WJNSE  Vol.3 No.4 , December 2013
Study of Physical, Chemical and Morphological Alterations of Smectite Clay upon Activation and Functionalization via the Acid Treatment
The present study was carried out on the effect of acid leaching on the modification and structure alteration of montmorillonite. A nanostructured, activated material was prepared by selective leaching of pure smectite clay with different concentrations of sulfuric acid (1 - 10 N/L) at 85°C for 120 min using a solid/liquid ratio of 1:20 and a reflux system. The Fourier transform infrared (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-Ray diffraction (XRD) techniques were used for the characterization and study of the acid-treated montmorillonite clay. Chemical structure of specimens was distinguished by FTIR. The results showed that the formation of Si-OH bonds and leaching of Al3+ ions increased progressively with severity of the acid treatment. As the FTIR studies indicated, acid treatment led to the removal of the octahedral Al3+ cations and an increase in the Si-OH bonds. The morphological alteration of the untreated and treated montmorillonite was investigated by using TEM and SEM. X-ray fluorescence (XRF) analysis revealed a considerable decrease in the relative content of Al by increasing the acid strength. Moreover, the XRD results showed that the treatment using highly concentrated acid resulted in the formation of an amorphous silica phase.

Cite this paper
M. Angaji, A. Zinali and N. Qazvini, "Study of Physical, Chemical and Morphological Alterations of Smectite Clay upon Activation and Functionalization via the Acid Treatment," World Journal of Nano Science and Engineering, Vol. 3 No. 4, 2013, pp. 161-168. doi: 10.4236/wjnse.2013.34019.
[1]   F. Kooli, Y. Z. Khimyak, S. F. Alshahateet and F. Chen, “Effect of the Acid Activation Levels of Montmorillonite Clay on the Cetyltrimethylammonium Cations Adsorption,” Langmuir, Vol. 21, No. 19, 2005, pp. 8717-8723. http://dx.doi.org/10.1021/la050774z

[2]   S. R. Wasserman and L. Soderholm, “Effect of Surface Modification on the Interlayer Chemistry of Iron in a Smectite Clay,” Chemical Material, Vol. 10, No. 2, 1998, pp. 559-566. http://dx.doi.org/10.1021/cm9705597

[3]   G. S. Groenewold, R. Avci, C. Karahan, K. Lefebre, R. V. Fox, M. M. Cortez, A. K. Gianotto, J. Sunner and W. L. Manner, “Characterization of Interlayer Cs+ in Clay Samples Using Secondary Ion Mass Spectrometry with Laser Sample Modification,” Analytical Chemistry, Vol. 76, No. 10, 2004, pp. 2893-2901. http://dx.doi.org/10.1021/ac035400u

[4]   M. I. Zaki, M. Abdel-Khalik and G. M. Habashy, “Acid-Leaching and Consequent Pore Structure and Bleaching Capacity Modifications of Egyptian Clays,” Colloids and Surfaces, Vol. 17, No. 3, 1986, pp. 241-249. http://dx.doi.org/10.1016/0166-6622(86)80249-9

[5]   J. Hrachová, P. Komadel, I. Janigova, M. ?louf and I. Chodák, “Properties of Rubber Filled with Montmorillonite with Various Surface Modifications,” Polymers for Advanced Technologies, Vol. 23, No. 10, 2012, pp. 1414-1421.

[6]   S. R. Ha and K. Y. Rhee, “Effect of Surface-Modification of Clay Using 3-Aminopropyltriethoxysilane on the Wear Behavior of Clay/Epoxy Nanocomposites,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 322, No. 3, 2008, pp. 1-5. http://dx.doi.org/10.1016/j.colsurfa.2008.03.007

[7]   F. Bergaya, B. K. G. Theng and G. Lagaly, “Handbook of Clay Science,” Elsevier, Amsterdam, 2006.

[8]   J. Eisele, D. Bauer and D. Shanks, “Bench-Scale Studies to Recover Alumina from Clay by a Hydrochloric Acid Process,” Industrial & Engineering Chemistry Product Research and Development, Vol. 22, No. 1, 1983, pp. 105-110. http://dx.doi.org/10.1021/i300009a024

[9]   K. Park and J. Jeong, “Manufacture of Low-Soda Alumina from Clay,” Industrial & Engineering Chemistry Reach, Vol. 35, No. 11, 1996, pp. 4379-4385. http://dx.doi.org/10.1021/ie950716g

[10]   B. Tyagi, C. Chudasama and R. Jasra, “Determination of Structural Modification in Acid Activated Montmorillonite Clay by FT-IR Spectroscopy,” Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 64, No. 2, 2006, pp. 273-278. http://dx.doi.org/10.1016/j.saa.2005.07.018

[11]   J. Madejova, “FTIR Techniques in Clay Mineral Studies,” Vibrational Spectroscopy, Vol. 31, 2003, pp. 1-10. http://dx.doi.org/10.1016/S0924-2031(02)00065-6

[12]   L. Boudriche, R. Calvet, B. Hamdi and H. Balard, “Effect of Acid Treatment on Surface Properties Evolution of Attapulgite CLay: An Application of Inverse Gas Chromatography,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 392, No. 1, 2011, pp. 45-54. http://dx.doi.org/10.1016/j.colsurfa.2011.09.031

[13]   M. Pentrák, A. Czímerová, J. Madejová and P. Komadel, “Changes in Layer Charge of Clay Minerals upon Acid Treatment as Obtained from Their Interactions with Methylene Blue,” Applied Clay Science, Vol. 35, 2012, pp. 100-107.

[14]   K. Bhattacharyya and S. Gupta, “Influence of Acid Activation of Kaolinite and Montmorillonite on Adsorptive Removal of Cd(II) from Water,” Industrial & Engineering Chemistry Research, Vol. 46, No. 11, 2007, pp. 3734-3742. http://dx.doi.org/10.1021/ie061475n

[15]   C. Volzone and J. Ortiga, “SO2 Gas Adsorption by Modified Kaolin Clays: Influence of Previous Heating and Time Acid Treatments,” Journal of Environmental Management, Vol. 92, No. 10, 2011, pp. 2590-2595. http://dx.doi.org/10.1016/j.jenvman.2011.05.031

[16]   K. Bhattacharyya and S. Gupta, “Adsorptive Accumulation of Cd(II), Co(II), Cu(II), Pb(II), and Ni(II) from Water on Montmorillonite: Influence of Acid Activation,” Journal of Colloid and Interface Science, Vol. 310, No. 2, 2007, pp. 411-424. http://dx.doi.org/10.1016/j.jcis.2007.01.080

[17]   K. Bhattacharyyaa and S. Guptab, “Influence of Acid Activation on Adsorption of Ni(II) and Cu(II) on Kaolin- ite and Montmorillonite: Kinetic and Thermodynamic Study,” Chemical Engineering Journal, Vol. 136, No. 1, 2008, pp. 1-13. http://dx.doi.org/10.1016/j.cej.2007.03.005

[18]   K. G. Bhattacharyya and S. Gupta, “Pb(II) Uptake by Kaolinite and Montmorillonite in Aqueous Medium: Influence of Acid Activation of the Clays,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 277, No. 1, 2006, pp. 191-200. http://dx.doi.org/10.1016/j.colsurfa.2005.11.060

[19]   S. Petrovic, T. Novakovic and L. Rozic, “Statistical Design of Experiments of Acid Activation of Smectite Clay from Serbia and Its Bleaching Capacity,” Journal of Chemical Technology and Biotechnology, Vol. 84, 2009, pp. 176-179. http://dx.doi.org/10.1002/jctb.2019

[20]   C. Briones and E. Agacino, “Br?nsted Sites on Acid-Treated Montmorillonite: A Theoretical Study with Probe Molecules,” Journal of Physical Chemistry A, Vol. 113, No. 31, 2009, pp. 8994-9001. http://dx.doi.org/10.1021/jp900236r

[21]   A. Panda, B. Mishra, D. Mishra and R. Singh, “Effect of Sulphuric Acid Treatment on the Physico-Chemical Characteristics of Kaolin Clay,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 363, No. 1, 2010, pp. 98-104. http://dx.doi.org/10.1016/j.colsurfa.2010.04.022

[22]   K. Okada, A. Shimai, T. Takei, S. Hayashi, A. Yasumori and K. MacKenzie, “Preparation of Microporous Silica from Metakaolinite by Selective Leaching Method,” Microporous and Mesoporous Materials, Vol. 21, No. 4, 1998, pp. 289-296. http://dx.doi.org/10.1016/S1387-1811(98)00015-8

[23]   J. Temuujina, T. Jadambaab, G. Burmaaa, S. Erdene- chimegb, J. Amarsanaab and K. J. D. MacKenziec, “Characterisation of Acid Activated Montmorillonite clay from Tuulant (Mongolia),” Ceramics International, Vol. 30, No. 2, 2004, pp. 251-255. http://dx.doi.org/10.1016/S0272-8842(03)00096-8

[24]   P. Kumar, R. Jasra and T. Bhat, “Evolution of Porosity and Surface Acidity in Montmorillonite Clay on Acid Activation,” Industrial & Engineering Chemistry Research, Vol. 34, 1995, pp. 1440-1448. http://dx.doi.org/10.1021/ie00043a053

[25]   J. Burba and J. Mcatee, “Adsorption of Ethylene Glycol on Amine-Substituted Montmorillonites,” Clays and Clay Minerals, Vol. 29, No. 1, 1981, pp. 60-67. http://dx.doi.org/10.1346/CCMN.1981.0290109

[26]   M. Aspandiar, T. Eggleton and U. Troitzsch, “Environmental Mineralogy Honours Shortcourse,” CRC LEME, Adelaide, 2007.

[27]   J. Temuujin, M. Senna and T. Jadambaa, “Characterization and Bleaching Properties of Acid-Leached Montmorillonite,” Journal of Chemical Technology and Biotechnology, Vol. 81, No. 4, 2006, pp. 688–693. http://dx.doi.org/10.1002/jctb.1469

[28]   K. Weiss, C. Wirth-Pfeifer and M. Hofmann, “Polymerization of Ethylene or Propylene with Heterogeneous Metallocene Catalysts on Clay Minerals,” Journal of Molecular Catalysis A: Chemical, Vol. 182-183, 2002, pp. 143-149. http://dx.doi.org/10.1016/S1381-1169(01)00481-2

[29]   I. Benito, C. Pesquera and C. Blanco, “Texture Evolution of Montmorillonite under Progressive Acid Treatment: Change from H3 to H2 Type of Hysteresis,” Langmuir, Vol. 3, 1987, pp. 676-681. http://dx.doi.org/10.1021/la00077a017