skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Solid–state synthesis of multicomponent equiatomic rare–earth oxides

Abstract

Phase formation in multicomponent rare–earth oxides is determined by a combination of composition, sintering atmosphere, and cooling rate. Polycrystalline ceramics comprising various combinations of Ce, Gd, La, Nd, Pr, Sm, and Y oxides in equiatomic proportions were synthesized using solid–state sintering. The effects of composition, sintering atmosphere, and cooling rate on phase formation were investigated. Single cubic or monoclinic structures were obtained with a slow cooling of 3.3°C/min, confirming that rare–earth oxides follow a different structure stabilization process than transition metal high–entropy oxides. In an oxidizing atmosphere, both Ce and Pr induce a cubic structure, while only Ce plays that role in an inert or reducing atmosphere. Samples without Ce or Pr develop a single monoclinic structure. The structures formed at initial synthesis may be converted to a different one, when the ceramics are annealed in an additional atmosphere. Phase evolution of a five–cation composition was also studied as a function of sintering temperature. In conclusion, the binary oxides used as raw materials completely dissolve into a single cubic structure at 1450°C in air.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [1];  [1]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1606694
Grant/Contract Number:  
AC05-00OR22725; DMR­1846935
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Ceramic Society
Additional Journal Information:
Journal Volume: 103; Journal Issue: 4; Journal ID: ISSN 0002-7820
Publisher:
American Ceramic Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; phase transformations; rare earths; reaction sintering

Citation Formats

Pianassola, Matheus, Loveday, Madeline, McMurray, Jake W., Koschan, Merry, Melcher, Charles L., and Zhuravleva, Mariya. Solid–state synthesis of multicomponent equiatomic rare–earth oxides. United States: N. p., 2019. Web. https://doi.org/10.1111/jace.16971.
Pianassola, Matheus, Loveday, Madeline, McMurray, Jake W., Koschan, Merry, Melcher, Charles L., & Zhuravleva, Mariya. Solid–state synthesis of multicomponent equiatomic rare–earth oxides. United States. https://doi.org/10.1111/jace.16971
Pianassola, Matheus, Loveday, Madeline, McMurray, Jake W., Koschan, Merry, Melcher, Charles L., and Zhuravleva, Mariya. Mon . "Solid–state synthesis of multicomponent equiatomic rare–earth oxides". United States. https://doi.org/10.1111/jace.16971. https://www.osti.gov/servlets/purl/1606694.
@article{osti_1606694,
title = {Solid–state synthesis of multicomponent equiatomic rare–earth oxides},
author = {Pianassola, Matheus and Loveday, Madeline and McMurray, Jake W. and Koschan, Merry and Melcher, Charles L. and Zhuravleva, Mariya},
abstractNote = {Phase formation in multicomponent rare–earth oxides is determined by a combination of composition, sintering atmosphere, and cooling rate. Polycrystalline ceramics comprising various combinations of Ce, Gd, La, Nd, Pr, Sm, and Y oxides in equiatomic proportions were synthesized using solid–state sintering. The effects of composition, sintering atmosphere, and cooling rate on phase formation were investigated. Single cubic or monoclinic structures were obtained with a slow cooling of 3.3°C/min, confirming that rare–earth oxides follow a different structure stabilization process than transition metal high–entropy oxides. In an oxidizing atmosphere, both Ce and Pr induce a cubic structure, while only Ce plays that role in an inert or reducing atmosphere. Samples without Ce or Pr develop a single monoclinic structure. The structures formed at initial synthesis may be converted to a different one, when the ceramics are annealed in an additional atmosphere. Phase evolution of a five–cation composition was also studied as a function of sintering temperature. In conclusion, the binary oxides used as raw materials completely dissolve into a single cubic structure at 1450°C in air.},
doi = {10.1111/jace.16971},
journal = {Journal of the American Ceramic Society},
number = 4,
volume = 103,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Entropy-stabilized oxides
journal, September 2015

  • Rost, Christina M.; Sachet, Edward; Borman, Trent
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9485

Colossal dielectric constant in high entropy oxides
journal, March 2016

  • Bérardan, David; Franger, Sylvain; Dragoe, Diana
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 10, Issue 4
  • DOI: 10.1002/pssr.201600043

Effective ionic radii in oxides and fluorides
journal, May 1969

  • Shannon, R. D.; Prewitt, C. T.
  • Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 25, Issue 5
  • DOI: 10.1107/S0567740869003220

Mechanical alloying and spark plasma sintering of CoCrFeNiMnAl high-entropy alloy
journal, July 2014


Kinetic Studies on Reactions of Praseodymium Oxides in an Oxygen Atmosphere: PrO 1.83 + O 2 ⇄ PrO 2
journal, May 1965

  • Hyde, B. G.; Garver, E. E.; Kuntz, U. E.
  • The Journal of Physical Chemistry, Vol. 69, Issue 5
  • DOI: 10.1021/j100889a037

A high-entropy metal oxide as chemical anchor of polysulfide for lithium-sulfur batteries
journal, December 2019


High-entropy fluorite oxides
journal, August 2018


Giant Enhancement of Exchange Coupling in Entropy-Stabilized Oxide Heterostructures
journal, October 2017


Nebulized spray pyrolysis of Al-doped Li7La3Zr2O12 solid electrolyte for battery applications
journal, October 2014


Tensile properties of high- and medium-entropy alloys
journal, August 2013


Microstructural development in equiatomic multicomponent alloys
journal, July 2004


Multicomponent equiatomic rare earth oxides
journal, August 2016


Synthesis and microstructure of the (Co,Cr,Fe,Mn,Ni) 3 O 4 high entropy oxide characterized by spinel structure
journal, April 2018


Characteristics of (TiAlCrNbY)C films deposited by reactive magnetron sputtering
journal, March 2010


Nanostructured High-Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes
journal, May 2004

  • Yeh, J.-W.; Chen, S.-K.; Lin, S.-J.
  • Advanced Engineering Materials, Vol. 6, Issue 5, p. 299-303
  • DOI: 10.1002/adem.200300567

Entropy-stabilized metal oxide solid solutions as CO oxidation catalysts with high-temperature stability
journal, January 2018

  • Chen, Hao; Fu, Jie; Zhang, Pengfei
  • Journal of Materials Chemistry A, Vol. 6, Issue 24
  • DOI: 10.1039/C8TA01772G

The Binary Rare Earth Oxides
journal, June 1998

  • Adachi, Gin-ya; Imanaka, Nobuhito
  • Chemical Reviews, Vol. 98, Issue 4
  • DOI: 10.1021/cr940055h

Stability and Compressibility of Cation-Doped High-Entropy Oxide MgCoNiCuZnO 5
journal, July 2019

  • Chen, Jian; Liu, Weixin; Liu, Junxiu
  • The Journal of Physical Chemistry C, Vol. 123, Issue 29
  • DOI: 10.1021/acs.jpcc.9b04992

Valencies of the lanthanides
journal, August 2017


High-Pressure B-Type Polymorphs of Some Rare-Earth Sesquioxides
journal, November 1964


A critical review of high entropy alloys and related concepts
journal, January 2017


A new class of high-entropy perovskite oxides
journal, January 2018


Room temperature lithium superionic conductivity in high entropy oxides
journal, January 2016

  • Bérardan, D.; Franger, S.; Meena, A. K.
  • Journal of Materials Chemistry A, Vol. 4, Issue 24
  • DOI: 10.1039/C6TA03249D

Is Li-doped MgAl2O4 a potential solid electrolyte for an all-spinel Li-ion battery?
journal, April 2016


Low temperature synthesis and characterization of single phase multi-component fluorite oxide nanoparticle sols
journal, January 2019

  • Anandkumar, Mariappan; Bhattacharya, Saswata; Deshpande, Atul Suresh
  • RSC Advances, Vol. 9, Issue 46
  • DOI: 10.1039/C9RA04636D

A five-component entropy-stabilized fluorite oxide
journal, September 2018


Processing, microstructure and properties of Al0.6CoNiFeTi0.4 high entropy alloy with nanoscale twins
journal, March 2013


Electrical, magnetic, and Hall properties of AlxCoCrFeNi high-entropy alloys
journal, February 2011


Mechanical and tribological properties of multi-element (AlCrTaTiZr)N coatings
journal, April 2008


High entropy oxides for reversible energy storage
journal, August 2018


Mechanochemical Synthesis of (Co,Cu,Mg,Ni,Zn)O High-Entropy Oxide and Its Physicochemical Properties
journal, August 2019

  • Balcerzak, Mateusz; Kawamura, Kenichi; Bobrowski, Rafał
  • Journal of Electronic Materials, Vol. 48, Issue 11
  • DOI: 10.1007/s11664-019-07512-z

High-entropy oxide phases with magnetoplumbite structure
journal, July 2019


Defect structure and transport properties in (Co,Cu,Mg,Ni,Zn)O high entropy oxide
journal, November 2019


Structure and magnetic properties of a multi-principal element Ni–Fe–Cr–Co–Zn–Mn alloy
journal, January 2016


High-Entropy Metal Diborides: A New Class of High-Entropy Materials and a New Type of Ultrahigh Temperature Ceramics
journal, November 2016

  • Gild, Joshua; Zhang, Yuanyao; Harrington, Tyler
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep37946

Multicomponent equiatomic rare earth oxides with a narrow band gap and associated praseodymium multivalency
journal, January 2017

  • Sarkar, Abhishek; Loho, Christoph; Velasco, Leonardo
  • Dalton Transactions, Vol. 46, Issue 36
  • DOI: 10.1039/C7DT02077E

A fracture-resistant high-entropy alloy for cryogenic applications
journal, September 2014


Microstructure, thermophysical and electrical properties in AlxCoCrFeNi (0≤x≤2) high-entropy alloys
journal, July 2009

  • Chou, Hsuan-Ping; Chang, Yee-Shyi; Chen, Swe-Kai
  • Materials Science and Engineering: B, Vol. 163, Issue 3
  • DOI: 10.1016/j.mseb.2009.05.024

High‐entropy, phase‐constrained, lanthanide sesquioxide
journal, July 2019

  • Tseng, Kuo‐Pin; Yang, Qun; McCormack, Scott J.
  • Journal of the American Ceramic Society, Vol. 103, Issue 1
  • DOI: 10.1111/jace.16689

Effect of temperature on mechanical properties of Al0.5CoCrCuFeNi wrought alloy
journal, February 2010


Charge-Induced Disorder Controls the Thermal Conductivity of Entropy-Stabilized Oxides
journal, October 2018

  • Braun, Jeffrey L.; Rost, Christina M.; Lim, Mina
  • Advanced Materials, Vol. 30, Issue 51
  • DOI: 10.1002/adma.201805004

Formation and Stability of Equiatomic and Nonequiatomic Nanocrystalline CuNiCoZnAlTi High-Entropy Alloys by Mechanical Alloying
journal, July 2010

  • Varalakshmi, S.; Kamaraj, M.; Murty, B. S.
  • Metallurgical and Materials Transactions A, Vol. 41, Issue 10
  • DOI: 10.1007/s11661-010-0344-x

Superconductivity in thermally annealed Ta-Nb-Hf-Zr-Ti high-entropy alloys
journal, February 2017


Multicomponent equiatomic rare earth oxides
text, January 2016