nÃo hà / Os benefÃcios do consumo de produtos alimentÃcios com propriedades funcionais vÃm aumentando e desenvolvendo interesse nas Ãltimas dÃcadas em muitos pesquisadores e consumidores. A linhaÃa (Linum usitatissimum L.) tem sido considerada um ingrediente funcional de grande importÃncia por conter combinaÃÃes funcionais como o Ãcido linolÃnico (ALA), lignanas e fibras. Diversas pesquisas evidenciam os efeitos positivos da alimentaÃÃo acrescentada com linhaÃa no tratamento e prevenÃÃo de muitas enfermidades como: doenÃas cardiovasculares, cÃncer, artrite, sintomas indesejÃveis da menopausa, constipaÃÃo, entre outras. A farinha do maracujà vem demonstrando possuir a capacidade de reduzir o chamado âmau colesterolâ (LDL) e aumentar o âbom colesterolâ (HDL), sendo indicada como auxiliar no tratamento do diabetes e reduÃÃo de peso. Assim este trabalho teve como objetivo desenvolver um produto de panificaÃÃo com caracterÃsticas funcionais. Foram elaboradas quatro formulaÃÃes de pÃo de forma, sendo uma formulaÃÃo padrÃo, sem adiÃÃo das farinhas de linhaÃa e maracujà (FP) e trÃs substituindo-se parcialmente a farinha de trigo por percentuais de farinha de linhaÃa 4% (FML4), 7% (FML7) e 10% (FML10), e todas com adiÃÃo de 3% de fibra alimentar (farinha de maracujÃ). As amostras foram avaliadas quanto Ãs suas caracterÃsticas fÃsicas, quÃmicas, fÃsico-quÃmicas, reolÃgicas, sensoriais e microbiolÃgicas. Foram submetidos a testes sensoriais de aceitaÃÃo global, aceitaÃÃo por atributos e intenÃÃo de compra. Os dados foram analisados estatisticamente atravÃs de anÃlise descritiva, anÃlise de variÃncia (ANOVA) e teste de Tukey para comparaÃÃo das mÃdias, utilizando nÃvel de significÃncia de 5% (p≤0,05). As modificaÃÃes mais significativas na composiÃÃo dos pÃes com adiÃÃo de farinha de linhaÃa e farinha de maracujà foram verificadas nos teores de proteÃnas, lipÃdios, carboidratos, fibras e valores calÃricos. A aceitabilidade dos pÃes foi avaliada por 60 provadores, quanto ao aroma, textura, sabor, sabor residual, aceitaÃÃo geral e intenÃÃo de compra atravÃs da escala hedÃnica e escala do ideal para avaliar aroma, maciez, sabor e sabor residual. Todas as formulaÃÃes analisadas receberam valores hedÃnicos na faixa e aceitaÃÃo em todas as variÃveis. Os resultados de intenÃÃo de compra sugeriram que os consumidores tiveram maior interesse nos pÃes FML4 e FML7. A adiÃÃo da farinha de linhaÃa e farinha de maracujà provocou aumento significativo nos teores de fibras, tornando os pÃes com alto teor de fibra alimentar / In the last decades, there is a growing in the interest research and consume foods product with functional properties. This happening due the public knowledge of these productâs benefits. The flaxseed (Linum usitatissimun L.) has been considerated a functional ingredient of great importance. This importance is due its functional combinations such as linolenic acid, lignans and fibers that are potentially beneficial to our health. Several researches evidence the positive effects of adding flaxseed to the food to the combat and prevention of many diseases, for example: cancer, constipation, menopause, disease cardiovascular, among others. The passion fruit flour has demonstrated its ability to reduce the bad cholesterol (LDL) and to increase the good cholesterol (HDL). Therefore, the passion fruit flour has been pointed out as an auxiliary in the treatment of diabetes and weight reduction. Thus, this research work has the purpose of developing bread with functional characteristics. We have formulated four experiments. The first one, the standard bread (FP), without the addition of flaxseed and passion fruit flour. In the other three experiments have received 3% of fiber food (fruit passion flour) and additionally 4% (FML4), 7% (FML7) and 10% (FML10) of flaxseed flour. The experiments were evaluated over their physic, chemical, physic-chemical, sensorial, microbiological and rheologic characteristics. They were put under sensorial tests to prove the global acceptance, acceptance for the attributes of purchasing intention. The data were statically investigated through descriptive analysis and variance analysis (ANOVA) and the Tukey test for comparison of the averages, using the significance level of 5% (p≤0,05). The most noteworthy modifications in the composition of the bread that were added flaxseed flour were verified into values of proteins, lipids, calories, fibers and carbohydrates. The acceptability of the bread was evaluated by 60 volunteers by the attribution of flavor, taste, texture, residual taste, smoothness, and general reception and purchase intention. These evaluations were made by hedonic scale and the ideal scale to value aroma, taste, texture and residual taste. All analyzed results had received hedonics values in the range and a global acceptance. The outcome of purchasing intention suggested that the volunteers have shown more interest to the bread FML4 and FML7. The addition of flaxseed flour and passion fruit flour has promoted a significant increase on the fiber amount, turning the bread with high amount of fiber food

The goal of this project was to create a simulator that was to produce data for research in the field of activity recognition. The simulator was to simulate a human entity moving around in, and interacting with, a PEIS environment. This simulator ended up being based on The Sims 3, and how this was done is described. The reader is expected to have some experience with programming.

Ce travail a pour objectif l’élaboration de surfaces permettant le contrôle de l’adsorption protéique et de l’adhésion cellulaire. Deux axes d’études permettent de répondre à cette problématique : d’une part l’optimisation des conditions de greffage par réaction thiol-ène de chaînes éthylène glycol (OEG ou PEG) comportant une fonction thiol sur une monocouche auto-assemblée de trichlorosilane d’undécényle, d’autre part la caractérisation chimique de surface (mesures d’angle de contact, ellipsométrie, microscopie de fluorescence, infrarouge en réflexion totale atténuée IR-ATR, spectroscopie de photoélectrons induits par rayons X XPS, spectrométrie de masse d’ions secondaires à temps de vol ToF-SIMS) à l’issue de chaque étape de traitement. L’étude méthodologique des conditions de greffage thiol-ène montre la mise au point d’un système bicouche structuré après 1 minute de réaction pour le greffage OEG, 1 heure pour le greffage PEG. Par l’emploi de divers substrats (oxyde de silicium, titane, verre), différentes molécules OEG-thiol ou PEG-thiol (longues de 7 à 220 unités éthyléniques, terminées –méthyle, -carboxyle ou –amine), nous mettons en avant les déclinaisons possibles de cette stratégie. Ces terminaisons chimiques conduisent, au choix, à l’inhibition de l’adsorption protéique ou à l’adsorption de biomolécules, albumine de sérum bovin (BSA) ou fibronectine (Fn), permettant de faire de l’adhésion spécifique. Le contrôle, dans le plan de l’échantillon, des zones exposées à la lumière par photochimie lors du greffage thiol-ène autorise le photopatterning des surfaces permettant la maîtrise de l’adsorption protéique et également de l’adhésion cellulaire à la surface. / The aim of this work is to design surfaces allowing controlling cellular adhesion by the study of protein adsorption and cell adhesion. Two main parts were investigated in order to answer this challenge: on one side the optimization of grafting conditions using the thiol-ene reaction of thiol-terminated ethylene glycol chains (OEG or PEG) on a undecenyltrichlorosilane self-assembled monolayer, on the other side the surface chemical characterization (angle contact measurement, ellipsometry, fluorescence microscopy, attenuated total reflection infrared IR-ATR, X-ray Photoelectron Spectroscopy XPS, Time-of-Flight Secondary Ion Mass Spectrometry ToF-SIMS) after each reaction step. The methodological investigation of thiol-ene grafting conditions exhibits the development of a bilayer structured system after a 1 minute reaction time concerning OEG grafting, 1 hour in case of PEG grafting. By using different substrates (silicon oxide, titanium, glass), different molecules OEG-thiol or PEG-thiol (from 7 to 220 ethylene unit long, methyl-, carboxyl- or amine-terminated), we highlight the range of available versions of this strategy. These chemical extremities lead on demand either to protein adsorption inhibition or to biomolecule adsorption, bovine serum albumin (BSA) or fibronectin (Fn) giving access to specific adhesion.By controlling the light-exposed areas in the sample plan, the photochemistry occurring during the thiol-ene grafting allows to design surface patterning for addressing both protein adsorption and cell adhesion on the sample surface.

Dans ce travail, Al-Cu échantillons modèle en alliage ont été chauffés sous vide ultra élevé, et on a trouvé que l'oxyde Al grandi et Cu pertage inceased en fonction de l'exposition à l'O2 en raison de l'oxydation préférentielle de Al. échantillons ont ensuite été recuits à 540 °C sous vide poussé et vieilli à 300 °C dans l'air, et corrodés en peu de temps dans l'électrolyte neutre et l'électrolyte alcalin contenant des ions Cl- en utilisant le système à trois électrodes, respectivement. Après immersion dans l'électrolyte neutre, corrosion morphologies (creusement de tranchées sur l'échantillon poli vs fosses creuses sur l'échantillon vieilli) se distinguent. Cependant, dans un électrolyte alcalin, la corrosion a à deux phases en raison de la dissolution de l'aluminium et de l'oxyde d'aluminium dans une solution alcaline: d'une part, un oxyde d'Al et la matrice d'Al ont été dissous en général, ce qui entraîne riche en Cu intermétalliques étant laissé isolément sur la surface; d'autre part, la corrosion générale a ensuite accompagné la dissolution préférentielle du substrat environnant riche en Cu intermétalliques résultant dans des tranchées autour des particules. Formation des mixtes Al-Cu oxydes riche en Cu2O et CuO dépôts ont été trouvés sur la surface corrodée. En outre, les échantillons Al-Cu recouvertes de revêtements Al2O3 déposés par procédé ALD à la surface ont été corrodés dans des conditions similaires. Comme on s'y attendait, une amélioration significative de la résistance à la corrosion des échantillons d'alliages revêtus a été observée, mais la couche d'ALD dans l'électrolyte alcalin est pas aussi stable que dans les électrolytes neutres. / In this work, Al-Cu model alloy samples were heated in ultra high vacuum (UHV), and it was found that the Al oxide grew and Cu percentage increased as a function of exposure to the O2 owing to the preferential oxidation of Al. Then samples were annealed at 540 °C in high vacuum and aged at 300 °C in air, and corroded in short time in the neutral electrolyte and the alkaline electrolyte containing Cl- ion using the three-electrode system, respectively. After immersion in the neutral electrolyte, corrosion morphologies (trenching on the polished sample vs. hollow pits on the aged sample) are distinguished due to the different distributions of Cu-rich intermetallics in the polished sample (distributed homogeneously) and the aged sample (mostly beneath the oxide layer). However, in alkaline electrolyte, corrosion went at two stages owing to the dissolution of aluminium and aluminium oxide in an alkaline solution: firstly, Al oxide and the Al matrix were dissolved generally, resulting in Cu-rich intermetallics being left isolatedly on the surface; secondly, general corrosion went on accompanied with the preferential dissolution of substrate surrounding Cu-rich intermetallics resulting in trenching around particles. Formation of mixed Al-Cu oxides/hydroxides layer rich in Cu2O and CuO deposits were found on the corroded surface. Furthermore, Al-Cu samples covered with Al2O3 coatings deposited by ALD process on the surface were corroded under similar conditions. As expected, a significant improvement of corrosion resistance of the coated alloy samples was observed, but the ALD layer in alkaline electrolyte is not as stable as in neutral electrolytes, and undergoes dissolution.

Les couches de conversion actuellement utilisées dans l'industrie aéronautique, pour protéger le métal de la corrosion et favoriser l'adhérence de la peinture, contiennent du chrome hexavalent, composé toxique et cancérigène dont l'utilisation va prochainement être interdite par la réglementation européenne REACh. L'une des pistes envisagée pour remplacer ces couches chromatées est l'utilisation de couches de conversion TCP (Trivalent Chromium Protection). Ces travaux portent sur l'étude des couches de TCP et s'attachent à caractériser chaque étape du traitement de surface industriel, incluant les étapes de prétraitement et de post-traitement. Des techniques d'analyse de surface (XPS, ToF-SIMS, AFM, MEB et PM-IRRAS) ont été utilisées pour analyser la composition chimique et la morphologie de la surface après chaque étape du traitement. Cette étude a été réalisée sur un alliage d'aluminium AA 2024-T3, très utilisé en aéronautique pour ses propriétés mécanique, mais présentant une faible résistance à la corrosion. Les résultats obtenus ont notamment mis en évidence que la couche de TCP se forme sur toute la surface de l'alliage (composés intermétalliques et cavités), et ont permis de comprendre comment le post-traitement permet d'améliorer la résistance à la corrosion de la couche de TCP. Ces travaux s'intéressent également à des couches de conversion sans chrome, à base de zirconium, étudiées ici pour servir de point de départ au développement d'une conversion sans chrome qui respecterait les exigences de résistance à la corrosion. / Conversion coatings are used in aerospace industry to protect the metal from corrosion and to promote paint adhesion. Currently, chromate conversion coatings are used, but chromate is toxic and carcinogenic and its use will be forbidden by the European REACh regulation. TCP (Trivalent Chromium Protection) conversion coatings, are considered as a promising alternative to replace chromate conversion coating. This work focuses on the characterisation of the TCP layer and considers each step of the industrial surface treatment, including pre-treatment and post-treatment steps. Surface analytical techniques (XPS, ToF-SIMS, AFM, SEM and PM-IRRAS) were used to analyse the chemical composition and morphology of the surface after each step in the process. This work was done on an aluminium alloy AA 2024-T3, commonly used in the aerospace industry for its good mechanical properties, but poorly resistant to corrosion. The results obtained demonstrate, among other things, that the TCP layer totally covers the surface (intermetallic compounds and cavities) and enable to understand how the post-treatment can improve the corrosion resistance of the TCP coating. This work also focuses on conversion coating based on zirconium, which are studied here to be used as a starting point to develop a new conversion coating without chromium, meeting the corrosion resistance requirement.

Extensive research has shown that electrochemistry is one of the factors that govern the flotation of sulfide minerals. Flotation is often adversely affected by uncontrolled oxidation, which is also an electrochemical process. The interest in pyrrhotite recovery arose after observing that there is a substantial loss of PGM due to the depression of pyrrhotite and the subsequent loss of any PGMs associated with it. The first part of this study focuses on the influence of chemical composition and crystal structure on the electrochemical behaviour of pyrrhotite in a 0.05 M Na2B4O7 solution. Rest potential and polarisation resistance measurements, as well as anodic polarisation diagrams, showed that the magnetic 4C type pyrrhotite is anodically more reactive than the non-magnetic 6C type pyrrhotite. It was also shown in cathodic polarisation diagrams that the non-magnetic 6C type pyrrhotite is a better substrate for oxygen reduction and is less susceptible to oxidation. ToF-SIMS showed the formation of an oxide layer on the pyrrhotite surface after oxidation. In the second part of this work, the influence of galvanic interactions on the electrochemical behaviour of pyrrhotite in contact with pentlandite was investigated. It was observed that, under oxygen-saturated conditions, as the amount of pentlandite increases, the reactivity towards oxidation of the mixed mineral system is reduced. Impedance measurements showed a decrease in capacitance values, indicating the formation of a continuous oxide layer on the surface and an increase in oxide layer thickness with decreasing pentlandite content. Anodic polarisation diagrams showed that under oxygen-deficient conditions and in the low potential region, pentlandite behaves as an inert material and does not have an influence on the oxidation behaviour of pyrrhotite. Hence, the anodic activities of the different magnetic 4C type pyrrhotites from Sudbury Gertrude, Phoenix and Russia were compared. It was shown that the oxidation reactivity decreased in the following order: Sudbury Gertrude magnetic 4C pyrrhotite > Phoenix magnetic 4C pyrrhotite > Russian magnetic 4C pyrrhotite; it also varied according to location. In the transpassive region, higher anodic currents were observed on the mixed samples because both pentlandite and pyrrhotite reacts. The reactivity increased in the order: pure pyrrhotite (Russia) < medium-pentlandite (Sudbury Gertrude) < high-pentlandite (Phoenix). In the presence of potassium ethyl xanthate, there was no change in the initial anodic reactivities of the different pyrrhotites. The anodic polarisation diagrams of the pure and mixed samples showed a reduction in the maximum anodic peak current, suggesting the presence of xanthate on the surface, which hinders oxidation of the mineral surface. In addition, the influence of cleaning of oxidised pyrrhotite with gaseous carbon dioxide was studied, using electrochemical and microflotation measurements. Electrochemical measurements indicated that CO2 treatment resulted in depassivation of the oxidised surfaces; this was supported by ToF-SIMS measurements that demonstrated a reduction in the oxide layer thickness after CO2 treatment. Anodic polarisation diagrams showed a higher anodic peak current, indicating that the surface is more reactive. Gaseous carbon dioxide conditioning of oxidised pyrrhotite resulted in improved flotation response of pyrrhotite with the aid of copper activation and higher air flow rate. Copyright / Dissertation (MEng)--University of Pretoria, 2010. / Materials Science and Metallurgical Engineering / unrestricted

This thesis studies comparison and connection of two spectrometric methods – low energy ion scattering spektrometry (LEIS) and secondary ion mass spectrometry (SIMS). SIMS method, despite its many positive qualities, suffers of so called matrix effect, which makes quantifiaction of data very difficult. LEIS method on the other hand is immune to this effect and so it’s suitable completion of SIMS method. As a convenient sample have been chosen AlGaN samples with various concentration of gallium and aluminium. In the first part of thesis is introduced physical essence of SIMS and LEIS method, experimental details and studied samples. In second part of the thesis there’s a description of measurements and comparison of data gained by each method.

The present work is the fourth (and final) contribution to an inter-laboratory collaboration that was planned at the 3rd International Summit on Organic Photovoltaic Stability (ISOS-3). The collaboration involved six laboratories capable of producing seven distinct sets of OPV devices that were degraded under well-defined conditions in accordance with the ISOS-3 protocols. The degradation experiments lasted up to 1830 hours and involved more than 300 cells on more than 100 devices. The devices were analyzed and characterized at different points of their lifetimes by a large number of non-destructive and destructive techniques in order to identify specific degradation mechanisms responsible for the deterioration of the photovoltaic response. Work presented herein involves time-of-flight secondary ion mass spectrometry (TOF-SIMS) in order to study chemical degradation in-plane as well as in-depth in the organic solar cells. Various degradation mechanisms were investigated and correlated with cell performance. For example, photo-oxidation of the active material was quantitatively studied as a function of cell performance. The large variety of cell architectures used (some with and some without encapsulation) enabled valuable comparisons and important conclusions to be drawn on degradation behaviour. This comprehensive investigation of OPV stability has significantly advanced the understanding of degradation behaviour in OPV devices, which is an important step towards large scale application of organic solar cells. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

This essay aims to investigate representation and diversity in novels used in the English teaching inupper secondary school, and whether teachers take representation into account when choosing whatnovels to work with. A web survey was used to ask 71 teachers of English open questions regardingwhat novels they use in their teaching and why. The results demonstrate that the majority of the usednovels depict normative protagonists and settings, although there is some diversity and representationof different genders, races, ages, abilities and settings. It is also shown in the results that the majorityof the responding teachers do not think about representation when choosing what novels to workwith, while some respondents do indicate that they take aspects of representation into account. Theresults are discussed by drawing on ideas about representation, diversity and an intersectional genderpedagogy from Rudine Sims Bishop and Nina Lykke. / Denna uppsats syftar till att undersöka representation och mångfald i romaner som används iengelskundervisning i gymnasiet, samt om lärare har representation i åtanke när de väljer vilkaromaner de skall arbeta med. En webbenkät användes för att fråga 71 engelsklärare öppna frågorangående vilka romaner de arbetar med och varför. Resultatet visar att en majoritet av användaromaner skildrar normativa protagonister och miljöer, även att det finns viss mångfald ochrepresentation av olika kön, etniska tillhörigheter, åldrar, funktionsvariationer och miljöer. Det visarsig även i resultatet att majoriteten av responderande lärare inte har representation i åtanke när deväljer vilka romaner de skall arbeta med, medan några respondenter indikerar att de tar hänsyn tillaspekter av representation. Resultaten diskuteras med hjälp av idéer om representation, diversitet ochintersektionell genuspedagogik från Rudine Sims Bishop och Nina Lykke.

Des études antérieures ont montré que l'incorporation de groupements méthyles par dépôt assisté par plasma (PECVD) dans des couches minces de silicium améliore leur cyclabilité lors de leur utilisation comme électrodes négatives pour les batteries Li-ion. Dans le cadre de cette thèse, plusieurs approches ont été adoptées pour mieux comprendre les phénomènes impliqués dans ce nouveau matériau lors de cyclages en condition réaliste.Nous avons montré que la spectroscopie infrarouge operando en géométrie de réflexions totales atténuées (ATR-FTIR) apporte des informations quantitatives sur les phénomènes mis en jeu lors de la lithiation et de la délithiation de la couche active. L'augmentation progressive de l'absorbance pendant la première lithiation permet notamment de suivre la formation d’une phase très riche en lithium LizSi qui envahit progressivement le matériau. Nous avons montré que la concentration z du lithium dans cette phase dépend de la teneur en groupements méthyles. Nous avons expliqué ce phénomène par deux effets distincts : (1) la fragilisation du matériau du fait de la diminution du degré de réticulation et de la cohésion. (2) la porosité qui augmente aux teneurs en méthyles plus élevées. Nous avons par ailleurs obtenu par microscopie électronique en transmission une mise en évidence directe de cette porosité à l’échelle nanométrique et de son accroissement avec la teneur en méthyle.Les mesures de spectrométrie de masse à ionisation secondaire à temps de vol (ToF-SIMS) en collaboration avec Chimie ParisTech ont montré que l’invasion du lithium à partir de la phase LizSi vers la zone non-lithiée est un phénomène très lent (correspondant à un coefficient de diffusion D ~10-19 cm2).Nous avons constaté par spectroscopie ATR-FTIR operando et mesures électrochimiques que l'évolution de la couche de passivation (SEI) dépend du taux du cyclage et de la teneur en groupements méthyles lors du premier cycle.Enfin, les phénomènes se produisant lors de l’interruption de la lithiation électrochimique ont été suivis à différents états de charge par spectroscopie ATR-FTIR operando et spectroscopie d'impédance électrochimique (EIS). Nous avons découvert qu'en début de lithiation, une partie du lithium inséré dans la couche repart vers l'électrolyte et contribue à l'augmentation de l'épaisseur de la SEI formée sur l'électrode. / Previous studies showed that the incorporation of methyl groups in silicon thin films obtained by Plasma Enhanced Chemical Vapor Deposition (PECVD) improves their stability as negative electrodes in Li-ion batteries. In this thesis, several approaches have been used to understand phenomena occurring in the so-called "methylated amorphous silicon" during realistic cycling condition.We have shown that infrared spectroscopy operando in attenuated total reflection geometry (ATR-FTIR) provides quantitative information on the phenomena involved during the lithiation and the delithiation of the active material. The gradual increase of the absorbance during the first lithiation makes it possible to follow the formation of a lithium-rich phase LizSi which gradually invades the material. We have shown that the concentration z of lithium in this phase depends on the content of methyl groups. This behavior has been explained by two distinct effects: (1) the weakening of the material due to the methyl-induced lowering of its reticulation degree and cohesion. (2) the increase of the material porosity at high enough methyl content. Transmission Electron Microscopy (TEM) measurements revealed that a porosity is present at the nanometer scale in the active material and increases with methyl content. Time-Of-Flight Secondary Ion Mass Spectroscopy measurements performed at Chimie ParisTech have shown that the lithium invasion of the pristine active material from the lithium-rich phase is an utterly slow phenomenon (corresponding to a diffusion coefficient D ~10-19 cm2).We observed Solid Electrolyte Interphase (SEI) evolution during first cycle depends on cycling rate and methyl content, using operando ATR-FTIR spectroscopy and electrochemical methods.The evolution of the material after interruption of the electrochemical lithiation at several states of charge has been monitored using operando ATR-FTIR spetroscopy and Electrochemical Impedance Spectroscopy (EIS). Those measurements show that part of the lithium initially inserted in the layer returns to the electrolyte during relaxation and contributes to the growth of the SEI.