Nanocrystalline titanium films of different thicknesses, sputtered on sapphire substrates, were charged electrochemically with hydrogen. Hydrogen absorption and the thermodynamics of the nanocrystalline Ti-H thin film system were studied using electromotive force (EMF) measurements. The phase boundaries obtained from the EMF-pressure-concentration curves were confirmed by X-ray dif-fraction, complemented by in situ stress measurements during hydrogen charging. The change in the stress increase with hydrogen con-centration was found to be in good agreement with the obtained phase boundaries. In comparison to bulk Ti-H system, considerable changes, such as shifted phase boundaries, and narrowed and sloped miscibility gaps, were observed in Ti-H thin films. These changes vary among the films of different crystalline orientation and are attributed to both microstructural effects and stress contributions, The influence of the initial crystallographic growth orientation of Ti films on the measured thermodynamic isotherms, phase transitions and stress development is discussed in detail.
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