Publications

It has been investigated the Ni-Co alloys (obtained from powder 0.1...0.3 mm under hot gaseous (in argon) isostatic pressure (up to 300 MPa) (Ni60Co15Cr8W8Al2Mo3) (Firth Rixon Metal Ltd Sheffield) and deformed (obtained by vacuum induced remealting) materials (Ni62Cr14Co10Mo5Nb3Al3Ti3) for gaseous turbine discs. Investigation has performed in the range of temperature 25…800°С and hydrogen pressure up to 70 MPa. By the 3D visualization of crack morphology it has been discovered the structure of fatigue crack surface and established the refer points on crack path including the boundary between the matrix and intermetallic particles (400×200 μm) crack opening structural elements distributions on the surface for selection of next local areas for more precision fracture surface and TEM examinations. Hydrogen influence on cyclic crack resistance parameters appears in the decreasing of loading cycles number (with amplitudes 15 MPa) in hydrogenated specimens of both alloys and increase with hydrogen concentration. At the highest hydrogen saturation regimes of Ni60Co15Cr8W8Al2Mo3 alloy (800°С 35 MPa Н2 36 hours С_Н = 32.7 ppm) number of cycles which necessary for crack initiation is 3 times less in comparison with specimen in initial state. At crack initiation step in hydrogenated Ni56Cr14Co15Mo5Al3Ti3 alloy it has been established that before intermetallic inclusion (400×200 μm) local stresses increased after its passing – has decreased. By fracture surface investigation it has been found the micro cracks up to 40 μm. Thin structure of heat resistant superalloys has characterises by disperse phase agglomeration with dimensions from 5 to 30 nm and crack propagation has a jumping character with no less then 50…70 nm steps.

Operating chemical looping process at mid-temperatures (550-750 oC) presents exciting potential for the stable production of hydrogen. However the reactivity of oxygen carriers is compromised by the detrimental effect of the relatively low temperatures on the redox kinetics. Although the reactivity at mid-temperature can be improved by the addition of noble metals the high cost of these noble metal containing materials significantly hindered their scalable application. In the current work we propose to incorporate earth-abundant metals into the iron-based spinel for hydrogen production in a chemical looping scheme at mid-temperatures. Mn0.2Co0.4Fe2.4O4 shows a high hydrogen production rate at the average rate of ∼0.62 mmol.g-1.min-1 and a hydrogen yield of ∼9.29 mmol.g-1 with satisfactory stability over 20 cycles at 550 oC. The mechanism studies manifest that the enhanced hydrogen production performance is a result of the improved oxygen-ion conductivity to enhance reduction reaction and high reactivity of reduced samples with steam. The performance of the oxygen carriers in this work is comparable to those noble-metal containing materials enabling their potential for industrial applications.

We evaluated the strain rate sensitivity of the micro-damage evolution behavior in a ferrite/martensite dual-phase steel. The micro-damage evolution behavior can be divided into three regimes: damage incubation damage arrest and damage growth. All regimes are associated with local deformability. Thus the total elongation of DP steels is determined by a combination of plastic damage initiation resistance and damage growth arrestability. This fact implies that hydrogen must have a critical effect on the damage evolution because hydrogen enhances strain localization and lowers crack resistance. In this context the strain rate must be an important factor because it affects the time for microstructural hydrogen diffusion/segregation at a specific microstructural location or at the damage tip. In this study tensile tests were carried out on a DP steel with different strain rates of 10^{− 2} and 10^{− 4} s⁻¹. We performed the damage quantification microstructure characterization and fractography. Specifically the quantitative data of the damage evolution was analyzed using the classification of the damage evolution regimes in order to separately elucidate the effects of the hydrogen on damage initiation resistance and damage arrestability. In this study we obtained the following conclusions with respect to the strain rate. Lowering the strain rate increased the damage nucleation rate at martensite and reduced the critical strain for fracture through shortening the damage arrest regime. However the failure occurred via ductile modes regardless of strain rate.

The role of hydrogen in fatigue failure of low strength steels is not as well understood as of high strength steels in very high cycle fatigue regime. In this work axially cyclic tests on a low strength Cr-Ni-Mo-V steel with charged hydrogen were carried out up to the very high cycle fatigue regime under ultrasonic frequency to examine the degradation of fatigue strength and associated failure mechanisms. Results show that the S-N curves show a continuously decreasing mode and hydrogen-charged specimens have lower fatigue strength and shorter fatigue lifetime as compared with as-received specimens. It is concluded that the hydrogen trapped by inclusions drives interior micro-defects as dominant crack initiation site and has a clear link to the initiation and early growth of interior fatigue cracks.

This paper reviews previous research by the author in the field of hydrogen effects on progressively cold-drawn pearlitic steels in terms of hydrogen degradation (HD) hydrogen embrittlement (HE) or at the micro-level hydrogen-assisted micro-damage (HAMD) thus affecting their microstructural integrity and compromising the (macro-)structural integrity of civil engineering structures such as prestressed concrete bridges. It is seen that hydrogen effects in pearlitic microstructure (either oriented or not) are produced at the finest micro-level by plastic tearing in the form in general of hydrogen damage topography (HDT) with different appearances depending of the cold drawing degree evolving from the so-called tearing topography surface (TTS) in hot-rolled (not cold-drawn at all) or slightly cold-drawn pearlitic steels to a sort of enlarged and oriented TTS (EOTTS) in heavily drawn steels (the pronounced enlargement and marked orientation being along the wire axis or cold drawing direction). Whereas the pure TTS mode (null or low degree of cold drawing) resembles the Michelangello stone sculpture texture (MSST) the EOTTS mode does the same in relation to the Donatello wooden sculpture texture (DWST).

The aim of this study is to provide a quantification of the internal pressure contribution to the SSRT properties of H-charged Type-316L steel tested in air at room temperature. Considering pre-existing penny-shaped voids the transient pressure build-up has been simulated as well as its impact on the void growth by preforming JIc calculations. Several void distributions (size and spacing) have been considered. Simulations have concluded that there was no impact of the internal pressure on the void growth regardless the void distribution since the effective pressure was on the order of 1 MPa during the SSRT test. Even if fast hydrogen diffusion related to dislocation pipe-diffusion has been assessed as a conservative case the impact on void growth was barely imperceptible (or significantly low). The effect of internal pressure has been experimentally verified via the following conditions: (I) non-charged in vacuum; (II) H-charged in vacuum; (III) H-charged in 115-MPa nitrogen gas; (IV) non-charged in 115-MPa nitrogen gas. As a result the relative reduction in area (RRA) was 0.84 for (II) 0.88 for (III) and 1.01 for (IV) respectively. The difference in void morphology of the H-charged specimens did not depend on the presence of external pressure. These experimental results demonstrate that the internal pressure had no effect on the tensile ductility and void morphology of the H-charged specimen.

Lamination-like defects in pipeline steels can be of both metallurgical and operational origin. In pipelines transporting hydrocarbon usually such defects are not a big challenge since they do not propagate under operating conditions. Nonetheless in presence of a corrosion phenomenon and sour gas (H2S) it is possible to observe blisters and cracks which may propagate in the steel. The observed damage mechanisms is Hydrogen Embrittlement and in spite of a huge amount of study and publications available it is quite difficult for a pipeline owner to get practical data (crack propagation rate for instance) allowing a reliable estimate of the fitness for service of a pipeline. Taking advantage of a pipeline spool containing internal defects that was in service for more than 10 years and recently removed a comprehensive study is underway to obtain a complete assessment of the pipeline future integrity. The program is comprehensive of study and comparison of ILI reports of the pipeline to determine the optimum interval between inspections assessment of inspection results via an accurate nondestructive (UT) and destructive examination of the removed section to verify ILI results lab tests program on specimens from the removed spool at operating conditions (75-80 bar and 30°-36° C) in presence of a small quantity of water H2S (5%) and CO2 (7%) in order to assess defect propagation and to obtain an estimate of crack growth rate and test in field of available methods to monitor the presence of Hydrogen and/or the growth of defects in in-service pipelines. This quite ambitious program is also expected to be able of offering a small contribution toward a better understanding of HE mechanisms and the engineering application of such complex often mainly academic studies.

This paper addresses the size and misorientation effects on hydrogen embrittlement of a four grain nickel aggregate. The grain interior is modelled with orthotropic elasticity and the grain boundary with cohesive zone technique. The grain misorientation angle is parameterized by fixing the lower grains and rotating the upper grains about the out-of-plane axis. The hydrogen effect is accounted for via the three-step hydrogen informed cohesive zone simulation. The grain misorientation exerts an obvious weakening effect on the ultimate strength of the nickel aggregate which reaches its peak at misorientation angles around 20◦ but such effect becomes less pronounced in the case with a pre-crack. The misorientation could induce size effect in the otherwise size independent case without a pre-crack. The contribution of misorientation to the size effect is negligible compare to that caused by the existence of a pre-crack. These findings indicate that the misorientation effect in cases with a deep pre-crack is weaker than expected in shallow-pre-crack situations. Most of these conclusions hold for the hydrogen charging situation except that the ultimate strength is lowered in all the sub-cases due to hydrogen embrittlement. Interestingly it is observed that the size effect becomes less pronounced with hydrogen taken into account which is caused by the fact that hydrogen takes more time to reach the failure initiation site in larger grains.

Alkaline water electrolysis (AWE) is a mature hydrogen production technology and there exists a range of economic assessments for available technologies. For advanced AWEs which may be based on novel polymer-based membrane concepts it is of prime importance that development comes along with new configurations and technical and economic key process parameters for AWE that might be of interest for further economic assessments. This paper presents an advanced AWE technology referring to three different sites in Europe (Germany Austria and Spain). The focus is on financial metrics the projection of key performance parameters of advanced AWEs and further financial and tax parameters. For financial analysis from an investor’s (business) perspective a comprehensive assessment of a technology not only comprises cost analysis but also further financial analysis quantifying attractiveness and supply/market flexibility. Therefore based on cash flow (CF) analysis a comprehensible set of metrics may comprise levelised cost of energy or respectively levelized cost of hydrogen (LCH) for cost assessment net present value (NPV) for attractiveness analysis and variable cost (VC) for analysis of market flexibility. The German AWE site turns out to perform best in all three financial metrics (LCH NPV and VC). Though there are slight differences in investment cost and operation and maintenance cost projections for the three sites the major cost impact is due to the electricity cost. Although investment cost is slightly lower and labor cost is significantly lower in Spain the difference can not outweigh the higher electricity cost compared to Germany. Given the assumption that the electrolysis operators are customers directly and actively participating in power markets and based on the regulatory framework in the three countries in this special case electricity cost in Germany is lowest. However as electricity cost is profoundly influenced by political decisions as well as the implementation of economic instruments for transforming electricity systems toward sustainability it is hardly possible to further improve electricity price forecasts.

Duplex Stainless Steels (DSSs) are an attractive class of materials characterized by a strong corrosion resistance in many aggressive environments. Thanks to the high mechanical performances DSSs are widely used for many applications in petrochemical industry chemical and nuclear plants marine environment desalination etc.<br/>Among the DSSs critical aspects concerning the embrittlement process it is possible to remember the steel sensitization and the hydrogen embrittlement.<br/>The sensitization of the DSSs is due to the peculiar chemical composition of these grades which at high temperature are susceptible to carbide nitrides and second phases precipitation processes mainly at grains boundary and in the ferritic grains. The hydrogen embrittlement process is strongly influenced by the duplex (austenitic-ferritic) microstructure and by the loading conditions.<br/>In this work a rolled lean ferritic-austenitic DSS (2101) has been investigated in order to analyze the hydrogen embrittlement mechanisms by means of slow strain rate tensile tests considering the steel after different heat treatments. The damaging micromechanisms have been investigated by means of the scanning electron microscope observations on the fracture surfaces.