma and heating effect on H2 permeation behavior through Pd–Cu40% membranes in 1mm gap length plate reactor

In this work, experimental analysis of hydrogen permeation behavior under heating only and plasma-heating effect were studied in 15  μm and 20  μm Pd–Cu40% membrane thicknesses. Apure hydrogen gas at feeding pressure of 100 kPa was injected in 1 mm gap length plate micro-channel reactor (PMCR). The permeated hydrogen flux through Pd–Cu40% membranes was measured under heating only experiment at PMCR heating temperature range of 423–573 K and hydrogen flow rates of 0.1–1 L/min. In the plasma-heating experiments, dielectric barrier discharge plasma (DBD) were used at the applied voltage ranges of 10–16 kV, PMCR heating temperatures 423–573 K and hydrogen flow rate 0.1 L/min. The hydrogen permeability was calculated according to the Fick's and Sievert's law equation. It was found that the hydrogen permeability of heating only experiments lower than that obtained from plasma-heating experiments for both Pd–Cu membrane thickness. Further, the hydrogen permeability of the plasma-heating experiments has shown anon-linearity effect which it was presented in the pre-exponential factor and the activation energy pattern. However, it was observed that the hydrogen permeability decreased while the DBD-plasma applied voltage was high, due to the hydrogen gas reverse reaction. A comparison between the hydrogen permeability and the permeation rate% of both experiments has been developed to investigate the dependence on the membrane thickness in both experiments. The analysis shows that the permeability of 15  μm membrane thickness was always higher than 20  μm membrane thickness results and the maximum hydrogen permeability was at PMCR heating temperature of 573 K.     

Effect of single atomic layer graphene film on the thermal stability and hydrogen permeation of Pd-coated Nb composite membrane

Pd coated Nb-base composite membranes are preferable in the fields of hydrogen permeation. However, the rapid reduction of hydrogen permeability caused by high-temperature interfacial diffusion of Pd and Nb atoms hinders their large-scale application. In this paper, a single atomic layer graphene film was used for improving the thermal stability of a hydrogen-permeable composite membrane comprising a Pd coating on the Nb substrate. First, the graphene film was transferred onto the surface of the “clean” niobium substrate. Then a thin palladium coating was deposited on it by magnetron sputtering to form the niobium/graphene/palladium (Nb/Gr/Pd) composite membrane. The interfacial stability was evaluated in the temperature range of 673–973 K under vacuum, and the hydrogen permeation behavior was studied by gas-driven permeation method at 573–823 K. The results show that the single atomic layer graphene film can effectively compress the interdiffusion of Pd coating and Nb substrate and achieve a good hydrogen permeability below 823 K. However, it would be broken due to the micro-deformation of Nb substrate, the high mobility of Pd atoms, and the grain growth at a higher temperature. Therefore, it is concluded that the single atomic layer graphene film is unsuitable as an intermediate hindering layer for Nb-based hydrogen-permeable membranes.     

Deuterium permeation and isotope effects in nickel in an elevated temperature range of 450–850 °C

A series of deuterium permeation experiments were carried out using a nickel membrane in an elevated temperature range of 450–850 °C for application to nuclear fusion and nuclear hydrogen technologies. A complete set of permeability, diffusivity, and solubility data for deuterium in nickel was successfully determined. The results of this study were compared with results previously reported by other authors. The results for deuterium were also compared with the results for hydrogen to estimate the isotope effect. The results for and a discussion of deuterium permeation and the isotope effects in nickel are presented.     

Hydrogen permeation across super‐thin membrane and the burning limitation in low‐temperature proton exchange membrane fuel cell

Hydrogen permeation across the membrane is unavoidable in proton exchange membrane fuel cells, especially for super‐thin membranes, which lowers the open‐circuit voltage and could even be a safety concern. In this paper, hydrogen permeation across two membranes (25‐um‐thick Nafion^® 211 and 18‐um‐thick reinforced composite membrane) are evaluated at various temperatures, relative humidity (RH), and gas pressure differences between the anode and cathode. The results indicate that the hydrogen permeation rate in both membranes increases almost exponentially with temperature and linearly with pressure differences. Compared with RH, the effects of temperature and pressure differences are more crucial to hydrogen permeability. However, the effect of RH on the hydrogen permeation is quite complicated. The permeability exhibits a minimum value at intermediate RH (approximately 40% RH) for both applied membranes. The permeability of Nafion^® 211 appears more sensitive to RH than that of reinforced composite membrane at elevated temperature. Copyright © 2013 John Wiley & Sons, Ltd.     

Permeability,solubility and diffusivity of hydrogen isotopes in stainless steels at high gas pressures

In this report, we provide a framework for describing the permeability, solubility and diffusivity of hydrogen and its isotopes in austenitic stainless steels at temperatures and high gas pressures of engineering interest for hydrogen storage and distribution infrastructure. We demonstrate the importance of using the real gas behavior for modeling permeation and dissolution of hydrogen under these conditions. A simple one-parameter equation of state (the Abel–Noble equation of state) is shown to capture the real gas behavior of hydrogen and its isotopes for pressures less than 200 MPa and temperatures between 223 and 423 K. We use the literature on hydrogen transport in austenitic stainless steels to provide general guidance on and clarification of test procedures, and to provide recommendations for appropriate permeability, diffusivity and solubility relationships for austenitic stainless steels. Hydrogen precharging and concentration measurements for a variety of austenitic stainless steels are described and used to generate more accurate solubility and diffusivity relationships.     

Strain gradient-induced diffusion of hydrogen in palladium and nickel membranes

The “uphill” diffusion of hydrogen during permeation through flat sheets of palladium and nickel has been studied by an electrochemical permeation method at 303 K. For both annealed and “as cold rolled” Pd samples, uphill diffusion effects on hydrogen absorption and desorption have been observed over a range of initial hydrogen contents from about H/Pd = 0.01, i.e. near or slightly less than the _max composition, up to H/Pd = 0.25–0.3. The occurrence of a non-Fickian component of permeation flux has been associated with temporary formation of lattice volume differences across the ( + β)/β and ( + β)/ interfaces during absorptions and desorptions, respectively. Influences of the magnitudes of galvanostatic hydrogen fluxes and of the membrane thickness on the uphill effects were examined. Analogous uphill effects were observed in similar studies with nickel membranes also in both annealed and “as cold rolled” states, which were much larger than those observed for palladium.     

The optimized composition and strong sustainability of hydrogen permeation of Nb30Ti35Co35 eutectic alloy membrane after 5 at%Fe substitution

The microstructure of Nb₃₀Ti₃₅Co₃₀Fe₅ eutectic alloy was investigated by using scanning electron microscope (SEM) and transmission electron microscope (TEM). The alloy exhibits typically lamellar eutectic structures which are composed of uniformly arranged nano-scale bcc-(Nb) phases and B2–Ti(Co, Fe) phases. 5 at% Fe partially substituting Co induced the composition modification of bcc-(Nb) phase such as the increasing Ti/Nb ratio and existing Fe solutes, which contributes to the enhanced hydrogen permeability. Nb₃₀Ti₃₅Co₃₀Fe₅ eutectic alloy shows strong sustainability during hydrogen permeation under continuous hydrogen pressure and thermal cycles, and the hydrogen permeation flux can restore when the hydrogen pressure or temperature recovered again. No hydrogen induced fractures were found during hydrogen permeation. The present work demonstrates that Nb₃₀Ti₃₅Co₃₀Fe₅ eutectic alloy exhibits excellent sustainability under the conditions of changing temperature and feed hydrogen pressure, which is very promising to be an alternative for Pd used for hydrogen separation and purification.     

Novel non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation

This study presents a new non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation. It shows that palladium and ruthenium can be deposited on an aluminum-oxide-modified porous Hastalloy by using our new EDTA-free plating bath at room temperature and 358 K, respectively. A 6.8 μm thick non-alloy Ru/Pd membrane film could be plated and helium leak test confirmed that the membrane was free of defects. Hydrogen permeation test showed that the membrane had a hydrogen permeation flux of 4.5 × 10⁻¹ mol m⁻² s⁻¹ at a temperature of 773 K and a pressure difference of 100 kPa. The hydrogen permeability normalized value with thickness of the membrane was 1.4 times higher than our pure Pd membrane having similar structure. The EDX profiles of the front and back side membrane, cross-sectional EDX line scanning and XRD profile show that there was no alloying progress between the palladium and ruthenium layer after hydrogen permeation test at 773 K.     

Hydrogen permeation in a Cr–Mo–V medium-carbon steel: Effect of the quenching medium and tempering temperature

Hydrogen permeation tests are carried out to evaluate the effect of the quenching medium and tempering temperature on the permeation parameters and density of hydrogen traps, of a Cr–Mo–V low-alloy medium-carbon steel. Three types of steel membranes are tested: 1) in the as-quenched condition, 2) tempered at 235 °C and 3) tempered at 530 °C; each one quenched in two different media: oil or brine. From the as-quenched condition, the apparent concentration of hydrogen and hydrogen flux, tend to decrease as the tempering temperature increases. The membranes in the as-quenched condition and tempered at 530 °C, show lower hydrogen diffusivity and higher density of hydrogen traps than membranes tempered at 235 °C. It is concluded that tempering at 235 °C, promotes hydrogen induced cracking, which is contrary to what has been previously determined. The cracking is related to a higher hydrogen diffusivity and lower density of hydrogen traps.     

Structure and hydrogen permeability of V–15Ni alloy

The structure of the V–15Ni at.% alloy before and after hydrogen permeability tests was investigated by means of XRD and SEM with EDS analysis. We have found that decomposition of supersaturated V-based solid solution with variable Ni content occurred during testing. The volume fraction of the solid solution decreased and the fraction of V₃Ni phase increased during permeability testing, thus bringing the alloy to nearly equilibrium. The membrane without Pd coating showed satisfactory hydrogen fluxes with a significant impact of the surface dissociation rate of hydrogen. The shape of hydrogen permeation curves at the downstream side of the membrane at various temperatures was unusual. We attribute it to the high concentration of dissolved hydrogen in the metal lattice and its effect on the hydrogen diffusivity and solubility. In addition, the multiphase structure with non-uniform distribution of nickel both between the phases and within the BCC solid solution (and, consequently, different hydrogen concentrations) may cause dilatation or compressing effect on neighbouring micro-volumes of the alloy.     

High-pressure gaseous hydrogen permeation test method -property of polymeric materials for high-pressure hydrogen devices (1)-

Polymeric materials are widely used in hydrogen energy system such as FCEV and hydrogen refueling stations under high-pressure condition. The permeation property (coefficients of permeation, diffusion and solubility) of polymers under high-pressure hydrogen condition should be discussed as parameters to develop those devices. Also the property should be determined to understand influence of the compression by the pressure on polymer materials. A device which can measure gas permeation property of polymer materials accurately in equilibrium state under high-pressure environment is developed, and the reliability of the measurements is ensured. High-pressure hydrogen gas permeability characteristics up to 100 MPa are measured for high-density polyethylene. An advantage of the method is discussed comparing with the non-equilibrium state method, focusing on the hydrostatic pressure effect. Deterioration of hydrogen permeability is observed along with the decrease of diffusion coefficient, which is supposedly affected by hydrostatic compression effect with the increase of environment pressure.     

Effect of Pd overlayer and mixed gases on hydrogen permeation of Pd/Nb30Hf35Co35/Pd composite membranes

Effect of Pd overlayer and mixed gases on hydrogen permeation of Pd/Nb₃₀Hf₃₅Co₃₅/Pd composite membranes was investigated. The diameter of Pd particle increases with increasing sputtering power. With this change, the membrane shows a signification reduction in hydrogen permeability/or flux, but its durability and stability increases significantly, which can be mainly attributed to a decrease in hydrogen solubility coefficient. In addition, H₂S impurity in mixed gases can greatly degrade membrane performance, especially the hydrogen permeability, whereas the Ar impurity content has less effect in the temperature range of 523–673 K. Lowering of permeability caused by the change of gas purity can be attributed to a decrease in hydrogen solubility, which is closely related to the stronger adsorption of H₂S molecules to the Pd overlayer of the membrane. Thus, it is concluded that aside from the optimum design for composition of Nb-based hydrogen permeable alloy to improve their permeability, the control of Pd overlayer film on membrane surface and gas purity in the feed gas is important.     

Hydrogen transport properties of several vanadium-based binary alloys

Vanadium-based alloys are an emerging alternative to palladium alloys for use in hydrogen-selective alloy membranes. The tendency of vanadium to embrittle, due to its high hydrogen absorption, means it lacks the robustness required for industrial hydrogen separation applications. Alloying vanadium with certain elements reduces hydrogen absorption, but also influences the diffusivity of hydrogen through the bulk material. Consequently, diffusivity and absorption data must be decoupled in order to fully evaluate the influence of various alloying additions on the hydrogen transport properties of vanadium alloys. To address this need, the hydrogen transport properties of V–Al (V₉₅Al₅, V₉₀Al₁₀, V₈₅Al₁₅, V₈₀Al₂₀, V₇₅Al₂₅, expressed as atom%) and V–Cr (V₉₅Cr₅, V₉₀Cr₁₀, V₈₅Cr₁₅) alloys have been compared through a series of absorption and flux measurements. Pd-coated alloy disks were formed from arc melted and sectioned ingots, and each alloy was subjected to a microstructural analyses and a detailed examination of hydrogen absorption and permeation properties. Additions of Al and Cr reduce the hydrogen absorption and diffusivity of vanadium, with V–Cr alloys exhibiting the greatest hydrogen diffusivity for a given hydrogen feed pressure. The diffusivity of each alloy showed strong concentration dependence. Diffusivity-concentration results have been overlayed with an isoflux curve corresponding to a target flux of 1.0 mol m⁻² s⁻¹, enabling prediction of the thickness and pressure required to achieve this target flux target for a given alloy.     

Measurement of lattice and apparent diffusion coefficient of hydrogen in X65 and F22 pipeline steels

The permeation through and desorption of hydrogen from cathodically charged micro-alloyed API 5L X65 and low alloy ASTM A182 F22 steels were investigated with the aim to analyse the trapping parameters by means of the electrochemical method developed by Devanathan and Stachurski. The lattice diffusivity of hydrogen as well as the amounts and distribution of the diffusible and trapped hydrogen were found by means of partial permeation transient.     

Hydrogen permeation in anisotropic Nb–TiNi two-phase alloys formed by forging and rolling

The formation of an anisotropic microstructure by forging and rolling of a Nb–TiNi two-phase alloy and the effects of direction and annealing on hydrogen permeability were investigated. After forging and rolling, the granular (Nb, Ti) phase was strongly elongated along the rolling direction (RD) and compressed along the normal direction (ND). Hydrogen permeability along the RD (ND) increased (decreased) dramatically. The hydrogen permeability of this anisotropic microstructure can be explained by the law of mixtures using the hydrogen permeabilities of (Nb, Ti) and TiNi single-phase alloys. The hydrogen permeabilities along RD and ND correspond to parallel- and series-type hydrogen permeability, respectively. The 94-μm-thick RD sample shows a large hydrogen flux of 0.57 mol H₂ m^?2 s^?1 (77 ccH₂ cm^?2 min^?1) without hydrogen embrittlement. Phase boundary between (Nb, Ti) and TiNi phases, aligned parallel to the hydrogen flux, is one of the hydrogen permeation path.