Thermal analyis of hexadecyltrimethylammonium–montmorillonites
Part 1. Thermogravimetry, carbon and hydrogen analysis and thermo-IR spectroscopy analysis
First Online: 12 February 2011 DOI:
Cite this article as: Lapides, I., Borisover, M. & Yariv, S. J Therm Anal Calorim (2011) 105: 921. doi:10.1007/s10973-011-1304-4 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 H
2O and CO 2 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 References
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.
Lagaly G. Interaction of alkylamines with different types of layered compounds. Solid State Ion. 1986;22:43–51.
Bergaya F, Lagaly G. Surface modification of clay minerals. Appl Clay Sci. 2001;19:1–3.
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.
Murray HH. Traditional and new applications for kaolin, smectite, and palygorskite: a general overview. Appl Clay Sci. 2000;17:207–21.
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.
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.
Ray SS, Okamoto M. Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci. 2003;28:1539–641.
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.
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:
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.
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.
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.
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.
Ovadyahu D, Lapides I, Yariv S. Thermal analysis of tributylammonium montmorillonite and Laponite. J Therm Anal Calorim. 2007;87:125–34.
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.
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.
Yariv S. The role of charcoal on DTA curves of organoclay complexes: an overview. Appl Clay Sci. 2004;24:225–36.
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.
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.
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.
Sonobe N, Kyotani T, Tomita A. Carbonization of polyacrilonitrile in a two dimensional space between montmorillonite lamellae. Carbon. 1988;26:573–8.
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.
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.
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.
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.
Ni R, Huang Y, Yao C. Thermogravimetric analysis of organoclays intercalated with the Gemini surfactants. J Therm Anal Calorim. 2009;96:943–7.
Lu L, Cai J, Frost RL. Desorption of stearic acid uoin surfactant adsorbed montmorillonite. J Therm Anal Calorim. 2010;100:141–4.
Dweck J. Qualitative and quantitative characterization of Brazilian natural and organophilic clays by thermal analysis. J Therm Anal Calorim. 2008;92:129–35.
Jordan JW. Alteration of the properties of bentonite by reaction with amines. Mineral Mag. 1949;28:598–605.
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.
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.
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.
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.
Tiwari RR, Khilar KC, Natarajan U. Synthesis and characterization of novel montmorillonites. Appl Clay Sci. 2008;38:203–8.
Onal M, Sarikaya Y. Thermal analysis of some organoclays. J Therm Anal Calorim. 2008;91:261–5.
Yariv S. Combined DTA-mass spectrometry of organo-clay complexes. J Therm Anal Calorim. 1990;36:1953–61.
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.
Yariv S. Wettability of clay minerals. In: Schrader ME, Loeb G, editors. Modern approach to wettability. New York: Plenum Press; 1992. p. 279–326.
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.
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.
Rao CNR. Chemical applications of infrared spectroscopy. New York: Academic Press; 1963. p. 125–281.
Ganguly S, Dana K, Ghatak S. Thermogravimetric study of
-alkylammonium-intercalated montmorillonites of different cation exchange capacity. J Therm Anal Calorim. 2010;100:71–8.
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