Thermodynamic properties and phase stability of the Ba-Bi system: A combined computational and experimental study

Jinming Liu, Pin Wen Guan, Cassie N. Marker, Nathan D. Smith, Nicole Orabona, Shunli Shang, Hojong Kim, Zi-kui Liu

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

The thermodynamic properties and phase stability of the Ba-Bi system are investigated computationally and experimentally in the present work. The enthalpies of formation and the finite temperature thermodynamic properties of seven compounds are predicted by first-principles calculations based on density functional theory (DFT), indicating five compounds (BaBi3, Ba11Bi10, Ba4Bi3, Ba5Bi3, and Ba2Bi) to be stable. Phase relations at 773 K and 858 K with composition xBa = 0.90 are established by isothermal annealing and powder X-ray diffraction (XRD) to clarify the previously observed phase transition at 796 K. The extremely low chemical activity of Ba in liquid for a wide range of temperatures and compositions indicates very strong short-range ordering in the liquid phase which is modeled in the present work by introducing the Ba4Bi3 and BaBi3 associates in the liquid phase. Both thermodynamic and phase equilibrium data are then used to evaluate the model parameters in Gibbs energy functions of the five stable compounds and three solution phases of liquid, bcc, and rhombohedral phases by the CALPHAD (CALculation of PHAse Diagram) technique. The present work shows that the Ba-Bi system consists of three eutectic reactions, two peritectic reactions, one peritectoid reaction, and two congruent reactions, as well as that the concentrations of associates are very high in the liquid phase with very low concentration of atomic Ba, which provides the fundamental understanding as to why Bi can be used to remove Ba ions from molten salt solutions.

Original languageEnglish (US)
Pages (from-to)281-289
Number of pages9
JournalJournal of Alloys and Compounds
Volume771
DOIs
StatePublished - Jan 15 2019

Fingerprint

Phase stability
Thermodynamic properties
Liquids
Isothermal annealing
Gibbs free energy
Chemical analysis
Phase equilibria
X ray powder diffraction
Eutectics
Density functional theory
Molten materials
Enthalpy
Salts
Phase transitions
Thermodynamics
Ions
Temperature

All Science Journal Classification (ASJC) codes

  • Mechanics of Materials
  • Mechanical Engineering
  • Metals and Alloys
  • Materials Chemistry

Cite this

Liu, Jinming ; Guan, Pin Wen ; Marker, Cassie N. ; Smith, Nathan D. ; Orabona, Nicole ; Shang, Shunli ; Kim, Hojong ; Liu, Zi-kui. / Thermodynamic properties and phase stability of the Ba-Bi system : A combined computational and experimental study. In: Journal of Alloys and Compounds. 2019 ; Vol. 771. pp. 281-289.
@article{05bd4631334b449083c59c0a57f677fa,
title = "Thermodynamic properties and phase stability of the Ba-Bi system: A combined computational and experimental study",
abstract = "The thermodynamic properties and phase stability of the Ba-Bi system are investigated computationally and experimentally in the present work. The enthalpies of formation and the finite temperature thermodynamic properties of seven compounds are predicted by first-principles calculations based on density functional theory (DFT), indicating five compounds (BaBi3, Ba11Bi10, Ba4Bi3, Ba5Bi3, and Ba2Bi) to be stable. Phase relations at 773 K and 858 K with composition xBa = 0.90 are established by isothermal annealing and powder X-ray diffraction (XRD) to clarify the previously observed phase transition at 796 K. The extremely low chemical activity of Ba in liquid for a wide range of temperatures and compositions indicates very strong short-range ordering in the liquid phase which is modeled in the present work by introducing the Ba4Bi3 and BaBi3 associates in the liquid phase. Both thermodynamic and phase equilibrium data are then used to evaluate the model parameters in Gibbs energy functions of the five stable compounds and three solution phases of liquid, bcc, and rhombohedral phases by the CALPHAD (CALculation of PHAse Diagram) technique. The present work shows that the Ba-Bi system consists of three eutectic reactions, two peritectic reactions, one peritectoid reaction, and two congruent reactions, as well as that the concentrations of associates are very high in the liquid phase with very low concentration of atomic Ba, which provides the fundamental understanding as to why Bi can be used to remove Ba ions from molten salt solutions.",
author = "Jinming Liu and Guan, {Pin Wen} and Marker, {Cassie N.} and Smith, {Nathan D.} and Nicole Orabona and Shunli Shang and Hojong Kim and Zi-kui Liu",
year = "2019",
month = "1",
day = "15",
doi = "10.1016/j.jallcom.2018.08.324",
language = "English (US)",
volume = "771",
pages = "281--289",
journal = "Journal of Alloys and Compounds",
issn = "0925-8388",
publisher = "Elsevier BV",

}

Thermodynamic properties and phase stability of the Ba-Bi system : A combined computational and experimental study. / Liu, Jinming; Guan, Pin Wen; Marker, Cassie N.; Smith, Nathan D.; Orabona, Nicole; Shang, Shunli; Kim, Hojong; Liu, Zi-kui.

In: Journal of Alloys and Compounds, Vol. 771, 15.01.2019, p. 281-289.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Thermodynamic properties and phase stability of the Ba-Bi system

T2 - A combined computational and experimental study

AU - Liu, Jinming

AU - Guan, Pin Wen

AU - Marker, Cassie N.

AU - Smith, Nathan D.

AU - Orabona, Nicole

AU - Shang, Shunli

AU - Kim, Hojong

AU - Liu, Zi-kui

PY - 2019/1/15

Y1 - 2019/1/15

N2 - The thermodynamic properties and phase stability of the Ba-Bi system are investigated computationally and experimentally in the present work. The enthalpies of formation and the finite temperature thermodynamic properties of seven compounds are predicted by first-principles calculations based on density functional theory (DFT), indicating five compounds (BaBi3, Ba11Bi10, Ba4Bi3, Ba5Bi3, and Ba2Bi) to be stable. Phase relations at 773 K and 858 K with composition xBa = 0.90 are established by isothermal annealing and powder X-ray diffraction (XRD) to clarify the previously observed phase transition at 796 K. The extremely low chemical activity of Ba in liquid for a wide range of temperatures and compositions indicates very strong short-range ordering in the liquid phase which is modeled in the present work by introducing the Ba4Bi3 and BaBi3 associates in the liquid phase. Both thermodynamic and phase equilibrium data are then used to evaluate the model parameters in Gibbs energy functions of the five stable compounds and three solution phases of liquid, bcc, and rhombohedral phases by the CALPHAD (CALculation of PHAse Diagram) technique. The present work shows that the Ba-Bi system consists of three eutectic reactions, two peritectic reactions, one peritectoid reaction, and two congruent reactions, as well as that the concentrations of associates are very high in the liquid phase with very low concentration of atomic Ba, which provides the fundamental understanding as to why Bi can be used to remove Ba ions from molten salt solutions.

AB - The thermodynamic properties and phase stability of the Ba-Bi system are investigated computationally and experimentally in the present work. The enthalpies of formation and the finite temperature thermodynamic properties of seven compounds are predicted by first-principles calculations based on density functional theory (DFT), indicating five compounds (BaBi3, Ba11Bi10, Ba4Bi3, Ba5Bi3, and Ba2Bi) to be stable. Phase relations at 773 K and 858 K with composition xBa = 0.90 are established by isothermal annealing and powder X-ray diffraction (XRD) to clarify the previously observed phase transition at 796 K. The extremely low chemical activity of Ba in liquid for a wide range of temperatures and compositions indicates very strong short-range ordering in the liquid phase which is modeled in the present work by introducing the Ba4Bi3 and BaBi3 associates in the liquid phase. Both thermodynamic and phase equilibrium data are then used to evaluate the model parameters in Gibbs energy functions of the five stable compounds and three solution phases of liquid, bcc, and rhombohedral phases by the CALPHAD (CALculation of PHAse Diagram) technique. The present work shows that the Ba-Bi system consists of three eutectic reactions, two peritectic reactions, one peritectoid reaction, and two congruent reactions, as well as that the concentrations of associates are very high in the liquid phase with very low concentration of atomic Ba, which provides the fundamental understanding as to why Bi can be used to remove Ba ions from molten salt solutions.

UR - http://www.scopus.com/inward/record.url?scp=85052908084&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85052908084&partnerID=8YFLogxK

U2 - 10.1016/j.jallcom.2018.08.324

DO - 10.1016/j.jallcom.2018.08.324

M3 - Article

AN - SCOPUS:85052908084

VL - 771

SP - 281

EP - 289

JO - Journal of Alloys and Compounds

JF - Journal of Alloys and Compounds

SN - 0925-8388

ER -