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A Novel µ-Fluidic Channel Assisted Encapsulation Technique for Layer-by-LayerPolymer Nano- and Microcarrier FabricationLi, Jingyu 15 September 2015 (has links)
No description available.
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Bio-inspired Cellulose NanocompositesPillai, Karthik 07 October 2011 (has links)
Natural composites like wood are scale-integrated structures that range from molecular to the macroscopic scale. Inspired by this design, layer-by-layer (LbL) deposition technique was used to create lignocellulosic composites from isolated wood polymers namely cellulose and lignin, with a lamellar architecture. In the first phase of the study, adsorption of alkali lignin onto cationic surfaces was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Complete coverage of the cationic surface with alkali lignin occured at low solution concentration; large affinity coefficients were calculated for this system at differing pH levels. Adsorption studies with organosolv lignin in an organic solvent, and spectroscopic analysis of mixtures of cationic polymer with alkali lignin revealed a non-covalent interaction. The work demonstrated how noncovalent interactions could be exploited to molecular organize thin polyphenolic biopolymers on cationic surfaces. The second phase of the study examined the adsorption steps during the LbL assembly process to create novel lignocellulosic composites. LbL assembly was carried out using oxidized nanocellulose (NC) and lignin, along with a cationic polymer poly(diallyldimethylammonium chloride) (PDDA). QCM-D was used to follow the sequential adsorption process of the three different polymers. Two viscoelastic models, namely Johannsmann and Voigt, were respectively used to calculate the areal mass and thickness of the adsorbed layers. Atomic force microscopy studies showed a complete coverage of the surface with lignin in all the disposition cycles, however, surface coverage with NC was seen to increase with the number of layers. Free-standing composite films were obtained when the LbL process was carried out for 250 deposition cycles (500 bilayers) on a cellulose acetate substrate, following the dissolution of the substrate in acetone. Scanning electron microscopy of the cryo-fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle was estimated to be 17 nm. The third phase of the study investigated the effect of LbL ordering of the polymers versus a cast film composed of a blended mixture of the polymers, using dynamic mechanical analysis. A tan ï ¤ peak was observed in the 30 – 40 ºC region for both films, which was observed in the neat NC film. Heating of the samples under a compressive force produced opposite effects in the films, as the LbL films exhibited swelling, whereas the cast films showed densification. The apparent activation energy of this transition (65 – 80 kJ mol-1) in cast films, calculated based on the Arrhenius equation was found to be coincident to those reported for the ï ¢ transition of amorphous cellulose. The peak was seen to disappear in case of LbL films in the second heat, whereas it was recurring in case of cast films of the blended mixture, and neat NC films. Altogether, the together the work details a novel path to integrate an organized lignin and cellulose molecular structure, albeit modified from their native form, into a three-dimensional composite material. / Ph. D.
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Fabrication and Characterization of Layer by Layer Assembled Single and Dual-Electrochrome Electrochromic DevicesMontazami, Reza 21 January 2010 (has links)
This thesis presents applications of the layer-by-layer (LbL) assembly technique in fabrication of thin films with a primary focus on design and development of electrochromic devices. The optical properties of electrochromic materials change as they alter between redox states. The morphology and properties of LbL-assembled thin films can be modified by varying several processing factors such as dipping duration, ion type, ion concentration, pH, molecular weight, and ionic strength. In the present work, several factors of LbL assembly process were manipulated to tailor electrochromic thin films of desired attributes.
An electrochromic device (ECD) with fast optical switching speed was designed and constructed based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). This device exhibited optical switching speeds of 31 and 6 ms for coloration and decoloration respectively, on a 60 mm2 area.
Poly(aniline 2-sulfonic acid) (PASA) is a relatively new ionic polymer, and its electrochromic properties have not been previously investigated in much detail. PASA thin film showed several redox states corresponding to color changes from dark blue to gray as it passed different redox states.
One particularly interesting and promising design for ECDs is dual electrochrome. Dual electrochrome ECDs based on PANI and polyaniline (PASA) are investigated in this thesis. The PANI/PASA thin film showed superior spectroelectrochemical properties compare to other ECDs reported here or elsewhere.
An electrode with single wall carbon nanotubes (SWCNTs) coating was tested as the substrate for an ECD based on poly[2-(3-thienyl) ethoxy-4-butylsulfonate] (PTEBS) to examine performance of the electrochromic polymer on a substrate other than an indium tin oxide (ITO) electrode. Compared to ITO, the SWCNT based device exhibited superior properties. / Master of Science
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Multicouches multifonctionnelles de polyelectrolytes pour des applications en filtration membranaire / Multifunctional weak polyelectrolyte multilayers for membrane applicationsIlyas, Shazia 16 February 2017 (has links)
Dans ce travail, nous démontrons que la technique de dépôt multicouche dite layer by layer (LbL) est une technique polyvalente où les propriétés des multicouches telles que l'épaisseur, la charge et la densité peuvent être facilement contrôlées par le choix des polyélectrolytes (PE), le nombre d'étapes et les conditions de dépôt (pH, force ionique, etc.). Nous démontrons que des multicouches de PE faible (PAH / PAA) peuvent être utilisées pour fournir une double fonction aux membranes (PEM) en tant que couche de séparation NF et comme revêtement sacrificiel permettant un nettoyage facile de la membrane. Ces membranes à base de PEM montrent des performances de rejet des solutés dans une gamme typique des membranes NF, c'est-à-dire rejetant peu les ions monovalents (NaCl) (<24%), tout en rejetant> 60% de l'ion divalent SO42- et la molécule organique neutre sulfaméthoxazole (SMX). Par un rinçage et un lavage à contre-courant à basse pression avec une solution stimuli appropriée, nous obtenons un nettoyage sacrificiel réussi d'une membrane colmatée, ce qui ramène la résistance d'une membrane colmatée à celle de la membrane vierge. Après un nouveau dépôt sur la membrane avec le même système PEM, la résistance de la membrane est égale à la résistance du PEM d'origine, ce qui démontre la réutilisation de cette approche. Le mécanisme de rejet des membranes étudiées s'est révélé principalement déterminé par l'exclusion stérique mais aussi par l'exclusion de Donnan. Nous avons étudié notre système PEM pour préparer des membranes pour des applications de nanofiltration résistant aux solvants (SRNF). Des membranes de SRNF avec une couche de séparation de PEM ont été préparées sur un support UF de polyacrylonitrile hydrolysé (PAN-H). Les résultats de cette étude montrent une manière simple et polyvalente d'utiliser le pH pendant le revêtement pour régler les performances de la membrane pour une application SRNF spécifique. Afin d'amener l'approche PEM et du nettoyage sacrificiel à leur maturité et de modifier des modules existants, nous avons simplifié la procédure LbL pour des membranes fibres creuses en utilisant un "dépôt dynamique" ou un "dépôt actif" qui consiste à rincer les solutions du PE à travers le canal interne de la membrane fibre creuse. Cette méthode de dépôt avec sa reproductibilité et son homogénéité permet de revêtir les modules de membrane UF existants. / In this work, we demonstrate that layer by layer (LbL) is a versatile technique where control over multilayer properties such as thickness, charge and density, can be easily achieved simply by the choice of polyelectrolytes, number of coating steps and coating conditions (pH, ionic strength etc.). We demonstrate that multilayers of weak PEs (PAH/PAA) can be used to provide a dual function to membranes (PEM) i.e., as NF separation layer and as a sacrificial coating that allows easy membrane cleaning. These PEM based membranes, shows rejection performance of solutes in a range typical for NF membranes i.e., hardly rejecting monovalent ions (NaCl) (<24%), while rejecting > 60% of the divalent ion SO42- and the neutral organic molecule sulfamethoxazole (SMX). By a rinse and a low pressure backwash with a suitable trigger solution, we obtain a successful sacrificial cleaning of a fouled membrane, bringing the resistance of a fouled membrane back to that of the pristine membrane. Recoating the clean membrane support with the same PEM system brings the resistance of the coated membrane equal to the resistance of the original PEM, demonstrating the re-usability of this approach. The rejection mechanism of the investigated membranes was found to be mainly determined by size exclusion, but influenced by Donnan exclusion. We investigated our weak PEM system to prepare membranes for solvent resistant nanofiltration (SRNF) applications. SRNF membranes with PEM separation layer were prepared on a UF hydrolyzed polyacrylonitrile (PAN-H) support by the LbL method. Results of this study show a simple and versatile way of using pH during coating to tune membrane performance for specific SRNF application. To bring PEM coating and sacrificial cleaning approach into maturity and to coat existing modules we present the simplification of the LbL procedure for hollow fibre membranes by employing "dynamic coating" or "active coating" which involves flushing the PE's solutions through the lumen of the hollow fibre membrane. This coating method with its reproducibility and homogeneity has the potential to coat existing UF membrane modules.
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Estudo da hemoglobina em filmes nanoestruturados como mediador eletroquímico na aplicação em biossensores / Study of hemoglobin in nanostructured films as eletrochemical mediator for biosensor applicationSouza, Tâmera Tais de Lima 24 February 2014 (has links)
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Previous issue date: 2014-02-24 / Financiadora de Estudos e Projetos / The layer-by-layer technique is one of the most used in the immobilization of molecules of biological interest, being largely employed in the fabrication of modified electrodes for biosensors. One of the main challenges in the development of biosensors is to eliminate interfering electroactive species within the detection system, therefore, this problem can be solved with the introduction of inorganic or organic electron mediators. Here, we carried out systematic studies for the application of hemoglobin acting as an electron mediator, and the self-assembly technique was used to immobilize haemoglobin in nanostructured thin films. The LbL films were tested with two polyelectrolytes, obtaining uniform films with activity kept during 15 days, without responses to possible interfering phospholipids. The layer-bylayer technique was also used to immobilize the enzyme cholesterol oxidase, alternated with different polyelectrolytes. The thin films showed a good performance as an amperometric biosensor for the detection of cholesterol at low concentrations (10-5 M), with the functioning of the biosensor attributed to the use of hemoglobin in mediating the effects of excluding interfering ascorbic acid and uric acid. Some tests were also performed in real samples using
egg yolk, with good results obtained. The high sensitivity and selectivity of the biosensor have been attributed to the nanostructured thin nature of the films, despite recognition capability of the biomolecules used, with a strong potential to contribute for new device
technologies for food analysis. / A técnica de automontagem ou layer-by-layer é uma das mais utilizadas na imobilização de moléculas de interesse biológico. Essa técnica é empregada na fabricação de eletrodos modificados utilizados, como por exemplo, os biossensores. Um dos desafios no
desenvolvimento de biossensores é eliminar interferentes de espécies eletroativas dentro do sistema de detecção. Esse problema pode ser solucionado com a introdução de mediadores de elétrons inorgânicos ou orgânicos. Nessa dissertação foram realizados estudos sistemáticos
para a aplicação da hemoglobina atuando como mediadora de elétrons. A técnica de automontagem foi utilizada para a imobilização da hemoglobina, testada com dois polieletrólitos, obtendo filmes uniformes, mantendo sua atividade por 15 dias e sem respostas
aos possíveis interferentes fosfolipídios. A automontagem também foi utilizada para imobilizar a enzima colesterol oxidase, alternada com diferentes polieletrólitos. Os filmes finos apresentaram um bom desempenho como biossensor amperométrico na detecção de
colesterol em baixas concentrações tais como 10-5 M. O bom funcionamento do biossensor deve- se ao emprego da hemoglobina com mediador excluindo os efeitos dos interferentes acido úrico e acido ascórbico. Também foram realizados testes com amostras reais utilizando a gema de ovo obtendo bons resultados. A alta sensibilidade e seletividade dos biossensores foram atribuídas à natureza do filme automontado e à capacidade de reconhecimento das biomoléculas. Este estudo abre caminho para novas tecnologias de dispositivos para análises de alimentos.
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Caracterização por espectroscopia vibracional de filmes Layer-by-Layer contendo ftalocianina, polímeros condutores e gomas naturaisKitagawa, Igor Lebedenco [UNESP] 19 June 2009 (has links) (PDF)
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kitagawa_il_me_bauru.pdf: 1240008 bytes, checksum: 9ebbdde64d8ef13b31f5e5e5f9a075cc (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Esta dissertação apresenta o estudo do crescimento (em escala nanométrica) e morfológica (em escala micrométrica) de filmes finos fabricados segundo a técnica Layer-by-Layer (LbL) contendo ftalocianina tetrasulfonada de níquel, polímeros condutores, o polímero poli(alilamina hidroclorada) (PAH), e gomas naturais. Três sistemas foram investigados: i) filmes LbL de NiTsPc e PAH; ii) filme LbL de NiTsPc, PAH e gomas naturais e iii) filmes LbL dos polímeros condutores polianilina (PANI) e poli(o-metoxianilina) (POMA) com gomas naturais. As gomas utilizadas neste trabalho foram extraídas das árvores cajueiro (Anacardium occidentale), chichá (Sterculia striata), caraia (Sterculia urens) e angico (Anadenanthera macrocarpa Benth). As caracterizações destes filmes foram realizadas por meio das técnicas de espectroscopia eletrônica utilizando absorção na região do ultravioleta-visível (UV-vis), espectroscopia vibracional por espalhamento micro-Raman e por absorção na região do infravermelho (IV) com transformada de Fourier (FTIR). Os resultados deste trabalho mostraram que, somente os filmes de NiTsPc e PAH em pH 8,5 e os filmes de NiTsPc, PAH e gomas naturais apresentaram crescimento controlado, uniformidade morfológica e química. / This dissertation presents the study of growth (in nano-scale thickness) and morphology (micrometric scale) of thin films produced using the Layer-by-Layer technique (LbL) containing nickel tetrasulfonated phthalocyanine, conducting polymers, the polymer poly(allylamine hydrochloride) (PAH), and natural gums. Three systems were investigated: i) LbL films of NiTsPc and PAH; ii) LbL films of NiTsPc, PAH and natural gums and iii) LbL films of the conducting polymers polyaniline (PANI) and poly (o-methoxyaniline) (POMA) with natural gums. The gums used in this work were obtained from the cashew (Anacardium occidentale), chicha (Sterculia striata), caraia (Sterculia urens) and angico (Anadenanthera macrocarpa Benth) trees. The characterizations of the LbL films were made using the ultraviolet-visible (UV-vis) absorption spectroscopy, vibrational spectroscopy through micro-Raman scattering and Fourier Transform infrared (FTIR) absorption. The results showed that only the LbL films of NiTsPc and PAH at pH 8.5 and the LbL films of NiTsPc, PAH and natural gums present controlled growth and morphological and chemical uniformity.
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Films multicouches nanocristaux de cellulose/Ge-Imogolite pour l'élaboration de nouveaux matériaux nanoporeux / Elaboration of cellulose nanocrystal/Ge-imogolite multilayered thin film to design new nanoporous materialsMauroy, Cyprien 06 November 2017 (has links)
Lors des dix dernières années, les films multicouches ont suscité l’intérêt de la communauté scientifique pour leurs propriétés innovantes. Principalement issus de l’association de polyélectrolytes et/ou de nanoparticules de différentes morphologies, ils ont ouvert la voie à la fabrication d’une nouvelle catégorie de matériaux nanoporeux, possédant des propriétés optiques attractives telles que la coloration structurale et l’antireflet. Les films multicouches à base de deux nanoparticules de charges opposées sont plus rares et permettent de jumeler les propriétés des deux nanoparticules utilisées et d’en faire émerger de nouvelles. Dans cette étude, nous nous sommes intéressés à deux nanoparticules anisotropes, de facteurs d’aspects contrôlés et respectivement bio/geosourcées : les nanocristaux de cellulose (NCC) et des nanotubes d’imogolite. Le but de cette étude est d’étudier la possibilité de créer un film multicouche bio-géo inspiré à base de ces deux nanoparticules par immersion et d’en étudier les propriétés optiques. Dans un premier temps, nous avons comparé les films multicouches NCC/Ge-imogolites à ceux plus communément décrits dans la littérature, à savoir, des films à base de NCC ou d’imogolite associés à un polyélectrolyte de charge opposée. Les différents paramètres de trempage comme le temps d’immersion et la force ionique de la suspension ont été variés afin d’obtenir une densité de film optimale. Pour finir la porosité des films et leur comportement dans l’eau ont été étudiés par QCM-D, ainsi que leurs propriétés optiques par mesure de transmittance. / In the past decade, multilayer thin films drew the scientific community attention for their unique properties. Indeed, principally made of an association of polyelectrolytes and/or nanoparticles, of various morphologies and chemistries, they allow the design of a range of porous nanomaterials with unique optical properties, such as structural colors or anti-reflectivity. Less commonly described, thin films made of two nanoparticles of opposite charges are gaining interest since they combine the properties of the two nanoparticles used, and generate new ones through their association. In this study, multilayer coatings were formed through the association of two anisotropic oppositely charged nanorods of well-controlled aspect ratio, i.e. bio-based anionic cellulose nanocrystals (CNC) and geo-based cationic Imogolites. This study deals with the feasibility to create a bio-geo-inspired multilayer thin film based on these two nanoparticles by dipping and characterize their optical properties. Firstly, elaboration of multilayered thin films from CNC and Ge-Imogolites nanorods, were studied in comparison with reference films incorporating CNC or Imogolites with polyelectrolytes bearing opposite charges of the nanorods. Multilayered thin films were assembled by the dipping procedure and various parameters (adsorption time, ionic strength, etc.) were varied to investigate the optimal density for the film. To finish, film porosities were investigated using QCM-D, and optical properties were investigated by transmittance measurements.
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Influence of level of cellulose oxidation and surface treatment on the adhesion between cellulose beads / Inverkan av oxidationsnivå och ytbehandling av cellulosasfärer på molekylär adhesion mellan kulornaKällgren, Rasmus January 2020 (has links)
With the growing impact of climate change on both political decisions and how companies develop their products, it is increasingly important to find environmentally friendly alternatives to fossil-based materials. One of the more interesting materials in this respect is cellulose, which is the world's most naturally occurring polymer and can be used in a variety of applications. One way to modify the fibers and to change their properties is to use a method called Layer-by-Layer (LbL) treatment where two polymers of opposite charge are alternately adsorbed to the fiber surface. Another possibility is to oxidize the cellulose in the fibers to obtain a higher charge. This means that the fibers can adsorb a higher amount of cationic additives and that the fibers swell more which means that they are plasticized and can create stronger joints between the fiber surfaces in the dry state, which results in stronger dry fiber networks. However, wood-based fibers are small and inhomogeneous, both chemically and morphologically, which means that it is necessary to use model systems to be able to clarify, in detail, how treated and untreated surfaces interact with each other at a molecular level. One model system that can be used to investigate how cellulose fibers are affected by coating using the LbL method is to use spherical beads made from regenerated cellulose. In the present work, these beads were treated with polyallylamine hydrochloride (PAH) and hylauronic acid (HA) as well as with PAH and alginate (Alg) before being allowed to dry together and then subjected to tensile testing to clarify the adhesion between the surfaces. The beads were treated with five and ten bi-layers of these polymers, respectively, and then dried together on an AKD-coated surface, to avoid adhesion to the underlying surface, to examine the adhesion between the beads. The adhesion increased when treated with LbL and became higher upon adsorption of multiple layers of polyelectrolytes and the Alg / PAH system showed the greatest increase. Ten-layer samples of Alg / PAH were also tested after a solution of calcium chloride was added during drying, resulting in poorer adhesion between the beads. / Med klimatfrågans växande inverkan på både politiska beslut och hur företagen utvecklar sina produkter så läggs det allt större vikt vid att hitta miljövänliga alternativ till fossilbaserade material. Ett av de mer intressanta materialen är cellulosa vilket är världens mest naturligt förekommande polymer och som kan användas i en rad olika tillämpningar. Ett sätt att modifiera fibrerna och att ändra deras egenskaper är att använda sig av en metod som kalls Layer-by-layer (LbL) behandling där två polymerer mot motsatt laddning växelvis adsorberas till fiberytan. En annan möjlighet är att oxidera cellulosan i fibrerna så att de erhåller de en högre laddning. Detta innebär dels att fibrerna kan adsorbera en högre mängd katjoniska tillsatskemikalier samt att fibrerna sväller mera vilket innebär att de plasticeras och kan skapa starkare fogar mellan fiberytorna i torrt tillstånd vilket resulterar i starkare torra fibernätverk. Vedbaserade fibrer är dock små och inhomogena såväl kemiskt som morfologiskt vilket innebär att det är nödvändigt att använda modellsystem för att kunna klarlägga, i detalj, hur behandlade och icke behandlade ytor växelverkar med varandra på en molekylär nivå. Ett modellsystem som kan användas för att undersöka hur cellulosafibrer påverkas av att beläggas med hjälp av LbL metoden är att använda sig av sfäriska kulor tillverkade från regenererad cellulosa. I föreliggande arbete behandlades dessa kulor med polyallylaminhydroklorid (PAH) och hylauronsyra (HA) samt med PAH och alginat (Alg) innan de tilläts torka ihop och därefter utsattes för dragprovning för att klarlägga adhesionen mellan ytorna. Kulorna behandlades med fem respektive tio bilager av dessa polymerer och torkades sedan ihop på en AKD-belagd yta, för att undvika adhesion till den underliggande ytan, för att undersöka adhesionen mellan kulorna. Adhesionen ökade när de behandlades med LbL och blev högre vid adsorption av flera lager polyelektrolyter och systemet med Alg/PAH resulterade i den största ökningen. Prover med tio lager av Alg/PAH testades även efter att en lösning av kalciumklorid tillsattes under torkningen vilket resulterade i en sämre adhesion mellan kulorna.
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Oberflächenfunktionalisierung von Layer-by-Layer-beschichteten kolloidalen SiO2-Mikropartikeln für eine spezifische Aufnahme durch ZellenGöse, Martin-Patrick 07 December 2016 (has links) (PDF)
Systemisch applizierte Therapeutika können erhebliche Nebenwirkungen auslösen, welche auf Grund eines unspezifischen Transports oder einer hohen Dosis von appliziertem Wirkstoff auftreten. Daher bedarf es der Entwicklung neuartiger Wirkstoff-Transportsysteme (Drug Delivery Systems) welche in der Lage sind, Wirkstoffe in genau definierbaren Dosen gezielt in die adressierte Zelle zu transportieren. Ein vielversprechender Ansatz, welcher diesen Anforderungen nachkommt, findet sich in der Layer-by-Layer-Technik (LbL), d.h. der wechselseitigen Assemblierung von Polymeren/Wirkstoffen auf soliden sphärischen Templaten, eines funktionellen Supported Lipid Bilayers sowie der Oberflächenfunktionalisierung mit spezifischen Antikörpern. Dabei ist die Homogenität und Regularität des Supported Lipid Bilayers von großer Bedeutung, um in biomedizinischen Anwendungen eine ungewollte Interaktion mit Serumkomponenten sowie eine Opsonierung zu verhindern. Insbesondere die funktionelle Lipidkomponente besitzt allerdings maßgebliche Auswirkungen auf diese Parameter.
In dieser Arbeit wurde die Idee der Oberflächenfunktionalisierung von LbL-beschichteten Silica-Mikropartikeln (SiO2) mit einem funktionellen Supported Lipid Bilayer aufgegriffen und weiterentwickelt, wobei insbesondere die Homogenität des Supported Lipid Bilayers auch auf sehr kleinen Längenskalen (wenige Nanometer) bestimmt wurde. In einem letzten Schritt konnte anhand zweier verschiedener Zelllinien (3T3 und Vero) die Adaptivität und Effektivität des entwickelten Drug Delivery Systems nachgewiesen werden.
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Eletroinserção de íons lítio em matrizes auto-organizadas de V2O5, poli(etilenoimina) e nanopartículas de carbono / Electroinsertion of lithium ions in self-assembled matrices composed of V2O5, poly(ethyleneimine), and carbon nanoparticlesSantos, Ana Rita Martins dos 01 August 2013 (has links)
Materiais auto-organizados constituídos de V2O5 xerogel, poli(etilenoimina) (PEI) e nanopartículas de carbono (NpCs) foram obtidos por meio da técnica camada-por-camada (LbL). A metodologia aplicada permitiu a obtenção de filmes finos com elevado controle de espessura além de permitir um crescimento linear dos filmes, denominados neste trabalho V2O5/PEI e V2O5/PEI/NpCs. Além disso, o desempenho eletroquímico dos materiais auto-organizados foi comparado a um eletrodo de V2O5. Análises de FTIR mostraram que interações específicas entre os grupos amina do PEI e os grupos carboxila do V2O5 são responsáveis pelo crescimento do filme. Estas interações permitem a formação de um campo eletrostático capaz de blindar as interações entre os íons lítio e os oxigênios da vanadila (V=O) e, por consequência, são responsáveis pelo aumento na mobilidade iônica dos íons lítio no interior da matriz hospedeira e, portanto, um aumento na capacidade de armazenamento de carga. Resultados obtidos através de medidas de carga/descarga mostram que o V2O5/PEI/NpCs apresenta uma melhor desempenho do que os demais materiais estudados neste trabalho. Estes resultados mostram que a capacidade específica do V2O5/PEI/NpCs foi de 137 mA h g-1 para a menor densidade de corrente aplicada e aproximadamente 1,6 vezes maior do que os valores de capacidade específica para os outros materiais para a maior densidade de corrente aplicada. Além disso, estas medidas permitiram a observação de uma menor variação na razão estequiométrica máxima (xmáx) em função das densidades de corrente aplicadas para os filmes auto-organizados, fato este relacionado a uma maior mobilidade iônica dos íons lítio no interior dessas matrizes. Os resultados obtidos a partir de espectroscopia de impedância eletroquímica (EIS) mostraram que a difusão dos íons lítio no interior das matrizes auto-organizadas é maior do que no caso do V2O5, cujos valores do coeficiente de difusão foram de 1,64 x 10-15, 1,21 x 10-14 e 2,26 x 10-14 cm2 s-1 para os filmes V2O5, V2O5/PEI e V2O5/PEI/NpCs, respectivamente. Sendo assim, o polímero e as NpCs promoveram novos caminhos condutores e permitiram a conexão elétrica entre camadas isoladas da matriz V2O5. Dessa forma, novos nanocompósitos foram obtidos visando demonstrar o método de auto-organização empregado para melhorar o transporte de carga em matrizes hospedeiras. / Self-assembled materials constituted of V2O5 xerogel, poly (ethyleneimine) (PEI), and carbon nanoparticles (CNPs) were obtained by the layer-by-layer (LbL) technique. The applied methodology permitted the obtainment of thin films with high thickness control and also permitted a linear growth of the films, which will be named V2O5/PEI and V2O5/PEI/CNPs. Besides, the electrochemical performance of the self-assembled materials was compared to a V2O5 electrode. FTIR analyses showed that the specific interactions between the amine groups of PEI and the vanadyl groups of the V2O5 are responsible for the film growth. These interactions permitted the formation of an electrostatic shield capable of hindering the interactions between the lithium ions and the vanadyl oxygen atoms (V=O) and are consequently responsible for the enhancement on the ionic mobility of the lithium ions within the host matrix, leading to a higher energy storage capability. Results obtained by the charge/discharge measurements showed that V2O5/PEI/CNPs presents a better performance than the other materials studied for this research. These results demonstrated that the specific capacity of the V2O5/PEI/CNPs was 137 mA h g-1 under the lowest current density applied and approximately 1.6 times higher than the specific capacity values obtained for the other materials under the highest current density applied. Moreover, it was observed that the variation of the maximum stoichiometric ratio (xmax) as a function of the current density is lower for the self-assembled materials than for the V2O5 electrode, which can be related to the higher ionic mobility of the lithium ion within the self-assembled materials. Electrochemical Impedance Spectroscopy (EIS) data demonstrated that the diffusion of the lithium ions within the self-assembled materials is higher than within the V2O5 electrode, and the diffusion coefficients were 1.64 x 10-15, 1.21 x 10-14 e 2.26 x 10-14 cm2 s-1 for V2O5, V2O5/PEI and V2O5/PEI/CNPs, respectively. Thus, the polymer and the CNPs provided new conducting pathways and connected isolated V2O5 chains in the host matrix. Therefore, novel spontaneous nanocomposites were formed, aiming to demonstrate the self-assembled method adopted for improving charge transport within host matrices.
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