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Diffusion of H2O in Smectite Gels: Obstruction Effects of Bound H2O Layers

Published online by Cambridge University Press:  01 January 2024

Yoshito Nakashima
Yoshito Nakashima*
Affiliation:
Exploration Geophysics Research Group, National Institute of Advanced Industrial Science and Technology, Central 7, Higashi 1-1-1, Tsukuba, Ibaraki 305-8567, Japan
*
*E-mail address of corresponding author: nakashima.yoshito@aist.go.jp
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Abstract

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In water-rich smectite gels, bound or less mobile H2O layers exist near negatively-charged clay platelets. These bound H2O layers are obstacles to the diffusion of unbound H2O molecules in the porespace, and therefore reduce the H2O self-diffusion coefficient, D, in the gel system as a whole. In this study, the self-diffusion coefficients of H2O molecules in water-rich gels of Na-rich smectites (montmorillonite, stevensite and hectorite) were measured by pulsed-gradient spin-echo proton nuclear magnetic resonance (NMR) to evaluate the effects of obstruction on D. The NMR results were interpreted using random-walk computer simulations which show that unbound H2O diffuses in the gels while avoiding randomly-placed obstacles (clay platelets sandwiched in immobilized bound H2O layers). A ratio (volume of the clay platelets and immobilized H2O layers)/(volume of clay platelets) was estimated for each water-rich gel. The results showed that the ratio was 8.92, 16.9, 3.32, 3.73 and 3.92 for Wyoming montmorillonite (⩽ 5.74 wt.% clay), Tsukinuno montmorillonite (⩽ 3.73 wt.% clay), synthetic stevensite (⩽ 8.97 wt.% clay), and two synthetic hectorite samples (⩽ 11.0 wt.% clay), respectively. The ratios suggest that the thickness of the immobilized H2O layers in the gels is 4.0, 8.0, 1.2, 1.4 and 1.5 nm, respectively, assuming that each clay particle in the gels consists of a single 1 nm-thick platelet. The present study confirmed that the obstruction effects of immobilized H2O layers near the clay surfaces are important in restricting the self-diffusion of unbound H2O in water-rich smectite gels.

Keywords

HectoriteMontmorillonitePorous MediaRandom WalkStevensiteWater
Type
Research Article
Information
Clays and Clay Minerals , Volume 51 , Issue 1 , February 2003 , pp. 9 - 22
Copyright
Copyright © 2003, The Clay Minerals Society

References

Borden, D. and Giese, R.F., (2001) Baseline studies of the Clay Minerals Society source clays: Cation exchange capacity measurements by the ammonia-electrode method Clays and Clay Minerals 49 444–445 10.1346/CCMN.2001.0490510.Google Scholar
Callaghan, P.T., (1991) Principles of Nuclear Magnetic Resonance Microscopy Oxford, UK Oxford University Press 492 pp.Google Scholar
Cebula, D.J. Thomas, R.K. and White, J.W., (1980) Small angle neutron scattering from dilute aqueous dispersions of clay Journal of the Chemical Society, Faraday Transactions 1 76 314–321 10.1039/f19807600314.Google Scholar
Chang, F-RC Skipper, N.T. and Sposito, G., (1998) Monte Carlo and molecular dynamics simulations of electrical double-layer structure in potassium-montmorillonite hydrates Langmuir 14 1201–1207 10.1021/la9704720.Google Scholar
Chipera, S.J. and Bish, D.L., (2001) Baseline studies of the Clay Minerals Society source clays: Powder X-ray diffraction analyses Clays and Clay Minerals 49 398–409 10.1346/CCMN.2001.0490507.Google Scholar
Duval, F.P. Porion, P. and Van Damme, H., (1999) Microscale and macroscale diffusion of water in colloidal gels. A pulsed field gradient and NMR imaging investigation Journal of Physical Chemistry B 103 5730–5735 10.1021/jp9909210.Google Scholar
Duval, F.P. Porion, P. Faugère, A.-M. and Van Damme, H., (2001) An NMR investigation of water self-diffusion and relaxation rates in controlled ionic strength laponite sols and gels Journal of Colloid and Interface Science 242 319–326 10.1006/jcis.2001.7806.Google Scholar
Feinauer, A. and Majer, G., (2001) Diffusion of 23Na and 39K in the eutectic melt Na0.32K0.68 Physical Review B 64 134302 10.1103/PhysRevB.64.134302.Google Scholar
Fripiat, J.J. Cases, J. Francois, M. and Letellier, M., (1982) Thermodynamic and microdynamic behavior of water in clay suspensions and gels Journal of Colloid and Interface Science 89 378–400 10.1016/0021-9797(82)90191-6.Google Scholar
Fripiat, J.J. Letellier, M. and Levitz, P., (1984) Interaction of water with clay surfaces Philosophical Transactions of the Royal Society of London A311 287–299 10.1098/rsta.1984.0029.Google Scholar
Furusawa, T., (1997) Synthesis and utilization of clay minerals Journal of Clay Science Society of Japan 37 112–117 (in Japanese with English abstract).Google Scholar
Grandjean, J. and Laszlo, P., (1989) Multinuclear and pulsed gradient magnetic resonance studies of sodium cations and of water reorientation at the interface of a clay Journal of Magnetic Resonance 83 128 137.Google Scholar
Ichikawa, Y. Kawamura, K. Nakano, M. Kitayama, K. and Kawamura, H., (1999) Unified molecular dynamics and homogenization analysis for bentonite behavior: Current results and future possibilities Engineering Geology 54 21–31 10.1016/S0013-7952(99)00058-7.Google Scholar
Ichikawa, Y. Kawamura, K. Nakano, M. Kitayama, K. Seiki, T. and Theramast, N., (2001) Seepage and consolidation of bentonite saturated with pure- or salt-water by the method of unified molecular dynamics and homogenization analysis Engineering Geology 60 127–138 10.1016/S0013-7952(00)00095-8.Google Scholar
Johnson, C.S. Jr., Grant, D.M. and Harris, R.K., (1996) Diffusion measurements by magnetic field gradient method Encyclopedia of Nuclear Magnetic Resonance New York John Wiley & Sons 1626 1644.Google Scholar
Kasama, T. Murakami, T. Kohyama, N. and Watanabe, T., (2001) Experimental mixtures of smectite and rectorite: Reinvestigation of ‘fundamental particles’ and ‘interparticle diffraction’ American Mineralogist 86 105–114 10.2138/am-2001-0111.Google Scholar
Latour, L.L. Kleinberg, R.L. Mitra, P.P. and Sotak, C.H., (1995) Pore-size distributions and tortuosity in heterogeneous porous media Journal of Magnetic Resonance A112 83–91 10.1006/jmra.1995.1012.Google Scholar
Mermut, A.R. and Cano, A.F., (2001) Baseline studies of the Clay Minerals Society source clays: Chemical analyses of major elements Clays and Clay Minerals 49 381–386 10.1346/CCMN.2001.0490504.Google Scholar
Mills, R., (1973) Self-diffusion in normal and heavy water in the range 1–45° Journal of Physical Chemistry 77 685–688 10.1021/j100624a025.Google Scholar
Monma, T. Kudo, M. and Masuko, T., (1997) Flow behaviors of smectite/water suspensions in terms of particle-coagulated structures Journal of the Clay Science Society of Japan 37 47–57 (in Japanese with English abstract).Google Scholar
Nakashima, Y., (2000) Effects of clay fraction and temperature on the H2O self-diffusivity in hectorite gel: A pulsed-field-gradient spin-echo nuclear magnetic resonance study Clays and Clay Minerals 48 603–609 10.1346/CCMN.2000.0480602.Google Scholar
Nakashima, Y., (2001) Pulsed field gradient proton NMR study of the self-diffusion of H2O in montmorillonite gel: Effects of temperature and water fraction American Mineralogist 86 132–138 10.2138/am-2001-0114.Google Scholar
Nakashima, Y. (2001b) Measurement of the water self-diffusivity in clay gels by nuclear magnetic resonance. Abstract of the Joint Meeting of Earth and Planetary Science (http://mc-net.jtbcom.co.jp/earth2001/session/pdf/mm/mm-p002_e.pdf).Google Scholar
Nakashima, Y., (2002) Effects of the pore size on proton transverse relaxation times: Laboratory experiments for the nuclear magnetic resonance logging BUTSURI-TANSA (Geophysical Exploration) 55 5–18 (in Japanese with English abstract).Google Scholar
Nakashima, Y., (2002) Self-diffusion of H2O in stevensite gel: Effects of temperature and clay fraction Clay Minerals 37 83–91 10.1180/0009855023710019.Google Scholar
Nakashima, Y., (2002) Measurement of H2O self-diffusion coefficients in clay gels by pulsed-field-gradient nuclear magnetic resonance: A review (in Japanese with English abstract) Journal of the Clay Science Society of Japan 42 37 50.Google Scholar
Nakashima, Y., (2002) Diffusion of H2O and I− in expandable mica and montmorillonite gels: Contribution of bound H2O Clays and Clay Minerals 50 1–10 10.1346/000986002761002603.Google Scholar
Nakashima, Y. Mitsumori, F. Nakashima, S. and Takahashi, M., (1999) Measurement of self-diffusion coefficients of water in smectite by stimulated echo 1H nuclear magnetic resonance imaging Applied Clay Science 14 59–68 10.1016/S0169-1317(98)00049-0.Google Scholar
Ohtaki, H. and Radnai, T., (1993) Structure and dynamics of hydrated ions Chemical Reviews 93 1157–1204 10.1021/cr00019a014.Google Scholar
Stauffer, D., (1985) Introduction to Percolation Theory London Taylor & Francis 10.4324/9780203211595 124 pp.Google Scholar
Stejskal, E.O. and Tanner, J.E., (1965) Spin diffusion measurements: Spin echos in the presence of a time-dependent field gradient Journal of Chemical Physics 42 288–292 10.1063/1.1695690.Google Scholar
Suzuki, S. Fujishima, A. Ueno, K. Ichikawa, Y. Kawamura, K. Fujii, N. Shibata, M. Sato, H. and Kitayama, K., (2001) Microstructural modeling of compacted sodium-bentonite and application of unified molecular dynamics/homogenization analysis for diffusion process Journal of the Clay Science Society of Japan 41 43–57 (in Japanese with English abstract).Google Scholar
Tokita, M. Miyoshi, T. Takegoshi, K. and Hikichi, K., (1996) Probe diffusion in gels Physical Review E 53 1823–1827 10.1103/PhysRevE.53.1823.Google Scholar
Watanabe, Y. and Nakashima, Y., (2002) RW3D.m: Three-dimensional random walk program for the calculation of the diffusivities in porous media Computers & Geosciences 28 583–586 10.1016/S0098-3004(01)00057-7.Google Scholar
Yong, R.N., (1999) Overview of modeling of clay microstructure and interactions for prediction of waste isolation barrier performance Engineering Geology 54 83–91 10.1016/S0013-7952(99)00064-2.Google Scholar
Yu, J.W. and Neretnieks, I., (1997) Diffusion and sorption properties of radionuclides in compacted bentonite SKB Technical Report 97–12 1–98 (Swedish Nuclear Fuel and Waste Management Co.).Google Scholar
Zhou, J. Lu, X. Wang, Y. and Shi, J., (2002) Molecular dynamics study on ionic hydration Fluid Phase Equilibria 194 257–270 10.1016/S0378-3812(01)00694-X.Google Scholar