[NiFe] hydrogenases are metalloenzymes that act as highly efficient molecular electrocatalysts for the interconversion of protons and molecular hydrogen. Unlike any other known molecular electrocatalyst, the members of a subgroup of respiratory membrane-bound [NiFe] hydrogenases are able to maintain H₂ catalysis in the sustained presence of O₂. This O₂-tolerance depends on the ability to respond to oxidative inactivation by O₂ by exclusively forming rapidly reactivated active site states, thus implying a catalytic cycle in which O₂ acts as a competing substrate to H₂. Using isotope ratio mass spectrometry it is proven that the O2-tolerant Escherichia coli Hydrogenase 1 responds to O₂ attack by acting as a four-electron oxidoreductase, catalysing the reaction 2 H₂ + O₂ → 2 H₂O, equivalent to hydrogen combustion. Special features of the enzyme’s electron relay system enable delivery of the required electrons. A small fraction of the H₂O produced arises from side reactions proceeding via reactive oxygen species, an unavoidable consequence of the presence of low-potential relay centres that release electrons from H₂ oxidation. While the ability to fully reduce O₂ to harmless H₂O at the active site to generate the rapidly reactivated state Ni-B, determines if a hydrogenase is O₂-tolerant, the ratio of oxidative inactivation to reductive reactivation rates determines how tolerant the enzyme is. It is shown by protein film electrochemistry that the (αβ)₂ dimeric assembly of Hyd-1 plays an important role in O₂-tolerance by aiding reactivation of one catalytic unit through electron transfer from the other. The teamwork between two redundant partners implicates a new role for dimerisation and represents a new example of cooperativity in biology. Finally, the non-natural amino acid p-azido-L-phenylalanine was synthesised and incorporated into Hyd-1, testing the possibility of introducing labels at specific sites.

The aim of this work was to investigate the effects that a magnetic field can induce during the electrodeposition of Ni and Ni-Fe alloys. Special regard was given to mass transport controlled effects. Magnetic field effects on the nucleation and growth of ferromagnetic layers and on the properties of electrodeposited layers (like grain size, texture, morphology or roughness) were investigated. The influence of a magnetic field on the magnetic properties of Ni layers and on the composition of Ni-Fe alloys was also studied. Nucleation and growth of thin Ni layers on gold electrodes under a superimposed magnetic field were analysed in-situ with the Electrochemical Quartz Crystal Microbalance technique. Three theoretical models were chosen for characterizing the Ni nucleation: Scharifker-Hills (SH), Scharifker-Mostany (SM) and Heerman-Tarallo (HT). The AFM images proved that more nuclei appear in a magnetic field in the case that the Lorentz force and the natural convection act in the same direction. From all the models, the HT model gave the best agreement with the AFM results. When the Lorentz force and the natural convection act in the same direction, an increase of the Ni partial current with the magnetic field was obtained. When they act in opposite directions, the Ni current was influenced just at the beginning of deposition (first 10 seconds). At longer times, the magnetic field has no effect on the Ni current. However, the total current (jNi+jHER) decreases with the magnetic field. In the absence of a macroscopic MHD convection, the Ni current decreases with the magnetic field the first 10-15 seconds of deposition. On longer time scales no influence of the magnetic field could be noticed for this configuration. When the magnetic field was applied perpendicular to the electric current, an increase of the hydrogen evolution reaction (HER) with the magnetic flux density was noticed. Hydrogen reduction is mass transport controlled. Therefore, the magnetic field will increase the limiting current of the HER. Optical microscopy images showed that the hydrogen bubbles were circular in the absence of the MHD convection and that they presented a tail when a Lorentz force was present. The direction of the tail depends on the net force induced by the natural and MHD convections. The interplay between the natural and MHD convections proved to be important during Ni-Fe alloy deposition, too. When the Lorentz force and the natural convection act in the same direction, an increase of the Fe content of the alloys with the magnetic field was observed. When the Lorentz force was perpendicular to the natural convection, no significant changes were observed in the composition of the layers. The alloy composition did not change with the magnetic field when the electric current was parallel to the magnetic field lines. Two surfactants were used in the case that Ni was electrodeposited from a sulfamate bath: SDS and sulfirol 8. The Ni layers obtained from a sulfamate bath with sulfirol 8 presented larger grains compared to the layers deposited from a bath free of surfactants. This increase of the grain size was attributed to the incorporation of the surfactant in the deposit. Coarser layers were obtained in a magnetic field (applied perpendicular to the electric current) when the electrodeposition was done from an electrolyte with surfactants. The number of grains increased with the magnetic field for the Ni layers electrodeposited from a bath free of surfactants and for a bath with SDS. As a consequence, the grain size decreased. In the case of the electrolyte with sulfirol 8, the number of grains decreased with the magnetic field, and their size increased. For the Ni-Fe alloys, which contained less than 10 at% Fe, the preferred crystalline orientation changes from (220), in the absence of a magnetic field, to (111), (when the magnetic field was applied perpendicular to the electric current). When the magnetic field lines were parallel to the electric current, both the (111) and (220) textures were preferred in almost the same proportion. As a general conclusion of this work it can be said that by choosing the right experimental condition, one can improve the morphology and the properties of the deposited layers by applying a magnetic field. At the same time, the mass transport processes can be influenced by a magnetic field.

No description available.

Development of microsized batteries plays an important role in the design of in-situ electrochemical investigation systems and portable/wearable electronics. This emerging field intimately correlates with the topics of rechargeable batteries, nanomaterials, on-chip microfabrication, flexibility with reliable mechanical properties etc. Among the various energy materials, conversion-type materials have been proposed as high-energy-density alternatives to traditional intercalation-based materials. However, these materials usually show complex reaction processes accompanied by multi-reaction intermediates, which poses a great challenge to understand the chemical mechanisms. Benefiting from the merits of microsized battery devices, we develop a novel strategy to investigate and then optimize the electrochemical performance of a specific conversion-type material: nickel-iron oxide (NFO). Subsequently, this kind of materials are employed for flexible minimized energy storage systems. Unlike traditional characterization methods based on slurry-coated electrodes, micro-platforms directly probe the intrinsic electrochemical properties of a single active material in real-time due to the elimination of other additives. In this thesis, we firstly design a micro-lithium batteries (MLBs), based on a single “Swiss-roll” microtubular nanomembrane electrode. This platform enables us to investigate the electrochemical mechanisms of electrode materials in lithium batteries by in-situ Raman spectroscopy, electrical conductivity measurements, and electrochemistry characterization. With this designed MLBs, we systematically studied NFO nanomembranes. Using in-situ Raman spectroscopy during the delithiation/lithiation process, we monitored the transition of the chemical component directly. Guided by our investigations of micro-batteries, composite NFO nanomembrane electrodes were fabricated and tested in coin cells, which showed an excellent rate performance: 440 mAh g-1 at a high rate of 20 A g-1 and a long-term stable cycling performance over 1600 cycles. One step further, a flexible energy storage micro-device is achieved using such optimized materials. We demonstrate a thin, lightweight, and flexible micro-full lithium-ion battery based on nickel-iron oxide with a high-rate performance and energy density that can be repeatedly bent to 180° without structural failure and performance loss. It delivers a stable output capacity of 140 mAh g-1 over 1000 charge/discharge cycles. Meanwhile, the excellent rate performance guarantees high energy output up to 255 W h kg-1 at a high power density of 12000 W kg-1 at the microscale.

The aim of this work was to investigate the effects that a magnetic field can induce during the electrodeposition of Ni and Ni-Fe alloys. Special regard was given to mass transport controlled effects. Magnetic field effects on the nucleation and growth of ferromagnetic layers and on the properties of electrodeposited layers (like grain size, texture, morphology or roughness) were investigated. The influence of a magnetic field on the magnetic properties of Ni layers and on the composition of Ni-Fe alloys was also studied. Nucleation and growth of thin Ni layers on gold electrodes under a superimposed magnetic field were analysed in-situ with the Electrochemical Quartz Crystal Microbalance technique. Three theoretical models were chosen for characterizing the Ni nucleation: Scharifker-Hills (SH), Scharifker-Mostany (SM) and Heerman-Tarallo (HT). The AFM images proved that more nuclei appear in a magnetic field in the case that the Lorentz force and the natural convection act in the same direction. From all the models, the HT model gave the best agreement with the AFM results. When the Lorentz force and the natural convection act in the same direction, an increase of the Ni partial current with the magnetic field was obtained. When they act in opposite directions, the Ni current was influenced just at the beginning of deposition (first 10 seconds). At longer times, the magnetic field has no effect on the Ni current. However, the total current (jNi+jHER) decreases with the magnetic field. In the absence of a macroscopic MHD convection, the Ni current decreases with the magnetic field the first 10-15 seconds of deposition. On longer time scales no influence of the magnetic field could be noticed for this configuration. When the magnetic field was applied perpendicular to the electric current, an increase of the hydrogen evolution reaction (HER) with the magnetic flux density was noticed. Hydrogen reduction is mass transport controlled. Therefore, the magnetic field will increase the limiting current of the HER. Optical microscopy images showed that the hydrogen bubbles were circular in the absence of the MHD convection and that they presented a tail when a Lorentz force was present. The direction of the tail depends on the net force induced by the natural and MHD convections. The interplay between the natural and MHD convections proved to be important during Ni-Fe alloy deposition, too. When the Lorentz force and the natural convection act in the same direction, an increase of the Fe content of the alloys with the magnetic field was observed. When the Lorentz force was perpendicular to the natural convection, no significant changes were observed in the composition of the layers. The alloy composition did not change with the magnetic field when the electric current was parallel to the magnetic field lines. Two surfactants were used in the case that Ni was electrodeposited from a sulfamate bath: SDS and sulfirol 8. The Ni layers obtained from a sulfamate bath with sulfirol 8 presented larger grains compared to the layers deposited from a bath free of surfactants. This increase of the grain size was attributed to the incorporation of the surfactant in the deposit. Coarser layers were obtained in a magnetic field (applied perpendicular to the electric current) when the electrodeposition was done from an electrolyte with surfactants. The number of grains increased with the magnetic field for the Ni layers electrodeposited from a bath free of surfactants and for a bath with SDS. As a consequence, the grain size decreased. In the case of the electrolyte with sulfirol 8, the number of grains decreased with the magnetic field, and their size increased. For the Ni-Fe alloys, which contained less than 10 at% Fe, the preferred crystalline orientation changes from (220), in the absence of a magnetic field, to (111), (when the magnetic field was applied perpendicular to the electric current). When the magnetic field lines were parallel to the electric current, both the (111) and (220) textures were preferred in almost the same proportion. As a general conclusion of this work it can be said that by choosing the right experimental condition, one can improve the morphology and the properties of the deposited layers by applying a magnetic field. At the same time, the mass transport processes can be influenced by a magnetic field.

As the major electricity consumer, electrical machines play a key role for global energy savings. Machine manufacturers put considerable efforts into the development of more efficient electrical machines for loss reduction and higher power density achievements. A consolidated knowledge of the occurring losses in electrical machines is a basic requirement for efficiency improvements. This thesis deals with iron losses in electrical machines. The major focus is on the influences of the stator core magnetic material due to the machine manufacturing process, temperature influences, and the impact of inverter operation. The first part of the thesis gives an overview of typical losses in electrical machines, with focus put on iron losses. Typical models for predicting iron losses in magnetic materials are presented in a comprehensive literature study. A broad comparison of magnetic materials and the introduction of a new material selection tool conclude this part. Next to the typically used silicon-iron lamination alloys for electrical machines, this thesis investigates also cobalt-iron and nickel-iron lamination sheets. These materials have superior magnetic properties in terms of saturation magnetization and hysteresis losses compared to silicon-iron alloys. The second and major part of the thesis introduces the developed measurement system of this project and presents experimental iron loss investigations. Influences due to machine manufacturing changes are studied, including punching, stacking and welding effects. Furthermore, the effect of pulse-width modulation schemes on the iron losses and machine performance is examined experimentally and with finite-element method simulations. For nickel-iron lamination sheets, a special focus is put on the temperature dependency, since the magnetic characteristics and iron losses change considerably with increasing temperature. Furthermore, thermal stress-relief processes (annealing) are examined for cobalt-iron and nickel-iron alloys by magnetic measurements and microscopic analysis. A thermal method for local iron loss measurements is presented in the last part of the thesis, together with experimental validation on an outer-rotor permanent magnet synchronous machine. / <p>QC 20140516</p>

Die langfristige Speicherung von überschüssiger Energie aus regenerativen Quellen ist ein ungelöstes Problem der Energiewende. Ein Ansatz zur Lösung dieses Problems bietet das Power-to-Gas-Konzept, bei dem Methan aus Wasserstoff und Kohlenstoffdioxid als Ersatz für Erdgas erzeugt wird. Da diese Reaktion kinetisch limitiert ist, ist die Verwendung eines geeigneten heterogenen Katalysators erforderlich. Aufgrund ihrer hohen Aktivität und ihres niedrigen Preises werden häufig nickelhaltige Katalysatoren eingesetzt. In der vorliegenden Arbeit wurde die Eignung von Fe-Ni-Hydrotalcit-basierten Katalysatoren für dieses Konzept untersucht, wobei der Schwerpunkt auf der Bestimmung der Abhängigkeit der katalytischen Aktivität vom Eisengehalt lag. Dabei zeigte sich, dass geringe Mengen an Eisen die Methanausbeute verbessern. Eine Erklärung für diese Aktivitätssteigerung liefern die Ergebnisse von in-situ-DRIFTS-Untersuchungen an eisenhaltigen und eisenfreien Ni-Hydrotalcit-Katalysatoren.

Microtrusses are hybrid materials composed of a three-dimensional array of struts capable of efficiently transmitting an externally applied load. The strut connectivity of microtrusses enables them to behave in a stretch-dominated fashion, allowing higher specific strength and stiffness values to be reached than conventional metal foams. While much attention has been given to the optimization of microtruss architectures, little attention has been given to the strengthening mechanisms inside the materials that make up this architecture. This thesis examines strengthening mechanisms in aluminum alloy and copper alloy microtruss systems with and without a reinforcing structural coating. C11000 microtrusses were stretch-bend fabricated for the first time; varying internal truss angles were selected in order to study the accumulating effects of plastic deformation and it was found that the mechanical performance was significantly enhanced in the presence of work hardening with the peak strength increasing by a factor of three. The C11000 microtrusses could also be significantly reinforced with sleeves of electrodeposited nanocrystalline Ni-53wt%Fe. It was found that the strength increase from work hardening and electrodeposition were additive over the range of structures considered. The AA2024 system allowed the contribution of work hardening, precipitation hardening, and hard anodizing to be considered as interacting strengthening mechanisms. Because of the lower formability of AA2024 compared to C11000, several different perforation geometries in the starting sheet were considered in order to more effectively distribute the plastic strain during stretch-bend fabrication. A T8 condition was selected over a T6 condition because it was shown that the plastic deformation induced during the final step was sufficient to enhance precipitation kinetics allowing higher strengths to be reached, while at the same time eliminating one annealing treatment. When hard anodizing treatments were conducted on O-temper and T8 temper AA2024 truss cores, the strength increase was different for different architectures, but was nearly the same for the two parent material tempers. Finally, the question of how much microtruss strengthening can be obtained for a given amount of parent metal strengthening was addressed by examining the interaction of material and geometric parameters in a model system.

Microtrusses are hybrid materials composed of a three-dimensional array of struts capable of efficiently transmitting an externally applied load. The strut connectivity of microtrusses enables them to behave in a stretch-dominated fashion, allowing higher specific strength and stiffness values to be reached than conventional metal foams. While much attention has been given to the optimization of microtruss architectures, little attention has been given to the strengthening mechanisms inside the materials that make up this architecture. This thesis examines strengthening mechanisms in aluminum alloy and copper alloy microtruss systems with and without a reinforcing structural coating. C11000 microtrusses were stretch-bend fabricated for the first time; varying internal truss angles were selected in order to study the accumulating effects of plastic deformation and it was found that the mechanical performance was significantly enhanced in the presence of work hardening with the peak strength increasing by a factor of three. The C11000 microtrusses could also be significantly reinforced with sleeves of electrodeposited nanocrystalline Ni-53wt%Fe. It was found that the strength increase from work hardening and electrodeposition were additive over the range of structures considered. The AA2024 system allowed the contribution of work hardening, precipitation hardening, and hard anodizing to be considered as interacting strengthening mechanisms. Because of the lower formability of AA2024 compared to C11000, several different perforation geometries in the starting sheet were considered in order to more effectively distribute the plastic strain during stretch-bend fabrication. A T8 condition was selected over a T6 condition because it was shown that the plastic deformation induced during the final step was sufficient to enhance precipitation kinetics allowing higher strengths to be reached, while at the same time eliminating one annealing treatment. When hard anodizing treatments were conducted on O-temper and T8 temper AA2024 truss cores, the strength increase was different for different architectures, but was nearly the same for the two parent material tempers. Finally, the question of how much microtruss strengthening can be obtained for a given amount of parent metal strengthening was addressed by examining the interaction of material and geometric parameters in a model system.