Silver is a precious metal that has traditionally been used for jewellery and money. It also possesses desirable properties such as being corrosion resistant and having good electrical conductivity, resulting in its use for industrial applications. Furthermore, it is also recognised for its tribological properties in non-cost prohibitive applications. Silver can be used as a surface coating and can be deposited using an electroplating process. The utilisation of silver as a surface coating is advantageous and sustainable, as the substrate material properties are enhanced while usage of silver is kept to a minimum. On the other hand, electroplating has been used for over a century. It is a process which is able to produce a layer of uniform and dense coating that adheres well to the substrate metal, thus modifying the properties of the substrate. It benefits from being relatively low cost and is scalable. Silver is electroplated onto stainless steel threaded compression fittings to prevent galling. Traditional silver electroplating, which contains the use of cyanide as a complexing agent in the electroplating bath, is still in use within industry, even to this day. Cyanide, in its various forms can be poisonous, toxic and even lethal, which presents a risk during the silver electroplating process. Furthermore, the toxic wastes created during the cyanide silver electroplating process are detrimental to the environment. The aim of this work is to develop a self-lubricating non-cyanide silver PTFE composite coating suitable for use in threaded compression fittings of the ferruled type. The composite can be considered self-lubricating when a concentration of 8% or more by volume of the self-lubricating PTFE substance is incorporated. My original contribution to knowledge is firstly the successful development and characterisation of a self-lubricating non-cynanide Ag-PTFE coating on stainless steel without a strike resulting in improved CoF of 0.06 from the CoF of 0.6 based on an unlubricated surface. Secondly is the application of a non-cyanide Ag-PTFE MMC for threaded compression fittings. Thirdly is the characterisation of the make-up process of threaded compression fittings through the proposed use of the torque-angle slope in assessing coating performance for threaded compression fittings during make-up. Conclusions that can be drawn for the work are that the performance non-cyanide Ag-PTFE coating exceeded the performance of the pure Ag coating made using the same non-cyanide process. Moreover, the performance of the Ag-PTFE coating shows promising results when compared to the performance of the commercial silver cyanide coating. As a viable replacement to the current silver cyanide process, the self-lubricating non-cyanide Ag-PTFE coating, will improve the working conditions and have a positive contribution to the environment. Moreover, a thinner coating with has the potential to reduce raw material usage and electroplating waste disposal costs.

No presente trabalho estudou-se uma nova rota para obter nanopartículas de prata e silício aleatoriamente dispersas em uma matriz nanoporosa de nanotubos de óxido de alumínio sobre alumínio. Além disso, estudou-se a aplicação deste novo material como ânodo em células a combustível alcalinas com etanol como combustível, usando a prata como catalisador na eletroxidação do etanol e da produção de H2. O processo proposto consiste na solidificação rápida mediante melt spinner de uma liga de alumínio-prata rica em alumínio (95.25% em peso de alumínio) para obter uma solução sólida supersaturada. Posteriormente foi feita uma anodização porosa em ácido oxálico e estudo eletroquímico em meio alcalino por meia hora. A morfologia da liga obtida foi caracterizada por Microscopia Eletrônica de Varredura, Difração de Raios-X, Microscopia Eletrônica de Transmissão equipado com Espectrometria de Raios X Dispersiva em Energia e avaliado o desempenho como ânodo mediante ensaios de voltametria cíclica Os resultados obtidos confirmam que o desenvolvimento de um novo processo para produzir nanopartículas cristalinas de prata com um tamanho que varia de 4 a 120 nm, com 95% delas entre 4 e 87 nm. A partir dos estudos eletroquímicos concluiu-se que a liga de Al-Ag produzida exibe um comportamento semelhante ao alumínio puro em NaOH 0.1 M e NaOH 0.1 M com 1 M de etanol. A reação entre o alumínio e o meio alcalino produz uma camada de hidrogênio que impede que a prata catalise a eletroxidação do etanol. Portanto, conclui-se que a liga de alumínio-prata produzida não é um material viável como ânodo em células a combustível alcalinas de etanol direto. Portanto, foi avaliado o método de produção de nanopartículas para uma liga Al-Si eutética (14.2% em peso). Esta liga com nanopartículas de silício apresentou um incremento no desempenho na produção de H2 de 17% comparado à liga Al-Si eutética sem o tratamento térmico. / In the present work a new route to obtain silver nanoparticles randomly dispersed in a porous Al2O3 nanotube matrix layer on aluminum was studied. Moreover, the use as an anode in alkaline fuel cells (AFC) with ethanol as combustible was studied, using the prepared surfaces as a catalyzer for the electrooxidation of ethanol. The developed process consists of the rapid solidification (quenching) through melt spinning of an aluminum-silver alloy (92.25 %wt. Al) to obtain a supersaturated solid solution, followed by a porous anodization in oxalic acid and electrochemical treatment in alkaline medium. The morphology of the alloy was characterized by Scanning Electron Microscopy, X-Ray Diffraction, Transmission Electron Microscopy and Energy Dispersive X. Ray Spectrometry and the performance of the ethanol electrooxidation was tested though cyclic voltammetry The obtained results confirm that this process produces crystalline silver nanoparticles with a size varying from 4 to 120 nm with 95% of the particles between 4 and 87 nm. The electrochemical study showed that the produced alloy exhibits a similar behavior to that of pure aluminum in the tested mediums. The reaction between the aluminum and the alkaline medium produces a gaseous hydrogen layer that impedes the catalytic action of silver on the ethanol oxidation. Moreover, it was concluded that the produced alloy is not a viable material for the use as anode for direct ethanol AFCs. Therefore, the nanoparticle production method was tested for an Al-Si near-eutectic alloy (14.2 %wt.). This alloy with silicon nanoparticles showed an increase in the performance of H2 production rate of 17% compared to that of the regular Al-Si near-eutectic alloy.

O trabalho foi conduzido em Colombo, Paraná, nas dependências da Unidade Regional de Pesquisa Florestal Centro-Sul, da Empresa Brasileira de Pesquisa Agropecuária - EMBRAPA, tendo os seguintes objetivos: detectar possíveis variações fenotipicas entre três procedências de Mimosa scabrella em características de crescimento inicial; verificar para cada procedência, a influência do tamanho da semente no padrão de qualidade e das mudas e avaliar a sobrevivência e o crescimento em altura após plantio. Para as procedências de Concórdia-SC e Caçador-SC, foram utilizadas as sementes retidas em peneiras de malhas circulares de 4,0, 3,0 e 3,5 mm de diâmetro, e para a procedência de Colombo-PR as retidas em malhas de 3,5, 3,0 e 2,5 mm. Em condições de peso de 100 sementes e porcentagem de germinação aos 21 dias após o início do teste. No viveiro, foram avaliadas a emergência das plântulas aos 21 dias após a semeadura, bem como sobrevivência, altura da parte aérea, diâmetro de colo e peso de matéria seca das mudas, aos dois meses após a semeadura. Aos seis meses após o plantio, foram avaliadas as sobrevivência e altura das plantas. O peso de 100 sementes variou em função da localização de procedência, sendo maior para as sementes de Caçador-SC. A porcentagem de germinação e de emergência das plântulas foi maior para a procedência de Concórdia-SC. Em condições de viveiro, a sobrevivência das mudas não foi afetada pela procedência. Diferenças no padrão de qualidade das mudas só foram obtidas entre procedências de Concórdia-SC e de Colombo-PR. As mudas da procedência de Concórdia foram de qualidade superior às de Colombo. Não houve influência da procedência na sobrevivência e altura das plantas aos seis meses após o plantio. Para as três procedências, o peso de 100 sementes aumentou com o aumento de tamanho das mesmas. Para as procedências de Caçador-SC e Colombo-PR, a porcentagem de germinação não foi afetada pelo tamanho da semente. Para a procedência de Concórdia-SC houve uma tendência de decréscimo da porcentagem de germinação com o aumento de tamanho das sementes. Porém a emergência das plântulas e a sobrevivênvia das mudas, para as três procedências, não foram afetadas pelo tamanho das sementes. Para as procedências de Concórdia-SC e Colombo-PR, a separação das sementes em classes de tamanho apenas permitiu agrupar mudas de crescimento semelhante, porém de mesma qualidade. Para a procedência de Caçador-SC, a separação das sementes em classes de tamanho permitiu também a obtenção de mudas de diferentes padrões, sendo provenientes das de 3,5 mm de melhor qualidade que as da classe de 4,0 mm. A sobrevivência e a altura das plantas não diferiram em função do tamanho das sementes, aos seis meses após o plantio.

Submitted by Izabel Franco (izabel-franco@ufscar.br) on 2016-10-26T17:47:35Z No. of bitstreams: 1 TeseBLS.pdf: 15809941 bytes, checksum: e94eb4f0e858901ec9568dacd81ecf51 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-11-08T18:28:27Z (GMT) No. of bitstreams: 1 TeseBLS.pdf: 15809941 bytes, checksum: e94eb4f0e858901ec9568dacd81ecf51 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-11-08T18:28:33Z (GMT) No. of bitstreams: 1 TeseBLS.pdf: 15809941 bytes, checksum: e94eb4f0e858901ec9568dacd81ecf51 (MD5) / Made available in DSpace on 2016-11-08T18:28:40Z (GMT). No. of bitstreams: 1 TeseBLS.pdf: 15809941 bytes, checksum: e94eb4f0e858901ec9568dacd81ecf51 (MD5) Previous issue date: 2016-10-07 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / The present research aims to develop a theoretical/experimental analysis of the combined effects of solidification thermal parameters, Bi content and addition of ternary elements (Cu, Ag) on the final microstructure aspects and on the final mechanical resistances of directionally solidified Sn-Bi, Sn-Bi-Ag and Sn-Bi-Cu solder alloys under transient heat flow conditions. Hence, experimental interrelations between microstructure and thermal parameters and between mechanical properties and microstructure could be established. The microstructures regarding the Sn-34wt.%Bi and Sn-52wt.%Bi alloys show the presence of β-Sn dendrites with Bi precipitates on their own, being enveloped by a lamellar binary Sn-Bi eutectic. The Sn-58wt.%Bi eutectic alloy show a variety of microstructures along the length of the directionally solidified casting, which includes binary eutectic, Bi plates, Bi trifoils and fishbone eutectic. In the case of the ternary Sn-Bi-Ag and Sn-Bi-Cu chemistries, microstructures are constituted by β-Sn dendrites decorated with Bi particles, Bi-Sn eutectic and Cu6Sn5 and Ag3Sn intermetallic particles for the Cu and the Ag bearing alloys, respectively. Experimental growth laws have been derived for both dendritic (λ1, λ2, λ3) and eutectic (λfine, λcoarse) arrangements considering the following alloys: binary Sn-34wt.%Bi, Sn-52wt.%Bi e Sn-58wt.%Bi alloys and ternary Sn- 34wt.%Bi-0.1wt.%Cu, Sn-34wt.%Bi-0.7wt.%Cu e Sn-33wt.%Bi-2wt.%Ag. Considering the binary Sn-Bi, it has been observed that increasing Bi content (34wt.%-->52wt.%-->58wt.%Bi), may cause a decrease on both strength and ductility, except for the sample at P=6mm of the Sn-52wt%Bi alloy. Hall-Petch type functional correlations have been able to represent the evolution of the tensile mechanical properties for the examined Sn-Bi and Sn-Bi-X alloys. / A presente proposta objetiva desenvolver uma análise teórico/experimental sobre os efeitos combinados dos parâmetros térmicos de solidificação (velocidade de solidificação VL e taxa de resfriamento, ṪL), do teor de Bi e das adições de terceiros elementos (Cu, Ag) na microestrutura e na resistência mecânica de ligas Sn-Bi, Sn-Bi-Ag e Sn-Bi-Cu solidificadas unidirecionalmente, estabelecendo correlações experimentais do tipo microestrutura/parâmetros térmicos e microestrutura/propriedades mecânicas. As microestruturas para as ligas binárias Sn-34%Bi e Sn-52%Bi são constituídas de dendritas de Sn com precipitados de Bi em seu interior, circundadas por um eutético lamelar binário, Sn-Bi. A liga eutética Sn-58%Bi mostrou uma ampla gama de microestruturas ao longo de todo o lingote, englobando o eutético binário Sn-Bi, placas e trifoils de Bi e eutético fishbone. Quanto às ligas ternárias Sn-Bi-Cu e Sn-Bi-Ag observa-se que as microestruturas são constituídas de dendritas β-Sn “decoradas” com partículas de Bi em seu interior, circundadas por uma mistura eutética irregular (Bi+Sn) e seus respectivos compostos intermetálicos primários Cu6Sn5 e Ag3Sn, respectivamente. As leis de crescimento experimentais dendrítico (λ1, λ2, λ3) e eutético (λfino, λgrosseiro) para as ligas binárias Sn-34%Bi, Sn-52%Bi e Sn-58%Bi e para as ligas ternárias Sn-34%Bi- 0,1%Cu, Sn-34%Bi-0,7%Cu e Sn-33%Bi-2%Ag em função de V e Ṫ foram caracterizadas por equações na forma de potência com aplicação de expoentes típicos. No caso das ligas binárias Sn-Bi, foi observado que com o aumento do teor de Bi (34%-->52%-->58%Bi), tanto o limite de resistência à tração (σt) quanto o alongamento específico diminuem, com exceção dos resultados para a amostra P=6mm da liga Sn-52%Bi. Relações funcionais do tipo Hall-Petch foram capazes de descrever a variação das propriedades mecânicas de tração de ligas Sn-Bi e Sn-Bi-X.

Submitted by Adelmo Fernandes de Oliveira Junior null (ligley@gmail.com) on 2017-01-27T18:02:21Z No. of bitstreams: 1 Dissertação Adelmo - 26-01-2017.pdf: 2029608 bytes, checksum: 09e6922ea4afa079b64bac18ef6882ba (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-01-31T16:02:22Z (GMT) No. of bitstreams: 1 oliveirajunior_af_me_guara.pdf: 2029608 bytes, checksum: 09e6922ea4afa079b64bac18ef6882ba (MD5) / Made available in DSpace on 2017-01-31T16:02:22Z (GMT). No. of bitstreams: 1 oliveirajunior_af_me_guara.pdf: 2029608 bytes, checksum: 09e6922ea4afa079b64bac18ef6882ba (MD5) Previous issue date: 2016-12-02 / A análise modal experimental é uma das técnicas mais importantes na caracterização dinâmica de estruturas. No setor aeroespacial a analise modal experimental é conhecida como Ground Vibration Test (GVT). Na Força Aérea Brasileira, o órgão responsável para executar o GVT é o Laboratório de Ensaios de Vibração (LEVI) da Divisão de Integração e Ensaio (AIE) do Instituto de Aeronáutica e Espaço (IAE). Esta pesquisa foi realizada neste laboratório que possui as facilidades para a execução de GVT. O objetivo principal deste estudo foi aprimorar a metodologia de ensaio de análise modal aplicada a um modelo de aeronave em alumínio do tipo GARTEUR SM-AG-19. O estudo desenvolvido possibilita que em ensaios futuros os resultados sejam replicados, no intuito de avaliar a integridade do sistema de medição, levando em consideração aspectos da influência do torque na junta aparafusada entre a asa e a fuselagem. Para validar a metodologia os resultados obtidos neste estudo foram comparados com os resultados de dois estudos desenvolvidos no Brasil. A contribuição principal desta pesquisa é relacionada ao estudo do efeito da variação do torque na junta aparafusada entre a asa e a fuselagem sobre os parâmetros modais da estrutura. / The experimental modal analysis is one of the most important techniques in the dynamic characterization of structures. In the aerospace industry, the experimental modal analysis is known as Ground Vibration Test (GVT). In the Brazilian Air Force, the institution responsible for executing the GVT is the Laboratory of Vibration Testing (LEVI) of the Integration and Testing Division (AIE) of the Institute of Aeronautics and Space (IAE). This research was carried out on this laboratory that has the facilities to perform the GVT. The main objective of this study was to improve the modal analysis test methodology applied to an aluminium aircraft model named GARTEUR SM-AG-19. This study allows the results to be replicated in future tests in order to evaluate the integrity of the measurement system, taking into account aspects of the influence of the torque on the bolted joint between wing and fuselage. In order to validate the methodology the results obtained in this study were compared to the results of two studies developed in Brazil. The main contribution of this research is the study of the torque variation effect on the bolted joint between wing and fuselage on the modal parameters of the structure.

Made available in DSpace on 2014-06-11T19:29:06Z (GMT). No. of bitstreams: 0 Previous issue date: 2005-02Bitstream added on 2014-06-13T19:37:59Z : No. of bitstreams: 1 maianeto_as_me_araiq.pdf: 907997 bytes, checksum: 246ee7468bbd3c17dd5762fc7651b5eb (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste trabalho, foi feito um estudo da cinética de precipitação da fase rica em prata, na liga Cu-7%Al-4%Ag, em peso, utilizando-se o modelo cinético isotérmico de Johnson-Mehl-Avrami e os modelos cinéticos nãoisotérmicos de Kissinger e Ozawa. A reação de precipitação da fase rica em prata foi acompanhada por medidas de variação da microdureza da liga com a temperatura de têmpera e o tempo de envelhecimento, e também por medidas de dilatometria. As fases presentes nas diversas temperaturas e tempos considerados, foram identificadas e caracterizadas por microscopia óptica e eletrônica de varredura, análise por dispersão de energias de raios X e por difratometria de raios X. Os resultados obtidos indicaram que a formação dos precipitados ricos em prata corresponde a um processo controlado por difusão da prata nos contornos de grão da matriz, no intervalo de temperaturas de 400 a 600 oC. O cálculo da energia de ativação para a formação dos precipitados, utilizando-se a equação de Johnson-Mehl-Avrami, forneceu um valor bastante próximo daquele encontrado na literatura, confirmando que o processo é controlado pela difusão da prata. O valor da energia de ativação para o crescimento dos precipitados ricos em Ag, calculado a partir de um método que considera o inverso do tempo necessário para o precipitado atingir seu tamanho máximo como proporcional à taxa de crescimento, ficou próximo daquele obtido utilizando-se a equação de Johnson-Mehl-Avrami, indicando que esse método pode ser utilizado para o cálculo da energia de ativação do processo cinético. Os valores da energia de ativação associados ao processo de precipitação de Ag, obtidos por métodos não isotérmicos, ficaram razoavelmente próximos daqueles encontrados na literatura e os valores assim obtidos associados à solubilização de Ag foram maiores do que aqueles encontrados na literatura... / In this work, the Ag-rich phase precipitation kinetics in the Cu-7wt.%Al-4wt.%Ag alloy, was studied using the Johnson-Mehl-Avrami isothermal kinetic model and the Kissinger and Ozawa non-isothermal kinetic models. The Ag-rich phase precipitation reaction was followed by microhardness changes measurements with quenching temperature and with aging time, and also by dilatometric measurements. The identification and characterization of the phases present at the considered temperatures and times were made by optical and scanning electronic microscopy, energy dispersive X-ray analysis and X-ray diffractometry. The results showed that the Ag-rich precipitates formation corresponds to a diffusion controlled process at the matrix grain boundaries, in the temperatures range from 400 to 600 oC. The activation energy value for the precipitates formation, calculated using the Johnson-Mehl-Avrami equation, is close to that found in the literature, thus confirming that the process is diffusion controlled. The activation energy value for the growing of Ag-rich precipitates, obtained considering that the inverse of the time to reach the precipitates maximum size is proportional to the growing rate, is close to that found using the Johnson-Mehl-Avrami equation, indicating that this method is useful to evaluate the activation energy for the kinetic process. The activation energy values obtained by non-isothermal methods and associated to the precipitation process were very close to those found in the literature, and the values associated to Ag dissolution were greater than those reported in the literature. This discrepancy may be associated to the presence of Al, and the Al-Ag interaction may be disturbing the diffusion process.

No presente trabalho estudou-se uma nova rota para obter nanopartículas de prata e silício aleatoriamente dispersas em uma matriz nanoporosa de nanotubos de óxido de alumínio sobre alumínio. Além disso, estudou-se a aplicação deste novo material como ânodo em células a combustível alcalinas com etanol como combustível, usando a prata como catalisador na eletroxidação do etanol e da produção de H2. O processo proposto consiste na solidificação rápida mediante melt spinner de uma liga de alumínio-prata rica em alumínio (95.25% em peso de alumínio) para obter uma solução sólida supersaturada. Posteriormente foi feita uma anodização porosa em ácido oxálico e estudo eletroquímico em meio alcalino por meia hora. A morfologia da liga obtida foi caracterizada por Microscopia Eletrônica de Varredura, Difração de Raios-X, Microscopia Eletrônica de Transmissão equipado com Espectrometria de Raios X Dispersiva em Energia e avaliado o desempenho como ânodo mediante ensaios de voltametria cíclica Os resultados obtidos confirmam que o desenvolvimento de um novo processo para produzir nanopartículas cristalinas de prata com um tamanho que varia de 4 a 120 nm, com 95% delas entre 4 e 87 nm. A partir dos estudos eletroquímicos concluiu-se que a liga de Al-Ag produzida exibe um comportamento semelhante ao alumínio puro em NaOH 0.1 M e NaOH 0.1 M com 1 M de etanol. A reação entre o alumínio e o meio alcalino produz uma camada de hidrogênio que impede que a prata catalise a eletroxidação do etanol. Portanto, conclui-se que a liga de alumínio-prata produzida não é um material viável como ânodo em células a combustível alcalinas de etanol direto. Portanto, foi avaliado o método de produção de nanopartículas para uma liga Al-Si eutética (14.2% em peso). Esta liga com nanopartículas de silício apresentou um incremento no desempenho na produção de H2 de 17% comparado à liga Al-Si eutética sem o tratamento térmico. / In the present work a new route to obtain silver nanoparticles randomly dispersed in a porous Al2O3 nanotube matrix layer on aluminum was studied. Moreover, the use as an anode in alkaline fuel cells (AFC) with ethanol as combustible was studied, using the prepared surfaces as a catalyzer for the electrooxidation of ethanol. The developed process consists of the rapid solidification (quenching) through melt spinning of an aluminum-silver alloy (92.25 %wt. Al) to obtain a supersaturated solid solution, followed by a porous anodization in oxalic acid and electrochemical treatment in alkaline medium. The morphology of the alloy was characterized by Scanning Electron Microscopy, X-Ray Diffraction, Transmission Electron Microscopy and Energy Dispersive X. Ray Spectrometry and the performance of the ethanol electrooxidation was tested though cyclic voltammetry The obtained results confirm that this process produces crystalline silver nanoparticles with a size varying from 4 to 120 nm with 95% of the particles between 4 and 87 nm. The electrochemical study showed that the produced alloy exhibits a similar behavior to that of pure aluminum in the tested mediums. The reaction between the aluminum and the alkaline medium produces a gaseous hydrogen layer that impedes the catalytic action of silver on the ethanol oxidation. Moreover, it was concluded that the produced alloy is not a viable material for the use as anode for direct ethanol AFCs. Therefore, the nanoparticle production method was tested for an Al-Si near-eutectic alloy (14.2 %wt.). This alloy with silicon nanoparticles showed an increase in the performance of H2 production rate of 17% compared to that of the regular Al-Si near-eutectic alloy.

Yolk-shell nanostructures/yolk-shell nanoparticles are defined as a hybrid structure, a mixture of core/shell and hollow particles, where a core particle is encapsulated inside the hollow shell and may move freely inside the shell. Of the various classifications of yolk-shell nanostructures, a structure with an inorganic core and inorganic shell (inorganic/inorganic) has been studied widely due to their unique optical, magnetic, electrical, mechanical, and catalytic properties. In the work presented here, among the different inorganic/inorganic yolk-shell nanostructures noble metal@silica yolk-shell nanostructures has been chosen as the topic of interest. Silica shell possesses many advantages such as chemical inertness, tunable pore sizes, diverse surface morphologies, increasing suspension stability, no reduction in LSPR properties of noble metal nanoparticles when used as a coating for such particles. Noble metal nanoparticles such as AgNPs and AuNPs, on the other hand, possess unique structural, optical, catalytic, and quantum properties. Hence yolk-shell nanostructures with a combination of Ag or Au core and a silica shell (Ag@SiO2 and Au@SiO2) would open to endless possibilities. In this study, four areas were mainly explored: mechanism of silica shell formation over a given template, the synthetic modifications of Ag@SiO2 and Au@SiO2 yolk-shell nanostructures, their application as a potential catalyst, and devising of a flow type catalytic reactor. Despite the growing number of contributions on the topic of yolk-shell nanostructures, particularly Au@SiO2 and Ag@SiO2 yolk-shell nanostructures, a potential for improvement lies in all four aforementioned areas. As an initial study, the effect of different processing conditions as well as the mechanism of silica shell formation over reactive block copolymer templates was investigated. An asymmetric PS-b-P4VP block copolymer was chosen as a structure directing component to deposit silica shell. In order to deposit silica shell, PS-b-P4VP micelles with a collapsed PS core and a swollen P4VP corona was prepared via a solvent exchange method. The growth of silica shell over the PS-b-P4VP micelles (reactive template) was done using in-situ DLS and TEM. The experimental data obtained revealed the 4 distinct stages involved in the silica shell formation over the reactive BCP micellar template starting from the accumulation of silica precursor around the P4VP corona followed by a reactive template mediated hydrolysis-condensation reaction of the silica precursor which eventually lead to the shell densification and shell growth around the micelles. An understanding of the mechanism of silica shell formation over reactive templates provides a direct way to encapsulate various active species such as metal nanoparticles and quantum dots and paves the way for the template mediated synthesis of hybrid nanostructures such as yolk-shell nanoparticles. These studies also serve as a platform to fine-tune the properties of such hybrid nanostructures by varying the reaction parameters during silica shell deposition and reaction time. The next part of the work focused mainly on the synthesis, process optimisation and characterization of Ag@SiO2 and Au@SiO2 yolk-shell nanostructures, and their potential use as a nanocatalyst. A well-known soft template mediated synthesis of the yolk-shell nanostructure was adopted for the present work. For this PS-b-P4VP micelle was used as a dual template for both encapsulation of nanoparticle and the deposition of silica shell. The nanoparticles were entrapped selectively to the BCP micellar core and silica deposition was done by reacting the nanoparticle-loaded micelles with an acidic silica sol which lead to the formation of Ag@PS-b-P4VP@SiO2 or Au@PS-b-P4VP@SiO2 particles with respect to the nanoparticle used. In the case of Ag@PS-b-P4VP particles, upon silica deposition, a partial dissolution of AgNPs was observed whereas AuNPs were stable against dissolution. Hence yolk-shell nanostructures with AuNPs were studied further. As-prepared Au@PS-b-P4VP@SiO2 particles were then subjected to pyrolysis to remove the BCP template. The resulting yolk-shell nanostructures comprised of an AuNP core and a hollow mesoporous silica shell. Upon removal of the BCP template, the Au@SiO2 particles fused together and formed large aggregates. The catalytic properties of Au@SiO2 yolk-shell nanoparticles were explored using a model reaction of reduction of 4-nitrophenol and proved to have good catalytic activity and efficient recyclability. It was observed that catalytic efficiency was hindered by the particle aggregates formed after pyrolysis by creating an inhomogeneity in the system and inaccessibility of the catalytic surface for the reactants. Hence synthetic modifications were needed to overcome such drawbacks. Next part of the work deals with the synthetic modification of Au@SiO2 yolk-shell nanoparticles done by embedding them in a porous silica structure (PSS). Such structural morphology was attained by gelating the excess silica precursor while synthesising the Au@PS-b-P4VP@SiO2 particles. The pyrolytic removal of block copolymer results in the formation of Au@SiO2@PSS catalyst and the porous nature of both the shell and the silica structure provides an easy access for the reactants to the nanocatalyst surface located inside. The catalytic properties of Au@SiO2@PSS were studied using a model reaction of catalytic reduction of 4-nitrophenol (4-NP) and reductive degradation of different dyes. Kinetic studies show that Au@SiO2@PSS catalyst possesses enhanced catalytic activity as compared to other analogous systems reported in the literature so far. Furthermore, catalytic experiments on the reductive degradation of different dyes show that Au@SiO2@PSS catalyst can be considered as a very promising candidate for wastewater treatment. Another proposed direction of applying the Au@SiO2 yolk-shells is by devising a continuous flow catalytic system composed of Au@SiO2 yolk-shell nanoparticles for the effective degradation of azo dyes as a promising candidate for wastewater treatment. This was done by infiltrating the Au@PS-b-P4VP@SiO2 particles inside a porous glass substrate (frits) and the subsequent pyrolytic removal of the BCP template resulting in the formation of Au@SiO2 yolk-shell nanostructures sintered inside the frit pores. The flow catalytic reactor was exploited in terms of studying its catalytic activity in the degradation of azo dyes and 4-nitrophenol and proved to have a catalytic efficiency of ca. 99% in terms of reagent conversion and has a long-term stability under flow. Thus, with a few modifications, these flow type systems can open the doors to a very promising continuous flow catalytic reactor in the future.

This research is motivated by two significant challenges facing the planet: reducing the emission of CO2 to the atmosphere and production of sustainable fuels by harnessing solar energy. The main objective of this work is the study of promising photocatalysts for CO2 reduction. DFT modeling of CO2, subnanometer Ag&Pt clusters, and anatase TiO2 (101) surface is employed to gain fundamental understanding of the catalytic process, followed by validation using a guided experimental endeavor. The binding mechanism of CO2 on the surface is investigated in detail to gain insights into the catalytic activity and to assist with characterizing the photocatalyst. For CO2 photoreduction, the cluster induced sub-bandgap and the preferred adsorbate in the first and key step of the CO2 photoreduction are explored. It is found that TiO2-supported Pt octamers offer key advantages for CO2 photoreduction: 1. by providing additional stable adsorption sites for favored CO2 species in the first step, and 2. by aiding in CO2- anion formation. Electronic structure analysis suggests these factors arise primarily from the hybridization of the bonding molecular orbitals of CO2 with d orbitals of the Pt atoms. Also, structural fluxionality is quantified to investigate geometry dependent (3D-2D) CO2 adsorption. Geometric information, electronic information, and C-O bond breaking tendency of adsorbed CO2 species are proposed to connect to experimental observables (IR frequency). The CO2 adsorption sites on supported Pt clusters are also identified using IR as the indicator. A cluster-induced CO2 dissociation to CO pathway is also discovered. Finally, experimental work including dendrimer-encapsulated technique, TPD, and UV-Vis is performed to validate the computational results, the availability of adsorption sites and CO2 binding strength on supported Pt clusters.

Comme le nucléole joue un rôle fondamental dans l’expression des protéines, via la synthèse des ARN ribosomiques, il n’est donc pas surprenant que des études aient révélé un lien étroit, entre des dysfonctionnements nucléolaires et l’origine de certaines maladies humaines. La découverte, il y a plusieurs années, d’un taux anormalement élevé de protéines nucléolaires dites argyrophiles ou AgNORs, dans les cellules tumorales, a permis d’envisager leur utilisation comme outil diagnostique ou pronostique du cancer. Détectées, de manière in vitro grâce à leur affinité pour l’argent, l’identification de quelques protéines AgNORs n’a pourtant pas permis d’établir une caractéristique commune à toutes les protéines argyrophiles détectées dans les extraits nucléolaires. Ainsi, bien que le test colorimétrique AgNOR soit utilisé dans de nombreux laboratoires académiques, l’absence d’identification de protéines AgNORs spécifiques du processus de cancérisation, a limité son utilisation en laboratoire clinique. Comme certaines limites technologiques et expérimentales ont limité leur caractérisation chez l’humain, nous avons donc décidé de reprendre les recherches sur ce sujet et de le réactualiser grâce aux avancées technologiques et scientifiques. Les protéines AgNORs étant étroitement liées à la biogenèse des ribosomes, nous avons donc décidé d’amorcer nos recherches chez la levure Saccharomyces cerevisiae, dans laquelle, la voie de biosynthèse des ribosomes a été particulièrement bien décrite. Devant l’intérêt biologique et médical de ces protéines, l’objectif de ce projet a donc été triple :<p>1-identifier des protéines AgNORs chez la levure<p>2-caractériser les propriétés physico-fonctionnelles et physico-chimiques de ces protéines AgNORs.<p>3-utiliser ces caractéristiques physico-chimiques pour rechercher de nouvelles AgNORs humaines, spécifiques de processus de cancérisation et potentiellement utilisables comme marqueurs tumoraux./The nucleolus is a subnuclear compartment that organized around ribosomal gene (rDNA) repeats NORs, which encode for ribosomal RNA. A peculiar group of acidic proteins which are highly argyrophilic are also localized at the same sites as NORs, thus allowing NORs to be very clearly and rapidly visualized by silver nitrate staining procedures. However, if three human argyrophilic proteins, UBF, C23 (nucleolin) and B23 (nucleophosmin), have been associated for staining of NOR, the exact number of AgNOR proteins and their intrinsic biochemical feature are unclear. Here, we have performed an heterologous screen in a genetically tractable eukaryotic organism (budding yeast) for the identification of novel AgNOR proteins and in vitro characterized an intrinsic feature that underlies silver binding and offers a strong predictive value for the identification of novel human AgNOR proteins. / Doctorat en Sciences / info:eu-repo/semantics/nonPublished