Graduation date: 2003

Graduation date: 1995

Graduation date: 1995

Graduation date: 1995

No description available.

Iron oxyhydroxides are ubiquitous in surface environments, playing a key role in many biogeochemical processes. Their characterization is made challenging by their nanophase nature. Magnetometry serves as a sensitive non-destructive characterization technique that can elucidate intrinsic physical properties, taking advantage of the superparamagnetic behaviour that nanoparticles may exhibit. In this work, synthetic analogues of common iron oxyhydroxide minerals (ferrihydrite, goethite, lepidocrocite, schwertmannite and akaganéite) are characterized using DC and AC magnetometry (cryogenic, room temperature), along with complementary analyses from Mössbauer spectroscopy (cryogenic, room temperature), powder X-ray diffraction and scanning electron microscopy. It was found that all of the iron oxyhydroxide mineral nanoparticles, including lepidocrocite, schwertmannite and akaganéite were superparamagnetic and therefore magnetically ordered at room temperature. Previous estimates of Néel temperatures for these three minerals are relatively low and are understood as misinterpreted magnetic blocking temperatures. This has important implications in environmental geoscience due to this mineral group’s potential as magnetic remanence carriers. Analysis of the data enabled the extraction of the intrinsic physical parameters of the nanoparticles, including magnetic sizes. The study also showed the possible effect on these parameters of crystal-chemical variations, due to elemental structural incorporation, providing a nanoscale mineralogical characterization of these iron oxyhydroxides. The analysis of the intrinsic parameters showed that all of the iron oxyhydroxide mineral nanoparticles considered here have a common magnetic moment formation mechanism associated with a random spatial distribution of iv uncompensated magnetic spins, and with different degrees of structural disorder and compositional stoichiometry variability, which give rise to relatively large intrinsic magnetization values. The elucidation of the magnetic nanostructure also contributes to the study of the surface region of the nanoparticles, which affects the particles’ reactivity in the environment.

Iron oxyhydroxides are ubiquitous in surface environments, playing a key role in many biogeochemical processes. Their characterization is made challenging by their nanophase nature. Magnetometry serves as a sensitive non-destructive characterization technique that can elucidate intrinsic physical properties, taking advantage of the superparamagnetic behaviour that nanoparticles may exhibit. In this work, synthetic analogues of common iron oxyhydroxide minerals (ferrihydrite, goethite, lepidocrocite, schwertmannite and akaganéite) are characterized using DC and AC magnetometry (cryogenic, room temperature), along with complementary analyses from Mössbauer spectroscopy (cryogenic, room temperature), powder X-ray diffraction and scanning electron microscopy. It was found that all of the iron oxyhydroxide mineral nanoparticles, including lepidocrocite, schwertmannite and akaganéite were superparamagnetic and therefore magnetically ordered at room temperature. Previous estimates of Néel temperatures for these three minerals are relatively low and are understood as misinterpreted magnetic blocking temperatures. This has important implications in environmental geoscience due to this mineral group’s potential as magnetic remanence carriers. Analysis of the data enabled the extraction of the intrinsic physical parameters of the nanoparticles, including magnetic sizes. The study also showed the possible effect on these parameters of crystal-chemical variations, due to elemental structural incorporation, providing a nanoscale mineralogical characterization of these iron oxyhydroxides. The analysis of the intrinsic parameters showed that all of the iron oxyhydroxide mineral nanoparticles considered here have a common magnetic moment formation mechanism associated with a random spatial distribution of iv uncompensated magnetic spins, and with different degrees of structural disorder and compositional stoichiometry variability, which give rise to relatively large intrinsic magnetization values. The elucidation of the magnetic nanostructure also contributes to the study of the surface region of the nanoparticles, which affects the particles’ reactivity in the environment.

Thermoelectric power generators can convert a temperature gradient into electrical energy, serving as a new energy resource by utilizing solar energy or by utilizing more waste heat. Thermoelectric coolers have the advantage of no moving parts, are quiet and release no gases that are harmful to the atmosphere, in contrast to compression-based refrigeration. While the low efficiency of “classical” thermoelectric devices limits their wide applications, the exploration of better thermoelectric materials is of great importance to improve the efficiency of thermoelectric devices. Good thermoelectric materials are usually narrow band gap semiconductors with a large Seebeck coefficient, reasonably high electrical conductivity and low thermal conductivity. This thesis deals with the exploration of new thermoelectric materials based on transition metal tellurides and the optimization of bulk materials based on oxides of low toxicity and high stability in air. In the first project, seven new ternary or quaternary tellurides, crystallizing in three different structure types, were synthesized and characterized. Single crystal X-ray diffraction was used for crystal structure determination; powder X-ray diffraction and energy dispersive X-ray analysis (EDAX) were used for phase and composition analyses. Physical properties of these compounds were predicted by electronic structure calculations and confirmed by physical property measurements. In the second project, two series of n-type doped perovskite SrTiO3 were prepared in a high temperature tube furnace under dynamic high vacuum of the order of 10–6 mbar, namely SrTi1-x(Nb,Ta)xO3, and Sr1-xLaxTi1-x(Nb,Ta)xO3. The phase purity was characterized by means of powder X-ray diffraction and electron probe micro analysis (EPMA). Rietveld refinements were performed to check for purity and symmetry reduction. The physical properties, such as Seebeck coefficient, electrical conductivity, and thermal conductivity, were measured at high temperatures for all the samples. Of the series of Nb/Ta-doped strontium titanates SrTi1-x(Nb,Ta)xO3, SrTi0.90Ta0.10O3 exhibits the highest ZT value, namely 0.17 for at 752 K. Of the double substituted series, Sr0.99La0.01Ti0.99Ta0.01O3 was best with ZT = 0.13 at 660 K. The rapid increases imply that higher ZT values are likely to occur at higher temperatures.

Thermoelectric power generators can convert a temperature gradient into electrical energy, serving as a new energy resource by utilizing solar energy or by utilizing more waste heat. Thermoelectric coolers have the advantage of no moving parts, are quiet and release no gases that are harmful to the atmosphere, in contrast to compression-based refrigeration. While the low efficiency of “classical” thermoelectric devices limits their wide applications, the exploration of better thermoelectric materials is of great importance to improve the efficiency of thermoelectric devices. Good thermoelectric materials are usually narrow band gap semiconductors with a large Seebeck coefficient, reasonably high electrical conductivity and low thermal conductivity. This thesis deals with the exploration of new thermoelectric materials based on transition metal tellurides and the optimization of bulk materials based on oxides of low toxicity and high stability in air. In the first project, seven new ternary or quaternary tellurides, crystallizing in three different structure types, were synthesized and characterized. Single crystal X-ray diffraction was used for crystal structure determination; powder X-ray diffraction and energy dispersive X-ray analysis (EDAX) were used for phase and composition analyses. Physical properties of these compounds were predicted by electronic structure calculations and confirmed by physical property measurements. In the second project, two series of n-type doped perovskite SrTiO3 were prepared in a high temperature tube furnace under dynamic high vacuum of the order of 10–6 mbar, namely SrTi1-x(Nb,Ta)xO3, and Sr1-xLaxTi1-x(Nb,Ta)xO3. The phase purity was characterized by means of powder X-ray diffraction and electron probe micro analysis (EPMA). Rietveld refinements were performed to check for purity and symmetry reduction. The physical properties, such as Seebeck coefficient, electrical conductivity, and thermal conductivity, were measured at high temperatures for all the samples. Of the series of Nb/Ta-doped strontium titanates SrTi1-x(Nb,Ta)xO3, SrTi0.90Ta0.10O3 exhibits the highest ZT value, namely 0.17 for at 752 K. Of the double substituted series, Sr0.99La0.01Ti0.99Ta0.01O3 was best with ZT = 0.13 at 660 K. The rapid increases imply that higher ZT values are likely to occur at higher temperatures.

Thesis (Ph. D.)--Washington State University, December 2009. / Title from PDF title page (viewed on Dec. 28, 2009). "Materials Science Program." Includes bibliographical references (p. 109-118).