A incorporação de nanocargas minerais e vegetais em matriz polimérica tem sido estudada, principalmente, com o objetivo de melhorar as propriedades de desempenho mecânico dos polímeros para aplicações industriais diversas. As argilas organofilizadas e as fibras vegetais estão entre os materiais que se destacam como cargas adicionadas ao polímero para a formação de nanocompósitos. Essa área de estudo tem despertado interesse também devido à obtenção de melhorias de propriedades físicas, químicas e mecânicas desses materiais quando comparadas às dos materiais compósitos tradicionais. O objetivo da pesquisa foi estudar algumas dessas propriedades em nanocompósitos produzidos com polipropileno, argila esmectítica brasileira e fibra do ouriço da castanha-do-brasil, com ênfase na melhora das propriedades mecânicas. Inicialmente, os materiais componentes foram caracterizados por diversos ensaios, tais como, difração de raios X, granulometria, infravermelho, microscopia eletrônica de varredura, temperatura de degradação térmica, além de ensaios específicos para medir características individuais da argila, como, viscosidade Fann, inchamento de Foster, limite de plasticidade, fluorescência de raios X, entre outros. Posteriormente, o polipropileno graftizado com anidrido maleico (PP-g-MA) foi incorporado ao PP puro (PP), em extrusora dupla rosca, nas proporções de 5%, 10% e 20% em peso e injetados os corpos de prova para os ensaios de tração e impacto. A partir dos resultados das propriedades mecânicas definiu-se o uso de 5% de PP-g-MA para preparação dos nanocompósitos definitivos. Finalmente, variou-se a quantidade de fibra na composição. Foram obtidos nanocompósitos de polipropileno (PP) e 5% PPg- MA reforçado com 5% em peso da argila organofilizada e fibra do ouriço da castanha-do-brasil em três proporções 5%, 10% e 15% em peso. As amostras foram caracterizadas por diferentes técnicas (DRX, MEV, FTIR, TG/DSC) e medidas as resistências mecânicas à tração, flexão e impacto. Todos os nanocompósitos apresentaram aumento na resistência mecânica quando comparados ao polímero sem argila e fibra. / The incorporation of vegetable and mineral nanofillers in polymer matrix has been studied mainly in order to improve the mechanical performance properties of polymers for various industrial applications. The organoclays and vegetable fibers are among the materials that stand out as fillers added to polymer for the formation of nanocomposites. This study has also attracted interest owing to achieve improvements in various properties when compared to other traditional composite materials. This study aims to investigate the effects of adding organophilic clay and brazilian nut fibers on the some physical, chemical and mechanical properties of polypropylene nanocomposite. Initially, The component materials were characterized by tests, such as X-ray diffraction, particle size, infrared, scanning electron microscopy, thermal degradation, as well as specific assays for measuring individual characteristics and properties of the clay, for example, viscosity Fann, Foster swelling, plasticity limit, X-ray fluorescence, among others. In the second step, the graftizado polypropylene with maleic anhydride (PP-g-MA) was incorporated into the pure PP, extruded in proportions of 5 weight%, 10 weight% and 20 weight% and injected the samples for tensile and impact tests. From the results of mechanical properties was defined using 5 weight% of PP-g-Ma for the incorporation into pure PP. Finally, samples were prepared containing only polymer, graftizado polymer/clay, graftizado polymer/clay/ fiber. The addition of clay was 5 weight% and the fiber was added to 5 weight%, 10 weight% and 15% by weight, respectively. The nanocomposites were prepared double-screw extruder and the samples injection molded, then, they were characterized by X-ray diffraction, scanning electron microscope (SEM), thermal analysis (TG/DSC), infrared spectroscopy and mechanical strength, flexural and impact test. All the nanocomposites increased mechanical properties as compared to polymer without clay and fibers.

Polymer nanocomposite technology has had significant impact on material design. With the environmental advantages of photopolymerization, a research has recently focused on producing nanocomposites utilizing inexpensive clay particles based on in situ photopolymerization. In this research, novel polymerizable organoclays and thiol-ene photopolymerization have been utilized to develop advanced photopolymer clay nanocomposites and to overcome several limitations in conventional free radical photopolymers. To this end, factors important in nanocomposite processes such as monomer composition, clay dispersion, and photopolymerization behavior in combination with the evolution of ultimate nanocomposite properties have been investigated. For monomer-organoclay compositions, higher chemical compatibility of components induces enhanced clay exfoliation, resulting in photopolymerization rate increases due to an amplified clay template effect. Additionally, by affecting the stoichiometric ratio between thiol and acrylate double bond in the clay gallery, thiolated organoclays enhance thiol-ene copolymerization with increased final thiol conversion while acrylated organoclays encourage acrylate homopolymerization. In accordance with the reaction behavior, incorporation of thiolated organoclays makes polymer chains more flexible with decreased glass transition temperature due to higher formation of thio-ether linkages while adding acrylated organoclays significantly increases the modulus. Photopolymer nanocomposites also help overcome two major drawbacks in conventional free radical photopolymerization, namely severe polymerization shrinkage and oxygen inhibition during polymerization. With addition of a low level of thiol monomers, the oxygen inhibition in various acrylate systems can be overcome by addition of only 5wt% thiolated organoclay. The same amount of polymerizable organoclay also induces up to 90% decreases in the shrinkage stress for acrylate or thiol-acrylate systems. However, nonreactive clays do not reduce the stress substantially and even decreases the polymerization rate in air. Additionally, the clay morphology and polymerization behavior are closely related with evolution of ultimate nanocomposite performance. Use of polymerizable organoclay significantly improves overall toughness of nanocomposites by increasing either modulus or elongation at break based on the type of polymerizable organoclay, which demonstrates the promise of this technology as a modulation and/or optimization tool for nanocomposite properties.

A incorporação de nanocargas minerais e vegetais em matriz polimérica tem sido estudada, principalmente, com o objetivo de melhorar as propriedades de desempenho mecânico dos polímeros para aplicações industriais diversas. As argilas organofilizadas e as fibras vegetais estão entre os materiais que se destacam como cargas adicionadas ao polímero para a formação de nanocompósitos. Essa área de estudo tem despertado interesse também devido à obtenção de melhorias de propriedades físicas, químicas e mecânicas desses materiais quando comparadas às dos materiais compósitos tradicionais. O objetivo da pesquisa foi estudar algumas dessas propriedades em nanocompósitos produzidos com polipropileno, argila esmectítica brasileira e fibra do ouriço da castanha-do-brasil, com ênfase na melhora das propriedades mecânicas. Inicialmente, os materiais componentes foram caracterizados por diversos ensaios, tais como, difração de raios X, granulometria, infravermelho, microscopia eletrônica de varredura, temperatura de degradação térmica, além de ensaios específicos para medir características individuais da argila, como, viscosidade Fann, inchamento de Foster, limite de plasticidade, fluorescência de raios X, entre outros. Posteriormente, o polipropileno graftizado com anidrido maleico (PP-g-MA) foi incorporado ao PP puro (PP), em extrusora dupla rosca, nas proporções de 5%, 10% e 20% em peso e injetados os corpos de prova para os ensaios de tração e impacto. A partir dos resultados das propriedades mecânicas definiu-se o uso de 5% de PP-g-MA para preparação dos nanocompósitos definitivos. Finalmente, variou-se a quantidade de fibra na composição. Foram obtidos nanocompósitos de polipropileno (PP) e 5% PPg- MA reforçado com 5% em peso da argila organofilizada e fibra do ouriço da castanha-do-brasil em três proporções 5%, 10% e 15% em peso. As amostras foram caracterizadas por diferentes técnicas (DRX, MEV, FTIR, TG/DSC) e medidas as resistências mecânicas à tração, flexão e impacto. Todos os nanocompósitos apresentaram aumento na resistência mecânica quando comparados ao polímero sem argila e fibra. / The incorporation of vegetable and mineral nanofillers in polymer matrix has been studied mainly in order to improve the mechanical performance properties of polymers for various industrial applications. The organoclays and vegetable fibers are among the materials that stand out as fillers added to polymer for the formation of nanocomposites. This study has also attracted interest owing to achieve improvements in various properties when compared to other traditional composite materials. This study aims to investigate the effects of adding organophilic clay and brazilian nut fibers on the some physical, chemical and mechanical properties of polypropylene nanocomposite. Initially, The component materials were characterized by tests, such as X-ray diffraction, particle size, infrared, scanning electron microscopy, thermal degradation, as well as specific assays for measuring individual characteristics and properties of the clay, for example, viscosity Fann, Foster swelling, plasticity limit, X-ray fluorescence, among others. In the second step, the graftizado polypropylene with maleic anhydride (PP-g-MA) was incorporated into the pure PP, extruded in proportions of 5 weight%, 10 weight% and 20 weight% and injected the samples for tensile and impact tests. From the results of mechanical properties was defined using 5 weight% of PP-g-Ma for the incorporation into pure PP. Finally, samples were prepared containing only polymer, graftizado polymer/clay, graftizado polymer/clay/ fiber. The addition of clay was 5 weight% and the fiber was added to 5 weight%, 10 weight% and 15% by weight, respectively. The nanocomposites were prepared double-screw extruder and the samples injection molded, then, they were characterized by X-ray diffraction, scanning electron microscope (SEM), thermal analysis (TG/DSC), infrared spectroscopy and mechanical strength, flexural and impact test. All the nanocomposites increased mechanical properties as compared to polymer without clay and fibers.

Organically modified montmorillonite has been extensively used as nanofiller in studies of polymer layered silicate nanocomposites, promising materials for today's automotive industry because the nano-materials reduce the overall weight of vehicle. However, industrial applications have not followed suit primarily due to cost/performance issues. Supercritical carbon dioxide is promising as an aid in the production of a fully exfoliated polymer layered silicate nanocomposite but has not been fundamentally studied in this regard at present. As the first stage in studies of using supercritical carbon dioxide for aiding the production of thermoplastic elastomer nanocomposites, this thesis investigates the influence of this unique supercritical fluid on the microstructure and surface chemistry of five organically modified clays. Four alkyl-based quaternary ammonium surfactants with different number and length of chains attached and one aromatic quaternary ammonium surfactant were chosen to vary the degree of C02-philicity exhibited by the organoclay. In a high pressure batch vessel, the different organoclays were suspended in the supercritical solvent at temperatures of 50°C and 200°C and pressures of 7.6 MPa and 9.7 MPa for a fixed time and then removed after depressurization at 0.2 MPa/s or 4.8 MPa/s. The structures of these treated clays were characterized by XRD, TEM, DSC, TGA, FT -IR, and SEM, and their chemical properties were analyzed by various methods including atomic absorption spectroscopy, and contact angle measurement. The potential role of water to favor the interaction between scC02 and an organoclay was also investigated. Solute-solvent interactions plasticized the organic modifier while suspended in the supercritical fluid, which resulted in greater chain mobility and further cation exchange. The results indicate that surfactants exhibiting a paraffin-type conformation within the galleries of the clay were most likely to experience significant basal expansion, provided the tilt angle was not already close to being perpendicular to the silicate surface. For those organoclays demonstrating basal expansion, it was noted that the resulting particle size was increased due to enhanced porosity. Water proved useful in clay expansion in certain cases and primarily while operating conditions allowed the co-solvent to remain adsorbed to the clay surface. / Thesis / Master of Applied Science (MASc)

Polymer/clay nanocomposites consisting of an epoxy resin matrix filled with organoclays have been investigated. The main objective of this study was to determine which combination of components led to the greatest enhancement in properties of the epoxy resin. Exfoliation of the clay was desired, as exfoliated nanocomposites are known to exhibit great improvements in mechanical properties [1]. The epoxy resins studied were di-functional DGEBA and tetra-functional TGDDM. The epoxy resin was cured with three different hardeners, these included: the high functionality amine hardener, TETA, and two anhydride hardeners, accelerated MTHPA and pure HHPA. The three organoclays used, contained alkylammonium cations and were also compared to the unmodified clay. Morphology was investigated by XRD and TEM, and the flexural properties of the resulting nanocomposites were studied. The effect that the addition of an organoclay has on the cure of the epoxy resin was investigated using MDSC. Both the temperatures required to cure the resin with, and without, the clay, and any changes in the total heat flow that occurred were studied. The Tg++ of the cured nanocomposites was also measured using MDSC. The heat flow results indicated that the clays added to the epoxy resins act as a physical barrier, which prevents the resin from reaching full cure. In the higher functional resin, the addition of clay resulted in a significant decrease in the total heat flow, suggesting that a large amount of epoxy remains uncured, and, as a result, there should be a reduction in the amount of cross-linking. The lower cross-link density led to a significantly lower Tg and the mechanical properties were also poorer. The reactivity of the hardener towards the resin was found to have the greatest impact on the cured nanocomposite morphology. Intragallery polymerisation occurring at a faster rate than the extragallery polymerisation causes exfoliation. In order to achieve a balance that favours intragallery polymerisation, it was found that the curing reaction was required to be catalysed by the alkylammonium cation of the organoclay, and not catalysed by other means. The DGEBA cured with HHPA provided the largest layer expansion in the clay structure due to the alkylammonium cation catalysing the anhydride ring-opening reaction. The effect was not seen with TGDDM due to the tertiary amine in its structure. The accelerator within the MTHPA assisted extragallery polymerisation of the resin and the TETA cured readily without additional catalysis.

Submitted by Gustavo Nascimento (gustavo.diniz@ufcg.edu.br) on 2018-02-02T11:24:55Z No. of bitstreams: 1 KALINE ROSÁRIO MORAIS FERREIRA - TESE PPGCMAT 2014.pdf: 4196427 bytes, checksum: cfa12a2731146e96138a50d4de35c10e (MD5) / Made available in DSpace on 2018-02-02T11:24:55Z (GMT). No. of bitstreams: 1 KALINE ROSÁRIO MORAIS FERREIRA - TESE PPGCMAT 2014.pdf: 4196427 bytes, checksum: cfa12a2731146e96138a50d4de35c10e (MD5) Previous issue date: 2014-08-29 / CNPq / Neste trabalho nanocompósitos à base de olefina termoplástica (TPO) formados pela mistura polipropileno (PP)/terpolímero de etileno-propileno-dieno (EPDM)/argila organofílica foram preparados pelo processo de intercalação por fusão. As TPOs, não compatibilizadas e compatibilizadas com polipropileno modificado com anidrido maleico (PP-g-MA), foram preparadas em um misturador interno de laboratório, empregando duas razões de PP/EPDM: 90:10 e 70:30. A estas TPOs foram incorporadas cinco tipos de argila organofílica em teores de 1, 3 e 5 pcr. A influência da razão PP/EPDM, da presença do compatibilizante orgânico (PP-g-MA), do tipo e do teor de argila na morfologia e propriedades mecânicas em tração destas TPOs foi avaliada. Os resultados obtidos por difratometria de raios X (DRX) sugerem que a adição de 1, 3 e 5 pcr das argilas organofílicas às TPOs, independente do tipo, resulta na formação de nanocompósitos com estrutura possivelmente intercalada desordenada e que as TPOs contendo as argilas organofílicas preparadas com tecnologia local apresentaram resultados semelhantes àquelas com argila organofílica comercial empregada como padrão de comparação para este estudo. Os dados de DRX mostraram também que a fase cristalina do polipropileno foi alterada pela presença do agente compatibilizante. A morfologia das TPOs, conforme dados de microscopia eletrônica de varredura (MEV), foi afetada pela razão PP/EPDM, pela presença do compatibilizante orgânico e pelo tipo e teor de argila. As TPOs com proporção PP/EPDM de 90:10, não compatibilizadas com PP-g-MA e com teor de argilas de 3 pcr apresentaram superfícies de fratura criogênica isentas de vazios. Para estas TPOs quatro das cinco argilas organofílicas estudadas atuaram como compatibilizantes para as misturas PP/EPDM favorecendo a forte interação entre fases, o que resultou no aumento da resistência à tração da referida TPO. Da mesma forma que a argila comercial, três das quatro argilas organofílicas v preparadas com tecnologia local foram efetivas em compatibilizar e, consequentemente, em aumentar a resistência mecânica em tração da TPO PP/EPDM 90:10, quando empregadas no teor de 3 pcr. Isto indica que é possível utilizar argilas organofílicas em substituição de compatibilizantes orgânicos (poliméricos ou oligoméricos) para aumentar a interação interfacial entre PP e EPDM. O PP-g-MA e as argilas organofílicas (independente do tipo e do teor) não favoreceram a compatibilização da TPO PP/EPDM 70:30; por esta razão as propriedades de resistência à tração destas foram inferiores aos da TPO sem argila ou sem compatibilizante orgânico. / In this work nanocomposites based on a thermoplastic olefin (TPO) formed by blending polypropylene (PP), ethylene-propylene-diene (EPDM), and organoclay were prepared by melt intercalation process. The TPOs, non-compatibilized and compatibilized with PP modified with maleic anhydride (PP-g-MA), were prepared in a laboratory internal mixer, employing two ratios PP/EPDM: 90:10 and 70:30. To these blends, five types of organoclay were incorporated, in amounts of 1, 3 and 5 phr. The influence of PP/EPDM ratio, the presence of organic compatibilizer (PP-g-MA), and the type and amount of clay in the morphology and tensile mechanical properties of theTPO was evaluated. The results obtained by X-ray diffractometry (XRD) suggest that the addition of organoclays, regardless of type, result in the formation of nanocomposites, possible disorderly sandwiched structures, and that the organoclays prepared with local technology showed similar results to those with commercial organoclay, employed as a standard of comparison in this study. The XRD data also showed that the crystalline phase of polypropylene was modified by the presence of coupling agent. The morphology of the TPO, as electron microscopy (SEM) data shows, was affected by the ratio PP/EPDM, the presence of organic compatibilizer, and the type and content of organoclay. The TPO with a proportion PP/EPDM 90:10, not compatibilized, and with 3 phr clay showed void-fee cryogenic fracture surfaces. For this TPO, four of the five organoclays studied acted as compatibilizers for the PP/EPDM mixture, favoring the strong interaction between phases, which resulted in increasing tensile strength. Similar to the commercial clay, three of the four organoclays prepared with local technology were effective as blend compatibilizers and increased the mechanical strength of the composite PP/EPDM 90:10 with 3 phr organoclay content. These findings suggest that organoclays may replace organic compatibilizers (polymeric or oligomeric) to increase the interfacial interaction vii between PP and EPDM. The PP-g-MA and organoclay (regardless of the type and content) did not favor promoted strong PP/EPDM interactions in 70:30 blend; for this reasons, tensile strength was lower than those of TPO without clay or organic without compatibilizer.

Submitted by MATHEUS ANTONIO DA SILVA null (0118999881999119725i@gmail.com) on 2016-08-12T01:55:42Z No. of bitstreams: 1 Corrigida dissertação2.pdf: 2484322 bytes, checksum: 10738553dadaaf9fdbd738efd3bb2d48 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-08-12T13:34:14Z (GMT) No. of bitstreams: 1 silva_ma_me_sjrp.pdf: 2484322 bytes, checksum: 10738553dadaaf9fdbd738efd3bb2d48 (MD5) / Made available in DSpace on 2016-08-12T13:34:14Z (GMT). No. of bitstreams: 1 silva_ma_me_sjrp.pdf: 2484322 bytes, checksum: 10738553dadaaf9fdbd738efd3bb2d48 (MD5) Previous issue date: 2016-07-08 / Tratou-se e modificou-se o argisolo caulinítico da região amazônica, a fim de se obter novos materiais para remoção de contaminantes da fase aquosa. As modificações fora realizadas por dois métodos: tratamento térmico em presença de fibra de cana de açúcar e modificação com surfactantes em solução; com posterior utilização dos materiais modificados na adsorção do corante Azul de Metileno (AM), usado como sonda espectrofotométrica. Tratou-se o argisolo com ataque ácido e troca de cátions e posterior calcinação a 400 0C com e sem fibra, e a 800 0C sem fibra. Os sólidos foram caracterizados por difratometria de raios X, espectrofotometria na região do infravermelho e análise térmica. Procedeu-se também a adsorção do AM em argisolo em presença de surfactante catiônico, Brometo de Cetiltrimetilamônio, e aniônico, Dodecil Sulfato de sódio. O argisolo sem calcinação apresentou apenas argila caulinita e quartzo como constituintes com cristalinidade. As amostras calcinadas a 400 0C com fibra e a 800 0C sofreram o processo de desidroxilação, ocasionando a mudança de fase da caulinita presente no argisolo; com a amostra calcinada a 400 0C sem fibra mantendo a estrutura característica da caulinita e do quartzo. Por meio da análise térmica, foi possível notar que a energia liberada pela fibra é suficiente para promover a mudança de fase da caulinita em temperaturas mais baixas em relação à mesma sem fibra, promovendo o processo de desidroxilação do material em condições ambientais mais brandas. Os estudos de variação no tempo de calcinação e de razão fibra:solo indicaram que ambos influenciam na desidroxilação do material e razões fibra:solo maiores que 1:2 e o tempo de três horas são as condições mais indicadas para a formação da metacaulinita. As isotermas de adsorção de AM evidenciam uma mudança na forma da isoterma de adsorção, onde o argisolo calcinado a 400 0C sem fibra e sem calcinação possuem isotermas do tipo L e maior correlação ao modelo de Freundlich, característicos de adsorção favorável e em multicamadas; enquanto os materiais calcinados a 800 0C e a 400 0C com fibra exibem isotermas do tipo C e correlação com o modelo de Langmuir, comuns a materiais de superfície microporosa e em monocamada. Os estudos de adsorção na presença de surfactantes evidenciaram que a interação do surfactante catiônico com o argisolo e do corante aniônico com o AM desfavoreceram a adsorção e resultaram em menor remoção do corante da fase aquosa. / Kaolinitic clay soil of Amazon region was treated and modified,in order to obtain new materials for removal of contaminants from aqueous phase. The modification was performed by two methods: thermal treatment in presence of sugar cane fiber and modification with surfactants; using the new materials in adsorption of Methylene Blue (AM), used as spectrophotometric probe. The clay soil was treated with acid attack, cation change and after calcination at 400 0C with and without sugar cane fiber, and at 800 0C. All material was characterized by X-ray Diffraction, Infrared spectrophotometry and thermal analysis. Adsorption of AM was proceed in presence of cationic (Cetyltrimethylammonium Bromide) and anionic (Sodium Dodecyl Sufate) surfactants. Samples of clay soil without calcination presents only kaolinite and quartz as compounds with cristallinity. Clay soil calcined at 400 0C with fiber and 800 0C were dehydroxyled, causing a phase change form kaolinite to metakaolin; when the kaolinite structure was maintained in clay soil calcined at 400 0C without fiber. In thermal analysis, the energy released by the fiber is sufficient to cause the phase change of kaolinite at lower temperatures relative to the same without fiber, promoting the process of dehydroxylation of the material in softer environmental conditions. The variation in time of calcination studies and ratio fiber:clay evidence that both influence the dehydroxylation and rates fiber:clay larger than 1:2 and the time of three hours are the best conditions for formation of metakaolin. Adsorption isotherms of AM exhibit changes in isotherms format, clay soil calcined at 400 0C without fiber and clay soil without calcination shows L-type isotherms and best correlation with Freundlich model, typical for favourable multiple layered adsorption; when the materials calcined at 400 0C with fiber and 800 0C shows C-type and correlation with Langmuir isotherms, typical monolayered adsorption in materials with microporous surface. The study of adsorption in presence of surfactants indicated that interactions among cationic surfactant with claysoil and anionic surfactant with AM prejudicing the adsorption of AM and results in less dye remotion of aqueous phase.

Submitted by Kilvya Braga (kilvyabraga@hotmail.com) on 2018-04-19T14:53:27Z No. of bitstreams: 1 MARIAUGUSTA FERREIRA MOTA - TESE (PPGEQ) 2015.pdf: 7929755 bytes, checksum: 46b508fdcbc2c553fa37592a200d2ae5 (MD5) / Made available in DSpace on 2018-04-19T14:53:27Z (GMT). No. of bitstreams: 1 MARIAUGUSTA FERREIRA MOTA - TESE (PPGEQ) 2015.pdf: 7929755 bytes, checksum: 46b508fdcbc2c553fa37592a200d2ae5 (MD5) Previous issue date: 2015-02-27 / CNPq / Este trabalho de Tese descreve a preparação de argilas organofílicas a partir da argila Brasgel e Verde-Lodo naturais que foram utilizadas como cargas para síntese de nanocompósitos via polimerização in situ em suspensão e polimerização in situ em massa-suspensão. A caracterização para avaliar as argilas organofílicas foi realizada a partir das técnicas de Difração de raios X (DRX), Espectroscopia na Região do Infravermelho por Transformada de Fourier (IV) Análise Térmica Diferencial e Termogravimétrica (ATD/TG) e ensaios de expansão (Capacidade de Adsorção e Inchamento de Foster). A produção de nanocompósitos poli(pivalato de vinila)/argila foi realizada a partir da polimerização in situ em suspensão do pivalato de vinila utilizando 2,5% e 5% de argila Brasgel ou Verde-Lodo modificadas com os sais Praepagen, Dodigen e Genamin. O processo de obtenção do nanocompósito poli(metacrilato de metila)/argila foi realizada a partir da polimerização in situ em massa-suspensão do metacrilato de metila utilizando 3% de argilas Verde-Lodo natural ou modificadas com os sais Praepagen, Dodigen e mistura de sais (Praepagen + Dodigen). Os nanocompósitos polímero/argila foram caracterizados a partir de DRX, IV, TG, Microscopia Óptica (MO), Microscopia Eletrônica de Varredura (MEV) e Calorimetria Diferencial de Varredura (DSC). Os resultados de DRX mostram a intercalação dos sais quaternários de amônio (Praepagen, Dodigen e Genamin) em todas as argilas (Verde-Lodo e Brasgel) no processo de organofilização. Os resultados de IV e ATD indicam que os sais foram incorporados à estrutura da argila, evidenciando assim o processo de organofilização. Os testes de Capacidades de Adsorção comprovaram as melhores eficiências das argilas Verde-Lodo e Brasgel organofilizadas com os sais quaternários de amônio em relação às argilas na sua forma natural independente do solvente orgânico utilizado. Os resultados dos testes de Inchamentos de Foster indicaram que as afinidades dos sais ocorreram nas argilas organofílicas avaliadas em todos os solventes orgânicos. Os resultados obtidos de DRX a partir da polimerização in situ em suspensão do pivalato de vinila/argila Brasgel ou Verde-Lodo organofílicas indicaram interações argila-polímero na forma intercalada e esfoliada. As análises de TG indicaram que ocorreu diminuição no intervalo de 3oC a 10oC da temperatura máxima de degradação assim como a diminuição da Temperatura de transição vítrea (Tg) dos nanocompósitos contendo 2,5 e 5% de argila na matriz polimérica Poli(pivalato- vinila). Para os nanocompósitos sintetizados a partir do metacrilato de metila e da argila Verde-Lodo natural e organofilizadas os resultados de DSC a partir da polimerização in situ em massa-suspensão do metacrilato de metila/argila VerdeLodo natural e organofílicas indicaram que as temperaturas de transição vítrea não foram alteradas com a adição da argila. As análises de TG mostraram que houve alterações pouco significativas na temperatura máxima de degradação e as imagens de MEV indicaram que a morfologia dos nanocompósitos obtidos com 3% de argila Verde-Lodo organofilizadas apresentaram partículas esféricas e lisas, indicando interação da argila com a matriz polimérica. / This Doctorate Thesis describes the preparation of organoclays from raw clays Brasgel and Green-Sludge, which were used as charge materials to synthesis of nanocomposites via in situ suspension and in situ mass-suspension polymerization reactions. The organoclays characterization was carried out by making use of techniques of X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Differential Thermal Analysis and Thermogravimetric Analysis (DTA/TGA), and analysis of adsorption of organic compounds (Adsorption Capacity and Foster’s experiment). The synthesis of nanocomposites poly (vinyl pivalate)/clays were performed from in-situ suspension polymerization reaction of vinyl pivalate with 2.5% w. and 5% w. of organoclays Brasgel or Green-Sludge, in which were organophilized by using the quaternary ammonium salts Praepagen®, Dodigen®, and Genamin®. The synthesis of nanocomposites poly (methyl methacrylate)/clays were realized from in-situ mass-suspension polymerization reaction of methyl methacrylate with 3% w. of raw clay Green-Sludge or organoclay Green-Sludge organophilized by using the quaternary ammonium salts Praepagen®, Dodigen®, and the mixer of these surfactants (Praepagen® + Dodigen®). The nanocomposites polymer/clay were characterized with the techniques XRD, FTIR, TGA, Optical Microscopy (OM), Scanning Electron Microscopy (SEM), and Differential scanning calorimetry (DSC). The characterization results have shown the intercalation of the cations from the quaternary ammonium salts (Praepagen®, Dodigen®, and Genamin®) within the raw clays (Green-Sludge and Brasgel) after the organophilization reaction. The results of FTIR and DTA indicate that the cations of the surfactants were incorporated in the raw clays, in which it is related the organophilization process. The results of adsorption capacity of organic compounds show that the organoclays Green-Sludge and Brasgel compared with its respective raw clay form have higher adsorption of organic compounds for all compounds analyzed. The Foster’s experiment shows that all the organoclays synthetized have high affinity with organic molecules for all compounds analyzed. The results of XRD analysis from in-situ suspension polymerization of vinyl pivalate/Brasgel raw clay or organoclays Green-Sludge have shown the clay-polymer interactions in intercalated and exfoliated forms. From TGA analysis has been observed a decreasing of the maximum temperature of degradation between 3°C and 10°C, as well the decreasing of the glass transition temperature (Tg) for the nanocomposites with 2.5% w. and 5% w. of clay in the polymeric matrix poly (vynil pivalate). By analyzing the nanocomposites synthetized from methyl methacrylate and Green-Sludge raw clay or organoclays, the results of DSC have shown that the glass transition temperature does not change with the presence of clays. The TGA analysis has demonstrated the occurrence of small variations of the maximum temperature of degradation. The SEM results indicate that the morphology of the nanocomposites synthetized from 3% w. of organoclay GreenSludge has smooth and spherical particles, which indicates the interaction between the clay within the polymeric matrix.

Made available in DSpace on 2015-05-14T13:21:47Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2304381 bytes, checksum: 383faaa5d2a0cb26ce8f49ef357849d1 (MD5) Previous issue date: 2009-03-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The selective leaching of clay minerals is an important method in the preparation of porous silicates presenting as a simple, effective and low cost route. In this study, vermiculite was submitted to acid treatment at concentrations 1, 2, 3, and 4 mol dm-3, resulting the precursor solids named as VacX (x=1 a 4), respectively. The lixiviated matrices and vermiculite reacted covalently with the organosilanes aminepropyl-, propyletilenediamine-, propyldietilenetriamine- and glycidoxypropyltrimethoxisilane (GPTS). The hybrid Vac3G, derived from silanization reaction between Vac3 and GPTS, was submitted to subsequent reactions with ethyl, propyl, butyldiamines and 2- aminepiridine resulting in the entrance of new basic centres. The products were characterized by chemical analysis, infrared spectroscopy, X-ray diffraction, 29Si and 27Al NMR in solid state, SEM, and pore volume and surface area determination. The lixiviation of sodic vermiculite originated the restructured porous solids with high superficial area showing the values133, 334, 673 e 575 m2 g-1 for VacX where X = 1,2,3,4, respectively. These solids and sodic vermiculite reacted covalently with each organosilane through methoxyl groups of silane and the hydroxyl surface of matrices. Independently of solid, it was observed that the lixiviation favored the reactivity of activated matrices compared with sodic vermiculite, showing the Vac3 as more reactive comparing with others solids. All modified solids presented high nitrogen content showing the values of 6,31 %. The set of modified vermiculites containing aminepropyl group was applied as adsorbent for divalent cations as copper and nickel in aqueous solution. These solid showed highest affinity for Ni2+ than Cu2+ ions as illustrated by Nf values of 2,97 and 1,23 mmol g-1, respectively. Clay porous solids obtained of leaching treatment of vermiculite are potential substrates for grafting of silanes showing important applications as adsorbents for contaminant species as heavy metals. / A lixiviação seletiva de argilominerais é um método importante na preparação de silicatos porosos constituindo-se em uma rota simples, efetiva e de baixo custo. Neste estudo a vermiculita foi submetida a tratamento ácido com acido nítrico nas concentrações 1, 2, 3 e 4 mol dm- 3, originando os sólidos precursores denominados VacX (x=1 a 4), respectivamente. As matrizes ativadas e a vermiculita reagiram covalentemente com os organosilanos aminopropil-, propiletilenodiamino-, propildietilenotriamino- e glicidóxipropiltrimetoxissilano (GPTS) através dos grupos metoxilas do silano e as hidroxilas da superfície das matrizes. O híbrido Vac3G, derivado da silanização do Vac3 com GPTS, sofreu reações subseqüentes com as diaminas etil, propil, butildiamina e 2- aminopiridina, possibilitando a entrada de novos centros básicos. Os diversos sólidos foram caracterizados por análise química, espectroscopia na região do IV, DRX, RMN 29Si e 27Al, MEV, volume de poro e área superficial. A lixiviação da vermiculita sódica originou sólidos porosos reestruturados com elevadas áreas superficiais cujos valores foram 133, 334, 673 e 575 m2 g-1 para os sólidos Vac1, Vac2, Vac3 e Vac4, respectivamente. Independentemente do sólido, observou-se que à medida que a lixiviação se torna mais acentuada, houve um aumento na reatividade das matrizes ativadas em relação à vermiculita original, sendo a matriz Vac3 a mais reativa diante das reações aqui propostas. Todos os sólidos modificados apresentaram altos teores de grupos orgânicos incorporados. A série de vermiculitas modificadas com o grupo aminopropil foi utilizada para a adsorção de cátions divalentes de cobre e níquel em solução aquosa, mostrando maior afinidade para os íons de Ni2+ (aq) do que para Cu2+ (aq) como ilustrado pelos valores Nf de 2,97 e 1,23 mmol g-1, respectivamente. Os sólidos porosos argilosos derivados de tratamento ácido da vermiculita são substratos potenciais para imobilização de silanos apresentando importantes aplicações como adosrventes para espécies poluentes como metais pesados.

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