Hostname: page-component-f554764f5-sl7kg Total loading time: 0 Render date: 2025-04-20T10:53:20.468Z Has data issue: false hasContentIssue false
  • English
  • Français

New Insight into the Relationships Between Structural and Ftir Spectroscopic Features of Kaolinites

Published online by Cambridge University Press:  01 January 2024

Victor A. Drits ,
Bella B. Zviagina Open the ORCID record for Bella B. Zviagina [Opens in a new window] ,
Boris A. Sakharov ,
Olga V. Dorzhieva  and
Aleksandr T. Savichev
Victor A. Drits
Affiliation:
Geological Institute of the Russian Academy of Science, Pyzhevsky per. 7, 119017 Moscow, Russia
Bella B. Zviagina*
Affiliation:
Geological Institute of the Russian Academy of Science, Pyzhevsky per. 7, 119017 Moscow, Russia
Boris A. Sakharov
Affiliation:
Geological Institute of the Russian Academy of Science, Pyzhevsky per. 7, 119017 Moscow, Russia
Olga V. Dorzhieva
Affiliation:
Institute of Ore Deposits, Petrography, Mineralogy, and Geochemistry of the Russian Academy of Science, Staromonetny per. 35, 7, 119017 Moscow, Russia
Aleksandr T. Savichev
Affiliation:
Geological Institute of the Russian Academy of Science, Pyzhevsky per. 7, 119017 Moscow, Russia
*
*E-mail address of corresponding author: [email protected]
Get access Rights & Permissions [Opens in a new window]

Abstract

To resolve the existing ambiguities in the interpretation of the OH-stretching vibrations of kaolinites, relationships were, for the first time, established between the structural and Fourier-transform infrared (FTIR) spectroscopic features for a set of kaolinite samples which differed in terms of their relative amounts of coexisting high- and low-ordered phases. For this purpose, a representative collection of kaolinites differing in origin, particle size, and degree of disorder was studied by powder X-ray diffraction (XRD) and FTIR spectroscopy. Modeling of the experimental XRD patterns based on the orthogonal layer unit cell having a mirror plane showed each sample to be a mixture of nearly defect-free high-ordered (HOK) and low-ordered (LOK) kaolinite phases, with HOK varying from 86 to 4%. The wavenumbers, heights, areas, and full widths at half-maximum (FWHM) were determined for the OH-stretching bands at ~3697 (ν1), ~3670 (ν2), ~3652 (ν3), and 3620 cm–1 (ν4) by decomposition and fitting of the FTIR spectra. The FWHM(ν1)/FWHM(ν4) and FWHM(ν3)/FWHM(ν2) values were related linearly to the HOK content, which may be associated with the in-phase and out-of-phase character of the corresponding pairs of vibrations, respectively. A novel interpretation was suggested for the variations in the relative integrated intensities of the OH bands with the amount of the HOK phase. The intensity distribution of the ν2 and ν3 bands is controlled by the triclinic structure symmetry in the defect-free kaolinite and the mirror symmetry of the layers in low-ordered structures, in agreement with the observed evolution of the corresponding band intensities. The ν1 and ν2 band positions for the low-ordered samples are within the wavenumber range for the high-ordered samples. In contrast, the ν3 and ν4 band positions for the low-ordered samples are shifted toward higher wavenumbers, indicating that some of the low-ordered kaolinites should contain dickite-like structural fragments distributed among kaolinite layers.

Keywords

Infrared spectroscopyKaoliniteOH absorption bandsStructural order/disorderX-ray diffraction
Type
Article
Information
Clays and Clay Minerals , Volume 69 , Issue 3 , June 2021 , pp. 366 - 388
Copyright
Copyright © Clay Minerals Society 2021

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

References

Artioli, G., Belloto, M., Gualtieri, A., & Pavese, A. (1995). Nature of stacking disorder in natural kaolinites: a new model based on computer simulation of powder diffraction data and electrostatic energy calculations. Clays and Clay Minerals, 43, 438–445.CrossRefGoogle Scholar
Bailey, S. W. (1963). Polymorphism of the kaolin minerals. American Mineralogist, 48, 1196–1209.Google Scholar
Bailey, S.W. (1993). Review of the structural relationships of the kaolin minerals. Pp. 25–42 in: Kaolin Genesis and Utilization (Murray, H., Bundy, W., & Harvey, C., editors). Special Publication No. 1. The Clay Minerals Society, Boulder, Colorado, USA.Google Scholar
Balan, E., Allard, T., Boizot, B., Morin, G., & Muller, J.-P. (2000). Quantitative measurement of paramagnetic Fe3+ in kaolinite. Clays and Clay Minerals, 48, 439–445.CrossRefGoogle Scholar
Balan, E., Saitta, A. M., Mauri, F., & Calas, G. (2001). First-principles modeling of the infrared spectrum of kaolinite. American Mineralogist, 86, 1321–1330.CrossRefGoogle Scholar
Balan, E., Lazzeri, M., Saitta, A. M., Allard, T., Fuchs, Y., & Mauri, F. (2005). First-principles study of OH-stretching modes in kaolinite, dickite and nacrite. American Mineralogist, 90, 50–60.CrossRefGoogle Scholar
Balan, E., Delattre, S., Guillaumet, M., & Salje, E. K. H. (2010). Low-temperature infrared spectroscopic study of OH-stretching modes in kaolinite and dickite. American Mineralogist, 95, 1257–1266.CrossRefGoogle Scholar
Beauvais, A., & Bertaux, J. (2002). In situ characterization and differentiation of kaolinites in lateritic weathering profiles using infrared microspectroscopy. Clays and Clay Minerals, 50, 314–330.CrossRefGoogle Scholar
Bish, D. L. (1993). Rietveld refinement of the kaolinite structure at 1.5 K. Clays and Clay Minerals, 41, 738–744.CrossRefGoogle Scholar
Bish, D. L., & von Dreele, R. B. (1989). Rietveld refinement of non-hydrogen atomic positions in kaolinite. Clays and Clay Minerals, 37, 289–296.CrossRefGoogle Scholar
Bish, D. L., & Johnston, C. T. (1993). Rietveld refinement and Fourier-transform infrared spectroscopy study of the dickite structure at low temperature. Clays and Clay Minerals, 41, 297–304.CrossRefGoogle Scholar
Bookin, A. S., Drits, V. A., Plançon, A., & Tchoubar, C. (1989). Stacking faults in kaolin-group minerals in the light of real structural features. Clays and Clay Minerals, 37, 297–307.CrossRefGoogle Scholar
Brindley, G. W., & Nakahira, M. (1958). Further consideration of the crystal structure of kaolinite. Mineralogical Magazine, 31, 781–786.CrossRefGoogle Scholar
Brindley, G. W., & Robinson, K. (1946). The structure of kaolinite. Mineralogical Magazine, 27, 242–253.CrossRefGoogle Scholar
Brindley, G. W., Kao, C.-C., Harrison, J. L., Lipsicas, M., & Raythatha, R. (1986). Relation between structural disorder and other characteristics of kaolinites and dickites. Clays and Clay Minerals, 34, 239–249.CrossRefGoogle Scholar
Chukhrov, F.V. & Zvyagin, B.B. (1966) Halloysite, a crystallochemically and mineralogically distinct species. In Heller, L. & Weiss, A. (Eds.) Proceedings of the International Clay Conference, Jerusalem, Israel (pp. 11–25). Jerusalem: Israel Program for Scientific TranslationGoogle Scholar
De Endredy, A. S. (1963). Estimation of free iron oxides in soils and clays by a photolytic method. Clay Minerals Bulletin, 5, 209–217.CrossRefGoogle Scholar
Drits, V. A., & Tchoubar, C. (1990). X-ray Diffraction by Disordered Lamellar Structures (p. 371). Springer.CrossRefGoogle Scholar
Drits, V. A., Środoń, J., & Eberl, D. D. (1997). XRD measurements of mean crystallite thickness of illite and illite/smectite: reappraisal of the Kubler index and the Scherrer equation. Clays and Clay Minerals, 45, 461–475.CrossRefGoogle Scholar
Drits, V. A., Lindgreen, H., Sakharov, B. A., Jakobsen, H. J., Salyn, A. L., & Dainyak, L. G. (2002a). Tobelitization of smectite during oil generation in oil-source shales. Application to North Sea illitetobelite-smectite-vermiculite. Clays and Clay Minerals, 50, 82–98.CrossRefGoogle Scholar
Drits, V. A., Sakharov, B. A., Dainyak, L. G., Salyn, A. L., & Lindgreen, H. (2002b). Structural and chemical heterogeneity of illite-smectites from UpperJurassic mudstones of East Greenland related to volcanic and weatheredparent rocks. American Mineralogist, 87, 1590–1607.CrossRefGoogle Scholar
Drits, V. A., Lindgreen, H., Sakharov, B. A., Jakobsen, H. J., & Zviagina, B. B. (2004). The detailed structure and origin of clay minerals at the Cretaceous/Tertiary boundary, Stevns Klint (Denmark). Clay Minerals, 39, 367–390.CrossRefGoogle Scholar
Drits, V. A., Derkowski, A., & McCarty, D. K. (2011a). Kinetics of thermal transformation of partially dehydroxylated pyrophyllite. American Mineralogist, 96, 1054–1069.CrossRefGoogle Scholar
Drits, V. A., Derkowski, A., & McCarty, D. K. (2011b). New insight into the structural transformation of partially dehydroxylated pyrophyllite. American Mineralogist, 96, 153–171.CrossRefGoogle Scholar
Drits, V. A., Sakharov, B. A., & Hiller, S. (2018). Phase and structural features of tubular halloysite (7Å). Clay Minerals, 53, 451–480.CrossRefGoogle Scholar
Farmer, V. C. (1974). The layer silicates. In Farmer, V. C. (Ed.), The Infrared Spectra of Minerals (pp. 331–363). Mineralogical Society.CrossRefGoogle Scholar
Farmer, V. C. (1998). Differing effects of particle size and shape in the infrared and Raman spectra of kaolinite. Clay Minerals, 33, 601–604.CrossRefGoogle Scholar
Farmer, V. C. (2000). Transverse and longitudinal crystal modes associated with OH-stretching vibrations in single crystals of kaolinite and dickite. Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy, 56, 927–930.CrossRefGoogle ScholarPubMed
Farmer, V. C., & Russell, J. D. (1964). The infra-red spectra of layer silicates. Spectrochimica Acta, 20, 1149–1173.CrossRefGoogle Scholar
Ferrage, E., Lanson, B., Sakharov, B. A., Geoffroy, N., Jacquot, E., & Drits, V. A. (2007). Investigation of dioctahedral smectite hydration properties by modeling of X-ray diffraction profiles: influence of layer charge and charge location. American Mineralogist, 92, 1731–1743.CrossRefGoogle Scholar
Johnston, C. T., Sposito, G., & Birge, R. R. (1985). Raman spectroscopic study of kaolinite in aqueous suspension. Clays and Clay Minerals, 33, 483–489.CrossRefGoogle Scholar
Johnston, C. T., Agnew, S. F., & Bish, D. L. (1990). Polarized singlecrystal Fourier-transform infrared microscopy of Ouray dickite and Keokuk kaolinite. Clays and Clay Minerals, 38, 573–583.CrossRefGoogle Scholar
Johnston, C. T., Helsen, J., Schoonheydt, R. A., Bish, D. L., & Agnew, S. F. (1998). Single-crystal Raman spectroscopic study of dickite. American Mineralogist, 83, 75–84.CrossRefGoogle Scholar
Johnston, C. T., Elzea-Kogel, J., Bish, D. L., Kogure, T., & Murray, H. H. (2008). Low-temperature FTIR study of kaolin-group minerals. Clays and Clay Minerals, 56, 470–485.CrossRefGoogle Scholar
Joswig, W., & Drits, V. A. (1986). The orientation of the hydroxyl groups in dickite by X-ray diffraction. Neues Jahrbuch für Mineralaogie Monatshefte, 1, 19–22.Google Scholar
Kogure, T. (2011). Stacking disorder in kaolinite revealed by HRTEM, a review. Clay Science, 15, 3–11.Google Scholar
Kogure, T., & Inoue, A. (2005a). Determination of defect structures in kaolin minerals by high-resolution transmission electron microscopy (HRTEM). American Mineralogist, 90, 85–89.CrossRefGoogle Scholar
Kogure, T., & Inoue, A. (2005b). Stacking defects and long-period polytypes in kaolin minerals from a hydrothermal deposit. European Journal of Mineralogy, 17, 465–474.CrossRefGoogle Scholar
Kogure, T., Johnston, C. T., Kogel, J. E., & Bish, D. L. (2010). Stacking disorder in a sedimentary kaolinite. Clays and Clay Minerals, 58, 63–72.CrossRefGoogle Scholar
Lanson, B., Sakharov, B. A., Claret, F., & Drits, V. A. (2009). Diagenetic smectite-to-illite transition in clay-rich sediments: a reappraisal of X-ray diffraction results using the multi-specimen method. American Journal of Science, 309, 476–516.CrossRefGoogle Scholar
McCarty, D. K., Sakharov, B. A., & Drits, V. A. (2009). New insight into smectite illitization: A zoned K-bentonite revisited. American Mineralogist, 94, 1653–1671.CrossRefGoogle Scholar
Murray, H. H. (1954). Structural variations of some kaolinites in relation to dehydrated halloysite. American Mineralogist, 39, 97–108.Google Scholar
Neder, R. B., Burghammer, M., Grasl, T. H., Schulz, H., Bram, A., & Fiedler, S. (1999). Refinement of the kaolinite structure from single-crystal synchrotron data. Clays and Clay Minerals, 47, 487–494.CrossRefGoogle Scholar
Newnham, R. E. (1961). A refinement of the dickite structure and some remarks on polymorphism in kaolin minerals. Mineralogical Magazine, 32, 683–704.CrossRefGoogle Scholar
Newnham, R. E., & Brindley, G. W. (1956). The crystal structure of dickite. Acta Crystallographica, 9, 759–764.CrossRefGoogle Scholar
Plançon, A., & Tchoubar, C. (1977). Determination of structural defects in phyllosilicates by X-ray diffraction. II. Nature and proportion of defects in natural kaolinites. Clays and Clay Minerals, 25, 436–450.CrossRefGoogle Scholar
Plançon, A., & Zacharie, C. (1990). An expert system for the structural characterization of kaolinites. Clay Minerals, 25, 249–260.CrossRefGoogle Scholar
Plançon, A., Giese, R. F., Snyder, R., Drits, V. A., & Bookin, A. S. (1989). Stacking faults in the kaolin-group minerals: defect structures of kaolinite. Clays and Clay Minerals, 37, 203–210.CrossRefGoogle Scholar
Post, J.E. & Bish, D.L. (1989). Rietveld refinement of crystal structures using powder X-ray diffraction data. Pp. 277–05 in: Modern Powder Diffraction (Bish, D.L. & Post, J.E., editors). Reviews in Mineralogy, 20. Mineralogical Society of America, Washington D.C.Google Scholar
Rozhdestvenskaya, I. V., Bookin, A. S., Drits, V. A., & Finko, V. I. (1982). Proton positions and structural peculiarities of dickite by X-ray diffraction. Mineralogicheskii Zhurnal, 4, 52–58 (in Russian).Google Scholar
Sakharov, B. A., Lindgreen, H., Salyn, A. L., & Drits, V. A. (1999). Determination of illite-smectite structures using multispecimen X-ray diffraction profile fitting. Clays and Clay Minerals, 47, 555–566.CrossRefGoogle Scholar
Sakharov, B. A., Lindgreen, H., Salyn, A. L., & Drits, V. A. (2004). Influence of the outer surface layers of crystals on the XRD intensity of basal reflections. Clays and Clay Minerals, 52, 680–692.CrossRefGoogle Scholar
Sakharov, B. A., Drits, V. A., & McCarty, D. K. (2016). Modeling of powder X-ray diffraction patterns of the Clay Minerals Society kaolinite standards: KGa-1, KGa-1b, and KGa-2. Clays and Clay Minerals, 64, 324–333.CrossRefGoogle Scholar
Samotoin, N. D., & Bortnikov, N. S. (2011). Formation of kaolinite nano- and microcrystals by weathering of phyllosilicates. Geology of Ore Deposits, 53, 340.CrossRefGoogle Scholar
Shoval, S., Yariv, S., Michaelian, K. H., Boudeulle, M., & Panczer, G. (2001). Hydroxyl-stretching bands in curve-fitted micro-Raman, photoacoustic, and transmission infrared spectra of dickite from St. Claire, Pennsylvania. Clays and Clay Minerals, 49, 347–354.CrossRefGoogle Scholar
Shoval, S., Yariv, S., Michaelian, K. H., Boudeulle, M., & Panczer, G. (2002). Hydroxyl-stretching bands in polarized micro-Raman spectra of oriented single-crystal Keokuk kaolinite. Clays and Clay Minerals, 50, 56–62.CrossRefGoogle Scholar
Suitch, P.R., & Young, R. A. (1983). Atom positions in highly ordered kaolinite. Clays and Clay Minerals, 31, 357–366.CrossRefGoogle Scholar
Tchoubar, C., Plançon, A., Ben Brahim, J., Clinard, C., & Sow, C. (1982). Caractéristiques structurales dés kaolinites desordonnées. Bulletin de Minéralogie, 105, 477–491.CrossRefGoogle Scholar
Tosoni, S., Doll, K., & Ugliengo, P. (2006). Hydrogen bond in layered materials: Structural and vibrational properties of kaolinite by a periodic B3LYP approach. Chemistry of Materials, 18, 2135–2143.CrossRefGoogle Scholar
Zheng, H., & Bailey, S. W. (1994). Refinement of the nacrite structure. Clays and Clay Minerals, 42, 46–52.CrossRefGoogle Scholar
Zvyagin, B. B. (1960). Electron diffraction determination of the structure of kaolinite. Soviet Physics and Crystallography, 5, 32–42.Google Scholar
Zvyagin, B. B. (1967). Electron Diffraction Analysis of Clay Mineral Structures (p. 364). Plenum Press.CrossRefGoogle Scholar
Zvyagin, B. B., Soboleva, S. V., & Fedotov, A. F. (1972). Refinement of the structure of nacrite by high-voltage electron diffraction. Soviet Physics and Crystallography, 17, 448–452.Google Scholar
Supplementary material: File

Drits et al. supplementary material
Download undefined(File)
File 1.6 MB
Supplementary material: File

Drits et al. supplementary material
Download undefined(File)
File 786.8 KB