The defect structure of Fe(3+)-, Cu(2+)-, Mn(4+)- and Gd(3+)-doped PbTiO(3) nano-powders has been studied by electron paramagnetic resonance (EPR) spectroscopy. Analogous to the situation for 'bulk' ferroelectrics, Fe(3+) and Cu(2+) act as acceptor-type functional centers that form defect complexes with charge-compensating oxygen vacancies. The corresponding defect dipoles are aligned along the direction of spontaneous polarization, P(S), and possess an additional defect polarization, P(D). Upon the transition to the nano-regime, the defect structure is modified such that orientations perpendicular to P(S), [Formula: see text] and [Formula: see text] also become realized. Moreover, the binding energy for the defect complexes is lowered such that instead 'free' Fe'(Ti) and V··(O)-centers are formed. As a consequence, the concentration of mobile V··(O) that enhances the ionic conductivity through drift diffusion is increased for the nano-powders. Finally, in the nano-regime the ferroelectric 'hardening' is expected to be considerably decreased as compared to the 'bulk' compounds. In contrast to the acceptor-type dopants, the donor-type Gd(3+) dopant is incorporated as an 'isolated' functional center, where charge compensation by means of lead vacancies is performed in distant coordination spheres.
Abstract:As potential hydrogen storage media, magnesium based hydrides have been systematically studied in order to improve reversibility, storage capacity, kinetics and thermodynamics. The present article deals with the electrochemical and optical properties of Mg alloy hydrides. Electrochemical hydrogenation, compared to conventional gas phase hydrogen loading, provides precise control with only moderate reaction conditions. Interestingly, the alloy composition determines the crystallographic nature of the metalhydride: a structural change is induced from rutile to fluorite at 80 at.% of Mg in Mg-TM alloy, with ensuing improved hydrogen mobility and storage capacity. So far, 6 wt.% (equivalent to 1600 mAh/g) of reversibly stored hydrogen in Mg y TM (1-y) H x (TM: Sc, Ti) has been reported. Thin film forms of these metal-hydrides reveal interesting electrochromic properties as a function of hydrogen content. Optical switching occurs during (de)hydrogenation between the reflective metal and the transparent metal hydride states. The chronological sequence of the optical improvements in optically active metal hydrides starts with the rare earth systems (YH x ), followed by Mg rare earth alloy hydrides (Mg y Gd (1-y) H x ) and concludes with Mg transition metal hydrides (Mg y TM (1-y) H x ). In-situ optical characterization of gradient thin films during (de)hydrogenation, denoted as hydrogenography, enables the monitoring of alloy composition gradients simultaneously.
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