The success of orthopaedic implants fixed in the skeletal system using bone ingrowth into porous surfaces is critically dependent on the extent and quality of the initial bone ingrowth and the subsequent long-term maintenance of the bone within the porous structure. Biologically-significant elements (Ca, Mg, Mn) were incorporated at concentrations up to 5 mol% in solid solution in yttia-stabilised tetragonal zirconia polycrystal (3YTZP), whilst controlling microstructure and phase composition, to investigate the effect of ceramic chemistry on cellular behaviour in vitro and bone ingrowth into porous structures in vivo. Cellular attachment, proliferation, and migration on the ceramics were investigated using in vitro assays using fibroblasts. Cells were able to adhere strongly and proliferate on all ceramic surfaces, exhibiting maximal proliferation and minimal migration on 3YTZP but significantly faster migration on doped-3YTZP. The TZP ceramics were therefore considered to support normal cellular processes and thus were suitable for further study in vivo. A technique based on pressure casting ceramic slurry into a polymer preform of the desire pore structure, followed by polymer burnout and then sintering, was developed for fabricating porous bioceramics containing highly-controlled three-dimensional pore geometries. The ability of a selected pore structure to support bone ingrowth was tested using hydroxyapatite by implanting samples into femoral cortical bone of adult sheep for 4 and 12 weeks. Bone was able to rapidly colonise the porous structure and remodel such that, by 12 weeks implantation time, the majority of the porosity was filled with mature lamellar bone. Porous scaffolds of pure 3YTZP and 3YTZP doped with 1 mol% Mg, 1 mol% Mn, 1 mol% Ca, or 5 mol% Ca were fabricated and tested in the sheep model. Bone ingrowth into the doped compositions was significantly greater than that into pure 3YTZP, and was similar to that into the porous hydroxyapatite, indicating that the dopants significantly promoted osteogenesis within the bioinert scaffolds. This finding has application in clinical applications in that the initial bone ingrowth and, potentially, the long-term maintenance of bone within the porous structure may be improved by the incorporation of small amounts of biologically significant elements.

Silicon oxycarbide (SiOC) is a ceramic obtained through the heating of a polymer precursor, which undergoes partial decomposition to go from an organic polymer to an inorganic ceramic. The microstructure of SiOC is not uniform at the nanometer scale, and contains nanometer sized silicon dioxide, carbon, and silicon carbide. Porous SiOC has shown great promise in applications such as lithium ion batteries, gas separation, and thermal barriers. The microstructure, and thus the properties of the SiOC, is influenced by the initial polymer and the processing conditions. In this thesis, SiOC is fabricated using a base polysiloxane polymer using different gases during heating, different additives that change the initial polymer chemical composition or polymer shape, and polymers with different reactive groups. Porosity was introduced into the SiOC ceramics through either etching the SiOC with hydrofluoric acid, which removes the silicon dioxide and produces pores with diameters less than 20 nanometers, or through decomposition during heating of a certain polymer in a two polymer mixture, producing pores that are dozens of microns in diameter. The effects of the processing parameters on the porosity and pore size are used to understand the differences in the microstructure during pyrolysis. / Master of Science / Silicon oxycarbide (SiOC) is a ceramic obtained through the heating of a polymer precursor, which undergoes partial decomposition to go from an organic polymer to an inorganic ceramic. The microstructure of SiOC is not uniform at the nanometer scale, and contains nanometer sized silicon dioxide, carbon, and silicon carbide. Porous SiOC has shown great promise in applications such as lithium ion batteries, gas separation, and thermal barriers. The microstructure, and thus the properties of the SiOC, is influenced by the initial polymer and the processing conditions. In this thesis, SiOC is fabricated using a base polysiloxane polymer using different gases during heating, different additives that change the initial polymer chemical composition or polymer shape, and polymers with different reactive groups. Porosity was introduced into the SiOC ceramics through either etching the SiOC with hydrofluoric acid, which removes the silicon dioxide and produces pores with diameters less than 20 nanometers, or through decomposition during heating of a certain polymer in a two polymer mixture, producing pores that are dozens of microns in diameter. The effects of the processing parameters on the porosity and pore size are used to understand the differences in the microstructure during pyrolysis.

Com o objetivo de reduzir o consumo energético, tem crescido o uso de cerâmicas porosas refratárias como isolantes térmicos para altas temperaturas. Entre as técnicas comumente empregadas na produção desses materiais, destaca-se aquela baseada na geração de poros por meio de transformação de fases. Esse método, que não libera voláteis tóxicos, apresenta uma importante limitação em relação ao uso prolongado em altas temperaturas: os compostos de transição formados após a desidroxilação tendem a acelerar a sinterização, reduzindo a porosidade. É bastante conhecido o fenômeno de que, durante a sinterização em temperaturas elevadas, peças de alumina com alta porosidade, sofrem a eliminação progressiva dos poros presentes. Por essa razão, compostos que dificultam a densificação das peças porosas têm sido adicionados para manter a porosidade originada pela decomposição do hidróxido de alumínio. O objetivo desse trabalho foi obter cerâmicas porosas moldáveis a partir de alumina, hidróxido de alumínio e diversas fontes de sílica (mulita eletrofundida, quartzo e microssílica), utilizando a técnica de decomposição de hidróxidos com o intuito de se formar mulita, composto capaz de diminuir a taxa de densificação em altas temperaturas e com aplicações na indústria petroquímica e do alumínio. As amostras foram sinterizadas entre 1100ºC e 1500ºC e os resultados mostraram que houve aumento da resistência mecânica com a elevação do teor de mulita eletrofundida, quartzo e microssílica incorporada ao sistema. Além disso, o sistema mulita eletrofundida para a composição 0,4-SMT apresentou uma PT = 53,58%, módulo elástico e resistência a compressão (E = 13,03 GPa e σR = 16,83 MPa). O sistema com a adição de quartzo, a amostra 0,2-SQZ, teve pequenas mudanças nos níveis de porosidade (PTG = 59,50%) e não apresentou um elevado aumento do módulo elástico e da resistência a compressão (E = 6,51 GPa e σR = 13,91 MPa) e o sistema contendo microssílica a composição 0,2-SMS apresentou os melhores resultados, tendo um ganho de propriedades mecânicas em temperaturas a 1100ºC e a 1500ºC manteve a porosidade (PTG = 56,23%), reduziu o tamanho médio de poros e apresentou também ótimas propriedades mecânicas (E= 15,39 GPa e σR = 36,79 MPa) proporcionando sua atuação como isolante térmico. / Refractory porous ceramics have largely been used as thermal insulators for high temperatures aiming to reduce energy consumption. The generation of pores through phase transformation (such as Al(OH)3 dehydroxilation) is one of the most interesting techniques employed to produce such materials. This method, which does not release toxic volatile, imposes an important limitation on the prolonged use at high temperatures. The transition compounds formed after the dehydroxylation tend to accelerate sintering and reduce porosity. It is well known that during sintering at high temperatures (above 1100ºC), parts of alumina with high porosity amounts undergo gradual pores\' elimination. Therefore, compounds that hinder densification of porous pieces have been added to these compositions in order to maintain the porosity generated by the decomposition of aluminum hydroxide. This thesis addresses the production of castables porous ceramics from alumina, aluminum hydroxide and different sources of silica (electrofuse mullite, quartz and microsilica), employed for the in situ formation of mullite, a compound that reduces the rate of densification at high temperatures. The applications include petrochemical and aluminum industries. Samples were sintered between 1100ºC and 1500ºC and the results of the systems which contained electrofused mullite, quartz and microsilica showed less intense porosity levels reduction. The system with addition of electrofused mullite showed PTG = 53,58%,E = 13,03 GPa and σR = 16,83 MPa. The system containing quartz, presented a lower change of porosity (PTG = 59,50%) and the system containing microsilica provided the best results and an increment in the mechanical properties at temperatures between 1100°C and 1500°C. This last system also kept porosity (PTG = 56,23%), and reduced the average pore size. Its good mechanical properties (E = 15,39 GPa and σR = 36,79 MPa) proved it can be used as a thermal insulator.

Com o objetivo de reduzir o consumo energético, tem crescido o uso de cerâmicas porosas refratárias como isolantes térmicos para altas temperaturas. Entre as técnicas comumente empregadas na produção desses materiais, destaca-se aquela baseada na geração de poros por meio de transformação de fases. Esse método, que não libera voláteis tóxicos, apresenta uma importante limitação em relação ao uso prolongado em altas temperaturas: os compostos de transição formados após a desidroxilação tendem a acelerar a sinterização, reduzindo a porosidade. É bastante conhecido o fenômeno de que, durante a sinterização em temperaturas elevadas, peças de alumina com alta porosidade, sofrem a eliminação progressiva dos poros presentes. Por essa razão, compostos que dificultam a densificação das peças porosas têm sido adicionados para manter a porosidade originada pela decomposição do hidróxido de alumínio. O objetivo desse trabalho foi obter cerâmicas porosas moldáveis a partir de alumina, hidróxido de alumínio e diversas fontes de sílica (mulita eletrofundida, quartzo e microssílica), utilizando a técnica de decomposição de hidróxidos com o intuito de se formar mulita, composto capaz de diminuir a taxa de densificação em altas temperaturas e com aplicações na indústria petroquímica e do alumínio. As amostras foram sinterizadas entre 1100ºC e 1500ºC e os resultados mostraram que houve aumento da resistência mecânica com a elevação do teor de mulita eletrofundida, quartzo e microssílica incorporada ao sistema. Além disso, o sistema mulita eletrofundida para a composição 0,4-SMT apresentou uma PT = 53,58%, módulo elástico e resistência a compressão (E = 13,03 GPa e σR = 16,83 MPa). O sistema com a adição de quartzo, a amostra 0,2-SQZ, teve pequenas mudanças nos níveis de porosidade (PTG = 59,50%) e não apresentou um elevado aumento do módulo elástico e da resistência a compressão (E = 6,51 GPa e σR = 13,91 MPa) e o sistema contendo microssílica a composição 0,2-SMS apresentou os melhores resultados, tendo um ganho de propriedades mecânicas em temperaturas a 1100ºC e a 1500ºC manteve a porosidade (PTG = 56,23%), reduziu o tamanho médio de poros e apresentou também ótimas propriedades mecânicas (E= 15,39 GPa e σR = 36,79 MPa) proporcionando sua atuação como isolante térmico. / Refractory porous ceramics have largely been used as thermal insulators for high temperatures aiming to reduce energy consumption. The generation of pores through phase transformation (such as Al(OH)3 dehydroxilation) is one of the most interesting techniques employed to produce such materials. This method, which does not release toxic volatile, imposes an important limitation on the prolonged use at high temperatures. The transition compounds formed after the dehydroxylation tend to accelerate sintering and reduce porosity. It is well known that during sintering at high temperatures (above 1100ºC), parts of alumina with high porosity amounts undergo gradual pores\' elimination. Therefore, compounds that hinder densification of porous pieces have been added to these compositions in order to maintain the porosity generated by the decomposition of aluminum hydroxide. This thesis addresses the production of castables porous ceramics from alumina, aluminum hydroxide and different sources of silica (electrofuse mullite, quartz and microsilica), employed for the in situ formation of mullite, a compound that reduces the rate of densification at high temperatures. The applications include petrochemical and aluminum industries. Samples were sintered between 1100ºC and 1500ºC and the results of the systems which contained electrofused mullite, quartz and microsilica showed less intense porosity levels reduction. The system with addition of electrofused mullite showed PTG = 53,58%,E = 13,03 GPa and σR = 16,83 MPa. The system containing quartz, presented a lower change of porosity (PTG = 59,50%) and the system containing microsilica provided the best results and an increment in the mechanical properties at temperatures between 1100°C and 1500°C. This last system also kept porosity (PTG = 56,23%), and reduced the average pore size. Its good mechanical properties (E = 15,39 GPa and σR = 36,79 MPa) proved it can be used as a thermal insulator.

Made available in DSpace on 2015-05-08T15:00:08Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3204458 bytes, checksum: 4a8187024ec992f09e7022c618f46049 (MD5) Previous issue date: 2011-03-14 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The present work consisted in the preparation of a ceramic filter, based on a reticulated porous ceramic, used as support for a catalyst with perovskite structure. The interest in these oxides is related to the easy modification of its catalytic properties, as a function of the adequate cation selection as well as to its high temperature stability. The ceramic filter was developed using an aqueous suspension containing natural raw materials (quartz, feldspar and kaolin) impregnated on a polymeric sponge. As catalyst, SrSnO3 was used in pure form or doped with 10 % of Ni (replacing Sr2+, Sn4+ or both), obtained by the polymeric precursor method. The filter was impregnated for 12 h in solution (SrSnO3), with 1, 3 and 5 baths, dried and sintered in O2 (350 oC) and air (700 oC) atmospheres, leading to the formation of the SrSnO3 film on the filter. Samples of pure and impregnated filters (SrSnO3:Ni) were characterized by Xray florescence, X-ray diffraction (XRD), Confocal Raman spectroscopy, infrared spectroscopy, scanning electronic microscopy and EDS (energy dispersive spectroscopy). XRD results for the pure filter presented quartz and mulite. For the supported filter, the presence of the perovskita phase was confirmed, being observed the crystallinity decrease with doping. SEM showed the non homogeneous formation of the film deposited on the filter. Broad bands in Raman and infrared spectra were not easily identified due to superposition of the filter and film peaks. In spite of this, it was possible to observe the Ni2+ presence in Sn4+ site in all samples. Ni2+ doping led to a short and long range disorder, confirmed by Raman and XRD. According to the photocatalytic tests, it was observed that the system filter:film, the so called catalytic filter, presented photocatalytic activity in the discoloration and degradation of the yellow remazol dye, while photolysis and the of the pure filter led only to the discoloration, with a higher half life. / O presente trabalho consistiu na preparação de um filtro cerâmico catalítico, com base em uma cerâmica porosa reticulada usada como suporte para um catalisador com estrutura perovskita. O interesse nesses óxidos é devido à fácil modificação das suas propriedades catalíticas, em função da adequada seleção do cátion e também à sua estabilidade a altas temperaturas. O filtro cerâmico foi desenvolvido utilizando uma suspensão aquosa contendo matérias primas naturais (quartzo, feldspato e caulim) impregnada sobre uma espuma polimérica. Como catalisador foi utilizado o SrSnO3 dopado com 10% Ni (em lugar do Sr2+ , do Sn4+ e em ambos), obtido pelo método dos precursores poliméricos. O filtro foi impregnado por 12 h na solução (SrSnO3), com 1, 3 e 5 banhos, seco e posteriormente queimado em O2 (350 0C) e ar (700 0C), para formação do filme de SrSnO3 sobre o filtro. As amostras do filtro puro e impregnado (SrSnO3:Ni) foram caracterizadas por fluorescência de raios X, difração de raios-X (DRX), espectroscopia Raman confocal, espectroscopia na região do infravermelho (IV), microscopia eletrônica de varredura e EDS (espectroscopia de energia dispersiva). O resultado de DRX para o filtro puro apresentou as fases quartzo e mulita. Para o filtro suportado foi confirmada a presença da fase perovskita, sendo que com a dopagem observa-se diminuição na cristalinidade do filme a longo alcance. O MEV mostrou a deposição do filme sobre o filtro de forma não homogênea. As bandas alargadas (Raman e IV) não são identificadas facilmente, devido à sobreposição de picos tanto da matriz como do filme. Entretanto, é possível observar a entrada do Ni2+ no sítio do Sn4+ em todas as amostras. Com a introdução do Ni2+ no sistema observa-se uma desorganização a curto e longo alcance, confirmado no Raman e DRX. A partir dos testes fotocatalíticos, foi observado que o conjunto filtro:filme que chamamos de filtro catalítico mostrou atividade fotocatalítica na descoloração e na degradação do corante remazol amarelo, enquanto a fotólise e o uso do filtro puro permitem apenas a descoloração e com maior tempo de meia vida.

abstract: This dissertation aims at developing novel materials and processing routes using alkali activated aluminosilicate binders for porous (lightweight) geopolymer matrices and 3D-printing concrete applications. The major research objectives are executed in different stages. Stage 1 includes developing synthesis routes, microstructural characterization, and performance characterization of a family of economical, multifunctional porous ceramics developed through geopolymerization of an abundant volcanic tuff (aluminosilicate mineral) as the primary source material. Metakaolin, silica fume, alumina powder, and pure silicon powder are also used as additional ingredients when necessary and activated by potassium-based alkaline agents. In Stage 2, a processing route was developed to synthesize lightweight geopolymer matrices from fly ash through carbonate-based activation. Sodium carbonate (Na2CO3) was used in this study to produce controlled pores through the release of CO2 during the low-temperature decomposition of Na2CO3. Stage 3 focuses on 3D printing of binders using geopolymeric binders along with several OPC-based 3D printable binders. In Stage 4, synthesis and characterization of 3D-printable foamed fly ash-based geopolymer matrices for thermal insulation is the focus. A surfactant-based foaming process, multi-step mixing that ensures foam jamming transition and thus a dry foam, and microstructural packing to ensure adequate skeletal density are implemented to develop foamed suspensions amenable to 3D-printing. The last stage of this research develops 3D-printable alkali-activated ground granulated blast furnace slag mixture. Slag is used as the source of aluminosilicate and shows excellent mechanical properties when activated by highly alkaline activator (NaOH + sodium silicate solution). However, alkali activated slag sets and hardens rapidly which is undesirable for 3D printing. Thus, a novel mixing procedure is developed to significantly extend the setting time of slag activated with an alkaline activator to suit 3D printing applications without the use of any retarding admixtures. This dissertation, thus advances the field of sustainable and 3D-printable matrices and opens up a new avenue for faster and economical construction using specialized materials. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2019

A fertirrigação tornou-se uma prática comum entre os agricultores mais tecnificados, constituindo uma das alternativas mais consistentes para se garantir altas produtividades. Tradicionalmente, o manejo da fertirrigação é feito mediante o uso curvas de absorção de nutrientes e recomendações para aplicação de fertilizantes. O monitoramento da concentração dos nutrientes na solução do solo através do uso de extratores com cápsula porosa aparece como uma técnica promissora para um manejo mais adequado da fertirrigação. O objetivo desta pesquisa foi estudar a resposta da cultura do meloeiro quando submetida a diferentes concentrações controladas de nitrogênio-nitrato e potássio na solução do solo. Foram realizados, simultaneamente, dois experimentos em vasos sob condições de casa de vegetação, um com solo arenoso e outro com solo argiloso, adotando-se 13 tratamentos dispostos em delineamento inteiramente aleatorizado com 4 repetições. Os tratamentos foram definidos através de uma matriz denominada quadrado duplo e resultaram do manejo controlado das concentrações de nitrogênio e potássio na solução do solo. A cultura utilizada foi o meloeiro tipo cantaloupe, que foi irrigada por gotejamento com base nos dados de leituras tensiométricas sendo fertirrigada somente quando foi necessário, com base nos dados de concentração de nitrogênio e potássio. Foi avaliado, o comprimento da haste principal, diâmetro do caule, número de folhas, área foliar, área foliar média e matéria seca, nos solos arenoso e argiloso e o número de frutos, a produção, o peso médio dos frutos, a porcentagem rendilhamento da superfície dos frutos, o diâmetro dos frutos, a espessura e a firmeza da polpa e os sólidos solúveis totais, no solo argiloso. Foi realizada análise de variância e de regressão com o uso do SAS. Observou-se uma diferença no consumo acumulado de água de 27,6% no solo arenoso e 51,5% no argiloso. A concentração ótima de nitrogênio na solução do solo arenoso situou-se entre 100 e 180 mg L-1 e a de potássio em 468 mg L-1. As plantas do solo arenoso apresentaram baixo desempenho, indicando que as condições nutricionais não foram favoráveis ao desenvolvimento da cultura. Nos primeiros 30 dias de cultivo no solo argiloso, as melhores concentrações de nitrogênio e de potássio foram 336 e 84 mg L-1, respectivamente. A primeira planta avaliada no solo argiloso apresentou um melhor desempenho que a mesma planta avaliada no solo arenoso. No final do ciclo de cultivo das plantas do solo argiloso, a melhor concentração de nitrogênio na solução do solo foi de 336 mg L-1 e a de potássio variou 35 e 44 mg L-1. Houve baixa produção e peso médio de frutos e os frutos colhidos tiveram, em geral, baixa qualidade. As melhores características de qualidade dos frutos foram obtidos com concentrações de nitrogênio na solução do solo entre 240 e 260 mg L-1, tendo o potássio variado entre 0 e 84 mg L-1. / The fertigation has become a common practice among farmers more advanced, constituting one of the most consistent alternative to ensure high yields. Traditionally, the fertigation management makes use of the uptake nutrients curves and recommendations to fertilizers apply. The tracking of the soil solution nutrients concentration through of the use porous cup extractors appears as a promising technique for the most appropriate management of fertigation. The aim of this research was to study the response of the melon crop when subjected to different controlled concentrations of nitrogen-nitrate and potassium in the soil solution. Two experiments were conducted simultaneously in pots on condition of greenhouse, an with sand soil and another with clay, adopting 13 treatments disposing in to fully randomized design with 4 replications. The treatments were defined by a matrix called double square and resulted the management of controlled concentrations of nitrogen and potassium in the soil solution. The crop used was the cantaloupe melon, which was drip irrigated based on readings tensiometer and fertigation was carried out only when necessary based on concentration of nitrogen and potassium. Were evaluated the length of the main stem, stem diameter, leaf number, leaf area, average leaf area and dry matter in sandy and clay soils and the number of fruits, production, the average weight of fruit, the percentage of the area tracery fruit, the fruit diameter, thickness and firmness of flesh and the soluble solids in the clay soil. Were performed analysis of variance and regression using the SAS. There was a difference in consumption of water accumulated in the sandy soil of 27.6% and 51.5% in the clay. The optimal concentration of nitrogen in the solution of the sandy soil was between 100 and 180 mg L-1 and potassium in 468 mg L-1. The plants in sandy soil showed low performance, indicating that the nutritional conditions were not favorable for the development of culture. In the first 30 days of crop in clay soil, the best concentrations of nitrogen and potassium were 336 and 84 mg L-1, respectively. The first plant evaluated in clay soil had a better performance than the same plant assessed in sandy soil. At the end of the cycle of crop of plants in clay soil, the best concentration of nitrogen in soil solution was of 336 mg L-1 and potassium ranged from 35 and 44 mg L-1. There was low yield and average weight of fruits and fruits harvested, in general, were low quality. The best features of the quality of fruits were obtained with concentrations of nitrogen in soil solution between 240 and 260 mg L-1, and the potassium varied between 0 and 84 mg L-1.

En compétition avec les alcanolamines, les liquides ioniques (LIs) sont connus pour interagir fortement et de façon réversible avec des gaz acides. Les propriétés remarquables des LIs ont conduit à la réalisation de ‘Supported Ionic Liquid Membranes’ (SILMs) qui sont des systèmes continus attractifs pour la séparation de gaz, et notamment du CO2. Dans les SILMs, il est possible d’adapter les propriétés d'adsorption/séparation en modifiant les caractéristiques du support (e.g. composition, structure poreuse, surface spécifique, etc.) et du LI (nature des cations et anions). En dépit de leur relative instabilité dans les procédés de séparation de gaz acides, les supports nanoporeux polymériques sont classiquement utilisés pour préparer des SILMs. Récemment, les supports céramiques poreux ont été considérés pour la réalisation de SILMs en raison de leurs excellentes résistances thermique et mécanique. La plupart de ces systèmes sont préparés par imprégnation/infiltration des LIs dans les pores du support céramique. Ce protocole conduit à la formation de matériaux composites dans lesquels le LI est physiquement piégé dans le support, mais souvent avec une distribution hétérogène du LI et une stabilité limitée dans le temps. Dans ce travail de thèse, réalisé en collaboration entre l’Institut Européen des Membranes (IEM) et l’Institut Charles Gerhardt de Montpellier (ICGM), nous avons développé une nouvelle génération de SILMs, dans lesquelles le LI est confiné dans les pores d'un support en céramique mésoporeux par greffage chimique. La préparation de ces systèmes se fait en trois étapes :i) Synthèse et caractérisation de nouveaux LIs portant des fonctions de couplage pour assurer leur greffage en surface des pores de la membrane céramique et détermination de la capacité d’absorption du CO2 des différents LIs synthétisés;ii) Optimisation des paramètres de greffage de ces LIs sur des poudres modèles de γ-Al2O3 et caractérisation des matériaux hybrides obtenus avec mise en évidence du greffage;iii) Transfert du protocole de greffage optimisé sur des membranes céramiques commerciales γ-alumine (fabrication de Grafted Ionic Liquid Membranes - GILMs) et évaluation de leurs performances pour la séparation du CO2.Ce travail, basé sur une approche originale, associant de nouveaux liquides ioniques et un nouveau concept de membrane à base de liquide ionique supporté, montre, au travers de plusieurs exemples l’intérêt d’une approche multi-étapes pour le développement de systèmes membranaires de séparation du CO2. / In competition with amines, ionic liquids (ILs) are known to interact strongly and reversibly with acid gases, making supported IL-membrane (SILMs) versatile materials for use in CO2 membrane separation applications. It is possible to finely tune SILMs properties for CO2 adsorption/separation by tailoring the characteristics of both the support (e.g., porosity, surface area, composition, etc.) and the ionic liquid (cations and anions). Up to now, nanoporous polymer supports have been favored for preparing SILMs, in spite of their relative instability during continuous separation processes in the presence of acidic gases. Recently, porous ceramic supports have been considered due to their excellent thermal and mechanical resistance. Most of the SILMs are prepared by impregnation/infiltration of IL in the pores of ceramic support which leads to the formation of composite membrane materials with either a physisorbed or mechanically trapped IL in the support. Despite their promising performance, such SILMs exhibit inherent limitations such as facile IL disarrangement, heterogeneous distribution, and limited stability upon ageing.In this Ph.D work, carried out in collaboration between the Institut Européen des Membranes (IEM) and the Institut Charles Gerhardt de Montpellier (ICGM), a new generation of SILMs has been developed in which ILs are confined within the pores of a mesoporous ceramic support by chemical grafting. The membranes are prepared in three steps:i) Synthesis and characterization of new ILs bearing a coupling function which allow the grafting on the surface of ceramic oxide supports and determination of the CO2 absorption capacity of the new ILs developed;ii) Elaboration and/or optimization of relevant synthesis protocols for grafting ILs on/in γ-alumina powders and physico-chemical characterizations of the hybrid materials;iii) Transfer of the optimized grafting protocols on commercial porous ceramic support with γ-alumina top-layer to produce Grafted Ionic Liquid Membranes (GILMs) and evaluate their performance for CO2 separation.An original research strategy, based on new ionic liquids and innovative membrane concepts have been addressed in this work, illustrating the contribution of a multi-step approach towards the development of membranes for CO2 separation.

A fertirrigação tornou-se uma prática comum entre os agricultores mais tecnificados, constituindo uma das alternativas mais consistentes para se garantir altas produtividades. Tradicionalmente, o manejo da fertirrigação é feito mediante o uso curvas de absorção de nutrientes e recomendações para aplicação de fertilizantes. O monitoramento da concentração dos nutrientes na solução do solo através do uso de extratores com cápsula porosa aparece como uma técnica promissora para um manejo mais adequado da fertirrigação. O objetivo desta pesquisa foi estudar a resposta da cultura do meloeiro quando submetida a diferentes concentrações controladas de nitrogênio-nitrato e potássio na solução do solo. Foram realizados, simultaneamente, dois experimentos em vasos sob condições de casa de vegetação, um com solo arenoso e outro com solo argiloso, adotando-se 13 tratamentos dispostos em delineamento inteiramente aleatorizado com 4 repetições. Os tratamentos foram definidos através de uma matriz denominada quadrado duplo e resultaram do manejo controlado das concentrações de nitrogênio e potássio na solução do solo. A cultura utilizada foi o meloeiro tipo cantaloupe, que foi irrigada por gotejamento com base nos dados de leituras tensiométricas sendo fertirrigada somente quando foi necessário, com base nos dados de concentração de nitrogênio e potássio. Foi avaliado, o comprimento da haste principal, diâmetro do caule, número de folhas, área foliar, área foliar média e matéria seca, nos solos arenoso e argiloso e o número de frutos, a produção, o peso médio dos frutos, a porcentagem rendilhamento da superfície dos frutos, o diâmetro dos frutos, a espessura e a firmeza da polpa e os sólidos solúveis totais, no solo argiloso. Foi realizada análise de variância e de regressão com o uso do SAS. Observou-se uma diferença no consumo acumulado de água de 27,6% no solo arenoso e 51,5% no argiloso. A concentração ótima de nitrogênio na solução do solo arenoso situou-se entre 100 e 180 mg L-1 e a de potássio em 468 mg L-1. As plantas do solo arenoso apresentaram baixo desempenho, indicando que as condições nutricionais não foram favoráveis ao desenvolvimento da cultura. Nos primeiros 30 dias de cultivo no solo argiloso, as melhores concentrações de nitrogênio e de potássio foram 336 e 84 mg L-1, respectivamente. A primeira planta avaliada no solo argiloso apresentou um melhor desempenho que a mesma planta avaliada no solo arenoso. No final do ciclo de cultivo das plantas do solo argiloso, a melhor concentração de nitrogênio na solução do solo foi de 336 mg L-1 e a de potássio variou 35 e 44 mg L-1. Houve baixa produção e peso médio de frutos e os frutos colhidos tiveram, em geral, baixa qualidade. As melhores características de qualidade dos frutos foram obtidos com concentrações de nitrogênio na solução do solo entre 240 e 260 mg L-1, tendo o potássio variado entre 0 e 84 mg L-1. / The fertigation has become a common practice among farmers more advanced, constituting one of the most consistent alternative to ensure high yields. Traditionally, the fertigation management makes use of the uptake nutrients curves and recommendations to fertilizers apply. The tracking of the soil solution nutrients concentration through of the use porous cup extractors appears as a promising technique for the most appropriate management of fertigation. The aim of this research was to study the response of the melon crop when subjected to different controlled concentrations of nitrogen-nitrate and potassium in the soil solution. Two experiments were conducted simultaneously in pots on condition of greenhouse, an with sand soil and another with clay, adopting 13 treatments disposing in to fully randomized design with 4 replications. The treatments were defined by a matrix called double square and resulted the management of controlled concentrations of nitrogen and potassium in the soil solution. The crop used was the cantaloupe melon, which was drip irrigated based on readings tensiometer and fertigation was carried out only when necessary based on concentration of nitrogen and potassium. Were evaluated the length of the main stem, stem diameter, leaf number, leaf area, average leaf area and dry matter in sandy and clay soils and the number of fruits, production, the average weight of fruit, the percentage of the area tracery fruit, the fruit diameter, thickness and firmness of flesh and the soluble solids in the clay soil. Were performed analysis of variance and regression using the SAS. There was a difference in consumption of water accumulated in the sandy soil of 27.6% and 51.5% in the clay. The optimal concentration of nitrogen in the solution of the sandy soil was between 100 and 180 mg L-1 and potassium in 468 mg L-1. The plants in sandy soil showed low performance, indicating that the nutritional conditions were not favorable for the development of culture. In the first 30 days of crop in clay soil, the best concentrations of nitrogen and potassium were 336 and 84 mg L-1, respectively. The first plant evaluated in clay soil had a better performance than the same plant assessed in sandy soil. At the end of the cycle of crop of plants in clay soil, the best concentration of nitrogen in soil solution was of 336 mg L-1 and potassium ranged from 35 and 44 mg L-1. There was low yield and average weight of fruits and fruits harvested, in general, were low quality. The best features of the quality of fruits were obtained with concentrations of nitrogen in soil solution between 240 and 260 mg L-1, and the potassium varied between 0 and 84 mg L-1.

Sintering is an important processing step for obtaining the necessary mechanical stability and rigidity of ceramic bulk materials. Both mass and heat transfer are essential in the sintering process. The importance of radiation heat transfer is significantly enhanced at high temperatures according to the well-known Stefan-Boltzmann’s law. In this thesis, we modified the pressure-less spark plasma sintering set-up to generate intense thermal radiation, aiming at rapid consolidation of ceramic bulk materials. This approach was named as “Sintering by Intense Thermal Radiation (SITR)” as only thermal radiation contributed. Firstly, the heat and mass transfer mechanisms during the SITR process were studied by choosing zirconia ceramics as references. The results revealed that the multiple scattering and absorption of radiation by the materials contributed to the heat diffusion. The observed enhanced densification and grain growth can be explained by a multiple ordered coalescence of zirconia nanocrystals using high heating rates. Secondly, the temperature distribution during the SITR process was investigated by both numerical simulation and experimental verifications. It showed that the radiator geometry, sample geometry and radiating area were influencing factors. Besides, the change of material and geometry of the radiators resulted in an asymmetric temperature distribution that favored the formation of SiC foams. The foams had gradient structures with different open porosity levels and pore sizes and size distributions. Finally, ceramic bulk materials were successfully fabricated by the SITR method within minutes. These materials included dense and strong ZrO2 ceramics, Si3N4 foams decorated with one-dimensional nanostructures, and nasal cavity-like SiC-Si3N4 foams with hierarchical heterogeneities. Sufficient densification or formed strong necks were used for tailoring these unique microstructures. The SITR approach is well applicable for fast manufacture of ceramic bulk materials because it is clean and requires low energy consumption and properties can be controlled and tuned by selective heating, heating speed or temperature distribution. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.</p><p> </p>