Using zirconium oxychloride solution as precursor, monoclinic zirconia crystallites withnarrow distribution of nanosize were obtained in the hydrothermal reaction. However, when thereaction was in weak acidic medium or base medium, whether directly using the colloidal precipi-tate prepared from zirconium salt solutions with base solution as precursor added, or using theprecipitate after filtrating, washing and drying treatments as precursor, the product of the hydro-thermal reaction was the mixture of both monoclinic and tetragonal polymorphs. As the pH of themedium rises, the content of tetragonal phase in the product, the morphologies and size of thecrystallites all change. There are three types of formation mechanisms under hydrothermal condi-tion, which can be called as saturation-precipitation mechanism in homogeneous solution, dissolu-tion-crystallization mechanism and in-situ crystallization mechanism, respectively. The formationmechanism of crystallites varies with different hydrothermal conditions, such as the states of theprecursor and the pH of the medium, which lead to changes in the phases, morphologies andsizes of the resulting crystallites.
The formation process of crystal polymorphs of titania under hydrothermal condition is studied.According to the experimental results and theoretic analysis,the formation process of crystal polymorphs can be described as a unit process.It includes the formation of growth units,the formation of nuclei through the polymerization of growth unit,and the growth of crystallites.The influence of the environmental phase and growth conditions on the formation of polymorphs is reflected in the changes of the structures of growth units.For example,when changing the pH of the reaction medium,the structure of growth unit with the highest stable energy in the hydrothermal system changes.Then different titania polymorphs can be prepared.The absorption,movement,crystallization or desorption of the growth unit are related to crystalline structure.On the other hand,the formation of crystal inner defects is related to the disturbance of the crystallizing process.
A new growth mechanism model, coordination polyhedron growth mechanism model, is introduced from the angle of the coordination of anion and cation to each other at the interface. It is pointed out that the force driving the growth unit to enter the crystal lattice is the electrostatic attraction force between ions, whose relative size can be approximately measured by the electrostatic bond strength (EBS) that reaches a nearest neighbor anion (or cation) in the parent phase from a cation (or anion) at the interface. The growth habits of NaCl, ZnS, CaF2 and CsI crystals are discussed, and a new growth habit rule is proposed as follows. When the growth rate of a crystal is determined by the step generation rate, the growth habit of this crystal is related to the coordination number of the ion with the smallest coordination rate at the interface of various crystal faces. The smaller the coordination number of the ion at the interface, the faster the growth rate of corresponding crystal face. When the growth of a crystal depends on the step movement rate, the growth habit of this crystal is related to the density of the ion with the smallest coordination rate at the interface of various crystal faces. The smaller the densities of the ion at the interface is, the faster the growth rate of corresponding crystal face will be.
