Journal of Structural Chemistry

, Volume 45, Issue 3, pp 454–464 | Cite as

Structure and thermal behavior of metastable sillenites prepared by mechanochemical synthesis

  • V. V. Zyryanov


The structure and thermal behavior of metastable solid solutions with nominal compositions Bi2PbO4, Bi4HgO7, Bi12TlO19.5, and Bi12Cd0.7O18.7 with the sillenite structure obtained by mechanochemical treatment in a planetary mill (thermal decomposition of the metastable Bi4CdO7 phase with a bcc structure above 700 K) have been studied. The large Pb2+ atoms occupy up to ~30% positions in the sillenite structure (Hg2+ and Hg(1) occupy up to ~15% of (24f) positions). The (2a) sites are partially occupied by bismuth with a minor shift along the [111] axis and are transformed into the (8c) site, forming an umbrella structure with c.n. 3. The relatively small Cd2+and Tl3+ cations partially occupy the (2a) sites. During annealing, the metastable Pb-sillenites are partially stabilized with a loss of oxygen and increasing content of bismuth. Sillenite with a high content of lead retains its structure until it melts at 923 K. Cadmium sillenite reacts with CdO, passing into a rhombohedral structure at 900 K (30 K below the melting point). Mercury sillenite Bi4HgO7 decomposes with isolation of metallic mercury at ~600 K.


sillenite metastable phase thermal stability mechanochemical synthesis 


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Copyright information

© Springer Science+Business Media, Inc. 2004

Authors and Affiliations

  • V. V. Zyryanov
    • 1
  1. 1.Institute of Solid State Chemistry and Mechanochemistry, Siberian BranchRussian Academy of SciencesNovosibirsk

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