Experiments were designed for an undergraduate instrumental analysis laboratory course, two in X-ray diffraction and two in electrochemistry. Those techniques were chosen due their underrepresentation in the Journal of Chemical Education. Paint samples (experiment 1) and pennies (experiment 2) were characterized using x-ray diffraction to teach students how to identify different metals and compounds in a sample. in the third experiment, copper from a penny was used to perform stripping analyses at different deposition times. As the deposition time increases, the current of the stripping peak also increases. the area under the stripping peak gives the number of coulombs passed, which allows students to calculate the mass of copper deposited on the electrode surface. the fourth experiment was on the effects of variable scan rates on a chemical system. This type of experiment gives valuable mechanistic information about the chemical system being studied.

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The lead-free tin telluride (SnTe) is considered as a potential candidate to substitute lead telluride (PbTe) for thermoelectric power generation based on their similar crystal and electronic structures. However, the relatively high lattice thermal conductivity and low Seebeck coefficient of pristine SnTe are detrimental for real-life applications. This dissertation explored elements-doping/substituting of SnTe to overcome those shortcomings and improve SnTe thermoelectric performance. A series of the Sn1-xGexTe phases were synthesized and studied. When the Ge amount reaches 50% or higher, Sn1-xGexTe undergoes a phase transition from the rock-salt structure (Fm3̅m) to the rhombohedral one (R3m). The Sn0.5Ge0.5Te phase was explored in more details because it delivers the best thermoelectric performance with the Sn1-xGexTe series. The electron-richer Sb and Bi were substituted on the Sn/Ge site to optimize the charge transport properties, and Cu2Te was added into the matrix to improve the thermoelectric performance further. The In/Sb and In/Bi co-doping on the Sn/Ge sites was employed for Seebeck coefficient optimization. A comparative study of the electronic structure of the Sn0.5Ge0.5Te-based samples was performed. The calculations indicated a band convergence and changes in the valence band, thus providing insight into the co-doping effects. Suppression of the lattice thermal conductivity of SnTe was performed via alloying with AgSnSe2 and PbTe, which introduced strong atomic disorder. Additionally, AgSnSe2 showed a hole donor behavior in SnTe, and the increased carrier concentration compensated for the reduction in the carrier mobility, thus rendering a decent electrical conductivity in alloyed samples. As a result, the alloying effectively improved the samples' thermoelectric performance. / Thesis / Doctor of Philosophy (PhD) / In recent decades, renewable energy has attracted a lot of attention due to an increase in the global energy use and depletion of fossil fuel reserves. Thermoelectric materials are expected to play a vital role as green energy generators to overcome the upcoming energy crisis as they can directly convert waste heat into electricity through the Seebeck effect. In this dissertation, the main goal is optimizing the thermoelectric performance of SnTe for the above room temperature applications. Different doping/ substituting/alloying strategies were applied to improve the performance. The obtained thermoelectric properties of the SnTe-based materials were rationalized in terms of the charge carrier behavior, changes in the electronic structure, and phonon propagation.

A series of new germanates was prepared and their structures were characterized with X-ray diffraction (XRD). We employed solid-state synthesis, flux growth, and crystallization from melts to obtain crystals of the new materials. The crystals were studied by means of single crystal XRD, providing the information on the structure and composition of the new materials. Germanates suitable to accommodate Mn4+ – a well-known activator ion for the preparation of the rare-earth-free red phosphors – were of a particular interest. The Ge4+ substitution for Mn4+ is possible if the crystal structure features octahedrally coordinated germanium atoms, and we indeed were able to prepare such germanates. The crystal structures of the following phases were characterized: Mg3Ge1-O4(1-)F2(1+2) ( ≈ 0.1), Mg14Ge4O20F4, Mg2Pb2Ge2O7F2, Sr3GeO4Cl2, Ba3GeO4Br2, Sr6Ge2O7Cl6, Ba5GeO4Br6, Na2BaGe8O18, Rb2BaGe8O18, Na0.36Sr0.82Ge4O9, Na2SrGe6O14, and K2SrGe8O18. Two phases, Mg3Ge1-O4(1-)F2(1+2) and Na0.36Sr0.82Ge4O9 demonstrate deficiency on certain crystallographic sites. We analyzed the connectivity of the GeO4 and GeO6 units in the new and reported tetra- and octagermanates. Despite the similar stoichiometry, the connectivity of GeOn polyhedra is different in RI2Ge4O9, RIIGe4O9 and RIRIIGe8O18 germanates (RI = alkali, RII = alkaline earth metal). The Ge4+ substitution for Mn4+ was successfully done for the Na2BaGe8O18, Rb2BaGe8O18, Na2SrGe6O14, and K2SrGe8O18 phases yielding new red phosphors. Based on the powder XRD data, the optimal synthetic strategies were developed yielding high purity (≈ 99 wt. %) samples. The photoluminescent excitation and emission spectra were collected for the new phosphors. Strong absorption of the UV light and emission in the far-red region of the visible spectra were confirmed, which is in a good agreement with the literature. The Mn4+ doping level was optimized to achieve the highest luminescence in the studied phases. Temperature-dependent luminescence spectra were collected for the Na2SrGe6O14 : Mn4+ and K2SrGe8O18: Mn4+, and the K2SrGe8O18: Mn4+ showed the highest resistance to temperature quenching. / Thesis / Doctor of Philosophy (PhD)

<p> A coarse grained amphibolite from the metamorphosed rim of the Whitestone Anorthosite was prepared in several ways for the purpose of determining the modal abundance of the constituent minerals by calibrated X-ray diffraction. A simple two component amphibolite consisting of plagioclase and amphibole was chosen and five major methods of mounting the specimens for X-ray diffraction were employed.</p> <p> It was hoped that a method could be found which would produce randomly oriented, homogeneous samples. A series of such samples each of a different component ratio would then provide a calibration curve from which the mode of a whole rock specimen could be estimated.</p> <p> The calibrated X-ray charts were produced on Philips scanning X-ray diffractometers.</p> <p> The inconsistencies in the results indicate that better technical procedures are required.</p> / Thesis / Bachelor of Science (BSc)

<p> The crystal structure of dioxotetrapyridine-rhenium(V) chloride dihydrate has been determined by single crystal x-ray diffraction methods. The structure has been found to belong to the trans-dioxo- group of compounds. The Re=O bond in the structure has been shown to have a bond-order of about 2, with the average Re=O bond length of 1.76(J) A. The probable structures of the monohydrate and anhydrous dioxotetrapyridine-rhenium(V) chloride have been discussed on the basis of the observed pseudo-symmetric structure for the dihydrate with a non-centrosymmetric space group. The nature and strength of the hydrogen bonds in the structure have also been discussed.</p> / Thesis / Master of Science (MSc)

<p> The crystal structure of k2SnBr6 has been reinvestigated using single crystal x-ray diffraction techniques. Three dimensional intensity data obtained photographically have been used to refine the structure, by the least square analysis. The structure is found to be slightly distorted from the regular cubic k2PtCl6 structure in a manner similar to K2TeBr6. The Sn-Br bond is found to be 2.601 A. </p> <p> The structure of k2SnBr6 is found to be monoclinic with space group P21/n and a = 7.435 ± 0.017 A, b= 7.437 ± 0.017 A, and c = 10.568 ± 0.006 A. </p> <p> A review of other crystals with similar structure is included in this thesis included the theory of x-ray diffraction and crystal structure as applicable to the present problem is discussed briefly. </p> / Thesis / Master of Science (MSc)

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Liquid crystalline materials forming columnar mesophases are of importance for both the fundamental research and technological applications due to their supramolecular architecture allowing for one-dimensional charge transport. The potential applications of these materials include light emitting diodes, solar cells, field effect transistors and photovoltaic cells. However, to design a LC material suitable for a particular application, a fundamental understanding of the structure-property relationships is needed. In the present thesis, a variety of systems forming columnar mesophases have been explored. They include small molecular weight compounds (triphenylene, phthalocyanine derivatives and star-shaped mesogens) and polymer materials. The research was focused on the study of the influence of the molecular architecture and specific interactions such as hydrogen bonding on the supramolecular organization in the mesophase, as well as on the influence of columnar mesophase on crystal growth. The main results of the thesis are summarized below. The influence of hydrogen bonding on the structure and charge carrier mobility was investigated for a triphenylene derivative, hexaazatriphenylene, having lateral alkyl chains linked to the core via amide groups. These linking groups provide the possibility to form inter- and intra-molecular hydrogen bonds. Acting as “clamps”, the inter-molecular hydrogen bonds are found to enforce the attractive interactions between the molecules in the column. Thus, the columnar mesophase formed by this system is characterized by the smallest inter-disk distance ever found in columnar mesophases (3.18 Å). The improved intra-columnar order brings about a higher charge carrier mobility (0.02 cm2/Vs) as compared to other triphenylene derivatives without hydrogen bonds. Phthalocyanine derivatives, which are liquid crystalline at ambient temperature, could be suitable for opto-electronic applications due to their improved processibility and self-healing of structural defects. Our interest in these systems was inspired by the fact that, in spite of numerous studies performed to date, only very a few phthalocyanine derivatives were found to exhibit columnar mesophases at ambient temperature. We observed that by introducing branches in alkyl chains close to the core, we were able to render the material LC at ambient temperature. Analysis of X-ray diffraction patterns measured on oriented samples showed that these systems form hexagonal and rectangular ordered columnar mesophases. This finding is in contradiction with the general view stating that non-hexagonal mesophases can be only disordered. Since the absolute majority of applications require fabrication of films, it was very important to achieve the visualization of the organization of the phthalocyanine derivatives at the nanometer scale. AFM images on thick spin-coated films with columnar resolution are presented for the first time. They allowed the examination of columnar curvatures and breaks at the boundaries between different single crystal-like domains. The possibility of templating columnar crystal growth was studied for a star-shaped mesogen using a combination of direct- and reciprocal-space techniques. AFM images with columnar resolution showed that the crystal growth initiated in the monotropic columnar mesophase occurs almost in register with the mesomorphic template. In the final crystalline structure, the placement of the crystalline columns is controlled by the mesomorphic tracks at the scale of an individual column, i.e. at the scale of approximately 3.5 nm. The mesophase-assisted crystallization was also studied for the case of a polymer material forming columnar mesophase, poly(di-n-propylsiloxane). X-ray diffraction on oriented fibers allowed us to correct the previous indexation and solve the structure of the unit cell. The crystallization process was studied on samples crystallized in different conditions. It was found that, depending on crystallization conditions, both folded-chain and extended-chain crystals can be obtained. Thus, crystallization of the material from the mesophase results in the formation of 100-150nm thick crystals, which corresponds to a nearly extended-chain conformation. By contrast, when crystallized from a dilute solution, folded-chain crystals result. The mechanisms of chain unfolding was studied by variable temperature atomic force microscopy on PDPS single crystals. It was found that crystals rapidly thicken above the initial melting point, up to 80 nm.

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