Universiẗat, Diss., 2004--Stuttgart.

Universiẗat, Diss., 2005--Bonn.

Techn. University, Diss., 2005--Dresden.

Universiẗat, Diss., 2005--Bielefeld.

Techn. Universiẗat, Diss., 2005--Berlin.

Universiẗat, Diss., 2005--Düsseldorf.

Zu Beginn der Arbeit werden thermodynamische, strukturelle und statistische Grundlagen und Modelle wiedergegeben, die einerseits Entmischungssysteme und andererseits flüssige Ober- und Grenzflächen betreffen. Hieran schließt sich eine umfangreiche Darstellung der Meßmethode an, die die theoretischen Zusammenhänge für die Beschreibung der Formen flüssiger Grenzflächen sowie eine Darstellung aller experimentell möglichen Kraftmeßkurven und deren Auswertung beinhaltet. Weiterhin folgt die Darstellung der Dichte-, Dichtedifferenz-, und Grenzflächenspannungsmeßergebnisse separat für die Systeme Ga-Hg, Ga-Pb, Al-Pb und Al-In. Die Temperaturabhängigkeit und die Absolutwerte der Grenzflächenspannung werden mit den vorgestellten Modellen verglichen. Im Anschluß daran werden die Oberflächenspannungsmeßergebnisse für das System Ga-Pb vorgestellt, dies geschieht unter Bezugnahme auf Benetzungsphänomene, Adsorptionserscheinungen und Keimbildungsprozesse. In einem relativ selbständigen Kapitel am Ende der Arbeit werden experimentelle Ergebnisse zur Durchmischung und Entmischung wiedergegeben und mit theoretischen Ergebnissen zum diffusionsgesteuerten Durchmischungsprozeß verglichen.

In this thesis, novel bulk Al-based alloys with high content of Al have been produced by powder metallurgy methods from amorphous and partially amorphous materials. Different processing routes, i.e. mechanical alloying of elemental powder mixtures, controlled pulverization of melt-spun glassy ribbons and gas atomization, have been employed for the production of the Al-based powders. Among the different processing routes, gas atomization is the best choice for the production of Al-based amorphous and partially amorphous powders as precursors for the subsequent consolidation step because it allows the production of large quantities of powders with homogeneous properties (e.g. structure and thermal stability) along with a uniform size distribution of particles. Amorphous and nanocrystalline powders have to be consolidated to achieve dense bulk specimens. However, consolidation of these phases is not an easy task and special care has to be taken with respect to accurate control of the consolidation parameters in order to achieve dense bulk specimens without inducing undesirable microstructural transformations (e.g. crystallization and grain coarsening) or insufficient particle bonding. Consequently, the effect of temperature on viscosity as well as on phase formation has been studied in detail in order to select the proper consolidation parameters. Following their characterization, the Al-based powders have been consolidated into bulk specimens by hot pressing (HP), hot extrusion and spark plasma sintering (SPS) and their microstructure and mechanical properties have been extensively investigated. Consolidation into highly-dense bulk samples cannot be achieved without extended crystallization of the glassy precursors. Nevertheless, partial or full crystallization during consolidation leads to remarkable mechanical properties. For example, HP Al84Gd6Ni7Co3 samples display a remarkably high strength of about 1500 MPa, which is three times larger than the conventional high-strength Al-based alloys, along with a limited but distinct plastic deformability (3.5 – 4%). Lower strength (930 MPa) but remarkably larger plastic strain exceeding 25 % has been achieved for the Al87Ni8La5 gas-atomized powders consolidated by SPS above their crystallization temperature. Similarly, HP Al90.4Y4.4Ni4.3Co0.9 bulk samples display high compression strength ranging between 820 and 925 MPa combined with plastic strain in the range 14 – 30%. Finally, preliminary tensile tests for the Al90.4Y4.3Ni4.4Co0.9 alloy reveal promising tensile properties comparable to commercial high-strength Al-based alloys. The mechanical behavior of the consolidated specimens is strictly linked with their microstructure. High strength and reduced plasticity are observed when a residual amorphous phase is present. On the other hand, reduced strength but enhanced plastic deformation is a result of the complete crystallization of the glass and of the formation of a partially or fully interconnected network of deformable fcc Al. These results indicate that the combined devitrification and consolidation of glassy precursors is a particularly suitable method for the production of Al-based materials characterized by high strength combined with considerable plastic strain. Through this method, the mechanical properties of the consolidated samples can be varied within a wide range of strength and ductility depending on the microstructure and the consolidation techniques used. This might open a new route for the development of innovative high-performance Al-based materials for transport applications.

Zu Beginn der Arbeit werden thermodynamische, strukturelle und statistische Grundlagen und Modelle wiedergegeben, die einerseits Entmischungssysteme und andererseits flüssige Ober- und Grenzflächen betreffen. Hieran schließt sich eine umfangreiche Darstellung der Meßmethode an, die die theoretischen Zusammenhänge für die Beschreibung der Formen flüssiger Grenzflächen sowie eine Darstellung aller experimentell möglichen Kraftmeßkurven und deren Auswertung beinhaltet. Weiterhin folgt die Darstellung der Dichte-, Dichtedifferenz-, und Grenzflächenspannungsmeßergebnisse separat für die Systeme Ga-Hg, Ga-Pb, Al-Pb und Al-In. Die Temperaturabhängigkeit und die Absolutwerte der Grenzflächenspannung werden mit den vorgestellten Modellen verglichen. Im Anschluß daran werden die Oberflächenspannungsmeßergebnisse für das System Ga-Pb vorgestellt, dies geschieht unter Bezugnahme auf Benetzungsphänomene, Adsorptionserscheinungen und Keimbildungsprozesse. In einem relativ selbständigen Kapitel am Ende der Arbeit werden experimentelle Ergebnisse zur Durchmischung und Entmischung wiedergegeben und mit theoretischen Ergebnissen zum diffusionsgesteuerten Durchmischungsprozeß verglichen.

Polymer electrolyte fuel cells (PEFCs) have emerged as a promising renewable emission-free technology to solve the worldwide increasing demand for clean and efficient energy conversion. Despite large efforts in academia and automotive industry, the commercialization of PEFC vehicles still remains a great challenge. Critical issues are high material costs, insufficient catalytic activity as well as longterm durability. Especially due to the sluggish kinetics of the oxygen reduction reaction (ORR), high Pt loadings on the cathode are still necessary which leads to elevated costs. Alloys of Pt with other less precious metals (Co, Ni, Fe, Cu, etc.) show improved ORR activities compared to pure Pt catalysts. However, state-of-the-art carbon-supported catalysts suffer from severe Pt and carbon corrosion during the standard operation of PEFCs, affecting their reliability and long-term efficiency. Multimetallic aerogels constitute excellent candidates to overcome these issues. Due to their large open pores and high inner surface areas combined with electrical conductivity, they are ideal for applications in electrocatalysis. In addition, they can be employed without any catalyst support. Therefore, the fabrication of bimetallic Pt-M (M=Ni, Cu, Co, Fe) aerogels for applications in fuel cell catalysis was the focus of this thesis. Based on a previously published synthesis for Pt–Pd aerogels, a facile one-step procedure at ambient conditions in aqueous solution was developed. Bimetallic aerogels with nanochain diameters of as small as 4 nm and Brunauer-Emmett-Teller (BET) surface areas of up to 60 m2/g could be obtained. Extensive structure analysis of Pt–Ni and Pt–Cu aerogels by powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy (STEM-EDX) and electrochemical techniques showed that both metals were predominantly present in their metallic state and formed homogeneous alloys. However, metal (hydr)oxide byproducts were observed in aerogels with higher contents of non-precious metal (>25 %). Moreover, electronic and geometric structures were similar to those of carbon-supported Pt alloy catalysts. As a result, ORR activites were comparable, too. A threefold improvement in surface-specific activity over Pt/C catalysts was achieved. The mass-specific activites met or exceeded the U.S. Department of Energy (DOE) target for automotive PEFC applications. Furthermore, a direct correlation between non-precious metal content in the alloy and ORR activity was discovered. Aerogels with nonprecious metal contents >25% turned out to be susceptible to dealloying in acid leaching experiments, but there was no indication for the formation of extended surface structures like Pt-skeletons. A Pt3Ni aerogel was successfully employed as the cathode catalyst layer in a differential fuel cell (1 cm2), which is a crucial step towards technical application. This was the first time an unsupported metallic aerogel was implemented in a PEFC. Accelerated stress tests that are usually applied to investigate the support stability of fuel cell catalysts revealed the excellent stability of Pt3Ni alloyed aerogels. In summary, the Pt alloy aerogels prepared in the context of this work have proven to be highly active oxygen reduction catalysts with remarkable stability.