Russian Federation

In this paper comparison studies of the hydrogen effect on the structural and phase state deformation behavior and mechanical properties of the fine- (average grain size 4 µm) and ultrafine-grained (average element size 0.3 and 0.4 µm) Zr–1wt.%Nb (hereinafter Zr–1Nb) alloy under tension at temperatures in the range of 293–873 K were conducted. The formation of an ultrafine-grained structure is established to increase the strength characteristics of the Zr–1Nb alloy by a factor of 1.5–2 with a simultaneous reduction of its resistance to the localization of plastic deformation at the macro level and the value of deformation to failure. The presence of hydrogen in the Zr–1Nb alloy in the form of a solid solution and hydride precipitates increases its resistance to the localization of plastic deformation at the macro level if the alloy has an ultrafine-grained structure and decreases if the structure of the alloy is fine-grained. In the studied temperature range the Zr–1Nb alloy in the ultrafine-grained state has a higher resistance to hydrogen embrittlement than the alloy in the fine-grained state.

Results are given of experimental study of propagation of explosion waves in hydrogen-air mixtures of different compositions under conditions of cumulation. The investigations are performed in a setup consisting of two parts namely the upper part in the form of a metal cone and the lower part in the form of a rubber envelope hermetically attached to the cone. The upper and lower parts of the experimental setup are separated by a thin rubber film and may be filled with hydrogen-air mixtures of different compositions.

In the present paper the two-stage model of detonative combustion of hydrogen is presented. The following improvements are described: accurate description of the heat release stage of combustion; the clear physics-based procedure for calculation of the parameters of the proposed model; sample calculations of the detonation wave in hydrogen/air mixtures in wide range of conditions showing that the proposed model performs well in a wide range of conditions (pressures temperatures mixture compositions). The results of the 2D simulations of the detonation cell are presented for the hydrogen/oxygen/argon mixture as example to show the performance and accuracy of the model presented in this paper.

Polymer electrolyte membrane (PEM) water electrolysis has demonstrated its potentialities in terms of cell efficiency (energy consumption ≈ 4.0-4.2 kW/Nm3 H2) and gas purity (> 99.99% H2). Current research activities are aimed at increasing operating pressure up to several hundred bars for direct storage of hydrogen in pressurized vessels. Compared to atmospheric pressure electrolysis high-pressure operation yields additional problems especially with regard to safety considerations. In particular the rate of gases (H2 and O2) cross-permeation across the membrane and their water solubility both increase with pressure. As a result gas purity is affected in both anodic and cathodic circuits and this can lead to the formation of explosive gas mixtures. To prevent such risks two different solutions reported in this communication have been investigated. First the chemical modification of the solid polymer electrolyte in order to reduce cross-permeation phenomena. Second the use of catalytic H2/O2 recombiners to maintain H2 levels in O2 and O2 levels in H2 at values compatible with safety requirements.

Platinum metals dispersed on a porous carrier e.g. -Al2O3 are used as catalysts for removal of small amounts of hydrogen from the air where the excess of oxygen is significant.<br/>The recombination reaction of H2 and O2 on smooth platinum proceeds at a high rate only in gas mixes with an excess of hydrogen. When the concentration of oxygen exceeds that of hydrogen in terms of stoichiometric ratio the process slows down sharply and eventually stops completely. In research undertaken at the Karpov Institute of Physical Chemistry (Moscow) forty years ago the electrochemical mechanism of red-ox reactions was proposed as an explanation for this inhibition by excess oxygen. The results of ellipsometric analysis pointed to the formation of a protective monolayer of PtO molecules on the Pt surface in an oxygen-rich atmosphere. It was observed that the recombination reaction proceeds at a high rate with the use of a porous catalyst at any concentrations of reactant gases. The reason for that lies in the mechanism of the catalysis: the reaction proceeds at a certain depth in the porous body of the catalyst. Hydrogen which has higher mobility penetrates in larger quantity than oxygen thus creating there the stoichiometric excess. To test the proposed mechanism of recombination the catalytic reaction was studied ) with porous carriers of various thicknesses and b) with metal grids of various porosities covering the catalyst. The data obtained have confirmed unequivocally the earlier hypothesis of hydrogenation of a porous catalyst.<br/>Such insight has allowed the authors to develop more effective prototypes of catalyst for removal of hydrogen. In particular by using a porous grid cover to remove excess heat in the reaction zone of the catalyst plate we achieved a considerable expansion of the region of hydrogen concentrations where the catalyst is both effective and reliable.

We use a detailed solid oxide fuel cell (SOFC) model for micro-grid applications to analyze the effect of failure and degradation on system performance. Design and operational constraints on a component and system level are presented. A degrees of freedom analysis identifies controlled and manipulated system variables which are important for control. Experimental data are included to model complex degradation phenomena of the SOFC unit. Rather than using a constant value a spatially distributed degradation rate as function of temperature and current density is used that allows to study trajectory based performance deterioration. The SOFC unit is assumed to consist of multiple stacks. The failure scenario studied is the loss of one individual SOFC stack e.g. due to breakage of sealing or a series of fuel cells. Simulations reveal that degradation leads to significant drifts from the design operating point. Moreover failure of individual stacks may bring the still operating power generation unit into a regime where further failures and accelerated degradation is more likely. It is shown that system design dimensioning operation and control are strongly linked. Apart from specific quantitative results perhaps the main practical contribution are the collected constraints and the degrees of freedom analysis.

This paper describes hydrogen self-ignition as a result of the formation of a shock wave in front of a high-pressure hydrogen gas propagating in the tube and the semi-confined space for which the numerical and experimental investigation was done. An increase in the temperature behind the shock wave leads to the ignition on the contact surface of the mixture of combustible gas with air. The required condition of combustible self-ignition is to maintain the high temperature in the mixture for a time long enough for inflammation to take place. Experimental technique was based on a high-pressure chamber inflating with hydrogen burst disk failure and pressurized hydrogen discharge into tube of round or rectangular cross section filled with air. A physicochemical model involving the gas dynamic transport of a viscous gas the detailed kinetics of hydrogen oxidation k-ω differential turbulence model and the heat exchange was used for calculations of the self-ignition of high-pressure hydrogen. The results of our experiments and model calculations show that self-ignition in the emitted jet takes place. The stable development of self-ignition naturally depends on the orifice size and the pressure in the vessel a decrease in which leads to the collapse of the ignition process. The critical conditions are obtained.

The effect of hydrogen on tensile behavior and fracture mechanisms of V-alloying and V-free high-nitrogen austenitic steels was evaluated. Two steels with the chemical compositions of Fe-23Cr–17Mn–0.1C–0.6N (0V-HNS) and Fe-19Cr–22Mn–1.5V–0.3C–0.9N (1.5V-HNS) were electrochemically hydrogen-charged in NaCl water-solution for 100 hours. According to X-ray diffraction analysis and TEM researches V-alloying promotes particle strengthening of the 1.5V-HNS. Despite differences in chemical compositions namely carbon and nitrogen concentrations a solid solution hardening is similar for both steels because of precipitate-assisted depletion of austenite by interstitial atoms (carbon and nitrogen) in 1.5V-HNS. For hydrogen-free state the values of the yield stress and the tensile strength are higher for particle-strengthened 1.5V-HNS as compared to 0V-HNS. Hydrogen-charging increases both the yield stress and the tensile strength of the steels but hydrogen-assisted fracture micromechanisms are different for 0V-HNS and 1.5V-HNS. Hydrogen-charging drastically reduces a total elongation in 0V-HNS but provides insufficient embrittlement in 1.5V-HNS. Hydrogen-assisted brittle layers form on lateral surfaces of the specimens and the widths and fracture micromechanisms in them are different for two steels. For 0V-HNS surface layers of 84 μm in width possess transgranular brittle fracture mechanism (quasi-cleavage mode). For 1.5V-HNS the brittle surface layers (31 μm width) destroy in intergranular brittle fracture mode. The central parts of steel specimens show dimple fracture similar to hydrogen-free steels. The possible reasons for different hydrogen-induced effects in 0V-HNS and 1.5V-HNS are discussed.

Hydrogen embrittlement has been intensively studied in the past. However its governing mechanism is still under debate. Particularly the details of the formation of specific cleavage-like or quasi-cleavage fracture surfaces related to hydrogen embrittled steels are unclear yet. Recently it has been found that the fracture surface of the hydrogen charged and tensile tested low-carbon steel exhibits quasi-cleavage facets having specific smoothly curved surface which is completely different from common flat cleavage facets. In the present contribution we endeavor to shed light on the origin of such facets. For this purpose the notched flat specimens of the commercial low carbon steel were tensile tested using ex- and in-situ hydrogen charging. It is found that in the ex-situ hydrogen charged specimens the cracks originate primarily inside the specimen bulk and expand radially form the origin to the specimen surface. This process results in formation of “fisheyes” – the round-shape areas with the surface composed of curved quasi-cleavage facets. In contrast during tensile testing with in-situ hydrogen charging the cracks initiate from the surface and propagate to the bulk. This process results in the formation of the completely brittle fracture surface with the quasi-cleavage morphology - the same as that in fisheyes. The examination of the side surface of the in-situ hydrogen charged specimens revealed the straight and S-shaped sharp cracks which path is visually independent of the microstructure and crystallography but is strongly affected by the local stress fields. Nano-voids are readily found at the tips of these cracks. It is concluded that the growth of such cracks occurs by the nano-void coalescence mechanism and is responsible for the formation of fisheyes and smoothly curved quasi-cleavage facets in hydrogen charged low-carbon steel.