The mechanism of gibbsite crystal growth in Bayer liquor.
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1998Supervisor
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Although the precipitation of aluminium trihydroxide as gibbsite, via the Bayer process has been widely studied, the mechanism of crystal growth is poorly understood. This work focus on the morphology of gibbsite and the relative growth rates of individual crystal faces.Initial work was carried out to characterize aluminium trihydroxide and it was found that bayerite, another polymorph, precipitated at temperatures below 50 [degrees] C and its morphology depended on the method of precipitation. Gibbsite however, precipitated above this temperature and its morphology depended on the type of alkali aluminate solutions used. The method of precipitation does not affect the morphology, only the size of the precipitate formed. The morphology of gibbsite can be altered by the addition of organic compounds which are known to inhibit gibbsite precipitation. Some of these compounds were found to selectively inhibit the growth of individual crystal faces, thus altering the overall morphology of gibbsite. Boehmite, a polymorph of aluminium hydroxide, can be produced by partial dehydration of gibbsite at 300T. The morphology of boehmite consisted of diamond shaped crystals.The influence of cation incorporation on the morphology of gibbsite was studied experimentally and computationally (molecular modelling). These studies showed that there is a linear relationship between the amount of cation incorporated and atomic radii and between the amount of cation incorporated and the defect energy calculated. The equilibrium morphology of gibbsite predicted in the absence of media matched the morphology of gibbsite grown slowly from sodium aluminate, implying that the amount of sodium incorporation is low in these crystals.The growth rates of individual crystal faces were measured in situ, and found to be a function of supersaturation squared for the prismatic faces, possibly indicating that E growth occurs by spiral growth mechanism. The growth of the basal face was found to follow the spiral growth mechanism below a relative supersaturation of 0.815 and the birth and spread mechanism above this level. The activation energies and kinetic coefficients for the individual prismatic faces were also determined.Growth rate dispersion was observed in these microscopic studies, but the question of size dependency remains unanswered.The overall growth rates of gibbsite crystal, determined using rapid dynamic light scattering, was found to be an exponential function of supersaturation indicative of a birth and spread growth mechanism.
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