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Structural Characterization of Reduced-Charge Montmorillonites. Evidence Based on FTIR Spectroscopy, Thermal Behavior, and Layer-Charge Systematics

Published online by Cambridge University Press:  01 January 2024

Evangelos N. Skoubris ,
Georgios D. Chryssikos ,
George E. Christidis  and
Vassilis Gionis
Evangelos N. Skoubris
Affiliation:
Department of Mineral Resources Engineering, Technical University of Crete, Chania, Greece 73100
Georgios D. Chryssikos
Affiliation:
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vass. Constantinou Ave., Athens, Greece 11635
George E. Christidis*
Affiliation:
Department of Mineral Resources Engineering, Technical University of Crete, Chania, Greece 73100
Vassilis Gionis
Affiliation:
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vass. Constantinou Ave., Athens, Greece 11635
*
*E-mail address of corresponding author: christid@mred.tuc.gr
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Abstract

In the present study, the gradual layer-charge reduction of two Li-saturated smectites, SAz-1 from Arizona, USA, and FEO-G from Troodos, Cyprus, with octahedral charge of 0.54 electrons per half unit cell (e/huc) and 0.39 e/huc, respectively, was monitored by X-ray diffraction of K-saturated, ethylene glycol-solvated samples, by thermogravimetry-differential thermogravimetry, and by mid- and near-Fourier transform infrared spectroscopy after heating at 80–300ºC. With increasing heating temperature, the layer charge and cation exchange capacity (CEC) of both smectites decreased gradually due to Li fixation. At temperatures >200ºC, ~25% residual CEC was observed, suggesting incomplete Li fixation due to kinetic constraints. Dehydration of the original Li-smectites occurred in two steps, one peaking at ~100ºC and another at 175–180ºC. The latter decreased upon progressive Li fixation and vanished from smectites treated above ~125ºC. Dehydroxylation occurred at 635–640ºC in both smectites and was not affected by Li fixation. The second derivative analysis of the infrared spectra showed that Li fixation was manifested in both smectites by the growth of two new sharp OH-stretching fundamentals at ~3640 and 3670 cm−1 and their overtones at ~7115 and 7170 cm−1. The new bands constitute pairs of fixed energy and relative intensity which grow simultaneously at the expense of the broad OH-stretching and overtone features of the original smectites. Based on this result, Li fixation is suggested to be accompanied by the simultaneous formation of two distinct trioctahedral-like structural OH species, which is compatible with Li+ occupying trans-octahedral vacancies in both smectites.

Keywords

Attenuated Total Reflectance SpectroscopyHofmann-Klemen EffectLayer ChargeLi FixationNear Infrared SpectroscopyResidual Cation Exchange CapacitySmectiteTrans-vacant

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 61 , Issue 2 , April 2013 , pp. 83 - 97
Copyright
Copyright © Clay Minerals Society 2013

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References

Alba, M.D. Alvero, R. Becerro, A.I. Castro, M.A. and Trillo, J.M., 1998 Chemical behaviour of lithium ions in reexpanded Li-montmorillonites Journal of Physical Chemistry B 102 2207–2213.CrossRefGoogle Scholar
Alvero, R. Alba, M.D. Castro, M.A. and Trillo, J.M., 1994 Reversible migration of lithium in montmorillonite Journal of Physical Chemistry 98 7848–7853.CrossRefGoogle Scholar
Bain, D.C. Smith, B.F.L., Wilson, M.J., 1987 Chemical analysis A Handbook of Determinative Methods in Clay Mineralogy Glasgow and London Blackie 248–274.Google Scholar
Besson, G. and Drits, V.A., 1997 Refined relationships between chemical composition of dioctahedral fine-dispersed mica minerals and their infrared spectra in the OH stretching region. Part I: Identification of the stretching bands Clays and Clay Minerals 45 158–169.CrossRefGoogle Scholar
Besson, G. and Drits, V.A., 1997 Refined relationships between chemical composition of dioctahedral fine-dispersed mica minerals and their infrared spectra in the OH stretching region. Part II: The main factors affecting OH vibration and quantitative analysis Clays and Clay Minerals 45 170–183.CrossRefGoogle Scholar
Bishop, J P CM and Edwards, J.O., 1994 Infrared spectroscopic analyses on the nature of water in montmorillonite Clays and Clay Minerals 42 702–716.CrossRefGoogle Scholar
Bishop, J. Madejová, J. Komadel, P. and Fröschl, H., 2002 The influence of structural Fe, Al and Mg on the infrared OH bands in spectra of dioctahedral smectites Clay Minerals 37 607–616.CrossRefGoogle Scholar
Brigatti, M.F. Galán, E. Theng, B.K.G., Bergaya, F. Lagaly, G. and Theng, B.K.G., 2006 Structures and mineralogy of clay minerals Handbook of Clay Science Elsevier, Amsterdam Developments in Clay Science, 1 19–86.CrossRefGoogle Scholar
Brindley, G.W. and Ertem, G., 1971 Preparation and solvation properties of some variable charge montmorillonites Clays and Clay Minerals 19 399–404.CrossRefGoogle Scholar
Bujdák, J. Janek, M. Madejová, J. and Komadel, P., 2001 Methylene blue interactions with reduced charge smectites Clays and Clay Minerals 49 244–254.CrossRefGoogle Scholar
Calvet, R. and Prost, R., 1971 Cation migration into empty octahedral sites and surface properties of clays Clays and Clay Minerals 19 175–186.CrossRefGoogle Scholar
Christidis, G.E., 2006 Genesis and compositional heterogeneity of smectites. Part III: Alteration of basic pyroclastic rocks — A case study from the Troodos Ophiolite Complex, Cyprus American Mineralogist 91 685–701.CrossRefGoogle Scholar
Christidis, G.E. and Eberl, D.D., 2003 Determination of layer charge characteristics of smectites Clays and Clay Minerals 51 644–655.CrossRefGoogle Scholar
Christidis, G.E. Blum, A.E. and Eberl, D.D., 2006 Influence of layer charge and charge distribution of smectites on the flow behaviour and swelling of bentonites Applied Clay Science 34 125–138.CrossRefGoogle Scholar
Chryssikos, G.D. Gionis, V. Kacandes, G.H. Stathopoulou, E.T. Suárez, M. García-Romero, E. and Sánchez del Río, M., 2009 Octahedral cation distribution in palygorskite American Mineralogist 94 200–203.CrossRefGoogle Scholar
Clark, R.N. King, T.V.V. Klejwa, M. Swayze, G.A. and Vergo, N., 1990 High spectral resolution reflectance spectroscopy of minerals Journal of Geophysical Research 95 12653–12680.CrossRefGoogle Scholar
Drits, V.A. and Zviagina, B.B., 2009 Trans-vacant and cis-vacant 2:1 layer silicates: Structural features, identification, and occurrence Clays and Clay Minerals 57 405–415.CrossRefGoogle Scholar
Drits, V.A. Besson, G. and Muller, F., 1995 An improved model for structural transformations of heat-treated aluminous dioctahedral 2:1 layer silicates Clays and Clay Minerals 43 718–731.CrossRefGoogle Scholar
Farmer, V.C., 1974 The layer silicates The Infrared Spectra of Minerals 331–363.CrossRefGoogle Scholar
Gates, W.P., Kloprogge, J.T., 2005 Infrared spectroscopy and the chemistry of dioctahedral smectites The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides Aurora, Colorado, USA CMS Workshop Lectures 13, The Clay Minerals Society 125–168.Google Scholar
Gates, W.P. Komadel, P. Madejová, J. Bujdák, J. Stucki, J.W. and Kirkpatrick, R.J., 2000 Electronic and structural properties of reduced-charge montmorillonites Applied Clay Science 16 257–271.CrossRefGoogle Scholar
Gates, W.P. Slade, P.G. Manceau, A. and Lanson, B., 2002 Site occupancies by iron in nontronites Clays and Clay Minerals 50 223–239.CrossRefGoogle Scholar
Gionis, V. Kacandes, G.H. Kastritis, I.D. and Chryssikos, G.D., 2006 On the structure of palygorskite by mid- and near-infrared spectroscopy American Mineralogist 91 1125–1133.CrossRefGoogle Scholar
Gionis, V. Kacandes, G.H. Kastritis, I.D. and Chryssikos, G.D., 2007 Combined near-infrared and X-ray diffraction investigation of the octahedral sheet composition of palygorskite Clays and Clay Minerals 55 543–553.CrossRefGoogle Scholar
Guggenheim, S. and Koster van Groos, A.F., 2001 Baseline studies of the Clay Minerals Society Source clays: Thermal Analysis Clays and Clay Minerals 49 433–443.CrossRefGoogle Scholar
Guisseau, D. P. Mas, P. Beaufort, D. Girard, J.-P. Inoue, A. Sanjuan, B. Petit, S. A. Lens, A. and Genter, A., 2007 Significance of the depth-related transition montmorillonite-beidellite in the Bouillante geothermal field (Guadeloupe, Lesser Antilles) American Mineralogist 92 1800–1813.CrossRefGoogle Scholar
Greene-Kelly, R., 1953 The identification of montmorillo-noids in clays Journal of Soil Science 4 233–237.CrossRefGoogle Scholar
Güven, N., Güven, N. and Pollastro, R.M., 1992 Rheological aspects of aqueous smectite suspensions Clay–Water Interface and its Rheological Implications Bloomington, Indiana, USA CMS Workshop Lectures 4, The Clay Minerals Society 81–125.Google Scholar
Hofmann, U. and Klemen, R., 1950 Verlust der Austauschfahigkeit von Lithiumionen an Bentonit durch Erhitzung Zeitschrift für Anorganische und Allgemeine Chemie 262 95–99.CrossRefGoogle Scholar
Hrobáriková, J. Madejová, J. and Komadel, P., 2001 Effect of heating temperature on Li fixation, layer charge and properties of fine fractions of bentonites Journal of Materials Chemistry 11 1452–1457.CrossRefGoogle Scholar
Jaynes, W.F. and Bigham, J.M., 1987 Charge reduction, octahedral charge, and lithium retention in heated, Lisaturated smectites Clays and Clay Minerals 35 440–448.CrossRefGoogle Scholar
Johnston, C.T. and Premachandra, G.S., 2001 Polarized ATR-FTIR study of smectite in aqueous suspension Langmuir 17 3712–3718.CrossRefGoogle Scholar
Karakassides, M.A. Petridis, D. and Gournis, D., 1997 Infrared Reflectance Study of Thermally Treated Li- and Cs-Montmorillonites Clays and Clay Minerals 45 649–658.CrossRefGoogle Scholar
Karakassides, M.A. Madejová, J. Arvaiová, B. Bourlinos, A. Petridis, D. and Komadel, P., 1999 Location of Li(I), Cu(II), and Cd(II) in heated montmorillonite: Evidence from specular reflectance infrared and electron spin resonance spectroscopies Journal of Materials Chemistry 9 1553–1558.CrossRefGoogle Scholar
Kloprogge, J.T. Ruan, H. and Frost, R.L., 2000 Near-infrared spectroscopic study of synthetic and natural pyrophyllite Neues Jahrbuch für Mineralogie, Monatshefte 2000 337–347.Google Scholar
Komadel, P., 2003 Chemically modified smectites Clay Minerals 38 127–138.CrossRefGoogle Scholar
Komadel, P. Bujdák, J. Madejová, J. Šucha, V. and Elsass, F., 1996 Effect of non-swelling layers on the dissolution of reduced-charge montmorillonite in hydrochloric acid Clay Minerals 31 333–345.CrossRefGoogle Scholar
Koster van Groos, A.F. and Guggenheim, S., 1987 Dehydration of a Ca-and a Mg-exchanged montmorillonite (SWy-1) at elevated pressures American Mineralogist 72 292–298.Google Scholar
Laird, D.A., 1999 Layer charge influences on the hydration of expandable 2:1 phyllosilicates Clays and Clay Minerals 47 630–636.CrossRefGoogle Scholar
Laird, D.A., 2006 Influence of layer charge on swelling of smectites Applied Clay Science 34 74–87.CrossRefGoogle Scholar
Laird, D.A. Fleming, P., Ulery, A. and Drees, R., 2008 Analysis of layer charge, cation and anion exchange capacities, and synthesis of reduced charge clays Methods of Soil Analysis. Part 5. Mineralogical Methods Madison, Wisconsin SSSA Book Series No 5..Google Scholar
Laird, D.A. Barriuso, E. Dowdy, R.H. and Koskinen, W.C., 1992 Adsorption of atrazine on smectites Soil Science Society of America Journal 56 62–67.CrossRefGoogle Scholar
Lantenois, S. Beny, J.-M. Muller, F. and Champallier, R., 2007 Integration of Fe in natural and synthetic Al-pyrophyllites: an infrared spectroscopic study Clay Minerals 42 129–141.CrossRefGoogle Scholar
Lim, C.H. and Jackson, M.L., 1986 Expandable phyllosilicate reactions with lithium on heating Clays and Clay Minerals 34 346–352.CrossRefGoogle Scholar
Luca, V C CM and Meinhold, R.H., 1989 High resolution multinuclear NMR study of cation migration in montmorillonite Clay Minerals 24 115–119.CrossRefGoogle Scholar
Madejová, J., 2005 Studies of reduced-charge smectites by near infrared spectroscopy The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides 13 169–202.Google Scholar
Madejová, J. and Komadel, P., 2005 Information available from infrared spectra of the fine fractions of bentonites The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides 13 65–98.Google Scholar
Madejová, J. Komadel, P. and Čicěl, B., 1994 Infrared study of octahedral site populations in smectites Clay Minerals 29 319–326.CrossRefGoogle Scholar
Madejová, J. Bujdák, J. Gates, W.P. and Komadel, P., 1996 Preparation and infrared spectroscopic characterization of reduced-charge montmorillonite with various Li contents Clay Minerals 31 233–241.CrossRefGoogle Scholar
Madejová, J. Bujdák, J. Petit, S. and Komadel, P., 2000 Effects of chemical composition and temperature of heating on the infrared spectra of Li-saturated dioctahedral smectites (I) Mid-infrared region Clay Minerals 35 739–751.CrossRefGoogle Scholar
Madejová, J. Bujdák, J. Petit, S. and Komadel, P., 2000 Effects of chemical composition and temperature of heating on the infrared spectra of Li-saturated dioctahedral smectites (II) Near-infrared region Clay Minerals 35 753–761.CrossRefGoogle Scholar
Madejová, J. Pálková, H. and Komadel, P., 2006 Behaviour of Li+ and Cu2+ in heated montmorillonite: Evidence from far-, mid-, and near-IR regions Vibrational Spectroscopy 40 80–88.CrossRefGoogle Scholar
Maes, A. and Cremers, A., 1977 Charge density effects in ion exchange. Part 1. Heterovalent exchange equilibria Journal of the Chemical Society Faraday Transactions 73 1807–1814.CrossRefGoogle Scholar
Maes, A. and Cremers, A., 1978 Charge density effects in ion exchange. Part 2. Homovalent exchange equilibria Journal of the Chemical Society Faraday Transactions 74 1234–1241.CrossRefGoogle Scholar
Maes, A. Stul, M.S. and Cremers, A., 1979 Layer charge-cation-exchange capacity relationships in montmorillonite Clay and Clay Minerals 27 387–392.CrossRefGoogle Scholar
Muller, F. Besson, G. Manceau, A. and Drits, V.A., 1997 Distribution of isomorphous cations within octahedral sheets in montmorillonite from Camp-Berteau Physics and Chemistry of Minerals 24 159–166.CrossRefGoogle Scholar
Odom, I.E., 1984 Smectite clay minerals: properties and uses Philosophical Transactions of the Royal Society of London A311 391–409.Google Scholar
Petit, S., 2005 Crystal-chemistry of talcs: A NIR and MIR spectroscopic approach The Application of Vibrational Spectroscopy to Clay Minerals and Layered Double Hydroxides 13 41–64.Google Scholar
Petit, S. Caillaud, J. Righi, D. Madejová, J. Elsass, F. and Köster, H.M., 2002 Characterization and crystal chemistry of an Fe-rich montmorillonite from Ölberg, Germany Clay Minerals 37 283–297.CrossRefGoogle Scholar
Petit, S. Decarreau, A. Martin, F. and Buchet, R., 2004 Refined relationship between the position of the fundamental OH stretching and the first overtones for clays Physics and Chemistry of minerals 31 585–592.CrossRefGoogle Scholar
Post, J.L. and Noble, P.N., 1993 The near-infrared combination band frequencies of dioctahedral smectites, micas and illites Clays and Clay Minerals 41 639–644.CrossRefGoogle Scholar
Russell, J.D., 1979 An infrared spectroscopic study of the interaction of nontronite and ferruginous montmorillonites with alkali metal hydroxides Clay Minerals 14 127–137.CrossRefGoogle Scholar
Russell, J.D. Fraser, A.R., Wilson, M.J., 1994 Infrared methods Clay Mineralogy: Spectroscopic and Chemical Determinative Methods London Chapman & Hall 11–67.CrossRefGoogle Scholar
Sainz-Diaz, C.I. Hernández-Laguna, A. and Dove, M.T., 2001 Theoretical modelling of cis-vacant and trans-vacant configurations in the octahedral sheet of illites and smectites Physics and Chemistry of Minerals 28 322–331.CrossRefGoogle Scholar
Sato, T. Watanabe, T. and Otsuka, R., 1992 Effects of layer charge, charge location and energy change on expansion properties of dioctahedral smectites Clays and Clay Minerals 40 103–113.CrossRefGoogle Scholar
Shainberg, I. Alperovitch, N.I. and Keren, R., 1987 Charge density and Na−K–Ca exchange on smectites Clays and Clay Minerals 35 68–73.CrossRefGoogle Scholar
Slade, P.G. Quirk, J.R. and Norrish, K., 1991 Crystalline swelling of smectite samples in concentrated NaCl solutions in relation to layer charge Clays and Clay Minerals 39 234–238.CrossRefGoogle Scholar
Sposito, G. Prost, R. and Gaultier, J.P., 1983 Infrared spectroscopic study of adsorbed water on reduced-charge Na/Li-montmorillonites Clays and Clay Minerals 31 9–16.CrossRefGoogle Scholar
Srasra, E. Bergaya, F. and Fripiat, J.J., 1994 Infrared spectroscopy study of tetrahedral and octahedral substitutions in an interstratified illite-smectite clay Clays and Clay Minerals 42 237–241.CrossRefGoogle Scholar
Stackhouse, S. and Coveney, P.V., 2002 Study of thermally treated lithium montmorillonite by ab initio methods Journal of Physical Chemistry 106 12470–12477.CrossRefGoogle Scholar
Tettenhorst, R., 1962 Cation migration in montmorillonites American Mineralogist 47 769–773.Google Scholar
Theng, B.K.G. Hayashi, S. Soma, M. and Seyama, H., 1997 Nuclear magnetic resonance and X-ray photoelectron spectroscopic investigation of lithium migration in montmorillonite Clays and Clay Minerals 45 718–723.CrossRefGoogle Scholar
Tombacz, E. and Szekeres, M., 2004 Colloidal behaviour of aqueous montmorillonite suspensions: the specific role of pH in the presence of indifferent electrolytes Applied Clay Science 27 75–94.CrossRefGoogle Scholar
Tsipurski, S.I. and Drits, V.A., 1984 The distribution of octahedral cations in the 2:1 layers of dioctahedral smectites studied by oblique-texture electron diffraction Clay Minerals 19 177–193.CrossRefGoogle 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
Wolters, F. and Emmerich, K., 2007 Thermal reactions of smectites — Relation of dehydroxylation temperature to octahedral structure Thermochimica Acta 462 80–88.CrossRefGoogle Scholar
Wang, L. Zhang, M. Redfern, S.A.T. and Zhang, Z., 2002 Dehydroxylation and transformations of the 2:1 phyllosili-cate pyrophyllite at elevated temperatures: An infrared spectroscopic study Clays and Clay Minerals 50 272–283.CrossRefGoogle Scholar
Zviagina, B.B. McCarty, D.K. Środoń, J. and Drits, V.A., 2004 Interpretation of infrared spectra of dioctahedral smectites in the region of OH-stretching vibrations Clays and Clay Minerals 52 399–410.CrossRefGoogle Scholar