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This thesis deals with preparation of organic molecular thin film compounds and its properties like morphology and purity. The vapour deposition was used for thin films preparation, because used materials are very few soluble. Thin films properties were characterized with the infrared spectroscopy (FTIR) and scanning electron microscope. There are described basics of infrared spectroscopy, spectra measurement and interpretation in the theoretical part. Process of thin film preparation is also described in this part. In the experimental part are described used vacuum technology and measuring instruments, process of sample measurement and there is the list of studied materials. 12 derivates of diketopyrrolopyrrols (DPP) were studied in this thesis. Diketopyrrolopyrroles (DPP) and its derivates have interesting chemical and physical properties, expecting wide range of applications, especially in electronics industry.

This thesis is focused on experimental work in the domain of vacuum evaporation efficiency improvement. The first part introduces theory of liquids evaporation and its influencing factors, then multi-stage flash distillation technology. The next part of theory is an overview of other technologies used for desalination of sea water and introduction to the design of experiments. In the practical part are selected factors affecting efficiency of device and experiment plan is designed for them. When the experiment is done, optimal operating conditions of technology are designed on basis of analysis.

Les poudres laitières sont obtenues par concentration du produit liquide (membranes, évaporation sous vide) puis séchage du concentré. Contrairement au séchage par atomisation, peu de travaux ont été menés sur la concentration par évaporation sous vide. Pourtant, la maîtrise du schéma global de production des poudres gagnerait en une meilleure compréhension de cette opération réalisée dans des évaporateurs à flot tombant. Le présent travail vise à étudier comment améliorer les performances des évaporateurs ; il s’appuie sur deux facteurs limitants de l’opération : l’encrassement des surfaces d’échange et la viscosité maximale en sortie des évaporateurs. La contribution des différents constituants des produits à l’encrassement a été étudiée grâce à une méthodologie développée sur un évaporateur pilote.Les résultats obtenus ont permis d’identifier les éléments minéraux qui contribuent à l’encrassement lors de la concentration de microfiltrat et d’ultrafiltrat de lait, de lactosérums acides chlorhydrique et lactique. Afin de dépasser l’extrait sec maximal en sortie des évaporateurs à flot tombant, deux évaporateurs rotatifs à couche mince, de conceptions différentes, ont été testés à l’échelle pilote. Les études de faisabilité ont été menées jusqu’à la poudre. Le potentiel des équipements a été évalué suivant les propriétés fonctionnelles des poudres et le coût énergétique d’élimination de l’eau. Dans l’un des cas, le remplacement de la tour de séchage par deux évaporateurs rotatifs en série constitue une rupture technologique pour la production de poudres de perméat et dimi / Dairy powders are produced using a two-step process: concentration of the liquid product (membrane, concentration by vacuum evaporation) and drying of the concentrate. Contrary to spray-drying, vacuum concentration has been poorly investigated. However, a better understanding of this unit operation carried out in falling-film evaporators would lead to an improved control of the global process scheme for the production of powders. This PhD project aims to highlight how to enhance the performances of falling-film evaporators; it focuses on two limiting factors of the vacuum concentration: the fouling of the heating surfaces and the maximal viscosity at the outlet of the falling-film evaporators. The contribution of the different product components to the fouling was investigated using a methodology developed at pilot-scale.Our results showed which mineral elements favored the fouling of falling-film evaporators during the concentration of milk microlfiltrate and ultrafiltrate as well as hydrochloric and lactic acid wheys. Besides, two thin-film rotative evaporators of different designs were tested at pilot-scale in order to exceed the maximum dry matter achieved in falling-film evaporators. The feasibility studies were conducted up to the production of powders. The capabilities of the equipment were evaluated according to the functional properties of powders and the specific energy costs relative to the removal of water. In one case, the combination of two rotative evaporators replacing the spray drier constitutes a technological breakthrough in the production of permeate p

Ultra-high strength steels is known to be susceptible for hydrogen embrittlement at very low concentrations of hydrogen. In this thesis three methods to prevent or reduce the hydrogen embrittlement in martensitic steel, with tensile strength of 1500 MPa, were studied. First, a barrier layer of aluminium designed to prevent hydrogen to enter the steel, which were deposited by vacuum evaporation. Second, a decarburization process of the steels surface designed to mitigate the induced stresses from cutting. Last, a hydrogen relief treatment at 150°C for 11 days and 200°C for 4 days, to reduce the hydrogen concentration in the steel. The effect of the hydrogen embrittlement was analyzed by manual measurements of the elongations after a slow strain rate testing at 5*10-6 mm/s, and the time to fracture in an in-situ constant load test with a current density of 1.92 mA/cm2 in a 0.5 M Na2SO4 solution. The barrier layer showed an increase in time to fracture, but also a decrease in elongations. The decarburized steel had a small increase in the time to fracture, but not enough to make it a feasible process. The hydrogen relief treatment showed a general decrease in hydrogen concentrations, but the elongation measurements was irregular although with a tendency for improvement. The simplicity of the hydrogen relief treatment makes it an interesting process to reduce the influence of hydrogen embrittlement. However, more investigations are necessary.

Les transistors organiques à effet de champ (OFETs) ont aujourd’hui des performances qui permettent d’envisager la réalisation de circuits électroniques plus ou moins complexes. Cependant, ces dispositifs doivent encore être améliorés en termes de performance et de stabilité sous air avant d’être commercialisés. Le premier objectif de cette thèse est de réaliser des OFETs stables à l’air avec des performances atteignant l’état de l’art, tout en simplifiant leur procédé de fabrication. Le dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT),petite molécule référence, a été choisie comme couche active des dispositifs pour chaque étude. En insérant une couche interfaciale d’oxyde entre le matériau de contact et le SCO de nos OFETs, une étude a été menée sur la réduction de la résistance de contact, qui affecte la mobilité effective des porteurs de charge mais peut également compliquer l’élaboration de circuits. Dans le but de réaliser des OFETs sur substrats flexibles opérant à de faibles tensions,un travail a été réalisé sur le dépôt d’un diélectrique à forte capacité dont la surface a ensuite été passivée et lissée par un polymère. Les transistors de type p obtenus présentent des performances hautes en termes de mobilité (2,4 cm2.V-1.s-1) et de ratio des courant On/Off (>106) avec une faible tension de seuil et aucune hystérésis. Le second objectif a été de réaliser des simulations sur ces OFETs optimisés avec le logiciel GoldenGate dans l’environnement Cadence Virtuoso®, pour obtenir les paramètres nécessaires à l’élaboration d’un circuit amplificateur. Enfin, des composants passifs (résistances) ont été développés et un circuit détecteur d’amplitude sur substrat flexible a été élaboré et testé. / Organic field effect transistors (OFETs) have huge potential in the applications of future electronics, such as flexible circuits and displays or medical application. However, stability and performances of OFETs need to be improved, so as to reach the real market applications.First objective of this work is to realize air stable OFETs with state of the art performance. To that end, several approaches have been applied with special focus on process simplification. Small molecule, dinaphtho[2,3-b:2',3‘-f]thieno[3,2-b]thiophene (DNTT) has been chosen as the active layer for all devices studies. Metal electrodes in combination with oxide interfacial layers were investigated to decrease the contact resistance, which not only affects eventual mobility that can be achieved but also complicates circuit design. A systematic study was carried out to fabricate high capacitance dielectric layer and passivating the surface with proper interfacial layers. These approaches allowed to obtain high performance OFET on plastic substrate with high mobility (2.4cm2.V-1.s-1), high current on/off ratio (> 106), low threshold voltage and no hysteresis As the second objective, OFET devices were simulated using GoldenGate (with Cadence Virtuoso® environment) to derive relevant parameters, which helped to design amplifier circuit. Finally, passive component (resistance) has been developed and final circuit was realized and characterized.

Les évaporateurs à flot tombant (EFT) sont largement utilisés dans les industries chimiques, de la réfrigération, du raffinage du pétrole, et alimentaires. Dans l'industrie laitière, les EFT sont appliqués pour la concentration de solutions avant l'étape de séchage. Malgré l'importance économique du procédé d'évaporation sous vide dans la fabrication de produits laitiers déshydratés, la connaissance du procédé est essentiellement empirique. Des recherches visant à améliorer l'efficacité du procédé sont donc nécessaires. L'objectif de ce projet de doctorat est de caractériser expérimentalement un EFT lors de la concentration de produits laitiers, par des approches thermo et hydro-dynamiques, afin d'étudier les interactions entre les propriétés des produits et les paramètres opérationnels. Un évaporateur à flot tombant, simple effet, à l’échelle pilote, qui décrit le même processus que celui à l'échelle industrielle, d'un point de vue hydrodynamique, a été instrumenté et utilisé pour établir les bilans massiques et énergétiques. La capacité évaporatoire et le coefficient global de transfert de chaleur ont été calculés à partir des données expérimentales. Une méthodologie pour la détermination expérimentale des fonctions distribution des temps de séjour (DTS) a été développée. En effet, les fonctions de DTS fournissent des informations essentielles sur l'écoulement des produits lors de la concentration dans un EFT. L'augmentation de la concentration, du débit massique et de la distance parcourue par le produit entraîne une augmentation de la dispersion des particules dans le flux. Ces fonctions ont été modélisées par une combinaison de réacteurs en cascade, parfaitement agités. D’après l'interprétation de ce modèle, deux flux, un principal et un secondaire, correspondant à deux couches superposées de produit circulant à travers des tubes d'évaporateur, a été proposé. La méthodologie développée pour le calcul des fonctions de DTS a été appliqué pour la concentration de produits laitiers (lait écrémé, lactosérum doux et acide). Par la suite, l'étude a été étendue à la formation de l'encrassement pendant la concentration par évaporation sous vide. Il a été montré que le temps de séjour moyen était plus sensible pour identifier l'encrassement que le coefficient global de transfert de chaleur et la capacité évaporatoire. Ainsi, cette étude a souligné le rôle crucial de l’importance de la caractérisation des EFT sous vide afin d’en améliorer leurs performances et la qualité des produits qui en sont issu. / Falling film evaporators (FFE) are widely used in the chemical, refrigeration, petroleum refining, desalination and food industries. In the dairy industry FFE is applied for the concentration of solutions prior to the drying step. Despite the economic importance of the vacuum evaporation process in the manufacture of dairy dried products, the knowledge about the process is mostly empirical. Research aiming to improve the efficiency of the process is therefore necessary. The objective of this PhD project was to characterize experimentally a FFE during the concentration of dairy products by means of thermodynamic and hydrodynamic approaches, in order to study the interactions between the products properties and the operating parameters. A pilot-scale, single-stage falling film evaporator that describes the same process as that of an industrial scale from a hydrodynamic point of view was instrumented and used to establish the mass and energy balances. The evaporation rate and the overall heat transfer coefficient were calculated from the experimental data to follow up the process. A methodology for the determination of the experimental residence time distribution (RTD) functions was developed. RTD functions provide global information about the flow of the products during concentration in a FFE. Increasing of the concentration of skim milk, mass flow rate and the distance covered by the product resulted in an increase in the dispersion of the products particles. The experimental RTD functions were modelled by a combination of two perfectly mixed reactor tanks in series. From the interpretation of this model, two different flows, a main and a minor flow, were identified. The RTD methodology developed on skim milk was applied to sweet whey and lactic acid whey and the study was extended to the formation of fouling during a 5-hour concentration. The mean residence time was more sensitive to identify fouling than the overall heat transfer coefficient and the evaporation rate. This study emphasized the crucial role of process characterization to improve the performance of FFE and product quality.

Made available in DSpace on 2016-06-02T19:55:41Z (GMT). No. of bitstreams: 1 6385.pdf: 11264050 bytes, checksum: cd77b4a424829bd8ae1b48ccd53f5616 (MD5) Previous issue date: 2014-10-08 / Introduced during the colonial period in Brazil, nowadays sugar cane is one of the main crops of the country's economy, generating more than 2 billion dollars per year in the Brazilian trade balance. Despite the benefits of expanding the sugarcane sector every year, the environmental impacts caused by burning straw cane sugar made the State of São Paulo Government create the Protocol of Agro-Environmental Cooperation in 2007, which aims the total elimination of cane burning by 2017. However, when the sugar cane stops being burned, some components of the plant, which remained in the field due to the burning, will start being in larger quantities in the process, and the effects of this future reality in sugar quality have not been studied In this doctoral thesis, the two components of great impact on the specifications or quality of the sugar were chosen: starch and dextran which were studied in the crystallization unit operation (by controlled cooling and vacuum evaporation), so that the impact on the final product (sugar) were evaluated. This current study used a reponse surface methodology, with 2 levels (309 and 1062 ppm), two factors (dextran and starch), 3 center points (one central point in triplicate) and 4 axial points, totaling 11 trials per type of crystallization. The experiments were conducted with sugar Type 2 solutions contaminated with starch and dextran, in an agitated and jacketed crystallizer (8 liters) in the laboratory. When the crystallization was performed, the matters were centrifuged, the sugars were separated from the honeys, and forwarded to the physico-chemical, textural and optical microscopy analyzes. In relation to the physicochemical analyzes of sugar, starch and dextran contamination interfered directly in the responses: starch, dextran, color, turbidity and alcoholic floc in both crystallization techniques, however, the controlled cooling under the same conditions of contamination (0-2000 ppm), presented sugars to lower rates, which kept the product according to the market specifications. The results of grain size analysis showed frequency curves with accumulation of smaller crystals at the opening of 0.5 mm, according to the increase of dextran in the tests. And the optical microscopy analysis identified the existence of a relationship between the amount of contaminants, and the appearance of agglomerated crystals, besides "needle-like" crystals were not observed. The experimental chosen design collaborated in the identification of starch and dextran agents, in the increase or decrease of the analyzed responses, besides suggesting the collaboration of the combined effect on the quality of sugar. Concerning the product quality, the use of crystallization technique by controlled cooling proved to be the most suitable in the reduction of contaminants in the sugar, particularly in solutions containing 2,000 ppm of dextran and starch. Given the crop of sugarcane in the coming years, and that the contamination of dextran and starch may be higher than those found in syrups of industrial processes currently, this work may contribute to the knowledge of the contaminants and their combined actions in the crystallization and in understanding of the differences in the product quality. / Introduzida no período colonial no Brasil, a cana-de-açúcar é hoje uma das principais culturas da economia do país, gerando mais de 2 bilhões de dólares por ano na balança comercial brasileira. Apesar dos benefícios da expansão do setor sucroalcooleiro a cada ano, os impactos ambientais causados pelas queimadas da palha de cana-de-açúcar, levaram o Governo Estadual Paulista a criar em 2007, o Protocolo de Cooperação Agroambiental, que visa a eliminação total da queima de cana até 2017. No entanto, quando a cana-de-açúcar deixar de ser queimada, alguns componentes da planta que ficavam no campo com a queima passarão a entrar no processo em maiores quantidades, e os efeitos dessa futura realidade na qualidade do açúcar ainda não foram estudados. Nesse trabalho de doutorado, foram escolhidos dois componentes de grande impacto nas especificações ou qualidade do açúcar: o amido e a dextrana, os quais foram estudados na operação unitária de cristalização (por resfriamento controlado e por evaporação a vácuo), para que o impacto no produto final (açúcar) fosse avaliado. O presente trabalho utilizou um delineamento composto rotacional, com 2 níveis (309 e 1062 ppm), dois fatores (dextrana e amido), 3 pontos centrais (1 ponto central em triplicata) e 4 axiais, totalizando 11 experimentos por tipo de cristalização. Os experimentos foram realizados com soluções de açúcar Tipo 2, contaminadas com amido e dextrana, em um cristalizador agitado e encamisado (8 litros), em laboratório. Realizadas as cristalizações, as massas foram centrifugadas, e os açúcares separados dos méis, e encaminhados para as análises físico-químicas, granulométricas e de microscopia óptica. Em relação às análises físico-químicas do açúcar, as contaminações de dextrana e amido interferiram diretamente nas respostas: amido, dextrana, cor, floco alcoólico e turbidez, nas duas técnicas de cristalização, no entanto, o resfriamento controlado, nas mesmas condições de contaminação (0 a 2000 ppm), apresentou açúcares com os menores índices, o que manteve o produto nas especificações do mercado. Os resultados das análises granulométricas demonstraram curvas de frequência com acúmulo de cristais menores na abertura de 0,5 mm, conforme o aumento de dextrana nos testes. E as análises de microscopia óptica identificaram a existência de uma relação entre a quantidade de contaminantes, e o aparecimento dos cristais aglomerados, além de não serem observados cristais tipo agulha . O planejamento experimental adotado colaborou na identificação dos agentes amido e dextrana, no aumento ou na diminuição das respostas analisadas, além de sugerir a colaboração do efeito combinado desses na qualidade do açúcar. Em termos de qualidade do produto, a aplicação da técnica de cristalização por resfriamento controlado mostrou-se mais indicada na redução dos contaminantes no açúcar, principalmente em soluções com 2000 ppm de dextrana e amido. Tendo em vista a colheita de cana crua nos próximos anos, e que as contaminações de dextrana e amido poderão ser superiores as encontradas nos xaropes dos processos industriais hoje, o presente trabalho pode contribuir no conhecimento dos contaminantes e de suas ações combinadas na cristalização, e no entendimento das diferenças na qualidade do produto.

Thin layers are widely used in many fields of technology and today we can say that they are found in all modern technologies. Thin layers can be created in two ways, namely by chemical or physical means. This work focuses on the latter method, more particularly a technology of thermal evaporation of thin layers in a vacuum. The work focuses on the process principles during and after the evaporation. Much of the work focuses on the development and design of experiments. These experiments illustrate some of the phenomena that take place on thin films produced by the aforementioned technology. Work helps to better understand processes during formation of thin layers and properties that influence the quality and stability of thin films. In conclusion we describe results of experiments and new developments in the field of thin films deposition using evaporation under vakuum are summarized.

Спроектирована установка для нанесения органических покрытий. Установка термовакуумного нанесения и виртуальный прибор «ThermoVAC&Co» позволяют осуществлять синтез тонкопленочных покрытий, контролируя температуру нагрева испаряемого вещества до 500 °C. Выполнен синтез тонких пленок 5,11-диметил-5,11-дигидроиндоло [3.2-b]карбазола 5,11-дигексил-5,11-дигидроиндоло[3.2-b]карбазола, 5,11-бис(2-метоксиэтил)-5,11-дигидроиндоло[3,2-b]карбазола и 5,11-бис[2-(2-метоксиэтокси)этокси]-5,11-дигидроиндоло[3,2-b]карбазола для исследования оптических и электрических характеристик. С помощью конфокального микроскопа Axio CSM 700 была проведена аттестация поверхности синтезируемых покрытий. Спектры оптического поглощения были получены на спектрометре Shimadzu UV-2450. Расчетный потенциал ионизации для исследованных соединений ICZ составляет 6,82-7,1 эВ. Обсуждается влияние отдельных блоков соединений на спектр оптического поглощения. На базе микрозондовой станции Cascade Microtech MPS150 произведены измерения вольтамперных характеристик структуры ITO/-ICZ/Al. По данным ВАХ были рассчитаны подвижности зарядов по модели инжекционных токов. Подвижность носителей заряда, оцененная по вольтамперным характеристикам, находится в диапазоне 2,2 ∙ 10-9–1,43 ∙ 10-6 см2 / (В·сек) для исследованных соединений ICZ. Установлена связь между интенсивностью полос поглощения с максимумом около 430 нм и подвижностью носителей заряда. / The installation for applying organic coatings is designed. The thermal vacuum deposition unit and the «ThermoVAC & Co» virtual instrument allow the synthesis of thin-film coatings, controlling the temperature of heating the evaporated substance up to 500 ° C. The thin films of 5,11-dimethyl-5,11-dihydroindolo [3.2-b] carbazole 5,11-dihexyl-5,11-dihydroindolo [3.2-b] carbazole, 5,11-bis (2-methoxyethyl) - 5,11-dihydroindolo [3,2-b] carbazole and 5,11-bis [2- (2-methoxyethoxy) ethoxy] -5,11-dihydroindolo [3,2-b] carbazole were synthesized to study optical and electrical characteristics. The surface of the synthesized coatings was certified using the Axio CSM 700 confocal microscope. Optical absorption spectra were obtained with the Shimadzu UV-2450 spectrometer. The calculated ionization potential is 6.82–7.1 eV for the studied ICZ compounds. The effect of individual blocks of compounds on the optical absorption spectrum is discussed. The current-voltage characteristics of the ITO / -ICZ / Al structure were measured with the Cascade Microtech MPS150 microprobe station. According to the I-V characteristics data, the charge mobility was calculated using the injection current model. The mobility of charge carriers, estimated by the current-voltage characteristics, is in the range 2,2 ∙ 10-9–1,43 ∙ 10-6 cm2/ (V·sec) for the studied ICZ compounds. The relationship between the intensity of absorption bands with a maximum near 430 nm, and the mobility of charge carriers were found.