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Characterization of Organo-Bentonites Obtained from Different Linear-Chain Quaternary Alkylammmonium Salts

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Clays and Clay Minerals

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.

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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).

    Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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).

    Google Scholar 

  • 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).

    Google Scholar 

  • 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.

    Google Scholar 

  • 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.

    Google Scholar 

  • 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.

    Article  Google Scholar 

  • Faci, H. (2001) Open gear lubricants. US Patent 6251839.

    Google Scholar 

  • Favre, H. and Lagaly, G. (1991) Organo-bentonites with quaternary alkylammonium ions. Clay Minerals, 26, 19–32.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • Kirsner, J., Miller, J., and Bracken, J. (2003) Additive for oil- based drilling fluids. US Patent 6620770.

    Google Scholar 

  • 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.

    Article  Google Scholar 

  • Klapyta, Z., Gawel, A., Fujita, T., and Iyi, N. (2003) Structural heterogeneity of alkylammonium-exchanged, synthetic fluorotetrasilicic mica. Clay Minerals, 38, 151–160.

    Article  Google Scholar 

  • Lagaly, G. (1986) Interaction of alkylamines with different types of layered compounds. Solid State Ionics, 22, 43–51.

    Article  Google Scholar 

  • 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.

    Google Scholar 

  • Lan, T. and Pinnavaia, T.J. (1994) Clay-reinforced epoxy nanocomposites. Chemistry of Materials, 6, 2216–2219.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • Liu, W., Hoa, S.V., and Pugh, M. (2005) Organoclay-modied high performance epoxy nanocomposites. Composites Science and Technology, 65, 307–316.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • Medrzycka, K. and Zwierzykowski, W. (2000) Adsorption of alkyltrimethylammonium bromides at the various interfaces. Journal of Colloid and Interface Science, 230, 67–72.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Google Scholar 

  • Paiva, L.B., Morales, A.R., and Diaz, F.R.V. (2008) Organoclays: properties, preparation and applications. Applied Clay Science, 42, 8–24.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Google Scholar 

  • 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.

    Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Google Scholar 

  • Tjandra, W., Yao, J., and Tam, K.C. (2006) Interaction between silicates and ionic surfactants in dilute solution. Langmuir, 22, 1493–1499.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • Vougaris, D. and Petridis, D. (2002) Emulsifying effect of dimethyldioctadecylammonium-hectorite in polystyrene/ poly(ethyl methacrylate) blends. Polymer, 43, 2213–2218.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Google Scholar 

  • Yang, L., Jiang, L., Zhou, Z., Chen, Y., and Wang, X. (2002) The sedimentation capabilities of hexadecyltrimethylammonium-modied montmorillonites. Chemosphere, 48, 461–466.

    Article  Google Scholar 

  • Yilmaz, N. and Yapar, S. (2004) Adsorption properties of tetradecyl- and hexadecyl trimethylammonium bentonites. Applied Clay Science, 27, 223–228.

    Article  Google Scholar 

  • Zhu, L., Li, Y., and Zhang, J. (1997) Sorption of organobentonites to some organic pollutants in water. Environmental Science and Technology, 31, 1407–1410.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

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Correspondence to Ïbrahim Alp.

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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

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  • DOI: https://doi.org/10.1346/CCMN.2010.0580607

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