Poly(dimethylsiloxan) (PDMS) ist ein wichtiges Polymer, das zunehmend in der Mikroelektronik aufgrund seiner hervorragenden Elastizität und thermischen Stabilität Verwendung findet. Ein limitierender Faktor für den Einsatz von PDMS ist aufgrund des Fehlens von reaktiven Gruppen und der niedrigen freien Oberflächenenergie seine geringe Adhäsion zu anderen Materialien. Zur Erhöhung der Adhäsion ist deshalb die Einführung von polaren, funktionellen Gruppen notwendig. Hier lag die Motivation der vorliegenden Arbeit, die sich eine gezielte Funktionalisierung von PDMS-Oberflächen als Aufgabe gesetzt hatte. Im ersten Teil der Arbeit wurde eine Verbesserung der Adhäsion zu einem fotostrukturierbaren Epoxidharz mittels der Sauerstoff- und Ammoniakplasmabehandlung angestrebt. In beiden Fällen führte die Plasmabehandlung zu der Einführung von unterschiedlichsten funktionellen Gruppen auf die Oberfläche und zu einer Verbesserung des Benetzungsverhaltens gegenüber Wasser. Zudem wurden Haftfestigkeiten erzielt, die um ein Vielfaches höher waren als jene zwischen Epoxidharz und einer unbehandelten PDMS-Oberfläche. Jedoch waren die hydrophilen Eigenschaften nach der Plasmabehandlung während der Lagerung an Luft zeitlich begrenzt, die PDMS-Oberfläche kehrt innerhalb kurzer Zeit in den einst hydrophoben Ausgangszustand zurück. Der Alterungsvorgang wird als „Hydrophobic Recovery“ bezeichnet und ist bei PDMS-Oberflächen, die höheren Plasmaleistungen und Behandlungszeiten ausgesetzt wurden, besonders auffällig. Die Vermeidung dieser Problematik war der Ausgangspunkt für den zweiten Teil der Arbeit. Auf der Grundlage der über die Plasmabehandlungen erzeugten funktionellen Gruppen wurden neue Konzepte für eine kovalente Anbindung von verschiedenen funktionellen Homo- und Copolymeren über die „Grafting to“-Technik entwickelt. Neben der Erhöhung der Adhäsion zu dem Epoxidharz war es möglich, das Benetzungsverhalten gegenüber Wasser durch die Unterbindung der „Hydrophobic Recovery“ zu stabilisieren. Des Weiteren gelang es, durch die Wahl der funktionellen Polymere, die PDMS-Oberfläche gezielt mit gewünschten Eigenschaften auszustatten. Somit ist der Einsatz der polymermodifizierten Oberflächen, außer in der Mikroelektronik, auch auf andere Anwendungen, wie der Biomedizin, der Mikrofluidik oder der Softlithografie übertragbar, in denen eine beständige, definierte Oberflächenfunktionalisierung ein wichtiges Kriterium darstellt.

High rolling contact fatigue parts are vital for the long service life of fuel pumps. Cummins Fuel Systems are currently using an M2 tool steel for one of the most important roller bearing application in their pumps, namely the cam follower. The future design of the cam follower is a pin-less tappet roller. The wear and fatigue properties of the roller is vital to ensure reliability of the fuel system. M2 tool steel is an expensive material and becomes even more so if diamond like coating (DLC) is needed to decrease the friction coefficients. To cut costs of the fuel pump it might be possible to replace the M2 tool steel with 52100 steel (100Cr6). Competitive methods have proven that carbonitrided 52100 can reach excellent wear and fatigue properties making it a candidate to replace M2 tool steel. How the properties of hardness, toughness and compressive residual stresses are developed in 52100 and how they affect the fatigue and wear resistance has been researched from the literature. A big part of this project was to do an extensive analysis of a roller bearing that was believed to have gone through one of these competitive methods that produce excellent wear and fatigue resistance. The analysis was done with background to the knowledge gathered from the literature. Finally process trials were set up to carbonitride 52100 steel samples. The trials were done to develop a better understanding of how adding carbon together with nitrogen to the surface of 52100 steel will influence the metallurgical parameters that results in good wear and fatigue resistance. From this analysis Cummins hope to create a process recipe that can be used for carbonitriding the cam follower and maybe other components in their fuel systems.

Dans les centrales solaires à concentration, le flux solaire est concentré sur des récepteurs pour chauffer un fluide de transfert jusqu’à 600°C. Dans le but d’améliorer leurs propriétés optiques, ces récepteurs peuvent être recouverts par des revêtements multicouches à sélectivité spectrale. Ces travaux portent sur le développement de structures optiquement sélectives innovantes, absorbantes dans le domaine du rayonnement visible et proche infrarouge (faible réflectivité) et peu émissives (forte réflectivité) pour le rayonnement infrarouge. Nous avons développé des empilements multicouches associant un métal réfractaire avec une céramique ce qui permet d’améliorer l’absorption dans le visible ainsi que la stabilité thermique. Les couches sont déposées par plasma combinant la PACVD et la PVD. L’étude de faisabilité du procédé transférable à l’industrie, son développement et son optimisation via la conception d’un réacteur innovant, le dépôt et la caractérisation des couches, leur association dans des empilements optiquement sélectifs performants et l’étude de leur vieillissement ont été réalisés. / In concentrated solar power (CSP) plants, solar flux is concentrated on receivers to heat a transfer fluid up to 600°C. In order to improve their optical properties, these receivers can be covered by multilayered spectrally selective coatings. This work is devoted to designing and developing innovative spectrally selective structures showing strong absorption (low reflectivity) in the visible and near infrared range and low emissivity (high reflectivity) in the infrared range. We developed such stacks associating a refractory metal with high IR reflectivity and a ceramic which improves absorption in the visible range and thermal stability. The coatings were synthesized by plasma techniques, combining PACVD and PVD. Pre-industrial process feasibility, its development and optimization through the design of an innovative reactor, layer deposition and characterization, their combination in efficient optically selective stacks and the study of their aging have been achieved.

Orientador: Maria Regina Wolf Maciel / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T04:13:19Z (GMT). No. of bitstreams: 1 Afonso_AdilsonPires_D.pdf: 2963967 bytes, checksum: 74c2f52074d8664fff323f72dc8f5730 (MD5) Previous issue date: 2005 / Resumo: O processo de separação de misturas homogêneas e não ideais é um problema comum nas indústrias. A separação de misturas complexas pode ser realizada a baixa pressão, para evitar a degradação de componentes sensíveis ou ainda, com a utilização de destilação com reação química para eliminar azeótropos e/ou aumentar a volatilidade relativa dos componentes a serem separados. A destilação reativa é uma técnica utilizada há muitos anos na indústria, porém, somente, recentemente, é que a modelagem matemática do problema permitiu que se desenvolvessem algorítmos para calcular e simular o processo de destilação onde ocorre simultaneamente o equilíbrio líquido-vapor- e o equilíbrio químico. Neste contexto, a destilação reat!va é uma das aplicações industriais mais efetivas para separar misturas complexas, uma vez que é baseada no conceito de reatores multifuncionais, isto é, na combinação de reações químicas com a destilação fracionada em um mesmo equipamento. Neste trabalho de tese, foram estudados os processos de destilação a baixas pressões para separar mono e diglicerídeos de glicerol, ácidos graxos e água, e o de destilação reativa para eliminar o fenol da mistura azeotrópica com água. Neste último, o reagente utilizado foi o anidrido acético com a formação de ácido acético e acetato de fenila. O esquema proposto demonstrou ser uma eficiente alternativa para a descontam inação de águas residuais. O simulador de processo HysysPlant@ foi utilizado para simular as destilações em estado estacionário e os resultados obtidos são inéditos na literatura publicada, contribuindo, portanto, com os desenvolvimentos na área de separação de misturas complexas. Para permitir a simulação da destilação reativa para separação do azeótropo água- fenol com anidrido acéticoé necessário se ter a cinética da reação. Como não existem na literatura dados experimentais deste sistema, neste trabalho foram apresentados alguns métodos para permitir a estimativa da cinética. Além disso, uma análise das misturas azeotrópicas formadas foi também realizada, para permitir a caracterização termodinâmica do sistema e, com isto, propor a separação física dos vários componentes. Este trabalho foi desenvolvido no I:aboratório de Desenvolvimento de Processos de Separação /DPQ/FEQ/UNICAMP / Abstract: The separation process of homogeneous and non ideal mixtures is a common problem in chemical industries. The complex mixture separations may happen at low pressure to prevent thermal degradation or using reactive distillation to eliminate existing azeotropes and/or in order to increase the rei ative volatility of the components to be separated. Reactive distillation has been used in industrial applications for many years ago, but only recently, with the availability of mathematical models, it is possible to develop algorithms in order to calculate and to simulate the distillation process where the vapor-liquid and the chemical equilibria occur simultaneously. So, in this way, reactive distillation is one. of the most effective industrial applications in order to separate complex mixtures, since it is based on the concept of multifunction reactors or, in other words, on the combination of chemical reactors with fractionating distillation in a single equipment. In this work, two important processes were studied. The first one was the separation of mono and diglycerides from glycerol, fatty acids and water using low pressure distillation. The second one was the proposition of a new reaction scheme to carry out the separation of the diluted system composed by phenol and water, using acetic anhydride as reactant forming acetic acid and phenyl acetate as product. The scheme seems to be a simple and efficient alternative to the decontamination of wastewaters. It was necessary, also, to develop methodologies to calculate the reaction kinetic and characterization of the mixtures being studied in the second case. Computational steady state simulations were performed using Hysys.Plant@ commercial simulator. The results obtained are inedit in the published literature, contributing, so, with the developments in co.mplex mixture separations. This work was developed in the Separation Process Development Laboratory, at the School of Chemical Engineering, at UNICAMP / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

Orientador: M. Angela de A. Meireles / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-12T23:30:07Z (GMT). No. of bitstreams: 1 Veggi_PriscillaCarvalho_M.pdf: 1761382 bytes, checksum: 637112e200f071539191361e637c14ed (MD5) Previous issue date: 2009 / Resumo: Neste trabalho é apresentado um estudo comparativo do custo de manufatura para diferentes técnicas de extração: extração com solventes a baixa pressão (LPSE: Low Pressure Solvent Extraction) em taque agitado e percolação, e extração supercrítica (SFE: Supercritical Fluid Extraction). As estimativas dos custos para os processos de extração LPSE por agitação e percolação foram realizadas por meio do simulador de processos SuperPro DesignerÒ. Foi realizado um estudo experimental para a obtenção, por extração supercrítica, de polifenóis de folhas de pitanga (Eugenia uniflora). Para o estudo do aumento de escala, assumiu-se que os parâmetros em escala laboratorial: rendimento da extração, tempo e a relação entre a massa de alimentação e solvente, são mantidos constantes para o equipamento em escala industrial. Assim, as estimativas foram realizadas tendo como base dados de literatura para a matriz vegetal macela (Achyrocline satureioides). Os estudos foram realizados para extratores de 50 L, 100 L e 300 L. Os custos de manufatura para LPSE em taque agitado e percolação foram: US$ 877,21/kg; US$ 698,73/kg; US$ 573,34/kg e US$ 814,46/kg; US$ 567,86/kg; US$ 384,00/kg, respectivamente em extratores de 50 L, 100 L e 300 L. Notou-se a influência dos parâmetros tempo e rendimento no custo dos extratos. Posteriormente, um estudo do custo do extrato através do processo SFE para mesma matriz vegetal foi realizado. Porém, para SFE o custo do extrato foi estimado através do parâmetro tCER, tempo em que aproximadamente 70 % do leito de extração é esgotado, sendo esta uma boa estimativa para o menor tempo de ciclo. O custo de manufatura do extrato obtido por SFE foi US$ 585,49/kg. Uma avaliação comparativa entre os três processos foi realizada e, dentre os principais custos obtidos: de investimento inicial, matéria-prima e utilidades, notou-se que o custo de investimento não é predominante na formação do custo de manufatura. O custo de matéria-prima para alguns dos tamanhos de extratores representou o fator preponderante. Posteriormente à esta etapa, foi realizado o estudo da cinética do processo de extração supercrítica para obtenção do extrato de folhas da pitanga (Eugenia uniflora) a partir de dados otimizados da literatura; este estudo foi realizado em coluna de extração de 300 mL. Utilizou-se temperatura e pressão de 333,15 K e 60 MPa sob diferentes condições de vazão a fim de estudar o comportamento cinético da extração em relação ao rendimento e à presença de compostos voláteis. Ainda foram realizadas análises para identificação dos compostos por cromatografia em camada delgada (CCD) e cromatografia gasosa acoplada à espectrometria de massas (CG-EM). O estudo do aumento de escala foi realizado usando-se uma unidade piloto equipada com dois extratores de 5 L contendo 3 separadores (S1, S2 e S3); como referência foi empregado o ensaio cinético realizado para folhas de pitanga na coluna de 300 mL. Seguindo o critério de aumento de escala em que se mantém constante a proporção entre a massa de solvente e a massa de matéria-prima, o aumento de escala foi de 17 vezes. Para os experimentos foram selecionadas as seguintes condições de operação para os três separadores S1, S2 e S3: 10 MPa/333,15 K; 7 MPa/303,15 K e 3 MPa /313,15 K, respectivamente. Quatro pontos selecionados da cinética de extração em coluna de 300 Ml foram então reproduzidos. O custo do extrato foi estimado utilizando o simulador SuperPro DesignerÒ obtendo-se um custo do manufatura de US$ 449,89/kg / Abstract: In this work a comparative study of the cost of manufacturing (COM) for different extraction techniques is presented: low pressure solvent extraction (LPSE) in agitation and percolation, and supercritical fluid extraction (SFE). The COM estimation was carried using the processes simulator SuperPro Designer®; agitation and percolation LPSE processes were developed in the simulator. An experimental study to obtain poliphenols by supercritical fluid extraction from leaves of pitanga (Eugenia uniflora) was also performed. For the scale-up study it was assumed that the parameters for the laboratorial scale SFE unit: yield of extraction, time and ratio between the feed mass and solvent mass are kept constant for the equipment in industrial scale. The estimations were carried using literature information for the vegetable matrix macela (Achyrocline satureioides). The studies were done for extraction vessels of 50 L, 100 L and 300 L. The COM for LPSE agitation and percolation processes were: US$ 877.21/kg; US$ 698.73/kg; US$ 573.34/kg and US$ 814.46/kg; US$ 567.86/kg; US$ 384.00/kg, respectively for extractors of 50 L, 100 L and 300 L. It was observed the influence of time and yield parameters on the COM. Later, a study of SFE process COM for the same vegetable matrix was done. For SFE the COM was estimated using the tCER parameter as cycle time, where approximately 70% of extraction bed is exhausted, being this a good estimation. The COM of extract obtained by SFE was US$ 585.49/kg. A comparative evaluation between the tree processes was carried out, and among the major costs factors: investment, raw material and utilities, it was observed that the investment cost is not predominant in the COM of the extracts. The raw material cost certain vessel sizes represented the major cost factor. After this step, a study of the SFE kinetics for leaves of pitanga (Eugenia uniflora) was carried out. The operating conditions were selected from optimized data from literature; this study was done in a 300 mL column vessel. It was utilized temperatures and pressure of 333.15 K and 60 MPa under different flow rates in order to study the kinetic behavior of the overall extraction curve and the presence of volatile compounds. Thin layer chromatography (TLC) and gas chromatography-mass spectrometry (GC-MS) analyses were used for identification of the compounds present in the extract. The scale-up study was carried out using a pilot unit equipped with two extractor of 5L vessel containing 3 separators vessels (S1, S2 and S3); as reference the kinetic assay for pitanga leaves in 300 mL column vessel was used. According to the scaleup criterion that the ratio between solvent mass and raw material mass is kept constant, the scale-up was of 17 times. For the experiment the following operation condition for the three separators S1, S2 and S3 were selected: 10 MPa/333.15 K; 7 MPa/303.15 K and 3 MPa /313.15 K, respectively. Four points selected from kinetic experiment in 300 mL column vessel were reproduced. The extract COM was estimated using simulator SuperPro DesignerÒ (US$ 449,89/kg) / Mestrado / Mestre em Engenharia de Alimentos

Les composés soufrés sont répandus dans divers secteurs industriels comme la chimie. La conception et/ou l'optimisation des procédés impliquant ces composés nécessite de connaître leurs propriétés thermodynamiques (corps purs et mélanges). Etant donnée la complexité des mélanges et pour des raisons économiques, des modèles thermodynamiques « prédictifs » sont souvent privilégiés. Le développement et la validation de ces modèles nécessitent des données expérimentales. Notre étude bibliographique ciblant les sulfures (R-S-R'), les 1-mercaptans (R-SH) et leurs éventuels solvants (les n-alcanes et les 1-alcools) nous a permis de mettre en évidence un manque de données concernant ces composés. De plus nous avons également observé un manque de techniques expérimentales adaptés, et de ce fait le besoin de développer un nouveau dispositif expérimental.Au cours de cette thèse, nous avons conçu un dispositif expérimental innovant permettant la mesure des équilibres liquide-vapeur à des pressions comprises entre 0,1 et 10 bar. Ce dispositif est basé sur la méthode « statique-analytique ». Nous avons mis en place deux adaptations spécifiques aux échantillonneurs capillaires ROLSITM pour permettre l'échantillonnage à ces pressions. De nouvelles données des mélanges binaires et ternaires d'intérêt ont été ainsi mesurées.Le modèle thermodynamique prédictif choisi est PC-SAFT couplé avec une méthode de Contribution de Groupes (GC-PC-SAFT). Un terme polaire a été introduit. Le travail s'est focalisé sur l'étude de deux familles représentatives de composés soufrés : les sulfures et les 1-mercaptans. Le modèle GC-PC-SAFT a montré sa capacité de bien corréler et prédire les propriétés thermodynamiques des corps purs. L'ajustement des paramètres s'est appuyé sur les données de la littérature et celles obtenues par le nouvel équipement. Les diagrammes de phases des mélanges binaires (sulfure + n-alcane, sulfure + 1-alcool, 1-mercaptan + n-alcane et 1-mercaptan + 1-alcool) et ternaires (1-mercaptan + n-alcane + 1-alcool) ont été prédits. / Sulfur compounds are widespread in various industrial fields. Design and/or optimization of the processes involving these compounds require accurate knowledge of thermodynamic properties of the concerned mixtures. Considering the complexity of industrial mixtures and for economical reasons, one may look to thermodynamic models with predictive features. To develop and validate these models, a minimum number of experimental data are required. Our literature review on sulfides (R-S-R'), 1-thiols (R-SH) and their possible solvents (n-alkanes and 1-alkanols) has shown a lack of data and of adapted experimental method. This observation leads to the need of developing a new experimental apparatus.In this work, we designed an innovative experimental apparatus for vapor-liquid-equilibrium measurements in the pressure range of [0.1 – 10] bar. The new apparatus is based on the “static-analytic” method. The key improvements are the two adaptations made for ROLSITM capillary samplers to achieve phase sampling in this pressure range. After validating the newly developed apparatus, new data of binary and ternary mixtures of interest were measured in order to develop a new predictive thermodynamic model focusing on sulfur compounds.The proposed predictive model is the PC-SAFT equation of state combined with a group contribution method (GC-PC-SAFT). We incorporated a polar term into PC-SAFT and investigated two representative families of sulfur compounds: sulfides and 1-thiols. The GC-PC-SAFT model proved reliable in correlating and predicting thermodynamic properties of pure compounds. Model parameters were fitted to the data found in the literature, as well as to those obtained through the new apparatus. Phase diagrams of some binary (sulfide + n-alkane, sulfide + 1-alkanol, 1-thiol + n-alkane and 1-thiol + 1-alkanol) and ternary (1-mercaptan + n-alkane + 1-alcool) mixtures were predicted.

Le tantale est un métal très dense (d = 16,6) et fond à très haute température (2996°C), ce qui en fait un matériau potentiellement utilisable pour des creusets utilisés en pyrochimie. La littérature montre qu'il est possible de renforcer encore ces propriétés anti-corrosion par un traitement de cémentation. En effet, la corrosion intergranulaire du tantale est stoppée par la présence de précipités de Ta2C aux joints de grains. L'obtention du Ta saturé carbone avec Ta2C aux joints de grains en surface (Ta(C) + Ta2C), très pauvre en carbone, demande une bonne compréhension et une maitrise de la cémentation du tantale.La réalisation d'un cycle de cémentation sur des échantillons de tantale provoque l'apparition à la surface du tantale d'une couche de TaC (en surface) et d'une couche de Ta2C sous jacente. Un travail sur la réduction du flux de carbone à la surface du tantale a permis d'étudier les premiers stades de formation des couches de carbures de tantale. Ces conditions particulières de cémentation favorisent la croissance en épitaxie des couches de carbures sur le substrat Ta. Les analyses EBSD ont permis de mettre en évidence les relations cristallographiques entre chaque phase.Lors d'un cycle de cémentation, la croissance des couches de carbures doit être contrôlée du fait que celles-ci soient très riches en carbone. Plusieurs types de paramètres peuvent influer sur la croissance des couches : les paramètres de cycles (temps et température de cémentation) et des paramètres extérieurs aux cycles de cémentation, tels que la surface des échantillons. L'influence de ces paramètres sur la cinétique de croissance des couches a été étudiée. En complément des essais, la simulation numérique avec le logiciel CASTEM© a été utilisée afin d'étudier la diffusion du carbone dans le tantale. Les données expérimentales permettent d’ajuster les variables du modèle comme le coefficient de diffusion du carbone dans le tantale.La réalisation d'un recuit sous vide après cémentation permet d'obtenir en surface des microstructures autres que le TaC. Le recuit fait diffuser le carbone contenu en surface vers le coeur du tantale. Une étude a permis de déterminer les paramètres du traitement de recuit, pour obtenir en surface, au choix : du TaC, ou du Ta2C, ou du Ta(C) + Ta2C. / Tantalum is a very dense metal (d = 16.6) and has a very high melting temperature of 2996°C. This material is particularly required for crucibles used for pyrochemical applications. Early studies show that a carburizing treatment enhances corrosion resistance from liquid metals. Indeed, the intergranular attack of tantalum is stopped by Ta2C precipitates, which occupy the grain boundary regions. The production of the carbon saturated tantalum with Ta2C precipitates requires a good understanding of tantalum carburizing.A carburizing treatment on tantalum sample causes the emergence of a TaC layer on surface and Ta2C layer just below. A reduction of carbon flow has enabled the study of the first steps of tantalum carbides formation. This specific condition of carburizing leads to an epitaxic growth of carbide layers on tantalum substrate. EBSD analysis highlights the crystallographic relations between each phase.Tantalum carbide layers are highly carbon concentrated. So the growth of carbide layers has to be controlled during the carburizing treatment. Several parameters may affect carbide layers growth : process parameters (time and temperature of carburizing treatment) and external parameters such as the reactive surface of the samples. The influence of these parameters on tantalum carbide growth kinetics has been studied. In addition, the diffusion of carbon in tantalum has been modeled with CASTEM© software. Experimental data are used to compute parameters of the model, such as carbon diffusion coefficient in tantalum.Other microstructures than TaC can be obtained on surface by applying an annealing treatment after carburizing. With this treatment, the carbon contained on surface diffuses to the bulk of the metal. Annealing treatment parameters have been determined to get on surface TaC, or Ta2C, or carbon saturated tantalum with Ta2C precipitates.

The objective of this study is to successfully deposit Titanium Ti-6Al-4V layers onto Ti-6Al-4V substrate using two new commercially available Cold Spray processes such as Low Pressure Cold Spray (LPCS) and Pulsed Gas Dynamic Spray (PGDS). The second objective of this work is to develop a technique to repair Titanium parts since there is currently no repair technique commercially available. It is envisioned that commercial cold spray systems could be used to repair gashes on Titanium components. The examination of both feedstock powders and coatings were performed by different techniques such as optical microscopy and Scanning Electron Microscopy (SEM). Porosity, hardness, adhesion strength, flattening ratio, wipe test, fracture surface, wear test, XRD and chemical composition of the coatings using EDS have been evaluated. Cold spray has shown to be a promising technique for the deposition of heat sensitive particles such as titanium. LPCS and PGDS both produced high quality coatings. Low porosity, high hardness, adhesion strength over 40 MPa, metallurgical bonding, similar to bulk material wear rate, no oxide and nitride phases inside coating were measured.

Le domaine de la physique des plasmas froids a émergé avec les premières découvertes fondamentales en physique atomique et en physique des plasmas il y a plus d’un siècle. Toutefois, ce domaine a été rapidement orienté vers les applications. L’une des plus importantes dans la première moitié du XXème est le "Calutron" (California University Cyclotron), inventé par E. Lawrence à Berkeley, qui faisait partie du projet Manhattan, et utilisé comme un spectromètre de masse pour séparer les isotopes de l’uranium. Dans un rapport du projet Manhattan daté de 1949, D. Bohm fait deux observations qui sont fondamentales pour la physique des plasmas froids :(i) Les ions doivent avoir une énergie cinétique minimales lorsqu’ils entrent dans la gaine du plasma, estimée à Te/2, Te étant la température électronique.(ii) Le transport du plasma à travers un champ magnétique est augmenté par des instabilités.La propulsion électrique par plasma est utilisée pour des satellites militaires et des sondes spatiales depuis les années 1960 et a suscité un intérêt grandissant ces vingt dernières années avec le développement des applications commerciales des technologies spatiales. Néanmoins, les mêmes questions que celles auxquelles D. Bohm était confronté, c’est-à-dire le transport multidimensionnel, l’interaction plasma-gaine, et les instabilités, se posent toujours. La théorie et les simulations sont d’autant plus importantes pour la conception des systèmes de propulsion électrique que les tests en conditions réelles nécessitent le lancement d’un satellite dans l’espace.Dans ce travail, nous établissons les équations du transport multidimensionnel dans un plasma isotherme, nous proposons un critère de gaine qui permet de rendre compte de la saturation du champ magnétique dans un plasma froid et faiblement ionisé, et nous modélisons le refroidissement des électrons à travers le filtre magnétique du propulseur PEGASES (Plasma Propulsion with Electronegative Gases). Toutes les théories sont motivées et validées par un grand nombre de simulations particulaires PIC bi-dimensionnelles, en utilisant le code LPPic qui a été partiellement développé dans le cadre du projet. Enfin, les cas de simulation sont étendus à une décharge inductive à plasma dans l’iode, avec un nouvel ensemble de section efficaces de réaction. / The field of low temperature plasma physics has emerged from the first fundamental discoveries in atom and plasma physics more than a century ago. However, it has soon become very much driven by applications. One of the most important of them in the first half of the XXth century is the "Calutron" (California University Cyclotron) invented by E.~Lawrence in Berkeley, that was part of the Manhattan project, and operated as a mass spectrometer to separate uranium isotopes. In a 1949 report of the Manhattan project, D.~Bohm makes two observations that are fundamental for low-temperature plasma physics.(i) The ions must have minimum kinetic energy when they enter the plasma sheath estimated to T_e/2 , Te being the electron temperature in eV ;(ii) Plasma transport across a magnetic field is enhanced by instabilities.Plasma electric propulsion is used on military satellites and space probes since the 1960s and has gained more and more interest for the last twenty years as space commercial applications were developing. However, the same questions as the ones D.~Bohm was faced with, namely multi-dimensional transport, plasma sheath interaction, and instabilities, arise. Theory and simulation are even more important for electric space propulsion systems design since testing in real conditions involves to launch a satellite into space.In this work, we derive the equations of the multi-dimensional isothermal plasma transport, we establish a sheath criterion that causes the magnetic confinement to saturate in low-temperature, weakly ionized plasmas, and we model the electron cooling through the magnetic filter of the PEGASES (Plasma Propulsion with Electronegative Gases) thruster. All the theories are driven and validated with extensive two-dimensional particle-in-cell (PIC) simulations, using the LPPic code that was partially developed in the frame of this project. Finally, the simulation cases are extended to an iodine inductively coupled plasma (ICP) discharge with a new set of reaction cross sections.

This diploma thesis builds on my bachelor thesis, which was focused on the application of low-pressure hydrogen plasma and argon-hydrogen plasma on layers of corrosion products. According to results of the experiments, an appropriate temperature for plasma chemical treatment of lead samples was detected. However, the process of corrosion removal through plasma chemical treatment needs to be further optimized to prevent potential damage to the original historical artefacts. Optimization of the treatment process is therefore the main subject of this work’s research. The model samples with artificial corrosion layers with dual composition were prepared. These samples were put to desiccator with sand and organic acid. The samples corroded in environment of acetic acid or formic acid with the aim of creating the corrosion, which would be at least partially simulated with corrosion on the original artefacts. The process of corrosion lasted for eleven months. After that, the samples were dried out under reduced pressure, put to the protecting foil with humid and oxygen absorbers. In contrast with my bachelor thesis where the continuous regime was chosen for the treatment, the pulse regime with three different condition settings is used. Process of experiment was monitored by OES, surface of samples was analyzed by SEM, EDX, XRD methods. Results from experiments with model samples were used for treatment of original artefacts with missing documentation, so their eventual damaging was acceptable.