Thermodynamics, stress release and hysteresis behavior in highly adhesive Pd-H films

We investigate the role of clamping on the thermodynamics of highly adhesive metal hydride thin films. Using Pd as a model system, we add Ti as an intermediate adhesion layer to increase the interaction with the substrate. We show that Pd/Ti films remain clamped during (de-)hydrogenation while the stress release occurs by means of rearrangement and pile-up of the material. The compressive stress build-up reaches a value of about 1.5 GPa during hydrogen absorption. The enthalpy of hydride formation and decomposition, measured using Hydrogenography is found to decrease and increase by about 2.7 and 1.3 kJ/mol H-2 respectively, as compared to buckled Pd films. A simple model confirms that the change in the thermodynamics and the asymmetric expansion of the hysteresis correlate with the mechanical work needed to accommodate the stress induced plastic deformations in clamped Pd/Ti films during the (de-)hydrogenation cycle. Copyright (C) 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.