The Pulsed Laser Deposition is an established method for the preparation of thin films and nm layer systems. In this work a cross beam PLD system is used as a special development for reduction of macro particle contamination in the growing layer. Two plasma plumes which overlap under a defined angle are produced on separated targets by two synchronized lasers. In the overlapping zone the direction of plasma expansion is changed by interaction of plasma particles. A diaphragm is used to guaranty that only the part of the plasma is deposited on the substrate that has changed the direction of expansion in the interaction zone. Detailed characterizations of plasma properties, deposition and growth conditions were carried out to demonstrate that cross beam PLD is an effective method to reduce macro particle contamination and allows layer growth under reduced energetic loading of the substrate. In the second part of this work cross beam PLD is used to produce Ni/C multilayers and artificial mixtures. The interest is focused on the mechanisms of layer disintegration and structure formation under thermal loading. Possible processes for layer disintegration are discussed on a theoretical background and verified in TEM examinations. / Die Pulsed Laser Deposition ist ein etabliertes Verfahren zur Herstellung dünner Schichten im nm-Bereich. Das in dieser Arbeit verwandte PLD-Zweistrahlverfahren ist eine besondere Entwicklung zur Verringerung der Makropartikelkontamination der Schichten. Zwei synchronisierte Laser erzeugen auf zwei benachbarten Targets zwei Plasmafackeln, die unter einem bestimmten Winkel überlappen, was zu einer Änderung der Ausbreitungsrichtung des Palmas führt. Ein spezielle Blendenanordnung garantiert, dass nur der abgelenkte Teil des Plasmas auf dem Substrat abgeschieden wird, welches für die anfänglichen Plasmafackeln im Schatten liegt. Anhand einer umfangreichen Charakterisierung der Plasma-, Abscheide- und Schichtwachstumseigenschaften wird gezeigt, dass das PLD-Zweistrahlverfahren eine effektive Verminderung der Makropartikelkontamination der Schichten ermöglicht und dass das Schichtwachstum unter deutlich verringertem Energieeintrag im Vergleich zur konventionellen PLD erfolgt. Das Verfahren wird im zweiten Teil der Arbeit angewandt um Ni/C-Multischichten und künstliche Mischungen herzustellen. Das Interesse liegt hierbei auf den Mechanismen des Schichtzerfalls und auf den entstehenden Strukturen bei thermischer Behandlung metastabiler Schichtsysteme. Anhand theoretischer Betrachtungen werden die möglichen Prozess des Schichtzerfalls eingegrenzt und mittels TEM-Untersuchungen verifiziert.

Im Rahmen dieser Dissertation wurden Hydrotalcit-basierte Nickelkatalysatoren zur CO2-Methanisierung synthetisiert, charakterisiert und katalytisch untersucht. Dabei konnten durch mehrere Ansätze deutliche Verbesserungen der katalytischen Aktivität erzielt werden. Einen wesentlichen Effekt zeigte dabei die Kombination der üblicherweise separat durchgeführten Präparationsschritte der Calcination und der Reduktion. Dadurch ließ sich die notwendige Reduktionstemperatur senken, was zum Erhalt einer größeren Katalysatoroberfläche führte. Zusätzlich wurde eine Vielzahl von Promotoren in Hydrotalcit-basierten Nickelkatalysatoren systematisch und vergleichend untersucht. Eine solche Untersuchung lässt sich in der Literatur bisher nicht finden. Dabei kristallisierte sich insbesondere Mangan als vielversprechender Promotor heraus. Spektroskopische Untersuchungen zum Einfluss des Mangans zeigten, dass Mangan die Bindungsstärke des Kohlenstoffdioxids am Katalysator erhöht. Durch Variation des Mangangehaltes ließ sich entsprechend die Bindungsstärke einstellen und somit die Katalysatoraktivität optimieren.

Call number: LD2668 .T4 1953 W57 / Master of Science

Call number: LD2668 .T4 1962 A82

Au cours de ce projet, il a été démontré qu’il était possible d’appliquer un procédé utilisant comme solvant du 2-MeTHF ainsi que du Nickel de Raney comme catalyseur afin de valoriser par hydroliquéfaction différentes formes de biomasse résiduelles. Dans un premier temps, ce procédé, résumé dans un premier article, s’est avéré efficace pour trois différentes sources de carbone : des déchets ménagers, des boues de station d’épuration et des microalgues. Malgré que la réaction soit affectée par le type de solvant ainsi que la température d’opération, il a été démontré que le 2-MeTHF (un solvant vert) pouvait remplacer la tétraline (un solvant de source fossile) pour l’hydroliquéfaction de ces différentes sources de carbone. L’hydroliquéfaction de ces biomasses a permis la production d’huiles à haute valeur énergétique, se comparant à celle d’un biocarburant. Dans un deuxième article, le même procédé (utilisant le même solvant et catalyseur) a été optimisé pour la liquéfaction d’une fraction de la biomasse lignocellulosique soit la fraction oligomérique issue de la dépolymérisation alcaline de la lignine. Une analyse complète de la liquéfaction d’oligomères d’induline, lignine provenant des liqueurs issus de l’industrie papetière, a révélé la production de trois fractions : une fraction gazeuse, une liquide (soluble dans l’hexane) et une solide (insoluble dans l’hexane). L’analyse élémentaire de la fraction solide a révélé une baisse massique de 15,4% d’oxygène et une augmentation massique de 1,4% d’hydrogène par rapport aux oligomères utilisés comme réactifs. Une chaleur massique (HHV) de 34,0 kJ/g a été mesurée par bombe calorimétrique pour la fraction solide. L’analyse par chromatographie en phase gazeuse couplée à un spectromètre de masse (GC-MS) de la fraction liquide a permis d’identifier la présence de nombreux monomères tel le 2-methoxy-phénol, de 4-éthylgaïacol et le crésol. Une HHV de 34,2 kJ/g a été mesurée par bombe calorimétrique de la fraction liquide. La fraction gazeuse était principalement constituée de méthane et de CO[indice inférieur 2].

Thesis (PhD (Process Engineering))--University of Stellenbosch, 2007. / Nickel-Copper sulphide ores are the most important Platinum Group Metal bearing ores. The South African deposits are exceptionally rich in the platinum group metals (PGMs) and production of the PGMs is the primary purpose of treating these ores. The methods used in the recovery of the PGMs from the nickel-copper ores generally consists of ore concentration by physical techniques, pyrometallurgical concentration and hydrometallurgical extraction of the base metals followed by the PGMs. Pyrometallurgical concentration produces Ni-Cu matte, which is treated by hydrometallurgical processes to recover the nickel, copper, cobalt and the precious metals. In this study, the leaching behaviour of a Ni–Cu matte in CuSO4–H2SO4 solution during the repulping (pre-leach) stage at Impala Platinum Refineries was studied. The repulping stage is basically a non–oxidative atmospheric leach stage, in which nickel, iron and cobalt are partially dissolved, while the copper is precipitated. To understand the nature of the leaching process during this stage of the base metal refining operation, the effects of variations in the key process variables such as temperature, stirring rate, particle size, pulp density, residence time, initial copper and acid concentrations were investigated. The pre-leached matte was then pressure leached to ascertain the effect of process conditions in the pre-leach stage on the subsequent pressure leach stage. It was found that the leaching mechanism entails dissolution of metal alloys out of sulphide minerals with transformation of Ni3S2 to NiS. Aqueous copper precipitates as metallic copper and as chalcocite. The matte is leached by both acid and the cementation process, especially in the early stage when the Cu2+ ions are present. Galvanic interaction of the sulphide minerals and/or the Ni alloy also enhances the leaching process. The leaching kinetics of Ni was characterized with the shrinking core model and was found to be controlled by diffusion through surface layer. An activation energy of 31 kJ/mol was obtained, which also suggested a diffusion controlled leaching reaction. Atmospheric leaching tests indicated that Ni extraction increased slightly in the temperature range 50 – 60 oC, however no significant increase was observed from 60 to 80 oC, probably because the leaching process was found to be diffusion controlled. The slight increase in nickel dissolution at higher temperatures (>60 oC) may be attributed to the transformation of Ni3S2 to NiS, which is easier to leach. Co extraction appeared to be insensitive to temperature changes, while Fe extraction was low at 50 oC but increased significantly at 60 – 80 oC. The Ni extraction increased gradually with increase in the stirring rate from 145 to 400 rpm while Co and Fe extractions were insensitive at 145 and 205 rpm, but increased substantially at 400 rpm. This was probably due to increased mass transfer rate and transformation of Ni3S2 to NiS. With pulp density, Ni and Co extractions appeared to be insensitive to changes in the pulp density as only a slight increase in extractions was observed when the density was reduced from 1.7 kg/L to 1.6 kg/L. Similar iron extractions were achieved at 1.7 and 1.75 kg/L but increased significantly at 1.6 kg/L. It was found that Ni and Co extractions were not significantly affected by changes in the particle size, probably because metal alloys were liberated and hence exposed to the leaching solution. Iron extraction could not be determined accurately because of iron precipitation at pH above 3. Generally the leaching of metals did not depend on the initial copper concentration in the investigated range of 25 - 48 g/L Cu. It was also observed that initial acid concentration did not have an effect on Ni extraction, probably due to the fact that most of the nickel was leached by the process of cementation. However, Co and Fe extractions increased when the acid increased from 90 g/L to 110 g/L, but no further increase was noted at 125 g/L. A residence time of 5 hours was found to be adequate as there was no significant increase in metal extractions when the residence time was increased beyond 5 hours. As much as 20% Ni, 40% Co and 80% Fe can be extracted from the Ni-Cu matte during the repulping stage of the leaching process studied, provided the investigated conditions prevail. Generally the rate of Cu cementation increased with increasing temperature and pulp density, but decreased with an increase in particle size, acid and copper concentrations. The rate of stirring did not affected Cu cementation. It was found that aqueous copper precipitated from the solution within 90 minutes when the temperature was raised to 80 oC. However, under the present pre-leach temperature of about 60 oC complete Cu cementation can only be achieved after about 5 hours. The cementation reaction was found to follow a mixed control mechanism, with two distinct activation energies namely 18.2 kJ/mol at 70 – 80 oC and 74.6 kJ/mol at 50 – 70 oC. This suggested that the rate of cementation reaction is probably controlled by a boundary layer diffusion mechanism at higher temperatures. At low temperatures the rate is probably controlled by a surface reaction mechanism. The pressure leaching experiments, which were aimed at investigating the response of pre-leached matte to the subsequent pressure leaching process, showed that Ni extractions were similar for the investigated pre-leach temperature of 50 – 80 oC and stirring rate of 145 – 400 rpm. For the pre-leach stage conditions of 60 – 80 oC and 205 – 400 rpm Ni3S2 was transformed into NiS, which is easier to leach in the pressure leaching stage. However, because of the aggressive conditions prevailing in the pressure leaching stage, all the nickel minerals were leached at about the same rate. In the case of pulp density, Ni extraction was comparable for all the investigated pulp densities (1.6 – 1.75 kg/L). This was probably due to the fact that Ni3S2 transformed to NiS in the pre-leach stage. It was found that Ni extraction increased with increasing residence time for the investigated time of 1 hour to 9 hours, probably due to the changes in the mineral phases of the matte as indicated above. The copper minerals (Cu2S and Cu1.96S) transformed into Cu2S and Cu1.8S with aqueous copper being precipitated, and were not leached under the applied conditions. All the cobalt and iron dissolved in the pressure leaching stage. A semi-empirical kinetic model was developed for the pre-leaching stage. A comparison of the model predictions and the experimental data for the dissolved species during the batch leaching process showed that the model can satisfactorily fit the trends in the leaching of the metals.

Over 70% of the Earth s economically recoverable nickel (Ni) resides in laterite ore deposits, however they account for less than half of the current global nickel production. During laterization, nickel and other soluble ions are taken into solution before re-precipitating within iron oxide minerals in the limonite zone, or as serpentines and other phyllosilicates in the layers below this zone. It is these laterite deposits that show the greatest potential for low energy, environmentally conscious processing. The major host of nickel in the limonite zone is the iron-oxyhydroxide mineral goethite, α-FeOOH, where up to 4 mol% Ni has been reported in natural specimens, and even higher levels in synthetic samples (5.5 mol%). The Ni is assumed to be incorporated in the crystal structure of the goethite, but previous characterisation work only demonstrated a weak to moderate correlation of mineral structure change with the nickel content in goethite. Mining companies working on the extraction and recovery of nickel from the limonite zone of lateritic deposits have noticed that the ease with which nickel can be extracted varies greatly; goethite rich ores that appear to have similar mineralogies/geologies can display extreme variation in their leachability. It is not clear why the ores behave in this way, but in order for extraction techniques and subsequent recovery of nickel to be improved, the reasons behind this variability need to be understood. The lateritic ore materials from which nickel is extracted are generally made up of a number of different mineral phases. The multiphase nature of the samples means that characterisation of the goethite-type phases from these materials is challenging. To simplify the system and allow the association of Ni into goethite and/or other iron oxyhydroxide phases to be studied in a controlled environment, a synthetic study was carried out. Ni-bearing goethites have been synthesised at a series of different temperatures and characterised by a range of analytical techniques including PXRD, IR, Raman, TGA, ICP-OES, SEM and TEM. It was found that a second phase, ferrihydrite, co-existed with the goethites, the proportion of which increased at lower synthesis temperatures and with increasing amounts of Ni. Ferrihydrite is known to be a precursor phase in the formation of goethite, but its poorly crystalline nature makes it difficult to identify using standard characterisation techniques such as PXRD. The introduction of Ni to the system increases the stability of the ferrihydrite phase, inhibiting its transformation to goethite. It is believed that some of the Ni thought to be incorporated into goethite could actually reside in an undetected ferrihydrite phase, which could account for the differences observed in the leachability of natural materials. Characterisation techniques were investigated to try and determine a simple way to identify ferrihydrite in these systems, which could ideally be used in the field to identify the presence of ferrihydrite in goethite rich ore materials. Thermal analysis proved to be particularly promising as a technique which could be used to identify ferrihydrite rich deposits before extraction, enabling the most efficient and environmentally conscious metal recovery process for each deposit to be identified. In order to investigate the way in which Ni partitions itself between structural incorporation into goethite and association with a secondary ferrihydrite phase, a new washing technique was developed using EDTA, which is capable of selectively removing the ferrihydrite phase whilst leaving the goethite intact. This investigation suggests that a maximum of ~2.5 mol% of Ni is structurally incorporated into goethite, regardless of how much is added during the synthesis. Any excess nickel, above that which is substituted into the goethite structure, was found to be associated with the poorly crystalline ferrihydrite phase. Despite being considered a metastable phase, the increased stability of ferrihydrite resulting from the presence of Ni suggests that it may persist in laterite deposits within geological systems. If ferrihydrite is indeed present in nickeliferous laterites, it may be a significant host for Ni, and potentially many other critical elements. Based on the methodology developed whilst studying synthetic samples, a characterisation program for materials from lateritic ore deposits was conducted to investigate the presence of ferrihydrite in natural systems. From the research presented and discussed in this thesis, proof of the presence or absence of ferrihydrite in laterite systems, causing variations in the leachability of the ore materials, could not be conclusively established. The thermal analysis technique developed here successfully identified and quantified ferrihydrite in the presence of goethite in synthetic systems, and showed great potential when used to characterise the lateritic goethite samples, certainly suggesting that ferrihydrite could be present in these natural ore materials. With further refinement of the methodology, to enable a larger range of sample types to be accurately analysed, TGA is a technique which could be used as a screening tool for laterite ores.

No description available.

This investigation was initiated by IBM to determine the types of cracks formed in hot-isostatic-pressed (HIP) Ni-Zn ferrite under impact and static loading conditions. A 1/8-inch tungsten carbide (WC) ball was used to apply the load in both cases. The impact loading condition was accomplished by dropping the WC ball from various heights between 40 and 200 cm. The static loading condition was accomplished by applying loads of 10 kg, 15 kg, and 30 kg on a Rockwell Hardness Tester. The response of HIP Ni-Zn ferrite to impact and static loading was elastic/plastic yielding permanent indentations. "Dimple" impressions, Hertzian-ring cracks, and radial cracks were formed upon applying increasing loads to the HIP Ni-Zn ferrite. As the grain size of the material was increased, both the Hertzian-ring and radial cracks were formed at lower loads compared to the as-received samples. The "dimple" impressions were not observed to follow this trend.

Heterogeneous enantioselective catalysis strives to create new successful catalysts. One of the most researched examples is the hydrogenation β-ketoesters using nickel-based catalysts. A hindrance in the industrial scale-up of this enantioselective hydrogenation reaction is the lack of exact details of how chirality is bestowed onto this achiral metal surface. While a number of mechanisms have been proposed to explain the enantioselective behaviour of this system, these are predominantly based on catalytic studies. An alternative approach is through surface science studies examining the morphology, structure and composition of this catalytic system. A range of ultrahigh vacuum based model studies investigating the structure and composition of ultrathin Ni films and Ni/Au surface alloys on Au{111} using the techniques of Scanning Tunnelling Microscopy (STM) and Medium Energy Ion Scattering (MEIS) are presented in this thesis. In addition, the adsorption of the chiral modifier (S)-glutamic acid has been studied on these surfaces using vibrational spectroscopy (Reflection Absorption Infrared Spectroscopy (RAIRS)) and Temperature Programmed Desorption (TPD). Furthermore, MEIS has been used to investigate the influence of (S)-glutamic acid on the surface composition of Au/Ni model catalysts detecting effects such as adsorbate induced segregation and de-alloying behaviour. In addition, colloidal preparative routes have been used to synthesise bimetallic Au/Ni nanoparticles supported on mesoporous silica. The catalysts are then modified by the adsorption of the chiral ligand, (R,R)-tartaric acid. Finally, the catalysts are tested for their activity and enantioselectivity with respect to methylacetoacetate hydrogenation. At each stage the catalysts are characterised by a combination of Extended X-ray Absorption Fine Structure (EXAFS); Transmission Electron Microscopy (TEM), Energy Dispersive X-ray Spectrometry (EDS) and Atomic Absorption Spectroscopy (AAS).