DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Design and Development of Stable Nanocrystalline High‐Entropy Alloy: Coupling Self‐Stabilization and Solute Grain Boundary Segregation Effects

Abstract

Abstract Grain growth is prevalent in nanocrystalline (NC) materials at low homologous temperatures. Solute element addition is used to offset excess energy that drives coarsening at grain boundaries (GBs), albeit mostly for simple binary alloys. This thermodynamic approach is considered complicated in multi‐component alloy systems due to complex pairwise interactions among alloying elements. Guided by empirical and GB‐segregation enthalpy considerations for binary‐alloy systems, a novel alloy design strategy, the “ pseudo‐binary thermodynamic ” approach, for stabilizing NC‐high entropy alloys (HEAs) and other multi‐component‐alloy variants is proposed. Using Al 25 Co 25 Cr 25 Fe 25 as a model‐HEA to validate this approach, Zr, Sc, and Hf, are identified as the preferred solutes that would segregate to HEA‐GBs to stabilize it against growth. Using Zr, NC‐Al 25 Co 25 Cr 25 Fe 25 HEAs with minor additions of Zr are synthesized, followed by annealing up to 1123 K. Using advanced characterization techniques— in situ X‐ray diffraction (XRD), scanning/transmission electron microscopy (S/TEM), and atom probe tomography, nanograin stability due to coupling self‐stabilization and solute‐GB segregation effects is reported in HEAs up to substantially high temperatures. The self‐stabilization effect originates from the preferential GB‐segregation of constituent HEA‐elements that stabilizes NC‐Al 25 Co 25 Crmore » 25 Fe 25 up to 0.5 T m ( T m –melting temperature). Meanwhile, solute‐GB segregation originates from Zr segregation to NC‐Al 25 Co 25 Cr 25 Fe 25 GBs; this results in further stabilization of the phase and grain‐size (≈14 nm) up to ≈0.58 and ≈0.64 T m , respectively.« less

Authors:
 [1];  [1];  [2];  [3];  [3];  [4]; ORCiD logo [1]
  1. Department of Mechanical and Manufacturing Engineering University of Calgary 2500 University Drive NW Calgary Alberta T2N 1N4 Canada
  2. Nuclear Science and Technology Department Brookhaven National Laboratory Upton NY 11973 USA, Department of Nuclear Science and Engineering Massachusetts Institute of Technology Cambridge MA 02139 USA
  3. Center for Functional Nanomaterials Brookhaven National Laboratory Upton NY 11973 USA
  4. Nuclear Science and Technology Department Brookhaven National Laboratory Upton NY 11973 USA
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Nuclear Physics (NP); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
OSTI Identifier:
2290437
Alternate Identifier(s):
OSTI ID: 2290440; OSTI ID: 2319180
Report Number(s):
BNL-225340-2024-JAAM
Journal ID: ISSN 1613-6810; 2309631
Grant/Contract Number:  
DE‐SC0012704; SC0012704
Resource Type:
Published Article
Journal Name:
Small
Additional Journal Information:
Journal Name: Small; Journal ID: ISSN 1613-6810
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English
Subject:
73 NUCLEAR PHYSICS AND RADIATION PHYSICS; AlCoCrFe HEA; grain boundary segregation; high-entropy alloys (HEAs); nanocrystalline alloys; nanograin stability; self-stabilization effect

Citation Formats

Adaan‐Nyiak, Moses A., Alam, Intekhab, Jossou, Ericmoore, Hwang, Sooyeon, Kisslinger, Kim, Gill, Simerjeet K., and Tiamiyu, Ahmed A. Design and Development of Stable Nanocrystalline High‐Entropy Alloy: Coupling Self‐Stabilization and Solute Grain Boundary Segregation Effects. Germany: N. p., 2024. Web. doi:10.1002/smll.202309631.
Adaan‐Nyiak, Moses A., Alam, Intekhab, Jossou, Ericmoore, Hwang, Sooyeon, Kisslinger, Kim, Gill, Simerjeet K., & Tiamiyu, Ahmed A. Design and Development of Stable Nanocrystalline High‐Entropy Alloy: Coupling Self‐Stabilization and Solute Grain Boundary Segregation Effects. Germany. https://doi.org/10.1002/smll.202309631
Adaan‐Nyiak, Moses A., Alam, Intekhab, Jossou, Ericmoore, Hwang, Sooyeon, Kisslinger, Kim, Gill, Simerjeet K., and Tiamiyu, Ahmed A. Mon . "Design and Development of Stable Nanocrystalline High‐Entropy Alloy: Coupling Self‐Stabilization and Solute Grain Boundary Segregation Effects". Germany. https://doi.org/10.1002/smll.202309631.
@article{osti_2290437,
title = {Design and Development of Stable Nanocrystalline High‐Entropy Alloy: Coupling Self‐Stabilization and Solute Grain Boundary Segregation Effects},
author = {Adaan‐Nyiak, Moses A. and Alam, Intekhab and Jossou, Ericmoore and Hwang, Sooyeon and Kisslinger, Kim and Gill, Simerjeet K. and Tiamiyu, Ahmed A.},
abstractNote = {Abstract Grain growth is prevalent in nanocrystalline (NC) materials at low homologous temperatures. Solute element addition is used to offset excess energy that drives coarsening at grain boundaries (GBs), albeit mostly for simple binary alloys. This thermodynamic approach is considered complicated in multi‐component alloy systems due to complex pairwise interactions among alloying elements. Guided by empirical and GB‐segregation enthalpy considerations for binary‐alloy systems, a novel alloy design strategy, the “ pseudo‐binary thermodynamic ” approach, for stabilizing NC‐high entropy alloys (HEAs) and other multi‐component‐alloy variants is proposed. Using Al 25 Co 25 Cr 25 Fe 25 as a model‐HEA to validate this approach, Zr, Sc, and Hf, are identified as the preferred solutes that would segregate to HEA‐GBs to stabilize it against growth. Using Zr, NC‐Al 25 Co 25 Cr 25 Fe 25 HEAs with minor additions of Zr are synthesized, followed by annealing up to 1123 K. Using advanced characterization techniques— in situ X‐ray diffraction (XRD), scanning/transmission electron microscopy (S/TEM), and atom probe tomography, nanograin stability due to coupling self‐stabilization and solute‐GB segregation effects is reported in HEAs up to substantially high temperatures. The self‐stabilization effect originates from the preferential GB‐segregation of constituent HEA‐elements that stabilizes NC‐Al 25 Co 25 Cr 25 Fe 25 up to 0.5 T m ( T m –melting temperature). Meanwhile, solute‐GB segregation originates from Zr segregation to NC‐Al 25 Co 25 Cr 25 Fe 25 GBs; this results in further stabilization of the phase and grain‐size (≈14 nm) up to ≈0.58 and ≈0.64 T m , respectively.},
doi = {10.1002/smll.202309631},
journal = {Small},
number = ,
volume = ,
place = {Germany},
year = {Mon Feb 05 00:00:00 EST 2024},
month = {Mon Feb 05 00:00:00 EST 2024}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/smll.202309631

Save / Share:

Works referenced in this record:

High-Entropy Alloys as a Platform for Catalysis: Progress, Challenges, and Opportunities
journal, September 2020


Excellent thermal stability and mechanical properties of bulk nanostructured FeCoNiCu high entropy alloy
journal, February 2022


Hardening of an Al0.3CoCrFeNi high entropy alloy via high-pressure torsion and thermal annealing
journal, July 2015


Phosphorus segregation in nanocrystalline Ni–3.6 at.% P alloy investigated with the tomographic atom probe (TAP)
journal, February 2000


High-entropy grain boundaries
journal, February 2023


Amorphous and nanocrystalline materials for applications as soft magnets
journal, October 1999

  • McHenry, Michael E.; Willard, Matthew A.; Laughlin, David E.
  • Progress in Materials Science, Vol. 44, Issue 4
  • DOI: 10.1016/S0079-6425(99)00002-X

Modelling the influence of grain-size-dependent solute drag on the kinetics of grain growth in nanocrystalline materials
journal, May 1999


Review of thermo‐kinetic correlation during grain growth in nanocrystalline materials
journal, March 2020

  • Peng, Haoran; Jian, Zengyun; Liu, Feng
  • International Journal of Ceramic Engineering & Science, Vol. 2, Issue 2
  • DOI: 10.1002/ces2.10040

Equilibrium surface composition of ternary alloys
journal, February 1989

  • Hoffmann, M. A.; Wynblatt, P.
  • Metallurgical Transactions A, Vol. 20, Issue 2
  • DOI: 10.1007/BF02670247

Effect of Ti on phase stability and strengthening mechanisms of a nanocrystalline CoCrFeMnNi high-entropy alloy
journal, May 2018

  • Shahmir, Hamed; Nili-Ahmadabadi, Mahmoud; Shafiee, Ahad
  • Materials Science and Engineering: A, Vol. 725
  • DOI: 10.1016/j.msea.2018.04.014

Spectrum of grain boundary segregation energies in a polycrystal
journal, December 2019


Research Progress of Refractory High Entropy Alloys: A Review
journal, November 2022


Competition between elements during mechanical alloying in an octonary multi-principal-element alloy system
journal, July 2009


In situ TEM study of grain growth in nanocrystalline copper thin films
journal, March 2010


High-Entropy Alloys: A Critical Review
journal, April 2014


Solute interaction effects on grain boundary segregation in ternary alloys
journal, December 2018


Thermal stability of nanocrystalline Fe–Zr alloys
journal, June 2010

  • Darling, K. A.; VanLeeuwen, B. K.; Koch, C. C.
  • Materials Science and Engineering: A, Vol. 527, Issue 15
  • DOI: 10.1016/j.msea.2010.02.043

Alloy effects in nanostructures
journal, January 1993


High-entropy alloys
journal, June 2019


Equilibrium segregation in a ternary solution: A model for temper embrittlement
journal, December 1975


An Overview of High-Entropy Alloys as Biomaterials
journal, April 2021

  • Castro, Diogo; Jaeger, Pedro; Baptista, Ana Catarina
  • Metals, Vol. 11, Issue 4
  • DOI: 10.3390/met11040648

Grain coarsening inhibited by solute segregation
journal, January 2002


Chemistry of solid–solid interfaces — A review of its characterization, theory, and relevance to materials science
journal, January 1980

  • Seah, M. P.
  • Journal of Vacuum Science and Technology, Vol. 17, Issue 1
  • DOI: 10.1116/1.570464

Nanoscale segregation behavior and high-temperature stability of nanocrystalline W–20at.% Ti
journal, July 2014


Thermo-Calc & DICTRA, computational tools for materials science
journal, June 2002


Understanding solute effect on grain boundary strength based on atomic size and electronic interaction
journal, October 2020


Stability of Nanocrystalline Structures in the Ti-Cu System
journal, January 1992


Segregation-induced changes in grain boundary cohesion and embrittlement in binary alloys
journal, August 2015


Design of Stable Nanocrystalline Alloys
journal, August 2012


Thermal stability of nano-RuAl produced by mechanical alloying
journal, February 2001


Nanocrystalline Ag-W alloys lose stability upon solute desegregation from grain boundaries
journal, December 2018


Deformation behavior of nanocrystalline and ultrafine-grained CoCrCuFeNi high-entropy alloys
journal, January 2019

  • Nam, Seungjin; Hwang, Jun Yeon; Jeon, Jonggyu
  • Journal of Materials Research, Vol. 34, Issue 5
  • DOI: 10.1557/jmr.2018.477

Enhanced solid solution effects on the strength of nanocrystalline alloys
journal, February 2011


Unraveling the nature of room temperature grain growth in nanocrystalline materials
journal, September 2008


The Scherrer equation versus the 'Debye-Scherrer equation'
journal, August 2011


Electrochemical characteristics of nano and microcrystalline Fe–Cr alloys
journal, May 2012

  • Gupta, Rajeev K.; Singh Raman, R. K.; Koch, C. C.
  • Journal of Materials Science, Vol. 47, Issue 16
  • DOI: 10.1007/s10853-012-6529-5

High-Temperature Stability and Grain Boundary Complexion Formation in a Nanocrystalline Cu-Zr Alloy
journal, September 2015


Effect of short-range ordering and grain boundary segregation on shear deformation of CoCrFeNi high-entropy alloys with Al addition
journal, December 2022


Processing and microstructure of Ti-Cu binary alloys: A comprehensive review
journal, June 2022


Effect of Atomic Size Difference on the Microstructure and Mechanical Properties of High-Entropy Alloys
journal, December 2018

  • Wu, Chan-Sheng; Tsai, Ping-Hsiu; Kuo, Chia-Ming
  • Entropy, Vol. 20, Issue 12
  • DOI: 10.3390/e20120967

Thermal stability of nanocrystalline Pd81Zr19
journal, July 2010


Inter-dependence of grain growth, Nb segregation, and chemical ordering in FeSiNb nanocrystals
journal, December 1994


Thermodynamics and design of nanocrystalline alloys using grain boundary segregation spectra
journal, September 2021


Effect of annealing on mechanical properties of a nanocrystalline CoCrFeNiMn high-entropy alloy processed by high-pressure torsion
journal, October 2016


Nanostructured high-entropy materials
journal, March 2020

  • Haché, Michel J. R.; Cheng, Changjun; Zou, Yu
  • Journal of Materials Research, Vol. 35, Issue 8
  • DOI: 10.1557/jmr.2020.33

Mechanical alloying synthesis and spark plasma sintering consolidation of CoCrFeNiAl high-entropy alloy
journal, March 2014


Stabilized Nanocrystalline Alloys: The Intersection of Grain Boundary Segregation with Processing Science
journal, July 2021


Alloy thermodynamics in nanostructures
journal, January 1994


Grain boundary segregation and thermodynamically stable binary nanocrystalline alloys
journal, March 2009


Stability criteria for nanocrystalline alloys
journal, June 2017


Microstructures and mechanical properties of ductile NbTaTiV refractory high entropy alloy prepared by powder metallurgy
journal, March 2019


Grain-size stabilization in nanocrystalline FeZr alloys
journal, September 2008


Structural nanocrystalline materials: an overview
journal, February 2007


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


Grain growth and the Hall–Petch relationship in a high-entropy FeCrNiCoMn alloy
journal, April 2013


Bismuth embrittlement of copper is an atomic size effect
journal, December 2004

  • Schweinfest, Rainer; Paxton, Anthony T.; Finnis, Michael W.
  • Nature, Vol. 432, Issue 7020
  • DOI: 10.1038/nature03198

Laves phases: a review of their functional and structural applications and an improved fundamental understanding of stability and properties
journal, December 2020


Toward a quantitative understanding of mechanical behavior of nanocrystalline metals
journal, July 2007


Estimation of grain boundary segregation enthalpy and its role in stable nanocrystalline alloy design
journal, August 2013

  • Murdoch, Heather A.; Schuh, Christopher A.
  • Journal of Materials Research, Vol. 28, Issue 16
  • DOI: 10.1557/jmr.2013.211

Thermal stability of nanocrystalline materials: thermodynamics and kinetics
journal, November 2016


High-entropy alloy: challenges and prospects
journal, July 2016


Materials Design and Discovery with High-Throughput Density Functional Theory: The Open Quantum Materials Database (OQMD)
journal, September 2013


A Review of Fatigue Behavior in Nanocrystalline Metals
journal, October 2009


Tailoring grain growth and solid solution strengthening of single-phase CrCoNi medium-entropy alloys by solute selection
journal, October 2020


Metal nanoparticle production by pulsed laser nanostructuring of thin metal films
journal, July 2007


Design and development of CoCrFeNiTa eutectic high entropy alloys
journal, January 2021

  • Mukarram, Muhammad; Mujahid, Mohammad; Yaqoob, Khurram
  • Journal of Materials Research and Technology, Vol. 10
  • DOI: 10.1016/j.jmrt.2020.12.042

Grain boundary energy effect on grain boundary segregation in an equiatomic high-entropy alloy
journal, May 2020


An in-situ tem study of the thermal stability of nanocrystalline NiP
journal, December 1991


Stabilization of nanocrystalline alloys at high temperatures via utilizing high-entropy grain boundary complexions
journal, November 2016


Design of self-stable nanocrystalline high-entropy alloy
journal, December 2023


Stability of binary nanocrystalline alloys against grain growth and phase separation
journal, April 2013


Grain growth and chemical ordering in (Fe,Mn)3Si
journal, March 1995


Grain boundary saturation and grain growth
journal, September 2004


Interplay between thermodynamic and kinetic stabilization mechanisms in nanocrystalline Fe-Mg alloys
journal, February 2018


Nanostructured materials: basic concepts and microstructure
journal, January 2000


Review of Atom Probe FIB-Based Specimen Preparation Methods
journal, November 2007

  • Miller, Michael K.; Russell, Kaye F.; Thompson, Keith
  • Microscopy and Microanalysis, Vol. 13, Issue 6
  • DOI: 10.1017/S1431927607070845

Effect of grain size on friction and wear of nanocrystalline aluminum
journal, February 1996


Phase formations in low density high entropy alloys
journal, March 2017


Network analysis of multivariate data in psychological science
journal, August 2021


Microstructures and Stabilization Mechanisms of Nanocrystalline Iron-Chromium Alloys with Hafnium Addition
journal, June 2015

  • Xu, Weizong; Li, Lulu; Saber, Mostafa
  • Metallurgical and Materials Transactions A, Vol. 46, Issue 9
  • DOI: 10.1007/s11661-015-2985-2

Ball milling process variables optimization for high-entropy alloy development using design of experiment and genetic algorithm
journal, September 2023


Effect of Zr content on microstructure and mechanical properties of AlCoCrFeNi high entropy alloy
journal, March 2016