Continuous Hydrothermal Synthesis of Metal Oxides in Sub-and Supercritical Water

"Supercritical water can provide an unique reaction atmosphere for synthesizing metal oxide nanoparticles. Due to the drastic change of properties of water around the critical point, including density, dielectric constant and ionic product, the reaction phase with O 2 or H2 gas and the reaction rate and equilibrium can be varied to synthesize new materials or define particle morphologies. In this work, hydrothermal crystallization experiments are performed with several types of flow apparatus that allow convenient manipulation of variables such as temperature, pressure, and residence time. Key features in the flow modes and material preparation are discussed. The proposed supercritical hydrothermal synthesis method has the following desirable features: i) nanoparticles can be produced, ii) morphology of the produced particles can be controlled with small changes in pressure or temperature, and iii) a reducing or oxidizing atmosphere can be applied by introducing oxygen or hydrogen or other gases. An overview of this method is given for functional material synthesis of significant industrial interest including barium hexaferrite magnetic particles, YAO/Tb phosphor fine particles and lithium cobalt fine crystals.IntroductionHydrothermal crystallization, a method of metal oxide formation from metal salt solutions, is typically used at temperatures ranging from 373 K to 473 K. We are developing a new process for hydrothermal crystallizations that uses temperatures in the range of 673 K to 723 K, which is just above the critical temperature of water1 • 8 • In this work, we refer to this process as supercritical hydrothermal synthesis. The supercritical state of water allows one to vary reaction rate and reaction equilibrium by shifting the dielectric constant and solvent density with pressure and temperature. From of our research on material production in supercritical water, we have identified the following specific features of the supercritical hydrothermal synthesis method: (i) ultrafine particles can be produced, (ii) morphology of the produced particles can be controlled to some extent with pressure and/or temperature, and (iii) a homogeneous reducing or oxidizing atmospheres can be provided by introducing gases, such as O 2, H2, H2O 2• and so on.1"