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1
DISTEFANO, GAETANO. « Nanoporous dipeptide crystals as selective gas sorbents and polymerization nanovessels ». Doctoral thesis, Università degli Studi di Milano-Bicocca, 2012. http://hdl.handle.net/10281/29103.
Texte intégralRésumé :
Hydrophobic dipeptide crystals recently emerged as novel “organic zeolites” featuring tailorable pore size. In fact, seven out of nine pairwise combinations of L-isoleucine, L-valine and L-alanine amino acids crystallize according to the same charge-assisted hydrogen bond pattern, generating a family of microporous materials with right-handed 1D channels, having diameters in the sub-nanometer domain (<6Å), aliphatic environment and different degrees of helicity. The relationship between pore size and material properties was investigated with respect to gas separation, exploiting the affinity of carbon dioxide for the hydrophobic nanochannels of L-alanyl-L-valine (AV), L-isoleucyl-L-valine (IV) and L-valyl-L-isoleucine (VI). Reversible CO2 capture from an equimolar mixture of CO2 and methane, at room temperature and 1 atmosphere, was demonstrated with increasing purification performance with decrease in pore size. Dipeptide were also used as nanovessels in radical polymerizations with the aim of controlling otherwise non-specific reactions. Diene monomers (trans-1,3-pentadiene and isoprene) only yield linear 1,4-trans polymer in accordance with 1-dimensional pore geometry, while poly(acrylonitrile) (PAN) could be obtained as a stereoregular isotactic product by acrylonitrile polymerization in AV dipeptide. Finally, taking advantage of the dipeptide lability and unique thermal properties of poly(acrylonitrile), AV-PAN nanocomposites were used as a scaffold to obtain carbon replicas of the starting nanocomposite crystals (carbon micro-fibrils) showing anisotropic arrangement of the graphite domains.
2
Carvalho, Fabiana Pires de. « Blendas de poli(metacrilato de metila) e do elastômero saturado poli(acrilonitrila-g-(etileno-co-propileno-co-dieno-g-estireno) obitdas por polimerização in situ ». [s.n.], 2010. http://repositorio.unicamp.br/jspui/handle/REPOSIP/248777.
Texte intégralRésumé :
Orientador: Maria Isabel FelisbertiTese (doutorado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo:Neste trabalho foram preparadas e caracterizadas blendas de poli(metacrilato de metila), PMMA e poli[acrilonitrila-g-(etileno-co-propileno-co-dieno)-g-estireno], AES. O AES é um polímero amorfo e um material complexo, composto de uma mistura de poli(etileno-co-propileno-co-2-etilideno-5-norboneno) (EPDM), poli(estireno-coacrilonitrila) (SAN), e copolímero de enxertia EPDM-g-SAN. As blendas PMMA-AES foram obtidas por polimerização in situ, tendo-se como variáveis o solvente, agitação e atmosfera inerte, a fim de avaliar a influência destas sobre as propriedades estruturais e morfológicas das blendas. As blendas foram caracterizadas por espectroscopia infravermelho (IV), ressonância magnética nuclear de C (RMN de C), microscopia eletrônica de varredura (SEM), microscopia eletrônica de transmissão (TEM), análise dinâmico-mecânica (DMA) e resistência ao impacto. Os resultados mostraram que as blendas são imiscíveis apresentando uma morfologia complexa de domínios elastoméricos dispersos em uma matriz vítrea, dependente das condições de polimerização. Em algumas blendas, uma fração de PMMA encontra-se incluso na fase elastómerica, sugerindo uma morfologia tipo core shell ou tipo salame. Porém, essa morfologia complexa é afetada após o processo de injeção, devido ao efeito de temperatura e de cisalhamento. Extração seletiva e análise por espectroscopia infravermelho dos componentes das blendas mostraram que ocorre enxertia e/ou reticulação durante a polimerização. A sindiotaticidade do PMMA obtido em presença de AES aumenta com a quantidade de AES na blenda, devido às possíveis interações entre os grupos carbonilas do PMMA e os grupos nitrilas e fenilas da fase SAN. As blendas PMMA-AES apresentam propriedades mecânicas dependentes do teor de AES, sendo a resistência ao impacto das blendas superiores a do PMMA puro. Ensaios de envelhecimento fotoquímico acelerado mostraram que as blendas PMMA-AES apresentam queda na resistência ao impacto após envelhecimento
Abstract: In this work, blends of the poly(methyl methacrylate), PMMA, and the poly[acrylonitrile-g-(ethylene-co-propylene-co-diene)-g-styrene], AES, were prepared. AES is a complex mixture of poly(styrene-co-acrylonitrile), SAN, and poly(ethylene-copropylene-co-diene), EPDM, and the graft copolymer EPDM-g-SAN. Blends PMMA-AES were obtained by polymerization in situ, varying the solvent, the agitation and the inert atmosphere in order to evaluate their influence on the morphological and structural properties of the blends. The blends were characterized by infrared spectroscopy (FTIR), carbon-13 nuclear magnetic resonance (C NMR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic mechanical analysis (DMA) and Izod impact resistance test. The results showed that the PMMA-AES blends are immiscible and present a complex morphology. The morphology of some PMMA-AES blends is made up of an elastomeric dispersed phase in the glassy matrix, with inclusion of the matrix in the EPDM domains, suggesting core shell or salami morphology. However, this morphology is affected by the moulding injection process, due the temperature and shear effects. The selective extraction of the blends¿ components and the infrared spectroscopy showed that crosslinked and/or grafting reactions occur on EPDM chains during MMA polymerization. The syndiotactic PMMA obtained in the presence of AES increases with the amount of AES, due to the possible interaction among the carbonyl groups of PMMA and the nitrile or phenyl groups of SAN copolymer. The mechanical properties of the blends were influenced by the composition of the blend and the impact strength of the blends is superior to near PMMA. Photochemical aging tests showed that PMMA-AES blends presented decrease in the impact strength after aging
Doutorado
Físico-Química
Doutor em Ciências
3
Macêdo, Neto José Costa de. « Produção e caracterização de nanocompósitos poliméricos obtidos por polimerização em emulsão utilizando Caulinita Amazônica ». [s.n.], 2011. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266818.
Texte intégralRésumé :
Orientador: Liliane Maria Ferrareso LonaTese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: Materiais nanocompósitos poliméricos utilizando argilas naturais como reforço tem sido bastante estudados por apresentar propriedades melhoradas em relação ao polímero sem reforço. Este trabalho tem como objetivo produzir e caracterizar materiais nanocompósitos polimérico com matriz de poliestireno por meio da polimerização in situ em emulsão utilizando com nanopartícula a caulinita amazônica. Os resultados obtidos mostraram que a caulinita utilizada como reforço neste trabalho apresentou alta razão de aspecto, foi possível ser intercalada por moléculas orgânicas de dimetilsulfóxido (DMSO) e acetato de potássio (AcK). Nesta tese foram produzidos nanocompósitos com 1, 3 e 5% de caulinita modificada com DMSO e outros com 1, 3 e 5% de argila modificada com AcK. A estabilidade do látex produzido pela polimerização foi medida por dynamic light scattering (DLS). O látex com 3% de argila modificada com DMSO apresentou melhor estabilidade em relação ao com 1% de argila e ao do poliestireno puro. As análises por difração de raios X (DRX) e microscopia eletrônica de varredura de alta resolução (HRSEM) revelaram que a utilização das quantidades 1 e 3% de argila modificada com DMSO são as ideais para a obtenção de nanocompósitos. A análise termogravimétrica (TGA) dos nanocompósitos com 1 e 3% apresentou melhores propriedades térmicas em relação ao polímero sem reforço. A análise por calorimetria exploratória diferencial (DSC) mostrou que a adição de 1 e 3% de argila não alterou a temperatura de transição vítrea em relação ao polímero sem reforço. A análise térmica dinâmico-mecânica (TDMA) mostrou que o módulo de armazenamento (E') foi maior para o poliestireno puro em relação aos nanocompósitos com 1 e 3% de argila durante o aquecimento. A TDMA também mostrou que a adição de 1 e 3% de argila não influenciou a temperatura de transição vítrea (Tg). O ensaio de inflamabilidade horizontal mostrou que a taxa de queima foi menor para o nanocompósito com 3% de argila em relação ao PS e 1%. Sendo assim, foi possível produzir nanocompósitos com a caulinita. O látex obtido com 3% de argila foi o mais estável. Os nanocompósitos com quantidades de1 e 3% de argila obtiveram melhores propriedades térmicas em relação ao poliestireno sem argila. O PS puro apresentou maior E' as quantidades de 1 e 3% de argila não influenciou a Tg. O nanocompósito com 3% de argila obteve menor taxa de queima
Abstract: Polymer nanocomposites materials using natural clays as reinforcement has been extensively studied by presenting improved properties compared to unreinforced polymer. The goal of This work is to produce and characterize a polymer nanocomposites materials with matrix od polystyrene and nanoparticle by kaolinite through in situ emulsion polymerization. The kaolinite used as reinforcement in this study had a high aspect ratio, could be intercalated by organic molecules of dimethylsulfoxide (DMSO) and potassium acetate (ACK). In this thesis were produced nanocomposites with 1, 3 and 5% kaolinite modified with DMSO and others with 1, 3 and 5% clay modified with AcK. The stability of the latex produced by polymerization was measured by dynamic light scattering (DLS). Latex with 3% clay modified with DMSO showed better stability compared with the 1% clay and the pure polystyrene. Analyses by X-ray diffraction (XRD) and scanning electron microscopy, high resolution (HRSEM) revealed that use of the quantities 1 and 3% clay modified with DMSO are ideal for obtaining nanocomposites. The thermogravimetric analysis (TGA) of the nanocomposites with 1 and 3% showed better thermal properties compared to unreinforced polymer. Analysis by differential scanning calorimetry (DSC) showed that the addition of 1 and 3% clay did not change the glass transition temperature compared to the unreinforced polymer. The dynamic mechanical thermal analysis (TDMA) showed that the storage modulus (E') was higher for the pure polystyrene compared to nanocomposites with 1 and 3% clay during heating. TDMA also showed that the addition of 1 and 3% clay did not influence the glass transition temperature (Tg). The horizontal flammability test showed that the burn rate was lower for the nanocomposite with 3% clay compared to PS and 1%. Therefore, it was possible to produce nanocomposites with kaolinite. The latex obtained with 3% clay was the most stable. Nanocomposites with quantities of 1 and 3% clay had better thermal properties compared to polystyrene clay. The pure PS had a higher E' quantities of 1 and 3% clay did not affect the Tg. The nanocomposite with 3% clay had lower burn rate
Doutorado
Desenvolvimento de Processos Químicos
Doutor em Engenharia Química
4
Cocco, Daniel Rotella. « Blendas de poli(metracrilato de metila) e do elastômero ASA obtidas por polimerização in situ ». [s.n.], 2011. http://repositorio.unicamp.br/jspui/handle/REPOSIP/248768.
Texte intégralRésumé :
Orientador: Maria Isabel FelisbertiDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química.
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Resumo: Neste trabalho foram preparadas e caracterizadas blendas de poli(metacrilato de metila), PMMA, e poli[acrilonitrila-co-acrilato de butila], ASA. O ASA é um polímero amorfo e constituído de uma mistura de poli(acrilato de butila) (PBA) e poli(estireno-co-acrilonitrila) (SAN). As blendas PMMA-ASA foram obtidas por polimerização in situ, tendo sido estudada a influência do agente de transferência de cadeia, da agitação e da atmosfera inerte sobre as propriedades estruturais e morfológicas das blendas. As blendas foram caracterizadas por cromatografia de permeação em gel (GPC), espectroscopia infravermelho (IV), análise termogravimétrica (TGA), ressonância magnética nuclear de C (RMN de C), análise dinâmico-mecânica (DMA), microscopia eletrônica de varredura (SEM), microscopia eletrônica de transmissão (TEM), e resistência ao impacto e tração. Os resultados mostraram que as blendas são imiscíveis apresentando uma morfologia complexa de domínios elastoméricos dispersos em uma matriz vítrea, dependente das condições de polimerização. Em algumas blendas, uma fração de PMMA encontra-se possivelmente inclusa na fase elastómerica, sugerindo uma morfologia tipo core shell ou tipo salame. Porém, essa morfologia complexa é afetada após o processo de injeção para algumas blendas, devido ao efeito de temperatura e de cisalhamento. Extração seletiva e análise por espectroscopia infravermelho dos componentes das blendas mostraram que ocorre enxertia e/ou reticulação durante a polimerização. A sindiotaticidade do PMMA obtido em presença de ASA aumenta com a quantidade de ASA na blenda, devido às possíveis interações entre os grupos carbonilas do PMMA e os grupos nitrilas e fenilas da fase SAN. As blendas PMMA-ASA apresentam propriedades mecânicas dependentes do teor de ASA e das condições de preparo, sendo a resistência ao impacto das blendas superiores à do PMMA puro
Abstract: In this work, blends of the poly(methyl methacrylate), PMMA, and the poly[acrylonitrile-co-styrene-co-butyl acrylate], ASA, were prepared. ASA is a complex mixture of poly(styrene-co-acrylonitrile), SAN, and poly(butyl acrylate), PBA. Blends PMMA-ASA were obtained by polymerization in situ, and the influence of a chain transfer agent, stirring and the inert atmosphere on the morphological and structural properties of the blends was studied. The blends were characterized by gel permeation chromatography (GPC), infrared spectroscopy (FTIR), C nuclear magnetic resonance ( C NMR), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), lzod impact resistance test and tensile tests. The results showed that the PMMA-ASA blends are immiscible and present a complex morphology. The morphology of some PMMA-ASA blends is made up of an elastomeric dispersed phase in the glassy matrix, with a possible inclusion of the matrix in the elastomeric domains, suggesting core shell or salami morphology. However, this morphology is affected by the moulding injection process, for some blend compositions, due the temperature and shear effects. The selective extraction of the blends components and the infrared spectroscopy showed that crosslinked and/or grafting reactions occur on ASA chains during MMA polymerization. The syndiotacticity of PMMA obtained in the presence of ASA increases with the amount of ASA, due to the possible interaction among the carbonyl groups of PMMA and the nitrile or phenyl groups of SAN copolymer. The mechanical properties of the blends were influenced by the composition of the blend and conditions of polymerization, and the impact strength of the blends is superior to neat PMMA
Mestrado
Físico-Química
Mestre em Química
5
Figueiredo, Ana Rita Parente. « Novel bacterial cellulose nanocomposites prepared through in situ polymerization ». Master's thesis, Universidade de Aveiro, 2013. http://hdl.handle.net/10773/11662.
Texte intégralRésumé :
Mestrado em Biotecnologia - Biotecnologia MolecularA celulose é o polissacarídeo mais abundante na Natureza, sendo o principal componente estrutural das plantas, e com uma importância industrial elevada principalmente na indústria papeleira e têxtil. Para além das plantas, a celulose é também produzida por algumas bactérias sendo designada de celulose bacteriana (BC). A BC apresenta propriedades únicas, como a elevada retenção de água, resistência mecânica, biodegradabilidade e biocompatibilidade, que tem atraído enorme atenção em diversas áreas. Uma das principais aplicações da BC é o desenvolvimento de nanocompósitos, com aplicações desde a área biomédica, como moldes para engenharia de tecidos, até áreas mais técnicas, como materiais de embalagem. Assim, este trabalho descreve a preparação de nanocompósitos de celulose bacteriana e poli(metacrilato de 2-aminoetilo) (PAEM) por polimerização radicalar in situ, com quantidades variáveis de N,N-metilenobis(acrilamida) (MBA) como reticulande. Deste processo resultaram filmes nanocompósitos mais transparentes que a BC com propriedades mecânicas melhoradas assim como maior estabilidade térmica, em relação aos polímeros puros. Para além disso, os nanocompósitos apresentam elevada capacidade de reabsorção de água após secos e cristalinidade reduzida, relativamente à BC pura, devido à incorporação do polímero amorfo. A atividade antibacteriana nos nanocompósitos foi também avaliada utilizando E. coli bioluminescente, tendo-se verificado que apenas o nanocompósito não reticulado (BC/PAEM) apresenta actividade antibacteriana.
Cellulose is the most abundant polysaccharide in Nature being the main structural component in plants, and having a high economic importance, namely in paper and textile industries. Besides plants, cellulose is also produced by some bacteria, the so called bacterial cellulose (BC). BC has unique properties such as high water holding ability, mechanical strength, biodegradability and biocompatibility; that attracted its attention towards several fields. One of the BC applications is the development of nanocomposite materials, with applications ranging from biomedical field, as tissue scaffolds, to more technical fields such as packaging materials. So, the aim of this work was to prepare bacterial cellulose-poly(2-aminoethyl methacrylate) (PAEM) nanocomposites by in situ radical polymerization, using variable amounts of N,N-methylenebis(acrylamide) (MBA) as crosslinker agent. Several nanocomposite films were prepared, showing to be significantly more transparent than BC, with improved mechanical properties and thermal stability, in comparison with the pristine polymers. Furthermore, the nanocomposite materials show high swelling ability in water after drying as well as decreased crystallinity, in comparison with pure BC, as a result of the incorporation of amorphous polymer. The antibacterial activity of the nanocomposites prepared was also assessed towards bioluminescent E. coli from which only the non-crosslinked nanocomposite (BC/PAEM) showed to have antibacterial activity.
6
Herrera-Alonso, Jose M. « Polymer/Clay Nanocomposites as Barrier Materials Used for VOC Removal ». Diss., Virginia Tech, 2009. http://hdl.handle.net/10919/28933.
Texte intégralRésumé :
The objective of this study was to determine if the method of incorporation of a silicate layered nanoclay into a polymer matrix can affect the barrier properties of the pristine polymer in order to decrease the transport of volatile organic compounds (VOC) in indoor air. Building materials are a primary source for VOCs. These emissions are a probable cause of acute health effects and discomfort among occupants and are known to diminish productivity. The predicted concentrations of several of the VOCs emitted by structural insulated panels (SIP) are of concern with respect to health and comfort of occupants. The main issue related to the barrier membranes is the dispersion properties of the nanoclays in the polymer matrix, and the generation of a tortuous pathway that will decrease gas permeation. The tortuous pathway is created by a nanoclay filler, whose ideal exfoliated structure has high surface area, and high aspect ratio. By choosing the appropriate surfactants, the nanoclays can be modified to allow improved molecular interactions between the nanoclay and the polymer matrix.
Several studies were performed in order to evaluate the dispersion properties of the nanoclay in the polymer matrix. Polymer/clay nanocomposites barrier membranes were generated via different synthesis methods. In the first study, barrier membranes were composed of a polyurethane, Estane ® 58315, and different nanoclays, Cloisite ® 10A, Cloisite ® 20A, Cloisite ® 30B. The interaction of the polyurethane and the different surfactants used to organically modify the nanoclay was evaluated. The dispersion of the clay platelets was analyzed by varying the pre-processing method; sonication vs stirring. The decrease in gas permeability results was enhanced by the effect of pre-processing via sonciation in comparison to plain stirring. These results also suggest that nanoclay platelets modified with alkylammonium groups with one tallow tail Cloisite ® 10A and Cloisite ® 30B, allow better dispersion and penetration of the polymer within the basal spacing of the nanoclays. Once the decrease in gas permeability was confirmed, the next challenge was to study and evaluate the performance of the polyurethane/clay nanocomposites barrier membranes in the determination of diffusivity coefficients for volatile organic compounds (VOCs). This was achieved via gravimetric sorption characterization. This method allowed for characterization of the sorption and desorption phenomena of VOC in barrier membranes. Barrier membranes pretreated with sonication demonstrated lower diffusivity coefficients than those only treated with stirring. At high clay loadings, 50 wt% of nanoclay in the polymer, the decrease in diffusivity coefficients for VOCs such as butanol and toluene, was found to be one order of magnitude. Other VOCs such as decane and tetradecane also showed a significant decrease in diffusivity coefficient. The results for VOC sorption studies suggest that there is some variability.
In order to enhance the exfoliation of the clay, we decided to examine in situ polymerization of poly (n-butyl methacrylate) in the presence of nanoclay. In this study the clay wt% was kept at a low concentration of 1-5 wt%. The surface modification of natural montmorillonite, Cloisite ® Na+, was achieved via ion exchange, and the effect of pre-processing was also explored. The modification rendered a tethered group on the surface of the clay that was able to react with the monomer/oligomer chains and thus expand and exfoliate the clay platelets. Gas permeation data suggest that sonication also produced better barrier properties than its counterpart stirring. XRD diffractograms also confirmed exfoliation of the clay platelets in the poly (n-butyl methacrylate) polymer matrix. Thermogravimetric analysis (TGA) suggested that exfoliation of the clay platelets led to improved thermal stability by increasing the decomposition temperature of the membranes. A small increase in Tg also suggested restricted segmental chain motion within the clay platelets. Overall gas permeation decreased even at low clay content.
Phenomenological models such as those of Cussler and Nielsen were used to model the experimental permeation results. These models suggest that although the aspect ratio of the clay platelets is within the specifications provided by the manufacturer, it does not reflect the ideal behavior of the models. The last step of this work was to achieve exfoliation of the modified nanoclay platelets via emulsion polymerization of poly (n-butyl methacrylate). The clay concentration in the emulsion was kept the same as in the in situ polymerization. DLS results suggest a uniform distribution of the polymer/clay nanocomposites particles in the emulsion. Permeation data indicated higher permeation values than the in situ method of synthesis of the nanocomposite membranes. This led us to explore the use of glassy co-polymer of poly(n-butyl methacrylate)-poly(methyl methacrylate) as the matrix. The addition of a more glassy component in the polymer matrix led to improved barrier properties of the nanocomposite membranes. As expected, the copolymer had a higher Tg than the PMMA polymer. Analysis via phenomenological models, also suggested that the chemistry of the co-polymer played an important role in decreasing gas permeability within the polymer/clay nanocomposite membranes, although the effect of the glassy component in the matrix was not quantified by the phenomenological models.Ph. D.
7
Botan, Rodrigo 1982. « Sintese e caracterização de nanocompositos de poliestireno - hidroxido duplo lamelar via polimerização in situ ». [s.n.], 2010. http://repositorio.unicamp.br/jspui/handle/REPOSIP/267081.
Texte intégralRésumé :
Orientador: Liliane Maria Ferrareso LonaDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica
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Resumo: Ao longo da última década, nanocompósitos poliméricos vêm atraindo grande atenção da comunidade científica e industrial. Este fato se deve a notável melhora em inúmeras propriedades que estes novos materiais apresentam com uma pequena quantidade de nano-reforços. Algumas das propriedades melhoradas incluem resistência a permeação de gases e resistência a chama. Neste trabalho foram sintetizados dois tipos de hidróxido duplo lamelar (HDL), tratados com dodecil sulfato de sódio (DS), com o objetivo de incorporá-los ao estireno e sintetizar in situ nanocompósitos de Poliestireno - Hidróxido Duplo Lamelar - Dodecil Sulfato de Sódio (PS-HDL/DS). Os hidróxidos duplos lamelares tratados com dodecil sulfato de sódio (HDL/DS) foram sintetizados pelo método de co-precipitação e os nanocompósitos foram produzidos por polimerização em massa. Estes hidróxidos duplos lamelares tratados com dodecil sulfato de sódio foram caracterizados por teste de inchamento Foster, difração de raios-X (DRX) e espectroscopia no infravermelho por transformada de Fourier (FTIR). Os nanocompósitos foram caracterizados por difração de raios-X (DRX), espectroscopia no infravermelho por transformada de Fourier (FTIR), microscopia eletrônica de transmissão (MET), análise termogravimétrica (TGA) e teste de inflamabilidade. A partir dos resultados obtidos neste trabalho, verificou-se que os nanocompósitos sintetizados apresentaram uma ótima interação (esfoliação) polímero - hidróxido duplo lamelar. Dentre as propriedades dos dois novos nanocompósitos sintetizados, a resistência à chama (anti-chama), apresentou um ganho significativo quando comparada com o polímero puro, fato que possibilita uma vasta gama de aplicação destes novos materiais em diversos campos da engenharia
Abstract: Over the past decade, polymer nanocomposites have attracted considerable interests in both academia and industry. This fact has connection with notable improvement in several properties these new materials have demonstrated with a small amount of nano-reinforcements. Some superior properties of polymer nanocomposites include barrier resistance and flame retardancy. The aim of this work was to synthesize two kinds of layered double hydroxide (LDH) modified with sodium dodecyl sulfate (SDS). Both layered double hydroxides (LDHs) were incorporated into styrene by bulk free radical polymerization in order to produce the nanocomposites polystyrene - layered double hydroxide - sodium dodecyl sulfate (PS - LDH/SDS). The layered double hydroxides modified with sodium dodecyl sulfate (LDH/SDS) were prepared by co-precipitation method and the nanocomposites have been synthesized by bulk free radical polymerization. These layered double hydroxides modified with sodium dodecyl sulfate were characterized by Foster swelling, X - rays diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) and the nanocomposites were characterized by X -rays diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and flammability test. These new materials formed in this work showed great interaction polymer -layered double hydroxide (exfoliation) as well as excellent improvements on their properties when compared with pure polymer. The property flame retardancy showed improvements in the two nanocomposites synthesized and in all ratios studied, this behavior induces application of these new materials in many fields of engineering
Mestrado
Desenvolvimento de Processos Químicos
Mestre em Engenharia Química
8
Walmet, Eric Robert. « In-situ monitoring of PMMA solution polymerization with dielectric microsensors ». Thesis, Georgia Institute of Technology, 1996. http://hdl.handle.net/1853/10036.
Texte intégral
9
Soltan, Omar. « Polypropylene/filler nanocomposites by melt compounding and in situ polymerization ». Thesis, Stellenbosch : University of Stellenbosch, 2010. http://hdl.handle.net/10019.1/5310.
Texte intégralRésumé :
Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2010.ENGLISH ABSTRACT: The properties of polymer nanocomposites depend greatly on the chemistry of the polymer matrices, the nature of the nanofillers, and the way in which they are prepared. Understanding the synthesis–structure–property relationship of nanocomposites is vital for the development of advanced polymer nanocomposites with enhanced mechanical strength, stiffness and toughness for structural engineering applications. To this end, the primary aim of this study was to determine the impact that the preparation methods have on the properties of PP/filler nanocomposites, with specific focus on the in situ polymerization of propylene via the methylaluminoxane (MAO) activated metallocene catalyst technique. Two different fillers (Silica and Calcium carbonate) were used as support for the metallocene catalysts. Different supporting methodologies for the synthesis of the supported catalyst were examined. A C2 symmetric metallocene catalyst ansa dimethylsilylbis(2-methyl benzoindenyl) zirconium dichloride (MBI) was used in this study. The catalyst systems were then evaluated for propylene polymerization. The early observation shows that a direct adsorption of the metallocene onto the filler has a diminishing effect on the catalyst productivity and the fillers had to be treated with MAO in order to avoid catalyst deactivation by the filler surface. Due to the low productivity of the supported active species, the presence of soluble catalyst active species, besides the supported active species is required in the synthesis of PP nanocomposites via in situ polymerizations. The syntheses of PP nanocomposites were carried out via in situ polymerization in which different quantities of MAO treated fillers were reacted with pre-activated catalyst solution. The effect of the addition of MAO-filler on the polymerization kinetics and consequently on PP matrix microstructure was investigated. Changes in the in situ polymerization kinetics, compared to kinetics of homogeneous polymerization, were observed. Therefore, the microstructure of the polymer matrix was also influenced by the presence of nanofillers in the polymerization media. The influence of the different synthesis methods on the performance of the nanocomposites was investigated using melt-mixed PP/filler nanocomposites obtained using PP homopolymer. The dispersed phase morphologies of the different nanocomposites were investigated by transmission electron microscopy (TEM). Results show that PP nanocomposites with improved filler dispersion were achieved by in situ polymerization compared to melt-mixed nanocomposites. The influence of the synthesis method on the crystallization behaviour of PP nanocomposites was also investigated. It was found that, for the in situ prepared nanocomposites the tacticity of the PP matrix plays the major role in determining the degree of crystallinity. Results also show that when nanocomposites with comparable PP matrices are compared, the overall crystallization rate of the in situ polymerized nanocomposites is higher than that of the melt mixed nanocomposites. The mechanical properties of in situ polymerized PP and melt mixed PP nanocomposite were also investigated and compared. Due to improved nanoparticle dispersion in the PP matrix, in situ polymerized nanocomposites show enhanced mechanical properties, especially tensile and impact properties, compared to pure PP and melt mixed prepared nanocomposites when a PP matrix of equivalent microstructure was used. Finally, the melt compounding method was further investigated using different fillers and commercial PP as a matrix. The effect of filler type, size and applied surface coating on the flow and mechanical properties of PP nanocomposites was studied. The aim of this part of this study is to obtain a good trade-off between the processability and the mechanical properties and to gain insight into the cause of the emergence of different properties for nanocomposites prepared by melt compounding.
AFRIKAANSE OPSOMMING: Die eienskappe van polimeer nanokomposiete hang grotendeels af van die chemie van die polimeer matriks, die wese van die nano-vullers, en die manier waarop hierdie materiale berei word. Om die sintese-struktuureienskap verwantskap te verstaan is noodsaaklik vir die ontwikkeling van gevorderde nanokomposiete met beter meganiese eienskappe, styfheid en taaiheid vir strukturele ingenieurstoepassings Die primêre doelstelling van hierdie studie was dus om die impak van voorbereidingsmetodes op die eienskappe van PP/vuller nanokomposiete te bestudeer, met spesifieke fokus op die in-situ polimerisasie van propileen met metiel alumoksaan-geativeerde metalloseen kataliste. Twee verskillende vullers (silika en kalsium karbonaat) is gebruik as ondersteuning vir die metalloseen kataliste. Verskillende metodiek is gebruik om die ondersteunde kataliste te berei. ‘n C2 simmetriese metalloseen katalis ansa-dimetielsiliel(2-metiel bensoindeniel) sirkonium dichloride (MBI) is in die studie gebruik. Die katalissisteme is daarna evalueer vir propileen polimerisasie. Daar is oorspronklik vasgestel dat direkte adsorpsie van die metalloseen op die vuller ‘n negatiewe effek op die katalis aktiwiteit gehad het, en dat die vuller oppervlak eers met MAO behandel moes word om deaktivering van die katalis deur die vuller-oppervlak te vermy. As gevolg van die lae aktiwiteit van die ondersteunde aktiwe katalisspesies, is die teenwoordigheid van opgeloste aktiewe katalis nodig vir die voorbereiding van PP nanokomposiete via in situ polimerisasie-reaksies. Die sintese van PP nanokomposiete is uitgevoer deur in –situ polimersiasie waartydens verskillende hoeveelhede MAO-behandelde vullers gereageer is met vooraf-geaktiveerde katalis oplossings. Die effek van die byvoeging van MAO-vuller op die polimerisasie-kinetika en gevolglik op die PP matriks mikrostruktuur is ondersoek. Dit is gevind dat die mikrostruktuur van die polimeer-matriks beinvloed word deur die teenwoordigheid van nanovullers in die polimerisasie-medium. Die invloed van verskillende bereidingsmetodes op die eienskappe van die nanokomposiete is ondersoek deur smelt-vermengde PP/vuller nanokomposiete te maak. Die dispersie-fase morfologie van verskillende nanokomposiete is ondersoek deur transmissie elektron mikroskopie (TEM). Resultate wys dat PP nanokomposiete met verbeterde vuller-dispersie berkry is deur in situ polimerisasie in vergelyking met die smelt-vermengde materiale. Die effek van die sintese-metode op die kristallisasie van die PP nanokomposiete is ook ondersoek. Daar is gevind dat, vir die in situ bereide nanokomposiete, die taktisiteit van die PP matriks die grootste rol speel in die bepaling van die persentasie kristalliniteit. Resultate het ook gewys dat, wanneer nanokomposiete met soortgelyke PP matrikse vergelyk word met die in situ nanokomposiete, die laasgenoemde se tempo van kristallisasie hoer is as vir die smelt-vermengde nanokomposiete. Die meganiese eienskappe van die in situ bereide en smelt-vermengde PP nanokomposiete is ook ondersoek en vergelyk. As gevolg van verbeterde nano-partikel dispersie in die PP matriks, het die in situ bereide nanokomposiete beter meganiese eienskappe openbaar, in vergelyking met die smelt-vermenge nanokomposiete, veral trek- en slagsterkte. . Laastens is die smelt-vermengings metode verder ondersoek deur gebruik te maak van verskillende vullers en kommersiële PP as matriks. Die effek van die tipe vuller, die grootte en die oppervlakbedekking van die vullerpartikels op die vloei en meganiese eienskappe van die PP nanokomposiete is ondersoek. Die doel van hierdie studie was om ‘n balans te kry tussen prosesseerbaarheid en meganiese eienskappe en om insig te verkry oor die verskille in eienskappe wat openbaar word wanneer smeltvermengde nanokomposiete bereie word.
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Lourenço, Emerson. « Sintese e caracterização de poliestireno de alto impacto a base de elastomeros saturados de EPDM ». [s.n.], 2007. http://repositorio.unicamp.br/jspui/handle/REPOSIP/248780.
Texte intégralRésumé :
Orientador: Maria Isabel FelisbertiTese (doutorado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: O poliestireno de alto impacto (HIPS) apresenta uma ampla variedade de utilização na indústria automobilística. Porém, a sua utilização é limitada, devido à degradação foto-oxidativa de sua fase elastomérica que apresenta alto grau de insaturações. Neste contexto, o objetivo deste trabalho foi preparar e caracterizar blendas de poliestireno com os elastômeros saturados: poli(etileno-co-propileno-co-2-etilideno-5-norboneno) (EPDM) e poli(acrilonitrila-g-EPDM-g-estireno) (AES), visando a obtenção de um material com boas propriedades mecânicas e resistente à degradação fotoquímica. As blendas foram obtidas por polimerização in situ nas temperaturas de 60 °C e 80 °C. As blendas PS/AES e PS/EPDM são imiscíveis. As blendas não injetadas preparadas neste trabalho apresentam uma morfologia que consiste em glóbulos de PS ou PS/SAN envoltos em uma fina película de EPDM para blendas de PS/EPDM e PS/AES, respectivamente. Após o processo de injeção, as blendas passam a apresentar uma morfologia de fase elatomérica dispersa (EPDM) em uma matriz rígida. A maioria das blendas PS/AES e PS/EPDM apresenta maior estabilidade térmica e termo-oxidativa do que o PS puro e a degradação destes materiais é influenciada pela composição e temperatura de polimerização. Os resultados apresentados neste trabalho evidenciam a maior resistência à degradação fotoquímica das blendas PS/AES e PS/EPDM em comparação com o HIPS comercial. Um importante resultado das blendas é que as suas propriedades pós-envelhecimento são superiores às propriedades do HIPS envelhecido. Portanto, o objetivo de preparação de um material mais resistente ao envelhecimento fotoquímico foi alcançado.
Abstract: High impact polystyrene (HIPS) shows a wide range of application in automotive industry, however its utilization is restricted by the photooxidative degradation of the elastomeric phase that contains high degree of unsaturation. In this way, the aim of this work was to prepare and characterize in situ polymerized blends of polystyrene (PS) with saturated elastomers: poly(ethylene-co-propylene-co-2-ethylidene-5-norbomene) (EPDM) and poly(acrylonitrile-g-EPDM-g-styrene) (AES), aiming the preparation of a material with good mechanical properties and higher resistance to photodegradation. The blends were prepared by in situ polymerization at 60 °C and 80 °C. The PS/AES and PS/EPDM blends are immiscible. The non injected blends prepared in this work present a morphology that consists of PS or PS/SAN globes covered by a thin layer of EPDM for PS/EPDM and PS/AES blends, respectively. Whereas the injected blends show a morphology of elastomeric dispersed phase into a rigid matrix. The PS/AES and PS/EPDM show higher thermal and thermo-oxidative stability than PS, and the blend's composition and polymerization's temperature influences the degradation of these materials. The results showed in this work evidence the higher photochemical resistance PS/AES and PS/EPDM blends in comparison with commercial HIPS. An important feature of blends is that their properties after aging are superior than photoaged HIPS properties. Hence, the goal of preparing a material with higher resistance to photochemical aging than HIPS was achieved.
Doutorado
Físico-Química
Doutor em Ciências
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Gurr, Julius [Verfasser]. « Applicability of Catalytic in situ Olefin Polymerization in Wood Technology / Julius Gurr ». Hamburg : Staats- und Universitätsbibliothek Hamburg Carl von Ossietzky, 2020. http://d-nb.info/1235244059/34.
Texte intégral
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Labde, Rohan Khushal. « Preparation and Characterization of Polyethylene Terephthalate/Montmorillonite Nanocomposites by In-situ Polymerization Method ». University of Toledo / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1271126238.
Texte intégral
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Monthunya, Mpho. « Mechanistic aspects of RAFT Mediated (Co) Polymerization by in situ ¹H NMR ». Thesis, Stellenbosch : Stellenbosch University, 2013. http://hdl.handle.net/10019.1/79829.
Texte intégralRésumé :
Thesis (MSc)--Stellenbosch University, 2013.ENGLISH ABSTRACT: In this study the kinetic and mechanistic aspects of the Reversible Addition Fragmentation Chain Transfer (RAFT) process on the copolymerization of acrylonitrile (AN) and vinyl acetate (VAc) are investigated by application of in situ 1H nuclear magnetic resonance (NMR) spectroscopy. The focus is on the early stages of the reaction where the first few monomer (M) additions occur; the change in concentration of the leaving group of RAFT species as a function of time is followed. Cumyl dithiobenzoate (CDB), S-sec propionic acid O-ethyl xanthate (PEX) and O-ethyl cumyl xanthate (ECX) were selected for use in this study. The basis for RAFT agent selection was solely the fact that more activated monomers, e.g. acrylonitrile (AN) are controlled by dithiobenzoates while the less activated monomers, e.g. VAc, are controlled by xanthates. Furthermore, the behaviour of the copolymerization, where the reaction medium is composed of a RAFT agent preferring one monomer in the reaction, is largely unexplored in the literature. First, the homopolymerization of each of these monomers was studied. In accordance with the literature, the AN showed good control when CDB was used as the chain transfer agent, whereas VAc showed good control when using PEX to mediate the polymerization. More emphasis is however placed on the CDB-mediated copolymerization as it still showed some preferential consumption of AN even in the presence of the VAc comonomer, although the reaction was retarded. The copolymerization mixtures comprised the monomer pair, the RAFT agent, and the 2,2’-azobis(isobutyronitrile) (AIBN) in mole ratios as specified for each experiment. When using the total monomer to RAFT to initiator ([M]:[CDB]:[AIBN]) ratio of 5:1:0.2, the AN initialization time was found to be 150 min at 60 °C. Copolymerization of AN with VAc under similar conditions resulted in retardation of the initialization reaction; the initialization period was now about 600 min at fVAc = 0.1. In all the copolymerization reactions undertaken under the conditions described, the VAc monomer conversion was 4–6%. This means that VAc, possibly, retards the copolymerization by binding to the cumyl radicals of the CDB, which it then releases due to weak bonds formed with CDB. The results showed excellent correlation between the experimental and fitted data for the CDB- and PEX-mediated systems, but within a narrow experimental data region for ECX at fAN=0.5, thus for [AN]/[VAc] ratios 0.65–0.93.
AFRIKAANSE OPSOMMING: In hierdie studie word die kinetiese en meganistiese aspekte van die proses van die kopolimerisasie van akrilonitriel (AN) en vinielasetaat (VAs) ondersoek met behulp van in situ 1H KMR. Die fokus is op die vroeë stadiums van die reaksie waar addisie van die eerste paar monomere (M) plaasvind. Die verandering in konsentrasie van die verlatende groep as ‘n funksie van tyd is tydens hierdie stadium gemeet. Kumielditiobensoaat (KDB), S-sek-propielsuur-O-etiel-xantaat (PEX) en O-etiel-kumiel-xantaat (ECX) is vir hierdie studie gekies. Die keuses is gebaseer op die feit dat meer geaktiveerde monomere, bv. AN, deur ditiobensoaat beheer word, terwyl die minder geaktiveerde monomere, bv. VAs, deur xantate beheer word. Daar is nie baie voorbeelde in die literatuur oor die gedrag van die kopolimerisasie waar een van die monomere deur die RAFT-agent bevoordeel word nie. Eerstens is die homopolimerisasie van elk van hierdie monomeerpare (AN en VAs) bestudeer. In ooreenstemming met die literatuur, het die AN goeie beheer getoon wanneer KDB gebruik is as die kettingoordragmiddel, terwyl VAs goeie beheer in die polimerisasie getoon het in die teenwoordigheid van PEX as bemiddelingsagent. Meer klem word egter geplaas op die KDB-bemiddelde kopolimerisasie omdat dit AN by voorkeur gebruik, selfs in die teenwoordigheid van die VAs komonomeer, alhoewel daar ‘n vertraging in die reaksie is. Die reaksiemengsel het bestaan uit die monomeepaar, die RAFT-agent en die afsetter (AIBN), in verhoudings soos uiteengesit vir elke eksperiment. Vir ‘n totale monomeer tot RAFT tot afsetter ([M]:[KDB]:[AIBN]) verhouding van 5:1:0.2 was die afsettingstyd vir AN 150 min by 60 °C. Kopolimerisasie van AN en VAs onder dieselfde omstandighede het tot ‘n vertraging in die afsettingstyd gelei. Die periode was 600 min by fVAs = 0.1. Die omsetting van VAs in al die kopolimerisasiereaksies was 4–6%, wat beteken dat VAs die reaksie vertraag deur aan die kumielradikale van die KDB te bind. Die radikale word weer vrygestel a.g.v. die swak bindings tussen die twee vorms. Tweedens is die reaktiwiteitsverhoudings bepaal deur middel van die nie-lineêre kleinstekwadrate passingsmetode. Die resultate het uitstekende ooreenstemming tussen die eksperimentele en gepaste data vir die KBD- en PEX-bemiddelde sisteme getoon. Dit was egter slegs vir ‘n kort eksperimentele area vir ECX by fAN = 0.5, dus vir [AN]/[VAs] verhoudings 0.65–0.93.
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Khan, Miftah Uddin. « Synthesis of polymer nanocomposites via in-situ emulsion polymerization from functionalized nanomaterials ». Thesis, The University of Sydney, 2016. http://hdl.handle.net/2123/15999.
Texte intégralRésumé :
Dual step process for nanomaterials functionalization was developed; the first step improved the dispersibility of the nanomaterial to assist improving efficiency of the second step, reaction with oleic acid in mild condition. The functionalization was efficient for CNT (carbon nanotubes) and silica, which assisted to utilize in-situ emulsion polymerization, not commonly reported though a versatile technique, to synthesize PS/CNT and PS/silica composites. Investigation revealed improvement of nanocomposites properties and potential for practical application. For the investigated properties, oleic acid functionalization showed superiority. The pH effect on raw CNT dispersion was found to improve the CNT dispersion, which was utilized to substitute the first step of the developed dual step approach of CNT functionalization. Organic acids, i.e., methacrylic acid and acrylic acid were investigated as functionalizing agents for CNT functionalization, and found effective via relevant investigation. Chain transfer agent (CTA) was introduced in nanocomposite syntheses with oleic acid functionalized CNT to investigate its effect, which reduced the molar mass. The major difference between the nanocomposites with or without CTA was the absence of free CNT for nanocomposites with CTA. This influenced the nanocomposites properties substantially. The electrical properties of PS/CNT nanocomposites with or without CTA were tested via electrochemical impedance spectroscopy (EIS), which were found altered at wide frequency range. The measurements and modeled electrical equivalent circuits (EEC) explained the structural orientation of the CNT in nanocomposites, which was in agreement with the microscopic images. Finally, polymer brush nanocomposites were synthesized via in-situ emulsion polymerization, not commonly reported for such synthesis. Oleic acid functionalized CNT were further modified via organo silane chemistry. The developed synthesis scheme was confirmed via identification of the functional groups and polymer attachment on CNT surface. Synthesized polymer brush nanocomposites displayed enhanced thermal and gas adsorption property.
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Dai, Xiaoshu. « Synthesis and Processing of Polymers for Biomedical Applications ». Digital WPI, 2010. https://digitalcommons.wpi.edu/etd-dissertations/431.
Texte intégralRésumé :
"In situ polymerizing hydrogel systems play an important role in many tissue engineering applications. They have proven to be useful in biomedical applications that require conversion of liquid macromer solution to tissue compliant hydrogel under physiological conditions. A series of poly(ethylene glycol)-co-poly(lactate) diacrylate macromers were synthesized with variable PEG molecular weight and lactate content. The macromer compositions were confirmed by NMR spectroscopy and ion chromatography. These macromers were polymerized to form hydrogels by free radical polymerization using either redox or photochemical initiators. The current study focused on the optimization of polymerization conditions. Compressive modulus and residual acrylate analysis were used to evaluate polymerization efficiency. To characterize the network structure, the swelling ratio values were converted to the average molecular weight between crosslinks ( ) and mesh sizes (ξ) using Flory-Rehner theory. Current study suggested hydrophobic modification is desired to achieve high polymerization efficiency. Electrospinning is a developing technique to produce ultra fine fibrous structures from polymer solutions. Current research efforts have focused on understanding the effects of principal parameters such as molecular weight distribution (MWD) and polymer surfactant interactions on the morphology of the electrospun patterns. Fundamental understanding of the dilute solution rheology of the polydisperse polymer/solvent and polymer/solvent/surfactant systems was first established. Using viscometry, the on-set of entanglement concentrations could be obtained for various systems. Electrospinning was then carried out to evaluate the effects of polymer molecular weight, molecular weight distribution (MWD) and the polymer-surfactant interaction on the fiber formation and morphological features. The importance of increased chain entanglements due to high molecular weight component within the polydisperse system and the expansion of the coil dimension by binding the surfactant micelles have been recognized. The critical concentrations for incipient as well as stable fiber formation were determined. "
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Pasquale, Anthony J. « Synthesis and Characterization of Multi-Component Polymeric Materials Prepared via Free Radical Polymerization ». Diss., Virginia Tech, 2002. http://hdl.handle.net/10919/27251.
Texte intégralRésumé :
High molecular weight star-shaped polystyrenes were prepared via the coupling of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) terminated polystyrene oligomers with divinylbenzene (DVB) in m-xylene at 138 °C. Linear polystyrene oligomers (Mn = 19,300 g/mol, Mw/Mn = 1.10) were synthesized in bulk styrene using benzoyl peroxide in the presence of TEMPO at approximately 130 °C. In situ mid-infrared spectroscopy was successfully utilized to follow initiation, monomer conversion, and polymer formation. Real-time data allowed for the determination of apparent rate constants of 2.1E-5 s-1 at 132 °C and 1.2E-5 s-1 at 126 °C from the profile of the decaying styrene vinyl carbon-hydrogen (=CH2) absorbance at 907 cm-1. Coupling of the TEMPO terminated oligomers under optimum conditions resulted in a compact and dense product with a number average molecular weight exceeding 300,000 g/mol (Mw/Mn = 3.03) after 24 h, suggesting the formation of relatively well-defined star-shaped polymers.
Synthetic factors that affected the molecular weight, yield, and composition of maleic anhydride (MAH), norbornene (Nb), and tert-butyl 5-norbornene-2-carboxylate (NbTBE) terpolymers were investigated. Pseudo first order kinetic analysis using in situ FTIR indicated that the observed rate of reaction was a strong function of the Nb/NbTBE ratio with a maximum of 6.7E-5 s-1 for a 50/0/50 Nb/NbTBE/MAH monomer ratio and a minimum of 1.1E-5 s-1 for a 0/50/50 Nb/NbTBE/MAH ratio. Polymer yields were also observed to be a function of the Nb/NbTBE ratio and also decreased with increasing NbTBE. Calculated work of adhesion values (Wadh) values were observed to increase as the content of NbTBE was increased. 193 nm photoresist formulations incorporating polymers with high NbTBE content showed increased imaging performance using 193 nm light and successfully produced sharp and defined features as small as 110 nm, which was demonstrated via scanning electron microscopy (SEM). Additional functionality was introduced via the copolymerization of MAH with several norbornene (Nb) derivatives that were synthesized from facile Diels-Alder cycloaddition reactions of cyclopentadiene with a-olefins containing electron withdrawing groups. Subsequent hydrolysis of the anhydride offered further versatility and provided an avenue to introduce aqueous base solubility into Nb/MAH copolymers.Ph. D.
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Pattaro, Ana Flávia 1982. « Desenvolvimento de nanocompósitos de nylon 6 em um reator de bancada em batelada = polimerização in situ em unidade experimental ». [s.n.], 2012. http://repositorio.unicamp.br/jspui/handle/REPOSIP/266702.
Texte intégralRésumé :
Orientadores: Rubens Maciel Filho, Maria Carolina Burgos CostaDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química
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Resumo: Este projeto envolve o estudo e desenvolvimento de materiais compósitos (polímero/carga) nanoestruturados (nanocompósitos), produzidos em uma unidade experimental de polimerização, destinada ao desenvolvimento de Nylon -6 (Poliamida-6 ou PA-6) para novas aplicações como plástico de engenharia. O estudo envolve o processo de polimerização de PA-6 e nanocompósitos de PA-6/argila organofílica a partir do monômero 'ÉPSILON '-Caprolactama, como também a produção das argilas organofílicas. A mistura é feita em um reator de bancada em batelada no qual argilas bentoníticas sódica e organofilizada são adicionadas à massa reacional (matriz polimérica) durante o processo de polimerização. Os estudos para o desenvolvimento de PA-6 e de seus nanocompósitos com diferentes características pretendem correlacionar os parâmetros reacionais e operacionais às propriedades finais do polímero obtido. Para isto, estudos de simulação do processo de polimerização foram desenvolvidos, juntamente com análises experimentais do produto. Dessa forma, a PA-6 e os nanocompósitos produzidos por meio do processo de polimerização in situ foram avaliados levando em consideração a eficiência da incorporação ou grau de esfoliação da argila no polímero, a massa molecular dos polímeros/nanocompósitos obtidos e suas características térmicas, determinadas por análises de DSC e TGA. Com base nos resultados obtidos, conclui-se que a polimerização in situ de nanocompósitos de PA-6/Argila Organofílica, utilizando o processo de polimerização hidrolítica da PA-6, é um processo viável de produção de nanocompósitos, uma vez que foi observada, através da técnica de DRX, uma possível formação de nanocompósitos esfoliados e/ou intercalados. Além disso, as simulações do processo de polimerização da PA-6, com ou sem a adição de argilas, apresentaram boa concordância com os valores obtidos experimentalmente
Abstract: This project involves the study and development of composite materials (polymer / filler) nanostructured (nanocomposites), produced in an experimental polymerization unit, for the development of Nylon-6 (Polyamide-6 or PA-6) for new applications such as engineering plastics. The study involves the PA-6 and PA-6/organoclay nanocomposites polymerization process using 'ÉPSILON '-caprolactam monomer, as well as the production of organoclays. The blend is done in a batch reactor in which organophilizated and sodic bentonite are added to the reaction mass (polymeric matrix) during the polymerization process. The studies on the development of PA-6 and its nanocomposites with different characteristics intend to correlate the reaction and operational parameters to the final properties of the obtained polymer. Thus, simulation studies of the polymerization process were developed, along with experimental analysis of the product. In this sense, PA-6 and nanocomposites produced by the in situ polymerization process were evaluated taking into account the incorporation efficiency or the exfoliation rate of the clay in the polymer, the molecular weight of polymers / nanocomposites obtained and their thermal characteristics, determined by DSC and TGA analysis. Based on these results, the conclusion is that the in situ polymerization of PA-6 and PA-6/organoclay nanocomposites using the PA-6 hidrolitic polymerization process, is a viable process for the production of nano-composites, since it was observed through the DRX technique a possible formation of exfoliated and/or intercalary nanocomposites. In addition, the PA-6 polymerization process simulations, with or without the addition of clays, presented a good fit with the experimental values
Mestrado
Desenvolvimento de Processos Químicos
Mestre em Engenharia Química
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Lizotte, Jeremy Richard. « Synthesis and Characterization of Tailored Macromolecules via Stable Free Radical Polymerization Methodologies ». Diss., Virginia Tech, 2003. http://hdl.handle.net/10919/28998.
Texte intégralRésumé :
The stable free radical polymerization methodology for production of controlled macromolecules was investigated using a novel monomer, 2-vinylnaphthalene. Initial polymerizations resulted in molecular weight distributions typical of conventional free radical polymerization techniques (>2.0). Manipulation of the initiator concentration and the molar ratio of initiator to nitroxide demonstrated no significant control over the resulting polymer products. Analysis of the polymerization kinetics for a 2-vinylnaphthalene polymerization performed in the presence and absence of the free radical initiator revealed identical monomer consumption profiles as well as pseudo first order kinetics indicating a significant degree of the thermal polymerization was occurring at the polymerization temperature (130°C). Comparison of the thermal polymerization propensity of 2-vinylnaphthalene and styrene revealed an increased tendency for 2-vinylnapthahlene to undergo thermal polymerization. Styrene is considered highly active in its propensity to thermally polymerize. However, an Arhenius analysis using in situ FTIR was employed to determine the activation energy for the thermal polymerization of styrene and 2-vinylnaphthalene. The 2-vinylnaphthalene activation energy for thermal polymerization was determined for the first time to be almost 30 kJ/mol less than styrene. A novel modified Mayo mechanism was proposed for the 2-vinylnaphthalene thermal initiation mechanism. Moreover, this thermal initiation was employed to initiate nitroxide mediated polymerizations of styrene. This first use of a 2-vinylnaphthalene initiating system resulted in polystyrene with a large macrocyclic initiating fragment. The presence of the initiating moiety was studied using both UV-Vis spectroscopy and 1H NMR spectroscopy.
The extension of stable free radical polymerization to the acrylate monomer family was examined using a novel nitroxide mediator, N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide (DEPN). The synthesis of DEPN was monitored using in situ FTIR spectroscopy to determine optimum reaction conditions. The purified nitroxide was subsequently employed in the synthesis of various block and random acrylate copolymers. The production of a unique amphiphilic block copolymer consisting of acrylic sequences was achieved. Poly(t-butyl acrylate-b-2ethylhexyl acrylate-b-t-butyl acrylate) was synthesized using the SFRP process. The t-butyl functionalities were subsequently removed in a post-polymerization acid catalyzed hydrolysis. The effect of steric bulk and electronic factors on the resulting SFRP process was also investigated and revealed similar polymerization kinetics for various alkyl acrylates. However, addition of a hydroxyl containing monomer, 2-hydroxyethyl acrylate, resulted in an increase in the polymerization rate up to 2 times. The rate enhancement was attributed to hydrogen bonding effects and this was confirmed using the unprecedented addition of dodecanol, which also demonstrated a significant rate enhancement.
Block copolymers were also achieved using a novel difunctional nitroxide synthesized from 4-hydroxy TEMPO and 1,6-hexamethylene diisocyanate. The identity of the nitroxide was confirmed using mass spectrometry and 1H NMR. The dinitroxide was used in the polymerization of styrene and subsequently used to produce symmetric ABA triblock copolymers with t-butyl styrene using a unique two-step polymerization route. In addition, the dinitroxide demonstrated an increased tendency for decomposition due to the complex mediation equilibrium. The decomposition was studied using GPC to evaluate the decomposition effects on the polymerization.
Results of the research efforts presented herein are written as individual research reports with contributing authors and pertinent literature reviews presented at the beginning of each chapter.Ph. D.
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Elgmati, Rugia Ali. « Electrochemical in-situ polymerization of graphene oxide/conducting star copolymer nanocomposite as supercapacitor electrode ». University of the Western Cape, 2017. http://hdl.handle.net/11394/5479.
Texte intégralRésumé :
>Magister Scientiae - MScThese days there are deep concerns over the environmental consequences of the rate of consumption of energy from non-renewable sources because of the accelerated increase in greenhouse effect. There is, therefore, increasing interest in research activities on renewable energy systems (e.g., supercapacitors, batteries, fuel cells and photovoltaic cells) and their materials. Supercapacitor materials have attracted much attention because of their high energy storage capacity, large surface area, high specific power density (watts/kg) and low cost. The development of advanced supercapacitor devices requires active electrode materials with high storage capacity and dispensability. Graphene oxide-dendritic star copolymer nanocomposites are fascinating as electrode materials, both scientifically and technologically, due to their exceptional properties, including light weight and high potential.
2020-08-31
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Zakrzewska, Sabina. « Synthesis of α-olefin-based copolymers and nanocomposites ». Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2015. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-166518.
Texte intégralRésumé :
The research goal of this work was dedicated to improvement of the properties and enhancement of the application potential of commodity polymer based on polyolefins by choosing different synthesis routes to create new structures and materials. More precisely, the presented study explores different aspects of metallocene and post-metallocene catalyzed olefin polymerization leading to synthesis of novel copolymers and nanocomposites.
The first part of this thesis deals with controlled polymerization of α-olefins catalyzed by post-metallocenes.
Bis(phenoxyamine) zirconium complexes with [ONNO]-type ligands bearing cumyl (bPA-c) and 1-adamantyl (bPA-a) ortho-substituents were applied. For the polymerization catalyzed by bPA catalyst quasi-living kinetic character is proposed. The bPA catalyst was applied for synthesis of block copolymers by employing the strategy of sequential monomer addition. The blocky structure of the copolymer was successfully achieved and confirmed by NMR techniques. Moreover, the monomodal distribution of molar mass in SEC chromatogram confirmed the absence of homopolymers.
In the second part of the work new defined comb-like copolymers (CLC) having a poly(10-undecene-1-ol) (PUol) backbone and densely grafted poly(ε-caprolactone) (PCL) side chains are presented. These copolymers were synthesized in two steps by means of metallocene polymerization followed by ring opening polymerization. Copolymers with varied and adjustable graft length (PCL segments) were synthesized. It was proved that the melting and crystallization temperatures of the CLC correlate with the PCL side chain length, i.e. longer chains result in higher Tm and Tc,o values. The melting enthalpy was found to be asymptotically dependent on the length of PCL side chains. The bulk morphology of the comb-like copolymers is proposed to be lamellar as judged from the TEM micrographs.
The third part of the thesis is focused on the synthesis of polypropylene nanocomposites via in situ polymerization. Thereby, organomodified aluminumphosphate with kanemite-type layered structure (AlPO-kan) has been used as novel filler. Melt compounding composites were prepared for comparison purposes to evaluate the influence of in situ synthesis on the dispersion quality of the filler in polymer matrix. Melt compounding of neat AlPO-kan with PP did not lead to formation of nanocomposites. TEM images show macro-composites with the lamellar solid remaining agglomerated. On the contrary, in situ polymerization of propene yielded materials with exfoliated nanocomposite morphology. In XRD, diffractions of the AlPO-kan pilling of layers are not detectable. It can be concluded that the primary existing layers are delaminated. Very fine distribution of the filler in the polypropylene matrix has been impressively demonstrated by TEM.
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Lakshmanan, Nethaji, et Logarasu Rangasamy. « Polymer Electrochromism on PEDOT coated fibres and design of electrochromic pixel using coated fibres ». Thesis, Linköping University, The Department of Physics, Chemistry and Biology, 2008. http://urn.kb.se/resolve?urn=urn:nbn:se:liu:diva-15101.
Texte intégralRésumé :
Polymer electrochromism on PEDOT coated fibres was successfully achieved. The electrochromic property of the PEDOT polymer is an excellent property. This feature gives way to many more research works at present and in the future also. The electrochromic property of the PEDOT polymer is utilized in this thesis work to design an electrochromic display pixel.
The polymer coating over the fibres were obtained by using In-situ polymerization technique. The coated-fibres were used to design a display-pixel. Electrochemistry is performed successfully on the designed pixel to study electrochromism over the pixels. An electrochemical fibre transistor is designed successfully using the polymer coated fibres.
Polymer Electrochromism on PEDOT coated fibres
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Sulcis, Roberta. « Preparation of composites through in-situ catalytic homo-and co-polymerization of olefins in the presence of Ground Tire Rubber ». Doctoral thesis, Scuola Normale Superiore, 2007. http://hdl.handle.net/11384/85809.
Texte intégral
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Pavani, Matheus 1989. « Persistência de fragrância em cabelo : influência das propriedades físico-químicas e da encapsulação de óleo essencial ». [s.n.], 2014. http://repositorio.unicamp.br/jspui/handle/REPOSIP/317622.
Texte intégralRésumé :
Orientadores: Marcos José Salvador, Inés JoekesDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Biologia
Made available in DSpace on 2018-08-24T13:48:04Z (GMT). No. of bitstreams: 1 Pavani_Matheus_M.pdf: 3408518 bytes, checksum: bdb62efa906a9a04de3a371f12ecd0f0 (MD5) Previous issue date: 2014
Resumo: A fragrância de um produto cosmético é um aspecto importante para determinar seu desempenho. É crescente o emprego de produtos naturais, bem como de fragrâncias encapsuladas na indústria cosmética. Entretanto, há escassos estudos descrevendo o perfil de liberação de fragrâncias a partir de matrizes complexas, muito menos a partir de cabelos. Este trabalho investigou a interação de uma fragrância livre ou encapsulada em cabelos virgens caucasianos. Óleo essencial de capim-limão (Cymbopogon citratus DC. Stapf), livre ou encapsulado, foi empregado como fragrância em formulações de xampu e condicionador sem enxágue. O processo de encapsulação deu-se por meio de polimerização in situ da resina de melamina-formaldeído, variando-se parâmetros reacionais como velocidade de agitação, acidificação do meio e teor de óleo essencial. Os perfis de liberação da fragrância proveniente de mechas de cabelo, tratadas com as formulações obtidas, foram tomados ao longo do tempo (0 a 12 h), com amostragem por microextração em fase sólida (SPME) e análise por cromatografia gasosa acoplada à espectrometria de massas (CG-MS). A liberação das substâncias da fragrância na forma livre variou em função do tipo de formulação cosmética (xampú ou condicionador sem enxágue). Neste caso, a persistência delas na fibra capilar se correlacionaou com seus valores de coeficiente de partição óleo-água (logP). Micropartículas esféricas (dH = 9 ± 1 µm) e rendimento de processo de 86 % foram obtidos com decaimento lento de pH aliado a agitação vigorosa durante a reação de formação. Estas partículas promoveram liberação sustentada para os constituintes linalol e citral (12 e 2 vezes mais duradoura em relação à forma livre, respectivamente), mostrando um aumento da persistência da fragrância encapsulada quando inserida em formulação sem enxágue, e modificando as forças de interação cabelo¿fragrância
Abstract: Fragrance plays an important role in the performance of a cosmetic formulation. The use of natural products in the cosmetic industry as well as encapsulated fragrances is growing. However, there are few studies describing the release profile of fragrances from complex matrices, much less from Human hair. This work investigates the interaction of a fragrance composition (free or encapsulated) with un-treated Caucasian hair. Lemongrass essential oil (Cymbopogon citratus DC. Stapf) was employed as fragrance in rinse-off shampoo or leave-on formulations. Encapsulation was performed by in situ polymerization of melamine and formaldehyde monomers, changing reaction parameters such as stirring rate, pH decay, and essential oil content. Fragrance release profiles from the hair tresses treated with the abovementioned formulations were acquired over the time (0 to 12 h) with a solid phase microextraction (SPME) device, and analyzed by gas chromatography-mass spectrometry (GC-MS). The release of free form fragrance constituents depended on the type of cosmetic formulation (shampoo or leave-on), but its persistence on hair fiber was correlated with its oil-water partition coefficient (logP) value in both cases. Spherical microparticles (dH = 9 ± 1 µm) and 86 % yield were obtained with slow pH decay combined with vigorous stirring during the encapsulation process. Sustained release of the fragrant components linalool and citral (12 times and twice longer-lasting compared to the free form, respectively) was found, showing an increased persistence of the encapsulated fragrance when inserted in the leave-on formulation and changing perfume¿hair interaction
Mestrado
Fármacos, Medicamentos e Insumos para Saúde
Mestre em Biociências e Tecnologia de Produtos Bioativos
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Travain, Silmar Antonio. « Caracterização elétrica, óptica e morfológica de filmes de polianilina para aplicações em dispositivos ». Universidade de São Paulo, 2006. http://www.teses.usp.br/teses/disponiveis/76/76132/tde-09102008-105022/.
Texte intégralRésumé :
Este trabalho descreve o estudo de preparação dos filmes de polianilina, Pani, depositados pelo método de polimerização in-situ para serem utilizados em dispositivos poliméricos emissores de luz (PLEDs) e em sensores químicos e de flexão mecânica. É descrita a síntese química da Pani, a produção de filmes pelo método de polimerização in-situ, o estudo do seu crescimento usando a espectroscopia de UV-Vis e as características morfológicsa da superfície pela técnica de varredura de AFM. Filmes de Pani depositados pela técnica in-situ sobre eletrodos interdigitados foram caracterizados através de medidas de condutividade elétrica contínua e alternada em função da temperatura e da dopagem do material. Os resultados elétricos obtidos, típicos de sistemas sólidos desordenados, foram interpretados usando o modelo de condução de Dyre. Investigou-se o uso de filmes finos de Pani como camada injetora de portadores de carga em PLEDs para diferentes métodos de conversão do precursor poli(xilideno tetrahidrotiofeno), PTHT, em poli(-fenileno vinileno), PPV. Mostrou-se que a camada de Pani pode ser usada como janela transparente da emissão luminosa do PPV, o que diminui a tensão de operação do PLED e protege o eletrodo de ITO contra a corrosão durante o processo de conversão. São mostrados estudos exploratórios de sensores de Pani depositados sobre o substrato de poli (tereftalato de etileno) (PET) para aplicação em dispositivos para medidas de pH de solução e de flexão mecânica.This work shows the study of Pani film prepared by the in-situ deposition technique aiming its use im polymeric light emission diodes (PLEDs) and in chemical sensors and of flection mechanics. The sysnthesis of the Pani, the production of films by the in-situ method, the film growth probed by UV-Vis spectroscopy and its surface morphology characteristics probed by the scanning AFM microscope are presented. Such in-situ films were deposited on the top of interdigitated electrodes and characterized usign ac and dc conductivity measurements as function of temperature and of the material doping level. The electric results were typical of non ordered materials and interpreted using the Dyre´s conduction model. It was investigated the use of Pani films as carrier layer injection in PLEDs employing different of conversion of poly(xylylidene tetrahydrothiophenium), PTHT, in to poly(-phenylene vinylene), PPV. It was showed that the Pani film act as a transparent window for the PPV light emission, the onset voltage of the PLED decreased and the Pani layers protects the ITO electrode against the corrosion during the conversion of the PTHT in to PPV. Exploratory studies were also performed using the Pani layer deposited on the top of a poly (ethylene terephtalate) substrate aiming its application for measuring the pH of a solution and as mechanical bending sensor.
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Saidi, Louise. « Bacterial cellulose/poly(N-methacryloyl glycine) nanocomposites prepared by in situ polymerization for biomedical applications ». Master's thesis, Universidade de Aveiro, 2015. http://hdl.handle.net/10773/14842.
Texte intégralRésumé :
Mestrado em Ciências e Engenharia de MateriaisCellulose is the most abundant polysaccharide on earth, it is the main structural component of plant cell walls. However, it is also produced by bacteria in a purer form called bacterial cellulose (BC). BC is well known and mainly used in several field for its peculiar 3D network that confers to it outstanding properties such as water high holding capacity, high porosity and excellent mechanical properties. BC is also biodegradable and biocompatible. Among the different fields of application, BC is greatly used, in its pure form or in the form of nanocomposites, in the biomedical field, as artificial blood vessels, controlled drug delivery systems, and in tissue engineering, etc. The present study reports the development of new nanocomposites made from BC and an acrylate polymer namely the poly(N-methacryloyl glycine) (PMGly) through an in situ free radical polymerization using N,N-methylenebis(acrylamide) (MBA) as cross linker agent. Several nanocomposites with different amounts of polymer and BC were prepared and characterized. The obtained nanocomposites displayed improved mechanical properties, thermal stability and crystallinity when compared to the homopolymer. Moreover, their cytotoxicity (MTT tests) in regard to HaCaT skin cells was also evaluated, and the results showed that the new nanocomposites were not cytotoxic until 48 hours of exposure. Finally, two different potential applications were tested for these materials, namely as systems for drug release and as scaffolds for bone regeneration. First, the membranes were tested as drug delivery system for diclofenac. The impregnation of the drug into the membrane was successfully assessed and the drug dissolution was studied for different pH values (pH 7.4 and 2.1) at 37 ºC during 24 hours. However, the drug release was always accompanied by polymer dissolution. Secondly, the membranes were immersed in a simulated body solution in order to grow hydroxyapatite particles on their surface, aiming an application in bone tissue engineering. However, this growth wasn’t detected by XRD and SEM analysis.
A celulose é o polissacarídeo mais abundante na terra, e é o principal constituinte das paredes celulares das plantas. Contudo, também é produzida por bactérias numa forma mais pura chamada “celulosa bacteriana” (BC). A BC é já bem conhecida e é utilizada em vários campos principalmente devido à sua estrutura 3D que lhe confere excelentes propriedades, nomeadamente elevada capacidade de retenção de água, elevada porosidade e excelente desempenho mecânico. A BC é também, biodegradável e, biocompatível. Em termos de aplicações, a BC é amplamente usada na área biomédica na forma pura ou de nanocompósitos como vaso sanguíneos artificiais, sistemas para libertação controlada de fármacos e na engenharia de tecidos, etc. Este trabalho relata o desenvolvimento de novos nanocompósitos de celulose bacteriana e poli(N-metacriliol glicina) preparados por polimerização radicalar in situ usando N,N-methylenebis(acrylamide) (MBA) como agente reticulante. Foram preparados e caracterizados vários nanocompósitos com quantidades variáveis de polímero e BC. Os materiais nanocompósitos obtidos apresentaram propriedades mecânicas e térmicas melhoradas assim como valores de cristalinidade superiores quando comparados com o polímero puro. A citotoxicidade (teste MTT) dos nanocompósitos em relação às celulas da pele (HaCaT) foi também avaliada e os resultados demonstraram que as membranas não são citotóxicas até 48 horas de exposição. Finalmente, foram testadas duas potenciais aplicações para os materiais obtidos, nomeadamente como sistemas de libertação de fármacos e como suportes para a regeneração óssea. Neste sentido, as membranas foram impregnadas com um fármaco, o diclofenac, e estudada a sua dissolução em condições de pH diferentes (pH 7.4 e 2.1) a 37 ºC durante 24h. No entanto, verificou-se que durante a libertação do fármaco ocorreu também a dissolução do polímero. Em segundo lugar, as membranas foram biomineralizadas com o objectivo de crescer partículas de hidroxiapatite na sua superfície para potencial aplicação na regeneração óssea. Contudo, o crescimento destas nanopatículas não foi confirmado por XRD e SEM.
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PIGA, DANIELE. « FROM HIGH-PRESSURE TO IN-SITU POLYMERIZATION : DESIGN AND SYNTHESIS, NEW CHALLENGING OF POROUS MATERIALS ». Doctoral thesis, Università degli Studi di Milano-Bicocca, 2019. http://hdl.handle.net/10281/241207.
Texte intégralRésumé :
Il lavoro si è diviso in due parti. La prima parte è stato uno studio sulle capacità di adsorbimento di gas dei materiali porosi, in particolare sulla capacità di sistemi porosi organici nello stoccaggio di metano. Il lavoro si è basato su uno studio sistematico di una serie di materiali porosi organici, delle capacità di stoccaggio di metano ad alta pressione. I materiali sintetizzati sono stati confrontati con alcuni materiali porosi commerciali con alte prestazioni nello stoccaggio e hanno evidenziato un aumento delle quantità di gas possibilmente trasportabile al loro interno. I materiali sono stati confrontanti anche con i metodi comunemente usati per il trasporto di metano, risultando dei potenziali candidati per tale applicazione, considerando la facilità di produzione e la stabilità sia termica che chimica. Un'altra serie di materiali porosi con leggere modifiche alla struttura principale, ha dimostrato invece, la possibilità di modificare l'interazione del materiale con i differenti gas andando a ottenere dei composti con leggere modifiche strutturali ma con interazioni fisiche differenti.
In una seconda parte mi sono concentrato sull'utilizzo dei pori di questi materiali come reattori per polimerizzazioni confinate. Il lavoro ha portato allo sviluppo per la prima volta della polimerizzazione anionica all'interno di tali materiali. Questa nuova e innovativa tecnica ha permesso di produrre polimeri con tatticità distinta e catene isolate. Successivamente, si è deciso di ancorare chimicamente il materiale poroso al polimero in crescita. Questo ha portato a polimeri con strutture diverse da quelle ottenibili con le classiche polimerizzazioni e allo sviluppo di un nuovo tipo di composito completamente carbonioso e chimicamente legato che impedisce il problema dello smiscelamento. Successivamente, l'utilizzo di materiali con pori monodimensionali, ha portato allo sviluppo di poliacrilonitrile all'interno dei canali del materiale. Il poliacrilonitrile successivamente è stato convertito attraverso trattamenti termici in fibra di carbonio, all'interno del materiale poroso. Il trattamento termico del poliacrilonitrile all'interno dei pori ha portato ad una struttura con meno difetti rispetto al trattamento in bulk, la miglior struttura, per successivi trattamenti termici porterà ad una fibra di carbonio con caratteristiche meccaniche migliori di quelle di una sintesi in bulk.The work was divided into two parts. The first part was a study on the gas adsorption capacity of porous materials, in particular on the capacity of porous organic systems in methane storage. The work was based on a systematic study of a series of organic porous materials, of high pressure methane storage capacities. The synthesized materials were compared with some commercial porous materials with high performance in storage and showed an increase in the quantities of gas possibly transportable inside them. The materials were also compared with the methods commonly used for the transport of methane, resulting in potential candidates for this application, considering the ease of production and both thermal and chemical stability. Another series of porous materials with slight changes to the main structure, has shown, however, the possibility of modifying the interaction of the material with the different gases going to obtain compounds with slight structural changes but with different physical interactions. In a second part I focused on using the pores of these materials as reactors for confined polymerizations. The work led to the development of anionic polymerization in these materials for the first time. This new and innovative technique has allowed us to produce polymers with distinct tactics and isolated chains. Subsequently, it was decided to chemically anchor the porous material to the growing polymer. This has led to polymers with structures different from those obtainable with the classic polymerizations and to the development of a new type of completely carbonaceous and chemically bound composite that prevents the problem of de-mixing. Subsequently, the use of materials with one-dimensional pores, led to the development of polyacrylonitrile within the material channels. Polyacrylonitrile was subsequently converted through carbon fiber thermal treatments into the porous material. The thermal treatment of polyacrylonitrile inside the pores has led to a structure with fewer defects than the bulk treatment, the best structure, for subsequent heat treatments will lead to a carbon fiber with mechanical characteristics better than those of a bulk synthesis.
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Kop, Erhan. « Synthesis And Characterization Of Mechanical, Thermal And Flammability Properties Of Epoxy Based Nanocomposites ». Master's thesis, METU, 2008. http://etd.lib.metu.edu.tr/upload/12609124/index.pdf.
Texte intégralRésumé :
Polymer-clay nanocomposites have received a lot of attention because of outstanding improvements in properties when compared with neat polymeric materials. The aim of this study was to prepare epoxy-clay nanocomposites by mixing organically modified montmorillonite with an epoxy resin and to investigate the effects of clay content on the mechanical, thermal and flammability properties of the resultant nanocomposites. The production of the epoxy-clay nanocomposites was accomplished by in-situ polymerization. In the nanocomposite synthesis, organically modified clay content was varied from 1 wt.% to 9 wt.%. Araldite LY556 epoxy resin, Aradur 918 anhydride hardener, and DY070 imidazole type accelerator were used in the epoxy system. Closite 30B, an organoclay modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH), was used as the clay material.
X-ray diffraction results showed that d-spacing between the platelets of organoclay increased from 1.80 nm to 4.4 nm. The microstructures of nanocomposites were investigated by scanning electron microscopy (SEM). The SEM micrographs indicated that at 1 wt.% clay loading, no clay aggregates were observed. On the other hand, beyond 1 wt.% clay loading, formation of clay agglomerations was observed. Tensile strength and tensile strain values of nanocomposites decreased with clay loading. The tensile strength value of neat epoxy resin decreased from 55 MPa to 29 MPa with 9 % clay loading. On the other hand, Young’
s modulus increased with clay content and a maximum value was obtained at 5 wt. % clay loading. At 9 % clay loading, Young&
#8217
s modulus value was 26 % higher than that of the neat epoxy resin. Impact strength property had a minimum value at 7 wt. % clay content. Flexural strength and flexural strain at break property behaved in a similar trend. They had a minimum value at 5 % clay loading. At this clay loading, flexural strength value became approximately 43 % lower compared to the flexural strength of the neat epoxy resin. On the other hand, at 9 wt.% clay loading flexural modulus value increased approximately 48 % compared to the pure epoxy resin. Up to 7 wt.% clay ratio, initial decomposition temperature of epoxy resin was slightly improved. Also, according to TGA results, amount of char formation increased with clay loading. DSC results indicate that Tg of the cured nanocomposite resins decreased from 147 oC to 129 oC with 9 wt. % clay loading. The flammability of neat epoxy resin was not significantly affected with Cloisite 30B addition.
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Lin, Feng. « Preparation and Characterization of Polymer TiO2 Nanocomposites via In-situ Polymerization ». Thesis, University of Waterloo, 2006. http://hdl.handle.net/10012/2849.
Texte intégralRésumé :
Polymer nanocomposites are already a part of many important of worldwide businesses: automotive (molded part in cars), electronics and electrical engineering, household products, packaging industry, aircraft interiors, appliance components, security equipments. Among many nanocomposite precursors, TiO2 nanopowder is increasingly being investigated due to its special properties. The objective of this work is to synthesize and characterize polymer-TiO2 hybrid nanocomposites. When dispersed at the nanoscale level TiO2 could act as visually transparent UV filters and high-thermomechanical-performance materials. The synthesis strategy involved two steps. Firstly, aggregated TiO2, as received, was modified by 3-trimethoxysilyl propylmethacrylate aimed at altering its surface characteristics. The effect of modifier concentration on changing the physicochemical properties of TiO2 surface was evaluated. Size distribution of unmodified and modified TiO2 nanopowders was measured using a particle size analyzer. The qualitative and quantitative grafting of vinyl groups on TiO2 surface was investigated with Fourier transform-infrared (FTIR) and proton nuclear magnetic resonance (1H-NMR) spectroscopy. Secondly, styrene monomer was then added to carry out copolymerization with vinyl groups on the modified TiO2 by free radical initiator 2,2-azobis isobutyronitrile (AIBN) in bulk medium. FTIR spectra confirmed the formation of nanocomposites with polystyrene chains chemically linked to the surface of TiO2 nanopowders. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) indicated that the resulting nanocomposites displayed higher thermal stability and maintained similar glass transition temperatures (Tg) compared with pure PS. Ultraviolet ?visible spectroscopy (UV-Vis) investigated that these nanocomposites have improved optical properties potentially acting as visually transparent UV filters. Such incremented properties were attributed to the nancoscale dispersion (20-50nm size) of TiO2 into polystyrene matrix, which morphology was observed by scanning electron microscopy (SEM).
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Deshpande, Anushree. « Synthesis and Characterization of in-situ Nylon-6/Epoxy Blends ». University of Cincinnati / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1480328231030708.
Texte intégral
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Punchaipetch, Prakaipetch. « Epoxy + Liquid Crystalline Epoxy Coreacted Networks ». Thesis, University of North Texas, 2000. https://digital.library.unt.edu/ark:/67531/metadc2705/.
Texte intégralRésumé :
Molecular reinforcement through in-situ polymerization of liquid crystalline epoxies (LCEs) and a non-liquid crystalline epoxy has been investigated. Three LCEs: diglycidyl ether of 4,4'-dihydroxybiphenol (DGE-DHBP) and digylcidyl ether of 4-hydroxyphenyl-4"-hydroxybiphenyl-4'-carboxylate (DGE-HHC), were synthesized and blended with diglycidyl ether of bisphenol F (DGEBP-F) and subsequently cured with anhydride and amine curing agents. Curing kinetics were determined using differential scanning calorimetry (DSC). Parameters for autocatalytic curing kinetics of both pure monomers and blended systems were determined. The extent of cure for both monomers was monitored by using Fourier transform infrared spectroscopy (FT-IR). The glass transitions were evaluated as a function of composition using DSC and dynamic mechanical analysis (DMA). The results show that the LC constituent affects the curing kinetics of the epoxy resin and that the systems are highly miscible. The effects of molecular reinforcement of DGEBP-F by DGE-DHBP and DGE-HHC were investigated. The concentration of the liquid crystalline moiety affects mechanical properties. Tensile, impact and fracture toughness tests results are evaluated. Scanning electron microscopy of the fracture surfaces shows changes in failure mechanisms compared to the pure components. Results indicate that mechanical properties of the blended samples are improved already at low concentration by weight of the LCE added into epoxy resin. The improvement in mechanical properties was found to occur irrespective of the absence of liquid crystallinity in the blended networks. The mechanism of crack study indicates that crack deflection and crack bridging are the mechanisms in case of LC epoxy. In case of LC modified epoxy, the crack deflection is the main mechanism. Moreover, the effect of coreacting an epoxy with a reactive monomer liquid crystalline epoxy as a matrix for glass fiber composites was investigated. Mechanical properties of the modified matrix were determined by tensile, flexural and impact testing. The improvement in toughness of the bulk matrix by the addition of a LCEs is seen also in the composites. The improvement is related to the enhancement of adhesion between the glass fibers and the matrix.
31
Ben, Mabrouk Aymen. « Elaboration de nanocomposites à base de whiskers de cellulose et de polymère acrylique par polymérisation in situ ». Thesis, Grenoble, 2011. http://www.theses.fr/2011GRENI089/document.
Texte intégralRésumé :
A stable aqueous nanocomposite dispersion containing cellulose whiskers and a polymer matrix was prepared via miniemulsion polymerization. We were able to prepare a stable dispersion with a 250 wt % solid content and a cellulose whiskers content ranging from 1 up to 5 wt % based on polymer content. Cellulose nanocrytals suspension was mixed with monomers phase in presence of anionic or cationic surfactant and a stabilizing additive acting as a hydrophobe. After sonication for a short time to obtain a stable emulsion of small droplet polymerisation reaction was trigged by the addition of the initiator. The nanocomposite dispersion was characterized using dynamic light scattering, ζ-potential measurement, transmission electron microscopy (TEM), atomic force microscopy (AFM) and FE-SEM. It was found that the particle size of the prepared suspensions is in the range of 90-600 nm, and the final nanocrystals composite is stable for months.Films obtained by casting followed by water evaporation and particle coalescence were analyzed by differential scanning calorimetry, dynamic mechanical analysis, and tensile testing. The nanocomposite maintained high transparency, and their storage elastic modulus increased tediously with the increasing nanowhiskers contentDes dispersions de nanocomposites stables à matrice polymérique et à base de whiskers de cellulose ont été préparées par polymérisation en miniémulsion, dont on peut atteindre 5 % en masse. Ce procédé permet d’obtenir une distribution homogène des nanofibres autour des particules de polymère, et empêche ainsi les risques d’agglomération.La caractérisation de ces dispersions a été réalisée en recourant à divers techniques comme la diffusion dynamique de la lumière, zetamètrie, le microscope électronique à transmission (MET), à force atomique (AFM) et à effet de champs. Nous avons montré que l’accroissement du taux de nanoparticules s’accompagne par une augmentation de la taille des particules de polymères.Les propriétés des films de nanocomposites, obtenus après évaporation de l’eau et coalescence des particules ont été analysées par calorimétrie différentiel à balayage (DSC), analyse mécanique dynamique (DMA) et par essai de traction
32
Toprak, Pelin. « A New Route To The Synthesis Of Nanocomposites By Using An Unsaturated Polyester Matrix ». Master's thesis, METU, 2004. http://etd.lib.metu.edu.tr/upload/12605430/index.pdf.
Texte intégralRésumé :
This study was conducted to investigate the effects of organoclay type and concentration on the nanocomposites synthesized by &ldquoIn-Situ Polymerization&rdquo
and &ldquo
Prepolymerization&rdquo
methods. In-Situ Polymerization Method was in fact a new route which consisted of dispersing the monomers
propylene glycol, maleic anhydride and o-phthalic anhydride into the galleries of montmorillonite followed by subsequent polymerization. The Prepolymerization Method involved the addition of montmorillonite to the previously synthesized unsaturated polyester. As the first step, all the compositions were prepared by Cloisite 30B, and then for comparison of clay type, nanocomposites containing 3 wt.% of Cloisite 15A and Cloisite 25A were also synthesized. The efficiency of the two methods were compared with regards to their structural, thermal and mechanical properties. According to the results of XRD analysis, in both methods, maximum intercalation was observed when Cloisite 30B was used. An exfoliated structure was obtained in the Prepolymerization Method at 3 wt. % Cloisite 30B content. In all clay types, the increase in the d-spacings of the organoclays was higher when the Prepolymerization Method was applied. With Cloisite 30B, maximum improvement in the impact strength was obtained at 3 wt. % organoclay loading and the In-Situ Method yielded better results leading to a 77% increase in the impact strength at this organoclay loading. Among the organoclay types, Cloisite 15A was found to give rise to maximum increase in the impact strength. With the Prepolymerization Method higher improvement in flexural strength and flexural modulus was obtained owing to the lower styrene content in the crosslinking medium. The elongation at break values followed a decreasing trend with increasing clay content but did not show any significant difference when the clay types were compared.
33
Ben, mabrouk Aymen. « Elaboration de nanocomposites à base de whiskers de cellulose et de polymère acrylique par polymérisation in situ ». Phd thesis, Université de Grenoble, 2011. http://tel.archives-ouvertes.fr/tel-00721813.
Texte intégralRésumé :
A stable aqueous nanocomposite dispersion containing cellulose whiskers and a polymer matrix was prepared via miniemulsion polymerization. We were able to prepare a stable dispersion with a 250 wt % solid content and a cellulose whiskers content ranging from 1 up to 5 wt % based on polymer content. Cellulose nanocrytals suspension was mixed with monomers phase in presence of anionic or cationic surfactant and a stabilizing additive acting as a hydrophobe. After sonication for a short time to obtain a stable emulsion of small droplet polymerisation reaction was trigged by the addition of the initiator. The nanocomposite dispersion was characterized using dynamic light scattering, ζ-potential measurement, transmission electron microscopy (TEM), atomic force microscopy (AFM) and FE-SEM. It was found that the particle size of the prepared suspensions is in the range of 90-600 nm, and the final nanocrystals composite is stable for months.Films obtained by casting followed by water evaporation and particle coalescence were analyzed by differential scanning calorimetry, dynamic mechanical analysis, and tensile testing. The nanocomposite maintained high transparency, and their storage elastic modulus increased tediously with the increasing nanowhiskers content.
34
Erdogan, Selahattin. « Synthesis Of Liquid Crystalline Copolyesters With Low Melting Temperature For In Situ Composite Applications ». Phd thesis, METU, 2011. http://etd.lib.metu.edu.tr/upload/12613306/index.pdf.
Texte intégralRésumé :
The objective of this study is to synthesize nematic-thermotropic liquid crystalline polymers (LCP) and determine their possible application areas. In this context, thirty different LCP&rsquos were synthesized and categorized with respect to their fiber formation capacity, melting temperature and mechanical properties. The basic chemical structure of synthesized LCP&rsquo
s were composed of p-acetoxybenzoic acid (p-ABA), m-acetoxybenzoic acid (m-ABA), hydroquinone diacetate (HQDA), terephthalic acid (TPA) and isophthalic acid (IPA) and alkyl-diacids monomers. In addition to mentioned monomers, polymers and oligomers were included in the backbone such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) polymers, and polybutylene naphthalate (PBN), polyhexylene naphthalate (PHN) and poly butylene terephthalate (PBT) oligomers that contain different kinds of alkyl-diols. We adjusted the LCP content to have low melting point (180oC-280oC) that is processable with thermoplastics. This was achieved by balancing the amount of linear (para) and angular (meta) groups on the aromatic backbones together with the use of linear hydrocarbon linkages in the random copolymerization (esterification) reaction. LCP species were characterized by the following techniques
Polarized Light Microscopy, Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Analysis (FTIR), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA), X-ray Scattering (WAXS, Fiber diffraction), surface free energy, end group analysis (CEG), intrinsic viscosity (IV) and tensile test. According to these analysis LCPs were classified into five main categories
(I) fully aromatics, (II) aromatics+ PET/PEN, (III) aromatics + oligomers (IV) aromatics + short aliphatic diacids, (V) aromatics + long aliphatic diacids. The foremost results of the analysis can be given as below. DSC analysis shows that some LCPs are materials that have stable LC mesogens under polarized light microscopy. In TGA analysis LCPs that have film formation capacity passed the thermal stability test up to 390oC. NMR results proved that predicted structures of LCPs from feed charged to the reactor are correct. In FTIR due to the inclusion of new moieties, several peaks were labeled in the finger-print range that belongs to reactants. In X-ray analysis, LCP24 (containing PET) was found to be more crystalline than LCP25 (containing PEN) which is due to the symmetrical configuration. Block segments were more pronounced in wholly aromatic LCP2 than LCP24 that has flexible spacers. Another important finding is that, as the amount of the charge to the reactor increases CEG value increases and molecular weight of the product decreases. Selected group V species were employed as reinforcing agent and mixed with the thermoplastics
acrylonitrile butadiene styrene (ABS), nylon6 (PA6), polyethylene terephthalate (PET), polypropylene (PP) and appropriate compatibilizers in micro compounder and twin screw extruder. The blends of them were tested in dog-bone and/or fiber form. In general LCPs do not improve the mechanical properties except in composite application with polypropylene. A significant increase in tensile properties is observed by LCP24 and LCP25 usage. Capillary rheometer studies show that the viscosity of ABS decreases with the inclusion PA6 and LCP2 together. In addition to the composite applications, some LCPs are promising with new usage areas. Such as nano fibers with 200nm diameter were obtained from LCP27 by electrospinning method. The high dielectric constant of LCP29 has shown that it may have application areas in capacitors.
35
Betatache, Amina. « Conception et réalisation de capteurs biomimétiques à base de polymères à empreintes moléculaires à transduction électrochimique ». Thesis, Lyon 1, 2013. http://www.theses.fr/2013LYO10250.
Texte intégralRésumé :
Les biocapteurs sont des moyens d'analyse en plein essor à la fois rapides, sélectifs et peu coûteux, applicables à des domaines très variés (environnement, santé, agroalimentaire…). La capacité de reconnaissance moléculaire extraordinaire de biomolécules telles que les enzymes ou les anticorps a été exploitée avec succès pour la réalisation de nombreux biocapteurs. Cependant, l'inconvénient majeur de ces récepteurs biologiques est qu'ils sont difficiles à produire et fragiles. Une manière de surmonter ces inconvénients consiste à les remplacer par des récepteurs artificiels présentant des propriétés de reconnaissance similaires. Parmi les matériaux biomimétiques prometteurs figurent les polymères à empreintes moléculaires (MIPs). Dans ce travail, nous nous sommes intéressés au développement de deux capteurs biomimétiques impédimétriques, le premier basé sur l'utilisation de poly(éthylène co-alcool vinylique) imprimé pour la détection de la créatinine et le deuxième sur des MIPs de polyméthacrylate pour la détection de la testostérone. Dans le premier cas, le polymère imprimé a été produit et déposé à la surface d'électrodes en or, soit par drop-coating, soit sous forme de nanofibres par la technique d'électrofilage. Dans le deuxième, le MIP a été synthétisé par polymérisation radicalaire de l'acide méthacrylique en présence d'éthylèneglycol diméthacrylate (réticulant), d'initiateur et de testostérone en utilisant la méthode du « grafting from » qui consiste à greffer d'abord l'initiateur sur la surface du transducteur mais pour la polymérisation on a utilisé deux approches (spin-coating d'une solution de prépolymérisation sur la surface du transducteur ou l'immersion de ce dernier dans la solution de monomère plus testostérone) suivie de l'exposition à une source d'energie pour effectuer la polymérisation. Les performances des capteurs (limite de détection, sélectivité, reproductibilité) ont ensuite été évaluéesBiosensors are rapid, selective and low-cost analytical devices of growing interest for a wide range of application fields (e.g. environment, food, health). The extraordinary molecular recognition capabilities of sensing biomolecules such as enzymes and antibodies have been successfully exploited in the elaboration of a number of biosensors. However, these biorecognition elements are often produced via complex and costful protocols and require specific handling conditions because of their poor stability. To circumvent these limitations, artificial receptors of similar recognition properties are now proposed as alternatives to natural receptors in sensor technology. Molecular imprinted polymers are among the most promising biomimetic materials reported. In this work, we developed two impedimetric biomimetic sensors. The first one is based on imprinted poly(ethylene co-vinyl alcohol) for creatinine detection and the second on polymethacrylate MIPs for testosterone analysis. In the first case, MIP was produced and deposited onto gold microelectrodes, either by spin-coating of a pre-polymerization solution, or by electrospinning. In the second case, MIPs were synthetized by photopolymerization of methacrylic acid in presence of ethyleneglycoldimethacrylate (cross-linker), an azo-initiator and testosterone as template using the “grafting from” method in which the initiator is first attached to the transducer surface but to effect polymerization we used two different approaches (dip-coating of a prepolymerization solution on the transducer surface functionalized with the initiator or immersing it in the solution of monomers and testosterone) followed by exposure to an energy source to effect polymerization. Then, analytical performances (linear range, detection limit, selectivity and reproducibility) of both creatinine and testosterone sensors were determined and compared
36
Pazat, Alice. « Chemical Modification of Graphite-based Derivates and Their Uses in Elastomer Nanocomposites ». Thesis, Lyon, 2017. http://www.theses.fr/2017LYSE1050/document.
Texte intégralRésumé :
L'objectif de la thèse a été d'explorer différentes voies de dispersion de charges graphitiques dans des élastomères de type polyisoprène dans le but d'améliorer les propriétés mécaniques et barrière. Pour augmenter les interactions entre le graphite et l'élastomère et donc diminuer les interactions entre charges, les charges graphitiques ont été modifiées chimiquement. Le graphite a été préalablement oxydé pour obtenir du graphite oxydé (GO) contenant des groupements époxyde, hydroxyle et acide carboxylique, susceptibles de servir comme sites d'ancrage de molécules et de chaînes polymères. Afin d'améliorer la compatibilité du GO avec la matrice polyisoprène, des amines et des alkoxysilanes ainsi que des chaînes polyisoprène ont été greffées sur le GO. Des taux de greffage variant de 4 à 50 % en poids ont été obtenus selon la technique de fonctionnalisation utilisée. Une expansion thermique du GO a aussi été étudiée et a conduit à la formation d'une structure graphitique poreuse. Des composites polyisoprène contenant 15 pce de ces charges graphitiques modifiées ont ensuite été préparés et ont montré une diminution de la perméabilité à l'air (-70 % pour les composites graphite traité thermiquement, par rapport à ceux chargés uniquement en noir de carbone) ainsi qu'une amélioration des propriétés mécaniques. Enfin, l'utilisation de liquides ioniques comme agents dispersants a été étudiée. Des composites caoutchouc-graphite avec 1 % en poids de liquides ioniques ont montré un renforcement plus élevé (+ 25 % pour la contrainte à 300 % d'élongation) tout en conservant un allongement à la rupture similaire par rapport à des composites contenant uniquement du noir de carboneThe aim of this study was the investigation of various dispersion methods for graphite-based fillers in elastomers such as polyisoprene, to enhance mechanical and barrier properties. To increase graphite-rubber interactions and so decrease filler-filler aggregation, graphite-based fillers have been chemically modified. Graphite was previously oxidized into graphite oxide (GO), bearing epoxide, hydroxyl and carboxylic acid groups, which could further act as anchor sites for molecules and polymer chains. To increase the compatibility between GO and the polymeric matrix, amines and alkoxysilanes, as well as polymer chains, were grafted on GO. Grafting contents between 4-50 wt% were obtained, depending on the functionalization technique which was used. A thermal modification path of GO was also investigated and led to the formation of porous graphite structure. Polyisoprene composites containing 15 phr of these graphite-based fillers were prepared and showed decreased air permeability (-70 % for composites containing thermally-treated graphite filler, as compared to those containing carbon black only) as well as enhanced tensile properties. Finally, the use of ionic liquids as dispersing agents was investigated. Natural rubber – graphite composites with 1 wt% of ionic liquid displayed enhanced reinforcement (+ 25 % for the stress at 300 % strain) while maintaining similar strain at break to composites containing carbon black only
37
Pierrot, François. « Polymérisation in-situ en milieu fondu et sous écoulement élongationnel pour l'élaboration de nouveaux matériaux ». Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAE011/document.
Texte intégralRésumé :
Dans ce travail de thèse, des mélanges réactifs de polymères thermoplastiques immiscibles PMMA,PE et PS ont été réalisés dans un mélangeur (RMX®) qui génère principalement des écoulements élongationnels connus pour leurs pouvoirs distributifs et dispersifs même lorsque les composants ont une différence de viscosité importante. La polymérisation in-situ du styrène a été conduite par auto-polymérisation thermique et grâce à des amorceurs radicalaires. Différentes méthodes de préparations et paramètres de mélanges ont été testés puis évalués par l’analyse d’images de microscopie électronique. Les plus petits nodules de PS que nous avons obtenus ont un rayon moyen de l’ordre de 50 nm. Des mélanges binaires 90/10 à base de PS ou PE et d’un thermodur polyépoxyde (MDEA/DGEBA) ont également été réalisés. Les nodules sphériques les plus petits que nous avons obtenus ont un rayon moyen de l’ordre de 65 nmIn this work, binary and ternary reactive blends based on immiscible thermoplastic polymers PMMA,PE and PS were realized. The in-situ polymerization of the styrene, precursor of PS, was led by thermal self-polymerization or still thanks to radical initiator. Blends were realized in a mixer named RMX who generates mainly extensional flows known for their distributive and dispersive skill even if components have an important viscosity difference. Various methods of preparation and parameters of mixtures were tested. Morphology was evaluated by the analysis of electronic microscopy images.The average radiuses of the dispersed PS phase were compared with those observed in the literature. The smallest that we obtained have an average radius of 50 nm. Binary mixtures 90/10 %m with PS or PE and with a thermodur polyepoxide (MDEA/DGEBA) were also realized. The smallest spherical nodules that we obtained have an average radius of the order of 65 nm
38
Dastjerdi, Zahra. « Cellulose Nanocrystals : Renewable Property Modifiers for Pressure Sensitive Adhesives ». Thesis, Université d'Ottawa / University of Ottawa, 2017. http://hdl.handle.net/10393/36649.
Texte intégralRésumé :
Pressure sensitive adhesives (PSAs) are polymeric materials with versatile applications in industrial and consumer products such as protective films, product labels, masking tape, and sticky notes, to name a few applications. World demand for emulsion–based products is on the rise due to worldwide legislation on solvent emissions. In order to completely replace emulsion-based PSAs with their solvent-based counterpart, the property modification of emulsion-based PSAs is required. The use of nanomaterials to modify polymer properties is well established. The aim of this thesis was to use cellulose nanocrystals (CNCs) as property modifiers for emulsion-based PSAs.
CNCs are recognized as a highly efficient reinforcement nanofiller. Owing to their environmentally friendly characteristics, low density, high aspect ratio, non-toxicity, and abundant availability, the application of CNCs in composite materials is gaining increasing attention. In this thesis, the inclusion of CNCs in emulsion-based PSAs was carried out through in situ emulsion polymerization and blending technique. To the best of our knowledge, there is limited information about the synthesis of CNC/PSAs nanocomposites via in situ emulsion polymerization and the evaluation of their mechanical performance.
The addition of CNCs to the polymerization formulation caused latex instability due to the negatively charged surfaces of the CNCs. After numerous attempts to overcome the stability issues, a stable polymerization formulation and protocol were developed. CNC/PSAs were synthesized via in situ seeded-semi batch emulsion polymerization, which is a common commercial production pathway for PSAs. The mechanical performance of the resulting PSA nanocomposite films, namely, shear strength, tack, and peel strength, was evaluated at several CNC loadings. All three PSA adhesive properties were simultaneously enhanced with increasing CNC loading. The inclusion of CNCs into the films increased their hydrophilicity. Consequently, the PSA films’ improved wettability on a stainless steel substrate imparted greater tack and peel strength. The blending of the CNCs with a base latex also led to improved adhesive properties. However, the property modification through blending was not as effective as that for the CNC/PSA films synthesized via in situ emulsion polymerization. Thus, CNCs are safe nanomaterials that have been shown to provide remarkable property enhancement of emulsion-based PSA films at low loadings (1wt%).
39
MOTA, Mariaugusta Ferreira. « Utilização de argilas esmectíticas modificadas na síntese de nanocompósitos poliméricos via polimerização IN SITU ». Universidade Federal de Campina Grande, 2015. http://dspace.sti.ufcg.edu.br:8080/jspui/handle/riufcg/426.
Texte intégralRésumé :
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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.
40
Lebert, Jenny [Verfasser], Eva M. [Akademischer Betreuer] Herzig, Peter [Gutachter] Müller-Buschbaum et Eva M. [Gutachter] Herzig. « Polythiophene thin films : Structure formation during in situ polymerization / Jenny Lebert ; Gutachter : Peter Müller-Buschbaum, Eva M. Herzig ; Betreuer : Eva M. Herzig ». München : Universitätsbibliothek der TU München, 2018. http://d-nb.info/1199005592/34.
Texte intégral
41
Kim, Sung-gi. « PET Nanocomposites Development with Nanoscale Materials ». Connect to Online Resource-OhioLINK, 2007. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1178043237.
Texte intégralRésumé :
Dissertation (Ph.D.)--University of Toledo, 2007.Typescript. "Submitted as partial fulfillment of the requirements for The Doctor of Philosophy Degree in Engineering." Bibliography: leaves 200-205.
42
Houf, Latifa. « Développement de nanocomposites à propriétés piézoélectriques et optiques non-linéaires ». Phd thesis, Université de Grenoble, 2011. http://tel.archives-ouvertes.fr/tel-00686925.
Texte intégralRésumé :
Le développement de nouveaux capteurs, transducteurs et de dispositifs intégrés optoélectroniques et piézo-électriques nécessite l'élaboration de nouveaux matériaux avec des propriétés mécaniques, optiques et électriques couplées. Dans cette perspective, les nanocomposites à base de nanocristaux inorganiques non centrosymétriques dispersés dans une matrice polymère peuvent donner à la fois des propriétés piézoélectriques et optiques non-linéaires. Cependant, la dispersion et l'orientation des nanocristaux dans la matrice sont primordiales si on souhaite un comportement collectif des nanocristaux individuels et des propriétés résultantes significatives. Dans ce travail, nous avons utilisé des cristaux d'iodate de fer (Fe(IO3)3) comme nano-charges inorganiques et le PMMA/ PTMPTA comme matrice polymère. La réponse optique non-linéaire du Fe(IO3)3 est comparable à celle des cristaux les plus efficaces tels que BaB2O4 et LiNbO3. Le comportement piézoélectrique du matériau massif n'étant pas référencé, sa structure cristalline laisse toutefois envisager des propriétés piézoélectriques intéressantes. Par ailleurs, la matrice polymère a été choisie pour sa simplicité d'utilisation et de production, son coût relativement faible, sa versatilité et sa facilité de mise en forme. Les nanocomposites peuvent être élaborés par deux voix différentes : la première consiste à disperser mécaniquement des nanocristaux fonctionnalisés dans un polymère ou dans un solvant de polymère approprié et la deuxième concerne la polymérisation in-situ de microémulsions composées du monomère liquide. Les synthèses en microémulsions inverses ont été privilégiées pour d'une part élaborer des nanocristaux d'iodate de fer de taille et de forme contrôlées puis, d'autre part, photo-polymériser des couches minces déposées à la tournette. Un aspect très original de ce travail consiste en l'utilisation de la Diffusion Hyper-Rayleigh pour étudier in-situ les cinétiques de cristallisation des particules d'iodate de fer en fonction des conditions expérimentales de synthèse à savoir, la température et la composition des microémulsions. Cette technique qui consiste à détecter les réponses optiques non-linéaires des suspensions de nanoparticules en microémulsions a été combinée avec d'autres méthodes expérimentales plus classiques comme la diffraction des rayons X, la diffusion dynamique de la lumière et la microscopie électronique en transmission. Cela a permis d'élucider les mécanismes de croissance des nanocristaux d'iodate de fer en microémulsions inverses. Par la suite, des couches minces nanocomposites ont été préparées après orientation sous champs électriques des nanocristaux polaires dispersés dans le MMA. Les caractérisations mécaniques, optiques non linaires et piézoélectriques de ces couches sont encourageantes.
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Djadoun, S., et S. Kadi. « Elaboration of Nanocomposites Based on Poly (Ethyl Methacrylate-co-Acrylonitrile) by in Situ Polymerization Using an Algerian Bentonite. Thermal Stability and Kinetic Study ». Thesis, Sumy State University, 2012. http://essuir.sumdu.edu.ua/handle/123456789/35084.
Texte intégralRésumé :
This contribution focuses on the synthesis and characterization of nanocomposites based on poly (ethyl
methacrylate-co-acrylonitrile) (PEMAN) and different loadings of an organically modified bentonite from
Algeria prepared via in situ polymerization.
TEM images and X-ray patterns revealed that depending on the loading of this clay, intercalated or
partially exfoliated nanocomposites were obtained. These nanocomposites showed an increase in their
glass transition temperature compared to the pure copolymer as investigated by Differential Scanning
Calorimetry and improved thermal stability as evidenced by Thermogravimetric analysis and kinetics of
their thermal degradation. Activation energies (Ea) of thermal decomposition of PEMAN and its nanocomposites
were determined by Flynn–Wall–Ozawa and Kissinger-Akahira-Sunose methods. The changes in
(Ea) value with the level of conversion suggest a significant improved thermal stability of the nanocomposites
compared to the copolymer matrix.
When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35084
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Miranda, Katiusca Wessler. « Síntese de copolímeros de l-lactídeo e ε-caprolactona para funcionalização in situ de partículas de celulose nanocristalina ». Universidade do Estado de Santa Catarina, 2015. http://tede.udesc.br/handle/handle/623.
Texte intégralRésumé :
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This paper studied ring opening polymerizations L-lactide (LLA) and ε-caprolactone (ε-CL) by bulk polymerization and solution polymerization, in order to evaluate the influence of initiator concentration, reaction time and reaction temperature on the yield and molecular weight of both polymers. Tin octoate and methanol was employed as initiators. It was observed that LLA and ε-CL speed ring opening polymerization, increases with temperature and that the monomer/polymer conversion immediately occurs in the first hours of synthesis when 2% of initiator is used. The molar mass, determined by capillary viscometry, was approximately 7x103 g/mol, for both polymers. It was also studied the copolymerization of LLA and ε-CL by solution polymerization employing different solvents. Weight percentages of LLA/ε-CL equal to 100/0, 95/5, 90/10, 85/15 and 80/20 were studied. The toluene was the only solvent that enabled the production of polymers and copolymers at 120 ° C. Initiator concentration equal to 0.015% and reaction time equal to 24 hours, were assessed, generating polymers with average molar mass (Mw) around 2x104 g / mol, determined by GPC. It was observed by proton and carbon 13 nuclear magnetic resonance (13 C-NMR and 1H-NMR) that reactions conducted with ε-CL concentrations lower than 15% do not yield copolymer, only PLLA. Bulk polymerization it was also studied and the main difference compared to solution polymerization is associated with the molar mass of the copolymer P(LLA-co-εCL)80/20. This product had a higher molar mass when synthesized by the first technique. After the study of copolymerization, the functionalization of nanocrystalline cellulose particles (CNC) with LLA and ε-CL, by polymerization in solution, was studied. Three compositions were analyzed: (i) PLLA-CNC, (II) P(LLA-co-εCL)85/15-CNC and (III) P(LLA-co εCL)80/20-CNC; the reactions were conducted at 120 ° C for 24 hours. It was possible to functionalize CNC particles in situ, using 80/20 LLA/ε-CL systems, with tin octoate (0.015 wt%) as catalyst and toluene as solvent (composition III). The functionalization was confirmed by Fourier transform infrared spectroscopy (FTIR). The compatibility of the P(LLA-co-εCL)80/20-CNC particle increased in toluene, confirming the reduction of hydrophilicity of these particles. Unlike occurred with the compositions (I) and (II), the composition (III) only allowed the production CNC functionalized particles. PLLA, PCL and / or P (LLA-co-εCL) were not produced. This fact indicates that the concentration of ε-CL and the presence of cellulose hydroxyl groups decreased the reactivity between the monomers.
Neste trabalho foram estudadas as reações de abertura de anel dos monômeros L-lactídeo (LLA) e ε-caprolactona (ε-CL), pela técnica de polimerização em massa com o intuito de avaliar a influência da concentração de iniciador, do tempo e da temperatura de reação sobre o rendimento reacional e a massa molar de ambos os polímeros. O iniciador empregado neste estudo foi o octoato de estanho e como co-iniciador, metanol foi empregado. Foi observado que a velocidade de reação de obtenção do poli(L-ácido láctico) (PLLA) e da poli(ε-caprolactona) (PCL) aumenta em função da temperatura e que com 2% de iniciador a conversão de monômero em polímero ocorre logo nas primeiras horas de síntese. A massa molar determinada por viscosimetria capilar foi de aproximadamente 7x103 g/mol para ambos os polímeros. Também foi estudada a obtenção de copolímeros de LLA e ε-CL por reações de polimerização em solução empregando diferentes solventes. As porcentagens mássicas de LLA/ε-CL empregadas foram 100/0, 95/5, 90/10, 85/15 e 80/20. O tolueno foi o único solvente que possibilitou a produção de polímeros e copolímeros a 120 °C. Para estas sínteses a concentração de iniciador foi igual a 0,015% e o tempo de reação foi de 24 horas, gerando polímeros com massa molar ponderal média (Mw) ao redor de 2x104 g/mol, determinadas por GPC. Foi observado por ressonância magnética nuclear de hidrogênio e de carbono 13 (RMN1H e RMN13C) que as reações conduzidas com concentrações de ε-CL inferiores à 15% não rendem copolímero, apenas PLLA é produzido. A obtenção de copolímeros pela técnica de polimerização em massa também foi estudada e a principal diferença em relação a polimerização em solução está associada à massa molar do copolímero P(LLA-co-εCL)80/20, sendo que o produto da polimerização em massa apresentou massa molar mais elevada que o obtido pela polimerização em solução. Após o estudo da obtenção dos copolímeros, foi estudada a funcionalização de partículas de celulose nanocristalina (CNC) com os monômeros de LLA e ε-CL pela técnica de polimerização em solução. Foram analisadas três composições: (I) PLLA-CNC, (II) P(LLA-co-εCL)85/15-CNC e (III) P(LLA-co-εCL)80/20-CNC; as reações foram conduzidas a 120°C durante 24 horas. Foi possível funcionalizar partículas de CNC in situ, empregando 80% de LLA, 20% de ε-CL, 0,015% de octoato de estanho e tolueno como solvente (composição III). A funcionalização foi confirmada por análises de espectroscopia de infravermelho por transformada de Fourier (FTIR). Testes de dispersão do P(LLA-co-εCL)80/20-CNC em tolueno confirmaram a diminuição da hidrofilicidade destas partículas. Ao contrário do ocorrido com as composições (I) e (II), a composição (III) permitiu somente a produção partículas de CNC funcionalizadas. PLLA, PCL e/ou P(LLA-co-εCL) não foram produzidos. Este fato indica que o aumento da concentração de ε-CL e a presença de grupos hidroxilas de celulose diminuíram a reatividade entre os monômeros.
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Damay, Jérémie. « Développement de nouveaux traitements du bois basés sur le procédé d'imprégnation axiale ». Thesis, Université de Lorraine, 2014. http://www.theses.fr/2014LORR0178/document.
Texte intégralRésumé :
L’évolution des lois relatives à l’utilisation de produits biocides impose d’étudier des méthodes innovantes de traitement du bois. Dans ce contexte, les travaux de recherche présentés s’intéressent à une nouvelle alternative dite « non-biocide » impliquant la fabrication de composites bois massif / polymères obtenus par imprégnation de monomères et polymérisation in situ provoquée par chauffage. Le méthacrylate de méthyle, quatre acrylates organiques et trois acrylates hydrosolubles, ainsi que l’alcool furfurylique ont été testés. Les composites fabriqués ont été caractérisés : le polymère est bien présent dans le bois et il peut être résistant au lessivage à l’eau. Le bois a été densifié, les composites sont alors moins hydrophiles et plus stables dimensionnellement ; les propriétés mécaniques sont améliorées. Le traitement peut induire une durabilité conférée élevée. Parallèlement, une méthode d’imprégnation innovante a été testée : l’imprégnation axiale. Ce procédé consiste en l’imprégnation basse pression de billons de bois vert par une solution de traitement transitant via les voies naturelles de circulation de la sève. Des billons ont été imprégnés avec une solution de cuivre, dosé ultérieurement afin de s’assurer de la bonne répartition du produit dans le bois ; cela a permis la validation du procédé d’imprégnation axiale pour le hêtre, le charme et le bouleau. Enfin, des composites ont été fabriqués par imprégnation axiale de solutions aqueuses polymérisables à base d’alcool furfurylique ; ils sont résistants à la lixiviation à l’eau et moins hydrophiles que le bois naturel. Leur durabilité face aux champignons lignivores est améliorée, particulièrement dans le cas du traitement le plus concentréThe evolution of laws on the use of biocide products makes it necessary to explore innovative methods of treating wood. In this context, the presented research focuses on a new alternative called a "non-biocide" treatment method involving the manufacture of solid wood-polymer composites obtained by impregnation of monomers and in situ polymerization caused by heating. Methyl methacrylate, four organic acrylates and three water-soluble acrylates, and furfuryl alcohol were tested. Composites manufactured were characterized: the polymer is present in the timber and may be resistant to leaching in water. Wood has been densified, while the composites are less hydrophilic and more dimensionally stable; the mechanical properties are improved. Treatment can induce high durability. Otherwise, an innovative method of impregnation was tested: axial impregnation. This process consists in the low-pressure impregnation of green wood ridges by treatment solution transiting via natural pathways of sap circulation. Ridges were impregnated with a copper solution, later determined to ensure good distribution of the product in the timber; this allowed the validation of the axial impregnation method for beech, hornbeam and birch. Finally, the composites were produced by axial impregnation of polymerizable aqueous solutions based on furfuryl alcohol; they are resistant to water leaching and less hydrophilic than the original wood. Their durability in the presence of wood-destroying fungi is improved, particularly in the case of the more concentrated treatment
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Ben, Haj Sihem. « Nanoparticules d'amidon : préparation, pouvoir renforçant et utilisation comme agent de stabilisation ». Thesis, Université Grenoble Alpes (ComUE), 2015. http://www.theses.fr/2015GREAI027/document.
Texte intégralRésumé :
Le présent travail examine un nouveau procédé "top-down" de production des nanoparticulesd’amidon basé sur l’utilisation des ultrasons comme moyen de désintégration physique desparticules d’amidon. Une caractérisation approfondie par diffusion dynamique de la lumière(DLS), par microscopie électronique à balayage (FE-SEM) et par diffraction des rayons-X , etdiffusion Raman (DRX, Raman et SAXS) montre que cette approche permet de produire desparticules d’amidon nanométrique, de forme plaquettaire, ayant un caractère amorphe. Lesnanoparticules issues ont été utilisées comme stabilisants de Pickering dans la polymèrisationen émulsion pour préparer in-situ des nanocomposites à matrice acrylique incorporant lesnanoparticules d’amidon à des taux allant de 2 à 12%Les propriétés mécaniques et optiques des films de nanocomposites, obtenus aprèsévaporation de l’eau et coalescence des particules, ont été étudiées par analyse mécaniquedynamique (DMA) et spectroscopie UV-visibleThe present work investigates a new process "top-down" of producing a starch nanoparticlesbased on the use of ultrasound as a means of physical disintegration. An extensivecharacterization using dynamic light scattering (DLS), Filed-effect scanning electronicmicroscopy (FE-SEM), and structural analysis (XRD, Raman and SAXS) shows that this wassuccessful in producing nanosized starch particles with platelet-like morphology. Theparticles produced were used as a Pickering stabilizer in the emulsion polymerization ofacrylic nanocomposite. The nanocomposite dispersion was characterized using dynamic lightscattering, ζ-potential measurement, transmission electron microscopy (TEM) and FE-SEM.A clear correlation between the particle size of the polymer particles and the content of thestarch nanoparticles was shown.The properties of the nanocomposite film prepared by casting and film-formation bycoalescence at room temperature were investigated using dynamic mechanical analysis andUV-Visible spectroscopy
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Fu, Hanzhuo. « Development of Advanced Capillary Electrophoresis Techniques with UV and Mass Spectrometry Detection for Forensic, Pharmaceutical and Environmental Applications ». FIU Digital Commons, 2014. http://digitalcommons.fiu.edu/etd/1531.
Texte intégralRésumé :
Capillary electrophoresis (CE) is a modern analytical technique, which is electrokinetic separation generated by high voltage and taken place inside the small capillaries. In this dissertation, several advanced capillary electrophoresis methods are presented using different approaches of CE and UV and mass spectrometry are utilized as the detection methods.
Capillary electrochromatography (CEC), as one of the CE modes, is a recent developed technique which is a hybrid of capillary electrophoresis and high performance liquid chromatography (HPLC). Capillary electrochromatography exhibits advantages of both techniques. In Chapter 2, monolithic capillary column are fabricated using in situ photoinitiation polymerization method. The column was then applied for the separation of six antidepressant compounds.
Meanwhile, a simple chiral separation method is developed and presented in Chapter 3. Beta cycodextrin was utilized to achieve the goal of chiral separation. Not only twelve cathinone analytes were separated, but also isomers of several analytes were enantiomerically separated. To better understand the molecular information on the analytes, the TOF-MS system was coupled with the CE. A sheath liquid and a partial filling technique (PFT) were employed to reduce the contamination of MS ionization source. Accurate molecular information was obtained.
It is necessary to propose, develop, and optimize new techniques that are suitable for trace-level analysis of samples in forensic, pharmaceutical, and environmental applications. Capillary electrophoresis (CE) was selected for this task, as it requires lower amounts of samples, it simplifies sample preparation, and it has the flexibility to perform separations of neutral and charged molecules as well as enantiomers.
Overall, the study demonstrates the versatility of capillary electrophoresis methods in forensic, pharmaceutical, and environmental applications.
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Delices, Annette. « Organized Organic Dye / Hole Transporting Materials for TiO2- and ZnO- based Solid-State Dye-Sensitized Solar Cells (s-DSSCs) ». Thesis, Sorbonne Paris Cité, 2017. http://www.theses.fr/2017USPCC066/document.
Texte intégralRésumé :
En raison des problèmes d'instabilité à moyen termes des cellules solaires à colorant (DSSC), l'électrolyte liquide à base d'iodure a été remplacé par plusieurs types de matériaux solides transport de trous (HTM) pour obtenir des DSSCs à l'état solide (s-DSSCs). Parmi ces matériaux, l’utilisation des polymères conducteurs(PC) a attiré une attention considérable en raison de leur bonne stabilité, de leur haute conductivité et de la facilité de leur dépôt sur le semi-conducteur mésoporeux TiO2. Dans ce travail de thèse, plusieurs s-DSSCs basées sur des PC utilisés comme HTM ont été développés dans le but d'améliorer leurs performances photovoltaïques en tenant compte des deux objectifs suivants: (i) l'optimisation des processus de transfert inter facial de charge dans la cellule solaire, et (ii) l'optimisation du transport de charge dans le semi-conducteur d'oxyde de type n. Pour atteindre ces objectifs, chaque composant de la s-DSSC a été modifié afin d'étudier son effet sur les performances du dispositif final. En première tentative, une étude analytique est réalisée en faisant varier le sensibilisateur afin de déterminer les fragments de la structure du colorant, qui ont un effet important sur le processus de photopolymérization électrochimique in-situ (PEP) à la fois en milieu organique et en milieu aqueux mais aussi sur les performances des s-DSSCs. Sur la base de ces résultats, un nouveau concept a été développé et consiste en la suppression totale de l'interface entre le colorant et le HTM. Ceci est obtenu par la synthèse de nouveaux colorants liés de façon covalente à un monomère électroactif qui est co-polymérisé par la PEP in-situ. Le copolymère résultant, utilisé comme HTM, est lié de manière covalente au colorant. En outre, la nature de la liaison chimique, reliant le résidu triphénylamine TPA au monomère, est également étudiée comme un facteur clé dans les performances de s-DSSC. En outre, et pour optimiser les processus de transport de charges dans ce type de s-DSSC, de nouvelles s-DSSC basées sur ZnO ont été réalisées et étudiéesDue to instability problems of dye sensitized solar cells (DSSCs) in longtime uses, the iodine based liquidelectrolyte has been replaced by several types of solid hole transporting materials (HTM) to perform solidstate DSSCs (s-DSSCs). Among them, the substitution by conducting polymers (CP) has attractedconsiderable attention because of their good stability, high hole-conductivity and simple deposition withinthe mesoporous TiO2 semiconductor. In this thesis work, several s-DSSCs based on CPs used as HTM havebeen developed in order to improve their photovoltaic performances taking into account the following twoobjectives: (i) the optimization of the interfacial charge transfer processes within the solar cell, and (ii) theoptimization of the charge transport within the n-type oxide semiconductor. To reach these goals, eachcomponent that constitutes the device was varied in order to investigate its effect on the device’sperformances. As first attempt, an analytical study is carried out by varying the sensitizer in order todetermine the fragments of the dyes structures, that have an important effect on the in-situ photoelectrochemical polymerization process (PEP) both in organic and in aqueous media and hence on theperformances of the s-DSSCs. Based on these results, a new concept of removing completely the interfacebetween the dye and the HTM is developed. This is achieved by the synthesis of new dyes covalently linkedto an electroactive monomer which is co-polymerized by in-situ PEP. The resulting co-polymer, used asHTM, is covalently linked to the dye. In addition, the nature of the chemical bond linking the triphenylamineresidue TPA to the monomer is also investigated as a key factor in the s-DSSCs performances. Besides, andto optimize the charge transport processes within this type of s-DSSC, the elaboration of novel ZnO baseds-DSSCs has been achieved and investigated
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Li, Shanghua. « Engineering nanomaterials with enhanced functionality ». Licentiate thesis, KTH, Materials Science and Engineering, 2006. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3906.
Texte intégralRésumé :
This thesis deals with the engineering of novel nanomaterials, particularly nanocomposites and nanostructured surfaces with enhanced functionalities. The study includes two parts; in the first part, an in situ sol-gel polymerization approach is used for the synthesis of polymer-inorganic hybrid material and its exceptional transparent UV-shielding effect has been investigated. In the second part, electrodeposition process has been adapted to engineer surfaces and the boiling performance of the fabricated nanostructured surfaces is evaluated.
In the first part of the work, polymer-inorganic hybrid materials composed of poly(methylmethacrylate) (PMMA) and zinc compounds were prepared by in situ sol-gel transition polymerization of zinc complex in PMMA matrix. The immiscibility of heterophase of solid organic and inorganic constituents was significantly resolved by an in situ sol-gel transition polymerization of ZnO nanofillers within PMMA in the presence of dual functional agent, monoethanolamine, which provided strong secondary interfacial interactions for both complexing and crosslinking of constituents.
In the second part of the work, nanoengineering on the surface of copper plates has been performed in order to enhance the boiling heat transfer coefficient. Micro-porous surfaces with dendritic network of copper nanoparticles have been obtained by electrodeposition with dynamic templates. To further alter the grain size of the dendritic branches, the nanostructured surfaces underwent a high temperature annealing treatment.
Comprehensive characterization methods of the polymer-inorganic hybrid materials and nanoengineered surfaces have been undertaken. XRD, 1H NMR, FT-IR, TGA, DSC, UV-Vis, ED, SEM, TEM and HRTEM have been used for basic physical properties. Pool boiling tests were performed to evaluate the boiling performance of the electrodeposited nanostructured micro-porous structures.
The homogeneous PZHM exhibited enhanced UV-shielding effects in the entire UV range even at very low ZnO content of 0.02 wt%. Moreover, the relationship between band gap and particle size of incorporated ZnO by sol-gel process was in good agreement with the results calculated from the effective mass model between bandgap and particle size. The fabricated enhanced surface has shown an excellent performance in nucleate boiling. At heat flux of 1 W/cm2, the heat transfer coefficient is enhanced over 15 times compared to a plain reference surface. A model has been presented to explain the enhancement based on the structure characteristics.
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Римша, Христина Володимирівна. « Синтез і властивості органо-неорганічних протонопровідних матеріалів ». Diss., Відділення фізико-хімії горючих копалин Інституту фізикоорганічної хімії і вуглехімії імені Л.М. Литвиненка Національної академії наук України, 2021. https://ena.lpnu.ua/handle/ntb/56455.
Texte intégralRésumé :
Дисертаційна робота присвячена розробленню нових полімерних та гібридних матеріалів із протонопровідними властивостями для використання у паливних елементах. Синтезовано амфіфільні полімерні та поліакрилат-кремнеземні матеріали різного складу на основі полі(акрилонітрил-ко-акриламід-ко-3-сульфопропілакрилату калію) та полі(акрилонітрил-ко-акрилова кислота-ко-3-
сульфопропілакрилату калію-ко-етиленглікольдиметилакрилату). Встановлено вплив співвідношення гідрофільно/гідрофобних мономерyих ланок, вмісту неорганічного компонента, природи сульфовмісного мономера на внутрішню морфологію отриманих матеріалів та їхні властивості: термічну стійкість,
водопоглинання, поглинання метанолу, вільну поверхневу енергію, протонну провідність.
Протонна провідність мембран на основі полі(акрилонітрил-ко-акрилова кислота-ко-3-сульфопропілакрилат калію- ко-етиленглікольдиметилакрилату) з додаванням 1-7 мас. % золь-гель системи досягає значення 1,12·10-2 См/cм. Обчислено енергію активації протонного переносу, яка складає 0,12-0,14 еВ. За моделлю Райса-Рота оцінено транспортні параметри мембран; за рівнянням
Нернста-Ейнштейна розраховано коефіцієнти дифузії протонів. Запропоновані матеріали володіють потенціалом для застосування як протонопровідні мембрани у технології паливних елементів. Диссертационная работа посвящена разработке новых полимерных и гибридных материалов с протонопроводящими свойствами для использования в топливных элементах. Синтезированы амфифильные полиакрилатные и полиакрилат-кремнеземные материалы на основе поли(акрилонитрил-ко-акриламидко-3-сульфопропил акрилат калия) и поли(акрилонитрил-ко-акрилова кислота-ко-3-
сульфопропилакрилат калия-ко-этиленгликольдиметилакрилат). Установлено влияние соотношения гидрофильно/гидрофобных мономерных звеньев, содержания неорганического компонента, природы сульфосодержащего мономера на внутреннюю морфологию полученных материалов и их свойства: термическую стойкость, водопоглощение, набухание в метаноле, свободную поверхностную энергию, протонную проводимость. Протонная проводимость мембран на основе поли(акрилонитрил-ко-акрилова
кислота-ко-3-сульфопропилакрилат калия-ко-этиленгликольдиметилакрилат) додавлением 1-7 масс. % золь-гель системы достигает значения 1,12·10-2См/см. Энергия активации протонного переноса составляет 0,12-0,14 эВ. С использованием модели Райса-Рота оценены транспортные параметры мембран; по уравнению Нернста-Эйнштейна рассчитаны коэффициенты диффузии протонов.
Предложенные материалы обладают потенциалом для применения их как протонпроводящие мембраны в технологии топливных элементов. The dissertation is devoted to the development of new polymer and hybrid organicinorganic materials with proton conductive properties, promising for in solid-state fuel cells. A synthesis strategy was proposed as follows: a polymer matrix of the composite was formed by UV-initiated copolymerization of acrylic monomers, and a silica network of the organic-inorganic materials was formed in situ due to simultaneous sol-gel process of the precursor – tetraethoxysilane. The spatially cross-linked hybrid structure of nanocomposites was formed both due to the presence of a cross-linker and by hydrogen bonding between polymer functional groups and the products of the sol-gel precursor transformation.
The effect of the ratio of hydrophilic/hydrophobic monomers in polymer matrix (based on acrylonitrile, acrylamide and 3-propylacrylate potassium salt) as well as the influence of inorganic component content on the morphology and properties of the obtained organic-inorganic materials were investigated. Proton conductivity, thermal stability, water uptake, methanol swelling, free surface energy of the synthesized membranes studied.
The formation and properties of organic-inorganic membranes with different acrylic sulfomonomers in polymer matrix: styrenesulfonic acid sodium salt and acrylamido-2-methyl-1-propanesulfonic acid were studied.
A new composition of organic-inorganic membranes was proposed: amphiphilic polymer matrix was synthesized from monomers: acrylic acid, acrylonitrile, 3-sulfopropylacrylate potassium salt, ethylene glycol dimethylacrylate; the content of the added sol-gel system was 1 – 7 mass %. SEM images showed homogeneity of the structure. The proton conductivity of membranes was studied depending on their
composition at temperatures 20 - 60°C and reaching the values up to 1,12·10-2 Sm/cm. The proton transfer activation energy, calculated from the temperature dependence of proton conductivity using the Arrhenius equation, was found to be 0,12-0,14 eV. According to the Rice and Roth model the transport parameters of the membranes (the number of mobile ions, the mobility of ions) were determined. Ion diffusion coefficients for the membranes were calculated using the Nernst-Einstein equation.The results of DMA analysis allow to conclude that the increase of silica content leads to the decrease of packing density and the increase of structural heterogeneity in synthesized polyacrylate/silica membranes.The stability of the membranes during operation in fuel cell was evaluated for its oxidation resistance in the Fenton reagent. Thus, the proposed method of synthesis and the developed composition of polymer and hybrid organic-inorganic membranes made it possible to ensure a high level of their proton conductivity and other characteristics necessary for operation in fuel cells.
Therefore, the synthesized materials have the potential for the application as proton conductive membranes in these devices.