Structural Characterization of Metal Hydrides for Energy Applications

Hydrogen can be an unlimited source of clean energy for future because of its very high energy density compared to the conventional fuels like gasoline. An efficient and safer way of storing hydrogen is in metals and alloys as hydrides. Light metal hydrides, alanates and borohydrides have very good hydrogen storage capacity, but high operation temperatures hinder their application. Improvement of thermodynamic properties of these hydrides is important for their commercial use as a source of energy. Application of pressure on materials can have influence on their properties favoring hydrogen storage. Hydrogen desorption in many complex hydrides occurs above the transition temperature. Therefore, it is important to study the physical properties of the hydride compounds at ambient and high pressure and/or high temperature conditions, which can assist in the design of suitable storage materials with desired thermodynamic properties. ^ The high pressure-temperature phase diagram, thermal expansion and compressibility have only been evaluated for a limited number of hydrides so far. This situation serves as a main motivation for studying such properties of a number of technologically important hydrides. Focus of this dissertation was on X-ray diffraction and Raman spectroscopy studies of Mg2FeH6, Ca(BH4) 2, Mg(BH4)2, NaBH4, NaAlH4, LiAlH4, LiNH2BH3 and mixture of MgH 2 with AlH3 or Si, at different conditions of pressure and temperature, to obtain their bulk modulus and thermal expansion coefficient. These data are potential source of information regarding inter-atomic forces and also serve as a basis for developing theoretical models. Some high pressure phases were identified for the complex hydrides in this study which may have better hydrogen storage properties than the ambient phase. The results showed that the highly compressible B-H or Al-H bonds and the associated bond disordering under pressure is responsible for phase transitions observed in brorohydrides or alanates. Complex hydrides exhibited very high compressibility suggesting possibility to destabilize them with pressure. With high capacity and favorable thermodynamics, complex hydrides are suitable for reversible storage. Further studies are required to overcome the kinetic barriers in complex hydrides by catalytic addition. A comparative study of the hydride properties with that of the constituting metal, and their inter relationships were carried out with many interesting features.^

Effects of climate variability on transparency and thermal structure in subtropical, monomictic Lake Annie, Florida

Lake Annie is a small (37 ha), relatively deep (21 m) sinkhole lake on the Lake Wales Ridge (LWR) of central Florida with a long history of study, including monthly limnological monitoring since June, 1983. The record shows high variability in Secchi disc transparency, which ranged from < 1 to 15 m with a trend toward decreasing values over the latter decade of record. We examined available regional meteorological, groundwater and limnological data to determine the drivers and thermal consequences of variability in water transparency. While total nutrient concentrations and chlorophyll-a were highest during years of low transparency, stepwise regression showed that none of these had a signifi cant effect on transparency after water color was taken into account. Repeated years of high precipitation between 1993–2005 caused an increase in water table height, increasing the transport of dissolved substances from the vegetated watershed into the lake. Groundwater stage explained 73 % of the interannual variability in water transparency. Transparency, in turn, explained 85 % of the interannual variability in the heat budget for the lake, which ranged from 1.8 × 108 to 4.1 × 108 Joules m–2 yr–1, encompassing the range reported across Florida lakes. While surface water temperature was not affected by transparency, depths below 5 m warmed faster during the stratifi ed period during years having a lower rate of light extinction. We show that an increase in precipitation of 20 cm per year reduces the depth of the summer euphotic zone and thermocline by 1.9 and 1.6 m, respectively, and causes a 1-month reduction in the duration of winter mixing in this monomictic lake. Because biota have been shown to respond to shifts in light and heat distribution of much smaller magnitude than exhibited here, our work suggests that subtle changes in precipitation linked to climate fl uctuations may have signifi cant physical as well as biotic consequences.