Thin films with the ability to impart oxygen and other types of gas barrier are crucial to commercial packaging applications. Commodity polymers, such as polyethylene (PE), polycarbonate (PC) and polyethylene terephthalate (PET), have insufficient barrier for goods requiring long shelf life. Current gas barrier technologies like plasma-enhanced vapor deposition (PECVD) often create high barrier metal oxide films, which are prone to cracking when flexed. Bulk composites composed of polymer and impermeable nanoparticles show improved barrier, but particle aggregation limits their practical utility for applications requiring high barrier and transparency. Layer-by-layer (LbL) assemblies allow polymers and nanoparticles to be mixed with high particle loadings, creating super gas barrier thin films on substrates normally exhibiting high gas permeability. Branched polyethylenimine (PEI) and poly (acrylic acid) (PAA) were deposited using LbL to create gas barrier films with varying pH combinations. Film thickness and mass fraction of each component was controlled by their combined charge. With lower charge density (PEI at pH 10 and PAA at pH 4), PEI/PAA assemblies exhibit the best oxygen barrier relative to other pH combinations. An 8 BL PEI/PAA film, with a thickness of 451 nm, has an oxygen permeability lower than 4.8 x 10^-21 cm^3 * cm/cm^2 * s * Pa, which is comparable to a 100 nm SiOx nanocoating. Crosslinking these films with glutaraldehyde (GA), 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide methiodide (EDC) or heating forms covalent bonds between PEI and/or PAA. Oxygen transmission rates (OTR) of 8 BL films crosslinked with 0.1M GA or 0.01M EDC show the best oxygen barrier at 100% RH. Graphene oxide (GO) sheets and PEI were deposited via LbL with varying GO concentration. The resulting thin films have an average bilayer thickness from 4.3 to 5.0 nm and a GO mass fraction from 88 to 91wt%. Transmission electron microscopy and atomic force microscopy images reveal a highly-oriented nanobrick wall structure. A 10 BL PEI/GO film that is 91 nm thick, made with a 0.2 wt% GO suspension, exhibits an oxygen permeability of 2.5 x 10^-20 cm^3 * cm/cm^2 * s * Pa. Finally, the influence of deposition time on thin film assembly was examined by depositing montmorillonite (MMT) or laponite (LAP) clays paired with PEI. Film growth and microstructure suggests that smaller aspect ratio LAP clay is more dip-time dependent than MMT and larger aspect ratio MMT has better oxygen barrier. A 30 BL PEI/MMT film made with 10 second dips in PEI has the same undetectable OTR as a film with 5 minute dips (with dips in MMT held at 5 minutes in both cases), indicating LbL gas barrier can be made more quickly than initially thought. These high barrier recipes, with simple and efficient processing conditions, are good candidates for a variety of packaging applications.

Energy storage devices are generally evaluated on two main requirements; power and energy. In supercapacitors these two performance criteria are altered by the capacitance, resistance and voltage. (For complete abstract open document)

Boundary-layer flows near leading edges of generally curved obstacles have been studied for a long time. Apart from having many practical applications, the theory and approaches prevailing in this area stimulate development of a variety of computational tools and form a ground for testing them. The specific aim of this work is to study two-dimensional laminar boundary layer flows near the leading edges of airfoils and other elongated bodies, and to explore geometries for which boundary layer separation can be avoided. This class of problems is relevant to optimal design of wings, aircraft and projectile noses, laminar flow control methods and adaptive wing technology. One of the findings of this work suggests that local modifications to parabolic wing noses can yield up to 11% increase in the unseparated angle of attack. Another result obtained here is the set of shortest possible generalised elliptic noses of long symmetric bodies which allow unseparated flow. Methods adopted in this work are based on the combined use of numerically solved Prandtl equations written in Gortler variables, and inviscid solutions obtained semi-analytically by the conformal mapping method. The resulting technique being reliable, fast and computationally inexpensive, can complement or test the results obtained using a comprehensive CFD approach. / Thesis (Ph.D.)--School of Mathematical Sciences, 2002.

Thesis (M. App. Sc.)--Carleton University, 2005. / Includes bibliographical references. Also available in electronic format on the Internet.

Thesis (Ph. D.)--Miami University, Dept. of Chemistry and Biochemistry, 2006. / Title from first page of PDF document. Includes bibliographical references.

Volvo Car Corporation (VCC) uses Computational Fluid Dynamics (CFD) and wind tunnel during the aerodynamic development of new vehicles. In the past VCC main focus has been on the drag force correlation to the wind tunnel measurements but in recent years improved methods for lift force correlations has been highly wanted. Three objectives were considered in this study to improve the lift force correlation between the CFD simulations and wind tunnel measurements for geometrical configurations of the V60 and S60 models.Poor mesh resolution for the wall bounded flow existed for the VCC mesh method and therefore prisms layers were considered in this thesis to increase the mesh resolution inside the boundary layer.As slick tyres generally were used in the CFD simulations better geometrical correlation was wanted to be studied as it could improve the lift force correlation between CFD simulations and wind tunnel measurements. Therefore detailed tyres were considered in this study.As the coarsest surface mesh size was used for the underbody and the components inside the engine bay, where some of the highest flow velocities occurred, mesh refinements were investigated for engine bay and underbody in this study.The prisms layers improved the predicted behavior for the boundary layer as it captured the large velocity gradients more accurately. Due to this, the skin friction prediction was also improved. Different flow behavior around the front wheels and rear wake occurred due to earlier separation. The different flow field caused an improved correlation for the lift force but worsened correlation for the drag force due to increased pressure at the rear of the cars. However, the front lift force trend correlation for the considered configurations was improved with the prisms layer mesh method.The detailed tyres caused slight more disturbances for the underbody flow which caused more attached flow around the rear of the car hence lowered pressure. Earlier separation around the front wheels also occurred for the detailed tyre geometry as the disturbed flow around the wheels was increased. Slight improved correlation for the front and rear lift forces to the wind tunnel measurements could be seen with the detailed tyre compared to the slick tyre.The mesh refinements for the engine bay and underbody showed significant differences for the flow at the underbody which had significant impact on the flow at the rear wake for the V60 model. Minor differences could be seen for the aerodynamic forces for the baseline configuration for the V60 model while great differences occurred for the configurations affecting the underbody. Due to this significant improved correlation for the front and rear lift force trends were achieved for the underbody configurations with the refined engine bay and underbody mesh method.Conclusions could be drawn that the prisms layer caused earlier separation due to its increased mesh resolution for the wall bounded flow. However, finer mesh resolution was needed inside the boundary layer to ensure consistent separation behavior for both the considered models. Improved correlation for the front lift force could however be seen. The detailed tyre only had minor effects on the flow field and aerodynamic forces and therefore not so important to include for further studies. The refined engine bay and underbody caused significant improved lift force trend correlation to the wind tunnel measurements and should be considered for future studies. To improve the correlation between CFD simulations and wind tunnel measurements increased mesh resolution for the wall bounded flow should be considered to better capture the large velocity gradients close to the wall.

Made available in DSpace on 2014-06-11T19:23:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-11-19Bitstream added on 2014-06-13T18:09:41Z : No. of bitstreams: 1 storti_fc_me_bauru.pdf: 1104117 bytes, checksum: f3374b86db01b726a613c1cc13d060e9 (MD5) / Nesta dissertação é apresentado um estudo envolvendo a arquitetura molecular (crescimento controlado, morfologia e organização molecular) de filmes Layer-by-Layer (LbL) contendo ftalocianina tetrasulfonada de cobre (CuTsPc). Inicialmente foram realizados estudos sobre a cinética de crescimento desses filmes para determinação do tempo de adsorção do material no substrato. Uma vez determinado este tempo, filme LbL foram fabricados utilizando soluções catiônica de poli(alilamina) hidroclorada - PAH) e aniônica de CuTsPc. Os filmes de PAH/CuTsPc foram produzidos de forma manual e utilizando um braço mecânico em valores de pHs 2,5; 5,5 e 8,5 sendo então caracterizados por espectroscopia eletrônica via absorção na região do ultravioleta-visível (UV-Vis), espectroscopia vibracional via espalhamento Raman e absorção na região do infravermelho com transformadora de Fourier (FTIR) e microscopias óptica e força atômica (AF,A). A espectroscopia de absorção na região do UV-Vis foi utilizada para acompanhar o crescimento do filme LbL assim como investigar a presença de agregados. A técnica de FTIR permitiu investigar as interações entre o PAH e a CuTsPc e determinar a organização molecular comparando filme LbL e cast. O acoplamento entre microscópio óptico e espectrógrafo Raman (técnica microRaman) possibilitou analisar a morfologia do filme LbL em escala micrométrica combinando informações ópticas e químicas. A morfologia do filme LbL em escala nanométrica foi investigada utilizando-se AFM. Foi observado que os filmes crescidos mecanicamente são mais espessos em relação aos crescidos manualmente, além de apresentarem maior rugosidade. Ainda em termos morfológicos, os filmes crescidos mecanicamente apresentam uma maior quantidade de agregados, porém, menores em termos de diâmetro médio, tanto em escala nano como micrométrica... / This dissertation presents a study involving the molecular architecture (controlled growth, morphology, and molecular organization) of layer-by-layer (LbL) films containing copper phthalocyanine tetrasulfonated (CuTsPc). Initially, the studies were performed on the kinetics of growth of these films to determine the time of adsorption of the material on the substrate. Once determined this time, LbL films were produced by using solutions of cationic poly (hydrochloric alilamina - PAH) and anionic CuTsPc. The films of PAH / CuTsPc were produced either manually or using a mechanical arm in pH values of 2.5, 5.5, and 8.5, and then characterized by electron spectroscopy via absorption in the ultraviolet-visible (UV-Vis), vibrational spectroscopy by Raman scattering and absorption in the infrared region with Fourier transform infrared (FTIR) and optical microscopy and atomic force microscopy (AFM). The absorption spectroscopy in the UV-Vis was used to follow the growth of the LbL film and to investigate the presence of aggregates. The FTIR technique allowed investigatin the interactions between the PAH and CuTsPc and determining the molecular organization comparing LbL films and cast. The coupling between optical microscope and Raman spectrograph (micro-Raman technique) allowed analyzing the morphology of the LbL film at micrometric scale combining optical and chemical information. The morphology of the LbL film at nanometer scale was investigated by using AFM. It was observed that the films grown mechanically are thicker in relation to grown manually and present greater roughness. Also in morphological terms, the films grown mechanically have an increased number of aggregates, however, smaller in terms of average diameter, at nano and micrometric scales. It was found that the pH is a key parameter to induce the formation of molecular clusters. For instance, more homogeneous LbL films in term... (Complete abstract click electronic access below)

No description available.

O objetivo do presente estudo foi avaliar a remoção da smear layer e a penetração intratubular do cimento obturador AH Plus utilizando diferentes protocolos de irrigação. Após aprovação do Comitê de Ética em Pesquisa da Faculdade de Odontologia de Ribeirão Preto - FORP/USP, noventa incisivos centrais superiores foram selecionados e fornecidos pelo banco de dentes da mesma instituição. Estes foram radiografados no sentido mésio - distal e vestíbulo - lingual para comprovar a presença de canais únicos, sem curvaturas abruptas, reabsorções ou tratamentos endodônticos prévios. Após a remoção da porção coronal para a obtenção de raízes com comprimentos padronizados de 15 milímetros, os diâmetros anatômicos foram determinados e as instrumentações realizadas por meio da técnica coroa ápice estabelecendo os diâmetros cirúrgicos utilizando 3 instrumentos acima dos anatômicos. Durante este processo, os espécimes foram divididos em seis grupos de acordo com os protocolos de irrigação: Grupo 1 (controle - n. 15) - 2,5ml de água destilada a cada troca de instrumentos e 2,5ml de água destilada por 3 minutos ao final da instrumentação; Grupo 2 (n. 15) - 2,5ml de hipoclorito de sódio a 2,5% a cada troca de instrumentos e 2,5ml de hipoclorito de sódio a 2,5% por 3 minutos ao final da instrumentação; Grupo 3 (n. 15) - 2,5ml de hipoclorito de sódio a 2,5% a cada troca de instrumentos e 2,5ml de EDTA a 17% por 3 minutos ao final da instrumentação; Grupo 4 (n. 15) - 2,5ml de hipoclorito de sódio a 2,5% e 2,5ml de EDTA a 17% a cada troca de instrumentos + 2,5ml de EDTA a 17% por 3 minutos ao final da instrumentação; Grupo 5 (n. 15) - 2,5ml de hipoclorito de sódio a 2,5% a cada troca de instrumentos e 2,5ml de ácido cítrico a 10% por 3 minutos ao final da instrumentação; Grupo 6 (n. 15) - 2,5ml de hipoclorito de sódio a 2,5% e 2,5ml de ácido cítrico a 10% a cada troca de instrumentos + 2,5ml de ácido cítrico a 10% por 3 minutos ao final da instrumentação. Após esta fase, cinco espécimes de cada grupo foram clivados no sentido mésio - distal para avaliação da remoção da smear layer em microscopia eletrônica de varredura por meio da análise de 3 imagens de cada terço em aumentos de 300, 1000 e 2000 vezes. Esta variável foi determinada por um score qualitativo estabelecido pelo consenso de 3 avaliadores calibrados. Os demais espécimes foram obturados pela técnica de condensação lateral com cones principais correspondentes ao último instrumento associados ao cimento AH Plus corado com Rodamina B, cones acessórios B8 e mantidos em ambiente com 100% de umidade por 7 dias. Em seguida, os espécimes foram seccionados transversalmente para obtenção de slices de aproximadamente 2mm de espessura em cada terço (cervical, médio e apical) e as faces cervicais submetidas a um tratamento metalográfico para análise da penetração intratubular do cimento obturador em microscopia confocal a laser. Os melhores índices de remoção de smear layer e as maiores porcentagens de penetração intratubular do cimento foram obtidos pelos grupos onde as soluções quelantes foram utilizadas (G3, G4, G5 e G6) com diferenças estatisticamente significantes (p<0,05) em relação aos grupos onde utilizou - se somente a água destilada (G1) e o hipoclorito de sódio a 2,5% (G2) durante o processo de instrumentação. Não foram observadas vantagens em relação ao uso associado do EDTA a 17% e do ácido cítrico a 10% ao hipoclorito de sódio pela ausência de diferenças estatísticas significantes entre os grupos 3 e 4 e 5 e 6, respectivamente. / The aim of this study was to evaluate the smear layer removal and tubular dentine sealer penetration of AH Plus after different irrigation protocols. After approval of the study by the Ethics Committee of the Ribeirão Preto Dental School - FORP/USP, ninety maxillary central incisors were selected and supplied by the tooth bank of the same institution. The teeth were radiographed in the mesiodistal and buccolingual directions to verify the presence of single canals, without abrupt curvatures, resorption or previous endodontic treatment. The coronal portion was removed and roots lengths were standardized at 15 mm. The anatomic diameters were then determined and instrumentations were carried out by the crown-down technique, using 3 higher-diameter instruments to establish the surgical diameters. During this process, the specimens were divided into six groups, according to the following irrigation protocols: Group 1 (control - n. 15) - 2.5ml of distilled water at each change of instruments + 2.5ml of distilled water for 3 minutes at the end of the instrumentation; Group 2 (n. 15) - 2.5ml of 2.5% sodium hypochlorite at each change of instruments + 2.5 ml of 2.5% sodium hypochlorite for 3 minutes at the end of the instrumentation; Group 3 (n. 15) - 2.5ml of 2.5% sodium hypochlorite at each change of instruments + 2.5ml of 17% EDTA for 3 minutes at the end of the instrumentation; Group 4 (n. 15) - 2.5ml of 2.5% sodium hypochlorite and 2.5ml of 17% EDTA at each change of instruments + 2.5ml of 17% EDTA for 3 minutes at the end of the instrumentation; Group 5 (n. 15) - 2.5ml of 2.5% sodium hypochlorite at each change of instruments + 2.5ml of 10% citric acid for 3 minutes at the end of the instrumentation; Group 6 (n. 15) - 2.5ml of 2.5% sodium hypochlorite and 2.5 ml of 10% citric acid at each change of instruments + 2.5 ml of 10% citric acid for 3 minutes at the end of the instrumentation. Following this phase, five specimens from each group were cleaved in the mesiodistal direction to evaluate the smear layer removal by scanning electron microscopy. Evaluation was performed by analyzing 3 images of each third at 300, 1000 and 2000X. This variable was determined by a qualitative score established by the consensus of 3 calibrated examiners. The remaining specimens were filled using lateral condensation with AH Plus sealer labeled with Rhodamine B and kept in an environment with 100% humidity for 7 days. Then, the specimens were sectioned to obtain approximately 2 mm thick slices of each third (cervical, middle and apical). The cervical surfaces were subjected to metallographic treatment for analysis of the tubular dentine sealer penetration by confocal laser microscopy. The highest smear layer removal rates and tubular dentine sealer penetration percentages were obtained by the groups that used chelating solutions (G3, G4, G5 and G6). These showed statistically significant differences (p<0.05) compared with the groups that used just distilled water (G1) and 2.5% sodium hypochlorite (G2) during instrumentation. No benefits were observed for the combined use of 17% EDTA or 10% citric acid with 2.5% sodium hypochlorite, considering that there were no statistically significant differences between groups 3 and 4, and between 5 and 6, respectively.

Made available in DSpace on 2014-06-11T19:30:19Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-02-15Bitstream added on 2014-06-13T20:00:21Z : No. of bitstreams: 1 aoki_phb_me_bauru.pdf: 3726182 bytes, checksum: c582cd9cf1e3d2f3af8f65685764355e (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A presente dissertação de mestrado trata da fabricação de filmes ultrafinos (nanômetros de espessura) de fosfolipídios aniônicos (DPPG e CLP) e zwiteriônicos (DPPC e DOPC) utilizando as técnicas layer-by-layer (LbL) e Langmuir-Blodgett (LB), possibilitando assim a obtenção de filmes com diferentes arquiteturas moleculares. O objetivo principal foi explorar a aplicação destas diferentes arquiteturas moleculares na detecção do fármaco fenotiazínico azul de metileno (AM) em soluções diluídas. O crescimento linear, camada por camada, desses filmes foi verificado e monitorado por espectroscopia de absorção no UV-Vis. Verificou-se por FTIR que o crescimento dos filmes LbL e LB é determinado por interações eletrostáticas entre os fosfolipídios e o polieletrólito catiônico PAH utilizado como camada de suporte, favorecendo o crescimento dos filmes com fosfolipídios aniônicos. A morfologia foi analisada através de microscopias ópticas, AFM e MEV, revelando que os fosfolipídios estruturam-se como vesículas nos filmes LbL e monocamadas nos filmes LB. Filmes LbL e LB de fosfolipídios com diferentes espessuras foram então depositados sobre eletrodos interdigitados de Pt formando unidades sensoriais que foram aplicadas na detecção de AM via espectroscopia de impedância. Os resultados mostraram que as diferentes arquiteturas moleculares dos filmes LbL e LB levam a respostas elétricas distintas e permitem a detecção de AM em concentrações de nanomolar. A técnica SERS foi utilizada para obter informações estruturais do sistema AM/fosfolipídios nos níveis de diluição alcançados via espectroscopia de impedância. Para tanto, monocamadas LB foram depositados sobre filmes evaporados com 6 nm de Ag e nanopartículas de Ag foram dispersas no interior dos filmes LbL. A presença da Ag na forma de nanopartículas em ambos os casos permitiu a obtenção... / Thin films of anionic (DPPG and CLP) and zwiterionic (DPPC and DOPC) phospholipids with different molecular architectures were fabricated using the layer-by-layer (LbL) and Langmuir-Blodgett (LB) techniques. The main goal of this work was to explore the Application of these distinct molecular architectures in the detection of high diluted solutions of methylene blue (MB), a phenothiazine derivative drug. The linear growth, layer by layer, of these films was verified and monitored by UV-Vis absorption spectroscopy. It was found by FTIR that electrostatic interactions among the phosholipids and the supporting layer of PAH (cationic electrolyte) are the main driving force allowing the growth of the LbL and LB films, which favors the growth of the cationic phospholipids. The morphology was analyzed through optical microscopy, AFM and SEM, revealing that the phospholipids are structured as vesicles in the LbL films and as monolayers in the LB films. Different thickness of LbL and as monolayers in the LB filma containing phospholipids were deposited onto Pt interdigitated electrodes forming sensingn units applied in the detection of MB using impedance spectroscopy. The results showed that the different molecular architectures of the LbL and LB films take to different eletrical responses and allow the MP detection in concentrations of nanomolar. The SERS technique was applied to obtain structural information of the system MP/phospholipids at the dilution levels reached via impedance spectroscopy at the dilution levels reached via impedance spectroscopy. Then, LB monolayers were deposited onto 6nm of Ag evaporated films with and Ag evaporated films with and Ag nanoparticles were dispersed within the LbL films. The presence of Ag forming nanoparticles in both cases played a key role in achieving the MB SERRS signal allowing obtaining the detection in high dilution levels, approaching... (Complete abstract click electronic access below)