Made available in DSpace on 2014-12-17T14:09:18Z (GMT). No. of bitstreams: 1 FatimaRDF_TESE.pdf: 1276993 bytes, checksum: e49848d3c2dd72aa79cb38ebe1d84d84 (MD5) Previous issue date: 2012-11-26 / Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages / No Brasil, desde o in?cio do Programa Nacional de Produ??o e Uso do Biodiesel, em 2004, diversas mat?rias primas foram avaliadas para a sua produ??o, tentando aliar a diversidade agr?cola do pa?s ao desejo de diminuir os custos de produ??o. Para determinar a composi??o qu?mica de amostras de biodiesel produzidas a partir dos ?leos mais comuns, os m?todos internacionais t?m sido largamente utilizados no Brasil. Por?m, para an?lises de biodiesel produzido a partir de algumas mat?rias primas alternativas, alguns problemas anal?ticos foram detectados. Esse foi o caso do biodiesel de mamona. Devido ? necessidade de contornar esses problemas, novas metodologias foram desenvolvidas, utilizando colunas cromatogr?ficas, padr?es e diferentes m?todos para quantifica??o, privilegiando a sempre simplifica??o dos equipamentos, a realiza??o de an?lises mais r?pidas, diminuindo os custos e facilitando a rotina dos laborat?rios de pesquisas e de produ??o do biodiesel. No caso das an?lises para quantifica??o da glicerina livre, o etilenoglicol, padr?o muito mais barato e de f?cil aquisi??o, foi utilizado no lugar do 1,2,4-butanotriol, sem perda da qualidade dos resultados. Nas an?lises do metanol a n?o utiliza??o do headspace, diminuiu os custos do equipamento utilizado. A determina??o detalhada dos ?steres presentes ajudou o conhecimento mais profundo da composi??o de amostras de biodiesel provenientes de mat?rias primas alternativas. O relato dos experimentos e as conclus?es das pesquisas que resultaram no desenvolvimento de metodologias alternativas para controle de qualidade da composi??o do biodiesel produzido no Brasil, pa?s com enorme variabilidade de esp?cies na agricultura, s?o os objetivos dessa tese e est?o relatados nas p?ginas seguintes

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2016-02-17T21:48:49Z No. of bitstreams: 1 NataliaDeFreitasDaudt_TESE.pdf: 11328330 bytes, checksum: dbd5828f503f9e2ae820e46b2ab41fab (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2016-02-17T23:30:27Z (GMT) No. of bitstreams: 1 NataliaDeFreitasDaudt_TESE.pdf: 11328330 bytes, checksum: dbd5828f503f9e2ae820e46b2ab41fab (MD5) / Made available in DSpace on 2016-02-17T23:30:27Z (GMT). No. of bitstreams: 1 NataliaDeFreitasDaudt_TESE.pdf: 11328330 bytes, checksum: dbd5828f503f9e2ae820e46b2ab41fab (MD5) Previous issue date: 2015-03-03 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / No presente estudo, amostras de tit?nio altamente porosas foram produzidas atrav?s de Moldagem por Inje??o de p?s Met?licos (Metal Injection Moulding - MIM) com adi??o de agente espa?ante (space holder). MIM permite a produ??o de amostras com geometrias complexas, alto grau de automatiza??o e custos reduzidos em larga escala de produ??o. A adi??o de part?culas de agente espa?ante ? MIM possibilita a produ??o de amostras com porosidade funcional, fazendo com que esse m?todo seja especialmente atrativo para a produ??o de implantes biom?dicos. Entretanto, a aplica??o desta t?cnica tem sido limitada pelo fato de que a porosidade na superf?cie das amostras ? parcialmente fechada e as condi??es de processamento n?o s?o est?veis quando a quantidade de agente espa?ante excede 55 Vol.%. Deforma??o e at? o colapso das amostras foram observados quando amostras contentando mais 55 Vol.% de retentor espacial foram sinterizadas. Contudo, para implantes de tit?nio, produzidos pelo m?todo do agente espa?ante, uma porosidade final no intervalo de 60-65 Vol.% e uma porosidade aberta na superf?cie s?o necess?rias para atingir uma porosidade interligada que permita o crescimento ?sseo. Portanto, neste estudo, tr?s abordagens foram conduzidas visando a produ??o de amostras de tit?nio altamente porosas com uma porosidade aberta na superf?cie atrav?s da MIM com adi??o de KCl como agente espa?ante. Primeiro, a quantidade de s?lidos (agente espa?ante e tit?nio) no material de trabalho foi otimizada. A quantidade de s?lidos foi aumentada at? 80 Vol.%. Evitar o bloqueio da injetora durante a inje??o do material de trabalho foi o principal desafio, consequentemente um grande esfor?o foi empregado para melhorar a homogeneiza??o do material de trabalho e a otimiza??o dos par?metros de processo e, assim, permitir a inje??o dos materiais de trabalho com at? 80 Vol.% de s?lidos. O aumento na quantidade de s?lidos melhorou a estabilidade geom?trica das amostras injetadas durante a extra??o t?rmica do ligante e a sinteriza??o, permitindo a sinteriza??o de amostras contendo 70 Vol.% de agente espa?ante sem deforma??o. Depois, remo??o agente espa?ante foi realizada atrav?s de sublima??o do KCl durante a sinteriza??o a v?cuo, o que permitiu omitir a etapa mais lenta do processo: a dessaliniza??o em solvente, e aumentar ainda mais a estabilidade geom?trica das amostras. E por ?ltimo, tratamento por plasma foi introduzido nas amostras antes da etapa final de sinteriza??o. Primeiramente, o tratamento por plasma foi aplicado ?s amostras porosas obtidas por compacta??o a quente do material de trabalho com 70 Vol.% de agente espa?ante. Os resultados obtidos para amostras compactadas foram transferidos para produ??o e tratamento por plasma das Abstract ________________________________________________________________________________ amostras injetadas. Uma investiga??o detalhada foi conduzida com o objetivo de determinar o mecanismo de modifica??o por plasma das amostras injetadas com agente espa?ante. Al?m disso, ligas de a?o bem conhecidas foram tratadas por plasma a fim de avaliar a temperatura durante o tratamento das amostras injetadas. As amostras porosas de tit?nio foram analisadas com rela??o ao efeito do tratamento por plasma e da composi??o do material de trabalho na contamina??o por elementos intersticiais, precis?o geom?trica ap?s cada etapa do processamento, microestrutura, porosidade no volume e na superf?cie da amostra. O tratamento por plasma aumentou a quantidade de poros abertos na superf?cie e melhorou a precis?o geom?trica das amostras. Logo, tratamento por plasma de amostras produzidas por MIM com adi??o de agente espa?ante tem potencial para ser aplicado como processo padr?o de produ??o de amostras altamente porosas. Resumindo, todas as rotas estudadas s?o promissoras para a produ??o de implantes de tit?nio porosos atrav?s da MIM, uma vez que permitem a sinteriza??o de tit?nio altamente poroso com boa precis?o geom?trica, porosidade aberta na superf?cie e porosidade final no intervalo adequado para o crescimento ?sseo (cerca de 65 Vol.%). / A combina??o da Moldagem por Inje??o de p?s Met?licos (Metal Injection Moulding MIM) e o M?todo do Retentor Espacial (Space Holder Method - SHM) ? uma t?cnica promissora para fabrica??o de pe?as porosas de tit?nio com porosidade bem definida como implantes biom?dicos, uma vez que permite um alto grau de automatiza??o e redu??o dos custos de produ??o em larga escala quando comparado a t?cnica tradicional (SHM e usinagem a verde). Contudo a aplica??o desta t?cnica ? limitada pelo fato que h? o fechamento parcial da porosidade na superf?cie das amostras, levando ao deterioramento da fixa??o do implante ao osso. E al?m disso, at? o presente momento n?o foi poss?vel atingir condi??es de processamento est?veis quando a quantidade de retentor espacial excede 50 vol. %. Entretanto, a literatura descreve que a melhor faixa de porosidade para implantes de tit?nio para coluna vertebral est? entre 60 - 65 vol. %. Portanto, no presente estudo, duas abordagens foram conduzidas visando a produ??o de amostras altamente porosas atrav?s da combina??o de MIM e SHM com o valor constante de retentor espacial de 70 vol. % e uma porosidade aberta na superf?cie. Na primeira abordagem, a quantidade ?tima de retentor espacial foi investigada, para tal foram melhorados a homogeneiza??o do feedstock e os par?metros de processo com o prop?sito de permitir a inje??o do feedstock. Na segunda abordagem, tratamento por plasma foi aplicado nas amostras antes da etapa final de sinteriza??o. Ambas rotas resultaram na melhoria da estabilidade dimensional das amostras durante a extra??o t?rmica do ligante e sinteriza??o, permitindo a sinteriza??o de amostras de tit?nio altamente porosas sem deforma??o da estrutura.

Made available in DSpace on 2014-12-17T15:01:26Z (GMT). No. of bitstreams: 1 TalithaAB_DISSERT.pdf: 2174474 bytes, checksum: 5fc9b46f49baf0082200961f74eed779 (MD5) Previous issue date: 2011-08-23 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Effluents from pesticide industries have great difficulty to decontaminate the environment and, moreover, are characterized by high organic charge and toxicity. The research group Center for Chemical Systems Engineering (CESQ) at the Department of Chemical Engineering of Polytechnical School of University of S?o Paulo and Department of Chemical Engineering, Federal University of Rio Grande do Norte have been applying the Advanced Oxidation Processes (AOP's) for the degradation of various types of pollutants. These processes are based on the generation of hydroxyl radicals, highly reactive substances. Thus, this dissertation aims to explore this process, since it has been proven to be quite effective in removing organic charge. Therefore, it was decided by photo-Fenton process applied to the degradation of the fungicide Thiophanate methyl in aqueous system using annular reactor (with lamp Philips HPLN 125W) and solar. The samples were collected during the experiment and analyzed for dissolved organic carbon (TOC) using a Shimadzu TOC (Shimadzu 5050A e VCP). The Doehlert experimental design has been used to evaluate the influence of ultraviolet radiation, the concentrations of methyl thiophanate (C12H14N4O4S2), hydrogen peroxide (H2O2) and iron ions (Fe2+), among these parameters, was considered the best experimental conditions, [Fe2+] = 0.6 mmol/L and [H2O2] = 0.038 mol/L in EXP 5 experiment and in SOL 5 experiment, obtaining a percentage of TOC removal of 60% in the annular reactor and 75% in the solar reactor / Os efluentes das ind?strias de agrot?xicos apresentam grande dificuldade quanto ? sua descontamina??o no meio ambiente e, al?m disso, s?o caracterizados por possu?rem alta carga org?nica e toxicidade. O grupo de pesquisa do Centro de Engenharia de Sistemas Qu?micos (CESQ) do Departamento de Engenharia Qu?mica da Escola Polit?cnica da Universidade de S?o Paulo e do Departamento de Engenharia Qu?mica da Universidade Federal do Rio Grande do Norte vem aplicando os Processos Oxidativos Avan?ados (POA) ? degrada??o de diversos tipos de poluentes. Estes processos s?o baseados na gera??o de radicais hidroxila, subst?ncias altamente reativas. Desta forma, buscou-se explorar esse processo, j? que o mesmo vem se apresentando bastante eficaz na remo??o de carga org?nica. Portanto, decidiu-se pelo processo foto- Fenton aplicado na degrada??o do fungicida tiofanato met?lico em sistema aquoso, utilizando reator anular (com l?mpada Philips, HPLN de 125W) e solar. As amostras foram coletadas durante o experimento e analisadas quanto ao teor de carbono org?nico dissolvido (COT) utilizando um analizador TOC (Shimadzu 5050A e Shimadzu VCH). O planejamento experimental Doehlert utilizado para avaliar a influ?ncia da radia??o ultravioleta, das concentra??es do tiofanato met?lico (C12H14N4O4S2), do per?xido de hidrog?nio (H2O2) e dos ?ons de ferro [Fe2+]. Dentre estes par?metros, foram consideradas as melhores condi??es experimentais, sendo: [Fe2+] = 0,600 mmol/L e [H2O2] = 0,038 mol/L no experimento EXP 5 e no experimento SOL 5, obtendo um percentual de remo??o de COT de 60% no reator anular e de 75% no reator solar

Made available in DSpace on 2014-12-17T15:01:35Z (GMT). No. of bitstreams: 1 SamuelAO_DISSERT.pdf: 6693517 bytes, checksum: 0be8bd399faaff3fe4e2da515c357889 (MD5) 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

Este trabalho apresenta resultados de estudos e caracterizações de Conjuntos Eletrodo/Membrana (MEAs) de Células a Combustível a Membrana Polimérica (PEMFC). Algumas condições de operação de células e diferentes processos de produção de MEA foram investigados. A técnica de Espectroscopia de Impedância Eletroquímica (EIE) (em situ - 0 a 16 A) foi usada \"on-line\" como uma ferramenta de diagnóstico, relativa ao desempenho de célula. As medidas de EIE foram feitas através do Sistema de EIE para células a combustível FC350 (GAMRY), junto a um PC4 Potentiostato/Galvanostato e conectado à carga dinâmica (TDI) para experimentos de EIE \"on-line\" (100 mHz - 10 kHz, dU = 5 mV). MEAs com 25 cm2 de área ativa, usando eletrocatalisadores PtM/C 20 % (M = Ru, Sn ou Ni) fabricados usando o Método de Redução por Álcool (MRA). A tinta catalítica foi diretamente aplicada no Tecido de Carbono (GDL) e este prensado na membrana de Nafion® (105). MEAs usando eletrocatalisadores Pt/C e PtRu/C 20 % da E-TEK foram fabricados para comparação. Todos os cátodos foram confeccionados com Pt/C 20% da E-TEK. Foram fixadas as concentrações de metal nobre em 0,4 mg Pt.cm-2 no anodo e 0,6 mg Pt.cm-2 no catodo (E-TEK). Diagramas de Nyquist dos MEAs com Pt/C e PtRu/C da E-TEK ou PtM/C MRA apresentaram as mesmas resistências de ôhmicas para os MEAs. Este fato pode ser explicado por supressão de aglomerados durante o processo de preparação do MEA ou pela homogeneidade do eletrocatalisador ancorado ao carbono. Também pôde ser observado, a baixas densidades atuais que há uma diferença de desempenho significante entre o eletrocatalisadores da ETEK e os preparados pelo MRA. Os resultados das curvas de polarização confirmaram que PtM/C MRA apresentara um aumento de atividade para as células alimentadas com metanol e etanol. A técnica de EIE se mostrou eficiente para a avaliação do método de preparação dos MEAs e do desempenho da célula, os resultados de EIE mostraram uma coerência na escolha do modelo do circuito elétrico para os MEAs utilizando hidrogênio, metanol e etanol. Esta coerência indica que outras resistências não consideradas no modelo não são relevantes na resistência total dos MEAs. / This work reports results of studies and characterization on Membrane Electrode Assemblies (MEAs) for Proton Exchange Membrane Fuel Cell (PEMFC). Some cell operation conditions and different processes of MEA production were investigated. The Electrochemical Impedance Spectroscopy Technique (EIS) (in situ - 0 to 16 A) was used \"on-line\" as a tool for diagnosis, concerning the cell performance. The EIS measurements were carried out with a FC350 Fuel Cell EIS System (GAMRY), coupled to a PC4 Potentiostat/Galvanostat and connected to the electronic load (TDI) for \"on-line\" EIS experiments (100 mHz - 10 kHz, dU = 5 mV). MEAs with 25 cm2 surface area, using PtM/C 20% (M = Ru, Sn or Ni) electrocatalysts were manufactured using the Alcohol Reduction Process (ARP). The catalytic ink was applied directly into the Carbon Cloth (GDL) and pressed in the NafionR membrane (105). MEAs using Pt/C and PtRu/C 20% from E-TEK electrocatalysts were manufactured by comparison. All the cathodes were sprayed with Pt/C 20% from E-TEK. The noble metal concentrations used were set to 0.4 mg Pt.cm-2 at the anode and 0.6 mg Pt.cm-2 at the cathode (E-TEK). Nyquist diagrams of the MEAs with Pt/C and PtRu/C from E-TEK or PtM/C (M = Ru, Sn or Ni) ARP showed essentially the same ohmic resistances for the MEAs. This fact can be explained by suppression of agglomerates during the MEA preparation process or by the homogeneity of the anchored electrocatalysts at the carbon surface. It could also be observed, at low current densities, that there was a significant performance difference between the electrocatalysts from E-TEK and those prepared with the Alcohol Reduction Process. The polarization curves results confirmed that the PtM/C (M = Ru, Sn or Ni) ARP showed an activity increase for the methanol and ethanol fed cells. The technique of EIE was shown efficient for the evaluation of the method preparation of MEAs and the acting of the cell, the results of EIE showed coherence in the choice of the model the electric circuit for MEAs using hydrogen, methanol and ethanol. This coherence indicates that other resistances no considered in the model are not relevant in the total resistance of MEAs.

Diferenças no timing da melanização e esclerotização do exoesqueleto são evidentes quando se compara a morfologia externa de abelhas de hábitos sociais e as solitárias. A esta diferença convencionamos chamar de heterocronia da maturação cuticular, o termo heterocronia significando variações no tempo relativo, ou ritmo, de um evento ontogenético em relação ao ancestral ou entre taxons. Propusemos que as abelhas sociais, que após a ecdise permanecem na colônia por vários dias, alcançariam a maturidade de alguns sistemas orgânicos, entre eles o tegumento, muito mais tarde que as espécies de abelhas solitárias que ao emergir partem imediatamente para atividades extra-nidais. Neste contexto, o objetivo deste trabalho consistiu em testar esta hipótese utilizando o tegumento em maturação das espécies de abelhas sociais, Apis mellifera e Frieseomelitta varia, e da espécie solitária Centris analis, em estudos comparativos de expressão gênica, ultraestrutura e quantificação de hidrocarbonetos cuticulares (CHCs). Para isto utilizamos sequenciamento de mRNA (RNA-seq), microscopia eletrônica de transmissão (MET) e cromatografia de gás e espectrometria de massas (CG/MS). Os perfis de expressão de genes da via de melanização/esclerotização cuticular (ebony e tan) diferenciaram as espécies sociais da solitária, assim como a expressão de genes com função na via de metabolismo de quitina (Cda5, Idgf4 e chitooligosacchariodolytic-domain-like) e de genes codificadores de proteínas estruturais da cutícula (CPR14, CPR17, CPR18, CPR25, CPR23, CPR26, Apd-3 e Apd-like). Genes com função na regulação da maturação cuticular (FTZ-F1, E74, Hr46 e Hr4) se mostraram co-expressos nas espécies sociais e os perfis de expressão destes genes, exceto Hr46, e de outros reguladores (Ethr, Hr38, Rickets e Ptx-1) também diferenciaram as espécies sociais da solitária. Ressaltamos em nossas análises os genes do ciclo circadiano, cuja expressão tem relação com a deposição de quitina cuticular, além de genes de vias de pigmentação não melanínicas. As análises de MET, abrangendo outras três espécies de abelhas (Bombus brasilienses: primitivamente eussocial; Euglossa cordata: facultativamente social; Tetrapedia diversipes: solitária), mostraram diferenças consistentes entre a ultraestrutura e espessura das cutículas das espécies sociais e solitárias, o que reforçou nossos resultados de RNA-seq. A quantificação absoluta dos CHCs diferenciou as abelhas sociais da solitária, consistente com a hipótese de heterocronia da maturação cuticular e com os perfis de expressão de genes envolvidos na biossíntese de CHCs. Assim, além de desvendar transcriptomas de tegumento de três espécies de abelhas, a comparação da expressão gênica aliada à análise de ultraestrutura da cutícula e quantificação de CHCs levaram à caracterização de diferenças no processo de maturação cuticular entre as espécies sociais e solitárias / Differences in the timing of exoskeleton melanization and sclerotization processes are evident when comparing the external morphology of social and solitary bee species. Such differences may constitute a relevant example of cuticular maturation heterochrony, this term referring to a genetic change in timing of an ontogenetic process relative to an ancestor or between taxons. We proposed that social bees, which remain protected inside the colony for many days before initiating outside nest activities, would reach the maturity of some organic systems, such as the integument (epidermis and cuticle), later than solitary bees, which start such activities immediately after ecdysis. We tested this hypothesis in a comparative study of the developing integument of eusocial bees, Apis mellifera and Frieseomelitta varia, and the solitary bee Centris analis. Using RNA-seq, we verified that the expression profiles of genes involved in cuticular melanization and sclerotization (ebony and tan), chitin deposition and organization (Cda5, Idgf4, chitooligosacchariodolytic-domain-like), and cuticle formation (CPR14, CPR17, CPR18, CPR25, CPR23, CPE26, Apd-3, Apd-like) were positively, correlated between the two eusocial species, but not between the eusocial and the solitary species. Some of the genes with roles in regulating exoskeleton maturation (FTZ-F1, E74, Hr46, Hr4) were co-expressed only in the eusocial species. The expression profiles of these genes (except Hr46) and other regulatory genes (Ethr, Hr38, Rickets, Ptx-1) were also positively correlated exclusively in the eusocial bees. We also highlighted the expression of genes involved in non-melanin pigment production and the expression of circadian rhythm genes that could be related to chitin layers deposition. Transmission electron microscopy analysis of the integument of the two eusocial and the solitary bee species, in addition to other three bee species (the primitively eusocial Bombus brasilienses; the facultatively social Euglossa cordata; the solitary bee Tetrapedia diversipes), showed differences in cuticle ultrastructure and thickness, thus supporting the RNA-seq data. In agreement with our hypothesis, CHC quantifications were consistent with the expression levels of genes involved in CHC biosynthesis, thus differentiating the superficial cuticle layer of the eusocial and solitary species. Together, the integument transcriptomes, ultrastructure, and CHC quantification allowed us to characterize differences in the timing of cuticle maturation in social and solitary bees

L’objectif de cette étude est de mieux comprendre le rôle joué par les défauts dans les propriétés optiques et électroniques des nanostructures d’oxyde de zinc. Pour ce faire, nous avons synthétisé des nanoparticules d’oxyde de zinc de 6 à 18 nm de diamètres pouvant être considérées comme modèle en terme de stœchiométrie, de cristallinité et de qualité de surface par une méthode physique originale : la Low Energy Cluster Beam Deposition.La caractérisation optique des défauts présents dans les nanoparticules de ZnO a été faite grâce à l’analyse des spectres d’émission visible et UV à différentes températures [10K-300K]. En particulier la luminescence excitonique à 3,31 eV, qui est un sujet controversé, a été étudiée en comparant la luminescence excitonique d’échantillons structurés à différentes échelles (nanoparticules, microcristaux et monocristal). Les temps de déclins très rapides des défauts donneurs ont été étudiés par spectroscopie à décalage de fréquence au CELIA à Bordeaux révélant une dépendance en fonction de la taille des NPs du type Giant Oscillator Strenght.Les propriétés de transport électronique des couches minces de NPs, naturellement dopées n, ont été caractérisées grâce à des expériences σ(T). Différents scénarios sont proposés pour expliquer les résultats des expériences de conductivité, et discutés en fonction des propriétés optiques des couches et de leur morphologie. En particulier, il est montré que la surface des NPs, très réactive, influence fortement le transport, ce qui laisse entrevoir la possibilité d’utiliser ces films nanostructurés comme capteurs de gaz. / This study deals with the influence of defects on the electronic properties of ZnO nanoparticles (NPs).In order to perform this study we have synthesized ZnO NPs using an original physical way : the Low Energy Cluster Beam Deposition. The NPs size can be adjusted between 6 and 18 nm depending the synthesis parameters and their analysis shows that the NPs have a good stoichiometry, cristallinity and surface quality.The photoluminescence properties of different ZnO samples structured at different scales (i.e. nanoparticle, microcrystal and monocrystal) have been analyzed at different temperature (10K-300K). The good cristallinity of the NPs is confirmed by the lack of visible luminescence. The comparison of the 3,31 eV excitonic emission of ZnO samples structured at different scales shows that this band is due to extended defect and/or exciton-phonon coupling rather than a surface luminescence. Moreover the lack of the 3.31 eV in the NPs luminescence shows that these defect does not occurs in ZnO NPs. At last, the time resolved study of the donor bounded exciton emission shows a variation of the decay time with the size of NPs suggesting a Giant Oscillator Strenght phenomenon.The transport properties of ZnO NPs assembled thin film are determined by conductivity measurements at variable temperatures. Different possibilities are considered in order to explain the temperature dependence of the conductivity and correlated with the optical properties of the NPs, showing a hopping type conductivity. The huge reactivity of the nanostructured film strongly influences the conductivity showing a possibility to use ZnO NPs as a gas sensor.

Le carbure de bore B4C est envisagé en tant qu'absorbeur de neutrons dans les réacteurs nucléaires à neutrons rapides et à caloporteur sodium, RNR-Na, de génération IV. Cette filière de réacteur constitue aujourd'hui la référence pour l'avenir du nucléaire en France. Ainsi, un premier concept de réacteur RNR-Na, nommé ASTRID, devrait être construit aux alentours de 2025. L'objectif de notre étude est de comprendre, d'un point du vue fondamental, les effets induits par les irradiations aux ions, sur la structure cristallographique de B4C, dans différents domaines de pouvoirs d'arrêt. Pour cela, des échantillons de B4C, frittés par Spark Plasma Sintering (SPS) au SPCTS de Limoges, ont été irradiés par des ions de différentes natures et de différentes énergies, nous permettant de favoriser: (i) le pouvoir d'arrêt nucléaire Sn, afin d'induire un endommagement dit balistique dans le matériau, ou (ii) le pouvoir d'arrêt électronique Se, pour induire un endommagement dit électronique. Les irradiations en régime balistique ont été réalisées à l'aide d'ions C+, Ar+ et Au+ à des énergies inférieures au MeV, sur le VdG 4 MV de l'IPNL et auprès de la plateforme JANNuSOrsay. Les modifications structurales de B4C dans des gammes d'endommagement compris entre 0 et 9 dpa ont ainsi pu être étudiées. Les irradiations en régime électronique ont été effectuées par des ions S9+ et I9+ de 60 et 100 MeV sur l'accélérateur Tandem de l'IPNO. L'impact des excitations électroniques sur B4C à des pouvoirs d'arrêt électronique compris entre 4 et 15 keV.nm-1 a été déterminé. Afin d'étudier également les effets couplés de l'irradiation et de la température, toutes les irradiations ont été réalisées à température ambiante (RT), à 500°C et à 800 °C. Les caractérisations microstructurales des échantillons irradiés ont été effectuées principalement par microspectrométrie Raman au CEA Saclay et par Microscopie Electronique en Transmission (MET) in situ à JANNuS-Orsay. Nos études ont permis de mettre en évidence un seuil d'amorphisation du B4C dans les deux régimes d'endommagement à RT. En régime balistique, l'amorphisation du matériau est atteinte pour un taux de 9 dpa environ. En régime électronique, un pouvoir d'arrêt de 9 keV.nm-1 a permis de mettre en évidence une amorphisation du matériau induite par la formation de traces latentes nanométriques amorphes, et leur recouvrement à hautes fluences. De plus, nous avons également montré que la température permettait de limiter l'endommagement dès 500°C dans B4C, voire de l'inhiber presque totalement à 800°C / Boron carbide B4C is a material considered as neutron absorber for the Sodium Fast reactors SFR of the fourth generation. This type of reactor is the reference for the future of the nuclear technology in France. A first prototype of SFR, called ASTRID, should be built around 2025. The aim of this study is to understand, from a fundamental point of view, the effects induced by ion irradiation on the crystallographic structure of B4C, in different energy ranges. So, boron carbide samples were sintered by Spark Plasma Sintering (SPS) technique at the SPCTS laboratory in Limoges (France) and then irradiated with ions of different natures and energies, favoring: (i) the nuclear stopping power, creating ballistic damage in the material, or (ii) the electronic stopping power, creating mainly electronic damage. For the irradiations in the ballistic regime, we used C+, Ar+ and Au+ ions with energies below 1 MeV, on the accelerator VdG 4 MV of the IPNL and on the JANNuS-Orsay plateform. The structural modifications of B4C were studied between 0 and 9 dpa. The irradiations in electronic regime were performed with S9+ and I9+ ions with energies of 60 and 100MeV, at the 15 MV Tandem accelerator of the IPNO. The electronic excitations values corresponding to those conditions are ranging between 4 and 15 keV.nm-1. The irradiations were carried out at room temperature, 500°C and 800°C to study the coupled effects of temperature and irradiation. The structural characterizations of the samples after irradiation were performed by Raman spectrometry at CEA Saclay and by in situ Transmission Electron Microscopy at the JANNuS-Orsay facility. Our study demonstrated the existence of an amorphisation threshold in boron carbide in both irradiation regimes at room temperature. In the ballistic regime, the amorphisation of the material is reached around a value of 9 dpa. In the electronic regime, from a stopping power in between 9 and 10 keV.nm-1 an amorphisation process, induced by the formation of latent tracks and their overlapping at high fluences was observed. Moreover, at 500°C, we showed that the temperature slowed down the damage induced by the irradiation in B4C, and almost totally prevented it at 800°C

Le procédé Smart CutTM, utilisé pour le transfert de films minces sur substrat est basé sur la fissuration du silicium. La propagation des fissures est initiée à partir de défauts bidimensionnels induits par implantation d'hydrogène, les « H-platelets ». Des études précédentes ont montré que la fissuration du Si peut également être obtenue à partir de défauts nommés « He-plates » qui ont la particularité d'avoir un diamètre dix fois supérieur. L'objectif de ce travail était d'étudier la formation de ces défauts et leur évolution sous flux d'hydrogène jusqu'à la propagation des fissures. Dans une première partie, la formation des « He-plates » a été étudiée pour différentes orientations de substrats et discutée par rapport à la contrainte compressive bi-axiale induite par l'implantation. Les résultats montrent que les mécanismes qui gouvernent la formation des « He-plates » sont les mêmes que pour les « H-platelets ». Dans une seconde partie, l'évolution des « He-plates » en présence d'H a été étudiée en utilisant une approche expérimentale originale qui couple implantations d'hydrogène et observations par microscopie électronique en transmission. Les expériences montrent que la croissance des « He-plates » est gouvernée par la diffusion de l'hydrogène qui dépend de la température et du taux d'endommagement. Enfin, leur croissance est décrite à l'aide d'un modèle cinétique et, leur coalescence a été analysée en relation avec un modèle élastique. La propagation rectiligne de fissures à partir de ces précurseurs offre des perspectives intéressantes pour une utilisation industrielle. / The Smart CutTM process, used in the transfer of thin films on substrates is based on the cracking of silicon. The crack propagation is initiated from bi-dimensional defects induced by H-implantation, the H-platelets. Previous studies showed that the propagation of cracks in Si can also be triggered from defects named He-plates which have the particular feature of having a diameter ten times larger. The aim of this work was to study the formation of these defects and their evolution until the crack propagation under H supply.In a first part, the formation of He-plates was studied for different substrate orientations and discussed regarding the bi-axial compressive stress induced by implantation. Results show that the mechanisms that govern the He-plate formation are the same than for H-platelet formation. In a second part, the evolution of He-plates under H supply was studied by using an original experimental approach that combines H-implantation and transmission electron microscopy observations. Experiments show that the growth of He-plates is controlled by the diffusion of hydrogen which depends on temperature and damage rate. Finally, the growth is described by a kinetic model and their coalescence was analyzed with regard to an elastic model. The straight propagation of cracks from He-plates offers promising outlook for an industrial use.

Dans le combustible nucléaire UO2, utilisé dans les réacteurs à eau pressurisée (REP), le Cs, élément volatil compte parmi les produits de fission (PF) les plus abondamment produits. De plus, l’isotope 137Cs est connu pour être particulièrement radiotoxique. En cas d’accident, le relâchement de cet isotope est donc problématique et son étude est cruciale pour la sûreté nucléaire. En France, l’IRSN (Institut de Radioprotection et de sureté nucléaire) développe des codes de prédictions du relâchement des PF depuis le combustible, tels que MFPR (Module for Fission Product Release). Ces codes nécessitent d’être alimentés par des données fondamentales sur le comportement des PF. Ainsi, la connaissance des coefficients de diffusion de ces éléments dans la matrice combustible en fonction de la température et de l’atmosphère (pouvant oxyder le combustible en UO2+x) est primordiale. Dans ce contexte, l’objectif de cette thèse, menée en collaboration avec l’IRSN, est d’étudier la migration du Cs dans le dioxyde d’uranium stœchiométrique et sur-stœchiométrique, en conditions représentatives d’un fonctionnement normal et accidentel d’un REP, avec et sans la présence de Mo. Ce dernier est un PF abondamment produit qui agit comme tampon d’oxydation du combustible et est capable d’avoir des interactions chimiques avec le césium. De telles interactions pourraient affecter le comportement du Cs, et donc son relâchement depuis le combustible. Il a donc été nécessaire d’envisager les éventuelles interactions entre le Cs et le Mo dans le cadre de notre étude. La démarche expérimentale a consisté à simuler la présence de Cs et/ou Mo dans des pastilles d’UO2 ou d’UO2+x. par implantations ioniques des isotopes stables 133Cs et/ou 95Mo. Des recuits à haute température (950-1600°C) sous atmosphère contrôlée ou des irradiations en régime électronique couplées en température ont ensuite été réalisés, permettant d’induire la migration du Cs et du Mo. La spectrométrie de masse à ionisation secondaire (SIMS) a été utilisée pour suivre l’évolution des profils de concentration des éléments implantés, permettant d’extraire les coefficients de diffusion apparents du Cs dans UO2 et UO2+x en fonction des différents traitements. Une étude complémentaire de la microstructure a été réalisée par spectroscopie Raman et microscopie électronique en transmission (MET). Le Cs est très mobile dans UO2 sous atmosphère réductrice même si une partie et piégée sous forme de bulles à faible profondeur. Nous avons mis en évidence que la présence de Mo diminuait fortement cette mobilité. La même tendance est observée dans UO2+x sous atmosphère oxydante. Néanmoins les mécanismes d’immobilisation du Cs par le Mo diffèrent selon les conditions redox de recuit. En atmosphère réductrice, les expériences MET ont montré la formation de paires bulles de Cs-précipités métalliques de Mo dans les échantillons co-implantés. En atmosphère oxydante, l’absence de mobilité du Cs pourrait être liée à l’oxydation du Mo rendant possible des interactions chimiques Cs-Mo. Pour la première fois, des potentiels semi-empiriques ont été utilisés pour réaliser des calculs de dynamique moléculaire sur la diffusion du Cs et du Mo dans UO2 et UO2+x. Ces calculs nous ont aussi permis de caractériser les mécanismes de diffusion de l’oxygène dans ces matériaux en présence de ces deux PF / In the nuclear fuel UO2, which is widely used in Pressurized Water Reactor (PWR), Cs is a volatile element and is one of the most abundant fission product (FP). Furthermore, 137Cs is known to be highly radiotoxic. During a hypothetical accident, release of Cs would be particularly problematic for the environment. Hence, study of this element is of major concern for nuclear safety. To assess this issue, the French nuclear safety institute (IRSN) develops codes to predict FP release from nuclear fuel in normal and accidental conditions. This code requires fundamental data on FP behavior such as diffusion coefficient of these elements in UO2 as a function of temperature and atmosphere conditions (leading to UO2+x formation in oxidative conditions). The aim of this PhD, supported by the IRSN, is to study Cs migration in stoichiometric and hyper-stoichiometric uranium dioxide with and without the presence of Mo, in normal and accidental conditions of a PWR. This latter element is also an abundant FP, which is important to consider because it acts as an oxygen buffer in the fuel and may interact chemically with Cs. Such interactions may affect Cs behavior, hence its release from the fuel. Therefore, Cs-Mo interactions are considered in our study. The experimental procedure consists in simulating the Cs and/or Mo presence in UO2 and UO2+x pellets by ion implantation of stable isotopes 133Cs and/or 95Mo. Then, high temperature annealing (950 °C - 1600 °C) under controlled atmosphere or electronic excitations induced by irradiation coupled with temperature are performed to induce Cs and Mo migration. Secondary Ion Mass Spectrometry (SIMS) is used to follow the concentration profile evolution of these elements, allowing extracting effective diffusion coefficients of Cs in UO2 and UO2+x as a function of irradiation or thermal treatment. Microstructure characterizations were made by Raman spectroscopy and transmission electron microscopy (TEM). We show that Cs is mobile in UO2 under reducing atmosphere, even though some of the Cs is trapped in Cs-bubbles located near the surface. We evidence that Mo presence prevents Cs to be mobile. The same tendency is observed in UO2+x under oxidizing atmosphere. Nevertheless, Cs immobilization mechanisms in presence of Mo vary upon redox conditions used during annealing. In reducing conditions, TEM experiments showed formation of Cs bubbles associated with Mo metallic precipitates in co-implanted samples. In oxidative conditions, absence of Cs mobility could be explained by Mo oxidation leading to possible Cs-Mo chemical interactions. For the first time, semi-empirical potentials were used to perform molecular dynamic (MD) calculations on Cs and Mo diffusion in UO2 and UO2+x. These simulations also allowed characterizing oxygen diffusion mechanisms in these matrixes in presence of Cs and Mo