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The Effect of Added Polymers on n-Butylammonium Vermiculite Swelling

Published online by Cambridge University Press:  28 February 2024

M. V. Smalley ,
H. Jinnai ,
T. Hashimoto  and
S. Koizumi
M. V. Smalley
Affiliation:
Hashimoto Polymer Phasing Project, ERATO, JRDC, Keihanna Plaza, 1–7 Hikari-dai, Seika-cho, Kyoto 619-02, Japan
H. Jinnai
Affiliation:
Hashimoto Polymer Phasing Project, ERATO, JRDC, Keihanna Plaza, 1–7 Hikari-dai, Seika-cho, Kyoto 619-02, Japan
T. Hashimoto
Affiliation:
Hashimoto Polymer Phasing Project, ERATO, JRDC, Keihanna Plaza, 1–7 Hikari-dai, Seika-cho, Kyoto 619-02, Japan Department of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 606, Japan
S. Koizumi
Affiliation:
Neutron Scattering Laboratory, Department of Materials Science and Engineering, Japan Atomic Energy Research Institute, Tokai-mura 319-11, Japan
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Abstract

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A 4-component clay-polymer-salt-water system was studied by neutron scattering. The clay-salt-water system consisted of n-butylammonium vermiculite, n-butylammonium chloride and heavy water, and the volume fraction of clay in the system was held constant, at r = 0.01. Three polymers in the molecular weight range 10,000 to 30,000 were studied, poly(vinyl methyl ether) (PVME), poly (ethylene oxide) (PEO) and poly(acrylic acid) (PAA), at a polymer volume fraction of v = 0.01. The addition of PAA suppressed the clay swelling, irrespective of the salt concentration, c. The addition of the neutral polymers had no effect on the phase transition temperature, Tc, between the gel and tactoid phases of the system, its value remaining at 14 °C for c = 0.1 M and 30 °C for c = 0.01 M. At c = 0.01 M, the neutral polymers also had a negligible effect on the lattice constant d along the swelling axis of the clay colloid, but at c = 0.1 M, the d-value was significantly lower than in the system without added polymer. For a PVME sample of molecular weight 18,000, both d and Tc were measured as a function of ν, for volume fractions between 0 and 0.04. The addition of polymer, up to v = 0.04, had no effect on Tc. However, even for v values as low as 0.001, the vermiculite layers in the gel phase were more parallel and more regularly spaced than in the system without added polymer. In the gel phase, d decreased exponentially as a function of v, from 12 nm at v = 0 to 8 nm at v = 0.04. In the tactoid phase, at T < 14 °C, the d-value in the crystalline regions was equal to 1.94 nm at v = 0 and v = 0.04, showing that the spacing between the vermiculite layers is not affected by the added polymer when they are collapsed by an increase in temperature. The addition of a PVME sample of molecular weight 110,000, at v = 0.001, had no noticeable effect on either d or Tc.

Keywords

Interlayer SpacingsNeutron DiffractionOsmotic SwellingPhase TransitionsPolymersVermiculite Gels
Type
Research Article
Information
Clays and Clay Minerals , Volume 45 , Issue 5 , October 1997 , pp. 745 - 760
Copyright
Copyright © 1997, The Clay Minerals Society

References

Braganza, L.F. Crawford, R.J. Smalley, M.V. and Thomas, R.K., 1990 Swelling of n-butylammonium vermiculite in water Clays Clay Miner 38 90–96 10.1346/CCMN.1990.0380112.CrossRefGoogle Scholar
Brandrup, J. and Immergut, E.H., 1989 Polymer handbook New York J. Wiley.Google Scholar
Crawford, R.J. Smalley, M.V. and Thomas, R.K., 1991 The effect of uniaxial stress on the swelling of n-butylammonium vermiculite Adv Colloid Interface Sci 34 537–560 10.1016/0001-8686(91)80057-Q.CrossRefGoogle Scholar
Fleer, G.J. Cohen Stuart, M.A. Scheutjens, J.M.H.M. Cosgrove, T. and Vincent, B., 1993 Polymers at interfaces London Chapman & Hall.Google Scholar
Garrett, W.G. and Walker, G.F., 1962 Swelling of some vermiculite-organic complexes in water Clays Clay Miner 9 557–567 10.1346/CCMN.1960.0090141.CrossRefGoogle Scholar
Humes, R.P., 1985 Interparticle forces in clay minerals [D. Phil, thesis] Oxford, UK Oxford Univ 140–153.Google Scholar
Jinnai, H. Smalley, M.V. Hashimoto, T. and Koizumi, S., 1996 Neutron scattering study of vermiculite-poly(vinyl methyl ether) mixtures Langmuir 12 1199–1203 10.1021/la9504265.CrossRefGoogle Scholar
Kleijn, W.B. and Oster, J.D., 1982 A model of clay swelling and tactoid formation Clays Clay Miner 30 383–390 10.1346/CCMN.1982.0300509.CrossRefGoogle Scholar
Lagaly, G., 1981 Characterization of clays by organic compounds Clay Miner 16 1–21 10.1180/claymin.1981.016.1.01.CrossRefGoogle Scholar
Low, P.F., 1987 Structural component of the swelling pressure of clays Langmuir 3 18–25 10.1021/la00073a004.CrossRefGoogle Scholar
Norrish, K. and Rausell-Colom, J.A., 1963 Low-angle X-ray diffraction studies of the swelling of montmorillonite and vermiculite Clays Clay Miner 10 123–149 10.1346/CCMN.1961.0100112.CrossRefGoogle Scholar
Rausel-Colom, J.A., 1964 Small-angle X-ray diffraction study of the swelling of butylammonium vermiculite Trans Faraday Soc 60 190–201 10.1039/tf9646000190.CrossRefGoogle Scholar
Rausell-Colom, J.A. Saez-Aunon, J. and Pons, C.H., 1989 Vermiculite gelation: Structural and textural evolution Clay Miner 24 459–478 10.1180/claymin.1989.024.3.01.CrossRefGoogle Scholar
Shibayama, M. and Hashimoto, T., 1986 Small-angle X-ray scattering analyses of lamellar microdomains based on a model of one-dimensional paracrystal with uniaxial orientation Macromolecules 19 740–749 10.1021/ma00157a043.CrossRefGoogle Scholar
Skipper, N.T. Soper, A.K. and Smalley, M.V., 1994 Neutron diffraction study of calcium vermiculite: Hydration of calcium ions in a confined environment J Phys Chem 98 942–945 10.1021/j100054a033.CrossRefGoogle Scholar
Smalley, M.V., 1990 Electrostatic interaction in macroionic solutions and gels Mol Phys 71 1251–1267 10.1080/00268979000102471.CrossRefGoogle Scholar
Smalley, M.V., 1994 Electrical theory of clay swelling Langmuir 10 2884–2891 10.1021/la00021a009.CrossRefGoogle Scholar
Smalley, M.V., 1994 One phase and two phase regions of colloid stability Progr Colloid Polym Sci 97 59–64 10.1007/BFb0115136.CrossRefGoogle Scholar
Smalley, M.V. Thomas, R.K. Braganza, L.F. and Matsuo, T., 1989 Effect of hydrostatic pressure on the swelling of n-butylammonium vermiculite Clays Clay Miner 37 474–478 10.1346/CCMN.1989.0370513.CrossRefGoogle Scholar
Sogami, I.S. Shinohara, T. and Smalley, M.V., 1991 Effective interaction of highly charged plates in an electrolyte Mol Phys 74 599–612 10.1080/00268979100102451.CrossRefGoogle Scholar
Sogami, I.S. Shinohara, T. and Smalley, M.V., 1992 Adiabatic pair potential of highly charged plates in an electrolyte Mol Phys 76 1–19 10.1080/00268979200101121.CrossRefGoogle Scholar
Tanaka, H., 1993 Dynamic interplay between phase separation and wetting in a binary mixture confined in a onedimensional capillary Phys Rev Lett 70 53–56 10.1103/PhysRevLett.70.53.CrossRefGoogle Scholar
Theng, B.K.G., 1979 Formation and properties of clay-polymer complexes Dev Soil Sci 9 37–94.Google Scholar
van Olphen, H., 1977 An introduction to clay colloid chemistry New York J. Wiley 254–255.Google Scholar
Walker, G.F., 1960 Macroscopic swelling of vermiculite crystals in water Nature 187 312–313 10.1038/187312a0.CrossRefGoogle Scholar
Williams, G.D. Moody, K.R. Smalley, M.V. and King, S.M., 1994 The sol concentration effect in n-butylammonium vermiculite swelling Clays Clay Miner 42 614–627 10.1346/CCMN.1994.0420514.CrossRefGoogle Scholar