Environmentally assisted cracking in the low pressure superheated hydrogen steam

Low pressure superheated H2-steam appears to be an interesting alternative to pressurized water environments, since it is capable of performing accelerated environmentally assisted cracking (EAC) experiments for nickel base and stainless steel alloys. Constant Extension Rate Tensile (CERT) tests were performed with displacement rates of 2×10-6 or 2×10-8 ms-1 at 350, 400, 440 and 480 °C on flat tapered specimens of Type 316L austenitic stainless steel. The tapered shape allows the determination of crack initiation over a range of stresses and strains simultaneously on one specimen and therefore the threshold stress value was obtained. The environment was 6 times more oxidizing than the dissociation pressure of NiO. The acquired mechanical properties are summarized and threshold stresses for EAC crack initiation are evaluated.

Exploring the Hydrogen-Induced Amorphization and Hydrogen Storage Reversibility of Y(Sc)0.95Ni2 Laves Phase Compounds

Rare-earth-based AB2-type compounds with Laves phase structure are readily subject to hydrogen-induced amorphization and disproportionation upon hydrogenation. In this work, we conducted the Sc alloying on Y0.95Ni2 to improve its hydrogen storage properties. The results show that the amorphization degree of Y0.95Ni2 deepens with the increasing hydrogenation time, pressure, and temperature. The Y(Sc)0.95Ni2 ternary compounds show a significant improvement in reversibility and dehydriding thermodynamics due to the reduced atomic radius ratio RA/RB and cell volume. Hydrogen-induced amorphization is fully eliminated in the Y0.25Sc0.7Ni2. The Y0.25Sc0.7Ni2 delivers a reversible hydrogen storage capacity of 0.94 wt.% and the dissociation pressure of 0.095 MPa at the minimum dehydrogenation temperature of 100 °C.

Modeling Dissociation Pressure of Semi-Clathrate Hydrate Systems Containing CO2, CH4, N2, and H2S in the Presence of Tetra-n-butyl Ammonium Bromide

In this study, the phase equilibria of semi-clathrate hydrates of methane (CH4), carbon dioxide (CO2), nitrogen (N2), and hydrogen sulfide (H2S) in an aqueous solution of tetra-n-butyl ammonium bromide (TBAB) were modeled using a correlation based on a two-stage formation mechanism: a quasi-chemical reaction that forms basic semi-clathrate hydrates and adsorption of guest molecules in the linked cavities of the basic semi-clathrate hydrate. The adsorption of guest molecules was described by the Langmuir adsorption theory and the fugacity of the gas phase was calculated by Peng–Robinson (PR) equation of state (EOS). The water activity in the presence of TBAB was calculated using a correlation, dependent on temperature, the TBAB mass fraction, and the nature of the guest molecule. These equations were coupled together and form a correlation which was linked to a genetic algorithm for optimization of tuning parameters. The results showed an excellent agreement between model results and experimental data. In addition, an outlier diagnostic was performed for finding any possible doubtful data and assessing the applicability of the model. The results showed that more than 97 % of the data were reliable and they were in the applicability domain of the model.

Thermochemistry of MgCr2O4, MgAl2O4, MgFe2O4 spinels in SO2−O2−SO3 atmosphere

The present paper investigates high-temperature sulphate corrosion of basic refractory ceramics containing magnesium spinels (MgAl2O4, MgFe2O4, MgCr2O4 and their solid solutions) widely used in metallurgy, chemical, ceramic and glass industry. This group of refractories are exposed to a number of destructive factors during a working campaign. One of such factors is gas corrosion caused by sulphur oxides. However, gas sulphate corrosion of basic refractory materials containing magnesium spinels, which has a great practical meaning for the corrosion resistance of the material main components, is not sufficiently examined. This work presents a thermodynamic analysis of (MgCr2O4, MgAl2O4, MgFe2O4)?SO2?O2?SO3 system aimed to calculate: i) the standard free enthalpy of chemical reactions, ii) the equilibrium composition of the gas mixture initially containing SO2 and O2 and iii) sulphates equilibrium dissociation pressure and equilibrium partial pressure for the reaction of SO3 with the spinels to predict the temperature range of corrosion products? stability. A thermochemical calculation provides information about equilibrium state in the analysed system. In real conditions the state of equilibrium does not have to be achieved. For this reason, the results of calculations were compared with experimental data. The experiment results were consistent with the theoretical predictions.

Effect of some Sulphur Additives on the Degradation of 9Cr-1Mo Steel after its 10 Years Service in the CCR Platforming Unit

The work shows the results of the tests of 9Cr-1Mo steel, which was for 10 years operated in the CCR platforming unit in Group Lotos SA in Gdańsk, and then in the laboratory was sulphidised during 166 h at a temperature of 600 °C. Sulphidation was performed in a mixture of H2-H2S gases at the vapour pressure of sulphur 4.1·10-14 atm, so the order of magnitude of vapour pressure was less than that of the dissociation pressure of FeS. Although sulphidising took place in conditions which preclude any iron sulphide formation, research results have demonstrated that after 166 hour exposure in reaction mixture in 9Cr-1Mo steel produces iron and chromium sulfides. Sulphide precipitates form under a layer of fine carbides, located directly on the surface of steel. Formation of scale sulphide here is most likely caused by the penetration of hydrogen sulphide through the porous layer of carbides that increases the pressure of hydrogen sulphide. Thus the vapour of sulphur in apertures and narrow passages occurs between the layer of carbides and the rest of oversaturated carbon layer top, until its pressure value is reached allowing the formation of sulphide scaling.