Transmission, Distribution & Storage

Hydrogen and its interaction with metal oxide surfaces is of major importance for a wide range of research and applied fields spanning from catalysis energy storage microelectronics to metallurgy. This paper reviews state of the art of first principles calculations on the well-known ruthenium oxide (RuO₂) surface in its (110) orientation and its interaction with hydrogen. In addition to it the paper also fills gaps in knowledge with new calculations and results on the (001) surface. Bulk and surface interactions are thoroughly reviewed. This includes systematic analysis of adsorption sites local agglomeration propensity of hydrogen and migration pathways in which literature data and their potential deviations are explained. We notably discuss novel results on propensity for agglomeration of hydrogen within bulk channels [001] oriented in which the proton-like behavior of adsorbed hydrogen hinders further agglomeration in adjacent channels. The paper brings new insights into the migration pathways on the surface and in bulk both exhibiting preferential diffusion paths along the [001] direction. The paper finally investigates the subsurface region. We show that while the subsurface has more stable sites for adsorption compared to bulk its accessibility from the surface shows prohibitive activation barriers inhibiting penetration into subsurface and bulk. We further calculate and discuss adsorption and penetration processes on the alternative RuO₂ (001) surface.

The development of hydrogen energy is hindered by the lack of high-efficiency hydrogen storage materials. To explore new high-capacity hydrogen storage alloys reversible hydrogen storage in AB₂-type alloy is realized by using A or B-side elemental substitution. The substitution of small atomic-radius element Zr and Mg on A-side of YNi₂ and partial substitution of large atomic-radius element V on B-side of YNi₂ alloy was investigated in this study. The obtained ZrMgNi₄ ZrMgNi₃V and ZrMgNi₂V₂ alloys remained single Laves phase structure at as-annealed hydrogenated and dehydrogenated states indicating that the hydrogen-induced amorphization and disproportionation was eliminated. From ZrMgNi₄ to ZrMgNi₂V₂ with the increase of the degree of vanadium substitution the reversible hydrogen storage capacity increased from 0.6 wt% (0.35H/M) to 1.8 wt% (1.0H/M) meanwhile the lattice stability gradually increased. The ZrMgNi₂V₂ alloy could absorb 1.8 wt% hydrogen in about 2 h at 300 K under 4 MPa H₂ pressure and reversibly desorb the absorbed hydrogen in approximately 30 min at 473 K without complicated activation process. The prominent properties of ZrMgNi₂V₂2 elucidate its high potential for hydrogen storage application.

In this study a novel analytical system was developed to monitor the environmental hydrogen embrittlement of Al-Zn-Mg-based aluminum alloys dynamically and quantitatively under atmospheric air pressure. The system involves gas chromatography using a SnO₂-based semiconductor hydrogen sensor a digital image correlation step and the use of a slow strain rate testing machine. Use of this system revealed that hydrogen atoms are generated during the plastic deformation of Al-Zn-Mg alloys caused by the chemical reaction between the water vapor in air and the alloy surface without oxide films. Digital image correlation also clarified that the generated hydrogen atoms caused numerous localized grain boundary cracks on the specimen surface resulting in a localized grain boundary fracture. The amount of hydrogen atoms evolved from the embrittled fracture surface was 2.7 times as high as that from the surface without embrittlement.

The susceptibility of high strength ferritic steels to hydrogen-assisted fracture in hydrogen gas is usually evaluated by mechanical testing in high-pressure hydrogen gas or testing in air after pre-charging the specimens with hydrogen. We have used this second methodology conventionally known as internal hydrogen. Samples were pre-charged in an autoclave under 195 bar of pure hydrogen at 450ºC for 21 hours.<br/>Different chromium-molybdenum steels submitted to diverse quenching and tempering heat treatments were employed. Diverse specimens were also used: small cylindrical samples to measure hydrogen contents and the kinetics of hydrogen egression at room temperature tensile specimens notched tensile specimens with a sharp notch and also compact fracture toughness specimens. Fractographic examination in SEM was finally performed in order to know the way hydrogen modify fracture micromechanisms.<br/>The presence of hydrogen barely affects the conventional tensile properties of the steels but it clearly alters their notched tensile strength and fracture toughness. This is due to the strong effect that stress triaxiality (dependent also on the steel yield strength) has on the accumulation of hydrogen on the notch/crack front region being the displacement rate used in the test another important variable to be controlled due to its influence on hydrogen diffusion to the embrittled process zone. Moreover the modification of fracture micromechanisms was finally determined being ductile (initiation growth and coalescence of microvoids) in the absence of hydrogen and brittle and intergranular under the material conditions of maximum embrittlement.

The effect of hydrogen on short crack propagation under cyclic loading in SA508 Grade 3 Class I low alloy steel is investigated. This low alloy steel is used in manufacturing of pressure vessel installed in Indian nuclear power plants. During operation these pressure vessels are subjected to continuous supply of pressurized hot water at 600 K and hence are susceptible to hydrogen embrittlement. In past research has been conducted on the effect of hydrogen embrittlement on long fatigue crack propagation in this material but the mechanistic understanding and correlation of hydrogen embrittlement with microstructural features in the material can be understood well by studying the effect of hydrogen embrittlement on short fatigue crack propagation. Short fatigue cracks are of the order of 10 µm to 1 mm and unlike long cracks these short cracks strongly interact with the microstructural features in the material such as grain/phase boundaries. The effect of hydrogen embrittlement on short crack propagation is studied by artificial hydrogen charging of the material through electrochemical process. The single edge notch tension (SENT) specimens with an initial notch of the order of 85 to 90 µm are used to study the short crack propagation. The short cracks in hydrogen charged samples initiated from the notch at lower number of loading cycles as compared to the uncharged notched samples for the same value of applied stress range (Δσ). After initiation the short fatigue crack in hydrogen charged samples propagated at higher rate as compared to uncharged samples. This dissimilarity in crack propagation behavior is due to the difference in the interaction of short fatigue crack with the microstructural features for a hydrogen charged and uncharged samples.

In order to reduce CO₂ emissions and fuel consumption and to respect current environmental norms the reduction of vehicles weight is a primary target of the automotive industry. Advanced High Strength Steels (AHSS) and Ultra High Strength Steel (UHSS) which present excellent mechanical properties are consequently increasingly used in vehicle manufacturing. The increased strength to mass ratio compensates the higher cost per kg and AHSS and UHSS are proving to be cost-effective solutions for the body-in-white of mass market products.

In particular aluminized boron steel can be formed in complex shapes with press hardening processes acquiring high strength without distortion and increasing protection from crashes. On the other hand its characteristic martensitic microstructure is sensitive to hydrogen delayed fracture phenomena and at the same time the dew point in the furnace can produce hydrogen consequently to the high temperature reaction between water and aluminum. The high temperature also promotes hydrogen diffusion through the metal lattice under the aluminum-silicon coating thus increasing the diffusible hydrogen content. However after cooling the coating acts as a strong barrier preventing the hydrogen from going out of the microstructure. This increases the probability of delayed fracture. As this failure brings to the rejection of the component during production or even worse to the failure in its operation diffusible hydrogen absorbed in the component needs to be monitored during the production process.

For fast and simple measurements of the response to diffusible hydrogen of aluminized boron steel one of the HELIOS innovative instruments was used HELIOS II. Unlike the Devanathan cell that is based on a double electrochemical cell HELIOS II is based on a single cell coupled with a solid-state sensor. The instrument is able to give an immediate measure of diffusible hydrogen content in sheet steels semi-products or products avoiding time-consuming specimen palladium coating with a guided procedure that requires virtually zero training.

Two examples of diffusible hydrogen analyses are given for Usibor®1500-AS one before hot stamping/ quenching and one after hot stamping suggesting that the increase in the number of dislocations during hot stamping could be the main responsible for the lower apparent diffusivity of hydrogen.

For the membrane and spiral walls of the new USC boilers the advanced T24 material was developed. In 2010 however extensive T24 tube weld cracking during the commissioning phase of several newly built boilers was observed. As the dominant root cause Hydrogen Induced - Stress Corrosion Cracking was reported. An investigation into the interaction of the T24 material with hydrogen was launched in order to compare its hydrogen embrittlement susceptibility with that of the T12 steel commonly used for older boiler evaporators. Both base materials and simulated Heat Affected Zone (HAZ) microstructures were tested. Total and diffusible hydrogen in the materials after electrochemical charging were measured. Thermo Desorption Spectrometry was used to gain insights into the trapping behaviour and the apparent diffusion coefficient at room temperature was determined. Based on the hardness and the diffusible hydrogen pick-up capacity of the materials it was concluded that T12 is less susceptible to hydrogen embrittlement than T24 as base material as well as in the HAZ condition and that the HAZ of T24 is more susceptible to hydrogen embrittlement than the base material both in the as welded and in the Post Weld Heat Treated (PWHT) condition. However based on the results of this investigation it could not be determined if the T24 HAZ is less susceptible to hydrogen embrittlement after PWHT.

Hydrogen in the UK is beginning to shift from hypothetical debates to practical demonstration projects. An ever-growing evidence base has showcased how the costs of hydrogen and its barriers to entry are reducing such that it now has practical potential to contribute to the decarbonisation of the UK's energy sector.

Despite this hydrogen has yet to have wide commercial uptake due in part to a number of barriers where measurement plays a critical role. To accelerate the shift towards the hydrogen economy these challenges have been identified and prioritised by NPL.

The report Energy transition: Measurement needs within the hydrogen industry outlines the challenges identified. The highest priority issues are:

• Material development for fuel cells and electrolysers to reduce costs and assess critical degradation mechanisms – extending lifetime and durability is key to the commercialisation of these technologies.
• Impact assessment of added odorant to hydrogen to aid leak detection. Measurement of its impact during pipeline transportation and on the end-use application (particularly fuel cell technology) will be important to provide assurance that it will not affect lifetime and durability.
• Determination of the blend ratio when hydrogen is mixed with natural gas in the gas grid. Accurate flow rate measurement and validated metering methods are needed to ensure accurate billing of the consumer.
• Measurement of the combustion properties of hydrogen including flame detection and propagation temperature and nitrogen oxides (NOx) emissions should it be used for heat applications to ensure existing and new appliances are suitable for hydrogen.
• Assessment of the suitability of existing gas infrastructure and materials for hydrogen transportation. Building an understanding of what adaptations might need to be made to avoid for example air permeation metal embrittlement and hydrogen leakage.
• Validated techniques for hydrogen storage which will require measurement of the efficiency and capacity of each mechanism through robust metering leakage detection and purity analysis to ensure they are optimised for the storage of hydrogen gas.

These challenges were identified through an industry-wide workshop in-depth interviews and consultation with key stakeholders within the hydrogen industry

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A novel Pd/templated carbon catalyst (Pd/TC) was developed characterized and tested in the dehydrogenation of formic acid (FA) under mild conditions with the possibility to control the H₂ generation rate in the absence or presence of HCOONa (SF) by adjusting the Pd:FA and/or FA:SF ratios. The characterization results of the templated carbon obtained by the chemical vapor deposition of acetylene on NaY zeolite revealed different structural and morphological properties compared to other C-based supports. Therefore it was expected to induce a different catalytic behavior for the Pd/TC catalyst. Indeed the TC-supported Pd catalyst exhibited superior activity in the decomposition of FA even at room temperature with turnover frequencies (TOFs) of up to 143.7 and 218.8 h⁻¹ at 60 °C. The H2 generation rate increased with an increasing temperature while the H₂ yield increased with a decreasing FA concentration. Constant generation of gaseous flow (H₂ + CO₂) was achieved for 11 days by the complete dehydrogenation of FA at room temperature using a 2 M FA solution and Pd:FA = 1:2100. The presence of SF in the reaction medium significantly enhanced the H₂ generation rate (535 h⁻¹ for FA:SF = 3:1 and 60 °C).

As the need for duplex stainless steel (DSS) increases it is necessary to evaluate hydrogen stress cracking (HSC) in dissimilar welded joints (WJs) of DSS and carbon steel. This study aims to investigate the effect of the weld microstructure on the HSC behaviour of dissimilar gas-tungsten arc welds of DSS and carbon steel. In situ slow-strain rate testing (SSRT) with hydrogen charging was conducted for transverse WJs which fractured in the softened heat-affected zone of the carbon steel under hydrogen-free conditions. However HSC occurred at the martensite band and the interface of the austenite and martensite bands in the type-II boundary. The band acted as an HSC initiation site because of the presence of a large amount of trapped hydrogen and a high strain concentration during the SSRT with hydrogen charging. Even though some weld microstructures such as the austenite and martensite bands in type-II boundaries were harmless under normal hydrogen-free conditions they had a negative effect in a hydrogen atmosphere resulting in the premature rupture of the weld. Eventually a premature fracture occurred during the in situ SSRT in the type-II boundary because of the hydrogen-enhanced strain-induced void (HESIV) and hydrogen-enhanced localised plasticity (HELP) mechanisms.