Permeation barriers for hydrogen embrittlement prevention in metals – A review on mechanisms,materials suitability and efficiency

To develop large-scale use of hydrogen as an environmentally sensible alternative to fossil energy sources, the design of safe and innovative storage and transportation infrastructure is a crucial issue. In direct contact with the high-pressure hydrogen, structural materials, especially traditional alloys, are indeed susceptible to degradation of their mechanical properties due to the diffusion of hydrogen atoms into their atomic lattice structure. This phenomenon leads to materials' embrittlement and results in severe damage to the employed components. Therefore, the prevention of hydrogen atom diffusion is one key consideration to avoid its adverse effects on materials' mechanical properties. This paper aims to review the mechanisms and factors responsible for the hydrogen embrittlement phenomenon. The main specifications to fulfill while selecting appropriate materials are hence considered for hydrogen energy uses. Finally, the effective surface modification solutions are reviewed for implementation as a permeation barrier to protect the structural materials from hydrogen degradation.     

Introducing a novel technique for measuring hydrogen crossover in membrane-based electrochemical cells

Hydrogen crossover that is the unwanted hydrogen permeation across the membrane driven by the difference of gas concentrations causes a critical concern of safety and efficiency for electrochemical cells, such as fuel cells and electrolyzer cells. Although the hydrogen crossover measurement in fuel cells that employ platinum based catalysts is simple and widely used in laboratory settings, it is questionable to apply existing limiting current method to water electrolyzer cells and alkaline exchange membrane (AEM) systems, which is due to the typical catalyst materials used and membrane properties, respectively. In this work, we demonstrate the operation of a compact and low-cost method of measuring hydrogen crossover that works for both AEM and proton exchange membrane (PEM) systems. The method entails a tandem configuration that utilizes an upstream crossover cell with a downstream cell in hydrogen pump configuration to measure the crossover in the cell of interest. We have successfully measured the hydrogen crossover with different membranes at various differential pressures. The developed method can be applied to catalyst-free membranes (both PEM and AEM) as well as PGM free catalyst containing cells. It will be a promising technique for measuring hydrogen crossover in-situ for a real operating membraned-based electrochemical cell or stack.     

Preparation and hydrogen penetration performance of TiO2/TiCx composite coatings

Titanium carbide is a good candidate for tritium permeation barrier in a fusion reactor. However, its oxidation susceptibility and the mismatch between the ceramic coating and substrate are still a challenge. In this study, a promising candidate as a hydrogen permeation barrier, comprising a titanium-based ceramic TiO₂/TiC_x composite coating, was proposed. The preparation process of this TiO₂/TiC_x composite coating involves two steps of carbon ion implantation and oxidation under ultra-low oxygen partial pressure. According to the results, the optimal oxidation temperature for TiO₂ coating is 550 °C, with the increase of the oxidation temperature, the particles on the surface of the oxide layer become coarse and loosely arranged, and the protective performance of the oxide layer is greatly reduced. The hydrogen barrier permeation behavior of the composite coating in a fusion reactor was simulated via hydrogen plasma discharge environment, the results show that the hydrogen barrier permeation performance of the composite is significantly better than that of a single TiO₂ coating. In addition, the coatings treated with hydrogen plasma showed a certain self-repairing performance through the diffusion growth of the TiC_x layer. These findings illustrate a novel method for preparing composite coatings to restrain hydrogen permeation, providing insight into the development of hydrogen permeation barrier materials.     

Challenges associated with hydrogen storage systems due to the hydrogen embrittlement of high strength steels

Hydrogen is a promising alternative to fossil fuels and is extensively used in process industries. The transportation industry is gearing up towards the use of fuel cells where hydrogen, as a fuel, plays a major role. Irrespective of the application/sector, safe handling and storage of hydrogen are crucial. Storing hydrogen in metal cylinders as compressed gas is a common practice. However, hydrogen embrittlement is a challenge in such cases and needs to be addressed. Embrittlement leads to the deterioration of the metal cylinders in which the hydrogen gas is stored and is therefore a safety concern. High-strength steels are more susceptible to hydrogen embrittlement as susceptibility to the phenomenon increases with strength. Safe hydrogen storage systems demand improved storage materials and modification of existing ones. Few materials and methods are available to reduce hydrogen diffusion in these steels. However, a detailed microstructural analysis of high-strength steel is necessary to make it a hydrogen-impermeable material. Multilayered coatings can be effective in the prevention of embrittlement. In this article, the analysis of current hydrogen storage methods along with the various coatings and deposition techniques that can reduce hydrogen permeation in high-strength steels is carried out.     

Influence of silicon on hot-dip aluminizing process and subsequent oxidation for preparing hydrogen/tritium permeation barrier

The development of the International Thermonuclear Experimental Reactor (ITER) requires the production of a material capable of acting as a hydrogen/tritium permeation barrier on low activation steel. It is well known that thin alumina layer can reduce the hydrogen permeation rate by several orders of magnitude. A technology is introduced here to form a ductile Fe/Al intermetallic layer on the steel with an alumina over-layer. This technology, consisting of two main steps, hot-dip aluminizing (HDA) and subsequent oxidation behavior, seems to be a promising coating method to fulfill the required goals. According to the experiments that have been done in pure Al, the coatings were inhomogeneous and too thick. Additionally, a large number of cracks and porous band could be observed. In order to solve these problems, the element silicon was added to the aluminum melt with a nominal composition. The influence of silicon on the aluminizing and following oxidation process was investigated. With the addition of silicon into the aluminum melt, the coating became thinner and more homogeneous. The effort of the silicon on the oxidation behavior was observed as well concerning the suppression of porous band and cracks.     

The effects of hydrogen-induced lattice distortion and Nb-D formation on its permeation through niobium

Abnormal permeation behavior of hydrogen through niobium has been investigated in this paper, i.e. the permeation flux saturated with long-term decrease after reaching a maximum. The diffusivity and permeability have been deduced from the decay edge of permeation transient. Three kinds of polycrystalline niobium foils with different annealing temperature have been compared, to verify the effect of defects and grain properties on the permeability and diffusivity. In the temperature range of (773–1023) K, the heat treatment along with the permeation cycles could either reduce or increase the permeability and diffusivity depending sensitively on temperature and showing a temperature threshold around 950 K. The permeation flux is proportional to square root of pressure, revealing that the abnormal permeation was still bulk diffusion-limited. The diffusivity gradually decreased with permeation cycles, and became more and more sensitive to pressure. The niobium foil expanded macroscopically along the gradient of hydrogen concentration, which reveals the strong and unrecoverable lattice distortion in this temperature and pressure range. The X-ray diffraction studies showed that splitting of all the Nb peaks and shifting of Nb-D peaks along with hydrogen loadings. The phase transition was expected to eliminate the lattice strain during hydrogen loading and which in turn acted as a diffusion barrier.     

A study on preparation of sulfur-iron compounds and their electrochemical and hydrogen barrier properties

Corrosion and hydrogen damage cause problems to oil and gas industry equipment. FeS (sulfur-iron) compounds generated by H₂S causes surface corrosion and covers the surfaces of the equipment where the extent of corrosion and hydrogen damage are influenced by these compounds. Different types of FeS compounds have different crystal structures, and there by influence their corrosion and hydrogen resistance. In this paper, single-structure pyrrhotite and pyrite were synthesized by hydrothermal method, which was controlled by controlling the temperature and Fe, S ratio. Their structures are hexagonal sheet and polyhedron respectively. The interfacial properties and hydrogen barrier properties of FeS were tested and the results show that pyrrhotite possesses anion selectivity. The electrochemistry shows low impedance modulus and high corrosion current density, which indicates low corrosion resistance. Pyrrhotite has the lowest hydrogen permeation current density and has good inhibition of hydrogen permeation ability. For the high impedance modulus and low corrosion current density pyrite possesses cation selective, which shows strong resistance to corrosion. However, its hydrogen permeation current density is high and hydrogen blocking effect is weak.     

Influence of the grain structure of yttria thin films on the hydrogen isotope permeation

Steel components are required in the infrastructure and the facilities of the hydrogen economy. The high hydrogen pressures in the hydrogen economy lead to embrittlement and surface corrosion of the steels. For the functionality of the facilities it is necessary to suppress the embrittlement and the surface corrosion of the steels by protective layers, e.g. ceramic thin films. With regard to fusion power plants ceramic thin films on the structural steel materials are also required. These thin films work as a tritium permeation barrier that is necessary to prevent the loss of the radioactive fuel inventory. Oxide thin films, e.g. Al₂O₃, Er₂O₃, and Y₂O₃, are promising candidates as tritium permeation barrier layers. In terms of the application in the first wall, this is especially true for yttrium due to its favorably short decay time after neutron activation compared to the other candidates. The Y₂O₃ layers with thicknesses of 0.5 μm–1 μm are deposited on both substrate sides by RF magnetron sputter deposition. Since the microstructure of the barrier layer plays an important role for the permeation reduction, layers with three different magnetron process modes and thus three different microstructures are prepared. After annealing the cubic crystal structure of all thin films is verified by X-ray diffraction and the different microstructures are investigated by scanning electron microscopy and transmission electron microscopy. The Y₂O₃ stoichiometry of all thin films and a chromium oxide material segregation at the interface are verified by analysis methods such as X-ray photoelectron spectroscopy. The permeation reduction factors of all thin films are determined in gas-driven deuterium permeation experiments. Corresponding to the three different microstructures, reduction factors of 25, 45, and 1100 are identified. Thus, the permeation reduction is strongly dependent on the Y₂O₃ microstructure. The measurement results suggest that a high density of grain boundaries leads to a high hydrogen permeation.     

Hydrogen interaction characteristic of nanoscale oxide films grown on iron–nickel based stainless steel by selective thermal oxidation

Hydrogen isotopes, the reaction ingredients in the nuclear fusion plant, can easily permeate through the stainless steel (SS) substrate, leading to the so-called hydrogen degradation. Generally, a widely accepted way to reduce the hydrogen permeation is to prepare a barrier coating on the substrate. Nevertheless, the coated layer has the inherent problem of incompatibility with the heterogeneous base materials. In this work, in-situ selective oxidation was used to explore the optimal oxides with the improved hydrogen resistance. Two types of layers thermally formed at 450 °C and 750 °C, respectively, were selected to investigate their hydrogen interaction characteristics. Comprehensive analyses, including Raman spectra, XPS, EIS and AES, indicate that the oxide formed at 450 °C is a better candidate of hydrogen permeation barriers, probably due to the formation of protective layers of chromia and FeCr₂O₄, while the oxides obtained at 750 °C, though exhibiting a much more stable phase, can rarely reduce hydrogen diffusion through the shortcuts of defects. This finding provides a potential new way to prepare a hydrogen permeation barrier.     

Design and optimization of Isochoric Differential Apparatus (IDA) to reduce uncertainty in H2 sorption process measurements

The quantification of hydrogen absorption and desorption in materials is a crucial step for the assessment of proper storage solutions and their applications. Unfortunately, volumetric instruments are in many cases affected by low accuracy due to several factors such as temperature uncertainty and misleading on calibration proceeding.In this work, we report the superior performance of a new kind of instrumental layout to characterize kinetics and thermodynamics properties of hydrogen storage materials. Hereby presented system is based on differential Sievert measurements, defined as Isochoric Differential Apparatus (IDA). IDA includes two coupled identical Sievert apparatus where pressure values are sampled in differential mode to compensate all temperature transient phenomena and nonlinear effects occurring during the gas expansion step that occurs during the measurements. A physical model to evaluate the sorbed gas at non-isothermal condition has been developed and reported. Detailed error analysis of the kinetic and thermodynamic models has been carried out considering a real gas. Palladium and Magnesium has been utilized as benchmark materials, to test the differential apparatus at ambient and high-temperature values > 300 °C). For both materials, kinetic and thermodynamic properties have been acquired by the differential layout in well agreement with reference data and with a higher accuracy than classic Sievert instrument, involving in identical size of expansion volume. This work demonstrates as the differential layout allows to reduce uncertainty in hydrogen sorption measurement exploiting the full accuracy of equipped transducers. At this level of performance, the impact of calibration procedures and the approach for the estimation of compressibility factor become extremely important to further reduce uncertainty on sorption measurements.     

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.     

Hydrogen permeation under high pressure conditions and the destruction of exposed polyethylene-property of polymeric materials for high-pressure hydrogen devices (2)-

Aiming to elucidate physical property affecting to hydrogen gas permeability of polymer materials used for liner materials of storage tanks or hoses and sealants under high-pressure environment, as model materials with different free volume fraction, five types of polyethylene were evaluated using two methods. A convenient non-steady state measurement of thermal desorption analysis (TDA), and steady-state high-pressure hydrogen gas permeation test (HPHP) were used both under up to 90 MPa of practical pressure. The limit of TDA method of evaluation for the specimens suffering fracture during decompression process after hydrogen exposure was found. Permeability coefficient decreased with the decrease of diffusion coefficient under higher pressure condition. Specific volume and degree of crystallinity under hydrostatic environment were measured. The results showed that the shrinkage in free volume caused by hydrostatic effects of the applied hydrogen gas pressure decreases diffusion coefficient, resulting in the decrease of permeability coefficient with the pressure rise.     

Hydrogen permeation barrier - Recognition of defective barrier film from transient permeation rate

Hydrogen permeation barrier films often exhibit lower efficiency than anticipated. The cause could be defects in the barrier film, high permeability of the defect-free (dense) barrier film, or a combination of both. It is very difficult to point at and quantify the responsible mechanism since the defects can be of submicrometer dimensions and very sparsely populated. This study addresses the recognition of the defects in the hydrogen permeation barrier films using the hydrogen permeation rate transient evolution analysis. For this purpose a mathematical model of the steady-state and transient hydrogen permeation through the membrane coated either with a defective or a defect-free barrier film was developed for the diffusion limited permeation regime. Analysis shows that a defective barrier film might be recognized only in a transient permeation experiment. The effective diffusion coefficient of the membrane with the defect-free barrier film is variable and depends mainly on the ratio of diffusion coefficients in the film and the substrate. Contrary to this, the transient permeation only through pinholes has a constant value of the effective diffusion coefficient. Result of the study is an experimentally useful criterion when and how the permeation through the defects in the barrier layer can be recognized and its extent determined.     

Effects of doping with a third element (Pd,Ru, Ta) on the structure and hydrogen permeation properties of V–10Mo solid solutions

Alloying is an effective method for improving the resistance of V metals to hydrogen embrittlement. The effects of the doping with a third element (Pd, Ru, Ta) on the structure and hydrogen permeation properties of V–10Mo solid solutions have been investigated in this study. As-prepared V–5Mo-5TM (TM = Mo, Pd, Ru, Ta) alloy samples composed of V-based solid solution with a bcc structure are hydrogenated into their corresponding solid solutions (α-phase). Structural changes caused by TM-doping have notable effects on the hydrogen permeation properties (particularly the hydrogen solubility) of V–10Mo alloy, and the ability of the doping element in decreasing the hydrogen solubility of the V–10Mo alloy follows the sequence: Pd > Ru > Ta. Their doping causes a slight decrease in the hydrogen diffusion coefficient as well as an increase in the Vickers hardness of the resulting alloys. This work demonstrates that the mechanical property of V–10Mo alloy can be improved via suitable structure control caused by alloying it with an appropriate element. In addition, this approach might be suitable for improving properties of other relevant binary alloys.     

Recent progress of nanotechnology in enhancing hydrogen storage performance of magnesium-based materials: A review

Hydrogen has attracted wide attention in the field of new energy, triggering a comprehensive study of hydrogen production, storage and application. This paper mainly studies the hydrogen storage capacity of magnesium-based materials with nanostructure. The reversible hydrogen capacity of Mg-based hydrogen storage materials can reach 7.6 wt%, but due to its poor kinetic and thermodynamic properties, its hydrogen storage performance is not as good as other hydrogen storage materials. In order to reduce the desorption temperature of materials, many studies have been carried out. Alloying, nanostructure and adding catalyst are feasible methods to improve the properties of Mg-based hydrogen storage alloys. By adding catalyst and alloy with other transition elements, the dehydrogenation temperature of magnesium-based materials has been reduced to less than 200 °C. The hydrogen storage of magnesium-based alloys has been practically applied.     

Hydrogen embrittlement in different materials: A review

Hydrogen embrittlement (HE) is a widely known phenomenon in high strength materials. HE is responsible for subcritical crack growth in material, fracture initiation and catastrophic failure with subsequent loss in mechanical properties such as ductility, toughness and strength. This hydrogen is induced in the material during electrochemical reaction and high-pressure gaseous hydrogen environment. LIST, SSRT and TDS techniques are performed to know the effect in mechanical properties and amount of hydrogen available in the material. For microstructure examination SEM, FESEM and TEM are performed to know the effect of hydrogen in the internal crystal structure. Also, various mechanisms which are responsible for crack growth and final fracture are discussed. This paper deals with HE definition, mechanisms which causes HE, subcritical crack growth, the concentration of hydrogen measurement and prevention activities are discussed which act as a barrier for hydrogen diffusion.     

Complex hydrides for energy storage

In the past decades, complex hydrides and complex hydrides-based materials have been thoroughly investigated as materials for energy storage, owing to their very high gravimetric and volumetric hydrogen capacities and interesting cation and hydrogen diffusion properties. Concerning hydrogen storage, the main limitations of this class of materials are the high working temperatures and pressures, the low hydrogen absorption and desorption rates and the poor cyclability. In the past years, research in this field has been focused on understanding the hydrogen release and uptake mechanism of the pristine and catalyzed materials and on the characterization of the thermodynamic aspects, in order to rationally choose the composition and the stoichiometry of the systems in terms of hydrogen active phases and catalysts/destabilizing agents. Moreover, new materials have been discovered and characterized in an attempt to find systems with properties suitable for practical on-board and stationary applications. A significant part of this rich and productive activity has been performed by the research groups led by the Experts of the International Energy Agreement Task 32, often in collaborative research projects. The most recent findings of these joint activities and other noteworthy recent results in the field are reported in this paper.     

Trace level analysis of reactive ISO 14687 impurities in hydrogen fuel using laser-based spectroscopic detection methods

Hydrogen fuelled vehicles can play a key role in the decarbonisation of transport and reducing emissions. To ensure the durability of fuel cells, a specification has been developed (ISO 14687), setting upper limits to the amount fraction of a series of impurities. Demonstrating conformity with this standard requires demonstrating by measurement that the actual levels of the impurities are below the thresholds. Currently the industry is unable to do so, for measurement standards and sensitive dedicated analytical methods are lacking. In this work, we report on the development of such measurement standards and methods for four reactive components: formaldehyde, formic acid, hydrogen chloride and hydrogen fluoride. The primary measurement standard is based on permeation, and the analytical methods on highly sensitive and selective laser-based spectroscopic techniques. Relative expanded uncertainties at the ISO 14687 threshold level in hydrogen of 4% (formaldehyde), 8% (formic acid), 5% (hydrogen chloride), and 8% (hydrogen fluoride) have been achieved.     

Mg-based metastable nano alloys for hydrogen storage

Mg-based materials have been widely researched for hydrogen storage development due to the low price of Mg, abundant resources of Mg element in the earth's crust and the high hydrogen capacity (ca. 7.7 mass% for MgH₂). However, the challenges of poor kinetics, unsuitable thermodynamic properties, large volume change during hydrogen sorption cycles have greatly hindered the practical applications. Here in this review, our recent achievements of a new research direction on Mg-based metastable nano alloys with a Body-Centered Cubic (BCC) lattice structure are summarized. Different with other metals/alloys/complex hydrides etc. which involve significant lattice structure and volume change from hydrogen introduction and release, one unique nature of this kind of metastable nano alloys is that the lattice structure does not change obviously with hydrogen absorption and desorption, which brings interesting phenomenon in microstructure properties and hydrogen storage performances (outstanding kinetics at low temperature and super high hydrogen capacity potential). The synthesis results, morphology and microstructure characterization, formation evolution mechanisms, hydrogen storage performances and geometrical effect of these metastable nano alloys are discussed. The nanostructure, fresh surface from ball milling process and fast hydrogen diffusion rate in BCC lattice structure, as well as the unique nature of maintaining original BCC metal lattice during hydrogenation result in outstanding hydrogen storage performances for Mg-based metastable nano alloys. This work may open a new sight to develop new generation hydrogen storage materials.