Hydrogen Exposure Research Articles

Mechanical Properties and Microstructural Characteristics of Steel Pipes after Long-Time Hydrogen Exposure

There are three possibilities to transport hydrogen by high pressure pipeline (i) blending hydrogen into the existing natural gas pipeline system, (ii) after checking the integrity, using the natural gas transporting pipeline system to transport hydrogen, (iii) building a new pipeline system to transport pure hydrogen. In all three cases should be known the behaviour of the pipe material and its welded joints influenced under high pressure hydrogen. For this aim pipeline sections made of P355NH base material were investigated without and with hydrogen exposure, where the exposure time was 41 days. Gas metal arc welding and hybrid tungsten arc welding / gas metal arc welding were applied for preparation of the girth weld joints. Tensile, three point bending and hardness tests, furthermore microstructural investigations were performed both on base materials and girth welds of the pipeline sections. The testing results were analysed and compared with each other (base material vs. welded joints, without exposure vs. with exposure) and with limit values can be found in the literature. Conclusions were drawn on the behaviour of the investigated pipe material and its welded joints.

Examining the Influence of Silver(I) Ion Coordination Environment in Ionic Liquids on Olefin-Paraffin Separations using Inverse Gas Chromatography.

Silver(I) ions (Ag+) undergo selective π-complexation with olefins and have been employed as separation media for the isolation of olefins from structurally similar paraffins. Ionic liquids (ILs) possess minimal vapor pressures, exceptional thermal stabilities, low melting points, as well as provide a favorable environment for π-complexation between Ag+ ions and olefins. The development of molecular drivers capable of highly selective olefin/paraffin separation systems with Ag+-containing ILs necessitates a comprehensive understanding of all factors that affect olefin solubility and selectivity. This study examines how coordinating different ligand species to Ag+ ions produces separation media with varying interaction strengths to olefins. Four coordination compounds, (4,4'-dimethyl-2,2'-bipyridine)silver(I) bis[(trifluoromethyl)sulfonyl]imide ([Ag+(DMBP)][NTf2-]), bis(pyridine)silver(I) [NTf2-] ([Ag+(Py)2][NTf2-]), bis(2,6-lutidine)silver(I) [NTf2-] ([Ag+(Lut)2][NTf2-]), and (triphenylphosphine)silver(I) [NTf2-] ([Ag+(PPh3)][NTf2-]) were dissolved in the 1-decyl-3-methylimidazolium [NTf2-] ([DMIM+][NTf2-]) IL and employed as stationary phases for inverse gas chromatography. Ligand coordination to the Ag+ ion was observed to modulate interactions of unsaturated hydrocarbons. The [Ag+(Py)2][NTf2-] complex offered the greatest olefin retention among the coordination complexes reaching 54% of the 1-octene retention factor of the uncoordinated [Ag+][NTf2-]. Hydrogen (H2) exposure studies showed ligand-dependent rates of reduction from Ag+ ion to elemental silver (Ag0). The [Ag+(PPh3)][NTf2-] complex exhibited superior stability, compared to the neat [Ag+][NTf2-] salt, reducing the retention factor of 1-octene by 15.3% and 19.4%, respectively, after 200 h of H2 exposure at 70 °C. The results from this study show that coordination complexes with Ag+ ions are useful in highly selective and efficient petroleum processing systems.

Sustainable rubber nanocomposites for hydrogen sealings: Impact of carbon nano-onions and bio-based plasticizer

Additives play a crucial role in modifying and enhancing the properties of rubbers, improving mechanical strength, thermal stability, and chemical resistance to make them more suitable for various applications. The rubber industry faces challenges related to high resource consumption and toxic emissions, which are further impacted by the use of performance-enhancing additives. In hydrogen storage systems, tailored additives are required for rubbers to withstand elevated temperatures and high pressures, preventing hydrogen-induced swelling, a major cause of sealing failure. Herein, a novel form of carbonaceous material, carbon nano-onions (CNOs), and the bio-based plasticizer additive epoxidized soybean oil (ESO) are utilized in conventional silica-filled nitrile butadiene rubber (NBR) nanocomposites to develop low-carbon manufacturing high pressure hydrogen resistant O-rings for sealing applications. The results reveal that the incorporation of CNOs increases the crosslinking density (vc), assisted by ESO, in silica-filled NBR nanocomposites. While the conventional adipate-based plasticizer and ESO were found to be susceptible to high pressure hydrogen exposures, ESO demonstrated sustained compressive sealing properties with increase in von-Mises stress and in elevated thermo-oxidative conditions over time. The results of the life cycle assessment (LCA) recommend ESO for low-carbon manufacturing in rubber processing over conventional plasticizer.

Study of the surface features of palladium-based alloys using atomic force microscopy and magnetic force microscopy

The surface state of palladium-based alloys, specifically Pd–6.0In–0.5Ru and Pd–7.0Y (the element content is given in wt.%) has been studied using magnetic force microscopy (MFM) and atomic force microscopy (AFM). The study was conducted within the framework of the current trend to enhance the safety of hydrogen separation and storage. The samples for the study were made of high-purity metals through arc alloying. They underwent reversible hydrogen alloying to investigate the impact of internal deformation of metal systems on their structure-sensitive properties. The study demonstrates the characteristics of the sample surface morphology and domain structure before and after hydrogenation. The local magnetic properties of alloy surfaces have been clarified, and their changes as a result of hydrogen exposure have been identified.

Effects of hydrogen on the fretting wear behavior of laser cladded FeCoCrNiMo0.2 high entropy alloy coating

This study investigates laser-cladded high entropy alloy (HEA) coatings on high-speed train axles to enhance wear resistance under specific fretting conditions. Axles in humid and acidic environments absorb hydrogen, leading to accumulation in grain boundaries, which weakens their structure and causes damage under alternating stress. Despite this, the impact of hydrogen damage on the fretting wear behavior of HEA coatings has not been explored. To address this, we performed fretting wear tests on a laser-cladded FeCoCrNiMo0.2 coating and a GCr15 steel ball friction system, evaluating their performance before and after hydrogen exposure. The results of the study indicate that under a constant load of Fn = 10N and a displacement amplitude of D = 50 μm, the friction coefficient, maximum wear depth, wear volume, and wear rate increased when the system was in the hydrogen charging state compared to the non-hydrogen charging state. Specifically, the friction coefficient increased from 0.60 to 0.93, the maximum wear depth increased from 2.82 μm to 3.63 μm, the wear volume increased from 14.106 × 104μm3 to 22.098 × 104μm3, and the wear rate increased from 28.213 × 10−6 mm/Nm to 36.600 × 10−6 mm/Nm. Under the hydrogen charging state, the friction coefficient, maximum wear depth, wear volume, and wear rate all increased. This is due to hydrogen damage, including the formation of pitting pits and cracks on the surface of the coating, stress concentration, and brittle failure caused by hydrogen infiltration into the material. The presence of hydrogen makes the surface of the coating more prone to detachment, resulting in finer wear debris, deeper grooves, and increased oxidation. These factors accelerate the wear of the coating. This finding will contribute to the development and improvement of advanced surface modification techniques for materials in the hydrogen environment.

Hot hydrogen testing of Mo30W matrix surrogate cermets

High temperature hydrogen exposure is one of the most challenging material issues for nuclear thermal propulsion (NTP) fuel development. Under legacy NTP programs, ceramic-metallic (cermet) fuel forms with a refractory metal matrix and dispersed uranium dioxide (UO2) fuel particles were developed and showed promising performance following hot hydrogen testing. However, since the conclusion of those programs, established fabrication techniques, material feedstocks, and the ability to use highly enriched have been reduced or lost all together. In this study, a cermet consisting of a solid solution alloy of molybdenum with 30 wt percent tungsten (Mo30W) was fabricated using spark plasma sintering. Fabrication process parameters were selected to optimize the cermet microstructure using lessons learned from historic NTP programs. Yttria stabilized zirconia particles (50 to 70 % volumetric loading) were used as a fuel particle surrogate. To evaluate whether as-fabricated microstructures exhibited similar resilience as legacy cermet fuels to a hot hydrogen environment, samples were exposed to hot flowing hydrogen from 1920 to 2500 °C (∼2290 to 2770 K). The cermets performed well with minimal mass loss, minor to no cracking, and good retention of internal surrogate particles. Based on these findings, recommendations for future studies with Mo30W-UO2 cermets as an NTP fuel form are provided.

Enhanced protonic and oxygen-ionic conductivity in Ga-doped Nd2Ce2O7 electrolytes for intermediate-temperature solid oxide fuel cell

Developing mixed oxygen-ion and proton conductors with high ionic conductivity is crucial for advancing intermediate temperature-solid oxide fuel cell (IT-SOFC). In this study, a novel Nd2-xGaxCe2O7 (NGCO, x = 0, 0.05, 0.075, 0.10 and 0.15) ceramic is synthesized by the citric acid-nitrate sol-gel combustion process. The influence of Ga doping on crystal structure, oxygen vacancy, morphology, proton transport characteristic and electrochemical performance of this materials is systematically investigated. It is found that the NGCO exhibits the fluorite-type structure and belongs to space group Fm3¯m. NGCO shows remarkable chemical stability, resisting harmful effects from CO2, water, and wet hydrogen exposure. Adding a small amount of Ga results in high-density ceramics with enlarged grain size and reduced grain boundary density. Nd1.925Ga0.075Ce2O7 (7.5NGCO) displays outstanding conductivities, exceeding Nd2Ce2O7 (NCO) by 271.4% and 248.6% in dry air and wet hydrogen conditions. Further, an anode-supported structure fuel cell with 7.5NGCO electrolyte is constructed and evaluated. The peak power density (PPD) at 700 °C reaches 702 mW/cm2, a 96% enhancement over the fuel cells with NCO electrolyte. These findings indicate that Ga-doped NCO electrolyte holds promise as a proton-conducting electrolyte suitable for IT-SOFC.

Consequences of repeated hyperbaric hydrogen exposures on mechanical properties and microstructure of polyamide 11

The objective was to evaluate the impact of repeated exposure to hyperbaric hydrogen (90 MPa; 30 °C) and pressure release on the microstructure and mechanical behavior of PA11. Samples were analyzed after 1, 2, 5 and 10 cycles, by SAXS, WAXS, DMA, DSC, and a series of mechanical tests with variable triaxiality ratio. The most visible change in the residual state after desorption was a stiffening of the amorphous phase. It mainly originated from the first cycle, especially the first pressurization. The crystalline phase was slightly affected and no evidence of nano-voiding was brought in the residual state up to 10 cycles. Similar analyses were conducted during the first cycle's desorption transient. They showed a reversible plasticizing effect and a trend of nano-voiding vanishing after desorption but might promote damage upon further triaxial loading.

Factors influencing hydrogen migration in cap rocks: Establishing new screening criteria for the selection of underground hydrogen storage locations

Safe and efficient underground storage of hydrogen requires cap rocks with effective sealing capabilities. This study investigates the interplay between various factors and their influence on hydrogen leakage from cap rocks. Compared to other commonly stored gases, hydrogen exhibits a significantly faster leakage rate. This study reveals that pore size and tortuosity of cap rocks play a crucial role. Larger pore sizes and lower tortuosity factors lead to increased leakage. Conversely, higher tortuosity (more twisted pores) enhances the sealing capability. Cap rocks with a tortuosity greater than 3 or an effective pore size below 5 nm demonstrated exceptional sealing capabilities. Beyond pore geometry, the study underscores the dependence of hydrogen diffusivity on prevailing underground conditions. Higher reservoir temperatures translate to a faster leakage rate, whereas increased pressure reduces the mean free path of hydrogen molecules, hindering diffusion and promoting retention within the storage formation. Reservoirs of temperature below 350 K and under a pressure exceeding 13.80MPa (2000 psi) exhibited minimal leakage. These findings underscore the crucial role of meticulous cap rock selection for safe and efficient underground hydrogen storage. This research paves the way for future investigations exploring the impact of additional factors such as the presence of other gases, the chemical composition of the cap rock itself, and the long-term effects of hydrogen exposure on cap rock integrity. A comprehensive understanding of these factors is essential for optimizing underground hydrogen storage strategies and ensuring long-term environmental sustainability.

Containment strategy for subsurface H2 storage based on time-dependent soft solids

We propose an innovative containment strategy based on time-dependent soft solids, namely 2 wt% Laponite suspensions, to reinforce natural subsurface seals and engineer flow barriers, with an eye toward making H2 subsurface storage scalable and geographically agnostic. This suspension can be injected at its initial low viscosity and elasticity into a porous medium, allowing for easy pumping and targeted delivery. Once inside the target zone, it matures into a soft solid with much higher viscosity and elasticity, acting as a potential flow barrier. We discuss the rheological properties of the suspensions and demonstrate that hydrogen does not adversely affect their microstructure, but rather increases the suspensions’ viscosity and elasticity. Moreover, the suspensions enhance the rock samples’ compressive strength, while hydrogen exposure increases their stiffness and ductility. The ability of rock samples saturated with the suspensions to contain higher injected gas pressures is enhanced by aging at higher temperatures.

Enhancement of gasochromic response to hydrogen of WO3 thin films by post-process modification and catalyst selection

The gasochromic properties of WO3 thin films deposited by electron beam evaporation were investigated, focusing on their structural, morphology and optical changes caused by heat treatment. Moreover, the influence of the thickness and type of catalyst on the gasochromic properties of WO3 was examined. X-ray diffraction measurements revealed that WO3 thin films annealed up to 473 K remained amorphous, whereas annealing at 673 K and above, initiated crystallization into a monoclinic structure. Gasochromic behaviour was observed in response to hydrogen exposure, with the most significant changes occurring in films annealed at 673 K with a thin adlayer of palladium catalyst. A gasochromic response of 1.84 was achieved for H2 concentration as low as 25 ppm. The process of gasochromic colouration was correlated with the changes of free charge carrier concentration calculated based on Drude free electron theory. XPS analysis confirms WO3 reduction under hydrogen exposure, validating proposed colouration mechanisms. These comprehensive findings offer insights into optimizing gasochromic thin films for various sensing applications.

Hydrogen exposure-enhanced superconductivity transition in FeSe/SrTiO3 monolayer

Interface-enhanced superconductivity in FeSe/SrTiO3 (FeSe/STO) monolayers provides the record for the highest transition temperature (Tc) in iron-based compounds. Long-term post annealing is the commonly adopted recipe to induce the superconductivity transition in the not-superconductive as-grown FeSe/STO monolayer. Here, we developed a kinetic method, i.e., hydrogen exposure followed by gentle annealing, to enhance the superconductivity of the FeSe/STO monolayer. Our approach is more efficient than the long-term post annealing. Scanning tunneling microscopy (STM) characterization demonstrated the so far largest superconducting gap of ∼22 mV, indicating an enhanced superconductivity. We believe that the hydrogen-induced lattice Fe diffusion facilitates to remove the interfacial excess Se atoms fatal to the superconductivity, resulting in the formation of a second layer FeSe. The subsequent annealing helps to annihilate the generated Fe vacancies and, thus, enhance the superconductivity in the FeSe/STO monolayer.

Exploring Hydrogen Embrittlement: Mechanisms, Consequences, and Advances in Metal Science

Hydrogen embrittlement (HE) remains a pressing issue in materials science and engineering, given its significant impact on the structural integrity of metals and alloys. This exhaustive review aims to thoroughly examine HE, covering a range of aspects that collectively enhance our understanding of this intricate phenomenon. It proceeds to investigate the varied effects of hydrogen on metals, illustrating its ability to profoundly alter mechanical properties, thereby increasing vulnerability to fractures and failures. A crucial section of the review delves into how different metals and their alloys exhibit unique responses to hydrogen exposure, shedding light on their distinct behaviors. This knowledge is essential for customizing materials to specific applications and ensuring structural dependability. Additionally, the paper explores a diverse array of models and classifications of HE, offering a structured framework for comprehending its complexities. These models play a crucial role in forecasting, preventing, and mitigating HE across various domains, ranging from industrial settings to critical infrastructure.

Determination of hydrogen influence on microhardness and microstructure characteristics of aviation alloys

This paper presents results of the studies of hydrogen exposure duration influence on the characteristics of two aviation alloys at atmospheric pressure and room temperature. First alloy (alloy 1) was obtained by hot isostatic pressing, and was used for the manufacture of gas turbine rotor discs. Second alloy (alloy 2) was obtained by directional crystallization, and was used for the manufacture of gas turbine blades. It was determined that microhardness of the samples increased during 1000 h of hydrogen exposure duration. The relative increase of the microhardness was insignificant, and for the sample of alloy 1 it was 2.5 %, and for the sample of alloy 2 – 2 %. Correlation analysis of the XRD diagram parameters indicated positive and negative statistically significant relationships correlation between XRD diagrams peaks parameters, hydrogen exposure duration and microhardness of the samples. It was revealed that XRD diagrams peaks of alloy 1 were broadened and their heights increased during hydrogenation, which can be associated with a decrease of dislocations in the grains and their local accumulation at the grains boundaries. Conterwise, XRD diagrams peaks of alloy 2 were narrowed, which can indicate an increase of dislocations in the material grain structure. XRD diagrams processing demonstrated that the crystallite size and dislocation density for alloy 1 decreased with a delay from the hydrogenation start, but for alloy 2 these parameters monotonically increased, and it corresponds to microhardness changes trends of the samples during hydrogenation.

Periodically structured Pd/PdO nanofilm as laser-written optical sensing element for hydrogen detection

In this investigation, we explore the optical detection capabilities of periodically structured nanofilms comprised of alternating regions of palladium and palladium oxide for hydrogen sensing. We introduce a straightforward and efficient method for inducing palladium oxidation by a laser, facilitating the rapid production of Pd/PdO nanostructures. The optical responses of these nanostructures to hydrogen exposure are examined in detail, taking into account variations in the structural periodicity and the laser power utilized during fabrication. The interaction with hydrogen triggers palladium oxide reduction, affecting the physical and chemical properties of the nanostructures. Given the catalytic role of the surrounding palladium, which speeds up the autocatalytic reaction, we discuss the optimal structural parameters for achieving enhanced responsiveness in these nanostructures. Through systematic investigation of a series of nanostructures, we illustrate their sensitivities across different fabrication parameters and successive sensing cycles.

An in-situ view cell system for investigating swelling behavior of elastomers upon high-pressure hydrogen exposure

The transition to hydrogen as a clean and efficient energy carrier is impeded by challenges in the compatibility of hydrogen with materials used within hydrogen infrastructure. Elastomers, crucial in sealing components, often exhibit premature failures in high-pressure hydrogen environments due to excessive swelling. This study employs an innovative in-situ view cell system to assess the swelling behavior of hydrogenated nitrile butadiene rubber (HNBR) under various hydrogen conditions. The system, designed to withstand pressures up to 96.5 MPa, incorporates Digital Image Correlation (DIC) for strain measurements and volume estimation. Results reveal non-linear volume increases during depressurization, challenging conventional assumptions. Furthermore, investigations into peak hydrogen pressures and pressure-holding scenarios during decompression highlight complex swelling trends. The introduction of a novel computer vision (CV) method enhances precision in volume estimation, overcoming DIC limitations. The study provides insights into mitigating elastomer swelling, crucial for developing robust materials to support future hydrogen-driven energy systems.

Ramsay 1 and Ramsay 2, learnings from the first natural hydrogen exploration wells in Australia

In October and November 2023, Gold Hydrogen, an ASX listed natural hydrogen explorer, drilled Ramsay 1 and Ramsay 2, the first natural hydrogen exploration wells in Australia. Twinning an historic well, the Ramsay Oil Bore 1 well in PEL687 in South Australia, the objective of the Ramsay 1 and Ramsay 2 wells was to find movable naturally generated hydrogen in the subsurface and establish the presence of a commercially attractive natural hydrogen resource base. This paper highlights some of the learnings from the process of designing and executing these natural hydrogen exploration wells and how the initial hurdles of demonstrating the presence of a hydrogen resource were overcome during the drilling phase. Using modified standard drilling technology and dedicated hydrogen detection tools (calibrated real time mud gas analysis), Gold Hydrogen has shown that exploration for natural hydrogen resources can be done safely and cost effectively. The main learnings included the application of a calibrated hydrogen detection methodology to derive a pseudo hydrogen saturation log and the successful selection of drilling mud and casing compliant with long term hydrogen exposure. As global drilling for natural hydrogen is still in its infancy, these modifications to the exploration well design and execution could have a significant impact on future drilling for this highly attractive carbon free energy source. With a program of seismic data acquisition and follow-up wells planned for 2024, Gold Hydrogen is leading a group of Australian natural hydrogen explorers, who are trying to unlock commercial natural hydrogen resources in the world.

Characteristics of highly sensitive hydrogen gas sensor based on Pt-SiO2/Si microring resonator

A hydrogen gas sensor based on a silicon microring resonator (MRR) with a Pt–SiO2 thin film as a hydrogen-sensitive film is proposed and investigated to realize a high-sensitivity hydrogen sensor. The sensor detects hydrogen on the basis of the resonant wavelength shift caused by the reaction heat generated in the Pt–SiO2 film. In the hydrogen exposure measurement, resonant wavelength shifts of approximately 5.0 and 2.4 nm were observed at hydrogen concentrations of 4.0 and 0.4 vol%, respectively, showing the high sensitivity of the proposed sensor. In addition, an MRR sensor with an upper Al2O3 cladding layer is proposed and its higher sensitivity is theoretically demonstrated.

Sorption properties of nanostructured ball-milled porous silicon for solid-state hydrogen storage up to 80 bar

Solid-state storage is a feasible solution to store hydrogen compared to commercially available techniques. The disadvantage of using metal and complex hydrides for storage is the elevated temperature operation (>400 °C) and slow reaction kinetics. Porous materials like carbon nanostructures, metal-organic frameworks, zeolites, and porous polymers possess high surface energy and hydrogen affinity. However, cryogenic temperature operation and low storage at ambient conditions are major limitations for practical storage applications. Modifying the material morphology and storage parameters to enhance hydrogen storage is under intense investigation. This study focuses on nanostructuring porous silicon (PS), evaluating its structural characteristics, and investigating its ability to store hydrogen at up to 80 bar. The challenges of large particle size and low-pressure hydrogen storage in the novel porous material is addressed with possible mechanisms. The discussion explored the potential of utilizing interconnected pores via nanoscale engineering and increased charging pressure to optimize hydrogen exposure. Nanostructuring the hand-grinded porous Si (HGPS) reduces crystallite size, boosts surface energy and enhances thermodynamics. At 80 bar and 120 °C, the ball-milled PS (BMPS) exhibits a hydrogen storage capacity of 10.7 wt%. The isosteric heat of adsorption is utilized to optimize storage conditions to achieve useable capacity. The hydrogen adsorption pressure is optimized between 40 and 60 bar, where the storage capacity ranges from 2 wt% and 6 wt% (meeting the hydrogen storage target set by the US Department of Energy). X-ray Photoelectron Spectroscopy investigates surface states and bonding involving silicon hydrides. The effect of nanostructuring on decomposition energy is observed by differential scanning calorimetry. The decreased crystallite size, examined through X-ray diffraction and Raman spectroscopy, exposes nanopores accessible to hydrogen. The accessibility enhances storage capacity in free and surface-affixed states, rendering BMPS for reversible storage applications. The lower temperature requirement for hydrogen adsorption and release from storage material aligns with Sustainable Development Goal 7 (SDG 7) on affordable and clean energy.

Pt/GaN Schottky Barrier Height Lowering by Incorporated Hydrogen

Changes in the hydrogen-induced Schottky barrier height (Φ B) of Pt/GaN rectifiers fabricated on free-standing GaN substrates were investigated using current–voltage, capacitance–voltage, impedance spectroscopy, and current–time measurements. Ambient hydrogen lowered the Φ B and reduced the resistance of the semiconductor space–charge region while only weakly affecting the ideality factor, carrier concentration, and capacitance of the semiconductor space–charge region. The changes in the Φ B were reversible; specifically, the decrease in Φ B upon hydrogen exposure occurred quickly, but the recovery was slow. The results also showed that exposure to dry air and/or the application of a reverse bias to the Schottky electrodes accelerated the reversion compared with the case without the applied bias. The former case resulted in fast reversion because of the catalytic effect of Pt. The latter case, by contrast, suggested that hydrogen was incorporated into the Pt/GaN interface oxides as positive mobile charges. Moreover, both exposure to dry air and the application of a reverse bias increased the Φ B of an as-loaded sample from 0.91 to 1.07 eV, revealing that the Φ B of Pt/GaN rectifiers was kept lower as a result of hydrogen incorporation that likely occurred during device processing and/or storage.