Boron carbide nano-powders, singly-doped over a range of compositions, were pressurelessly-sintered at identical temperature and atmospheric conditions in a dif- ferential dilatometer to investigate sintering behavior. Samples that achieved relative densities greater than 93% of theoretical density were post-HIPed. Post-HIPing re- sulted in an increase in relative density as well as an increase in Vicker's hardness. To optimize the sintering behavior, nano-powders with multiple dopants were prepared based on the results of single dopant experiments. These powders were studied using the same heating schedule as the single dopant samples. The powder with optimized composition was selected, and 44.45 mm diameter disks were pressed to determine the effects of sample size. Powder composition #166 with Al, Ti, W and Mg additions was processed using di¢çerent methods in order to create defect-free green bodies after uniaxial press- ing. The 44.45 mm diameter compacts were heat-treated to remove organics and B₂O₃coatings on particles and then encapsulated in an evacuated fused silica am- pule. Encapsulated samples were HIPed at temperatures below the coarsening region observed in the dilatometric traces of multiply-doped nano-powders. The E-HIPed sample showed a relative density of 96% with a limited extent of nano-sized grain microstructure.

The objective of the proposed research is to develop low-cost, screen-printed 20% efficient silicon solar cells. In the first part of this thesis, a ~19% efficient, screen-printed cell was fabricated using the commercially-dominant aluminum back surface field (Al-BSF) cell structure. Device modeling was then used to determine that increasing the efficiency to 20% required improvements in both back surface passivation and rear reflectance. In the second part of this thesis, a passivated, transparent boron BSF (B-BSF) structure was proposed as a high-throughput method for realizing these improvements. The first step in fabricating the proposed B-BSF cell involved the successful development of a water-based, spin-on solution of boric acid as a low-cost, non-toxic and non-pyrophoric alternative to common boron diffusion sources such as boron tribromide. A review of the literature shows that a common problem with boron diffusion is severe bulk lifetime degradation, with Fe contamination being commonly speculated as the cause. An experimental study was therefore devised in which the impact of boron diffusion and subsequent cell process steps on the bulk lifetime and bulk iron contamination was tracked. From this study, a model for boron diffusion-induced Fe contamination was developed along with methods for gettering Fe from the substrate. A key achievement of this thesis was the discovery of a novel, negatively charged, aluminum-doped spin-on glass (SOG) which can, in a short thermal step, simultaneously getter Fe and provide stable, high-quality passivation of planar, boron-diffused Si surfaces. Since past attempts at achieving low-cost, high-efficiency, boron-diffused cells have suffered from bulk lifetime degradation and difficulties with passivating a boron-diffused Si surface, the Al-doped SOG provides a solution to both challenges. Since a high rear reflectance is important for achieving high-efficiencies, an experimental study of various reflectors was undertaken and a silver colloid material was found which exhibits both high electrical conductivity and Lambertian reflectance >95%. The work on boric acid diffusion, iron gettering, surface passivation and rear reflectors was successfully integrated into a 20.2% efficient, screen-printed, B-BSF cell fabricated on 300 µm thick, p-type float-zone (FZ) Si wafers. Both device theory and modeling was used to show that, due to its well-passivated surfaces, this cell would suffer a large loss in efficiency due to light-induced degradation (LID) if it were fabricated on commercial p-type Czochralski (Cz) Si substrates. Since n-type Si substrates do not suffer from LID, the p-type process was slightly tweaked and applied to n-type FZ wafers, resulting in 20.3% efficient cells on 190 µm thick wafers. Computer modeling shows that both the p-type and n-type cells can maintain efficiencies of 20% for wafers as thin as 100 µm.

In Siedewasserreaktoren ist ein Boreinspeisesystem diversitär wirkend zur Reaktorschnellabschaltung installiert. Dieses System garantiert, dass der Reaktor beim Versagen des Schnellabschaltesystems in einen unterkritischen Zustand überführt werden kann. Der aufgrund der Nachzerfallsleistung entweichende Dampf trägt jedoch ständig einen Teil des eingespeisten Bors in Form von Borsäure mit sich. Da dieser Prozess bisher nicht quantifiziert wurde, ist somit das Eintreten einer Rekrititkalität während der Transiente ohne weitere Untersuchungen nicht auszuschließen. In der vorliegenden Arbeit erfolgt die Erstellung einer fundierten Datenbasis zur Quantifizierung des Borverlusts an verschiedenen Betriebspunkten. Dazu stehen nach vorheriger Konstruktion und Inbetriebnahme zwei Versuchsanlagen zur Verfügung, ein Versuchsautoklav und der Siedewasserreaktor-Simulator BORAN. Das in diesen Versuchsanlagen enthaltene und als Kühlmedium genutzte entionisierte Wasser wird wie bei einem Siedewasserreaktor mit einer hochkonzentrierten Lösung der Borverbindung Dinatrium-Pentaborat-Dekahydrat versetzt. Für weiterführende Untersuchungen findet auch Borsäure Verwendung. Die Bestimmung des Borgehalts der Kondensate des entwichenen Dampfes erfolgt mit Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS). Die durch Variation von Borkonzentration, Temperatur, pH-Wert und Volumendampfgehalt erzeugten Messdaten fließen in einem Flüchtigkeitsmodell in Form einer empirischen Gleichung zusammen, welches in den Thermohydraulikcode ATHLET implementiert wird. Experimente am SWR-Simulator BORAN und entsprechende Rechnungen mit dem modifizierten Code ATHLET von Langzeit-Deborierungstransienten bei unterschiedlichen Randbedingungen bestätigen das Flüchtigkeitsmodell. Gleichzeitig erfolgt mittels dieser Experimente die Validierung des Modells im ATHLET mit hinreichender Genauigkeit. Mit den Ergebnissen aus Rechnungen und Experimenten wird das Boreinspeisesystem in seiner aktuellen Konfiguration bewertet und mit zukünftigen Konzepten verglichen. Schlussendlich erfolgt der Nachweis, dass die Funktionalität des Boreinspeisesystem aus dem Blickwinkel der durchgeführten Analysen, trotz der nachgewiesenen Borflüchtigkeit, die Forderungen der KTA 3103 erfüllt und aufgrund der nachgewiesenen Borflüchtigkeit binnen der ersten beiden Stunden der Transiente keine Rekritikalität verursacht wird. / In boiling water reactors a boron injection system as an alternative system is installed to guarantee that the reactor shut down in case of a total or partial ATWS accident. Because of the heat generated by the fission products after shutting down a part of the injected boron is evaporated as boron acid. This process is not characterized quantitatively yet. This is the reason that the incidence of recriticality during a transient cannot be excluded without further research. In the following studies a funded database quantifying the loss of boron is established. The volatility of the boron solution was measured by experiments in a small autoclave and in a boiling water reactor simulator called BORAN after construction. The deionised water used as coolant in the facilities will be enriched with boron by a high concentrated solution of Disodium-Pentaborate-Decahydrate. The measurement of the boron concentration in the condensates of the exhausted vapour is carried out by inductively-coupled-plasma mass-spectrometry (ICP-MS). For additional analysis boron acid is also used. The boron concentration in the vapour mainly depends on the temperature and void fraction of the two-phase-flow. This volatility model in form of an empiric equation is implemented in the thermo hydraulic ATHLET-code. Furthermore the reason of the volatility of the analysed solutions will be discussed within a chemical and physical background. Experiments at the BORAN facility and corresponding calculation with the modified ATHLET-code of long time deboration transients with different boundary conditions prove the volatility model. Thereby the code will be validated with sufficient accuracy. The modified code with an adapted Input-Dataset provides the possibility to calculate transients with the loss of boron. With the consideration of the volatility the demand of the KTA-rule 3103 on the Boron injection system is also grantable.

Submitted by Aelson Maciera (aelsoncm@terra.com.br) on 2017-08-16T18:44:54Z No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-30T17:35:55Z (GMT) No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Approved for entry into archive by Ronildo Prado (bco.producao.intelectual@gmail.com) on 2018-01-30T17:36:40Z (GMT) No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) / Made available in DSpace on 2018-01-30T17:44:12Z (GMT). No. of bitstreams: 1 DissDGM.pdf: 5323739 bytes, checksum: 447d6c5ecd08953e14c16e2d47d03040 (MD5) Previous issue date: 2017-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Sintering additives (AS) have great potential to be applied in refractory castables as they reduce the densification temperature of these products. Additionally, these components may induce the generation of a transient liquid phase in the microstructure at high temperatures, which can react with the other materials of the composition to give rise novel solid refractory phases. Considering these aspects, the present work evaluated the role of five different AS (boron oxide, boric acid, sodium borosilicate, magnesium borate and boron carbide) when added to alumina-based castable compositions containing hydratable alumina as binder. Based on the thermomechanical characterization, XRD analysis and the in situ elastic modulus measurement, boron carbide (B4C) have been selected as a promising AS because this material sped up the sintering process at lower temperatures and induced the aluminum borates formation due to the reaction between the liquid phase and the fine alumina contained in the castable matrix. Afterwards, the effects of B4C was evaluated in ultra-low calcium oxide castables bonded with: colloidal alumina (AC), hydratable alumina (AB) and/ or SioxX®-Zero (SZ). SZ-bonded materials (4 wt.%) had good performance at temperatures around 1100°C due to the mullite generation. On the another hand, castables containing AC as binder (4 wt.% of solids) and 0.5 wt.% of B4C are promising options to be used in working conditions between 600-815°C, whereas the same mixture without B4C could only be densified above 1100°C. Similar effect was observed when 1.0 wt.% B4C was added to SZ-containing castables as the aluminum borates generation allows these compositions to be used in working conditions around 815°C. Therefore, an appropriate AS selection for high-alumina castables with ultra-low CAC content has the potential to favour the earlier sintering of the refractory and improve its thermomechanical properties, which can fulfill the requirements of the petrochemical industry. / Os aditivos sinterizantes (AS) possuem potencial para serem aplicados em concretos refratários, pois diminuem a temperatura de densificação destes produtos. Adicionalmente, tais componentes podem atuar favorecendo a formação de líquidos transientes na microestrutura em altas temperaturas, os quais têm a capacidade de reagir com os outros constituintes da composição para formar novas fases refratárias. Diante desta possibilidade, neste trabalho foram avaliados os efeitos da adição de cinco fontes de boro como AS (óxido de boro, ácido bórico, borosilicato de sódio, borato de magnésio e carbeto de boro) em concretos de alta alumina contendo alumina hidratável como ligante. Baseado na caracterização das propriedades termomecânicas destes refratários, assim como nas análises de DRX e da avaliação do módulo elástico in situ, foi selecionado o carbeto de boro (B4C) como o AS promissor, pois este promoveu o início da sinterização dos concretos em temperaturas inferiores e induziu a formação de boratos de alumínio a partir da reação do líquido com a alumina da matriz dos concretos refratários. Posteriormente, avaliou-se o efeito da adição do B4C em concretos com ultra-baixo teor de óxido de cálcio e ligados com: alumina coloidal (AC), alumina hidratável (AB) e/ou SioxX®-Zero (SZ). Materiais ligados com SZ (4%-p) são promissores em temperaturas próximas a 1100°C devido à formação de mulita. Por outro lado, concretos contendo AC (4%-p de sólidos) e 0,5%-p B4C são indicados para condições de serviço entre 600-815°C, pois sem a fonte de boro densificaram apenas acima de 1100°C. Efeito similar foi observado quando adicionado 1,0%-p B4C no concreto contendo SZ, visto que também foram formados boratos de alumínio possibilitando sua utilização em condições de serviço próximas aos 815°C. Desta forma, realizando-se a correta seleção do AS adicionado em concretos de alta alumina com ultra-baixo teor de CAC, tem o potencial de aumentar a sinterabilidade do material e melhorar suas propriedades termomecânicas, podendo assim atender os requisitos da indústria petroquímica.

Cette thèse s’articule autour de matériaux à base de bore pour des applications « énergie ». Nous avons développé deux classes de matériaux. (i) La première classe est dédiée au stockage chimique de l’hydrogène. Les matériaux étudiés dans cette partie sont produits par déstabilisation par mécanosynthèse de l’hydrazine borane N2H4BH3 en substituant un hydrogène protique de ce dernier par un cation alcalin. Nous avons particulièrement étudié la modification chimique de l’hydrazine borane par l’amidure de lithium LiNH2, puis par l’hydrure du calcium CaH2. Dans le premier cas, un nouveau composé de formule LiN2H3BH3.0,25NH3 a été obtenu. Dans le second cas, l’hydrazinidoborane de calcium Ca(N2H3BH3)2 a été synthétisé dans des conditions expérimentales spécifiques. (ii) La deuxième classe de matériaux concerne les polyboranes anioniques solubles dans l’eau pour une utilisation comme combustible anodique de pile à combustible liquide. Nous avons synthétisé et pleinement caractérisé le closo-décaborane de sodium Na2B10H10 et le 1-oxa-nido-dodécaborate de sodium NaB11H12O, puis leur électrooxydation a été étudiée et discutée sur différentes électrodes massives (platine, or et argent). Tous nos résultats sont présentés, discutés en détail et mis en perspective dans ce manuscrit de thèse. / The present work is structured around boron-based materials expected to be used in the field of “energy”. We especially worked on two types of materials. (i) With the first type, solid-state hydrogen storage was targeted. Hydrazine borane N2H4BH3 was used as precursor of novel derivatives obtained by mechanosynthesis. We first made it react with lithium amide LiNH2 to obtain LiN2H3BH3.0,25NH3. Then, we considered calcium hydride CaH2; it reacted with N2H4BH3 at 67°C (after ball-milling) to form a new phase, calcium hydrazinidoborane of formula Ca(N2H3BH3)2. (ii) The second type of boron-based materials we investigated is about anionic polyboranes. They are known to be stable in aqueous solution and accordingly could be used as anodic fuel of direct liquid-fed fuel cell. We aimed at synthesizing and fully characterizing two salts: sodium closo-decaborane Na2B10H10 and sodium 1-oxa-nido-dodecaborate NaB11H12O. Their potential for the aforementioned application was tested by cyclic voltammetry by using bulk electrodes of platinum, silver and gold. All of our results are presented, discussed in detail and put into perspective in the present thesis.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16808号 / 工博第3529号 / 新制||工||1534(附属図書館) / 29483 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 杉野目 道紀, 教授 村上 正浩, 教授 吉田 潤一 / 学位規則第4条第1項該当

In Siedewasserreaktoren ist ein Boreinspeisesystem diversitär wirkend zur Reaktorschnellabschaltung installiert. Dieses System garantiert, dass der Reaktor beim Versagen des Schnellabschaltesystems in einen unterkritischen Zustand überführt werden kann. Der aufgrund der Nachzerfallsleistung entweichende Dampf trägt jedoch ständig einen Teil des eingespeisten Bors in Form von Borsäure mit sich. Da dieser Prozess bisher nicht quantifiziert wurde, ist somit das Eintreten einer Rekrititkalität während der Transiente ohne weitere Untersuchungen nicht auszuschließen. In der vorliegenden Arbeit erfolgt die Erstellung einer fundierten Datenbasis zur Quantifizierung des Borverlusts an verschiedenen Betriebspunkten. Dazu stehen nach vorheriger Konstruktion und Inbetriebnahme zwei Versuchsanlagen zur Verfügung, ein Versuchsautoklav und der Siedewasserreaktor-Simulator BORAN. Das in diesen Versuchsanlagen enthaltene und als Kühlmedium genutzte entionisierte Wasser wird wie bei einem Siedewasserreaktor mit einer hochkonzentrierten Lösung der Borverbindung Dinatrium-Pentaborat-Dekahydrat versetzt. Für weiterführende Untersuchungen findet auch Borsäure Verwendung. Die Bestimmung des Borgehalts der Kondensate des entwichenen Dampfes erfolgt mit Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS). Die durch Variation von Borkonzentration, Temperatur, pH-Wert und Volumendampfgehalt erzeugten Messdaten fließen in einem Flüchtigkeitsmodell in Form einer empirischen Gleichung zusammen, welches in den Thermohydraulikcode ATHLET implementiert wird. Experimente am SWR-Simulator BORAN und entsprechende Rechnungen mit dem modifizierten Code ATHLET von Langzeit-Deborierungstransienten bei unterschiedlichen Randbedingungen bestätigen das Flüchtigkeitsmodell. Gleichzeitig erfolgt mittels dieser Experimente die Validierung des Modells im ATHLET mit hinreichender Genauigkeit. Mit den Ergebnissen aus Rechnungen und Experimenten wird das Boreinspeisesystem in seiner aktuellen Konfiguration bewertet und mit zukünftigen Konzepten verglichen. Schlussendlich erfolgt der Nachweis, dass die Funktionalität des Boreinspeisesystem aus dem Blickwinkel der durchgeführten Analysen, trotz der nachgewiesenen Borflüchtigkeit, die Forderungen der KTA 3103 erfüllt und aufgrund der nachgewiesenen Borflüchtigkeit binnen der ersten beiden Stunden der Transiente keine Rekritikalität verursacht wird.:1 Einleitung und Motivation 1 A Theoretische Vorbetrachtung 2 Die Borchemie 9 2.1 Bor 9 2.2 Borverbindungen 9 2.3 Beeinflussung der Ionenzusammensetzung gelöster Borat-Ionen 15 2.4 Flüchtigkeit von Borsäure und Boraten 18 2.5 Veränderungen der Oberflächenspannung von Wasser durch Borverbindungen 23 3 Probenpräparation 24 4 RAMAN-Spektroskopie und Thermogravimetrie / Differenzthermoanalyse 25 B Beschreibung der Versuchsanlagen und des Simulationsprogramms 5 Versuchsanlage – Autoklav 29 6 Versuchsanlage – Umlaufschleife BORAN 31 7 Zweiphasenmesstechnik und Phasenschlupf 40 8 Leitfähigkeit und pH-Messungen an Borlösungen 46 9 Konzentrationsbestimmung 48 10 Konzentrationsmesssystem in der Umlaufschleife BORAN 51 C Messwerteerfassung und Modellbildung 11 Borausbreitung in einphasiger und zweiphasiger Strömung 55 12 Flüchtigkeit des Bors mit Wasserdampf 57 12.1 Vorbetrachtungen 57 12.2 Flüchtigkeitsmessungen am Autoklav 59 12.2.1 Einfluss von Substanz, Konzentration und Temperatur 59 12.2.2 Einfluss vom pH-Wert 62 12.2.3 Einfluss des Füllstandes 63 12.3 Flüchtigkeitsmessungen an der BORAN – Anlage 64 12.3.1 Vorteile gegenüber dem Autoklav 64 12.3.2 Einfluss von Temperatur und Dampfgehalt 64 12.3.3 Einfluss des Massenstroms 67 12.3.4 Einfluss des pH-Wertes 70 12.3.5 Transiente Messpunkte 71 13 Modellbildung – Beschreibung über empirische Gleichungen 73 14 Borflüchtigkeit mit eingeperltem Dampf oder Luft 77 14.1 Einperlung von Dampf in die BORAN – Anlage 77 14.2 Lufteinperlung in borsaure Lösung in Lufteinperlanlage 81 15 Ergebnisvergleich von BORAN – Anlage und Autoklav 84 16 Einordnung der Experimente in das Flüchtigkeitsmodell 85 17 Zusammenfassende Ergebnisdarstellung – Diskussion 87 17.1 Volumendampfgehalt und Phasengrenzflächendichte 89 17.2 Bormassenstromdichte 91 D Simulationen mit ATHLET und Deborierung 18 ATHLET – ein Simulationsprogramm der Thermohydraulik 93 18.1 Einführung in das Simulationsprogramm 93 18.2 Erstellen und Anpassen des Eingabedatensatzes für BORAN 96 19 Modifikation des ATHLETs für Deborierungsrechnungen 99 20 Flüchtigkeitsverhalten bei zeitlich langem Ausdampfen 101 21 Bewertung der bisherigen Ergebnisse 103 E Bezug zur Realanlage 22 Abschätzung des Borverlustes bei Transienten 105 23 Möglichkeiten der Reduktion der Borflüchtigkeit 107 24 Zukünftige Einspeisekonzepte 108 F Zusammenfassung 25 Zusammenfassung der Ergebnisse 113 26 Danksagung 117 27 Quellen- und Literaturverzeichnis 119 28 Tabellenverzeichnis 125 29 Abbildungsverzeichnis 126 G Anhänge 30 Anhang 1 Exakte Berechnung des pH-Wertes der Lösung beim Erwärmen 133 31 Anhang 2 ATHLET-Rechnung für Autoklav 135 32 Anhang 3 Konstruktionsbeschreibung der Versuchsanlage BORAN 137 / In boiling water reactors a boron injection system as an alternative system is installed to guarantee that the reactor shut down in case of a total or partial ATWS accident. Because of the heat generated by the fission products after shutting down a part of the injected boron is evaporated as boron acid. This process is not characterized quantitatively yet. This is the reason that the incidence of recriticality during a transient cannot be excluded without further research. In the following studies a funded database quantifying the loss of boron is established. The volatility of the boron solution was measured by experiments in a small autoclave and in a boiling water reactor simulator called BORAN after construction. The deionised water used as coolant in the facilities will be enriched with boron by a high concentrated solution of Disodium-Pentaborate-Decahydrate. The measurement of the boron concentration in the condensates of the exhausted vapour is carried out by inductively-coupled-plasma mass-spectrometry (ICP-MS). For additional analysis boron acid is also used. The boron concentration in the vapour mainly depends on the temperature and void fraction of the two-phase-flow. This volatility model in form of an empiric equation is implemented in the thermo hydraulic ATHLET-code. Furthermore the reason of the volatility of the analysed solutions will be discussed within a chemical and physical background. Experiments at the BORAN facility and corresponding calculation with the modified ATHLET-code of long time deboration transients with different boundary conditions prove the volatility model. Thereby the code will be validated with sufficient accuracy. The modified code with an adapted Input-Dataset provides the possibility to calculate transients with the loss of boron. With the consideration of the volatility the demand of the KTA-rule 3103 on the Boron injection system is also grantable.:1 Einleitung und Motivation 1 A Theoretische Vorbetrachtung 2 Die Borchemie 9 2.1 Bor 9 2.2 Borverbindungen 9 2.3 Beeinflussung der Ionenzusammensetzung gelöster Borat-Ionen 15 2.4 Flüchtigkeit von Borsäure und Boraten 18 2.5 Veränderungen der Oberflächenspannung von Wasser durch Borverbindungen 23 3 Probenpräparation 24 4 RAMAN-Spektroskopie und Thermogravimetrie / Differenzthermoanalyse 25 B Beschreibung der Versuchsanlagen und des Simulationsprogramms 5 Versuchsanlage – Autoklav 29 6 Versuchsanlage – Umlaufschleife BORAN 31 7 Zweiphasenmesstechnik und Phasenschlupf 40 8 Leitfähigkeit und pH-Messungen an Borlösungen 46 9 Konzentrationsbestimmung 48 10 Konzentrationsmesssystem in der Umlaufschleife BORAN 51 C Messwerteerfassung und Modellbildung 11 Borausbreitung in einphasiger und zweiphasiger Strömung 55 12 Flüchtigkeit des Bors mit Wasserdampf 57 12.1 Vorbetrachtungen 57 12.2 Flüchtigkeitsmessungen am Autoklav 59 12.2.1 Einfluss von Substanz, Konzentration und Temperatur 59 12.2.2 Einfluss vom pH-Wert 62 12.2.3 Einfluss des Füllstandes 63 12.3 Flüchtigkeitsmessungen an der BORAN – Anlage 64 12.3.1 Vorteile gegenüber dem Autoklav 64 12.3.2 Einfluss von Temperatur und Dampfgehalt 64 12.3.3 Einfluss des Massenstroms 67 12.3.4 Einfluss des pH-Wertes 70 12.3.5 Transiente Messpunkte 71 13 Modellbildung – Beschreibung über empirische Gleichungen 73 14 Borflüchtigkeit mit eingeperltem Dampf oder Luft 77 14.1 Einperlung von Dampf in die BORAN – Anlage 77 14.2 Lufteinperlung in borsaure Lösung in Lufteinperlanlage 81 15 Ergebnisvergleich von BORAN – Anlage und Autoklav 84 16 Einordnung der Experimente in das Flüchtigkeitsmodell 85 17 Zusammenfassende Ergebnisdarstellung – Diskussion 87 17.1 Volumendampfgehalt und Phasengrenzflächendichte 89 17.2 Bormassenstromdichte 91 D Simulationen mit ATHLET und Deborierung 18 ATHLET – ein Simulationsprogramm der Thermohydraulik 93 18.1 Einführung in das Simulationsprogramm 93 18.2 Erstellen und Anpassen des Eingabedatensatzes für BORAN 96 19 Modifikation des ATHLETs für Deborierungsrechnungen 99 20 Flüchtigkeitsverhalten bei zeitlich langem Ausdampfen 101 21 Bewertung der bisherigen Ergebnisse 103 E Bezug zur Realanlage 22 Abschätzung des Borverlustes bei Transienten 105 23 Möglichkeiten der Reduktion der Borflüchtigkeit 107 24 Zukünftige Einspeisekonzepte 108 F Zusammenfassung 25 Zusammenfassung der Ergebnisse 113 26 Danksagung 117 27 Quellen- und Literaturverzeichnis 119 28 Tabellenverzeichnis 125 29 Abbildungsverzeichnis 126 G Anhänge 30 Anhang 1 Exakte Berechnung des pH-Wertes der Lösung beim Erwärmen 133 31 Anhang 2 ATHLET-Rechnung für Autoklav 135 32 Anhang 3 Konstruktionsbeschreibung der Versuchsanlage BORAN 137

The aim of this study was to understand the processing – structure – property relationships in spark plasma sintered (SPS) boron carbide (B4C) and B4C-titanium diboride (TiB2) ceramic composites. SPS allowed for consolidation of both B4C and B4C-TiB2 composites without sintering additives, residual phases, e.g., graphite, and excessive grain growth due to long sintering times. A selection of composite compositions in 20% TiB2 feedstock powder increments from 0% to 100%, was sintered at 1900°C for 25 minutes hold time. A homogeneous B4C-TiB2 composite microstructure was determined with excellent distribution of TiB2 phase, while achieving ~99.5% theoretical density. An optimum B4C-23 vol.% TiB2 composite composition with low density of ~3.0 g/cm3 was determined that exhibited ~30-35% increase in hardness, fracture toughness, and flexural bend strength compared to commercial armor-grade B4C. This is a result of a) no residual graphitic carbon in the composites, b) interfacial microcrack toughening due to thermal expansion coefficient differences placing the B4C matrix in compression and TiB2 phase in tension, and c) TiB2 phase aids in crack deflection thereby increasing the amount of intergranular fracture. Collectively, the addition of TiB2 serves as a strengthening and toughening agent, and SPS shows promise for the manufacture of hybrid ceramic composites.

This thesis entitled “Electronic Structure and Bonding in Metallaboranes and Main Group Compounds” consists of five chapters. Chapter 1 gives an exposition of concepts and techniques used in understanding the electronic structure and bonding in some chemically interesting molecules. Heuristics concepts like isolobal analogy and electron counting rules are used in analyzing and predicting some novel chemical systems. A brief description of computational techniques such as density functional theory (DFT) based methods are used to quantitatively examine the structures and energies of these systems. In chapter 2 we present a critical analysis of bonding in neutral and dianionic stannadiphospholes and compare the potential energy surfaces with the isoelectronic Cp+ and Cp- species. The analysis indicates that Sn can be a better isolobal analogue to P+ than to BH or CH+. In chapter 3 we present new strategy to stabilize B2H4 in planar configuration using transition metal fragments. This requires the metal to donate two electrons into the empty B-B π orbital. Such complexes present a unique case study to the classical DCD model of metal-π complex. In chapter 4 we study the bonding in some recently synthesized metallaboranes which does not follow conventional electron counting rules. The complex and non-canonical nature of these metallaboranes feature some unique bonding patterns which are elucidated using theoretical techniques. In the final chapter we present new approach to build metal coated boron fullerenes. We use electron counting rules to device new structures which show enhanced metal boron bonding.

Orientador: Ciro Antonio Rosolem / Banca: Dirceu Maximino Fernandes / Banca: José Carlos Casagrande / Resumo: Em algumas condições não se têm obtido correlações entre os teores de B do solo, extraído com água quente, o teor de boro na planta e a produtividade da soja no Estado do Mato Grosso, mais precisamente na região de Campo Novo do Parecis. Sabe-se que o boro é um nutriente fortemente adsorvido nas partículas minerais do solo. Objetivou-se com este trabalho submeter amostras de solo de uma determinada área de estudo, na qual foi cultivada soja por três anos consecutivos e posteriormente cultivado algodão, a diferentes métodos de extração de boro, a fim de se estabelecer correlações entre a dose de boro na planta, a dose de nutriente aplicada e o teor de boro no solo disponível às plantas e, ainda, com a produtividade da soja. Amostras de solo, cultivadas com soja, coletadas por ocasião da condução do experimento no campo, foram analisadas quanto à concentração de B extraída pelos métodos: água quente modificado com solução de BaCl2 1,25 g L-1 (recomendado e chamado de método da água quente pelo IAC); água quente modificado com solução de CaCl2 0,01 mol L-1,a quente e água quente tradicional (o qual é preconizado por muitos autores como o método oficial) para dessa forma, tentar quantificar a real disponibilidade de boro neste solo, caracterizado como um LATOSSOLO VERMELHO AMARELO (LVA), possibilitando a determinação de um nível crítico. Ainda, durante o período de condução do trabalho, foi feito um estudo de adsorção de B nas amostras, e um estudo do comportamento da lixiviação do nutriente em colunas de solo, procurando verificar o efeito das adubações na dinâmica do nutriente. Em relação aos métodos de extração de boro no solo, o CaCl2 foi o que apresentou correlação positiva e significativa com o boro presente no tecido vegetal nos três anos agrícolas. Os métodos do BaCl2 e ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In some conditions, doesn't have obtained correlations among boron content in soil, boron extracted by hot water, boron content in plants and soybean productivity in a region (Campo Novo do Parecis) of the state of Mato Grosso/Brazil. This work was carried out to submit soil samples from determined area of study where was tillage soybean for three subsequent years and after tillage cotton, to differents extraction methods by boron with the aim to establish correlations among, amount of boron content in plants, amount of nutrient putted in soil, boron content in soil disponible to plants and the productivity. Soil samples obtained during the conduction of experiment on field were analyzed to predict the amount of boron in soil by the methods: hot water modified with BaCl2 solution (recommended and called by hot water from IAC - Instituto Agronômico de Campinas/SP-Brazil), hot water modified CaCl2 0,01 mol L-1 solution and hot water traditional (which is preconized by many authors like the official method) to this way try to quantify the real situation of boron disponibility in this soil, characterized like a Yellow Red Latossol, to take the determination of a critical level. During the conduction period of this work was made an adsorption study in the samples, and still a study of boron leaching behavior in soil columns, to verify fertilizer effect in nutrient dynamic. The extraction method with CaCl2 presented positive and significative correlation with boron present in soybean leaves on three subsequent farm work years. BaCl2 method and hot water traditional also presented positives and significatives correlations each one in two farm work years, this results were expected in function of similarity among three methods, it's an evidence that there is a method with capacity to predict boron disponibility in soils of Mato Grosso... (Complete abstract, click eletronic address below) / Mestre