In situ oxidation studies of high-entropy alloy nanoparticles

Boao Song; Yong Yang; Muztoba Rabbani; Timothy T. Yang; Kun He; Xiaobing Hu; Yifei Yuan; Pankaj Ghildiyal; Vinayak P. Dravid; Michael R. Zachariah; Wissam A. Saidi; Yuzi Liu; Reza Shahbazian-Yassar

doi:10.1021/acsnano.0c05250

In situ oxidation studies of high-entropy alloy nanoparticles

Boao Song, Yong Yang, Muztoba Rabbani, Timothy T. Yang, Kun He, Xiaobing Hu, Yifei Yuan, Pankaj Ghildiyal, Vinayak P. Dravid, Michael R. Zachariah^*, Wissam A. Saidi^*, Yuzi Liu^*, Reza Shahbazian-Yassar^*

^*Corresponding author for this work

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

104 Scopus citations

Abstract

Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe_0.28Co_0.21Ni_0.20Cu_0.08Pt_0.23HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner’s theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe₂O₃, CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.

Original language	English (US)
Pages (from-to)	15131-15143
Number of pages	13
Journal	ACS nano
Volume	14
Issue number	11
DOIs	https://doi.org/10.1021/acsnano.0c05250
State	Published - Nov 24 2020

Funding

R.S.-Y. acknowledges financial support from the National Science Foundation (award no. DMR-1809439). W.S. acknowledges financial support from the National Science Foundation (award no. DMR-1809085). T.Y. acknowledges a graduate student award from the Pittsburgh Quantum Institute. The computational work is supported in part by the University of Pittsburgh Center for Research Computing through the resources provided and the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under contract DE-AC02-06CH11357. This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under contract no. DE-AC02-06CH11357. This work made use of the JEOL JEM-ARM 200CF and JEOL JEM-3010 in the Electron Microscopy Service (Research Resources Center, UIC). The acquisition of the UIC JEOL JEM-ARM 200CF was supported by a MRI-R2 grant from the National Science Foundation (DMR-0959470). We thank Dr. Fengyuan Shi from UIC for the assistance on (S)TEM experiments. Some of this work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois, through the IIN. M.Z. acknowledges support from an ONR MURI. R.S.-Y. acknowledges financial support from the National Science Foundation (award no. DMR-1809439). W.S. acknowledges financial support from the National Science Foundation (award no. DMR-1809085). T.Y. acknowledges a graduate student award from the Pittsburgh Quantum Institute. The computational work is supported in part by the University of Pittsburgh Center for Research Computing through the resources provided and the Argonne Leadership Computing Facility, which is a DOE Office of Science User Facility supported under contract DE-AC02-06CH11357. This work was performed, in part, at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and supported by the U.S. Department of Energy, Office of Science, under contract no. DE-AC02-06CH11357. This work made use of the JEOL JEM-ARM 200CF and JEOL JEM-3010 in the Electron Microscopy Service (Research Resources Center, UIC). The acquisition of the UIC JEOL JEM-ARM 200CF was supported by a MRI-R2 grant from the National Science Foundation (DMR-0959470). We thank Dr. Fengyuan Shi from UIC for the assistance on (S)TEM experiments. Some of this work made use of the EPIC facility of Northwestern University?s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, the International Institute for Nanotechnology (IIN), the Keck Foundation, and the State of Illinois, through the IIN. M.Z. acknowledges support from an ONR MURI.

Keywords

High-entropy alloys
In situ transmission electron microscopy
Kirkendall
Nanoparticles
Oxidation
Phase segregation

ASJC Scopus subject areas

General Materials Science
General Engineering
General Physics and Astronomy

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10.1021/acsnano.0c05250

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title = "In situ oxidation studies of high-entropy alloy nanoparticles",

abstract = "Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe0.28Co0.21Ni0.20Cu0.08Pt0.23HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner{\textquoteright}s theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe2O3, CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.",

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author = "Boao Song and Yong Yang and Muztoba Rabbani and Yang, {Timothy T.} and Kun He and Xiaobing Hu and Yifei Yuan and Pankaj Ghildiyal and Dravid, {Vinayak P.} and Zachariah, {Michael R.} and Saidi, {Wissam A.} and Yuzi Liu and Reza Shahbazian-Yassar",

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T1 - In situ oxidation studies of high-entropy alloy nanoparticles

AU - Song, Boao

AU - Yang, Yong

AU - Rabbani, Muztoba

AU - Yang, Timothy T.

AU - He, Kun

AU - Hu, Xiaobing

AU - Yuan, Yifei

AU - Ghildiyal, Pankaj

AU - Dravid, Vinayak P.

AU - Zachariah, Michael R.

AU - Saidi, Wissam A.

AU - Liu, Yuzi

AU - Shahbazian-Yassar, Reza

PY - 2020/11/24

Y1 - 2020/11/24

N2 - Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe0.28Co0.21Ni0.20Cu0.08Pt0.23HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner’s theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe2O3, CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.

AB - Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe0.28Co0.21Ni0.20Cu0.08Pt0.23HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner’s theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe2O3, CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.

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ER -

In situ oxidation studies of high-entropy alloy nanoparticles

Abstract

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Keywords

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