期刊
APPLIED SURFACE SCIENCE
卷 620, 期 -, 页码 -出版社
ELSEVIER
DOI: 10.1016/j.apsusc.2023.156797
关键词
TiN; Oxidation mechanism; N2 nanobubbles; Structural failure; Aberration-corrected scanning transmission; microscopy
This study reports the oxidation pathways of TiN with different grain sizes through careful atomic structure characterization. Nano-sized TiN single crystal undergoes a two-step phase transformation, while micron-sized TiN single crystal or polycrystals directly convert to rutile TiO2 upon oxidation. N2 nanobubbles are generated in the micron-sized TiN oxidation process, which preferentially embed inside of rutile TiO2 grain boundaries for single crystals and the oxide/nitride interface for polycrystals. The oxidation induces great volume expansion in all types of TiN, but only micron-sized single crystals are fractured and pulverized dramatically, impairing the mechanical properties.
TiN, as a classic ceramic material, has been widely used in a variety of practical applications due to its unique physical and inert chemical properties. The oxidation behavior of TiN is detrimental to both its engineering and functional applications. However, the intuitive recognition of the oxidation mechanism and corresponding structural failure is ambiguous so far. This work reports the oxidation pathways of TiN with different grain sizes via careful atomic structure characterization. Nano-sized TiN single crystal undergoes a two-step phase trans-formation, i.e. anatase and subsequently rutile TiO2, whereas micron-sized TiN single crystal or polycrystals directly convert to rutile TiO2 upon oxidation. Notably, numerous N2 nanobubbles generate in the micron-sized TiN oxidation process, which preferentially embedded inside of rutile TiO2 grain boundaries for single crystal and the oxide/nitride interface for polycrystals. The atomic structure of a nanobubble edge indicates it is generally epitaxial bonding with {101} and {200} of rutile TiO2. Besides, the oxidation induces great volume expansion in all types of TiN, but only micron-sized single crystals are fractured and pulverized dramatically, accompanying with rationally impairing the mechanical properties. The fundamental exploration of oxidation behavior at atomic scale would help to guide rational structural/phase design of advanced ceramic materials.
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