Results of this research are available online in two published papers. / The main focus of this research was to synthesize and then to characterize the potential high-performance thermoelectric materials. In this regard, we have prepared a series of pure RECuSe2 (with RE = Pr, Sm, Gd, Dy and Er) and RECuTe2 (with RE = Er, Dy and Gd) and analyzed their crystal structure, electronic and physical properties. We used powder and single crystal X-ray diffraction techniques to analyze their crystal structures and employed energy dispersive X-ray spectrometry (EDS) to verify their chemical compositions. The temperature stability of the synthesized samples was examined by differential thermal and gravimetrical analysis. The high-purity consolidated pellets were prepared for physical properties measurements. We analyzed the relationship between their crystal structures and pertinent electronic properties through the LMTO calculations. The RECuSe2 phases adopt two structures, monoclinic and trigonal. The monoclinic structure (P21/c, z = 4) is observed for lighter rare earths (RE = Pr, Sm and Gd) and Cu-disordered trigonal structure for heavier rare earths (P m1, z = 1, RE = Dy and Er). The resistivity and Seebeck coefficient measurements indicate that the studied selenides are p-type semiconductors with relatively small activation energies (0.045-0.12 eV). However, their electrical resistivities are too high (0.49-220 Ohmcm at room temperature) to make them competitive thermoelectric materials. Electronic structure calculations indicate presence of a band gap in the RECuSe2 phases. The synthesized RECuTe2 phases (RE = Er, Dy and Gd) adopt a monoclinic-distorted variant (C2/m, z = 2) of the trigonal structure (P m1, Z= 1) observed for the RECuSe2 (with RE = Dy, Er). While such disorder may be beneficial for lowering their thermal conductivity, large values of electrical resistivity (0.02-0.87 Ohmcm at room temperature) make these phases unsuitable for practical applications. Comparing to the corresponding semiconducting selenides, the tellurides have lower resistivities, and display a metallic type resistivity. Such behavior stems from the closure of band gaps, which is verified by the electronic structures calculations. Structurally the RECuTe2 phases (with RE = Er, Dy and Gd) are similar to RECuSe2 with the P m1 structure. The monoclinic distortion in RECuTe2 is driven by Cu displacement inside the larger tetrahedral voids in the hexagonal close packing of the Te atoms. Most likely, Cu shifts to one side of the Te tetrahedra to optimize the Cu-Te interactions. / Thesis / Candidate in Philosophy

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The Fennoscandian Shield as a part of a large Precambrian basement area is located in northern Europe and hosts economically important mineral deposits including base metals and precious metals. Regional geophysical data such as potential field and magnetotelluric data in combination with other geoscientific data contain information of importance for an understanding of the crustal and upper mantle structure. Knowledge about regional-scale structures is important for an optimized search for mineralisation. In order to investigate in more detail the spatial distribution of regional electrically conductive structures and near-surface mineral deposits, complementary magnetotelluric measurements have been done within the Precambrian Shield in the north-eastern part of the Norrbotten ore province. The potential field data provided by the Geological Survey of Sweden have been included in the current study. Processing of magnetotelluric data was performed using a robust multi-remote reference technique. The dimensionality analysis of the phase tensors indicates complex 3D structures in the area. A 3D crustal model of the electrical conductivity structure was derived based on 3D inversion of the data using the ModEM code. The final inversion 3D resistivity model revealed the presence of strong crustal conductors with the conductance of more than 3000 S at depth of tens of kilometres within a generally resistive crust. A significant part of the middle crust conductors is elongated in directions that coincide with major ductile deformation zones that have been mapped from airborne magnetic data and geological fieldwork. Some of these conductors have near-surface expression where they spatially correlate with the locations of known mineralisation. Processing and 3D inversion of the regional magnetic and gravity field data were performed, and the structural information derived from these data by using an open-source object-oriented package code written in Python called SimPEG. In this study, a new approach is proposed to extract and analyse the correlation between the modelled physical properties and for domain classification. For this, a neural net Self-Organizing Map procedure (SOM) was used for data reduction and simplification. The input data to the SOM analysis contain resistivity, magnetic susceptibility, and density model values for some selected depth levels. The domain classification is discussed with respect to geological boundaries and composition. The classification is furthermore applied for prediction of favourable areas for mineralisation. Based on visual inspection of processed regional gravity and magnetic field data and a SOM analysis performed on higher-order derivatives of the magnetic data, an interpretation of a sinistral fault with 52 km offset is proposed. The fault is oriented N10E and can be traced 250 km from Karesuando at the Swedish-Finish border southwards to the Archaean-Proterozoic boundary marked by the Luleå-Jokkmokk Zone.

The application of the entropy concept to stabilize oxide systems opens the possibility of discovering new materials with unique structural and functional properties. High-entropy alloys and oxides, which are based on the entropy stabilization concept and composed of multi-principal elements, have the potential to tailor structural and functional properties to meet specific needs. The study of lanthanum-based perovskite materials that benefit from the entropy stabilization approach is a promising area of research.However, the inherent randomness of multi-principal elements presents new challenges, making it difficult to predict their behavior. To understand these difficulties, we have initiated a methodical investigation of La-based medium- and high-entropy perovskite oxides. This study focuses on the synthesis, characterization, sintering mechanism, and electrical conductivity properties of nine La1-xCax(A1/3, B1/3, C1/3)O3 medium-entropy perovskite oxide systems (A, B, and C = three combination of Cr or Co or Fe or Ni or Mn) and one La1-xCax(Cr0.2Co0.2Fe0.2Ni0.2Mn0.2)O3 high-entropy perovskite oxide system (for x = 0.1 to 0.3). This research aims to provide better understanding of: (1) synthesis process, (2) temperature of single-phase formation, (3) the impact of various combinations of multiple B-site transitional elements and Ca doping on crystal structure, and microstructure (4) sintering mechanism and (5) electrical conductivity properties.

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<p>The microstructure of the ZEBRA cells was examined at different cycle lifetimes. Various methods of sample preparation were used to remove the NaAlCl₄ electrolyte and expose the cathode microstructure. Features such as layered NiCl₂ crystals, large NaCl grains and needle-like FeCl₂ phases were observed by SEM. The results indicate that nickel particles grow in size with age of the cell. Moreover, the presence of both Na₆FeCl₈ and NiAl₂Cl₈ phases was confirmed by XRD. Thermodynamic modeling was used to predict the phases expected when a cell has undergone overcharge or overdischarge during cycling. It is postulated that some phases observed in the cathode at room temperature may be artifacts due to transformations that occur during cooling and do not exist at the operating temperature.</p> <p>The presence of isolated nickel particles within the cathode was confirmed by SEM and FIB techniques. Furthermore, the conductivity of the NaAlCl₄ electrolyte was measured at high temperatures and various additives were used to make the electrolyte a mixed ionic-electronic conductor.</p> <p>A special cell was designed to measure the conductivity of hygroscopic and volatile electrolyte at high temperatures. The best conductivity was obtained when using 0.2 mole fraction Bi as an additive to the NbCl₅+NaAlCl₄ mixture (Nb:Na=0.3, Bi:Nb=0.2). The conductivity values were doubled between 190 and 500˚C. The DC measurements confirm the presence of electronic conductivity in Bi+NbCl₅+NaAlCl₄ mixtures. In addition, the effect of NaF and Na₂S on the conductivity of the NaAlCl₄ electrolyte was measured.</p> / Doctor of Philosophy (PhD)