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Crystal chemistry and properties of mullite-type Bi2M4O9: An overview

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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 103 Issue 4

Abstract

Bi2M4O9 (M = Al3+, Ga3+, Fe3+) belongs to the family of mullite-type crystal structures. The phases are orthorhombic with the space group Pbam. The backbones of the isostructural phases are edge-connected, mullite-type octahedral chains. The octahedral chains are linked by dimers of M2O7 tetrahedral groups and by BiO polyhedra. The Bi3+ cations in Bi2M4O9 contain stereo-chemically active 6s2 lone electron pairs (LEPs) which are essential for the stabilization of the structure. Although the octahedral chains of the closely related Bi2Mn4O10 are similar to those of Bi2M4O9, Bi2Mn4O10 contains dimers of edge-connected, five-fold coordinated pyramids instead of four-fold coordinated tetrahedra. Also the 6s2 LEPs of Bi3+ in Bi2Mn4O10 are not stereo-chemically active. Complete and continuous solid solutions exist for Bi2(Al1–xFex)4O9 and Bi2(Ga1–xFex)4O9 (x = 0–1). Things are more complex in the case of the Bi2(Fe1–xMnx)4O9+y mixed crystals, where a miscibility gap occurs between x = 0.25–0.75. In the Fe-rich mixed crystals most Mn atoms enter the octahedra as Mn4+, with part of the tetrahedral dimers being replaced by fivefold coordinated polyhedra, whereas in the Mn-rich compound Fe3+ favorably replaces Mn3+ in the pyramids.

The crystal structure of Bi2M4O9 directly controls its mechanical properties. The stiffnesses of phases are highest parallel to the strongly bonded octahedral chains running parallel to the crystallographic c-axis. Perpendicular to the octahedral chains little anisotropy is observed. The temperature-induced expansion perpendicular to the octahedral chains is probably superimposed by contractions. As a result the c-axis expansion appears as relatively high and does not display its lowest value parallel to c, as could be inferred.

Maximally 6% of Bi3+ is substituted by Sr2+ in Bi2Al4O9 corresponding to a composition of (Bi0.94Sr0.06)2Al4O8.94. Sr2+ for Bi3+ substitution is probably associated with formation of vacancies of oxygen atoms bridging the tetrahedral dimers. Hopping of oxygen atoms towards the vacancies should strongly enhance the oxygen conductivity. Actually the conductivity is rather low (σ = 7 · 10−2 S m−1 at 1073 K, 800°C). An explanation could be the low thermal stability of Sr-doped Bi2Al4O9, especially in coexistence with liquid Bi2O3. Therefore, Bi2Al4O9 single crystals and polycrystalline ceramics both with significant amounts of M2+ doping (M = Ca2+, Sr2+) have not been produced yet. Thus the question whether or not M2+-doped Bi2M4O9 is an oxygen conducting material is still open.

Keywords: Bi2M4O9; Mullite-type; Crystal chemistry; Doping; Electrical conductivity; Thermo-mechanical properties
* Correspondence address Prof. Dr. Hartmut Schneider Institute of Crystallography University of Köln Greinstr. 6 50939 Köln, Germany Tel.: +49 221 470 25 32 Fax: +49 221 470 49 63 E-mail:

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Received: 2011-12-1
Accepted: 2012-1-21
Published Online: 2013-06-11
Published in Print: 2012-04-01

© 2012, Carl Hanser Verlag, München

Articles in the same Issue

  1. Contents
  2. Contents
  3. Editorial
  4. Mullite 2011
  5. Original Contributions
  6. Mullite and mullite-type crystal structures
  7. Faradaic current in different mullite materials: single crystal, ceramic and cermets
  8. Metakaolin–nanosilver as biocide mullite precursor
  9. Sintering of mullite–β-eucryptite ceramics with very low thermal expansion
  10. Crystal chemistry and properties of mullite-type Bi2M4O9: An overview
  11. Temperature-dependent 57Fe Mössbauer spectroscopy and local structure of mullite-type Bi2(FexAl1–x)4O9 (0.1≤x≤1) solid solutions
  12. Thermal expansion and elastic properties of mullite-type Bi2Ga4O9 and Bi2Fe4O9 single crystals
  13. Single crystal growth and characterization of mullite-type Bi2Mn4O10
  14. Synthesis and electrical conductivity of mullite-type Bi2Al4O9 and (Bi,Ca)2Al4O9 ceramics
  15. New pressure induced phase transitions in mullite-type Bi2(Fe4–xMnx)O10–δ complex oxides
  16. Morphological characterization of the Al–Ag–Cu ternary eutectic
  17. Bainite: Fragmentation of crystallographically homogeneous domains
  18. Influence of grain size on the dynamic recrystallization behavior of AISI 304 stainless steel during hot deformation
  19. Li–Cr substituted nickel–zinc–copper ferrite powders: structural and magnetic properties
  20. A model to calculate the viscosity of silicate melts
  21. Lattice dynamics analysis of the thermal properties of liquid iron
  22. Evaluation of the mechanical properties of natural asphalt-modified hot mixture
  23. Prediction of the transverse Young's modulus of unidirectional triangle-section carbon fiber reinforced plastics
  24. People
  25. Prof. Dr. Bernd Stritzker – 65th birthday
  26. Professor Dr.-Ing. Rainer Schmid-Fetzer – 65 Years
  27. DGM News
  28. DGM News
https://doi.org/10.3139/146.110716
Keywords for this article
Bi2M4O9; Mullite-type; Crystal chemistry; Doping; Electrical conductivity; Thermo-mechanical properties

Articles in the same Issue

  1. Contents
  2. Contents
  3. Editorial
  4. Mullite 2011
  5. Original Contributions
  6. Mullite and mullite-type crystal structures
  7. Faradaic current in different mullite materials: single crystal, ceramic and cermets
  8. Metakaolin–nanosilver as biocide mullite precursor
  9. Sintering of mullite–β-eucryptite ceramics with very low thermal expansion
  10. Crystal chemistry and properties of mullite-type Bi2M4O9: An overview
  11. Temperature-dependent 57Fe Mössbauer spectroscopy and local structure of mullite-type Bi2(FexAl1–x)4O9 (0.1≤x≤1) solid solutions
  12. Thermal expansion and elastic properties of mullite-type Bi2Ga4O9 and Bi2Fe4O9 single crystals
  13. Single crystal growth and characterization of mullite-type Bi2Mn4O10
  14. Synthesis and electrical conductivity of mullite-type Bi2Al4O9 and (Bi,Ca)2Al4O9 ceramics
  15. New pressure induced phase transitions in mullite-type Bi2(Fe4–xMnx)O10–δ complex oxides
  16. Morphological characterization of the Al–Ag–Cu ternary eutectic
  17. Bainite: Fragmentation of crystallographically homogeneous domains
  18. Influence of grain size on the dynamic recrystallization behavior of AISI 304 stainless steel during hot deformation
  19. Li–Cr substituted nickel–zinc–copper ferrite powders: structural and magnetic properties
  20. A model to calculate the viscosity of silicate melts
  21. Lattice dynamics analysis of the thermal properties of liquid iron
  22. Evaluation of the mechanical properties of natural asphalt-modified hot mixture
  23. Prediction of the transverse Young's modulus of unidirectional triangle-section carbon fiber reinforced plastics
  24. People
  25. Prof. Dr. Bernd Stritzker – 65th birthday
  26. Professor Dr.-Ing. Rainer Schmid-Fetzer – 65 Years
  27. DGM News
  28. DGM News
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