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.

The choice not to use computers: A case study of community college faculty who do not use computers in teaching

The primary purpose of this investigation is to study the motives of community college faculty who decide not to use computers in teaching. In spite of the fact that many of the environmental blocks that would otherwise inhibit the use of the computers have been eliminated at many institutions, many faculty do not use a computer beyond its word-processing function. For the purpose of the study non-adoption of computers in teaching is defined as not using computers for more than word-processing. ^ The issues in the literature focus on resistance and assume a pro-innovation and pro-adoption bias. Previous research on the questions is primarily surveys with narrowly focused assumptions. This qualitative research directly asks the participants about their feelings, beliefs, attitudes, experiences, and behaviors in regard to computers in teaching. Through the interview process a number of other correlated issues emerge. ^ The investigation was conducted at Miami-Dade Community College, a large urban multicampus institution, in Miami-Dade, Florida. It was conducted through a series of in-depth phenomenological interviews. There were nine interviews; eight within the profile; two were pilots; and one was an extreme opposite of the profile. Each participant was interviewed three times for about 45 minutes. ^ The results indicate that the computer conflicts with the participants' values in regard to their teaching and their beliefs in regard to the nature of knowledge, learning, and the relationship that they wish to maintain with students. Computers require significant changes in the values, beliefs, and consequent behaviors. These are changes that the participants are not willing to make without overwhelming evidence that they are worth the sacrifice. For the participants, this worth is only definable as it positively improves learning. For even the experts the evidence is not there. Unlike the innovator, the high end computer user, these participants are not willing to adopt the computer on faith. ^

The importance of marine subsidies for terrestrial consumers in coastal Peru

The Peruvian coast is one the best examples of cross-ecosystem food web exchanges, in which resources from one of the richest marine ecosystems subsidize consumers in one of the driest deserts on Earth. Marine subsidies are resources that originate in the marine ecosystem, and that contribute to increase the density of consumers in the recipient ecosystem. I examined the effects of marine subsidies on animal populations in the Peruvian coastal desert. ^ I combined several approaches to study the linkages between marine resources and terrestrial consumers, such as surveying the spatial distribution and estimating the relative abundance of terrestrial consumers, studying the diet of geckos and lizards through stomach content analyses, and examining the desert food web with carbon and nitrogen stable isotope analyses. ^ I found that the distribution and diet of desert consumers were tightly coupled to the availability of marine subsidies. I revealed linkages along two pathways of nutrient fluxes: tidal action that washes ashore macroalgae and cadavers of marine organisms, and animal transport in places where pinnipeds and seabirds congregate for reproduction. In the first pathway, intertidal algivivores made marine resources available to terrestrial consumers by moving between the intertidal and supratidal zone. The relative contribution of terrestrial and algal carbon sources varied among terrestrial consumers, because scorpions assimilated a lower proportion of energy from macroalgae than did geckos and solifuges. In the second pathway, I found that pinniped colonies influenced the diet of desert consumers, and contributed to support large populations of lizards and geckos. By combining field observations, and stomach and stable isotope analyses, I constructed a simplified food web for a large sea lion colony, showing the number of trophic levels that originate from pinniped-derived nutrients. ^ My study demonstrates the enormous importance of marine resources for the diet of desert consumers. The near absence of rainfall along the Peruvian coast promotes an extreme dependence of terrestrial consumers on marine resources, and causes permanent food web effects that are affected by temporal variability in marine productivity, rather then temporal patterns of desert plant growth. ^

Tracking rates of ecotone migration due to salt-water encroachment using fossil mollusks in coastal South Florida

We determined the rate of migration of coastal vegetation zones in response to salt-water encroachment through paleoecological analysis of mollusks in 36 sediment cores taken along transects perpendicular to the coast in a 5.5 km2 band of coastal wetlands in southeast Florida. Five vegetation zones, separated by distinct ecotones, included freshwater swamp forest, freshwater marsh, and dwarf, transitional and fringing mangrove forest. Vegetation composition, soil depth and organic matter content, porewater salinity and the contemporary mollusk community were determined at 226 sites to establish the salinity preferences of the mollusk fauna. Calibration models allowed accurate inference of salinity and vegetation type from fossil mollusk assemblages in chronologically calibrated sediments. Most sediments were shallow (20–130 cm) permitting coarse-scale temporal inferences for three zones: an upper peat layer (zone 1) representing the last 30–70 years, a mixed peat-marl layer (zone 2) representing the previous ca. 150–250 years and a basal section (zone 3) of ranging from 310 to 2990 YBP. Modern peat accretion rates averaged 3.1 mm yr)1 while subsurface marl accreted more slowly at 0.8 mm yr)1. Salinity and vegetation type for zone 1 show a steep gradient with freshwater communities being confined west of a north–south drainage canal constructed in 1960. Inferences for zone 2 (pre-drainage) suggest that freshwater marshes and associated forest units covered 90% of the area, with mangrove forests only present along the peripheral coastline. During the entire pre-drainage history, salinity in the entire area was maintained below a mean of 2 ppt and only small pockets of mangroves were present; currently, salinity averages 13.2 ppt and mangroves occupy 95% of the wetland. Over 3 km2 of freshwater wetland vegetation type have been lost from this basin due to salt-water encroachment, estimated from the mollusk-inferred migration rate of freshwater vegetation of 3.1 m yr)1 for the last 70 years (compared to 0.14 m yr)1 for the pre-drainage period). This rapid rate of encroachment is driven by sea-level rise and freshwater diversion. Plans for rehydrating these basins with freshwater will require high-magnitude re-diversion to counteract locally high rates of sea-level rise.

Rapid responses of vegetation to hydrological changes in Taylor Slough, Everglades National Park, Florida, USA

We analyzed the dynamics of freshwater marsh vegetation of Taylor Slough in eastern Everglades National Park for the 1979 to 2003 period, focusing on cover of individual plant species and on cover and composition of marsh communities in areas potentially influenced by a canal pump station (‘‘S332’’) and its successor station (‘‘S332D’’). Vegetation change analysis incorporated the hydrologic record at these sites for three intervals: pre-S332 (1961–1980), S332 (1980–1999), post-S332 (1999–2002). During S332 and post-S332 intervals, water level in Taylor Slough was affected by operations of S332 and S332D. To relate vegetation change to plot-level hydrological conditions in Taylor Slough, we developed a weighted averaging regression and calibration model (WA) using data from the marl prairies of Everglades National Park and Big Cypress National Preserve. We examined vegetation pattern along five transects. Transects 1–3 were established in 1979 south of the water delivery structures, and were influenced by their operations. Transects 4 and 5 were established in 1997, the latter west of these structures and possibly under their influence. Transect 4 was established in the northern drainage basin of Taylor Slough, beyond the likely zones of influence of S332 and S332D. The composition of all three southern transects changed similarly after 1979. Where muhly grass (Muhlenbergia capillaris var. filipes) was once dominant, sawgrass (Cladium jamaicense), replaced it, while where sawgrass initially predominated, hydric species such as spikerush (Eleocharis cellulosa Torr.) overtook it. Most of the changes in species dominance in Transects 1–3 occurred after 1992, were mostly in place by 1995–1996, and continued through 1999, indicating how rapidly vegetation in seasonal Everglades marshes can respond to hydrological modifications. During the post-S332 period, these long-term trends began reversing. In the two northern transects, total cover and dominance of both muhly grass and sawgrass increased from 1997 to 2003. Thus, during the 1990’s, vegetation composition south of S332 became more like that of long hydroperiod marshes, but afterward it partially returned to its 1979 condition, i.e., a community characteristic of less prolonged flooding. In contrast, the vegetation change along the two northern transects since 1997 showed little relationship to hydrologic status.

Hydrogeophysical characterization of anisotropy in the Biscayne Aquifer using geophysical methods

The anisotropy of the Biscayne Aquifer which serves as the source of potable water for Miami-Dade County was investigated by applying geophysical methods. Electrical resistivity imaging, self potential and ground penetration radar techniques were employed in both regional and site specific studies. In the regional study, electrical anisotropy and resistivity variation with depth were investigated with azimuthal square array measurements at 13 sites. The observed coefficient of electrical anisotropy ranged from 1.01 to 1.36. The general direction of measured anisotropy is uniform for most sites and trends W-E or SE-NW irrespective of depth. Measured electrical properties were used to estimate anisotropic component of the secondary porosity and hydraulic anisotropy which ranged from 1 to 11% and 1.18 to 2.83 respectively. 1-D sounding analysis was used to models the variation of formation resistivity with depth. Resistivities decreased from NW (close to the margins of the everglades) to SE on the shores of Biscayne Bay. Porosity calculated from Archie's law, ranged from 18 to 61% with higher values found along the ridge. Higher anisotropy, porosities and hydraulic conductivities were on the Atlantic Coastal Ridge and lower values at low lying areas west of the ridge. The cause of higher anisotropy and porosity is attributed to higher dissolution rates of the oolitic facies of the Miami Formation composing the ridge. The direction of minimum resistivity from this study is similar to the predevelopment groundwater flow direction indicated in published modeling studies. Detailed investigations were carried out to evaluate higher anisotropy at West Perrine Park located on the ridge and Snapper Creek Municipal well field where the anisotropy trend changes with depth. The higher anisotropy is attributed to the presence of solution cavities oriented in the E-SE direction on the ridge. Similarly, the change in hydraulic anisotropy at the well field might be related to solution cavities, the surface canal and groundwater extraction wells.^

The international legal thought of Carl Schmitt : towards a critique of the contemporary international order

The aim of the thesis is to develop a critique of current liberal conceptualizations of international order. In order to conduct this critique, this thesis revisits the arguments first put forth by the German legal and political theorist Carl Schmitt. Schmitt conceptualizes a tripartite unity between law, order, and place. This unity, established at the constituent moment of land-appropriation, forms a concrete nomos, which subsequently creates the contours of the legal and political order. The establishment of the concrete order is necessarily the construction of a territorial boundary that designates an inside and an outside of the polity. By speaking of a nomos of the earth, Schmitt globalized this understanding of concrete order by looking at the various historical developments that created a "line" between the concrete applicability of interstate norms and a region where the exceptional situation prevails. The critique presented in this thesis is concerned with the lack of concrete boundary conditions within the current international legal order. It is argued that this lack of a well-defined boundary condition is what results in extreme forms of violence that were traditionally bracketed.