Hydrogen Absorption Research Articles

STUDY OF HYDROGEN-HELIUM PERMEABILITY OF SILICATE MICROSPHERES AND SORBENT BASED ON THEM

The work is devoted to research on the applicability of the membrane-sorption method for the separation of hydrogen-helium mixtures. The sorption dependences of hydrogen and helium absorption were experimentally obtained for synthetic hollow microspheres made of sodium borosilicate glass of the MS-V-1L type, silica microspheres and granular sorbent based on MS-V-1L microspheres. A significant difference in the rates of sorption processes of hydrogen and helium for the sorbents under study was shown. Based on the gas diffusion model, the kinetic characteristics of absorption, permeability and selectivity coefficients, and dynamic characteristics of the processes of sorption of hydrogen and helium of heliumhydrogen mixtures of various compositions by these sorbents were determined. For silica microspheres, the selectivity coefficient with respect to hydrogen and helium at T = 24 C exceeds 130, and for a granular sorbent based on MS-V-1L microspheres it is about 1000 at T =110 C. The high selectivity values of the studied sorbents confirm the possibility and efficiency of using the membrane-sorption method for the separation of hydrogen-helium mixtures.

A novel carbon-induced-porosity mechanism for improved cycling stability of magnesium hydride

MgH2 has been extensively studied as one of the most ideal solid hydrogen storage materials. Nevertheless, rapid capacity decay and sluggish hydrogen storage kinetics hamper its practical application. Herein, a Ni/C nano-catalyst doped MgH2 (MgH2Ni/C) shows an improved hydrogen absorption kinetics with largely reduced activation energy. Particularly, the MgH2Ni/C displays remarkable cycling stability, which maintains a high capacity of 6.01 wt% (98.8 % of initial capacity) even after 50 full hydrogen ab/desorption cycles, while the undoped MgH2 counterpart retains only 85.2 % of its initial capacity. Detailed microstructure characterizations clearly reveal that particle sintering/growth accounts primarily for the deterioration of cycling performance of undoped MgH2. By comparison, MgH2Ni/C can maintain a stable particle size with a growing porous structure during long-term cycling, which effectively increases the specific surface of the particles. A novel carbon-induced-porosity stabilization mechanism is proposed, which can stabilize the proportion of rapid hydrogen absorption process, thus dominating the excellent cycling performance of MgH2Ni/C. This study provides new insights into the cycling stability mechanism of carbon-containing Mg-based hydrogen storage materials, thus promoting their practical applications.

Correlation between hydrogen absorption capacity and microstructure of Fe-rich Sm-Co-Fe-Cu-Zr permanent magnetic alloys

The correlation between hydrogen absorption capacity (HAC) and the microstructure of Sm26.2CobalFexCu4.0Zr2.3 (x = 23 wt%, 25 wt%, 27 wt%, 30 wt%) ingots and cast strips was systematically investigated. As the temperature rises from 373 to 423 K, the activation time, hydrogen absorption time and HAC of the Sm26.2CobalFe23Cu4.0Zr2.3 ingot decrease by 14.4%, 14.1%, and 19.3%, respectively. Dispersed 1:5 phase provides more channels for hydrogen diffusion, which is the main reason that HAC increases with the x increasing. The HAC of the same compound strips increases as the particles size of the pre-crushed decreases. However, no further embrittlement behavior appears in pre-crushed strips, which reaches an equal HAC as ingots. Micro-computerized tomography reveals that ingots contain small spherical-like holes and large flake micro-cracks, whereas strips mainly contain elliptical pores. The effects of grain size and inner defects size on structure stability were invested by Abaqus. Simulation results reveal that the superior embrittlement behavior of the ingots is predominantly influenced by the presence of large flake-like micro-cracks.

Effect of double substitution on hydrogen absorption-desorption properties of Ti2CrV alloy

Doubly substituted Ti2CrV alloy with composition Ti1.5Sc0.3CrVNi0.2 was prepared by arc melting method followed by annealing. The annealed alloy exists in body centred cubic (BCC) structure and shows fast kinetics for hydrogen absorption and desorption at room temperature. BCC phase of the alloy undergoes phase transformation to face centred cubic (FCC) hydride phase with H atoms occupying tetrahedral sites in the lattice, reaching an overall H/M ratio >2.2 (storage capacity ∼ 4 wt%). Storage capacity decreases by 40% in the 2nd cycle and then stabilizes at a value of ∼2.5 wt% for the subsequent 10 cycles. A drastic reduction in hydride desorption temperature upon double substitution (Sc and Ni substitution in Ti2CrV alloy) has been confirmed by DSC studies. Furthermore, the change in isotope effect in doubly substituted Ti2CrV alloy is discussed in light of thermal stabilities of the hydrides and deuterides.

Passive high explosive neutron inspection (PHENIX): a new method to confirm the presence or absence of high explosives for nuclear treaty verification

Advanced instruments and methods need to be developed now to create a technical basis to support the negotiation of future nuclear arms control treaties. One new capability that is anticipated is the ability to confirm either the declared presence or declared absence of high explosive (HE) material in the presence of special nuclear material (SNM). Towards this goal, Passive HE Neutron Inspection (PHENIX) has been developed and demonstrated as a method for confirming the presence or absence of HE in the presence of plutonium. The method exploits the inherent presence of neutrons associated with the decay of plutonium as an internal probe source for performing prompt gamma-ray neutron activation analysis (PGNAA), searching for the presence of HE as revealed by the emission of characteristic gamma rays following neutron absorption in hydrogen and nitrogen which are building blocks of present-day, military-grade HE. Tests using stoichiometrically-correct hemishells of mock HE with plutonium show that a system can be expected to positively confirm the presence or absence of these signatures, supporting determination of HE presence or absence with Pu, in a few hours. To protect other potentially sensitive gamma-ray signatures from a treaty accountable item, an analog information barrier has been conceptualized and tested which physically prevents the collection of gamma-ray spectral data outside of user selected energy windows strategically chosen to view only narrow spectral regions corresponding to the hydrogen (2223.2 keV) and nitrogen (9807.2 keV, 10,318.2 keV, and 10,829.2 keV) PGNAA signatures.

Hydrogen permeation resistance of ZrN thin film deposited by ion-plating

Hydrogen absorption of Zircaloy nuclear fuel cladding, used in light water reactor at nuclear power plants, poses an increased risk of delayed hydride cracking during interim dry storage. Consequently, novel surface technologies aimed at reducing hydrogen absorption have become a critical area of research. Zirconium nitride coatings, renowned for their high hardness, corrosion resistance, and wear resistance, have seen widespread application in various industries, including medical devices, cutting tools, and decoration. This study explores the effectiveness of ZrN coating in suppressing hydride formation in Zircaloy-4, a material commonly used for nuclear fuel cladding. In this research, ZrN coatings were deposited onto recrystallized Zircaloy-4 substrates using a hollow cathode discharge ion-plating (HCD-IP) system. The coated and uncoated Zircaloy-4 samples were then subjected to electrochemical and gaseous hydriding processes. The study further investigates the differences in microstructure and hydrogen content of coated and uncoated Zircaloy-4. From these results, it is evident that the ZrN thin film deposited by HCD-IP exhibited great resistance to hydrogen permeation against both hydriding conditions. It is concluded that the ZrN thin films can serve as an excellent hydrogen barrier layer for Zircaloy-4.

Peculiarity of hydrogen absorption in duplex steels: Phase-selective lattice swelling and stress evolution

Electrochemical hydrogen absorption in duplex steels is not fully understood. In this work, an in-situ synchrotron cross-sectional X-ray micro-diffraction analysis is performed on steel with comparable phase fractions of ferrite and austenite, coupled with electrolytic hydrogen charging. The results reveal that charging with a constant current density of 10 mA/cm² for 5 h leads to expanding the austenitic lattice to a depth of approximately 250 µm, up to ≥0.15 %. In contrast, the lattice parameter of the ferrite phase remains unchanged during this process. As the austenite expansion progresses, it generates different amounts of equivalent in-plane compressive stresses, which amount to approximately -150 and -450MPa in the austenite and ferrite phases at the sample surface, respectively. Using a finite element model of grain interaction, this difference is qualitatively interpreted by mutual mechanical constraints between ferrite and austenite, as well as between the hydrogen-charged surface layer and the underlying material.

Microstructure and fracture toughness of 850°C quenched and aged Zr-2.5Nb alloy

The Zr-2.5Nb alloy pressure tubes manufactured by Water Quenched and Aged (WQA) fabrication route has reportedly exhibited superior resistance against in-reactor dimensional changes. WQA route comprises three consecutive thermo-mechanical treatments viz., solution heat treatment (SHT), cold working and vacuum aging, which govern the final microstructure and therefore fracture toughness of the pressure tube material. This work describes the influence of SHT soaking duration, degree of cold working and aging temperature on the microstructure and fracture toughness of WQA Zr-2.5Nb alloy. WQA pressure tubes are expected to have better resistance to in-reactor dimensional changes. However, if proper care of hydrogen absorption during thermo-mechanical processing is not taken, though resistance to creep will improve expectedly but fracture toughness at ambient temperature will deteriorate.

Hydrogen trapping and embrittlement of titanium- and vanadium carbide-containing steels after high-temperature hydrogen charging

This work studies the effect of TiC and VC precipitate sizes on hydrogen trapping and embrittlement. Two experimental ferritic HSLA steels containing either TiC or VC carbides for precipitation strengthening are annealed in nitrogen and hydrogen gas. This results in a hydrogen uptake of up to 0.91 and 0.44 wppm in the TiC and VC steels, respectively. TEM and TDS analysis indicate that semi-coherent TiC particles trap hydrogen in misfit dislocations with an activation energy of 43 kJ/mol. Coherent VC particles are suggested to trap hydrogen in interface carbon vacancies, with an energy between 53 and 72 kJ/mol. Carbon vacancies are the likely trapping site in incoherent precipitates, where SIMS imaging confirms that incoherent TiC precipitates trap preferentially near the interface, whereas incoherent VC precipitates trap throughout their bulk. Neither alloy is embrittled in SSRT tests after hydrogen absorption, which shows that these precipitates can be used as both a hydrogen sink and a strengthening mechanism in steels.Graphical abstract

The study of La and Mg elements on the improved structure and hydrogen storage performance of Ca2MgNi9 alloy

In order to improve the comprehensive hydrogen storage performance of AB3-type (RE/Ca)-Mg-Ni alloys, a new series of Ca(Ca0.75La0.25)2-xMgxNi9 (x = 0.8, 0.9, 1.0, 1.1, 1.2) alloys is designed and prepared. Based on the as-cast Ca2MgNi9 alloy, La is introduced, and the ratio of rare earth (RE) to Mg is adjusted using the induction melting method. This alteration modifies the microstructure of the alloy and significantly enhances its hydrogen storage performance. The effects of microstructure on hydrogen storage performance and mechanism are analyzed. The phase composition and lattice parameters of the main phase are regularly regulated by appropriate element substitution. The lattice parameter of the main phase is increased, the capacity and kinetics of hydrogen storage are significantly improved. The initial hydrogen absorption capacity of the alloy increases from 1.744 wt% for Ca2MgNi9 to 1.975 wt% for Ca(Ca0.75La0.25)1.2Mg0.8Ni9 alloy. Furthermore, the synergistic regulation of La and Mg elements can increase the hydrogen desorption ratio and crystal structure stability of the alloy. This leads to the concurrent enhancement of effective hydrogen storage and cycle performance of the Ca2MgNi9 hydrogen storage alloy. The retention rate of hydrogen absorption capacity for the 50th cycle is increased from 77.13% for Ca2MgNi9 to 84.26% for Ca(Ca0.75La0.25)0.8Mg1.2Ni9. At the same time, owing to the adjustment of the cell volume and phase composition, the platform pressures of hydrogen absorption and desorption of the alloy have also experienced a multi-fold increase between 0.002 and 0.5 MPa at 303 K. This enhancement is advantageous for expanding the potential applications of this type of alloy. This work presents new ideas for enhancing the hydrogen storage performance of Ca2MgNi9 hydrogen storage alloys.

Magnetic property changes of NdGa upon hydrogen absorption

Magnetic property changes of NdGa upon hydrogen absorption

A Phenomenological Model for Interstitial Hydrogen Absorption in Niobium

A Phenomenological Model for Interstitial Hydrogen Absorption in Niobium

Porous Silicone Rubber Composite Supported 1,4-Diphenylethynyl Benzene for Hydrogen Absorption with Pd/C Catalyst.

Hydrogen is a dangerous gas as it reacts very easily with oxygen and may explode; therefore, the accumulation of hydrogen in confined spaces is a safety hazard. Composites consisting of unsaturated polymers and catalysts are a common getter, where the commonly used polymer is 1,4- diphenylethynyl benzene (DEB). Silicone rubber (SR) is a good carrier for hydrogen-absorbing materials due to its excellent chemical stability and gas permeability. In this work, polysiloxane, water, and a emulsifier are ultrasonically injected into a uniform emulsion, and the hydrogen getter DEB-Pd/C (Palladium on carbon) is then added. Under the catalysis of platinum (Pt), the cross-linking agent undergoes a hydrosilylation reaction to cross-link polysiloxane in emulsion to form silicone rubber. Then, the water was removed by freeze-drying, and the loss of water constructed a porous frame structure for silicone rubber, thus obtaining porous silicone rubber. The difference in hydrogen absorption performance between porous silicone rubber and ordinary silicone rubber was compared. It was found that, with the increase in water in the emulsion, the porous frame of silicone rubber was gradually improved, and the hydrogen absorption performance was improved by 243.4% at the highest, almost reaching the theoretical saturated hydrogen absorption capacity. Porous silicone rubber was prepared by emulsion mixing, which provided a new idea for further improving the hydrogen absorption performance of silicone rubber.

Study on hydrogen storage properties of Ti–V–Fe–Mn alloys by modifying Ti/V ratio

The high stability of hydride phase has limited the improvement for the hydrogen storage properties of Ti–V based alloy at room temperatures. In this work, the stability of hydride was reduced by designing a low-price Ti–V–Fe–Mn alloy, and the effect of Ti/V ratio on the crystal structure and hydrogen storage properties was systematically investigated. The Ti40-xV40+xFe15Mn5 (x = 0, 2, 4, 6, 8) alloys were synthesized using arc melting, and the as-prepared alloys are all composed of single BCC phase. The lattice constant and cell volume decrease linearly with a lessening in Ti/V ratio. The reduction of cell volume makes it difficult for hydrogen atoms to diffuse, resulting in a sluggish hydrogen absorption rate. The dehydrogenation plateau in PCI curve rises and corresponding thermodynamics is optimized with a decrease in the lattice constant, and the hydrogen atoms are more readily to release, especially for Ti32V48Fe15Mn5 alloy with the dehydrogenation capacity of 1.83 wt% at 373 K. The result indicates the thermodynamic properties can be optimized by adjusting the lattice constant of Ti–V–Fe–Mn alloys, and hydrogen storage capacity is improved effectively. This study provides a reference for composition design of Ti–V–Fe–Mn alloys for high-density hydrogen storage.

A corrosion failure analysis of a titanium tank used for production and storage of molten sodium sulfide

The corrosion failure of a titanium tank operating under high temperature of 220 °C for the production and storage of molten Na2S was thoroughly analyzed in this study. The various materialcharacterization methods, such as visual inspection, microscopic observation, chemical analysis, and mechanical assessment, demonstrated that hydride-inducedembrittlement plays a considerable role in the failure of the titanium tank. The key finding was that side products of H2, H2S, and Na2SO3 cause the destruction of the passive oxide film and, thus, provide the conditions for the absorption and penetration of atomic hydrogen, resulting in the formation of brittle TiH2 and subsequent flaking on the surface. To failure prevention of the titanium tank in such environments, the selection of tank material from Monel®400, blowing nitrogen gas into the system, and loading Na2CO3 into the reactive media were proposed. By complementary electrochemical investigations, it was clarified that Na2CO3 can stabilize the passive oxide film on the titanium surface and, therefore, enhance the resistance of the titanium tank against corrosion and failure. Notably, the present study can provide helpful references for enhancing the safety maintenance management of similar types of equipment.

The relationship between thermal management methods and hydrogen storage performance of the metal hydride tank

Solid-state hydrogen storage tanks are key equipment for fuel cell vehicles and hydrogen storage. However, the low heat transfer properties of hydrogen storage tanks result in the inability to meet the hydrogen supply requirements of fuel cells. In this study, different thermal management approaches were explored through the design of LaNi5-based solid-state hydrogen storage tanks. We experimentally studied the effects of different internal heat transfer methods, that is, expanded natural graphite (ENG), copper foam, and copper fins on the hydrogen absorption and desorption performance. We also studied the effects of external cooling methods with natural convection, air cooling, and water cooling, respectively. Under the same external cooling method of natural convection, a solid hydrogen storage tank filled with 5 wt.% ENG has similar performance to a tank filled with copper foam. Compared to natural convection, air and water cooling can significantly improve the heating performance of metal hydride (MH) beds by increasing the external heat transfer coefficient. The effect of water cooling is better than that of air cooling, and in these two enhanced performance conditions, the tank filled with copper foam performs better than with ENG. In the case of water cooling, by adding copper fins to a hydrogen storage tank filled with 5 wt.% ENG, the tank was saturated with hydrogen absorption in only 29.4 min, which is 55.6 % shorter than the hydrogen uptake time in a hydrogen storage reactor without copper fins. And its stable hydrogen desorption (1 NL/min) has reached 98.1 % of the total hydrogen released. The results show that the effective thermal conductivity and heat transfer area of metal hydride bed play key roles in improving heat transfer and reaction rate. In addition, heat transfer is more important than mass transfer to improve the performance of the hydrogen storage tank.

Hydrogen storage and handling with hydrides

Abstract After production and before the use in different applications, hydrogen may need to be purified, transported, compressed and stored. Hydrogen is conventionally stored in high pressure gas cylinders and, as a liquid phase at low temperatures, in opened tanks. These methods present several economic and security problems. So, hydrogen storage in liquid or solid carriers is a suitable method for future applications. Hydrogen absorption and desorption in metal and complex hydrides will be discussed. Examples are provided, including the role of additives in promoting hydrogen sorption reactions. Some case studies using metal hydrides as hydrogen carrier are presented. The HyCARE project, focussed on the development of an efficient metal hydride-based system for the storage of renewables energies is presented, giving evidence of about 50 kg of hydrogen stored in metal hydrides. A small-scale hydrogen refuelling station developed to provide hydrogen for a fuel cell driven drone will be described. The Life Cycle Assessment (LCA) methodology to evaluate the environmental impacts associated with developed systems is also shortly described. Finally, main open challenges will be outlined, suggesting possible approaches for their overcoming.

Effect of Buoyancy Force in Phase Change Material-Based Metal Hydride Reactor

Abstract In Phase Change Material (PCM) simulations, buoyancy force is used to capture the melting contour. However, for the sake of simplicity, most of the PCM-based Metal Hydride (MH) simulations have ignored the influence of buoyancy in PCM which is crucial in analyzing the heat flow within PCM. This study incorporates the buoyancy term in mathematical models to capture the contour of a melted PCM and also its heat transfer capacity during the hydrogen absorption process. A PCM model with buoyancy force is validated against the experimental values and applied to the MH-PCM models. Incorporating the buoyancy force improves the heat transfer rate in the PCM during melting which benefits in better heat removal from the MH bed. Two designs of MH-PCM models having PCM placed in ring-type and tube-type configurations are discussed. Further, the design optimization in ring-type models was done by changing the PCM-MH volume and sandwiching ratios.

An experimental platform for investigation of the Zeeman effect in strong magnetic fields.

An experimental platform is developed for the investigation of the Zeeman effect in strong magnetic fields. Mega-Gauss magnetic fields are generated by a 1 MA Zebra pulsed power machine using metal rod loads. A gas jet or CH oil on the load is the source of hydrogen. Excited hydrogen atoms are backlit by black body radiation from the rod load. Hydrogen absorption spectra are recorded with a grating spectrometer and intensified gated CCD camera. The experimental platform enables the observation of the quadratic Zeeman effect in hydrogen gas jets using the spectral shift of the central line in the Zeeman triplet. Other gases can be studied using the gas jet method.

Hydrogen contribution to low temperature embrittlement during PWR exposure of an alloy 82 weld metal

The embrittlement of alloy 82 welds exposed to a simulated pressurised water reactor (PWR) environment was analysed and compared with that observed for cathodically hydrogen-precharged specimens. Similarities in mechanical behaviour, i.e. the evolution of the constitutive equations with a decrease in flow stress compared with non-precharged specimens, and in the fracture modes, with brittle zones in the outer layer, enabled us to conclude that the embrittlement observed in simulated PWR environment corresponded to a two-step hydrogen-assisted cracking mechanism. The first step corresponded to hydrogen absorption into the surface layer leading to crack initiation, and the second step to hydrogen localisation ahead of the crack tip promoting crack propagation.