Embora cristais boratos dopados com ions de terras raras sejam amplamente investigados, vidros boratos desses sistemas vêm sendo pouco estudados. O cristal NdAl3(BO3)4(NAB) cujas propriedades laser e de geração de segundo harmônico (GSH) são conhecidas e continuamente relatadas na literatura, vem sendo recentemente considerado como um forte candidato para dispositivo \"microchip laser\". Alem disso, cristais dopados com íons de neodímio têm demonstrado ser excelentes para o bombeio com laseres de diodo, devido ao intenso pico de absorção próximo a 800 nm. Entretanto, existe na literatura um número muito limitado de estudos relatando as propriedades de vidros do sistema Nd2O3-Al2-O3-B2O3. Partindo dessa premissa, o objetivo principal deste trabalho foi obter vidros neste sistema, para elevadas concentrações de Nd2O3 (5-20 mol%), por meio das técnicas de fusão/moldagem convencional e fusão a laser. Dentre os materiais preparados foram obtidos três vidros transparentes, um material com separação de fases e, onde ocorreu cristalização. Os vidros obtidos, NAB136, NAB152560 e NAB226 foram caracterizados através das técnicas de análise térmica diferencial (ATD), difratometria de raios X (DRX), absorção óptica (AO) e ICP-OES (análise de composição). De acordo como os resultados de ATD, os vidros não apresentaram uma variação significativa na temperatura de transição vítrea (Tg) com o aumento da concentração de Nd2O3. O vidro NAB136, obtido com composição próxima a do cristal NdAl3(BO3)4(NAB), foi submetido a um tratamento térmico de cristalização a uma temperatura de 820°C por 2 horas. Os resultados de DRY indicaram a presença das fases cristalinas majoritárias Al4B2O9 e NAB. Medidas de absorção Óptica (AO) dos vidros no intervalo espectral de 300-1000 nm indicaram intensa absorção nos comprimentos de onda 500 nm e 800 nm. As análises de ICP-OES indicaram alta pureza dos vidros e composições próximas das composições nominais / Although borate crystals doped with rare earth ions have already been extensively investigated, borate glasses of these systems were not widely studied. The NdAl3(BO3)4(NAB) crystal, which laser and second harmonic generation (SGH) properties are well know and continuously mentioned in literature, has been recently considered as a strong candidate for microchip laser devices. Moreover, neodymium doped crystals are known for their excellent performance when pumped with diode lasers due to its intense absorption peak near to 800 nm. However, a limited number of papers have been published referring to the properties of glasses in the system Nd2O3-Al2-O3-B2O3. Based on this premise, the main purpose of this work was to prepare glasses in this system for Nd2O3 elevate concentrations (5-20 mol%) by the conventional melting/molding and laser heated methods. Among the prepared materials it was obtained three clear glasses, a material with phase separation and another one, which has crystallized. The obtained glasses, NAB136, NAB152560 and NAB226, where characterized by differential thermal analysis (DTA), X-ray diffractometry (XRD), optical absorption (OA) and ICP-OES (compositional analysis). According to the DTA results, the glasses have not presenteá a rneaningfut change in the glass transition temperature (Tg) with the increase of Nd2O3 content. The NAB136 glass, with the closest composition to the crystal NdAl3(BO3)4(NAB), was submitted to a crystallization thermal treatment at 820°C for 2 hours. XRD results showed the existence of the main crystalline phases and NAB. Optical absorption (OA) measurements of the glasses in the spectral range 300-1000 nm indicated intense absorpâion in the 500 nm and 800 nm wavelengths. ICP-OES analysis showed that the glasses posses high purity stoichiometry, close to the nominal ones

Vidros boratos contendo óxidos modificadores vêm sendo estudados por apresentarem um número atômico efetivo próximo ao do tecido humano, o que os tornam materiais interessantes para o desenvolvimento de dosímetros termoluminescentes. O objetivo deste trabalho foi estudar as propriedades térmicas e estruturais do sistema xCaB4O7-(100-x)CaB2O4, com x variando de 0 a 100 % em massa. As amostras sem dopantes foram previamente estudadas a fim de determinar uma composição que apresentasse a melhor resposta termoluminescente (TL) para a inclusão do íon Dy como dopante e Li como co-dopante, aumentando a eficiência TL da mesma. Pelo método de fusão e moldagem, foram obtidos amostras vítreas e vitrocerâmicas. A fase cristalina presente nas amostras vitrocerâmicas foi determinada por difratometria de raios X e identificada como fase única CaB2O4. A composição vitrocerâmica 20CaB4 (% em massa) apresentou a melhor resposta TL, sendo dopada com Dy e co-dopada com Li para o estudo das propriedades dosimétricas. Este estudo mostrou uma resposta linear num intervalo de 5 a 70 minutos de exposição à radiação ultravioleta e uma boa reprodutibilidade do sinal TL provando ser um material promissor para a utilização em dosimetria pessoal e clínica. / Borate glasses containing modified oxides have been studied on account of their effective atomic number close to that of the human tissue, what makes them interesting materials for the development of the thermoluminescent dosimeters. The purpose of this work was to study the thermal and structure properties of the xCaB4O7-(100-x)CaB2O4 system with x ranging from 0 to 100 wt%. The undoped samples were previously studied in order to determine a composition that would present a better thermoluminescent response for the incluision of the Dy íon as dopant and Li as co-dopant, thus increasing its TL efficiency. By the melting/molding method, the glass-ceramic samples was determined by the X-ray difractometry and identified as a unique CaB2O4 phase. The glass-ceramic 20 CaB2O4 (wt%) composition presented the best TL response being doped with Dy and co-doped with Li for the study of the dosimetric properties. This study has shown a linear response within an interval of 5 to 70 minutes of exposure to the UV radiation and good reproducibility of the TL signal, thus proving to be a promising material for using in the personal and clinical dosimetry.

Ao longo dos últimos anos tem aumentado o interesse da comunidade científica no desenvolvimento de estruturas de borato de magnésio. Geralmente, o borato de magnésio é utilizado em conjunto com outros materiais como metais, polímeros, cerâmicas ou macromoléculas formando compósitos. Este borato tem sido largamente utilizado para reduzir o coeficiente de fricção e aprimorar as propriedades mecânicas de compósitos, atuando como material anti-desgaste e inibidos de corrosão. Dentre as fases de borato de magnésio, o Mg2B2O5 se destaca por apresentar potencial para aplicações tais como catalisador para conversão de hidrocarbonetos, agente para tratamento eletrocondutivo, semicondutor e material luminescente para aplicação em tubos de raios catódicos. Acredita-se que ao reduzir as dimensões do bulk de borato de magnésio a dimensões nanométricas, pode-se oferecer excelentes características para desenvolver e melhorar as potenciais aplicações acima mencionadas. Em geral, estruturas em nanoescala como tubos, fios, rods, cintos e whiskers têm sido o foco de intensiva pesquisa. Buscando a compreensão dos mecanismos para produção de nanoestruturas de boratos de magnésio, este trabalho está focado no desenvolvimento de uma rota de síntese de nanorods de Mg2B2O5 que permita a produção de um material com elevada pureza e homegeneidade estrutural a fim de possibilitar uma futura aplicação em dispositivos nanotecnológicos. Os nanorods foram sintetizados utilizando como precursor B2O3 e Mg metálico em um reator de CVD. Foi analisado o emprego de diferentes atmosferas para a reação, partindo de H2, Ar e acetonitrila (CH3CN). Foi estudado também a influência da temperatura na morfologia e composição dos nanorods. As propriedades físico-químicas das estruturas desenvolvidas foram caracterizadas por FTIR e DRX. A estrutura morfológica foi analisada por MEV e MET e as propriedades óticas por DRS. De acordo com os resultados, os nanorods foram obtidos com alto grau de pureza e homogeneidade morfológica utilizando uma atmosfera redutora composta por H2 e CH3CN. / Over the last few years the interest of the scientific community has increased in the development of magnesium borate structures. Borato has been widely used to reduce the coefficient of friction and improve the mechanical properties of composite materials such as anti-wear and corrosion. Generally, the magnesium borate is used together with other materials such as metals, polymers, ceramics and macromolecules to form compounds. Among the borate magnesium phases, Mg2B2O5 contrasts for presenting potential for applications such as acting as a catalyst for hydrocarbon conversion, as an agent for electroconductive treatment, as a semiconductor and luminescent material for application in cathode ray tubes. It is believed that by reducing the borate magnesium bulk dimensions to dimensions of nanostructures, it can provide excellent characteristics to develop and improve the potential applications mentioned above. In general, nanoscale structures such as tubes, wires, rods, belts and whiskers have been the focus of intensive research. Seeking to understand the mechanisms for production of magnesium borate nanostructures, this work is focused on the development of a synthesis method for Mg2B2O5 nanorods, enabling the production of a material with high purity and structural homogeneity to enable future application in nanotechnological devices. The physicochemical properties of the structures developed were characterized by FTIR and XRD. The morphological structure was examined by SEM and TEM and the optical properties by DRS. According to the results, high purity and morphological uniform nanorods were obtained using a H2 and CH3CN reducing atmosphere.

Graphite and graphitic materials underpin a number of modern technologies such as electrodes for energy storage and conversion systems. Due to their aromatic honeycomb-type lattice and layered structure, these carbons host a rich variety of foreign elements in their interstices. Whether possessing a tubular morphology - that enables the encapsulation of inorganic compounds, or a planar texture - where anions and molecules can intercalate, the chemical analysis of graphite and graphitic materials is often confronted with the need to disintegrate the carbon matrix to quantify target elements, most often metals. However, the resilience of the sp2-hybridized carbon lattice to chemical attacks is an obstacle to its facile solubilization, a necessary step to perform some of the most common elemental analysis measurements. Over the years, a range of alternative approaches have sprung out to address this issue such as the combustion of the carbon matrix followed by the acid dissolution of its ash product. Unfortunately, none of these represents a viable method that can be applied to batteries, in great part because of the different components that make up the carbon-based electrodes. In this dissertation, a new protocol has been developed to digest graphitic materials aiming to access their elemental composition in bulk scale. The approach is based on the use of molten alkaline salts to promote the oxidation of the carbon lattice and leach out metals into a dilute acid solution. As a model sample, given the existence of standards with a matching matrix, single-walled carbon nanotubes were examined. After being subjected to the alkaline oxidation (a.k.a. fusion), they were solubilized and analyzed with Inductively Coupled Plasma-Optical Emission Spectroscopy, a widely popular tool for elemental analysis of metals. Structural analysis ensued to understand the interaction of the molten salts with the nanotubes. After evaluating the applicability of the protocol to other carbons, a more complex system was investigated, namely the carbon-based anode of an intercalation-type potassium ion battery. In this process, a direct way to quantify the mass of the alkali metal was discovered, one which makes use of complementary chemical and structural analytical tools.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第23020号 / 理博第4697号 / 新制||理||1674(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 時任 宣博, 教授 若宮 淳志, 教授 依光 英樹 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

Diese Arbeit beschäftigt sich mit der Synthese, Reaktivität und den physikalischen Eigenschaften verschiedener Cyanoborate. Es gelang die optimierte Synthese des Tricyanofluoroborates M[BF(CN)3] (M = Na, K) mittels Lewis-Säure-Katalyse. Aus diesem Borat wurde mittels Reduktion das Bor-zentrierte Nukleophil B(CN)3 2− hergestellt, welches ebenfalls über die äußerst ungewöhnliche Depronotierung des [BH(CN)3]− -Anions zugänglich ist. Das B(CN)3 2− -Dianion wurde erfolgreich mit diversen Elektrophilen wie z.B. Alkylhalogeniden, CO2, CN+-Quellen sowie per- und teilfluorierten Aromaten umgesetzt. Darüber hinaus ergibt die Synthese mit Tricyanohalogenoborat-Anionen das ungewöhnlich stabile gekoppelte Diborat-Dianion [B2(CN)6]2−, welches über einen SN2-Mechanismus entsteht und eine elektronenpräzise B-B-Bindung aufweist. Ferner wurden Ionische Flüssigkeiten mit Perfluoraklylcyanoboraten hergestellt und die physikalischen Parameter systematisch und ausführlich untersucht. / In this work the syntheses, reactivity and physical properties of different cyanoborates are presented. The synthesis of the tricyanofluoroborates M[BF(CN)3] (M = Na, K) was optimized via a Lewis-acid-catalysis. Reducing this anion resulted in the formation of the boron-centered nucleophile B(CN)3 2−, which is accessible by the highly unusual deprotonation of [BH(CN)3]−, too. The B(CN)3 2− -dianion was successfully treated with various electrophiles such as alkylhalides, CO2, CN+ -sources as well as partly and perfluorinated arenes. Moreover, the synthesis with halidotricyanoborate anions provide the unusually stable coupled diborat-dianion [B2 (CN)6]2−, which is formed via a SN2-mechanismusm and exhibits an electron-precise B-B-bond. Furthermore, Ionic Liquids based on perlfuorocyanoborates were synthesized and their physical properties were studied systematically in detail.

Diese Arbeit beschäftigt sich mit der Synthese, Charakterisierung und Eigeschaften neuer Monopentafluorethylborat-Anionen der Form [C2F5BH2X]- (X= F, Cl, Br), [C2F5BH2(CN)]-, [C2F5BH(CN)2]-, [C2F5BH(CN)X]- (X= F, Cl, Br) und [C2F5B(CN)X2]- (X= Cl, Br)sowie den Bis-pentafluorethylborat-Anionen [(C2F5)2B(OMe)(CN)]-, [(C2F5)2BF(CN)]- und [(C2F5)2B(CN)2]-. Von einigen dieser Verbindungen wurden Ionische Flüssigkeiten basierend auf dem 1-Ethyl-3-methylimidazolium-Kation synthetisiert und deren physikalischen Parameter ausführlich untersucht. Zudem wurden Pentafluorethylboran-Addukte mit verschiedenen Lewis-Basen der Form C2F5BH2-L (L= THF, SMe2, CH3CN, Pyridin, PPh3, CAAC, IDipp, SIDipp, Me4Im, (iPr)2Me2Im, tBu2Im) hergestellt welche zum Teil als Startmaterialien für die Synthese von Monopentafluorethylboraten verwendet wurden. / In this work, syntheses, characterisation and properties of new monopentafluoroethylborate anions like [C2F5BH2X]- (X= F, Cl, Br), [C2F5BH2(CN)]-, [C2F5BH(CN)2]-, [C2F5BH(CN)X]- (X= F, Cl, Br) and [C2F5B(CN)X2]- (X= Cl, Br) as well as bis-pentafluoroethylborate anions [(C2F5)2B(OMe)(CN)]-, [(C2F5)2BF(CN)]- and [(C2F5)2B(CN)2]- are presented. Furthermore, several of these compounds were transformed into Ionic Liquids by isolation of the corresponding 1-ethyl-3-methylimidazolium salt and their physical propterties were studied in detail. Besides, pentafluoroethylborane adducts with different lewis bases like C2F5BH2-L (L=thf, SMe2, CH3CN, pyridin, PPh3, CAAC, IDipp, SIDipp, Me4Im, (iPr)2Me2Im, tBu2Im) were synthesized which turned out to be good starting materials for the synthesis of monopentafluoroethylborates.

Diese Arbeit beschäfftig sich mit der Synthese und Charakterisierung neuartiger Tricyanoborate der Hauptgruppe 4, sowie der Synthese und Charakterisierung neuartiger Polymere mit Tricyanoboratgruppen. / This work deals with the synthesis and characterization of novel tricyanoborates of the main group 4 together with the synthesis and characterization of novel polymers with tricyanoborate groups.

<p> Hydroxypropyl guar (HPG) is an effective ingredient in lubricant eye drops used by patients with dry eye disease. The overall goal of the work described in this thesis is to understand the physical-chemical properties of HPG in the presence ofmodel surfaces and solutes with view to understanding the behavior of HPG in the tear film. </p> <p> HPG behaviors are complex because borate ions bind to HPG, which converts nonionic HPG into anionic polyelectrolyte, RPG-borate. The borate binding constants are very low, meaning the charges on RPG-borate are labile. Another consequence ofweak binding is that the equilibrium electrolyte concentration with HPG-borate is relatively high. Mathematical models were developed to predict the structure of HPG-borate as functions of pH. </p> <p> This thesis probes the question "When does HPG-borate behave as an anionic polyelectrolyte?" This work shows that HPG-borate exhibits deviant behaviors of an anionic polyelectrolyte: does not interact with cationic surfactants below the CMC; does not interact with lysozyme (cationic protein), and does not adsorb onto cationic liposomes. By contrast, anionic polyelectrolytes such as carboxymethyl guar display generic behaviors. On the other hand, HPG-borate forms polyelectrolyte complexes with cationic polyelectrolytes at low ionic strength and other work from our laboratory has shown that HPG-borate flocculates cationic polystyrene latex. </p> <p> This complex range of RPG-borate behaviors was rationalized by proposing that the labile nature ofthe charge groups means that the charge density on RPG-borate is regulated by the local electrostatic environment. Near a cationic surface HPG-borate charge density increases whereas near an anionic surface the charge density is lower. </p> <p> Anionic liposome interactions with HPG-borate were characterized. HPG concentrations close to clinical levels induced depletion flocculation ofthe anionic liposomes. This is the first example we have found depletion interactions were proposed for the tear film. </p> <p> To summarize the main implications for the ophthalmic application of HPG are: 1) under ophthalmic conditions HPG-borate behaves as a nonionic water soluble polymer; 2) RPG-borate will adsorb onto hydrophobic domains but will not interact with lysozyme; 3) depletion interactions are important and have the potential to stabilize the lipid layer and destabilize emulsion droplets and other dispersed species in the tear film. </p> / Thesis / Doctor of Philosophy (PhD)

<p> A number of new ternary borate compounds have been synthesized, and their crystal structures have been characterized via X-ray and neutron diffraction techniques. A series of new compounds with the composition PbMBO4 (M = Cr, Mn, Fe, Ga) has been prepared from solid-state reactions and from single crystal growths using PbO as a flux. They crystallize in the orthorhombic Pnma space group and represent a new structure-type for the family of anhydrous borates. The PbAlBO4 compound undergoes a phase transformation at high temperatures, which has been investigated by in-situ powder neutron diffraction experiments. The structure of β-PbAlBO4 has been solved from powder X-ray diffraction data and subsequently confirmed by a Rietveld refinement of powder neutron diffraction data. The investigation of the SrO - Ga2O3 - B2O3 system has led to the synthesis of a new structure-type, SrGaBO4, from solid-state reactions. Its crystal structure has been determined from powder X-ray diffraction data. It crystallizes in the orthorhombic Pbam space group, and is structurally related to the previously known alumino-borate compounds, SrAlBO4 and CaAlBO4. The "Ba2Ti2B2O9" compound has been re-formulated as Ba3Ti3B2O13, and its crystal structure has been determined by single crystal X-ray diffraction. This compound crystallizes in the non-centrosymmetric P6 2m space group. It is isostructural with K3Ta3B2O12 and the high temperature phase of K3Nb3B2O12.</p> / Thesis / Master of Science (MSc)