Please read the abstract in the section 00front of this document / Dissertation (MSc (Chemistry))--University of Pretoria, 2007. / Chemistry / unrestricted

A review of the geotectonic settings of granitoids and various tin-tungsten provinces in Europe, Malaysia and southern Africa shows a close spatial and temporal association of mineralisation to S-type ilmenite series granitoids. Granitoids with these affinities are derived from crustal anatexis and are most commonly found in continental collision and different ensialic, intraplate orogenic settings, (e.g. SW England, Malaysia, Namibia) as well as in association with anorogenic magmatism (Nigeria, Brazil, South Africa). Tin-tungsten mineralisation is related to late- to post-tectonic granites, emplaced into areas of substantial tectonic thickening. Crustal anatexis leads to an observable calcalkaline chemical trend, with a source of gabbroic or amphibolite composition through anatexis to; mafic-intermediate enclaves, para-autochthonous anatectic granitoids (tonalite, granodiorite), to intermediate level quartz monzonite, granodiorite, biotite-granite, to late-tectonic highly fractionated muscovite-bearing granites, and high level porphyry intrusions. Mineralisation is spatially related to apical protrusions of the youngest most differentiated granite. Various mineralised environments are recognised, including endogranitic veins, primary disseminations, pegmatites and pipes, and exogranitic stockwork and fissure veins, and replacement bodies. A common factor to all these deposits is the inherent greisen environment, characterised by postmagmatic metasomatic alteration and mineral deposition. Common alteration mineral assemblages include albite, quartz, muscovite, tourmaline, and fluorite ∓ topaz. Ore mineral assemblages commonly display a paragenetic sequence of oxides (cassiterite, wolframite, scheelite), followed by sulphides (molybdenite, pyrite, pyrrhotite, chalcopyrite sphalerite, arsenopyrite/loëllingite, Pb-Bi(Ag) sulphosalts) and then lower temperature carbonates (calcite, siderite, ankerite). Analysis of Pan African orogenic provinces in southern Africa (Damara and Saldanian Provinces) shows there is good potential for applying integrated exploration techniques in search of endo-exogreisen Sn-W systems. Careful analysis and interpretation of granitoid geochemistry (K₂0, Na₂0, FeO/Fe₂0₃, F, B, Sn, W, Mo, Cu, Rb, Sr, Ti, Zr) should aid delineation of Sn-W and Mo-Cu metallogenic provinces in these regions. Magnetic susceptibility determinations should also aid distinction of S-type ilmenite series (less than 1 x lO⁻⁴emu/g ) from I-type magnetite series (more than 1 x lO⁻⁴emu/g ) granitoids

The present study involves the use of main group organometallics: organostannanes and organolithiums as precursors to chromium Fischer carbene complexes. Fischer carbenes are well stabilized by the π‐donor substituents such as alkoxy and amino groups and low oxidation state metals such as Group 6 (Chromium, Molybdenum or Tungsten). Carbenes are an important intermediate in the synthesis of a range of compounds through cyclopropanations, insertions, coupling and photochemical reactions. Synthesis and successful characterisation of three α‐alkoxystannanes was achieved via nucleophilic addition of tributylstannyllithium to the respective aldehydes, followed by an immediate MOM protection of the resulting alcohol. Six α‐aminostanannes were synthesised, consisting of N‐BOC, N‐acetyl and N‐ethyl derivatives of pyrrolidine and piperidine, via α‐lithiation and subsequent tinlithium transmetallation in the presence of TMEDA. The ¹³C NMR analysis highlighted an interesting phenomenon of tin‐carbon coupling that revealed unique structural information of both types of stannanes. DFT analysis was completed on the series of stannanes; a predicted frequency analysis was obtained which complemented the experimental Infra‐red data in elucidation of the compounds. The α‐alkoxy and α‐aminostannanes provided stable precursors to the organolithiums required for the synthesis of the novel Fischer chromium carbenes. The organolithiums were obtained via tinlithium exchange at low temperatures, followed by the addition of chromium hexacarbonyl to form the acylpentacarbonyl‐chromate salt. Alkylation of this intermediate using a Meerwein salt, Me₃OBF₄, gave rise to the novel Fischer chromium carbene complexes. Fischer chromium carbenes derived from the two isomeric butyl and isobutyl stannanes and the two N‐ethyl α‐aminostannanes were successfully synthesised. The difficulty encountered in the purification of the Fischer carbene complexes hindered the full characterisation, due to the presence of a by‐product, tetrabutyltin.

The purpose of this thesis was to compare graphene nanoplatelets (GNP) and WS2 as solid lubricant additives to aluminum in order to reduce friction and wear. The central hypothesis of this work relied on lubricating properties of 2D materials, which consist layers that slip under a shear force. Two aluminum composites were made (Al-2 vol.% GNP and Al-2 vol.% WS2) by spark plasma sintering. Tribological properties were evaluated by ball-on-disk wear tests at room temperature (RT) and 200°C. WS2 not only presented the lowest COF (0.66) but also improved the wear resistance of aluminum by 54% at RT. Al-2 vol.% GNP composite displayed poor densification (91%) and low hardness resulting in poor wear resistance. The wear rate of Al-2 vol.% GNP composite increased by 233% at RT and 48% at 200°C as compared to pure aluminum. GNP addition also resulted in lower COF (0.79) as compared to pure aluminum (0.87).

Metal-insulator transition is one of the most important properties observed in certain materials which has been studied widely using a wide range of experimental techniques as well as theoretical models. This kind of a transition, observed in several systems, can take place by tuning several parameters such as pressure, temperature or the composition itself. In this thesis we study a few selected transition metal oxide bronzes exhibiting such phenomenon, each of which has a different cause for undergoing the transition. In Chapter 1, we discuss briefly several mechanisms and models that have been used to understand metal-insulator transitions. We also briefly discuss the role of disorder, electron-electron correlations or both to understand the different ways in which such transitions can occur. In Chapter 2, we describe the different experimental as well as theoretical techniques that have been used in this thesis. In Chapter 3, we study the fermi-edge of the NaxWO3 systems, as a function of x, to understand the origin of the metal-insulator transition occurring in this series of compounds. The system undergoes a metal-insulator transition at the critical composition xc=0.25, below which it is found to be insulating. At the lowest temperature, the very low x compounds behave as disordered and correlated materials. Above the transition composition, the compounds behave as disordered and correlated metals. In the insulating regime, close to the critical composition, we find that the system behaves in a way that cannot be described by any known theories for metals or insulators. We have also done a systematic analysis of the Fermi-edge data for the insulating samples as a function of temperature and we find that they cannot be described by any of the known theories for solid-state systems. Further development is necessary in the theoretical side to understand and interpret our data. In Chapter 4, we study the angle-resolved photoemission data for the highly metallic sodium tungsten bronze Na0.8WO3. We have synthesized the single-crystals by high-temperature electrochemical synthesis and we have performed angle-resolved photoemission experiments to understand the band structure of this system. The experimental results have been supported by theoretical calculations. We find that the rigid band model is valid in describing the electronic structure in these systems. We also find the existence of electron-like pockets along certain symmetry directions. Further, photon energy dependent studies on the x=0.8 sample suggest that there is a difference in the surface with the bulk of the sample. The bulk is perfectly periodic and ordered, whereas the surface shows a distortion due to the rotation or deformation of the WO6 octahedra. In Chapter 5, we have studied the electronic structure of the low dimensional molybdenum oxide La2Mo2O7, which is expected to have a charge density wave(CDW)driven metal-insulator transition around 125K. We indeed observed the presence of CDWs in this system, which was observed in the angle-resolved photoemission spectra as back-folding of bands below the transition temperature. We have also studied the temperature evolution of the bands close to the Fermi level and we see a gradually weakening and finally disappearance of the back-folded bands close to and above the transition temperature. We have studied the angle-integrated spectra of this system from which we conclude that La2Mo2O7 is a CDW non-Fermi liquid system. We have also evaluated the total and partial density of states in this system using Vienna ab-initio simulation package. We find the results consistent with our experimental findings. In Chapter 6, we study the metal-insulator transition in another low-dimensional molybdenum oxide KMo4O6, which is expected to show a metal-insulator transition around 120K due to the formation of spin-density waves. We observed back-folding of bands with lower intensities at low temperature, suggesting the formation of spin density waves in the system. The angle-integrated spectra suggested that the system is a non-CDW non-Fermi liquid system. We have also evaluated the density of states and the results are in agreement with our experimental findings. In conclusion we have investigated the electronic structure of different classes of systems and we have given clue to the origin of the metal-insulator transition in these systems.

In this thesis, drill bit buttons with cobalt, nickel and iron binders in different compositions have been tested against granite and sandstone and the wear and friction have been measured. Furthermore, the wear and degradation of the buttons have been categorized. Buttons with cobalt binder were tested against granite and sandstone and buttons with alternative binders (Ni, Fe, Co) were tested against granite. Cobalt buttons were used as a reference and the wear and friction of the alternative binders was compared to the reference. The amount of worn rock was also measured. Furthermore, post treated drill bit buttons with a composition of Fe-Ni-Co were compared to buttons with the same composition that had not been post treated The results show that buttons with an alternative composition of Fe-Co-Ni and Fe- Ni wears less than the cobalt reference. The post treatment process does not decrease the wear of the drill bit but lowers the deviation from the mean wear. The amount of worn rock does not differ between the samples except for between the post treated and not post treated buttons with a composition of Fe-Ni-Co. The post treated buttons produces more rock debris than the not post treated. No apparent difference could be seen on the surface of the tested buttons after the test. However, composition specific cracks could be found underneath the surface of the samples. EDS-analysis showed signals of oxygen inside of all of the investigated cracks. For some compositions at depths of 20 micrometers. The curves of friction shows similar appearance but the values of the coefficient of friction differs. No apparent correlation was found between the wear and friction of the samples. Furthermore, no apparent correlation was found between the hardness and the wear of the buttons.

Flash photolysis techniques were applied to studies of solvent displacement by Lewis bases (L) from solvated metal carbonyl complexes of Cr, Mo, and W. On the basis of extensive studies of the reaction rate laws, activation parameters , and linear-free-energy-relationships, it was concluded that the mechanisms of solvent displacement reactions depend on the electronic and steric properties of the solvents and L, as well as the identities of the metal atoms. The strengths of solvent-metal bonding interactions, varying from ca. 7 to 16 kcal/mol, and the bonding "modes" of solvents to metals are sensitive to the structures of the solvent molecules and the identities of the metal centers. The results indicate dissociative desolvation pathways for many arene solvents in (solvent)Cr(CO)_5 (solvent = benzene, fluorobenzene, toluene, etc.) complexes, and are consistent with competitive interchange and dissociative pathways for (n-heptane)M(CO)_5. Different types of (arene)-Cr(CO)_5 interactions were suggested for chlorobenzene (CB) vs. fluorobenzene and other non-halogenated arenes, i.e. via σ-halogen-Cr bond formation in the CB solvate vs. π-arene-Cr bond formation through "isolated" double bonds in solvates of the other arenes. The data also indicate the increasing importance of interchange pathways for solvent displacement from the solvates of Mo and W vs. that of Cr.

No description available.

The objective of this doctoral thesis is to develop, engineer and investigate an amorphous metal tungsten nitride (aWNx) and to study its functionality for applications focused on electromechanical system at the nano-scale. Charge transport based solid state device oriented complementary metal oxide semiconductor (CMOS) electronics have reached a level where they are scaled down to nearly their fundamental limits regarding switching speed, off state power consumption and the on state power consumption due to the fundamental limitation of sub-threshold slope (SS) remains at 60 mV/dec. NEM switch theoretically and practically offers the steepest sub-threshold slope and practically has shown zero static power consumption due to their physical isolation originated from the nature of their mechanical operation. Fundamental challenges remain with NEM switches in context of their performance and reliability: (i) necessity of lower pull-in voltage comparable to CMOS technology; (ii) operation in ambient/air; (iii) increased ON current and decreased ON resistance; (iv) scaling of devices and improved mechanical and electrical contacts; and (v) high endurance. The “perfect” NEM switch should overcome all the above-mentioned challenges. Here, we show such a NEM switch fabricated with aWNx to show (i) sub-0.3-volt operation; (ii) operation in air and vacuum; (iii) ON current as high as 0.5 mA and ON resistance lower than 5 kΩ; (iv) improved mechanical contact; and the most importantly (v) continuous switching of 8 trillion cycles for more than 10 days with the highest switching speed is 30 nanosecond without hysteresis. In addition, tungsten nitride could be the modern life vine by fulfilling the demand of biodegradable material for sustainable life regime. Transient electronics is a form of biodegradable electronics as it is physically disappearing totally or partially after performing the required function. The fabricated aWNx suites this category very well, despite not being a universal bio-element. It has been found that aWNx dissolves in ground water with a rate of ≈ 20-60 nm h-1. This means that a 100 nm thick aWNx disappears in ground water in less than a day and three days are enough to dissolve completely a 300 nm thickness device.

Strengthening, resistant and shielding properties, to name a few, can be achieved by implementing a surface material coating onto an engineering component. Various elements of these compounded parts can augment the functionality of the part, such as, increased life time and more interactive surfaces. Tungsten has proven to be a challenge to plate with other metals, but if done correctly, the results can allow for the cold spray of tungsten. Cold spraying tungsten particles alone provides a challenge because the powder is too hard and instead of adhering, it erodes the surface it is attempting to plate. Coating tungsten in a softer metal, like copper, will allow for the particles to adhere to the surface and create a strengthened and radiation shielded component. It also yields a better surface to electroplate onto in the future, as tungsten itself is hard to plate onto, so the copper layer provides the ability to easily plate other metals. The purpose of this thesis project is to encapsulate tungsten powder within copper, then scale up the process to produce bulk amounts of the material in a batch process. The particles will be encased using an electroplating method, that has been vi turned into a semi-autonomous process for the ease of producing bulk powder. While electroless deposition has previously shown positive results for attaining a uniform coating, making it a semi-batch process for bulk material would have an extreme cost in comparison to electrolytic deposition. The tungsten particles have been successfully enclosed in copper by electrolytic deposition in this set of experimentation using an HF electro-etch pretreatment and ultrasonic agitation during electroplating. Further experimentation will include improved methods of stirring and transferring powder, as the transfer takes too long between the etch and the onset of plating and the stirring method is bulky and reduces the area that can be efficiently plated on.