A ureia (UR) é atualmente o fertilizante nitrogenado mais utilizado na agricultura brasileira. No entanto, quando aplicada na superfície do solo está sujeita a perdas de nitrogênio (N) por volatilização de NH3. Uma das formas de minimizar as perdas de N-NH3 é o tratamento do fertilizante com inibidores de urease. A associação desses compostos com substâncias húmicas (SH), no tratamento da UR poderia aumentar a eficiência de uso dos nutrientes pelas plantas. O objetivo desse trabalho foi avaliar a eficiência de inibidores de urease, associados ou não com SH no revestimento da UR como fonte de N em cobertura para o milho. O experimento foi conduzido em casa de vegetação durante 62 dias em delineamento experimental de blocos ao acaso, com três repetições, no esquema fatorial completo, com UR recoberta três inibidores de urease (0,40% B + 0,15% Cu; 0,64% B; NBPT) e um tratamento adicional sem inibidor (Ausente), três doses de SH (0, 0,6, e 1,2%) e um controle. Os tratamentos com N constaram da aplicação de fonte única do nutriente [CO(15NH2)2] aplicada em faixa e em superfície na dose de 180 mg kg-1 de N no estádio fisiológico V4 das plantas de milho. As plantas foram amostradas nos estádios V8 e VT do milho, respectivamente, aos 52 e 62 dias após a semeadura, quando foram avaliados: biometria de parte aérea, área foliar, biomassa seca de raízes e da parte aérea, caracterização morfológica do sistema radicular, e a eficiência de uso do N-fertilizante (EUN) pelo método do balanço isotópico (15N). Também se quantificou as perdas de N por volatilização de NH3 por meio de coletores semi-estáticos com espuma embebida em H3PO4- para avaliação comparativa entre tratamentos. Embora a concentração mais elevada de ácido bórico na UR (0,64% B) tenha reduzido mais as perdas de NH3 por volatilização em comparação ao 0,40 % B + 0,15 % Cu, isso não resultou em maior eficiência de uso do N-fertilizante pelo milho em VT, que ocorreu somente em V8. Em ambos os estádios, o NBPT apresentou-se como melhor inibidor de urease na ausência de SH. A aplicação de SH não aumentou a EUN pelo milho em V8 ou VT quando associados com 0,40% B + 0,15% Cu, 0,64% B, ou mesmo na UR convencional. Entretanto, quando associado com o NBPT, ocorreu aumento das perdas de NH3 por volatilização e redução na EUN em VT, o que pode ter ocorrido devido ao elevado pH das SH (8,5-9) e ao seu baixo poder tampão. A aplicação da UR convencional ou revestida com inibidores de urease não aumentou a taxa de crescimento ou biomassa seca de raízes e parte aérea do milho em nenhum dos períodos avaliados quando comparado ao controle. Da mesma forma, não foram observadas diferenças expressivas entre tratamentos na caracterização morfológica do sistema radicular em V8 ou VT. A ausência de diferença entre tratamentos pode ser explicada pelo curto período de tempo entre a adubação de cobertura e as avaliações das plantas, à aplicação superficial das fontes recobertas com SH e ao método de irrigação adotado, que impediu que as SH entrassem totalmente em contato com as raízes da planta. Além disso, é possível, também, que a dose de SH empregada tenha sido muito baixa para ser efetiva. / Urea (UR) is the most widely applied nitrogen (N) fertilizer in Brazilian agriculture. However, UR is more prone to ammonia (NH3) volatilization losses than other N sources when surface-applied. One alternative to improve nitrogen use efficiency (NUE) of surface-applied UR is through application of urease inhibitors as coating materials of UR. The association of these composts with humic substances (HS) as UR coating materials may also improve nutrient recovery by plants. The aim of this study was to evaluate the efficiency of urease inhibitors, associated or not with HS, as coating materials of UR as new top-dress N sources for maize. A greenhouse pot trial was carried out over 62 days with maize (Zea mays L.), in a completely randomized block design, with three replicates in a full factorial design, with UR coated with three urease inhibitors (0,40% B + 0,15% Cu; 0,64% B; NBPT) and one additional treatment without inhibitor, three doses of HS (0, 0.6, and 1.2%), and one control treatment. All treatments imposed had CO(15NH2)2 as N source, application rate of 180 mg kg-1of N, and side-dressing application at the V4 maize growth stage. Maize plants were assessed at V8 and VT growth stages, at 52 and 62 days after sowing, respectively, when it was evaluated: above and below-ground plant dry matter weight; leaf area; root morphological traits (length, surface area, and volume); and fertilizer use efficiency by the 15N balance method. In addition, semi-open static collectors with foam discs previously soaked in H3PO4- were used to quantify comparatively the NH3 volatilized from all treatments. Although the addition of a higher dose of boric acid on UR (0,64% B) promoted lower ammonia losses by volatilization in comparison to 0,40 % B + 0,15 % Cu, it did not result in higher NUE by maize in VT, which occurred at V8. In both growth stages, NBPT presented the best performance as urease inhibitor in the absence of HS. The application of HS did not increase NUE by maize in V8 and VT when associated with 0,40% B + 0,15% Cu, 0,64% B or even conventional UR. However, when added in conjunction with NBPT, it increased ammonia volatilization and reduced NUE in VT which may have occurred due to the high pH of the HS (8.5-9) and low buffering capacity. Moreover, the application of conventional UR or UR treated with HS and urease inhibitors did not increase maize growth rate or shoot/root dry matter weight in comparison to the control treatment at both growth stages. Likewise, there was no major significant differences between treatments on root morphological traits (length, surface area, and volume) at both growth stages assessed. The lack of sizable outcome differences between treatments could be explained by the application of a single N dose, the short period of time between the side-dressing application and assessment of maize plants, and to the surface-application of the HS and method of irrigation which prevented HS to have full contact with maize roots. Furthermore, HS application rate may have been too low to be effective.

A ureia (UR) é atualmente o fertilizante nitrogenado mais utilizado na agricultura brasileira. No entanto, quando aplicada na superfície do solo está sujeita a perdas de nitrogênio (N) por volatilização de NH3. Uma das formas de minimizar as perdas de N-NH3 é o tratamento do fertilizante com inibidores de urease. A associação desses compostos com substâncias húmicas (SH), no tratamento da UR poderia aumentar a eficiência de uso dos nutrientes pelas plantas. O objetivo desse trabalho foi avaliar a eficiência de inibidores de urease, associados ou não com SH no revestimento da UR como fonte de N em cobertura para o milho. O experimento foi conduzido em casa de vegetação durante 62 dias em delineamento experimental de blocos ao acaso, com três repetições, no esquema fatorial completo, com UR recoberta três inibidores de urease (0,40% B + 0,15% Cu; 0,64% B; NBPT) e um tratamento adicional sem inibidor (Ausente), três doses de SH (0, 0,6, e 1,2%) e um controle. Os tratamentos com N constaram da aplicação de fonte única do nutriente [CO(15NH2)2] aplicada em faixa e em superfície na dose de 180 mg kg-1 de N no estádio fisiológico V4 das plantas de milho. As plantas foram amostradas nos estádios V8 e VT do milho, respectivamente, aos 52 e 62 dias após a semeadura, quando foram avaliados: biometria de parte aérea, área foliar, biomassa seca de raízes e da parte aérea, caracterização morfológica do sistema radicular, e a eficiência de uso do N-fertilizante (EUN) pelo método do balanço isotópico (15N). Também se quantificou as perdas de N por volatilização de NH3 por meio de coletores semi-estáticos com espuma embebida em H3PO4- para avaliação comparativa entre tratamentos. Embora a concentração mais elevada de ácido bórico na UR (0,64% B) tenha reduzido mais as perdas de NH3 por volatilização em comparação ao 0,40 % B + 0,15 % Cu, isso não resultou em maior eficiência de uso do N-fertilizante pelo milho em VT, que ocorreu somente em V8. Em ambos os estádios, o NBPT apresentou-se como melhor inibidor de urease na ausência de SH. A aplicação de SH não aumentou a EUN pelo milho em V8 ou VT quando associados com 0,40% B + 0,15% Cu, 0,64% B, ou mesmo na UR convencional. Entretanto, quando associado com o NBPT, ocorreu aumento das perdas de NH3 por volatilização e redução na EUN em VT, o que pode ter ocorrido devido ao elevado pH das SH (8,5-9) e ao seu baixo poder tampão. A aplicação da UR convencional ou revestida com inibidores de urease não aumentou a taxa de crescimento ou biomassa seca de raízes e parte aérea do milho em nenhum dos períodos avaliados quando comparado ao controle. Da mesma forma, não foram observadas diferenças expressivas entre tratamentos na caracterização morfológica do sistema radicular em V8 ou VT. A ausência de diferença entre tratamentos pode ser explicada pelo curto período de tempo entre a adubação de cobertura e as avaliações das plantas, à aplicação superficial das fontes recobertas com SH e ao método de irrigação adotado, que impediu que as SH entrassem totalmente em contato com as raízes da planta. Além disso, é possível, também, que a dose de SH empregada tenha sido muito baixa para ser efetiva. / Urea (UR) is the most widely applied nitrogen (N) fertilizer in Brazilian agriculture. However, UR is more prone to ammonia (NH3) volatilization losses than other N sources when surface-applied. One alternative to improve nitrogen use efficiency (NUE) of surface-applied UR is through application of urease inhibitors as coating materials of UR. The association of these composts with humic substances (HS) as UR coating materials may also improve nutrient recovery by plants. The aim of this study was to evaluate the efficiency of urease inhibitors, associated or not with HS, as coating materials of UR as new top-dress N sources for maize. A greenhouse pot trial was carried out over 62 days with maize (Zea mays L.), in a completely randomized block design, with three replicates in a full factorial design, with UR coated with three urease inhibitors (0,40% B + 0,15% Cu; 0,64% B; NBPT) and one additional treatment without inhibitor, three doses of HS (0, 0.6, and 1.2%), and one control treatment. All treatments imposed had CO(15NH2)2 as N source, application rate of 180 mg kg-1of N, and side-dressing application at the V4 maize growth stage. Maize plants were assessed at V8 and VT growth stages, at 52 and 62 days after sowing, respectively, when it was evaluated: above and below-ground plant dry matter weight; leaf area; root morphological traits (length, surface area, and volume); and fertilizer use efficiency by the 15N balance method. In addition, semi-open static collectors with foam discs previously soaked in H3PO4- were used to quantify comparatively the NH3 volatilized from all treatments. Although the addition of a higher dose of boric acid on UR (0,64% B) promoted lower ammonia losses by volatilization in comparison to 0,40 % B + 0,15 % Cu, it did not result in higher NUE by maize in VT, which occurred at V8. In both growth stages, NBPT presented the best performance as urease inhibitor in the absence of HS. The application of HS did not increase NUE by maize in V8 and VT when associated with 0,40% B + 0,15% Cu, 0,64% B or even conventional UR. However, when added in conjunction with NBPT, it increased ammonia volatilization and reduced NUE in VT which may have occurred due to the high pH of the HS (8.5-9) and low buffering capacity. Moreover, the application of conventional UR or UR treated with HS and urease inhibitors did not increase maize growth rate or shoot/root dry matter weight in comparison to the control treatment at both growth stages. Likewise, there was no major significant differences between treatments on root morphological traits (length, surface area, and volume) at both growth stages assessed. The lack of sizable outcome differences between treatments could be explained by the application of a single N dose, the short period of time between the side-dressing application and assessment of maize plants, and to the surface-application of the HS and method of irrigation which prevented HS to have full contact with maize roots. Furthermore, HS application rate may have been too low to be effective.

Ziel dieser Arbeit war es, die Auswirkungen der im Kühlmittel von Leichtwasserreaktoren zur Reaktivitätssteuerung eingesetzten Borverbindungen auf Siedeprozesse – und damit indirekt auf die Wärmeabfuhr der Brennelemente – zu untersuchen. Bei den Siedeversuchen, die Gegenstand der vorliegenden Arbeit sind, wurde besonders auf eine realitätsnahe Annäherung an die Reaktorparameter Wert gelegt. Als Unterstützung zur Interpretation der Ergebnisse dienten eigene Messungen von signifikanten physikalischen Stoffdaten an wässrigen Borsäure- und Pentaboratlösungen. Die Siedeprozesse wurden in einer eigens für diese Analysen konzipierten und errichteten Versuchsanlage SECA unter Verwendung eines Leitfähigkeitsgittersensors sowie einer Hochgeschwindigkeitskamera bei Drücken von maximal 40 bar und Temperaturen bis zu 250 °C untersucht. Entsprechend der in den Untersuchungen gewonnenen Erkenntnis wird für reale Reaktoren fol-gendes angenommen: Die Anwesenheit von Borsäure hat keinen Einfluss auf großvolumige Sie-devorgänge im betrachteten Störfallszenario eines Druckwasserreaktors, und die Auswirkungen auf das unterkühlte Sieden sind vernachlässigbar gering. Es ist nicht zu erwarten, dass der Wärmeübergang von den Brennelementen an das Kühlmittel beeinflusst wird. Bei einer Einspeisung von Pentaborat in Siedewasserreaktoren kann jedoch davon ausgegangen werden, dass der Wärmeübergang durch eine Verkleinerung der Blasen verbessert wird. Weitere Untersuchungen bezüglich des Austrages von Pentaborat an der Phasengrenze sowie der Bildung von Schäumen sind jedoch notwendig, und es ist den Fragen nachzugehen, ob sich diese Schäume auch bei der Einspeisung von Pentaborat in einen Siedewasserreaktor bilden können und welche Auswirkungen diese auf die oberhalb des Kerns befindlichen Dampfabscheiderzyklone und Dampftrockner haben.

L’excès de réactivité neutronique dans les centrales nucléaires est compensé par des sys-tèmes actifs de contrôle du réacteur : acide borique et barres de contrôle. L’apport d’antiréactivité peut se faire passivement avec des poisons consommables, c'est-à-dire des absorbants de neutrons, en particulier du gadolinium (Gd).Dans le cadre d’une augmentation de l’enrichissement en U²³⁵ et de réduction de l’utilisation d’acide borique, cette thèse a pour objectif d’optimiser la distribution du ga-dolinium dans des céramiques d’UO₂ afin d’obtenir un apport optimisé d’antiréactivité dans un Réacteur à Eau sous Pression.Dans ce sens, le travail est orienté à trouver des nouveaux matériaux riches en gadolinium. Le diagramme de phase U-O-Gd a donc été exploré dans le domaine des fortes teneurs en Gd. Deux phases cubiques ont été trouvées et caractérisées : les phases C1 et C2. En vue d’une application industrielle, la phase C1 a été retenue comme candidate pour l’ajout du Gd dans les pastilles d’UO₂.La distribution optimale de cette phase C1 dans les assemblages de combustible nucléaire a été étudiée avec le code de calcul neutronique APOLLO2.8. Des études paramétriques ont été réalisées. Ces études neutroniques ont aboutit à un concept performant de pastille empoisonnée. Finalement, des pastilles prototype ont été fabriquées en laboratoire suivant ce concept. L’ensemble des résultats obtenus montre qu’un concept de pastille avec un dépôt superficiel neutrophage de phase C1 est une manière d’apporter de l’antiréactivité de manière optimisée dans le cadre de cycles longs. Ceci pourrait potentiellement être appliquée à l‘échelle industrielle. Un brevet a été déposé en ce sens. / Reactivity excess in Nuclear Power Plants is controlled by reactor’s active systems: boric acid dilution and control rods. Alternatively, negative reactivity insertion can be made in a passive way using burnable poisons, i.e. neutron absorbers, this is the case of gadolinium (Gd).In the industrial framework of U²³⁵ enrichment increase and boric acid restraint, the goal of this thesis is to optimize the distribution of gadolinium in UO₂ ceramics to obtain a high-performance provision of negative reactivity in Pressurized Water Reactors.In this sense, the work is focus on new gadolinium-rich materials. Thus, U-Gd-O phase diagram was explored in the field of high Gd contents. Two cubic phases were found and characterized: the C1 and C2 phases. With the aim of an industrial application, C1 phase was selected as candidate for Gd addition into UO₂ pellets.The optimal distribution of C1 phase within a nuclear fuel assembly was studied using APOLLO 2.8 neutron transport code. Parametrical calculations were performed. These neutronic studies have ends in a successful “concept of poisoned pellet”.Finally, some prototype pellets following this concept were made in laboratory to proof it feasibility.All the obtained results shows that the proposed concept of a neutrophage C1-phase coating on UO₂ pellets is a convenient way to reduce reactivity excess within the framework of long irradiation cycles. This concept could be potentially applied in industrial scale. Consequently a patent application process was initiated.

The main goal of the diploma thesis is to design the hydraulic part of the new piping system, which is added to the existing project of the Dukovany Nuclear Power Plant. At the beginning of the work is theoretical basis for the design of the hydraulic part. The next part is the selection of piping material for aggressive refrigerant with subsequent verification of the pipe wall thickness. The piping system is designed with specific components from the companies SIGMA GROUP a.s., ARAKO spol. s.r.o. and ARMATURY Group a.s. In the last part, hydraulic solution is developed and commented using the excel program. The piping system is processed into the drawing documentation including bill of materials.

Ziel dieser Arbeit war es, die Auswirkungen der im Kühlmittel von Leichtwasserreaktoren zur Reaktivitätssteuerung eingesetzten Borverbindungen auf Siedeprozesse – und damit indirekt auf die Wärmeabfuhr der Brennelemente – zu untersuchen. Bei den Siedeversuchen, die Gegenstand der vorliegenden Arbeit sind, wurde besonders auf eine realitätsnahe Annäherung an die Reaktorparameter Wert gelegt. Als Unterstützung zur Interpretation der Ergebnisse dienten eigene Messungen von signifikanten physikalischen Stoffdaten an wässrigen Borsäure- und Pentaboratlösungen. Die Siedeprozesse wurden in einer eigens für diese Analysen konzipierten und errichteten Versuchsanlage SECA unter Verwendung eines Leitfähigkeitsgittersensors sowie einer Hochgeschwindigkeitskamera bei Drücken von maximal 40 bar und Temperaturen bis zu 250 °C untersucht. Entsprechend der in den Untersuchungen gewonnenen Erkenntnis wird für reale Reaktoren fol-gendes angenommen: Die Anwesenheit von Borsäure hat keinen Einfluss auf großvolumige Sie-devorgänge im betrachteten Störfallszenario eines Druckwasserreaktors, und die Auswirkungen auf das unterkühlte Sieden sind vernachlässigbar gering. Es ist nicht zu erwarten, dass der Wärmeübergang von den Brennelementen an das Kühlmittel beeinflusst wird. Bei einer Einspeisung von Pentaborat in Siedewasserreaktoren kann jedoch davon ausgegangen werden, dass der Wärmeübergang durch eine Verkleinerung der Blasen verbessert wird. Weitere Untersuchungen bezüglich des Austrages von Pentaborat an der Phasengrenze sowie der Bildung von Schäumen sind jedoch notwendig, und es ist den Fragen nachzugehen, ob sich diese Schäume auch bei der Einspeisung von Pentaborat in einen Siedewasserreaktor bilden können und welche Auswirkungen diese auf die oberhalb des Kerns befindlichen Dampfabscheiderzyklone und Dampftrockner haben.

The aim of this thesis was to introduce and apply the possibilities of using waste glycerol from biodiesel production and partly waste low-stiffen coolant from cars that could be applied in industry. At the beginning of the thesis is summarized biodiesel production and its world production. There is more developed biodiesel production in the Czech Republic and in the European Union and some European legal regulations and standards for biodiesel. Also described herein is a composition of biodiesel and the description of the technology of its production. In the theoretical section summarizes the physical and chemical properties of glycerol and there is also summarized the traditional use of glycerol as food, explosives, etc. There are also new procedures that were performed in the experimental part of the thesis. There are described the ion exchange mechanism, ion exchange resin properties and the properties of the acids and salts generated by neutralization with NaOH contained in the waste glycerol. Also is described herein the wood protection and properties of ethylene glycol coolants and properties of boroglycerol and boroglycol as protection for wood and mechanism of their preparation. Next is described the mechanism of dehydration of glycerol to acrolein and options which can perform the synthesis. In the experimental part, the pH of waste glycerol was measured, then was measured the exact amount of NaOH in the glycerol. There is also desribed cleaning of waste glycerol from NaOH using acidic cation exchange resins on columns, or by neutralization with oleic acid, lactic acid and CO2. Further syntheses were performed glycerol borate and ethylene glycol borate. Water amount in ethylene glycol and methanol with water amount in glycerol were found by distillation. Then were prepared boroglycol and boroglycerol. By the amount resulting from the amount of reaction water were observed reaction conditions H3BO3, Na2B4O7•10 H2O and glycerol. At the end was carried out experimental dilution resulting boroglycerol and boroglycol by ethanol, methanol, TMB. Finally, the diluted boroglycerol was deposited on wood. Dehydration of glycerol to acrolein under the catalytic action of KHSO4 was performed. The results are given all the results and discussed the possibility of using the knowledge gained in this work in the industry. In conclusion, there are listed the economic comparison using waste glycerol and crude oil as a raw material and also charts the development of oil prices in 40 years since 1970, and graph of the price of waste glycerol.

At the beginning of the thesis is summarized biodiesel production and its world production. There is more developed biodiesel production in the Czech Republic and in the European Union and some European legal regulations and standards for biodiesel. Also described herein is a composition of biodiesel and the description of the technology of its production. In the theoretical section summarizes the physical and chemical properties of glycerol and there is also summarized the traditional use of glycerol as food, explosives, etc. There are also new procedures that were performed in the experimental part of the thesis. Then, here are the proposed new procedures for processing waste glycerol and glycol, which were conducted in the experimental part of the thesis. There are described the ion exchange properties of the cation exchangers and also properties of salts generated by neutralization of NaOH in the waste glycerol with organic acids and CO2. There is also described wood protection, properties of ethylene glycol as coolant and properties of boroglycerols and boroglycols as protection for wood and mechanism of their preparation. Then there is described a mechanism of dehydration of glycerol to acrolein and options which can perform the synthesis. In the experimental part, the pH of waste glycerol was measured and then was measured the amount of NaOH in the waste glycerol. There is also desribed cleaning of waste glycerol from NaOH using acidic cation exchange resins on columns, or by neutralization with oleic acid, lactic acid and CO2. Further syntheses were performed glycerol borate and ethylene glycol borate. Water amount in ethylene glycol and methanol with water amount in glycerol were found by distillation. Then were prepared boroglycol and boroglycerol. By the amount resulting from the amount of reaction water were observed reaction conditions H3BO3, Na2B4O7•10 H2O and glycerol. At the end was carried out experimental dilution resulting boroglycerol and boroglycol by ethanol, methanol, TMB. Finally, the diluted boroglycerol was deposited on wood. Dehydration of glycerol to acrolein under the catalytic action of KHSO4 was performed. The results are given all the results and discussed the possibility of using the knowledge gained in this work in the industry. In conclusion, there are listed the economic comparison using waste glycerol and crude oil as a raw material and also charts the development of oil prices in 40 years since 1970, and graph of the price of waste glycerol. There is also discussed technological applicability of the methods used in practice.