La recapture du dioxyde de carbone est aujourd'hui un défi mondial majeur pour minimiser son impact sur le réchauffement climatique. La capture par adsorption physique pourrait être un procédé viable si le bon adsorbant est trouvé, mais cette capture dans les fumées de combustion impose des contraintes comme les faibles concentrations en CO2 (< 20%), la faible pression totale (1 bar) et la présence éventuelle d'eau. Cette thèse avait pour but l'évaluation de l'impact de la vapeur d'eau lors d'adsorption de CO2 sur des matériaux poreux hybrides, les Metal Organic Frameworks. En premier lieu, ce travail a consisté à étudier l'adsorption de CO2 et de vapeur d'eau séparément sur un grand nombre de MOFs. Une sélection de MOFs, prenant en compte des critères de stabilité et de capacité d'adsorption, a ensuite été effectuée afin d'évaluer l'effet de la vapeur d'eau lors d'adsorption du CO2 sur ces derniers. Un dispositif expérimental a été développé où sont obtenues simultanément des enthalpies d'adsorption et des courbes de percées. Dans nos travaux, nous avons pu établir trois types de comportements en présence de vapeur d'eau :- Négatif/Préjudiciable sur l'adsorption du CO2 : dû à un empoisonnement ou à l'instabilité des matériaux en présence d'eau (cas du HKUST-1). - Neutre : quantités de CO2 captées constantes (cas de l'UiO-66).- Positif : amélioration (cas du MIL-101(Cr)) ou remarquable accroissement d'adsorption de CO2 suite à la pré-adsorption de vapeur d'eau (MIL-100(Fe) & MIL-127(Fe)).Ce travail s'inscrit dans le cadre du 7ieme projet européen Macademia "MOFs as Adsorbents and Catalysts: Discovery and Engineering of Materials for Industrial Applications". / The elimination of carbon dioxide has become a worldwide challenge to minimize its impact on global warming. Capture using physical adsorption is viable as long as the right adsorbent is found. CO2 capture from flue gases poses a number of problems in terms of low CO2 concentration (below 20%), low total pressure, and the eventual presence of water. This study focuses on the impact of water vapour during CO2 adsorption on different porous materials. An experimental device has been developed to assess the impact of water vapour during CO2 adsorption: both the heats of adsorption and the breakthrough curves were obtained. The uptakes of CO2 at 0.2 bar have been studied in porous materials after having been pre-equilibrated under different relative humidity's (3 and 40%). The enthalpies allow a better understanding of the phenomena involved. Several MOFs, like HKUST-1(Cu), UiO-66(Zr), MIL-100(Fe), MIL-101(Cr), MIL-127(Fe) have been compared to a zeolite NaX and an activated carbon Takeda-5A.Three different behaviours are shown: - Where water has a negative impact on CO2 adsorption. This can be due to poisoning or the poor stability of the materials like HKUST-1. - Where water seems to have little effect on CO2 adsorption like case of UiO66. - Where water has a positive effect on CO2 uptake. Slight improvement for MIL-101(Cr) and remarkable enhancement of CO2 uptake through pre-adsorption of water vapor has been highlighted here in two cases: the mesoporous MIL-100(Fe) and the bifunctional MIL-127(Fe).This work is part of the European project FP7 Macademia "MOFs as Adsorbents and Catalysts: Discovery and Engineering of Materials for Industrial Applications".

The elimination of natural organic matter (NOM) is an important aim of water treatment in demineralisation plants of power stations. NOM is regarded as corrosion risk factor in the steam water cycle because of its potential to decompose into low-molecular-weight (LMW) acids and carbon dioxide. Further, the removal of NOM is also one of the main objectives in the drinking water production, since it can cause i) colour, taste and odour problems, ii) formation of carcinogen halogenated disinfection by-products (DBPs) after disinfection with chlorine and iii) bacterial growth in the water distribution system. In earlier studies, it was found that anion exchange is a successful method to remove NOM fractions. However, NOM fractions with low charge density (LMW neutrals and hydrophobic organic carbon (HOC)) and/or large molecular size (biopolymers and particulate organic carbon (POC)) could not be removed in some cases in satisfying quantities. The aim of the present work was to investigate the uptake performance of different anion exchange resins (AERs) in regard to problematic NOM fractions. The AERs differ especially in their functional groups (tertiary versus quaternary amines) and matrix material (polystyrene versus polyacrylic resins). The use of different AERs provides an option to identify possible interactions between adsorbate (NOM fractions) and adsorber (AERs) as well as the mechanism which determine the removal efficiency. The NOM fraction adsorption onto AERs was studied in equilibrium and fixed-bed experiments with three types of starch with different molecular size distributions (model substances for biopolymer fraction) as well as 2-naphthol (model substance for the LMW neutral fraction) at acidic pH (relevant for water in demineralisation plants of power stations) and neutral pH (covering most raw waters). Furthermore, the NOM fraction uptake from “real” acidic and neutral water samples, obtained from a demineralisation plant of a power station, was estimated for different AERs. Results were discussed in terms of size-exclusion, anion exchange and hydrophilic/hydrophobic repulsion. In case that size-exclusion influences the NOM uptake onto AERs, it was found that the smaller the size of the NOM molecules and the higher the water content of the AERs, the more effective the uptake is. Thus, for the removal of biopolymers and POC, polyacrylic resins with high water content could be a good choice. Contrary, polystyrene AERs are the most effective resins in the removal of NOM fractions, if no size-exclusion occurs. They seem to be able to uptake more hydrophilic NOM fractions by polar/ionic interactions between acids/acidic components and tertiary/quaternary amines as well as to remove more hydrophobic NOM fractions by π-π stacking and/or hydrophobic interactions on the polystyrene matrix. Further, it was found that the higher the total volume (anion exchange) capacity of an AER, the higher its NOM removal by polar/ionic interactions can be. At acidic pH, weak/medium base AERs have higher total volume (anion exchange) capacities than strong base AERs, whereas, at neutral pH, strong base AERs have the highest ones. In view of these results, the application of polyacrylic AERs with high water content can be recommended to remove NOM components with large molecular size in demineralisation and drinking water plants. If there is a higher amount of smaller NOM fractions, especially LMW neutrals, than polystyrene weak/medium base AERs should be favoured in demineralisation plants and polystyrene strong base AERs in drinking water treatment plants. From the engineering point of view, breakthrough curve (BTC) prediction models are important for the design of fixed-bed filter. Therefore, two different BTC model approaches were tested in the present study to describe the single-solute adsorption onto AERs: i) the homogenous surface diffusion model (HSDM) with linear driving force (LDF) approach for surface diffusion, known from activated carbon adsorption, and ii) the Glueckauf/Helfferich formulae as an extension of the height equivalent to a theoretical plate (HETP) model, initially used to describe ion exchange processes. It was found that the Glueckauf/Helfferich approach is not only a suitable tool for the fast calculation of BTCs for ionic components, but it can also successfully be applied, after considering the Freundlich model for the mass balance, for the rapid prediction of BTCs for single-solute organic molecules. For competitive BTC predictions, the ideal adsorbed solution theory (IAST) within the LDF model was applied. All calculated BTCs fit the experimental data in a good manner. Thus, the investigated BTC models can be applied for estimating the breakthrough bed volumes of different AERs to avoid leakage of NOM in the drinking or demineralised water caused by overloading. / Die Entfernung von natürlichen organischen Substanzen (NOM) ist ein wichtiges Ziel für die Herstellung von Reinstwasser im Kraftwerksbetrieb, da diese sich im Wasser/Dampf-Kreislauf zu niedermolekularen Säuren und Kohlenstoffdioxid zersetzen können und so ein potentielles Korrosionsrisiko darstellen. Außerdem ist die Elimination von natürlichen organischen Substanzen einer der Schwerpunkte in der Trinkwasseraufbereitung, da NOM im Trinkwasser folgende Konsequenzen verursachen können i) Farb-, Geschmacks- und Geruchsprobleme, ii) Bildung von kanzerogen halogenierten Desinfektionsnebenprodukten nach der Desinfektion mit Chlor und iii) Bakterienwachstum im Wasserverteilungssystem. In früheren Untersuchungen wurde festgestellt, dass Anionenaustauscherharze (AERs) die NOM-Fraktionen in der Regel erfolgreich aufnehmen können. Nur NOM-Fraktionen mit geringer Ladungsdichte (niedermolekulare Neutralstoffe und hydrophober organischer Kohlenstoff) und/oder großer Molekülgröße (Biopolymere und partikulärer organischer Kohlenstoff) können unter bestimmten Bedingungen nicht in zufriedenstellender Menge entfernt werden. Ziel dieser Arbeit war es, das Aufnahmeverhalten unterschiedlicher AERs hinsichtlich problematischer NOM-Fraktionen zu untersuchen. Die AERs unterscheiden sich vor allem in ihren funktionellen Gruppen (tertiäre versus quaternäre Amine) und ihrer Matrix (Polystyren- versus Polyacryl-Harze). Die Verwendung unterschiedlicher AERs erlaubt es, mögliche Wechselwirkungen zwischen Adsorbat (NOM-Fraktionen) und Adsorber (AERs) und die Mechanismen, die die NOM-Aufnahme entscheidend bestimmen, zu identifizieren. Die Entfernung von NOM-Fraktionen durch AERs wurde in Gleichgewichts- und Festbett-versuchen mittels dreier Stärketypen mit unterschiedlicher Molekülgrößenverteilung (Modellsubstanzen für die Biopolymere) und 2-Naphthol (Modellsubstanz für die Neutralstoffe) unter sauren pH-Bedingungen (relevant für die Herstellung von Reinstwasser im Kraftwerksbetrieb) und neutralen pH-Bedingungen (bedeutsam für die meisten Rohwässer) untersucht. Außerdem sollte das Adsorptionsverhalten von AERs bezüglich verschiedener NOM-Fraktionen unter Einsatz von „real“ neutralen und sauren Wasserproben aus einer Wasseraufbereitungsanlage eines Kraftwerksbetriebes eingeschätzt werden. In dieser Arbeit konnte gezeigt werden, dass falls Größenausschluss die NOM-Aufnahme von AERs beeinflusst, dann ist die Adsorption der NOM-Fraktionen umso größer, je kleiner die NOM-Moleküle sind und je höher der Wassergehalt der AERs ist. Daher kann für die Entfernung von größeren Biopolymeren, der Einsatz von AERs mit Polyacryl-Matrix und hohem Wassergehalt die beste Option sein. AERs mit Polystyren-Matrix besitzen die höchste Aufnahmekapazität für NOM-Fraktionen, falls kein Größenausschluss auftritt. Es scheint für sie möglich zu sein, sowohl hydrophile NOM-Fraktionen durch polare/ionische Wechselwirkungen zwischen NOM Säuren/sauren Komponenten und tertiären/quaternären Aminen aufzunehmen als auch hydrophobe NOM-Fraktionen durch π-π Anziehungen und/oder hydrophobe Interaktionen an die Polystyren-Matrix zu binden. Weiterhin konnte gezeigt werden, dass je höher die Gesamtvolumenkapazität eines AERs, desto größer ist die NOM-Entfernung auf Grund von polaren/ionischen Wechselwirkungen. Es gilt, dass schwach/mittel basische AERs im Vergleich zu stark basischen AERs höhere Gesamtvolumenkapazitäten unter sauren pH-Bedingungen besitzen und stark basische AERs die höchsten Gesamtvolumenkapazitäten unter neutralen pH-Bedingungen aufweisen. Auf Grund dieser Ergebnisse ist es möglich, die Verwendung von AERs mit Polyacryl-Matrix und hohem Wassergehalt für die Entfernung von NOM-Fraktionen mit großer Molekülgröße in Reinst- und Trinkwasseraufbereitungsanlagen zu empfehlen. Falls es einen höheren Anteil von kleineren NOM-Fraktionen, im Besonderen Neutralstoffen, gibt, sollte die Verwendung von schwach/mittel basischen AERs in Vollentsalzungsanlagen von Kraft-werksbetrieben und stark basischen AERs in Trinkwasseraufbereitungsanlagen bevorzugt werden. Vor allem im Hinblick auf technische Anwendungen ist es wichtig, Durchbruchskurven (BTC) vorausberechnen zu können. In der vorliegenden Arbeit wurden zwei Modellansätze für die Berechnung von BTCs für die Einkomponentenadsorption getestet: i) das homogene Oberflächendiffusionsmodell mit linearer Triebkraft (LDF), bekannt aus Untersuchungen zur Aufnahme von NOM an Aktivkohle, und ii) die Glueckauf/Helfferich-Formeln, primär verwendet für die Beschreibung von Ionenaustauschprozessen. Es konnte gezeigt werden, dass das Glueckauf/Helfferich-Verfahren nicht nur ein geeignetes Instrument für die schnelle Berechnung von BTCs für ionische Komponenten ist, sondern dass dieses, nach Berücksichtigung des Freundlich-Ansatzes in der Massenbilanz, auch erfolgreich angewendet werden kann, um BTCs für Einkomponentenadsorption von Organika zu berechnen. Für die Vorausberechnung von BTCs für Mehrkomponentensysteme wurde die Theorie der idealen adsorbierten Lösung im LDF-Modell genutzt. Die berechneten BTCs stimmen in guter Qualität mit den experimentell ermittelten BTCs überein. Die Ergebnisse verdeutlichen, dass die untersuchten BTC-Modelle eingesetzt werden können, um Durchbruchspunkte für die jeweiligen AERs zu bestimmen und damit die Gefahr des Schlupfes von NOM ins Trink- bzw. Reinstwasser zu minimieren.

Transport phenomenon of gas and vapors through polymer barrier materials as well as the factors affecting permeability of gaseous and liquid toxic compounds were investigated and results are presented in this thesis. Permeation characteristics investigation methods were elaborated and verified with focusing on utilization of gas chromatographic method and its instrumental modifications.

No description available.

Successful product development has been a fundamental part of many of today's companies and their continued prosperity depends on continuing to develop new products in the future. There are many models of product development. The two most common classes of development are market pull (MP) and technology push (TP). TP product development differs from MP in that the development begins with a specified technology rather than a specified customer. Because TP development is generally considered more difficult and challenging, most of the product development research has focused on MP development and many researchers and practitioners favor MP development over TP development. However, successful TP development has been shown to be a source of innovation that cannot be realized through MP development and is performed by many companies. The research in this thesis focuses on developing a comprehensive TP model to guide product developers on how to implement TP development successfully. This new TP model is developed by comparing recently published TP models to published best practices of TP development and known deficiencies of TP models. The comprehensive TP model makes improvements to the existing TP models through the addition of processes and tools that overcome deficiencies and incorporate best practices. The new comprehensive TP model includes elements of existing generic MP models, a "Technology Application Selection" (TAS) process and several new processes and tools associated with prototypes and network groups. Some of the new processes and tools are demonstrated through a case example. The comprehensive TP model provides product developers with the necessary step-by-step guide to TP product development. The model effectively deals with deficiencies of previous TP models, is sufficiently comprehensive and detailed to guide product developers, is complimentary and consistent to existing design processes and terms, is applicable to most TP product development projects, and is useful and repeatable in making product development decisions.

No description available.

Increased water- and fertilizer-use-efficiency in containerized crop production, via reduced water loss, enhances crop-available nutrients while reducing non-point source agrichemical contributions in accordance with regulatory standards. Previous studies detailed nutrient leaching patterns throughout crop production seasons, leaving little known about water and dissolved nutrient (solute) movement through soilless substrates during irrigation. The following experiments evaluated fundamental water and solute transport principles through pine-bark based substrates. 1) Ilex crenata Thunb. 'Bennett's Compactum' were grown in 2.7 L containers. Tensiometers detected wetting front (WF) movement throughout the substrate during irrigation. 2) Tracer solution (containing NO3-, PO43- and K+) and deionized water (DI) were applied to substrate-filled columns to characterize tracer breakthrough under saturated and unsaturated conditions. 3) Controlled-release fertilizer (CRF) was topdressed (surface-applied), incorporated (throughout substrate), dibbled (center of substrate) or not applied to fallow substrate, irrigated with DI and leachate analyzed to determine nutrient concentrations throughout irrigation. Tensiometers revealed that seasonal root growth affected substrate pre-irrigation moisture distribution. Wetting fronts channeled through the substrate before becoming thoroughly wetted. Tracer breakthrough occurred with less effluent volume under unsaturated conditions. Breakthrough of NO3- and PO43- was relatively conservative, though 37% of K+ was retained by the substrate. Leachate concentrations for topdressed and incorporated CRF peaked early (first 50mL effluent) before diminishing with continued leaching. Leachate concentrations for dibbled CRF initially increased (first 150mL leachate), plateaued and then diminished. These results show the relative rapidity which water and solutes move through pine-bark during irrigation and demonstrate methods for future research on within-irrigation solute transport. / Master of Science

This essay examines possible subject positions offered to a female in relations to the decadence genre in the novel Berta Funcke (1885) by Stella Kleve, pseudonym for Mathilda Malling. The aim is to study how a female can be decadent. I analyze subject positions and examine how they enable decadent expressions of the female character. To understand subject positions in relations to the historical context I use Chris Weedon’s approach to feminist poststructuralism. I define decadence as a relative concept and understand it as a wider experience of decadence and dissolution in society. The methodological framework is based on hermeneutic reading. The result shows that the female protagonist is under the influence of many subjectivities simultaneously. Her decadence can be seen as both a source of emancipation and of constraint. From the analysis, I’ve been able to distinguish four characteristic subject positions: The Erotic, The Hermaphrodite, The Actress and The Hothouse Plant. The subject positions are bound to stereotypes of the time but also permits the female protagonist to transcend gender definitions. The result shows that the decadent aesthetics, expressions and vocabulary open up new ways of being for the female character.

This dissertation deals with international company law, namely with piercing the corporate veil doctrine. The dissertation is divided, apart from introduction and conclusion, into 5 chapters. Chapter I deals with general definition of the doctrine. Chapter II explains that the complexity of the doctrine is caused by a fact that it actually consists of several related questions. This Chapter offers an answer to the most serious one - the predictability of use of the doctrine. Chapter III discusses current questions related to the piercing. Chapter IV brings an analysis of use of the piercing in chosen developed legal orders including a comparison summary. Finally, Chapter V is devoted to possibility of use of the doctrine in Czech law. Key words: International company law; piercing the corporate veil; breakthrough of the property independence; limited liability of shareholders; capital companies; economic analysis of law; closely held corporations; voluntary and involuntary creditors.

Atualmente, o tipo de propelente para produtos em aerossol mais usado no mundo é uma mistura de hidrocarbonetos leves (butano e propano - sendo o primeiro em maior proporção). Parte de seu processo de produção é a dessulfurização do butano líquido, através de adsorção em leito fixo usando peneiras moleculares 13X. A literatura científica não apresenta muitas publicações sobre o tema e considerando que a técnica de adsorção é fortemente dependente de dados experimentais para seu maior entendimento, é objetivo deste trabalho estudar este processo através do equilíbrio de adsorção, das curvas de ruptura e do desenvolvimento de um modelo matemático que represente o funcionamento de uma coluna de adsorção de leito fixo a temperatura constante. Obtiveram-se dados sobre o equilíbrio de adsorção por meio de ensaios em banho finito comparando-se a interação de diferentes compostos de enxofre com a peneira molecular 13X e o efeito da temperatura. Utilizou-se a técnica de cromatografia gasosa como método analítico para obtenção dos teores de compostos sulfurados e de hidrocarbonetos. O modelo de Langmuir apresentou bom ajuste aos dados experimentais. Avaliando-se a interação dos componentes sulfurados com a zeólita 13X, identificou-se diferenças significativas, sendo a maior em ordem decrescente: etil-mercaptana, n-propil-mercaptana e terc-butil-mercaptana, respectivamente. A dinâmica do processo de adsorção foi estudada através da obtenção das curvas de ruptura em leitos em escala laboratorial e piloto. Avaliaram-se as influências da variação da concentração de entrada da n-propil-mercaptana e da velocidade do fluido em leito fixo recheado com zeólitas 13X, mantendo os demais parâmetros constantes. Conforme esperado o aumento da concentração inicial reduz o tempo de ruptura, aumenta a quantidade total adsorvida pelo leito e não altera o comportamento da zona de transferência de massa (ZTM). Analisando-se a elevação da velocidade, nota-se também uma diminuição no tempo de ruptura e um aumento da ZTM. O modelo matemático apresentado considera os balanços de massa microscópicos aplicados ao leito, os fenômenos de transporte de massa com modelo de dispersão axial e transporte por convecção da fase líquida para a superfície da partícula e as isotermas de adsorção. As equações diferenciais parciais resultantes foram adimensionalizadas e resolvidas empregando-se o método de diferenças finitas, implementado por código Matlab®. A partir da simulação matemática das condições experimentais obtiveram-se os parâmetros de dispersão axial e de transferência de massa que possibilitaram uma boa reprodução do tempo de ruptura quanto do perfil da zona de transferência de massa para os experimentos em escala laboratorial e piloto. / Currently, the kind of propellant for aerosol products most widely used in the world is a blend of light hydrocarbons (butane and propane - the first in greater proportion). Part of the production of propellant is the desulfurization of liquid-phase butane by molecular sieves 13X in a fixed bed. The scientific literature concerning the adsorption of the mercaptans using zeolite are scarce and considering that the adsorption technique is strongly dependent on experimental data for its better knowlegde, the aim of this work was to study this process by adsorption equilibrium, the breakthrough curves and the development of a mathematic model, simulation and comparison with the operation of a fixed-bed pilot and laboratory-scale column. Adsorption equilibrium parameters were obtained using finite bath experiment and comparing the interaction of different sulfur compounds with molecular sieve 13X and the temperature effect. It was used the gas chromatography as an analytical method in order to obtain the levels of hydrocarbons and sulfur compounds. The Langmuir model well fit the experimental data. Significant differences were identified in the interaction of the sulfur components with zeolite 13X. The major interactions of the sulfur components are in decreasing order: ethyl-mercaptan, n-propyl-mercaptan and terc-butyl-mercaptan. The dynamic of the adsorption process was studied by obtaining the breakthrough curves in laboratory and pilot scale. It was investigated the influence of the initial concentration of n-propyl mercaptan and the fluid velocity in a fixed bed packed with zeolite 13X keeping the other parameters constant. As it was expected, as the inlet sulfur concentration increases the break point time decrease, and enhances the total amount adsorbed by the bed. Analyzing the increase in velocity on the breakthroug profile, it was noted that also decreases the break point time and causes a greater decline of the curve resulting in greater ZTM and anticipating the bed saturation time. The model equations account the mass balance applied in the flowing liquid phase in the column, transport phenomena as the effect of axial dispersion and convection from liquid phase to the adsorbent surface and adsorption isotherm. Finite difference method was used to solve the dimensionless general partial differential equations and it was implemented by Matlab® software. From mathematical simulation of experimental conditions it were obtained the axial dispersion parameters and mass transfer coefficient which allowed a fair agreement in predicting break point time and the mass transfer zone profile.