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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.
101

Perfil bioquímico sanguíneo e ganho de peso corporal em suínos submetidos a dietas com diferentes níveis de fósforo / Blood biochemical profile and body weight gain in swine subjected to diets enriched with different levels of phosphorous

Dantas, Waleska de Melo Ferreira 11 December 2009 (has links)
Made available in DSpace on 2015-03-26T13:46:47Z (GMT). No. of bitstreams: 1 texto completo.pdf: 642555 bytes, checksum: 84f19fa5cd3e984062d000d213268e2e (MD5) Previous issue date: 2009-12-11 / The biochemical profile of plasma and blood serum can provide important information about the clinical, metabolic and production of an animal, which represents an application of clinical biochemistry. This study aimed to evaluate the influence of diets containing different levels of phosphorus on the constituents of blood serum and plasma and body weight gain in pigs. A total of 60 hybrid pigs, steers, with initial body weight of 61.07 ± 0.86kg, with approximately 110 days of age. The animals were distributed in randomized blocks, subjected to five treatments, with twelve repetitions each. The treatments were distributed as follows: Treatment 1 - basal diet without supplemental phosphorus (P), containing 0.410% total phosphorus; Treatment 2 - basal diet supplemented with dicalcium phosphate trade (0.475% total phosphorus), Treatment 3 - feed basal supplemented with dicalcium phosphate trade (0.540% total phosphorus), Treatment 4 - basal diet supplemented with dicalcium phosphate trade (0.605% total phosphorus) and Treatment 5 - basal diet supplemented with dicalcium phosphate trade (0.670% phosphorus total). The animals received the experimental diets and water ad libitum, were weighed at the beginning (day 1) and at the end of the experimental period (day 30) for determination of weight gain. Blood samples to obtain serum and plasma were collected at baseline (T0 - Day 1) and at the end of the trial period (T1 - 30 th day), to measure the following parameters: sodium, potassium, chloride, total protein , albumin, alkaline phosphatase, total magnesium, urea, creatinine, phosphorus, ionized calcium, glucose, lactate, alkaline phosphatase, TSH and free T4. The data were tested by the Lilliefors and Cochran & Bartlet to verify data normality and homogeneity of variances, respectively. Given the assumptions of ANOVA were analyzed by analysis of variance and those variables that did not attend, were analyzed by nonparametric procedures using the Kruskal-Wallis. Regression analysis was performed for all the features and Pearson correlations were performed between weight gain with the other traits. Significant difference (p <0.05), with an increase in body weight (p <0.002), where there was a quadratic function in the treatments. Of serum phosphorus (p <0.0005) was found in a quadratic function of the treatments. His serum showed a steady increase in line with the increase of available phosphorus in the diet. Serum concentrations of total magnesium showed a quadratic (p <0.001) in the treatments. Concentrations decreased to T4, where values remained stable. The calcium ion also showed a quadratic (p <0.0001) while serum alkaline phosphatase showed a cubic behavior (p <0.008). Therefore, it was weight gain than in the treatments supplemented with phosphorus. Increased levels of phosphorus in the diet causes an increase in their serum and decrease in serum ionized calcium and magnesium. / O perfil bioquímico do plasma e soro sanguíneos pode prover importantes informações a respeito do estado clínico, metabólico e produtivo de um animal, o que representa uma das aplicações da bioquímica clínica. O presente estudo teve como objetivo avaliar a influência de dietas contendo diferentes níveis de fósforo sobre constituintes do soro e plasma sanguíneos e ganho de peso corporal em suínos. Foram utilizados 60 suínos híbridos comerciais, machos castrados, com peso corporal médio inicial de 61,07±0,86kg, com aproximadamente 110 dias de idade. Os animais foram distribuídos em blocos casualizados, submetidos a cinco tratamentos, com doze repetições cada. Os tratamentos foram assim constituídos: Tratamento 1 - ração basal, sem suplementação de fósforo (P), contendo 0,410% de fósforo total; Tratamento 2 - ração basal com suplementação de fosfato bicálcico comercial (0,475% de fósforo total); Tratamento 3 - ração basal com suplementação de fosfato bicálcico comercial (0,540% de fósforo total); Tratamento 4 - ração basal com suplementação de fosfato bicálcico comercial (0,605% de fósforo total) e Tratamento 5 - ração basal com suplementação de fosfato bicálcico comercial (0,670% de fósforo total). Os animais receberam as rações experimentais e água à vontade, foram pesados no início (dia 1) e no final do período experimental (dia 30) para determinação do ganho de peso. Amostras de sangue para a obtenção de soro e plasma foram coletadas no início (T0 - 1°dia) e no final do período experimental (T1 - 30°dia), para a mensuração das seguintes variáveis: sódio, potássio, cloreto, proteínas totais, albumina, fosfatase alcalina sérica, magnésio total, uréia, creatinina, fósforo, cálcio ionizado, glicose, lactato, fosfatase alcalina óssea, TSH e T4 livre. Os dados foram avaliados pelos testes de Lilliefors e Cochran & Bartlet para verificar a normalidade dos dados e homogeneidade das variâncias, respectivamente. Atendendo a premissas da ANOVA, foram analisadas pela análise de variância e aquelas variáveis que não atenderam, foram analisadas por procedimentos não paramétricos pelo teste de Kruskal-Wallis. A análise de regressão foi realizada para todas as características e correlações de Pearson foram efetuadas entre o ganho de peso com as demais características estudadas. Foi encontrada diferença significativa (p<0,05), com aumento no peso corporal (p<0,002), onde observou-se comportamento quadrático em função dos tratamentos. Nos valores séricos de fósforo (p<0,0005), foi verificado comportamento quadrático em função dos tratamentos. Seus valores séricos apresentaram um aumento crescente de acordo com o aumento do fósforo disponível na dieta. As concentrações séricas do magnésio total apresentaram comportamento quadrático (p<0,001) em função dos tratamentos. Suas concentrações diminuíram até o T4, onde seus valores se mantiveram estáveis. O cálcio iônico também demonstrou comportamento quadrático (p<0,0001) enquanto que as concentrações séricas de fosfatase alcalina demonstraram um comportamento cúbico (p<0,008). Portanto, constatou-se ganho de peso corporal superior nos tratamentos suplementados com fósforo. O aumento dos níveis de fósforo na dieta ocasiona acréscimo na sua concentração sérica e diminuição nos valores séricos de cálcio ionizado e magnésio.
102

Gazéification de déchets organiques dans un réacteur à flux entrainé : impact des inorganiques sur le fonctionnement du réacteur et choix des céramiques réfractaires / Gasification of organic wastes in an entrained flow reactor : behaviour of mineral matters and choice of ceramic refractories

Boigelot, Romain 12 November 2012 (has links)
La gazéification de la biomasse permet d’obtenir un gaz de synthèse riche en CO et H2 utilisable pour la production d’électricité, de biocarburants ou de composés chimiques. Ce procédé permet de palier à l’épuisement des ressources fossiles. L’utilisation de boues d’épuration comme ressources de biomasse assurerait à ce type de déchets organiques une valorisation énergétique. Cependant, les boues contiennent une forte charge minérale (entre 30 et 50% massique). Cette fraction est composée d’une vingtaine d’oxyde notamment la silice, la chaux et l’oxyde de phosphore, P2O5 (plus de 15%).Les boues sont des systèmes complexes très peu étudiés jusqu'à présent. Il est donc nécessaire de connaitre le comportement en température des inorganiques afin de mesurer leur impact lors du processus de gazéification et de se prémunir contre les risques de corrosion et de pollution du gaz liés à leur présence. - Dans un premier temps, les températures de liquidus de deux fractions minérales de boues ont été déterminées. Il s’avère que celles-ci, comprises entre 1257°C et 1358°C, sont dans la plage opératoire d’un gazéifieur à lit entrainé. De plus, une étude menée sur le binaire SiO2-P2O5 a permis d’améliorer les bases de données thermodynamiques. - Dans un second temps, les études thermodynamiques et cinétiques de volatilisation du phosphore ont mis en évidence le faible relâchement en température du phosphore grâce à la formation de phases réfractaires associant l’oxyde de phosphore et la chaux tel que Ca3(PO4)2 et Ca9Fe(PO4)7. La volatilité des inorganiques des boues est inférieure à 0.5% massique. - Enfin, l’interaction entre les inorganiques liquides et plusieurs céramiques réfractaires a été étudiée, par des essais de corrosion statique et dynamique. Un matériau, constitué d’alumine et d’oxyde de chrome, s’est révélé être un excellent candidat pour le garnissage du réacteur de gazéification. / Synthesis gas can be obtained by biomass gasification. It is composed of CO and H2 and can be used for the production of electricity, organic coumpounds and biofuels. The use of sewage sludges allows exploiting this kind of waste as biomass resources. However, sewage sludges contain a large percentage of minerals (30 to 50 % wt) composed of at least 20 different oxides including silica, lime and phosphorous oxide, P2O5 (15 % wt of the minerals). Mineral matters of sludges are complex and not well known. So, it is necessary to study their behaviour in function of temperature to understand their impact during gasification process and avoid gas pollution and corrosion of the ceramic refractories. Firstly, liquidus temperatures of two different mineral matters were determined. The result shows that these temperatures, between 1257 and 1358°C, are in the operating range of the gasifier. Thus, a study of the binary system SiO2-P2O5 had enabled to enhance thermodynamic databases. Secondly, thermodynamic and kinetic studies, confirmed the low release of P2O5 in function of temperature due to the formation of refractory compounds like Ca3(PO4)2 and Ca9Fe(PO4)7. Release of inorganics from the sludge is less than 0.5 % wt. Finally, interaction between slag and different ceramic refractories was studied. Static and dynamic trials were performed to choose the most resistant ceramic refractory. One of them composed of alumina and chrome oxide proved to be a good choice to build the gasifier wall.
103

Sintese e marcacao com P-32 de fosfatos de monoalquila e do fosfato de monofenila sob forma de sais de bis-ciclohexilamonio. Determinacao de espectros de absorcao em infra-vermelho e de ressonancia nuclear magnetica

ALMEIDA, MARIA A.T.M. de 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:23:11Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:29Z (GMT). No. of bitstreams: 1 00636.pdf: 4746331 bytes, checksum: 49aa6e0eb3bdd9da261862a04bcb4b58 (MD5) / Dissertacao (Mestrado) / IEA/D / Instituto de Quimica, Universidade de Sao Paulo - IQ/USP
104

Micellar-enhanced ultrafiltration for the removal of heavy metals from phosphorous-rich wastewaters:from end-of-pipe to clean technology

Landaburu-Aguirre, J. (Junkal) 25 September 2012 (has links)
Abstract Fertilizer industry often generates phosphorous rich wastewaters containing heavy metals. While phosphorous is a valuable compound for the industry, heavy metals hinder the recovery of phosphorous due to their detrimental effects on human health and the environment. Consequently, heavy metals must be removed from the wastewaters. In this study the use of micellar-enhanced ultrafiltration (MEUF) was evaluated for the removal of cadmium, copper, zinc and nickel from phosphorous rich wastewaters. This study has been conducted following a systematic methodology from single metal synthetic wastewaters to more complex synthetic and real wastewaters. The experimental work was conducted in a laboratory scale stirred cell using 3, 5 and 10 kDa regenerated cellulose membranes and in a cross flow semi-pilot scale equipment using a 10 kDa spiral wound polyethersulphone membrane. Statistical design of experiments was used as the research methodology to evaluate the effect of factors on the MEUF process performance as well as for finding optimal conditions. The factors studied were heavy metal, phosphorous and surfactant feed concentrations, pH, membrane nominal molecular weight limits, transmembrane pressure and cross flow velocity. The membrane performance was characterized by the heavy metal retention/rejection coefficients and the permeate flux. The experimental results showed that the removal of heavy metals from single synthetic wastewaters by MEUF is more efficient for more diluted systems. In complex systems containing phosphorous, simultaneous removal of heavy metals was successfully achieved obtaining rejection coefficients up to 80%. Phosphorous was not retained by the membrane showing the potential applicability of MEUF to purify phosphorous rich wastewaters. The study of metal complex formation and heavy metal competition has been shown to be very important in order to predict the MEUF results. Concentration polarization phenomenon was insignificant in the synthetic wastewaters but it was more severe when applying MEUF to real wastewaters. In addition, with real wastewaters SDS leakage was insignificant. This study has provided new and valuable knowledge regarding the applicability of MEUF to industrial wastewater treatment. / Tiivistelmä Lannoiteteollisuus tuottaa usein jätevesiä, jotka sisältävät huomattavia määriä fosforia, sekä pieniä määriä raskasmetalleja. Vaikka fosfori on tärkeä raaka-aine lannoiteteollisuudelle, jätevesissä olevat raskasmetallit kuitenkin estävät sen hyötykäyttöä fosforin lähteenä. Raskasmetallit ovat haitallisia sekä luonnolle että ihmisten terveydelle, joten niiden erottaminen jätevesistä on tärkeää. Tässä työssä tutkittiin miselliavusteisen ultrasuodatuksen (MEUF) käyttöä kadmiumin, kuparin, sinkin ja nikkelin poistamiseen fosforipitoisista jätevesistä. Väitöskirjatyössä tutkittiin systemaattisesti synteettisiä jätevesiä, jotka sisälsivät joko yhtä tai useita raskasmetalleja, sekä lannoitetehtaalta kerättyjä jätevesiä. Kokeet tehtiin laboratoriomittakaavan sekoituskennolla, jossa käytettiin 3, 5 ja 10 kDa:n regeneroituja selluloosakalvoja, sekä semi-pilot -mittakaavan spiraalielementillä, jonka materiaalina oli 10 kDa:n polyeetterisulfonikalvo. Väitöskirjatyössä hyödynnettiin tilastollista koesuunnittelua, jonka avulla arvioitiin muuttujien vaikutuksia MEUF-prosessin käyttäytymiseen. Koesuunnittelua hyödynnettiin myös optimiolosuhteiden määrittelemisessä. Koesuunnitelmien muuttujina olivat raskasmetallien, fosforin ja pinta-aktiivisen aineen pitoisuudet, pH, suodatuskalvojen katkaisukoot, paine sekä ristikkäisvirtauksen nopeus. Kalvon käyttäytymistä arvioitiin raskasmetallien erotustehokkuuden ja permeaattivuon avulla. Koetulokset osoittivat raskasmetallien erotuksen olevan tehokkainta synteettisistä, yhtä metallia sisältävistä jätevesistä, joiden raskasmetallipitoisuus oli pieni. Fosforia sisältävistä monimetalliliuoksista saavutettiin 80&#160;%:inen raskametallien poistotehokkuus. Kalvoerotuksessa fosforipitoisuus ei muuttunut merkittävästi, mikä osoittaa MEUF:n olevan potentiaalinen menetelmä raskasmetallien poistamiseen fosforipitoisista jätevesistä. Metallikompleksien muodostumisen ja raskasmetallien välisen kilpailun ymmärtäminen osoittautuivat erittäin tärkeiksi MEUF-tuloksien ennustamisessa. Konsentraatiopolarisaatioilmiö ei ollut merkittävä käsiteltäessä synteettisiä jätevesiä, mutta teollisten jätevesien käsittelyssä ilmiöllä oli huomattava vaikutus permeaattivuohon. Kuitenkin teollisen jätevesien käsittelyssä SDS:n vuotaminen kalvon läpi oli merkityksetöntä. Tämä tutkimus on antanut uutta ja merkittävää tietoa MEUF:n soveltuvuudesta teollisten jätevesien käsittelyn.
105

Sol-gel synthesis of vanadium phosphorous oxides for the partial oxidation of n-butane to maleic anhydride

Salazar, Juan Manuel January 1900 (has links)
Doctor of Philosophy / Department of Chemical Engineering / Keith L. Hohn / Vanadium phosphorous oxide (VPO) is traditionally manufactured from solid vanadium oxides by synthesizing VOHPO[4subscript][dot in middle of line]0.5H[2subscript]O (the precursor) followed by in-situ activation to produce (VO)[2subscript]P[2subscript]O[subscript]7 (the active phase). These catalysts considerably improve their performance when prepared as nanostructured materials and this study discusses an alternative synthesis method based on sol-gel techniques capable of producing nanostructured VPO. Vanadium(V) triisopropoxide oxide was reacted with ortho-phosphoric acid in tetrahydrofuran (THF). This procedure yielded a gel of VOPO[4subscript] with interlayer entrapped molecules. The gels were dried at high pressure in an autoclave with controlled excess and composition of THF-2-propanol mixtures. The surface area of the obtained materials was between 50 and 120 m[2superscript]/g. Alcohol produced by the alkoxide hydrolysis and incorporated along with the excess solvent reduced the vanadium during the drying step. Therefore, after the autoclave drying, the solid VOPO[4subscript] was converted to the precursor; and, non-agglomerated platelets were observed. Use of additional 2-propanol increased the amount of precursor in the powder but reduced its surface area and increased its crystallite size. In general, sol-gel prepared catalysts were significantly more selective than the traditionally prepared materials, and it is suggested that the small crystallite size obtained in the precursor influenced the crystallite size of the active phase increasing their selectivity towards maleic anhydride. The evaluation of these materials as catalysts for the partial oxidation of n-butane at 673 K under mixtures of 1.5% n-butane in air yielded selectivity of 40% at 50% conversion compared to 25% selectivity at similar level of conversion produced by the traditionally prepared catalysts. Variations in the catalytic performance are attributed to observed polymorphism in the activated materials, which is evidenced by remarkable differences in the intrinsic activity. All precursors and catalysts were characterized by IR, XRD, SEM and BET, and the products of the catalytic tests were analyzed by GC.
106

The relevance of fog and dew precipitation to succulent plant hydrology in an arid South African ecosystem

Matimati, Ignatious January 2009 (has links)
Magister Scientiae (Biodiversity and Conservation Biology) / Fog and dew interception and utilization by plant canopies remains one of the least considered aspects of vegetation studies at any scale yet the few studies that have been conducted point to their considerable influence on ecological processes and a critical role in modulating climate in southern African arid ecosystems. Their relevance to succulent plant hydrology was investigated in this study.The first study measured stable 18O and 2H isotope ratios in samples of rain, fog and dew water and compared these with those assayed monthly in stem xylem water of six succulent shrub species over a one year period. Negative 18O and 2H ratios were observed in the stem xylem water of all six species signifying a predominance of water derived from fog and dew precipitation which was most conspicuous during the wet winter. This implied that fog and dew are even more important sources of water than rain and corroborated by significant correspondence found between fog and dew frequencies, succulent foliar water contents and quantum yields of photochemistry.The second study monitored variations in stem diameter at 2-hourly intervals in 8 succulent shrub species of diverse growth form over a 9-month period. Two groups of species were distinguished based on whether their daily amplitudes in stem diameter were consistently positively correlated with daily fluxes in vapour pressure deficit, which were indicative of a persistent CAM photosynthetic mode, or intermittently correlated with daily fluxes in vapour pressure deficit, which were indicative of mixed CAM and C3 photosynthetic modes. Among species displaying a persistent CAM photosynthetic mode, high nocturnal fog and dew precipitation amounts corresponded with low daily amplitudes in stem diameter, and vice versa, which pointed to reduced nocturnal stomatal water loss. These patterns, which were indistinct among species displaying mixed CAM and C3 photosynthetic modes, were corroborated by small daily amplitudes in stem diameter also consistently observed in one species displaying a CAM photosynthetic mode in ambient than artificially fog and dew excluded environments.The third study monitored changes in water mass at hourly intervals of quartz gravel substrates with different dwarf succulent species assemblages over an 8-month period.Consistently greater net amounts of water were intercepted daily by quartz gravel substrates containing Agyroderma pearsonii than Cephalophylum spissum plants as well as those without plants. These attributed to a high water repellence of A. pearsonii leaves and less radiation absorbed by the paler silvery to grey-green leaves of A. pearsonii leaves than the dark green leaves of C. spissum resulting in lower leaf temperatures and less water loss by transpiration. Quartz gravel soils devoid of plants intercepted nearly 5-times greater amounts of precipitation contributed by fog and dew than that contributed by rain. These precipitation amounts exceeding the high percentages of total hydrological input contributed by fog and dew reported in other ecosystems.The study concludes that fog and dew are a vital source of water for succulent shrubs in arid South African ecosystems and imply that diminished fog and dew frequencies associated with elevated night time temperatures accompanying global warming could exacerbate plant drought stress.
107

Nouvelles formulations de résines polyesters insaturés pour l’amélioration du comportement au feu / New formulations of polyester resins to improve fire resistance

Tibiletti, Lucie 19 July 2011 (has links)
Les polyesters insaturés sont des résines thermodurcissables particulièrement appréciées pour leur facilité de mise en œuvre et leur coût modéré. Cependant, comme tous les polymères organiques ils ont une réaction au feu médiocre, ce qui est critique dans un certains nombres de d'applications. L'objectif de cette thèse était d'élaborer de nouvelles formulations de résines ayant un comportement au feu amélioré. La première stratégie développée a été le greffage de monomères phosponés dans la matrice polyester. Des monomères méthacryliques et styrénique ont été synthétisés et utilisés pour remplacer une partie du styrène dans la résine. La stabilité thermique des résines modifiées est diminuée, mais leur comportement au feu est globalement meilleur. Des effets du phosphore en phase gazeuse et en phase condensée ont pu être mis en évidence.Dans une seconde partie, une sélection de particules se distinguant par leur nature, leur taille et leur facteur de forme a été testée. Si l'impact des ces charges est assez limité lorsqu'elles sont utilisées individuellement, des tests calorimétriques ont révélé que certaines combinaisons de particules pouvaient améliorer significativement la réaction au feu des résines. Enfin, des associations d'additifs phosphorés et de particules submicroniques ont été investiguées. Le polyphosphate d'ammonium se distingue des autres additifs par un impact très important sur le comportement au feu et particulièrement par le charbonnement important qu'il engendre, cependant sa combinaison avec des charges inorganiques ne s'est pas révélée probante. / Unsaturated polyesters are thermoset resins particularly appreciated for their low cost and easy processing. Nevertheless one of their main drawbacks is their poor fire resistance. The aim of this PhD thesis was to prepare new resin formulations with an improved fire behaviour. The first part of this work was dedicated to the grafting of phosphorous monomers in the polyester matrix. Methacrylic and styrenic monomers were synthesized and used to replace of part of the styrene in the resin. Resin thermal stability was decreased, but on the whole their fire behaviour was improved. Condensed phase and gas phase effects of phosphorus were highlighted.In a second part, a screening of various kinds of particles with different sizes was performed. Calorimetric tests revealed that, while the effect of these particles used alone is limited, a decrease of resin flammability could be achieved with specific combinations. Finally, commercial phosphorous additives were associated with submicronic fillers. From all the additives tested, ammonium polyphosphate stands out, with a powerful impact on the resin fire reaction and especially a much increased charring. However, its combination with inorganic particles was not conclusive.
108

Efficiency of Nitrate and Phosphorus Removal in a Working Rain Garden

Strong, Patrick 08 1900 (has links)
Rain gardens are low impact developments designed to mitigate a suite of issues associated with urban stormwater runoff. The site for this study was a Denton City rain garden at the Denton Waste Water Treatment Plant. Nitrogen and phosphorus removal was examined in light of two overflow events comprised of partially treated wastewater from an upslope anaerobic digester pond. Nitrate removal efficiency was examined across differing dry spell intervals of 5, 8, and 12 d, displaying a moderate negative correlation (r2 = 0.59). Continued phosphorus removal capacity was assessed, showing phosphorus removal in cases where P was in excess of 0.8 mg/L, reflecting an equilibrium phosphorus concentration. A high expanded shale component in the soil media (25%) was likely a factor in the continued removal of phosphorus. Overall the rain garden proved to be a large source of nitrate (+425%) and total nitrogen (+61%) by mass. The study showed that while the rain garden intercepted a large volume of partially treated wastewater during the overflow events, preventing it from reaching a nearby creek, the mitigation of an acute event has extended to a chronic one as nitrogen is gradually processed and flushed from the system as nitrate.
109

Microsystème électrostatique tridimensionnel de récupération d'énergie pour alimenter un stimulateur cardiaque sans sonde / 3D electrostatic energy harvester to power a leadless pacemakers

Risquez, Sarah 28 February 2017 (has links)
Cette thèse s’inscrit dans un contexte d’activité en forte croissance dans le domaine des implants médicaux, stimulée par de nombreux progrès dans le domaine des micro-capteurs et de la micro-électronique. L’autonomie en énergie des implants demeure cependant un facteur limitant. Notre travail a pour objectif de repousser les limites actuelles en termes de miniaturisation et de durée de vie. Il contribue au développement d’une solution basée sur la récupération d’énergie mécanique du cœur pour alimenter durablement un pacemaker miniaturisé sans sonde de nouvelle génération, dit « pacemaker leadless ».Le microsystème de récupération d’énergie étudié est composé d’un résonateur mécanique de type masse-ressort associé à un transducteur électrostatique. Il a pour particularité une architecture tridimensionnelle, dont la forme permet de profiter au maximum de l’espace disponible dans la capsule cylindrique du pacemaker. L'utilisation de la troisième dimension associée à un design original permet en outre d’obtenir un effet de pseudo multiplication de fréquence qui doit conduire, d’après les modèles que nous avons développés, à des densités de puissance nettement supérieures à celles présentées dans l'état de l'art. Pour réaliser ce microsystème tridimensionnel, nous avons développé un procédé de fabrication additif qui repose sur des étapes de micro moulage d'un matériaux structurel obtenu par croissance électrolytique (nickel), de croissance d'un matériau sacrificiel (cuivre) et de polissage. L’identification d’imperfections géométriques dues au procédé et aux matériaux utilisés nous a amené à améliorer la conception du transducteur. Par ailleurs, de nombreux verrous de fabrication ont été levés au cours de cette thèse grâce à la mise en œuvre d’une instrumentation dédiée. Ce procédé nous a permis de fabriquer un premier prototype tridimensionnel du micro-transducteur électrostatique composé de 10 couches de nickel. D’autres métaux élaborés par croissance électrolytique pourraient être envisagés pour réaliser des microsystèmes tridimensionnels, suivant les besoins de l’application considérée. Afin d’anticiper d’éventuels problèmes de compatibilité des micro-dispositifs avec l'imagerie par résonance magnétique, nous avons mis au point le procédé de croissance électrolytique d’un matériau non-magnétique à base de nickel dopé au phosphore. / This thesis contributes to the medical implants field, which is stimulated by many advances in the fields of microelectronics and microsensors. However, electrical energy lifespan of implants and large size of batteries are still a problem. Our work aims at pushing back these limits. It contributes to the development of a solution based on mechanical energy harvesting from the heart motion. The objective is to sustainably power a new generation of pacemakers without lead, so-called "leadless pacemakers."The studied energy harvesting microsystem consists in a spring-mass-type mechanical resonator associated with an electrostatic transducer. Its originality comes from a three-dimensional architecture, whose shape fits pretty well with the cylindrical shape of the pacemaker capsule. The use of the third dimension combined with an original design enables to get a pseudo multiplication frequency effect. Thanks to this effect, our simulation models predict power densities significantly higher than state-of-the-art figures reported in literature. To fabricate this three-dimensional microsystem, we have developed an additive manufacturing process based on steps of micro-molding of a structural material (electroplated nickel), electroplating of a sacrificial material (copper) and planarization. Identification of imperfections related to the fabrication process and the materials used allowed us to improve the design of the transducer. Moreover, many manufacturing obstacles were overcome during this thesis through the implementation of dedicated instrumentation. This new process has enabled us to fabricate a first three-dimensional prototype of the electrostatic micro-transducer made of 10 layers of nickel. Other electroplated metals can be envisaged to achieve three-dimensional microsystems, depending on the application requirements. In order to anticipate any compatibility issue of our microsystem with magnetic resonance imaging, we have developed the electrodeposition process of a nonmagnetic material: phosphorous doped nickel.
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Etude Multimodale IRM et Electrophysiologique de la Sclérose en Plaques / Multimodal Study of Multiple Sclerosis by MRI and Clinical Neurophysiology

Kauv, Paul 06 July 2018 (has links)
1ère Etude (Fatigue et ATP dans la SEP): La fatigue dans la SEP est un symptôme fréquent et retentit sur la qualité de vie. L’évaluation clinique est réalisée par le score FSS (fatigue scale score). Cependant, il est nécessaire d’avoir des biomarqueurs fiables et objectifs, notamment si une perspective thérapeutique est envisagée. L’ATP (adénosine tri-phosphate) est un marqueur du métabolisme énergétique et peut être mesuré in vivo à l’étage cérébral par spectroscopie du phosphore (31P-MRS). L’objectif de cette étude est d’évaluer s’il existe une corrélation du β-ATP (spécifique de l’ATP) avec la fatigue évaluée par le FSS. 30 patients présentant une SEP progressives ont été explorés en IRM 3T avec une antenne spécifique du phosphore par une séquence 31P-MRS multivoxel centrée sur les centres semi-ovales. 2 régions ont été segmentées: (a) les hémisphères fronto-pariétaux et (b) substance blanche normale repérée à partir d’une séquence FLAIR. Les ratios des métabolites énergétiques évalués étaient le PCr% et le β-ATP%. Les corrélations statistiques entre les métabolites énergétiques avec le FSS ont été calculées par les tests de Spearman. Les résultats ont montré que le β-ATP% était corrélé avec le FSS (r=0.46; p=0,01) dans les hémisphères fronto-pariétaux.2ème Etude (Cortex moteur et faisceau cortico-spinal évalués par IRM et excitabilité corticale dans la SEP): Les lésions corticales, notamment de l’aire motrice, sont source de handicap. Les séquences de double (DIR) et phase sensitive inversion récupération (PSIR) permettent d’évaluer les lésions corticales et la séquence en imagerie en tenseur de diffusion (DTI) permet quant à elle d’évaluer le faisceau cortico-spinal (CS). L’excitabilité corticale permet aussi d’évaluer ces régions anatomiques par SMT (stimulation magnétique transcrânienne). L’objectif de cette étude a été de rechercher une corrélation entre les données IRM et d’excitabilité corticale. 25 SEP progressives ont eu une SMT pour évaluer l’excitabilité corticale du cortex moteur pour obtenir les paramètres de FICmoy, FICmax, IICmoy, IICmax (facilitation et inhibition intra-corticale). Ces patients ont aussi eu une IRM avec les séquences: 3D DIR (0,7x0,7x0,8mm), axiales PSIR (0,6x0,6x3mm) pour compter le nombre de lésion du cortex moteur du côté ipsilatéral, et une séquence DTI 12 directions pour extraire les paramètres de fraction d’anisotropie (FA), coefficient apparent de diffusion (ADC), diffusivité radiale et axiale du CS ipsilatéral. Les corrélations entre les données IRM avec les données d’excitabilité sont calculées par tests de Spearman. Les résultats ne montrent pas de corrélation entre le nombre de lésions corticales avec les données d’excitabilité corticale. Il existe en revanche une corrélation entre FICmoy et FICmax avec la diffusivité radiale (r=0.56 ; p=0.004 et r=-0.59 ; p=0.002, respectivement) et avec l’ADC (r=-0.44; p=0.03 et r=-0.45 ; p=0.02, respectivement) suggérant un épuisement de compensation de la FIC par les lésions de démyélinisation. / 1st Study (Fatigue and ATP in MS): Fatigue in MS is a common symptom and impact on quality of life. Clinical examination relies on FSS (fatigue scale score). However, it is important to have reliable and objective biomarkers. ATP (adenosin tri-phosphate) is an energetic metabolite which can be measured by brain phosphorous magnetic spectroscopy (31P-MRS) in vivo. We aimed to assess correlation between β-ATP (specific of ATP) with FSS. 30 progressive MS were assessed by 3T MRI with a phosphorous coil and a multivoxel 31P-MRS sequence. 2 areas were segmented in: (a) fronto-parietal hemispheres and (b) normal appearing white matter (NAWM) defined by FLAIR sequence. The energetic metabolites ratios assessed were: PCr% and β-ATP%. Correlations between energetic metabolites with FSS were computed by Spearman tests. Results showed β-ATP% correlated with FSS (r=0.46; p=0,01) in fronto-parietal hemispheres.2nd Study (Motor cortex and cortico-spinal tract assessed by MRI et cortical excitability in MS): Cortical lesions, especially from motor cortex, result in disability. Double and phase sensitive inversion recovery sequences can assess cortical lesions while diffusion tractography imaging (DTI) can assess cortico-spinal tract (CST). Cortical excitability can also assess these anatomical areas by transcranial magnetic stimulation (TMS). We aimed to assess correlation between MRI data with cortical excitability. 25 progressive MS had cortical excitability from motor cortex assessed by TMS: ICFmean, ICFmax, ICImean, ICImax (intra-cortical facilitation and inhibition). These patients also had a MRI with the following sequences: 3D DIR (0,7x0,7x0,8mm), axial PSIR (0,6x0,6x3mm) to count ipsitaleral motor cortical lesions, and a 12-directions DTI sequence to obtain fractional anisotropy (FA), apparent diffusion coefficient (ADC), radial and axial diffusivity parameters of ipsilateral CST. Correlations between MRI data with cortical excitability data were computed by Spearman tests. The results did not show correlation between cortical lesions count and cortical excitability data. There was a correlation between ICFmean and ICFmax with radial diffusivity (r=0.56; p=0.004 et r=-0.59; p=0.002, respectively) and with ADC (r=-0.44; p=0.03 et r=-0.45; p=0.02, respectively) which suggests a defective ICF by demyelinated lesions.

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