Le talc naturel est utilisé en tant que charge de haute performance des matrices polymères, car il permet d'améliorer leurs propriétés mécaniques. Pour cela, la dispersion de la charge dans la matrice doit être de qualité, ce qui implique que les particules soient nanométriques. Or, obtenir des particules nanométriques par broyage s'avère coûteux énergétiquement et économiquement. L'étude d'une opération de précipitation a conduit à la synthèse de silicate de magnésium amorphe constitué de particules primaires nanométriques. L'analyse de surface du solide par chromatographie gazeuse inverse a été employée afin de prédire les interactions entre le solide et la matrice polymère. La constante d'équilibre du solide amorphe et les vitesses de cristallisation ont pu être identifiées après modélisation des équilibres chimiques. / Natural talc is used as an high performance filler in polymer matrices because it enables to improve mechanical properties. In order to improve these properties, a good-quality dispersion of the filler in the polymer matrix is necessary, that involves particles being nano-sized. However, getting nano-sized particles by milling processes is expensive and very energetic. The study of a precipitation operation has led to the synthesis of amorphous magnesium silicate whose primary particles are nano-sized. Solid surface analysis by inverse gas chromatography has been made in order to predict interactions between solid and polymer matrix. Equilibrium constant of amorphous solid and crystallization rates have been identified after modelling of chemical equilibria.

La croissance des plantes est limitée par la toxicité métallique. Des études suggèrent que le stress métallique peut être limité par l'absorption de silicium (Si). Cependant la phytodisponibilité du silicium n'a pas encore été clairement évaluée. Ainsi dans un premier temps cette étude a pour objectifs d'évaluer la disponibilité de Si issu de différents minéraux du sol et la signification des différents extractants utilisés pour l'extraction de Si du sol en terme de disponibilité lors d'une culture en continu de blé dur. Pour ce faire, des extractants acides et alcalins ont été comparés sur une série de sols non contaminés de nature différente, puis la validité de Na2CO3 pour l'estimation de la fraction disponible de Si pour une culture continue de blé dur (Triticum turgidum L.) a été testée sur une série de sols contrastés. Ensuite on a tenté de déterminer le rôle spécifique de Si dans la croissance de plantules de blé dur et la suppression des stress associés à la présence de Cd et Cu dans le milieu de croissance, à la fois en conditions hydroponiques et sur support solide simplifié en comparant un alumino-silicate et une diatomite. Finalement, l'apport de silicium amorphe (ASi) (et disponible) a été testé en pot sur les plantes de blé ayant poussé sur des sols multi-contaminés ou contaminés en Cd. ASi extrait par Na2CO3 (ASiNa) est apparu bien corrélé aux concentrations dans les parties aériennes du blé dur ayant poussé en pot sur différents sols non contaminés et, pour cette raison, pourrait être utilisé pour l'évaluation de la fraction phytodisponible. / Plant growth is seriously limited by heavy metal toxicity. Studies suggest that silicon (Si) can alleviate the metal stress in plants but its bioavailability in soil is not well defined. This study aims at assessing the bioavailability of Si from different soil minerals, the meaning of various extractants in terms of availability in relation with continuous plant uptake, and the specific role of Si on the plant growth and alleviation of cadmium (Cd) and copper (Cu) toxicity in durum wheat. For this purpose a series of experiments were performed both in soil and hydroponic conditions. Firstly, the significance of acid and alkaline methods was assessed in order to determine the bioavailable Si in soil and the applicability of the Na2CO3 extraction method was determined by repeated croppings of durum wheat on a variety of soils. Secondly, two hydroponic experiments were carried out to study the physiological response of wheat under Cd and Cu stress treated or not with Si. Thirdly, efficiency of different minerals to release bioavailable silica and its effect on reducing Cd and Cu toxicity was assessed. Finally, the effects of amorphous silica (ASi) application were investigated on metal stressed wheat plant grown in uncontaminated and contaminated soils. ASi extracted with Na2CO3 (ASiNa) was well correlated with the Si in plants shoots in our pot experiment with different soils. We showed that ASiNa can also be used for a good proxy of Si bioavailable to plants. Si present as amorphous Si (diatomite) added to the soil is available for plant uptake. However, in soils with large clay content, clay may be a significant source of Si for plants.

The deposition of amorphous silica from aqueous solution on to rutile particles has been studied with the aim of elucidating the nature of the silica-titania interactions occurring and of following the progressive build up of the silica coating. The coating process, which involves the addition of an aqueous sodium silicate solution to an aqueous dispersion of titanium dioxide, has been investigated by performing a series of controlled preparations and using the technique of microelectrophoresis. Prepared silica-coated rutile samples ranging from partial to full silica coatings have been characterized using transmission electron microscopy, microelectrophoresis and nitrogen, argon and water sorption. Nitrogen and argon adsorption isotherms have been analysed using the equation of Brunauer, Emmett and Teller (BET). Differential energies of adsorption of nitrogen and argon have been determined calorimetrically. Water sorption isotherms have been analysed using the BET equation and the Frenkel - Halsey - Hill (FHH) equation. It has been shown that uniform silica coatings can be produced if adsorption of monomeric silica is followed by polymerization of silica at the solid/liquid interface. Surface cations on rutile may be hydroxylated or co-ordinately bound to water molecules and it appears that monomeric silica adsorbs preferentially by replacing ligand water molecules. Rutile particles with silica coatings thicker than approximately 2.5nm exhibit characteristics typical of silica and not of the base rutile. Silica coatings deposited at pH 10 contain narrow channels which are accessible to water molecules but not to nitrogen or argon. Neutralization to pH 7 reduces the volume in the coating accessible to water molecules.

Orientador: Lucia Helena Innocentini Mei / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-12T10:58:35Z (GMT). No. of bitstreams: 1 Sato_AlexKazuo_M.pdf: 2098023 bytes, checksum: 44db955a219d9ed4ecd602a6d9c1ea7d (MD5) Previous issue date: 2008 / Resumo: Um dos grandes desafios que enfrentamos neste novo século de avanços tecnológicos é o desenvolvimento de novos materiais que atendam as necessidades pré-requeridas no que diz respeito às propriedades mecânicas e térmicas das peças e seu custo, reunindo assim uma excelente relação de custo beneficio. Este trabalho visou o estudo de um compósito híbrido termoplástico, usando polipropileno como matriz polimérica associado a uma micro fibra de sílica amorfa (MFSA) e uma fibra natural originada da madeira, para se testar a viabilidade de sua utilização na área dos materiais de engenharia. Foram testadas várias formulações com diferentes proporções de MFSA e de fibra de madeira, bem como compósitos com e sem agentes de acoplamento, funcionalizados com anidrido maleico. A eficiência desses agentes e as propriedades térmicas, mecânicas e morfológicas das diferentes formulações foram avaliadas por meio de testes de resistência à tração, impacto Izod, dureza Shore D, HDT, Vicat e por calorimetria e microscopia eletrônica de varredura dos compósitos obtidos. Os resultados mostraram que o compósito híbrido de homo polipropileno carregado como micro fibra de sílica amorfa e fibra de madeira, auxiliada com o agente de acoplagem estudado, possui boas propriedades térmicas e mecânicas em relação aos compósitos de polipropileno contendo cargas minerais, utilizados hoje em aplicações automobilísticas. Os resultados obtidos abrem novas possibilidades de estudo e apontam os compósitos híbridos como opções interessantes em aplicações práticas na área automobilística, com seus respectivos testes no produto final, como montabilidade e desempenho do produto em campo. / Abstract: One of the great challenges that we face in this new century of technological advances is the development of new materials that meet the pre-required needs regarding to thermal and mechanical properties of parts and their cost thus, leading to an excellent relationship of cost benefit analysis. This work aimed the study hybrid thermoplastic polypropylene composites, using a polymeric matrix combined with a micro fiber of amorphous silica (MFSA) and a natural fiber origined from wood. In this study different proportions of filled composites as well as composites with and without a coupling agent with maleic anydride functionality were tested. The effectiveness of these agents in the different formulations of the composites obtained was evaluated through mechanical and thermal resistance since the transfer of mechanical efforts of the matrix for the filled depends on the efficiency of the accession interfacial between the two components. The results showed that the hybrid composites of homo polypropylene filled with amorphous silica micro fiber and wood fiber together with coupling agent with maleic functionality, has good thermal and mechanical properties in relation to polypropylene composites filled with mineral reinforcement used today in automobile applications. From the above findings, new opportunities can be opened for study in practical applications in a product for automotive application with their tests at the final product, as assembly and performance of the product on the final application. / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

Le fluide chaud produit par les forages de la centrale géothermique de Bouillante (Guadeloupe) est enrichi en espèces dissoutes telles que la silice qui peuvent précipiter sous forme de dépôts solides lors de son refroidissement et gêner fortement la production électrique. L’un des principaux objectifs de ce travail de thèse a donc été d’améliorer l’état des connaissances sur les conditions physiques, chimiques et cinétiques de la précipitation de la silice amorphe à Bouillante. Après une étude des caractéristiques physico-chimiques des fluides et des dépôts associés au champ de Bouillante, des expériences sur la cinétique de précipitation de la silice, sur site, pour une large gamme de température (25 - 90°C) et de pH (4 - 12) ont été menées et analysées en détail.Pour l’ensemble de ces expériences, seule la polymérisation (réversible) de la silice dissoute, sous forme de suspensions colloïdales très stables en solution, a été observée. La modélisation des données expérimentales de cinétique montre que la vitesse de polymérisation de la silice suit une loi d’ordre 2 vis-à-vis de la silice dissoute jusqu’à l’équilibre en accord avec une dimérisation de la silice. Par contre, durant l’étape initiale de la réaction, une loi d’ordre 4 semble mieux adaptée, suggérant des réactions de polymérisation plus complexes avec formation de tétramères. La température a un effet limité sur la cinétique de polymérisation de la silice comparé à l’effet du pH qui est beaucoup plus important. L’énergie d’activation de la réaction globale est de 41 - 54 kJ pour des pH compris entre 5 et 8.La caractérisation de la silice précipitée a mis en évidence des différences notables entre la structure poreuse de la silice solide prélevée sur les installations de surface et celle de la silice colloïdale obtenue par polymérisation lors des expériences de cinétique, ce qui semble indiquer que des mécanismes différents interviennent dans ces deux contextes de précipitation de la silice dissoute.Le deuxième objectif de cette thèse était d’évaluer la possibilité de valoriser la silice extraite de l’eau géothermale de Bouillante dans un procédé de traitement des eaux naturelles par adsorption. Pour cela, les propriétés d’adsorption de la silice géothermale brute et fonctionnalisée par le poly(ethylèneimine) (ou PEI) ont été étudiées pour deux polluants : un colorant, le bleu de méthylène et un métal lourd, le plomb. Les résultats obtenus montrent que la silice brute possède une grande capacité d’adsorption vis-à-vis du bleu de méthylène. En outre, la fonctionnalisation de la silice par le PEI permet d’améliorer sa capacité d’adsorption vis-à-vis du plomb en solution, en accord avec un modèle cinétique du pseudo-second ordre suggérant une chimisorption. Le modèle d’isotherme de Redlich-Peterson est également en très bon accord avec les données expérimentales. / The hot geothermal fluid produced by the geothermal power plant of Bouillante (Guadeloupe) contains various dissolved components such as silica that can precipitate as solid deposits during their cooling and cause serious problems on the electricity generation. One of the aim of this study is to improve the understanding on the physical, chemical and kinetics conditions of the amorphous silica precipitation in the Bouillante geothermal field. After a study on the physical and chemical characteristics of the Bouillante fluids and deposits which can form during their exploitation, experiments on the kinetics of silica precipitation, on site, under a large range of temperature (25 – 90°C) and pH (4 – 12) have been carried out and analyzed in detail.During on site kinetics experimentations only dissolved silica polymerization (reversible) as colloidal gel, very stable in solution, was observed. Modeling of the experimental data showed that the kinetics polymerization is characterized by a 2-order kinetic law relative to dissolved silica until the equilibrium that is consistent with silica dimerization. On the other side, the initial stage of the reaction is better characterized by a 4-order kinetic law that suggested more complex polymerization reactions with tetramers formation.Temperature has a little effect on the polymerization kinetics compared with the pH which has an effect more important. The activation energy of silica precipitation calculated between 25 and 90°C, is about 41 - 54 kJ for pH ranging to 5 - 8.The characterization of the silica precipitate reveals significant differences in the porous structure of the silica collected on the surface installations and the one obtained from kinetic experiments that suggests different precipitation mechanisms. The second objective of this thesis was to evaluate the possibility to promote geothermal silica for the treatment of natural waters containing contaminants by adsorption. Adsorption properties of the untreated and functionalized by poly(ethylèneimine) (ou PEI) geothermal silica have been investigated for two pollutants: a colorant, the methylene blue and a heavy metal, the lead.Results showed that untreated silica has a great adsorption capacity concerning the methylene blue. Besides, silica functionalization by the PEI allows improving the adsorption capacity for lead in solution. The adsorption kinetics curves followed a pseudo-second order model consistent with a chimisorption. The isotherm model of Redlich-Peterson fitted well the experimental data.

This thesis is focused on the study of the properties of mortars and pastes with active pozzolanic materials. It deals with monitoring cementitious composites which describes both the effect of compensation pozzolanic cement mortar admixtures active based on amorphous silica and the modifying polymeric additive. The main criteria for the assessment of these modified mortars and pastes are particularly adhesive and achieved strength compared with the reference mortar. The detailed work also examined the microstructure past through images from REM, records RTG, DTA and high pressure mercury porosimetry.

A thermo-chemical treatment method was used to produce biogenic amorphous silica from South African sugarcane and maize residues. Different fractions of South African sugarcane (leaves, pith, and fiber) were processed for silica production. The biomass samples were leached with either 7 wt% citric acid or 7 wt% sulfuric acid at 353 K for 2 h prior to being rinsed, dried and combusted using a four-step program ranging from room temperature to 873 K in a furnace. The characterization of the pre-treated biomass samples was conducted using thermogravimetric analysis (TG/DTA), X-ray fluorescence analysis (XRF) and elemental analysis (CHN), while the final products were characterized by XRF, X-ray diffraction (XRD), elemental analysis, nitrogen physisorption and scanning electron microscopy (SEM). Citric acid pre-treatment proved to be an attractive alternative to mineral acids. Amorphous biogenic silica was produced from sugarcane leaves in good quality (0.1 wt% residual carbon and up to 99.3 wt% silica content). The produced biogenic silica also had great textural properties such as a surface area of up to 323 m2 g−1, average pore diameter of 5.0 nm, and a pore volume of 0.41 cm3 g−1.

Matérias-primas cerâmicas são tecnologicamente muito importantes, pois são aplicadas desde a indústria de base, como isolamento térmico dos fornos siderúrgicos feito pelas cerâmicas refratárias, por exemplo; até a produção de materiais para a construção civil, componentes eletrônicos, entre outros. Devido a essa ampla aplicação, muitos estudos se desenvolveram com o intuito de conhecer as propriedades desses materiais, bem como suas interações com o processamento. Tais propriedades são determinantes para as aplicações e também para as rotas de produção que podem ser empregadas. A principal técnica de processamento cerâmico para consolidação das peças e ganho de propriedades mecânicas é a sinterização. Este processo sofre grande influência das propriedades físicas das partículas que compõem as matérias-primas. O presente estudo se propõe a investigar e monitorar, através de modificações estruturais controladas, quais as características das partículas que mais afetam esta etapa do processamento. Para tal estudo escolheu-se o sistema Al2O3-SiO2 em proporção estequiométrica (3:2) para obtenção de Mulita. Dentre as matérias-primas componentes do sistema, a sílica (SiO2) é a que mais sofre modificações estruturais em uma faixa de temperatura relativamente baixa; logo, foi selecionada para ter suas propriedades modificadas mediante tratamentos térmicos variados, de 700°C, 900°C e 1100°C. As modificações causadas nas propriedades físicas e seus efeitos foram monitorados. Avaliou-se a influência causada na obtenção de mulita estequiométrica, as alterações nas propriedades mecânicas dos corpos de prova sinterizados em temperaturas diferentes (1100°C, 1300°C e 1500°C) durante 3 horas, e a estabilidade dimensional. A sílica aplicada no estudo foi uma sílica amorfa precipitada, disponível comercialmente. Os resultados mostraram que a sílica teve sua área superficial específica (ASE) variando de cerca de 150 m²/g até valores próximos de 0,5 m²/g. Ficou evidente ainda que a variação da ASE das partículas foi responsável por grandes interferências na sinterização ou densificação das estruturas. Este processo depende da movimentação dos átomos para regiões da superfície onde ocorrerá o contato entre as partículas e sua junção. Com a redução da ASE, a sinterização se torna menos efetiva e a estabilidade dimensional é favorecida. Por outro lado, quando a sinterização das partículas é proeminente, a densificação das estruturas dá origem a componentes com boas propriedades mecânicas, aplicáveis em situações estruturais. Os resultados mostraram ainda que é possível obter estruturas com propriedades mecânicas semelhantes, como resistência à ruptura e módulo elástico, mesmo tendo partido de matérias-primas muito diferentes, permitindo o nivelamento e adequação dessas propriedades às aplicações desejadas. / Ceramic raw-materials are technologically very important, once they are applied since basic industry, such as thermal insulating for steel furnace made by refractory ceramics until the production of materials for construction, electronics compounds and others. Due to its wide hall of applications, many studies were developed for understand these materials\' properties and its interaction with processing. Such properties are application and processing route determinant. The main processing technique for consolidating and gaining of mechanical properties is sintering. This process is highly influenced by particles\' physical properties. This very study is proposed to investigate and monitor, by controlled structure modifications, which particles\' characteristics affects sintering more intensely. For such objective, the system Al2O3-SiO2 on stoichiometric proportion (3:2) for mullite obtaining was chosen. Among system\'s raw-material, silica (SiO2) is easier to be modified by temperature in a relatively low range, so it was selected to have its properties changed by different thermal treatment of 700°C, 900°C and 1100°C. Physical properties\' modifications and its effects were monitored. The influence on stoichiometric mullite obtaining, variations on mechanical properties of 3 hours long sintered samples (1100°C, 1300°C and 1500°C), and dimensional stability were measured. Market-available precipitate amorphous silica was employed. Results showed that thermal treatment of silica was able to vary its specific surface area (SSA) from 150 m2g-1 to values near of 0,5 m2g-1. It was also clear that SSA variation was responsible for interfering on sintering. This process depends on atoms movement to surface regions where will occur contact and particles bonding. With SSA reduction, sintering is less effective and dimensional stability is favored. On the other hand, when particles\' sintering is more effective structure densification will end on components with good mechanical properties, finding uses on structural application. Results also showed that is possible to obtain similar mechanical properties structures even when raw-materials exhibit different characteristics.

L’étude de la précipitation de la silice amorphe à partir de TétraEthylOrtoSilicate (TEOS) et d’eau, selon le procédé Stöber, a permis de quantifier la cinétique de réaction par spectroscopie Infra Rouge à Transformée de Fourrier. Nous avons montré que la croissance des particules se fait par agrégation des nuclei, qui sont formés tout au long de la réaction. La transposition de ce procédé en microémulsion eau-dans-huile a permis de synthétiser des nanoparticules de silice de tailles contrôlées. L’hydrolyse du TEOS est ici dix fois plus faible qu’en phase homogène. Lors de l’ajout du TEOS à la microémulsion, on observe une coalescence des gouttelettes accompagnée d’échanges inter-micellaires. Ce phénomène a pu être décrit par un noyau d’agrégation qui dépend des concentrations en tensioactif et en TEOS non hydrolysé. L’étude de ce procédé en macroémulsion a montré l’effet déstabilisateur de l’éthanol et la nécessité de stabiliser l’émulsion pour synthétiser des particules sphériques / The study of the precipitation of amorphous silica starting from Tetraethoxysilane (TEOS) and water according to the Stöber process, made it possible to quantify the kinetics of the reaction by Fourier-Transform Infrared spectroscopy. We demonstrated that the particles grow by aggregation of the nuclei, which are formed throughout the reaction.The transposition of this process in water-in-oil microemulsion made it possible to synthesize silica nanoparticules with controlled sizes. The hydrolysis of the TEOS is here ten times weaker than in homogeneous phase. When we add the TEOS to the microemulsion, we observe a coalescence of the droplets accompanied by inter-micellar exchanges. This coalescence is well described by a core of aggregation which depends on the concentrations of the surfactant and the non-hydrolysed TEOS. The study of this process in macroemulsions showed the destabilizing effect of ethanol and the need for stabilizing the emulsion to synthesize spherical particles

No description available.