Hostname: page-component-cd9895bd7-lnqnp Total loading time: 0 Render date: 2024-12-26T17:16:45.783Z Has data issue: false hasContentIssue false
  • English
  • Français

Vibrational Analysis of Palygorskite and Sepiolite

Published online by Cambridge University Press:  01 January 2024

David A. McKeown ,
Jeffrey E. Post  and
Edgar S. Etz
David A. McKeown*
Affiliation:
Vitreous State Laboratory, The Catholic University of America, 620 Michigan Ave., N.E. Washington D.C., 20064, USA
Jeffrey E. Post
Affiliation:
Department of Mineral Sciences, Smithsonian Institution, Washington D.C. 20560-0119, USA
Edgar S. Etz
Affiliation:
Surface and Microanalysis Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-0001, USA
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Lattice dynamic calculations for the sepiolite and palygorskite structures using polarized Raman and FTIR spectra provide a fundamental basis for interpreting spectral features by assigning vibrational modes. The Si-O stretch and O-Si-O bond bending force constants determined for palygorskite are similar to equivalent values calculated previously for other phyllosilicates. The Mg-O bond stretch values, on the other hand, are about half of those determined for the equivalent Al-O and Mg-O bond stretch environments in other phyllosilicates, suggesting that the bonding within the octahedral ribbons in palygorskite and sepiolite is weaker than that in the continuous octahedral sheets in micas. The weaker bonding allows more flexible octahedral environments in palygorskite and sepiolite, giving rise to higher probabilities for cation substitutions and vacancies relative to the micas. Above ∼700 cm−1 in the IR and 750 cm−1 in the Raman spectra, the eigenmodes are dominated by atomic displacements within the silicate sheets. Below 700 cm−1 the eigenmodes become mixed with motions among the Mg octahedra and the silicate sheets; the eigenmodes assigned to the most prominent peaks in the Raman spectra (near 700 cm−1) belong to this group. As mode frequencies decrease, the corresponding eigenmodes evolve from more localized Mg-O stretch, O-Mg-O bend and O-Si-O bend motions to longer-range motions such as silicate sheet deformations caused by silicate tetrahedra rotation and silicate sheet shearing around the Mg-octahedral sheets.

Keywords

FTIRPalygorskiteRamanSepiolite
Type
Research Article
Information
Clays and Clay Minerals , Volume 50 , Issue 5 , October 2002 , pp. 667 - 680
Copyright
Copyright © 2002, The Clay Minerals Society

References

Ahlrichs, J.L. Serna, C. and Serratosa, J.M., (1975) Structural hydroxyls in sepiolites Clays and Clay Minerals 23 119–124 10.1346/CCMN.1975.0230207.Google Scholar
Akyuz, S. Akyuz, T. and Davies, J.E.D., (1993) An FT-IR spectroscopic investigation of the adsorption of benzidine by sepiolite from Eskisehir (Turkey) Journal of Molecular Structure 293 279–282 10.1016/0022-2860(93)80067-6.Google Scholar
Akyuz, S. Akyuz, T. Davies, J.E.D. Esmer, K. and Erbolukbas Ozel, A., (1995) Fourier transform Raman and Fourier transform IR spectroscopic investigation of pyrazine adsorbed by sepiolite and bentonite from Anatolia Journal of Raman Spectroscopy 26 883–888 10.1002/jrs.1250260840.Google Scholar
Belzunce, M.J. Mendioroz, S. and Haber, J., (1998) Modification of sepiolite by treatment with fluorides: structural and textural changes Clays and Clay Minerals 46 603–614 10.1346/CCMN.1998.0460601.Google Scholar
Blanco, C. Herrero, J. Mendioroz, S. and Pajares, J.A., (1988) Infrared studies of surface acidity and reversible folding in palygorskite Clays and Clay Minerals 36 364–368 10.1346/CCMN.1988.0360412.Google Scholar
Bradley, W.F., (1940) The structural scheme of attapulgite American Mineralogist 25 405 410.Google Scholar
Brauner, K. and Preisinger, A., (1956) Struktur und Entstehung des S epioliths Tschermaks Mineralogische und Petrographische Mitteilungen 6 120–140 10.1007/BF01128033.Google Scholar
Chisholm, J.E., (1992) Powder diffraction patterns and structural models for palygorskite The Canadian Mineralogist 30 61 73.Google Scholar
Christ, C.L. Hathaway, J.C. Hostetler, P.B. and Shepard, A.O., (1969) Palygorskite: new X- ray data American Mineralogist 54 198 205.Google Scholar
Dowty, E., (1987) Fully automated microcomputer calculation of vibrational spectra Physics and Chemistry of Minerals 14 67–79 10.1007/BF00311150.Google Scholar
Drits, V.A. and Sokolova, G.V., (1971) Structure of palygorskite Soviet Physics and Crystallography 16 183 185.Google Scholar
Fateley, W.G. Dollish, F.R. McDevitt, N.T. and Bentley, F.F., (1972) Infrared and Raman Selection Rules for Molecular and Lattice Vibrations: the Correlation Method New York Wiley.Google Scholar
Frost, R.L. Cash, G.A. and Kloprogge, J.T., (1998) ‘Rocky Mountain leather’, sepiolite and attapulgite — an infrared emission spectroscopic study Vibrational Spectroscopy 16 173–184 10.1016/S0924-2031(98)00014-9.Google Scholar
Galán, E. and Carretero, M.I., (1999) A new approach to compositional limits for sepiolite and palygorskite Clays and Clay Minerals 47 399–409 10.1346/CCMN.1999.0470402.Google Scholar
Hayashi, H., (1969) Infrared study of sepiolite and palygorskite on heating American Mineralogist 53 1613 1624.Google Scholar
Jones, B.F. Galán, E. and Bailey, S.W., (1988) Sepiolite and palygorskite Hydrous Phyllosilicates Washington, D.C. Mineralogical Society of America 631–674 10.1515/9781501508998-021 Reviews in Mineralogy, 19 .Google Scholar
Kim, C.C. Bell, M.I. and McKeown, D.A., (1993) Vibrational analysis of benitoite and the Si3O9 ring Physical Review B47 7869–7877 10.1103/PhysRevB.47.7869.Google Scholar
Loh, E., (1973) Optical vibrations in sheet silicates Journal of Physics, C: Solid State Physics 6 1091–1104 10.1088/0022-3719/6/6/022.Google Scholar
Loudon, R., (1964) Raman scattering from crystals Advances in Physics 13 423–482 10.1080/00018736400101051.CrossRefGoogle Scholar
McKeown, D.A. Bell, M.I. and Etz, E.S., (1999) Raman spectra and vibrational analysis of the trioctahedral mica phlogopite American Mineralogist 84 970–976 10.2138/am-1999-5-633.Google Scholar
McKeown, D.A. Bell, M.I. and Etz, E.S., (1999) Vibrational analysis of the dioctahedral mica: 2M 1 muscovite American Mineralogist 84 1041–1048 10.2138/am-1999-7-806.Google Scholar
Mendelovici, E., (1973) Infrared study of attapulgite and HCL treated attapulgite Clays and Clay Minerals 21 115–119 10.1346/CCMN.1973.0210207.Google Scholar
Mendelovici, E. and Portillo, D.C., (1976) Organic derivatives of attapulgite — I. Infrared spectroscopy and X-ray diffraction studies Clays and Clay Minerals 24 177–182 10.1346/CCMN.1976.0240405.Google Scholar
Myriam, M. Suarez, M. and Martin-Pozas, J.M., (1998) Structural and textural modifications of palygorskite and sepiolite under acid treatment Clays and Clay Minerals 46 225–231 10.1346/CCMN.1998.0460301.Google Scholar
Preisinger, A., (1963) Sepiolite and related compounds: its stability and application Clays and Clay Minerals 10 365–371 10.1346/CCMN.1961.0100132.Google Scholar
Ruiz-Hitzky, E., (2001) Molecular access to intracrystalline tunnels of sepiolite Journal of Materials Chemistry 11 86–91 10.1039/b003197f.Google Scholar
Serna, C. VanScoyoc, G.E. and Ahlrichs, J.L., (1977) Hydroxyl groups and water in palygorskite American Mineralogist 62 784 792.Google Scholar
VanScoyoc, G.E. Serna, C.J. and Ahlrichs, J.L., (1979) Structural changes in palygorskite during dehydration and dehydroxylation American Mineralogist 64 215 223.Google Scholar
Vicente-Rodriguez, M.A. Suarez, M. Bañares-Munoz, M.A. and de Dios Lopez-Gonzalez, J., (1996) Comparative FT-IR study of the removal of octahedral cations and structural modifications during acid treatment of several silicates Spectrochimica Acta A52 1685–1694 10.1016/S0584-8539(96)01771-0.Google Scholar
Wang, Q.K. Matsuura, T. Feng, C.Y. Weir, M.R. Detellier, C. Rutadinka, R.L. and Van Mao, R.L., (2001) The sepiolite membrane for ultrafiltration Journal of Membrane Science 184 153–163 10.1016/S0376-7388(00)00605-0.Google Scholar