Ziel dieser Arbeit war es, die mechanistischen Abläufe bei der Papierleimung mit ASA besser zu verstehen und weiter aufzuklären, um vor allem Wechselwirkungen mit Füllstoffen und anderen chemischen Additiven zu minimieren. Dazu sollten analytische Verfahrensmethoden entwickelt werden, welche die bilanztechnische Verfolgung von ASA und dessen Reaktionsprodukten ermöglichen, um anschließend den Einfluss und die Wechselwirkungen verschiedenster Parameter auf die ASA-Leimung untersuchen zu können. Weiterhin sollte bei Untersuchungen zur Emulgierung versucht werden, die wichtigsten Einflussgrößen auf die Partikelgröße, Stabilität und Hydrolyse des ASA aufzuzeigen. Im ersten Teil der Arbeit konnten bei den Untersuchungen zur Emulgierung wichtige Einflussgrößen auf die Partikelgröße, Stabilität und Hydrolyse von ASA-Emulsionen aufgeklärt werden. Weiterhin wurde eine Methode zur genauen Bestimmung der Reaktionskinetik der ASA-Hydrolyse sowie der Ablagerungsneigung entwickelt. Bei den Untersuchungen zur analytischen Bestimmung wurde über die NIR-Spektroskopie ein einfaches Analyseverfahren zur exakten quantitativen Bestimmung von ASA und AKD entwickelt. Es wurde gefunden, dass eine quantitative Erfassung von synthetischen Leimungsmitteln (ASA / AKD) mittels NIR in den Regionen der CH2-Schwingungen um 4300 cm-1 und 5750 cm-1 mit hoher statistischer Genauigkeit möglich ist. Der Methodenfehler für die Bestimmung von AKD liegt bei ± 0,010 % und bei ± 0,013 % für ASA. Dadurch ist eine wesentlich genauere Bewertung von Wechselwirkungen bei der Leimung als bisher möglich, da nicht nur die Leimungswirkung, sondern über NIR auch Menge und Art (gebunden / ungebunden) an Leimungsmittel in einer bisher nicht erreichbaren Messzeit betrachtet werden können. Mittels HPLC und Pyrolyse-GC/MS konnten die erstellten NIR-Kalibrationen erfolgreich validiert werden. Im letzten Teil der Arbeit wurden Wechselwirkungen von ASA mit Füllstoffen und chemischen Additiven aufgeklärt, sowie mechanistische Grundlagen zur Leimung mit ASA erarbeitet. Hier hat sich gezeigt, dass der Mechanismus der ASA-Leimung nicht nur, wie oft in der Literatur beschrieben, auf eine Veresterung mit den Hydroxylgruppen der Cellulose zurückzuführen ist. Vielmehr ist die optimale Wirkung von Leimungsmitteln sehr stark von deren Verteilung, Mobilität und Orientierung abhängig. Weiterhin konnte festgestellt werden, dass der größte Anteil des Leimungsmittels im Papier in ungebundener (hydrolisierter) Form vorliegt und somit zur Wanderung (Migration) durch das Papiergefüge befähigt ist. Trotzdem kann der hydrolisierte Anteil deutlich zur Hydrophobierung des Papiers beitragen, wenn dieser richtig orientiert und fein verteilt ist. Schlecht orientierte Leimungsmittel tragen nicht zur Leimung bei bzw. können diese sogar reduzieren. In der vorliegenden Arbeit wurden unter Einsatz moderner Methoden wichtige Grundlagen zur Papierleimung mit ASA erarbeitet. Dabei wurden insbesondere Beiträge zu den Themen Emulgierung, Hydrolyse- und Ablagerungsneigung, analytische Bestimmung, Wechselwirkungen sowie Mechanismen von ASA geleistet. Diese Ergebnisse zeigen Möglichkeiten auf, wie in Unternehmen der Papierindustrie zukünftig ASA-Leimungsmittel gezielter dosiert, Produktionsstörungen vermieden und Kosten reduziert werden können. / The purpose of this work was to develop a deeper understanding of the mechanisms in ASA sizing and to minimise interactions with fillers and other chemical additives. Therefore analytical test methods were developed, to enable a simple mass balance approach for ASA and its reaction products. Afterwards, the influence of various factors affecting ASA sizing and retention could be investigated and explained. Furthermore, the most important factors which influence particle size, stability, and hydrolysis of ASA emulsions had to be determined. In the first part of this work, studies regarding the emulsification of ASA were carried out. Here, the most important factors with regard to particle size, stability, and hydrolysis of ASA emulsions were investigated. Furthermore, a method for the exact determination of ASA hydrolysis as well as the agglomeration tendency was developed. For the investigations regarding the analytical determination, a fast and easy-to-use method for the quantification of ASA and AKD has been developed. The investigations have shown that a quantitative determination of synthetic sizing agents (ASA / AKD) is possible using NIR spectroscopy. With the help of multivariate data analysis and PLS regression, mainly the region of the CH2-bands around 4300 cm-1 and 5750 cm-1 were evaluated. The prediction error (RMSEP) for the determination of AKD is 0.01 %, and 0.013 % for ASA. Even an analysis of the percentage of bound and unbound ASA / AKD is possible by NIR spectroscopy of extracted paper samples. Thus, a fast and detailed investigation of mechanisms as regards sizing is possible. The developed NIR methods were validated using HPLC and Pyrolysis-GC/MS. In the last part of the work, interactions of ASA with fillers and chemical additives were investigated, and mechanisms of ASA sizing were studied. It was shown that the mechanism of ASA sizing - as often described in the literature - can not only be attributed to the esterification with the hydroxyl groups of the cellulose. In fact, the optimal effect of sizing agents is much more dependant on a fine distribution, mobility and orientation of ASA molecules. It was observed that the main part of the ASA is present in an unbound (hydrolysed) form and therefore is able to migrate through the paper structure. However, the hydrolysed ASA can significantly contribute to sizing when it is finely distributed and well orientated. Sizing agents orientated in the opposite do not contribute to sizing but they can even decrease the existing sizing level. To summarize, it can be concluded that, in this work important fundamentals as regards ASA sizing were developed using modern test methods. Thereby important contributions were made to the topics of emulsification, hydrolysis- and emulsion-stability, analytical determination, interactions and mechanisms of ASA. These results show possibilities how ASA sizing agents can be used more effectively, process disturbances avoided, and costs reduced.

This dissertation - The Yugoslavian model of Socialism as possible inspiration for economic reforms of the sixties in the German Democratic Republic, Czechoslovakia and Hungary - deals with the topic of creating certain modifications and specific features of the economic systems within the Eastern Bloc. The so called Yugoslavian experiment, which had developed in the Balcan state from the times of the Soviet-Yugoslavian rift of the late forties of last century, was, in fact, considered to be the only alternative to the predominant, directively centralized Soviet model for several years. It was in the sixties when many Eastern Bloc states, which practically hitherto copied the Soviet economic model, attempted to implement economic reforms which would assisst in eliminating disadvantages of the current economic system, and thus to stabilize and streamline the economic development. It is quite natural that for searching new possibilities and incentives, the Yugoslavian self-governing model represented one of potential inspiring ways how to reform the often nonfunctional economic systems. The main purpose of the dissertation is to show how the planners of economic reforms in the German Democratic Republic, Czechoslovakia and Hungary recfleted the Yugoslavian model tested in practice, and to which...

This document describes the possibilities of increasing the mechanical efficiency of the crank train of an internal-combustion engine. For this purpose, a concept with a reduced number of main bearings is chosen and its contribution is verified experimentally. The proposed solution consists of an innovative crankshaft design of a four-cylinder spark-ignition engine with only three main journal bearings and laser-welded sheet metal crank webs. The new design is compared to the mass-produced one in terms of friction losses, vibrations and loading of engine parts by means of simulations of crank train dynamics using the Multi-Body System. The increase in vibration, accompanied by a reduction in friction losses, is compensated by a torsional vibration damper and its effect is experimentally verified. Experimental research of laser welds on the crankshaft in terms of fatigue life is also described. The overall potential is also summarised and further possible development of this innovative and patented design is outlined.

The masters thesis with the name Nursery school and multifunctional building Želivec solves preparation and realization of building. The aim of masters thesis is to design of time, financial and material resources. The thesis contains budget, time schedule, building-site, technological standard, control and trial plan, assessment of lifting mechanism and study of realization of the main stages. The thesis is prepared on the basis of technical documents submitted by the designer. Part of the thesis is specialization.

Annually, about 40-60 million tons of postharvest straw are generated in Vietnam. Although considered as renewable resources and economic goods, straw is still burned in the field because there is no longer needed for cooking, roofing and fodder as before 1990s. The general economic development of the country and the rural area changed all the previous practices of using straw. This paper analyzes the socio-economic and technical causes of this phenomenon and summarizes the economic and environmentally friendly uses of rice straw in the future. In addition, it points out that policy failures in the management of straw currently exist and that policies for integrated straw management are needed to improve the value chain in the supply and consumption of straw products; to enhance the effectively use of this resource and minimize environmental pollution. / Hàng năm phát sinh khoảng 40-60 triệu tấn rơm sau thu hoạch ở Việt Nam. Mặc dù được coi là tài nguyên tái tạo và hàng hóa kinh tế, song rơm vẫn bị đốt bỏ ở ngoài ruộng do không còn nhu cầu nhiều cho đun nấu, lợp mái nhà và chăn nuôi như trước những năm 1990. Tình hình phát triển kinh tế chung của đất nước và khu vực nông thôn đã làm thay đổi tất cả thói quen dùng rơm rạ trước đây. Bài báo này phân tích một cảnh tổng quan những nguyên nhân kinh tế - xã hội và kỹ thuật dẫn đến hiện tượng này, tổng hợp những khả năng sử dụng kinh tế và thân thiện môi trường của rơm rạ trong tương lai. Ngoài ra chỉ ra những thất bại về chính sách trong quản lý rơm rạ hiện nay và cần có các chính sách quản lý tổng hợp rơm rạ để nâng cao chuỗi giá trị trong cung ứng và tiêu thụ các sản phẩm rơm rạ, tăng cường việc sử dụng có hiệu quả tài nguyên này và giảm thiểu ô nhiễm môi trường.

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The goal of my thesis on Supervision over the banking industry in the EU member states is to describe critically and to define newly engendering concept of the banking union. It is a very actual topic because the effective mechanism creation, which should solve problems of the European banking sector, is currently one of the primary goals of the European Union. The study is divided into three chapters. The first chapter is the theoretical one. The definition and differentiation of the essential terms such as supervision and surveillance can be found there. Further the basic theoretical modules can be found there, from which it is possible to stem during the banking supervision implementation in practice. The second and the third chapters are the analytical parts. The introduction of the second chapter glances at the backgrounds of the legislative proposals acceptance in this area. Afterwards the chapter is already focused on four pillars of the proposed Banking union. The first pillar is formed with so called "single rule book", thus the uniform regulatory rules that are the implementation of the requirements expressed in so called Basel III. In this part of the study there is outlined why it is not quite happy at present to burden the credit institutions in the European Union even more through...

Die vorliegende Arbeit beschäftigt sich mit der Oxygenierung von ungesättigten Kohlenwasserstoffen durch Übergansmetalle und katalytischer Oxidation von Olefinen und Aliphaten. Sie ist in die folgenden drei Teile gegliedert: 1. Matrixisolationsstudien zum System MnO3Cl/Allen: Das System Permanganylchlorid/Allen wurde in einer Argonmatrix durch Photolyse (546 nm) zu Reaktion gebracht. Die entstandenen Komplexe (O=)2MnCl(O=CCH2CH2) 37R und (O=)2MnCl(H2COCCH2) 38R wurden mit Hilfe der IR-Spektroskopie, Isotopenmarkierungs-Experimenten (18O, D) und DFT-Rechnungen (B3LYP/LANL2DZ) zweifelsfrei identifiziert und der Reaktionsmechanismus Hilfe von mit weiteren DFT-Rechnungen (B3LYP/6-311Gd) aufgeklärt. 2. Synthese eines neuen dinuklearen Vanadium-Silsesquioxan-Komplexes Silika geträgerte Vanadium-Komplexe sind vor allem als Katalysatoren für die Oxidation von Kohelnwasserstoffen interessant. Man geht davon aus, dass vor allem die tetraedrisch koordinierten VO4-Spezies für die katalytische Aktivität bzw. Selektivität verantwortlich sind. Da nur eine Vanada-Silsesquioxan-Modellverbindung bekannt war, wurden Versuche unternommen weitere zu synthetisieren. Es konnte eine neue Verbindung erhalten werden, die vollständig charakterisiert wurde und auf ihre katalytische Aktivität getestet wurde. 3. Quantenmechanische Rechnungen zur Lösung ausgewählter Fragestellungen des Systems Mo/Bi Mit Hilfe von DFT-Rechnungen wurden verschiedene Mo-Bi-Verbindungen, die im Rahmen der mechanistischen Aufklärung des SOHIO-Verfahrens durch Synthese von Modellverbindungen erhalten wurden, auf ihre besondere Bindungssituation hin untersucht. Dazu wurden unter anderem die Bader sowie die NBO-Analyse verwendet. / Submitted thesis deals with the oxygenation of unsaturated hydrocarbons by transition metals and catalytic oxidations of olefins and aliphats. It is divided into the following three parts: 1. Matrixisolationstudies of the system MnO3Cl/allene: The light-induced (546 nm) reaction of MnO3Cl with allene has been investigated in low-temperature argon matrices at 11 K. IR spectroscopic studies in combination with isotopic enrichment experiments (18O, D) and DFT calculations (B3LYP/LANL2DZ) allowed the identification of (O=)2MnCl(O=CCH2CH2), 37R, and (O=)2MnCl(H2COCCH2), 38R as products. First of all, possible ways for their formation are discussed qualitatively in the context of the literature available, and then quantitatively with the background of DFT data (B3LYP/6-311G(d)) obtained for starting materials, products, transition states and intermediates. Based on the results a reaction mechanism was proposed. 2. Synthesis of a novel dinuclear vanadium-silsesquioxane-complex Silica-supported vanadium complexes have attracted the interest as catalyst for the oxidation of hydrocarbons. Especially tetrahedrally coordinated VO4-Spezies are supposed as active/selective sites. To investigate the chemical behaviour and –properties of such species, Feher et al. synthesized a vanadium-silsesquioxane-complex in 1991 since silsesquioxanes are known to be excellent structural models for the silica surface. The synthesis and catalytic activity of a new complex, that was successfully synthesised, is reported here. 3. Quantum mechanical calculations for solving selected problems at Mo/Bi-systems. During the investigation of the reaction mechanism of the SOHIO-process some very unusual Mo-Bi-complexes could be isolated in the workgroup of Prof. Dr. Ch. Limberg. The bonding situation of four special complexes was analysed by means of calculations based of density functional theory (DFT) in combination with natural bond orbital analysis (NBO) respectively Bader-theory. 1

Gegenstand der Untersuchungen war die Reduktion von Stickoxiden (NOx und N2O) an verschiedenartig präparierten Eisenkatalysatoren (Fe-MF, Fe-beta, Fe-SBA-15). Die Katalysatoren wurden nach Synthese, Kalzinierung und Katalyse mittels EPR und UV/VIS-DRS charakterisiert, und darüber hinaus auch in-situ während des Kalzinierens. Isolierte Eisenspezies aggregieren im Verlauf der Kalzinierung bei 873 K. Sowohl höhere Heizraten beim Kalziniervorgang, als auch ein höheres Si/Al-Verhältnis des Trägermaterials verstärken die Neigung zur Aggregatbildung leicht. Die Verwendung des Katalysators für die SCR von NO führt zu weiterem Wachstum und zur Restrukturierung der FexOy-Cluster. Die Eisenkatalysatoren wurden weiterhin mittels in-situ Methoden (EPR, UV/VIS-DRS, FTIR) untersucht während der SCR von NO durch NH3 und Isobutan, der SCR von N2O mit CO, und im Strom der entsprechenden reinen Eduktgase. Die Ergebnisse korrelieren mit dem katalytischen Verhalten der Materialien. Verschiedene Fe3+-Spezies, welche sich durch ein unterschiedliches Redoxverhalten auszeichnen, wurden identifiziert. UV/VIS-Messungen erlauben die Schlußfolgerung, daß isolierte, oktaedrisch koordinierte Fe3+?Spezies leichter zu reduzieren sind als tetradrisch koordinierte. Im Gegensatz zu isoliertem Fe3+ lassen sich FexOx-Cluster leichter oxidieren als reduzieren, und verbleiben daher unter Reaktionsbedingungen trivalent. Durch ihr hohes Oxidationspotential kommt es, vor allem für die Reaktion mit Isobutan, zur unerwünschten Totaloxidation des Reduktanden. Der Anteil isolierter Fe3+ Spezies korreliert mit der Aktivität der Katalysatoren für die SCR von NO und N2O. Weiterhin hängt zumindest für die Reaktion zwischen N2O und CO der Reaktionsmechanismus von der Art der vorliegenden Eisenspezies ab: an isolierten Plätzen erfolgt die Reduktion des N2O an dem an Fe3+ gebundenen CO. An FexOy-Clustern hingegen läuft die Reaktion als Redoxprozeß (Fe3+ / Fe2+) unter Bildung eines radikalischen Intermediates O-. Der Einfluß der Porengeometrie des Trägermaterials auf die katalytische Aktivität wurde an Katalysatoren mit ähnlichem Eisengehalt und ähnlicher Art und Verteilung der Eisenspezies studiert (Fe-MFI, Fe-SBA-15). Die drastisch höhere Aktivität von Fe-MFI belegt, daß die Lokalisierung der aktiven Komponente in einer Pore mit passender Geometrie (Größe und Struktur) essentiell für die katalytischen Eigenschaften ist. Als weitere, die Aktivität stark beeinflussen Größe, wurde für die Reaktion von NO mit Ammoniak und auch mit Isobutan die Azidität identifiziert, die jedoch für die katalytische Zersetzung oder Reduktion mit N2O keine Rolle spielt. / The reduction of nitrogen oxides (NOx and N2O) was investigated over Fe-catalysts (Fe-MFI, Fe-beta and Fe-SBA-15) which were prepared by different methods have been analyzed by EPR and UV/VIS-DRS ex situ after synthesis, calcination and use in catalysis as well as in situ during calcination. It was found that aggregated species are formed at the expense of isolated Fe species upon calcination at 873 K, and that aggregate formation is slightly favored by calcination with higher heating rates as well as by high Si/Al ratio of the support. Use in SCR of NO leads to further growth and restructuring of FexOy clusters. These Fe-catalysts were studied by in situ EPR, in situ UV/VIS-DRS and in situ FT-IR spectroscopy during SCR of NO with NH3 or isobutane and during SCR of N2O with CO as well as during interaction with single feed components. The results were related to the catalytic behaviour. Different types of isolated Fe3+ sites with different reducibility were identified. Based on FT-IR results which revealed that NO reacts preferably with trivalent Fe, it is concluded that Fe3+ ions reduced under reaction conditions to Fe2+ do probably not contribute to catalytic activity. In general, the degree of steady-state Fe site reduction during NH3-SCR is markedly lower than during isobutane-SCR. This might be the reason for the lower activity of Fe-catalysts in the latter reaction. UV/VIS-DRS results suggest that isolated Fe3+ in octahedral coordination is easier reduced than tetrahedral Fe3+. In contrast to isolated Fe3+ species, FexOy clusters are much faster reoxidized than reduced and, thus, remain essentially trivalent under reaction conditions. Due to their higher oxidation potential, they cause undesired total oxidation of the reductant being much more severe in the case of isobutane. A correlation was found between the fraction of isolated Fe+3 sites in the catalysts and their activity for SCR of NO and N2O. The reaction mechanism of SCR of N2O with CO is Fe site dependent. Over isolated Fe sites, the reduction of N2O occurs via coordinated CO species on Fe3+ sites. The reaction over FexOy sites proceeds via a redox Fe3+/Fe2+ process with intermediate formation of O- radicals. The effect of pore geometry of the support on the catalytic activity was studied by comparing catalytic performance of Fe-MFI and Fe-SBA-15 which contain similar iron content and show similar nature and distribution of Fe species as evidenced by UV/VIS-DRS and EPR. Fe-MFI revealed to be much more active than Fe-SBA-15 in all reactions studied. This clearly illustrates that the confinement of the iron species in pores of suitable geometry (structure and size) is essential to originate their remarkable catalytic properties. Acidity is essential for SCR of NO with NH3 or isobutane but it is not mandatory for direct decomposition or SCR of N2O.

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