No description available.

No description available.

No description available.

Platinum-group elements (pGEs) are recovered from UG2 chromitite by milling and flotation. The mechanisms involved during beneficiation of this type of ore are still poorly understood, partly because of its complex nature. Image-analysis techniques were used to characterise the mineralogy ofUG2 chromitite from diverse geological environments, as well as the milling and flotation products derived from each of these ores. Postmagmatic alteration ofUG2 chromitite has a profound effect on the mineralogy, chemistry and recovery characteristics of the UG2 chromitite. Relatively unaltered UG2 chromitite consists predominantly of chromite and primary silicates, mostly bronzite and plagioclase with minor phlogopite, and small amounts of secondary silicates such as talc and chlorite. Trace quantities of base-metal sulphides, predominantly pentlandite, pyrrhotite and chalcopyrite ± pyrite, generally occur at chromite-silicate grain boundaries. PGEs are present both as discrete PGE minerals, and, to a lesser extent, sub-microscopically in other phases, mostly palladium and rhodium in pentlandite. The PGE mineral assemblage is characterised by sulphide minerals, mostly braggite, cooperite, nickeloan malanite and laurite, and is closely associated with the base¬metal sulphides. Recovery of PGE minerals is strongly dependent on the degree of liberation, with liberated PGE minerals and PGE minerals associated with liberated base-metal sulphides, the fastest-floating particles. PGE minerals report to flotation tailings predominantly as fine-grained inclusions in coarse silicate particles. In places, the footwall rocks have been replaced by iron-rich ultrabasic pegmatoid. As a result of interaction with Fe- and Ti-rich fluids, the chromite grains in the UG2 chromitite have been enlarged due to sintering, and the PGE mineral assemblage replaced by one consisting predominantly of laurite, Pt-Fe alloy and other non¬sulphide PGE minerals. The non-sulphide PGE mineral grains appear to be slower ¬floating than sulphide PGE minerals. Low temperature hydrothermal alteration appears to have caused relatively widespread alteration of the UG2 chromitite in some areas, resulting in corrosion and redistribution of sulphide minerals, as well as the replacement of primary magmatic silicates by secondary silicates such as pumpellyite, epidote, prehnite, albite, talc, chlorite and quartz. Ore from such areas are characterised by a base-metal sulphide assemblage consisting predominantly of millerite, chalcopyrite, and pyrite. Base¬metal sulphide and PGE minerals occur in fine-grained intergrowths with silicates, resulting in poor liberation. In the samples investigated, composite particles were often faster-floating than expected, at least partly due to the presence of naturally floatable talc. The effect of faulting on the mineralogy of the UG2 chromitite probably depends on distance from the fault zone, and possibly also timing of faulting, and can cause cataclasis of the ore. Where cataclasis occurred, broken mineral grains are cemented by secondary, hydrous silicates. Liberation of base-metal sulphides and PGE minerals are poor, and recoveries consequently very low. It was demonstrated that reasonable estimates of total PGE+Au recovery can be made from the mineralogical characteristics ofUG2 chromitite ore. Based on the mineralogy of ore from a specific area, provision can be made for appropriate adjustments to metallurgical flowsheets. / Thesis (PhD)--University of Pretoria, 2006. / Geology / Unrestricted

This work aims to develop solvent extractants to recover platinum and palladium from highly acidic chloride solutions bearing other platinum group metals (PGMs). In general, metal values can be recovered by solvent extraction through three different mechanisms: metal cation extraction (1); metalate anion extraction (2); or metal salt extraction (3). Mn- + n(LH)(org) ⇌ [M(L)n](org) + nH+ (1) MClx n- + nL(org) + nH+ ⇌ [MClx(LH)n](org) (2) MClx + nL(org) ⇌ [MClxLn](org) (3) The main objective of this thesis is to establish whether ditopic extractants can be developed which have chemical functionalities that allow both mechanisms (2) and (3) to operate, co-extracting Pt(IV) and Pd(II) as their chloridometalates in an outer sphere binding site (2) and allowing their separation by raising pH to transfer the more kinetically labile Pd(II) to an inner sphere binding site (3) and releasing H2PtCl6 to the aqueous strip solution. A review of the literature is presented in Chapter 1, noting current commercially available extractants and the processes in which they are, or have been, applied. Particular attention is paid to the mode of action of the reported extractants and whether they extract metal cations, anions or metal salts. This chapter also outlines the proposed solvent extraction circuit in which new reagents developed in this thesis would be incorporated and the methods applied during the screening of candidate extractants. Chapter 2 deals exclusively with the use of reagents with inner-sphere binding sites for the selective extraction of palladium over platinum. Work on a series of oxime reagents synthesised for palladium extraction as part of preliminary MSci research (Andrew M. Wilson, MSci Thesis, University of Edinburgh, 2011) is reviewed. Studies of the hydrolytic stability of oximes indicate that they are unsuitable for incorporation into ditopic reagents for use in a circuit with a highly acidic feed solution. Thioethers were studied as alternatives as they show high kinetic selectivity for palladium over platinum and are more stable under acidic conditions. The synthesis and extraction properties of model reagents (largely arylalkyl thioethers) are reported and compared with those of the commercially available di-n-hexylsulfide. Incorporation of a polar group such as an amide provides phase transfer catalysis, accelerating the rate of transport of Pd(II) into the organic phase, but reducing selectivity over Pt(IV). The identification of functionalities that operate as receptors for chloridometalates by forming outer-sphere assemblies is explored in Chapter 3. The synthesis of amine, amide and amino-amide extractants from acid chloride streams and the effects of variations of functional groups on the extraction of PtCl6 2− are described. Secondary amides were found to be stronger extractants than tertiary amides, and aliphatic amides also show better metalate extraction than aromatic amides. The interactions between protonated aminoamide reagents and PtCl6 2− werre analysed by X-ray crystallography, noting that C-H∙∙∙Cl interactions with the “soft” chloridometalate anion are more common than with the “hard” chloride ion which shows a preference for more conventional N-H∙∙∙Cl interactions. Chapter 4 combines the reagent types explored in Chapters 2 and 3, in ditopic extractants that have both inner- and outer sphere binding sites. The synthesis and characterisation of a series of thioether amide reagents are reported and the selective extraction of platinum and palladium over other PGMs are discussed. In-house screenings of aryl- and alkylthioetheramide extractants showed selective co-extraction of Pd(II) and Pt(IV), rejecting Ir(III). Pt(IV) can be selectively water-stripped followed by ammonia-stripping of Pd(II). Industrial screenings at Johnson Matthey Technology Centre further exemplified the selectivity of these extractants over Ru(III) and Rh(III), although third phases were formed when the reagents were used for recovery from highly concentrated metal-feed solutions. The mode of action of the ditopic extractants is discussed, based on DFT calculations, crystal structure determinations and NMR studies, which support the formation of outersphere metalate assemblies and inner-sphere palladium complexes. Chapter 5 describes new difunctional (inner + outer sphere complexation) extraction by a single chemical entity, in this case an unsaturated N-heterocycle (an azole). The synthesis and characterisation of a series of hydrophobic azoles are described. These have basicities which allow protonation when contacted with strongly acidic solutions (2), but can be deprotonated in contact with water to allow their neutral forms to form inner-sphere complexes with Pd(II). Triazole-based reagents show the selective co-extraction of Pt(IV) and Pd(II) and, as with the ditopic thioetheramide reagents reported in Chapter 4, allow the selective water stripping of Pt(IV) and subsequent ammonia stripping of Pd(II).

The importance of platinum group metals for catalytic and microelectronic applications has prompted research into the development of novel molecular precursors for chemical vapor deposition of thin films of these metals. A variety of molecular architectures, ligand systems, as well as deposition conditions are investigated and related to the morphology and composition of the resultant films. For example, amorphous thin films of ruthenium and phosphorus alloys are deposited using single source metal hydride precursors, while use of the 3,5-di-substituted pyrazolate ligand in conjunction with various rhodium starting materials leads to a variety of different volatile monomeric and dimeric complexes. Synthesis of pyrazole and pyrazolate complexes of tungsten and palladium are also explored. In a related research area, progress towards the development of novel synthetic routes to mesostructured transition metal phosphides and borates for Li-ion battery electrode applications is summarized. Traditional routes to these materials involve high-temperature syntheses, allowing limited control over morphology. Identification of low-temperature reaction conditions necessary to afford a desired composition, morphology and electrochemical performance of the bulk material are the main goals of this project, and results are discussed with various early transition metals. / text

Thesis (Ph.D.) --Murdoch University, 2004. / Thesis submitted to the Division of Science and Engineering. Includes bibliographical references (leaves 300-336).

A series of polydentate POM-selective, sulfur-containing amide ligands have been synthesized from ro-dibromoalkanes and mercaptoacetanilide, The resulting 3,6- dithiaoctanediamides and 3,7-dithianonanediamides, some of which contain a polymerisable group, were all characterized by high-resolution MS, IR, I Hand I3C NMR spectroscopic methods. Various approaches to the polymerisable ligands were explored, the most efficient proving to be the incorporation of an allyl ether moiety in the mercaptoacetanilide. The corresponding Pd(U) and Pt(II) complexes were also prepared from the metal chloride salts and characterized by elemental analysis and spectroscopic methods. The NMR data indicates that both the cis- and transcomplexes were formed, while the IR data indicates cis- coordination of the chlorine . ligands. Molecularly imprinted polymers (MIP's), prepared using platinum(II) mercaptoacetanilide and 3,6-dithiadiamide complexes, showed high selectivity for , , palladium(II) [in the presence of Pt(II), CoCII), Cu(II) and Ni(II)] as determined by . ICP-MS analysis. The more kinetically inert Pt(II) ions however, slowly displaced Pd(II), confirming the Pt(II) selectivity of the MIP's. Solvent extraction studies were conducted to explore the selectivity of the 3,6- dithiaoctanediamides and 3,7-dithianonanediamides for Pd(U) over CoCII), Cu(U) and Ni(II). The ICP-MS data indicate that, in general, equilibration was achieved within ten minutes and that the longer-chain amides were less selective than the shorter-chain analogues. / KMBT_363 / Adobe Acrobat 9.54 Paper Capture Plug-in

In recent years numerous complexes have been reported in which olefins were chelated to transition metals.Ever since the generally regarded first olefin complex, Zeise's salt (32) KPt(C2H43, the interest in this field of organometallic chemistry has expanded to several families of olefinic ligands and metals like palladium(II), platinum(II) copper(I), silver(I), and more recently vanadium and titanium The nature of the bonding of olefins to metal atoms seemed to involved the interaction between pi electrons in the unsaturated molecule and the hybrid orbitals of the metal rather than a localized sigma bonds between the metal atom and a particular carbon atom. The metal was complexed to a hydrocarbon which possessed a surplus of electrons. The direct overlap of a sigma orbital of the metal anad the p-orbital of the carbon atom formed a sigma type bond. The ligand carbon atom donated a surplus bonding pi-p electrons to a vacant sigma orbital of the metal while at the same time the excess negative charge was released back to the olefin from from a pi-d orbital of the metal to an empty antibonding pi-p orbital of the carbon atom. Dewar (9) illustrated this point by molecular orbital diagram. (See figure B) [see PDF file for Formula] The metal to olefin bond consisted of two parts: (a) overlap of the pi electron density of the olefin with sigma type acceptor orbital on the metal atom and (b) a "back-bonding" resulting from the flow of electron density from filled metal dxy or other dπ - pπ hybrid orbitals into antibonding orbital on the carbon atom. A schematic diagram of platinum olefin complexes can be shown as: [see PDF file for Formula] It was the intention of this research to increase our understanding of these stable diolefin complexes. In particular, the occurrence of rearrangement upon complexation of certain ligands to most likely a more stable configuration posed an interesting project. They syntheses of diolefin complexes provided an establishment of good technique and verification of reported data. The program of study was concentrated on the complexation of cyclic diolefins with primarily palladium(II) and platinum(II) chloride.

Thesis (MSc)--Stellenbosch University, 2013. / Please refer to full text to view abstract.