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No. of bitstreams: 1 TiagoRobertoDaCosta_TESE.pdf: 4624767 bytes, checksum: b882489e2f56b6e0d740f5f1aaf85b08 (MD5) Previous issue date: 2016-08-05 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / A matriz energ?tica mundial ? basicamente constitu?da a base de combust?veis f?sseis, sendo que diferentes estudos indicam que nas pr?ximas d?cadas n?o haver? mudan?as significativas nesse cen?rio e isso impacta de modo significativo no meio ambiente, pois a queima desses combust?veis para gera??o de energia produz bastante CO2. Sendo o di?xido de carbono o principal g?s de origem antropog?nica, respons?vel pela intensifica??o do efeito estufa. Devido a isso, cientistas e pol?ticos de todo mundo tem sugerido diversas medidas e tecnologias que objetivam a diminui??o das emiss?es de CO2 na atmosfera para as pr?ximas d?cadas. Entre as tecnologias, a Captura e Armazenamento de CO2 (CAC) tem tido um destaque especial nos ?ltimos anos. Estudos realizados pela Ag?ncia Internacional de Energia (International Energy Agency-IEA) quanto o Painel Intergovernamental sobre Mudan?as Clim?ticas (IPCC), sugerindo diversos cen?rios de crescimento econ?micos e de demanda energ?tica, indicam que na maioria dos casos as tecnologias de captura e armazenamento do CO2 contribuem entre 10-55% do esfor?o mundial para reduzir as concentra??es de CO2 na atmosfera at? 2100. Nesse contexto, a combust?o indireta com transportadores s?lidos de oxig?nio (processo Chemical-Looping Combustion-CLC), ? considerada uma das melhores alternativas para reduzir os custos da captura do CO2, principalmente quando comparadas aos processos convencionais, pois n?o necessita da separa??o do CO2 do N2, pois o combust?vel n?o ? misturado diretamente com ar ou oxig?nio. Esta tese de doutorado est? focada no desenvolvimento de cinco transportadores de oxig?nio ? base de mangan?s, os quais foram primeiramente caracterizados com objetivo de determinar quais deles s?o mais promissores para serem avaliados em processos de CLC. As t?cnicas e metodologias de caracteriza??es utilizadas durante a primeira etapa foram: porosimetria por inje??o de merc?rio, resist?ncia ? fratura, difra??o de raios X (DRX), redu??o e oxida??o ? temperatura programada (TPR e TPO), capacidade de transporte de oxig?nio (Roc), composi??o qu?mica, reatividade por termogravimetria e ?ndice de velocidade. Conclu?da essas etapas, verificou-se que os transportadores Mn-ZrMF e Mn-ZrSG apresentaram propriedades apropriadas para serem avaliados em um reator de leito fluidizado descont?nuo, onde os experimentos se assemelham ?s condi??es de CLC. Ao fim dos testes no reator, os transportadores de oxig?nio foram submetidos a algumas t?cnicas de caracteriza??o: DRX, TPR e MEV (Microscopia Eletr?nica de Varredura). O transportador Mn-ZrMF apresentou problemas de aglomera??o durante os testes no reator, sendo considerado inapropriado para prosseguir com os experimentos. Por outro lado, o Mn-ZrSG apresentou elevada reatividade com os combust?veis utilizados (CO > H2 > CH4), n?o sendo verificado o problema da aglomera??o, tendo baixa perda por atrito, com vida m?dia superior a 11.000 horas. Esse material ? bastante promissor para seu uso em CLC de combust?veis s?lidos. / The world?s energy matrix is essentially composed of fossil fuels and different studies show indicate that in the next decades there will be no significant changes in this scenario, which impacts significantly on the environment, since the burning of fossil fuels for power generation gives there main contibution to antropogenic CO2 emissions produces greatest amount of CO2. Carbon dioxide is the main anthropogenic gas responsible for intensifying the greenhouse effect. Because of this, scientists and politicians around the world have suggested a number of strategies and technologies to reduce CO2 emissions to the atmosphere for the next decades. Among these technologies, CO2 capture and storage (CCS) has gained attention in recent years. Studies conducted by the International Energy Agency (IEA) and the Intergovernmental Panel on Climate Change (IPCC) suggest various scenarios of economic growth and energy demand, indicating that in most cases the CO2 capture and storage technologies will contribute between 10-55% of the global effort to reduce CO2 concentrations in the atmosphere by 2100. In this context, the Chemical-Looping Combustion is considered one of the better alternatives to reduce the cost of CO2 capture, especially when compared to conventional capture processes, since it does not require the separation of CO2 from N2, once fuel is not mixed directly with air or oxygen. This doctoral thesis is focused in the development of five manganese-based oxygen carriers, which were first characterized in order to determine which of them are most promising to be evaluated in CLC processes. The techniques and characterization methods used during the first stage were: mercury porosimetry, fracture resistance, X-ray diffraction (XRD), temperature programmed reduction and oxidation (TPR and TPO), oxygen transport capacity (Roc), chemical composition, redox by thermogravimetry and rate index. Completed these steps, it was found that the carriers Mn- ZrMF and ZrSG presented appropriate properties to be evaluated in a discontinuous fluidized bed reactor, where the experiment conditions are subject to the CLC conditions. After the testing reactor, the oxygen carriers were submitted to the following characterization techniques: DRX, TPR and SEM (Scanning Electron Microscopy). Mn-ZrMF carrier presented problems of agglomeration during testing in the reactor, being considered inappropriate for CLC. On the other side, the Mn-ZrSG carrier showed high reactivity with the fuels used (CO> H2> CH4). Due this Mn-ZrSG is appropriate for CO + H2 combustion, but suffer deactivation during CH4 combustion. Do not showed agglomeration problems. The attrition rate was low and the lifetime was than 11.000 hours. Thus this material can be considered suitable to be used in solid fuels CLC.

Production of cellulase and polygalacturonase by Aspergillus niger and Aureobasidium pullulans was studied in submerged (SmF) and solid state fermentation (SSF) systems. Substrates used in fermentation systems were mandarin peels and grape pomace. With Aspergillus niger used on grape pomace as a sole carbon source, cellulase production was detected after 72 hours in SSF and after 24 hours in SmF systems. The activity of cellulase per gram of substrate was higher in a submerged than in a solid state fermentation system. The longer time for higher polygalacturonase production was necessary in submerged fermentation systems and polygalacturonase activity was higher in SmF. The SSF fermentation with mandarin peels as a sole carbon source was similar, the highest detected activity of cellulase was determined after 72 hours. Different production of polygalacturonase was observed on mandarin peels in SmF systems. A comparison of enzyme productivities on grape pomace and mandarin peels showed that polygalacturonase activity per gram of substrate is highest in SmF system with mandarin peels as a sole carbon source. With Aureobasidium pullulans used on grape pomace as a sole carbon source, cellulase production was detected after 48 hours in SmF and SSF fermentation systems. The activity of cellulase per gram of substrate was higher in solid state system than in a submerged fermentation system. Longer time for higher polygalacturonase production was necessary in both fermentation systems. Polygalacturonase activity was higher in SmF. The SSF fermentation with mandarin peels as a sole carbon source was similar, the highest detected activity of cellulase was determined after 48 hours. Different production of polygalacturonase was observed on mandarin peels in SmF systems. A comparison of enzyme productivities on grape pomace and mandarin peels showed that polygalacturonase activity per gram of substrate is highest in SmF system with mandarin peels as a sole carbon source. For both systems and both substrates manganese-dependent peroxidase was detected for the first time. Differences in the enzyme synthesis by Aspergillus niger and Aureobasidium pullulans depend on both the substrates used as well as on the fermentation system.

The subject of this graduation thesis is low-cost alkaline power cells and especially electrodes with alternative catalyst made of MnOx + dopant. The thesis expands the bachelor´s thesis [1] and previous research [4] [12] [13] [14]. Volt-ampere characteristics and power characteristics of the katodes for AFC, subsidized with various dopants, are the outcome of this project. The project presents the optimalisation of preparation process of AFC electrodes. The aim is to prepair several electrodes with identical construction, which varies only with the type of the dopant.

Människan har påverkat klimatet på ett negativt sätt genom olika sorters aktiveter vilket lett till att en global uppvärmning är på gång. Temperaturen på jorden kommer därmed att förändras vilket i sin tur kommer leda till en förändring i vattnets kretslopp. Råvattenkvaliteten förväntas försämras och leda till stora anpassningskostnader. Klimatförändringarna kommer att innebära ökade mängder av organiskt material i både ytvatten och grundvatten vilket i sin tur kommer leda till ökade halter av järn och mangan. Luftning och abiotisk/biotisk oxidation används idag för att avskilja järn och mangan från råvattnet. Biologisk oxidation anses idag vara den snabbaste och mest energi- och kostnadseffektiva metoden för avskiljning av både järn och mangan. Biologisk oxidation kan tillämpas även om järnet är komplexbundet till organiskt material eller om vattnet inte har ett optimalt pH. Två typer av pilotfilter för biologisk oxidation testades och utvärderades i detta arbete, ett med kalcedonmassa och ett med HUFO-diskar. Pilotfiltret med kalcedonmassa fungerade bra och avlägsnade ungefär 85% av järnet och cirka 30% av manganet i råvattnet. Pilotfiltret kunde redan första driftveckan filtrera järn och mognadstiden för den biologiska oxidationen av mangan var ungefär 50 dagar. Pilotfiltret med HUFO-diskar lyckades inte avlägsna utfällt järn som inte adsorberat på HUFO-diskarna vilket med stor sannolikhet berodde på att den metod vi valt för pilotförsöket (störttappning) inte fungerat optimalt för denna typ av filter. Analysresultaten blev till följd av detta svårtolkade då de visade en förhöjd halt av järn på utgående vatten. Även mognadstiden för den biologiska oxidationen av mangan blev svårbestämd för pilotfiltret med HUFO-diskar p.g.a. ovan nämnda orsaker. Det finns därmed en stor förbättringspotential vad gäller genomförandet av HUFO-försöket. En annan metod än störttappning som t.ex. backspolning skulle troligtvis göra det möjligt att avskilja även de järn- och manganpartiklar som inte lyckats få fäste på HUFO-diskarna. Sammanfattningsvis så visar resultaten från pilotfilterförsöken att det är möjligt att avskilja järn och mangan på ett bra sätt med hjälp av kalcedonmassa, utan tillsatser av kemikalier eller behov av kraftig luftning. / Humans have affected the climate negative through various types of activities which have led to global warming. This will lead to a change in temperature which in turn will change the hydrological cycle. The quality of raw water is expected to deteriorate and lead to large adjustment costs.  Climate change will also lead to increased amounts of organic matter in both surface water and groundwater, which in turn will lead to increased levels of iron and manganese. Aeration and abiotic/biotic oxidation are used today to separate iron and manganese from the raw water. The biological oxidation is considered to be the fastest method for the separation of both iron and manganese. Not only is it the fastest but also more energy- and cost efficient. Biological oxidation is also applicable if the iron is complex bound to organic material or if the water does not have optimal pH.  Two types of pilot filter for biotic oxidation were tested and evaluated in this work, one with chalcedony sand and the other one with HUFO-discs. The pilot filter with chalcedony sand worked well and removed 85% of the iron and about 30% of the manganese in the raw water. The pilot filter could already during the first week of operation filtrate iron, and the ripening time for the biotic oxidation of manganese was approximately 50 days. The pilot filter with HUFO-discs did not manage to remove precipitated iron, which probably depended on the pouring method chosen for the trials, which did not turn out to be optimal for this type of filter. This is also why the results were difficult to interpret since the content of iron in the water was actually higher after the filtration compared to the raw water. Even the ripening time was difficult to determine for the biotic oxidation of manganese because of the non-effective pouring method for removing precipitated elements. This is also why there is a great potential for improvement considering the pilot filter with HUFO-discs. Another method such as backwashing would probably make it possible to wash out the precipitated iron- and manganese particles that had not adsorbed onto the HUFO-discs. In summary, the results from the pilot filter experiments show that it is possible to separate iron and manganese from water with the help of chalcedony sand without addition of chemicals or the need for a more vigorous aeration.

Die Uferfiltration und die unterirdische Enteisenung / Entmanganung (UEE) sind bewährte Verfahren für die natürliche, unterirdische Voraufbereitung von Wasser. In Abhängigkeit von der Wasserbeschaffenheit und den geochemischen Eigenschaften des Grundwasserleiters können Redoxreaktionen, Sorptions- und Auflösungsprozesse oder eine ungünstige Bewirtschaftung der Brunnen bei beiden Verfahren zu erhöhten Mangankonzentrationen im Rohwasser führen. Erhöhte Mangankonzentrationen sind häufig für Verockerungsprozesse im Filterbereich der Brunnen und Ablagerungen in Pumpen und Steigleitungen verantwortlich. Diese beeinträchtigen den langfristigen Brunnenbetrieb und führen zu höheren Kosten der Wasseraufbereitung. Außerdem führt Mangan zur Färbung des Wassers und muss in der Trinkwasseraufbereitung auf < 0,05 mg/L verringert werden. Für Wasserwerksbetreiber ist die Kenntnis über die Ursache und das Verhalten von Mangan essentiell für einen optimalen Betrieb. Die ägyptische Hauptstadt Kairo steht einem stark wachsenden Wasserbedarf gegenüber. Für die Bewertung einer möglichen Anwendung der Uferfiltration am Nil wurden vorhandene Versuchsbrunnen teufenabhängig beprobt und das Flusssohlsediment untersucht. Das Flusssohlsediment wies hohe Eisen- und Mangangehalte auf und wurde als Ursache für erhöhte Eisen-, Mangan- und Ammoniumkonzentrationen im Uferfiltrat identifiziert. Für den Uferfiltrationsstandort Dresden-Tolkewitz wurde der Einfluss von Temperatur und Infiltrationsrate auf die Manganfreisetzung aus der Elbsohle untersucht. Betriebsdaten der Jahre 2006 bis 2016 und Säulenversuche bildeten die Grundlage. Die Manganfreisetzung wurde primär von der Temperatur kontrolliert, die Infiltrationsrate war weniger wichtig und verlor mit steigender Temperatur weiter an Bedeutung. Eine Manganfreisetzung wurde bei Wassertemperaturen von 20 °C und Infiltrationsraten von ≥ 0,3 m³/(m²×d) ausgelöst. Während der Inbetriebnahme eines UEE-Wasserwerks in Khabarovsk (Russland) wurde an einigen Brunnen eine intensive Manganfreisetzung beobachtet. Außerdem führte biologische Kolmation zu einem raschen Leistungsverlust und erforderte die Desinfektion der Brunnen. Die Auswertung der ersten 194 UEE-Zyklen eines Förderbrunnens und ergänzende Batchversuche ergaben, dass die Auflösung des im Grundwasserleiter vorhandenen, manganhaltigen Siderits die Ursache der Mn-Freisetzung war. Die Auflösungsprozesse hingen stark von der Korngröße des GWL-Materials und dem pH-Wert des Grundwassers ab. Die Filterkiesschüttung des Brunnens zehrte weniger als 1 % des infiltrierten Chlors und das Natriumhypochlorit drang ca. 2 bis 3,5 m in den Grundwasserleiter ein. Das Wasserwerk Eggersdorf nutzt die UEE für die Voraufbereitung von eisenhaltigem Grundwasser und dient, entgegen den Empfehlungen für die UEE, der Abdeckung von Bedarfsspitzen. In einem Feldversuch wurde die mögliche Umnutzung der UEE-Brunnen für die dauerhafte Grundwasserförderung getestet. Die dabei aufgetretene Manganfreisetzung wurde auf die chemische Reduktion von abgeschiedenen Mangan(hydr)oxiden durch eisenhaltiges Grundwasser zurückgeführt.:Kurzfassung i Abstract iii Danksagung iv Inhaltsverzeichnis v Abkürzungsverzeichnis vii 1 Einleitung 1 1.1 Ausgangssituation 1 1.2 Motivation und Ziele 3 1.3 Gliederung der Arbeit 5 2 Auftreten und Verhalten von Mangan bei der Uferfiltration 6 2.1 Eintragspfade von Mangan in das Uferfiltrat 6 2.2 Einflussgrößen auf den Mangangehalt im Uferfiltrat 7 3 Erkundung eines neuen Uferfiltrationsstandortes in Embaba 9 3.1 Einleitung und Standortbeschreibung 9 3.2 Teufenabhängige Probennahme während des regulären Betriebes 9 3.3 Ursache der Manganfreisetzung und Bewirtschaftung des Standortes 10 4 Einfluss der Infiltrationsrate und der Temperatur auf die Manganfreisetzung aus der Elbsohle in Dresden 12 4.1 Einleitung und Standortbeschreibung 12 4.2 Einfluss der Temperatur auf die Manganfreisetzung 12 4.3 Einfluss der Infiltrationsrate auf die Manganfreisetzung 13 5 Freisetzung von Mangan beim Start einer UEE in Khabarovsk 15 5.1 Einleitung und Standortbeschreibung 15 5.2 Untersuchungen zur Ursache der Manganfreisetzung 15 5.3 Begrenzung der Leistungsabnahme der UEE-Brunnen 16 6 Manganfreisetzung bei der geplanten Umstellung des UEE-Wasserwerks Eggersdorf auf kontinuierliche Förderung 18 6.1 Einleitung und Standortbeschreibung 18 6.2 Umstellung eines UEE-Brunnens auf dauerhafte Förderung 18 6.3 Ursache der Manganfreisetzung aus dem ehemaligen Reaktionsraum 19 7 Zusammenfassung und Ausblick 21 Literaturverzeichnis 24 Beiliegende Publikationen 29 Beiliegende Publikation 1 31 Beiliegende Publikation 2 53 Beiliegende Publikation 3 69 Beiliegende Publikation 4 83 Beiliegende Publikation 5 103 Beiliegende Publikation 6 135 Beiliegende Publikation 7 167 Beiliegende Publikation 8 189 / Bank filtration and Subsurface Iron Removal (SIR) are proven technologies for the natural subsurface pre-treatment of water. Depending on the water quality and the geochemical properties of the aquifer, redox reactions, sorption and dissolution or unfavorable well management can lead to increased manganese concentrations in both treatment options. Increased manganese concentrations often cause filter screen clogging of the well or deposits in pumps and standpipes. This can affect the long-term well operation and lead to higher costs of water treatment. Furthermore, increased manganese concentrations can cause a coloring of the water and must be lowered to < 0.05 mg/l during drinking water treatment. For waterworks operators, the knowledge about the source and the behavior of manganese is essential for an optimal operation. The Egyptian capital Cairo faces a growing water demand. To evaluate a potential riverbank filtration site, depth-dependent sampling at existing test wells was carried out and sediment samples from the Nile riverbed were taken. The riverbed sediment showed elevated iron and manganese contents and was identified as cause of increased iron, manganese and ammonium concentrations in the riverbank filtrate. For the bank filtration site Dresden-Tolkewitz, the impact of temperature and infiltration rate on the manganese release from the riverbed sediment of the Elbe river was investigated. The investigations were based on monitoring data of the years 2006 to 2016 and column experiments. The manganese release was primarily controlled by temperature, the infiltration rate was less important. With increasing temperature, the infiltration rate became even less critical. Manganese was released at water temperatures of 20 °C and infiltration rates of ≥ 0.3 m³/(m²×d). During the start-up phase of a SIR waterworks in Khabarovsk, Russia, an intense manganese release was observed in several wells. In addition, biological clogging led to a rapid perfor-mance loss of the wells and required well disinfection. The evaluation of the first 194 SIR cycles of a production well and accompanying batch experiments indicated that the dissolution of the manganese-bearing siderite, which was present in the aquifer, caused the Mn release. The dissolution heavily depended on the grain size of the aquifer material and the pH of the groundwater. The filter gravel pack of the well consumed less than 1 % of the infiltrated chlorine and the sodium hypochlorite approximately penetrated between 2 and 3.5 m into the aquifer. The waterworks Eggersdorf has been using SIR for the pre-treatment of ferrous groundwater and, contrary to general recommendations for SIR well operation, served for covering peaks in water demand. In a field trial, the possible conversion of the SIR wells for permanent groundwater extraction was tested. An observed manganese release was attributed to the chemical reduction of former precipitated Mn(hydr)oxides by iron-containing groundwater.:Kurzfassung i Abstract iii Danksagung iv Inhaltsverzeichnis v Abkürzungsverzeichnis vii 1 Einleitung 1 1.1 Ausgangssituation 1 1.2 Motivation und Ziele 3 1.3 Gliederung der Arbeit 5 2 Auftreten und Verhalten von Mangan bei der Uferfiltration 6 2.1 Eintragspfade von Mangan in das Uferfiltrat 6 2.2 Einflussgrößen auf den Mangangehalt im Uferfiltrat 7 3 Erkundung eines neuen Uferfiltrationsstandortes in Embaba 9 3.1 Einleitung und Standortbeschreibung 9 3.2 Teufenabhängige Probennahme während des regulären Betriebes 9 3.3 Ursache der Manganfreisetzung und Bewirtschaftung des Standortes 10 4 Einfluss der Infiltrationsrate und der Temperatur auf die Manganfreisetzung aus der Elbsohle in Dresden 12 4.1 Einleitung und Standortbeschreibung 12 4.2 Einfluss der Temperatur auf die Manganfreisetzung 12 4.3 Einfluss der Infiltrationsrate auf die Manganfreisetzung 13 5 Freisetzung von Mangan beim Start einer UEE in Khabarovsk 15 5.1 Einleitung und Standortbeschreibung 15 5.2 Untersuchungen zur Ursache der Manganfreisetzung 15 5.3 Begrenzung der Leistungsabnahme der UEE-Brunnen 16 6 Manganfreisetzung bei der geplanten Umstellung des UEE-Wasserwerks Eggersdorf auf kontinuierliche Förderung 18 6.1 Einleitung und Standortbeschreibung 18 6.2 Umstellung eines UEE-Brunnens auf dauerhafte Förderung 18 6.3 Ursache der Manganfreisetzung aus dem ehemaligen Reaktionsraum 19 7 Zusammenfassung und Ausblick 21 Literaturverzeichnis 24 Beiliegende Publikationen 29 Beiliegende Publikation 1 31 Beiliegende Publikation 2 53 Beiliegende Publikation 3 69 Beiliegende Publikation 4 83 Beiliegende Publikation 5 103 Beiliegende Publikation 6 135 Beiliegende Publikation 7 167 Beiliegende Publikation 8 189

Groundwater is an important source of fresh water on earth. A source that is also affected by climate change. Climate change is expected to influence both the groundwater quality and the groundwater level, where elevated levels of iron and manganese in the groundwater are to be expected. In Sweden guideline values are set for iron and manganese in drinking water, which means that waterworks that use groundwater as raw water must treat the water when the guidline values are exceeded. A common treatment step to remove iron and manganese is abiotic oxidation with a chemical oxidant. A relatively new method is biological oxidation where microorganisms oxidize the metals. Biological oxidation has proven to be a faster process than chemical oxidation and better adapted to variations in raw water quality. In this work the possibility of biological oxidation of iron and manganese at smaller groundwater plants with day-to-day production breaks has been studied. The study also concern how seasonal variations in raw water quality might affect the oxidation ability of the microorganisms. During the study a pilot filter for biological oxidation was constructed where the efficiency of the filter and the raw water quality was measured during a one-year test. After a short start-up time for iron oxidation the pilot filter reduced iron in the raw water up to 92 % and after a longer start-up time for manganese oxidation the pilot filter reduced manganese from the raw water up to 97 % during the rest of the test period. The results show that biological oxidation is possible at smaller groundwater plants despite production breaks. The results also show that biological oxidation is not affected by the vaiations i raw water quality that was measured during the test period. Furthermore, the results show that biological oxidation is equally efficient as the chemical oxidation, at the investigated groundwater plant, in terms of removing iron and even more efficient in terms of removing manganese. In addition the biological oxidation do not require pH adjustment or addition of any chemicals. The results indicate that biological oxidation of iron and manganese is a more favorable alternative to chemical oxidation in smaller groundwater plants on the impact of climate change on raw water quality.

Im Zentrum dieser Arbeit standen ramanspektroskopische Untersuchungen der elektronischen spin-flip-Übergänge an semimagnetischen (Zn,Mn)Se Proben. Hierbei wurden sowohl Quantentrogstrukturen untersucht als auch volumenartige Proben. Ziel der Forschung war dabei, ein tieferes Verständnis der Wechselwirkungen der magnetischen Ionen mit den Leitungsbandelektronen der Materialien zu gewinnen. Im Hinblick auf mögliche zukünftige spin-basierte Bauelemente lag das Hauptaugenmerk auf dem Einfluss von n-Dotierung bis zu sehr hohen Konzentration. Hierfür standen verschiedene Probenreihen mit unterschiedlichen Dotierungskonzentrationen zur Verfügung. / In the present doctoral thesis, spin flip Raman studies of semimagnetic (Zn,Mn)Se samples were in the focus of interest. Quantum wells as well as bulk-like materials were investigated. The main goal was a better understanding of the exchange interaction behaviour of heavily n-doped semimagnetic samples. The influence of doping on the exchange interaction is of special relevance with regard to spintronics applications. Several series of high quality MBE-grown (Zn,Mn)Se -samples samples were available.

Made available in DSpace on 2014-12-17T15:42:00Z (GMT). No. of bitstreams: 1 Mariele ISM_DISSERT.pdf: 4704397 bytes, checksum: 9fa1538bc3d6948d492f9a6c378eaf62 (MD5) Previous issue date: 2012-07-20 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The oxidative desulfurization process (ODS) of a commercial diesel fuel was performed under mild conditions in the presence of catalysts based on vanadium or manganese, supported on alumina, clays (commercial, natural and pillared) and zeolites (NaX, NaY, beta, mordenite and ZSM-5). The catalysts were synthesized by wet impregnation and characterized by X-ray diffraction, textural analysis by N2 adsorption and scanning electron microscopy. The dibenzothiophene (DBT) was used as sulfur compound in catalytic evaluation. The reactions were performed using acetonitrile as solvent and the hydrogen peroxide as oxidant at 55?C. The reaction products were analized by gas chromatography (GC-FID). In the studied conditions, the process was efficient due to the DBT was converted to its corresponding sulfone. Both DBT and corresponding sulfone were extracted by the solvent. Removals and oxidations up to 100% of sulfur compound were achieved. The catalysts supported on ZSM-5 zeolite showed are more effective for oxidation reaction of sulfur compound, presenting the best results. It was observed for oxidation reaction, that vanadium catalysts were more effective and manganese catalysts showed best results for removal of sulfur compounds / O processo de Dessulfuriza??o Oxidativa (ODS) de um diesel comercial foi realizado em condi??es suaves na presen?a de catalisadores ? base de van?dio ou mangan?s, suportados em aluminas, argilas (comerciais, naturais e pilarizadas) e ze?litas (NaX, NaY, beta, mordenita, ZSM-5). Os catalisadores foram sintetizados via impregna??o ?mida e caracterizados por difra??o de raios-X, an?lise textural por adsor??o e dessor??o de nitrog?nio e microscopia eletr?nica de varredura. O dibenzotiofeno (DBT) foi utilizado como o composto de enxofre nos testes catal?ticos. As rea??es foram realizadas usando como solvente acetonitrila e como oxidante o per?xido de hidrog?nio a temperatura de 55?C. Os produtos de rea??o foram analisados por cromatografia gasosa (CG-FID). Nas condi??es estudadas o processo mostrouse eficiente, o DBT foi convertido para sua respectiva sulfona. Ambos DBT e a sulfona foram extra?dos pelo solvente. Remo??es e oxida??es de 100% do composto de enxofre foram alcan?adas. Os catalisadores suportados na ze?lita ZSM-5 mostraram-se mais efetivos para a rea??o de oxida??o do composto sulfurado, apresentando os melhores resultados. Observa-se para a rea??o de oxida??o que os catalisadores de van?dio foram mais efetivos, e os catalisadores de mangan?s apresentaram melhores resultados na extra??o dos compostos sulfurados

Made available in DSpace on 2014-12-17T14:07:17Z (GMT). No. of bitstreams: 1 OsvaldoCS_TESE.pdf: 5419870 bytes, checksum: 262730b1c0403826588e3ca7137507e0 (MD5) Previous issue date: 2013-07-19 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The production of waste from urban and industrial activities is one of the factors of environmental contamination and has aroused attention of the scientific community, in the sense of its reuse. On the other hand, the city of Salvador/Ba, with approximately 262 channels, responsible for storm water runoff, produces every year, by the intervention of cleaning and clearing channels, a significant volume of sediments (dredged mud), and thus an appropriate methodology for their final destination. This study aims to assess the influence of incorporation of these tailings in arrays of clay for production of interlocked block ceramic, also known as ceramic paver. All the raw materials from the metropolitan region of Salvador (RMS) were characterized by x-ray fluorescence, x-ray diffraction, thermal analysis (TG and TDA), particle size analysis and dilatometry. With the use of statistical experimental planning technique, ternary diagram was defined in the study region and the analyzed formulations. The specimens were prepared with dimensions of 60x20x5mm?, by uniaxial pressing of 30 MPa and after sintering at temperatures of 900?, 1000? and 1100?C the technological properties were evaluated: linear shrinkage, water absorption, apparent porosity, apparent specifies mass, flexural rupture and module. For the uniaxial compression strength used cylindrical probe body with ? 50 mm. The standard mass (MP) was prepared with 90% by weight of clay and 10% by weight of Channel sediment (SCP), not being verified significant variations in the properties of the final product. With the incorporation of 10% by weight of manganese residue (PFM) and 10% by weight of the Ceramic waste (RCB) in the mass default, in addition to adjusting the plasticity due to less waste clay content, provided increased linear firing shrinkage, due the significant concentration of K2O, forming liquid phase at low temperature, contributing to decreased porosity and mechanical resistance, being 92,5 MPa maximum compressive strength verified. After extract test leachate and soluble, the piece containing 10% of the PFM, was classified as non-hazardous and inert material according to NBR10004/04 ABNT. The results showed the feasibility on using waste, SCP, RCB and PFM clay mass, at temperatures above 900?C, paver ceramic production, according to the specifications of the technical standards, so that to exceed the 10% of the PFM, it becomes imperative to conduct studies of environmental impacts / A produ??o de res?duos provenientes das atividades urbanas e industriais ? um dos fatores de contamina??o ambiental e tem despertado aten??o da comunidade cientifica, no sentido do seu reaproveitamento. Por outro lado, a cidade do Salvador/Ba, com aproximadamente 262 canais, respons?veis pelo escoamento de ?guas pluviais, produz todo ano, pela necessidade de interven??o de limpeza e desobstru??o de canais, um volume significativo de sedimentos (lama dragada), impondo dessa forma uma metodologia adequada para sua destina??o final. Este trabalho tem como objetivo avaliar a influ?ncia da incorpora??o desses rejeitos em matrizes de argila para produ??o de bloco intertravado cer?mico, tamb?m conhecido como paver cer?mico. Todas as mat?rias primas oriundas da Regi?o Metropolitana de Salvador (RMS) foram caracterizadas por fluoresc?ncia de raios -X, difra??o de raios -X, analise t?rmica (TG e TDA), analise granulom?trica e dilatometria. Com a utiliza??o da t?cnica estat?stica de planejamento experimental, foi definida em diagrama tern?rio a regi?o de estudo e as formula??es analisadas. Foram preparados os corpos de prova com dimens?es de 60x20x5mm3, por prensagem uniaxial de 30 MPa e, ap?s sinteriza??o nas temperaturas de 900?, 1000? e 1100?C, as propriedades tecnol?gicas avaliadas foram: retra??o linear, absor??o de ?gua, porosidade aparente, massa especifica aparente, m?dulo de ruptura ? flex?o. Para a resist?ncia ? compress?o uniaxial utilizou-se o corpo de prova cil?ndrico com ? de 50mm. A massa padr?o (MP) foi preparada com 90% em peso de argila e 10% em peso do sedimento de canais (SCP), n?o sendo verificadas varia??es significativas nas propriedades do produto final. Com a incorpora??o de 10% em peso do res?duo de mangan?s (PFM) e 10% em peso do rejeito cer?mico (RCB) na massa padr?o, al?m do ajuste da plasticidade, em fun??o de menor teor de argilominerais dos res?duos, proporcionou aumento da retra??o linear de queima, devido a significativa concentra??o de K2O, formando fase liquida em baixa temperatura, contribuindo para diminui??o da porosidade e aumento da resist?ncia mec?nica, sendo 92,5 MPa a m?xima resist?ncia ? compress?o verificada. Ap?s teste do extrato lixiviado e solubilizado, a pe?a contendo 10% do PFM, foi classificada como material n?o perigoso e inerte segundo NBR10004/04 da ABNT. Os resultados mostraram viabilidade na utiliza??o dos res?duos SCP, RCB e PFM em massa argilosa, em temperaturas acima de 900?C, para produ??o de bloco intertravado, paver cer?mico, de acordo com as especifica??es das normas t?cnicas, de forma que, para teores superiores a 10% do PFM, torna-se imperativo a realiza??o de estudos de impactos ambientais

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-06-10T19:03:35Z No. of bitstreams: 1 BrunoFerreiraAmorim_TESE.pdf: 4546675 bytes, checksum: f3babdd1005205365d367583411ae46c (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-06-13T20:09:02Z (GMT) No. of bitstreams: 1 BrunoFerreiraAmorim_TESE.pdf: 4546675 bytes, checksum: f3babdd1005205365d367583411ae46c (MD5) / Made available in DSpace on 2016-06-13T20:09:02Z (GMT). No. of bitstreams: 1 BrunoFerreiraAmorim_TESE.pdf: 4546675 bytes, checksum: f3babdd1005205365d367583411ae46c (MD5) Previous issue date: 2015-12-07 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico (CNPq) / As ferritas de cobalto-mangan?s (Co1?xMnxFe2O4 e Co1,2Fe1,8?xMnxO4) possuem uma estrutura do tipo espin?lio mista, e t?m sido consideradas como um das candidatas competitivas para grande variedade de aplica??es em dispositivos, desde a gera??o e detec??o de ultra-som, sensores, transformadores, bem como na ind?stria m?dica. Ferritas de cobaltomangan?s nanoestruturadas foram produzidas via moagem de alta energia, com subsequente tratamento t?rmico, e foram caracterizados por difra??o de raios X, fluoresc?ncia de raios X, microscopia eletr?nica de varredura e magnetiza??o. Amostras do tipo Co1?xMnxFe2O4 e Co1,2Fe1,8?xMnxO4 foram obtidas a partir dos p?s precursores Fe3O4, Co3O4 e Mn3O4, os quais foram estequiometricamente misturados e mo?dos por 10h e tratados termicamente ? 900?C por 2h. A difratometria confirma a forma??o das fases nanocristalinas puras para s?rie Co1,2Fe1,8?xMnxO4 com umdi?metro m?dio de cerca de 94nm. Verificou-se que o par?metro de rede aumenta com a substitui??o do Fe3? pelo Mn3?. A fluoresc?ncia de raios X revelou que as por??es de metais nas amostras estavam pr?xima das composi??es estequiom?tricas nominais. As caracter?sticas microestruturais observadas nas micrografias demonstraram que as part?culas formadas apresentam morfologia e granulometria bastante distintas. As medidas de histerese magn?ticas realizadas em baixa temperatura, mostraram que a magnetiza??o de satura??o e reman?ncia aumentaram com a concentra??o de mangan?s, enquanto que o campo coercivo diminuiu. A constante de anisotropia (Ke f ), foi calculada a partir dos ajustes dos dados pela lei de aproxima??o de satura??o. Verificou-se que a anisotropia diminui substancialmente com a substitui??o do ferro pelomangan?s. / The cobalt-manganese ferrites (Co1?xMnxFe2O4 and Co1,2Fe1,8?xMnxO4) has a mixed structure of spinel type and it has been regarded as one of candidates for petitive wide variety of applications in devices from ultrasonic generation and detection, sensors, transformers, as well as in medical industry. Ferrites cobalt-manganese nanostructured were produced via mechanical alloying with subsequent heat treatment and were characterized by X-ray diffraction, X-ray fluorescence, scanning electron microscopy and magnetization. Samples of Co1?xMnxFe2O4 and Co1,2Fe1,8?xMnxO4 were obtained from the precursor powders Fe3O4, Co3O4 and Mn3O4 which were stoichiometrically mixed and ground by 10h and heat treated at 900?C for 2h. The diffraction confirmed the formation of the pure nanocrystalline phases to series Co1,2Fe1,8?xMnxO4 with an average diameter of about 94nm. It was found that the lattice parameter increases with the substitution of Fe3? by Mn3?. The x-ray fluorescence revealed that the portions of metals in samples were close to the nominal stoichiometric compositions. The microstructural features observed in micrographs showed that the particles formed show very different morphology and particle size. The magnetic hysteresis measurements performed at low temperature showed that the saturation magnetization and remanence increased as the concentration of manganese, while the coercive field decreased. The anisotropy constant (Ke f ), was estimated from the data adjustments the law of approaching saturation. It was found that the anisotropy decreases substantially with the substitution of Fe by Mn.