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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
221

Self-organization in thin metal films under laser irradiation / Plonų metalų sluoksnių savitvarkos lazerio spinduliuotės poveikyje tyrimas ir modeliavimas

Gedvilas, Mindaugas 22 November 2011 (has links)
The aim of this PhD thesis is to find out mechanisms of the ripple initiation and formation in the chromium thin film on the glass substrate. To learn to control the ripple formation and to apply it for fabrication of diffraction gratings. In this thesis, the experimental and theoretical results of new self-organization effect of the metal thin film on the glass substrate under irradiation with a sequence of partially overlapping laser pulses are presented. The method for formation of the regular ripples and results on investigation of diffractive properties of the self-organized gratings is presented. Different types of metals are used in experiments in order to understand the reasons of regular structure formation in chromium film. A diverse behavior of the films under laser irradiation is observed depending on the metal when burst of partially overlapping pulses was applied. Experimental data is compared with simulations based on different physical phenomena in order to develop and confirm a model of ripple formation in thin chromium film under its irradiation with pulses of a nanosecond laser. The Plateau-Rayleigh instability of the cylindrical ridge formation during laser ablation appears to be the most probable process responsible for initiation of the ripple formation. The Marangoni convection of the molten metal from hot areas to cold is the stabilizing process of steady ripple formation. / Disertacijos darbo tikslas yra suprasti pagrindinius fizikinius mechanizmus, lemiančius raibulių susidarymą. Išmokti kontroliuoti raibulių formavimąsi. Panaudoti raibulių formavimąsi difrakcinių gardeliu gamybai. Rasti sąlygas, kada raibulių formavimosi galima išvengti, siekiant sumažinti kodinės stiklinės liniuotės periodą. Ištirti galimą raibulių formavimąsi skirtingų metalų dangose. Šioje daktaro disertacijoje pristatomi eksperimentiniai ir teoriniai rezultatai naujo savi-organizacijos reiškinio metalo dangos ant stiklo padėklo nanosekundinio lazerio į juostą sufokusuoto pluošto spinduliuotės poveikyje. Pristatomas naujas difrakcinių gardelių formavimo metodas panaudojant metalo savitvarką. Siekiant suprasti kas inicijuoja raibulių formavimąsi ir ar jis įmanomas visiems metalams, dangos apdribimas persiklojančiais lazerio impulsais aštriai į juostą sufokusuotu lazerio pluoštu išbandytas skirtingiems metalams. Skirtingas dangos elgesys stebimas kiekvienam metalui. Nagrinėjami pagrindiniai fizikiniai mechanizmai sukeliantys griežtai periodinių raibulių formavimąsi. Parodoma, kad raibulių formavimosi pradžia atsiranda dėl Plato-Reilio nestabilumo cilindrinės užvartos susidarymo metu. Taip pat parodoma, kad Marangoni konvekcija skystame metale yra pagrindinė jėga, lemianti nusistovėjusį periodinių raibulių formavimąsi.
222

Plonų metalų sluoksnių savitvarkos lazerio spinduliuotės poveikyje tyrimas ir modeliavimas / Self-organization in thin metal films under laser irradiation

Gedvilas, Mindaugas 22 November 2011 (has links)
Disertacijos darbo tikslas yra suprasti pagrindinius fizikinius mechanizmus, lemiančius raibulių susidarymą. Išmokti kontroliuoti raibulių formavimąsi. Panaudoti raibulių formavimąsi difrakcinių gardeliu gamybai. Rasti sąlygas, kada raibulių formavimosi galima išvengti, siekiant sumažinti kodinės stiklinės liniuotės periodą. Ištirti galimą raibulių formavimąsi skirtingų metalų dangose. Šioje daktaro disertacijoje pristatomi eksperimentiniai ir teoriniai rezultatai naujo savi-organizacijos reiškinio metalo dangos ant stiklo padėklo nanosekundinio lazerio į juostą sufokusuoto pluošto spinduliuotės poveikyje. Pristatomas naujas difrakcinių gardelių formavimo metodas panaudojant metalo savitvarką. Siekiant suprasti kas inicijuoja raibulių formavimąsi ir ar jis įmanomas visiems metalams, dangos apdribimas persiklojančiais lazerio impulsais aštriai į juostą sufokusuotu lazerio pluoštu išbandytas skirtingiems metalams. Skirtingas dangos elgesys stebimas kiekvienam metalui. Nagrinėjami pagrindiniai fizikiniai mechanizmai sukeliantys griežtai periodinių raibulių formavimąsi. Parodoma, kad raibulių formavimosi pradžia atsiranda dėl Plato-Reilio nestabilumo cilindrinės užvartos susidarymo metu. Taip pat parodoma, kad Marangoni konvekcija skystame metale yra pagrindinė jėga, lemianti nusistovėjusį periodinių raibulių formavimąsi. / The aim of this PhD thesis is to find out mechanisms of the ripple initiation and formation in the chromium thin film on the glass substrate. To learn to control the ripple formation and to apply it for fabrication of diffraction gratings. In this thesis, the experimental and theoretical results of new self-organization effect of the metal thin film on the glass substrate under irradiation with a sequence of partially overlapping laser pulses are presented. The method for formation of the regular ripples and results on investigation of diffractive properties of the self-organized gratings is presented. Different types of metals are used in experiments in order to understand the reasons of regular structure formation in chromium film. A diverse behavior of the films under laser irradiation is observed depending on the metal when burst of partially overlapping pulses was applied. Experimental data is compared with simulations based on different physical phenomena in order to develop and confirm a model of ripple formation in thin chromium film under its irradiation with pulses of a nanosecond laser. The Plateau-Rayleigh instability of the cylindrical ridge formation during laser ablation appears to be the most probable process responsible for initiation of the ripple formation. The Marangoni convection of the molten metal from hot areas to cold is the stabilizing process of steady ripple formation.
223

Optical emission spectroscopy of laser induced plasmas containing carbon and transitional metals.

Motaung, David Edmond. January 2008 (has links)
<p>The spectroscopic, SEM and Raman measurements on carbon nanotubes under the exact conditions of which OES analysis were made showed that at<br /> a pressure of 400 Torr and a flow rate of 200 sccm, the quality and quantity of single-walled carbon nanotubes was the highest.</p>
224

Development of novel analytical and interpretational protocols to facilitate the provenance establishment of glass and plastic evidence

May, Christopher David January 2009 (has links)
[Truncated abstract] The analysis and subsequent interpretation of trace evidence is of paramount importance to the forensic scientist. While a variety of methods are available to facilitate comparison between recovered and control samples, the use of a specific analytical method depends upon both the physical and chemical nature of the material itself and the material to which it is to be compared. Elemental analysis of evidentiary material is one such method of sample comparison and has been extensively applied to this purpose following the introduction of neutron activation analysis in the early 1960s. However, over the last 15 years, another instrumental technique has taken centre stage in the analytical armoury of the forensic scientist: laser ablation–inductively coupled plasma-mass spectrometry (LA-ICP-MS). The modification and adaptation of this technique, to a point where it is possible to distinguish between glass materials produced only hours apart on the same production line, is detailed in this thesis. Additional protocols have also been developed for the analysis of fibreglass and plastic crime scene debris. Finally, a method for quantification of elemental concentrations in headlamp plastics has also been developed to facilitate inter-comparison of data between both different analytical techniques and different laboratories. Glass material is one of the most common varieties of trace evidence and the forensic examination of glass traditionally involves the determination of its refractive index (RI). ... The analytical protocol involves the analysis of 46 analytes on material comprising the exterior surface of the lens. Using this data, it was found that although minor variations in elemental composition exist within a single headlamp lens, discrimination between lenses produced from a single manufacturing plant over a short period of time could still be achieved. Discrimination between all headlamp lenses, with the exception of some lenses produced on the same day, could be facilitated using the analytical protocol developed. Furthermore, an interpretational protocol has been developed that has successfully classified all unknown headlamp lens samples investigated in this study, within the discrimination limits of the analytical method. The semi-quantitative analysis of glass and plastic samples has also been examined using LA-ICP-MS. The concentrations of 16 analytes in container and float glass samples were determined. However, the levels of discrimination afforded by the semi-quantitative data were inferior to those achieved using qualitative data. Finally, a series of plastic-based standards, containing 25 analytes of known concentrations, was produced. Using these standards, relative concentrations of the study analytes were determined in polycarbonate headlamp lenses. Interpretation of the data produced made it possible to discriminate between all study samples. Consequently, the total analytical and interpretational protocol developed in this study has established the foundation for LA-ICP-MS to be adopted internationally as a recognised method for the analysis of plastic crime scene debris.
225

Provenance establishment and authentication of South-East Asian ceramics using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS)

Bartle, Emma Kathleen January 2009 (has links)
[Truncated abstract] The sale of fraudulent South-East Asian ceramics constitutes a large proportion of the illegal artefact and antique trade and threatens to undermine the legitimate international market. The sophistication and skill of forgers has reached a level where, using traditional appraisal by eye and hand, even the most experienced specialist is often unable to distinguish between a genuine and fraudulent piece. In addition, the current scientific method of authentication used by the international antiques and art industry, thermoluminescence (TL) dating, carries severe limitations. The technique has an error margin of +/-20 % and requires the removal of a significant piece of the sample being tested, which decreases both the monetary and cultural value of the artefact. Of more concern, forgers have developed methods which produce false test results and which appear to corroborate false claims for the age of artefacts. Consequently, the use of TL dating for authentication of ancient ceramics, especially those of South-East Asian origin, has now come into serious question. The most suitable method for authenticating ceramics is through provenance establishment. Studies published in the literature have investigated the application of various analytical techniques to provide this information for ceramic wares and have highlighted their potential to be used for provenance establishment. However, the value of each of these techniques is limited rendering them generally unsuitable for practical use in the international antiques and art world to authenticate high-value South-East Asian artefacts. Consequently, there is a desperate need for the development of a robust, accurate and non-destructive method which can be practically applied in the industry to authenticate South-East Asian ceramics. ... Minor variations between spectral profiles of artefacts produced in the same country have also been used to further provenance artefacts to a specific production region or kiln site. The results of analyses have been compiled to form a unique reference database which can be added to in the future and used by experts internationally. Adaptation of the developed sampling and analytical methodologies to allow in-situ sampling of large artefacts using the
226

Single-cell tracking of therapeutic cells using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry

Managh, Amy J. January 2014 (has links)
Cellular therapy is emerging as a clinically viable strategy in the field of solid organ transplantation, where it is expected to reduce the dependency on conventional immunosuppression. This has produced a demand for highly sensitive methods to monitor the persistence and tissue distribution of administered cells in vivo. However, tracking cells presents significant challenges. In many cases transplanted cells are autologous with the immune system of the transplant recipient, and hence are invisible to typical methods of detection. To enable their differentiation, the cells must be labelled with a suitable, non-toxic and long lifetime label, prior to their administration to patients. In addition, administered cells represent only a small fraction of the recipient's endogenous cells, which necessitates the use of an extremely sensitive detection method. Laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) is an exquisitely sensitive analytical technique, capable of imaging trace elements in complex samples, at high spatial resolution.
227

[en] SPECTROSCOPIC STUDIES OF FLUOROQUINOLONES AND THEIR COPPER(II) COMPLEXES: INTERACTION WITH MICELLES, LIPOSOMES AND GOLD NANOCOMPOSITES / [pt] ESTUDOS ESPECTROSCÓPICOS DE FLUORQUINOLONAS E SEUS COMPLEXOS DE COBRE(II): INTERAÇÃO COM MICELAS, LIPOSSOMAS E NANOCOMPÓSITOS DE OURO

JIMMY LLONTOP INCIO 10 January 2019 (has links)
[pt] Norfloxacina (NFX) é um antibiótico fluorescente de amplo espectro bacteriológico, membro da família das fluorquinolonas (FQs). A interação das FQs com íons metálicos pode incrementar a ação bactericida e agir contra a resistência das bactérias frente aos antibióticos. Diversos exemplos de complexos mistos de norfloxacina e Cu(II) podem ser encontrados na literatura. A compreensão dos mecanismos moleculares de interação desses antibióticos com os diferentes componentes das células e com nanopartículas de ouro, como transportadores do fármaco, é extremamente importante. Para entender essas interações, neste trabalho utilizamos diferentes técnicas espectroscópicas, como espectroscopia de fluorescência estacionária e resolvida no tempo, absorção de luz UV-Visível e ressonância paramagnética eletrônica (RPE). A interação de NFX e do complexo ternário Cu(II):L:NFX, onde o ligante L é a 1,10-fenantrolina (Phen) ou 2,2-bipiridina (Bipy), com micelas e lipossomas unilamelares pequenos de fosfatidilcolina de ovo (PC) foi estudada usando espectroscopia de fluorescência em estado estacionário e resolvida no tempo. Foi estudada a estabilidade dos complexos ternários formados em micelas. Foram obtidas constantes de estabilidade no interior de micelas de SDS, as quais mostraram valores muito maiores do que em tampão. Já os espectros de RPE deram maiores detalhes sobre a estrutura dos complexos e confirmaram a formação do complexo ternário dentro das micelas. Foram estudadas as interações de FQs e seus complexos de cobre com lipossomas de PC preparados com diferentes densidades superficiais de carga elétrica negativa. No estudo da interação de FQs com nanopartículas de ouro sintetizadas por ablação a laser (nanocompósitos, AuNCs), NFX mostrou maiores mudanças, tanto na absorbância como na fluorescência, do que as FQs ciprofloxacina (CFX) e levofloxacina (LFX). Os resultados sugerem mudanças no índice de refração na superfície dos AuNCs, por associação com o fármaco e/ou formação de aglomerados como resultado da interação. Observou-se também uma supressão lenta, porém significativa, na fluorescência da NFX, sem mudança na posição do pico, indicando que NFX mantém o seu estado inicial de protonação ligando-se à superfície dos AuNCs. Também foi observada a liberação de FQs ligadas à superfície de AuNPs mediante substituição por tióis, que ocasiona recuperação parcial da fluorescência da fluorquinolona. Por último, como o surfactante aniônico SDS se mostrou promissor na interação com NFX, em comparação com surfactantes catiônicos e neutros, e como os AuNCs são estáveis em SDS, estudamos a interação de NFX com AuNCs sintetizados em presença de SDS e, para comparação, com AuNCs colocados em solução de SDS após a síntese. / [en] Norfloxacin (NFX) is a fluorescent antibiotic of broad bacteriological spectrum, member of the fluoroquinolone (FQ) family. The interaction of FQs with metal ions can increase the bactericidal action and act against antibiotics bacterial resistance. Several examples of mixed-ligand norfloxacin Cu (II) complexes can be found in the literature. Understanding the molecular mechanisms of interaction of these antibiotics with different cell components and with gold nanoparticles as drug transporters is extremely important. To clarify these interactions, we used different spectroscopic techniques, such as steady-state and time-resolved fluorescence spectroscopy, UV-Visible light absorption, and electron paramagnetic resonance (EPR). The interaction of NFX and the ternary complex Cu(II):L:NFX, where the L is the ligand 1,10-phenanthroline (Phen) or 2,2-bipyridine (Bipy), with micelles and small unilamellar liposomes of egg phosphatidylcholine (PC) was studied using steady-state and time-resolved fluorescence spectroscopy. The stability of the ternary complexes formed in micelles was studied, and stability constants were obtained inside SDS micelles, which showed values much larger than in buffer. The EPR spectra gave further details on the structure of the complexes, and confirmed the formation of the ternary complex inside the micelles. The interactions of FQs and their copper complexes with PC liposomes prepared with different surface densities of negative electrical charge were studied. In the study of the interaction of FQs with gold nanoparticles synthesized by laser ablation (nanocomposites, AuNCs), NFX showed greater changes than FQs ciprofloxacin (CFX) and levofloxacin (LFX) in both absorbance and fluorescence. The results suggest changes in the surface refractive index of the AuNCs and/or cluster formation, as result of the interaction with the drug. A slow but significant quenching of NFX fluorescence was also observed, with no change in peak position, indicating that NFX maintains its initial state of protonation by binding to the surface of the AuNCs. Release of FQs attached to the surface of AuNCs by thiols has also been observed, which causes partial recovery of FQ fluorescence. Finally, as the anionic surfactant SDS showed to be promising in the interaction with NFX, compared to cationic and neutral surfactants, and because the AuNCs are stable in SDS, we studied the interaction of NFX with AuNCs synthesized in the presence of SDS and, for comparison, with AuNCs placed in SDS solution after synthesis.
228

Ecophysiologie de l'allocation du cadmium au grain chez le blé dur / Ecophysiology of cadmium allocation to grains in durum wheat

Yan, Bo-Fang 12 July 2018 (has links)
Le cadmium (Cd) est un élément toxique. Les activités humaines ont contaminé un large éventail de sols agricoles. L'exposition de l'homme au Cd se fait majoritairement par voie alimentaire, notamment à travers les aliments de base tels que les céréales. Le blé dur accumule naturellement plus de Cd dans ses grains que les autres céréales. Une fraction significative de la production française de blé dur dépasse la limite réglementaire européenne fixée pour le Cd. Il est donc nécessaire de réduire l'accumulation de Cd dans les grains de blé dur. Cette thèse portant sur l'écophysiologie de l'allocation du Cd aux grains chez le blé dur a pour ambition d'aider au développement de stratégies agronomiques visant à réduire le niveau de contamination en Cd du blé dur et de ses dérivés.Dans un premier temps, nous avons étudié la relation entre la structure de la biomasse aérienne et l'allocation de Cd aux grains. Nous avons fait l'hypothèse que la répartition de la biomasse aérienne entre pailles et grains était un facteur déterminant de l'allocation du Cd aux grains. Huit cultivars Français de blé dur - de hauteur de paille contrastée - ont été cultivés en présence de Cd. Comme prévu, le principal facteur expliquant la différence d'accumulation de Cd dans le grain était la structure de la biomasse aérienne. Les cultivars allouant une plus grande proportion de leur biomasse aérienne aux pailles - autrement dit les cultivars à longue tige - avaient tendance à accumuler moins de Cd dans leurs grains, car les tiges et les feuilles sont des puits de Cd en concurrence avec les grains lors de leur remplissage.Les minéraux importés dans les grains proviennent soit de leur absorption directe par la racine après l'anthèse, soit de leur remobilisation depuis des réserves constituées avant l'anthèse. La deuxième partie de ce travail a été consacrée à déterminer l'importance quantitative de ces deux « sources » pour le Cd chez le blé dur, et de préciser comment leur contribution relative varie entre cultivars et avec le niveau d'azote (N). Le traçage isotopique a été utilisé pour suivre le flux de Cd absorbé après l'anthèse. L'impact du niveau d'azote a été testé en privant la moitié des plantes de N après l'anthèse, sur deux cultivars montrant une capacité contrastée à accumuler le Cd dans leurs grains. La contribution de la remobilisation a été estimé à 50%, ce qui signifie que la moitié du Cd accumulé dans les grains provenait du Cd prélevé après l'anthèse. Le Cd a été remobilisé à partir des tiges, peut-être des racines, mais pas à partir des feuilles. La contribution de la remobilisation n'a pas varié entre les deux cultivars, de sorte qu'aucune relation entre la « source » de Cd et son niveau d'accumulation dans le grain n'a été mise en évidence. La privation d'azote en phase de remplissage a stimulé la remobilisation de N sans affecter celle de Cd, ce qui suggère que la remobilisation de Cd est un processus indépendant de la sénescence.En troisième lieu, nous avons examiné comment les caractéristiques d'allocation de Cd aux grains étaient modulées par le niveau d'exposition au Cd. [...]Enfin, nous nous sommes intéressés à la localisation de Cd dans le grain. [...] Ce travail a fourni la première carte de localisation de Cd dans un grain de blé dur. La distribution de Cd s'est caractérisée par une forte accumulation de Cd dans le sillon et par une dissémination dans l'endosperme amylacé plus prononcée que celle de Fe et Zn. / Cadmium (Cd) is a toxic element. Human activities have contaminated a wide range of agricultural soils. Most of Cd entering human bodies is through the dietary intake, and especially through staple food like cereals. Durum wheat naturally accumulates more Cd in its grains than other cereals. A significant fraction of the French durum wheat production has been found to exceed the European regulatory limit set for Cd. There is thus a need to reduce the accumulation of Cd in durum wheat grains. This thesis is dedicated to a better understanding of the ecophysiology of Cd allocation to the grains in durum wheat, with the ambition of helping to find agronomic strategies to reduce the Cd contamination level of durum wheat products.In first, we investigated the relationship between the aboveground partitioning of Cd and the shoot allometry. We hypothesized that the partitioning of shoot biomass between grains and straws is a driver of the allocation of Cd to the grains. Eight French durum wheat cultivars differing in their stem height were grown in presence of Cd. As expected, the main factor explaining the difference in their grain Cd was the shoot biomass partitioning. Cultivars allocating a higher proportion of their aerial biomass to the straws, i.e. long-stem cultivars, tended to accumulate less Cd in their grains because stems and leaves are sinks for Cd in competition with developing grains.Minerals imported into cereal grains originate from either direct post-anthesis root uptake or from the remobilization of pre-anthesis stores. The second part of this work was dedicated to determine the quantitative importance of these two pathways for Cd in durum wheat, and how their relative contribution vary between cultivars and with the level of nitrogen (N) supply. Stable isotopic labelling was used to trace the flux of Cd taken up post-anthesis. The impact of N supply was tested by depriving half of the plants of N after anthesis, in two cultivars showing a contrasted ability to accumulate Cd in their grains. The contribution of Cd remobilization was around 50%, which means that half of Cd in grains originated from Cd taken up pre-anthesis. Cd was remobilized from stems, possibly from roots, but not from leaves. The contribution of remobilization did not vary between the two cultivars so that no relationship between the pathway and the level of accumulation of Cd in grain was evidenced. Post-anthesis N deprivation triggered the remobilization of N without affecting that of Cd, which suggests that Cd remobilization is a senescent-independent process.In third, we investigated how the characteristics of Cd allocation to the grains was affected by the level of Cd exposure. [...]In last, we focused on how Cd was distributed within durum wheat grains. [...] This work provided the first map of Cd localization in durum wheat grains. Cd distribution was characterized by a strong accumulation of Cd in the crease and by a non-negligible dissemination in the starchy endosperm, as compared to Fe and Zn.
229

Electrode transparente en nanofils d’argent : intégration dans les cellules et modules photovoltaïques organiques sur substrat souple / Silver nanowire transparent electrode : integration in organic photovoltaic cells and modules on a flexible substrate

Laurans, Gildas 30 June 2016 (has links)
Une cellule photovoltaïque organique (OPV) consiste en un empilement de couches minces et comporte une électrode transparente, constituée le plus souvent par une couche mince d’oxyde d’indium dopé à l’étain (ITO). Des matériaux alternatifs sans indium, déposables par voie liquide à l’air ambiant, et sur de grandes surfaces souples plus adaptées à la filière OPV, sont actuellement l’objet d’un grand nombre de recherches. Les nanofils d’argent (Ag NWs) représentent un sérieux candidat pour remplacer l’ITO et sont l’objet de ce travail de thèse. Une méthode de dépôt des Ag NWs par spray à air sur des substrats de PET a été développée en vue de réaliser des films conducteurs et transparents sur une grande surface souple. Puis ces électrodes transparentes ont été intégrées dans des cellules OPV sur substrat souple avec des rendements comparables à l’ITO. Les dépôts par voie liquide ont été privilégiés (spray-coating, Dr Blade), excepté pour l’électrode supérieure en argent, évaporée sous vide. Enfin les cellules ont été interconnectées en série pour former un module OPV, plus efficace en termes de puissance électrique délivrée. Une étude sur l’ablation sélective de couches de l’empilement OPV par laser est également présentée pour la fabrication de modules. / An organic photovoltaic (OPV) cell consists of a thin-layer stack which includes a transparent electrode, usually made of indium tin-doped oxide (ITO). Alternative, indium-free materials, deposited in air with a wet deposition process on large, flexible substrates that are more compatible with the OPV field are currently widely investigated. Silver nanowires (Ag NWs), which represent a serious candidate to replace ITO, are the subject of this thesis. In this work a method to deposit Ag NWs on PET substrates by air spray-coating has been developed : efficient patterned conductive and transparent coatings could be processed on a large, flexible substrate. This transparent electrode was then integrated in flexible and large area OPV cells, with efficiencies comparable to ITO. Wet deposition techniques were preferred except for the silver top electrode, evaporated under vacuum. OPV cells were eventually interconnected in series in order to make an OPV module, delivering a higher electrical output. A study on selective laser ablation of layers in the OPV stack is also shown towards module processing.
230

Nouvelles méthodes de détermination des métaux dans les cendres volantes / New methods of metals determination in fly ash samples

Stankova, Alice 08 February 2010 (has links)
Les déchets solides générés par notre société sont nombreux. Les cendres volantes sont des déchets solides produits lors de la combustion de déchets domestiques ou industriels dans des incinérateurs. Les cendres volantes sont également produites par la combustion du charbon dans les centrales à charbon. Les cendres volantes sont des résultats de ces combustions et représentent importante quantité de déchets produits chaque année par notre société. Les possibilités de recyclage de ces déchets sont nombreuses : dans la construction, l'industrie routière. Elles sont également stockées pour une utilisation ultérieure. Les origines différentes des charbons et déchets incinérés conduisent à une minéralogie et une composition élémentaire complexe. En tant que sous-produit le devenir des cendres volantes est important à déterminer, aussi la détermination de la composition élémentaire de ces cendres volantes est-elle indispensable.Les méthodes classiques de préparation des échantillons solides sont la minéralisation acide ou la fusion alcaline. Ces procédures prennent du temps et supposent l’utilisation de réactif, de plus la digestion complète n'est pas toujours assurée. Le risque de contamination par les réactifs employés est important au cours de ces méthodes classiques de préparation. Au cours de la dernière décennie, le développement d’analyse directe d'échantillons solides en utilisant des méthodes d'ablation laser a été important en raison de la nécessité de réduire le temps d'analyse et de réduire aussi la consommation de réactifs. Dans ce travail, deux méthodes basées sur l'ablation par laser seront étudiées pour l'analyse des cendres: Laser Induced Breakdown Spectroscopy (LIBS) et Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). La spectrométrie LIBS sera étudiée pour la détermination quantitative des éléments majeurs dans les échantillons de cendres alors que le couplage ablation laser ICP / MS sera employé pour détermination des éléments traces. L'optimisation de la sensibilité et les stratégies d'étalonnage sont les principaux problèmes traités dans ce travail. La préparation des échantillons et l’optimisation ont été effectuées pour déterminer les éléments tels que Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V et Zn par les deux méthodes.Les performances analytiques telles que les limites de détection, justesse ont été obtenus à la suite d'optimisations appropriées des liants et de la sélection de l’étalon interne approprié. En conclusion, l’analyse directe de solides en utilisant les techniques basées sur l’ablation laser développées dans ce travail conduisent à une justesse acceptable pour la détermination des éléments majeurs et traces dans les cendres volantes / Solid waste generated by our society are numerous, fly ashes are produced during the combustion of domestic or industrial waste in incinerators. Fly ashes are also produced through coal combustion in coal fired power plants. Fly ashes are results of these combustions and represent important quantity of waste produced every year by our society. They have variable use – in construction, road industry, or they can be stocked for further use. As they are result of different origin, they have complex mineral and elemental composition. As a by-product or as a recycled product fly ashes fate is important to determine. In this view the determination of the elemental composition of fly ashes is the aim of this work.Conventional methods of sample preparation are acid digestion or alkali fusion. These procedures are time and reagent consuming and complete digestion is not assured. The potential contamination of the reagents employed is important during these classical sample preparation methods. During the past decade, development of direct solid sampling using laser ablation methods was important due to the need of reducing analysis time and also reducing reagent consumption. In this work, two methods based on laser ablation will be studied for fly ash analysis: Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LIBS will be studied for quantitative determination of major elements in fly ash samples while Laser ablation / ICP MS will be employed for trace element determination.The sensitivity optimization and different calibration strategies are key problems of laser sampling methods. Sample preparation and condition optimisation were performed to determine major, minor and trace elements such as Al, As, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Sr, V and Zn by both methods – LIBS for major elements and LA-ICP-MS for minor and trace elements.Analytical properties such as detection limits, accuracy and analytical working curves were obtained following suitable optimisation of binders and internal standards. Compromise binder and analytical conditions were selected to determine the elements in fly ash samples.In conclusion, direct solid sampling using laser ablation followed by LIBS or for solid introduction into ICP was found to determine major, minor and trace elements in fly ashes, improving pellets mechanical stability, high samples sensitivity and acceptable accuracy and detection limits.

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