Ultrasonics Sonochemistry xxx (2013) xxx–xxx

Contents lists available at ScienceDirect

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

Dispersion of nanoparticles: From organic solvents to polymer solutions

Van Son Nguyen, Didier Rouxel ⇑, Brice Vincent
Institut Jean Lamour, UMR CNRS 7198, Faculté des Sciences et Techniques, Université de Lorraine, 54506 Vandœuvre-lès-Nancy, France

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

Article history: This work is devoted to a systematic study of nanoparticle dispersion by ultrasonication in different solu-
Received 8 March 2013 tions: from organic solvents to polymer solutions. The cluster size of nanoparticles at different concen-
Received in revised form 19 July 2013 trations in both organic solvents and polymer solutions were directly characterized by Dynamic Light
Accepted 25 July 2013
Scattering to study the effect of solid concentration, surfactant and polymer on the dispersion. It reveals
Available online xxxx
that in stabilized suspensions, the smallest attainable size or aggregate size of nanoparticles is indepen-
dent of solvent type and solid content over the tested range. Furthermore, nanoparticles in simple solvent
Keywords:
and in polymer solutions had the similar evolution of cluster size and almost the same final size, which
Dispersion
Nanoparticles
could be very helpful to optimize the dispersion of nanofillers in polymer solutions and nanocomposites.
Ultrasonication It is also shown that, with appropriate sonication amplitudes, the dispersion procedure developed for
Polymer suspensions very dilute suspensions could be transferred to higher concentration suspensions or even to polymer
Aluminium oxide suspensions.
Zinc oxide Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction of nanofillers in polymer nanocomposites. Furthermore, there are

very different or even opposite results about the optimum process-
Suspensions of fine particles, especially nanoparticles, have at- ing conditions of nanoparticle dispersion in polymer solutions, for
tracted significant interest due to their large variety of application example in epoxy resin ([16] and references therein). The disper-
in chemistry, biology, medicine and material science [1–8]. Mixing sion quality was usually characterized indirectly from transmis-
of dry powders in a liquid phase has been one of the basic human sion electron microscopy or scanning electron microscope image
operations in many areas of daily life. However, homogenous dis- analysis or by measuring the particle size in diluted suspensions.
persion allowing taking full advantage of nanoparticles still remain It is worth noting that the cluster size in suspensions can be af-
a great challenge in numerous areas including coating, paints, inks, fected by various parameters including particle content, colloidal
drug delivery, ceramic and nanocomposite processing. stabilization (electrical charges, absorbed surface layers) and also
During synthesis processes and post-processes, for example polymer interaction. Thus, the cluster size could change upon sus-
heating stage necessary to obtain the crystalline phase [9] or mi- pension dilution.
celle removal stage in the reverse micelle-based synthesis tech- In this work, a systematic study of nanoparticle dispersion with
nique [10], primary particles often form large clusters. Depending different concentrations in Methyl Ethyl Ketone (MEK) and solu-
on the bond strength between primary particles, clusters can be di- tions of copolymer of vinylidene difluoride and trifluoroethylene
vided into two types: aggregate created by covalent bonds be- (P(VDF-TrFE)) was accomplished. The cluster size was character-
tween primary particles and agglomerates defined as looser and ized directly in suspension at high nanofiller concentration, even
more open structures that can be separated into primary compo- in polymer solutions and compared with the result of aqueous sus-
nents [11–13]. In agglomerate structure, the components are held pensions in the previous study [18] to evaluate the dispersion
together by weak forces such as electrostatic, magnetic forces, or quality.
by weak material bridges between particles including hydrogen
bonds or interaction of flocculants in suspensions [12]. 2. Experimental
High intensity ultrasound has been widely used to disperse
powder in a liquid [14–20]. In spite of abundant studies on ultra- In the present study, commercial nanoparticles of Al2O3 (Aerox-
sonic dispersion in aqueous and non-aqueous solutions, very little ide AluCÒ, Degussa, Germany) and ZnO (NanoGardÒ) were used.
is known about the dispersion of nanoparticles in high viscosity The primary particle size of Al2O3 and ZnO nanoparticles were
polymer solutions, which is essential to optimize the dispersion respectively 13 nm and 60 nm, which were determined from
Transmission Electron Microscopy (TEM) images. The diethyl octa-
⇑ Corresponding author. Tel.: +33 (0)3 83 68 46 47; fax: +33 (0)3 83 68 49 33. decyl phosphonate, C18H37P(O)(OC2H5)2 (P18Et2) was synthesized
E-mail address: didier.rouxel@univ-lorraine.fr (D. Rouxel). using the method adopted by Gaboyard [21]. The copolymer of

1350-4177/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.ultsonch.2013.07.015

Please cite this article in press as: V.S. Nguyen et al., Dispersion of nanoparticles: From organic solvents to polymer solutions, Ultrason. Sonochem. (2013),
http://dx.doi.org/10.1016/j.ultsonch.2013.07.015
2 V.S. Nguyen et al. / Ultrasonics Sonochemistry xxx (2013) xxx–xxx

vinylidene difluoride and trifluoroethylene (P(VDF-TrFE)) (70/ with large agglomerates (1700 nm) and smaller components
30 mol.%), Mw = 1370000 from Piezotech S.A.S. (France) was dis- (220 nm) (Fig. 1). With increase of ultrasonication time, the large
solved in Methyl Ethyl Ketone (MEK) (Acros Organics) by stirring agglomerates were broken into smaller fragments and progres-
at 80 °C to prepare a 12 wt.% solution, which is often used to elab- sively reduced to aggregates.
orate composites and devices [22–26]. The evolutions of alumina mean cluster size as a function of
The dispersion of nanoparticles in solutions was carried out ultrasonication time in water and MEK are presented in Fig. 2.
with a Transducer Digital SonifierÒ Model 450 (Branson Ultrason- The values of the final size of alumina clusters in both solutions
ics Corporation, USA). Its maximum power input and frequency were identical. This result reveals that when nanoparticles were
are 400 W and 20 kHz, respectively. The ultrasonic horn that was stabilized, the smallest size of aggregates after ultrasonication
immerged in suspension has a tip diameter of 13 mm and the son- was independent of solvent. However, in the same conditions,
ication amplitude (tip movement) is in the range of 10–65 lm. To the cluster size was reduced faster in water than in MEK. In aque-
reduce the heating up of suspensions during sonication, the ultra- ous suspensions, the nanoparticles are stabilized by electrostatic
sonic mode with a pulse ratio on/off 0.1/0.1 (s/s), which showed repulsion of the permanent electrical charges on their surface. In
the same efficiency of deagglomeration with continuous irradia- non-aqueous systems, colloidal stability is mostly controlled by
tion [18], was used. The vessel of suspension was cooled using steric repulsion induced by adsorbed dispersant layers (adlayers).
an ice-water bath. Such organic molecules should be strongly anchored around the
The mean cluster size based on the intensity of scattered light particle surface. However, the bonding between surfactant and
(often given with the symbol Z-average) was measured by Dy- particles can be broken under ultrasonic irradiation [17] and the
namic Light Scattering (DLS, Zetasizer Nano ZS, Malvern Instru- steric stabilization is therefore slowed down. As can be seen in
ments Ltd.). The viscosity of suspensions was characterized by a Fig. 2, the cluster size decreases faster in the suspension of
rheometer (RheolabQC, Anton Paar). The available shear rate of this P18Et2/MEK at 1 mg/ml than that at 0.8 mg/ml. Since the adsorp-
device is between 0.1 s1 and 5000 s1. The relationship between tion rate increases with concentration of the surfactant, the new
particle size and viscosity is described by the Stokes–Einstein surfaces of cluster could be stabilized more quickly against re-
equation: agglomeration with higher concentration of surfactant. However,
there is a greater tendency to form larger agglomerates due to
kT the material bridge between particle surfaces at high surfactant
dðHÞ ¼
3pgD concentration [18].
where d(H) is hydrodynamic diameter, D is translational diffusion
coefficient, k is Boltzmann’s constant, T is absolute temperature, g 3.2. Dispersion of nanoparticles at high concentration in solvent
is dynamic viscosity.
The nanoparticles were also characterized by Transmission Nanoparticle concentration could affect the cluster size and vis-
Electron Microscopy (TEM, Philips CM 200). The samples were pre- cosity of the suspension. The rheological behavior of suspensions
pared by placing a drop of suspension after ultrasonication on a depends strongly on the solid loading and has been studied in sev-
carbon film coated copper grid and then dried at room conditions. eral contributions [27,28]. In the present study, the suspensions of
For analyzing the dispersion of nanoparticles in polymer nancom- alumina in water up to 50 mg/ml exhibited the Newtonian viscosity
posite, TEM images of 100-nm thick films prepared by spin-coating plateau at shear rate between 500 s1 and 1100 s1 (Fig. 3). The val-
directly on copper grid from solution of the polymer in MEK were ues of the Newtonian plateau, at the shear rate of 880 s1, were
done. The average cluster diameters were measured manually used to calculate the size of the clusters in the Stokes–Einstein
from the images. equation. The Newtonian viscosity (Fig. 3) and cluster size (Fig. 4)
of Al2O3 suspensions decreased with increasing ultrasonication
time. The similar results were also observed for TiO2 nanoparticle
3. Results and discussion
suspensions [14].
As shown in Fig. 4, between 1 and 50 mg/ml, the cluster size
3.1. Dispersion of nanoparticles at low concentration in solvent
showed almost the same final value and evolution as a function
of ultrasonic time. It reveals that the concentration of alumina
The dispersion of alumina nanoparticles in low concentration
suspension was investigated in previous work [18]. The results
showed that aqueous suspensions of Al2O3 nanoparticles are stabi-
lized by electrostatic forces and the enhancement of colloidal sta-
bility using electrostatic repulsion (by changing pH or ionic
strength), steric hindrance (using surfactants) has no significant ef-
fect on the aggregate size. Despite the Al2O3 primary particle size
of 13 nm, the agglomerates are reduced to hard aggregates that
could not be broken into individual nanoparticles and the smallest
attainable size is about 150 nm (the value from intensity distribu-
tion). This aggregate size could not be reduced even for a very long
irradiation time, but the reagglomeration could be occurred during
long ultrasonication [15,18]. For low viscosity suspensions, the
sonication amplitude is optimized at 30% as higher amplitudes
do not improve the deagglomeration of nanoparticle clusters [18].
In organic solvents, the nanoparticles are generally stabilized by
steric effect. In this study, diethyl octadecyl phosphonate (P18Et2)
was used for the stabilization. The suspensions of alumina at 1 mg/
ml in MEK were stabilized against reagglomeration by adding
0.8 mg/ml P18Et2. Particle size distribution (PSD) of Al2O3 in Fig. 1. Particle population of Al2O3/P18Et2/MEK 1 mg/1 mg/ml as a function of
MEK suspensions after magnetic stirring showed bi-modal feature ultrasonic time.

Please cite this article in press as: V.S. Nguyen et al., Dispersion of nanoparticles: From organic solvents to polymer solutions, Ultrason. Sonochem. (2013),
http://dx.doi.org/10.1016/j.ultsonch.2013.07.015
 V.S. Nguyen et al. / Ultrasonics Sonochemistry xxx (2013) xxx–xxx 3

nanoparticles in the studied range had a very low effect on the

cluster size. This result should be emphasized because the disper-
sion procedure of very low concentration suspensions could be
transferred to higher concentration suspensions. This is very inter-
esting because we can characterize the cluster size to optimize the
nanoparticle dispersion with a very low quantity of solid but the
dispersion parameters could be used in a quite large range of
concentration.

3.3. Dispersion of nanoparticles at high concentration in polymer

solutions

A long term stability of Al2O3 up to 10 wt.% (in the final nano-

composites) in the P(VDF-TrFE)/MEK solutions was reported in
the previous study [29]. The stability without surfactant is attrib-
uted to hydrogen bonding between the surface hydroxyl groups
Fig. 2. Evolution of mean cluster size of alumina 1 mg/ml versus ultrasonic time in
of alumina and the fluorine in the copolymer. It is noted that nano-
different suspensions. composites filled with 10 wt.% of nanoparticles are prepared by
adding 13 mg/ml of nanofillers in 12 wt.% polymer solutions. Since
it is difficult to manipulate with the volume of viscous polymer
solutions, the weight percent concentration of nanoparticles in
the final nanocomposites is used henceforth.
The effect of ultrasonic amplitude, duration, and suspension
volume on the particle cluster size in polymer solutions, in partic-
ular in epoxy resin, was investigated by Bittmann et al. [16]. The
authors reported that there exists a final cluster size for certain
ultrasonication parameters and this final particle size can only be
reduced by changing the process parameters, especially the ultra-
sonic amplitude. It means that higher sonication amplitude leads
to better dispersion. In our study, the amplitude of 60% of the max-
imum movement, almost the highest value recommended by the
device supplier, was used to disperse nanoparticles in the polymer
solutions. However, during the ultrasonication at this amplitude,
the polymer suspensions were heated up strongly, for example
from 0 °C to more than 40 °C after 90 s of irradiation, and have to
be cooled externally to reduce the solvent evaporation.
The presence of the copolymer in suspensions increases consid-
erably the viscosity. The suspensions of Al2O3/P(VDF-TrFE) 10 wt.%
in the solution of P(VDF-TrFE)/MEK 12 wt.% showed the Newtonian
Fig. 3. Evolution of the viscosity of the suspensions of Al2O3/water at 50 mg/ml viscosity plateau at shear rate between 30 s1 and 100 s1 (Fig. 5).
versus shear rate at different durations of ultrasonication.
At the same shear rate, the viscosity increased slightly with ultra-
sonic time. Although the degradation of polymer [30] and the
reduction of cluster size reduced the suspension viscosity, the

Fig. 5. Evolution of the viscosity of the suspension of Al2O3/P(VDF-TrFE) 10 wt.% in

Fig. 4. Evolution of mean cluster size versus ultrasonic time of alumina in waterat the solution of P(VDF-TrFE)/MEK 12 wt.% versus shear rate at different durations of
different concentrations. ultrasonication.

Please cite this article in press as: V.S. Nguyen et al., Dispersion of nanoparticles: From organic solvents to polymer solutions, Ultrason. Sonochem. (2013),
http://dx.doi.org/10.1016/j.ultsonch.2013.07.015
4 V.S. Nguyen et al. / Ultrasonics Sonochemistry xxx (2013) xxx–xxx

evaporation of the solvents during the ultrasonic irradiation in- The results were confirmed by the experiments with ZnO nano-
creased the viscosity. particles (Fig. 6b). The final cluster sizes of ZnO in MEK and in the
Alumina nanoparticles in MEK at very low concentration and in copolymer solution were very close. The small difference in the fi-
P(VDF-TrFE) solutions at high solid concentration exhibited almost nal cluster sizes might be due to the error of viscosity measure-
the similar final cluster size (Fig. 6a). It confirms once again that ments. The result also reveals that P(VDF-TrFE) could play the
the characteristic aggregate size of nanoparticles depends only role of surfactant and did not lead to large reagglomeration of
on the particle preparation procedure. This could be very helpful nanoparticles, unlike polyelectrolytes, e.g. poly(acrylic acid) [18].
for optimizing the dispersion of nanoparticle in polymer solutions TEM images of Al2O3 and ZnO from MEK suspensions and in
which is usually a difficult procedure and requires a lot of P(VDF-TrFE) nanocomposites were presented in Fig. 7a–d. It can
materials. be seen that there are some single nanoparticles but rather clusters

Fig. 6. Evolution of mean cluster size of (a) Al2O3 and (b) ZnO versus ultrasonic time in MEK and solutions of P(VDF-TrFE).

Fig. 7. TEM images of Al2O3/P18Et2/MEK 1 mg/1 mg/ml (a), nanocomposites of P(VDF-TrFE)/Al2O3 10 wt.% (b), ZnO/P18Et2/MEK 1 mg/1 mg/ml (c) and nanocomposites of
P(VDF-TrFE)/ZnO 10 wt.% (d).

Please cite this article in press as: V.S. Nguyen et al., Dispersion of nanoparticles: From organic solvents to polymer solutions, Ultrason. Sonochem. (2013),
http://dx.doi.org/10.1016/j.ultsonch.2013.07.015
 V.S. Nguyen et al. / Ultrasonics Sonochemistry xxx (2013) xxx–xxx 5

consisting of several primary particles connected by solid bonds [9] M. Aufray, S. Menuel, Y. Fort, J. Eschbach, D. Rouxel, B. Vincent, New synthesis
of nanosized niobium oxides and lithium niobate particles and their
and thus, cannot be broken up by conventional dispersion meth-
characterization by xps analysis, J. Nanosci. Nanotechnol. 9 (2009) 4780–4785.
ods. The nanofiller clusters were well distributed within the [10] J. Eastoe, M.J. Hollamby, L. Hudson, Recent advances in nanoparticle synthesis
copolymer matrix without phase separation or de-cohesion be- with reversed micelles, Adv. Colloid Interf. Sci. 128–130 (2006) 5–15.
tween the matrix and fillers. In addition, the mean cluster sizes [11] A.P. Tinke, R. Govoreanu, I. Weuts, K. Vanhoutte, D. De Smaele, A review of
underlying fundamentals in a wet dispersion size analysis of powders, Powder
of both Al2O3 and ZnO determined graphically from MEK suspen- Technol. 196 (2009) 102–114.
sions and in the final P(VDF-TrFE) nanocomposites were close to [12] J. Tomas, Adhesion of ultrafine particles – A micromechanical approach, Chem.
the values of the aggregate sizes measured by DLS in suspensions. Eng. Sci. 62 (2007) 1997–2010.
[13] S.M. Iveson, J.D. Litster, K. Hapgood, B.J. Ennis, Nucleation, growth and
This confirms the good dispersion in the copolymer solutions and breakage phenomena in agitated wet granulation processes: a review, Powder
in MEK. The results also show that the nanocomposite film pro- Technol. 117 (2001) 3–39.
cessing did not modify the dispersion. [14] K. Sato, J.G. Li, H. Kamiya, T. Ishigaki, Ultrasonic dispersion of TiO2
nanoparticles in aqueous suspension, J. Am. Ceram. Soc. 91 (2008) 2481–2487.
[15] N. Mandzy, E. Grulke, T. Druffel, Breakage of TiO2 agglomerates in
4. Conclusion electrostatically stabilized aqueous dispersions, Powder Technol. 160 (2005)
121–126.
[16] B. Bittmann, F. Haupert, A.K. Schlarb, Ultrasonic dispersion of inorganic
The dispersion of Al2O3 and ZnO nanoparticles at different con- nanoparticles in epoxy resin, Ultrason. Sonochem. 16 (2009) 622–628.
centrations in organic solvent and in polymer solutions was di- [17] N.L. Ngoc, K. Takaomi, Ultrasound stimulus effect on hydrogen bonding in
rectly investigated. The results indicate that under optimum networked alumina and polyacrylic acid slurry, Ultrason. Sonochem. 17 (2010)
186–192.
ultrasonic parameters, the stabilized nanoparticles exhibited the [18] V.S. Nguyen, D. Rouxel, R. Hadji, B. Vincent, Y. Fort, Effect of ultrasonication
same final cluster size in aqueous, organic and polymer suspen- and dispersion stability on the cluster size of alumina nanoscale particles in
sions. Over the tested range, the solid concentration had very aqueous solutions, Ultrason. Sonochem. 18 (2011) 382–388.
[19] F. Müller, W. Peukert, R. Polke, F. Stenger, Dispersing nanoparticles in liquids,
low effect on the cluster size. It shows that the dispersion results Int. J. Miner. Process. 74 (Suppl.) (2004) S31–S41.
in low concentration suspensions could be transferred to concen- [20] C. Schilde, C. Mages-Sauter, A. Kwade, H.P. Schuchmann, Efficiency of different
trated suspensions or even to polymer solutions. The analysis of dispersing devices for dispersing nanosized silica and alumina, Powder
Technol. 207 (2011) 353–361.
TEM images of the nanocomposites also reveals that both Al2O3 [21] M. Gaboyard, Y. Hervaud, B. Boutevin, Synthese et Etude Structurale D’acides
and ZnO nanoparticles were well dispersed in the P(VDF-TrFE) ma- Alkylphosphoniques a Longue Chaine Hydrocarbonee, Phosphorus, Sulfur
trix with the cluster sizes close to the aggregate sizes. Silicon Relat. Elem. 177 (2002) 877–891.
[22] R. Hadji, V. Nguyen, B. Vincent, D. Rouxel, F. Bauer, Preparation and
characterization of P(VDF-TrFE)/Al2O3 nanocomposite, IEEE Trans. Ultrason.
Acknowledgment Ferroelectrics Frequency Control 59 (2012) 163–167.
[23] S. Chen, K. Yao, F.E.H. Tay, L.L.S. Chew, Comparative investigation of the
structure and properties of ferroelectric poly(vinylidene fluoride) and
This work was funded by the French National Agency for Re-
poly(vinylidene fluoride-trifluoroethylene) thin films crystallized on
search (No. ANR-08-NANO-041) and labelled by the French com- substrates, J. Appl. Polym. Sci. 116 (2010) 3331–3337.
petitiveness clusters PLASTIPOLIS and MATERALIA. [24] T. Sharma, S.-S. Je, B. Gill, J.X.J. Zhang, Patterning piezoelectric thin film PVDF–
TrFE based pressure sensor for catheter application, Sensors Actuators A Phys.
177 (2012) 87–92.
References [25] S. Wi, N. Senthilkumar, S.W. Rhee, Characterization of poly (vinylidene
fluoride-trifluoroethylene) 50/50 copolymer films as a gate dielectric, J.
[1] W. Schartl, Current directions in core-shell nanoparticle design, Nanoscale 2 Mater. Sci. Mater. Electron. 19 (2008) 45–50.
(2010) 829–843. [26] V.S. Nguyen, D. Rouxel, B. Vincent, L. Badie, F.D.D. Santos, E. Lamouroux, Y.
[2] A.H. Abbass, Smart Nanoparticles Technology, InTech, Rijeka, Croatia, 2012. Fort, Influence of cluster size and surface functionalization of ZnO
[3] M.-C. Daniel, D. Astruc, Gold nanoparticles: assembly, supramolecular nanoparticles on the morphology, thermomechanical and piezoelectric
chemistry, quantum-size-related properties, and applications toward biology, properties of P(VDF-TrFE) nanocomposite films, Appl. Surf. Sci. 279 (2013)
catalysis, and nanotechnology, Chem. Rev. 35 (2004) 293–346. 204–211.
[4] J.A. Lewis, Colloidal processing of ceramics, J. Am. Ceram. Soc. 83 (2000) 2341– [27] W.J. Frith, J. Mewis, T.A. Strivens, Rheology of concentrated suspensions:
2359. experimental investigations, Powder Technol. 51 (1987) 27–34.
[5] H. Kamiya, M. Iijima, Surface modification and characterization for dispersion [28] D.H. Watanabe, M.-L. Yao, K. Osaki, T. Shikata, H. Niwa, Y. Morishima,
stability of inorganic nanometer-scaled particles in liquid media, Sci. Technol. Nonlinear rheology of a concentrated spherical silica suspension, Rheol. Acta
Adv. Mater. 11 (2010) 044304. 36 (1997) 524–533.
[6] J. Jiang, G. Oberdorster, P. Biswas, Characterization of size, surface charge, and [29] V.S. Nguyen, R. Hadji, B. Vincent, D. Rouxel, F. Sarry, F. Bauer, P(VDF-TrFE)/
agglomeration state of nanoparticle dispersions for toxicological studies, J. Al2O3 piezoelectric nanocomposite thin films, in: 2010 IEEE International
Nanopart. Res. 11 (2009) 77–89. Symposium on the applications of Ferroelectrics (ISAF) Edinburgh, United
[7] K.W. Powers, S.C. Brown, V.B. Krishna, S.C. Wasdo, B.M. Moudgil, S.M. Roberts, Kingdom, 2010, pp. 1–4.
Research strategies for safety evaluation of nanomaterials. Part VI. [30] A.M. Basedow, K.H. Ebert, Ultrasonic degradation of polymers in solution, in:
Characterization of nanoscale particles for toxicological evaluation, Toxicol. Physical Chemistry, Advances in Polymer Science, Springer, Berlin, Heidelberg,
Sci. 90 (2006) 296–303. 1977, pp. 83–148.
[8] R. Greenwood, Review of the measurement of zeta potentials in concentrated
aqueous suspensions using electroacoustics, Adv. Colloid Interf. Sci. 106 (2003)
55–81.

Please cite this article in press as: V.S. Nguyen et al., Dispersion of nanoparticles: From organic solvents to polymer solutions, Ultrason. Sonochem. (2013),
http://dx.doi.org/10.1016/j.ultsonch.2013.07.015