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Thermodynamic modeling of the sodium alanates and the Na–Al–H system

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Published/Copyright: January 21, 2022
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International Journal of Materials Research
From the journal International Journal of Materials Research Volume 97 Issue 11

Abstract

The thermodynamic properties of the Al –Na and Na–Al – H systems have been assessed by combining the “calculation of phase diagram” approach with first-principles predictions. The Gibbs energies of the individual phases were thermodynamically modeled, where the model parameters were obtained from best fit optimizations to combined experimental and first-principles predicted finite temperature data. The first-principles thermodynamic predictions were based upon density functional theory ground state minimizations and direct method lattice dynamics. The predictions proved to be important adjuncts to the assessments whenever experimental measurements were lacking or not feasible. It was shown that the phase stability conditions of sodium alanates, NaAlH4 and Na3AlH6, were well described with the present models.

Keywords: Sodium alanates; Thermodynamics; First-principles; Density functional theory; Direct method lattice dynamics
Susanne M. Opalka, Ph. D. United Technologies Research Center, 411 Silver Lane, MS 129-22 East Hartford, CT, USA 06108 Tel.: +1 860 610 7195

  1. This work was financially supported by the United States Department of Energy under contract DE-FC04-02AL67610, managed by United Technologies Research Center, East Hartford, Connecticut, USA. S. M. Opalka gratefully acknowledges valuable discussions with Paul Saxe of Materials Design, Inc., Taos, New Mexico, USA.

    You will find the article and additional material by entering the document number MK101410 on our website at www.ijmr.de

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Appendix

Summary of thermodynamic parameters describing the Na–Al –H system. Values are given in SI units (Joule, mole, Kelvin, and Pa) and correspond to one mole of formula units of the phases. The parameters marked with an asterisk (*) were evaluated in the present work. Gibbs energy for gas and pure elements can be found in References [39] and [51], respectively.

Liquid with formula (Al, H, Na)

(*) °GHliq=8035+25T+2Tln(T)+0.5×F10784TLAl,Hliq=50942−11.1007TLAl,Naliq=14130+56.0985T−1827×(xAl−xNa)LH,Naliq=−70264+45.2458T+(−56577+21.8825T)                 ×(xH−xNa)
(*) BCCA2withformula(Al,Na)1(H,Na)3°GAl:Hbcc=200000+°GAl:HAlH3°GNa:Hbcc=215965+3RTln[exp(0.5×215/T)                    −exp(−0.5×215/T)]−0.0095113T2for 0 K<T<298.15 K               =206754+258.2187T−42.90288TlnT−0.004047T2                    +1.889×10−7T3+696986/Tfor 298.15 K<T<2000 KLAl,Na:Vabcc=27715
(*) FCCA1with formula(Al,Na)1(H,Va)1°GAl:Hfcc=100000+°GAlfcc+0.5°GH2gas°GNa:Hfcc=130T+°GNabcc+0.5°GH2gasLAl:H,Vafcc=−45805+56.4302TLAl,Na:Vafcc=−6210+76.4864T
 AlH 3 with formula (Al)1(H)3°GAl:HAlH3=−28415+213.712933T                −41.75632Tln(T)−0.014548469T2+446400/TNaH with formula (Na)1(H)1°GNa:HNaH=−66593+3RTln[exp(0.5×268/T)                    −exp(−0.5×268/T)]−0.0188755T2 for 0 K<T<298.15 K                =−75768+293.7188T−48.6935TlnT                     −2.614×10−4T2+1.8048×10−8T3+632658/T
 for 298.15 K<T<2000 KNaAlH4 with formula (Na)1(Al)1(H)4°GNa:Al:HNaAlH=−128890−0.10258 T2                       +3RTln[exp(0.5×220/T)−exp(−0.5×220/T)]
(*)  for 0 K<T<298.15 K                  =−150434+592.2826 T                     −99.0677TlnT−0.018466T2                     +1.0858×10−6T3+1091420/T
(*) for 298.15 K<T<2000 Kα−Na3AlH6 with formula (Na)3(Al)1(H)6°GNa:Al:H α− Na3AlH6 =−267960−0.17245T2                              +6RTln[exp(0.5×217/T)−exp(−0.5217/T)]
(*)  for 0 K<T<298.15 K                         =−309621+1122.177 T                             −187.24TlnT−0.0226T2                             +1.3138×10−6T3+2200845/T  
(*) for 298.15 K<T<2000 K
(*)   β   − N a 3 Al H 6  with formula  ( Na ) 3 ( Al ) 1 ( H ) 6 o G Na : Al : H β − Na 3 AlH 6 = 3497 − 6.6587 T + o G Na : Al : H α − Na 3 AlH 6
Received: 2006-01-30
Accepted: 2006-07-10
Published Online: 2022-01-21

© 2006 Carl Hanser Verlag, München

Articles in the same Issue

  1. Frontmatter
  2. Editorial
  3. Diffusion of 65Zn in the Mg17Al12 intermetallic compound and in the Mg-33.4 wt.% Al eutectic
  4. Thermodynamic modeling of the sodium alanates and the Na–Al–H system
  5. Thermodynamic assessment of the systems La2O3–Al2O3 and La2O3–Y2O3
  6. Re-evaluation of phase equilibria in the Al–Mo system
  7. EBSD and EDX analysis at the cladding–substrate interface of a laser clad railway wheel
  8. Thermodynamic properties of liquid silver–indium–antimony alloys determined from e.m.f. measurements
  9. Density and excess volumes of liquid copper, cobalt, iron and their binary and ternary alloys
  10. Thermodynamic investigation of Co–Cr alloys, III: Thermo-analytical measurements using DSC and DTA techniques
  11. Effect of a low frequency electromagnetic field on the direct-chill (DC) casting of AZ80 magnesium alloy ingots
  12. Microstructure of the “white layer” formed on nitrided Fe-7 wt.% Cr alloys
  13. The effect of ageing on tensile behaviour, mode I and mixed mode I/III fracture toughness of 7010 aluminium alloy
  14. Plane bending fatigue behavior of interstitial-free steel at room temperature
  15. Fracture behaviour of ultrafine-grained materials under static and cyclic loading
  16. Influence of process parameters on particle characteristics using a combined pressure-swirl-gas atomizer
  17. Processing and mechanical behaviour of a dual scale particle strengthened copper composite
  18. Electrochemical characterisation of magnesium and wrought magnesium alloys
  19. Progress in understanding the metallurgy of 18% nickel maraging steels
  20. Quality Management Basics on a High Level
  21. Personal
  22. News
  23. Frontmatter
  24. Editorial
  25. Editorial
  26. Basic
  27. Diffusion of 65Zn in the Mg17Al12 intermetallic compound and in the Mg-33.4 wt.% Al eutectic
  28. Thermodynamic modeling of the sodium alanates and the Na–Al–H system
  29. Thermodynamic assessment of the systems La2O3–Al2O3 and La2O3–Y2O3
  30. Re-evaluation of phase equilibria in the Al–Mo system
  31. EBSD and EDX analysis at the cladding–substrate interface of a laser clad railway wheel
  32. Thermodynamic properties of liquid silver–indium–antimony alloys determined from e.m.f. measurements
  33. Density and excess volumes of liquid copper, cobalt, iron and their binary and ternary alloys
  34. Thermodynamic investigation of Co–Cr alloys, III: Thermo-analytical measurements using DSC and DTA techniques
  35. Applied
  36. Effect of a low frequency electromagnetic field on the direct-chill (DC) casting of AZ80 magnesium alloy ingots
  37. Microstructure of the “white layer” formed on nitrided Fe-7 wt.% Cr alloys
  38. The effect of ageing on tensile behaviour, mode I and mixed mode I/III fracture toughness of 7010 aluminium alloy
  39. Plane bending fatigue behavior of interstitial-free steel at room temperature
  40. Fracture behaviour of ultrafine-grained materials under static and cyclic loading
  41. Influence of process parameters on particle characteristics using a combined pressure-swirl-gas atomizer
  42. Processing and mechanical behaviour of a dual scale particle strengthened copper composite
  43. Electrochemical characterisation of magnesium and wrought magnesium alloys
  44. History
  45. Progress in understanding the metallurgy of 18% nickel maraging steels
  46. Notifications
  47. Quality Management Basics on a High Level
  48. Personal
  49. News
https://doi.org/10.3139/ijmr-2006-0233
Keywords for this article
Sodium alanates; Thermodynamics; First-principles; Density functional theory; Direct method lattice dynamics

Articles in the same Issue

  1. Frontmatter
  2. Editorial
  3. Diffusion of 65Zn in the Mg17Al12 intermetallic compound and in the Mg-33.4 wt.% Al eutectic
  4. Thermodynamic modeling of the sodium alanates and the Na–Al–H system
  5. Thermodynamic assessment of the systems La2O3–Al2O3 and La2O3–Y2O3
  6. Re-evaluation of phase equilibria in the Al–Mo system
  7. EBSD and EDX analysis at the cladding–substrate interface of a laser clad railway wheel
  8. Thermodynamic properties of liquid silver–indium–antimony alloys determined from e.m.f. measurements
  9. Density and excess volumes of liquid copper, cobalt, iron and their binary and ternary alloys
  10. Thermodynamic investigation of Co–Cr alloys, III: Thermo-analytical measurements using DSC and DTA techniques
  11. Effect of a low frequency electromagnetic field on the direct-chill (DC) casting of AZ80 magnesium alloy ingots
  12. Microstructure of the “white layer” formed on nitrided Fe-7 wt.% Cr alloys
  13. The effect of ageing on tensile behaviour, mode I and mixed mode I/III fracture toughness of 7010 aluminium alloy
  14. Plane bending fatigue behavior of interstitial-free steel at room temperature
  15. Fracture behaviour of ultrafine-grained materials under static and cyclic loading
  16. Influence of process parameters on particle characteristics using a combined pressure-swirl-gas atomizer
  17. Processing and mechanical behaviour of a dual scale particle strengthened copper composite
  18. Electrochemical characterisation of magnesium and wrought magnesium alloys
  19. Progress in understanding the metallurgy of 18% nickel maraging steels
  20. Quality Management Basics on a High Level
  21. Personal
  22. News
  23. Frontmatter
  24. Editorial
  25. Editorial
  26. Basic
  27. Diffusion of 65Zn in the Mg17Al12 intermetallic compound and in the Mg-33.4 wt.% Al eutectic
  28. Thermodynamic modeling of the sodium alanates and the Na–Al–H system
  29. Thermodynamic assessment of the systems La2O3–Al2O3 and La2O3–Y2O3
  30. Re-evaluation of phase equilibria in the Al–Mo system
  31. EBSD and EDX analysis at the cladding–substrate interface of a laser clad railway wheel
  32. Thermodynamic properties of liquid silver–indium–antimony alloys determined from e.m.f. measurements
  33. Density and excess volumes of liquid copper, cobalt, iron and their binary and ternary alloys
  34. Thermodynamic investigation of Co–Cr alloys, III: Thermo-analytical measurements using DSC and DTA techniques
  35. Applied
  36. Effect of a low frequency electromagnetic field on the direct-chill (DC) casting of AZ80 magnesium alloy ingots
  37. Microstructure of the “white layer” formed on nitrided Fe-7 wt.% Cr alloys
  38. The effect of ageing on tensile behaviour, mode I and mixed mode I/III fracture toughness of 7010 aluminium alloy
  39. Plane bending fatigue behavior of interstitial-free steel at room temperature
  40. Fracture behaviour of ultrafine-grained materials under static and cyclic loading
  41. Influence of process parameters on particle characteristics using a combined pressure-swirl-gas atomizer
  42. Processing and mechanical behaviour of a dual scale particle strengthened copper composite
  43. Electrochemical characterisation of magnesium and wrought magnesium alloys
  44. History
  45. Progress in understanding the metallurgy of 18% nickel maraging steels
  46. Notifications
  47. Quality Management Basics on a High Level
  48. Personal
  49. News
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