Thickness and composition of native oxides and near-surface regions of Ni superalloys

Alfred Larsson; Giulio D'Acunto; Mariya Vorobyova; Giuseppe Abbondanza; Ulrich Lienert; Zoltan Hegedüs; Alexei Preobrajenski; Lindsay R. Merte; Josefin Eidhagen; Anna Delblanc; Jinshan Pan; Edvin Lundgren

doi:10.1016/j.jallcom.2021.162657

Thickness and composition of native oxides and near-surface regions of Ni superalloys

Alfred Larsson, Giulio D'Acunto, Mariya Vorobyova, Giuseppe Abbondanza, Ulrich Lienert, Zoltan Hegedüs, Alexei Preobrajenski, Lindsay R. Merte, Josefin Eidhagen, Anna Delblanc, Jinshan Pan, Edvin Lundgren

Research output: Contribution to journal › Article › peer-review

Abstract

The surface chemistry and thickness of the native oxide, hydroxide, and modified sub-surface layer of three Ni superalloys (alloy 59, 625, and 718) were determined by synchrotron X-ray Photoelectron Spectroscopy (XPS) and X-ray Reflectivity (XRR). Taking advantage of the synchrotron radiation techniques, a procedure for normalizing the photoelectron intensity was employed, which allowed for accurate quantitative analysis revealing a total oxide thickness for all samples of 12–13 Å, a hydroxide layer of 2–3 Å, and a thickness of the sub-surface alloy layer of 20–35 Å. The thickness results were compared to structural atomic models suggesting that the oxide thickness corresponds to four planes of metal cations in the oxide matrix. The XPS data revealed that the native oxides were enriched in Cr³⁺, Mo^(4,5,6)+, and Nb⁵⁺, while no Ni oxide was detected. The hydroxide layer mainly contained Ni²⁺ and Cr³⁺ hydroxide. The sub-surface layer was enriched in Ni and depleted in Cr, Fe, Mo, and Nb. The obtained oxide composition can be explained using thermodynamics, and it was found that the oxide composition correlates with the enthalpy of oxide formation for the metal elements in the alloys. Finally, the advantages of synchrotron radiation for composition and thickness determination are discussed.

Original language	English
Article number	162657
Journal	Journal of Alloys and Compounds
Volume	895
DOIs	https://doi.org/10.1016/j.jallcom.2021.162657
Publication status	Published - 2022 Feb 25

Bibliographical note

Funding Information:
Financial support is acknowledged from the Swedish Research Council (2018-03434 and 2020-06154) and the Swedish Foundation for Strategic Research under contract ID19-0032. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Malte Blankenburg for assistance in using the Swedish Material Science beamline P21.2. Beamtime was allocated for proposal 20200219EC. We acknowledge FlexPES beamline scientists at MAX IV for assistance with XPS measurements. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152, the Swedish Governmental Agency for Innovation Systems under contract 2018-04969, and Formas under contract 2019-02496. The authors would like to thank Dmytro Orlov and Zoran Markovski for their help with sample preparation.

Funding Information:
Financial support is acknowledged from the Swedish Research Counci l ( 2018-03434 and 2020-06154 ) and the Swedish Foundation for Strategic Research under contract ID19-0032 . We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Malte Blankenburg for assistance in using the Swedish Material Science beamline P21.2. Beamtime was allocated for proposal 20200219EC. We acknowledge FlexPES beamline scientists at MAX IV for assistance with XPS measurements. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152 , the Swedish Governmental Agency for Innovation Systems under contract 2018-04969 , and Formas under contract 2019-02496 . The authors would like to thank Dmytro Orlov and Zoran Markovski for their help with sample preparation.

Publisher Copyright:
© 2021 The Authors

Subject classification (UKÄ)

Materials Chemistry

Free keywords

Corrosion
Cr
Fe
Mo
Native oxide
Nb
Ni
Nickel alloy
Oxide
Passive film
Superalloy
Synchrotron
X-ray photoelectron spectroscopy
X-ray reflectivity
XPS
XRR

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10.1016/j.jallcom.2021.162657

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title = "Thickness and composition of native oxides and near-surface regions of Ni superalloys",

abstract = "The surface chemistry and thickness of the native oxide, hydroxide, and modified sub-surface layer of three Ni superalloys (alloy 59, 625, and 718) were determined by synchrotron X-ray Photoelectron Spectroscopy (XPS) and X-ray Reflectivity (XRR). Taking advantage of the synchrotron radiation techniques, a procedure for normalizing the photoelectron intensity was employed, which allowed for accurate quantitative analysis revealing a total oxide thickness for all samples of 12–13 {\AA}, a hydroxide layer of 2–3 {\AA}, and a thickness of the sub-surface alloy layer of 20–35 {\AA}. The thickness results were compared to structural atomic models suggesting that the oxide thickness corresponds to four planes of metal cations in the oxide matrix. The XPS data revealed that the native oxides were enriched in Cr3+, Mo(4,5,6)+, and Nb5+, while no Ni oxide was detected. The hydroxide layer mainly contained Ni2+ and Cr3+ hydroxide. The sub-surface layer was enriched in Ni and depleted in Cr, Fe, Mo, and Nb. The obtained oxide composition can be explained using thermodynamics, and it was found that the oxide composition correlates with the enthalpy of oxide formation for the metal elements in the alloys. Finally, the advantages of synchrotron radiation for composition and thickness determination are discussed.",

keywords = "Corrosion, Cr, Fe, Mo, Native oxide, Nb, Ni, Nickel alloy, Oxide, Passive film, Superalloy, Synchrotron, X-ray photoelectron spectroscopy, X-ray reflectivity, XPS, XRR",

author = "Alfred Larsson and Giulio D'Acunto and Mariya Vorobyova and Giuseppe Abbondanza and Ulrich Lienert and Zoltan Heged{\"u}s and Alexei Preobrajenski and Merte, {Lindsay R.} and Josefin Eidhagen and Anna Delblanc and Jinshan Pan and Edvin Lundgren",

note = "Funding Information: Financial support is acknowledged from the Swedish Research Council (2018-03434 and 2020-06154) and the Swedish Foundation for Strategic Research under contract ID19-0032. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Malte Blankenburg for assistance in using the Swedish Material Science beamline P21.2. Beamtime was allocated for proposal 20200219EC. We acknowledge FlexPES beamline scientists at MAX IV for assistance with XPS measurements. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152, the Swedish Governmental Agency for Innovation Systems under contract 2018-04969, and Formas under contract 2019-02496. The authors would like to thank Dmytro Orlov and Zoran Markovski for their help with sample preparation. Funding Information: Financial support is acknowledged from the Swedish Research Counci l ( 2018-03434 and 2020-06154 ) and the Swedish Foundation for Strategic Research under contract ID19-0032 . We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Malte Blankenburg for assistance in using the Swedish Material Science beamline P21.2. Beamtime was allocated for proposal 20200219EC. We acknowledge FlexPES beamline scientists at MAX IV for assistance with XPS measurements. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152 , the Swedish Governmental Agency for Innovation Systems under contract 2018-04969 , and Formas under contract 2019-02496 . The authors would like to thank Dmytro Orlov and Zoran Markovski for their help with sample preparation. Publisher Copyright: {\textcopyright} 2021 The Authors",

year = "2022",

month = feb,

day = "25",

doi = "10.1016/j.jallcom.2021.162657",

language = "English",

volume = "895",

journal = "Journal of Alloys and Compounds",

issn = "0925-8388",

publisher = "Elsevier",

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TY - JOUR

T1 - Thickness and composition of native oxides and near-surface regions of Ni superalloys

AU - Larsson, Alfred

AU - D'Acunto, Giulio

AU - Vorobyova, Mariya

AU - Abbondanza, Giuseppe

AU - Lienert, Ulrich

AU - Hegedüs, Zoltan

AU - Preobrajenski, Alexei

AU - Merte, Lindsay R.

AU - Eidhagen, Josefin

AU - Delblanc, Anna

AU - Pan, Jinshan

AU - Lundgren, Edvin

N1 - Funding Information: Financial support is acknowledged from the Swedish Research Council (2018-03434 and 2020-06154) and the Swedish Foundation for Strategic Research under contract ID19-0032. We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Malte Blankenburg for assistance in using the Swedish Material Science beamline P21.2. Beamtime was allocated for proposal 20200219EC. We acknowledge FlexPES beamline scientists at MAX IV for assistance with XPS measurements. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152, the Swedish Governmental Agency for Innovation Systems under contract 2018-04969, and Formas under contract 2019-02496. The authors would like to thank Dmytro Orlov and Zoran Markovski for their help with sample preparation. Funding Information: Financial support is acknowledged from the Swedish Research Counci l ( 2018-03434 and 2020-06154 ) and the Swedish Foundation for Strategic Research under contract ID19-0032 . We acknowledge DESY (Hamburg, Germany), a member of the Helmholtz Association HGF, for the provision of experimental facilities. Parts of this research were carried out at PETRA III, and we would like to thank Malte Blankenburg for assistance in using the Swedish Material Science beamline P21.2. Beamtime was allocated for proposal 20200219EC. We acknowledge FlexPES beamline scientists at MAX IV for assistance with XPS measurements. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152 , the Swedish Governmental Agency for Innovation Systems under contract 2018-04969 , and Formas under contract 2019-02496 . The authors would like to thank Dmytro Orlov and Zoran Markovski for their help with sample preparation. Publisher Copyright: © 2021 The Authors

PY - 2022/2/25

Y1 - 2022/2/25

N2 - The surface chemistry and thickness of the native oxide, hydroxide, and modified sub-surface layer of three Ni superalloys (alloy 59, 625, and 718) were determined by synchrotron X-ray Photoelectron Spectroscopy (XPS) and X-ray Reflectivity (XRR). Taking advantage of the synchrotron radiation techniques, a procedure for normalizing the photoelectron intensity was employed, which allowed for accurate quantitative analysis revealing a total oxide thickness for all samples of 12–13 Å, a hydroxide layer of 2–3 Å, and a thickness of the sub-surface alloy layer of 20–35 Å. The thickness results were compared to structural atomic models suggesting that the oxide thickness corresponds to four planes of metal cations in the oxide matrix. The XPS data revealed that the native oxides were enriched in Cr3+, Mo(4,5,6)+, and Nb5+, while no Ni oxide was detected. The hydroxide layer mainly contained Ni2+ and Cr3+ hydroxide. The sub-surface layer was enriched in Ni and depleted in Cr, Fe, Mo, and Nb. The obtained oxide composition can be explained using thermodynamics, and it was found that the oxide composition correlates with the enthalpy of oxide formation for the metal elements in the alloys. Finally, the advantages of synchrotron radiation for composition and thickness determination are discussed.

AB - The surface chemistry and thickness of the native oxide, hydroxide, and modified sub-surface layer of three Ni superalloys (alloy 59, 625, and 718) were determined by synchrotron X-ray Photoelectron Spectroscopy (XPS) and X-ray Reflectivity (XRR). Taking advantage of the synchrotron radiation techniques, a procedure for normalizing the photoelectron intensity was employed, which allowed for accurate quantitative analysis revealing a total oxide thickness for all samples of 12–13 Å, a hydroxide layer of 2–3 Å, and a thickness of the sub-surface alloy layer of 20–35 Å. The thickness results were compared to structural atomic models suggesting that the oxide thickness corresponds to four planes of metal cations in the oxide matrix. The XPS data revealed that the native oxides were enriched in Cr3+, Mo(4,5,6)+, and Nb5+, while no Ni oxide was detected. The hydroxide layer mainly contained Ni2+ and Cr3+ hydroxide. The sub-surface layer was enriched in Ni and depleted in Cr, Fe, Mo, and Nb. The obtained oxide composition can be explained using thermodynamics, and it was found that the oxide composition correlates with the enthalpy of oxide formation for the metal elements in the alloys. Finally, the advantages of synchrotron radiation for composition and thickness determination are discussed.

KW - Corrosion

KW - Cr

KW - Fe

KW - Mo

KW - Native oxide

KW - Nb

KW - Ni

KW - Nickel alloy

KW - Oxide

KW - Passive film

KW - Superalloy

KW - Synchrotron

KW - X-ray photoelectron spectroscopy

KW - X-ray reflectivity

KW - XPS

KW - XRR

U2 - 10.1016/j.jallcom.2021.162657

DO - 10.1016/j.jallcom.2021.162657

M3 - Article

AN - SCOPUS:85118843201

SN - 0925-8388

VL - 895

JO - Journal of Alloys and Compounds

JF - Journal of Alloys and Compounds

M1 - 162657

ER -

Thickness and composition of native oxides and near-surface regions of Ni superalloys

Abstract

Bibliographical note

Subject classification (UKÄ)

Free keywords

Access to Document

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