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By starting from a known phase diagram for the Al2O3-Na3AlF6 system and applying the same laws which govern crystallisation in aqueous solutions, a model has been developed which allows the behaviour of this system to be predicted theoretically during the crystallisation process in corundum and cryolite forms by the flux growth technique. A series of experiments have been carried out with the same technique and system.The entrance variables of these experiments have been used to develop the theoretical procedure which supports the model. The agreement between the experimental and theoretical results supposes an advance in the formal knowledge of the crystallisation process through the flux growth technique. A method has been developed to improve the quality of previously obtained corundum specimens based on this model.