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Formation of clathrates Ba–M–Ge(M = Mn, Fe, Co)

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Published/Copyright: June 11, 2013
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International Journal of Materials Research
From the journal International Journal of Materials Research Volume 100 Issue 2

Abstract

In order to define the ability of magnetic elements M = Mn, Fe, Co to stabilise clathrate structures, alloys of the Ba – M – Ge system were investigated in the as-cast state and after annealing at 700°C and 800°C by means of X-ray powder diffraction, light optical and electron-probe microanalysis. Temperatures of phase transformations were derived from differential thermal analysis. Results are summarised in (i) isothermal sections at 700°C and 800°C, (ii) solidus and liquidus surfaces covering the region of existence for both clathrate phases in these systems. Invariant reactions during crystallisation are presented in form of Schultz – Scheil diagrams.

In all three cases only limited solubility of the M element was found for clathrate IX (Ba6Ge25) i. e. the Ge-framework in the crystal structure of Ba6MxGe25 – x dissolves 0.6 atom of Mn, and about 1 atom of Fe and Co per unit cell. The maximum solubility of iron in clathrate type I (Ba8Ge46 – x) was found to be less than 0.5 Fe atom per unit cell, and clathrates with Mn and Co contain up to 1.0 and 2.5 atoms in the unit cell, respectively. Whilst Fe does not decrease the formation temperature of the clathrate phase, Mn and Co decrease it from 770°C (for binary Ba8Ge43) to 766°C and 749°C, respectively.

Keywords: Intermetallic clathrates; Phase equilibria; Crystal structure; Scheil diagram
* Correspondence address, Prof. Peter Rogl Institute of Physical Chemistry, University of Vienna Währingerstraße 42, A-1090 Wien, Austria Tel.: +43 1 4277 52 456 Fax: +43 1 4277 95 245 E-mail:

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Received: 2008-11-17
Accepted: 2008-12-3
Published Online: 2013-06-11
Published in Print: 2009-02-01

© 2009, Carl Hanser Verlag, München

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https://doi.org/10.3139/146.110012
Keywords for this article
Intermetallic clathrates; Phase equilibria; Crystal structure; Scheil diagram

Articles in the same Issue

  1. Contents
  2. Contents
  3. Feature
  4. Materials constitution and computational thermodynamics in the context of 100 years of IJMR – Zeitschrift für Metallkunde
  5. Upgrading CALPHAD to microstructure simulation: the phase-field method
  6. Prediction, determination and validation of phase diagrams via the global study of energy landscapes
  7. Alloy development using modern tools
  8. Phase equilibria and thermal analysis in the Fe–Mn–Ni system
  9. Integrated approach to thermodynamics, phase relations, liquid densities and solidification microstructures in the Al–Bi–Cu system
  10. Formation of clathrates Ba–M–Ge(M = Mn, Fe, Co)
  11. New paradigm of a metastable phase diagram presenting structural transformations induced by annealing of Si–C–N amorphous ceramics derived from polymer precursors
  12. Basic
  13. Thermodynamic assessment of the Ce–Si, Y–Si, Mg–Ce–Si and Mg–Y–Si systems
  14. Thermodynamic re-assessment of the Ti–Al–Nb system
  15. Effect of varying oxygen partial pressure on the properties of reactively evaporated zinc aluminate thin films
  16. Applied
  17. Matrix induced synthesis of Y3Al5O12: Ce phosphor through the Pechini method
  18. Microstructure and room temperature compressive properties of holmium doped DS NiAl-Cr(Mo)-Hf eutectic alloy
  19. Evaporation mechanism of aluminum during electron beam cold hearth melting of Ti64 alloy
  20. 560°C isothermal section of the Zn–Fe–Ni–Si quaternary system at the zinc-rich corner
  21. DGM News
  22. Personal
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