Abstract
The effects of surfactants on bentonites have been of great scientific interest for many years. Even though quaternary alkylammonium salts (QAS) have been studied, very few data are available on the comparative performance of different chain-length QAS for the modification of the surface properties and adsorption properties of bentonites. The objective of this study was to investigate the effect of chain length on the adsorption of cationic surfactants onto bentonite. The surface and adsorption properties of different chain-length QAS, i.e. hexadecyltrimethylammonium bromide (HTAB, C16), tetradecyltrimethylammonium bromide (TTAB, C14), and dodecyltrimethylammonium bromide (DTAB, C12), to produce organo- bentonites (OB) were studied. The concentrations of QAS were selected based on the cation exchange capacity (CEC) of the clay mineral. Zeta potential, swelling, and viscosity measurements and scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier-transform infrared (FTIR) analyses were used to explain the changes in surface properties. The results indicated that the best modification of bentonite was obtained using a 16-carbon chain length QAS (HTAB) in a 1:1 ratio of QAS to CEC. The basal spacing at this concentration was measured to be 22.19 A, which also corresponded to the maximum adsorption density. The OB produced at this concentration showed the best hydrophobic character based on the swelling tests in toluene. The extent of hydrophobicity and adsorption density was correlated with the CEC and alkyl chain of the QAS. All these properties were used to elucidate the mechanism of modification governing the bentonite/QAS system.
Similar content being viewed by others
Explore related subjects
Discover the latest articles, news and stories from top researchers in related subjects.References
Akin, Y. and Çelik, M.S. (1995) Electrokinetic behavior of montmorillonite type clays. Pp. 135–142 in: Proceedings of the Industrial Raw Materials Symposium 95 (H. Kose and M.S. Kizil, editors). The Chamber of Mining Engineers of Turkey, izmir, Turkey (in Turkish).
Baldassari, S., Komarneni, S., Mariani, E., and Villa, C. (2006) Microwave versus conventional preparation of organoclays from natural and synthetic clays. Applied Clay Science, 31, 134–141.
Boylu, F., Cinku, K., Cetinel, T., Erkan, I., and Demirer, N. (2007) The separation efficiency of Re§adiye Na+ bentonite by hydrocyclone. Pp. 213–227 in: Proceedings of the 13th National Clay Symposium (M. Ku§cu, O. Cengiz, and E. Çener, editors). Turkish National Committee on Clay Science, Van, Turkey (in Turkish).
Can, F., Erkan, I., Yildiz, E., and Celik, M.S. (2007) Organoclay preparation and characterization from Na+ bentonites modified with cetyl pyridinium chloride (CPC) monohydrate. Pp. 365–377 in: Proceedings of the 13th National Clay Symposium (M. Ku§cu, O. Cengiz, and E. Çener, editors). Turkish National Committee on Clay Science, Van, Turkey (in Turkish).
Erkan, I. (2008) Amine modification of Re§adiye bentonite and preparation of epoxy based nanocomposite (in Turkish). MSc thesis, Karadeniz Technical University, Trabzon, Turkey, 125 pp.
Erkan, I., Alp, I., Can, F.C., Karaka§, F., Celik, M.S., and Yüzer, H. (2008) Adsorption, rheology and electrokinetic properties of organo modified sodium bentonites from Re§adiye region. Pp. 743–748 in: Proceedings of the 11th International Mineral Processing Symposium (G. Ozbayoğlu, A.Ï. Arol, Ç. Hoşten, and Ü. Atalay, editors). Turkish Mining Development Foundation, Antalya, Turkey.
Ersoy, B. and Celik, M.S. (2003) Effect of hydrocarbon chain length on adsorption of cationic surfactants onto clinoptilolite. Clays and Clay Minerals, 51, 173–181.
Faci, H. (2001) Open gear lubricants. US Patent 6251839.
Favre, H. and Lagaly, G. (1991) Organo-bentonites with quaternary alkylammonium ions. Clay Minerals, 26, 19–32.
Forland, G.M. and Blokhus, A.M. (2007) Adsorption of phenol and benzyl alcohol onto surfactant modied silica. Journal of Colloid and Interface Science, 310, 431–435.
Frost, R., Xi, Y., and He, H. (2007) Modification of the surfaces of Wyoming montmorillonite by the cationic surfactants alkyl trimethyl, dialkyl dimethyl and trialkyl methyl ammonium bromides. Journal of Colloid and Interface Science, 305, 150–158.
Gorassi, G., Tortora, M., Vittoria, V., Kaempfer, D., and Miilhaupt, R. (2003) Transport properties of organic vapor in nanocomposites of organophilic layered silicate and syndiotactic polypropylene. Polymer, 44, 3679–3685.
Ïşçι, S., Ece, O.I., and Giingor, N. (2006) Characterization of rheology, electrokinetic properties, and surface micromorphology of DTABr-MMT and CPBr-MMT organoclays. Journal of Composite Materials, 40, 1105–1115.
Kirsner, J., Miller, J., and Bracken, J. (2003) Additive for oil- based drilling fluids. US Patent 6620770.
Klapyta, Z., Fujita, T., and Iyi, N. (2001) Adsorption of dodecyl- and octadecyltrimethylammonium ions on a smectite and synthetic micas. Applied Clay Science, 19, 5–10.
Klapyta, Z., Gawel, A., Fujita, T., and Iyi, N. (2003) Structural heterogeneity of alkylammonium-exchanged, synthetic fluorotetrasilicic mica. Clay Minerals, 38, 151–160.
Lagaly, G. (1986) Interaction of alkylamines with different types of layered compounds. Solid State Ionics, 22, 43–51.
Lagaly, G., Ogawa, M., and Dekany, I. (2006) Clay Mineral Organic Interactions. Pp. 309–377 in: Handbook of Clay Science, Developments in Clay Science, Vol.1 (F. Bergaya, B.K.G. Theng, and G. Lagaly, editors). Elsevier, Amsterdam.
Lan, T. and Pinnavaia, T.J. (1994) Clay-reinforced epoxy nanocomposites. Chemistry of Materials, 6, 2216–2219.
Lee, J.F., Crum, J.R., and Boyd, S.A. (1989) Enhanced retention of organic contaminants by soils exchanged with organic cations. Environmental Science and Technology, 23, 1365–1372.
Liu, W., Hoa, S.V., and Pugh, M. (2005) Organoclay-modied high performance epoxy nanocomposites. Composites Science and Technology, 65, 307–316.
Marras, S.I., Tsimpliaraki, A., Zuburtikudis, I., and Panayiotou, C. (2007) Thermal and colloidal behavior of amine-treated clays: The role of amphiphilic organic cation concentration. Journal of Colloid and Interface Science, 315, 520–527.
Medrzycka, K. and Zwierzykowski, W. (2000) Adsorption of alkyltrimethylammonium bromides at the various interfaces. Journal of Colloid and Interface Science, 230, 67–72.
Mohammad, A. and Bhawani S.A. (2008) LC separation of coexisting cetylpyridinium chloride, tetradecyltrimethylammonium bromide and dodecyltrimethylammonium bromide on silica TLC plates with aqueous-organic eluents. Chromatographia, 67, 659–663.
Nuntiya, A., Sompech, S., Aukkaravittayapun, S., and Pumchusak, J. (2008) The effect of surfactant concentration on the interlayer structure of organoclay. Chiang Mai Journal of Science, 35, 199–205.
Paiva, L.B., Morales, A.R., and Diaz, F.R.V. (2008) Organoclays: properties, preparation and applications. Applied Clay Science, 42, 8–24.
Patel, H.A., Somani, R.S., Bajaj, H.C., and Jasra, R.V. (2006) Nanoclays for polymer nanocomposites, paints, inks, greases and cosmetics formulations, drug delivery vehicle and waste water treatment. Bulletin of Materials Science, 29, 2, 133–145.
Reid, V.W., Longman, G.F., and Heinerth, E. (1967) Determination of anionic active detergents by two phase titration. Tenside Surfactants Detergents, 4, 292–304.
Sabah, E., Kara, M., Hancer, M., and Celik, M.S. (1998) Adsorption mechanism of organic and inorganic ions by a clay absorbent: sepiolite, Preprint No. 98–152 in: SME Annual Meeting, Florida.
Sabah, E., Mart, U., Cinar, M., and Celik, M.S. (2007) Zeta potentials of sepiolite suspensions in concentrated monovalent electrolytes. Separation Science and Technology, 42, 2275–2288.
Smith, J.A., Jaffe, P.R., and Chlou, C.T. (1990) Effect of ten quaternary ammonium cations on tetrachloromethane sorption to clay from water. Environmental Science and Technology, 24, 1167–1172.
Somasundaran, P., Healy, T.W., and Fuerstenau, D.W. (1964) Surfactant adsorption at the solid-liquid interface-dependence of mechanism on chain length. The Journal of Physical Chemistry, 68, 3562–3566.
Sompech, S., Nuntiya, A., Aukkaravittayapun, S., and Pumchusak, J. (2008) Interlayer expansion of organoclay by cationic surfactant. Chiang Mai University Journal of Natural Science Special Issue on Nanotechnology, 7, 89–93.
Tjandra, W., Yao, J., and Tam, K.C. (2006) Interaction between silicates and ionic surfactants in dilute solution. Langmuir, 22, 1493–1499.
Vazquez, A., Lopez, M., Kortaberria, G., Martin, L., and Mondragon, I. (2008) Modification of montmorillonite with cationic surfactants. Thermal and chemical analysis including CEC determination. Applied Clay Science, 41, 24–36.
Vougaris, D. and Petridis, D. (2002) Emulsifying effect of dimethyldioctadecylammonium-hectorite in polystyrene/ poly(ethyl methacrylate) blends. Polymer, 43, 2213–2218.
Xi, Y., Martens, X., He, H., and Frost, R.L. (2005) Thermogravimetric analysis of organoclays intercalated with the surfactant octadecyltrimethylammonium bromide. Journal of Thermal Analysis and Calorimetry, 81, 91–97.
Xie, W., Gao, Z., Liu, K., Pan, W.-P., Vaia, R., Hunter, D., and Singh, A. (2001) Thermal characterization of organically modified montmorillonite. Thermochimica Acta, 367–368, 339–350.
Yang, L., Jiang, L., Zhou, Z., Chen, Y., and Wang, X. (2002) The sedimentation capabilities of hexadecyltrimethylammonium-modied montmorillonites. Chemosphere, 48, 461–466.
Yilmaz, N. and Yapar, S. (2004) Adsorption properties of tetradecyl- and hexadecyl trimethylammonium bentonites. Applied Clay Science, 27, 223–228.
Zhu, L., Li, Y., and Zhang, J. (1997) Sorption of organobentonites to some organic pollutants in water. Environmental Science and Technology, 31, 1407–1410.
Zhu, L., Zhu, R., Xu, L., and Ruan, X. (2007) Influence of clay charge densities and surfactant loading amount on the microstructure of CTMA-montmorillonite hybrids. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 304, 41–48.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Erkan, Ï., Alp, Ï. & Çelik, M.S. Characterization of Organo-Bentonites Obtained from Different Linear-Chain Quaternary Alkylammmonium Salts. Clays Clay Miner. 58, 792–802 (2010). https://doi.org/10.1346/CCMN.2010.0580607
Received:
Revised:
Published:
Issue Date:
DOI: https://doi.org/10.1346/CCMN.2010.0580607