Skip to main content
SpringerLink
Log in

Mild microwave-assisted synthesis of aluminum-pillared bentonites

Thermal behavior and potential applications

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

Two types of bentonites were modified using a cleaner method to prepare aluminum-pillared clays. This methodology involved a purifying stage, an intercalation process, and a microwave irradiation step at low energy power. Structural changes induced by pillaring process were demonstrated by thermal behavior, as well as morphological characterization. The effect of pillaring process on thermal stability of clays was studied, and the mass lost associated with the dehydroxylation of the octahedral clay sheets was not detected for modified bentonites. In addition, an analysis of their chemical composition and crystalline structure was also performed. Concerning industrial applications of these bentonites, two potential uses were proposed: (1) as reinforcement of different polymers matrices such as thermoplastic starch (TPS), high-density polyethylene (HDPE), and poly (styrene-b-butadiene-b-styrene), SBS; and (2) as removal agent for cadmium (Cd) species present in wastewaters. Bentonite particles reinforced thermoplastic starch matrix and increased ultraviolet barrier capacity of HDPE composites. Besides, bentonites improved the mechanical performance and modified barrier properties of SBS. Regarding effluents purification, an adequate Cd adsorption from aqueous solutions was observed (77%), proving their feasibility to be used as non-conventional removal agents.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Bertagnolli C, Kleinübing SJ, da Silva MGC. Preparation and characterization of a Brazilian bentonite clay for removal of copper in porous beds. Appl Clay Sci. 2011;53:73–9.

    Article  CAS  Google Scholar 

  2. Manohar DM, Noeline BF, Anirudhan TS. Adsorption performance of Al-pillared bentonite clay for the removal of cobalt(II) from aqueous phase. Appl Clay Sci. 2006;31:194–206.

    Article  CAS  Google Scholar 

  3. Alvarez-Ayuso E, Garćia-Sánchez A. Removal of heavy metals from wastewater by natural and Na-exchanged bentonites. Clays Clay Min. 2003;51:475–80.

    Article  CAS  Google Scholar 

  4. Choo KY, Bai K. Effects of bentonite concentration and solution pH on the rheological properties and long-term stabilities of bentonite suspensions. Appl Clay Sci. 2015;108:182–90.

    Article  CAS  Google Scholar 

  5. Bergaya F, Lagaly G. Introduction to clay science: techniques and applications. In: Bergaya, F., Lagaly G, editors. Developments in clay science. Handbook of Clay Science; 2013. pp. 1–7.

  6. Abu-Jdayil B. Rheology of sodium and calcium bentonite-water dispersions: effect of electrolytes and aging time. Int J Miner Process. 2011;98:208–13.

    Article  CAS  Google Scholar 

  7. Bhattacharyya KG, Gupta SS. Adsorption of a few heavy metals on natural and modified kaolinite and montmorillonite: a review. Adv Colloid Interface Sci. 2008;140:114–31.

    Article  CAS  Google Scholar 

  8. Işci S, Günister E, Ece ÖI, Güngör N. The modification of rheologic properties of clays with PVA effect. Mater Lett. 2004;58:1975–8.

    Article  Google Scholar 

  9. Caglar B, Cubuk O, Demir E, Coldur F, Catir M, Topcu C, et al. Characterization of AlFe-pillared Unye bentonite: a study of the surface acidity and catalytic property. J Mol. 2015;1089:59–65.

    CAS  Google Scholar 

  10. Schoonheydt R, Johnston C. Surface and interface chemistry of clay minerals [Internet]. 2nd ed. Handb Clay Sci Elsevier Ltd.; 2006.

  11. Rohlmann CO, Horst MF, Quinzani LM, Failla MD. Comparative analysis of nanocomposites based on polypropylene and different montmorillonites. Eur Polym J. 2008;44:2749–60.

    Article  CAS  Google Scholar 

  12. Magalhães NF, Andrade CT. Calcium bentonite as reinforcing nanofiller for termoplastic starch. J Braz Chem Soc. 2010;21:202–8.

    Article  Google Scholar 

  13. Zhou Y, Hu N, Zeng Y, Rusling JF. Heme-protein-clay films: direct electrochemistry and electrochemical catalysis. Langmuir. 2002;18:211–9.

    Article  Google Scholar 

  14. Liao R, Bin Yang WY, Chixing Z. Isothermal cold crystallization kinetics of polylactide/nucleating agents. J Appl Polym Sci. 2007;104:310–7.

    Article  CAS  Google Scholar 

  15. Huang H, Xiao X, Yan B, Yang L. Ammonium removal from aqueous solutions by using natural Chinese (Chende) zeolite as adsorbent. J Hazard Mater. 2010;175:247–52.

    Article  CAS  Google Scholar 

  16. Yuan P, Annabi-Bergaya F, Tao Q, Fan M, Liu Z, Zhu J, He H, Chen T. TC. A combined study by XRD, FTIR, TG and HRTEM on the structure of delaminated Fe-intercalated/pillared clay. J Colloid Interface Sci. 2008;324:142–9.

    Article  CAS  Google Scholar 

  17. Katdare SP, Ramaswamy V, Ramaswamy AV. Factors affecting the preparation of alumina pillared montmorillonite employing ultrasonics. Microporous Mesoporous Mater. 2000;37:329–36.

    Article  CAS  Google Scholar 

  18. Bertella F, Pergher SBC. Pillaring of bentonite clay with Al and Co. Microporous Mesoporous Mater. 2015;201:116–23.

    Article  CAS  Google Scholar 

  19. Gil A, Korili SA, Trujillano R, Vicente MA. A review on characterization of pillared clays by specific techniques. Appl Clay Sci. 2011;53:97–105.

    Article  CAS  Google Scholar 

  20. Jobstmann H, Singh B. Cadmium sorption by hydroxy-aluminium interlayered montmorillonite. Water Air Soil Pollut. 2001;131:203–15.

    Article  CAS  Google Scholar 

  21. Cyras VP, Manfredi LB, Ton-That M-T, Vázquez A. Physical and mechanical properties of thermoplastic starch/montmorillonite nanocomposite films. Carbohydr Polym. 2008;73:55–63.

    Article  CAS  Google Scholar 

  22. Sarifuddin N, Ismail H. Comparative study on the effect of bentonite or feldspar filled low-density polyethylene/thermoplastic sago starch/kenaf core fiber composites. 2013;8:4238–4257.

  23. Ranelovic MS, Purenovic MM, Matovic BZ, Zarubica AR, Momčilovic MZ, Purenovic JM. Structural, textural and adsorption characteristics of bentonite-based composite. Microporous Mesoporous Mater. 2014;195:67–74.

    Article  Google Scholar 

  24. Erdem B, Ozcan A, Gök O, Ozcan AS. Immobilization of 2,2′-dipyridyl onto bentonite and its adsorption behavior of copper(II) ions. J Hazard Mater. 2009;163:418–26.

    Article  CAS  Google Scholar 

  25. Yang S, Li J, Lu Y, Chen Y, Wang X. Sorption of Ni(II) on GMZ bentonite: effects of pH, ionic strength, foreign ions, humic acid and temperature. Appl Radiat Isot. 2009;67:1600–8.

    Article  CAS  Google Scholar 

  26. Fernández-Nava Y, Ulmanu M, Anger I, Marañón E, Castrillón L. Use of granular bentonite in the removal of mercury(II), cadmium (II) and lead(II) from aqueous solutions. Water Air Soil Pollut. 2010;215:239–49.

    Article  Google Scholar 

  27. Ding SL, Sun YZ, Yang CN, Xu BH. Removal of copper from aqueous solutions by bentonites and the factors affecting it. Min Sci Technol. 2009;19:489–92.

    CAS  Google Scholar 

  28. Morante JA, Pesquera C, Blanco C, González F. Textural characterization of montmorillonite pillared with aluminum/lanthanum polyoxycations. Stud Surf Sci Catal. 2002;144;617–24.

  29. Zhang X, Wang Q, Jiang H. research on the preparation of the environmental friendly pillared bentonite and its catalytic properties. In: 2nd international conference on electronic and mechanical engineering and information technology (EMEIT-2012), 2012;959–962.

  30. Tomul F. Effect of ultrasound on the structural and textural properties of copper-impregnated cerium-modified zirconium-pillared bentonite. Appl Surf Sci. 2011;258:1836–48.

    Article  CAS  Google Scholar 

  31. Olaya A, Blanco G, Bernal S, Moreno S, Molina R. Synthesis of pillared clays with Al–Fe and Al–Fe–Ce starting from concentrated suspensions of clay using microwaves or ultrasound, and their catalytic activity in the phenol oxidation reaction. Appl Catal B Environ. 2009;93:56–65.

    Article  CAS  Google Scholar 

  32. Soliman EA, Furuta M. Influence of phase behavior and miscibility on mechanical, thermal and micro-structure of soluble starch-gelatin thermoplastic biodegradable blend films. Food Nutr Sci. 2014;5:1040–55.

    Article  Google Scholar 

  33. Piermaría J, Bosch A, Pinotti A, Yantorno O, García MA, Abraham A. Kefiran films plasticized with sugars and polyols: water vapor barrier and mechanical properties in relation to their microstructure analyzed by ATR/FT-IR spectroscopy. Food Hydrocoll. 2011;25:1261–9.

    Article  Google Scholar 

  34. Modabberi S, Namayandeh A, López-Galindo A, Viseras C, Setti M, Ranjbaran M. Characterization of Iranian bentonites to be used as pharmaceutical materials. Appl Clay Sci. 2015;116–117:193–201.

    Article  Google Scholar 

  35. Sun Z, Qu X, Wang G, Zheng S, Frost RL. Removal characteristics of ammonium nitrogen from wastewater by modified Ca-bentonites. Appl Clay Sci. 2015;107:46–51.

    Article  CAS  Google Scholar 

  36. Naswir M, Arita S, Marsi, Salni. Characterization of bentonite by XRD and SEM-EDS and use to increase PH and color removal, Fe and organic substances in peat water. J Clean Energy Technol. 2013;1:313–7.

    Article  CAS  Google Scholar 

  37. Pramanik S, Das G, Karak N. Facile preparation of polyaniline nanofibers modified bentonite nanohybrid for gas sensor application. RSC Adv. 2013;3:4574–45981.

    Article  CAS  Google Scholar 

  38. Ding M, Zuo S, Qi C. Preparation and characterization of novel composite AlCr-pillared clays and preliminary investigation for benzene adsorption. Appl Clay Sci. 2015;115:9–16.

    Article  CAS  Google Scholar 

  39. Tomul F, Balci S. Characterization of Al, Cr-pillared clays and CO oxidation. Appl Clay. 2009;43:13–20.

    Article  CAS  Google Scholar 

  40. Sanabria N, Álvarez A, Molina R, Moreno S. Synthesis of pillared bentonite starting from the Al–Fe polymeric precursor in solid state, and its catalytic evaluation in the phenol oxidation reaction. Catal Today. 2008;133–135:530–3.

    Article  Google Scholar 

  41. Andrini L, Toja RM, Gauna MR, Conconi MS, Requejo FG, Rendtorff NM. Extended and local structural characterization of a natural and 800 °C fired Na-montmorillonite–Patagonian bentonite by XRD and Al/Si XANES. Appl Clay Sci. 2017;137:233–40.

    Article  CAS  Google Scholar 

  42. Chen J, Li J, Qiying L, Xiumin H, Wenjie S. Facile synthesis of Ag-hollandite nanofibers and their catalytic activity for ethanol selective oxidation. Chin J Catal. 2007;28(12):1034–6.

    Article  CAS  Google Scholar 

  43. Mahmoudi S, Bennour A, Meguebli A, Srasra E, Zargouni F. Characterization and traditional ceramic application of clays from the Douiret region in South Tunisia. Appl Clay Sci. 2016;127–128:78–87.

    Article  Google Scholar 

  44. Sakizci M, Burcu EA, Ertuǧrul Y. Thermal behavior and immersion heats of selected clays from Turkey. J. Therm Anal Calorim. 2009;98:429–36.

    Article  CAS  Google Scholar 

  45. Ursu AV, Jinescu G, Gros F, Nistor ID, Miron ND, Lisa G, Silion M, Djelveh G, Azzouz A. Thermal and chemical stability of Romanian bentonite. J Therm Anal Calorim. 2011;106:965–71.

    Article  CAS  Google Scholar 

  46. Tomul F. Adsorption and catalytic properties of Fe/Cr-pillared bentonites. Chem Eng J. 2012;185–186:380–90.

    Article  Google Scholar 

  47. Tomul F. Influence of synthesis conditions on the physicochemical properties and catalytic activity of Fe/Cr-pillared bentonites. J Nanomater. 2012;2012:3.

    Article  Google Scholar 

  48. Bahranowski K, Włodarczyk W, Wisła-Walsh E, Gaweł A, Matusik J, Klimek A, et al. [Ti, Zr]-pillared montmorillonite—a new quality with respect to Ti- and Zr-pillared clays. Microporous Mesoporous Mater. 2015;202:155–64.

    Article  CAS  Google Scholar 

  49. Roca Jalil ME, Vieira RS, Azevedo D, Baschini M, Sapag K. Improvement in the adsorption of thiabendazole by using aluminum pillared clays. Appl Clay Sci. 2013;71:55–63.

    Article  CAS  Google Scholar 

  50. Ouellet-Plamondon C, Lynch RJ, Al-Tabbaa A. Comparison between granular pillared, organo- and inorgano-organo-bentonites for hydrocarbon and metal ion adsorption. Appl Clay Sci. 2012;67–68:91–8.

    Article  Google Scholar 

  51. Bayram H, Önal M, Yılmaz H, Sarıkaya Y. Thermal analysis of a white calcium bentonite. J Therm Anal Calorim. 2011;101:873–9.

    Article  Google Scholar 

  52. de Melo C, Salomao GP, Eiras GM, Yamashita F, Dall’Antonia L, Mali S. Properties of extruded xanthan-starch-clay nanocomposites films. Braz Arch Biol Technol. 2011;54:1223–333.

    Article  Google Scholar 

  53. Castillo L, López O, López C, Zaritzky N, García MA, Barbosa S, et al. Thermoplastic starch films reinforced with talc nanoparticles. Carbohydr Polym. 2013;95:664–74.

    Article  CAS  Google Scholar 

  54. Ninago MD, López OV, Lencina MMS, García MA, Andreucetti NA, Ciolino AE, et al. Enhancement of thermoplastic starch final properties by blending with poly(ɛ-caprolactone). Carbohydr Polym. 2015;134:205–12.

    Article  CAS  Google Scholar 

  55. Park H-M, Lee S-R, Chowdhury SR, Kang T-K, Kim H-K, Park SH, Chang SH. Tensile properties, morphology, and biodegradability of blends of starch with various thermoplastics. J Appl Polym Sci. 2002;86:2907–15.

    Article  CAS  Google Scholar 

  56. Huang M-F, Yu J-G, Ma X-F. Studies on the properties of Montmorillonite-reinforced thermoplastic starch composites. Polymer. 2004;45:7017–23.

    Article  CAS  Google Scholar 

  57. Suhaida SI, Ismail H, Palaniandy S. Study of the effect of different shapes of ultrafine silica as fillers in natural rubber compounds. Polym Test. 2011;30:251–9.

    Article  Google Scholar 

  58. Ismail H, Mathialagan M. Comparative study on the effect of partial replacement of silica or calcium carbonate by bentonite on the properties of EPDM composites. Polym Test. 2012;31:199–208.

    Article  CAS  Google Scholar 

  59. Mbey JA, Hoppe S, Thomas F. Cassava starch–kaolinite composite film. Effect of clay content and clay modification on film properties. Carbohydr Polym. 2012;88:213–22.

    Article  CAS  Google Scholar 

  60. Lietz S, Yang JL, Bosch E, Sandler JKW, Zhang Z, Altstädt V. Improvement of the mechanical properties and creep resistance of SBS block copolymers by nanoclay fillers. Macromol Mater Eng. 2007;292:23–32.

    Article  CAS  Google Scholar 

  61. Liao M, Zhu J, Xu H, Li Y, Shan W. Preparation and structure and mechanical properties of poly(styrene-b-butadiene)/clay nanocomposites. J Appl Polym Sci. 2004;92:3430–4.

    Article  CAS  Google Scholar 

  62. Pedroni LG, Araujo JR, Felisberti MI, Nogueira AF. Nanocomposites based on MWCNT and styrene-butadiene-styrene block copolymers: effect of the preparation method on dispersion and polymer-filler interactions. Compos Sci Technol. 2012;72:1487–92.

    Article  CAS  Google Scholar 

  63. Huang W, Chen J, He F, Tang J, Li D, Zhu Y, et al. Effective phosphate adsorption by Zr/Al-pillared montmorillonite: insight into equilibrium, kinetics and thermodynamics. Appl Clay Sci. 2015;104:252–60.

    Article  CAS  Google Scholar 

  64. Schütz T, Dolinská S, Hudec P, Mockovčiaková A, Znamenáčková I. Cadmium adsorption on manganese modified bentonite and bentonite–quartz sand blend. Int J Miner Process. 2016;150:32–8.

    Article  Google Scholar 

  65. Volzone C, Beatriz GL. Use of modified hydroxy-aluminum bentonites for chromium(III) removal from solutions. J Environ Manag. 2008;88:1640–8.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We express our gratitude to the Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET, Argentina, Grant PIP 0428) and the Universidad Nacional del Sur (UNS, Argentina, Grant PGI 24/M135) for their financial support.

Author information

Authors and Affiliations

  1. Planta Piloto de Ingeniería Química, PLAPIQUI (UNS-CONICET), Camino ‘‘La Carrindanga’’ Km 7, CP: 8000, Bahía Blanca, Buenos Aires, Argentina

    Mario D. Ninago, Olivia V. López, M. Gabriela Passaretti, Andrés E. Ciolino & Marcelo A. Villar

  2. Instituto de Química del Sur, INQUISUR (UNS-CONICET), Av. Alem 1253, CP: 8000, Bahía Blanca, Buenos Aires, Argentina

    M. Fernanda Horst & Verónica L. Lassalle

  3. Facultad de Ciencias Aplicadas a la Industria (FCAI), Universidad Nacional de Cuyo (UNCuyo), Bernardo de Irigoyen 375, CP: 5600, San Rafael, Mendoza, Argentina

    Mario D. Ninago, Irene Carbajal Ramos & Rogelio Di Santo

  4. Departamento de Ingeniería Química, Universidad Nacional del Sur (UNS), Av. Alem 1253, CP: 8000, Bahía Blanca, Buenos Aires, Argentina

    Andrés E. Ciolino & Marcelo A. Villar

Authors
  1. Mario D. Ninago
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Olivia V. López
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. M. Gabriela Passaretti
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. Fernanda Horst
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Verónica L. Lassalle
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Irene Carbajal Ramos
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Rogelio Di Santo
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Andrés E. Ciolino
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Marcelo A. Villar
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mario D. Ninago.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Ninago, M.D., López, O.V., Gabriela Passaretti, M. et al. Mild microwave-assisted synthesis of aluminum-pillared bentonites. J Therm Anal Calorim 129, 1517–1531 (2017). https://doi.org/10.1007/s10973-017-6304-6

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-017-6304-6

Keywords

Search

Navigation