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Thermal behavior and dehydroxylation kinetics of naturally occurring sepiolite and bentonite

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Abstract

Sepiolite and bentonite have a wide range of industrial applications based on their physicochemical properties such as surface area, thermal behavior, chemical composition, and mineralogic composition. The thermal behavior and kinetics of naturally occurring sepiolite and bentonite were determined in order to give an idea about the potential use of naturally occurring clay minerals in possible applications. Naturally occurring sepiolite and bentonite samples were heated to the temperature that was achieved at the end of the dehydroxylation process. Mineralogic and thermal characteristics of raw and heat treated samples were investigated by X-ray diffraction, Fourier transform infrared spectroscopy, and nitrogen adsorption/desorption analyses. Changes in the structure following heat treatment were used for the evaluation of the dehydroxylation properties of the samples. The dehydroxylation properties of the minerals are strongly affected by the crystal structure. Kinetic analyses, which were related to the dehydroxylation of naturally occurring sepiolite and bentonite, were conducted using dynamic thermogravimetry/derivative thermogravimetry analysis under nitrogen atmosphere. Flynn–Wall–Ozawa, Kissenger–Akahira–Sunose, and Friedman isoconversional methods were used to determine the activation energies of the dehydroxylation reactions of the samples. The results indicate that the activation energy of naturally occurring sepiolite showed a little variation at a particular conversion rate (0.3–0.7), while the activation energy of naturally occurring bentonite showed a significant variation within the range of variation of the conversion rate. The present study shows that the dehydroxylation reactions of naturally occurring sepiolite and bentonite were single mechanism reaction and complex mechanism reaction, respectively.

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References

  1. Murray HH. Overview-clay mineral applications. Appl Clay Sci. 1991;5:379–95.

    Article  CAS  Google Scholar 

  2. Breen C, Watson R, Madejova J, Komadel P, Klapyta Z. Acid-activated organoclays: preparation, characterization and catalytic activity of acid-treated tetraalkylammonium-exchanged smectites. Langmuir. 1997;13:6473–9.

    Article  CAS  Google Scholar 

  3. Mahmoud S, Saleh S. Effect of acid activation on the de-tert-butylation activity of some Jordanian clays. Clay Clay Miner. 1999;47:481–6.

    Article  CAS  Google Scholar 

  4. Barker RM. Shape-selective sorbents based on clay minerals: a review. Clay Clay Miner. 1989;37(5):385–95.

    Article  Google Scholar 

  5. Sarıkaya Y, Önal M, Baran B, Alemdaroğlu T. The effect of thermal treatment on some of the physicochemical properties of a bentonite. Clay Clay Miner. 2000;48:557–62.

    Article  Google Scholar 

  6. JrAS Reis, Ardisson JD. Exchangeable ion and thermal treatment effects on basal spacings of Al-hydroxy pillared montmorillonites. Clay Clay Miner. 2003;51:33–40.

    Article  Google Scholar 

  7. Komadel P. Chemically modified smectites. Clay Miner. 2003;38:127–38.

    Article  CAS  Google Scholar 

  8. Yıldız N, Sarıkaya Y, Çalımlı A. The effect of the electrolyte concentration and pH on the rheological properties of the original and Na2CO3-activated Kütahya bentonite. Appl Clay Sci. 1999;14:319–27.

    Article  Google Scholar 

  9. Yalçin H, Bozkaya Ö. Sepiolite–Palygorskite from the Hekimhan region (Turkey). Clay Clay Miner. 1995;43(6):705–17.

    Article  Google Scholar 

  10. Karakaya N, Çelik Karakaya M, Temel A, Küpeli Ş, Tunaoğlu C. Mineralogical and chemical characterization of sepiolite occurrences at Karapınar (Konya Basin, Turkey). Clay Clay Miner. 2004;52(4):495–509.

    Article  CAS  Google Scholar 

  11. Kadir S, Baş H, Karakaş Z. Origin of sepiolite and loughlinite in a neogene volcano-sedimentary lacustrine environment, Mihalliç–Eskişehir, Turkey. Can Miner. 2002;40:1091.

    Article  CAS  Google Scholar 

  12. Günister E. Na-Aktif bir bentonit-su sisteminde partikül etkileşimleri üzerine DTABr ve BDTDACl katyonik yüzey aktiflerinin etkisinin reolojik ve elektrokinetik yöntemlerle incelenmesi. Master thesis, University Istanbul Technical, İstanbul, Turkey (In Turkish) 2003.

  13. Alvarez A. Sepiolite: properties and uses, developments in sedimentology. New York: Elsevier; 1984.

    Google Scholar 

  14. Weir MR, Rutinduka E, Detellier C, Feng CY, Wang Q, Matsuura T, Le VanMao R. Fabrication, characterization and preliminary testing of all-inorganic ultrafiltration membranes composed entirely of a naturally occurring sepiolite clay mineral. J Membr Sci. 2001;182:41–50.

    Article  CAS  Google Scholar 

  15. Grimm RE, Güven N. Bentonites geology, mineralogy, properties, and uses. Amsterdam: Elsevier; 1978.

    Google Scholar 

  16. Gunay E, Ozkan TO. Production of porous ceramics from sepiolite based minerals. Ind Ceram. 2001;21:145–9.

    CAS  Google Scholar 

  17. Blanco J, Yates M, Avila P, Bahamonde A. Characterization of alumina:sepiolite monoliths for use as industrial catalyst supports. J Mater Sci. 1994;29:5927–33.

    Article  CAS  Google Scholar 

  18. Gonzalez-Pradas E, Socias-Viciana M, Urena-Amate MD, Cantos-Molina A, Villafranca-Sanchez M. Adsorption of chloridazon from aqueous solution on heat and acid treated sepiolites. Water Res. 2005;39:1849–57.

    Article  CAS  Google Scholar 

  19. Wang MC, Benway JM, Arayssi AM. The effect of heating on engineering properties of clays physicochemical aspects of soil and related materials. Philadelphia: ASTM STP 1095; 1990. p. 1139–58.

    Google Scholar 

  20. Abu-Zreig MM, Al-Akhras NM, Attom MF. Influence of heat treatment on the behavior of clayey soils. Appl Clay Sci. 2001;20:129–35.

    Article  CAS  Google Scholar 

  21. Cebulak S, Langier-Kuzniarowa A. Some remarks on the methodology of thermal analysis of clay minerals. J Therm Anal Calorim. 1998;53:375–81.

    Article  CAS  Google Scholar 

  22. Perez-Rodriguez JL, Galan E. Determination of impurity in sepiolite by thermal analysis. J Therm Anal Calorim. 1994;42:131–41.

    Article  CAS  Google Scholar 

  23. Frost RL, Ding Z. Controlled rate thermal analysis and differential scanning calorimetry of sepiolites and palygorskites. Thermochim Acta. 2003;397:119–28.

    Article  CAS  Google Scholar 

  24. Önal M, Sarıkaya Y. Thermal behavior of a bentonite. J Therm Anal Calorim. 2007;90:167–72.

    Article  Google Scholar 

  25. Bayram H, Önal M, Yılmaz H, Sarıkaya Y. Thermal analysis of a white calcium bentonite. J Therm Anal Calorim. 2010;101:873–9.

    Article  CAS  Google Scholar 

  26. Koc S, Toplan N, Yildiz K, Toplan HO. Effects of mechanical activation on the non-isothermal kinetics of mullite formation from kaolinite. J Therm Anal Calorim. 2011;103:791–6.

    Article  CAS  Google Scholar 

  27. Cheng FKH, Sahoo NG, Lu X, Li L. Thermal kinetics of montmorillonite nanoclay/maleic anhydride modified polypropylene nanocomposites. J Therm Anal Calorim. 2012;109:17–25.

    Article  CAS  Google Scholar 

  28. Sahnoune F, Saheb N, Khamel B, Takkouk Z. Thermal analysis of dehydroxylation of Algerian kaolinite. J Therm Anal Calorim. 2012;107:1067–72.

    Article  CAS  Google Scholar 

  29. Kantürk Figen A, İsmail O, Pişkin S. Devolatilization non-isothermal kinetic analysis of agricultural stalks and application of TG-FT/IR analysis. J Therm Anal Calorim. 2012;107:1177–89.

    Article  Google Scholar 

  30. Sarı Yılmaz M, Kasap S, Piskin S. Preparation, characterization and thermal dehydration kinetics of titanate nanotubes. J Therm Anal Calorim. 2012. doi:10.1007/s10973-012-2688-5.

    Google Scholar 

  31. Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29(11):1702–6.

    Article  CAS  Google Scholar 

  32. Akahira T, Sunose T. Joint convention of four electrical institutes. Res Rep Chiba Inst Technol. 1971;16:22.

    Google Scholar 

  33. Flynn JH, Wall LA. General treatment of thermogravimetry of polymers. J Res Natl Bur Stand A Phys Chem. 1966;70A(6):487–523.

    Article  Google Scholar 

  34. Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.

    Article  CAS  Google Scholar 

  35. Friedman HL. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. J Polym Sci Part C. 1964;6:183–95.

    Google Scholar 

  36. Yener N, Önal M, Üstünışık G, Sarıkaya Y. Thermal behavior of a mineral mixture of sepiolite and dolomite. J Therm Anal Calorim. 2007;88(3):813–7.

    Article  CAS  Google Scholar 

  37. Harris WG, White GN. X-ray diffraction techniques for soil mineral identification. In: Ulery A, Drees R, editors. Methods of soil analysis: part 5 mineralogical methods. Soil Sci Soc Am, Madison; 2008.

  38. Casal B, Merino J, Serratosa J, Ruiz-Hitzky E. Sepiolite-based materials for the photo- and thermal-stabilization of pesticides. Appl Clay Sci. 2001;18:245–54.

    Article  CAS  Google Scholar 

  39. Vicente-Rodriguez M, Suarez M, Banares-Munoz M, Lopez-Gonzalez J. Comparative FT-IR study of the removal of octahedral cations and structural modifications during acid treatment of several silicates. Spectrochim Acta A. 1996;52:1685–94.

    Article  Google Scholar 

  40. Frost RL, Locos OB, Kloprogge HTR. Near-infrared and mid-infrared spectroscopic study of sepiolites and palygorskites. Vib Spectrosc. 2001;27:1–13.

    Article  CAS  Google Scholar 

  41. Kalinkina EV, Kalinkin AM, Forsling W, Makarov VN. Sorption of atmospheric carbon dioxide and structural changes of Ca and Mg silicate minerals during grinding-II. Enstatite, akermanite and wollastonite. Int J Miner Process. 2001;61:289–99.

    Article  CAS  Google Scholar 

  42. Madejova J. FTIR techniques in clay mineral studies. Vib Spectrosc. 2003;31:1–10.

    Article  CAS  Google Scholar 

  43. Davarcıoğlu B, Çiftçi E. Investigation of central Anatolian clays by FTIR spectrocopy (Arapli-Yesilhisar-Kayseri, Turkey). Int J Nat Eng Sci. 2009;3(3):167–74.

    Google Scholar 

  44. Davarcıoğlu B. Investigation of central Anatolian region Nigde-Dikilitas (Turkey) clays by FTIR spectroscopy. Mater Technol. 2010;62:55–60.

    Google Scholar 

  45. Rouquerol F, Rouquerol J, Sing K. Adsorption by powders and porous solids. London: Academic Press; 1999.

    Google Scholar 

  46. Brown ME, Maciejewski M, Vyazovkin S, Nomen R, Sempere J, Burnham A, Opfermann J, Strey R, Anderson HL, Kemmler A, Keuleers R, Janssens J, Desseyn HO, Li CR, Tang TB, Roduit B, Malek J, Mitsuhashi T. Computational aspects of kinetic analysis part A: the ICTAC kinetics project-data, methods and results. Thermochim Acta. 2000;355:125.

    Article  CAS  Google Scholar 

  47. Hong J, Guo G, Zhang K. Kinetics and mechanism of non-isothermal dehydration of nickel acetate tetrahydrate in air. J Anal Appl Pyrol. 2006;77:111–5.

    Article  CAS  Google Scholar 

  48. Vyazovkin S, Wight CA. Kinetics in solids. Annu Rev Phys Chem. 1997;48:125–49.

    Article  CAS  Google Scholar 

  49. Vyazovkin S. Kinetic concepts of thermally stimulated reactions in solids: a view from a historical perspective. Int Rev Phys Chem. 2000;19:45.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Chemical Engineering, Yıldız Technical University, Davutpasa Campus, Topkapı, Istanbul, Turkey

    Müge Sarı Yılmaz, Yasemen Kalpaklı & Sabriye Pişkin

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  1. Müge Sarı Yılmaz
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  2. Yasemen Kalpaklı
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Correspondence to Sabriye Pişkin.

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Sarı Yılmaz, M., Kalpaklı, Y. & Pişkin, S. Thermal behavior and dehydroxylation kinetics of naturally occurring sepiolite and bentonite. J Therm Anal Calorim 114, 1191–1199 (2013). https://doi.org/10.1007/s10973-013-3152-x

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  • DOI: https://doi.org/10.1007/s10973-013-3152-x

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