The objective of this study was to compare time dependent micro-hardness of several bioactive cement compositions as compared to that of non-bioactive cement, a conventional glass ionomer. Materials & Methods: Three bioactive materials Ceramir Crown & Bridge Cement (CCB), Mineral Trioxide Aggregate (MTA), Biodentine (BD)], and a glass ionomer cement, Fuji I luting cement (F1), were utilized in this study. Samples of the materials were prepared in a standard cylindrical mold 1.5 mm in height and 12.0 mm in diameter and stored in Phosphate-Buffered-Saline (PBS) at 37 degrees C. prior to testing to determine Vickers micro-hardness in a CSM micro-indentation testing device. Micro-hardness values were collected via 2 x 2 micro-indentation matrices on the exposed surfaces of the specimens. All materials were tested at 24 hours and 2 months and 11 + 1 month's incubation time. The bioactive materials displayed significant differences in Vickers hardness as a function of storage time as compared the Vickers hardness values over the similar timeframe for the control material, the glass ionomer material Fuji 1. The control glass ionomer cement did not displayed significant changes in Vickers hardness after prolonged liquid storage. The experimental bioactive materials both demonstrated long-term trends with significant increases (CCB) and decreases (Biodentine) in Vickers hardness after storage in the simulated body fluid (PBS). The mean Vickers hardness of the calcium aluminate/glass ionomer (CCB) material was significantly greater than the mean Vickers hardness values for the other three materials tested at all time-points evaluated. The conclusions of this study were as follows: Unlike conventional glass ionomer cement, both the calcium silicate and calcium aluminate/glass ionomer cement displayed significant changes in surface micro-hardness after prolonged storage in a simulated body fluid (PBS) that has been demonstrated to induce the formation of a surface bioactive layer. The calcium silicate cement had a significant reduction in surface micro-hardness over a period up to year; while the calcium aluminate/glass ionomer cement displayed a significant increase in surface micro-hardness over that same time period. The formation of and changes in the bioactive surface layers formed on these materials may account for changes in the micro-hardness of these bioactive materials. / Oral Biology

Inclusion removal is critical for the production of clean steel. A better understanding of removal processes require knowledge of the effect of process parameters on dissolution kinetics. The present research focuses on the kinetics of calcium aluminate inclusion dissolution in relevant steelmaking slags that contain CaO, Al2O3 and SiO2. In-situ observation of inclusion dissolution in slag is conducted using a high temperature, confocal scanning laser microscope (HT-CSLM). The particles used in this experimental work are produced in the laboratory and the production technique is explained in detail. The change in particle size is recorded with time and the effects of temperature, slag composition and inclusion morphology are investigated. The images are extracted from video and they are analysed to record the change in equivalent radius of a single particle during the dissolution process. The original and normalized dissolution data is used to determine the dissolution mechanism and to improve existing dissolution models. It has been found that an increase in temperature increases the dissolution rate. At 1550°C and 1600°C, there is no product layer formation at the slag-inclusion interface and so, the dissolution process is faster. Slag composition shows a significant influence on the dissolution kinetics due to differences in the dissolution driving force and viscosity. Additionally, the dissolution rate depends on the morphology of inclusion as available reaction sites vary significantly. Rate limiting steps are discussed based on the shrinking core model and diffusion in stagnant fluid model. It is shown that the rate limiting step for dissolution is the diffusion v through a product layer at 1500°C whereas it is mass transfer in slag at 1550°C and 1600°C. The diffusion coefficient of alumina is obtained by applying a one-dimension diffusion model. The calculated results varied between 5.5×10-11 and 2.6×10-10 m2/s depending on experimental conditions. Slag viscosity was found to be an important parameter for the modelling of the dissolution process. A modification to the correlation between the correction coefficient and slag viscosity was proposed. This modification improved the prediction of the dissolution path for calcium aluminate and alumina inclusions in steelmaking slags. This novel study provides an understanding of dissolution mechanisms and it offers data on the dissolution rate of CA2 inclusions in the slags related to the process of steelmaking. The results from this work can be used by steelmakers to aid in process design. / Thesis / Master of Applied Science (MASc) / The present work is a pioneer study on the dissolution of calcium aluminate particles in liquid oxide mixtures using the unique real-time observation approach. Experiments were conducted to provide a better understanding of the effects of various steelmaking conditions on inclusion removal during the refinement of liquid steel. An existing dissolution model is further refined by introducing an additional parameter that is correlated to the properties of oxide mixtures. It has been found that the dissolution model can be applied not only to calcium aluminate inclusions but also to alumina inclusions. Hence, the approach proves the potential university nature of the dissolution model. A clear understanding of the dissolution kinetics of inclusions helps to optimize the current steelmaking routes and enhance the removability of inclusions. Steel with a minimum amount of inclusions has better properties from all aspects, which improves its applicability in all fields.

No / Hydration of five Roman and American natural cements was analyzed using X-ray diffraction, mercury intrusion porosimetry, and scanning electron microscopy of cement pastes. Two cements were prepared in the laboratory by burning marls from geological sources in Poland (Folwark) and Austria (Lilienfeld). The selection of raw materials and burning conditions were optimized so that the hydraulic nature and appearance of the final burnt materials matched as closely as possible historic Roman cements widely used in the 19th and the beginning of the 20th centuries in Europe to decorate buildings. Three other cements are produced commercially: quick setting Prompt cement from Vicat, France, and Rosendale cements from Edison Coatings Inc., USA. The hydration of the cements studied was shown to comprise two distinct stages. The immediate setting and early strength is due to the formation of calcium aluminum oxide carbonate (or sulfate) hydroxide hydrates. The development of long-term strength is brought about by the formation of calcium silicate hydrates. Similarities and differences between the individual cements are discussed.

Ce travail de thèse a porté sur de nouveaux implants intervertébraux en céramique. Au cours du projet dans son ensemble (projet européen Longlife), un nouveau matériau et de nouveaux designs d’implants ont été développés, ainsi qu’un nouveau test destiné à simuler les sollicitations subies in vivo par les implants afin d’estimer leur durée de vie. Le nouveau matériau développé est un composite triphasé composé d’une matrice de zircone dopée à l’oxyde de cérium (pour sa résistance au vieillissement), d’une phase globulaire d’alumine α (pour affiner la microstructure) et d’une phase allongée composée d’aluminates de strontium (pour augmenter la ténacité). La première partie du travail a consisté à caractériser ce matériau afin de connaître son comportement en termes de résistance mécanique, stabilité thermique, et de résistance à la stérilisation. Une deuxième partie a été consacrée au développement d’un test multiphysique regroupant les différentes sollicitations attendues par une prothèse in vivo (fatigue axiale, micro-séparation, vieillissement et usure). Il a fallu pour cela s’appuyer sur des simulations numériques qui ont permis de développer le système. Les données de la littérature ont été utilisées afin de choisir les paramètres du test (durée, fréquence, milieu d’essai). Enfin, la dernière partie de ce travail a été la mise à l’épreuve de différents prototypes à travers le test multiphysique et leur caractérisation en cours d’essai. Les principaux résultats de ce travail de thèse sont les suivants : le composite montre un comportement pseudo-plastique sous charge, avec une nette transformation de phase avant rupture, ce qui est positif dans le cadre de son utilisation. De plus, il ne semble pas affecté par la stérilisation. Du point de vue des implants développés, peu passent le test multiphysique. Le design, ainsi que la géométrie (notamment la clearance des échantillons) sont des leviers d’amélioration qui permettront d’augmenter la fiabilité des implants. / This work deals with the development of new intervertebral prostheses, made with ceramics. A whole European project, Longlife, was dedicated to the development of such implants. To achieve this goal, several axes have been followed: the synthesis of a new material, the development of new designs of intervertebral bodies, and the set-up of a new test aimed at reproducing in vitro the different solicitations undergone by an intervertebral implant in vivo. The new material developed is a triphasic composite composed of a matrix of ceria-doped zirconia (insensitive to ageing), a secondary globular phase of α-alumina (to reduce the grain size), and a third, elongated phase composed of strontium aluminates platelets (in order to improve fracture toughness). The first part of this work was to characterize this new material in order to forecast its behaviour under mechanical solicitation, thermal stability and resistance to sterilization. Secondly, the set-up of the new test is exposed. Different steps were chosen (axial fatigue, micro-separation, ageing and wear) in order to reproduce the “real-life” solicitations. To achieve this goal, Finite Elements simulations were performed, allowing the development of specific specimen holders that mimic the fixation of the implants in the vertebrae. The parameters of the test (duration, frequency, medium) were chosen after a details survey of the literature and of standards. At the end, we tested different prototypes trough this new multiphysic assessment set up. As a main result of this thesis, the chosen ceramic composite exhibits a pseudo-plastic behaviour, with a large deformation due to phase transformation before fracture, which is a positive result in the framework of the forecast applications. Moreover, the material doesn’t seem degraded by the sterilization processes. Concerning the multiphysic test, only a few implants resisted it. The design of the implants is a key-point, as well as the geometry (in particular, clearance seems to be critical).

Neste trabalho, foram caracterizados eletricamente capacitores MOS com alumina (Al2O3) e aluminato de háfnio (AlxHf1-xOy) como dielétricos de porta, além disso, estes filmes dielétricos foram caracterizados fisicamente. A alumina foi obtida da oxidação anódica de filmes de alumínio evaporados sobre p-Si (100) através de imersão em ácido nítrico por 4 ou 6 min, para diferentes etapas de limpeza finais do substrato: solução diluída de ácido fluorídrico (DHF) ou solução de peróxido sulfúrico (SPM). Análises de retroespalhamento de Rutherford (RBS), espectroscopia por dispersão em energia (EDS) e espectroscopia por dispersão de comprimento de onda (WDS) indicam a formação da alumina estequiométrica, sendo que a difração de raios-X (XRD), mostrou o caráter amorfo do dielétrico. Por intermédio de curvas capacitância x tensão (CV) foram obtidas a espessura equivalente ao óxido de silício (EOT2,8nm), a densidade de estados de interface (Dit1,4x1011ev-1cm-2) e a permissividade elétrica da alumina (high-k10,6). A admitância associada à corrente de fuga em capacitores MOS foi modelada através de emissão por Frenkel-Poole, tunelamento por Fowler-Nordheim e/ou corrente de fuga constante. Os aluminatos de háfnio (AlxHf1-xOy) foram obtidos sobre p-Si (100), através de deposição atômica por camadas (ALD) para diferentes proporções molares de háfnio (25, 50 ou 75%) e para diferentes tratamentos posteriores (1000ºC, 60s em N2 ou N2+O2 ou laser). A espessura e a rugosidade foram obtidas com a ajuda da técnica de reflectometria de raios-X (XRR). A proporção molar de háfnio adotada no processo de obtenção dos filmes foi confirmada através de análises RBS e WDS. Por XRD, foi verificado o caráter amorfo e a separação de fases nos aluminatos e, por espalhamento de raios-X em ângulo-rasante e pequena abertura (GISAXS), foram analisadas as novas fases formadas. Por fim, da análise CV, foram obtidos EOT9,54nm, resistência série (Rs68,3) e a permissividade elétrica para o aluminato de háfnio (high-k15,2). Finalmente, uma modelagem da admitância associada à corrente de fuga em função da frequência foi proposta para as estruturas MOS. / In this work, MOS capacitors were electrically characterized using alumina (Al2O3) and hafnium aluminate (AlxHf1-xOy) as gate dielectrics; also, the same dielectrics films were physically characterized. Anodic alumina was obtained from oxidation of evaporated aluminum films immersed in nitric acid for 4 or 6 min for different last step cleanings of the p-Si (100) substrates: diluted hydrofluoric acid (DHF) or sulfur peroxide mixture (SPM). Rutherford Backscattering (RBS), Energy Dispersive Spectroscopy (EDS) and Wavelength Dispersive Spectroscopy (WDS) have shown the formation of stoichiometric alumina and the dielectric amorphous structure was revealed by X-Ray Diffraction (XRD). From Capacitance x Voltage curves (CV), it was obtained the equivalent oxide thickness (EOT2.8nm), interface trap density (Dit1.4x1011ev-1cm-2) and Al2O3 dielectric constant (high-k10.6). The admittance that represents the leakage process was modeled according to Frenkel-Poole emission, Fowler-Nordheim tunneling and/or constant leakage admittance. Hafnium aluminates (AlxHf1-xOy) were obtained on (100) silicon wafer surfaces by Atomic Layer Deposition (ALD) for different hafnium molar ratios (25, 50 or 75%) and for different treatments (1000ºC, 60s in N2 or N2+O2 or laser). Thickness and roughness were extracted from X-Ray Reflectometry (XRR) spectra. The hafnium molar ratios used in ALD process were confirmed by RBS and WDS. XRD analysis was used to establish the amorphous structure and phase separation in the aluminates after thermal treatments and Grazing-Incidence Small-Angle X-Ray Scattering (GISAXS) was used to analyze the new phases formed. From CV analysis, it was extracted EOT9.54nm, series resistance (Rs68.3) and dielectric constant from hafnium aluminate (high-k15.2). Finally, the admittance that represents the leakage was modeled in function of the frequency for the MOS structures.

Neste trabalho, foram caracterizados eletricamente capacitores MOS com alumina (Al2O3) e aluminato de háfnio (AlxHf1-xOy) como dielétricos de porta, além disso, estes filmes dielétricos foram caracterizados fisicamente. A alumina foi obtida da oxidação anódica de filmes de alumínio evaporados sobre p-Si (100) através de imersão em ácido nítrico por 4 ou 6 min, para diferentes etapas de limpeza finais do substrato: solução diluída de ácido fluorídrico (DHF) ou solução de peróxido sulfúrico (SPM). Análises de retroespalhamento de Rutherford (RBS), espectroscopia por dispersão em energia (EDS) e espectroscopia por dispersão de comprimento de onda (WDS) indicam a formação da alumina estequiométrica, sendo que a difração de raios-X (XRD), mostrou o caráter amorfo do dielétrico. Por intermédio de curvas capacitância x tensão (CV) foram obtidas a espessura equivalente ao óxido de silício (EOT2,8nm), a densidade de estados de interface (Dit1,4x1011ev-1cm-2) e a permissividade elétrica da alumina (high-k10,6). A admitância associada à corrente de fuga em capacitores MOS foi modelada através de emissão por Frenkel-Poole, tunelamento por Fowler-Nordheim e/ou corrente de fuga constante. Os aluminatos de háfnio (AlxHf1-xOy) foram obtidos sobre p-Si (100), através de deposição atômica por camadas (ALD) para diferentes proporções molares de háfnio (25, 50 ou 75%) e para diferentes tratamentos posteriores (1000ºC, 60s em N2 ou N2+O2 ou laser). A espessura e a rugosidade foram obtidas com a ajuda da técnica de reflectometria de raios-X (XRR). A proporção molar de háfnio adotada no processo de obtenção dos filmes foi confirmada através de análises RBS e WDS. Por XRD, foi verificado o caráter amorfo e a separação de fases nos aluminatos e, por espalhamento de raios-X em ângulo-rasante e pequena abertura (GISAXS), foram analisadas as novas fases formadas. Por fim, da análise CV, foram obtidos EOT9,54nm, resistência série (Rs68,3) e a permissividade elétrica para o aluminato de háfnio (high-k15,2). Finalmente, uma modelagem da admitância associada à corrente de fuga em função da frequência foi proposta para as estruturas MOS. / In this work, MOS capacitors were electrically characterized using alumina (Al2O3) and hafnium aluminate (AlxHf1-xOy) as gate dielectrics; also, the same dielectrics films were physically characterized. Anodic alumina was obtained from oxidation of evaporated aluminum films immersed in nitric acid for 4 or 6 min for different last step cleanings of the p-Si (100) substrates: diluted hydrofluoric acid (DHF) or sulfur peroxide mixture (SPM). Rutherford Backscattering (RBS), Energy Dispersive Spectroscopy (EDS) and Wavelength Dispersive Spectroscopy (WDS) have shown the formation of stoichiometric alumina and the dielectric amorphous structure was revealed by X-Ray Diffraction (XRD). From Capacitance x Voltage curves (CV), it was obtained the equivalent oxide thickness (EOT2.8nm), interface trap density (Dit1.4x1011ev-1cm-2) and Al2O3 dielectric constant (high-k10.6). The admittance that represents the leakage process was modeled according to Frenkel-Poole emission, Fowler-Nordheim tunneling and/or constant leakage admittance. Hafnium aluminates (AlxHf1-xOy) were obtained on (100) silicon wafer surfaces by Atomic Layer Deposition (ALD) for different hafnium molar ratios (25, 50 or 75%) and for different treatments (1000ºC, 60s in N2 or N2+O2 or laser). Thickness and roughness were extracted from X-Ray Reflectometry (XRR) spectra. The hafnium molar ratios used in ALD process were confirmed by RBS and WDS. XRD analysis was used to establish the amorphous structure and phase separation in the aluminates after thermal treatments and Grazing-Incidence Small-Angle X-Ray Scattering (GISAXS) was used to analyze the new phases formed. From CV analysis, it was extracted EOT9.54nm, series resistance (Rs68.3) and dielectric constant from hafnium aluminate (high-k15.2). Finally, the admittance that represents the leakage was modeled in function of the frequency for the MOS structures.

Medidas de Termoluminescência (TL), Luminescência Opticamente Estimulada (LOE), EPR (Ressonância Paramagnética de Elétron) e RL (Radioluminescência) foram obtidas de amostras de óxido de alumínio e óxido de alumínio dopado com magnésio. As amostras foram calcinadas em três diferentes temperaturas (1100, 1350 e 1600°C) para observar a variação do comportamento das propriedades luminescentes. Ao final, constatou-se que a temperatura de calcinação é um parâmetro de grande importância para a produção de materiais dosimétricos, pois a amostra com melhores resultados LOE foi o material sem dopante tratada a 1600°C. Em trabalhos anteriores, a composição de óxido de alumínio dopado com magnésio havia apresentado nanoestruturas de aluminato de magnésio, observadas através de Microscopia Eletrônica de Transmissão (MET), que influenciaram a sensibilidade do material à radiação. Amostras de aluminato de magnésio puro e dopado com terras raras foram obtidas na forma de pó e calcinadas a 1100, 1350 e 1600°C. Medidas de TL e LOE de amostras irradiadas com fonte de partículas foram analisadas e comparadas com resultados de EPR e Difração de Raios-X (DRX). Como resultado, foi concluído que, nas condições trabalhadas, somente o elemento gadolínio proporcionou aumento de emissão LOE e TL no espectro visível. DRX indicou a formação dos compostos Al5Er3O12 e Al5Yb3O12; gadolínio e európio também formaram estruturas secundárias que não puderam ser determinadas. A partir do óxido de alumínio em pó, foram produzidos alvos para deposição de filmes finos empregando um sistema de sputtering magnetron e lâminas de silício monocristalino (100) tipo P para substrato. Parâmetros de deposição e de tratamento térmico foram variados de modo a produzir amostras com diferentes características. Curvas de TL foram levantadas e analisadas com relação aos resultados de DRX. Imagens de Microscopia Eletrônica de Varredura (MEV) foram obtidas de algumas amostras para visualizar o estado dos filmes depositados após tratamentos térmicos de 500 e 1100°C. Resultados mostraram a formação de picos de difração de a-Al2O3 em algumas das amostras espessas. Medidas de TL de amostras expostas à radiação ambiente exibiram picos de emissão em posições que variaram de acordo com a composição e espessura do filme depositado. / Thermoluminecent (TL), Optically Stimulated Luminescence (OSL), EPR (Electron spin Resonance) and Radioluminescence (RL) measurements were obtained from aluminum oxide and magnesium doped aluminum oxide samples. The samples were calcinated at three different temperatures (1100, 1350 and 1600°C) in order to observe variation of luminescent properties. As results, it was found that the calcination temperature is of great importance in the production of dosimetric materials, since the undoped sample calcinated at 1600°C showed the highest sensibility. In early works, magnesium doped aluminum oxide samples exhibited the formation of nanostructured layer composed by magnesium aluminate, observed using Transmission Electron Microscopy (TEM), which induced an increase of the luminescent properties. Samples of undoped and rare-earths doped magnesium aluminate, calcinated at 1100, 1350 and 1600°C, were produced. TL and OSL measurements were obtained from irradiated aliquots, analyzed and compared to EPR and XRD results. Results showed that, under the parameters used in this work, only gadolinium doped samples exhibited increase in TL and OSL emissions. XRD indicated the formation of Al5Er3O12 and Al5Yb3O12 structures in doped samples; gadolinium and europium doped samples also showed new structures, which couldnt be identified. Powder aluminum oxide was used to produce deposition targets, which were employed in the deposition of thin films over P type monocrystalline silicon (100) wafers. Variations of deposition parameters and heat treatment induced the formation of thin films with different characteristics, observed by XRD and luminescent analysis (TL). XRD results indicated the occurrence of alpha-Al2O3 in some of the thick films. Samples exposed to natural radiation produced TL emission in the visible spectrum.

Cerâmicas porosas encontram um vasto campo de aplicações tecnológicas, tais como isolantes térmicos em equipamentos siderúrgicos, filtros de fluidos em altas temperaturas e biomateriais. A obtenção dessas estruturas por meio de moldagem direta de suspensões aquosas é uma interessante técnica de conformação, pois, peças com geometrias complexas e de grandes volumes podem ser produzidas. Neste caso, a consolidação ocorre, geralmente, pela ação de um ligante hidráulico, cuja função é garantir níveis mínimos de resistência mecânica à verde. Em sistemas refratários, os ligantes mais utilizados são o cimento de aluminato de cálcio (CAC) e alumina hidratável (AH), devido à alta refratariedade e custos competitivos destes materiais. Nas estruturas porosas à base de alumina, particularmente, eles podem proporcionar valores distintos de porosidade e diferentes tipos de microestruturas. Este trabalho teve como objetivo entender como o CAC e a AH interagem com a alumina. Foram avaliados a evolução microestrutural e os efeitos do teor (10 até 40% em volume de ligante hidráulico) e do tamanho das partículas da matriz (alumina fina e grossa) nas amostras à verde e durante o aquecimento inicial até 1500°C. De modo geral, maiores volumes de ligantes permitiram a obtenção de estruturas à verde mais rígidas e resistentes, porém menos porosas. Além da porosidade total (PT), as microestruturas decorrentes das transformações de fases cristalinas ou amorfas também influenciaram os resultados mecânicos. No caso do CAC, as fases formadas durante as reações in situ ajudaram a melhorar as propriedades mecânicas das amostras, mesmo que acompanhado por um acréscimo em porosidade. Em proporções estequiométricas, os cristais de hexaluminato de cálcio (CA6) formados após tratamento a 1500°C inibiram a densificação, ajudando na manutenção da PT (36,7-46,5%), ainda com boa resistência (acima de 20 MPa em compressão diametral). Nos sistemas ligados com AH, observou-se grandes perdas em propriedades mecânicas antes da sinterização, as quais foram relacionadas ao aumento de densidade real dos precipitados do ligante e à perda de conexão entre as partículas da matriz. Em altas temperaturas, os precipitados de AH auxiliaram a sinterização e garantiram a obtenção de peças porosas quando se utilizou alumina grossa (PT: 44,3-47,7%). / Porous ceramics have a wide range of technological applications, such as thermal insulation in steelmaking furnaces, filter for high temperature fluids and as biomaterials. Obtaining these structures through the direct casting of aqueous suspensions is an interesting conformation method since pieces with complex geometries and large volumes can be produced. In this case, the consolidation usually occurs by the action of a hydraulic binder, which provides the minimum levels of mechanical strength in green samples. In refractory systems, the most used binders are calcium aluminate cement (CAC) and hydratable alumina (HA), due to the high refractoriness and competitive costs of these materials. Particularly, in porous alumina-based structures, they can provide distinct values of porosity and different types of microstructures. The purpose of the present work is to understand how CAC and HA interact with alumina. The effects of the binder content (from 10 up to 40% in volume) and the particle size of the matrix (fine and coarse) during initial heating up to 1500°C were studied. In general, larger volumes of binders provided green samples with less porosity but higher mechanical strength. Besides total porosity (TP), the microstructures generated from the transformations of crystalline or amorphous phases also influenced the mechanical results. In the case of CAC, the phases formed by in situ reactions improved the mechanical properties of the samples, despite the increase in porosity. In stoichiometric proportions, the crystals of calcium hexaluminate (CA6) formed after treatment at 1500°C inhibited the densification, favoring to maintain total porosity (36.7-46.5%), even with acceptable mechanical properties (above 20 MPa under diametric compression). In HA-bonded systems, before the sintering begins, a decrease in mechanical properties was noted and related to the increase in density of the precipitates and loss of connection between the matrix particles. At high temperature, the precipitates from HA aided the sintering and guaranteed porous samples in coarse alumina composition (TP: 44.3- 47.7%).

Revegetation of bauxite residue is hampered by a lack of understanding of the limitations imposed on plant growth in highly saline and alkaline growth mediums. In this study, several of these growth limiting factors were investigated. The toxicity of the hydroxyl ion (OH-) was examined using a solution culture system developed to allow studies at high pH without nutritional limitations. Also using this solution culture system, the effect of the high Na and Mg concentrations of bauxite residue on the Ca nutrition of plants was investigated. As the toxicity of Al at high pH is not known, a study was conducted to examine the rhizotoxicity of aluminate (Al(OH)4-) and polycationic Al at high pH. The ability of plant roots to reduce rhizosphere pH in bauxite residue was also considered. A novel gypsum application method was assessed for its efficiency at improving the Ca status of bauxite residue. Manual adjustment, ion exchange resins and automated titration were examined for their suitability for nutrient solution pH control in alkaline conditions. For short-term studies, it was found that a solution without supply of Cu, Fe, Mn and Zn, and aerated with CO2 depleted air, greatly reduced nutrient precipitation at high pH, thus eliminating nutritional differences between treatments. Manual pH adjustment and the use of ion exchange resins as pH buffers were unsuitable methods of pH control. In contrast, pH control by automated titration had little effect on solution composition while maintaining constant pH. The solution culture system was used to examine OH- toxicity in mungbeans (Vigna radiata (L.) Wilczek cv. Emerald), with root length reduced at a bulk solution pH of 8.5 and greater. The effect of Ca activity ratio (CAR) and pH on Ca uptake by mungbeans and Rhodes grass (Chloris gayana cv. Pioneer) in Na dominated solution cultures and in soil was investigated. Changes in pH in the alkaline range were shown to have no effect on the critical CAR of 0.024 (corresponding to 90 % relative root length) for mungbeans grown in solution culture. Results from soil grown mungbeans confirmed those from solution culture, with a critical CAR of 0.025. A critical CAR of 0.034 was also established for soil grown Rhodes grass. However, using dilute nutrient solutions dominated by Mg at pH 9.0, root growth was found to be more limited than had been observed for Na solutions, with growth reduced beneath a critical CAR of 0.050. Using a CAR equation modified with plasma membrane binding constants (to incorporate the differing antagonistic effects of Mg and Na), new critical CAR values were calculated for Na (0.56) and Mg (0.44) dominated solutions. This modified CAR equation permits the calculation of CAR irrespective of the dominant salt present. Solubilities of various gypsum sources and size fractions in seawater were studied to investigate the effectiveness of gypsum addition to the residue sand pipeline, rather than as a direct field application. The dissolution rate constant varied with gypsum source (analytical grade (AR) > phosphogypsum (PG) > mined gypsum (MG)) due to reactivity and surface area differences, generally reaching saturation within 15 s (AR) to 30 min (MG > 2.0). The ability of bauxite residue to remove Ca from solution (due to cation exchange and precipitation) was also examined; the quantity of the total solution Ca adsorbed was found to be small (5 %). These low rates of solution Ca adsorption, comparatively rapid dissolution rates, and long pumping times (20 min), preclude the application of gypsum to the residue sand/seawater slurry as a method for residue amelioration. Dilute, alkaline (pH 9.5) nutrient solutions were used to investigate the effects of aluminate (Al(OH)4-) on mungbean root growth. Although root growth in Al(OH)4- solutions was slightly limited, the symptoms associated with this growth reduction were observed to be similar to those caused by the Al13 polycation at concentrations lower than that which can be detected. Also, when roots displaying these symptoms were transferred to fresh Al(OH)4- solutions, no root tip lesions were observed, and root hair growth on the lateral roots improved. Thus, Al(OH)4- is considered to be non-toxic, with the observed reduction in root growth in solutions containing Al(OH)4- due to the gradual formation of toxic Al13 in the bulk nutrient solution resulting from the acidification of the alkaline nutrient solution by the plant roots. The effect of Mn deficiency in Rhodes grass and of legume inoculation in lucerne (Medicago sativa L. cv. Hunter River), on the rhizosphere pH of plants grown in highly alkaline bauxite residue was investigated. In response to Mn deficiency in residue sand, Rhodes grass was observed to increase acidification of its rhizosphere (being up to 1.22 pH units lower than the bulk soil). Due to its ability to fix atmospheric N2 rather than relying on soil N (NO3-) reserves, inoculated lucerne (1.75 pH unit decrease) was also found to acidify its rhizosphere to a greater extent than non-inoculated lucerne (1.16 pH unit decrease).

Revegetation of bauxite residue is hampered by a lack of understanding of the limitations imposed on plant growth in highly saline and alkaline growth mediums. In this study, several of these growth limiting factors were investigated. The toxicity of the hydroxyl ion (OH-) was examined using a solution culture system developed to allow studies at high pH without nutritional limitations. Also using this solution culture system, the effect of the high Na and Mg concentrations of bauxite residue on the Ca nutrition of plants was investigated. As the toxicity of Al at high pH is not known, a study was conducted to examine the rhizotoxicity of aluminate (Al(OH)4-) and polycationic Al at high pH. The ability of plant roots to reduce rhizosphere pH in bauxite residue was also considered. A novel gypsum application method was assessed for its efficiency at improving the Ca status of bauxite residue. Manual adjustment, ion exchange resins and automated titration were examined for their suitability for nutrient solution pH control in alkaline conditions. For short-term studies, it was found that a solution without supply of Cu, Fe, Mn and Zn, and aerated with CO2 depleted air, greatly reduced nutrient precipitation at high pH, thus eliminating nutritional differences between treatments. Manual pH adjustment and the use of ion exchange resins as pH buffers were unsuitable methods of pH control. In contrast, pH control by automated titration had little effect on solution composition while maintaining constant pH. The solution culture system was used to examine OH- toxicity in mungbeans (Vigna radiata (L.) Wilczek cv. Emerald), with root length reduced at a bulk solution pH of 8.5 and greater. The effect of Ca activity ratio (CAR) and pH on Ca uptake by mungbeans and Rhodes grass (Chloris gayana cv. Pioneer) in Na dominated solution cultures and in soil was investigated. Changes in pH in the alkaline range were shown to have no effect on the critical CAR of 0.024 (corresponding to 90 % relative root length) for mungbeans grown in solution culture. Results from soil grown mungbeans confirmed those from solution culture, with a critical CAR of 0.025. A critical CAR of 0.034 was also established for soil grown Rhodes grass. However, using dilute nutrient solutions dominated by Mg at pH 9.0, root growth was found to be more limited than had been observed for Na solutions, with growth reduced beneath a critical CAR of 0.050. Using a CAR equation modified with plasma membrane binding constants (to incorporate the differing antagonistic effects of Mg and Na), new critical CAR values were calculated for Na (0.56) and Mg (0.44) dominated solutions. This modified CAR equation permits the calculation of CAR irrespective of the dominant salt present. Solubilities of various gypsum sources and size fractions in seawater were studied to investigate the effectiveness of gypsum addition to the residue sand pipeline, rather than as a direct field application. The dissolution rate constant varied with gypsum source (analytical grade (AR) > phosphogypsum (PG) > mined gypsum (MG)) due to reactivity and surface area differences, generally reaching saturation within 15 s (AR) to 30 min (MG > 2.0). The ability of bauxite residue to remove Ca from solution (due to cation exchange and precipitation) was also examined; the quantity of the total solution Ca adsorbed was found to be small (5 %). These low rates of solution Ca adsorption, comparatively rapid dissolution rates, and long pumping times (20 min), preclude the application of gypsum to the residue sand/seawater slurry as a method for residue amelioration. Dilute, alkaline (pH 9.5) nutrient solutions were used to investigate the effects of aluminate (Al(OH)4-) on mungbean root growth. Although root growth in Al(OH)4- solutions was slightly limited, the symptoms associated with this growth reduction were observed to be similar to those caused by the Al13 polycation at concentrations lower than that which can be detected. Also, when roots displaying these symptoms were transferred to fresh Al(OH)4- solutions, no root tip lesions were observed, and root hair growth on the lateral roots improved. Thus, Al(OH)4- is considered to be non-toxic, with the observed reduction in root growth in solutions containing Al(OH)4- due to the gradual formation of toxic Al13 in the bulk nutrient solution resulting from the acidification of the alkaline nutrient solution by the plant roots. The effect of Mn deficiency in Rhodes grass and of legume inoculation in lucerne (Medicago sativa L. cv. Hunter River), on the rhizosphere pH of plants grown in highly alkaline bauxite residue was investigated. In response to Mn deficiency in residue sand, Rhodes grass was observed to increase acidification of its rhizosphere (being up to 1.22 pH units lower than the bulk soil). Due to its ability to fix atmospheric N2 rather than relying on soil N (NO3-) reserves, inoculated lucerne (1.75 pH unit decrease) was also found to acidify its rhizosphere to a greater extent than non-inoculated lucerne (1.16 pH unit decrease).