<!--[if !mso]> <object classid="clsid:38481807-CA0E-42D2-BF39-B33AF135CC4D" id=ieooui></object><mce:style><! st1\:*{behavior:url(#ieooui) } --> The present work was initiated to study the synthesis and properties of lanthanum gallate based oxides as intermediate temperature electrolyte for solid oxide fuel cells. The wet chemical method, polymer complexing route, was used to prepare the precursor powders. To further investigate the polymer complexing method, it was also applied to the preparation of lanthanum aluminate based oxides.   Single perovskite phase La0.8Sr0.2Ga0.83Mg0.17O2.815 can be prepared by the polymer complexing method using PVA as complexing agent. The thermal decomposition of the precursor powder undergoes three stages. While complete decomposition of the precursor is obtained at 1000°C. Further investigation of LaGaO3 doped with various amounts Sr or/and Mg was conducted. Three secondary phases were identified by X-ray diffraction, e.g. LaSrGaO4, LaSrGa3O7 and La4Ga2O9. The relative amount of these secondary phases depends on the doping compositions. Sr doping produced more Sr rich secondary phases with increasing content, while enhanced solid solubility was observed with Mg addition. Sintered samples showed dense microstructures with well-developed equiaxed grains, and the secondary phases were mainly in the grain boundaries. The oxygen ionic conductivity was enhanced by doping with Sr and Mg. Mg doping showed the increased activation energy of conductivity.   Preliminary study showed that the lanthanum gallate and ceria composite electrolyte is mainly fluorite CeO2 phase after sintering. The minority secondary phase, Sm3Ga5O12, was also detected by XRD. The composite electrolyte showed superior electrical performance. It exhibited the highest conductivity in the temperature range of 250–600°C, compared with lanthanum gallate and ceria specimens.   The phase pure perovskite La0.9Sr0.1Al0.85Mg0.1Co0.05O2.875 powders can easily be obtained by the polymer method using PVA as complexing agent. No secondary phase was detected after calcination at various temperatures (500–1100°C). The fully crystallized LaAlO3 phase was prepared after calcination at 900°C. Meanwhile the secondary phases were difficult to eliminate in the Sr- and Mg- doped LaGaO3 powder prepared by the same polymer method. It is thus concluded that the polymer, PVA in this work, provides more homogeneous mixing for cations of lanthanum aluminate based oxides, compared with the one for doped lanthanum gallate.   The influence of different complexing agents, e.g. PVA and PEG, was investigated in the synthesis of lanthanum aluminate powders. Minority impurity La2O3 existed in the PEG powder, but it could be eliminated after sintering at high temperatures. Although the pure phase LaAlO3 can be easily obtained in PVA powders calcined at 950°C, more seriously aggregated particles existed. PEG showed advantages over PVA in terms of better densification and microstructure control in the sintered products. To select proper polymers in complex oxide synthesis, the agglomeration and morphology of the powder are the most important factors to be considered. / QC 20100727

Compared to the knowledge base for ordinary portland cement concrete (OPCC), relatively little information exists for calcium aluminate cement concrete (CACC), despite its existence for over 100 years. There is particularly a lack of knowledge related to early-age behavior of CACC, specifically volume change and cracking potential. To assess these early-age properties, two unique pieces of equipment were developed and employed: a rigid cracking frame and free deformation frame which enabled quantification of restrained stress generation and unrestrained autogenous deformation, respectively. These two pieces of equipment employed active temperature control and allowed a wide range of isothermal and realistic temperature conditions to be imposed upon hydrating cementitious samples. Match-cured samples (i.e. identical temperature curing to that in the frames) enabled the quantification of mechanical property development. Samples cured at discrete isothermal temperatures up to 30 °C developed tensile forces in the rigid cracking frame and exhibited shrinkage phenomena in the free deformation frame. At temperatures above 30 °C, the converse was true and significant compressive forces developed in restrained testing and expansion was observed in unrestrained testing. It was found that this was a direct result of microstructural development related to the formation of metastable phases (associated with shrinkage) and stable phases (expansion as a result of conversion from metastable to stable phases). Proper use of this material must take into account behavior associated with both types of hydrate assemblages, metastable and stable. Realistic time-temperature histories were also investigated based on field-scale concrete cast as part of this research project. It was found that volume change at earlyage was dominantly controlled by thermal history. Furthermore, it was not simply the maximum temperature reached, but the rate of temperature rise during hydration and the resulting duration of time spent at high temperature that profoundly influenced volume change and property development. The research described in this dissertation represents a significant advancement of the state-of-knowledge of this unique material and has further elucidated the role of temperature during hydration of CACC. / text

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).

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).

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).

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).

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%).