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La couleur dans la civilisation Nasca : production tinctoriale et picturale / Colour in the Nasca civilization : the production of dyes and paintsBoucherie, Nathalie 14 June 2014 (has links)
Cette thèse se propose d’étudier de manière approfondie les matières colorantes et les techniques de coloration appliquées aux textiles de la culture Nasca. Cette civilisation préhispanique, sans écriture, s’est développée sur la côte sud du Pérou pendant environ neuf siècles (200 ans av. J.-C. ; 700 ans apr. J.-C.). Parmi sa culture matérielle, les textiles sont abondants et nombre d’entre eux sont de grande finesse avec des décors polychromes. La polychromie avait probablement une signification dans la cosmogonie Nasca et le textile est particulièrement chargé de sens dans la culture andine. Pourtant, les matériaux de la couleur demeurent un sujet encore méconnu dans le domaine textile. Il semblait donc intéressant d’identifier au moyen de méthodes physico-chimiques les matières colorantes utilisées par les artistes textiles Nasca. Pour ce faire, une enquête de terrain a été menée en amont pour récolter et identifier les sources colorantes susceptibles d’avoir été employées. Puis un corpus textile a été constitué avec des textiles inédits, issus de fouilles récentes menées sur les sites de Los Molinos, Estaqueria et Cahuachi, l’ancien centre politico-cérémoniel des Nasca. Quelques tissus d’autres cultures (Topará, Mochica et Nasca drivé) ont aussi été analysés pour établir des comparaisons.Les résultats fournissent de précieuses informations qui caractérisent la production tinctoriale et picturale des textiles Nasca. Au-delà de cet aspect technique, ces données sont utiles pour aborder sous un autre angle des problématiques archéologiques plus complexes notamment lorsque l’attribution culturelle des textiles est inconnue ou discutée, comme ceux de la péninsule de Paracas. / This thesis’ aim is to propose an in-depth study of the dye-sources and dyeing and colouring techniques used for textiles in the Nasca civilization. This Pre-Columbian, pre-literate civilization flourished on the southern coast of Peru during some nine centuries (200 BC to 700 AD). In its material culture, textiles are very numerous and many of them are of outstanding quality, with a rich polychromatic ornamentation. Polychromy probably was of great significance among the Nasca and textiles seem to always have been of particular importance in Andean culture. Nevertheless, the material sources of the colours on these dyed and painted textiles have remained a comparatively poorly explored research field. It therefore appeared as a promising, innovative quest to try and identify the colouring matters used by Nasca textile artists, using state-of-the art physico-chemical analytical methods. To this effect, botanical and anthropological field missions were first conducted in order to identify and collect colouring sources that might have been employed by the Nasca dyers and textile painters. A corpus of archaeological textiles was assembled, selecting textiles discovered in the course of recent archaeological excavations on the sites of Los Molinos, Estaqueria and Cahuachi, the latter being the antique political and ceremonial centre of the Nasca civilization. A number of textiles from other cultures (Topará, Mochica and Nasca-derived) were also analyzed to allow comparisons.Our results bring precious new information on the production of dyes and paints on Nasca textiles. Allowing even further prospects than these important technical discoveries, they bring new light into complex archaeological issues, such as the cultural attribution of archaeological textiles whose provenance is unknown or disputed, which is the case for some textiles from the Paracas peninsula.
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ANÁLISE DA VISCOSIDADE E SUA CORRELAÇÃO COM OS CONSTITUINTES DOS VINHOS FINOS DA REGIÃO DA CAMPANHA / ANALYSIS OF VISCOSITY AND ITS CORRELATION WITH THE CONSTITUENTS OF THE FINE WINES FROM REGION OF CAMPANHASchirmer, Velcir Rubenich 30 August 2013 (has links)
Rio Grande do Sul is the largest producer in Brazil, it produced about 90% of the wine national in 2011. Among the wine sector of the state, Region of Campanha has been standing out in the production of fine wines. The color, aroma, flavor, body and the phenolic composition are quality attributes of the wines, and the viscosity property is the one that correlated the most with the body of the wine. The ethanol concentration has correlation with the viscosity of the wine, but also with other constituents of it. This study aims to compare the physical and chemical characteristics, phenolic compounds and viscosity of the fine wines, white and red. Furthermore, correlate the viscosity in relation to the varieties that are being studied. We analyzed a total of 26 commercial wines from Region of Campanha. Significant differences existed among the finest red and white wines for pH, total acidity and dry extract, reducing sugars and phenolic compounds. However, no significant difference to the alcohol content and viscosity. To be carried out the correlation between the viscosity and the parameters analyzed for fine wines reds strong correlation was observed between the viscosity and the parameters of alcohol content and dry extract. In fine white wines, the pH showed a weak correlation, the dry extract a moderate correlation and the alcohol content was a highly significant correlation From the measured results, it was possible to contribute with a pioneering study of the determination of viscosity as well as to produce relevant information to the characterization of the wines from Region of Campanha. / O Rio Grande do Sul é o maior produtor de vinhos do Brasil, em 2011 produziu cerca de 90% dos vinhos nacionais. Das regiões vitivinícolas do Estado, a Região da Campanha vem se destacando na produção de vinhos finos. Cor, aroma, sabor, corpo e a composição fenólica são atributos de qualidade dos vinhos, sendo a viscosidade a propriedade que mais se correlaciona com o corpo do vinho. A concentração de etanol possui correlação com a viscosidade dos vinhos, mas outros constituintes também. Este estudo teve como objetivo comparar algumas características químicas, físico-químicas, compostos fenólicos e a viscosidade em vinhos finos tintos e brancos. Fazendo uma correlação entre a viscosidade e as variáveis em estudo. Foi analisado um total de 26 vinhos comerciais provenientes da Região da Campanha, RS. Existiu diferenças significativas entre os vinhos tintos e brancos para o pH, acidez total, extrato seco, açúcares redutores e compostos fenólicos. Porém, não ocorreu diferença significativa para o teor de álcool e para a viscosidade. Ao ser realizada a correlação entre a viscosidade e os parâmetros analisados para os vinhos finos tintos foi encontrada correlação significativa forte entre a viscosidade e os parâmetros de teor de álcool e extrato seco. Nos vinhos finos brancos, o pH apresentou uma fraca correlação, o extrato seco uma moderada correlação e para o teor de álcool ocorreu uma correlação altamente significativa. A partir dos resultados mensurados, foi possível contribuir com um estudo pioneiro da determinação da viscosidade bem como produzir informações relevantes para a caracterização dos vinhos da Região da Campanha.
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Contribution à la compréhension du colmatage membranaire lors de la microfiltration de jus de fruits : identification de leur potentiel colmatant / Contribution to the understanding of membrane fouling during fruit juices microfiltration : identification of their fouling potentialDahdouh, Layal 10 July 2015 (has links)
La microfiltration est un procédé baro-membranaire largement utilisé pour stabiliser et clarifier les jus de fruits ou pour concentrer leur fraction pulpeuse. Toutefois le colmatage membranaire limite la productivité économique du procédé. Même si de nombreuses études ont été menées pour comprendre et limiter le colmatage, aucun véritable outil n'est aujourd'hui disponible pour prévoir la filtrabilité d'un jus de fruits. Le développement de ce type d'outils prévisionnels est pourtant essentiel pour faciliter l'optimisation des conditions de filtration et pour une meilleure maitrise du colmatage membranaire. Dans ce contexte, l'étude a été axée sur l'identification de nouveaux critères de filtrabilité des jus de fruits au travers de la compréhension et de la caractérisation des mécanismes de colmatage qui interviennent.En choisissant le jus d'orange comme modèle, une approche statistique a permis, dans un premier temps, une sélection rapide et pertinente des caractéristiques physico-chimiques des jus de fruits directement corrélées à leur filtrabilité, à savoir la matière sèche totale, l'extrait sec soluble, le pH, la conductivité et la granulométrie. Ensuite, des stratégies expérimentales complémentaires basées sur des filtrations à l'échelle du laboratoire ont été proposées pour identifier les différentes fractions colmatantes en fonction de leur taille ainsi que les mécanismes de colmatage associés. Ces stratégies novatrices ont permis d'étudier le pouvoir colmatant du jus d'orange en prenant en compte toute sa complexité et de proposer par la suite des cartographies de composés colmatants. Ces cartographies s'avèrent particulièrement intéressantes pour anticiper le comportement colmatant des jus de fruits sans avoir recours à des filtrations longues et coûteuses à grande échelle. Les résultats ont montré que le phénomène le plus important qui régit le colmatage membranaire global au cours de la filtration du jus d'orange semble être le colmatage externe par dépôt. Les objectifs de la dernière partie du travail, ont été de considérer plus fortement le caractère complexe et hétérogène des jus de fruits, pouvant les conduire à des changements brutaux de comportement lors de leur filtration. Pour cela des mesures rhéologiques en mode dynamique couplées à une stratégie d'isolement spécifique des différentes fractions colmatantes du jus d'orange ont été menées pour déterminer le comportement viscoélastique de la fraction insoluble du jus d'orange au cours de sa concentration. Les observations ont montré que les énergies des interactions entre les particules insolubles sont des fonctions croissantes de la concentration de la fraction insoluble et dépendent de la taille des particules. De plus, la transition vers un comportement « solide » du jus d'orange semble être favorisée par la présence des fractions particulaire et supra-colloïdale. Ces observations sont cohérentes avec le mécanisme de colmatage prédominant dû à l'accumulation de ces fractions à la surface de la membrane. La confrontation de nouvelles études de filtrabilité à l'échelle du laboratoire avec la performance de la filtration à grande échelle permettra de généraliser les stratégies proposées pour prédire la performance de la filtration de nouveaux jus de fruits. / Microfiltration is a pressure driven process successfully used to clarify and stabilize fruit juices or to concentrate their pulpy fraction. However, membrane fouling remains the critical factor governing the overall economic productivity of this process. Even if, many studies have been made to understand and limit membrane fouling, to date, there stills a lack of predicting tools to evaluate the filterability of fruit juices. However, it is interesting to develop practical and efficient tools for the prediction of fruit juices filterability in order to adapt and optimize filtration conditions to the fouling behavior of the filtered juice. In this respect, this study focused on the identification of new criteria of fruit juices filterability through the comprehension and the characterization of the potential fouling mechanisms.First, orange juice was chosen as test matrix and a statistical approach was used to select simple and relevant physico-chemical characteristics of this juice in relation with its filterability, namely dry matter, TSS, pH, conductivity, and particles size. Later, additional experimental strategies based on filtration tests at lab-scale were developed to identify the relevant size-classes of foulant compounds and related fouling mechanisms. These innovative strategies allowed studying the fouling potential of orange juice with the consideration of its complexity and proposing cartographies of foulant compounds. These cartographies are particularly interesting to anticipate the fouling behavior of fruit juices without any costly filtration operation at large scale. Moreover, results showed that external fouling seems to be the predominant fouling mechanism governing the overall membrane fouling during orange juice filtration. Finally, the aim of the last part of the work was to highlight the role of the complex and heterogeneous nature of fruit juices in their unexpected behavior during their filtration. For this purpose, the viscoelastic behavior of orange juice suspended solids during their concentration was obtained from rheological measurements in dynamic mode coupled with specific isolation of orange juice foulant fractions. Results showed that the energy of the interactions between juice particles increased as the suspended solids concentration increased and depends on the particles size. Furthermore, the solid-like behavior of the juice was enhanced by the presence of supra-colloids and large particles. These observations are in accordance with the predominant fouling mechanism that is due to the accumulation of these fruit fractions on the membrane surface. The confrontation of new filterability studies at laboratory scale with the performance of large-scale filtration will enable to generalize the proposed strategies to predict the performance of filtration of new fruit juices.
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Comparaison physico-chimique et des [sic] activités catalytiques dans les réactions d'oxydation entre deux séries de catalyseurs Ag/CeO₂ préparés par imprégnation et dépôt-précipitation / Physico-chemical and catalytic activity comparaison in the oxidation reactions, between two series of Ag/CeO₂ solids, prepared by two different methods : Impregnation and Deposition-precipitationSkaf, Mira 16 December 2013 (has links)
La cérine est connue pour être très performant en tant que support, dans le domaine de l'oxydation catalytique. L'ajout de métaux de transitions améliore en général cette activité. Dans ce travail, l'argent a été ajouté sur la cérine. Deux méthodes de préparation ont été utilisées : l'imprégnation (Imp), connue par la formation de particules de tailles différentes sur la surface du support, et le dépôt-précipitation (DP) qui conduit en général à la formation de nanoparticules dispersées sur la surface et dans la masse du support. Deux séries de catalyseurs x%Ag/CeO₂(Imp) et x%Ag/CeO₂(DP) où x est le pourcentage massique de l'argent par rapport à la cérine, ont été préparés dans le but de comparer leurs propriétés physico-chimiques. Ensuite leurs activités catalytiques dans les réactions d'oxydation. Les catalyseurs ont été caractérisés par différentes techniques telles que la BET, la DRX, la RPE, l'ATD-ATG, la SPX, l'UV et la RTP. Dans les deux séries de catalyseurs, la DRX a montré que des particules de Ag⁰ ont été obtenues pour les fortes teneurs en argent ; ces particules sont plus grosses dans les imprégnés que dans les (DP). La présence des nanoparticules dans les deux séries de solides a été aussi confirmée par l'UV (résonance plasmonique). Ces nanoparticules sont de formes sphériques dans les (DP) et mi-sphériques, ou déformées, dans les (Imp). Trois états d'oxydation : Ag⁰, Ag⁺ et Ag²⁺ ont été identifiés dans les imprégnés et seulement deux : Ag⁰ et Ag⁺ dans les DP. La formation des ions Ag²⁺ semble être due à la présence de AgNO₃ sur la cérine au cours de la calcination du solide, ce qui était le cas pour les imprégnés et non pour les DP. De plus, les deux isotopes ¹⁰⁷Ag²⁺ et ¹⁰⁹Ag²⁺ ont été mis en évidence par la technique de la RPE ; ce résultat est considéré comme original et primordial. Par la suite, les deux séries de catalyseurs ont été testés dans les réacctions d'oxydations catalytique du propène, du monoxyde de carbone et du noir de carbone. Le résultat inattendu dans ce travail c'est que, contrairement à la bibliographie, les catalyseurs imprégnés étaient plus actifs que les (DP) pour les trois réactions. La performance catalytique des imprégnés a été reliée à la présence des espèces Ag²⁺ qui sont absents dans les DP. Autrement exprimé à la présence de trois couples redox Ag²⁺/ Ag⁺, Ag²⁺/ Ag⁰ et Ag⁺/ Ag⁰ dans le cas des solides (Imp), pour seulement un couple redox Ag⁺/ Ag⁰ dans le cas des solides (DP). Une présence adéquate dans les rapports de concentrations de ces trois couples redox dans le catalyseur 10%Ag/CeO₂(Imp) a rendu ce dernier le plus performant comparé aux autres de la même série. / Ceria is a well known support in the world of catalytic oxidation reactions. Adding transition metals tend to enhance the catalytic activity. Silver was used in our work, and was added using two different preparation methods : the impregnation (Imp) and the deposition-precipitation (DP). The first known by the formation of different particles size on the surface of the support, whereas the second is known by the formation of nanoparticles with a good dispersion on the surface and in the bulk of the support. Two catalysts series x%Ag/CeO₂(Imp) and x%Ag/CeO₂(DP) (where x is the weight percentage of silver over ceria) were prepared in order to compare their physico-chemical properties and afterward their catalytic performances in three different oxydation reactions. The catalysts were characterized using BET, XRD, EPR, DSG-TG, XPS, UV and TPR techniques. XRD showed on both series the formation of Ag⁰ particles for the catalysts with high weight percentages. The sizes of these particles are larger in the (Imp) solids compared to the (DP) ones. Beside of these particles, the formation of Ag⁰ nanoparticles was confirmed by the plasmonic resonance in the UV technique. The nanoparticles are spherical in the (DP) solids and half spherical (misshaped) in the (Imp) solids. Three oxidation states were found in the (Imp) catalysts : Ag⁰, Ag⁺ et Ag²⁺ compared to only two in the (DP) : Ag⁰ et Ag⁺. The nitrate present in the AgNO₃ (silver precursor) during the calcination might be the reason of the formation of the Ag²⁺. That is not the case for the (DP) solids. The two isotopes for Ag²⁺ (¹⁰⁷Ag²⁺ and ¹⁰⁹Ag²⁺) were identified with the EPR technique. This result is considered as original and very important. Afterward, the catalysts were tested in the total oxidation of the propylene, carbon monoxide and carbon black. The catalytic results were unexpected and oppose the literature results. (Imp) catalysts showed a higher activity than the (DP) in all the reactions. The catalytic performance of the (Imp) was ascribed to the presence of Ag²⁺ species that are missing in the (DP) catalysts. In other words, this performance is related to the presence of the 3 redox couples Ag²⁺/ Ag⁺, Ag²⁺/ Ag⁰ et Ag⁺/ Ag⁰ for the (Imp), compared to only one : Ag⁺/ Ag⁰ for the (DP). The 10%Ag/CeO₂(Imp) solid showed an appropriate concentration ratio of the redox couples, that's why it showed the highest catalytic activity among the other solids from the same series.
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Propriétés physico-chimiques et impact environnemental de liquides ioniques / Physico-chemical properties and environmental impact of ionic liquidsDeng, Yun 08 June 2011 (has links)
Les liquides ioniques sont des composés uniquement constitués d‘ions souvent volumineux, asymétriques et flexibles. Ils possèdent des températures de fusion basses, typiquement au-dessous de 100°C. Ils sont considérés comme des solvants prometteurs pour une chimie durable du fait, notamment, de leur tension de vapeur négligeable. Ils présentent d‘autres propriétés intéressantes : grande stabilité thermique, pression de vapeur quasiment nulle, non-inflammabilité, propriétés modulables par changement de l‘anion ou du cation, etc. Ils sont classiquement organisés par familles, en fonction de la structure chimique de leur cation : imidazolium, pyridinium, pyrrolidinium, etc. Leurs domaines d‘application sont très variés : synthèse, catalyse, séparation et extraction. Cependant, l‘utilisation des liquides ioniques à l‘échelle industrielle est encore limitée par manque de connaissances fondamentales et par l‘absence de données fiables sur leurs propriétés, leur devenir et leur impact environnementaux. La toxicité des liquides ioniques a récemment été démontrée ainsi qu'une résistance à la biodégradation. Dans ce contexte et en vue du développement à grande échelle de l‘utilisation de ces composés, la recherche de liquides ioniques à faible impact environnemental (moins toxiques, facilement biodégradables) devient essentielle. L‘introduction dans les chaînes latérales alkyles des imidazolium et pyridinium de groupements fonctionnels oxygenés, qui peuvent être reconnus par des enzymes (ex. esters, éthers, alcools terminaux), a grandement amélioré leur biodégradabilité. En même temps, il est important de garantir que la présence de ces groupements n‘affecte pas les propriétés physico-chimiques des liquides ioniques requises pour un usage spécifique dans des procédés chimiques. Dans ce projet de doctorat, nous avons sélectionné divers liquides ioniques basés sur les cations imidazolium, pyridinium, pyrrolidinium et ammonium, avec ou sans groupements fonctionnels (alcool/ester/éther) et avec trois types d‘anions, comme cibles d‘étude. L‘objectif était d‘examiner si les modifications de structures peuvent effectivement baisser leur impact environnemental tout en gardant leurs propriétés intéressantes pour des applications industrielles. Dans un premier temps, nous avons étudié plusieurs propriétés physico-chimiques importantes pour des applications ultérieures et/ou indicatrices de leur impact environnemental : les propriétés volumiques, la viscosité, la solubilité de gaz, la solubilité dans l‘eau, le coefficient de partage octanol-eau et le coefficient de diffusion dans l‘eau. Dans un deuxième temps, nous avons étudié leur impact environnemental par la mesure de la toxicité sur quatre microorganismes différents et l‘étude de leur biodégradation en présence de souches pures de bactéries. En complément, nous avons essayé de trouver des modèles basés sur les informations structurales pour estimer certaines propriétés. L‘insertion de groupements oxygénés sur la chaîne alkyle des cations ne change pas significativement les propriétés volumiques ; ni le coefficient de diffusion dans l‘eau. Les propriétés de solvatation des liquides ioniques basés sur des cations imidazolium et ammonium ne sont pas modifiées significativement, mais celles des pyridinium sont réduites, à cause d'une contribution entropique défavorable à l'énergie de Gibbs de solvatation. La présence de groupements oxygénés dans la chaîne alkyle du cation augmente la viscosité d‘un ordre de grandeur comparativement aux liquides ioniques sans groupements oxygénés. Dans le cas de l‘anion octylsulfate la viscosité augmente de deux ordres de grandeur. La présence de groupements oxygénés augmente la biodégradabilité des liquides ioniques. La présence de groupements esters rend les liquides ioniques plus sensibles à l‘ hydrolyse dans les conditions abiotiques et biotiques, toutefois le noyau imidazolium n‘en devient pas biodégradable pour autant. L‘introduction de groupements oxygénés augmente la solubilité dans l‘eau, diminue la valeur du coefficient de partage octanol-eau et entraine une baisse de la toxicité ce qui signifie que ces liquides ioniques présentent un plus faible impact environnemental. / Ionic liquids are the salts composed only by bulky, unsymmetrical and flexible organic cations and inorganic or organic anions. Their melting points are particularly low, usually below 100°C. The ionic liquids present several interesting properties : high thermal stability, low vapor pressure, non-flammability and tunable properties by changing the anion or cation. They are considered as promising high performance fluids with low environmental impact that can be applied in the fields of chemistry, chemical engineering or materials science both in processes (separation, catalysis) or as devices (optical components or lubricants).The application of ionic liquids at an industrial scale is still limited and fundamental information and reliable data on their properties, environmental fate and impact are rare. In this context and for the development of applications in wide scale, the research on ionic liquids with an expected low environmental impact (less toxic, readily biodegradable) is essential. The introduction of oxygenated functional groups – ester, ether or hydroxyl – in the alkyl side chains of imidazolium and pyridinium-based ionic liquids is expected to greatly improve their biodegradability. The effect of the functionalization on the physico-chemical properties of the ionic liquids is important in order to propose efficient, low environmental impact, ionic liquids for different applications and chemical processes. In this work, we have selected different ionic liquids based on the imidazolium, pyridinium, pyrrolidinium and ammonium cations, with or without functional groups (hydroxyl/ester/ether), and with three types of anions. Our objective was to examine if the modification of chemical structures of the ions effectively have lower environmental impact, and if they their interesting properties are remained. We have studied, for all the ionic liquids, several physico-chemical properties considered important to quantify the environmental impact of chemicals : the density, the viscosity, the gas solubility, the aqueous solubility, the octanol-water partition coefficient and the aqueous diffusivity. We have also tested their toxicity towards four different microorganisms and their biodegradation in presence of pure strain of bacteria. Finally, we have tried to develop some empirical and semi-empirical models based on molecular structure information for predicting some of these properties.The introduction of oxygenated groups in the alkyl chains on cations does not change significantly the volumetric properties of ionic liquids, or their diffusion coefficient in water, but increases the viscosity of the pure salts up to one order of magnitude. Carbon dioxide solubilities in ionic liquids are not significantly influenced by the introduction of oxygen functional groups in the cations of the ionic liquids except in the case of the pyridinium based ionic liquids for which the carbon dioxide solubility decreases significantly due to a defavourable entropic contribution to the Gibbs energy of solvation. The modification of the ionic liquids by introducing oxygenated chemical functions makes them more biodegradable. In the case of imidazolium-based ionic liquids, the presence of the ester group makes the cation more susceptible to hydrolysis, the imidazolium ring being still resistant to the degradation. The functionalization of the cation also increases the solubility in water of the resulting ionic liquids and reduces the octanol-water partition coefficient and their toxicity, leading us to conclude that they are more environmental friendly than the non-functionalized ionic liquids.
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Efeito do eletrodo de platina e da passivação com enxofre na formação de filmes dielétricos sobre germânioRolim, Guilherme Koszeniewski January 2014 (has links)
As estruturas metal-óxido-semicondutor (MOS) são o coração dos transistores de efeito de campo. O estudo e caracterização físico-química desses dispositivos foram a chave para o avanço da tecnologia do Si na indústria microeletrônica. Hoje, a ciência busca novos materiais para a produção de dispositivos de alta mobilidade. Um dos materiais visados é o Ge, pois apresenta mobilidade de cargas superior ao Si (duas vezes para elétrons e quatro vezes para lacunas). Porém, a interface Ge/GeO2 é de natureza reativa, limitando seu uso na construção de tais dispositivos. Muitos esforços têm sido feitos para superar as limitações. Entre eles, encontram-se a passivação da superfície do Ge a partir de solução aquosa de (NH4)2S, previamente a deposição do dielétrico. Outra etapa do processamento desse material na indústria a ser investigada são os tratamentos térmicos posteriores à deposição: a caracterização de estruturas MOS de Pt/HfO2/Ge submetidas a tratamentos térmicos levaram a melhoria das propriedades elétricas. Nesse sentido, o trabalho tem como objetivos investigar o papel da passivação sulfídrica em estruturas dielétrico/Ge e a influência do eletrodo de Pt nas estruturas Pt/HfO2/Ge quando submetidas a tratamentos térmicos. / The heart of field effect transistors is the metal-oxide-semiconductor (MOS) structure. Physico-chemical characterization of the materials employed in such structures enabled the development of Si technology. Nowadays, in order to build high mobility devices, new material are needed. Ge is an alternative material, since its carrier mobilities are higher than those of Si (almost two times for electrons and four times higher for holes). However, the GeO2/Ge interface is not thermally stable, which is a problem for its use on electronic devices. Many attempts to enhance this stability were already investigated. Among them, sulfur passivation of the Ge surface was employed using (NH4)2S aqueous solution prior to the deposition of dielectric layers. Another important step in the fabrication of MOS structures is post-deposition annealing. Pt/HfO2/Ge MOS structures presented improved electrical characteristics following post deposition annealing. The main objectives of this work are to investigate the role of sulfur passivation on dielectric/Ge structures and the influence of Pt electrode in Pt/HfO2/Ge structures submitted to post deposition annealing.
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Avaliação microbiologica e fisico-quimica do polen apicola in natura e desidratado sob diferentes temperaturas / Evaluation microbiological and physico-chemical in nature the pollen and dried at different temperaturesHervatin, Heloisa Litholdo 14 August 2018 (has links)
Orientador: Lucia Regina Durrant / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-14T12:37:36Z (GMT). No. of bitstreams: 1
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Previous issue date: 2009 / Resumo: O pólen apícola é a aglutinação do pólen presente nas flores coletados pelas abelhas operarias, e depositados na entrada da colméia. O estudo visou avaliar a qualidade microbiológica e físico-química do pólen IN NATURA e do submetido a diferentes processos de secagem, simulando as condições de processamento do produto comercializado. Também avaliou as amostras adquiridas no comercio do estado de São Paulo. Registrou-se a escassez das pesquisas sobre a qualidade microbiológica do pólen apícola. Primeiramente a pesquisa, analisou amostras de pólen apícola obtidas através de coletores instalados nas colméias pertencentes ao apiário experimental do Pólo Regional de Desenvolvimento Tecnológico dos Agronegócios do Vale do Paraíba, localizado em Pindamonhangaba-SP, pertencente à Agência Paulista de Tecnologia dos Agronegócios. A coleta ocorreu nos intervalos de 24horas, 48horas e 72horas, objetivando a presença e/ou quantidade de microrganismos patogênicos no pólen com relação ao tempo de permanência do produto no campo. As amostras foram congeladas por 48horas, e submetidas a dois processos de secagem (circulação de ar em sistema aberto a 40-42°C e sistema de circulação de ar fechado a 30°C). Foram realizadas as análises físico-químicas para os parâmetros de pH, umidade e atividade de água e as microbiológicas com avaliação de Bacillus cereus, Estafilococos coagulase positiva, coliformes a 45°C, Escherichia coli, Salmonella sp, bolores e leveduras, além de microrganismos sulfitos redutores. Amostras de pólen apícola desidratado foram adquiridas no mercado vajerista do Estado de São Paulo, com registro no Serviço de Inspeção Federal (SIF), submetidas aos mesmos parâmetros. Através dos cálculos estatísticos observaram-se possíveis diferenças e/ou correlações existentes entre os parâmetros analisados (microbiológicos, físico-químicos) para os tratamentos propostos (frequência de coleta e processos de desidratação). Verificou-se que as amostras analisadas, as IN NATURA e as desidratadas, mostraram-se isentas dos principais patógenos como Salmonella sp e Estafilococos coagulase positiva, porém, a população de bolores e leveduras foi relativamente elevada. Podendo concluir que os bolores e leveduras são os parâmetros microbiológicos mais significativos para o pólen apícola, seguido por Bacillus cereus e por bactérias coliformes totais, sendo parâmetros que devem ser introduzidos na legislação; além do processo de desidratação normalmente utilizado para pólen, não reduzir a população fúngica. Com base na Legislação atual para padrões microbiológicos em alimentos, considerando o grupo da granola, todas as amostras analisadas, encontram-se dentro dos padrões estabelecidos. Bolores e leveduras não estão incluídos na Legislação do MAPA. A época do ano teve influência na contaminação de Bolores e Leveduras, paralelamente com o tempo de permanência do pólen no campo, sendo indicada a coleta do material a cada 24horas. Assim os processos de secagem devem ser otimizados para permitirem a obtenção de produto livre de contaminantes microbiológicos; juntamente com a higienização do material nas diferentes etapas de produção e processamento do pólen, com foco na busca de materiais que substituam a madeira que é extremamente porosa, de forma a permitir higienização adequada e satisfatória. Outro parâmetro a ser considerado é a embalagem para o produto que merece atenção de especialistas nesta área / Abstract: The bee pollen is the agglutination of pollen present in flowers collected worker bees, and deposited at the entrance of the hive. The study aimed to evaluate the microbiological quality and physico-chemistry of the pollen in nature and subject to different processes of drying, simulating the processing conditions of the product sold. Also evaluated the samples acquired in the trade of the state. We have registered the scarcity of research on the microbiological quality of bee pollen. First the research, analyzed samples of bee pollen obtained from collectors installed in the experimental apiary hives belonging to the Regional Technology Development Center of Agribusiness of the Paraíba Valley, located in Pindamonhangaba-SP, belonging to the Agency of Technology Agribusiness Paulista. Frequency of collection in intervals of 24 hours, 48 hours and 72 hours, to the presence and/or amount of pathogenic microorganisms in pollen with the time of product in the field. The samples were frozen by 48 hours, and subjected to two drying processes (movement of air in the open system 40-42°C and a system of closed circulation of air at 30°C). Performed the analysis for the physical-chemical parameters of pH, humidity and water activity and with the microbiological assessment of Bacillus cereus, Coagulase positive Staphylococci, coliforms at 45°C, Escherichia coli, Salmonella, molds and yeasts, and micro sulphites reducing. Acquired samples of dried bee pollen market of the State of São Paulo, with registration at the Federal Inspection Service (SIF), subject to the same parameters. Through statistical calculations were observed possible differences and/or correlations between the analyzed parameters (microbiological, physico-chemical) for the proposed treatments (frequency of collection and processes of dehydration). It was found that the samples analyzed, the IN NATURE and dehydrated, were free of major pathogens such as Salmonella and Coagulase positive Staphylococci, however, the population of yeasts and molds is relatively high. May conclude that the yeasts and molds are the most significant microbiological parameters for the bee pollen, followed by Bacillus cereus bacteria and total coliforms, and parameters to be introduced into legislation, in addition to the dehydration process typically used for pollen, is not able to eliminate fungal its population, based on current legislation for microbiological standards in food, considering the group of granola, all the samples, are within the standards set. Yeast and molds are not included in the legislation of the MAP. The time of year influences the contamination of molds and yeasts, along with the time of pollen in the field, being given the collection of material every 24 hours. Thus the process of drying must be optimized to allow the achievement of product free of microbiological contaminants, together with the cleaning of equipment in various stages of production and processing of pollen constantly, with a focus in the search for materials to replace the wood that is extremely porous to enable proper cleaning and satisfactory. Another parameter to be considered is the packaging for the product deserves the attention of specialists in this area / Mestrado / Mestre em Ciência de Alimentos
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Ligação e troca iônica em interfaces zwitteriônicas / Ion Binding and Exchange in zwitterionic interfacesMauricio da Silva Baptista 10 July 1992 (has links)
Investigou-se o efeito do \"caráter iônico\" de interfaces zwitteriônicas, formalmente neutras, representadas por micelas e vesículas obtidas de monômeros com cabeça hidrofílica dipolar, nas propriedades de acumulação e troca de espécies iônicas. Os sistemas estudados incluíram, micelas de 1-(N-hexadecil-N,N-dimetilamônio) propanossulfonato (HPS), Hexadecil fosforil colina (C16PN), 3-hexadecil glicerofostidil colina (lisoPC) e vesículas de fosfatidil colina (PC). O estudo da ligação e troca iônica nestas interfaces foi monitorado a partir de efeitos sobre reações prototrópicas de sondas como a 8-hidroxi-1,3,6-pirenotrisulfonato de sódio (piranina). Observou-se a ligação crescente da piranina na seguinte ordem lisoPC < C16PN < HPS e troca iônica com sais adicionados (função do ânion) na ordem inversa, isto é, lisoPC > C16PN > HPS. Estudos de reprotonação de 1 e 2 naftóis incluídos nestes agregados, via salto de pH induzido por laser, revelaram um perfil de concentração de prótons inverso àquele das cargas do dipolo, isto é, concentração nos polos negativos e exclusão nos positivos. Este resultados foram ainda reforçados por estudos de excitação de volume, via espalhamento de luz, com micelas de HPS em função de sal adicionado. A partir destes resultados propôs-se um modelo de capacitor esférico imerso em meio eletrolítico para estas interfaces, o qual se mostrou bastante versátil na análise e previsão de resultados experimentais. Em suma, estabeleceu-se no presente trabalho a visão de que interfaces dipolares são geradoras de assimetria iônica na circunvizinhança da interface, assimetria esta de polaridade invertida àquela do dipolo radialmente disposto à interface. A generalidade deste modelo pode ser extrapolado para outras interfaces e colaborar na compreensão de diversos processos que dependem da acumulação e troca iônica. / The effect of ionic domains of formally neutral zwitterionic interfaces, represented by micelles and vesicles obtained with dipolar headgroups amphiphiles, on the binding and exchange of ionic species were investigated. The systems studied included: aqueous micelles of 1-(N-hexadecyl-N,N-dimethylammonio) Propane Sulfonate (HPS), Hexadecyl Phosphoryl Choline (C16PN), and 1-hexadecylglycerophostidyl Choline (lisoPC) and vesicles of Phosphatidylcholine (PC). Binding and ion-exchange processes were assessed from the effect of these agreggates on prototropic reactions of probes such as 8-hydroxy-1,3,6-pyrenetrisulfonate pyranine). Binding of pyranine increased in the following order lisoPC < C16PN < HPS. The effectiveness of anion dependent salt displacement of the probe from the aggregates was opposite to that of affinities, i.e. lisoPC > C16PN > HPS. Laser pH jump studies with 1 and 2 naphtols incorporated in these aggregates revealed a proton concentration profile inverse to that of the charged dipole, that is, accumulation in the region vicinal to the negatively charged group and exclusion from the positive end of the dipole. This finding were substantiated by HPS micelle excluded volume data, obtained from light scattering studies as function of added salt. A model of a spherical capacitor immersed in an electrolyte media for these interfaces was proposed. This model accounts for satisfactorily the observed characteristics of these interfaces. The model establishes that dipolar interfaces generate ionic asymmetries in the neighborhood of the interface that opposes the radially extended monomer dipole. The generality of the model can be very helpful in the analysis and understanding of several processes occurring in/at zwitterionic interfaces.
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Características microbiológicas, físico-químicas e sensoriais do leite de cabra submetido à pasteurização e ao congelamento comercializados em AlfenasSouza, Alan Kardec de 24 August 2012 (has links)
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Previous issue date: 2012-08-24 / Goat's milk is a complete food, rich in proteins, fats, vitamins and minerals. Having very small lipid molecules, it is highly digestible when compared to other types of milk. One of the great challenges for the popularization of goat milk is that many potential consumers reject it because of its odor, flavor and high price when compared to pasteurized cow milk. This study aimed at analyzing the quality of the milk commercialized in Alfenas, MG, Brazil and evaluating the effect of pasteurization and freezing on its microbiological, physico-chemical and sensory characteristics. During 270 days, 3 batches of raw, pasteurized, and pasteurized and frozen goat milk were analyzed. Each batch was assessed every 90 days. The data were submitted to ANOVA and the Tukey test. The results showed that the slow pasteurization was effective in improving the microbiological quality of the milk, while no change was found in freezing it for 90 days. The physico-chemical and sensory characteristics of the milk was not changed by pasteurization and 90-day freezing. It was concluded that the goat milk commercialized in Alfenas, MG, Both pasteurized and pasteurized and frozen, have microbiological, physico-chemical and sensory quality within the standards established by law. / O leite de cabra é um alimento completo, rico em proteínas, gorduras, vitaminas e sais minerais, possui moléculas de gordura de tamanho reduzido, apresentando alta digestibilidade comparado aos demais tipos de leites. Um dos maiores desafios para a popularização do leite de cabra é a grande rejeição por parte do público consumidor em potencial, devido ao forte odor, sabor e preço elevado comparado ao leite de vaca pasteurizado. Este trabalho objetivou analisar a qualidade do leite de cabra comercializado na cidade de Alfenas-MG e avaliar o efeito da pasteurização e do congelamento sobre suas características microbiológicas, físico-químicas e sensoriais. Durante 270 dias, foram realizadas análises microbiológicas, físico-químicas e sensoriais de 3 lotes de leite de cabra cru, pasteurizado e pasteurizado e congelado. Cada lote foi analisado a cada 90 dias. Os dados obtidos foram submetidos à análise de variância e teste de Tukey. Verificou-se que a pasteurização lenta foi eficiente para melhorar a qualidade microbiológica do leite e que o congelamento por 90 dias não a alterou. As características físico-químicas e sensoriais não foram alteradas pela pasteurização e nem após o congelamento por 90 dias. Concluiu-se que o leite de cabra, pasteurizado e pasteurizado e congelado, comercializado na cidade de Alfenas-MG possui qualidade microbiológica, físico-química e sensorial dentro dos padrões estabelecidos pela legislação.
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Características físico-químicas e sensoriais do arroz (Oryza sativa L.) irradiado e o efeito no desenvolvimento de Sitophilus oryzae L. / Physico-chemical and sensorial characteristics of rice (Oryza sativa L.) irradiated and the effect in Sitophilus oryzae L. developmentCíntia Fernanda Pedroso Zanão 02 August 2007 (has links)
O arroz sofre danos principalmente pelo ataque de insetos, causando grandes perdas qualitativas e quantitativas, devido a isso, a presente pesquisa teve como objetivo verificar a viabilidade da radiação gama como método de conservação do arroz (Oryza sativa L.), sua eficiência no controle de uma importante praga de grão armazenado Sitophilus oryzae L. e os efeitos que a irradiação pode apresentar nos grãos irradiados considerando o aspecto sensorial e alteração no amido. As amostras foram constituídas de arroz polido e as doses de radiação gama utilizadas foram 0,5; 1,0; 3,0; e 5,0 kGy, sendo mantidas em temperatura ambiente. Foram realizadas análises da porcentagem de quebra do grão durante o beneficiamento e análise da longevidade e reprodução do gorgulho arroz. Foram realizadas também, as análises da composição centesimal, ácido fítico, conteúdo de amilose aparente e propriedades de pasta dos amidos além das análises para cor (instrumental) em arroz e a aceitabilidade (teste hedônico) visando à determinação da qualidade sensorial do arroz cru e cozido. Verificou-se que a irradiação não alterou de maneira significativa à quebra dos grãos durante o beneficiamento e causou efeito negativo no desenvolvimento dos insetos. A irradiação não alterou de maneira significativa à composição centesimal. Não foi encontrado valor significativo de ácido fítico, devido ao arroz ter sofrido o beneficiamento, retirando a parte externa (farelo) onde contém 85 – 92% de fitatos totais. Foram encontrados valores de 17,33 a 18,44% para conteúdo de amilose aparente, sendo que a irradiação não afetou significativamente a conteúdo de amilose do amido do arroz. Os resultados da propriedade de pasta foram significativamente alterados, ocorrendo à redução da temperatura de pasta, diminuição do tempo para ocorrência do pico viscosidade, redução nos valores de viscosidade máxima e viscosidade final e a tendência de retrogradação se tornou menos acentuada nos amidos com doses crescente de radiação gama. Foram detectadas diferenças estatísticas (p<0,05) no aspecto sensorial entre as amostras irradiadas e não irradiadas, sendo que a amostra irradiada com a dose de 1,0 kGy obteve maiores médias para os atributos sensoriais. Para os resultados encontrados na cor instrumental observou a diferença estatística nos valores b* indicando que o arroz sofreu mudanças de branco para amarelada com o aumento da dose de radiação gama. Conclui-se que o uso da radiação gama, especialmente a dose de 1,0 kGy, mesmo apresentando diferença significativa (p< 0,05) nas propriedades de pasta, proporcionou maior aceitação pelos provadores, não afetou as análises físico-químicas, assegurando maior vida-útil contra o ataque de insetos, desde que não haja reinfestação, sendo portanto a dose recomendável para a conservação do arroz polido. / Rice is exposed to injuries especially due to the attack of insects, which represent great qualitative and quantitative losses. The aim of the present research was to verify the viability of the gamma irradiation as rice (Oryza sativa L.) conservation method; its efficiency in the control of an important pest for stored grains Sitophilus oryzae L. and the effects that irradiation may present in irradiated grains in relation to the sensory aspect and starch alterations. Samples were composed of polished rice and the gamma irradiation dosages used were 0.5; 1.0; 3.0; and 5.0 kGy, and kept at room temperature. Analyses of the grain breakage percentages during processing and the longevity and reproduction of the rice weevil were performed. Analyses of the centesimal composition, phytic acid, apparent amylose content and starch paste properties were also conducted, as well as analyses of the rice color (instrumental) and acceptability (hedonic test), aimed at the determination of the raw and cooked rice sensory quality. It was verified that the gamma irradiation did not change the grain breakage percentage significantly and caused a negative effect on the insect development. Irradiation did not change the centesimal composition significantly. No significant values of phytic acid were found because during rice processing, the outer part (bran) containing 85-92% of total phytates was removed. Values from 17.33 to 18.44% for the apparent amylose content were found, and irradiation did not affect the rice starch amylose content significantly. The paste properties results were significantly changed, where reduction on the paste temperature, decrease on the time for the occurrence of the peak viscosity, reduction on the final viscosity values were observed. The retrogradation tendency became less intense in starches with increasing irradiation dosages. Statistical differences (p<0.05) were detected in the sensory aspect between irradiated and non-irradiated samples, and the sample irradiated with 1.0 kGy obtained the highest means for the sensory attributes. For results obtained for instrumental color, a statistical difference was observed in b* values, indicating that the rice color changed from white to yellowish with increased irradiation dosages. One concluded that the use of the gamma irradiation especially at dosage of 1.0 kGy, even presenting significant difference (p<0.05) in the paste properties, obtained higher acceptance; this irradiation level did not affect the rice physical-chemical analyses and provided longer shelf-life against the attack of insects, being therefore, the recommended dosage for the conservation of the polished rice.
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