Skip to main content
SpringerLink
Log in

Formation and Restacking of Disordered Smectite Osmotic Hydrates

  • Published:
Clays and Clay Minerals

Abstract

Clay swelling, an important phenomenon in natural systems, can dramatically affect the properties of soils and sediments. Of particular interest in low-salinity, saturated systems are osmotic hydrates, forms of smectite in which the layer separation greatly exceeds the thickness of a single smectite layer due to the intercalation of water. In situ X-ray diffraction (XRD) studies have shown a strong link between ionic strength and average interlayer spacing in osmotic hydrates but also indicate the presence of structural disorder that has not been fully described. In the present study the structural state of expanded smectite in sodium chloride solutions was investigated by combining very low electron dose, high-resolution cryogenic-transmission electron microscopy observations with XRD experiments. Wyoming smectite (SWy-2) was embedded in vitreous ice to evaluate clay structure in aqua. Lattice-fringe images showed that smectite equilibrated in aqueous, low-ionic-strength solutions, exists as individual smectite layers, osmotic hydrates composed of parallel layers, as well as disordered layer conformations. No evidence was found here for edge-to-sheet attractions, but significant variability in interlayer spacing was observed. Whether this variation could be explained by a dependence of the magnitude of long-range cohesive (van der Waals) forces on the number of layers in a smectite particle was investigated here. Calculations of the Hamaker constant for layer-layer interactions showed that van der Waals forces may span at least five layers plus the intervening water and confirmed that forces vary with layer number. Drying of the disordered osmotic hydrates induced re-aggregation of the smectite to form particles that exhibited coherent scattering domains. Clay disaggregation and restacking may be considered as an example of oriented attachment, with the unusual distinction that it may be cycled repeatedly by changing solution conditions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
$34.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or eBook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Amorim, C.L.G., Lopes, C.L.G., Barroso, R.C., Queiroz, J.C., Alves, D.B., Perez, C.A., and Schelin, H.R. (2007) Effect of clay—water interactions on clay swelling by X-ray diffraction. Nuclear Instruments and Methods in Physics Research A, 580, 768–770.

    Article  Google Scholar 

  • Anderson, R.L., Ratcliffe, I., Greenwell, H.C., Williams, P.A., Cliffe, S., and Coveney, P.V. (2010) Clay swelling — a challenge in the oilfield. Earth-Science Reviews, 98, 201–216.

    Article  Google Scholar 

  • Bailey, S.W. (1988) Hydrous Phyllosilicates (exclusive of Micas). Reviews in Mineralogy, 19, Mineralogical Society of America, Washington, D.C.

    Book  Google Scholar 

  • Cheng, Y. (2015) Single-particle cryo-EM at crystallographic resolution. Cell, 161, 450–457.

    Article  Google Scholar 

  • Comolli, L.R., Luef, B., and Chan, C.S. (2011) High-resolution 2D and 3D cryo-TEM reveals structural adaptations of two stalk-forming bacteria to an Fe-oxidizing lifestyle. Environmental Microbiology, 13, 2915–2929.

    Article  Google Scholar 

  • Davies, B. and Ninham, B.W. (1972) Van der Waals forces in electrolytes. Journal of Chemical Physics, 56, 5792–5801.

    Google Scholar 

  • Dazas, B., Lanson, B., Delville, A., Robert, J.L., Komarneni, S., Michot, L.J., and Ferrage, E. (2015) Journal of Physical Chemistry C, 119, 4158–4172.

    Article  Google Scholar 

  • Delhorme, M., Jönsson, B., and Labbez, C. (2011) Monte Carlo simulations of a clay inspired model suspension: The role of rim charge. Soft Matter, 8, 9691–9704.

    Article  Google Scholar 

  • Faisandier, K., Pons, C.H., Tchoubar, D., and Thomas, F. (1998) Structural organization of Na- and K-montmorillonite suspensions in response to osmotic and thermal stresses. Clays and Clay Minerals, 46, 636–648.

    Article  Google Scholar 

  • Ferrage, E., Lanson, B., Sakharov, B.A., and Drits, V.A. (2005) Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns: Part I. Montmorillonite hydration properties. American Mineralogist, 90, 1358–1374.

    Article  Google Scholar 

  • Foster, M.D. (1955) The relation between composition and swelling in clays. Clays and Clay Minerals, 3, 205–220.

    Article  Google Scholar 

  • Frandsen, C., Legg, B., Comolli, L.R., Zhang, H., Gilbert, B., Johnson, E., and Banfield, J.F. (2014) Aggregation-induced growth and transformation of β-FeOOH nanorods to micronsized α-Fe2O3 spindles. CrystEngComm, 16, 1451–1458.

    Article  Google Scholar 

  • French, R.H., Müllejans, H., and Jones, D.J. (1998) Optical properties of aluminum oxide: determined from vacuum ultraviolet and electron energy-loss spectroscopies. Journal of the American Ceramic Society. 81, 2549–2557.

    Article  Google Scholar 

  • Greathouse, J.A., Feller, S.E., and McQuarrie, D. (1994) The modified Gouy-Chapman theory: comparisons between electrical double layer models of clay swelling. Langmuir, 10, 2125–2130.

    Article  Google Scholar 

  • Grodzinsky, A.J. (2011) Fields, Forces, and Flows in Biological Systems. Garland Science

  • Guthrie, G.D. and Veblen, D.R. (1989) High-resolution transmission electron microscopy of mixed-layer illite/smectite: Computer simulations. Clays and Clay Minerals, 37, 1–11.

    Article  Google Scholar 

  • Hou, J., Li, H., and Zhu, H. (2009) Determination of clay surface potential: A more reliable approach. Soil Science Society of America Journal, 73, 1658–1663.

    Article  Google Scholar 

  • Huang, F., Zhang, H.Z., and Banfield, J.F. (2003) The role of oriented attachment crystal growth in hydrothermal coarsening of nanocrystalline ZnS. Journal of Physical Chemistry B, 107, 10470–10475.

    Article  Google Scholar 

  • Jönsson, B., Labbez, C., and Cabane, B. (2008) Interaction of nanometric clay platelets. Langmuir, 24, 11406–11413.

    Article  Google Scholar 

  • Klein, W.B. and Oster, J.D. (1982) A model of clay swelling and tactoid formation. Clays and Clay Minerals, 30, 383–390.

    Article  Google Scholar 

  • Laird, D.A. (2006) Influence of layer charge on swelling of smectites. Applied Clay Science, 34, 74–87.

    Article  Google Scholar 

  • Legg, B., Zhu, M., Comolli, L.R., Gilbert, B., and Banfield, J.F. (2014) Determination of the three-dimensional structure of ferrihydrite nanoparticle aggregates. Langmuir, 30, 9931–9940.

    Article  Google Scholar 

  • Li, D., Nielsen, M.H., Lee, J.R.I., Frandsen, C., Banfield, J.F., and De Yoreo, J.J. (2012) Direction-specific interactions control crystal growth by oriented attachment. Science, 336, 1014–1018.

    Article  Google Scholar 

  • Lifshitz, E.M. (1956) The theory of molecular attractive forces between solids. Soviet Physics 2, 73–83.

    Google Scholar 

  • Liu, L. (2013) Prediction of swelling pressures of different types of bentonite in dilute solutions. Colloids and Surfaces A, 343, 303–318.

    Article  Google Scholar 

  • Low, P.F. and Margheim, J.F. (1979) Swelling of clay. 1. Basic concepts and empirical equations. Soil Science Society of America Journal, 43, 473–481.

    Article  Google Scholar 

  • Luckham, P.F. and Rossi, S. (1999) The colloidal and rheological properties of bentonite. Advances in Colloidal Science, 82, 43–92.

    Article  Google Scholar 

  • Luef, B., Fakra, S.C., Csencsits, R., Wrighton, K.C., Williams, K.H., Wilkins, M.J., Downing, K.H., Long, P.E., Comolli, L.R., and Banfield, J.F. (2012) Iron-reducing bacteria accumulate ferric oxyhydroxide nanoparticle aggregates that may support planktonic growth. ISME Journal, 2012, 1–13.

    Google Scholar 

  • Marra, J. (1985) Direct measurements of attractive van der Waals and adhesion forces between uncharged lipid bilayers in aqueous solutions. Journal of Colloid and Interface Science, 109, 11–20.

    Article  Google Scholar 

  • Miller, S.E. and Low, P.F. (1990) Characterization of the electrical double layer of montmorillonite. Langmuir 6, 572–578.

    Article  Google Scholar 

  • Missanna, T. and Adell, A. (2000) On the applicability of DLVO theory to the prediction of clay colloids stability. Journal of Colloid and Interface Science, 230, 150–156.

    Article  Google Scholar 

  • Norrish, K. (1954) Manner of swelling of montmorillonite. Nature, 173, 256–257.

    Article  Google Scholar 

  • Paineau, E., Bihannic, I., Baravian, C., Philippe, A.-M., Davidson, P., Levitz, P., Funari, S.S., Rochas, C., and Michot, L.J. (2011) Aqueous suspensions of natural swelling clay minerals. 1. Structure and electrostatic interactions. Langmuir, 27, 5562–5573.

    Article  Google Scholar 

  • Parsegian, V.A. (2006) Van der Waals Forces. Cambridge University Press, Cambridge, UK.

    Google Scholar 

  • Penn, R.L. and Banfield, J.F. (1998) Imperfect oriented attachment: Dislocation generation in defect-free nanocrystals. Science, 281, 969–971.

    Article  Google Scholar 

  • Penn, R.L., Oskam, G., Strathmann, T.J., Searson, P.C., Stone, A.T., and Veblen, D.R. (2001) Epitaxial assembly in aged colloids. Journal of Physical Chemistry B, 105, 2177–2182.

    Article  Google Scholar 

  • Podgornik, R. and Parsegian, V.A. (2004) Van der Waals interactions across stratified media. Journal of Chemical Physics, 120, 3401–3405.

    Article  Google Scholar 

  • Pons, C.H., Rousseaux, F., and Tchoubar, D. (1981) Utilisation du rayonnement synchrotron en diffusion aux petits angles pour l’etude du gonflement des smectites: I. Etude du systeme eau-montmorillonite-Na en fonction de la temperature. Clay Minerals, 16, 23–42.

    Article  Google Scholar 

  • Quirk, J.P. and Marčelja, S. (1997) Application of double-layer theories to the extensive crystalline swelling of Li-montmorillonite. Langmuir, 13, 6241–6248.

    Article  Google Scholar 

  • Rajter, R.F., French, R.H., Ching, W.Y., Podgornik, R., and Parsegian, A.V. (2013) Chirality-dependent properties of carbon nanotubes: electronic structure, optical dispersion properties, Hamaker coefficients and van der Waals—London dispersion interactions. RSC Advances, 3, 823–842.

    Article  Google Scholar 

  • Schuman, D., Hesse, R., Sears, S.K., and Vali, H. (2014) Expansion behavior of octadecylammonium-exchanged lowto high-charge reference smectite-group minerals as revealed by high-resolution transmission electron microscopy on ultrathin sections. Clays and Clay Minerals 62, 336–353.

    Article  Google Scholar 

  • Schuman, D., Hesse, R., Sears, S.K., and Vali, H. (2014) Expansion behavior of octadecylammonium-exchanged lowto high-charge reference smectite-group minerals as revealed by high-resolution transmission electron microscopy on ultrathin sections. Clays and Clay Minerals 62, 336–353.

    Article  Google Scholar 

  • Segad, M., Hanski, S., Olsson, U., Ruokolainen, J., Akesson, T., and Jonsson, B. (2012) Microstructural and swelling properties of Ca and Na montmorillonite: (in situ) observations with cryo-TEM and SAXS. Journal of Physical Chemistry C, 116, 7596–7601.

    Article  Google Scholar 

  • Slade, P.G., Quirk, J.P., 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.

    Article  Google Scholar 

  • Svensson, P.D. and Hansen, S. (2013) Combined salt and temperature impact on montmorillonite hydration. Clays and Clay Minerals, 61, 328–341.

    Article  Google Scholar 

  • Tan, G.L., Lemon, M.F., Jones, D.J., and French, R.H. (2005) Optical properties and London dispersion interaction of amorphous and crystalline SiO2 determined by vacuum ultraviolet spectroscopy and spectroscopic ellipsometry. Physical Review B, 72, 205117.

    Article  Google Scholar 

  • Tournassat, C., Ferrage, E., Poinsignon, C., and Charlet, L. (2004) The titration of clay minerals II. Structure-based model and implications for clay reactivity. Journal of Colloid and Interface Science, 273, 234–246.

    Article  Google Scholar 

  • van Olphen, H. (1977) An Introduction to Clay Colloid Chemistry. Interscience Publishers, New York.

    Google Scholar 

  • Viani, B.E., Low, P.F., and Roth, C.B. (1983) Direct measurement of the relation between interlayer force and interlayer distance in the swelling of montmorillonite. Journal of Colloid and Interface Science, 96, 229–244.

    Article  Google Scholar 

  • Wilson, J., Cuadros, J., and Cressey, G. (2004) An in situ time-resolved XRD-PSD investigation into Na-montmorillonite interlayer and particle rearrangement during dehydration. Clays and Clay Minerals, 52, 180–191.

    Article  Google Scholar 

  • Yuwono, V.M., Burrows, N.D., Soltis, J.A., and Penn, R.L. (2010) Oriented aggregation: Formation and transformation of mesocrystal intermediates revealed. Journal of the American Chemical Society, 132, 2163–2165.

    Article  Google Scholar 

  • Zhang, F., Zhang, Z.Z., Low, P.F., and Roth, C.B. (1993) The effect of temperature on the swelling of montmorillonite. Clay Minerals, 28, 25–31.

    Article  Google Scholar 

  • Zhang, F.S., Low, P.F., and Roth, C.B. (1995) Effects of monovalent, exchangeable cations and electrolytes on the relation between swelling pressure and interlayer distance in montmorillonite. Journal of Colloid and Interface Science, 173, 34–1578.

    Article  Google Scholar 

Download references

Author information

Author notes

  1. Equal co-authors

Authors and Affiliations

  1. Energy Geoscience Division, Lawrence Berkeley National Laboratory, Berkeley, USA

    Benjamin Gilbert, Ruth M. Tinnacher & Jillian F. Banfield

  2. Life Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA

    Luis R. Comolli

  3. Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, USA

    Martin Kunz

  4. Earth and Planetary Sciences, University of California — Berkeley, Berkeley, USA

    Jillian F. Banfield

Authors
  1. Benjamin Gilbert
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Luis R. Comolli
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Ruth M. Tinnacher
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Martin Kunz
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jillian F. Banfield
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jillian F. Banfield.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gilbert, B., Comolli, L.R., Tinnacher, R.M. et al. Formation and Restacking of Disordered Smectite Osmotic Hydrates. Clays Clay Miner. 63, 432–442 (2015). https://doi.org/10.1346/CCMN.2015.0630602

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1346/CCMN.2015.0630602

Key Words

Search

Navigation