Ultrasonics - Sonochemistry 65 (2020) 105061

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

Ultrasonic-assisted de-agglomeration and power draw characterization of T

silica nanoparticles
Vikash, Vimal Kumar
⁎

Department of Chemical Engineering, Indian Institute of Technology Roorkee, Uttarakhand 247667, India

ARTICLE INFO ABSTRACT

Keywords: Breakage of nanoparticle cluster require high-intensity devices for stable and uniform distribution of aggregates.
Ultrasonication The ultra-sonication process is a high energy-intensive technique that produces cavitation effect to break the
Ultrasonication power aggregates. In the present study, ultra-sonication is used for the de-agglomeration of fumed silica nanoparticles
De-agglomeration in low to high viscosity liquids. Water- and glycerol-based dispersion has been investigated at different solid
Nanoparticles
loadings (up to 10 wt% for water-based dispersion and 5 wt% in glycerol-based dispersion) and viscosity of
Fumed silica
Rheology
continuous phase (1–100 mPa.s). Breakup mechanism and kinetics have been studied at optimized operating
conditions and no significant effect is found at different solid loadings on breakup mechanism. Particle size
measurements are reported and found that volume of fine generation increased with an increase in sonication
time. Further, it is observed that the stability of dispersion in the liquid is very high even at high concentration of
solid used. Larger agglomerates are found at high viscosity of continuous phase and a lag is also observed for
100 mPa.s glycerol solution even at low solid loading (1 wt%). From, rheological characterizations it is found
that the behavior of dispersed solution changed with time, temperature and solid loading. Erosion is found to be
the breakup mechanism and further, validated with scattering light characterization. Furthermore, power draw
increased with an increase in the viscosity of continuous phase, however, no significant effect of solid loading is
observed. It is also observed that process is more energy-efficient at higher solid loading as the volume of fine
produced is more as compared to low solid loading. Therefore, it can be concluded that the stable and uniform
dispersion of nanoparticles can be achieved using an ultra-sonication device at high solid loading in viscous
liquids.

1. Introduction
Nanoparticles are used widely in different products available in the
market due to their unique properties such as strength, reactivity,
conductivity, and stability. Commercialized product such as health and
personal care, coating, paints, and rubber products, etc. are a few ex-
amples in the current use. Further, incorporation of nanoparticles in
liquids, de-agglomeration of nanoparticle cluster and stabilization re-
quired for the manufacturing of products that contain the nano-
particles. Several devices used for the fine and stable dispersion, and de-
agglomeration of nanoparticles as a strong bond between the cluster
cannot be break with simple hydrodynamic stresses. High shearing is
required to break the nanoparticle cluster, and that can be generated
using rotor–stator mixers, high-pressure homogenizers, ultra-sonication
devices, etc.
Several studies have been done for the dispersion and break-up of
silica nanoparticle cluster using different high shear devices. Kowalski
et al. [1] used ball mill for the dispersion of nanoparticles of hydro-
philic silica (Aerosil 200 V) and reported that re-agglomeration oc-
curred after some time. Higher energy dissipation can be achieved in
rotor–stator devices as compared to ball mill or stirred type devices,
which also helped in breaking clusters of nanoparticles. The dispersion
of nanoparticles of densified fumed silica have been carried out either
using batch [2,3] or in-line [4–6] rotor–stator mixers. Kamaly et al. [3]
performed an experimental study using two different batch rotor–stator
mixers and reported the mechanism and break-up kinetics of nano-
particle cluster. They observed that erosion was the cluster breakup
mechanism and reported Sauter mean diameter of 350–400 nm for the
smallest fines generated.
Özcan-Taşkın et al. [6], studied the effect of stator head of in-line
rotor–stator mixers for de-agglomeration of silica in water. Three dif-
ferent heads of different make were used to predict the break-up me-
chanism, and smallest size of aggregates was achieved up to
150–200 nm. It was reported that the best performance for cluster

⁎
Corresponding author.
E-mail address: vimal.kumar@ch.iitr.ac.in (V. Kumar).

https://doi.org/10.1016/j.ultsonch.2020.105061
Received 11 November 2019; Received in revised form 6 March 2020; Accepted 7 March 2020
Available online 12 March 2020
1350-4177/ © 2020 Elsevier B.V. All rights reserved.
Vikash and V. Kumar Ultrasonics - Sonochemistry 65 (2020) 105061

Fig. 1. (a) Experimental setup, and (b) schematic rig configuration.

Fig. 2. Particle size distribution in water of (a) 1 wt%, (b) 2 wt%, (c) 5 wt%, and (d) 10 wt% Aerosil 200 at different time interval.

breakup can be achieved by using the smaller size holes with high
number of holes in the mixer head. Padron and Özcan-Taşkın [7] car-
ried out de-agglomeration of silica nanoparticles at different con-
centrations of solid and viscosity of liquids. Water and glycerol were
used as dispersion medium to vary viscosity. Power draw was char-
acterized at different Reynolds number and Flow numbers. It was re-
ported that more efficiency can be achieved at a high concentration of
solid as large amount of solids can be processed in a given time. It was
also reported that the rate of de-agglomeration was less at high
viscosity of continuous phase and erosion was the breakup mechanism.
Bałdyga et al. [4] numerically modeled the dispersion of nanoparticles
using quadrature method of moments (QMOM) population balance. The
modeled predictions were compared with their own experimental data
for different devices such as rotor–stator, high-pressure nozzle, and
ultra-sonication system, and the results were found out to be in good
agreement.
A very high rate of energy dissipation can be achieved with the help
of ultra-sonication device, which can help in the de-agglomeration and

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Vikash and V. Kumar
Fig. 3. Z-average as a function of time in days of 1 wt% and 10 wt% of Aerosil
200 in water.
cluster breakup. Recently, Asadi et al. [8], reviewed the effect of ultra-
sonication on different properties of nanofluids such as stability, dis-
persion, thermophysical, and heat transfer properties. According to
them, direct sonication provided better results on dispersion with better
stability and particle size distribution.
Further, different studies provided a deep insight of dispersion of
nanoparticles in assisted with ultra-sonication for alumina [9–11], ti-
tanium [8,11,12], and however, limited literature was found on dis-
persion and de-agglomeration of silica [13–16] using ultra-sonication
Fig. 4. Particle size distribution in 10 mPa.s glycerol of (a) 1 wt%, (b) 2 wt%, and (c) 5 wt% Aerosil 200 at different time interval.
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Ultrasonics - Sonochemistry 65 (2020) 105061
device. Petzold et al. [13], studied the dispersion of different grade of
fumed silica using different devices such as magnetic stirrer, rotor–-
stator mixer, and ultra-sonication. According to them, smallest particle
size distribution with high stability can be obtained using ultra-soni-
cation device with very short period time (10 min) as compared to other
devices. Mondragon et al. [14], characterized the dispersion of silica
nanoparticles in water using probe ultra-sonication device and further,
analyzed the physical properties and stability of the dispersion. They
reported the effect of pH, and solid and salt content on the properties of
dispersed nanoparticle solution. According to them, a stable silica na-
nofluids can be obtained at certain solid content, pH and salt con-
centration in 5 min of ultrasound. Further, different nanostructured
materials such as pyrogenic alumina, silica, titania were dispersed using
probe-sonication [15]. The strategies to cope up with contamination
that occurred due to the abrasion of sonotrode during the sonication
process was discussed. Babick [16] proposed a characterization method
for ultrasonic dispersion of pigments and fillers that included the
sample preparation for ultrasonic dispersion and analytical cen-
trifugation technique for particle size analysis. Different ultrasonic
systems were used to study the ultrasonic dispersion of carbon black,
pyrogenic SiO2, TiO2 pigment and TiO2 photo-catalyst. Marín et al. [17]
studied the effect of sample preparation on particle size distributions of
precipitated, fumed, gel and colloidal silica in suspensions using ultra-
sonication system. Size distribution was not affected by ultrasonic dis-
persion for colloidal and gel silica over a range of energy, however,
particle size decreased with energy in ultrasonic dispersion of pre-
cipitated and fumed silica. Recently, Wiemann et al. [18] observed the
effect of ultrasonic energy on preparation of amorphous silica for the
application in pharmaceuticals industries and found a small impact of
ultrasonic energy on vitro bioactivity of silica. Further, high-pressure
devices can also be used for the dispersion of nanoparticles [4,19,20].
In the present study, de-agglomeration of fumed silica (Aerosil®
Vikash and V. Kumar Ultrasonics - Sonochemistry 65 (2020) 105061

Fig. 5. Particle size distribution in 50 mPa.s glycerol of (a) 1 wt%, (b) 2 wt%, and (c) 5 wt% Aerosil 200 at different time interval.

Fig. 6. Particle size distribution in 100 mPa.s glycerol of (a) 1 wt%, (b) 2 wt%, and (c) 5 wt% Aerosil 200 at different time interval.

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Vikash and V. Kumar
Fig. 7. Z-average as a function of Aerosil 200 loading in water and glycerol.
200) was studied by using probe-type ultra-sonication device, as it is
found to have numerous applications, being a reinforcing agent,
modifier, processing aids in formulations, and to enhance the surface
effect of the numerous products. Further, silica nanoparticles are easily
available in the market in large quantity. The effect of solid con-
centration and viscosity of continuous medium was investigated on the
de-agglomeration of nanoparticle clusters. It also included the char-
acterization of well-dispersed nanoparticle agglomerates considering
products having higher viscosity of continuous phase and industrial
requirement of higher concentration, for solid loading ≈10% in water
and ≈5% in glycerol-water solution, using ultra-sonication device.
2. Experimental setup and conditions
2.1. Material
Hydrophilic fumed silica (Aerosil® 200) was used as agglomerated
particles in the present study supplied by Evonik industries. Aerosil®
200 can be used in the products like paints, printing inks, adhesives,
cable gels, plant protection, sealants and coatings as a modifier, to
improve the free flow, anticaking, anti-settling, thickening and anti-
sagging agent. According to industry specifications, the specific surface
area was 175–225 m2/g with a SiO2 content of > 99.8%. The tapped
density of Aerosil® 200 was approximately 50 g/l. The primary particle
size diameter of fumed silica particles was 12 nm. Millipore water was
used with a solid loading of 1, 2, 5 and 10 wt% to study the effect of
solid loadings. Further, for experiments on the effect of viscosity of
continuous phase, glycerol purchased from the local market was used at
different viscosity such as 10, 50 and 100 mPa.s, approx. The solid
loading of Aerosil® 200 was used as 1, 2 and 5 wt% in the aqueous
glycerol.
2.2. Equipment
The experimental setup consisted of Hielscher Ultrasonics GmbH,
UP400S, made in Germany having useful output power of 400 W and
the experimental setup and schematic rig configuration can be seen in
Fig. 1. An ultrasonic processor housing integrated with the ultrasonic
transducer and sonotrode (H22 Horn 22) was coupled with horn. The
ultrasonic processor was having a 24 kHz working frequency with >
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Ultrasonics - Sonochemistry 65 (2020) 105061
90% efficiency. It has a steplessly adjusted power output of 20% and
100%. The basic principle of ultrasonic device was cavitation and it was
based on the electric excitation (reversed piezoelectric effect) effect that
generated the longitudinal mechanical vibrations. The sonotrode am-
plified the vibrations (formed as a λ/2 vibrator) and irradiate happened
due to the transfer of vibration through the end face of sonotrode to the
medium. The tip diameter of sonotrode was 22 mm and maximum
submerged depth can be 45 mm (equal to the length of sonotrode below
horn). The maximum amplitude was 100 μm with an acoustic power
density of 85 W.cm−2. However, in this study, 90% of the sonotrode
was submerged for maximum penetration in the solution. The working
capacity for the current study was 700 gm with respect to different
water, Aerosil® 200 and glycerol concentrations.
2.3. Characterization
2.3.1. Particle size analysis
Particle size measurements were done using a nanoparticle size
analyzer, nano partica SZ-100 make Horiba Scientific, Japan. The
particle size analyzer measures the particle size based on the dynamic
light scattering (DLS) technique and can measure the particle size of
0.3 nm to 8 μm. 1.46 + 0.1i was the refractive index (RI) used in this
study for Aerosil® 200.
2.3.2. Rheological measurement
Rheological properties of Aerosil® 200 dispersion with water and
aqueous glycerol solutions were examined using an Anton-Paar
TwineDrive Rheometer, MCR 702 (Anton Paar, GmbH, Austria). Cone-
plate (CP-50) measuring system was used to measure the flow proper-
ties of solutions. Cone-plate measuring system of stainless steel has the
diameter of 50 mm, cone plate has an angle of 1° and cone truncation
was 102 μm. The measuring gap was kept constants at 0.102 mm
throughout the measurement. Flow properties were measured at dif-
ferent temperatures and time to investigate the effect of temperature
and time. Both before dispersion and after dispersion behaviors were
analyzed at different time and temperatures.
2.3.3. Calorimetry technique
Calorimetric tests were performed for both continuous phase
medium, such as water and glycerol solution, with Aerosil® 200. In
calorimetric technique, power input was measured as function of tem-
perature. The temperature was measured as a function of time at the
optimum operating condition of 0.6 cycle and 60% amplitude. It was
assumed that all the power supplied to the ultra-sonication device will
eventually be dissipated in term of heat and the difference in the
temperature can be used to measure the power input. The temperature
was measured by using a thermocouple, which was placed inside the
solution, within the vicinity of the sonotrode. Millipore water and three
aqueous glycerol solutions were used in these tests and glycerol con-
certation was approx. 60, 78 and 84%. The corresponding viscosities of
aqueous glycerol solutions at 20 °C were 10, 50 and 100 mPa.s approx.
Separate experiments were performed without cooling for calorimetric
measurements.
2.4. Operating procedure and conditions optimization
Dry Aerosil® 200 was weighted and simply mixed with required
quantity of millipore water and aqueous glycerol. Different concentra-
tions 1, 2, 5, and 10 wt% of Aerosil® 200 was taken as solid loading for
water experiments, however 1, 2, and 5 wt% was used for aqueous
glycerol solutions of 10, 50 and 100 mPa.s. For higher concentration of
solid particles such as 10 wt% produced a gel-like slurry that cannot be
sonicated with ultra-sonication device, therefore it is not recommended
Vikash and V. Kumar
Fig. 8. Flow curve of the dispersion of Aerosil 200 in (i) water, and (ii) glycerol ((a) 10 mPa.s, (b) 50 mPa.s, and (c) 100 mPa.s) at 20 °C temperature.
to perform the experiments above 5 wt% of Aerosil® 200 in viscous
fluids. Fluid temperature was kept constant at 20 ± 2 °C throughout
the experiments. Samples were taken periodically during the experi-
ment and a total of three hours of experiments were run. The ultrasonic
device input parameters, such as amplitude and cycle, were optimized
before performing the de-agglomeration experiments, and the optimum
values obtained were 60% amplitude and 0.6 cycle.
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Ultrasonics - Sonochemistry 65 (2020) 105061
3. Results and discussions
3.1. Particle de-agglomeration
De-agglomeration of different concentration of Aerosil particles
(1 wt%, 2 wt%, 5 wt%, and 10 wt%) in millipore water over a periodic
time interval is shown in Fig. 2, which shows monomodal distribution
based on frequency of fines generated in all the cases. From Fig. 2, it
was found that as the sonication time increased, volume of fine particle
Vikash and V. Kumar
Fig. 9. Flow curve of the dispersion of Aerosil 200 (a) 1 wt%, (b) 2 wt%, (c) 5 wt%, and (d) 10 wt% in water at 20 °C temperature at different time interval.
generation increased; therefore, volume fraction of fines generated was
a function of sonication time. Particle drop size distribution became
narrow as the concertation of nanoparticles increased from 1 wt% to
10 wt%. Therefore, frequency of fines generation increased with in-
crease in the solid loading of nanoparticles. Average particle size of the
fine generated was found fairly constant (< 15 nm size difference)
throughout the de-agglomeration process in water-based dispersion, i.e.
independency of size on the operating conditions. In the present study
the Z-average size of the fine particles measured from 65 nm to 250 nm
for dispersion in water. Agglomerates were still present in the final
solution as the primary size of the solid particle was 12 nm. This might
be because of the production process of fumed silica (Aerosil 200). In
the manufacturing of fumed silica, primary particles were fused into the
aggregates during the pyrolysis at high temperature. Further, it can be
said that the predominated mechanism for the breakup of de-agglom-
eration of Aerosil 200 nanoparticles was erosion, i.e. smaller aggregates
were chipped of from the surface of larger agglomerates due to presence
of smaller and larger agglomerates in the final dispersion. Similar ob-
servations were made by Padron et al. [7] for the de-agglomeration of
Aerosil 200 V nanoparticles (densified version of Aerosil 200) in an in-
line rotor–stator mixer using volume based dispersion analysis, how-
ever the size of fines and coarse was much higher than that was found
in the present study. Further, the breakup mechanism can be validated
later in the section of dispersion morphology using scattering light
characterization. Also, the stability of nanoparticle dispersion was in-
vestigated over one month (Fig. 3) for minimum (1 wt%) and maximum
(10 wt%) solid loading in water. Dispersion was found to be very stable,
and negligible change was found for 1 wt% Aerosil; hence, no ag-
gregation was seen after long time. However, slight change in the Z-
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Ultrasonics - Sonochemistry 65 (2020) 105061
average over a month for 10 wt% Aerosil was seen; hence further ag-
gregation starts after longer duration storage.
Dispersion of nanoparticles in aqueous solution of glycerol at dif-
ferent viscosities and at different solid loadings are reported in Figs. 4, 5
and 6. Large agglomerates were found in aqueous solution of glycerol,
however, volume fraction of fines produced in glycerol-based disper-
sion decreased as the viscosity increase. Form Fig. 4, it was clearly seen
that both nano- and micro-size particles were also present when the
solution was deagglomerated in the 10 mPa.s aqueous glycerol solution.
However, the fines present in the dispersion were smaller than the fines
presented in the water-based dispersion. Further, the volume fraction of
fines increased with increase in sonication time, i.e. Z-average de-
creased with time. Dispersion data of solid particles for 10 mPa.s gly-
cerol solution at different concentrations showed a negligible change in
Z-average, similar observation was seen with water-based dispersion.
Volume fraction of fines produced during the dispersion process in-
creased with an increase in viscosity of glycerol solution to 50 mPa.s
(Fig. 5), however a small lag was observed in the production of fines for
higher viscosity to 100 mPa.s glycerol (Fig. 6). Form Figs. 5 and 6, it
can be seen that volume fraction of nanoparticles varied from 25 nm to
1000 nm, however Z-average was less as compared to water-based
dispersion.
From Fig. 6(a) and (b), a slight lag in the production of fines was
found and dispersion had started after 45 min (there might be larger
particles than the capacity of particle size analyzer) for 1 wt%, and for
2 wt% solid particles and lag was further increased with an increase in
concentration of solid particles to 5 wt% (only 6 wt% increase in con-
centration of pure glycerol from 78 wt% for 50 mPa.s to 84 wt%
100 mPa.s). However, the smallest size of agglomerate was found to be
Vikash and V. Kumar
Fig. 10. Flow curve of the dispersion of Aerosil 200 in (i) 10 mPa.s, (ii) 50 mPa.s, and (iii) 100 mPa.s glycerol at 20 °C temperature at different time interval.
nearly the primary size of Aerosil 200. If, the concentration of solid
particles further increased to 10 wt%, gel-type solution was formed and
that could not be sonicated. Therefore, it is recommended to have a
maximum concentration of 5 wt% in nearly 100 mPa.s liquids for better
dispersion and de-agglomeration process. It was also observed that
there was an effect of concentration on the production of fines in the
high viscous glycerol-based dispersion as compared to negligible effect
in water-based dispersion. Further, Z-average size at a sonication time
of 180 min decreased with an increase in viscosity of the continuous
phase (Fig. 7). However, the effect of concentration was negligible on Z-
average of the dispersed nanoparticles. The polydispersity index (PDI)
for the dispersion of Aerosil 200 in different viscous medium is reported
in Supplementary Table 1, which is increasing with an increase in
viscosity of continuous media.
3.2. Dispersed particles rheology
Fig. 8 shows shear stress as a function of shear rate (flow curve) for
1 wt%, 2 wt%, 5 wt% and 10 wt% Aerosil in water (Fig. 8(i)) as well as
1 wt%, 2 wt% and 5 wt% Aerosil in 10, 50 and 100 mPa.s glycerol
solutions (Fig. 8(ii)). Viscosity of 1 wt% Aerosil in water was near to the
water and it increased with an increase in the solid loading. All mea-
surements were performed at 20 °C, sonication time was 180 min, and
scaling was deliberately reported at linear scale, to understand the flow
behavior of the fluids. Rheogram of dispersed particles showed New-
tonian behavior in both water and glycerol solutions at all solid load-
ings. However, non-Newtonian behavior can be seen at higher
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Ultrasonics - Sonochemistry 65 (2020) 105061
concertation and glycerol viscosity. Power law model was fitted to
measure the consistency index and flow index. It was found that con-
sistency index increased with an increase in solid loading, however,
flow index decreased with an increase in solid loading and glycerol
viscosity (Supplementary Table 2). The viscosities of dispersed nano-
particles were ~1 mPa.s for 1 wt% and 2 wt%, ~2 mPa.s for 5 wt%, and
~3.5 mPa.s for 10 wt% Aerosil-water solutions. Similar findings were
also reported for batch rotor–stator mixer having viscosity 6.7 mPa.s
[3], and in-line rotor–stator mixer [5] having viscosity 4.7 mPa.s for
10 wt% fumed silica dispersion in water. For dispersion of Aerosil 200
in aqueous glycerol solution, the viscosities were 9.7 (~10), 48 (~50)
and 98 (~100) mPa.s.
Further, variation of viscosity with respect to sonication time at
20 °C temperature for dispersion of Aerosil 200 in water can be seen in
Fig. 9. It was observed that the dispersed particles behavior changed
with sonication time from non-Newtonian to Newtonian. Non-New-
tonian behavior was clearly seen at the sonication time of 15 min for
10 wt% Aerosil 200-water solution (Fig. 9(d)). However, no significant
change was observed at higher sonication time of 60, 120 and 180 min.
Furthermore, the viscosity of the dispersion decreased with increase in
sonication time, as the change in behavior from Non-Newtonian to
Newtonian fluid. Glycerol based dispersion rheology with respect to
sonication time can be seen in Fig. 10. Three different solid loadings
such as 1, 2 and 5 wt% were investigated in aqueous glycerol solution.
The viscosity of 1 wt% Aerosil dispersed particles in glycerol was nearly
to the initial viscosity of glycerol without solid particles. However, if
the solid loading increased from 1 wt% to 5 wt%, the viscosity
Vikash and V. Kumar
Fig. 10. (continued)
increased drastically at lower sonication time. Further, the viscosity
decreased with increased in sonication time. This verified the reason for
the lag in the generation of fines at higher viscosity and at higher solid
loading. At higher loading of solid nanoparticles, the lag was around
45 min to 60 min for fine generation in 100 mPa.s glycerol solution.
Fig. 11 showed the variation of viscosity with respect to shear rate
at different temperatures for a sonication time of 180 min. It was ob-
served that viscosity decreased with an increase in temperature and it
also verified the effect of solid loading on the behavior of the disper-
sion. Non-Newtonian behavior was observed at higher concentration as
viscosity decreased with shear rate and Newtonian at low solid loading
as viscosity remains constant. Larger change can be seen in viscosity of
glycerol-based dispersion as compared to water-based dispersion as the
temperature changed from 20 °C to 40 °C. The viscosity of glycerol-
based dispersion decreased from ~100 mPa at 20 °C temperature s to
~40 mPa.s at 40° C, even at 5 wt% Aerosil 200 nanoparticles. Similar
observation can be seen for other viscous solutions.
3.3. Dispersion morphology
Scanning electron microscope (SEM) and transmission electron mi-
croscopic (TEM) images can be seen in the Fig. 12. A field emission
scanning electron microscope (FESEM) was used to capture the well-
defined images of de-agglomerated Aerosil 200 in water (Fig. 12(i)).
Images were captured at different magnification power of 20,000,
50,000 and 100,000× magnification. Spherical structures were clearly
seen in 1 µm to 5 µm range. It was clear from the analysis that larger
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Ultrasonics - Sonochemistry 65 (2020) 105061
agglomerates were formed due to strongly branching of smaller ag-
glomerates. The aggregates were made of primary particles and that
cannot be separated further. The larger agglomerates might be due to the
drying process prior to the SEM image capturing and smaller particles
merged together and cannot be separated out. However, some individual
particles can be identified on the surface of larger agglomerates.
Further, TEM images as shown in Fig. 12(ii), were used for the
precise measurements of particle and agglomerate sizes. High energy
electron were radiated through the aggregates and capture the images.
100, 200 and 500 nm scales were used to capture the images and it was
found that aggregates were still there (or may be due to the same reason
of drying as in SEM) that cannot be separated out. Primary particles
were merged with each other and formed the aggregates, however,
individual particles were still there having the size near to the primary
size. The final size of the aggregates measured from the TEM analysis
were in agreement with the size measurement with particle size ana-
lyzer (Horiba SZ-100). TEM images also confirmed that erosion was the
breakup mechanism for the agglomerates. Breaking the aggregates re-
quired high energy devices and ultra-sonication device produced very
high rate of energy, and therefore, size of the aggregates generated
were very smaller in size as compared rotor–stator mixers [7].
3.4. Power draw
Power draw was measured using the calorimetric technique, where
power was measured as a function of temperature. Power draw was
calculated at an amplitude of 60% and a cycle of 0.6. The total acoustic
Vikash and V. Kumar
Fig. 10. (continued)
power density of ultra-sonication device was 85 W/cm2. Power draw as
a function of solid loading and viscosity at different time interval can be
seen in Fig. 13. The power draw varied from 2 W (energy density
~28 MJ/m3) to 5 W (energy density ~88 MJ/m3) for water- and gly-
cerol-based dispersion at a sonication time of 180 min, respectively. It
was found that power draw was nearly constant for water-based dis-
persion and it decreased with an increase in sonication time. For gly-
cerol-based dispersion, power draw was high as compared to water-
based dispersion. Further, the power draw increased with an increase in
viscosity of continuous phase, however, nearly constant for solid con-
centrations. Therefore, there was no significant effect of solid loading
on the power draw, except for viscosity of continuous phase. From,
particle size measurement, it was found that volume of fine generation
increased with increase in solid loading in both water- and glycerol-
based dispersion. Therefore, it can be concluded that dispersion was
more energy efficient at high solid concentration.
4. Conclusions
In the present study de-agglomeration of Aerosil 200 assisted with
ultra-sonication was carried and the effect of solid loading and viscosity
of continuous phase were studied on the breakage of nanoparticle
cluster. In first, characterization of nanoparticle de-agglomeration was
performed in terms of particle size measurements for water- and gly-
cerol-based dispersion. Monomodal distribution of particle size was
observed based on frequency of fines generation, which increased with
an increase in sonication time. The de-agglomeration was found
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Ultrasonics - Sonochemistry 65 (2020) 105061
constant throughout the process in water-based dispersion. Further,
stability of dispersion of nanoparticles in water was observed for one
month of time at 1 wt% and 10 wt% Aerosil concentration and negli-
gible change in average particle size was found. For glycerol-based
dispersion, it was found that there was much effect of viscosity of
continuous phase on the dispersion of nanoparticles. Larger agglomer-
ates were found and a lag was also observed at higher viscosity.
However, volume of fine particle size distribution increased with an
increase in viscosity at the final processing time of 180 min. Average
particle size of dispersed nanoparticles were found lower for glycerol-
based dispersion as compared to water-based dispersion. It was also
found that erosion was the predominating breakup mechanism.
Further, it was observed that viscosity changed with time, temperature
and solid concentration, however, there was no significant change in
viscosity for water-based dispersion as compared to glycerol-based
dispersion. It was also found that behavior of solutions changed with
respect to sonication time from non-Newtonian to Newtonian.
Furthermore, the agglomeration breakup mechanism of erosion was
validated with scattering light characterization, which showed smaller
particles having particle size near to primary size of fumed silica along
with the larger agglomerates. The power draw to de-agglomerate the
nanoparticles of Aerosil 200 was estimated using calorimetric technique
and it was found that power draw increased with an increase in visc-
osity of continuous phase. However, there was no significant effect of
solid concentration on the power draw. Therefore, it can be concluded
that process was more energy efficient at higher solid concentration to
produce the higher volume of fines.
Vikash and V. Kumar Ultrasonics - Sonochemistry 65 (2020) 105061

Fig. 11. Viscosity curve of the dispersion of Aerosil 200 in (a) water, (b) 10 mPa.s, (b) 50 mPa.s, and (c) 100 mPa.s glycerol at different temperature.

Fig. 12. (i) SEM and (ii) TEM images of Aerosil 200 particles after processing with ultra-sonication device. (a) 20,000× magnification, (b) 50,000× magnification,
(c) 100,000× magnification, and (a) 100 nm scale, (b) 200 nm scale, (c) 500 nm scale, respectively.
11
Vikash and V. Kumar
Fig. 13. Power draw as a function of Aerosil 200 particle concentrations at different time interval (a) 15 min, (b) 60 min, (c) 120 min, and (d) 180 min in water and
glycerol.
CRediT authorship contribution statement
Vikash: Conceptualization, Methodology, Validation, Formal ana-
lysis, Investigation, Writing - original draft, Visualization. Vimal
Kumar: Conceptualization, Formal analysis, Writing - review & editing,
Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgment
One of the authors (Vikash) gratefully acknowledges the financial
support of the Ministry of Human Resource Development (MHRD),
Government of India in the form of a research fellowship and Institute
Instrumentation Center (IIC), Indian Institute of Technology Roorkee
for the usage of SEM, and TEM facilities.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ultsonch.2020.105061.
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