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M.Sc. (Chemistry) / Cobalt is mainly associated with copper, both in the primary ores and in the oxidation zone. In Southern Africa cobalt metal is produced as a by-product of the extraction of copper, nickel and platinum group metals. The hydrometallurgical route is commonly used, since cobalt bearing materials are acid leached prior to the clarification and impurity removal process preceding the electrowinning of the value. In order to understand the dissolution behaviour of cobalt and copper bearing minerals from Co-Cu oxide ores, the relationship between and the impact of physical, chemical and mineralogical properties of the materials and the dissolution behaviour of cobalt and copper bearing minerals contained in the feed materials was studied. Four Co-Cu oxide ore samples namely; high cobalt ore (HCo), high copper ore (HCu), low cobalt ore 1 (LCo1) and low cobalt ore 2 (LCo2) were characterised in terms of elemental composition, cobalt and copper species, functional groups, mineral phases, mineral abundances, mineral/ore grains size distribution, particle specific surface area, particle ore density and porosity, in order to elucidate the impact of these properties on the dissolution rate and percentage recovery of cobalt and copper in the acid generated leachate...

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The first part of this dissertation explores the chemistry of an inhibitor complexation with Cu. First, the Cu oxidation state of the complex was +1. Second, identified by differential RAIRS, one source of Cu(I) for the Cu(I)-inhibitor complex could be Cu(I) oxide. The characteristic Cu(I) oxide peak at 650 cm⁻¹ was observed to decrease after CVD coating process was applied. This led to a major hypothesis that in order for the reaction between Cu(I) oxide and the inhibitor to proceed, protons from the inhibitor and oxygen from Cu₂O are stabilized by reacting to form water. The applicability of the passivation nature of Cu(I)-inhibitor films was explored for Cu-Al wire-bonded devices in its ability to protect from Cu-Al peripheral galvanic corrosion and the galvanic corrosion of the Cu-Al intermetallic compounds in their roles for corrosion-induced liftoff. The second part of this work studied the effect of replacing Al bond pad with Cu on the corrosion induced liftoff of wire-bonds when exposed to low ppm levels of chloride contamination. Applying protective coating to the Cu pad surface before wire-bonding was found to suppress the thermally induced oxidation of Cu in air, helping to enable successful Cu-Cu direct wire-bonding. Compared to Cu-Al devices with passivation coating, which has a few wires liftoff with 6 hours, the Cu-Cu bonded devices survived much longer, over 40 days, with almost no liftoff observed. This demonstrates that removing the galvanic contact, the root cause of the corrosion induced failure, is a more robust and permanent solution to the corrosion experienced by these devices.

Diss. (sammanfattning) Uppsala : Sveriges lantbruksuniv., 2003. / Härtill 3 uppsatser.

abstract: Programmable Metallization Cell (PMC) devices are, in essence, redox-based solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Organic water pollutants such as dyes are difficult to biodegrade. In this study Fenton, photo-Fenton and photocatalysis were used to degrade methylene blue dye in the presence of copper oxide catalysts. The copper oxide catalysts were prepared with a precipitation reduction method. The effect of different preparation parameters on the catalyst properties and catalytic activity were investigated. The reducing agents, ascorbic acid (ASC, C6H8O6), hydrazine (N2H4), sodium boron hydride (NaBH4) and glucose (C₆H₁₂O₆) could be used to obtain the desired Cu2O phase. ASC, N2H4 and NaBH4 were able to reduce copper (II) to copper (I) at room temperature whereas glucose required a higher reduction temperature. Stoichiometric amounts of the reducing agents ASC, N2H4 and glucose and double the stoichiometric amount of NaBH4 were required to obtain Cu2O. A further increase in the amounts of NaBH4 and N2H4 resulted in the formation of copper metal (Cu (0)). High amounts of ASC did not over-reduce the copper. ASC also functioned as capping molecule and anti-oxidant preventing the oxidation of the Cu2O to CuO in air after preparation. Hydrazine was thus not able to protect the Cu2O against oxidation. The SEM results showed that an increase in the amount of the precipitating agent, NaOH, resulted in an increase in the particle sizes. The particle shapes changed from spherical to cubic when a high amount of NaOH was used with hydrazine as reducing agent. Smaller particle sizes were obtained when CuCl2 was used instead of CuSO4 and Cu(NO3)2. Larger crystallites formed when the preparation temperature was increased from room temperature to 100°C with glucose as reducing agent. TEM and XRD analyses showed that the micro-particles seen in SEM analyses are made up of nano-particles. The catalysts were not active for photocatalysis which may be explained by the oxidation of these nano-particles to form the photocatalytic inactive CuO. The catalysts were shown to be active for Fenton and photo-Fenton degradation. The addition of graphene and activated carbon to the Cu2O catalysts were detrimental to the catalytic activity. The percentage degradation of methylene blue by the Fenton reaction increased with an increase in the BET surface area from 1.5 m2/g to 10 m2/g and a further increase in the surface area resulted in a decrease in the percentage degradation. A direct correlation between the Fenton catalytic activity and the pore size were found which indicate that the reaction was mass transfer limited.

Thesis (M. Tech.(Chemistry)--Vaal University of Technology)), 2010 / Mining industry produces metals which are economical and serve as high valuable commodities in South Africa. This country is regarded as the world leading producer of precious metals such as platinum group metals (PGMs). Silver (Ag), which is also a precious metal, contribute to the country’s economy wealth due to its significance during industrial applications. Base metals such as copper (Cu) and nickel (Ni), though they are low valued, play a significant role in the republics economic wealth. Mining wastewater contains some of these metals, which end up polluting the environment. A possibility to recover this was investigated using NF membranes. Mine effluent was simulated by using relevant reagents. Characterization of NF90, NF- and NF270 membranes, was done by using scanning electron microscopy (SEM), clean water permeability, single charged salts of NaCl and MgCl2 and binary mixture of NaCl/MgCl2 studies. All the rejection experiments were conducted at pH 2.0 with varying pressure and concentrations. Flux measurements indicated that water permeability through the membranes trend, NF270 > NF90 > NF-. The experiments were performed at pressures of 5 bar, 10 bar, 15 bar and 20 bar. For NF90 membrane, a rejection of Na+ monovalent ion in 20 ppm solution was less than of Mg2+ (divalent) ion. Percentage rejections of 90% (Na+) and 98% (Mg2+) were achieved. NF- had rejection of 83% and 90% for Na+ and Mg2+, respectively. In the case of NF270, the membrane had rejection of 92% (Na+) and 94% (Mg2+), respectively. At 100 ppm, all three membranes showed a decreasing trend in rejection while increasing pressure. For binary-solution mixture, Mg2+ ion still had the highest rejection compared to Na+ ion with about 94% and 85% on NF90 than on NF270 and NF-. The high rejection of divalent ion as compared to monovalent ion for charged solutes was due to solute size and electrostatic interaction between the membrane surface layer and the solute. In the case of transition metal rejection studies, Pd2+ ion had an average of 90%, with Ni2+ ion ≈ 95% and Cu2+ ion ≈ 98% as single salts on NF90 compared to NF270 and NF-. However, as for binary and trinary solution mixture, the competition amongst ions was high, where Pd2+ ion rejection was ≈ 99,0%, while Ni2+ and Cu2+ ions was > 90% on NF90 and NF-. Therefore it was excluded from the tests. For the monovalent metal ions (Ag+ and Cu+), the rejection was > 90% in almost all concentrations mixtures. During membrane fouling evaluation, AgCl salt fouled the most, compared to other metal ions, forming a concentration polarization accumulation on the membrane surface for both 20 and 100 ppm solutions. This situation leads to cake layer formation which causes a flux decline, reduces membrane life time and lowers the rejection performance of NF membranes. The aim of this study was to evaluate the performance of three commercial polymeric membranes (NF90, NF270 and NF-) during rejection of the metal