New challenges in nanotechnology arise in the assembly of nanoobjects into three-dimensional superstructures, which may carry synergetic properties and open up new application fields. Within this new class of materials nanostructured, porous functional metals are of great interest since they combine high surface area, gas permeability, electrical conductivity, plasmonic behavior and size-enhanced catalytic reactivity. Even though a large variety of preparation pathways for the fabrication of porous noble metals has already been established, several limitations are still to be addressed by research developments. The new and versatile approach that is presented in this work makes use of a templatefree self-assembly process for the fabrication of highly porous, metallic nanostructures. Thereby, nanochains are formed by the controlled coalescence of noble metal NPs in aqueous media and their interconnection and interpenetration leads to the formation of a self-supported network with macroscopic dimensions. Subsequently, the supercritical drying technique is used to remove the solvent from the pores of the network without causing a collapse of the fragile structure. The resulting highly porous, low-weighted, three-dimensional nanostructured solids are named aerogels. The exceptional properties of these materials originate from the conjunction of the unique properties of nanomaterials magnified by macroscale assembly. Moreover, the combination of different metals may lead to synergetic effects regarding for example their catalytic activity. Therefore, the synthesis of multimetallic gels and the characterization of their structural peculiarities are in the focus of the investigations. In the case of the developed preparation pathways the gelation process starts from preformed, stable colloidal solutions of citrate capped, spherical noble metal (Au, Ag, Pt, Pd) NPs. In order to face various requirements several methods for the initiation of the controlled destabilization and coalescence of the nanosized building blocks were developed and synthesis conditions were optimized, respectively. Multimetallic structures with tunable composition are obtained by mixing different kinds of monometallic NP solutions and performing a joint gel formation. The characterization of the resulting materials by means of electron microscopy reveals the formation of a highly porous network of branched nanochains that provide a polycrystalline nature and diameters in the size range of the initial NPs. Furthermore, synthesis conditions for the spontaneous gel formation of glucose stabilized Au and Pd NPs were investigated. In order to gain a detailed knowledge of the structural properties of bimetallic aerogel structures a versatile set of characterization techniques was applied. A broad pore size distribution dominated by meso- and macropores and remarkably high inner surface areas were concluded from the N2 physisorption isotherms and density measurements. As investigated, a specific thermal treatment could be used to tune the ligament size of Au-Ag aerogels, whereas Au-Pd and Pt-Pd structures provide thermal stability under mild conditions. Further investigations aimed to the enlightenment of the elemental distribution and phase composition within the nanochains of multimetallic gel structures. The different approaches provide complementary and consistent results. Phase analyses based on XRD measurements revealed separated phases of each metal in the case of Ag-Pd and Au-Pd aerogels. They further proved the possibility of temperature induced phase modifications that lead to complete alloying of Au and Pd. In addition, separated domains of Pt and Pd were established from the EXAFS analysis of the corresponding aerogel. STEM EDX high resolution elemental mappings confirmed the separated domains of different metals in the case of Au-Pd and Pt-Pd aerogels. Moreover, a complete interdiffusion and alloy formation of Au and Ag within the corresponding aerogel structure is suggested from STEM EDX results. Finally, the presented investigations further promote the field of metallic aerogels by addressing the challenging issue of processability and device fabrication. Hybrid materials with organic polymers as well as various kinds of coatings on glass substrates and glassy carbon electrodes were prepared whereas the network structure was preserved throughout all processing steps. Moreover, it was illustrated that the NP-based aerogels carry metallic properties as expressed by their low Seebeck coefficients and high electrical conductivities.

No description available.

Zur Darstellung von Edelmetallnanopartikelüberstrukturen werden zunächst kolloidale Lösungen von Gold, Silber, Platin und Palladium synthetisiert. Dafür wird eine modifizierte Syntheseprozedur für Citrat stabilisierte Goldnanopartikel in wässriger Lösung unter Verwendung gleicher Konzentrationen auf die Systeme Silber, Platin und Palladium übertragen. Die Nanopartikellösungen werden mittels Absorptionsspektroskopie und Elektronenmikroskopie in mittlerer und hoher Auflösung charakterisiert. Die Platinnanopartikel werden verwendet, um mittels Keim vermitteltem Wachstum größere Platinnanopartikel darzustellen. Die resultierenden annähernd sphärischen Partikel haben eine sehr enge Größenverteilung mit einer Standardabweichung von drei bis sieben Prozent. Mit bis zu zwei Schritten des Keim vermittelten Wachstums können Partikel mit einem mittleren Durchmesser im Bereich von 10 bis 100 Nanometern hergestellt werden. Hochauflösende Elektronenmikroskopie zeigt, dass die Oberfläche der Partikel aus Platinkristalliten mit Durchmessern weniger Nanometer besteht, was zu einer Oberflächenrauhigkeit von drei bis zehn Nanometern führt. Mittels eines Kern-Schale-Modells werden Einzelteilchenextinktionsspektren berechnet, welche in sehr guter Übereinstimmung mit den experimentell bestimmten Extinktionsspektren des dispergierten Ensembles sind. Eine über weite Bereiche des sichtbaren Spektralbereichs lineare Abhängigkeit des Extinktionsmaximums vom Partikeldurchmesser wird beobachtet. Dadurch und zusammen mit der Einheitlichkeit der synthetisierten Platinsphären eröffnen sich Anwendungsmöglichkeiten im Bereich der Photonik, der Nanooptik und der oberflächenverstärkten Ramanspektroskopie. Geordnete Überstrukturen der Edelmetallnanopartikel können durch Infiltrieren von Templaten aus Block-Copolymer-Filmen mit wässriger Nanopartikellösung synthetisiert werden. In Abhängigkeit von der Vorbehandlung der Polymerfilme werden entweder zweidimensional periodische Anordnungen mit einer Periodizität von weniger als 30 Nanometern oder Fingerabdruck ähnliche Anordnungen mit einem Rillenabstand im selben Größenbereich hergestellt. Durch Entfernen des Polymers entstehen ein- bzw. zweidimensionale Anordnungen aus Platinnanodrähten bzw. -Nanopartikeln auf einem Siliziumwafer. Diese hochgeordneten Strukturen sind von fundamentalem Interesse für die Entwicklung von nanometerskaligen Schaltkreisen, Sensoren und als Substrate für die oberflächenverstärkte Ramanspektroskopie. Für die Herstellung ungeordneter Überstrukturen werden zwei unterschiedliche Ansätze gewählt: direkte Destabilisierung von Nanopartikellösungen, welche zu Hydrogelen und durch Trocknung zu Aerogelen führt, und Immobilisierung von Nanopartikeln auf einem in die Lösung implantierten Pilzmycel. Aus Gold-, Silber- und Platinnanopartikeln werden monometallische Hydro- und Aerogele synthetisiert. Unterschiedliche Destabilisierungsmittel sowie unterschiedliche Methoden zur Aufkonzentration der Nanopartikellösungen werden getestet. Abhängig von der Methode werden gelartige Überstrukturen mit teilweise komplexen Morphologien aus hierarchischen Anordnungen von Primär-, Sekundär-, Tertiärpartikeln beobachtet. Bimetallische Hydro- und Aerogele können aus Mischungen von Gold- oder Platin- mit Silbernanopartikellösungen hergestellt werden. Hochauflösende TEM-Aufnahmen zeigen ein polykristallines Netzwerk aus 2 bis 10 Nanometer dicken Drähten. Erste BET-Messungen zeigen, dass die Gold-Silber-Netzwerke eine Oberfläche von etwa 48 m2/g besitzen. Diese Systeme aus monometallischen und bimetallischen Nanopartikeln stellen erste Ansätze für hochporöse templatfreie Hydro- und Aerogele dar und besitzen großes Potential für den Einsatz in der heterogenen Gasphasenkatalyse, da fast die gesamte Oberfläche aus Übergangsmetall besteht. Es wird für eine Auswahl an unterschiedlichen Pilzen gezeigt, dass deren Wachstum direkt in den synthetisierten Nanopartikellösungen möglich ist. Ohne weitere Funktionalisierung findet eine Anlagerung von Nanopartikeln auf der Pilzoberfläche statt. Starke Variationen in den Affnitäten verschiedener Pilze zu den unterschiedlichen Metallnanopartikeln werden beobachtet. Auch werden Unterschiede der Nanopartikelaffnität mit Variation der Morphologie innerhalb desselben Hybridsystems beobachtet. Ein Platin-Pilz-Hybrid wird in wässriger Lösung erfolgreich als Katalysator einer Redoxreaktion getestet. Solche Hybridstrukturen besitzen ebenso wie die oben beschriebenen Aerogele großes Potential für den Einsatz in der heterogenen Katalyse, wobei die Verwendung von Pilzmycel als Trägermaterial eine kostengünstige Darstellung größerer Katalysatormengen ermöglichen könnte.

Denna studie undersöker de estetiska värderingarna av materialet trä i möbelproduktion och hur det påverkar materialåtgången. Tidigare forskning har främst undersökt träslaget furu och det estetiska urvalet som händer redan i träproduktion. Resultat i denna studie har visat att ett så homogent material som möjligt är att föredra, utan kvistar, färgförändring och ojämn fiberriktning. Större produktionsbolag ser till att spillmaterial som blir över efter sortering blir pappersmassa eller spån. Möbeltillverkare har inte resurser för att ge sitt spill ett andra liv utan eldar upp det. Liknande studier har kommit fram till att det finns estetiska preferenser på trä men inte hur man kan påverka konsumentens val. Hur kan man genom design förändra den estetiska värderingen kring valet av material och förhindra onödigt svinn? Syftet med detta projekt är att genom kritisk design belysa problematiken kring hur vi konsumerar material utifrån estetiska värderingar och konsekvenserna det medför. Kvalitativa metoder i form av expertintervjuer har gjorts för att samla information om hur möbelproducenter väljer sitt material utifrån estetiska preferenser. Resultatet påvisar att en möbel kan generera spill på upp till 70 procent av en planka. Ur ett hållbarhetsperspektiv är det viktigt att visa på de negativa följderna som kommer av att välja bort ett värdefullt material för att det inte är estetiskt tilltalande. / This study examines the aesthetic values of the material wood in furniture manufacturing and how it affects material consumption. Previous research has mainly examined the wood species pine and the aesthetic selection that occurs in wood production. Results in this study have shown that a homogeneous material as possible is preferable, without knots, irregular coloration, and uneven grain. Larger production companies ensure that waste material that remains after sorting becomes pulp or flakes. Furniture manufacturers do not have the resources to give their waste another life, instead they burning the wood for heat. Similar studies have concluded that there are aesthetic preferences on wood but not how to influence consumer choice. How can design change the aesthetic value of the choice of material and prevent unnecessary waste? The purpose of this project is to shed light on the problem of how we consume materials based on aesthetic values and the consequences it has through a critical design perspective. Qualitative methods in the form of expert interviews have been made to gather information on how furniture manufacturers choose their materials based on aesthetic preferences. The results show that a piece of furniture can generate wood waste up to 70 percent of a plank. From a sustainability perspective, it is important to point out the negative consequences that will opt out of a valuable material because it is not aesthetically pleasing.

В диссертационном исследовании рассматривается жилой квартал Дворянское гнездо, расположенный в микрорайоне Уралмаш города Екатеринбурга. Объект исследования - дворовая территория ансамбля, которая проанализирована с точки зрения качества и удобства пространства, комфортного ее использования всеми категориями проживающих граждан. Используя методику датского архитектора Яна Гейла выявлены проблемы комплекса по двенадцати критериям и предложены варианты их решений. Дана оценка жилого комплекса с точки зрения устойчивой архитектуры. Разработано концептуальное решение благоустройства прилегающей территории с учетом доступности для всех групп населения. Проведена оценка проекта по критериям устойчивости по системе экологической сертификации GreenZoom. В заключение о важности сохранения жилого фонда первой половины XX века, а также рассматривается вопрос о необходимости проведения реновации на территории общественного пространства Дворянского гнезда. / The dissertation research examines the residential quarter of the Noble Nest (Dvoryanskoe gnezdo), located in the Uralmash microdistrict of the city of Yekaterinburg. The object of the study is the courtyard area of the ensemble, which is analyzed from the point of view of the quality and convenience of space, its comfortable use by all categories of living citizens. Using the methodology of the Danish architect Jan Gale, the problems of the complex were identified according to twelve criteria and options for their solutions were proposed. An assessment of the residential complex from the point of view of sustainable architecture is given. A conceptual solution for the improvement of the adjacent territory has been developed, taking into account accessibility for all groups of the population. The project was evaluated according to sustainability criteria according to the Green Zoom environmental certification system. In conclusion, the importance of preserving the housing stock of the first half of the XX century, as well as the need for renovation on the territory of the public space of the Noble Nest (Dvoryanskoe gnezdo).

No description available.

Les viroles en acier microallié 18MND5, destinées aux générateurs de vapeur, présentent une composition hétérogène à plusieurs échelles. Un écart au procédé de fabrication ou une teneur en hydrogène excessive, peuvent conduire à la formation des Décohésions Dues à l’Hydrogène. Ces DDH résultent de la désorption de l’hydrogène interne lors du refroidissement jusqu’à température ambiante. La pression interne n’étant pas mesurables expérimentalement, une modélisation du phénomène est requise. Afin de préciser les mécanismes sous-jacents, il est proposé un scénario de formation de ces défauts s’appuyant conjointement sur une expertise et la modélisation des processus de diffusion-désorption-propagation. Les observations ont révélé une corrélation entre les DDH, les zones ségrégées et les amas de MnS (sites préférentiels d’initiation). Un modèle de diffusion dans un milieu hétérogène a été proposé afin d’évaluer la pression interne associée. La pression maximale excède ainsi 8600 bar en considérant une loi d’Abel-Noble optimisée du gaz réel. Le couplage de ce modèle avec la mécanique de la rupture a permis de quantifier l’évolution des paramètres relatifs à la propagation (pression interne, taille finale, vitesse, …). Un scénario de formation des DDH industriel a ainsi pu être formulé sur la base d’une étude paramétrique. Bien que les simulations préliminaires corroborent le retour d’expérience, le modèle raffiné et la prise en compte du gonflement de la DDH semblent sous-estimer la cinétique. Le caractère multi-fissuré des amas de MnS (homogénéisation des propriétés mécaniques) associé à un critère de rupture à l’échelle locale permettrait d’ajuster ce modèle. / Heat generators are manufactured from ingots of 18MND5 (A508cl3) low alloy steel and present composition heterogeneities at different scales. Under specific conditions (non-respect of guidelines or high initial content of H), Hydrogen Induced Cracks (HIC) may result from diffusion-desorption of internal hydrogen during cooling down to room temperature. Since neither hydrogen redistribution nor its internal pressure within cavities could be measured by experimental techniques, quantitative investigation is based on the modelling of related physical phenomena. A scenario of HIC formation, based on industrial feedback and modelling, has been proposed. A correlation between these defects, segregated areas and clusters of MnS (preferred initiation sites) has been revealed by expertise of HIC. A model of diffusion in heterogeneous alloys has then been proposed to assess the maximal pressure of H2 in such HIC. Simulation has shown that internal pressures above 860MPa are reached by considering an optimized Abel-Noble real gas behavior. The previous model has then been coupled to a failure mechanics procedure to characterize and quantify the crack growth parameters. Based on a parametric study, a scenario of HIC formation during the cooling has been proposed regarding process. Although results from preliminary simulations matched with feedback, the refined model based on the pressure induced elastic deformation of HIC has been developed but provided an underestimated kinetic of crack growth. Consequently, the multi-cracked nature of MnS clusters (homogenization of mechanical properties) and the updated local failure criterion appear to be a viable path to adjust predictions.

Cardinal Richelieu is traditionally accredited with defeating the power of the grands, the upper echelon of the French nobility, as part of his supposedly successful project for monarchical absolutism. Modern historians have recast Richelieu as a nobleman of his time, who advanced himself within the social and political hierarchies through marriage alliances and patronage. He therefore worked hard to forge alliances with the grands rather than trying to destroy them. Yet his ministry was riven by persistent noble conspiracies and rebellions, which have gone largely without systematic investigation. This study examines the nature and causes of that unrest during Richelieu’s final six years, offering a radical re-assessment of the opposition and the politics of the period. Noble conspiracy was not just a by-product of government by a first minister, but reflected the factional nature of Richelieu’s approach. Factional rivalry was exacerbated by the emergence, after 1638, of a struggle for the anticipated regency. After this, Richelieu took a more hostile approach to his adversaries, forcing them to adopt strong countermeasures in order to preserve their positions. Richelieu’s opponents were surprisingly successful in asserting their independence. As well as enjoying widespread domestic support, they allied with the Habsburg powers to engineer military rebellion, posing a major threat to the Cardinal and undermining the war effort against Spain. The Spanish set their stall out for a long-term war, expecting that Richelieu’s opponents would eventually gain power and negotiate peace on more flexible terms. The ability of the grands to re-assert themselves was still a dominant characteristic of French politics. Richelieu’s legacy, on his death in 1642, was a highly volatile political situation in which success was still a long way off for France. These findings suggest the catalytic impact of Habsburg power on France’s internal divisions, which should consequently be seen as integral to the forging of the ancien régime.

No description available.

Diploma thesis Power of the First Generations of the Ronov Noble Family and Their Position Within Czech Mediaeval Society was dealing with the position and power of the first three generations of the representatives of Ronov noblemen in the direct line towards Hynek from Dubá. In the prosopographical part of the thesis the lines of testimony were analysed and these proved clearly that the maximum of their court career was occurring during the reign of Wenceslaus the First. This maximum is also reflected in the other part of the thesis - which is the analysis of possession- holding. At the age of Wenceslaus the First Ronov noblemen built up a vast area of their particular possessions in Northern Bohemia and gradually they were developing colonisation of this region. Even though Ronov noble family did not take up any posts at the court, the exception is the position of Budysin administrator, they created a very tight connection to Premyslid kings due to the common childhood with Wenceslaus the First and they also supported him politically and also militarily in his inner and foreign policy. After the death of Castoslov from Zitava the position of power in the direct family line began to deteriorate, the peak of power was now for Lichtenburg family. The minimum of the court career comes after their left the...