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Abstract: In this work, we investigate the effects of powder chemistry on the sintering of MgO‐doped specialty alumina. The stages at which MgO influences densification of Al2O3 were identified by comparing dilatometry measurements and the sintering kinetics of MgO‐free and MgO‐doped specialty alumina powders. MgO is observed to reduce the grain boundary thickness during densification using TEM. We show that MgO increases the solubility of SiO2 in alumina grains near the boundaries using EDS. First‐principles DFT calculations demonstrate that the co‐dissolution of MgO and SiO2 in alumina is thermodynamically favored over the dissolution of MgO or SiO2 individually in alumina. This study experimentally demonstrates for the first time that removal of SiO2 from the grain boundaries is a key process by which MgO enhances the sintering of alumina. [ABSTRACT FROM AUTHOR]

To determine how grain-boundary composition affects the liquid phase sintering of MgO-free Bayer process aluminas, samples were singly or co-doped with up to 1029 ppm Na2O and 603 ppm SiO2 and heated at 1525°C up to 8 h. Na2O retards densification of samples from the onset of sintering and up to hold times of 30 min at 1525°C compared to the undoped samples, but similar to the as-received, MgO-free Al2O3, Na2O-doped samples sinter to 98% density with average grain sizes of ~3 μm after 8 h. Increasing SiO2 concentration significantly retards densification at all hold times up to 8 h. The estimated viscosities (20−400 Pa·s) of the 0.3 to 1.8 nm thick siliceous grain-boundary films in this study indicate that diffusion greatly depends on the composition of the liquid grain-boundary phase. For low Na2O/SiO2 ratios, densification of Bayer Al2O3 at 1525°C is controlled by diffusion of Al3+ through the grain-boundary liquid, whereas for high Na2O/SiO2 ratios, densification can be governed by either the interface reaction (i.e., dissolution) of Al2O3 or diffusion of Al3+. Increasing Na2O in SiO2-doped samples increases diffusion of Al3+ and Al2O3 solubility in the liquid, and thus densification increases by 1%. Based on these findings, we conclude that Bayer Al2O3 densification can be manipulated by adjusting the Na2O to SiO2 ratio. [ABSTRACT FROM AUTHOR]

To determine how grain-boundary composition affects the liquid phase sintering of MgO-free Bayer process aluminas, samples were singly or co-doped with up to 1029 ppm Na2O and 603 ppm SiO2 and heated at 1525°C up to 8 h. Na2O retards densification of samples from the onset of sintering and up to hold times of 30 min at 1525°C compared to the undoped samples, but similar to the as-received, MgO-free Al2O3, Na2O-doped samples sinter to 98% density with average grain sizes of ~3 μm after 8 h. Increasing SiO2 concentration significantly retards densification at all hold times up to 8 h. The estimated viscosities (20−400 Pa·s) of the 0.3 to 1.8 nm thick siliceous grain-boundary films in this study indicate that diffusion greatly depends on the composition of the liquid grain-boundary phase. For low Na2O/SiO2 ratios, densification of Bayer Al2O3 at 1525°C is controlled by diffusion of Al3+ through the grain-boundary liquid, whereas for high Na2O/SiO2 ratios, densification can be governed by either the interface reaction (i.e., dissolution) of Al2O3 or diffusion of Al3+. Increasing Na2O in SiO2-doped samples increases diffusion of Al3+ and Al2O3 solubility in the liquid, and thus densification increases by 1%. Based on these findings, we conclude that Bayer Al2O3 densification can be manipulated by adjusting the Na2O to SiO2 ratio. [ABSTRACT FROM AUTHOR]

Abstract: In this work, we investigate the effects of powder chemistry on the sintering of MgO‐doped specialty alumina. The stages at which MgO influences densification of Al2O3 were identified by comparing dilatometry measurements and the sintering kinetics of MgO‐free and MgO‐doped specialty alumina powders. MgO is observed to reduce the grain boundary thickness during densification using TEM. We show that MgO increases the solubility of SiO2 in alumina grains near the boundaries using EDS. First‐principles DFT calculations demonstrate that the co‐dissolution of MgO and SiO2 in alumina is thermodynamically favored over the dissolution of MgO or SiO2 individually in alumina. This study experimentally demonstrates for the first time that removal of SiO2 from the grain boundaries is a key process by which MgO enhances the sintering of alumina. [ABSTRACT FROM AUTHOR]