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Oxygen Ion Conduction in Bulk and Grain Boundaries of Nominally Donor‐Doped Lead Zirconate Titanate ( PZT ): A Combined Impedance and Tracer Diffusion Study
Author(s) -
Slouka Christoph,
Holzlechner Gerald,
Andrejs Lukas,
Navickas Edvinas,
Hutter Herbert,
Fleig Jürgen
Publication year - 2015
Publication title -
journal of the american ceramic society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.9
H-Index - 196
eISSN - 1551-2916
pISSN - 0002-7820
DOI - 10.1111/jace.13769
Subject(s) - grain boundary , analytical chemistry (journal) , ionic conductivity , conductivity , grain boundary diffusion coefficient , vacancy defect , ionic bonding , materials science , dielectric spectroscopy , diffusion , ion , annealing (glass) , chemistry , electrode , crystallography , electrochemistry , electrolyte , thermodynamics , metallurgy , microstructure , physics , organic chemistry , chromatography
Oxygen ion conduction in Nd 3+ ‐doped Pb(Zr x Ti 1− x )O 3 ( PZT ) was investigated by impedance spectroscopy and 18 O‐tracer diffusion with subsequent secondary ion mass spectrometry ( SIMS ) analysis. Ion blocking electrodes lead to a second relaxation feature in impedance spectra at temperatures above 600°C. This allowed analysis of ionic and electronic partial conductivities. Between 600°C and 700°C those are in the same order of magnitude (10 −5 –10 −4 S/cm) though very differently activated (2.4 eV vs. 1.2 eV for ions and electron holes, respectively). Oxygen tracer experiments showed that ion transport mainly takes place along grain boundaries with partly very high local ionic conductivities. Numerical analysis of the tracer profiles, including a near‐surface space charge zone, revealed bulk and grain‐boundary diffusion coefficients. Calculation of an effective ionic conductivity from these diffusion coefficients showed good agreement with conductivity values determined from impedance measurements. Based on these data oxygen vacancy concentrations in grain boundary and bulk could be estimated. Annealing at high temperatures caused a decrease in the grain‐boundary ionic conductivity and onset of additional defect chemical processes near the surface, most probably due to cation diffusion.