Hostname: page-component-7dd5485656-hw7sx Total loading time: 0 Render date: 2025-10-31T03:34:00.372Z Has data issue: false hasContentIssue false
  • English
  • Français

Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance

Published online by Cambridge University Press:  01 January 2024

A. E. Blum  and
D. D. Eberl
A. E. Blum*
Affiliation:
US Geological Survey, 3215 Marine St., Boulder, CO 80303, USA
D. D. Eberl
Affiliation:
US Geological Survey, 3215 Marine St., Boulder, CO 80303, USA
*
*E-mail address of corresponding author: aeblum@usgs.gov
Get access Rights & Permissions [Opens in a new window]

Abstract

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ∼0.99 mg/m2, which corresponds to ∼0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (∼725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

Keywords

ClayIlliteIntercalationMontmorillonitePolyvinylpyrrolidonePVPQuantitative MineralogySmectiteSurface Area

Information

Type
Research Article
Information
Clays and Clay Minerals , Volume 52 , Issue 5 , October 2004 , pp. 589 - 602
Copyright
Copyright © 2004, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

Footnotes

An erratum to this article is available online at https://doi.org/10.1346/CCMN.2011.0590210.

References

Aylmore, L.A.G. and Quirk, J.P., (1967) The micropore size distributions of clay mineral systems Journal of Soil Science 18 1–17 10.1111/j.1365-2389.1967.tb01481.x.10.1111/j.1365-2389.1967.tb01481.xCrossRefGoogle Scholar
Barnett, K.G. Cosgrove, T. Vincent, B. and Sissons, D.S., (1981) Measurement of the polymer-bound fraction at the solid-liquid interface by pulsed nuclear magnetic resonance Macromolecules 1981 1018–1020 10.1021/ma50005a023.10.1021/ma50005a023CrossRefGoogle Scholar
Blum, A.E., Nagy, K. and Blum, A., (1994) Determination of illite/smectite particle morphology using scanning force microscopy Scanning Probe Microscopy of Clay Minerals Boulder, Colorado Clay Minerals Society 171–202.10.1346/CMS-WLS-7.4CrossRefGoogle Scholar
Blum, A.E. and Eberl, D.D., (1992) Determination of clay particle thicknesses and morphology using Scanning Force Microscopy Proceedings of the 7th International Symposium on Water-Rock Interaction, Utah. A.A Rotterdam Balkema 133–136.Google Scholar
Chiou, C.T. and Rutherford, D.W., (1997) Effects of exchanged cation and layer charge on the sorption of water and EGME vapors on montmorillonite clays Clays and Clay Minerals 45 867–880 10.1346/CCMN.1997.0450611.10.1346/CCMN.1997.0450611CrossRefGoogle Scholar
Cihacek, L.J. and Bremner, J.M., (1975) A simplified ethylene glycol monoethyl ether procedure for assessment of soil surface area Soil Science Society of America Journal 43 821–822 10.2136/sssaj1979.03615995004300040045x.10.2136/sssaj1979.03615995004300040045xCrossRefGoogle Scholar
Cohen Stuart, M.A. Fleer, G.J. and Scheutjens, JMHM, (1984) Displacement of polymers. II. Experiment. Determination of segmental sorption energy of poly(vinyl-pyrrolidone) on silica Journal of Colloid and Interface Science 97 526–535 10.1016/0021-9797(84)90324-2.10.1016/0021-9797(84)90324-2CrossRefGoogle Scholar
Drits, V.A. Eberl, D.D. and Środoń, J., (1998) XRD measurement of mean thickness, thickness distribution and strain for illite and illite-smectite crystallites by the Bertaut-Warren-Averbach technique Clays and Clay Minerals 46 38–50 10.1346/CCMN.1998.0460105.10.1346/CCMN.1998.0460105CrossRefGoogle Scholar
Dudek, T. Środoń, J. Eberl, D.D. Elsass, F. and Uhlík, P., (2002) Thickness distribution of illite crystals in shales. 1: X-ray diffraction vs. high-resolution transmission electron microscopy measurements Clays and Clay Minerals 50 562–577 10.1346/000986002320679305.10.1346/000986002320679305CrossRefGoogle Scholar
Eberl, D.D., Drits, V.A., Środoń, J. and Nüesch, R. (1996) MUDMASTER; a program for calculating crystallite size distributions and strain from the shapes of X-ray diffraction peaks. US Geological Survey Open File Report 96-0171.Google Scholar
Eberl, D.D. Nüesch, R. Šuchá, V. and Tsipursky, S., (1998) Measurement of fundamental illite particle thicknesses by X-ray diffraction using PVP-10 intercalation Clays and Clay Minerals 46 89–97 10.1346/CCMN.1998.0460110.10.1346/CCMN.1998.0460110CrossRefGoogle Scholar
Esumi, K. and Oyama, M., (1993) Simultaneous sorption of poly(vinylpyrrolidone) and cationic surfactant from their mixed solutions on silica Langmuir 9 2020–2023 10.1021/la00032a021.10.1021/la00032a021CrossRefGoogle Scholar
Esumi, K. Takaku, Y. and Otsuka, H., (1994) Interaction between aerosol OT and poly(vinylpyrrolidone) on alumina Langmuir 10 3250–3254 10.1021/la00021a057.10.1021/la00021a057CrossRefGoogle Scholar
Esumi, K. Iitaka, M. and Torigoe, K., (2000) Kinetics of simultaneous sorption of poly(vinylpyrrolidone)and sodium dodecyl sulfate on alumina particles Journal of Colloid and Interface Science 232 71–75 10.1006/jcis.2000.7188.10.1006/jcis.2000.7188CrossRefGoogle Scholar
Frances, C.W., (1973) Sorption of polyvinylpyrrolidone on reference clay minerals Soil Science 115 40–54 10.1097/00010694-197301000-00007.10.1097/00010694-197301000-00007CrossRefGoogle Scholar
Gargallo, L. Peírez-Cotapos, J. Santos, J.G. and Radic, D., (1993) Poly(N-vinyl-2-pyrrolidone)-monoalkyl xanthates. 1. Sorption and chemical reaction Langmuir 9 681–684 10.1021/la00027a012.10.1021/la00027a012CrossRefGoogle Scholar
Gultek, A. Seckin, T. Onal, Y. and Ickuygu, M.G., (2001) Preparation and phenol captivating properties of polyvinylpyrrolidone montmorillonite hybrid materials Journal of Applied Polymer Science 81 512–519 10.1002/app.1465.10.1002/app.1465CrossRefGoogle Scholar
Gun’ko, V.M. Zarko, E.F. Voroin, E.F. Turov, V.V. Mironyu, I.F. Gerashchenko, I.I. Goncharuk, E.V. Pakhlov, E.M. Guzenko, N.V. Leboda, R. Skubiszewska-Zieba, J. Janusz, W. Chibowski, S. Levchunk, Y.N. and Klyueva, A.V., (2002) Impact of some organics on structural and sorptive characteristics of fumed silica in different media Langmuir 18 581–596 10.1021/la0103867.10.1021/la0103867CrossRefGoogle Scholar
Haung, C.P. and Stumm, W., (1973) Specific sorption of cations on hydrous α-Al2O3 Journal of Colloid and Interface Science 22 231–259.Google Scholar
Israel, L. Guler, C. Yilmaz, H. and Guler, S., (2001) The sorption of polyvinylpyrrolidone on kaolinite with sodium chloride Journal of Colloid and Interface Science 238 80–84 10.1006/jcis.2001.7465.10.1006/jcis.2001.7465CrossRefGoogle Scholar
Jackson, M.L., (1985) Soil Chemical Analysis — Advanced Course 2nd Madison, Wisconsin Published by the author.Google Scholar
Kennedy, M.J. Pevear, D.R. and Hill, R.J., (2002) Mineral surface control of organic carbon in black shale Science 295 657–660 10.1126/science.1066611.10.1126/science.1066611CrossRefGoogle ScholarPubMed
Levy, R. and Francis, C.W., (1975) Interlayer sorption of polyvinylpyrrolidone on montmorillonite Journal of Colloid and Interface Science 50 442–450 10.1016/0021-9797(75)90167-8.10.1016/0021-9797(75)90167-8CrossRefGoogle Scholar
Levy, R. and Francis, C.W., (1975) A quantitative method for the determination of montmorillonite in soils Clays and Clay Minerals 23 85–89 10.1346/CCMN.1975.0230201.10.1346/CCMN.1975.0230201CrossRefGoogle Scholar
May, H.M. Kinniburgh, D.G. Helmke, P.A. and Jackson, M.L., (1986) Aqueous dissolution, solubilities and thermodynamic stabilities of common aluminosilicate clay minerals; kaolinite and smectites Geochimica et Cosmochimica Acta 50 1667–1677 10.1016/0016-7037(86)90129-8.10.1016/0016-7037(86)90129-8CrossRefGoogle Scholar
Misselyn-Bauduin, A. Thibaut, A. Grandjean, J. Broze, G. and Jérôme, R., (2001) Investigation of the interactions of polyvinylpyrrolidone with mixtures of anionic and nonionic surfactants or anionic and zwitterionic surfactant by pulsed field gradient NMR Journal of Colloid and Interface Science 238 1–7 10.1006/jcis.2001.7451.10.1006/jcis.2001.7451CrossRefGoogle ScholarPubMed
Moore, D.M. and Reynolds, R.C. Jr., (1989) X-ray Diffraction and the Identification and Analysis of Clay Minerals New York Oxford University Press 332 pp.Google Scholar
Nadeau, P.H., (1985) The physical dimensions of fundamental clay particles Clay Minerals 20 499–514 10.1180/claymin.1985.020.4.06.10.1180/claymin.1985.020.4.06CrossRefGoogle Scholar
Nadeau, P.H. Wilson, M.J. McHardy, W.J. and Tait, J.M., (1984) Interstratified clays as fundamental particles Science 225 923–925 10.1126/science.225.4665.923.10.1126/science.225.4665.923CrossRefGoogle ScholarPubMed
Otsuka, H. and Esumi, K., (1994) Simultaneous sorption of poly(vinylpyrrolidone) and anionic hydrocarbon/fluorocarbon surfactant from their binary mixtures on alumina Langmuir 10 45–50 10.1021/la00013a006.10.1021/la00013a006CrossRefGoogle Scholar
Quirk, J.P. and Murray, R.S., (1999) Appraisal of the ethylene glycol monoethyl ether method for measuring the hydratable surface area of clays and soils Soil Science Society of America Journal 63 839–849 10.2136/sssaj1999.634839x.10.2136/sssaj1999.634839xCrossRefGoogle Scholar
Robie, R.A., Hemingway, B.S. and Fisher, J.R. (1979) Thermodynamic properties of mineral and related substances at 298.15 K and 1 bar pressure and at higher temperatures. US Geological Survey Bulletin, 1452.Google Scholar
Rovira-Bru, M. Giralt, F. and Cohen, Y., (2001) Protein sorption onto zirconia modified with terminally grafted polyvinylpyrrolidone Journal of Colloid and Interface Science 235 70–79 10.1006/jcis.2000.7355.10.1006/jcis.2000.7355CrossRefGoogle Scholar
Rutherford, D.W. Chiou, C.T. and Eberl, D.D., (1997) Effects of exchanged cation on the microporosity of montmorillonite Clays and Clay Minerals 45 534–543 10.1346/CCMN.1997.0450405.10.1346/CCMN.1997.0450405CrossRefGoogle Scholar
Sequaris, J.-M. Hind, A. Narres, H.D. and Schwuger, M.J., (2000) Polyvinylpyrrolidone sorption on Na-montmorillonite. Effect of the polymer interfacial conformation on the behavior and binding of chemicals Journal of Colloid and Interface Science 230 73–83 10.1006/jcis.2000.7046.10.1006/jcis.2000.7046CrossRefGoogle Scholar
Sequaris, J.-M. Decimavilla, S.C. and Ortega, J.A.C., (2002) Polyvinylpyrrolidone sorption and structural studies on homoioic Li-, Na-, K- and Cs-montmorillonite colloidal suspensions Journal of Colloid and Interface Science 252 93–101 10.1006/jcis.2002.8422.10.1006/jcis.2002.8422CrossRefGoogle Scholar
Smith, J.N. Meadows, J. and Williams, P.A., (1996) Sorption of polyvinylpyrrolidone onto polystyrene lattices and the effect on colloid stability Langmuir 12 3773–3778 10.1021/la950933m.10.1021/la950933mCrossRefGoogle Scholar
Środoń, J. Elsass, F. McHardy, W.J. and Morgan, D.J., (1992) Chemistry of illite-smectite inferred from TEM measurements of fundamental particles Clay Minerals 27 137–158 10.1180/claymin.1992.027.2.01.10.1180/claymin.1992.027.2.01CrossRefGoogle Scholar
Środoń, J. Drits, V.A. McCarty, D.K. Hsieh, J.C.C. and Eberl, D.D., (2001) Quantitative X-ray diffraction analysis of clay-bearing rocks from random preparations Clays and Clay Minerals 49 514–528 10.1346/CCMN.2001.0490604.10.1346/CCMN.2001.0490604CrossRefGoogle Scholar
Sun, T. and King, H.E., (1996) Aggregation behavior in the semidilute poly(N-vinyl-2-pyrrolidone)/water system Macromolecules 29 3175–3181 10.1021/ma951734c.10.1021/ma951734cCrossRefGoogle Scholar
Thibaut, A. Misselyn-Bauduin, A.M. Broze, G. and Jerome, R., (2000) Sorption of poly(vinylpyrrolidone)/surfactant(s) mixtures at the silica/water interface Langmuir 16 9841–9849 10.1021/la000834v.10.1021/la000834vCrossRefGoogle Scholar
Uhlík, P. Šuchá, V. Elsass, F. and Čaplovičová, M., (2000) High-resolution transmission electron microscopy of mixed-layer clays dispersed in PVP-10; A new technique to distinguish detrital and authigenic illitic material Clay Minerals 35 781–789 10.1180/000985500547232.CrossRefGoogle Scholar