Failure of pump systems operating in highly corrosive mine water at Otjihase mine

A thesis submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfillment of the requirements for the degree of Doctor of Philosophy Johannesburg, March 2018In the Namibian Otjihase underground mine, water is pumped from natural underground reservoirs to the surface using mild steel pumps that have cast iron valves and shaft sleeves coated with a Ni-Cr-Fe alloy. As these components failed very frequently in the highly corrosive mine water environment, it became necessary to provide recommendations for alternative pump materials. The Ni-Cr-Fe coated, carbon steel shaft sleeves were mechanically worn by abrasion in contact with debris trapped in packing glands. The highly corrosive mine water contained solid soil particles, which contributed to internal erosion-corrosion of the pump components. Once the protective coating was breached, the exposed steel corroded rapidly when reacting with the corrosive mine water, resulting in leakages. The main objective of this work was therefore to characterise the steel and cast iron components used in the pump system, determine methods to improve the tribocorrosion resistance of the pump components and recommend a hardfacing material with improved performance in the tribocorrosive mine environment. To simulate and study the synergistic effect of electrochemical and mechanical interaction between the pump components and highly corrosive mine water, the hardness and electrochemical response in synthetic mine water of the following proposed bulk materials were tested: Hastelloy G30, ULTIMET, Stellite 6B and ToughMet 3. Hastelloy G30 demonstrated good corrosion resistance, but had low hardness and poor abrasion resistance. ToughMet 3 had high hardness, but low corrosion resistance. As ULTIMET and Stellite 6B both had high hardness and good corrosion resistance, they were selected for further investigation to assess sliding abrasive wear and tribocorrosion behaviour in synthetic mine water. The possibility of enhancing the corrosion resistance of ULTIMET and Stellite 6 (not 6B) alloys as protective coatings by adding minor amounts of ruthenium was investigated. ULTIMET and Stellite 6 powders were each mixed with nominal 0.3 wt% Ru and nominal 0.6 wt% Ru additions. The powders with no Ru, nominal 0.3 wt% Ru and nominal 0.6 wt% Ru were then thermally sprayed by the high velocity oxy-fuel flame (HVOF) process onto a carbon steel substrate, and compared to a Cr2O3 coated steel as a benchmark. The powders and the coatings were characterised using optical and scanning electron microscopy with energy dispersive X-ray spectroscopy, and X-ray diffraction. Hardness, sliding abrasive wear, and corrosion and tribocorrosion behaviour of the coatings and the substrate in synthetic mine water were then determined. Comparison of the hardness showed that the nominal 0.3 wt% Ru ULTIMET coating had higher hardness than the same coatings with no Ru and nominal 0.6 wt% Ru, the nominal 0.6 wt% Ru Stellite 6 coating had the highest hardness and overall, the Stellite 6 coatings had higher hardness values than both ULTIMET and Cr2O3 coatings. At pH 6, the ULTIMET and Stellite 6 coatings with and without Ru additions had low corrosion current densities and consequently low corrosion rates in synthetic mine water. For the ULTIMET coatings, the corrosion rates decreased as the Ru content increased. The Stellite 6 coating had slightly lower corrosion current densities and corrosion rates than ULTIMET under all tested conditions. Stellite 6 coatings had lower abrasive wear rates at the tested loads than the other materials. The lowest abrasive wear rates were recorded with additions of nominal 0.3 wt% Ru (5 N), and nominal 0.6 wt% Ru (10 N). As expected, tribocorrosive wear rates increased with increasing load for all alloys. Ruthenium additions to ULTIMET and Stellite 6 coatings decreased the tribocorrosive wear rate. The best tribocorrosion resistance was achieved by the Stellite 6 coatings. Stellite 6B bulk samples and Stellite 6 coatings with Ru had higher hardnesses, lower corrosion rates, lower wear rates and lower tribocorrosion rates than the carbon steel substrate, Cr2O3 coating, and ULTIMET bulk material and coatings. Stellite 6 coating with nominal 0.6 wt% Ru exhibited lower corrosion rates at pH 6 and 3 than the ULTIMET coating. Therefore, the Stellite 6 coating were recommended for use in pump shaft sleeves and the Stellite 6B bulk alloy in valves at Otjihase Underground Mine. The cost saving for using the proposed alternative materials was calculated as US$ 8 546.68 (R 128 200.20) per year. This is a major economic incentive for Otjihase Underground Mine.MT 201

The Effects of Composition and Heat Treatment on the Microstructure and Performance of Cobalt-based Alloys for Molten Zinc Applications

The purpose of this research was to identify and develop cobalt-based superalloys for journal bearing applications by improving the stability and service life of submerged galvanising pot hardware. To achieve this goal the mechanical properties and chemical resistance of four cast cobalt superalloys were investigated. The alloys were subjected to three heat treatments which included a high temperature annealing treatment, a solution treatment and additional age hardening, and a plasma nitriding treatment. The heat-treated alloys were examined and compared to untreated samples to identify any microstructural changes or improvements in material performance. Four commercially available cobalt-based superalloys were identified for analysis including three cast CoCrW alloys and one cast CoCrMo Tribaloy. It was identified that increasing the carbon and tungsten content, with the CoCrW alloys, increased the area fraction of chromium and tungsten carbide phases in addition to increasing the concentration of alloying elements retained in solid solution. Both factors contributed to increased material hardness. The substitution of tungsten with molybdenum and the absence of carbon, with the CoCrMo Tribaloy, replaced the formation of eutectic carbides with a primary Laves phase that dominated the Tribaloys microstructure. This provided the CoCrMo alloy with enhanced hardness properties compared to the CoCrW alloys. The untreated alloys were submerged in a molten zinc alloy bath containing 0.35wt.% Al in a series of static immersion tests where the alloys were submerged for times ranging between 1-4 weeks. All the materials reacted with the molten zinc bath resulting in the diffusion of bath species into the alloys microstructure as well as the leaching of alloying elements into the bath. With each alloy, molten metal ingress preferentially occurred in the cobalt rich solid solution phase whereas the carbide and Laves phases were more resistant to bath reactivity. The high area fraction of Laves phase and increased molybdenum concentrations retained in eutectic solid solution with the T-800 Tribaloy, provided the alloy with enhanced chemical resistance to the bath in comparison to the CoCrW alloys. The improved chemical resistance reduced the depth of diffusion and reduced the quantity of cobalt-aluminide formation at the alloys surface. A plasma nitriding treatment resulted in the formation of a nitrogen rich diffusion layer at the surface of each of the alloys. Increasing the treatment temperature or treatment time produced a thicker diffusion layer with increased concentrations of nitrogen. The formation a nitride layer significantly improved the surface hardness of each of the alloys where increased material hardness correlated with a thicker diffusion layer. The plasma treated samples were dip tested in a molten zinc bath containing 0.35wt.% Al. The formation of the nitride diffusion layer improved the long-term chemical performance of the alloys where reduced zinc and aluminium diffusion depths were recorded with the CoCrW alloys after 4-weeks of testing. The nitride treatment generally improved the surface integrity of the alloys where increased levels of alloying elements were retained within the matrix diffusion layer after prolonged bath exposure and each alloy experienced less material loss. There was also a noticeable reduction in the quantity of cobalt-aluminide phases at the alloy’s surfaces. An annealing heat treatment slightly changed the morphology of the alloy’s microstructure where phase precipitation within the solid solution phase occurred in addition to low levels of carbide dissolution. Small improvements in material hardness were recorded with the CoCrW alloys whereas the annealing treatment had detrimental effects on the hardness properties of the CoCrMo alloy. Using the nano-properties of the matrix to calculate the mean H/E ratio it was predicted that the wear performance of the matrix of the WT-4 and WT-12 alloys were slightly improved by the annealing process. A solution treatment significantly changed the microstructure morphology of the WT-6 and WT-12 alloys. The solution treatment resulted in extreme coarsening of the chromium and tungsten carbides with the WT-12 alloy and coarsening of the chromium carbides and the precipitation of tungsten rich phases with the WT-6 alloy. Low levels of carbide dissolution were also recorded. A drop in material hardness was recorded with both alloys after the solution treatment. Additional aging treatments did not significantly alter the alloys microstructures further but precipitation within the matrix occurred. This coincided with significant improvements in the hardness properties of both alloys. Calculating the mean H/E ratio of the matrix phase in both alloys estimated that no improvements in matrix wear resistance occurred with WT-6 alloy whereas an improvement with the WT-12 matrix was calculated