Silicon and aluminium site distributions in 2:1 layered silicate clays

Abstract

Although the layer charge in 2:1 phyllosilicate minerals is known to result from the replacement of tetrahedral Si or octahedral Al, Fe and Mg by ions of lower charge, there is only limited information concerning the distribution of layer charge from X-ray crystallographic data1–3. Here we use 29Si and 27Al magic angle spinning (MAS) NMR spectroscopy to examine the site distribution of tetrahedral Si and Al in a series of synthetic trioctahedral clays with (Si/Al)tetr values in the range 2.74–7.69. Analysis of the 29Si spectra shows that Loewenstein's rule for Al occupancy of the tetrahedral sheet is obeyed and that there is some short-range ordering for Al sites. The nature of the ordering is explained in part by the results of electrostatic potential energy calculations. In general, strong 27Al resonances are observed for Al in tetrahedral sites, but the resonances due to Al in octahedral sites are considerably weaker than would be expected on the basis of chemical analysis. Consequently, no quantitative analysis of the 27Al spectra is possible.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

References

  1. 1

    Gatineau, L. Bull. Soc. Fr. Miner. Crystallogr. 87, 321–355 (1964).

  2. 2

    Guggenheim, S. & Bailey, S. W. Am. Miner. 60, 1023–1027 (1975).

  3. 3

    Bailey, S. W. Am. Miner. 60, 175–187 (1975).

  4. 4

    Loewenstein, W. Am. Miner. 39, 92–96 (1954).

  5. 5

    Lippmaa, E., Magi, M., Samoson, A., Engelhardt, G. & Grimmer, A. R. J. Am. chem. Soc. 102, 4889–4893 (1980).

  6. 6

    Klinowski, J., Thomas, J. M., Fyfe, C. A. & Hartman, J. S. J. phys. Chem. 85, 2590–2594 (1981).

  7. 7

    Fyfe, C. A., Thomas, J. M., Klinowski, J. & Gobbi, G. C. Angew. Chem. 22, 259–275 (1983).

  8. 8

    Fyfe, C. A., Gobbi, G. C., Hartman, J. S., Klinowski, J. & Thomas, J. M. J. phys. Chem. 86, 1247–1250 (1982).

  9. 9

    Oldfield, E. et al. J. Am. chem. Soc. 104, 919–920 (1982).

  10. 10

    Hamilton, D. L. & Henderson, C. M. B. Miner. Mag. 36, 832–838 (1968).

  11. 11

    Vega, A. J. Am. chem. Soc. Symp. Ser. 218, 217–230 (1983).

  12. 12

    Giese, R. F. Crystal Structures of Ideal, Ordered, 1-Layer Micas (AFCRL-TR-75-0438, Envir. Res. Pap. 526, United States Air Force, Cambridge Research Laboratories, 1975).

  13. 13

    Giese, R. F. Crystal Structures of Ideal, Ordered, 2-Layer Micas (AFCRL-TR-75-0471, Envir. Res. Pap. 533, United States Air Force, Cambridge Research Laboratories, 1975).

  14. 14

    Meier, W. M. & Villiger, H. Z. Kristallogr. 129, 411–423 (1969).

  15. 15

    Barron, P. F., Wilson, M. A., Campbell, A. S. & Frost, R. L. Nature 299, 616 (1982).

Download references

Author information

Affiliations

Authors

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Lipsicas, M., Raythatha, R., Pinnavaia, T. et al. Silicon and aluminium site distributions in 2:1 layered silicate clays. Nature 309, 604–607 (1984). https://doi.org/10.1038/309604a0

Download citation

Further reading

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.