Pour rester compétitives dans l'industrie aéronautique, les entreprises développent des stratégies diverses pour gagner un avantage concurrentiel comme l'augmentation du Coût Total de Possession (TCO) avec l'acquisition aéronautique complexe et des programmes de support. Les clients concentrent leurs besoins sur la disponibilité opérationnelle de tels systèmes et ne sont plus enclins à payer un prix supplémentaire pour un tel service, par conséquent le fournisseur est amené à minimiser le TCO tout en conservant un haut niveau de performance de flotte. Dans de tels accords, une partie du risque de performance opérationnelle est transférée vers le fournisseur sous forme de pénalité financière, engendrant ainsi un risque financier sur la rentabilité du contrat. Cette recherche aborde le problème du point de vue du fournisseur en considérant différentes options stratégiques pour la commercialisation de l'offre de services aéronautiques basés sur la performance, garantissant la disponibilité de la flotte. La méthodologie considère un système complexe, représentatif des systèmes aéronautiques actuels et les mécanismes de support rattachés, avec de multiples objectifs contradictoires à atteindre en tant que fournisseur. La méthodologie proposée couvre les catégories suivantes : disponibilité, fiabilité, maintenabilité et supportabilité. Elle considère le système complexe comme un tout incluant l'ensemble des interactions dans ce système et les relations entre la performance de disponibilité et le coût. D'autres facteurs de contribution additionnels sont aussi considérés dans ce mécanisme de support, comme les types d'incertitude de la performance du système, des données, des risques financiers et des coûts. Un modèle de pénalité pour l'utilisation avec les Services Basés sur la Performance (PBS) des offres dans l'industrie aéronautique est aussi fourni. Une méthodologie d'analyse de pénalité est proposée au travers de deux études de cas présentées dans cette thèse, offrant un avantage compétitif au fournisseur, de par la capacité de prévoir la distribution de probabilité de performance du système, et de quantifier le risque financier pour le modèle de pénalité en question. La méthodologie d'analyse démontre aussi que la capacité d'effectuer une analyse de risque sur des pénalités contractuelles est tout aussi importante pour le fournisseur que la capacité de prévoir la performance globale du système. Les conclusions montrent qu'il est tout à fait possible d'avoir une grande exposition de risque financier si un scénario de pénalité inadapté est choisi, même si la performance de disponibilité de la flotte prévue est au-dessus du taux ciblé ou contracté. / To remain competitive within the aeronautic industry, companies are developing various strategies to gain a competitive edge as the Total Cost of Ownership (TCO) increases with complex aeronautical acquisition and support programs. Customers are focusing their needs on the operational availability of such systems and are no longer willing to pay a premium for such a service, consequently the supplier is challenged to minimize the TCO whilst retaining a high level of fleet performance. In such accords, some of the operational performance risk is transferred back to the supplier and are usually in the form of financial penalties, which consequently creates a financial risk on the profitability of the contract for the supplier. This research addresses the problem from the point of the supplier when considering different strategic options for the sale and offer of performance-based aeronautic services that guarantee fleet availability. The methodology considers the complex system, as is typical with current aeronautic systems, relating support mechanisms, and the multiple yet contradictory objectives to achieve as a supplier. The methodology proposed covers the categories of Availability, Reliability, Maintainability and Supportability; it considers the complex system as a whole including the interactions within this system and the relationships between availability performance and cost. Additional other contributing factors are also considered within this support mechanism, such as the types of uncertainty on system performance, data, financial risks and costs. The introduction of a penalty model for use with Performance-Based Service (PBS) offers within the aeronautic industry is also provided. A methodology for penalty analysis is proposed through the two case studies presented in this thesis, giving the supplier a competitive advantage through the ability to predict the probability distribution of system performance and to quantify the financial risk for the penalty model in question. The analysis 5 methodology also demonstrates that the ability to perform risk analysis on contractual penalties is just as important to the supplier as the ability to predict overall system performance, as the findings present that it is quite possible to have a large financial risk exposure if the wrong penalty scenario is chosen even if the predicted Fleet Availability performance is above the targeted or contracted rate.

Kvantprickar är intressanta för tillverkning av solceller på grund av möjligheten att justera bandgapet beroende på kvantpricksstorleken. I detta examensarbete har alternativa arkitekturer av PbS kvantprickssolceller testats samt att påverkan av olika lager har utvärderats. Först framställdes en kort reproducerbarhetsstudie av PbS kvantprickssolceller, där de tillverkade solcellerna gav låg effektivitet jämfört med litteraturen. En jämförelse av att använda ZnO eller magnesiumdopat ZnO (MZO) utfördes, där solcellerna med MZO presterade bättre än solcellerna med ZnO. Vidare testades påverkan av att ta bort hål- jämfört med elektrontransporterande lagret, där det elektrontransporterande lagret visade sig vara väsentligt för att solcellen skulle fungera medan solcellen fortfarande kunde fungera utan det håltransporterande lagret. Dessutom testades en inverterad solcellstruktur, där alla producerade solceller hade en effektivitet under 0,09 %. Det testades också att använda en annan ligandlösning och lösningsmedel för det ligandutbyte som behövs för det ljusabsorberande kvantprickslagret i solcellen. Detta gjordes med ammoniumjodid för ligandutbytet för att senare använda lösningmedlet propylenkarbonat, filmerna som producerades med det nya ligandutbytet var av dålig kvalitet och gav solceller med låg effektivitet. Slutligen genomfördes en kort studie av glödgningstemperaturen för ett tunt lager av MZO, där man fann att MZO kristalliserade vid 250℃, 300℃ och 350℃ när det glödgades i 30 minuter. / Quantum dots are of great interest for producing solar cells due to the possibility of tuning the bandgap depending on the quantum dot size. In this Masters's thesis project alternative architectures of PbS quantum dot solar cells have been tested and the influences of different layers have been evaluated. First, a short reproducibility study of the PbS quantum dot solar cell was produced, where it could be seen that the fabricated solar cells gave low efficiencies compared to literature. A comparison of using ZnO or magnesium doped ZnO (MZO) was performed, where the solar cells using MZO performed better than the solar cells using ZnO. Furthermore, the influence of removing the hole compared to the electron transporting layer was tested, where the electron transporting layer proved to be essential for the solar cell to function while it still could function without the hole transporting layer. Additionally, an inverted solar cell structure was tested, but only produced solar cells with efficiencies below 0.09 %. It was also tested to use another ligand solution and solvent for the ligand exchange needed for the light-absorbing quantum dot layer in the solar cell. This was done using ammonium iodide for the ligand exchange to later disperse the quantum dots in propylene carbonate, although the films produced with the new ligand exchange were of poor quality and gave low-efficiency solar cells. Lastly, a short study of the annealing temperature of an MZO thin-film was realised, where it was found that the MZO crystallised at 250℃, 300℃, and 350℃ when annealed for 30 minutes.

The thesis describes the synthesis of PbS nano-, micro-structures by colloidal and hydrothermal techniques. Size and morphology dependent luminescence studies were carried out in detail. Application oriented studies like ion sensing and modulation of luminescence are carried out on colloidal PbS QDs. Photoelectrical studies are carried out on various morphologies of PbS microstructures. We observe the persistent photoconductivity, growth and quenching of photocurrent, and a few novel phenomena in flower shaped PbS microstructures. This work is presented in eight chapters inclusive of summary and directions for future work. CHAPTER 1 provides a brief introduction to optical and photoelectrical properties of semiconductor quantum dots and hydrothermal technique in preparation of quantum structures. A review of PbS nanostructures and its technological applications are discussed. CHAPTER 2 provides the experimental techniques used in this work. First, the synthesis of PbS nano-, micro-structures by various methods, and characterization tools used in this work are briefly presented. CHAPTER 3 deals with the synthesis of PbS quantum dots in poly vinyl alcohol with various precursor concentrations to identify the surface states by temperature dependent photoluminescence (PL) measurements. Average bandgap value calculated from absorption measurements was 2.1 eV. We have observed that high-energy PL bands (>1.3 eV) are due to electron traps (Pb dangling bonds) and low-energy bands (<1 eV) are due to hole traps (S dangling bonds). By capping with thiol compounds (mercaptoethanol-C2 H5OSH), absence of the 1.67 eV band indicates the passivation of Pb dangling bonds. To explain above observed results, we propose a band diagram with distributed shallow to deep states and attributed them to the specific surface related defects (Pb or S). CHAPTER 4 discusses the ion sensing applications of PbS quantum dots. We found that the sulfur related dangling bonds are quite sensitive to different metallic ions (since mercaptoethanol passivates only Pb atoms). Sulfur related PL band (~ 1 eV) have shown an order of magnitude improvement in its intensity for Hg, Ag ions and relatively low enhancement for Zn, Cd ions at 1 µmol concentrations. However Cu quenches the luminescence. An important distinction may have to be made between PbS and Cd related quantum structures. The PbS QDs can distinguish between Cu & Hg, however Cd related QDs couldn’t distinguish between these two ions. Photo-brightening and photo-darkening is an interesting phenomena indicative of photo-induced ionic migration that either helps in enhancing the emission of sulfur related defect emission or degrades the emission properties depending on the ion concentration. This report is the first of its kind in ion sensing applications using PbS QDs. CHAPTER 5 discusses the results of duel beam excitation on trap luminescence of PbS QDs. By using different lasers simultaneously (514 nm and 670 nm), we have observed the reversible luminescence quenching of trap emission. The high-energy PL band (1.67 eV) has double the quenching effect compared to low-energy PL band (1.1 eV). The luminescence quenching mechanism is attributed to the re-emission of the charge carriers from the traps (photo-ionization) due to the simultaneous excitation with the second beam. The dependence of the temperature, the effect of two beam excitation intensities and modulation frequency dependent quenching mechanism are primarily focused in this chapter. The quenching mechanism is considered to be quite useful in the optical modulation devices. CHAPTER 6 discusses the PL results on various morphologies of PbS nano-, microstructures. Interestingly, after protecting the surface with organic ligands such as mercaptoethanol (C2 H5OSH), dendrite structures have shown high-energy bands (~ 1.0 eV) in the PL spectra, which indicate the existence of various quantum confinement regimes in different branches of dendrites. The anomalous temperature dependent behavior of PL intensity is attributed to the size distribution. CHAPTER 7 discusses the results of photoconductivity measurements on various morphologies of PbS nano-, micro-structures. Flower shaped structures have shown persistent photoconductivity (PPC). This observed PPC is attributed to the presence of potential barriers, which are created by the different confinement regimes or due to the lattice relaxation, which occurs due to the carrier trapping at surfaces. In PPC, the estimated time constants of both build up and decay transients using the stretched exponentials are of the order of few tens of seconds. In PPC measurements, we observe the PC quenching below 40 K and growth above this temperature. PC quenching is attributed to the transfer of photo-excited carriers to a metastable state. The presence of metastable state is supported by the dark conductivity measurements in flower shaped structures. CHAPTER 8 presents the summary and directions for the future work.

La prise de conscience sociétale vis-à-vis des problèmes environnementaux augmente et conduit à une forte demande en matériaux issus de ressources renouvelables, comme les biocomposites. La sensibilité thermique et le comportement au feu restreint leur utilisation pour certaines applications comme le bâtiment. La réglementation en matière de sécurité incendie est très importante et nécessite donc de trouver des solutions adaptées pour améliorer le comportement au feu de ces matériaux. Dans ce contexte, nous avons dans un premier temps étudié la dégradation thermique et le comportement au feu des fibres naturelles seules et particulièrement l'impact de ses composants sur le comportement au feu. Ensuite, nous avons étudié la réactivité de quatre fonctions (amine, acide carboxylique, alcoxysilane et acide phosphonique) sur la fibre de lin et ses composants (cellulose, hemicellulose, lignine). La caractérisation des greffages a été réalisée de manière originale par des techniques de dégradation thermique.Ensuite, nous nous sommes intéressés à la dégradation thermique et au comportement au feu de biocomposites. Nous avons étudié le comportement au feu de biocomposite à base de PBS et de fibres naturelles en faisant varier différents paramètres comme le taux de fibres, la nature des fibres et l'influence d'un retardateur de flamme phosphoné. Deux stratégies d'ignifugation ont été testées : l'ajout en masse dans la matrice et le greffage sur les fibres naturelles de retardateur de flamme. Pour aller plus loin dans les stratégies d'ignifugation par greffage de retardateur de flamme, nous avons comparé l'influence du greffage d'une molécule et d'une macromolécule sur le comportement au feu du lin et du biocomposite PBS/lin. / The environmental awareness in the society is increasing and leads to a strong demand in material from renewable resources, such as biocomposites. The thermal sensitivity and the flammability restrict their use for certain applications such as building. The fire safety regulation is of prime importance and requires adaptive solutions to be found to improve the fire behavior of these materials.In this context, we have studied the thermal degradation and the fire behavior of natural fibers and particularly the effect of its components on the fire behavior. Then, we studied the reactivity of four moieties (amine, carboxylic acid, alkoxisilane and phosphonic acid) on the natural fibers. The grafting characterization was carried out with original techniques based on thermal degradation.Then, we are interested on the thermal degradation and the fire behaviour of biocomposites. We studied the fire behaviour of biocomposite based on PBS and natural fibers varying different parameters such as the amount of fibers, the type of natural fibers and the influence of a phosphonated fire retardant. Two fireproofing strategies have been tested: the addition in polymer matrix and the grafting on natural fibers of fire retardant. To go further in the fireproofing strategy by fire retardant grafting, we have compared the influence of the molecule or macromolecule grafting on the fire behaviour of flax and PBS/flax biocomposite.

Fundação de Amparo a Pesquisa do Estado de Minas Gerais / PbS quantum dots has been grown in oxide glasses by two distinct methodologies according to the dopants, using the fusing method at 1200ºC. The host glass matrices used were SNAB (SiO2.Na2CO3.Al2O3.B2O3) and SNABP (SiO2.Na2CO3.Al2O3.B2O3.PbO2), with PbS bulk and S (sulphur) added as dopants, respectively. Thermal treatments were applied in a systematic way in order to allow a controlled growth of quantum dots. Different experimental techniques were realized in order to study the growth kinetic of dots as a function of thermal treatment times and dopant concentrations. It was analyzed thermal properties of the glass matrices by Calorimetry Scanning Diferencial (DSC). Many techniques have allowed discussion of the optical properties by Optical Absorption (OA) and Photoluminescence (PL), morphologic properties by Atomic Force Microscopy (AFM), and structural properties by X-Ray Diffractometry (DRX) of the nanocrystals. Qualitative and quantitative analyse of the chemical composition of the samples has been possible by spectrometry of Fluorescence of Raios-X (FRX). Using the ] 4 4 [ . × p k r r method we were able to estimate the avarage diameter of the PbS quantum dots. Calculations of dispersion sizes of PbS quantum dots, from the AO bands, has been presented. We have found the dependence between the quantum dot gap and the dopant concentrations. The relation between the Stokes Shift and the average size of the PbS quantum dots was also presented. Through the previous results, we have defined the methodology referring the host glass matrix SNABP with S bulk added as the most favorable to the growth PbS quantum dots with low size dispersion. / Pontos Quânticos de PbS foram sintetizados em vidros à base de óxidos, a partir duas metodologias distintas quanto a dopagens, pelo método da fusão a 1200ºC. As matrizes vítreas hospedeiras utilizadas foram: SNAB (SiO2.Na2CO3.Al2O3.B2O3) e SNABP (SiO2.Na2CO3.Al2O3.B2O3.PbO2), e os dopantes adicionados à elas foram PbS bulk e S (enxôfre), respectivamente. Tratamentos Térmicos variados e adequados foram efetuados nestas amostras para permitir o crescimento controlado dos pontos quânticos de PbS. Com o objetivo de estudar e acompanhar a cinética de crescimento destes pontos em função dos tempos de tratamentos térmicos e das variadas concentrações de dopantes, foram efetuadas várias técnicas de caracterizações. Estas permitiram análises das propriedades térmicas dos vidros por Calorimetria Exploratória Diferencial (DSC); ópticas, por Absorção Óptica (AO) e Fotoluminescência (PL); morfológicas, por Imagens de Microscopia de Força Atômica (AFM); e estruturais, por Difratometria de Raios-X (DRX) dos referidos nanocristais. Análises qualitativas e quantitativas das composições químicas das amostras sintetizadas neste trabalho foram possíveis através da técnica de espectrometria de Fluorescência de Raios-X (FRX). Com o auxilio do método ] 4 4 [ . × p k r r , foi possível estimar o diâmetro médio dos pontos quânticos de PbS. Cálculos de dispersão de tamanhos &#958; a partir da largura a meia altura (W) das bandas de AO e discussões sobre a dependência de energia e o tamanho médio dos pontos quânticos foram apresentados e discutidos. Mostrouse graficamente a relação de dependência entre o Gap dos pontos quânticos e as concentrações de dopantes adicionados às matrizes vítreas. Apresentou-se de forma gráfica a relação entre o deslocamento Stokes e o tamanho médio dos pontos quânticos de PbS. A partir de análises dos resultados obtidos, definiu-se então a metodologia correspondente à matriz SNABP dopada com S bulk como sendo a mais favorável para a formação e crescimento dos pontos quânticos de PbS com menor dispersão de tamanhos entre si. / Mestre em Física

L’objectif premier de ce travail de thèse concerne la réalisation et la caractérisation de différents films multicouches afin d’étudier l’impact du phénomène de confinement des couches de polymères sur les propriétés barrières du polymère confiné et du film multicouche. Des films multicouches constitué de polycarbonate (PC) et de poly(m-xylène adipamide) (MXD6), polymères actuellement utilisés par les industries de l’emballage, ont tout d’abord été étudiés. Puis, dans un second temps, des films multicouches composés de polyesters biodégradables, à savoir des films multicouches d’acide polylactique (PLA) avec comme polymère confiné soit du poly(butylène succinate-co-butylène adipate) (PBSA) ou du poly(butylène succinate) (PBS), ont été élaborés.Une fois la structure multicouche obtenue et avoir confirmé l’amélioration de l’effet barrière grâce au phénomène de confinement, le deuxième objectif a été d’incorporer des charges lamellaires de type montmorillonite (Cloisite® 30B) dans la couche de polymère confiné dans le but d’accroitre davantage l’effet barrière du film multicouche sélectionné.Pour comprendre l’amélioration des propriétés barrières aux gaz et à l’eau des films multicouches élaborés, une analyse de la microstructure par DSC et DRX ainsi qu’une analyse des propriétés mécaniques ont été menées conjointement avec une observation par microscopie. / The objective of the work was the elaboration and the characterization of different multilayer films in order to study the impact of the confinement effect of the polymer layers on the barrier properties. Multilayer films of polycarbonate (PC) and poly(m-xylene adipamide) (MXD6), which are usual polymers for packaging industries, have been studied. Then, multilayer films composed of biodegradable polyesters, such as polylactic acid (PLA) with poly(butylene succinate-co-butylene adipate) (PBSA) or poly(butylene succinate) (PBS) as the confined layers, have been prepared and characterized.For the multilayer structure presenting improved barrier performances due to the confinement effect, the second objective was to insert lamellar clays (Cloisite® 30B) into the confined polymer layers to again improve the barrier properties of the multilayer film. To understand the gas and water barrier improvement of the multilayer films, a microscopic observation of the films and an analysis of the microstructure by DSC and XRD have been performed with mechanical properties measurements.

Ce travail de recherche consiste à étudier les relations structure-propriétés de mélanges biopolymères à base de poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) et poly(butylène succinate) (PBS). Il est divisé en trois parties. La première partie est consacrée à l'étude des propriétés des mélanges PHBV/PBS préparés par voie fondue en fonction de la composition en termes de morphologie et de propriétés rhéologiques, mécaniques, thermiques et barrières. Les résultats obtenus ont été discutés par rapport aux polymères de base. La deuxième partie est consacrée à la compatibilisation des mélanges PHBV/PBS et l'amélioration des interactions à l'interface. Les effets de l'incorporation de la sépiolite à 5% en masse et du PHBV greffé par de l’anhydride maléique (PHBV-g-MA) à 5% en masse ont été étudiés en termes de changements morphologiques montrant un effet synergique entre le compatibilisant et la nanocharge sur les l’ensemble des propriétés des mélanges PHBV/PBS. Enfin, une étude sur le recyclage a été menée à travers une évaluation des effets du nombre de cycles d'extrusion sur les propriétés des matériaux. Elle révèle qu'après 6 cycles d'extrusion, la dégradation thermo-mécanique du PHBV est significativement réduite en présence du PBS. / The main objective of this work was to study the structure-properties relationships of biopolymerblends based on poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polybutylene succinate (PBS). The work was devised into three parts. The first part was devoted to the study of the properties of PHBV/PBS blends prepared by melt compounding at different weight ratio in terms of morphology and properties. The results obtained were discussed in terms of properties and compared with the neat polymers. The second part was devoted to the study of compatibility of PHBV/PBS blends aiming to improve the interactions at the interface between the two components. The effects of both sepiolite (5% wt.) and PHBV-g-MA (5% wt.) were studied in terms of properties. The results showed a synergistic effect between the compatibilizer PHBV-g-MA and the nanofiller sepiolite though an increase in thermal, mechanical and rheological properties. The last part dealing with the recyclability of PHBV/PBS through the study of the effects of repeated extrusion cycles on the properties of materials. The results showed that after 6 reprocessing cycles the thermo-mechanical degradation of PHBV is significantly reduced in the presence of PBS.

No description available.

La synthèse dans un verre d'agrégats métalliques ou semiconducteurs permet l'étude de leurs<br />propriétés intrinsèques et la réalisation de dispositifs pour l'optoélectronique. L'implantation ionique per-<br />met en principe de s'affranchir des limites de solubilité, mais permet-elle un contrôle de la densité, la taille<br />moyenne et de la distribution de tailles des agrégats réalisés ? Nous avons étudié les effets de l'implantation :<br />écart à l'équilibre thermodynamique, et dépôt d'énergie générateur de porteurs (électrons et trous) chargés.<br />Nous montrons l'importance de l'oxydoréduction due au passage et à l'arrêt des ions, et faisons varier la<br />densité d'énergie déposée pour induire des conditions réductrices favorables à la précipitation d'agrégats<br />métalliques. Le mécanisme d'agrégation de Ag dans le verre est analogue à celui de la photographie. Nous<br />avons ensuite étudié la croissance d'agrégats de semiconducteurs composés - les chalcogénures de plomb<br />(PbS, PbSe, PbTe), aux propriétés optiques intéressantes. Nous mettons en évidence les effets complexes de<br />la chimie redox des chalcogènes, et leur lien avec la perte de contrôle de la croissance d'agrégats synthétisés<br />après implantation séquentielle de Pb et S. Nous développons une nouvelle synthèse contrôlée d'agrégats de<br />PbS consistant, avant recuit, à implanter du soufre dans des verres au Pb. Le choix de la composition du<br />verre permet de contrôler la croissance, et l'implantation de S permet d'atteindre des fractions volumiques<br />importantes. Les propriétés d'émission optique de ces agrégats dans l'infrarouge (vers 1,5 µm) font appa-<br />raître une section efficace d'excitation très importante et l'existence d'un niveau d'"exciton noir".

This study evaluated the use of the Prevent-Teach-Reinforce (PTR) model with two four-year-old children in a community preschool classroom. A multiple baseline design across activities was used to assess the teacher implementation of the behavior intervention strategies developed during the PTR team process and the changes in child problem behavior and engagement. Additional measures associated with the outcomes, such as researcher procedural integrity and social validity were assessed. The results suggest that the team of teachers were able to implement the PTR intervention with fidelity, which resulted in a decrease in the children’s problem behavior and an increase in their engagement. The PTR process was deemed feasible and acceptable by the teaching staff, and that the child behavioral outcomes were evaluated as acceptable by naïve observers.