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Mechanism and Kinetics of Oxidation of ZrN Ceramics
Author(s) -
Harrison Robert W.,
Lee William Edward
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.13575
Subject(s) - ceramic , materials science , oxide , diffusion , tetragonal crystal system , monoclinic crystal system , zirconium , layer (electronics) , kinetics , chemical engineering , metallurgy , crystallography , chemistry , crystal structure , composite material , thermodynamics , physics , quantum mechanics , engineering
Oxidation of ZrN ceramics from 973–1373 K under static conditions reveals parabolic rate behavior, indicative of a diffusion‐controlled process. In‐situ high temperature powder XRD found the oxidation mechanism begins with destabilization of ZrN through formation of a ZrN 1− x phase with oxide peaks initially detected at around 773 K. The zirconium oxide layer was found to be monoclinic by in‐situ XRD with no evidence of tetragonal or cubic polymorphs present to 1023 K. Bulk ceramic samples oxidized at 1173 and 1273 K underwent slower oxidation than those oxidized at 973 and 1073 K. This change in oxidation rate and hence mechanism was due to formation of a denser c‐ZrO 2 polymorph stabilized by nitrogen defects. This N‐doped dense ZrO 2 layer acts as a diffusion barrier to oxygen diffusion. However, at an oxidation temperature of 1373 K this layer is no longer protective due to increased diffusion through it resulting in grain boundary oxidation.