Correlation between susceptibility to environment-assisted cracking of super-elastic TiNi alloy and the states and their amount of hydrogen in it

Susceptibility to environment-assisted cracking (EAC) of super-elastic TiNi alloy has been correlated with the states and their amount of hydrogen in the material. The TiNi alloy specimen was immersed in sulfate solutions at a given pH, and a giving cathodic potential was applied to it for 13 ks to absorb hydrogen into it. The specimen was subjected to X-ray diffraction (XRD) test to detect hydride, and to thermal gas desorption spectroscopy (TDS) test to determine the state and its amount of hydrogen in it. In the case that a potential of -0.5 VAg/AgCl was applied to the specimen in the solution of pH 3, the XRD detected no hydride on it. Whereas, application of -1.5 VAg/AgCl was induced formation of hydride. The TDS indicated that the specimen treated at -0.5 VAg/AgCl involved hydrogen desorbing around 810 K, and the one at -1.5 VAg/AgCl involved hydrogen desorbing around 500 as well as 810 K. Therefore, it was suggested that the hydrogen desorbing at lower and higher temperatures obtained by the TDS were of hydride state and solid-solution state, respectively. The specimens treated under various conditions were analyzed by the same way as mentioned before, and an amount of the hydrogen in each state as well as a cathodic charge density applied to the specimen were obtained to be correlated. A logarithm of the amount of the hydrogen in the each state increased almost linearly with an increase in a logarithm of a charge density. Susceptibility to the EAC of the material suddenly increased around a charge density of 0.025 MC·m-2, and the charge density was considered to induce the amounts of hydrogens in hydride and solid-solution state of 10 and 100 mass ppm, respectively.

The State of Hydrogen Desorbing from Intermediates Formed by Ammonia Interaction with Tungsten Surfaces

Ammonia interaction with a tungsten surface can generate dense adlayers containing nitrogen and hydrogen, i.e. an η-species of surface stoichiometry Ws2N3H. In thermal desorption mass spectrometry experiments, hydrogen desorbing from the η-species interacts with the glass wall in a manner similar to that previously observed for atomic hydrogen. This paper describes two mass spectrometric techniques designed to confirm this conclusion directly. The first method uses a line-of-sight geometry between the tungsten filament and the ionization source of the mass spectrometer and the results indicate that, at least, part of the hydrogen desorbing from the η-species does so atomically. In the second method a multiple wall collision geometry is used but prior saturation of the wall with D atoms will result in an HD+ ion current for desorbing H atoms. The results suggest that 26% of the hydrogen desorbs atomically. Hydrogen atom desorption from the η-species occurs at tungsten filament temperatures below those required for hydrogen atom evaporation from a pure hydrogen adlayer. It is proposed that a reduced binding energy for adsorbed hydrogen atoms and a reduced mobility of these adatoms arises from the presence of a large surface concentration of nitrogen. This will result in the rates of atomic hydrogen desorption and bimolecular recombination becoming comparable at temperatures lower than is the case for pure hydrogen interaction with tungsten. The implications of these results for the ammonia synthesis reaction are discussed.