Th. doct.-ing.--Génie électrique--Grenoble--I.N.P., 1983. N°: DI 336.

Many of the world's economic rare earth element (REE) deposits are formed from, or have been subsequently upgraded by, hydrothermal fluids. Some of the most important REE minerals are the light REE (LREE) enriched fluorocarbonates and carbonates, which are commonly found in carbonatites. Textural and mineralogical evidence from these and other sites point towards wall rock composition as a major control on the observed REE mineralisation, with the supply of carbonate, and possibly fluoride, thought to be the limiting factor. Despite theoretical and experimental studies focussed on REE speciation in hydrothermal fluids, and a few on REE mineral solubility, there remains a lack of understanding of the processes occurring at the uid-rock interface during REE carbonate and fluorocarbonate mineralisation. Many of the issues surrounding this topic stem from the difficulty of working at elevated temperatures, low REE concentrations, and with the corrosive fluoride ion. The synthesis of REE carbonates under simple, low temperature conditions is a useful starting point for understanding REE mineralisation, and as such has been the focus of research for decades. Despite this, cross-series trends are rarely assessed together under the same conditions, and multi-REE-bearing systems - useful for assessing REE fractionation - have scarcely been explored. Furthermore, wall rock experiments, whereby REE-rich fluids are reacted directly with carbonate rocks, are absent from the literature. The same is true for systems containing fluoride, necessary for studying the formation of fluorocarbonates. A fuller understanding of REE mineralisation cannot be achieved until empirical experimental results can be compared with theoretical data and field observations. This thesis documents the laboratory synthesis of single- and multiple-REE-bearing carbonates and fluorocarbonates, and compares the findings with a mineralogical and textural study of two REE-bearing carbonatite deposits. The REEs La, Nd, Gd, Er and Yb were investigated as representatives of the entire series. The experiments constituted titrations of REE chloride solutions with sodium carbonate, and `wall rock reactions' of REE chloride with dolomite, or dolomite plus fluorite. Batch and flow-through setups were used, and the experiments were performed, or the products aged, at temperatures ranging from ambient to 200 °C. Products were characterised by techniques such as PXRD and SEM to document their structure and morphology as a function of temperature, and assess the influence of single vs multiple REE on the final material (whether mixed or separate phases formed). Results showed that in titration experiments, the LREEs crystallised easily and at low temperatures (as low as room temperature), HREEs either do not crystallise (in some cases even at 200 °C) or are more diffcult to crystallise, and mixed LREE + HREE precipitates behaved more like HREE-only examples. The HREEs and LREEs + HREEs mostly produced X-ray amorphous materials, identified as carbonates using FTIR. These were analysed by XAS (XANES and EXAFS) to assess whether they possessed the same short-range structure as the crystalline phase into which are known to form, thus adding to the non-classical nucleation pathway argument as previously suggested for these materials. Results suggested the short-range order of most phases analysed were similar to known bulk phases, but that these were probably different to the earlier precipitates formed in solution. Additionally, in the mixed LREE + HREE systems (Nd+Er), REEs were well dispersed (as opposed to Nd- and Er-rich clusters). In contrast to the titration results were those of wall rock reactions, in which excellent crystallisation was observed for almost every REE configuration (single- or up to five- REE mix), or ageing duration. All but three of the phases produced were previously described natural or synthetic minerals. When fluorite was included in batch reactions the results were more varied: REE carbonates, fluorides and fluorocarbonates were all observed, but never together in the same sample (except in one example). A textural and mineralogical assessment of two carbonatite deposits, Bayan Obo, China and Tundulu, Malawi, which were analysed by EMPA, revealed multiple stages of hydrothermal activity, some of which related to REE fluorocarbonate mineralisation. REE fluorocarbonates, identified at both sites, were typically LREE enriched. No REE carbonates or fluorides were observed, despite the presence of fluorite (REE-barren) and carbonates at Bayan Obo, and carbonates (low REE content) at Tundulu. However, at both sites apatite contained considerable REE. The REE fluorocarbonates were not solely associated with carbonate wall rocks, although the Ca-REE fluorocarbonate synchysite was only observed in the significantly more carbonate-rock-rich Tundulu samples. At Bayan Obo, bastnasite and huanghoite (Ba-REE fluorocarbonate) were observed, the latter of which is reportedly replacing earlier Ca-REE fluorocarbonates. The results demonstrate the varying behaviour of REEs during precipitation under different conditions, and highlights the influence of dissolved carbonate supply rate to morphology, structure and crystallinity of the products. The occurrence of only one class of REE mineral (carbonate, fluoride or fluorocarbonate) in the synthetic experiments with fluoride may help explain the lack of natural REE carbonates and fluorides - and predominance of REE fluorocarbonates - in hydrothermal systems, as was observed in the natural samples studied. In addition, the lack (absence?) of naturally occurring HREE carbonates and fluorocarbonates in the studied carbonatites (and the literature) is suggested to result not from factors such as structural constraints, but instead from the relative crustal abundances of the individual REEs. It is shown that HREE carbonates and fluorocarbonates are valid species under certain conditions, but that these are not likely to occur naturally.

M.Sc. / Dissolved salts, mainly carbonates and sulphates such as those of calcium and magnesium, form hard water, which when heated produces an insoluble precipitate of scale forming crystals. Scale formation affects performance in industry and ouseholds. Besides the problem of energy costs, there are all the additional problems and maintenance costs of scale removal. Traditional methods of combatting scale build-up based on chemical water treatment do exist. These include: the addition of strong acid to remove the bicarbonate ion from the water, the use of chemicals to prevent or retard the formation of hard scale and, other techniques such as ion exchange process. A cost-effective alternative to these methods is Physical Water Treatment (PWT). Many different types of equipment claiming to treat water physically, for scale reduction are commercially available. These include magnetic, electric (high frequency or radio frequency) or electrostatic, catalytic and ultrasonic devices. In this work attempts have been made to unravel the mechanisms involved in PWT. For this it was necessary to develop experimental methods to determine the effect of electromagnetic fields and selected magnetic and radio frequency (rf) water treatment devices on precipitation reactions. The most significant finding of this study involves the effect of Zn on scale formation. When supersaturated Ca(HCO3 )2 solutions were tested in a glass heat exchanger, a 77% reduction in the formation of scale was found when the solutions were spiked with Zn.

M.Sc. / Calcium carbonate scale formation is a major problem in industrial water and cooling systems as well as in household systems. The resulting reduction in heat transfer and the removal of the scale are very costly processes. One of the methods used in the past 50 years and investigated for nearly a century, is the use of physical fields to reduce, remove and / or inhibit scale formation. These physical fields are usually magnetic fields, but RF electric and electrostatic fields are also used. These fields are claimed to reduce the cost involved in the removal of scale to a minimum. To investigate these claimed effects on scale formation, a pure calcium bicarbonate solution was exposed to some of the commercial available units: The exposed solution was then forced to precipitate by elevating the temperature. The pH was monitored against time, to investigate the nucleation process of CaCO 3 and the resulting precipitate analysed for changes in crystal morphology. The principle conclusions made from the results were, firstly that the nucleation of CaCO 3 was significantly delayed in one of the units tested and that the preferred morphology was changed from the thermodynamically more stable calcite to the more unstable aragonite in that unit. Secondly, that a direct correlation existed between the release of trace amounts of metals from the unit and the observed effects.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第17131号 / 工博第3621号 / 新制||工||1550(附属図書館) / 29870 / 京都大学大学院工学研究科社会基盤工学専攻 / (主査）教授 松岡 俊文, 教授 大津 宏康, 准教授 水戸 義忠 / 学位規則第4条第1項該当

Autocausticizing, a new method to regenerate sodium hydroxide from the sodium carbonate, is intended to replace the conventional Kraft Recovery System which uses calcium hydroxide produced in a lime kiln for this purpose. It is defined as the self-induced expulsion of carbon dioxide bound in the smelt by using certain amphoteric oxides. Thus autocausticizing can eliminate the need for a lime cycle and hence reduce the Kraft process capital and operating costs. The reactions between sodium carbonate and a number of amphoteric oxides have been reported in the literature. Patents have been issued on the use of titanium dioxide, iron oxide and sodium borates for this purpose. The sodium borates have the advantage of a high reaction rate, but are totally soluble and must be carried throughout the whole Kraft cycle. In this research colemanite (calcium borate) which is mined as a cheap mineral in California and in Turkey was studied as an autocausticizing agent. Since it is partially soluble and most likely can be recycled, it would eliminate the problems associated with the use of soluble borates. Experiments were performed both isothermally and under constant heating rate conditions. Isothermal studies were made with Ti0₂, alumina and colemanite to compare their performances as autocausticizing agents at 900°C and 1000°C for various reaction times in an electric furnace. The second group of experiments was made using a differential Chermogravimetric (TG) analyzer. In these experiments mixtures with 20 to 80 weight percent colemanite in sodium carbonate were heated at a constant heating rate of 10°K/min in the range of 190-1000°C. The results indicate that two reaction were involved. Above the stoichiometric colemanite concentration the colemanite and sodium carbonate had reacted completely by a temperature of about 700°C. Above that temperature the impurities in the colemanite appeared to catalyze the decomposition of sodium carbonate if the colemanite concentration was less than the stoichiometric amount needed. TG data were analyzed for the first and second reactions between the temperature ranges of 190-700°C and 700-1000°C respectively. Kinetic models were developed In terms of the reaction order, activation energy and frequency factor. The first reaction was found to be zero order on sodium carbonate concentration. The results also showed that the activation energy and frequency factor were functions of the colemanite concentration in the mixtures. As a result the rate was affected by the amount of colemanite used. The same was true for the second reaction except the reaction was first order. The concentrations predicted for the isothermal tests by the model were compared with the results of the isothermal study for various colemanite concentrations. Reasonable agreement was found except for the values at lower conversions, which might be due to the Increased importance of the diffusion of CO₂ from the mixtures in the case of Isothermal runs. It was also found that it is possible to obtain conversions as high as 85 percent with 40 percent colemanite in 20 minutes. Promising results were obtained from the recycle tests as well. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Titanium dioxide (TiO2) is an essential component in a white paint formulation due to its excellent light scattering ability. TiO2 also happens to make up most of the raw materials cost. Viable replacements to TiO2 do not currently exist in a feasible manner. Rising costs in the recent TiO2 supply shortage have forced coatings formulators to find a balance between cost and performance. One method includes partial substitution of TiO2 with cheaper material such as calcium carbonate (CaCO3), which serves to occupy volume. The purpose of this study was to compare the coating spread rate of paints with varying TiO2 and CaCO3 pigment volume concentration (PVC). Different sized CaCO3 particles were used in this study. A series of PVC ladder studies were performed at keeping CaCO3 PVC constant. Paints were formulated at the same volume solids to minimize variability. Weighed coating draw-downs were prepared to measure the contrast ratio. The coating spread rates were obtained with the DuPont Spread Rate program, which relies on Kubelka-Munk relationships, which takes into account the physical properties of the paint. These spread rate values were compared to one another across type and size to find common trends. Critical pigment volume concentration (CPVC) values were determined through regression of the spread rate values and compared to oil absorption tests. It was found that replacement of up to 20 PVC of TiO2 with CaCO3 could marginally increase the spread rate, thus increasing the efficiency of TiO2. The spread rate increased modestly as similarly sized extender particles were initially introduced, then dropped at higher extender levels. Data analysis revealed that CPVC was influenced based on the size and amount of the extender particle present, which can be used to predict resin demand of a paint system.

Three questions were asked during this research. 1) Does the Sr content of Caribbean speleothems have a direct relationship with the age of the host rock at the time of speleothem precipitation?; 2) do older speleothems contain less Sr than younger speleothems in the same climatic setting?; and 3) will speleothems record the change in Sr concentration of eogenetic carbonates as a faster depletion in climates of higher precipitation as opposed to drier climates? The speleothems and cave rocks in this study were analyzed with various methods in an attempt to understand the rock processes that affect speleothem Sr concentrations. Evidence to support the hypothesis that younger host rock contributes higher concentrations of Sr to speleothems was found in the stalagmites of Curacao while Bahamian stalagmites indicated climatic variations. The results have implications for using stalagmites from relatively young, eogenetic limestone as a proxy for Sr-related paleoclimate data.

Mg/Ca and d18O derived from marine biogenic carbonates have been widely used as reliable paleoenvironmental proxy for seawater temperature, salinity and water mass circulation reconstructions. The use of Mg/Ca is based on long residence time in seawater and uniform distribution with habitat depth of planktonic foraminifera. Fluid Mg/Ca affects mineralogy of CaCO3, thus high seawater Mg/Ca favors precipitation of aragonite instead of calcite. The records of d18O in carbonates yield strong correlation with seawater temperature, salinity and d18O. Distribution of d18O in water is highly heterogeneous within longitude, latitude and depth. Therefore a combination of foraminieral d18O and Mg/Ca could resolve temperature, d118Owater, and hence salinity, which is linked to variability in fresh water balance and glacial ice volume throughout geologic history. In this work we study the effects of important seawater/fluid parameters on Mg/Ca in inorganic and d18O in natural samples and provide data for improving paleoceanographic reconstructions.

The objective of this study was to develop a protocol to test the reactivity of glauconite, a Fe/Mg bearing aluminosilicate mineral, in carbon storage. A selected glauconite-rich sample from the Cambrian Riley Formation of Central Texas was used containing glauconite 38 wt%, quartz 58 wt%, and calcite 4 wt%. Ten experiments were conducted using two techniques where total pressure was: 1) controlled by delivering CO2 to a high-pressure apparatus; 2) kept at saturated vapor level in autoclaves. The treated glauconite samples were analyzed with Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (SEM), and X-ray Diffraction techniques (XRD). Although the reaction between glauconite and CO2 was not visible, calcite crystallized in solution when its pH exceeded the value of 6.88. The research provides a foundation to develop further investigations of rock reactions under CO2 saturated conditions.