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Avalia??o da efici?ncia qu?mica de catalisadores heterog?neos baseados em min?rios e rejeitos de minera??o nas rea??es de transesterifica??o de triacilglicer?is de bio-?leoRocha, B?rbara Gon?alves 18 December 2017 (has links)
?rea de concentra??o: Produtos e coprodutos. / Submitted by Jos? Henrique Henrique (jose.neves@ufvjm.edu.br) on 2018-06-22T19:43:47Z
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Previous issue date: 2018 / A diversifica??o da matriz energ?tica, por raz?es econ?micas, ambientais e da pr?pria pol?tica
energ?tica das na??es, tem suscitado foco especial nos biocombust?veis, particularmente no
bioetanol e no biodiesel. Na ind?stria, o biodiesel (?steres de ?cidos graxos com um ?lcool de
cadeia molecular curta) ?, mais comumente, produzido pela transesterifica??o de triacilglicer?is
de ?leos vegetais ou gordura animal, com metanol ou etanol, sob cat?lise homog?nea com uma
base (KOH ou NaOH). Por representarem alternativas potencialmente mais sustent?veis, dos
pontos de vistas econ?micos e ambientais, o presente trabalho foi dedicado a avaliar a efici?ncia
qu?mica de catalisadores heterog?neos baseados em materiais de min?rios: (i) de ni?bio,
enriquecido em Nb2O5 (Geo.Nb2O5); (ii) de areia monaz?tica (Geo.Mona), uma fonte mineral
de terras raras, e (iii) de rejeitos de minera??o de fosfato, ricos em magnetita (Geo.Mag.CMT
e Geo.Mag.CMA). Os materiais minerais foram preparados em mistura com componentes
?cidos (H2SO4; HCl ou HF) ou b?sicos (KOH; , KBr, NaOH; CaO; KI; KF ou KCl). As rea??es
de transesterifica??o foram conduzidas sob refluxo, com ?leo de soja comercial e metanol, sob
a??o dos catalisadores s?lidos. A raz?o molar padr?o ?leo:metanol foi de 1:100, com 10% de
catalisador em rela??o ao ?leo, a 60 ?C. Dos testes realizados com os materiais preparados com
CaO sint?tico comercial, nas mesmas condi??es, a mistura calcinada a 800 ?C por 4 h rendeu
?steres met?licos sempre acima de 99%; o menor tempo de rea??o (2 h, para completar a
transesterifica??o) foi conseguido com o catalisador baseado na Geo.Mona, em rela??o ao
Geo.Nb2O5 (5 h), ao Geo.Mag.CMT (3 h) e o Geo.Mag.CMA tamb?m (2 h). Analisou-se o
reuso consecutivo do catalisador. Ap?s cada rea??o, o catalisador s?lido era lavado com
metanol e seco a 100 oC. O melhor resultado foi obtido com o rejeito magn?tico com CaO
calcinados a 200 ?C por 4 h, para o que se conseguiu at? 8 rea??es consecutivas. Nas
impregna??es com ?cidos e bases, os melhores resultados foram com a mistura Geo.Nb2O5 e
KOH calcinada a 600 ?C, para a qual conseguiu 8 rea??es consecutivas, com rendimento
qu?mico em ?steres met?licos de praticamente 100% e tempo reacional de 10 min, no primeiro
uso. O efeito catal?tico sin?rgico mais significativo foi conseguido com o catalisador baseado
em cada um dos tr?s materiais avaliados em mistura com CaO: nenhum efeito catal?tico
significativo na rea??o de transesterifica??o de triacilglcier?is do ?leo foi observado apenas
com o material mineral puro calcinado. O CaO puro como catalisador, tamb?m calcinado e
usado em rea??o, levou a rendimentos qu?micos pouco acima de 80%. A mistura individual do
material mineral com CaO, nas mesmas condi??es de prepara??o anteriores, levaram a
rendimentos qu?micos de efetivamente 100%. Os presentes resultados revelam a excepcional
potencialidade, dos pontos de vista qu?mico, econ?mico e ambiental, dos catalisadores mistos,
dos materiais minerais com CaO, ora avaliados, nos processos de produ??o industrial de
biodiesel. / Tese (Doutorado) ? Programa de P?s-gradua??o em Biocombust?veis, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2017. / The diversification of the energy matrix has been drawing special attention to biofuels,
especially bioethanol and biodiesel, mainly for economic and environmental reasons and
national energy policies. In industry, biodiesel (esters of fatty acids with a short-chain alcohols)
is most commonly produced by the transesterification of triacylglycerols in vegetable oils or
animal fats with methanol or ethanol using homogeneous catalysis with a base (KOH or NaOH).
The present work was devoted to the evaluation of the chemical efficiency of heterogeneous
catalysts based on mineral materials: (i) niobium, enriched in Nb2O5 (Geo.Nb2O5); (ii) monazite
sand (Geo.Mona), a mineral source of rare earths, and (iii) phosphate mining tailings, rich in
magnetite (Geo.Mag.CMT e Geo.Mag.CMA). The mineral materials were prepared in
admixture with acidic (H2SO4, HCl or HF) or basic (KOH, KBr, NaOH, CaO, KI, KF or KCl)
components. The transesterification reactions were conducted under reflux with commercial
soybean oil and methanol in the presence of the solid catalysts. The standard molar ratio of
oil:methanol was 1:100, using 10% catalyst relatively to the quantity of oil, at 60 ?C. According
to the tests performed with the materials prepared with commercial synthetic CaO under the
same conditions, the yield of methyl esters with the mixture calcined at 800 ?C for 4 h was
always greater than 99%. The shortest reaction time (2 h to complete the transesterification)
was achieved with the Geo.Mona catalyst; the reaction times with Geo.Nb2O5 (5 h), the
Geo.Mag.CMT (3 h) and the Geo.Mag.CMA also (2 h) were longer. The consecutive reuse of
the catalyst was also verified. After each reaction, the solid catalyst was washed with methanol
and dried at 100 ?C. The best result was obtained with the magnetic waste with CaO calcined
at 200 ?C for 4 h, with which up to eight consecutive reactions were achieved. On impregnating
with acids or bases, the best results are obtained with the Geo.Nb2O5 and KOH mixture calcined
at 600 ?C, with which eight consecutive reactions were completed. Virtually 100% yields of
methyl esters were obtained in a reaction time of 10 min in the first use. The most significant
synergistic catalytic effect was achieved with each of the three minerals mixed with CaO. No
significant catalytic effect on the transesterification reaction of triacylglycerols in the oil was
observed with the pure calcined minerals. When the calcined CaO is used alone as catalyst, the
reaction yielded just over 80%. For the mixture of the individual minerals with CaO under the
same preparation conditions described above, the transesterification reaction led to virtually
100% yields. The present results reveal an outstanding potential regarding the chemical,
economic and environmental aspects of the mixed catalysts (the mineral material with CaO) for
chemical processes leading to the industrial production of biodiesel.
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Caracter?sticas estruturais e fotocatal?ticas do comp?sito oxihidr?xido de ni?bio/vermiculita / Structural and photocatalytic characteristics of niobium oxyhydroxide/vermiculite ? basead compositeBatista, Luana M?rcia Bezerra 31 October 2014 (has links)
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Previous issue date: 2014-10-31 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / A prepara??o de novos comp?sitos usando argilas naturais como suporte, vem sendo estudada
na literatura, em virtude das mesmas serem encontradas na natureza e como consequ?ncia,
apresentarem um baixo pre?o. As argilas podem ser empregadas como suportes para ?xidos
met?licos aumentando a quantidade de s?tios ativos presentes na sua superf?cie, e assim,
podem ser aplicadas para os mais variados fins como adsor??o, cat?lise e fotocat?lise. Uns
dos materiais que estam em destaque s?o os compostos de ni?bio, em especial os ?xidos, por
apresentarem ?timas propriedades oxidativas e fotocatal?ticas. Neste cen?rio, o trabalho teve
como objetivo sintetizar o comp?sito oxihidr?xido de ni?bio (NbO2OH)/vermiculita, bem
como avaliar sua efic?cia com rela??o ? vermiculita s?dica (V0) e ao NbO2OH. O comp?sito
foi preparado atrav?s do m?todo de precipita??o-deposi??o. Em seguida, foi caracterizado por
difratometria de raios-X (DRX), espectroscopia de absor??o do infravermelho (IV),
espectroscopia de energia dispersiva de raios-X (EDS), an?lise termogravim?trica (TG/DTG),
microscopia eletr?nica de varredura (MEV), adsor??o e dessor??o de N2 pelo m?todo B.E.T e
investiga??o da distribui??o de carga. A aplica??o do material NbO2OH/V0 foi dividida em
duas etapas: (I) atrav?s dos m?todos de adsor??o e oxida??o e (II) por meio da oxida??o
fotocatal?tica usando a irradia??o solar. Os estudos de adsor??o, oxida??o e oxida??o
fotocatal?tica foram monitorados com rela??o a porcentagem de remo??o da cor do corante
azul de metileno (AM) atrav?s da espectroscopia de UV-Vis. Os resultados de DRX
evidenciaram diminui??o e alargamento na reflex?o d(001) da argila ap?s modifica??o, o IV
indicou a presen?a tanto da argila quanto do oxihidr?xido de ni?bio ao apresentar bandas em
1003 e 800 cm-1 referentes, respectivamente, ao estiramento Si-O e Nb-O. A presen?a do
ni?bio foi confirmada tamb?m por EDS que indicou quantidade 17 % em massa do metal. A
an?lise t?rmica constatou a estabilidade do comp?sito em 217 ?C e as micrografias mostraram
que houve diminui??o no tamanho das part?culas da argila. A investiga??o da distribui??o de
carga do NbO2OH/V0 constatou que o material apresentou uma superf?cie heterog?nea com
cargas negativas baixa, m?dia e elevada. O teste de adsor??o mostrou que o comp?sito
NbO2OH/V0 apresentou maior capacidade adsortiva conseguindo remover 56 % da cor do
AM, enquanto o material V0 removeu apenas 13 %. O NbO2OH n?o apresentou capacidade
adsortiva em virtude da forma??o de agregados-H. A porcentagem de remo??o da cor do
corante para os testes de oxida??o apresentou pouca diferen?a com rela??o a adsor??o, sendo
18 e 66 % de remo??o da cor do corante para V0 e NbO2OH/V0, respectivamente. O material
NbO2OH/V0 apresentou excelente atividade fotocatal?tica conseguindo remover em apenas
180 minutos 95,5 % da cor do AM comparado a 41,4 % da V0 e 82,2 % do NbO2OH,
comprovando a forma??o de um novo comp?sito com propriedades distintas dos seus
precursores. / The preparation of nanostructured materials using natural clays as support, has been studied in
literature under the same are found in nature and consequently, have a low price. Generally,
clays serve as supports for metal oxides by increasing the number of active sites present on
the surface and can be applied for various purposes such as adsorption, catalysis and
photocatalysis. Some of the materials that are currently highlighted are niobium compounds,
in particular, its oxides, by its characteristics such as high acidity, rigidity, water insolubility,
oxidative and photocatalytic properties. In this scenario, the study aimed preparing a
composite material oxyhydroxide niobium (NbO2OH) / sodium vermiculite clay and evaluate
its effectiveness with respect to the natural clay (V0) and NbO2OH. The composite was
prepared by precipitation-deposition method and then characterized by X-ray diffraction,
infrared spectroscopy (XRD), energy dispersive X-ray (EDS), thermal analysis (TG/DTG),
scanning electron microscopy (SEM), N2 adsorption-desorption and investigation of
distribution of load. The application of the material NbO2OH/V0 was divided in two steps:
first through oxidation and adsorption methods, and second through photocatalytic activity
using solar irradiation. Studies of adsorption, oxidation and photocatalytic oxidation
monitored the percentage of color removal from the dye methylene blue (MB) by UV-Vis
spectroscopy. The XRD showed a decrease in reflection d (001) clay after modification; the
FTIR indicated the presence of both the clay when the oxyhydroxide niobium to present
bands in 1003 cm-1
related to Si-O stretching bands and 800 cm-1
to the Nb-O stretching. The
presence of niobium was also confirmed by EDS indicated that 17 % by mass amount of the
metal. Thermal analysis showed thermal stability of the composite at 217 ?C and
micrographs showed that there was a decrease in particle size. The investigation of the surface
charge of NbO2OH/V0 found that the material exhibits a heterogeneous surface with average
low and high negative charges. Adsorption tests showed that the composite NbO2OH/V0
higher adsorption capacity to remove 56 % of AM, while the material removed from V0 only
13 % showed no NbO2OH and adsorptive capacity due to the formation of H-aggregates. The
percent removal of dye color for the oxidation tests showed little difference from the
adsorption, being 18 and 66 % removal of dye color for V0 and NbO2OH/V0 respectively.
The NbO2OH/V0 material shows excellent photocatalytic activity managing to remove just
95,5 % in 180 minutes of the color of MB compared to 41,4 % and 82,2 % of V0 the
NbO2OH, proving the formation of a new composite with distinct properties of its precursors.
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S?ntese, caracteriza??o e avalia??o da atividade catal?tica de comp?sitos de ni?bio/argila em rea??es de oxida??oAra?jo, Marcella Jordanna Silva Montoril 25 July 2016 (has links)
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Previous issue date: 2016-07-25 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / A ind?stria t?xtil gera um grande volume de efluentes que, muitas vezes, s?o descartados no meio ambiente sem estarem devidamente tratados. Esses efluentes s?o formados de mol?culas org?nicas e caracterizam-se por apresentar cor, que alteram as propriedades da ?gua deixando-a impr?pria para o consumo. Para o tratamento desses efluentes, a utiliza??o de processos catal?ticos heterog?neos de custo baixo pode ser vantajoso. As argilas v?m sendo bastante estudadas como suportes catal?ticos em raz?o de sua abund?ncia na crosta terrestre e seu baixo custo. Portanto, neste trabalho as argilas vermiculita e bentonita foram usadas como suporte para o catalisador oxihidr?xido de ni?bio e pelo m?todo de deposi??o-precipita??o foram obtidos comp?sitos formados por esses materiais. Os comp?sitos Nb/argila foram caracterizados e as principais t?cnicas mostraram que ocorreu uma modifica??o em cada argila. Os resultados de difratrometria de raios X (DRX) indicaram que ocorreu uma diminui??o da intensidade da reflex?o e um deslocamento do pico principal de ambas as argilas quando o oxihidr?xido de ni?bio ? adicionado na estrutura. As an?lises de espectroscopia na regi?o do infravermelho mostram bandas de adsor??o de ambos os materiais nos comp?sitos Nb/argila, dando a indicativa de que o comp?sito foi realmente formado. As imagens de microscopia eletr?nica de varredura tamb?m confirmaram essa modifica??o de estrutura. Foram realizados testes de oxida??o e oxida??o fotocatal?tica com os comp?sitos obtidos e o teste de oxida??o fotocatal?tica foi o que apresentou melhores resultados, pois o comp?sito de vermiculita (Nb/V0) apresentou uma maior atividade fotocatal?tica removendo 98% da cor do corante alaranjado de metila em 90 minutos de rea??o enquanto que o material comp?sito de bentonita (Nb/B0) removeu apenas 63% durante o mesmo tempo de rea??o. Essa atividade ? devido o comp?sito Nb/V0 ter apresentado um menor valor de band gap (3,08eV) que o comp?sito Nb/B0 (3,33eV). / The textile industry produces a large volume of waste that often is discarded into the environment without being properly treated. These effluents are made of organic molecules and are characterized by their color that alter the properties of water which leave it unfit for consumption. For the treatment of these effluents, the use of heterogeneous catalytic processes of low cost can be advantageous. Clays have been widely studied as catalyst supports because of their abundance in the Earth's crust and its low cost. Therefore, in this study the clays vermiculite and bentonite were used as support for the catalyst oxyhydroxide niobium and by the method of deposition-precipitation it was obtained composites formed from these materials. The composite Nb/clay were characterized and the main techniques showed that was changes in each clay. The results X-ray diffractometer (XRD) showed that there was a decrease in reflection intensity and a shift of the main peak of both clays when oxyhydroxide niobium is added to the structure. The spectroscopic analyzes show infrared adsorption bands of in both materials composite Nb/clay which indicates that the composite was actually formed. The scanning electron microscopy images also confirmed that structure modification. Oxidation and photocatalytic oxidation tests were performed with the obtained composite and photocatalytic oxidation test showed the best results, because the vermiculite composite (Nb/V0) showed higher photocatalytic activity by removing 98% of the color orange dye methyl in 90 minutes of reaction while the composite material of bentonite (Nb/B0) removed only 63% over the same reaction time. This activity is due to the composite Nb/V0 have presented a smaller value of band gap (3,08eV) than the composite Nb/B0 (3,33eV).
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Avalia??o cin?tica e potencial do Nb2O5 obtido a partir de um complexo de ni?bio para forma??o do oleato de metila atrav?s da rea??o de esterifica??o do ?cido oleico / Evaluation of the kinetic and potential Nb2O5 obtained from a niobium complex to the formation of methyl oleate by esterification of oleic acidOliveira, Samuel Alves de 30 January 2014 (has links)
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Previous issue date: 2014-01-30 / Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600?C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450?C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production / Dentre os catalisadores heterog?neos os materiais a base de ni?bio mostram-se como uma alternativa para suprir a demanda de catalisadores para a produ??o de biodiesel. O presente trabalho visa avaliar o potencial de um catalisador heterog?neo derivado de um complexo de ni?bio na rea??o de esterifica??o met?lica do ?cido oleico. O catalisador foi sintetizado ap?s a calcina??o em diferentes temperaturas de um complexo de ni?bio ((NH4)3[NbO(C2O4)3].H2O) gerando um ?xido de ni?bio com uma nanoestrutura diferente do ?xido de ni?bio comercial, usado para sintetizar o complexo. O ?xido de ni?bio comercial, o complexo de ni?bio e o catalisador de ni?bio foram caracterizados por termogravimetria (TG e DTA), an?lise de ?rea superficial (BET), microscopia eletr?nica de varredura (MEV) e difra??o de raios-X (DRX), demostrando que o catalisador pesquisado possui caracter?sticas morfol?gicas e cristalogr?ficas que indicam um potencial catal?tico superior ao ?xido de ni?bio comercial. Foi realizado um planejamento fatorial composto com ponto central, com tr?s fatores (temperatura de calcina??o, raz?o molar de ?lcool/?cido oleico e percentual m?ssico de catalisador). Verificando que o ponto ?timo experimental se deu mediante a temperatura de calcina??o do complexo em 600?C, uma raz?o molar de ?lcool/?cido oleico de 3,007/1 e percentual m?ssico de catalisador de 7,998%, apresentando uma convers?o de 22,44% do ?cido oleico em oleato de metila em 60 min de rea??o. Realizou-se uma regress?o linear e quadr?tica composta para se determinar de um ponto ?timo estat?stico da rea??o, sendo a temperatura de calcina??o do complexo em 450?C, raz?o molar de ?lcool/?cido oleico de 3,3408/1 e percentual m?ssico de catalisador de 7,6833%. Foi realizada uma modelagem cin?tica para estima??o de par?metros para a cat?lise heterog?nea que se ajustou satisfatoriamente aos resultados experimentais com uma convers?o final de 85,01% com catalisador e de 42,38% sem o catalisador em 240 min de rea??o. Permitindo avaliar que o catalisador estudado possui potencial catal?tico para ser utilizado na produ??o de biodiesel
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S?ntese e caracteriza??o de CuNb2O6 e CuNbC atrav?s de rea??o s?lido- s?lido e g?s- s?lido a baixa temperatura / Synthesis and characterization of CuNb2O6 and CuNbC through reaction solid-solid and gas-solid low temperatureSouto, Maria Veronilda Macedo 31 October 2013 (has links)
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Previous issue date: 2013-10-31 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The refractory metal carbides have proven important in the development of engineering materials due to their properties such as high hardness, high melting point, high thermal conductivity and high chemical stability. The niobium carbide presents these characteristics. The compounds of niobium impregnated with copper also have excellent dielectric and magnetic properties, and furthermore, the Cu doping increases the catalytic activity in the oxidation processes of hydrogen. This study aimed to the synthesis of nanostructured materials CuNbC and niobium and copper oxide from precursor tris(oxalate) oxiniobate ammonium hydrate through gas-solid and solid-solid reaction, respectively. Both reactions were carried out at low temperature (1000?C) and short reaction time (2 hours). The niobium carbide was produced with 5 % and 11% of copper, and the niobium oxide with 5% of copper. The materials were characterized by X-Ray Diffraction (XRD), Rietveld refinement, Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF), infrared spectroscopy (IR), thermogravimetric (TG) and differential thermal analysis (DTA , BET and particle size Laser. From the XRD analysis and Rietveld refinement of CuNbC with S = 1.23, we observed the formation of niobium carbide and metallic copper with cubic structure. For the synthesis of mixed oxide made of niobium and copper, the formation of two distinct phases was observed: CuNb2O6 and Nb2O5, although the latter was present in small amounts / Os carbetos de metais refrat?rios t?m se revelado importantes no desenvolvimento de materiais de engenharia devido as suas propriedades, tais como: alta dureza, alto ponto de fus?o, alta condutividade t?rmica e alta estabilidade qu?mica. O carbeto de ni?bio apresenta essas caracter?sticas. Os compostos de ni?bio impregnados com cobre tamb?m possuem excelentes propriedades diel?tricas e magn?ticas e, al?m disso, a dopagem com Cu aumenta a atividade catal?tica em processos de oxida??o de hidrog?nio. Este trabalho teve como objetivo a s?ntese dos materiais CuNbC e ?xido de ni?bio e cobre nanoestruturados a partir do precursor tris(oxalato)oxiniobato de am?nio hidratado, atrav?s de rea??o g?s-s?lido e s?lido-s?lido, respectivamente. Para ambos, as rea??es foram realizadas a baixa temperatura (1000?C) e curto tempo de rea??o (2 horas). O carbeto de ni?bio foi produzido com 5% e 11% de cobre e o ?xido de ni?bio e cobre com 5% de cobre. Os materiais obtidos foram caracterizados atrav?s dos ensaios de Difra??o de Raios X (DRX), Refinamento Rietveld, Microscopia Eletr?nica de Varredura (MEV), Espectroscopia por Fluoresc?ncia de Raios-X (FRX), Espectroscopia de Infravermelho (IV), Termogravim?trica (TG), An?lise Termodiferencial (DTA), BET e granulometria a Laser. A partir das an?lises de DRX e do refinamento Reitiveld para o CuNbC com S= 1,23, observou-se a forma??o do carbeto de ni?bio e cobre puro com estrutura c?bica. Na s?ntese realizada do ?xido misto de ni?bio e cobre correu a forma??o de duas fases distintas: CuNb2O6 e Nb2O5, embora a ?ltima tenha sido formada em pequena quantidade / 2020-01-01
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