Improved hydrogen gas sensing performance of Pd–Ni alloy thin films

This study examined the palladium (Pd)-nickel (Ni) alloy films' ability to detect hydrogen (H₂) at various Ni concentrations. The co-sputtering method was used to make the Pd–Ni alloy sensors. The response of the Pd–Ni alloys sensor reduced linearly as Ni_8% concentration was added to Pd, and the resistance of the Pd–Ni alloys was reversible upon exposure to H₂ gas with absorption and desorption characteristics. The experimental findings demonstrated that the Pd–Ni alloy sensor response time of 11 s was much faster than that of pure Pd, with great selectivity and stability for a period of 90 days.     

Superior electrochemical hydrogen storage properties of binary Mg–Y thin films

Mg–Y thin films capped with Pd have been prepared by direct current magnetron co-sputtering system. It is found that Mg alloyed with Y in film state forms ultrafine nanocrystalline intermetallic compounds. The structure together with the catalytic effect of Y gives rise to a high electrochemical hydrogen storage capacities and superior activation properties. It is worthy to note that Mg₇₈Y₂₂ film achieves a high discharge capacity of 1590 mAh g⁻¹ without requiring activation process. Moreover, Mg alloyed with Y effectively improves the cyclic stability of Mg-based films ascribing to the anti-corrosion role of Y. For Mg₃₇Y₆₃ film, more than 92％ of the maximum discharge capacity can be maintained after 100 charge–discharge cycles.     

Atom doping in α-Fe2O3 thin films to prevent hydrogen permeation

Prevention of hydrogen (H) penetration into passive films and steels plays a vital role in lowering hydrogen damage. This work reports effects of atom (Al, Cr, or Ni) doping on hydrogen adsorption on the α-Fe₂O₃ (001) thin films and permeation into the films based on density functional theory. We found that the H₂ molecule prefers to dissociate on the surface of pure α-Fe₂O₃ thin film with adsorption energy of −1.18 eV. Doping Al or Cr atoms in the subsurface of α-Fe₂O₃ (001) films can reduce the adsorption energy by 0.03 eV (Al) or 0.09 eV (Cr) for H surface adsorption. In contrast, Ni doping substantially enhances the H adsorption energy by 1.08 eV. As H permeates into the subsurface of the film, H occupies the octahedral interstitial site and forms chemical bond with an O atom. Comparing with H subsurface absorption in the pure film, the absorption energy decreases by 0.01–0.22 eV for the Al- and Cr-doped films, whereas increases by 0.82–0.96 eV for the Ni-doped film. These results suggest that doping Al or Cr prevents H adsorption on the surface or permeation into the passive film, which effectively reduces the possibility of hydrogen embrittlement of the underlying steel.     

Hydrogen environment embrittlement of an ODS RAF steel – Role of irreversible hydrogen trap sites

The microstructure and the effects of 10 MPa hydrogen atmosphere on the tensile properties of a oxide dispersion strengthened (ODS) reduced activation ferritic (RAF) steel were investigated. The microstructure consists of a fine grained ferritic matrix with Me₃O₄ (Me = Cr, Fe or Mn), VN and Cr₂₃C₆ grain boundary precipitates as well as dispersed yttrium oxide nano precipitates in the ferritic matrix. The yield and ultimate tensile strength were unaffected by the H₂ atmosphere whereas elongation at fracture and reduction in area were markedly reduced. In H₂ atmosphere, the fracture morphology was found to be a mixture of intergranular H-assisted fracture and a smaller amount of transgranular hydrogen enhanced localized plasticity (HELP) fracture. The sensitivity of the ODS RAF steel to hydrogen embrittlement is attributed to the large number grain boundary precipitates which enhance the tendency for intergranular fracture.     

Experimental study of hydrogen explosion in repeated pipe congestion – Part 2: Effects of increase in hydrogen concentration in hydrogen-methane-air mixture

Hydrogen is seen as an important energy carrier for the future which offers carbon free emissions. At present it is mainly used in refueling hydrogen fuel cell cars. However, it can also be used together with natural gas in existing gas fired equipment with the benefit of lower carbon emissions. This can be achieved by introducing hydrogen into existing natural gas pipelines. These pipelines are designed, constructed and operated to safely transport natural gas, which is mostly methane. Because hydrogen has significantly different physical and chemical properties than natural gas, any addition of hydrogen my adversely affect the integrity of the pipeline network, increasing the likelihood and consequences of an accidental leak. Since it increases the likelihood and consequences of an accidental leak, it increases the risk of explosion. In order to address various safety issues related to addition of hydrogen in to a natural gas pipeline a EU project NATURALHY was introduced. A major objective of the NATURALHY project was to identify how much hydrogen could be introduced into the natural gas pipeline network. Such that it does not adversely impact the safety of the pipeline network and significantly increase the risk to the public. This paper reports experimental work conducted to measure the explosion overpressure generated by ignition of hydrogen-methane-air mixture in a highly congested region consisting of interconnected pipes. The composition of the methane/hydrogen mixture used was varied from 0% hydrogen (100% methane) to 100% hydrogen (0% methane) to understand its effect on generated explosion overpressure. It was observed that the maximum overpressures generated by methane-hydrogen mixtures with 25% (by volume) or less hydrogen content are not likely to be significantly greater than those generated by methane alone. Therefore, it can be concluded that the addition of less than 25% by volume of hydrogen into pipeline networks would not significantly increase the risk of explosion.     

Hydrogen storage in thin film metal hydride—a review

During the last decade hydrogen has attracted world wide interest as a secondary energy carrier resulting in a lot of research work on its production, storage and use. The incorporation of hydrogen into thin film form discussed in this article is a relatively new field of research. The main advantages of thin film metal hydrides are that these provide large surface area with fast charging discharging rate for hydrogen, pulverization is slower, both critical pressure and critical temperature are significantly lower, better heat transfer arrangements, protective surface coating could be done to stop poisoning by oxygen and activation of thin film hydrides is possible by coating with a layer of catalytic material.     

Hydrogen quality for fuel cell vehicles – A modeling study of the sensitivity of impurity content in hydrogen to the process variables in the SMR–PSA pathway

As fuel cell vehicles approach wide-scale deployment, the issue of the quality of hydrogen dispensed to the vehicles has become increasingly important. The various factors that must be considered include the effects of different contaminants on fuel cell performance and durability, the production and purification of hydrogen to meet fuel quality guidelines, and the associated costs of providing hydrogen of that quality to the fuel cell vehicles. In this paper, we describe the development of a model to track the formation and removal of several contaminants over the various steps of hydrogen production by steam-methane reforming (SMR) of natural gas, followed by purification by pressure-swing adsorption (PSA). We have used the model to evaluate the effects of setting varying levels of these contaminants in the product hydrogen on the production/purification efficiency, hydrogen recovery, and the cost of the hydrogen. The model can be used to track contaminants such as CO₂, CO, N₂, CH₄, and H₂S in the process. The results indicate that a suggested specification of 0.2 ppm CO would limit the maximum hydrogen recovery from the PSA under typical design and operating conditions. The steam-to-carbon ratio and the process pressure are found to have a significant impact on the process efficiency. Varying the CO specification from 0.1 to 1 ppm is not expected to affect the cost of hydrogen significantly, although the cost of gas analysis to comply with such stringent requirements may add 2–10 cents/kg to the cost of hydrogen.     

Hydrogen gas sensing properties of WO3 sputter-deposited thin films enhanced by on-top deposited CuO nanoclusters

Magnetron-based gas aggregation cluster source (GAS) was used to prepare high-purity CuO (cupric oxide) nanoclusters on top of sputter-deposited thin film of tungsten trioxide (WO₃). The material was assembled as a conductometric hydrogen gas sensor and its response was tested and evaluated. It is demonstrated that addition of CuO clusters noticeably enhances the sensitivity of the pure WO₃ thin film. With an increasing amount of CuO clusters the sensitivity of CuO/WO₃ system rises further. When CuO clusters form a sufficiently thick and compact layer, the resistance response is reversed. Based on the sensorial behavior, conventional and near-ambient pressure X-Ray photoemission spectroscopies, and resistivity measurements, we propose that the sensing mechanism is based on the formation of nano-sized p-n junctions in between p-type CuO and n-type WO₃. The advantages of the GAS technique for preparing sensorial and/or catalytically active materials are emphasized.     

Experimental study of hydrogen explosion in repeated pipe congestion – Part 1: Effects of increase in congestion

Experimental studies were conducted with the objective of gaining a better understanding of the potential explosion hazard consequences that could be associated with a high-pressure leak from a hydrogen vehicle refuelling system. The first part of the study, described in this paper, was a series of experiments designed to establish hydrogen–air explosion overpressures in a well-defined and well understood 3 m × 3 m x 2 m (high) repeated pipe congestion. The results of the experiments are discussed in terms of the conditions leading to the greatest overpressures. It is concluded from the study that stoichiometric ratio in the range of 1.2–1.3 gives highest overpressure. Moreover, it was observed that increasing the congestion from 4-gate to 9-gate congestion leads to significant increase in the overpressure. In addition, it was concluded that, explosion in a hydrogen-air mixture is significantly more severe than the explosion in an ethane-air, methane-air or propane-air mixtures. This is attributed to higher laminar flame speed of hydrogen-air mixtures.     

“Eigen-periodic”-in-space surface heating in conduction with application to conductivity measurement of thin films

A two-dimensional heat conduction problem in Cartesian coordinates subject to a periodic-in-space boundary condition is analyzed by the Green’s functions approach. It is pointed out that when the frequency of the spatial periodic heating equates one of the natural frequencies (eigenvalues) of the system, the solution of the 2D heat conduction problem can be written down very simply as the product of the periodic surface condition (termed the “eigen-periodic”) by the solution of a 1D fin problem along the nonhomogeneous direction. This result suggests a novel and simple algebraic equation for determining the thermal conductivity of thin films placed on substrates under steady state conditions. High space frequencies of the sinusoidal heating, larger than the deviation frequency, are used to make negligible the thermal deviation effects due to the presence of the substrate.     

Li-N-H system – Reversible accumulator and store of hydrogen

The statistical theory of phase transformations in the course of chemical reactions on hydrogen absorption–desorption in the lithium nitride with the formation of lithium amide and hydride has been developed. The calculation of free energies of all constituent phases of chemical reactions has been performed on the basis of molecular-kinetic notions, their dependences on temperature, pressure, hydrogen concentration and energetic parameters have been ascertained. The hydrogen solubility in phases has been estimated, it has been ascertained the possibility of manifestation of peculiarities of its temperature dependence. The constitution diagram for the system being investigated has been constructed. The actual conditions of manifestation of hysteresis effect has been justified. The calculation results have been compared with experimental literature data for the examined system.     

Salt domes in Poland – Potential sites for hydrogen storage in caverns

Salt bearing formations have world-wide distribution. The geological structures of Permian salt bearing deposits in Poland are similar to those in the other parts of the Central European salt basin, to which they belong as its SE part. There is a notable trend to use salt domes as sites for underground storage of various gases, fuels and other substances, including hydrogen. Possibilities of using salt domes in Poland for underground hydrogen storage are presented with the focus on the option of using the underground space for energy storage. Usefulness of the 27 hitherto studied salt domes in the Polish Lowlands for underground hydrogen storage in caverns is evaluated using analytical methods of the geology of mineral deposits.Seven not yet developed salt domes are selected as the most promising ones, taking into account geological and reservoir criteria: Rogó?no, Damas?awek, Lubień, ?ani?ta, Goleniów, Izbica Kujawska and D?bina. Initial experience in underground hydrogen storage in salt caverns is presented. Geological conditions favourable for hydrogen storage in underground caverns leached in salt domes are outlined. Their advantage relative to underground storage sites in porous rocks (depleted hydrocarbon deposits and deep aquifers) is discussed.     

Electrodeposition of CuIn alloys for preparing CuInS2 thin films

Copper-indium alloys were prepared by electroplating from citric acid (C₆H₈O₇·H₂O) baths onto Ti substrate. Formation of the alloys was carried out by direct codeposition of the elements and by sequential electrodeposition of copper and indium. Studies of the alloy formation by electrochemical measurements and X-ray diffraction were performed. The presence of Cu₇In₄ in direct deposit as well as in sequentially electrodeposited material was observed during the alloy formation. The as-deposited layers were heated in H₂S. X-ray diffraction showed the annealed layers to be CuInS₂ with the chalcopyrite structure, where the CuIn₅S₈ phase was included during the annealing process.Photoelectrochemical characterization of the samples allowed us to determine the photoconductivity which is related with the Cu/In ratio in the samples. The energy gap for CuInS₂ photoelectrodes in polysulphide solution was 1.57 eV.     

Hydrogen diffusion and hydrogen influenced critical stress intensity in an API X70 pipeline steel welded joint – Experiments and FE simulations

An API X70 pipeline steel has been investigated with respect to hydrogen diffusion and fracture mechanics properties. A finite element cohesive element approach has been applied to simulate the onset of hydrogen-induced fracture. Base metal, weld simulated heat affected zone and weld metal have been investigated. The electrochemical permeation technique was used to study hydrogen diffusion properties, while in situ fracture mechanics testing was performed in order to establish the hydrogen influenced threshold stress intensity. The average effective diffusion coefficient at room temperature was 7.60 × 10⁻¹¹ m²/s for the base metal, 4.01 × 10⁻¹¹ m²/s for weld metal and 1.26 × 10⁻¹¹ m²/s for the weld simulated heat affected zone. Hydrogen susceptibility was proved to be pronounced for the heat affected zone samples. Fracture toughness samples failed at a net section stress level of 0.65 times the yield strength; whereas the base metal samples did not fail at net section stresses lower than the ultimate tensile strength. The initial cohesive parameters which best fitted the experimental results were σ_c = 1500 MPa (3.1·σ_y) for the base metal, σ_c = 1800 MPa (3.0·σ_y) for weld metal and σ_c = 1840 MPa (2.3·σ_y) for heat affected zone. Threshold stress intensities K_Ic,HE were in the range 143–149 MPa√m.     

Hydrogen economy transition in Ontario – Canada considering the electricity grid constraints

This paper investigates the feasibility of electrolytic hydrogen production for the transport sector during off-peak periods in Ontario. This analysis is based on the existing electricity system infrastructure and its planned future development up to 2025. First, a simplified but realistic zonal based model for Ontario's electricity transmission network is developed. Then, based on Ontario's Integrated Power System Plan (IPSP), a zonal pattern of generation capacity procurement in Ontario from 2008 to 2025 is proposed, specifying the total effective generation capacity in each zone that contributes to base-load energy. Finally, an optimization model is developed to find the optimal size of hydrogen production plants to be developed in different zones, as well as optimal hydrogen transportation routes to achieve a feasible hydrogen economy penetration in Ontario up to 2025. The proposed model is shown to be an effective planning tool for electrolysis based hydrogen economy studies. The results of the present study demonstrate that the present and projected electricity grid in Ontario can be optimally exploited for hydrogen production, achieving 1.2–2.8% levels of hydrogen economy penetration by 2025 without any additional grid or power generation investments beyond those currently planned.     

Wind hydrogen energy system and the gradual replacement of natural gas in the State of Ceará – Brazil

The original model for the solar hydrogen energy system created by Veziroglu and Basar in the 70’s was adapted to the State of Ceará – Brazil. The State of Ceará has one of the greatest wind potentials in Brazil and it is estimated to be around 35 GW. At the present year, there are 494 MW wind farms in operation. The aforementioned State also has a natural gas grid of pipelines serving a great number of consumers. There are studies in literature considering the injection of hydrogen into the natural gas pipeline up to 20% in volume without substantial modifications in the natural gas infrastructure. The main objective of this article is to use that model in order to evaluate long term scenarios in which the off peak wind generated hydrogen gradually replaces natural gas in such important State of Brazil. The system is supposed to start in the year 2015 and the economical revenue when it is fully implemented can reach respectively US$ 730 million or US$ 1 billion in the slow or fast scenario of hydrogen introduction into the energy matrix of that important State of Brazil.     

Impacts of nano-metal oxides on hydrogen production in anaerobic digestion of palm oil mill effluent – A novel approach

In the present study, hydrogen production from palm oil mill effluent (POME) was investigated with the incorporation of nanoparticles (NPs) comprising of nickel (NiO) and cobalt oxides (CoO). The NPs of NiO and CoO were prepared using hydrothermal method and were further applied to analyse, their effect on hydrogen production. The results demonstrated that, a maxima volumetric hydrogen production rate of 21 ml H₂/L-POME/h with the hydrogen yield of 0.563 L H₂/g-COD_removed was obtained with 1.5 mg/L concentration of NiO NPs. On the other hand, the addition of CoO NPs produced maximum volumetric hydrogen production rate of 18 ml H₂/L-POME/h with a hydrogen yield of 0.487 L H₂/g-COD_removed with 1.0 mg/L of CoO NPs. Results showed that addition of optimal concentration of NiO and CoO NPs to the POME enhances the hydrogen yield by 1.51 and 1.67 fold respectively. Besides, this addition of NiO and CoO enhanced the COD removal efficiency by 15 and 10% respectively as compared to an un-additive NPs POME. The toxicity of NPs was also tested using bacterial viability test, which revealed that application of 3.0 mg/L of NiO and CoO NPs to modified Luria-Bertani (LB) medium had 63% and 83% reduction in bacterial cell growth. The results concluded that supplementation of NiO and CoO NPs under an optimal range to the wastewater can improve the hydrogen productivity.     

Enhancement of energy generation efficiency in industrial facilities by SOFC – SOEC systems with additional hydrogen production

Industry is one of the highest energy consumption sector: some facilities like steelworks, foundries, or paper mills are highly energy-intensive activities. Many countries have already implemented subsidies on energy efficiency in generation and utilisation, with the aim of decreasing overall consumption and energy intensity of gross domestic product. Meanwhile, researchers have increased interest into alternative energy systems to decrease pollution and use of fossil fuels. Hydrogen, in particular, is proposed as a clean alternative energy vector, as it can be used as energy storage mean or to replace fossil fuels, e.g. for transport.This work analyses the re-vamping of the energy generation system of a paper mill by means of reversible solid oxide cells (RSOCs). The aim is not only to increase efficiency on energy generation, but also to create a polygeneration system where hydrogen is produced. Application on a real industrial facility, based in Italy with a production capacity of 60000 t/y of paper, is analysed. First, the current energy system is studied. Then, a novel system based on RSOC is proposed. Each component of the systems (both existing and novel) is defined using operational data, technical datasheet, or models defined with thermodynamic tools. Then, the interaction between them is studied. Primary energy analysis on the novel system is performed, and saving with respect to the current configuration is evaluated. Even if the complexity of the system increases, results show that saving occurs between 2 and 6%. Hydrogen generation is assessed, comparing the RSOC integrated system with proton exchange membrane (PEM) electrolysis, in terms of both primary energy and economics. Results exhibit significant primary energy and good economic performance on hydrogen production with the novel system proposed (hydrogen cost decreases from 10 €/kg to at least 8 €/kg).     

The effect of a perforated plate on the propagation of laminar hydrogen flames in a channel – A numerical study

Laminar hydrogen flame propagation in a channel with a perforated plate is investigated using 2D reactive Navies-Stokes simulations. The effect of the perforated plate on flame propagation is treated with a porous media model. A one step chemistry model is used for the combustion of the stoichiometric H₂–air mixture. Numerical simulations show that the perforated plate has considerable effect on the flame propagation in the region downstream from the perforated plate and marginal effect on the upstream region. It is found to squeeze the flame front and result in a ring of unburned gas pocket around the flame neck. The resulting abrupt change in flow directions leads to the formation of some vortices. Downstream of the perforated plate, a wrinkled “M”-shape flame is observed with “W” shape flame speed evolution, which lastly turns back to a convex curved flame front. Parametric studies have also been carried out on the inertial resistance factor, porosity, perforated plate length and its location to investigate their effects on flame evolution. Overall, for parameter range studied, the perforated plate has an effect of reducing the flame speed downstream of it.