Fliesslochformen und Gewindefurchen in dünne Bleche und Rohre aus Kupfer und Kupferlegierungen

This thesis in Thermal Flow Drilling and Flowtap in thin metal sheet and pipes of copper and copper alloys had as objectives to know the comportment of copper and copper alloys sheet metal during the Thermal Flow Drill processes with normal tools, to know the best Speed and Feed machine data for the best bushing quality, to known the best Speed for Form Tapping processes and to know the best bush long in pure copper pipes for water solar interchange equipment. Thermal Flow Drilling (TFD) and Form Tapping (FT) is one of the research lines of the Institute of Production and Logistics (IPL) at University of Kassel. At December 1995, a work meeting of IPL, Santa Catarina University, Brazil, Buenos Aires University, Argentine, Tarapacá University (UTA), Chile members and the CEO of Flowdrill B.V. was held in Brazil. The group decided that the Manufacturing Laboratory (ML) of UTA would work with pure copper and brass alloys sheet metal and pure copper pipes in order to develop a water interchange solar heater. The Flowdrill BV Company sent tools to Tarapacá University in 1996. In 1999 IPL and the ML carried out an ALECHILE research project promoted by the DAAD and CONICyT in copper sheet metal and copper pipes and sheet metal a-brass alloys. The normal tools are lobed, conical tungsten carbide tool. When rotated at high speed and pressed with high axial force into sheet metal or thin walled tube generated heat softens the metal and allows the drill to feed forward produce a hole and simultaneously form a bushing from the displacement material. In the market exist many features but in this thesis is used short and longs normal tools of TFD. For reach the objectives it was takes as references four qualities of the frayed end bushing, where the best one is the quality class I. It was used pure copper and a-brass alloys sheet metals, with different thickness. It was used different TFD drills diameter for four thread type, from M-5 to M10. Similar to the Aluminium sheet metals studies it was used the predrilling processes with HSS drills around 30% of the TFD diameter (1,5 – 3,0 mm D). In the next step is used only 2,0 mm thick metal sheet, and 9,2 mm TFD diameter for M-10 thread. For the case of pure commercial copper pipes is used for ¾” inch diameter and 12, 8 mm (3/8”) TFD drill for holes for 3/8” pipes and different normal HSS drills for predrilling processes. The chemical sheet metal characteristics were takes as reference for the material behaviour. The Chilean pure copper have 99,35% of Cu and 0,163% of Zinc and the Chilean a-brass alloys have 75,6% of Cu and 24,0% of Zinc. It is used two German a-brass alloys; Nº1 have 61,6% of Cu, 36,03 % of Zinc and 2,2% of Pb and the German a-brass alloys Nº2 have 63,1% of Cu, 36,7% of Zinc and 0% of Pb. The equipments used were a HAAS CNC milling machine centre, a Kistler dynamometer, PC Pentium II, Acquisition card, TESTPOINT and XAct software, 3D measurement machine, micro hardness, universal test machine, and metallographic microscope. During the test is obtained the feed force and momentum curves that shows the material behaviour with TFD processes. In general it is take three phases. It was possible obtain the best machining data for the different sheet of copper and a-brass alloys thick of Chilean materials and bush quality class I. In the case of a-brass alloys, the chemical components and the TFD processes temperature have big influence. The temperature reach to 400º Celsius during the TFD processes and the a-brass alloys have some percents of Zinc the bush quality is class I. But when the a-brass alloys have some percents of Lead who have 200º C melting point is not possible to obtain a bush, because the Lead gasify and the metallographic net broke. During the TFD processes the recrystallization structures occur around the Copper and a-brass alloy bush, who gives more hardness in these zones. When the threads were produce with Form Tapping processes with Flowtap tools, this hardness amount gives a high limit load of the thread when hey are tested in a special support that was developed for it. For eliminated the predrilling processes with normal HSS drills it was developed a compound tool. With this new tool it was possible obtain the best machining data for quality class I bush. For the copper pipes it is made bush without predrilling and the quality class IV was obtained. When it is was used predrilling processes, quality classes I bush were obtained. Then with different HSS drill diameter were obtained different long bush, where were soldering with four types soldering materials between pipes with 3/8” in a big one as ¾”. Those soldering unions were tested by traction test and all the 3/8” pipes broken, and the soldering zone doesn’t have any problem. Finally were developed different solar water interchange heaters and tested. As conclusions, the present Thesis shows that the Thermal Flow Drilling in thinner metal sheets of cooper and cooper alloys needs a predrilling process for frayed end quality class I bushings, similar to thinner sheets of aluminium bushes. The compound tool developed could obtain quality class I bushings and excludes predrilling processes. The bush recrystalization, product of the friction between the tool and the material, the hardness grows and it is advantageous for the Form Tapping. The methodology developed for commercial copper pipes permits to built water solar interchange heaters.

Ferrocene-Based Pyridylphosphine Ligands – Coordination Chemistry of Group 10, 11 and 12 Metals

English: The present thesis describes the synthesis of 1,1’-ferrocendiyl-based pyridylphosphine ligands, the exploration of their fundamental coordination chemistry and preliminary experiments with selected complexes aimed at potential applications. One main aspect is the synthesis of the bidentate ferrocene-based pyridylphosphine ligands 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene, 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene and 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. A specific feature of these ligands is the ball-bearing like flexibility of the ferrocenebased backbone. An additional flexibility element is the rotation around the C–C single bonds. Consequently, the donor atoms can realise a wide range of positions with respect to each other and are therefore able to adapt to the coordination requirements of different metal centres. The flexibility of the ligand also plays a role in another key aspect of this work, which concerns the coordination mode, i. e. bridging vs. chelating. In addition to the flexibility, also the position of the donor atoms to each other is important. This is largely affected by the position of the pyridyl nitrogen (pyrid-2-yl vs. pyrid-3-yl) and the methylen group in 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene. Another interesting point is the combination of a soft phosphorus donor atom with a harder nitrogen donor atom, according to the HSAB principle. This combination generates a unique binding profile, since the pi-acceptor character of the P site is able to stabilise a metal centre in a low oxidation state, while the nitrogen sigma-donor ability can make the metal more susceptible to oxidative addition reactions. A P,N-donor combination can afford hemilabile binding profiles, which would be ideal for catalysis. Beyond 1,2-substituted ferrocene derivatives, which are quite successful in catalytic applications, 1,1’-derivatives are rather underrepresented. While a low-yield synthetic pathway to 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene was already described in the literature [I. R. Butler, Organometallics 1992, 11, 74.], it was possible to find a new, improved and simplified synthetic pathway. Both other ligands were unknown prior to this work. Satisfactory results in the synthesis of 1-(Pyrid-3-yl)-1’-diphenylphosphinoferrocene could be achieved by working in analogy to the new synthetic procedure for 1-(Pyrid-2-yl)-1’-diphenylphosphinoferrocene. The synthesis of 1-[(Pyrid-2-yl)methyl]-1’-diphenylphosphinoferrocene has been handled by the group of Prof. Petr Stepnicka from Charles University, Prague, Czech Republic. The synthesis of tridentate ligands with an analogous heterodentate arrangement, was investigated briefly as a sideline of this study. The major part of this thesis deals with the fundamental coordination chemistry towards transition metals of the groups 10, 11 and 12. Due to the well-established catalytic properties of analogous palladium complexes, the coordination chemistry towards palladium (group 10) is of particular interest. The metals zinc and cadmium (group 12) are also of substantial importance because they are redox-inert in their divalent state. This is relevant in view of electrochemical investigations concerning the utilisation of the ligands as molecular redox sensors. Also mercury and the monovalent metals silver and gold (group 11) are included because of their rich coordination chemistry. It is essential to answer questions concerning aspects of the ligands’ coordination mode bearing in mind the HSAB principle.

Many-body theory of laser-induced ultrafast demagnetization and angular momentum transfer in ferromagnetic transition metals

An electronic theory is developed, which describes the ultrafast demagnetization in itinerant ferromagnets following the absorption of a femtosecond laser pulse. The present work intends to elucidate the microscopic physics of this ultrafast phenomenon by identifying its fundamental mechanisms. In particular, it aims to reveal the nature of the involved spin excitations and angular-momentum transfer between spin and lattice, which are still subjects of intensive debate. In the first preliminary part of the thesis the initial stage of the laser-induced demagnetization process is considered. In this stage the electronic system is highly excited by spin-conserving elementary excitations involved in the laser-pulse absorption, while the spin or magnon degrees of freedom remain very weakly excited. The role of electron-hole excitations on the stability of the magnetic order of one- and two-dimensional 3d transition metals (TMs) is investigated by using ab initio density-functional theory. The results show that the local magnetic moments are remarkably stable even at very high levels of local energy density and, therefore, indicate that these moments preserve their identity throughout the entire demagnetization process. In the second main part of the thesis a many-body theory is proposed, which takes into account these local magnetic moments and the local character of the involved spin excitations such as spin fluctuations from the very beginning. In this approach the relevant valence 3d and 4p electrons are described in terms of a multiband model Hamiltonian which includes Coulomb interactions, interatomic hybridizations, spin-orbit interactions, as well as the coupling to the time-dependent laser field on the same footing. An exact numerical time evolution is performed for small ferromagnetic TM clusters. The dynamical simulations show that after ultra-short laser pulse absorption the magnetization of these clusters decreases on a time scale of hundred femtoseconds. In particular, the results reproduce the experimentally observed laser-induced demagnetization in ferromagnets and demonstrate that this effect can be explained in terms of the following purely electronic non-adiabatic mechanism: First, on a time scale of 10–100 fs after laser excitation the spin-orbit coupling yields local angular-momentum transfer between the spins and the electron orbits, while subsequently the orbital angular momentum is very rapidly quenched in the lattice on the time scale of one femtosecond due to interatomic electron hoppings. In combination, these two processes result in a demagnetization within hundred or a few hundred femtoseconds after laser-pulse absorption.