Journal of Thermal Analysis and Calorimetry

, Volume 105, Issue 1, pp 39–51

Thermal analysis of hexadecyltrimethylammonium-montmorillonites

Part 2. Thermo-XRD-spectroscopy-analysis
Article

Abstract

Na-montmorillonite (Na-MONT) was loaded with hexadecyltrimethylammonium cations (HDTMA) by replacing 41 and 90% of the exchangeable Na with HDTMA. The organoclays were labeled OC-41 and OC-90, respectively. Freeze-dried Na-MONT, OC-41, and OC-90 were heated in air at 150, 250, 360, 420, 550, 700, and 900 °C. The thermally treated samples were suspended in water, air-dried, and desiccated over silica during 40 days. All samples were diffracted by X-ray and fitting calculations were performed on each diffractogram. These calculations gave information on basal spacings, relative concentrations, and homogeneity of the different tactoids obtained at each temperature, before and after suspending and desiccating. HDTMA-MONT tactoids with spacing ≥1.41 nm appeared between 25 and 250 °C. OC-41 or OC-90 intercalated monolayers or bilayers of HDTMA, respectively. At 250 °C OC-41 was air-oxidized to a smaller extent than OC-90, resulting in charcoal-MONT tactoids. With further heating the organic matter was gradually oxidized and at 700 °C both clays were collapsed. During the thermo-XRD-analysis of both organoclays three types of charcoal-MONT complexes appeared: (1) LTSC-MONT tactoids with a basal spacing 1.32–1.39 nm, between 250 and 420 °C in both clays; (2) HTSC-α-MONT tactoids with spacing 1.22–1.28 nm, between 360 or 250 and 500 or 550 °C in OC-41 or OC-90, respectively; (3) HTSC-β-MONT with spacing 1.12–1.18 nm, between 360 and 550 °C in both clays, where LTSC and HTSC are low- and high-temperature stable charcoal, respectively. HTSC-β-MONT differs from HTSC-α-MONT by having carbon atoms keying into the ditrigonal holes of the clay-O-planes.

Keywords

Hexadecyltrimethylammonium Montmorillonite Organoclays Tactoids Thermal analysis X-ray 

References

  1. 1.
    Theng BKG. The chemistry of clay-organic reactions. London: Adam Hilger; 1974.Google Scholar
  2. 2.
    Lagaly G. Clay organic ractions. Philos Trans R Soc Lond. 1984;A311:89–167.Google Scholar
  3. 3.
    Giese RF, van Oss CJ. Organophilicity and hydrophobicity of organoclays. In: Yariv S, Cross H, editors. Organo-clay complexes and interactions. New York: Marcel Dekker; 2002. p. 175–91.Google Scholar
  4. 4.
    Murray HH. Clays for our future. In: Kdama H, Mermut AR, Kennet Torrance J, editors. Proc 11th intern clay conf Ottawa 1997. Boulder: The Clay Mineral Society; 1999. p. 3–11.Google Scholar
  5. 5.
    Borisover M, Bukhanovsky N, Lapides I, Yariv S. Thermal treatment of organoclays: effect on the aqueous sorption of nitrobenzene on n-hexadecyltrimethyl ammonium montmorillonite. Appl Surf Sci. 2010;256:5539–44.CrossRefGoogle Scholar
  6. 6.
    Burstein F, Borisover M, Lapides S, Yariv S. Secondary adsorption on nitrobenzene and m-nitrophenol by hexadecyltrimethylammonium-montmorillonite: Thermo-XRD-analysis. J Therm Anal Calorim. 2008;92:35–42.CrossRefGoogle Scholar
  7. 7.
    Borisover M, Gerstl Z, Burshtein F, Yariv S, Mingelgrin U. Organic sorbate-organoclay interactions in aqueous and hydrophobic environments: sorbate-water competition. Environ Sci Technol. 2008;42:7201–6.CrossRefGoogle Scholar
  8. 8.
    Ovadyahu D, Lapides I, Yariv S. Thermal analysis of tributylammonium montmorillonite and Laponite. J Therm Anal Calorim. 2007;87:125–34.CrossRefGoogle Scholar
  9. 9.
    Langier-Kuzniarowa A. Thermal analysis of organo-clay complexes. In: Yariv S, Cross H, editors. Organo-clay complexes and interactions. New York: Marcel Dekker; 2002. p. 273–344.Google Scholar
  10. 10.
    Yariv S. Differential thermal analysis (DTA) in the study of thermal reactions of organo-clay complexes. In: Ikan R, editor. Natural and laboratory simulated thermal geochemical processes. Dordrecht: Kluwer Academic Publishers; 2003. p. 253–96.Google Scholar
  11. 11.
    Yariv S. The role of charcoal on DTA curves of organoclay complexes: an overview. Appl Clay Sci. 2004;24:225–36.CrossRefGoogle Scholar
  12. 12.
    Yermiyahu Z, Landau A, Zaban A, Lapides I, Yariv S. Monoionic montmorillonites treated with Congo-red: differential thermal analysis. J Therm Anal Calorim. 2003;72:431–41.CrossRefGoogle Scholar
  13. 13.
    Yermiyahu Z, Lapides I, Yariv S. Thermo-XRD-analysis of montmorillonite treated with protonated Congo-red: curve fitting. Appl Clay Sci. 2005;30:33–41.CrossRefGoogle Scholar
  14. 14.
    Yermiyahu Z, Kogan A, Lapides I, Pelly I, Yariv S. Thermal study of naphthylammonium- and naphthylazonaphthylammonium-montmorillonite. XRD and DTA. J Therm Anal Calorim. 2008;91:125–35.CrossRefGoogle Scholar
  15. 15.
    Green-Kelly R. The montmorillonite minerals (smectites). In: Mackenzie RC, editor. The differential thermal investigation of clays. London: Mineralogical Society (Clay Minerals Group); 1957. p. 140–64.Google Scholar
  16. 16.
    Yariv S, Borisover M, Lapides I. Few introducing comments on the thermal analysis of organoclays. J Therm Anal Calorimim. 2011. doi:10.1007/s10973-010-1221-y.
  17. 17.
    Lapides I, Borisover M, Yariv S. Thermal-analysis of hexadecyltrimethylammonium-montmorillonites. Part 1: thermogravimetry, carbon and hydrogen analysis and thermo-IR-spectroscopy-analysis. J Therm Anal Calorimim. 2011. doi:10.1007/s10973-011-1304-4.
  18. 18.
    He H, Ding Z, Zhu J, Yuan P, Xi Y, Yang D, Frost RL. Thermal characterization of surfactant-modified montmorillonite. Clays Clay Min. 2005;53:287–93.CrossRefGoogle Scholar
  19. 19.
    Yariv S, Lapides I. The use of thermo-XRD-analysis in the study of organo-smectite complexes. J Therm Anal Calorim. 2005;80:11–26.CrossRefGoogle Scholar
  20. 20.
    Yariv S. Wettability of clay minerals. In: Schrader ME, Loeb G, editors. Modern approach to wettability. New York: Plenum Press; 1992. p. 279–326.Google Scholar
  21. 21.
    Cases J, Berend I, Besson G, Francois M, Uriot JP, Thomas F, Poirier JE. Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite: I the sodium exchanged form. Langmuir. 1992;11:2734–41.Google Scholar
  22. 22.
    MacEwan DMC, Wilson MJ. Interlayer and intercalation complexes of clay minerals. In: Brindley GW, Brown G, editors. Crystal structures of clay minerals and their X-ray identification. Monograph. Vol 5. London: Mineralogical Society; 1980. p. 197–248.Google Scholar
  23. 23.
    Newman ACD, Brown G. The chemical constitutions of clays. In: Newman ACD, editor. Chemical composition of clays and clay. Minerals mineralogical society monograph no 6. London: Longman Scientific and Technical; 1987. p. 1–128.Google Scholar
  24. 24.
    Marshall CE. The colloid chemistry of silicate minerals. New York.: Academic Press, Inc.; 1949.Google Scholar
  25. 25.
    Jordan JW. Organophilic bentonites I. Swelling in organic liquids. J Phys Colloid Chem. 1949;53:294–306.CrossRefGoogle Scholar
  26. 26.
    Jordan JW. Alteration of the properties of bentonite by reaction with amines. Mineralog Mag. 1949;28:598–605.CrossRefGoogle Scholar
  27. 27.
    Earley JW, Milne IH, McVeagh WJ. Dehydration of montmorillonite. Am Miner. 1953;38:770–83.Google Scholar
  28. 28.
    JCPDS. International center for diffraction data. Quartz, PDF # 89-1961; cristobalite, PDF # 82-0512; 2001.Google Scholar
  29. 29.
    Vianna MMGR, Dweck J, Quina FH, Carvalho FMS, Nascimento CAO. Toluene and naphthalene sorption by iron oxide/clay composites Part II. Sorption experiments. J Therm Anal Calorim. 2010;101:887–92.CrossRefGoogle Scholar
  30. 30.
    Ganguly S, Dana K, Ghatak S. Thermogravimetric study of n-alkylammonium-intercalated montmorillonites of different cation exchange capacity. J. Therm. Anal. Cal. 2010;100:71–8.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2011

Authors and Affiliations

  • Isaak Lapides
    • 1
  • Mikhail Borisover
    • 2
  • Shmuel Yariv
    • 1
  1. 1.Institute of ChemistryThe Hebrew University of JerusalemJerusalemIsrael
  2. 2.Institute of Soil, Water and Environmental Sciences, The Volcani Center, Agricultural Research OrganizationBet DaganIsrael

Personalised recommendations