Dissertationen zum Thema „BDS 1308“

Die Anwendung von optischen Parametern zur Stoffcharakterisierung wird diskutiert. Dabei ist der Schwerpunkt der Diskussion auf absorptions- und fluoreszenzspektroskopische Methoden gesetzt. Beide Methoden können schnell und zuverlässig – auch im on-line Betrieb – eingesetzt werden. Der Beitrag soll einen Überblick über die grundlegenden Möglichkeiten der Anwendung beider Methoden geben.

A great deal of interest currently surrounds the development of electrophosphorescent materials, as they may exhibit efficiencies greater than the theoretical limit of 25% for purely fluorescent materials. The most studied material for such purposes is jac-Ir(ppY)3, which exhibits efficient green phosphorescence in solution and in electroluminescent devices. Europium(III) complexes have also received attention for their narrow bandwidth red emission. A number of charge-neutral iridium(III) complexes have been prepared as potential electrophosphorescent materials. Bis-terdentate coordination has been investigated, in a quest to provide improved stability with respect to jac-Ir(ppY)3 derivatives, an important objective in commercial development. The complexes described herein are the first examples of iridium bound to NACAN coordinating 1,3- di(2-pyridyl)benzene derivatives. Methyl substitution at C4 and C6 of the phenyl ring (i.e. 1,5-di(pyridin-2-yl)-2,4-dimethylbenzene (dpydmbH)) is required to inhibit competitive cyc1ometalation at these positions. Efficient red emission was observed from Ir(dpydmb-N,C,N)(dppy-C,N,C) (dppyH2 = 2,6-diphenylpyridine) (Am ax = 585 nm, <l>PL = 0.21 in degassed CH3CN). Fluorination of the dppy ligand at the 2 and 4 positions of the phenyl rings results in a simultaneous blue-shift and increase in efficiency (Amax = 547 nm, <l>PL = 0.41 in degassed CH3CN). These complexes exhibit an unusual meridional geometry, difficult to achieve for tris-bidentate complexes. The complex Ir( dpydmb-N,C,N)(ppy-C,N)Cl is exceptionally emissive (Amax = 508 nm, <l>PL = 0.76 in degassed CH3CN). Ir( dpydmb-N,C,N)(tppic-C,N,0) and Ir( dpydmb-N,C,N)(hbqcC, N,O) (tppicH2 = 4-p-tolyl-6-phenylpicolinic acid; hbqcH2 = 4-hydroxybenzo[h]quinoline- 2-carboxylic acid) were poorly emissive, attributed to a photo activated labilisation of the Ir-C bond in solution. The effect of substitution position of a senslt1s1ng aminobenzophenone chromophore was investigated in a series of europium(III) macrocyc1ic complexes. Maximum photoluminescence quantum yield was observed for the para-substituted isomer, attributed to the distance dependence of the efficiency of energy transfer. An unexpected rearrangement was observed for the ortho-substituted ligand, resulting in a quinoline derivative with a rare N-arylated substitution pattern.

Fixed bed reactors are widely applicable in a range of chemical process industries. Their ease of use and simplified operation make them an attractive and preferred option in reactor selection, however the geometric complexities within the bed as a result of the unstructured packing has made the design of such beds historically based on pseudo-homogenous models together with correlation-based transport parameters. Low tube-to-particle diameter ratio (N) beds, in particular, are selected for highly exothermic or endothermic reactions, such as in methane steam reforming or alkane dehydrogenation. Due to the large fraction of tube to catalyst particle contact in these low N beds, wall effects induce a mass transfer boundary layer at the wall, and in the case of thermal beds, a simultaneous resistance to heat transfer. Computational Fluid Dynamics (CFD) has been shown to be an accurate tool for experimental validation and predictive analysis of packed beds, and may be used to derive more accurate design parameters for fixed bed reactors. More specifically, the elucidation of dispersion, or the transport of reactant and product within the bed due to molecular diffusion and convective flow is of fundamental interest to the design of fixed beds. Computational Fluid Dynamics was used in this research to study solute dispersion in eight beds of varying N at a range of particle Reynolds numbers in the laminar flow regime. In the first stage of research, flow development was simulated in three-dimensional packed beds of spheres. Then, the reactor wall was sectioned to include a boundary condition of pure methane, from which the solute could laterally disperse into the bed. In the second stage, a two-dimensional representation of the bed was created using the commercial Finite Element Analysis software COMSOL Multiphysics. In these models, axial velocity profiles and radial methane concentration profiles taken from the 3-D models were supplied, and a fitting procedure by use of the Levenberg-Marquardt Least-Squares optimization algorithm was completed to fit radial dispersion coefficients and near-wall mass transfer coefficients to the CFD data. These optimization runs were conducted for all N at a number of bed depths in each case. Two sub-studies were conducted in which a constant velocity profile and a local velocity profile were supplied to the 2-D model, and the optimization re-run. It was found that this two parameter model did not fully account for various mechanisms of dispersion in the bed, namely the increasing rate of dispersion from the tube wall boundary layer up to the bed center, but only accounted for a diffusive-dispersion at the wall and a constant-rate, convective-dispersion everywhere else in the bed. Length dependency of dispersion coefficients were also noted, particularly in the developing sections of the bed. Nevertheless, the combined CFD and optimization procedure proved to be an accurate and time-efficient procedure for the derivation of dispersion coefficients, which may then lend themselves to the standard design of packed bed reactors.

The current study examined the relationship between depression and uncertainty within the stress-diathesis model. Depression is a mental health disorder that is wide spread within our society. However, few causes of this disease have been able to be identified. Studies in uncertainty have shown that it is a major stressor in day-to-day life. Previous research has shown that individuals with high levels of uncertainty show higher levels of depression. The stress-diathesis model, a model originally developed to explain differences in development of schizophrenia, provides a theoretically meaningful way to combine these two concepts. The model states that a person who is likely to develop a disease has an internal mechanism, a diathesis, that will be triggered upon presentation of a stressor. This study tested the idea that uncertainty can be used as a stressor to activate diathesis within an individual, aiding in the prediction of depression. In total, 163 participants were randomly assigned one of three conditions, an uncertainty threat, an affirmation condition, and a control condition. Participants were given pre and post independent variable measures of depression and anxiety. Findings suggest that uncertainty activated negative emotions differentially within the participants, resulting in higher levels of negative affects after the uncertainty threat, especially for participants who already scored relatively higher on depression indicators. These results hint at a possible understanding of why depression rates and diagnosis rates of mental health issues rise during economic downturn and other times of strong uncertainty.

Texte remanié de: Diss.--Fakultät für Geschichts- und Geowissenschaften--Otto-Friedrich-Universität Bamberg, 2000.<br>Chronologie de la croisade contre les Albigeois. Liste des chroniques relatant les principaux événements. Bibliogr. p. 264-284. Index.

The dissertation thesis deals with the analysis of prospective environmentally compatible electrical insulating fluids for electrical engineering in relation to their chemical structure. The thesis starts with the overview of the current state of the art and of the latest trends in the use of synthetic and biodegradable natural oils. In the experimental part were studied these oils: mineral oils, rapeseed oil, sunflower oils, soybean oil, methyl oleate, peanut oil, MCT oil, castor oil and other. Dielectric properties were measured using LRC meter Agilent 4980A including dielectric liquid test fixture Agilent 16452A and also by the Novocontrol Alpha-A analyzer. Electrical properties are presented in the frequency range 10 mHz – 1 MHz range in the temperature interval 253 K to 363 K. The work goes on with the study of the suitability of individual oils for lower temperature, including the impact of the chemical structure and formulation on electrical properties.

Cette thèse comporte une étude sur les contrats dans le droit coutumier et la pratique contractuelle du Nord de la France et de la Belgique entre l’an 1000 et 1300. D’abord, l’auteur cerne qui concluaient alors quels contrats pour quelle raison. Les sources de cette étude sont constituées des chartes de libertés que les villes se font octroyer dès le 12e siècle ; des actes de la pratique émanant des seigneurs territoriaux et des échevins urbains dont les chirographes enregistraient les opérations commerciales les plus diverses. Seulement à compter des années 1280, s’y ajoutent des coutumiers qui confirment les conclusions tirées des milliers d’actes de la pratique. Du fait des mutations sociales et économiques qui affectaient l’Europe aux 12e et 13e siècles, l’on constate une naissance du droit contractuel autour du renouveau urbain, de la renaissance commerciale et de l’affermissement du pouvoir, notamment juridictionnel, des princes territoriaux.La question centrale du droit des obligations est de savoir comment contraindre le débiteur à respecter ses engagements. Pour y répondre, encore faut-il être certain que le débiteur se soit engagé. Pour cela, le droit du 12e siècle a recours aux techniques déjà connues en matière de droit des biens, à savoir conférer légitimité et sécurité en faisant conclure les opérations les plus importantes devant les puissants d’abord, devant les juges ensuite. La pratique du record de cour est ainsi née. Aussi, le formalisme dans la conclusion des contrats a toujours été souple et la question de la naissance du consensualisme, abordée dans certaines coutumes, semblait causer un désarroi tant elle était étrangère au droit coutumier. Ensuite la contrainte s’exerçait par l’emprisonnement pour dette ; par l’exécution sur les meubles et sur les immeubles. Pour améliorer les chances du créancier, le droit coutumier a recours à la plévine coutumière, sûreté personnelle par excellent<br>His PhD is a study of the law of contract and its practice in the customs of Northern France andBelgium between the years 1000 and 1300. he authors opens with an analysis of who entered intowhich contracts for what reasons.he sources of this study are the various liberty charters granted to townships as early as the mid12th century as well as the practical contracts laid down by lords such as counts, dukes and abbeysand, in the 13th century the chirographs that aldermen used to register the most divers contracts. Asof the years 1280, customs books made their appearance. hey conirm the indings resulting thestudy of the thousands of practical sources of the 3 preceding centuries.As a result of the social and economic transformations that took place in Europe in the 12th and 13thcenturies, an entire new contractual law was shaped around newly formed and growing towns,commercial renaissance and the territorial lords’ increase of power, including jurisdictional.A central question of the law of contract is how to force the debtor to respect its engagements. Inorder to answer that question, the validity of the engagement must irst be ascertained. For this, thecustoms of the 12th century used techniques already in place for the transfer of immovable property,i.e. effecting the transaction publicly before the local lords or before their justice. Record contracts,i.e. establishing a specially qualiied witness’ testimony, before aldermen seemed the natural mannerof achieving the necessary publicity, legitimacy and publicity. herefore the accomplishment offormal requirements was never, even in the early beginning of the period here studied, ixed.Formalities existed; formal contracts didn’t. Likewise, the question of consensual contracts, timidlyaddressed in certain custom books, seemed to cause consternation for that question is distant fromthe customs already in place. Finally, enforceability was achieved through imprisonment, seizure ofchattels and inally that of immovable property. In order to increase the creditor’s chances of beingpaid, customary law had recourse to the pledges, against whom the debt could likewise be enforced

Over the last 20 years, selected disperse dyes and bis-3-carboxypyridinium-striazine reactive dyes have been widely promoted for the exhaust dyeing of polyester/cotton blends in a one-bath-one-stage ('All-in') process under neutral conditions. However, despite the time and energy savings afforded by this elegant dyeing process, there is a belief in the dyeing industry that economical production is limited to pale and medium depths of shade. The two dye classes (disperse dyes on polyester and bis-3-carboxypyridinium-striazine reactive dyes on cotton) were investigated to understand why heavy depths of shade could not readily be obtained, economically, using this process. The bis-3carboxypyridinium- s-triazine reactive dyes were responsible for the inability to achieve heavy depths of shade, economically, when dyeing at 130°C and neutral pH. The poor colour yield of the dyes was due to their low exhaustion level and low fixation efficiency at 130°C and pH 7.0-7.5, particularly when compared with the parent bis-monochlorotriazine dyes, fixed under alkaline conditions at 80°C. The synthesis and evaluation of some bis-3-carboxypyridinium-s-triazine reactive dye structures, possessing highly substantive chromophores, were investigated as a mecm of obtaining high colour yield, on 100% unmercersised cotton, at 130°C and pH 7.0-7.5. When a highly substantive bis-3-carboxypyridinium-s-triazine dye chromophore was incorporated into the reactive dye structures, heavy depths of shade could be readiiy obtained when dyeing at 130°C and neutral pH, using conventional salt concentrations. However, the wet fastness properties of the dye were poor, due to the slow removal of the hydrolysed dye and its propensity for back-staining adjacent white areas. If the high substantivity of a dye could be assigned to the reactive group, which is removed during the fixation of the dye, it may be possible to offer both acceptably high levels of build-up (and costeffectiveness) and wet fastness. The synthesis and evaluation of novel reactive dye structures, possessing substantivity-conveying reactive groups, when applied to cotton at 130°C and pH 7.0 - 7.5, were investigated. When a substantivity-conveying reactive group was incorporated into a reactive dye structure, as a replacement for a chlorine atom, the dye exhibited a higher substantivity than the parent monochlorotriazine dye. The use of amide derivatives of nicotinic acid as the reactive group in a s-triazinyl reactive dye resulted in an increase in the substantivity, compared with the parent 3carboxypyridinium- s-triazinyl dye. When two substantivity-conveying reactive groups were incorporated into a dye molecule, without changing the reactivity of the dye, the above effect is enhanced, resulting in higher colour yield than from the corresponding Kayacelon React dye. Since the substantivity-conveying reactive group is removed during the fixation of the dye, the high substantivity of the parent dye should not be an impediment to achieving good wet-fastness properties, without the need to use excessively long wash-off sequences.

La présente thèse consiste en une biographie de Wenceslas de Bohême, duc de Luxembourg et de Brabant, du point de vue des relations « internationales » entre la France et le Saint Empire romain et du rôle joué par le duc dans les grands projets politiques européens de la seconde moitié du XIVe siècle. Elle se concentre en outre sur le mécénat littéraire du duc Wenceslas, notamment sur sa relation avec Jean Froissart, s’appuyant d’une part sur les Chroniques de ce dernier pour la narration des événements et établissant d’autre part un rapport direct entre la vie du duc et les oeuvres littéraires qu’il commanda au poète, le roman Méliador et le « dit » de la Prison Amoureuse. La thèse esquisse également un tableau de la cour de Luxembourg-Brabant, de son milieu culturel ainsi que de ses rapports possibles avec les cours princières des Pays Bas et celles de l’empereur et du roi de France<br>This doctoral thesis is based on a biography of Wenceslas of Bohemia, duke of Luxembourg and of Brabant, concieved from the point of view of the familial and “international” relations between France and the Holy Roman Empire. It describes the role of the duke in several great political projects in the 2nd half of the 14th century. The thesis also deals with the literary patronage of the duke, in particular with his relation to Jean Froissart. On the one hand, the Froissart’s Chroniques are one of the sources of this Wenceslas’s biography, on the other hand, the thesis finds an affinity between the duke’s life and the particular poetic work by Froissart, namely the romance Meliador and the “dit” La Prison Amoureuse owing to the Wenceslas’s patronnage. It also pictures the cultural milieu of the court of Luxembourg-Brabant in relation to the other courts of the Netherlands as well as to the emperor’s and to the the French king’s courts

Puisqu’il est désormais avéré que les différents arguments avancés par les parlements de la monarchie à l’époque moderne afin de légitimer leur prétention à vérifier librement les édits royaux avaient des racines médiévales, il n’était pas injustifié de rechercher si leur propension à élever leurs arrêts de règlement au rang de véritables lois n’était pas, elle aussi, déjà en germe au Moyen Âge tardif. Une enquête dans les archives du parlement de Paris contemporaines du règne de Charles VI (1380-1422) et de la double monarchie franco-anglaise (1422-1436) permet de confirmer cette hypothèse. Il en ressort en effet qu’au tournant des XIVe et XVe siècles, dans le milieu parlementaire parisien, on considérait non seulement que par sa jurisprudence la « cour souveraine et capitale du royaume » dégageait des règles qui faisaient lois, mais en outre que les arrêts de règlement qu’elle édictait, ou du moins certains d’entre eux, étaient des actes normatifs souverains, voire constituaient de véritables ordonnances royales. Cette faculté reconnue à la cour suprême d’être un véritable co-législateur était au demeurant logique et naturelle, si l’on prend la peine de la replacer dans le contexte à la fois institutionnel, politique et idéologique du temps<br>Since it is now recognized that the various arguments put forward by the parliaments of the monarchy in modern age in order to legitimize their claim to freely check the royal edicts had medieval roots, it was not unjustified to inquire whether their inclination to raise their regulation judgments to the rank of actual laws was not, similarly, already raising in the Late Middle Ages. An investigation of the archives of the Parliament of Paris contemporaneous with the reign of Charles VI (1380-1422) and with the double Franco-English monarchy (1422-1436) confirms this hypothesis. The investigation indeed shows that, at the turn of the 14th and 15th centuries, in the Parisian parliamentary environment, it was considered not only that, by its jurisprudence, the “sovereign and capital court of the kingdom” emanated regulations which made laws, but also that the regulation judgments it enacted, or at least some of them, were sovereign normative acts, or even constituted genuine royal rulings. This acknowledged ability of the Supreme Court to be a genuine co-legislator was, as it happens, logical and natural, if one takes the trouble to place it in the institutional, political, and ideological context of the period

Ce travail de thèse s’appuie sur les données d’un suivi à long-terme mené à une échelle régionale pour mieux appréhender les facteurs gouvernant la diversité des fonds marins côtiers. En considérant de multiples échelles spatiales et temporelles ainsi que différentes facettes de la diversité de ces communautés, l’objectif principal a été de fournir des connaissances permettant de mieux prédire les potentielles réponses des communautés benthiques face aux changements environnementaux à venir. Cette thèse s’inscrit en particulier dans un contexte de la menace de l’homogénéisation des fonds marins et de la disparition à large échelle des habitats biogéniques, réservoirs de biodiversité formés par des espèces fondatrices. La comparaison de deux de ces habitats, les herbiers de Zostères intertidaux et les bancs de mäerl subtidaux, à des sédiments dépourvus d’espèces fondatrices a mis en évidence le rôle fondamental de ces habitats biogéniques dans le maintien de la diversité et du fonctionnement des fonds marins à long-terme. Ils contrôlent profondément les dynamiques temporelles des communautés et leurs capacités de réponse aux variations des conditions environnementales, assurent une plus grande stabilité des structures spatiales des communautés à une échelle régionale. Ils semblent par-là essentiels au maintien à long-terme des fonctions écologiques auxquelles contribuent les espèces benthiques. Cependant, ce travail montre que ces espèces fondatrices opèrent selon des mécanismes différents et que les implications en terme de vulnérabilité des communautés sont donc aussi différentes. Cette étude montre enfin qu’au sein d’un habitat donné, la richesse locale des communautés est relativement stable dans l’espace et le temps et met en évidence le besoin de caractériser les variations de compositions de communautés pour guider les actions de conservations à larges échelles. À ce titre, et à l’échelle régionale, les variations de composition contribuent à une richesse taxinomique et fonctionnelle dans les sédiments dépourvus d’espèces fondatrices aussi importante que dans les habitats biogéniques.Ce résultat impose de réévaluer la valeur de conservation qui pourrait leur être attribué de part leur richesse locale limitée. Les suivis à grandes échelles spatiales et temporelles sont dans ce contexte essentiels pour fournir un lien entre les connaissances empiriques et théoriques existantes à des échelles locales, et les échelles supérieures auxquelles s’intéressent les politiques de conservation<br>This thesis takes advantage of long-term monitoring data covering a regional scale to better apprehend the maindrivers of the diversity of coastal seafloors. Through consideration of multiple spatial and temporal scales and different facets o fcommunity diversity, the main objective of this work was to provide a better predictive understanding of the responses of benthic communities to environmental changes. In particular, this thesis addressed the potential consequences of the on-going homogenisation of the seafloor and the global loss of biogenic habitats, havens of diversity made by foundation species. Through comparison of two such habitats, intertidal seagrass meadows and subtidal maerl beds, with bare sediment devoid of foundationspecies, this thesis has highlighted the key role of biogenicstructures for long-term maintenance of the diversity andfunctioning of benthic communities. Indeed, these habitats mediate the dynamics and responses of benthic communities to environmental conditions, ensure a greater stability of their spatial structures at regional scale, and appeared essential for the long-term maintenance of the ecological functions benthic invertebrates are associated with. This work also highlighted that foundation species may affect benthic communities through different mechanisms, and that has implications on the structure and vulnerability of these communities. Lastly, this the sisemphasized a strong spatial and temporal stability of community richness despite important underlying changes in composition and there by stressed the need to better characterise these compositional variations to guide conservation. These variations contributed, for instance, to an unexpectedly high taxonomic and functional richness of bare sediment at regional scale,similar to those of biogenic habitats, despite being locally depauperate. Overall, broad-scale monitoring programs are fundamental assets to bridge local empirical and theoretical ecological knowledge to the broader scales at which society manage and benefits from natural ecosystems

Mit dieser Arbeit ist weltweit zum ersten Mal die molekulare Dynamik von vereinzelten,d.h. einander nicht berührenden Polymerketten experimentell bestimmt worden. Die Grundlagen dafür sind einerseits die breitbandige dielektrische Spektroskopie mit ihrer außerordentlich hohen experimentellen Empfindlichkeit und andererseits die Weiterentwicklung einer speziellen Probenanordnung, bei der hochleitfähige Silizium-Elektroden durch elektrisch isolierende Siliziumdioxid-Nanostrukturen in einem vordefinierten Abstand gehalten werden und so den Probenkondensator bilden. Im Rahmen dieser Arbeit wurde die Höhe der Nanostrukturen (und damit des Elektrodenabstands) auf nur 35 nm reduziert. Damit gelang der Nachweis, dass selbst vereinzelte kondensierte Polymer-Knäuel - im Rahmen der Messgenauigkeit - dieselbe Segmentdynamik (bzw. denselben dynamischen Glasübergang), gemessen in ihrer mittleren Relaxationsrate, wie die makroskopische Schmelze („bulk“) aufweisen. Nur ein kleiner Anteil der Segmente zeigt eine langsamere Dynamik, was auf attraktive Wechselwirkungen mit dem Substrat zurückzuführen ist, wie komplementäre Untersuchungen mittels Infrarot-Spektroskopie zeigen. Zudem bieten diese Experimente die Möglichkeit, nach der dielektrischen Messung die mit Nanostrukturen versehene obere Elektrode zu entfernen und die Verteilung der vereinzelten Polymerketten, deren Oberflächenprofile und Volumen mit dem Rasterkraftmikroskop zu bestimmen. Erst damit gelingt der Nachweis, dass die Polymer-Knäuel im Mittel aus einer einzelnen Kette bestehen. Die Kombination dieser drei unabhängigen Messmethoden liefert ein schlüssiges und detailliertes Bild, gekennzeichnet dadurch, dass attraktive Oberflächenwechselwirkungen die Glasdynamik nur über ca. 0,5nm direkt beeinflussen. In einem zweiten Teil trägt die Arbeit mit der Untersuchung dünner Polymerschichten im Nanometer-Bereich zu einer international geführten, kontroversen Diskussion um die Frage, ob sich im Falle solcher räumlichen Begrenzungen der dynamische und kalorimetrische Glasübergang ändern, bei. Dabei zeigt mit den präsentierten dielektrischen und ellipsometrischen Messungen eine Kombination aus einer Methode, die im Gleichgewichtszustand misst und einer, die den Übergang in den Nichtgleichgewichtszustand bestimmt, dass sich sowohl Polystyrol-Schichten verschiedener Molekulargewichte bis zu einer Dicke von nur 5 nm als auch Polymethylmethacrylat-Schichten auf unterschiedlichen (hydrophilen und hydrophoben) Substraten bis zu einer Dicke von 10 nm weder in ihrem dynamischen noch ihrem kalorimetrischen Glasübergang von der makroskopischen Schmelze unterscheiden.:Inhaltsverzeichnis I Abbildungsverzeichnis III Tabellenverzeichnis V 1 Einleitung 1 2 Theoretische Grundlagen 5 2.1 Glasübergang und Glasdynamik . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.1.1 Kristallisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 2.1.2 Der kalorimetrische Glasübergang . . . . . . . . . . . . . . . . . . . 7 2.1.3 Der dynamische Glasübergang . . . . . . . . . . . . . . . . . . . . . 7 2.1.4 Theoretische Modelle . . . . . . . . . . . . . . . . . . . . . . . . . . 9 2.2 Polymere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11 2.2.1 Molekulare Struktur . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 2.2.2 Molekulare Dynamik . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 2.2.3 „Confinement effects“ - der Einfluss räumlicher Begrenzung . . . . . 19 2.3 Wechselwirkung von elektromagnetischen Feldern mit Materie . . . . . . . . 22 2.3.1 Polarisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 2.3.2 Elektrostatik . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 2.3.3 Dielektrische Relaxation und Retardation . . . . . . . . . . . . . . . 26 3 Material und Methoden 39 3.1 Experimentelle Methoden . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39 3.1.1 Dielektrische Spektroskopie . . . . . . . . . . . . . . . . . . . . . . . 39 3.1.2 Rasterkraftmikroskopie . . . . . . . . . . . . . . . . . . . . . . . . . 43 3.1.3 Ergänzende Methoden . . . . . . . . . . . . . . . . . . . . . . . . . . 46 3.2 Datenauswertung . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52 3.2.1 Analyse der dielektrischen Messungen . . . . . . . . . . . . . . . . . 52 3.2.2 Analyse der Rasterkraftmikroskopaufnahmen . . . . . . . . . . . . . 61 3.2.3 Verfahren zur Auswertung der ergänzenden Methoden . . . . . . . . 74 3.3 Probenmaterial . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 3.4 Probenpräparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.4.1 Präparation dünner Polymerfilme und vereinzelter Polymerknäuel . . 84 3.4.2 Probenkondensatoren mit nanostrukturierten Elektroden . . . . . . . 90 3.4.3 Aufdampfen von Elektroden . . . . . . . . . . . . . . . . . . . . . . . 95 3.4.4 Tempern . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 3.4.5 Besonderheiten der Präparation für die ergänzenden Methoden . . . 96 3.5 Reproduzierbarkeit . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98 3.5.1 Unerwünschte Veränderungen der Probe und Gegenmaßnahmen . . 98 3.5.2 Prüfung der Probenstabilität . . . . . . . . . . . . . . . . . . . . . . . 101 3.5.3 Partikelkontamination . . . . . . . . . . . . . . . . . . . . . . . . . . 102 4 Ergebnisse und Diskussion 105 4.1 Modellierung der dielektrischen Spektren . . . . . . . . . . . . . . . . . . . 105 4.1.1 Probenaufbau und Ersatzschaltbilder . . . . . . . . . . . . . . . . . . 106 4.1.2 Vergleich modellierter und gemessener Spektren . . . . . . . . . . . 111 4.1.3 Modell eines Polymer-Knäuels im Plattenkondensator . . . . . . . . . 119 4.1.4 Schlussfolgerungen . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 4.2 Dünne Polymerschichten . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127 4.2.1 Polystyrol-Schichten verschiedener Molekulargewichte . . . . . . . . 128 4.2.2 Polymethylmethacrylat-Schichten auf unterschiedlichen Substraten . 135 4.2.3 Literaturdiskussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138 4.2.4 Die präsentierten Ergebnisse im Kontext der Literatur . . . . . . . . . 155 4.3 Vereinzelte Polymer-Knäuel . . . . . . . . . . . . . . . . . . . . . . . . . . . 158 4.3.1 Charakterisierung der Oberfläche . . . . . . . . . . . . . . . . . . . . 158 4.3.2 Molekulare Dynamik . . . . . . . . . . . . . . . . . . . . . . . . . . . 166 4.3.3 Wechselwirkungen mit der Oberfläche . . . . . . . . . . . . . . . . . 170 4.3.4 Interpretation - das molekulare Bild . . . . . . . . . . . . . . . . . . 174 5 Zusammenfassung 177 A Übersicht der Messungen und Experimentatoren 181 Literaturverzeichnis 182 Publikationsliste 205 Danksagung 209 Lebenslauf 211 Selbstständigkeitserklärung 213

The marine industry has increased its adoption of pure-electric, diesel-electric, and other non-traditional propulsion architectures to reduce ship emissions and fuel consumption. While these technologies can improve performance, the design of a propulsion system becomes challenging, given that no single technology is superior across all vessel types. Furthermore, even identical ships with different operating patterns may be better suited to different propulsion technologies. Addressing this problem, previous research has shown that if key elements of a vessel's operational pro file are known, simulation and optimization techniques can be employed to evaluate multiple propulsion architectures and result in a better propulsion system design and energy management strategy for a given vessel. While these studies have demonstrated the performance improvements that can be achieved from optimizing clean marine propulsion systems, they rely on vessel operational profiles obtained through physical measurement from existing ships. From a practical point of view, the optimization of a vessel's propulsion system needs to occur prior to a vessel's construction and thus precludes physical measurement. To this end, this thesis introduces a marine simulation platform for producing vessel operational profiles which enable propulsion system optimization during the ship design process. Core subsystem modules are constructed for simulating ship motions in 3 degrees of freedom and result in operational profile time-series, including propulsion power. Data is acquired from a benchmark vessel to validate the simulation. Results show the proposed approach strikes a balance between speed, accuracy, and complexity compared with other available tools.<br>Graduate