Electron microscopy studies of the morphological evolution in hydrothermally derived lead titanate

Zhiyuan Ye, Purdue University

Abstract

Hydrothermal processing is a promising technique to synthesize perovskite ceramic powders. Understanding the reaction mechanisms and the factors that affect the particle morphologies is essential to optimize the hydrothermal processing. In this dissertation, the reaction mechanisms and nucleation processes in hydrothermally derived lead titanate (PbTiO3) are examined and established by morphological studies. The initial concentration of potassium hydroxide [KOH]i had a strong influence on the reaction. As [KOH] i increased from 0.01 M to 0.1 M to 1.0 M, the resultant morphology changed from irregular spherical to dendritic to faceted rectangular platelet morphology. The morphological evolution was well explained in the context of a supersaturation-nucleation relation. As the [KOH]i increased, the supersaturation increased and the nucleation mechanism changed from weak heterogeneous nucleation to strong heterogeneous nucleation or even homogeneous nucleation. These different nucleation mechanisms resulted in the different morphologies. Kinetic and morphological studies suggest that the reaction starting from nanocrystalline titania is dominated by dissolution-precipitation. The titanium precursors strongly affected the reaction. Increasing the particle size of precursors significantly reduced the reaction rate, especially at the low [KOH]i case. In situ transformations play important roles under the conditions of low [KOH] i and/or large particle size of precursors. Investigation using amorphous titania indicated that the nucleation of lead titanate at low and intermediate [KOH]i is via a in situ transformation while at high [KOH]i a dissolution-precipitation mechanism dominates. Ferro electricity of PbTiO3 also affects the particle morphology. The hydrothermal lead titanate particles could grow as a single domain during the processing. The ferroelectric polarization of PbTiO3 induced different local ionic environment between the positively and negatively charged surfaces, resulting a one-sided dendritic morphology at intermediate [KOH] i. The platelet morphology at high [KOH]i gave rise to a new type of size effect. For platelets with size less than a critical size of ∼70 nm, the domain polarization reoriented from perpendicular to the platelet during the processing, to parallel to the platelet after the particles were washed and dried (so that the depolarization energy builds up). This domain reorientation is attributed to strong depolarization effects and anisotropic geometry factors.

Degree

Ph.D.

Advisors

Slamovich, Purdue University.

Subject Area

Materials science

Off-Campus Purdue Users:
To access this dissertation, please log in to our
proxy server
.

Share

COinS