Review of Cation Ordering in Micas

S. W. Bailey
Department of Geology and Geophysics, University of Wisconsin—Madison, Madison, Wisconsin 53706
Note added in proof: Sokolova, C. V., Aleksandrova, V. A., Drits, V. A., and Vairakov, V. V. (1979) Crystal structure of two lithian brittle micas: in Crystal Chemistry and Structures of Minerals, Nauka, Moscow, 55–66 (in Russian). The above reference, which has just come to the author's attention, describes two additional mica structures that are ordered in subgroup symmetry. For ephesite-1M: R = 11.5% in C2, 284 refl. Mean tet. bonds for Si2.2Al1.8: T(1) = 1.609 Å, T(2) = 1.764 Å, Δ = 11.0σΔ. Mean oct. bonds for Al1.97Fe0.02Li0.67Na0.10: M(1) = 2.128 Å, M(2) = M(3) = 1.927 Å. For bityite-2M1: R = 11.5% in Cc, 450 refl. Mean tet. bonds for Si2.00Al1.29Be0.71: T(1) = 1.642 Å, T(2) = 1.710 Å, T(11) = 1.717 Å, T(22) = 1.622 Å, ave. Δ = 5.7σΔ. Mean oct. bonds for Al2.00Li0.48Mg0.10Fe0.03: M(1) = 2.184 Å, M(2) ≅ M(3) = 1.898 Å.

Abstract: Long-range ordering of tetrahedral cations in micas is favored by phengitic compositions, by the 3T stacking sequence of layers, and by tetrahedral Si:Al ratios near 1:1. Phengites of the 1M, 2M1, and 2M2 polytypes are said to show partial ordering of tetrahedral cations, although the amounts of tetrahedral substitutions are small and the accuracies of determination are not as large as desired. The 3T structures of muscovite, paragonite, lepidolite, and protolithionite show tetrahedral ordering, as do the 2M1 brittle micas margarite and an intermediate between margarite and bityite. Muscovite-3T and margarite-2M1 are also slightly phengitic relative to their ideal compositions. Examples of octahedral cation ordering in micas are more abundant and are to be expected when cations of different size and charge are present. Octahedron M(1) with its OH,F groups in the trans orientation tends to be larger than the mean of the two cis octahedra as a result of the ordering of cations and vacancies. In some samples ordering has reduced the true symmetry to a subgroup of that of the ideal space group. If ordering in subgroup symmetry results in ordered patterns of different geometries but similar energies in very small domains, the average over all unit cells may simulate long-range disorder.

Key Words: Cation ordering • Lepidolite • Margarite • Mica • Muscovite • Paragonite • Phengite

Clays and Clay Minerals; April 1984 v. 32; no. 2; p. 81-92; DOI: 10.1346/CCMN.1984.0320201
© 1984, The Clay Minerals Society
Clay Minerals Society (www.clays.org)