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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
251

Fluid mechanics of fibre suspension related to paper making

Holm, Richard January 2005 (has links)
<p>This thesis deals with fluid dynamic mechanisms related to papermaking, specif- ically: the initial dewatering mechanisms during roll-forming and fibre motion in sedimentation and in shear flow. </p><p>Pressure and wire position measurements have been conducted in a model resembling the forming zone and the measured pressure distributions are shown to have more complex patterns than the simple model p / T/R (where T is the wire tension and R is the roll radius). It is shown that an increase in wire tension has a similar effect as a decrease in flow-rate on the shape of the pressure distribution. In addition, it is shown that the drainage has a stabilizing effect on the dewatering pressure. </p><p>The flow around the forming roll has also been modelled with the assump- tion that the wire is impermeable. A non-linear equation for the position of the wire is derived that clearly shows that the Weber number, We, is an im- portant parameter. The equation is linearized around the trivial solution and has a standing wave solution with a specific wavelength that scales with the We-number. </p><p>Motion of non-Brownian fibre settling in a Newtonian fluid at a small but finite Reynolds number has been studied experimentally. Two different regimes of sedimentation were identified. For dilute suspensions, fibres gener- ally fall without flipping and may travel at velocities larger than that of an isolated particle. In the semi-dilute regime we found the settling process to be dominated by large-scale fluctuations. The velocity fluctuations scale with the suspension volume concentrationφ according toφ1/3, which is similar to the findings for settling spheres. </p><p>The influence of shear on fibre orientation in the near wall region was studied in cellulose acetate fibre suspensions. At low concentration and low aspect ratio fibres were observed to orient perpendicular to the streamwise direction (named rollers) in the near wall region whereas the orientation further into the suspension was unchanged. As the concentration and aspect ratio increased the fraction of rollers decreased. </p><p>Finally, an evaluation of a commercial Ultra Velocity Profiler unit in fibre suspensions are presented. The idea was to determine the velocity and characterise the turbulence from ultra sound echoes from particles in the fluid. However, the spatial and/or temporal resolution of the measurements did not permit turbulence characterisation. These limitations might be possible to overcome and some procedures are proposed and evaluated.</p>
252

Theoretical and numerical calculations for the dynamics of colloidal suspensions of molecular particles in flowing solution inside mesopores

Atwi, Ali 02 May 2012 (has links) (PDF)
The purpose of this thesis is to develop a comprehensive model analysis in a three-dimensional spatial frame for the dynamics of molecular particles in dilute colloidal suspensions in solutions flowing inside pores of variable width, subject to hydrodynamic forces, Brownian motion and diffusive collisions at the rough pore boundaries, by using numerical simulations. The approach by simulations is necessary because it is extremely complex to use analytical tools at present to deal with the problem of diffusive collisions of the particles at the solid pore boundaries. The algorithms which we have developed and the corresponding simulations are sufficiently general and refined to be directly applied to the study of the dynamics of a wide variety of polymer and biological particles in dilute solutions under diverse physical and applicable hydrodynamic conditions inside pores. Moreover, the mechanisms leading to the adhesion of particles of nano sizes under what would be non-equilibrium conditions, due to the conflicting influence of the mechanical diffusive collisions and the attractive Hamaker forces at the boundaries, are of major interest. We have hence investigated a theoretical model to calculate the restitution coefficient from basic physical principles. The objective is to quantify the energy balance during the process of a diffusive collision of a nano particle under the influence of the repulsive forces on one hand, and the attractive Hamaker forces acting on the nano particle on the other. This is done by developing a model, based on the JKR and Hertz theories, to account for the energy losses during collisions, and for the energy gains due to the Hamaker interactions. Adhesion becomes an outcome if the energy balance permits this. Our theoretical model is developed by proposing a special analytic approach based on the Hamaker potential. We derive from the theoretical analysis a characteristic nonlinear equation for the restitution coefficient, and analyze its properties which determine under given physical conditions the outcome for adhesion or not.
253

Ingénierie des interactions cellule/ matrice extracellulaire et cellule/cellule pour contrôler le comportement d'écoulements de suspensions de cellules à hautes fractions volumiques

Maisonneuve, Benoît 02 December 2013 (has links) (PDF)
L'attention de la communauté scientifique, ainsi que le développement, pour les bioprocédés dédiés à la culture et à l'expansion de cellules souches mésenchymateuses (MSCs) pour la thérapie cellulaire et la médecine régénérative a considérablement grandi pendant ces dernières décennies. Une plus ample compréhension du lien entre la structure, la fonction et les propriétés des suspensions de cellules mésenchymateuses est devenue de première importance. Dans cette thèse, nous présentons tout d'abord les résultats d'une étude expérimentale portant sur l'écoulement de suspensions concentrées de cellules vivantes d'origine mésenchymateuse pour une grande gamme de concentration cellulaire. Nous caractérisons l'évolution de la viscosité relative en fonction de la contrainte de cisaillement appliquée pour des fractions volumiques cellulaires allant de 20 à 60%. Ces matériaux ont des empreintes rhéologiques compliquées mais très reproductibles, incluant des comportements de fluide à seuil, rhéofluidifiants ainsi que des fractures liées à la contrainte de cisaillement. Les propriétés rhéologiques de la suspension sont ensuite étudiées avec l'addition d'acide hyaluronique (HA), une biomolécule avec des séquences d'adhésion pour des récepteurs à la surface des cellules étudiées. Nous montrons que l'addition d'acide hyaluronique modifie substantiellement le comportement de la suspension et nous permet de contrôler les propriétés d'écoulement de la suspension à toutes les fractions volumiques. Cytométrie de flux et imagerie confocal à l'appui, nous montrons que l'effet observé est dû à un important changement dans la formation d'agrégats cellulaires dans la suspension, et donc dans l'envergure du réseau correspondant. La troisième partie de cette thèse porte sur l'ajout de polyéthylène glycol, une molécule qui n'est pas naturellement présente dans l'organisme mais fréquemment utilisée dans la formulation d'hydrogel. En utilisant trois types de PEG, l'influence de la charge des molécules est étudiée. Les résultats montrent que la charge est un paramètre important dans le contrôle des propriétés d'écoulement de suspensions cellulaires, car déterminant dans la formation et la compacité des agrégats. En considérant les agrégats comme des objets fractals, nous montrons qu'en prenant en compte les modifications de fractions volumiques avec le cisaillement, nous pouvons obtenir une courbe maitresse pour l'ensemble des conditions testées, et en extraire la force d'adhésion moyenne entre les cellules, au travers une population de plusieurs millions de cellules. Cette étude livre de nouveaux aspects sur la complexité des propriétés en écoulement de suspensions de cellules méchymateuses, adhérentes et concentrées, sur leur sensibilité à l'ajout de molécules, qu'elles soient naturellement présentes dans les tissues ou non, ainsi qu'une nouvelle méthode pour mesurer la force d'adhésion entre les cellules.
254

Estudo experimental do escoamento e da concentração de mistura no processo de filtração tangencial de suspensões macromoleculares / Experimental study of the flow and mixture concentration in the cross-flow filtration of macromolecular suspensions

Queiroz, Viviane Miceli Silva 30 April 2004 (has links)
O processo de microfiltração tangencial com membranas tubulares inorgânicas e tubos microporosos, respectivamente de origem importada e nacional, foi investigado tendo-se como objeto de separação as misturas macromoleculares preparadas com os agentes polissacarídeos gomas Xantana e Guar em suspensão aquosa. São evidenciados neste processo os efeitos de sinergia compreendidos nas misturas elaboradas puras e em diferentes proporções, na concentração final de 1000 ppm. A investigação experimental acompanha o comportamento reológico de cada mistura ao longo do processo e os resultados foram investigados a partir de propriedades físico-químicas relevantes como: concentração de carbono orgânico total (Total Organic Carbon - TOC) e análise de absorbância no espectômetro de infravermelho. Resultados de TOC indicaram que em apenas um meio filtrante tubular microporoso (C1T+), o desempenho do processo na retenção dos polissacarídeos foi acima de 90%, em relação ao processo com a membrana comercial importada cuja retenção de TOC foi da ordem de 80%. De acordo com as análises de absorbância, conclui-se que as membranas com tamanho do poro nominal de 0,2 \'mü\'m e 0,4 \'mü\'m tiveram uma retenção mais eficiente do que os tubos microporosos em estudo. A temperatura foi um parâmetro significativo, pois a retenção, na maioria dos casos, foi maior na temperatura de 25ºC, independente da pressão e da velocidade média. Na análise dos procedimentos envolvendo cada mistura, foi constatada a boa sinergia entre as gomas, sem modificação de estrutura (formação de gel) ou fenômenos de superfície que impedissem o processo de microfiltração. A vazão transmembrana das misturas ficou limitada entre os máximos valores para mistura pura de Xantana e mínimos para Guar. Todas as misturas apresentaram comportamento pseudoplástico, sem mudanças na reologia, reforçando a adequada sinergia quanto a este aspecto. / The present dissertation reports cross-flow microfiltration with national and imported inorganic tubular membranes and microporous tubes. The object of separation is the macromolecular mixtures prepared with polysaccharide agents Xanthan and Guar gum in aqueous solution. The process shows the synergism effects in pure and different mixture proportions, with 1000 ppm final concentration. The experiments established the rheologic behaviour of each mixture along the process and significant physical and chemical properties, such as Total Organic Carbon concentration (TOC) and absorbency analysis in infrared spectrometer were analyzed. TOC retention shows that only one microporous tubular filtering medium (C1T+) had better performance (retention 90%) than the imported commercial membrane (retention about 80%). Absorbency analysis show a better retention efficiency of membranes with pore size of 0,2 \'mü\'m and 0,4 \'mü\'m than microporous tube. The temperature was a significant parameter, as the better retention was obtained at 25ºC, independently of pressure and mean velocity. There is good synergism between Xanthan and Guar gums without structure modifications or surface phenomena that would impede the microfiltration process. The transmembrane flux of proportional mixtures has been limited between maximum values of pure Xanthan and minimum values of pure Guar mixtures. All mixtures have pseudoplastic behaviour, without changes in rheology, intensifying the good synergism.
255

Estudo do metabolismo secundário em Piper crassinervium (Piperaceae) / Study of the secondary metabolism in Piper crassinervium (Piperaceae)

Danelutte, Ana Paula 16 May 2001 (has links)
Este trabalho descreve o estudo do metabolismo secundário em folhas diferenciadas e em suspensões celulares de Piper crassinervium (Piperaceae). Este estudo foi monitorado pela análise do extrato de folhas por CLAE, assim como pela comparação entre os diferentes tecidos desta espécie (folhas, caule e raízes). Do extrato das folhas foram isoladas duas flavanonas, duas hidroquinonas preniladas e uma hidroquinona com um endoperóxido na cadeia lateral. A análise do óleo volátil das folhas através de CG e CG-EM, revelou a presença de trinta e seis componentes, sendo majoritários o germacreno-D (10,05%) seguido por &#946;-cariofileno (9,91 %) e 6-metil-5-hepten-2-ona (7,47%). Todas as substâncias isoladas foram submetidas ao ensaio antifúngico bioautográfico contra Cladosporium sphaerospermun, sendo que as flavanonas, as duas hidroquinonas e o óleo volátil mostraram-se ativos. As suspensões celulares foram desenvolvidas a partir de calos, iniciados a partir de ápices, em meio B5 modificado, contendo ácido naftalenoacético (ANA) e 6-benzilamino purina (BAP) como reguladores de crescimento. As células não produziram flavonóides, mas alcalóides do tipo aristolactamas, que são parcialmente excretados para o meio de cultura. A curva de crescimento estabelecida para as células foi analisada quanto à atividade específica da fenilalanina amônia-liase (PAL), à variação do pH e o acúmulo dos alcalóides. Alguns experimentos de eliciação demonstraram respostas positivas face ao uso de luz UV, adição de L-fenilalanina e uso de extratos de levedura. / The present work studies the secondary metabolism in leaves of Piper crassinervium (Piperaceae) and in its cell suspension culture as well. The profile of secondary compounds in differenciatted and undifferenciated tissues were evaluated by HPLC. The aerial parts of Piper crassinervium yielded two flavanones and three prenylated hydroquinones, one having an endoperoxide group in the side chain. The analysis of the volatile oil of Piper crassinervium by GC-MS allowed the identification of 36 compounds, germacrene-D (10,05%), &#946;-cariofilene (9,91 %) and 6-methyl-5-heptene-2-one (7,47%) being detected as the major ones. Ali isolated substances were evaluated using a bioautography technique against the fungus Cladosporium sphaerospermun. The isolated flavanones, two hydroquinones and the essential oil were found to be active against the fungus. The cell suspensions had their growth curve established on basis of the dry weight and pH variations. The cells were showed to accumulate several aristolactams alkaloids instead. Determinations of these alkaloids by HLPC indicated that the cells excreted them partially to the culture media. Determinations of specific activity of PAL and concentration of alkaloids during the growth cycle were further performed. Additional experiments revealed that UV light and the addition of either phenylalanine or yeast extract cause elicitation response with increased production of alkaloids.
256

Avaliação da tensão superficial, parâmetros reológicos e atenuação acústica de suspensões de açaí / Analysis of surface tension, ultrasound attenuation and rheological parameters of açai\' suspensions

Trevisan, Bruno Peruchi 14 October 2011 (has links)
Nesta pesquisa teve-se como objetivo estudar as propriedades físicas de polpas de açaí disponíveis comercialmente, tais como: pH, condutividade, viscosidade, tensão superficial e atenuação acústica, em função da temperatura e de particulados presentes na suspensão de açaí. Foram selecionadas quatro marcas comerciais de polpa de açaí originárias da região norte do Brasil. As amostras foram estudadas na forma pura (sem diluição) e diluídas. As análises de tensão superficial foram conduzidas utilizando o tensiômetro da Sensadyne (modelo QC6000) na faixa de temperatura de 15ºC a 60ºC. Observou-se uma variação da tensão superficial entre as marcas estudadas e em todos os casos a polpa de açaí diluída apresentou tensão superficial superior à polpa pura. Para valores de temperatura maiores que 45ºC, a tensão superficial aumentou com a temperatura para duas marcas estudadas. A verificação da atenuação e do tamanho de partículas foi realizada utilizando a técnica de espectroscopia de atenuação acústica com o equipamento APS-100 (Matec Applied Science, Northborough, USA). A polpa diluída apresentou uma menor atenuação com relação à polpa pura. As polpas de açaí, pura e diluída, apresentaram partículas com tamanho inferior a 0,6 µm de diâmetro, sendo que a polpa pura apresentou partículas com diâmetros maiores. Na investigação reológica foram utilizados reômetros rotacionais (Modelo DVIII+) da marca Brookfield com geometrias de cone-placa e cilindros concêntricos na faixa de temperatura de 15ºC a 60ºC. Os reogramas obtidos foram ajustados aos modelos de Ostwald-de-Waale (Lei da Potência) e Herschel-Bulkley, sendo que o melhor ajuste foi obtido com o modelo de Lei da Potência. Todas as amostras estudadas apresentaram comportamento reológico não-Newtoniano, com características de fluidos tixotrópicos. Foi investigado também o comportamento reológico de polpas de açaí tratadas enzimaticamente para posterior processamento por microfiltração tangencial. As enzimas comerciais Pectinex Ultra SP-L, Biopectinase KK Plus e Ultrazym AFPL foram avaliadas separadamente e a respectiva eficiência foi analisada pela redução da viscosidade no reômetro rotacional com a geometria de cone-plana. A enzima comercial Ultrazym foi mais eficiente na redução da viscosidade aparente da polpa de açaí, sendo que as enzimas Pectinex e Biopectinase não apresentaram alteração significativa da viscosidade. A análise da viscosidade aparente dos produtos (permeado e retentado) da microfiltração utilizando membranas cerâmicas comerciais de 0,8 e 0,2 \'mü\'m foi feita utilizando o reômetro rotacional com a geometria de cone-placa, na temperatura de 25ºC. Para o processamento por microfiltração sem tratamento enzimático, o retentado apresentou valores de viscosidade aparente superior ao permeado e à polpa diluída, enquanto que a polpa diluída apresentou viscosidade aparente superior ao permeado. Na microfiltração com tratamento enzimático a polpa diluída apresentou viscosidade aparente inferior ao permeado, comportamento observado para as duas membranas estudadas (0,8 e 0,2 \'mü\'m). Com os resultados obtidos foi possível verificar a grande variação nas propriedades físicas de polpas comerciais de açaí e com isso, a importância de se realizar tais medidas para a otimização de processos como a microfiltração tangencial. / The main objective of this research was the study of physical properties of commercial types of açaí pulp; including pH, electric conductivity, viscosity, surface tension and acoustic attenuation as a function of temperature and particulates of açaí suspension. Four types of açaí pulp from north region of Brazil were selected. The samples were analyzed in pure (undiluted) and diluted form. Surface tension was measured with Sensadyne tensiometer (model QC6000) in the temperature range: 15º to 60º Celsius. In all types of pulp studied the surface tension of diluted sample was higher than pure sample. For temperatures above 45º Celsius surface tension increased for two types of açai pulp studied. Acoustic attenuation and particle size of samples were analyzed with the equipment APS-100 from Matec Applied Science, Northborough, USA. Acoustic attenuation of diluted samples is smaller for pure samples; the açaí pulp (pure and diluted) has particle sizes below 0,6 µm and the particle sizes of the pure samples were larger than the diluted samples. Brookfield/USA rotational rheometers (Model DVIII+) was employed for rheological analysis with two geometries: cone-plate and concentric cylinders in the temperature range: 15º to 60º Celsius. The rheological behavior was adjusted by Ostwald-de-Waale model (or Power-law model) and Herschel-Bulkley model; the Ostwald-de-Waale model showed a better fit. All brands of pulp studied presented non-Newtonian behavior with tixotropic characteristics. It also investigated the rheological behavior of açaí pulp treated enzymatically for later processing by tangential microfiltration. The commercial enzymes: Pectinex Ultra SP-L (Novozymes - Bagsvaerd, Dinamarca), Biopectinase KK Plus (Kerry Bio-Science) and Ultrazym AFPL (Novozymes - Bagsvaerd, Dinamarca), were utilized to reduce viscosity and the effect was evaluated with the cone-plate geometry of the Brookfield/USA rheometer (Model DVIII+). The data shows that the Ultrazym enzyme was the best option for viscosity reduction of açaí pulp, and the other presented no changes in the viscosity. The viscosity of the retentate and permeate from the microfiltration process (membranes with cut-off 0,8 and 0,2 µm) was determined with the cone-plate geometry of the Brookfield/USA rheometer (Model DVIII+) at 25º Celsius. In microfiltration process without enzymatic action, the apparent viscosity of retentate was always higher than the retentate from diluted pulp. With the results we observed the large variation in physical properties of commercial açaí pulp and thus, the importance of carrying out such measures for the optimization of processes such as tangential microfiltration.
257

Inkjet printed drops and three-dimensional ceramic structures

Liu, Yuanyuan January 2017 (has links)
Inkjet printing is a versatile manufacturing method with applications beyond its traditional application in graphics and text printing, particularly in structural and functional materials. This thesis aims to enhance the understanding of DOD inkjet printing processes by investigating the behaviour of solvent mixtures and nanoparticle suspensions to identify the key parameters affecting drop ejection, drying and stacking processes. Drop ejection and flight were investigated with two modes of inkjet printheads, using a range of fluids formulated from solvent mixtures and characterised by the dimensionless Z number. The printable range was found to be 1.17 smaller or equal to Z smaller or equal to 36.76 for a 10 pl (21.5 micro metre diameter) shear-mode Dimatix printhead. However, with an 80 micro metre diameter squeeze-mode MicroFab printhead, the range was found to be narrower with 4.02 smaller or equal to Z smaller or equal to 16.2. However, both printheads were found to show a printable range of Weber number with 0.4 &lt;We &lt;20. Weber number is determined by the drop velocity and hence the actuating pulse. When designing inks for future printing work, not only the fluid properties, but also the pulse voltages need to be considered. The drop stacking and solidification processes of drops containing nano ZrO2 particles were investigated to enhance the understanding of drop drying and drop/drop interactions. In-situ synchrotron X-ray radiography provides a promising method to track the time-evolved solid segregation within printed drops during drying. Both the initial contact angle and substrate temperature during printing strongly influence the drying process and the final dried deposit shape. The drops were first pinned and then there was a slight sliding of the three-phase contact line. Drops were deformed by the stacking of overprinted drops when printed on Kapton tapes and silicon wafer surfaces, but not on glass slides due to the small contact angle of water on glass slides. Crack-like defects were found at the edge of the final dried stacking structures. The coffee stain effects within a single inkjet printed droplet and the 3D structures before and after sintering were investigated to find out the influence of ink properties, printing parameters and substrate temperature on inkjet printed structures. It was found coffee staining was more obvious at high substrate temperatures. When adding 25 vol% ethylene glycol (EG) or 5 wt% polyethylene glycol (PEG), the coffee stain effect is reduced or eliminated under room temperature drying. X-ray tomography has been demonstrated as a valuable tool for the characterization of 3D printed objects and defects that form during their manufacture. Defects were characterised as microvoids or large-scale crack-like defects. The majority of the microvoids revealed are associated with mechanisms and processes within a single drop, e.g. segregation during dryings such as the formation of coffee stains or coffee rings. The size or distribution of microvoids can be controlled by changing the ink formulation, with higher PEG content inks showing lower concentrations of microvoids.
258

Stability of Extemporaneously Prepared Lansoprazole Suspension at Two Temperatures

Morrison, Jordan T., Lugo, Ralph A., Thigpen, Jim C., Brown, Stacy D. 01 January 2013 (has links)
OBJECTIVE The purpose of this study was to examine the stability of a generic lansoprazole product in a 3 mg/mL sodium bicarbonate suspension under room temperature and refrigerated conditions. METHODS Lansoprazole suspensions (3 mg/mL) were prepared in triplicate using an 8.4% sodium bicarbonate vehicle for each storage condition (room temperature and refrigerated). During 1 month, samples from each replicate were periodically removed and analyzed for lansoprazole concentration by liquid chromatography–tandem mass spectrometry (LC-MS/MS). Each sample was spiked with 10 mg/L omeprazole to serve as the internal standard. A positive electrospray LC-MS/MS method was validated over the calibration range of 5 to 25 mg/L using Food and Drug Administration Guidance. The identities of the analyte and internal standard in the samples were verified by monitoring the MS/MS transitions of m/z 370 to m/z 252 and m/z 346 to m/z 198 for lansoprazole and omeprazole, respectively. Additionally, the pH of the suspensions was monitored throughout the study. RESULTS The stability of lansoprazole in the oral sodium bicarbonate suspension under refrigeration is compromised prior to what has been previously reported in the literature. Samples kept at room temperature lost >10% of the lansoprazole after 48 hours compared with the refrigerated samples, which maintained integrity up to 7 days. No statistically significant difference was found between the pH of the room temperature and refrigerated suspension samples, indicating that this factor is not the cause for the differences in stability at these two conditions. CONCLUSIONS This study suggests that the extemporaneously compounded lansoprazole oral suspension prepared in 8.4% sodium bicarbonate should not be stored in plastic oral syringes longer than 48 hours at room temperature and no longer than 7 days when refrigerated. These data indicate an expiration time earlier than that previously reported for the refrigerated product (14 days).
259

The Relationship Between Middle School Configurations and Student Success

Ali-Hawkins, Asia 01 January 2015 (has links)
Public schools have used varying school configurations for middle grades-typically K-8 or traditional middle school arrangements-to improve students' academic outcomes. A small Northeastern school district was experiencing problems with student achievement, suspensions, and truancy, and was considering school configuration as a potential method of improving student performance. The purpose of this quantitative study was to explore the associations between school configuration and student achievement, suspensions, and truancy. Erikson's psychosocial theory of development and Dickinson's middle school philosophy guided this study since both address the needs of adolescents. Five years of archival data were collected from 2 demographically comparable Northeast school districts: one with K-8 schools and one with a traditional middle school configuration. Student sample sizes for each of the 5 years ranged from 1,841 to 2,076. Chi-square analyses for each year of data were used to examine the associations between configuration (elemiddle/middle) and the 4 independent variables: math achievement (proficient/not proficient), reading achievement (proficient/not proficient), suspensions (suspended/not suspended), and truancy (truant/not truant). Key results yielded statistically significant associations in certain years for each independent variable. The K-8 school students had higher achievement in math 3 of the 5 years and in reading for 2 of the 5 years. This group also had a lower percentage of truancy 4 of the 5 years, but a greater proportion of suspensions 4 of the 5 years. Results of this study can influence positive social change as district administrators can use the data to guide their decisions regarding which school configuration is most beneficial for middle school aged students.
260

Etude des propriétés de nanoparticules de LiCoO2 en suspension pour une application redox-flow microfluidique / Study of LiCoO2 nanoparticles suspensions for a microfluidic redox-flow application

Rano, Simon 25 September 2017 (has links)
Ce travail de thèse porte sur la réalisation d’une batterie redox-flow fonctionnant grâce à la circulation de suspensions de matériaux d’insertion du lithium afin d’accroitre leur densité d’énergie. Le recours à des cellules microfluidiques permet de s’affranchir des limitations causées par les membranes échangeuses d’ions. Il s’articule dans un premier temps sur la synthèse contrôlée par voie hydrothermale de nanoparticules de LiCoO2 et leur caractérisation en suspension aqueuses. Cette étape permet de déterminer à la fois les propriétés électrochimiques des suspensions, leur état d’agrégation ainsi que leur comportement rhéologique en vue d’une utilisation redox-flow. Le transfert électronique entre une particule en suspension et les électrodes de la cellule est un aspect fondamental de ce type de batteries. Ce transfert est étudié grâce la technique de collision électrochimique dans laquelle la réponse de chaque agrégat est détecté individuellement par une ultramicroélectrode ce qui permet d’établir de nombreuses propriétés physique-chimiques de ces suspensions. Ce travail propose ensuite de s’affranchir de l’utilisation des membranes et de leurs limitations par le recours aux techniques de la microfluidique. La formation d’un écoulement co-laminaire en microcanal permet d’obtenir une cellule redox-flow opérationnelle. La conception et le fonctionnement de ces cellules est étudié en vue de la mise en circulation de suspensions de nanoparticules dans ce type de systèmes. / The aim of this work is to make a redox-flow battery that runs on lithium insertion material suspensions in order to increase the energy density of such systems. The use of microfluidic technics allows to solve the issues and limitations of ion exchange membrane by removing them. In the first part controlled size LiCoO2 nanoparticles are synthesized by hydrothermal route and dispersed into suspensions. The aggregation state of these suspensions are investigated using diffusion light scattering and transmission electronic cryoscopy. Rheological properties were also characterized for redox-flow use. The electronic transfer between a particle in suspension and the flow cell electrodes is crucial for their performances. This transfer is studied in the second part using the single event collision technic which consist of isolating individual aggregate electrochemical response at the surface of an ultramicroelectrode. This approach allows an extensive investigation of suspensions aggregates size, mobility and insertion reaction kinetic. Finally this works propose to replace the conventional ion exchange membrane by the mean of microfluidic technics. In co-laminar condition the fluid interface acts as a separation membrane to create a membrane-less redox-flow battery. The last part focuses on the fabrication of microfluidic cells and the behavior of suspensions in micro-channels.

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