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.

Structural insights into the allosteric activation mechanism of cGMP-dependent protein kinase I

Cyclic GMP-dependent protein kinase (PKG) is a key transducer in the NO-cGMP signaling pathway. In this line, PKG has been considered an important drug target for treating hypertensive cardiovascular and pulmonary diseases. However, the investigation of PKG’s allosteric activation mechanism has been hampered by a lack of structural information. One of the fundamental questions on the cGMP-dependent activation of PKG is how the enzyme can distinguish cGMP over cAMP and selectively respond to cGMP. To ensure proper signaling, PKG must have developed unique features to ensure its activation upon the right activation signal. In this thesis, the cGMP-selective activation mechanism of PKG was studied through determining crystal structures of three truncated constructs of the regulatory domain [CNB-A (92-227), CNB-B (271-369), and CNB-A/B (92-351)] of PKG Iβ in the absence or presence of cyclic nucleotides. Herein, two individual CNB domain structures with biochemical data revealed that the C-terminal CNB domain (CNB-B) is responsible for cGMP selectivity, while the N-terminal CNB-domain (CNB-A) has a higher binding affinity for both cGMP and cAMP without showing any selectivity. Based on these crystal structures, mutagenesis studies were performed in which the critical residues for cyclic nucleotide selectivity and activation were identified. Furthermore, we discovered that the conformational changes of the C-terminal helix of the CNB-B that bridges between the regulatory and catalytic domains including the hydrophobic capping interaction are crucial for PKG activation. In addition, to observe the global conformation of the activated R-domain, I solved a co-crystal structure of the CNB-A/B with cGMP. Although a monomeric construct was crystallized, the structure displays a dimer. Strikingly, the CNB-A domain and its bound cGMP provide a key interface for this dimeric interaction. Using small angle X-ray scattering (SAXS), the existence of the cGMP-mediated dimeric interface within the CNB domains was confirmed. Furthermore, measuring cGMP-binding affinities (EC50) of the dimeric interface mutants as well as determining activation constants (Ka) revealed that the interface formation is important for PKG activation. To conclude, this thesis study provides a new mechanistic insight in PKG activation along with a newly found interface that can be targeted for designing PKG-specific activity modulators.

Surface modifications of nanocrystalline diamond films and their functionalization with phthalocyanines

Boron-doped diamond is a promising electrode material for a number of applications providing efficient carrier transport, a high stability of the electrolytic performance with time, a possibility for dye-sensitizing with photosensitive molecules, etc. It can be functionalized with electron donor molecules, like phthalocyanines or porphyrins, for the development of light energy conversion systems. For effective attachment of such molecules, the diamond surface has to be modified by plasma- or photo-chemical processes in order to achieve a desired surface termination. In the present work, the surface modifications of undoped and boron-doped nanocrystalline diamond (NCD) films and their functionalization with various phthalocyanines (Pcs) were investigated. The NCD films have been prepared by hot filament chemical vapor deposition (HFCVD) on silicon substrates and were thereafter subjected to modifications with O2 or NH3 plasmas or UV/O3 treatments for exchange of the H-termination of the as-grown surface. The effectiveness of the modifications and their stability with time during storage under different ambients were studied by contact angle measurements and X-ray photoelectron spectroscopy (XPS). Furthermore, the surface roughness after the modifications was investigated with atomic force microscopy (AFM) and compared to that of as-grown samples in order to establish the appearance of etching of the surface during the treatment. The as-grown and the modified NCD surfaces were exposed to phthalocyanines with different metal centers (Ti, Cu, Mn) or with different side chains. The results of the Pc grafting were investigated by XPS and Raman spectroscopy. XPS revealed the presence of nitrogen stemming from the Pc molecules and traces of the respective metal atoms with ratios close to those in the applied Pc. In a next step Raman spectra of Ti-Pc, Cu-Pc and Mn-Pc were obtained with two different excitation wavelengths (488 and 785 nm) from droplet samples on Si after evaporation of the solvent in order to establish their Raman fingerprints. The major differences in the spectra were assigned to the effect of the size of the metal ion on the structure of the phthalocyanine ring. The spectra obtained were used as references for the Raman spectra of NCD surfaces grafted with Pc. Finally, selected boron doped NCD samples were used after their surface modification and functionalization with Pc for the preparation of electrodes which were tested in a photoelectrochemical cell with a Pt counter electrode and an Ag/AgCl reference electrode. The light sources and electrolytes were varied to establish their influence on the performance of the dye-sensitized diamond electrodes. Cyclic voltammetry measurements revealed broad electrochemical potential window and high stability of the electrodes after several cycles. The open circuit potential (OCP) measurements performed in dark and after illumination showed fast responses of the electrodes to the illumination resulting in photocurrent generation.