Study of the physical properties of metals and oxides at extreme pressure and temperature conditions

The high-pressure and temperature investigations on transition metals, metal doped-oxide system, nanocrystalline materials are presented in this dissertation. The metal-doped oxide systems are technologically important because of their applications, e.g. LSC, opto electronic applications, luminescence from lasers, etc., and from the earth sciences point of view, e.g. the study of trace elements in the MgO-SiO2 system, which accounts for 50% of the Earth's chondritic model. We have carried out thorough investigations on Cr2O3 and on chromium bearing oxides at high PT-conditions using in situ X-ray diffractometry and florescence spectroscopy techniques. Having obtained exciting results, an attempt to focus on the mechanism of the coordination of transition metals in oxides has been made. Additionally, the florescence from the metals in host oxides was found to be helpful to obtain information on structural variations like changes in the coordination of the doped element, formation of new phases, the diffusion processes. The possible reactions taking place at extreme conditions in the MgO-SiO2 system has been observed using florescence as markers. A new heating assemblage has been designed and fabricated for a precise determination of temperature at high pressures. An equation combining pressure shifts of ruby wavelength and temperature has been proposed. We observed that the compressibility of nanocrystalline material (MgO and Ni) is independent of crystallite size. A reduction in the transition pressure of nanocrystalline ceria at high-pressure has been observed as compare to the corresponding bulk material. ^

Sources of metals and sulfur in the mineral deposits of central Idaho, USA

A variety of mineral deposits occur in the Paleozoic sedimentary rocks and Late Cretaceous granitic rocks of central Idaho. The main objective of this project is to identify the sources of metals and sulfur in central Idaho ores. Lead isotope compositions of various crustal rocks were determined and compared with the ore lead composition in order to trace sources of lead, and by inference other metals. Sulfur isotope compositions of various sulfide minerals were also determined to trace the sources of sulfur and to explore the coupling or decoupling of metal and sulfur sources. ^ On the basis of lead and sulfur isotope compositions, two groups of ores are recognized: a sedimentary group and an igneous group. The sedimentary group ores are characterized by radiogenic lead and heavy sulfur typical of upper crustal rocks. The sedimentary group ores were formed by meteoric water-dominated hydrothermal systems that leached metals and sulfur from host Paleozoic sedimentary rocks and the underlying Precambrian crystalline basement rocks. The igneous group ores can be divided into two types, the Carrietown-type, and the non Carrietown-type. The Carrietown-type ores are isotopically different from their host granites and are characterized by low uranogenic lead isotope ratios (206Pb/204Pb and 207Pb/ 204Pb) and variable thorogenic lead isotope ratios (208Pb/ 204Pb) typical of lower crustal rocks. The non Carrietown-type ores are similar to host granites and are more radiogenic in their uranogenic lead isotope ratios when compared to the Carrietown-type ores. The differences in the lead isotope compositions of the igneous group ores are attributed to two different phases of magmatic activity. The magmatic phase exposed on the surface involved melting of shallow crustal Precambrian crystalline rocks as well as mid/lower crustal rocks while the underlying phase was derived by melting of mid/lower crustal rocks only. Igneous group ores have both light and heavy sulfur associated with them and it is a function of interaction of hydrothermal fluids with Paleozoic sedimentary rocks. ^ Paleozoic sedimentary rocks and Precambrian basement rocks are the sources of radiogenic lead, and the granites are the sources of light sulfur. Heavy sulfur comes almost entirely from Paleozoic sedimentary rocks. ^

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.^

Synthesis, characterization and study of physical properties of novel M(n+1)AX(n) compounds

Mn+1AXn compounds, the ternary layered nanolaminates have gathered momentum in the last decade since its advent because of their unusual but exciting properties. These technologically important compounds combine some of the best properties of metals and ceramics. Like ceramics they are refractory, oxidation resistant, elastically stiff and relatively light. They also exhibit metallic properties like excellent machinability, thermal and electrical conductivity. This dissertation concentrates on the synthesis of germanium-based 211 Mn+1AXn compounds. The main objective of the research was to synthesize predominantly single phase samples of Cr2GeC, V2GeC and Ti2GeC. Another goal was to study the effect of solid substitutions on the M-site of Mn+1AXn compounds with Ge as an A-element. This study is in itself the first to demonstrate the synthesis of (Cr0.5V0.5)2GeC a novel Mn+1AXn compound. Scanning electron microscopy coupled with energy dispersive spectroscopy, x-ray diffraction and electron probe microanalysis were employed to confirm the presence of predominantly single phase samples of M2GeC compounds where M = Ti, V, Cr and (Cr 0.5V0.5). A large part of the dissertation also focuses on the effect of the compressibility on the Ge-based 211 Mn+1AXn compounds with the aid of diamond anvil cell and high energy synchrotron radiation. This study also concentrates on the stability of these compounds at high temperature and thereby determines its suitability as high temperature structural materials. In order to better understand the effect of substitutions on A-site of 211 Mn+1 AXn compounds under high pressure and high temperature, a comparison is made with previously reported 211 Mn+1AXn compounds with Al, Ga and S as A-site elements.

Exploring thermal and mechanical properties of selected transition elements under extreme conditions: Experiments at high pressures and high temperatures

Transition metals (Ti, Zr, Hf, Mo, W, V, Nb, Ta, Pd, Pt, Cu, Ag, and Au) are essential building units of many materials and have important industrial applications. Therefore, it is important to understand their thermal and physical behavior when they are subjected to extreme conditions of pressure and temperature. This dissertation presents: • An improved experimental technique to use lasers for the measurement of thermal conductivity of materials under conditions of very high pressure (P, up to 50 GPa) and temperature (T up to 2500 K). • An experimental study of the phase relationship and physical properties of selected transition metals, which revealed new and unexpected physical effects of thermal conductivity in Zr, and Hf under high P-T. • New phase diagrams created for Hf, Ti and Zr from experimental data. • P-T dependence of the lattice parameters in α-hafnium. Contrary to prior reports, the α-ω phase transition in hafnium has a negative dT/dP slope. • New data on thermodynamic and physical properties of several transition metals and their respective high P-T phase diagrams. • First complete thermodynamic database for solid phases of 13 common transition metals was created. This database has: All the thermochemical data on these elements in their standard state (mostly available and compiled); All the equations of state (EoS) formulated from pressure-volume-temperature data (measured as a part of this study and from literature); Complete thermodynamic data for selected elements from standard to extreme conditions. The thermodynamic database provided by this study can be used with available thermodynamic software to calculate all thermophysical properties and phase diagrams at high P-T conditions. For readers who do not have access to this software, tabulated values of all thermodynamic and volume data for the 13 metals at high P-T are included in the APPENDIX. In the APPENDIX, a description of several other high-pressure studies of selected oxide systems is also included. Thermophysical properties (Cp, H, S, G) of the high P-T ω-phase of Ti, Zr and Hf were determined during the optimization of the EoS parameters and are presented in this study for the first time. These results should have important implications in understanding hexagonal-close-packed to simple-hexagonal phase transitions in transition metals and other materials.

Risk based post closure care analysis for Florida landfills

Subtitle D of the Resource Conservation and Recovery Act (RCRA) requires a post closure period of 30 years for non hazardous wastes in landfills. Post closure care (PCC) activities under Subtitle D include leachate collection and treatment, groundwater monitoring, inspection and maintenance of the final cover, and monitoring to ensure that landfill gas does not migrate off site or into on site buildings. The decision to reduce PCC duration requires exploration of a performance based methodology to Florida landfills. PCC should be based on whether the landfill is a threat to human health or the environment. Historically no risk based procedure has been available to establish an early end to PCC. Landfill stability depends on a number of factors that include variables that relate to operations both before and after the closure of a landfill cell. Therefore, PCC decisions should be based on location specific factors, operational factors, design factors, post closure performance, end use, and risk analysis. The question of appropriate PCC period for Florida’s landfills requires in depth case studies focusing on the analysis of the performance data from closed landfills in Florida. Based on data availability, Davie Landfill was identified as case study site for a case by case analysis of landfill stability. The performance based PCC decision system developed by Geosyntec Consultants was used for the assessment of site conditions to project PCC needs. The available data for leachate and gas quantity and quality, ground water quality, and cap conditions were evaluated. The quality and quantity data for leachate and gas were analyzed to project the levels of pollutants in leachate and groundwater in reference to maximum contaminant level (MCL). In addition, the projected amount of gas quantity was estimated. A set of contaminants (including metals and organics) were identified as contaminants detected in groundwater for health risk assessment. These contaminants were selected based on their detection frequency and levels in leachate and ground water; and their historical and projected trends. During the evaluations a range of discrepancies and problems that related to the collection and documentation were encountered and possible solutions made. Based on the results of PCC performance integrated with risk assessment, projection of future PCC monitoring needs and sustainable waste management options were identified. According to these results, landfill gas monitoring can be terminated, leachate and groundwater monitoring for parameters above MCL and surveying of the cap integrity should be continued. The parameters which cause longer monitoring periods can be eliminated for the future sustainable landfills. As a conclusion, 30 year PCC period can be reduced for some of the landfill components based on their potential impacts to human health and environment (HH&E).

Risk Based Post Closure Care Analysis for Florida Landfills

Subtitle D of the Resource Conservation and Recovery Act (RCRA) requires a post closure period of 30 years for non hazardous wastes in landfills. Post closure care (PCC) activities under Subtitle D include leachate collection and treatment, groundwater monitoring, inspection and maintenance of the final cover, and monitoring to ensure that landfill gas does not migrate off site or into on site buildings. The decision to reduce PCC duration requires exploration of a performance based methodology to Florida landfills. PCC should be based on whether the landfill is a threat to human health or the environment. Historically no risk based procedure has been available to establish an early end to PCC. Landfill stability depends on a number of factors that include variables that relate to operations both before and after the closure of a landfill cell. Therefore, PCC decisions should be based on location specific factors, operational factors, design factors, post closure performance, end use, and risk analysis. The question of appropriate PCC period for Florida’s landfills requires in depth case studies focusing on the analysis of the performance data from closed landfills in Florida. Based on data availability, Davie Landfill was identified as case study site for a case by case analysis of landfill stability. The performance based PCC decision system developed by Geosyntec Consultants was used for the assessment of site conditions to project PCC needs. The available data for leachate and gas quantity and quality, ground water quality, and cap conditions were evaluated. The quality and quantity data for leachate and gas were analyzed to project the levels of pollutants in leachate and groundwater in reference to maximum contaminant level (MCL). In addition, the projected amount of gas quantity was estimated. A set of contaminants (including metals and organics) were identified as contaminants detected in groundwater for health risk assessment. These contaminants were selected based on their detection frequency and levels in leachate and ground water; and their historical and projected trends. During the evaluations a range of discrepancies and problems that related to the collection and documentation were encountered and possible solutions made. Based on the results of PCC performance integrated with risk assessment, projection of future PCC monitoring needs and sustainable waste management options were identified. According to these results, landfill gas monitoring can be terminated, leachate and groundwater monitoring for parameters above MCL and surveying of the cap integrity should be continued. The parameters which cause longer monitoring periods can be eliminated for the future sustainable landfills. As a conclusion, 30 year PCC period can be reduced for some of the landfill components based on their potential impacts to human health and environment (HH&E).