Hostname: page-component-586b7cd67f-2plfb Total loading time: 0 Render date: 2024-11-26T23:12:26.086Z Has data issue: false hasContentIssue false
  • English
  • Français

Thermodynamic properties of rare-earth alloys by electrochemical emf measurements

Published online by Cambridge University Press:  03 September 2020

Timothy Lichtenstein Open the ORCID record for Timothy Lichtenstein [Opens in a new window] ,
Sanghyeok Im ,
Chen-Ta Yu  and
Hojong Kim Open the ORCID record for Hojong Kim [Opens in a new window]
Timothy Lichtenstein
Affiliation:
Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania16802, USA
Sanghyeok Im
Affiliation:
Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania16802, USA
Chen-Ta Yu
Affiliation:
Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania16802, USA
Hojong Kim*
Affiliation:
Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania16802, USA
*
a)Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

Thermodynamic properties of Nd–Bi and Nd–Sn alloys were determined via electromotive force (emf) measurements at 725–1075 K. The emf measurements of an Nd–Bi alloy at mole fraction xNd = 0.20 were conducted using a solid CaF2–NdF3 electrolyte relative to pure Nd(s). The emf values from the CaF2–NdF3 electrolyte were verified in separate experiments in molten LiCl–KCl–NdCl3 where pure Nd(s) was electrodeposited. The Nd–Bi (xNd = 0.20) exhibited two-phase behavior with a peritectic reaction (L + NdBi = NdBi2) at 926 K from differential scanning calorimetry. The two-phase Nd–Bi (xNd = 0.20) was employed as a stable reference electrode in molten LiCl–KCl–NdCl3 for emf measurements of Nd–Bi (xNd = 0.15–0.40) and Nd–Sn (xNd = 0.10) alloys. The emf measurements of these alloys were reproducible during thermal cycles over 50 h and were used to calculate thermodynamic properties, including the partial molar Gibbs energy, entropy, and enthalpy.

Keywords

thermodynamic propertiesemf measurementsrare-earth elementsrare-earth alloysNd–BiNd–Sn
Type
Article
Information
Journal of Materials Research , First View , pp. 1 - 9
Check for updates
Copyright
Copyright © Materials Research Society 2020

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

U.S. Department of Energy, Critical Materials Strategy, DOE/PI-0009 (2011).Google Scholar
Romero, J.L. and McCord, S.A.: Rare Earth Elements: Procurement, Application, and Reclamation. Report number SAND2012-6316 (2012).Google Scholar
Price, J.G.: Energy critical elements: Securing materials for emerging technologies. Miner. Eng. 63, 33 (2011).Google Scholar
Foster, M.S., Wood, S.E., and Crouthamel, C.E.: Thermodynamics of binary alloys. I. The lithium-bismuth system. Inorg. Chem. 3, 1428 (1964).CrossRefGoogle Scholar
Weppner, W. and Huggins, R.A.: Thermodynamic properties of the intermetallic systems lithium-antimony and lithium-bismuth. J. Electrochem. Soc. 125, 7 (1976).CrossRefGoogle Scholar
Yih, T. and Thompson, J.C.: Chemical potentials and related thermodynamic properties of molten Na-Cs and Na-Bi alloys. J. Phys. F Met. Phys. 12, 1625 (1982).CrossRefGoogle Scholar
Kim, H., Boysen, D.A., Bradwell, D.J., Chung, B., Jiang, K., Tomaszowska, A.A., Wang, K., Wei, W., and Sadoway, D.R.: Thermodynamic properties of calcium-bismuth alloys determined by emf measurements. Electrochim. Acta 60, 154 (2012).CrossRefGoogle Scholar
Lichtenstein, T., Smith, N.D., Gesualdi, J., Kumar, K., and Kim, H.: Thermodynamic properties of barium-bismuth alloys determined by emf measurements. Electrochim. Acta 228, 628 (2017).CrossRefGoogle Scholar
Smith, N.D., Lichtenstein, T., Gesualdi, J., Kumar, K., and Kim, H.: Thermodynamic properties of strontium-bismuth alloys determined by electromotive force measurements. Electrochim. Acta 225, 584 (2017).CrossRefGoogle Scholar
Liu, K., Liu, Y.L., Chai, Z.F., and Shi, W.Q.: Evaluation of the electroextractions of Ce and Nd from LiCl-KCl molten salt using liquid Ga electrode. J. Electrochem. Soc. 164, D169 (2017).CrossRefGoogle Scholar
Masset, P., Konings, R.J.M., Malmbeck, R., Serp, J., and Glatz, J.P.: Thermochemical properties of lanthanides (Ln = La, Nd) and actinides (An = U, Np, Pu, Am) in the molten LiCl-KCl eutectic. J. Nucl. Mater. 344, 173 (2005).CrossRefGoogle Scholar
Hayashi, H., Akabori, M., Ogawa, T., and Minato, K.: Spectrophotometric study of Nd2+ ions in LiCl-KCl eutectic melt. Z. Naturforsch. A 59, 705 (2004).CrossRefGoogle Scholar
Novoselova, A. and Smolenski, V.: Electrochemical behavior of neodymium compounds in molten chlorides. Electrochim. Acta 87, 657 (2013).CrossRefGoogle Scholar
Lebedev, V.A., Kober, V.I., and Yamshchikov, L.F.: Thermochemistry of Rare-Earth Metals and Actinide Elements Alloys (Metallurgiya, Chelaybinsk, 1989).Google Scholar
Kulagima, N.G. and Bayanov, A.P.: An electromotive force study of the thermodynamic properties of neodymium tristannide and its solutions in liquid tin. Russ. J. Phys. Chem. 48, 273 (1974).Google Scholar
Lebedev, V.A. and Akhmedov, C.C.: Thermodynamic properties of solid and liquid neodymium-magnesium alloys. Russ. Metall. 2011, 133 (2011).CrossRefGoogle Scholar
Hamel, C., Chamelot, P., and Taxil, P.: Neodymium(III) cathodic processes in molten fluorides. Electrochim. Acta 49, 4467 (2004).CrossRefGoogle Scholar
Lichtenstein, T., Gesualdi, J., Nigl, T.P., Yu, C.T., and Kim, H.: Thermodynamic properties of barium-antimony alloys determined by emf measurements. Electrochim. Acta 251, 203 (2017).CrossRefGoogle Scholar
Nigl, T.P., Lichtenstein, T., Smith, N.D., Gesualdi, J., Kong, Y., and Kim, H.: Thermodynamic properties of strontium-lead alloys determined by electromotive force measurements. J. Electrochem. Soc. 165, H991 (2018).CrossRefGoogle Scholar
Smith, N.D., Orabona, N., Lichtenstein, T., Gesualdi, J., Nigl, T.P., and Kim, H.: Thermodynamic properties of Sr-Sb alloys via emf measurements using solid CaF2-SrF2 electrolyte. Electrochim. Acta 305, 547 (2019).CrossRefGoogle Scholar
Wang, C.P., Zhang, H.L., Tang, A.T., Pan, F.S., and Liu, X.J.: Thermodynamic assessments of the Bi–Nd and Bi–Tm systems. J. Alloys Compd. 502, 43 (2010).CrossRefGoogle Scholar
Ovchinnikov, A., Makongo, J.P.A., and Bobev, S.: Yet again, new compounds found in systems with known binary phase diagrams. Synthesis, crystal and electronic structure of Nd3Bi7 and Sm3Bi7. Chem. Commun. 54, 7089 (2018).CrossRefGoogle ScholarPubMed
Sharma, R.A. and Seefurth, R.N.: Thermodynamic properties of the lithium-silicon system. J. Electrochem. Soc. 123, 1763 (1976).CrossRefGoogle Scholar
Poizeau, S., Kim, H., Newhouse, J.M., Spatocco, B.L., and Sadoway, D.R.: Determination and modeling of the thermodynamic properties of liquid calcium-antimony alloys. Electrochim. Acta 76, 8 (2012).CrossRefGoogle Scholar
Newhouse, J.M., Poizeau, S., Kim, H., Spatocco, B.L., and Sadoway, D.R.: Thermodynamic properties of calcium–magnesium alloys determined by emf measurements. Electrochim. Acta 91, 293 (2013).CrossRefGoogle Scholar
Kane, M.M., Newhouse, J.M., and Sadoway, D.R.: Electrochemical determination of the thermodynamic properties of lithium-antimony alloys. J. Electrochem. Soc. 162, A421 (2015).CrossRefGoogle Scholar
Kim, J., Thibodeau, E., Tetley-Gerard, K., and Jung, I.H.: Critical evaluation and thermodynamic optimization of the Sn–RE systems: Part I. Sn–RE system (RE = La, Ce, Pr, Nd and Sm). Calphad 55, 113 (2016).CrossRefGoogle Scholar
Downs, R.T. and Wallce-Hall, M.: The American mineralogist crystal structure database. Am. Mineral. 88, 247 (2003).Google Scholar
Boettinger, W.J., Kattner, U.R., Moon, K-W., and Perepezko, J.H.: DTA and Heat-Flux DSC Measurements of Alloy Melting and Freezing, NIST, Special Publication 960-15 (2006).Google Scholar