Skip to main content

Identification and Quantification of the Interaction Mechanisms Between the Cationic Surfactant HDTMA-Br and Montmorillonite


Several detailed studies have been done on the characterization of organoclays and the type of structures developed when they interact with alkylammonium molecules. Few published contributions exist, however, on the distribution of surfactant within the organoclays and the mechanism by which they are intercalated. Also, although X-ray photoelectron spectroscopy (XPS) is a suitable technique for the study of the surface characteristics of organoclays, very few such XPS studies have been carried out. With the aim of contributing to a better understanding of the intercalation process, a series of organoclays was synthesized using a montmorillonite and the cationic surfactant hexadecyltrimethylammonium bromide (HDTMABr), with an increasing surfactant load of between 0.2 and 4.0 times the cation exchange capacity of the starting clay. By means of XPS, zeta potential, and thermal analysis techniques, distinguishing the strongly interacting fraction from the weakly interacting fraction of the adsorbed surfactant molecules was possible. Adsorption isotherms of each of these processes were constructed and then adjusted using the Langmuir and Dubinin-Radusquevich adsorption models. Three types of interaction between the surfactant and the clay were identified and described qualitatively and quantitatively. Two of these interactions, strong and weak, involved the hexadecyltrimethylammonium cation (HDTMA+). The third was a weak interaction involving the ion pair HDTMA+Br. The results of this study may be useful for the comprehensive design of organoclays with specific physicochemical properties according to the application for which they are destined.

This is a preview of subscription content, access via your institution.


  • Akçay, G., Akçay, M., and Yurdakoç, K. (2006) The characterization of prepared organomontmorillonite (DEDMAM) and sorption of phenoxyalkanoic acid herbicides from aqueous solution. Journal of Colloid and Interface Science, 296, 428–433.

    Article  Google Scholar 

  • Azejjel, H., del Hoyo, C., Draoui, K., Rodríguez-Cruz, M.S., and Sánchez-Martín, M.J. (2009) Natural and modified clays from Morocco as sorbents of ionizable herbicides in aqueous medium. Desalination, 249, 1151–1158.

    Article  Google Scholar 

  • Bilgiç, C. (2005) Investigation of the factors affecting organic cation adsorption on some silicate minerals. Journal of Colloid and Interface Science, 281, 33–38.

    Article  Google Scholar 

  • Briggs, D. (1998) Surface Analysis of Polymers by XPS and Static SIMS. Cambridge University Press, New York.

    Book  Google Scholar 

  • Carrado, K.A. (2000) Synthetic organo- and polymer-clays: preparation, characterization, and materials applications. Applied Clay Science, 17, 1–23.

    Article  Google Scholar 

  • de Paiva, L.B., Morales, A.R., and Valenzuela Díaz, F.R. (2008) Organoclays: Properties, preparation and application. Applied Clay Science, 42, 8–24.

    Article  Google Scholar 

  • Donat, R., Akdogan, A., Erdem, E., and Cetisli, H. (2005) Thermodynamics of Pb2+ and Ni2+ adsorption onto natural bentonite from aqueous solutions. Journal of Colloid and Interface Science, 286, 43–52.

    Article  Google Scholar 

  • Giles, C., Smith, D., and Huitson, A. (1974) A general treatment and classification of the solute adsorption isotherm. I. Theoretical. Journal of Colloid and Interface Science, 47, 755–765.

    Article  Google Scholar 

  • He, H., Ding, Z., Zhu, J., Yuan, P., Xi, Y., Yang, D., and Frost, R.L. (2005) Thermal characterization of surfactant-modified montmorillonites. Clays and Clay Minerals, 53, 287–293.

    Article  Google Scholar 

  • He, H., Frost, R.L., Bostrom, T., Yuan, P., Duong, L., Yang D., Xi, Y., and Kloprogge, J.T. (2006) Changes in the morphology of organoclays with HDTMA+ surfactant loading. Applied Clay Science, 31, 262–271.

    Article  Google Scholar 

  • He, H., Zhou, Q., Frost, R.L., Wood, B.J., Duong, L.V., and Kloprogge, J. T. (2007) A X-ray photoelectron spectroscopy study of HDTMAB distribution within organoclays. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 66, 1180–1188.

    Article  Google Scholar 

  • Jouniaux, L. and Ishido, T. (2010) Electrokinetics in earth sciences: A tutorial. International Journal of Geophysics, Volume 2012, 16 pages, doi: 10.1155/2012/286107.

    Google Scholar 

  • Liu, G., Wu, S., van de Ven, M., Molenaar, A., and Besamusca, J. (2010) Characterization of surfactant on montmorillonite nanoclay to be used in bitumen. Journal of Materials in Civil Engineering, 22, 794–799.

    Article  Google Scholar 

  • Mahramanlioglu, M., Kizilcikli, I., and Bicer, I. (2002) Adsorption of fluoride from aqueous solution by acid treated spent bleaching earth. Journal of Fluorine Chemistry, 115, 41–47.

    Article  Google Scholar 

  • Seki, Y. and Yurdakoç, K. (2005) Paraquat adsorption onto clays and organoclays from aqueous solution. Journal of Colloid and Interface Science, 287, 1–5.

    Article  Google Scholar 

  • Su, K., Radian, A., Mishael, Y., Yang, L., and Stucki, J.W. (2012) Nitrate reduction by redox-activated, polydiallyldi-methylammonium-exchanged ferruginous smectite. Clays and Clay Minerals, 60, 464–472.

    Article  Google Scholar 

  • Tahani, A., Karroua, M., Van Damme, H., Levitz, P., and Bergaya, F. (1999) Adsorption of a cationic surfactant on Na-montmorillonite: Inspection of adsorption layer by X-ray fluorescence spectroscopies. Journal of Colloid and Interface Science, 216, 242–249.

    Article  Google Scholar 

  • Xi, Y., Martens, W., 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 

  • Yariv, S., Lapides, Y., and Borisover, M. (2012) Thermal analysis of tetraethylammonium and benzyltrimethylammonium montmorillonites. Journal of Thermal Analysis and Calorimetry, 110, 385–394.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations


Corresponding author

Correspondence to Pablo M. Naranjo.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Naranjo, P.M., Sham, E.L., Castellón, E.R. et al. Identification and Quantification of the Interaction Mechanisms Between the Cationic Surfactant HDTMA-Br and Montmorillonite. Clays Clay Miner. 61, 98–106 (2013).

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI:

Key Words

  • Alkylammonium molecules
  • Cationic Surfactant HDTMA-Br
  • Montmorillonite