Journal of Thermal Analysis and Calorimetry

, Volume 105, Issue 3, pp 921–929 | Cite as

Thermal analyis of hexadecyltrimethylammonium–montmorillonites

Part 1. Thermogravimetry, carbon and hydrogen analysis and thermo-IR 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, labeled OC-41 and OC-90, respectively. Na-MONT, OC-41, and OC-90 were heated in air up to 900 °C. Unheated and thermally treated organoclays heated at 150, 250, 360, and 420 °C are used in our laboratory as sorbents of different hazardous organic compounds from waste water. In order to get a better knowledge about the composition and nature of the thermally treated organoclays Na-MONT and the two organo-clays were studied by thermogravimetry (TG) in air and under nitrogen. Carbon and hydrogen contents in each of the thermal treated sample were determined and their infrared spectra were recorded. The present results showed that at 150 °C both organoclays lost water but not intercalated HDTMA cations. At 250 °C, many HDTMA cations persisted in OC-41, but in OC-90 significant part of the cations were air-oxidized into H2O and CO2 and the residual carbon formed charcoal. After heating both samples at 360 °C charcoal was present in both organo clays. This charcoal persisted at 420 °C but was gradually oxidized by air with further rise in temperature. TG runs under nitrogen showed stepwise degradation corresponding to interlayer water desorption followed by decomposition of the organic compound, volatilization of small fragments and condensation of non-volatile fragments into quasi-charcoal. After dehydroxylation of the clay the last stages of organic matter pyrolysis and volatilization occurred.

Keywords

Carbon content curves Charcoal Hydrogen content curves Organo-montmorillonite Thermo-infrared spectroscopy Thermogravimetry 

Notes

Acknowledgements

Help from Nadezhda Bukhanovsky (The Volcani Center, Agricultural Research Organization, Israel) in preparing thermally treated organoclay samples is appreciated. This research was supported by a grant from the Israeli Science Foundation (No 919/08) and by a grant from the Ministry of Science, Culture & Sport, Israel & the Ministry of Research (Infrastructure 3-4136).

References

  1. 1.
    Jordan JW. Organophilic clay-base thickeners. In: Proceedings of 10th National Conference on Clays and Clay Mineral, vol 10. Oxford: Pergamon; 1963. p. 299–308.Google Scholar
  2. 2.
    Lagaly G. Interaction of alkylamines with different types of layered compounds. Solid State Ion. 1986;22:43–51.CrossRefGoogle Scholar
  3. 3.
    Bergaya F, Lagaly G. Surface modification of clay minerals. Appl Clay Sci. 2001;19:1–3.CrossRefGoogle Scholar
  4. 4.
    Ruiz-Hitzky E, Van Meerbeek A. Clay mineral and organoclay-polymers nanocomposites. In: Bergaya F, Theng BKG, Lagaly G, editors. Handbook of clay science. Amsterdam: Elsevier; 2006. p. 583–621.CrossRefGoogle Scholar
  5. 5.
    Murray HH. Traditional and new applications for kaolin, smectite, and palygorskite: a general overview. Appl Clay Sci. 2000;17:207–21.CrossRefGoogle Scholar
  6. 6.
    Churchman GJ, Gates WP, Theng BKG, Yuan G. Clays and clay minerals for pollution control. In: Bergaya F, Theng BKG, Lagaly G, editors. Handbook of clay science. Amsterdam: Elsevier; 2006. p. 625–75.CrossRefGoogle Scholar
  7. 7.
    Adebajo MO, Frost RL, Kloprogge JT, Carmody O. Porous materials for oil spill cleanup: a review of synthesis and absorbing properties. J Porous Mater. 2003;10:159–70.CrossRefGoogle Scholar
  8. 8.
    Ray SS, Okamoto M. Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci. 2003;28:1539–641.CrossRefGoogle Scholar
  9. 9.
    Vianna MMGR, Dweck J, Quina FH, Carvalho FMS, Nascimento CAO. Toluene and naphthalene sorption by iron oxide/cly composites. Part II. Sorption experiments. J Therm Anal Calorim. 2010;101:887–92.CrossRefGoogle Scholar
  10. 10.
    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. 2009. doi: 10.1016/j.apsusc.2009.12.133.
  11. 11.
    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
  12. 12.
    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
  13. 13.
    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
  14. 14.
    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
  15. 15.
    Ovadyahu D, Lapides I, Yariv S. Thermal analysis of tributylammonium montmorillonite and Laponite. J Therm Anal Calorim. 2007;87:125–34.CrossRefGoogle Scholar
  16. 16.
    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
  17. 17.
    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
  18. 18.
    Yariv S. The role of charcoal on DTA curves of organoclay complexes: an overview. Appl Clay Sci. 2004;24:225–36.CrossRefGoogle Scholar
  19. 19.
    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
  20. 20.
    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
  21. 21.
    Sonobe N, Kyotani T, Hishyama Y, Shiraishi M, Tomita A. Formation of highly oriented graphite from poly (acrilonitrile) prepared between the lamellae of montmorillonite. J Phys Chem. 1988;92:7029–34.CrossRefGoogle Scholar
  22. 22.
    Sonobe N, Kyotani T, Tomita A. Carbonization of polyacrilonitrile in a two dimensional space between montmorillonite lamellae. Carbon. 1988;26:573–8.CrossRefGoogle Scholar
  23. 23.
    Sonobe N, Kyotani T, Tomita A. Carbonization of poly(furfuryl alcohol) and poly(vinil acetate) prepared between the lamellae of montmorillonite. Carbon. 1990;28:483–8.CrossRefGoogle Scholar
  24. 24.
    Sonobe N, Kyotani T, Tomita A. Formation of graphite thin film from poly(furfuryl alcohol) and poly(vinil acetate) prepared between the lamellae of montmorillonite. Carbon. 1991;29:61–7.CrossRefGoogle Scholar
  25. 25.
    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
  26. 26.
    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
  27. 27.
    Ni R, Huang Y, Yao C. Thermogravimetric analysis of organoclays intercalated with the Gemini surfactants. J Therm Anal Calorim. 2009;96:943–7.CrossRefGoogle Scholar
  28. 28.
    Lu L, Cai J, Frost RL. Desorption of stearic acid uoin surfactant adsorbed montmorillonite. J Therm Anal Calorim. 2010;100:141–4.CrossRefGoogle Scholar
  29. 29.
    Dweck J. Qualitative and quantitative characterization of Brazilian natural and organophilic clays by thermal analysis. J Therm Anal Calorim. 2008;92:129–35.CrossRefGoogle Scholar
  30. 30.
    Jordan JW. Alteration of the properties of bentonite by reaction with amines. Mineral Mag. 1949;28:598–605.CrossRefGoogle Scholar
  31. 31.
    Gao Z, Xie W, Hwu JM, Wells L, Pan WP. The characterization of organic modified montmorillonite and its filled pmma nanocomposite. J Therm Anal Calorim. 2001;64:467–75.CrossRefGoogle Scholar
  32. 32.
    Xie W, Gao Z, Pan WP, Hunter D, Singh A, Vala R. Thermal degradation chemistry of alkyl quaternary ammonium montmorillonite. Chem Mater. 2001;13:2979–90.CrossRefGoogle Scholar
  33. 33.
    Xi Y, Martens W, He H, Frost RL. Thermogravimetric analysis of organoclays intercalated with the surfactant octadecyltrimethylammonium. J Therm Anal Calorim. 2005;81:91–7.CrossRefGoogle Scholar
  34. 34.
    Cervantes-Uc JM, Cauich-Rodriguez JV, Vazquez-Torres H, Grafias-Mesias LF, Paul DR. Thermal degradation of commercially available organoclays studied by TGA-FTIR. Thermochim Acta. 2007;457:92–102.CrossRefGoogle Scholar
  35. 35.
    Tiwari RR, Khilar KC, Natarajan U. Synthesis and characterization of novel montmorillonites. Appl Clay Sci. 2008;38:203–8.CrossRefGoogle Scholar
  36. 36.
    Onal M, Sarikaya Y. Thermal analysis of some organoclays. J Therm Anal Calorim. 2008;91:261–5.CrossRefGoogle Scholar
  37. 37.
    Yariv S. Combined DTA-mass spectrometry of organo-clay complexes. J Therm Anal Calorim. 1990;36:1953–61.CrossRefGoogle Scholar
  38. 38.
    Heller Kallai L, Yariv S. Swelling of montmorillonite containing coordination complexes of amines with transition metal cations. J Colloid Interface Sci. 1981;79:479–85.CrossRefGoogle Scholar
  39. 39.
    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
  40. 40.
    Yariv S. The effect of tetrahedral substitution of Si by Al on the surface acidity of the oxygen plane of clay minerals. Int Rev Phys Chem. 1992;11:345–75.CrossRefGoogle Scholar
  41. 41.
    Newman ACD, Brown G. The chemical constitution of clays. In: Newman ACD, editor. Chemistry and composition of clays and clay minerals. Mineralogical society monograph no. 6. London: Longman Scietific & Technical; 1987. p. 1–128.Google Scholar
  42. 42.
    Rao CNR. Chemical applications of infrared spectroscopy. New York: Academic Press; 1963. p. 125–281.Google Scholar
  43. 43.
    Ganguly S, Dana K, Ghatak S. Thermogravimetric study of n-alkylammonium-intercalated montmorillonites of different cation exchange capacity. J Therm Anal Calorim. 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 CenterAgricultural Research OrganizationBet DaganIsrael

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