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Although remarkable development of titanate‐based glasses has been achieved, challenge remains to elucidate the correlation between structure and glass‐forming properties in these systems due to their complex structure that is inconsistent with the classic Zachariasen's model. In this work, we aim to correlate the structural evolution of titanate melts to their glass‐forming ability (GFA). The prototypical material barium dititanate (BaTi2O5, BT2) melts with different GFA were rendered by controlled melting atmospheres, and the corresponding structural changes were determined using in situ high‐energy synchrotron X‐ray diffraction combined with empirical potential structure refinement and ab initio molecular dynamics. The results show that BT2 melt in reducing atmosphere shows poor GFA but that in oxidizing atmosphere presents good GFA. Structural analysis demonstrates the mean coordination number of [TiOm] polyhedra is analogous in the melt under two different atmospheres but an enhanced heterogeneous cations aggregation takes place in the melt under reducing atmosphere, which is closely related to oxygen‐deficiencies. Furthermore, we reveal that the enhanced heterogeneous cations aggregation promotes crystallization (and therefore hinders glass formation) through disordering the distribution of [TiOm] and [BaOn] polyhedra, changing the connectivity between these polyhedra, creating more crystal‐like Ti‐Ti clusters, and decreasing topological disorder of BT2 melt. Our work provides a new viewpoint to understand the GFA of titanates melt from structural heterogeneity beyond the previous perspectives that only focus on [TiOm] polyhedra. [ABSTRACT FROM AUTHOR]

The crystallization processes of titanates are central to the fabrication of optical and electrical crystals and glasses, but their rich polymorphism is not fully understood. Here, we show when and how polymorphic selection occurs during the crystallization of barium titanate (BaTiO3, BT) using in situ high energy synchrotron X-ray diffraction and ab initio molecular dynamic simulation. An anomalous structure transition is found in molten BT during cooling across the cubic-hexagonal transition temperature, which enables nucleation selection of BT by manipulating the undercooling: a cubic phase is preferred if nucleation is triggered at large undercooling, whereas a hexagonal phase is promoted at small undercooling. We further reveal that the nucleation selection between the cubic and the hexagonal phase is regulated by the intrinsic structure property of the melt, in particular, the degree of polymerization between Ti-O polyhedra. These findings provide an innovative perspective to link the polymorphic crystallization to the non-isomorphic structure transition of the melt beyond the conventional cognition of structural heredity. The crystallization processes of titanates are central to the fabrication of optical and electrical crystals and glasses, but their rich polymorphism is not fully understood. Here, authors identify when and how polymorphic selection takes place during the crystallization of an undercooled barium titanate melt using aerodynamic levitation, in situ time resolved high energy X-ray diffraction and ab initio molecular dynamics simulations. [ABSTRACT FROM AUTHOR]