Ultrasonics Sonochemistry 18 (2011) 238–242

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Synthesis and characterization of Nano-bentonite by sonochemical method

Zahra Darvishi, Ali Morsali *
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14155-4838, Tehran, Islamic Republic of Iran

a r t i c l e i n f o a b s t r a c t

Article history: Nano-bentonite with novel nano-wire morphology has been fabricated by a sonochemical method in dif-
Received 9 October 2009 ferent ultrasound powers, times and concentrations. The nano-bentonite was characterized by X-ray
Received in revised form 28 April 2010 fluorescence analysis (XRF), X-ray powder diffraction (XRD), thermal gravimetry analysis (TGA), differen-
Accepted 26 May 2010
tial thermal analysis (DTA) and infrared spectroscopy. Scanning electron microscopy (SEM) and transmis-
Available online 4 June 2010
sion electron microscopy (TEM) revealed that using ultrasound irradiation led to a bentonite
nanostructure. The surface area of the bulk and nano-bentonite was determined by BET.
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Sonochemistry
X-ray diffraction
Nano-bentonite
Electron microscopy

1. Introduction
Clays are used for different purposes [1]. Clay–drug interactions
are rather complex phenomena as well as many clay-organics
reciprocal actions [2] because they involve physical or Van der
Waals forces, hydrogen bonds, ion-exchange, coordination, and
chemisorptions.
Clay minerals include some minerals such as bentonite [3], atta-
pulgite, mica [4], kaolinite [5] which have different molecular
structures and are used in different purposes. These materials
can be found in the nature from different sources and can also be
synthesized in the laboratory.
Bentonite is an aluminium phyllosilicate, a generally impure
clay consisting mostly of montmorillonite. There are a few types
of bentonites and their names depend on the dominant elements,
such as K, Na, Ca, and Al. Industrial bentonite is a very rich clay
mineral, consisting of layers of two tetrahedral silica sheets
sandwiching one octahedral alumina sheet [6]. Bentonite–water
systems are of great importance for agricultural, industrial, envi-
ronmental and civil engineering activities such as desiccant prepa-
ration, sealant, ceramic, cat box adsorbent, iron ore pellet, molding
sand for foundry, drilling mud and arrieres for water and protec-
tion from nuclear waste [7–9].
The change in the physical state of a bentonite from an anhy-
drous solid to gel is especially due to the smectite minerals
[10–12]. The swelling of smectites, which occurs by intra- and
interparticle interactions in the face-to-face arrangement of the
2:1 (TOT) layers, is a very complex process [13–15]. Recently, org-
* Corresponding author. Tel.: +98 2182884416; fax: +98 2188009730.
E-mail addresses: morsali_a@modares.ac.ir, morsali_a@yahoo.com (A. Morsali).
ano-clays have been used as new adsorbents in the field of pollu-
tion control [16]. They have been used in the treatment of
wastewater from oil [17,18] detergents, solvents [19], phenols
[20] and heavy metal ions. Bentonite is one of the clays that is com-
monly used in the fabrication of organo-clays due to its high cation
exchange capacity, swelling capacity, high specific surface area and
high adsorption capacity [21].
In the present work we have developed a simple sonochemical
method to prepare bentonite nanostructures. Ultrasound induces
chemical changes due to cavitation phenomena, which involve
the formation, growth, and instantaneously implosive collapse of
bubbles in liquid, which can generate local hot spots having a tem-
perature of roughly 5000 °C, pressures of about 500 atm, and a life-
time of a few microseconds. These extreme conditions can drive
chemical reactions which have been developed to fabricate a vari-
ety of nano-compounds [22]. A suspension of bentonite under dif-
ferent sonication powers at different times and concentrations was
used for the preparation of nanostructural bentonite. The bentonite
nanostructure has been characterized by X-ray powder diffraction
(XRD), thermal gravimetry analysis (TGA), differential thermal
analysis (DTA), IR spectroscopy, and also the morphology and size
of the nanorods have been observed by scanning electron micros-
copy (SEM) and transmission electron microscopy (TEM).
2. Experimental
The bentonite sample was obtained from Merck. A suspension
of bentonite in ethanol was prepared and sonicated with different
powers. The suspension was ultrasonically irradiated for 30 min,
1,2,4 h with a high-intensity ultrasonic probe immersed directly
into the solution under various conditions (Table 1). Under all

1350-4177/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2010.05.012
 Z. Darvishi, A. Morsali / Ultrasonics Sonochemistry 18 (2011) 238–242 239

Table 1 were performed using an X’pert diffractometer of Philips company

Experimental conditions for the preparation of nano-bentonite at 25 °C. with mono chromatized Cuka radiation. The crystallite sizes of se-
Sample Time (h) Solvent (ml) Ultrasound power Mass of Bentonite lected samples were estimated using the Sherrer formula. The
(W) Sonicated chemical composition of the materials was determined with X-
1 4 50 40 0.18 ray fluorescence analysis (XRF), using a MagiXPRO spectrometer
2 4 50 50 0.18 (Phillips). TGA and DTA curves were recorded using a PL-STA
3 4 50 60 0.18 1500 device manufactured by Thermal Sciences. IR spectra were
4 4 50 70 0.18
5 4 50 80 0.18
recorded on a SHIMADZU-IR460 spectrometer in a KBr matrix.
6 4 50 90 0.18 The samples were characterized with a scanning electron micro-
7 4 50 100 0.18 scope (SEM) (Philips XL 30) with gold coating and a transmission
8 2 50 50 0.18 electron microscope (TEM) [Zeiss CEM 902 A]. The BET surface area
9 1 50 50 0.18
of the samples were determined from N2 adsorption–desorption
10 0.5 50 50 0.18
isotherms using a Surface Area Analyzer (BET, BELSORP mini-II).
The nitrogen adsorption–desorption isotherms were measured at
77 K after outgassing the samples at 100 °C for 3 h.

conditions the results were the same and the consequences of

changing the sonochemical parameters were marginal. However,
under various conditions different particle sizes were achieved,
and the best morphology and particle sizes obtained were for sam-
ple 2. A multiwave ultrasonic generator (Sonicator_3000; Misonix,
Inc., Farmingdale, NY, USA), equipped with a converter/transducer
and titanium oscillator (horn), 12.5 mm in diameter, operating at
20 kHz with a maximum power output of 600 W, was used for
the ultrasound at 25 °C. The powders were characterized by XRD,
TGA/DTA, IR spectroscopy, BET, SEM and TEM. The nanostructural
bentonite was calcined at 800 °C for 4 h, then the powders were
characterized by XRD, IR spectroscopy and scanning electron
microscopy (SEM). X-ray powder diffraction (XRD) measurements
3. Results and discussion
The chemical composition of the raw material was determined
by XRF analysis and the results show aluminium silicate as the
most prevalent compound. There are, in addition, some impurity
due to compounds containing Fe, Mg and Na.
Fig. 1 shows the XRD patterns of nano-bentonite prepared by
the sonochemical process (bottom) and bulk bentonite (middle).
The patterns show peaks at 2h = 26.639 (quartz) 7.123, 19.801
and 28.775 (beidellite). The crystalline phases of quartz and beid-
ellite are hexagonal, with the lattice parameters (a = 4.91344 Å,
c = 5.40524 Å, z = 3) for quartz and (a = 5.172 Å and c = 12.389 Å)

Fig. 1. The XRD pattern of nano-bentonite (bottom) and bentonite as bulk powder (middle) and nanoparticles of dolomite produced from calcination of nano-bentonite (top).
240 Z. Darvishi, A. Morsali / Ultrasonics Sonochemistry 18 (2011) 238–242
for beidellite. Acceptable matches are observed indicating the pres-
ence of same crystalline phase in nano-bentonite prepared by the
sonochemical process and bulk bentonite. Using the Sherrer for-
mula for the calculation of particle sizes from the broadening of
the XRD peaks (D = 0.891k/b cos h, where D is the average grain
size, lambda is the X-ray wavelength (0.15405 nm), and h and b
are the diffraction angle and full-width at half maximum of an ob-
served peak, respectively [23–26]), the average size of the particles
prepared via the sonochemical method was found to be around
30 nm, which is in agreement with the value obtained from the
SEM images (Fig. 2).
Fig. 2 shows the SEM images of the bulk bentonite, obtained un-
der the same temperature conditions with stirring only and no
sonication (Fig. 2a), along with nano-bentonite prepared by the
sonochemical process (Fig. 2b) obtained for sample No 2 (Table
1). The particle size histogram of nano-bentonite (Fig. 2c) shows
that particle size ranged from 5 to 50 nm. The minimum particles
size was obtained for the sample number 2 (Table 1). The TEM of
the nano-bentonite (Fig. 3) shows that the nano-bentonite has a
wire or fiber structure, and dispersed very effectively in water.
EDAX was performed to further confirm the composition of the
as-prepared nano-bentonite. Fig. 4 shows that sample No. 2 of ben-
tonite nanostructures is composed of Mg, Si, Al, Ca, and Fe.
Fig. 5 shows the IR spectra of bulk bentonite (Fig. 5a) and nano-
bentonite prepared by the sonochemical process (Fig. 5b). There
are no changes in the IR absorption peaks, and the IR spectra of
Fig. 2. SEM photographs of (a) bulk bentonite (b) nano-bentonite, (sample 2) and
(c) the particle size histogram of nano-bentonite.
Fig. 3. TEM images of nano-bentonite.
the nanostructure bentonite and of the bulk bentonite material
are indistinguishable. The relatively weak IR absorption bands
around 3600–3300 cm–1 are ascribed to O–H stretching vibration.
The sharp absorption peak at 1035 cm–1 corresponds to the
stretching vibration of the Si–O bond. The peaks at 471–526 cm–1
are due to an Si–O bending vibration, and the peak at 800 cm 1
may correspond to the stretching vibration of Al–O–Si [27]. The
bands at 3396 and 1653 cm–1 are attributed to water molecules
in the bentonite structure. The band at 1031 cm–1 has been attrib-
uted to the asymmetric stretching modes of Si–O–Si. The OH bend-
ing bands appear at 985 cm–1 [28–30].
To examine the thermal stability of the nano-sized and bulk
material of attapulgite, thermal gravimetric (TG) and differential
thermal analyses (DTA) were carried out between 30 and 700 °C
in a static atmosphere of nitrogen. Fig. 6a shows the TGA diagram
of a bulk sample of bentonite and Fig. 6b shows the TGA diagram of
nano-bentonite prepared by the sonochemical process (sample No.
2).
The TGA curves show a weight loss of 6% between 30C and 60 °C
which is due to the removal of the physically adsorbed water mol-
ecules in nano-bentonite and bulk bentonite. Also, the TGA curve
shows a second loss of 4% between 60 and 600 °C which is due
to the removal of chemisorbed water, water molecules coordinated
to the pillars and dehydroxylation of the pillars in nano-bentonite
and the bulk sample of bentonite. The clay structure collapse con-
tinues even at 800 °C. Fig. 1c shows the pattern of nano-bentonite
after calcination.
BET surface area measurements were performed on two sam-
ples, the sample without sonication, and sample 2. The results
are illustrated in Table 2. The average pore diameters and total
pore volumes were also calculated. For sample 2, the measured
surface area was less than the pure sample of bentonite, probably
due to the much lower number of pores in the nano-sized
bentonite.
Fig. 1 (top) shows the pattern of a sample of bentonite which
was calcinated at 800 °C for 4 h. The peak at 2h = 8.14 has disap-
peared and the lattice parameters are a = 4.8092 Å, c = 16.020 Å
and z = 3. The pattern that has been obtained matches the standard
pattern of dolomite in the rhombohedral crystal system. The
IR spectrum after calcination shows that the bands at 3600–
3300 cm–1 have disappeared. Fig. 7 shows the SEM image of the
nanoparticles of dolomite produced from calcination of nano-ben-
tonite. Calcination seems to result in a complete decomposition
 Z. Darvishi, A. Morsali / Ultrasonics Sonochemistry 18 (2011) 238–242 241

Fig. 4. EDAX analysis of nano-bentonite.

Fig. 5. IR spectrum of (a) nanostructure bentonite (sample 2), (b) bulk bentonite and (c) nanoparticles of dolomite produced from calcination of nano-bentonite.
242 Z. Darvishi, A. Morsali / Ultrasonics Sonochemistry 18 (2011) 238–242

and break up of the compound and with changes in both morphol-

ogy and nanostructure.

4. Conclusion

We have successfully synthesized nano-wires of bentonite by a

sonochemical method. The process proceeding under ultrasonic
conditions results in bentonite nano-wires. All the results obtained
by SEM, TEM images and XRD, TG/DTA and FT-IR analyses confirm
the production of uniform nano-wires of bentonite. The sonication
of bulk bentonite would produce wire-like nanostructures and the
morphology change upon sonication occurs. This method can
potentially be used on an industrial scale because it does not need
special conditions, such as high temperature, special surfactants,
long time periods or temperature and pressure controlling.

Acknowledgement

Support of this investigation by Pars Oil and Gas Company

Fig. 6. TGA diagrams of (a) bentonite (b) nano-bentonite (sample 2).
gratefully acknowledged.

Table 2
BET surface area values and mean pore diameters. References
2
Sample Surface area(m /g) Mean pore diameter (nm) [1] M.T. Droy-Lefaix, F. Tateo, Dev. Clay Sci. 1 (2006) 743.
Bentonite (WU) 24.08 1.97 [2] G.W. Beall, M Goss, Appl.Clay Sci. 27 (2004) 179.
Nano-bentonite 11.08 2.34 [3] G. Guan, C. Li, D. Zhang, J Appl Polym Sci 95 (2005) 1443.
[4] C. Saujanya, Y. Imai, H. Tateyama, Polym Bull 49 (2002) 69.
WU = without sonication. [5] L. Cabedo, E. Giménez, J.M. Lagaron, R. Gavara, J.J. Saura, Polymer 45 (2004)
5233.
[6] Q.H. Hu, S.Z. Qiao, F. Haghseresht, M.A. Wilson, G.Q. Lu, Ind. Eng. Chem. Res. 45
(2006) 733.
[7] A. Neaman, M. Pelletier, F. Villieras, App.Clay Sci. 22 (2003) 53.
[8] R.N. Yong, Engi.Geolo. 54 (1999) 3.
[9] H. Komine, S. Ogata, Soil Founds 39 (1999) 83.
[10] F.F. Low, Soil Sci.Soc.of Am.J. 44 (1980) 667.
[11] H. Komine, N. Ogata, Cana. Geotec.J. 31 (1994) 478.
[12] H. Komine, S. Ogata, Cana.Geotech.J. 33 (1996) 11.
[13] U.D. Pennino, E. Mazzoga, S. Valari, A. Alietti, M.F. Brigatti, L. Poppi, J. Colloid
Interface Sci. 84 (1981) 301.
[14] K. Norrish, Faraday Discuss. Soc. 18 (1954) 120.
[15] J.C. Parker, L.W. Zelazny, D.F. Amos, Clays Clay Min. 28 (1980) 135.
[16] H. Zhao, G.F. Vance, Water Res. 32 (1998) 3710.
[17] Gary.W. Beall, Appl. Clay Sci. 24 (2003) 11.
[18] O. Carmody, R. Frost, Y. Xi, S. Kokot, J. Coll. Interf. Sci. 305 (2007) 17.
[19] L. Zhu, X. Ren, S.Yu, Environ. Sci. Technol. 32 (1998) 3374.
[20] Y.-H. Shen, Physicochem. Eng. Aspects 232 (2004) 143.
[21] S. Peker, S. Yapar, N. Besun, Coll. Surf. A 104 (1995) 249.
[22] H. Zhan, X.G. Yang, Inorg. Chem. Commun. 2 (1999) 447.
[23] K.-T. Wong, J.-M. Lehn, S.-M. Peng, G.-H. Lee, Chem. Commun. (2000) 2259.
[24] J.A. Ramsden, W. Weng, A.M. Arif, J.A. Gladysz, J. Am. Chem. Soc. 114 (1992)
5890.
[25] W. Weng, J.A. Ramsden, A.M. Arif, J. Am. Chem. Soc. 115 (1993) 3824.
[26] N.Le. Narvor, L. Toupet, C. Lapinte, J. Am, Chem. Soc. 117 (1995) 7129.
[27] R.L. Frost, G.A. Cash, J.T. Kloprogge, Vibrat. Spectrosc. 16 (1998) 173.
[28] R.L. Frost, O.B. Locos, H. Ruan, J.T. Kloprogge, Vibrat. Spectrosc. 27 (2001) 1.
[29] J. Madejova, Vibrat. Spectrosc. 31 (2003) 1.
[30] D.M. Araújo Melo, J.A.C. Ruiz, M.A.F. Melo, M. Schmall, Micropor. Mesopor.
Fig. 7. SEM photographs of nanostructure of dolomite produced from calcination of Mater. 8 (2000) 345.
nano-bentonite.