O Brasil é produtor de argilas e conta com grandes reservas deste recurso natural. Porém, grande parte da sua produção é comercializada seca e moída. O desenvolvimento de argilas para seu uso como reforço em nanocompósitos poliméricos constitui uma opção para os produtores desta matéria prima que teriam assim um produto com maior valor agregado. Este trabalho visa avaliar o potencial uso como nanocarga de duas argilas nacionais provenientes da Bacia de Taubaté, São Paulo, denominadas ALIGRA e SANTA FÉ. As frações de tamanho de partícula médio menor de 0,02 mm, obtidas por peneiramento á úmido da argila homogeneizada e seca, foram utilizadas no desenvolvimento do trabalho experimental. Os estudos de caracterização, envolvendo análise granulométrica, química, mineralógica, morfológica, térmica e textural, revelaram características muito semelhantes em ambas às argilas. Fração argila, maior de 70% em massa. Composição química conforme a definição química de uma argila e os teores de seus componentes mostram valores intermédios entre as apresentadas pelas bentonitas e argila caulinítica usadas com fins de comparação. Ressaltamse boas propriedades adsorventes. Área superficial específica BET ao redor de 120 m2/g, valor maior do que o apresentado por muitas bentonitas naturais (74,5 m2/g). Predominantemente mesoporosas, com poros, maiormente em forma de fenda, característicos da estrutura em camadas das argilas. Baixa capacidade de troca catiônica, 12 meq/100g. Difratogramas de raios-X revelaram a predominância do estratificado ilita/esmectita, caulinita e quartzo na argila ALIGRA, e de ilita, caulinita e quartzo na argila SANTA FÉ. Prosseguiu-se com a argila ALIGRA a preparação da argila organofílica. A argila organofílica foi obtida por troca catiônica com o sal quaternário de amônio: cloro cetril trimetil amônio, depois de homogeneizada em sódio com cloreto de sódio. Análises FTIR e TGA indicaram que houve inserção dos cátions orgânicos. Testes preliminares foram feitas, preparando misturas das argilas com matriz de polipropileno e usando como agente compatibilizante polipropileno enxertado com anidrido maleico. Resultados de ensaios de tração reportam algumas melhoras nas propriedades testadas com as composições preparadas com as argilas purificadas. Com as composições com argilas organofílicas somente foi melhorado o alongamento na rotura. Estudos ais aprofundados são recomendados. / Brazil is a producer of clay and has large reserves of this natural resource. However, most of its production is sold dried and milled." The development of clays for use as reinforcement in polymer nanocomposites is an option for these raw material producers, who would thus have a product with higher added value. This study aims to evaluate the potential use as nanofiller of two national clays from Taubaté basin, São Paulo, called ALIGRA and SANTA FE. In this experiment, the fractions of particles with average size of less than 0.02 obtained through wet sieving were used. The characterization studies involving granulometric, chemical, mineralogical, morphological, thermal and textural analysis, revealed very similar characteristics in both the clays. Clay fraction (< 2&#956;m) is higher 70%. Chemical composition as the definition of clay and its components show intermediate values between those present by bentonite and kaolinitic clays used here for purposes of comparison. It should be underlined good adsorptive properties. Specific surface area BET (aBET) around of 120 m2/g, this value is higher than showed by many bentonites (74.5 m2/g). They are predominantly mesoporous, the pores predominantly in slit-shape in accordance to the characteristic layered structure of the clays. Low cationic exchange capacities (CEC), 12 meq/100 g. XRD results for samples saturated with ethylene glycol and heated revealed the predominance of illite/smectite, kaolinite and quartz in ALIGRA clay, and illite, kaolinite and quartz in the clay SANTA FE. Work continued with the clay ALIGRA the preparation of organoclay. The organoclay was obtained by ion exchange with the quaternary ammonium salt: cetril trimethyl ammonium chloride, after homogenized in sodium with sodium chloride. FTIR and TGA analyzes indicated that there was integration of organic cations Preliminary tests were performed by preparing mixtures of clays with a polypropylene matrix, and using polypropylene grafted with maleic anhydride as a compatibilizer. Results of tensile tests made in the polypropilene- purified clay compositions have reported some improvements in some tested properties. With polipropilene-organofilized compositions only improved elongation on break. More detailed studies are which would be required.

The reversible and topotactic insertion of guest species within layered host lattices, known as intercalation is a widely studied phenomena. The Layered Double Hydroxides (LDHs) or Anionic Alloys are important class of layered solids with its own distinct ion-exchange host-Guest Chemistry. The LDH structure may be derived from that of Brucite, Mg(OH)2, by random isomorphous substitution of Mg2+ ions by trivalent cations like Al3+, Ga3+ etc. This substitution leaves an excess positive charge on the layers, which is compensated by interlamellar anions. These ions are exchangeable and thus new functionalities can be introduced to ion exchange reactions. Insertion of neutral, non-polar or poorly water-soluble guest molecules remains a challenge. In the present study, two methodologies were adopted to extend the host-guest chemistry of LDHs to neutral and non-polar species, first by using Hydrophobic interaction and second, charge transfer (CT) interaction as driving force. Hlydrophobic interaction as driving force involves functionalization of the Mg-Al-LDH galleries as bilayers, thus covering the essentially hydrophilic interlamellar space of the LDH to one that is hydrophobic and able to solubilize neutral molecules like Anthracene. CT interaction as driving force, involves pre-functionalization of the galleries of the LDH with a donor species e.g. 4-aminobenzoic acid by conventional ion exchange methods to form a LDH-donor intercalated compound. This compound can selectively adsorb acceptor species like Chloranil, Tetracyanoquinodimethane etc. into the interlamellar space of the solid by forming donor-acceptor complexes. The confined donor-acceptor complexes have been characterized by X-Ray Diffraction, UV-Visible, Fourier Transformed Infra-Red and Raman Spectroscopy, Molecular Dynamics Simulations were able to reproduce the experimental results. One dimensional gold nanostructure like nanorods (AuNRs) have received great attention due to their size dependent optical properties, Extending these applications requires assembling the AuNRs into one-, two- and if possible three-dimensional architectures. Several approaches have been developed to assemble AuNRs in two-orientation modes namely end-to-end and side-to-side. The present study self-assembly of the AuNRs has been achieved by anchoring β-cyclodextrin (β-CD) cavities to the nanorods surface. The host-guest chemistry of β-CD has been exploited to assemble the AuNRs. Our strategy was to use a guest molecule that is capable to link β-CD into 1:2 host-guest fashions to link up two β-CD capped nanorods. The guest molecule chosen for the present study was 1,10-phenanthroline. Linkage between the ends of rods leading to V-shaped rods dimmer assembly and side-to-side assembly was achieved by varying the extent of cyclodextrin capping of the AuNRs followed by the addition of linker, 1,10-phenanthroline. The formation of the assembly was characterized using UV-Visible-Near-IR Spectoscopy and Transmission Electron Microscopy.

O Brasil é produtor de argilas e conta com grandes reservas deste recurso natural. Porém, grande parte da sua produção é comercializada seca e moída. O desenvolvimento de argilas para seu uso como reforço em nanocompósitos poliméricos constitui uma opção para os produtores desta matéria prima que teriam assim um produto com maior valor agregado. Este trabalho visa avaliar o potencial uso como nanocarga de duas argilas nacionais provenientes da Bacia de Taubaté, São Paulo, denominadas ALIGRA e SANTA FÉ. As frações de tamanho de partícula médio menor de 0,02 mm, obtidas por peneiramento á úmido da argila homogeneizada e seca, foram utilizadas no desenvolvimento do trabalho experimental. Os estudos de caracterização, envolvendo análise granulométrica, química, mineralógica, morfológica, térmica e textural, revelaram características muito semelhantes em ambas às argilas. Fração argila, maior de 70% em massa. Composição química conforme a definição química de uma argila e os teores de seus componentes mostram valores intermédios entre as apresentadas pelas bentonitas e argila caulinítica usadas com fins de comparação. Ressaltamse boas propriedades adsorventes. Área superficial específica BET ao redor de 120 m2/g, valor maior do que o apresentado por muitas bentonitas naturais (74,5 m2/g). Predominantemente mesoporosas, com poros, maiormente em forma de fenda, característicos da estrutura em camadas das argilas. Baixa capacidade de troca catiônica, 12 meq/100g. Difratogramas de raios-X revelaram a predominância do estratificado ilita/esmectita, caulinita e quartzo na argila ALIGRA, e de ilita, caulinita e quartzo na argila SANTA FÉ. Prosseguiu-se com a argila ALIGRA a preparação da argila organofílica. A argila organofílica foi obtida por troca catiônica com o sal quaternário de amônio: cloro cetril trimetil amônio, depois de homogeneizada em sódio com cloreto de sódio. Análises FTIR e TGA indicaram que houve inserção dos cátions orgânicos. Testes preliminares foram feitas, preparando misturas das argilas com matriz de polipropileno e usando como agente compatibilizante polipropileno enxertado com anidrido maleico. Resultados de ensaios de tração reportam algumas melhoras nas propriedades testadas com as composições preparadas com as argilas purificadas. Com as composições com argilas organofílicas somente foi melhorado o alongamento na rotura. Estudos ais aprofundados são recomendados. / Brazil is a producer of clay and has large reserves of this natural resource. However, most of its production is sold dried and milled." The development of clays for use as reinforcement in polymer nanocomposites is an option for these raw material producers, who would thus have a product with higher added value. This study aims to evaluate the potential use as nanofiller of two national clays from Taubaté basin, São Paulo, called ALIGRA and SANTA FE. In this experiment, the fractions of particles with average size of less than 0.02 obtained through wet sieving were used. The characterization studies involving granulometric, chemical, mineralogical, morphological, thermal and textural analysis, revealed very similar characteristics in both the clays. Clay fraction (< 2&#956;m) is higher 70%. Chemical composition as the definition of clay and its components show intermediate values between those present by bentonite and kaolinitic clays used here for purposes of comparison. It should be underlined good adsorptive properties. Specific surface area BET (aBET) around of 120 m2/g, this value is higher than showed by many bentonites (74.5 m2/g). They are predominantly mesoporous, the pores predominantly in slit-shape in accordance to the characteristic layered structure of the clays. Low cationic exchange capacities (CEC), 12 meq/100 g. XRD results for samples saturated with ethylene glycol and heated revealed the predominance of illite/smectite, kaolinite and quartz in ALIGRA clay, and illite, kaolinite and quartz in the clay SANTA FE. Work continued with the clay ALIGRA the preparation of organoclay. The organoclay was obtained by ion exchange with the quaternary ammonium salt: cetril trimethyl ammonium chloride, after homogenized in sodium with sodium chloride. FTIR and TGA analyzes indicated that there was integration of organic cations Preliminary tests were performed by preparing mixtures of clays with a polypropylene matrix, and using polypropylene grafted with maleic anhydride as a compatibilizer. Results of tensile tests made in the polypropilene- purified clay compositions have reported some improvements in some tested properties. With polipropilene-organofilized compositions only improved elongation on break. More detailed studies are which would be required.

Submitted by Maria Eneide de Souza Araujo (mearaujo@ipen.br) on 2017-03-10T14:39:39Z No. of bitstreams: 1 22066.pdf: 9119613 bytes, checksum: 0b28a0c36e553b4d7b70c8a8a0d8d601 (MD5) / Made available in DSpace on 2017-03-10T14:39:39Z (GMT). No. of bitstreams: 1 22066.pdf: 9119613 bytes, checksum: 0b28a0c36e553b4d7b70c8a8a0d8d601 (MD5) / O polímero Acrilonitrila Butadieno Estireno (ABS) é um dos polímeros mais versáteis disponíveis nos dias de hoje. Atualmente o Brasil não produz o ABS, o que limita a indústria brasileira de plásticos a utilizar as variações deste polímero importadas, ofertadas no mercado nacional por distribuidores locais. Este estudo avaliou os efeitos da adição das argilas Cloisite Na® e Branca de Cubati na matriz polimérica ABS e também os efeitos decorrentes do tratamento por radiação ionizante no ABS e nos compósitos ABS/Argila como formas de modificação de um ABS convencional. Visando avaliar a diferença entre uma argila organofílica e uma organofóbica, a argila Branca de Cubati foi organofilizada e a argila Cloisite Na® foi utilizada como recebida. Foram preparados, utilizando uma extrusora dupla rosca, concentrados a 30 % em massa da argila Branca de Cubati, previamente organofilizada e da Cloisite Na® em Estireno Acrilonitrila (SAN). Os concentrados foram adicionados ao ABS a 1, 3 e 5 % em massa das argilas e foram injetados corpos de prova. Parte dos corpos de prova foi submetida à irradiação por feixe de elétrons à uma dose de 600 kGy. Os compósitos irradiados e não irradiados foram caracterizados por meio de ensaios de resistência a tração, resistência a flexão, resistência ao impacto, temperatura de distorção térmica, ponto de amolecimento Vicat, análise de termogravimétrica (TG), difração de raios X e microscopia eletrônica de varredura com emissão de campo (MEVFEG) e a correlação entre os resultados foi discutida. Foram observadas melhorias nas propriedades mecânicas, exceto resistência ao impacto, nos materiais aditivados com as argilas, sendo os melhores resultados obtidos com a argila Branca de Cubati. O tratamento por radiação ionizante favoreceu o processo de reticulação do ABS. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

A extensa utilização de pesticidas na agricultura moderna tem contribuído para um aumento na contaminação do meio ambiente. Os Hidróxidos Duplos Lamelares (HDLs) ou argilas aniônicas, apresentam uma estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas. Estes materiais lamelares podem ser utilizados em processos de adsorção/sorção e como suporte para a liberação lenta de compostos químicos. Assim, os principais objetivos deste trabalho foram: o estudo da sorção de ânions orgânicos de herbicidas ácidos 2,4-D, MCPA e Picloram utilizados na agricultura nacional, pela regeneração de HDLs de Mg-Al-CO3 calcinado e por troca aniônica em HDLs de Mg-Al-Cl. Para isso foram investigados a cinética do processo de sorção, além da determinação das isotermas em dois valores diferentes de pH. Assim, estes herbicidas foram intercalados em HDLs de Mg-Al, utilizando dois métodos de síntese indireta: regeneração do material calcinado e troca aniônica em solução, além do método de síntese direta por coprecipitação, sendo os materiais devidamente caracterizados. Todos os materiais obtidos, intercalados com cada um dos herbicidas, foram utilizados para o estudo da cinética de liberação dos mesmos em água. Os materiais obtidos por regeneração contendo cada um dos três herbicidas foram utilizados também no estudo da lixiviação em colunas de solo e no estudo de bio-ensaio com plantas, para testar a eficiência dos HDLs como suportes na liberação lenta dos herbicidas. A partir do estudo da cinética do processo de sorção dos ânions orgânicos presentes em solução utilizando HDLs de Mg-Al contendo cloreto ou carbonato após a calcinação, observou-se que a remoção dos ânions ocorreu através dos processos de troca aniônica no caso do HDL contendo cloreto, ou de regeneração da estrutura lamelar no caso do HDL calcinado. A intercalação dos ânions orgânicos na posição vertical foi verificada no processo de adsorção/sorção, e se mostrou dependente da concentração do herbicida em solução. O HDL calcinado apresentou a maior eficiência na remoção dos ânions da solução. Os herbicidas suportados em HDLs, apresentaram uma liberação em água mais lenta do que os mesmos em sua forma livre, e não se mostrou dependente do método de preparação da matriz utilizada. Os resultados dos estudos de lixiviação utilizando como matriz o HDL obtido por regeneração, demonstraram que os HDLs são bons suportes para os herbicidas pois apresentaram uma liberação lenta do ingrediente ativo, principlamente para o herbicida Picloram. O bio-ensaio mostrou que a forma de liberação dos herbicidas suportados foi eficiente no controle da germinação das sementes de plantas em aplicações pré-emergenciais. / The extensive use of pesticides in modern agriculture has been contributing to an increase in environmental contamination. Layered Double Hydroxides (LDHs), or anionic clays, bear a layered structure, and a variety of anions can be intercalated between these layers through electrostatic interactions. These layered materials can be used in adsorption/sorption processes and in the slow release of chemical compounds. So this work aims at studing the sorption of the acid herbicides bearing organic anions 2,4-D, MCPA and Picloram, used in national agriculture, through regeneration of calcined Mg-Al-CO3 LDH and anion exchange of Mg-Al-Cl ? LDH. For this purpose, the kinetics of the sorption process was investigated, and the determination of isotherms in two different pH values was carried out. The herbicides were intercalated in Mg-Al ? LDH using two indirect synthesis methods: regeneration of the calcined material and anion exchange in solution; besides the direct synthesis method by coprecipitation. The obtained materials were properly characterized. All the obtained materials, intercalated with each of the herbicides, were used in a kinetic release study in water. The materials obtained by regeneration were also used in a leaching and in a bioassay study, to test the efficiency of LDHs as supports for the slow release of herbicides. From the kinetic sorption process of the organic anions in solution using Mg-Al ? LDH containing chloride or carbonate after calcination, it was observed that the removal of anions occurred through an anionic exchange process in the case of the LDH containing chloride, or through regeneration of the layered structure in the case of the calcined LDH. The intercalation of organic anions in a vertical position was observed in the adsorption/sorption process, and it was shown to be dependent on the herbicide concentration in solution. The calcined LDH was the most efficient for removal of anions in solution. The herbicides supported on LDHs, presented a slower release in water than the same compounds in their free form, and the release behavior was not dependent on the methodology used for the preparation of the matrix. Leaching study results using the LDH obtained by regeneration as matrix demonstrated a slow release of the active ingredient, mainly for the Picloram herbicide. The bioassay showed that the release behavior of the supported herbicides was efficient in the control of plant seeds germination at preemergence applications.

Made available in DSpace on 2017-07-10T18:07:57Z (GMT). No. of bitstreams: 1 Layani Crystini Antonio da Silva.pdf: 3602080 bytes, checksum: 549974109a316672aa67e6aa29fdb910 (MD5) Previous issue date: 2013-02-15 / The demand for renewable energy sources that are environmentally friendly is increasing every year, especially for biodiesel, a biofuel for use in internal combustion engines biodegradable and nontoxic. In turn, biodiesel is commercially produced by transesterification process using homogeneous catalysts such as NaOH or KOH, which possess good yields despite purification steps of biodiesel quite costly, and the raw material used has a high cost. The replacement of homogeneous catalysts by heterogeneous transesterification reactions is very promising because this method has some advantages such as easy separation of the biodiesel formed in the reaction and the catalyst and the possibility of reuse of the catalyst. This study aimed to produce biodiesel using modified clays as heterogeneous catalyst. Clays are abundant natural raw materials and therefore have a low cost, and enable manipulation of their properties. Thus, natural clays have been chemically modified by treatment with KF. After treatment the catalysts were characterized structurally by the techniques of XRF, XRD, IR, SEM and BET then applied to transesterification reactions. Tests using Hammett indicators were applied on fresh catalysts and clay, where the results confirmed a greater number of basic sites for the catalysts compared to untreated clay with KF. To achieve the goal of producing biodiesel was performed 23 factorial design for three catalysts. Thus the best yield obtained was 89% using the catalyst KF-Clay 1 in molar ratio 1:9 reaction conditions, amount of catalyst of 25% over the mass of the oil temperature of 80 ° C and 1 hour of reaction. Test was conducted with catalyst reuse Clay KF-1 that showed a gradual loss of catalytic activity and leaching tests showed that among the three catalysts used at work, Clay KF-1 shows greater stability. / A procura por fontes renováveis de energia que sejam ambientalmente corretas vem aumentando a cada ano, em especial para o biodiesel, um biocombustível para uso em motores a combustão interna biodegradável e não tóxico. Por sua vez, o biodiesel é produzido comercialmente pelo processo de transesterificação utilizando catalisadores homogêneos tais como NaOH ou KOH, que apesar de bons rendimentos possuem etapas de purificação do biodiesel bastante onerosas e, a matéria prima utilizada possui um alto custo. A substituição de catalisadores homogêneos por heterogêneos em reações de transesterificação é bastante promissora, pois este método possui algumas vantagens como fácil separação entre o biodiesel formado na reação e o catalisador e possibilidade de reuso do catalisador. Este trabalho teve como objetivo produzir biodiesel empregando argilas modificadas como catalisador heterogêneo. As argilas são matérias-primas naturais abundantes e, portanto, possuem baixo custo, além de possibilitar manipulação de suas propriedades. Desta forma, argilas naturais foram modificadas quimicamente por tratamento com KF. Após o tratamento os catalisadores obtidos foram caracterizados estruturalmente pelas técnicas de FRX, DRX, IV, MEV e BET, depois aplicados em reações de transesterificação. Testes utilizando indicadores de Hammett foram aplicados sobre as argilas in natura e catalisadores, onde os resultados comprovaram um maior número de sítios básicos para os catalisadores, quando comparados com argila sem tratamento com KF. Para alcançar o objetivo de produção de biodiesel foi realizado planejamento fatorial 23 para três catalisadores. Assim o melhor rendimento obtido foi de 89% utilizando o catalisador KF-Argila 1, nas condições reacionais razão molar 1:9, quantidade de catalisador de 25% em relação a massa do óleo, temperatura de 80 oC e 1 hora de reação. Foi realizado teste de reuso com o catalisador KF-Argila 1 que apresentou uma gradativa perda na atividade catalítica e, testes de lixiviação comprovaram que dentre os três catalisadores utilizados no trabalho, o KF-Argila 1 apresenta maior estabilidade.

Made available in DSpace on 2017-07-10T18:08:09Z (GMT). No. of bitstreams: 1 Rodrigo Tartari.pdf: 9550409 bytes, checksum: 139b195eb1b11dbe7bfc7a238de6d98b (MD5) Previous issue date: 2008-12-05 / The objective of this work is to research the development of methods for utilizing the sludge generated in the Tamanduá water treatment plant, located in the city of Foz do Iguaçu - PR, as a prime material for the production of red ceramic. For this purpose, it was used beyond the mud, four clays originating geological region of western Paraná, called: Plastic (OP) and Sand (AO) from Santa Rita Ceramic and Plastic (AP) and Sand (AA) from de Artisans Cooperative of Foz do Iguaçu PR (COOAFOZ), used for production of red ceramic. The methodology is divided into: characterization of the 5 materials for determination of humidity, organic matter, loss by fire, limits of sil consistency, residues, grain fineness, chemical and mineralogy, in the second phase of the investigation, seven binary mistures were made among the clays from Santa Rira Cermics and from COOAFOZ, varying the weight of both in proportion of 0, 30, 40, 50, 60, 70 and 100%. Were up 336 bodies of evidence by uniaxial pressing, tested dry and after sintering at temperatures of 950 o and 1050 °C, measured before the following tests: total linear contraction, water absorption, apparent porosity, loss by fire, apparent specific mass, strength the bending, scanning electron microscopy and microanalysis. It was found that the clay AP and OP showed characteristics of high plasticity with major composition of SiO2, Al2O3 and Fe2O3 and grains < 2&#956; equivalent to 19.4 and 21.6, respectively. When these clays the AP and OP in greater weight percentages in the mixtures, the intensities of interaction between clay processing were positively evaluate the physical-mechanical properties of bodies of evidence. Mixtures A1 (100% AP), A2 (70% AP + 30% AA), B1 (100% AP) and A2 (70% AP + 30% AA), showed better results on water absorption of less than 25% and resistance to bending than 60 kgf/cm2 at a temperature of 950 °C and more than 80 kgf/cm2 to 1050 oC. In these compositions, is incorporated 4, 8, 12 and 16% of dry sludge to determine the maximum permissible load without causing cracks and deformations. It was found that the sludge presented characteristics of silty clay of low plasticity, can replace clay similar to 8% in the production of red ceramic. According to analysis of results, have been building blocks of 6 holes for the method of extrusion incorporating 8% of wet mud is found that the physical mechanical properties evaluated were: linear contraction of 8.6%, 24% water absorption and 46 kgf /cm2 of resistance to compression, and within the rules for production of red ceramic coating for (bricks). It appears that the sludge was incorporated as the mass of wet clay, about 75% of initial water when received from the water treatment plant Tamanduá, contributing to process of maturation. It was concluded that based on the results obtained in the laboratory that the sludge generated in the water treatment plant of the unit Tamanduá in Foz do Iguaçu - PR can be used as an additive in the manufacture of bodies for red ceramic. / Este trabalho tem por objetivo pesquisar o desenvolvimento de métodos para utilizar o lodo gerado na Estação de Tratamento de Água Tamanduá, localizada na cidade de Foz do Iguaçu/PR, como matéria-prima para produção de cerâmica vermelha. Para atingir a finalidade proposta, utilizaram-se além do lodo, quatro argilas de formação geológica da região oeste do Paraná, denominadas por: Plástica (OP) e Areia (OA) da Cerâmica Santa Rita e Plástica (AP) e Areia (AA) da Cooperativa de Artesões de Foz do Iguaçu PR (COOAFOZ), empregadas para produção de cerâmica vermelha. A metodologia subdividiu-se em: caracterização das 5 matérias-primas pela determinação da umidade, matéria orgânica, perda ao fogo, limites de consistência de solos, resíduos, granulometria, composição química e mineralógica. Na segunda fase da investigação, fez-se sete misturas binárias entre as argilas da Cerâmica Santa Rita e da COOAFOZ, variando o peso de ambas em 0, 30, 40, 50, 60, 70 e 100%. Foram confeccionados 336 corpos de prova por prensagem uniaxial, analisados a seco e após sinterização nas temperaturas de 950 e 1050 oC, avaliados perante os seguintes ensaios: contração linear total, absorção de água, porosidade aparente, perda ao fogo, massa específica aparente, resistência à flexão, microscopia eletrônica de varredura e microanálise. Verificouse que as argilas AP e OP apresentaram características de alta plasticidade com presença majoritária de SiO2, Al2O3, e Fe2O3 e grãos < 2&#956;, iguais a 19,4 e 21,6 respectivamente. As argilas AP e OP em maiores porcentagens peso nas misturas intensificaram as interações entre os argilominerais, isto é, no processamento obtiveram-se resultados positivos diante a avaliação das propriedades físico mecânicas dos corpos de prova. As misturas A1 (100% AP), A2 (70% AP + 30% AA), B1 (100% OP) e B2 (70% OP + 30% OA), apresentaram melhores resultados com relação à absorção de água menor que 25% e resistência à flexão superior a 60 kgf/cm2 na temperatura de sinterização a 950 oC e superior a 80 kgf/cm2 à 1050 oC. Nestas composições, incorporaram-se 4, 8, 12 e 16% de lodo seco para determinar a carga máxima admissível sem causar trincas e deformações. Verificou-se que o lodo apresentou características de argilas siltosas de baixa plasticidade, podendo substituir argilas similares em até 8% na produção de cerâmica vermelha. De acordo com análise dos resultados obtidos, fizeram-se blocos estruturais de 6 furos pelo método de extrusão incorporando 8% de lodo úmido, e verificou-se que as propriedades físico-mecânicas avaliadas foram as seguintes: 8,6% de contração linear, 24% de absorção de água e 46 kgf/cm2 de resistência à compressão, estando dentro das normas de produção de cerâmica vermelha para revestimento (tijolos). Destacou-se que o lodo incorporado na forma úmida à massa de argila, com cerca de 75% de água inicial quando recebido da Estação de Tratamento de Água Tamanduá, contribuiu no processamento de maturação da mesma. Portanto, conclui-se com base nos resultados que o lodo gerado na Estação de Tratamento de Água da unidade Tamanduá em Foz do Iguaçu PR pode ser utilizado como aditivo na fabricação de massas para cerâmica vermelha.

Marine clay deposits are characterized by very soft to soft consistencies (undrained strength 1-50 kPa), presence of saline pore solution and low-swelling clays. Besides, loss of metastable structure on disturbance, poor undrained strengths of soft clays is contributed by high water contents. Presence of saline pore solution and low-swelling clays (illite, chlorite, kaolinite) play an important role in developing metastable structure of soil sediments deposited in marine environment. The pore solution salinity regulates the “physico-chemical (A - R) stress” that in turn has significant bearing on development of the metastable structure. Metastable structure refers to edge-face, edge-edge associations in card-house arrangement of platy/elongate particles that develop during deposition. Loss of metastable structure of soft marine clays upon disturbance leads to excessive settlements and slope failures. Besides A - R forces, metastable structure of marine clays is contributed by cementation bonds, thixotropic hardening, ion leaching, formation or addition of dispersing agents and chemical weathering. Secondary compression also causes bonding of micro-structural units that increase stiffness and strength of the metastable structure. Review of literature brings out that majority of studies examining the role of physico-chemical factors on the engineering behavior of marine clays have focused on illite rich sediments. However, non-swelling clay, namely, kaolinite is also encountered in marine deposits (example, Pusan clay, Singapore clay, Sarapui soft clays). Kaolinites differ from illites in being 1:1 mineral (unit layer comprises of 1 silica sheet bonded to 1 gibbsite sheet) and having strong hydrogen bonding between unit layers. Consequently, kaolinite particles are thick (0.3 to 3 ìm thickness) with low surface area (10 to 20 m2/g). Also the hydrogen bonding between unit layers do not allow them to separate on hydration. Combination of very low isomorphous substitution (Al for Si 1 in 400), low cation exchange capacity (3 meq/100g), and low surface area, lead to negligible development of diffuse double layer repulsion forces between kaolinite particles. Strong positive edge (developed on broken bonds at particle edges from adsorption of hydrogen ions) negative face attraction between kaolinite particles, encourages flocculation of particles at range of water contents. It was therefore considered of interest to examine the engineering response of kaolinites to changes in pore solution salinity from leaching effects. The focus of the thesis is hence to gain better understanding of physico-chemical (pore solution salinity, A - R forces) and mechanical (secondary compression, loss of overburden) factors towards development of metastable structure of kaolinite clays deposited in synthetic seawater environments in the context of their compressibility and undrained strength characteristics. Laboratory experiments are performed with kaolinites that are slurry consolidated in conventional consolidometers in saline and synthetic seawater solutions. The metastable structure developed by consolidated specimens is relevant to alluvial marine sediments that contain kaolinite (example, Pusan clay, Singapore clay, Sarapui soft clays). The structure of the thesis is as follows: Chapter 1 gives an introduction to the thesis. Chapter 2 provides a detailed review of literature on the role of chemical factors (pore solution composition, A - R forces, osmotic suction) and mechanical processes (secondary compression and overconsolidation) in developing metastable structure of kaolinite specimens subjected to slurry consolidation and the consequent influence of metastable structure on compression, undrained strength and sensitivity characteristics of clay specimens. The Chapter also defines the scope and objectives of the study. Chapter 3 details the experimental program undertaken to bring out the role of chemical factors and mechanical processes in influencing the 1-dimensional compression and undrained strength characteristics of slurry consolidated kaolinites prepared in saline medium. Chapter 4 delineates the role of chloride salt solutions (sodium, magnesium and calcium) and synthetic seawater solution in contributing to the metastable structure developed by slurry consolidated kaolinites at various vertical effective stress (óv’) and the consequent influence of metastable structure on 1-dimensional compression, undrained strength and sensitivity characteristics of the clay. Chapter 5 examines influence of secondary compression on metastable structure developed by kaolinites that were slurry consolidated in 24.53 g/L sodium chloride and synthetic seawater solutions and the consequence of the developed metastable structure on undrained strength and sensitivity. The chapter also examines the consequences of secondary compression experienced by soft overconsolidated kaolinites on their undrained strength and sensitivity characteristics. Chapter 6 examines the relative influence of differential osmotic stress and electrochemical stress on the consolidation behaviour of kaolinite specimens that are slurry consolidated in sodium chloride solutions. The osmotic efficiencies (á) of kaolinite were obtained using the Fritz-Marine Membrane Model. Chapter 7 summarizes the major conclusions of the thesis.

De nos jours les ressources en eau potable sont fortement réduites suite à une augmentation démographique accompagnée d’une forte industrialisation et d’un développement intensif de l’agriculture. Les rejets de micropolluants d’origine variable (pesticides, colorants, phénols, métaux lourds…) dans l’environnement ne cessent d’augmenter. Ces polluants, toxiques et peu dégradables, sont en général à l’origine de nombreux effets nocifs sur la santé. Ils affectent aussi directement l’équilibre des écosystèmes suite à la dégradation de la qualité des différents milieux de l’environnement (sol, eau, air). D’où le souci de développer des procédés qui œuvrent à la préservation des ressources hydriques contre la pollution par le traitement à la source des eaux polluées. L’application des adsorbants naturels et abondants comme l’argile pour le traitement des eaux est une voie légitime pour préserver le capital hydrique. C’est pourquoi le présent travail de recherche s’est articulé autour de la caractérisation physico-chimique d’une série d’argiles naturelles échantillonnées dans la région Nord du Maroc. Plusieurs techniques ont été sollicitées : La DRX, SFX, FTIR, ATG, la volumétrie d’adsorption d’azote, l’électrophorèse, outre la détermination de quelques propriétés physico-chimiques comme la CEC et le COT. Ceci nous a permis d’établir une série de données avec les différentes propriétés de ces matériaux. Elle peut être ainsi sollicitée pour orienter l’utilisation de ces matériaux selon le besoin. Dans une deuxième étape, nous avons étudié l’adsorption de l’arsenic et des contaminants organiques (le bleu de méthylène et le violet de méthylène) par les argiles / Today drinking water resources are greatly reduced due to population increase accompanied by high industrialization and intensive agricultural development. Releases of varying micropollutants (pesticides, dyes, phenols ...) in the environment are increasing. These pollutants, toxic and poorly degradable, are usually the source of many harmful health effects. They also directly affect the balance of ecosystems following the deterioration of the quality of various environmental medium (soil, water, air). Hence the concern to develop methods that work to preserve water resources against pollution by treating polluted sources. The application of natural and abundant adsorbents like clay in the water treatment is a legitimate way to preserve the water capital. That is why my research is articulated around the physicochemical characterization of a series of natural clays sampled in the northern region of Morocco. Several techniques have been sought: XRD, XRF, FTIR, TGA, The BET-N2 specific surface area, electrophoresis. Furthermore the determination of some physicochemical properties such as CEC and TOC. This allowed us to establish a database with the different properties of these materials. This database may be sought to guide the use of these materials according to their nature. In a second step, we studied the adsorption of arsenic and organic contaminants (methylene blue and methylene violet) by clays. The kinetics of equilibrium adsorbent / adsorbate is an essential step to optimize the conditions for determination of adsorption isotherms

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