- Library Home /
- Search Collections /
- Open Collections /
- Browse Collections /
- UBC Theses and Dissertations /
- Surface science studies of Oxidized zirconium
Open Collections
UBC Theses and Dissertations
UBC Theses and Dissertations
Surface science studies of Oxidized zirconium Wang, Yangmei
Abstract
Oxidized zirconium surfaces have been studied by X-ray photoelectron spectroscopy (XPS) and low-energy electron diffraction (LEED). The aim is to provide a fundamental understanding of the chemistry and structure of such surfaces as well as for metal-oxide interfaces; the motivation is to help establish understanding in relation to problems associated with nuclear reactor pressure tube corrosion. The chemistry of a thin film (-20 Å) of oxidized zirconium was studied by XPS. The film, prepared by depositing zirconium onto Au foil in the presence of a H₂0 atmosphere in the low 10⁻⁹ Torr range, has an outer region of Zr0₂and inner regions containing a lower oxidation state material, ZrOx, as well as Zr-Au alloy. Initially both ZrOx and the Zr-Au alloy are oxidized by either H₂0 or 0₂ at 300°C, although this process is hindered as the Zr0₂layer gets thicker. However, even with the protective oxide layer, heating in 4xl0"7 Torr D₂(with a partial pressure of H₂0 at around lxlO"9 Torr) can result in all the zirconium being converted to the +4 oxidation state; the process is apparently facilitated by migrating D atoms. The evolution of structure at the Zr(0001) surface, after exposure to 0₂and an ordering anneal at 220°C, has been studied systematically using LEED crystallography. Additionally, a new analysis was undertaken for the clean Zr(0001) surface, which is confirmed to have a regular hep-type structure, with a slight contraction (about 1.6%) in the first Zr-Zr interlayer spacing with respect to the bulk value (2.57 Å). The surface formed by a 0.5 monolayer (ML) of O manifests a (2x2)-type LEED pattern. A detailed analysis showed a novel structure with 0.25 ML of O at octahedral hole sites in (2x2) arrays, both between the first and second metal layers and between the second and third layers; these O arrays are displaced laterally from one another, apparently to minimize the 0...0 repulsions. The incorporated O atoms induce vertical and lateral relaxations in the metallic structure, which are most significant in the second metal layer. The average O-Zr bond length of 2.28 Å is close to the value (2.30 A) in bulk ZrO, which also has 6-coordinated O atoms. For the surface formed by 1 ML of O at Zr(0001), the LEED analysis indicates a structural model where 0.5 ML of O is distributed randomly over octahedral holes between the first and second metal layers, with another 0.5 ML between the second and the third layers. The structural type changes for 2 ML of O at Zr(0001); now O bonds at 1 ML coverage in overlayer hollow sites of three-fold coordination, while there is another 1 ML of O atoms in tetrahedral hole sites between the first and second metal layers. The stacking sequence, designated as (C)B(A)AB.., corresponds to the first three layers of anion-terminated cubic Zr0₂, although some lateral compression is needed for superposition on the regular hep Zr structure. The absorption of O in tetrahedral holes between the first and second metal layers results in a significant expansion to about 3.44 Å. The O-Zr bond lengths are estimated to equal 2.07 Å for the overlayer O atoms, and 2.22 Å for the O atoms in tetrahedral hole sites.
Item Metadata
Title |
Surface science studies of Oxidized zirconium
|
Creator | |
Publisher |
University of British Columbia
|
Date Issued |
1996
|
Description |
Oxidized zirconium surfaces have been studied by X-ray photoelectron spectroscopy
(XPS) and low-energy electron diffraction (LEED). The aim is to provide a fundamental
understanding of the chemistry and structure of such surfaces as well as for metal-oxide
interfaces; the motivation is to help establish understanding in relation to problems associated with nuclear reactor pressure tube corrosion. The chemistry of a thin film (-20 Å) of oxidized zirconium was studied by XPS. The film, prepared by depositing zirconium onto Au foil in the presence of a H₂0 atmosphere in the
low 10⁻⁹ Torr range, has an outer region of Zr0₂and inner regions containing a lower oxidation state material, ZrOx, as well as Zr-Au alloy. Initially both ZrOx and the Zr-Au alloy are oxidized by either H₂0 or 0₂ at 300°C, although this process is hindered as the Zr0₂layer gets thicker.
However, even with the protective oxide layer, heating in 4xl0"7 Torr D₂(with a partial pressure of H₂0 at around lxlO"9 Torr) can result in all the zirconium being converted to the +4 oxidation state; the process is apparently facilitated by migrating D atoms. The evolution of structure at the Zr(0001) surface, after exposure to 0₂and an ordering anneal at 220°C, has been studied systematically using LEED crystallography. Additionally, a
new analysis was undertaken for the clean Zr(0001) surface, which is confirmed to have a regular hep-type structure, with a slight contraction (about 1.6%) in the first Zr-Zr interlayer spacing with respect to the bulk value (2.57 Å). The surface formed by a 0.5 monolayer (ML) of O manifests
a (2x2)-type LEED pattern. A detailed analysis showed a novel structure with 0.25 ML of O at octahedral hole sites in (2x2) arrays, both between the first and second metal layers and between the second and third layers; these O arrays are displaced laterally from one another, apparently to
minimize the 0...0 repulsions. The incorporated O atoms induce vertical and lateral relaxations in the metallic structure, which are most significant in the second metal layer. The average O-Zr
bond length of 2.28 Å is close to the value (2.30 A) in bulk ZrO, which also has 6-coordinated O atoms.
For the surface formed by 1 ML of O at Zr(0001), the LEED analysis indicates a
structural model where 0.5 ML of O is distributed randomly over octahedral holes between the first and second metal layers, with another 0.5 ML between the second and the third layers. The structural type changes for 2 ML of O at Zr(0001); now O bonds at 1 ML coverage in overlayer
hollow sites of three-fold coordination, while there is another 1 ML of O atoms in tetrahedral hole sites between the first and second metal layers. The stacking sequence, designated as (C)B(A)AB..,
corresponds to the first three layers of anion-terminated cubic Zr0₂, although some lateral compression is needed for superposition on the regular hep Zr structure. The absorption of O in
tetrahedral holes between the first and second metal layers results in a significant expansion to about 3.44 Å. The O-Zr bond lengths are estimated to equal 2.07 Å for the overlayer O atoms, and 2.22 Å for the O atoms in tetrahedral hole sites.
|
Extent |
6908015 bytes
|
Genre | |
Type | |
File Format |
application/pdf
|
Language |
eng
|
Date Available |
2009-04-06
|
Provider |
Vancouver : University of British Columbia Library
|
Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
|
DOI |
10.14288/1.0059550
|
URI | |
Degree | |
Program | |
Affiliation | |
Degree Grantor |
University of British Columbia
|
Graduation Date |
1997-05
|
Campus | |
Scholarly Level |
Graduate
|
Aggregated Source Repository |
DSpace
|
Item Media
Item Citations and Data
Rights
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.