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Polarized Single-Crystal Fourier-Transform Infrared Microscopy of Ouray Dickite and Keokuk Kaolinite

Published online by Cambridge University Press:  02 April 2024

C. T. Johnston ,
S. F. Agnew  and
D. L. Bish
C. T. Johnston
Affiliation:
Department of Soil Science, 2169 McCarty Hall, University of Florida, Gainesville, Florida 32611
S. F. Agnew
Affiliation:
INC-4 Mail Stop C346, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
D. L. Bish
Affiliation:
EES-1 Mail Stop D469, Los Alamos National Laboratory, Los Alamos, New Mexico 87545
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Abstract

Single-crystal Fourier-transform infrared (FTIR) spectra of Keokuk kaolinite and Ouray dickite were obtained with an FTIR microscope. Although numerous IR, FTIR, and Raman spectra of polycrystalline kaolinite and dickite can be found in the literature, the present data represent the first reported single-crystal vibrational spectra for these clay minerals. The orientation of the crystallographic axes of dickite was determined using a cross-polarizing optical microscope fitted with an 550-nm optical retardation plate. Assignment of the inner hydroxyl group OH1 to the 3623-cm-1 band was confirmed, and the angle of this OH group to the b-axis was determined to be 47° based upon the measured dichroic ratio. The 3702-3710-cm−1 absorption feature appeared to consist of two closely spaced bands having slightly different polarization behavior. The inner-surface hydroxyl group OH3 was assigned to the absorption bands at 3710 cm−1. The calculated angle of the OH3 groups to the b-axis was found to be 22°, which agrees well with the angles determined by X-ray powder diffraction and neutron diffraction. The remaining hydroxyl groups, OH2 and OH4, were assigned to the 3656 cm-1 band; the angle of the OH2 and OH4 groups to the b-axis was measured at 45°. The polarization behavior of the OH-deformation bands of dickite at 911, 937, and 952 cm−1 was found to be similar to that observed in the OH-stretching region. Single-crystal FTIR spectra of Keokuk kaolinite showed that rotation of the electric vector around the c/z axis in the ab plane of kaolinite resulted in a behavior distinct from that of dickite. The OH-stretching bands of kaolinite were found to be considerably more polarized than the corresponding bands of dickite. This is related directly to the fact that dickite possesses a glide plane (space group Cc) compared with kaolinite, which does not (space group C1).

Keywords

Crystal structureDickiteFourier-transform infrared microscopyHydroxyl orientationKaoliniteSingle crystal
Type
Research Article
Information
Clays and Clay Minerals , Volume 38 , Issue 6 , December 1990 , pp. 573 - 583
Copyright
Copyright © 1990, The Clay Minerals Society

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References

Adams, J. M., 1983 Hydrogen atom positions in kaolinite by neutron profile refinement Clays & Clay Minerals 31 352 – 356.CrossRefGoogle Scholar
Adams, J. M. and Hewat, A. W., 1981 Hydrogen atom positions in dickite Clays & Clay Minerals 29 316 – 319.CrossRefGoogle Scholar
Bailey, S. W., 1963 Polymorphism of the kaolin minerals Amer. Mineral. 48 1196 – 1209.Google Scholar
Barrios, J., Plançon, A., Cruz, M. I. and Tchoubar, C., 1977 Qualitative and quantitative study of stacking faults in a hydrazine treated kaolinite. Relationship with the infrared spectra Clays & Clay Minerals 25 422 – 429.CrossRefGoogle Scholar
Bish, D. L. and Von Dreele, R. B., 1989 Rietveld refinement of non-hydrogen atomic positions in kaolinite Clays & Clay Minerals 37 289 – 296.CrossRefGoogle Scholar
Bookin, A. S., Drits, V. A., Plançon, A. and Tchoubar, C., 1989 Stacking faults in kaolin-group minerals in the light of real structural features Clays & Clay Minerals 37 297 – 307.CrossRefGoogle Scholar
Brindley, G. W., Kao, C., Harrison, J. L., Lipsicas, M. and Raythatha, R., 1986 Relation between structural disorder and other characteristics of kaolinites and dickites Clays & Clay Minerals 34 239 – 249.CrossRefGoogle Scholar
Farmer, V. C. and Farmer, V. C., 1974 The layer silicates The Infrared Spectra of Minerals London Mineralogical Society 331 – 363.CrossRefGoogle Scholar
Farmer, V. C. and Russell, J. D., 1964 The infra-red spectra of layer silicates Spectrochimica Acta 20 1149 – 1173.CrossRefGoogle Scholar
Giese, R. F., 1982 Theoretical studies of the kaolin minerals: Electrostatic calculations Bull. Mineral. 105 417 – 424.Google Scholar
Giese, R. F. and Bailey, S.W., 1988 Kaolin minerals: Structures and stabilities Hydrous Phyllosilicates (exclusive of Micas) 29 – 66.CrossRefGoogle Scholar
Giese, R. F. and Datta, P., 1973 Hydroxyl orientation in kaolinite, dickite, and nacrite Amer. Mineral. 58 471 – 479.Google Scholar
Johnston, C. T., Sposito, G., Bocian, D. F. and Birge, R. R., 1984 Vibrational spectroscopic study of the interlamellar kaolinite-dimethylsulfoxide complex J. Phys. Chem. 88 5959 – 5964.CrossRefGoogle Scholar
Johnston, C. T., Sposito, G. and Birge, R. R., 1985 Raman spectroscopic study of kaolinite in aqueous suspension Clays & Clay Minerals 33 483 – 489.CrossRefGoogle Scholar
Johnston, C. T. and Stone, D. A., 1990 Influence of hydrazine on the vibrational modes of kaolinite Clays & Clay Minerals 38 121 – 128.CrossRefGoogle Scholar
Joswig, W. and Drits, V. A., 1986 The orientation of the hydroxyl groups of dickite by X-ray diffraction N. Jb. Miner. Mh. 19 – 22.Google Scholar
Keller, W. D., 1977 Scan electron micrographs of kaolins collected from diverse environments of origin—IV. Georgia kaolin and kaolinizing source rocks Clays & Clay Minerals 25 311 – 345.CrossRefGoogle Scholar
Kerr, P. F., 1977 Optical Mineralogy 4th ed. New York McGraw-Hill 458 – 459.Google Scholar
Ledoux, R. L. and White, J. L., 1964 Infrared study of selective deuteration of kaolinite and halloysite at room temperature Science 145 47 – 49.CrossRefGoogle ScholarPubMed
Michaelian, K. H., 1986 The Raman spectrum of kaolinite #9 at 21 deg. C Can. J. Chem. 64 285 – 289.CrossRefGoogle Scholar
Prost, R., 1984 Etude par spectroscopie infrarouge a basse temperature des groupes OH de structure de la kaolinite, de la dickite et de la nacrite Agronomie 4 403 – 406.CrossRefGoogle Scholar
Prost, R., Dameme, A., Huard, E., Driard, J., Schultz, L. G., van Olphen, H. and Mumpton, F. A., 1987 Infrared study of structural OH in kaolinite, dickite, and nacrite at 300 to 5 K Proc. Int. Clay Conf., Denver, 1985 Bloomington, Indiana The Clay Minerals Society 17 – 23.Google Scholar
Prost, R., Dameme, A., Huard, E., Driard, J. and Leydecker, J. P., 1989 Infrared study of structural OH in kaolinite, dickite, nacrite, and poorly crystalline kaolinite at 5 to 600 K Clays & Clay Minerals 37 464 – 468.CrossRefGoogle Scholar
Raupach, M., Barron, P. F. and Thompson, J. G., 1987 Nuclear magnetic resonance, infrared, and X-ray powder diffraction study of dimethylsulfoxide and dimethylselenoxide intercalates with kaolinite Clays & Clay Minerals 35 208 – 219.CrossRefGoogle Scholar
Rouxhet, P. G., Samudacheata, N., Jacobs, H. and Anton, O., 1977 Attribution of the OH stretching bands of kaolinite Clay Miner 12 171 – 178.CrossRefGoogle Scholar
Sen Gupta, P. K., Schlemper, E. O., Johns, W. D. and Ross, F., 1984 Hydrogen positions in dickite Clays & Clay Minerals 32 483 – 485.CrossRefGoogle Scholar
Suitch, P. R. and Young, R. A., 1983 Atom-positions in highly-ordered kaolinite Clays & Clay Minerals 31 357 – 366.CrossRefGoogle Scholar
Thompson, J. G., FitzGerald, J. D. and Withers, R. L., 1989 Electron diffraction evidence for C-centering of non-hydrogen atoms in kaolinite Clays & Clay Minerals 37 563 – 565.CrossRefGoogle Scholar
Thompson, J. G. and Withers, R. L., 1987 A transmission electron microscopy contribution to the structure of kaolinite Clays & Clay Minerals 35 237 – 239.CrossRefGoogle Scholar
Turrell, G., 1972 Infrared and Raman Spectra of Crystals London Academic Press 153 – 158.Google Scholar
Vedder, W. and McDonald, R. S., 1963 Vibrations of the OH ions in muscovite J. Chem. Phys. 38 1583 – 1590.CrossRefGoogle Scholar
Wada, K., 1967 A study of hydroxyl groups in kaolin minerals utilizing selective-deuteration and infrared spectroscopy Clay Miner 7 51 – 61.CrossRefGoogle Scholar
Wieckowski, T. and Wiewiora, A., 1976 New approach to the problem of the interlayer bonding in kaolinite Clays & Clay Minerals 24 219 – 223.CrossRefGoogle Scholar
Wiewiora, A., Wieckowski, T. and Sokolowska, A., 1979 The Raman spectra of kaolinite sub-group minerals and of pyrophyllite Arch. Mineral. 35 5 – 14.Google Scholar
Young, R. A. and Hewat, A. W., 1988 Verification of the triclinic crystal structure of kaolinite Clays & Clay Minerals 36 225 – 232.CrossRefGoogle Scholar