This study is part of the multidisciplinary research program funded by the EPSRC aimed at further understanding the mechanisms behind the oxidation, transition and breakaway of zirconium alloys. The current study concentrates on the effect of artificially introduced hydride rich rim region upon the corrosion performance of zirconium alloys. The methodology of cathodic hydrogen charging of zirconium specimen has been described. The intention is to create a hydride rich rim similar to observation made in end-of-life fuel claddings from nuclear reactor. The overall hydrogen levels in the samples were determined via inert gas fusion and the local hydride volume fractions via laboratory x-ray diffraction. The residual stress state in the rim was investigated by synchrotron x-ray diffraction. The rim was determined to have local hydrogen levels about 11,000 wt.ppm and predominantly δ-hydrides. Hydrided samples and their references were tested in autoclaves simulating primary water environment. Reference samples exhibited typical corrosion kinetics with a change from pre- to post-1st transition. The duration before 1st transition varies with alloy chemistry and heat treatment conditions. Hydrided samples generally experienced accelerated corrosion while the extent to which the material was affected depends on alloy chemistry. Parabolic rather than cubic oxide growth with a very slow early corrosion rate was recorded in hydrided alloys. Both hydrided and reference samples of three Zr-Sn-Nb alloys, ZIRLOTM, low tin ZIRLO and X2 with tin concentration ranging from 0.14 to 0.92 wt.% became the gravity of further characterisations since they exhibited improved corrosion performance with decreasing tin content. The microstructure of the oxide was investigated via cross-sectional Scanning Electron Microscope (SEM). The residual stress state in tetragonal and monoclinic phases as well as tetragonal phase fraction were studied via synchrotron x-ray diffraction, showing high in-plane compressive stresses in the oxide of different levels depending on the phase and alloy. The presence of a hydride rim lowered the residual stress. White oxide in hydrided samples displays lower residual stress level, smaller tetragonal phase fraction and higher degree of oxide grain misorientation when compared to black oxide regions of reference and hydrided samples. It was also found that the hydride rim region undergoes local depletion of hydrides in alloy with low Sn content during the early stage of aqueous corrosion. Finally a model was given to describe the different roles played by individual oxide and hydride phases during the oxidation of zirconium alloys.

Zirconium tetrachloride (ZrF4) is extensively used in the manufacturing of zirconium metal. The concept of producing zirconium tetrafluoride from dissociated zircon and ammonium bifluoride is well established at the South African Nuclear Energy Corporation (Necsa) State Owned Company (SOC) Limited. Zirconium and hafnium are always found in the same minerals. In nuclear application zirconium is used for structural construction and as a cladding material for fuel, because of the low thermal neutron absorption, while hafnium is used as control rod in nuclear reactor, because of the high thermal neutron absorption. The methods of separating hafnium from zirconium prefer the use of ZrCl4 than ZrF4. This is because of the high solubility in both aqueous solutions and organic solvents and low sublimation temperature of ZrCl4, while ZrF4 is almost insoluble in organic solvent and has a high sublimation temperature. Thermodynamic evaluations showed that chlorinating ZrF4 with either CaCl2, KCl, LiCl or NaCl respectively was not favourable, while chlorinating ZrF4 with either BeCl2 or MgCl2 was favourable. But due to cost consideration chlorinating ZrF4 with BeCl2 was not investigated. A thermogravimetric apparatus was used to investigate the isothermal and the non-isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2. The thermogravimetric apparatus revealed that chlorination of ZrF4 commence at temperature above 350°C. Isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2 was investigated at temperatures of 400, 450, 480, 500°C. The reaction progressed towards completion prematurely before the isothermal temperatures were reached, due to a low heating rate of 20 °C/minutes was used to heat up the reaction mixture to the desired isothermal temperatures. As a result, the isothermal kinetics could not be determined. Heating rates of 5, 10, 15 and 20 °C/minutes were used to investigate the non-isothermal kinetics. The apparent activation energy of chlorinating ZrF4 with MgCl2 varied significantly when the non-isothermal kinetics was investigated. The variation was due to changes in the reaction mechanism. As a result, rate law of chlorinating ZrF4 with MgCl2 could not be determined due to variation of the apparent activation energy. Crude ZrF4 prepared at Necsa SOC ltd. was chlorinated with MgCl2, a mixture of MgCl2 and KCl, a mixture of MgCl2 and LiCl, and a mixture of MgCl2 and NaCl respectively. Chlorination of the crude ZrF4 was conducted at temperatures of 400, 450 and 500°C respectively. The aim of chlorinating the crude ZrF4 was to investigating the effect of the chlorinating on the purity of the produced ZrCl4. A batch reactor was used in this study. The reactor was divided into two sections, namely the reaction zone and the condensation zone. The diameter of the condensation zone was larger than that of the reaction zone. Reactants were placed into the reaction zone and the products were collected at the reaction zone and the condensation zone. Samples were collected from these products and analysed using for X-Ray Diffraction analysis (XRD) and Inductive Coupled Plasma Optical Emissions Spectroscopy (ICP-OES). XRD was used to identify the compounds that were present in the products and ICP-OES was used to determine the concentration of the elements that were present in the products. The analysis of the results obtained showed that the highest recovery of zirconium in the products collected from the condensation zone, the sublimed products, was achieved by chlorinating ZrF4 with MgCl2 at 500°C. About 80% was recovered. About 96% of the concentration of the impurities in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and LiCl at 450°C. About 36% of hafnium in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and NaCl at 400°C. / Chemical Engineering / M.Tech. (Chemical Engineering)

Zirconium tetrachloride (ZrF4) is extensively used in the manufacturing of zirconium metal. The concept of producing zirconium tetrafluoride from dissociated zircon and ammonium bifluoride is well established at the South African Nuclear Energy Corporation (Necsa) State Owned Company (SOC) Limited. Zirconium and hafnium are always found in the same minerals. In nuclear application zirconium is used for structural construction and as a cladding material for fuel, because of the low thermal neutron absorption, while hafnium is used as control rod in nuclear reactor, because of the high thermal neutron absorption. The methods of separating hafnium from zirconium prefer the use of ZrCl4 than ZrF4. This is because of the high solubility in both aqueous solutions and organic solvents and low sublimation temperature of ZrCl4, while ZrF4 is almost insoluble in organic solvent and has a high sublimation temperature. Thermodynamic evaluations showed that chlorinating ZrF4 with either CaCl2, KCl, LiCl or NaCl respectively was not favourable, while chlorinating ZrF4 with either BeCl2 or MgCl2 was favourable. But due to cost consideration chlorinating ZrF4 with BeCl2 was not investigated. A thermogravimetric apparatus was used to investigate the isothermal and the non-isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2. The thermogravimetric apparatus revealed that chlorination of ZrF4 commence at temperature above 350°C. Isothermal kinetics of chlorinating analytical grade ZrF4 with MgCl2 was investigated at temperatures of 400, 450, 480, 500°C. The reaction progressed towards completion prematurely before the isothermal temperatures were reached, due to a low heating rate of 20 °C/minutes was used to heat up the reaction mixture to the desired isothermal temperatures. As a result, the isothermal kinetics could not be determined. Heating rates of 5, 10, 15 and 20 °C/minutes were used to investigate the non-isothermal kinetics. The apparent activation energy of chlorinating ZrF4 with MgCl2 varied significantly when the non-isothermal kinetics was investigated. The variation was due to changes in the reaction mechanism. As a result, rate law of chlorinating ZrF4 with MgCl2 could not be determined due to variation of the apparent activation energy. Crude ZrF4 prepared at Necsa SOC ltd. was chlorinated with MgCl2, a mixture of MgCl2 and KCl, a mixture of MgCl2 and LiCl, and a mixture of MgCl2 and NaCl respectively. Chlorination of the crude ZrF4 was conducted at temperatures of 400, 450 and 500°C respectively. The aim of chlorinating the crude ZrF4 was to investigating the effect of the chlorinating on the purity of the produced ZrCl4. A batch reactor was used in this study. The reactor was divided into two sections, namely the reaction zone and the condensation zone. The diameter of the condensation zone was larger than that of the reaction zone. Reactants were placed into the reaction zone and the products were collected at the reaction zone and the condensation zone. Samples were collected from these products and analysed using for X-Ray Diffraction analysis (XRD) and Inductive Coupled Plasma Optical Emissions Spectroscopy (ICP-OES). XRD was used to identify the compounds that were present in the products and ICP-OES was used to determine the concentration of the elements that were present in the products. The analysis of the results obtained showed that the highest recovery of zirconium in the products collected from the condensation zone, the sublimed products, was achieved by chlorinating ZrF4 with MgCl2 at 500°C. About 80% was recovered. About 96% of the concentration of the impurities in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and LiCl at 450°C. About 36% of hafnium in the sublimed products was reduced when ZrF4 was chlorinated with a mixture of MgCl2 and NaCl at 400°C. / Chemical Engineering / M.Tech. (Chemical Engineering)