Thesis (Ph. D.)--University of Wisconsin--Madison. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 167-175).

No description available.

The production of magnetic materials is of great interest for use in the micro-fabrication industry. In particular, Permalloy (Ni80Fe20) is used in the production of micro-electromechanical systems (MEMS) due to its favourable magnetic properties (high relative permeability, low coercivity and high magnetic saturation). This leads to applications in devices such as inductors, transformers and micro-actuators. The electrodeposition of NiFe is also of fundamental electrochemical interest, as there is anomalous thermodynamic behaviour, with the less noble (iron) metal depositing preferentially to the more noble (nickel) metal. To enable consistent alloy deposition nickel and nickel-iron baths are currently almost exclusively based on boric acid. Boric acid has an important role in the deposition of NiFe films but its role(s) in the electro-deposition mechanism is (are) not wholly understood. Recently (2011) boric acid has been identified as a “substance of very high concern” based on the criteria established by EU chemical regulation, REACH. In anticipation of increased regulation an alternative was sought to provide a benign alternative to boric acid in the NiFe plating bath suitable for use in micro-fabrication. Initial work was performed to benchmark the performance of existing boric acid based electro-deposition baths. Cyclic voltammetry was performed, which demonstrated the deposition of nickel and nickel-iron from boric acid baths. Coulombic efficiencies up to 93 % were measured for the deposition of nickel using the electrochemical quartz crystal microbalance (EQCM) on platinum electrodes. For nickel-iron deposition control of the film composition was demonstrated on copper electrodes through varying the iron (II) concentration, current density and temperature. A citrate bath for the deposition of nickel-iron was then developed and characterised. Cyclic voltammetry was performed in these citrate baths demonstrating the deposition of nickel and nickel-iron. Optimal conditions for depositing Ni80Fe20 were demonstrated to be an elevated temperature (60 °C) with a current density of 20 mA cm-2 and a pH of 3. Using the EQCM the efficiency for nickel deposition was measured to be > 80 %. The effects of sodium saccharin and sodium dodecyl sulfate as additives were investigated; these were shown to influence morphology but not the coulombic efficiency. Decreasing the pH was shown to lower the efficiency of nickel deposition from the citrate bath. Comparisons of key properties were made between NiFe films deposited from a boric acid bath and the citrate bath developed in this work. Test structures were used to compare the strain in the films; no significant difference was found. For 2.2 μm thick Ni80Fe20 films the sheet resistance was measured using Greek cross structures as 0.078 ± 0.004 Ω/square for films deposited from the boric acid bath and 0.090 ± 0.006 Ω/square from the citrate bath. The magnetic saturation, Ms, was measured as 895 ± 66 emu cm-3 for deposits from the boric acid bath and 923 ± 111 emu cm-3 from the citrate bath. These again show no significant difference in these values within experimental error. Coercivities for these films were measured to be between 20 and 120 A m-1. In combination, this work demonstrates the development and characterisation of a new citrate based electrodeposition bath for nickel and nickel-iron. Similar chemical, electrical, mechanical and magnetic properties were found from films deposited from both baths, thus demonstrating the suitability of the citrate bath for the deposition of nickel-iron films in microfabrication.

This research work presents the first comprehensive study on nanocrystalline materials produced in bulk quantities using a novel continuous electrodeposition process. A series of nanocrystalline Ni and Ni-Fe alloy continuous foils were produced and an intensive investigation into their structure and various properties was carried out. High-resolution transmission electron microscopy (HR-TEM) revealed the presence of local strain at high and low angle, and twin boundaries. The cause for these local strains was explained based on the interpretation of non-equilibrium grain boundary structures that result when conditions of compatibility are not satisfied. HR-TEM also revealed the presence of twin faults of the growth type, or “growth faults”, which increased in density with the addition of Fe. This observation was found to be consistent with a corresponding increase in the growth fault probabilities determined quantitatively using X-ray diffraction (XRD) pattern analysis. Hardness and Young’s modulus were measured by nanoindentation. Hardness followed the regular Hall-Petch behaviour down to a grain size of 20 nm after which an inverse trend was observed. Young’s modulus was slightly reduced at grain sizes less than 20 nm and found to be affected by texture. Microstrain based on XRD line broadening was measured for these materials and found to increase primarily with a decrease in grain size or an increase in intercrystal defect density (i.e., grain boundaries and triple junctions). This microstrain is associated with the local strains observed at grain boundaries in the HR-TEM image analysis. A contribution to microstrain from the presence of growth faults in the nanocrystalline Ni-Fe alloys was also noted. The macrostresses for these materials were determined from strain measurements using a two-dimensional XRD technique. At grain sizes less than 20 nm, there was a sharp increase in compressive macrostresses which was also owed to the corresponding increase in intercrystal defects or interfaces in the solid.

This research work presents the first comprehensive study on nanocrystalline materials produced in bulk quantities using a novel continuous electrodeposition process. A series of nanocrystalline Ni and Ni-Fe alloy continuous foils were produced and an intensive investigation into their structure and various properties was carried out. High-resolution transmission electron microscopy (HR-TEM) revealed the presence of local strain at high and low angle, and twin boundaries. The cause for these local strains was explained based on the interpretation of non-equilibrium grain boundary structures that result when conditions of compatibility are not satisfied. HR-TEM also revealed the presence of twin faults of the growth type, or “growth faults”, which increased in density with the addition of Fe. This observation was found to be consistent with a corresponding increase in the growth fault probabilities determined quantitatively using X-ray diffraction (XRD) pattern analysis. Hardness and Young’s modulus were measured by nanoindentation. Hardness followed the regular Hall-Petch behaviour down to a grain size of 20 nm after which an inverse trend was observed. Young’s modulus was slightly reduced at grain sizes less than 20 nm and found to be affected by texture. Microstrain based on XRD line broadening was measured for these materials and found to increase primarily with a decrease in grain size or an increase in intercrystal defect density (i.e., grain boundaries and triple junctions). This microstrain is associated with the local strains observed at grain boundaries in the HR-TEM image analysis. A contribution to microstrain from the presence of growth faults in the nanocrystalline Ni-Fe alloys was also noted. The macrostresses for these materials were determined from strain measurements using a two-dimensional XRD technique. At grain sizes less than 20 nm, there was a sharp increase in compressive macrostresses which was also owed to the corresponding increase in intercrystal defects or interfaces in the solid.

No description available.

Philosophiae Doctor - PhD / Energy storage systems represent a viable option to integrate renewable energy sources into the grid network. Multiple energy storage technologies are available such as mechanical, electrical, thermal, and electrochemical storage technologies. Battery Energy Storage Systems are considered as an accepted solution for energy storage with advantages such as, sustained power delivery, geographical independence and, fast response capability. This thesis describes the development of rechargeable bipolar Nickel-Iron batteries as potential candidates for cost effective energy storage solutions. The first objective of this work was to design a bipolar electrode comprising an Iron (Fe)-based anode, a Nickel (Ni)-based cathode and a flexible bipolar plate and to optimise its production process in order to attain high performance in terms of capacity and efficiency. Research questions to be answered included;

<p> This investigation is concerned with the development of a general ternary diffusion analysis for the diffusion-controlled oxidation of binary alloys based on the concept of local equilibrium and phenomenological diffusion theory and its application to appropriate experimental systems. </p> <p> The theoretical analysis is in two parts. In the first part diffusion equations for the alloy and oxide phases are obtained and tested against experiments for Ni-10.9% Co alloy at 1000°C. In the second part phenomena observed in binary alloy oxidation such as supersaturation, internal oxidation and morphological instability are qualitatively discussed and the concept ot the stationary diffusion path on the isotherm is applied to binary alloy oxidation. In general the ternary diffusion analysis satisfactorily accounts for the diffusion-controlled oxidation properties of several binary alloys. </p> <p> An experimental investigation of the oxidation of nickel-iron alloys at 1000°C is described. In the first part of the experimental investigation, thermodynamics of the ternary iron-nickel-oxygen system at 1000°C has been investigated in support of the oxidation studies. The second part is comprised of a detailed kinetic and metallographic study of nickel-iron alloys containing upto 25% iron exposed to oxygen atmospheres at 1000°C and determination of the metal concentration profiles in the oxide and alloy phases. The experimental results for these alloys are in good agreement with the theoretical calculations. </p> / Thesis / Doctor of Philosophy (PhD)

No description available.

No description available.