This thesis focuses on a number of aspects governing the transformation of gibbsite, via intermediate phases, to a-alumina. These aspects include the size and morphology of the gibbsite grains, the influence of additions of foreign elements, the effect of a mechanical treatment of the gibbsite prior to calcination, and combinations of these factors. The materials were characterisedb y scanninge lectron microscopy, X-ray diffraction and surfacea rea measurementsF. or someo f the calcined materials an attempt was made to sinter the powders to a dense body to investigate if any of the treatments during calcination had an effect on this process. The literature review covers the current state of understanding of the production of bulk alumina powder by the Bayer process and the phase changes seen on calcination of precursors to the stable a-alumina phase. A detailed description of the phase changes is given and the various routes and conditions necessary for the transformations to occur are considered. The transformations are examined in relation to the morphology of the crystals and the variables controlling the phase transformation route are discussed. Calcination in air showed that the size of the gibbsite grain governs the calcination route taken to reach a-alumina. The standard gibbsites used in this work show a mixed calcination sequence transforming both via the boehmite phase, followed by the y, 8 and 0 phases, and via the x and K phases. The formation of boehmite is attributed to retention of water vapour within the grainDifferences in morphology of the starting materials showed that for the range of materials seen, the morphology of the grain is less important than its size. The super fine material confirmed that a small grain size transforms via the non-boehmite route only, with the other gibbsites taking intermediate routes as for the standard gibbsites. Of the additions made prior to calcination, aluminium fluoride was found to reduce the transformation temperature to a-alumina by approximately 300°C. Other additions had little effect on the transformation temperature although a reduction in grain size was seen with aluminium chloride. It was found that good mixing of the alumina fluoride was essential to obtain reliable and reproducible results. This is due to the small amounts of additive that are needed and the sensitivity of the process to concentration variations. Mineralisation of a range of gibbsites showed that the presence of sodium in the starting material was crucial in reducing the calcination temperature. This led to the conclusion that the sodium and fluoride react to form a liquid phase. The presence of a liquid phase increases the mobility of the aluminium and oxygen atoms resulting in a reduction of the transformation temperature. Fluoride additions to the gibbsites with different morphologies showed that the presence of sodium was the governing factor in reduction of the transformation temperature. Milling of the starting materials showed that there was a small reduction in the transformation temperature between some of the phases. The energy involved in milling leads to activation of the gibbsite. This activation takes the form of a reduction in the grain size and in a reduction of the crystallinity seen in the XRD patternFluoride additions during the calcination of sapphire with a standard gibbsite powder showed preferential grain growth. It was possible to initiate growth of small plate-like crystals on the polished surface of a piece of sapphire parallel to the basal plane. Crystal growth was also seen in scratches on a polished surface perpendicular to the basal plane

This work examined the effects of thermal and chemical treatments on zeolite reactivity and determined the zeolite properties governing the development of compressive strengths and pozzolanic reactivity. Zeolites are naturally occurring aluminosilicate minerals found abundantly around the world. Incorporation of zeolites in cement mixtures has been shown by past research to increase concrete’s compressive strength and durability. In addition, use of zeolites as SCMs can decrease the environmental impact and energy demands associated with cement production for reinforced concrete structures. Further, in contrast to man-made SCMs such as fly ash, zeolite minerals provide a reliable and readily available SCM source, not affected by the production limits and regulations of unrelated industries such as the coal power industry. In this work, six sources of naturally occurring clinoptilolite zeolite were examined. The zeolites were first characterized using x-ray fluorescence, quantitative xray diffraction, thermal analysis, particle size analysis, pore size distribution and surface area analysis, and scanning electron microscopy. Cation exchange capacity was also tested for one of the zeolites. Following comprehensive material characterization, the six pozzolanic reactivity of the natural zeolites was determined by measuring the quantity of calcium hydroxide in paste after 28 or 90 days, by measuring calcium hydroxide consumption of the zeolite in solution and by tracking the development of strengths of zeolite-cement mortars. Pretreatments that attempted to increase the reactivity of the zeolites, including calcination, acid treatment, milling and cation exchange, were then tested and evaluated using the same methods of material characterization and testing mentioned previously. Last, the results of the reactivity testing were reanalyzed to determine which properties of natural zeolites, including particle size, nitrogen-available surface area, and composition, govern the development of compressive strengths, pozzolanic reactivity and improved cement hydration parameters of pastes and mortars using natural zeolites as SCMs. Pretreatment testing showed that milling and acid treatment successfully increased the reactivity of zeolites used as SCMs. Additionally, particle size was shown to be the dominant property in determining the development of compressive strengths while particle size and surface area of the zeolites contributed to zeolite pozzolanic reactivity. / text

Lime is one of the largest manufactured chemicals in the United States. The conversion of calcium carbonate into calcium oxide is an endothermic reaction and requires approximately two to four times the theoretical quantity of energy predicted from thermodynamic analysis. With the skyrocketing costs of fossil fuels, how to decrease the energy consumption in the calcination process has become a very important problem in the lime industry. In the present study, many chemicals including lithium carbonate, sodium carbonate, potassium carbonate, lithium chloride, magnesium chloride, and calcium chloride have been proved to be the catalysts to enhance the calcination rate of calcium carbonate. By mixing these chemicals with pure calcium carbonate, these additives can increase the calcination rate of calcium carbonate at constant temperatures; also, they can complete the calcination of calcium carbonate at relatively low temperatures. As a result, the energy required for the calcination of calcium carbonate can be decreased. The present study has aimed at developing a physical model, which is called the extended shell model, to explain the results of the catalytic calcination. In this model, heat transfer and mass transfer are two main factors used to predict the calcination rate of calcium carbonate. By using the extended shell model, not only the catalytic calcination but also the inhibitive calcination of calcium carbonate have been explained.

The strength, thermal stability, pore structure and morphology are keys to success for wider deployment of aerogels. Furthermore, co or subsequent functionalization of the surfaces are equally, if not more important. This study addresses these issues through a new method. The path involves successful use of surfactant templating, supercritical extraction and drying, and supercritical fluid aided functionalization of the surface. Alumina support and alumina supported nickel catalyst particles are used to evaluate the approach. Initially thermally stable surfactant alumina was synthesized. The surfactant template was removed completely with the aid of a supercritical solvent mixture. Surfactant-templated alumina aerogel showed remarkable thermal stability and gave specific surface area above 500m2 /g both before and after calcination. The alumina support is subsequently impregnated with nickel. BET and BJH method (Nitrogen adsorption-desorption isotherms) were used to follow the removal of solvents and templates as well as tracking the textural properties for the synthesized gel. Meanwhile, co-precipitated nickel oxide/alumina system was also synthesized for comparison with the supercritical impregnation nickel oxide/alumina system. SEM-EDS and XPS were employed to study the distribution of the nickel on the alumina support and the percentage was compared with the initial mixture of the sol gels.

The ever increasing global demand for materials has placed aluminium as the world’s second most used metal, with world annual production currently >24 million tons. Consequently, the global alumina industry is perpetually striving to meet demands in conjunction with research, development and implementation of more efficient and sustainable processes and practises. Of specific concern for many proponents within the industry is that increased alumina production inadvertently results in increased Bayer Process-derived alkaline solid and liquid waste loads. Furthermore, in-house power generation at all Australian alumina refineries contributes to acid gas emissions, particularly SOx and NOx, both of which have environmental and anthropogenic impacts of global concern. The focus of this work is SO2 emission. SOx emission control measures can be achieved before, during or after combustion; the latter is termed flue gas desulphurisation (FGD). Commercially available FGD systems are dominated by once-through wet processes whereby the flue gas passes up through an absorbtion tower. The most favourable medium for industrial use is seawater, followed by limestone, and in some cases, a combination of both. However, the ever-increasing stringency of environmental emission legislation continues to inflict tighter controls on power production and is forcing industry to investigate alternative cost-effective FGD mediums. Therefore much research is currently dedicated to the utilisation of high volume, alkaline waste streams over manufactured sorbents. Modern environmental engineering approaches to waste product minimisation, neutralisation and/or reuse have lead to many new processes which change the view of many materials from waste product to environmental resource. Subsequently, this work examines the application of an isolated Bayer Process waste product, tricalcium aluminate hexahydrate (TCA6), as a FGD medium. Initial research assessed the dissolution behaviour and performance of the proposed medium with sulphuric acid, followed by batch reactor trials with a simulated flue gas. Data derived from this research indicated the suitability of TCA6 as a FGD medium and was subsequently applied to a preliminary model and proposed design parameters required for further pilot scale investigations. This work provides strong support for an economically viable and more sustainable approach to FGD for the alumina industry.

Chaque année, prés de 50 millions de m3 de sédiments sont extraits des ports et des cours d'eau français. Dans le Nord-Pas de Calais, région ayant connu un important essor industriel au XXe siècle, une proportion importante des boues draguées présente des teneurs en métaux lourds et/ou en matière organique élevées. Les filières d'élimination classiques telles que l'épandage ou le stockage n'étant pas ou peu adaptées aux matériaux fortement pollués, des procédés de traitement ont été mis au point. Une fois traités, il est possible d'envisager la valorisation des sédiments dans les matériaux du Génie Civil.<br /><br />L'objet de ce travail de thèse concerne la valorisation de sédiments fluviaux, pollués et traités par le procédé Novosol®, développé par la société Solvay, dans le domaine de la construction routière. Une première étape de caractérisation physico-chimique et géotechnique des sédiments traités Novosol® (STN) a établi la faisabilité de leur valorisation en couche de forme. Il a également été mis en évidence qu'ils présentaient une réactivité hydrique et pouzzolanique. L'influence de la nature du liant sur le traitement des STN a ensuite été abordée. D'après les résultats des essais mis en œuvre (aptitude au traitement, gonflement, portance, résistance en compression et en traction Brésilienne), 2 des 5 liants testés se distinguent particulièrement et présentent un niveau de performance de classe 3 selon le Guide du Traitement des Sols. Il s'agit du Roc Sol et la chaux vive.<br /><br />Enfin, une étude complémentaire a montré qu'il était également possible de valoriser les STN en remblais autocompactant. Cependant, cette voie nécessiterait d'être approfondie.

L'accumulation des sédiments au fond des cours d'eau conduit à leur envasement. Une grande quantité de ces sédiments est contaminée par des polluants organiques et inorganiques. Leur gestion soulève donc des défis technologiques, économiques et environnementaux de plus en plus importants. C'est dans ce contexte que la société Solvay a mis au point le procédé de traitement Novosol® qui se décompose en deux phases : la phosphatation et la calcination. La présente étude porte sur la valorisation des sédiments fluviaux pollués, après traitement avec le procédé Novosol®, dans la brique cuite. Le sédiment traité (ST) est composé majoritairement de quartz, de calcite et d'hématite. Sa masse volumique absolue est de 2,66 g.cm-3 comparable à celle du quartz. L'étude expérimentale menée en laboratoire a montré la faisabilité d'incorporation de ST dans la brique cuite comme un matériau de substitution au sable et à l'argile. Il a également été montré que la résistance à la compression est influencée par la quantité de sédiment. En effet, l'augmentation de cette dernière entraine une diminution de la résistance mécanique. Deux essais industriels ont été réalisés en se basant sur les résultats obtenus en laboratoire. Ils ont montré que le ST peut se substituer au sable et à l'argile avec des taux de substitution allant jusque 28% sans aucun changement de processus de fabrication. Les briques produites avec 28% de ST ont une résistance mécanique supérieure à celle de la brique standard. Enfin, il a été également montré que la granulométrie et la minéralogie du sédiment sont des facteurs déterminants qui influencent la qualité des briques produites.

Titanium Dioxide (TiO 2) has been considered an ideal photocatalyst due to factors such as its photocatalytic properties, chemical stability, impact on the environment and cost. However, its application has been primarily limited to ultraviolet (UV) environments due to its high band gap (3.2 eV). This high band gap limits the harvesting of photons to approximately 4% of sunlight radiation. Research today is focused on lowering this gap by doping or coupling TiO 2 with other semiconductors, transition metals and non-metal anions, thereby expanding its effectiveness well into the visible range. This thesis explores the effects of thermal and thermochemical ammonia treatment of nano-particulated TiO 2. The objective is to synthesize a photocatalytic activity in the visible range while at the same time retaining its photocatalytic properties in the UV range. Specifically, this study utilizes pure commercial nano-particulated TiO 2 powder (Degussa P-25), and uses this untreated TiO2 as a baseline to investigate the effects of thermal and thermochemical treatments. Nitrogen-doping is carried out by gas phase impregnation using anhydrous ammonia as the nitrogen source and a tube furnace reactor. The effects of temperature, time duration and gas flow rate on the effectiveness of thermally and thermochemically treated TiO 2 are examined. Thermally treated TiO 2 was calcinated in a dry inert nitrogen (N2) atmosphere and the effects of temperature and treatment duration are investigated. The band gap of the thermally treated and thermochemically ammonia treated TiO 2 have been measured and calculated using an optical spectrometer. The photocatalytic properties of all materials have been investigated by the degradation of methyl orange (MO) in an aqueous solution using both visible simulated solar spectrum (VSSS) and simulated solar spectrum (SSS) halogen light sources. Methyl orange degradation has been measured and calculated using an optical spectrometer. The phase structure and particle size of the materials is determined using x-ray diffraction (XRD). The BET surface area of the samples has been obtained using an Autosorb. Surface or microstructure characterization has also been obtained by scanning electron microscopy (SEM) and transmission electron microscopy (TEM).

The cement industry releases large quantities of CO₂ into the atmosphere during the manufacture of Portland Cement. The intrinsic property of the cement to reabsorb some of this CO₂ over its life time through a process called recarbonation has been investigated. This thesis reports on the development of an accelerated recarbonation apparatus for studying the recarbonation of crushed concrete under controlled conditions. The apparatus involved a series of airtight desiccators into which were placed the crushed concrete samples. The desiccators were then filled to ~50,000 ppm CO₂, which is significantly greater than the ~380 ppm by volume CO₂ available in the earth’s atmosphere. The CO₂ concentration was then monitored with respect to time inside the desiccator using CO₂ specific infrared probes. Two concrete design strengths of 20MPa and 40MPa with various crushed particle sizes were exposed to conditions of 50-60 % relative humidity, a temperature of 20 ± 1.5 °C, an exposure period of 21 days and a maximum CO₂ concentration of ~50,000 ppm by volume. The CO₂ uptake measured by the infrared probes was verified using other detection methods of FTIR, TGA, XRF, phenolphthalein indicator and the weight gain of the crushed concrete samples. The research found that a concrete of 20 MPa design strength and a water to cement ratio of 0.67 could absorb 12-83 % of the original calcination emissions for particle sizes <40, <20 and <10 mm in the 21 day time period. Similar behaviour was also exhibited by the 40 MPa design strength (w/c 0.49) but the extent of CO₂ uptake was not as pronounced. The 40 MPa (w/c 0.49) design mix absorbed 9-70 % of the original calcination emissions for the same particle sizes of <40, <20 and <10 mm. It was found that significant quantities of CO₂ could be absorbed by the smaller crushed sizes of <10 and <20 mm for both design mixes, owing to their much larger surface area. It was also found that about 80 % of the total CO₂ absorbed occurred within the first 10 days of exposure. It is envisaged that the results contained in this thesis will assist in future investigations into crushed concrete recarbonation.

The long term goal of this research is to improve the fire resistance of gypsum wallboard (GWB). Gypsum wallboard consists mainly of gypsum, i.e. calcium sulfate dihydrate, CaSO4•2H2O. In buildings, the chemical, mechanical and thermal properties of gypsum wallboard play an important role in delaying the spread of fire. To build a fire resistant GWB, it is very important to study the thermal, mechanical, physical and chemical properties of regular GWB and various types of fire-resistant wallboards available commercially in the market. Various fire-resistant GWBs have been compared and contrasted with reference to a standard wallboard in this study. Regardless of the type of wallboard, the main component is gypsum. The fire resistance property is mainly attributed to the absorption of energy related with the loss of hydrate water going from the dihydrate (CaSO4•2H2O) form to the hemihydrate (CaSO4•½H2O) and from the hemihydrate to the anhydrous form (CaSO4) in a second dehydration. The present paper is a comparative study of commercially available standard, fire-rated Type X and firerated Type C gypsum wallboards. Type X wallboards are typically reinforced with noncombustible fibers so as to protect the integrity of the wallboard during thermal shrinkage, while the Type C wallboards are incorporated with more glass fibers and an additive, usually a form of vermiculite. These Type C wallboards have a shrinkage adjusting element that expands when exposed to elevated temperature. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), thermomechanical analysis (TMA), scanning electron microscopy (SEM) and powder X-ray diffraction (XRD) were used to characterize and compare the materials. Various properties, such as the heat flow, weight loss, dimensional changes, morphology and crystalline structures of the gypsum wallboards were studied using these techniques.