Transmission, Distribution & Storage

To find suitable sealing material with low permeability against hydrogen the elaborated evaluation techniques for hydrogen transport properties are necessary. We developed two techniques determining the permeability of hydrogen including software for diffusion behavior analysis. The techniques contain gas chromatography and volumetric collection of hydrogen gas. By measuring the hydrogen released from polymer samples with respect to the elapsed time after being decompressed from the high pressure total amount of adsorption and diffusivity (D) of hydrogen are evaluated with self-developed program of Fick's diffusion equation specified to a sample shape. The solubility (S) and permeability (P) of the polymers are determined through Henry's law and a relation of P=SD respectively. Developed techniques were applied to three kinds of spherical-shaped sealing rubbers NBR EPDM and FKM. The D S and P have been measured as function of pressure. The permeability obtained by both methods are discussed with Comsol simulation.

The ultrafine-grained (UFG) duplex microstructure of medium-Mn steel consists of a considerable amount of austenite and ferrite/martensite achieving an extraordinary balance of mechanical properties and alloying cost. In the present work two heat treatment routes were performed on a cold-rolled medium-Mn steel Fe-12Mn-3Al-0.05C (wt.%) to achieve comparable mechanical properties with different microstructural morphologies. One heat treatment was merely austenite-reverted-transformation (ART) annealing and the other one was a successive combination of austenitization (AUS) and ART annealing. The distinct responses to hydrogen ingression were characterized and discussed. The UFG martensite colonies produced by the AUS + ART process were found to be detrimental to ductility regardless of the amount of hydrogen which is likely attributed to the reduced lattice bonding strength according to the H-enhanced decohesion (HEDE) mechanism. With an increase in the hydrogen amount the mixed microstructure (granular + lamellar) in the ART specimen revealed a clear embrittlement transition with the possible contribution of HEDE and H-enhanced localized plasticity (HELP) mechanisms.

Hydrogen embrittlement (HE) is a critical issue that hinders the reliability of hydrogenation reactors. Hence it is of great significance to investigate the effect of hydrogen on fracture toughness of 2.25Cr-1Mo-0.25V steel and weld. In this work the fracture behavior of 2.25Cr-1Mo-0.25V steel and welds was studied by three-point bending tests under hydrogen-free and hydrogen-charged conditions. The immersion charging method was employed to pre-charge hydrogen inside specimen and the fracture toughness of these joints was evaluated quantitatively. The microstructure and grain size of the specimens were observed by scanning electron microscopy (SEM) and by metallurgical microscopy to investigate the HE mechanisms. It was found that fracture toughness for both the base metal (BM) and the weld zone (WZ) significantly decreased under hydrogen-charged conditions due to the coexistence of the hydrogen-enhanced decohesion (HEDE) and hydrogen-enhanced localized plasticity (HELP) mechanisms. Moreover the formation and growth of primary voids were observed in the BM leading to a superior fracture toughness. In addition the BM compared to the WZ shows superior resistance to HE because the finer grain size in the BM leads to a larger grain boundary area thus distributing more of the diffusive hydrogen trapped in the grain boundary and reducing the hydrogen content.

The present research focuses on the investigation of an in situ hydrogen charging effect during Crack Tip Opening Displacement testing (CTOD) on the fracture toughness properties of X65 pipeline steel. This grade of steel belongs to the broader category of High Strength Low Alloy Steels (HSLA) and its microstructure consists of equiaxed ferritic and bainitic grains with a low volume fraction of degenerated pearlite islands. The studied X65 steel specimens were extracted from pipes with 19.15 mm wall thickness. The fracture toughness parameters were determined after imposing the fatigue pre-cracked specimens on air on a specific electrolytic cell under a slow strain rate bending loading (according to ASTM G147-98 BS7448 and ISO12135 standards). Concerning the results of this study in the first phase the hydrogen cations’ penetration depth the diffusion coefficient of molecular and atomic hydrogen and the surficial density of blisters were determined. Next the characteristic parameters related to fracture toughness (such as J KQ CTODel CTODpl) were calculated by the aid of the Force-Crack Mouth Open Displacement curves and the relevant analytical equations.

Our contribution demonstrates that hydrogen storage in stationary Liquid Organic Hydrogen Carrier (LOHC) systems becomes much simpler and significantly more efficient if both the LOHC hydrogenation and the LOHC dehydrogenation reaction are carried out in the same reactor using the same catalyst. The finding that the typical dehydrogenation catalyst for hydrogen release from perhydro dibenzyltoluene (H18-DBT) Pt on alumina turns into a highly active and very selective dibenzyltoluene hydrogenation catalyst at temperatures above 220 °C paves the way for our new hydrogen storage concept. Herein hydrogenation of H0-DBT and dehydrogenation of H18-DBT is carried out at the same elevated temperature between 290 and 310 °C with hydrogen pressure being the only variable for shifting the equilibrium between hydrogen loading and release. We demonstrate that the heat of hydrogenation can be provided at a temperature level suitable for effective dehydrogenation catalysis. Combined with a heat storage device of appropriate capacity or a high pressure steam system this heat could be used for dehydrogenation.

High-strength steel fasteners characterized by tensile strengths above 1100 MPa are often used in critical applications where a failure can have catastrophic consequences. Preventing hydrogen embrittlement (HE) failure is a fundamental concern implicating the entire fastener supply chain. Research is typically conducted under idealized conditions that cannot be translated into know-how prescribed in fastener industry standards and practices. Additionally inconsistencies and even contradictions in fastener industry standards have led to much confusion and many preventable or misdiagnosed fastener failures. HE susceptibility is a function of the material condition which is comprehensively described by the metallurgical and mechanical properties. Material strength has a first-order effect on HE susceptibility which increases significantly above 1200 MPa and is characterized by a ductile--brittle transition. For a given concentration of hydrogen and at equal strength the critical strength above which the ductile–brittle transition begins can vary due to second-order effects of chemistry tempering temperature and sub-microstructure. Additionally non-homogeneity of the metallurgical structure resulting from poorly controlled heat treatment impurities and non-metallic inclusions can increase HE susceptibility of steel in ways that are measurable but unpredictable. Below 1200 MPa non-conforming quality is often the root cause of real-life failures.

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The objective of this study is to analyze a government proposal from a panoramic perspective concerning the economic and environmental effects associated with the construction and operation of hydrogen utilization systems by the year 2030. We focused on a marine transport system for hydrogen produced offshore hydrogen gas turbine power generation fuel cell vehicles (FCVs) and hydrogen stations as well as residential fuel cell systems (RFCs). In this study using an Input-Output Table for Next Generation Energy Systems (IONGES) we evaluated the induced output labor and CO2 emissions from the construction and operation of these hydrogen technologies using a uniform approach. This may be helpful when considering future designs for the Japanese energy system. In terms of per 1 t-H2 of hydrogen use CO2 reductions from the use of FCVs are considerably higher than the additional CO2 emissions from foreign production and transportation of hydrogen. Because new construction of a hydrogen pipeline network is not considered to be realistic RFCs is assumed to consume hydrogen generated by refining town gas. In this case the CO2 reductions from using RFCs will decline under the electricity composition estimated for 2030 on the condition of a substantial expansion of electricity generation from renewable energy sources. However under the present composition of electricity production we can expect a certain amount of CO2 reductions from using RFCs. If hydrogen is directly supplied to RFCs CO2 reductions increase substantially. Thus we can reduce a significant amount of CO2 emissions if various unused energy sources dispersed around local areas or unharnessed renewable energies such as solar and wind power can be converted into hydrogen to be supplied to FCVs and RFCs.

A model has been derived for the magnesium hydrogenation reaction at conditions close to equilibrium. The reaction mechanism involves an adsorption element where the model is an extension of the Langmuir adsorption model. The concept of site availability (σs) is introduced whereby it has the capability to reduce the reaction rate. To improve representation of σs an adaptable semi-empirical equation has been developed. Supplement to the surface reaction a rate equation has been derived considering resistance effects. It was found that close to equilibrium surface resistance dominated the reaction.

Hydrogen intrudes into the steel during pickling process which is a pre-processing before a joining process promoting crack formation. In a mechanical clinching which is one of joining method in the automotive industry cracks due to large strain sometimes forms. In order to guarantee reliability it is important to clarify the influence of hydrogen on crack formation of the joint. In this study we clarified the influence of hydrogen for the crack formation on the mechanical clinching. Hydrogen charge was carried out using an electrolytic cathode charge. After the charging mechanical clinching was performed. Mechanical clinching was carried out with steel plate and aluminium alloy plate. To clarify the influence of hydrogen mechanical clinching was conducted without hydrogen charring. To investigate the crack formation the test piece was cut and the cut surface was observed. When the joint was broken during the clinching the fracture surface was observed using an optical microscope and an electron microscope. The load-displacement diagram showed that without hydrogen charging the compressive load increased as the displacement increased. On the other hand the compressive load temporarily decreased with high hydrogen charging suggesting that cracks formed at the time. The cut surface observation showed that interlock was formed in both cases with low hydrogen charging and without hydrogen charging. With low hydrogen charging no cracks were formed in the joint. When high hydrogen charging was performed cracks were formed at the joining point. Fracture analysis showed brittle-like fracture surface. These results indicate that hydrogen induces crack formation in the mechanical clinching.

Multiscale characterization of the hydrogenation process of silicon solar cell contacts based on c-Si/SiO_x/nc-SiC_x(p) has been performed by combining dynamic secondary ion mass-spectrometry (D-SIMS) atom probe tomography (APT) and transmission electron microscopy (TEM). These contacts are formed by high-temperature firing which triggers the crystallization of SiCx followed by a hydrogenation process to passivate remaining interfacial defects. Due to the difficulty of characterizing hydrogen at the nm-scale the exact hydrogenation mechanisms have remained elusive. Using a correlative TEM-SIMS-APT analysis we are able to locate hydrogen trap sites and quantify the hydrogen content. Deuterium (D) a heavier isotope of hydrogen is used to distinguish hydrogen introduced during hydrogenation from its background signal. D-SIMS is used due to its high sensitivity to get an accurate deuterium-to-hydrogen ratio which is then used to correct deuterium profiles extracted from APT reconstructions. This new methodology to quantify the concentration of trapped hydrogen in nm-scale structures sheds new insights on hydrogen distribution in technologically important photovoltaic materials.