Chemical Engineering Journal 484 (2024) 149462

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Characteristics of emulsion preparation in an ultrasonic microreactor:

cavitation, droplet size and energy efficiency
Li Ding a, b, Shuainan Zhao b, c, Lixue Liu b, Wei Wang a, Chaoqun Yao b, c, *, Guangwen Chen b, c, *
a
School of Chemistry & Chemical Engineering, Yantai University, Yantai 264005, China
b
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
c
University of Chinese Academy of Sciences, Beijing 100049, China

A R T I C L E I N F O A B S T R A C T

Keywords: An ultrasonic assisted microreactor (USMR) for emulsification was designed. Uniform sound distribution in the
Microreaction technology microchannel and effective temperature control were realized. The oscillation behavior of cavitation bubbles in
Emulsification coarse oil-in-water emulsion was investigated in two other ultrasonic microreactors with similar structure. It was
Cavitation
found that bubble clusters composed of many fine bubbles vibrated as a whole, similar to the vibration of single
Emulsion size
Microfluidics
bubbles. It was easier for the bubble clusters to oscillate under the transient oscillation mode, compared to a
cavitation bubble. Due to the secondary sound field, it formed a uniform array of bubble clusters in straight
channel and stagnant bursting cavitation zones with strong shocking wave in meandering channel. Parametric
study on the emulsification performance was also conducted. A semi-empirical correlation was proposed and
showed excellent predicting performance over the emulsion size. Due to the controlled sound field and cavitation
bubbles of the USMR, the energy efficiency ranged from 0.03 to 2.77%, which was at least one order of
magnitude higher than conventional ultrasonic devices that do not directly couple the microchannel and
vibrator.

ultrasonic emulsification is that ultrasound excites the acoustic cavita­

1. Introduction tion in the liquid medium, which generates microstreaming and shock
waves to break the emulsion droplets [9,10]. The ultrasonic energy was
Emulsion is widely utilized in the area of pharmaceutical [1], food concentrated at the surface and nearby of the cavitation bubbles through
[2], cosmetics and other industries [3,4]. Emulsification typically re­ this phenomenon. As a result, the energy efficiency should be substan­
quires intensive external shear forces to be applied. To this end, many tially increased, which has been reported by various researches [11–13].
methods have been developed, including mechanical agitation, rotor–­ Besides, previous studies also found that significant reduction of sur­
stator, colloid mill and high-pressure homogenizer. Currently, the en­ factant usage and improvement of emulsion quality (i.e., smaller size,
ergy efficiency in these methods is still very low [3,5]. Generally, for less polydispersity, and higher stability) can be achieved with ultrasonic
droplet size in microns, the total energy (power) density applied into the emulsification [14]. For, example, Kamogawa et al. [13] realized the
fluids lies in the range of 103-106 W/kg; while for droplet size in nano- preparation of oleic acid/water emulsions by tandem ultrasonic emul­
scale, the energy density can be as large as108-1010 W/kg [6,7]. The sification, in the absence of surfactant. However, the ultrasonic emul­
energy efficiency in the latter case is typically smaller than 0.1 % with sification has been mainly restricted to lab scale, despite numerous
99.9 % of the energy transferred to heat [3,5]. successful applications in literature. The main reason is that the cavi­
The application of ultrasonic dispersion is an effective method for tation in the liquid medium is very difficult to control, especially in large
emulsion preparation [3]. Because ultrasonic equipments contain scale equipment [3,15]. As the equipment size is usually much larger
separate ultrasound generator and fluid container, it facilitates advan­ than the radiating area, it leads to very uneven sound field: the sound
tages of easy-cleaning and easy-maintenance, compared to mechanical intensity is large only in the radiating area and decreases with increase
devices such as valve devices and microfluidizers. Thus, ultrasonic of distance. In addition, there are large amounts of cavitation bubbles
emulsification has great potential in aseptic processing, which is that can shield the transmission of sound field. Therefore, the acoustic
essential in pharmaceuticals, food, cosmetics [8]. The basic principle of cavitation is a complex non-linear coupling of bubble vibration and

* Corresponding authors at: Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
E-mail addresses: superyao@[Link] (C. Yao), gwchen@[Link] (G. Chen).

[Link]
Received 5 November 2023; Received in revised form 8 January 2024; Accepted 6 February 2024
Available online 9 February 2024
1385-8947/© 2024 Elsevier B.V. All rights reserved.
L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

empirical correlation was proposed to predict the emulsion size. Finally,

Nomenclature the energy efficiency was calculated and compared to other studies.

PA Acoustic pressure, kPa 2. Experimental setup

P0 Atmospheric pressure, kPa
R1 Transition size of shape to transient oscillation, μm 2.1. Materials
ω Angular frequency of the ultrasonic wave, kHz
P Load power, W Tween 20 (99.0 wt% purity, Biological Reagent), and Span 80
Pth power density, W/mL (Chemically Pure) were all purchased from Shanghai Macklin
EV Energy density, J/m3 Biochemical Technology Co., Ltd, Glycerol (Analytical Reagent) was
μC Dynamic viscosity of the continuous phase, mpa•s purchased from Tianjin Damao Chemical Reagent Factory, Octane
μD Dynamic viscosity of the oil phase, mpa•s (Analytical Reagent) was purchased from Tianjin Kermel Chemical Re­
ε Energy density, W/kg agent Co., Ltd, Soybean oil was purchased from a local supermarket.
ṙ Shear rate, s− 1 Wahaha pure water (electrical conduct smaller than 2 us/cm) was used
Cacrit Critical capillary number for preparation of all solutions.
σ Interfacial tension, mN/m The coarse emulsion was prepared by a rotor-static mixer (ADS25,
Wecrit Critical Weber number Shang Hai OuHor Mechanical Equipment co., Itd), in order to obtain a
ρ Density, kg/m3 particle size near 1–2 μm. Typically, a rotating speed of 19000 rpm and
τ Local eddy shear, N/m2 processing time of 1–5 min was applied for the coarse emulsion prepa­
τapplied Applied shear stress, N/m2 ration. The coarse emulsion contained 1.8 % Tween 20 (w/w), 0.2 %
d The average emulsion size measured by DLS method, Span 80 and different contents of the oil phase.
um
d0 The average emulsion size of the coarse emulsion, um
φ Volume percent of the dispersed phase 2.2. Ultrasonic microreactor

Fig. 1a shows the configuration of the Ultrasonic microreactor

(USMR) designed for emulsion production. It consists of a 3D printed
sound propagation. It is necessary to develop novel methods to address microreactor and a Langevin ultrasonic transducer (ZFHN-100–21.6
the problems of regulation of sound field and cavitation bubbles. kHz). The microreactor comprises a cylindrical aluminum alloy
The combination of ultrasound and microfluidics has been shown to container with a height of 8 mm and an outer wall thickness of 1 mm.
be effective in controlling the bubble field [16–19]. The small charac­ The choice of aluminum alloy as the reactor material stems from its
teristic dimension on the order of a few mm or less enables a uniform excellent impedance ratio and impedance matching performance with
sound field in the microfluidics inherently. The synergistic effects pro­ the transducer’s front section, which facilitates optimal energy output.
vide a high possibility to increase the utilization efficiency of the ul­ In this way, it retained the characteristic of the transducer as a half-wave
trasonic energy. Kanda et al. [20] designed an ultrasonic microreactor vibrator. This design guaranteed that the maximum energy plane
(USMR) based on piezoelectric plane (2.3 MHz) and realized prepara­ located at the microreactor plane with uniform sound distribution
tion of fine emulsion with about 200 nm in size. Nieves et al. [21] and [18,28]. The relatively large space enabled large amount of cooling
Freitas et al. [22] utilized power ultrasound (61 and 24 KHz, respec­ water to flow through. A serpentine pipe with an inner diameter of 1 mm
tively) to fabricate USMRs, and produced emulsion in very short time of was integrated into the container (Fig. 1b). Three outlets were designed
0.2–3.4 min and low power of 5 ~ 32 W. These results show obviously to investigate the effects of processing volume (88.7, 233.6 and 312.3
better performance of USMR than conventional ultrasonic equipments μL, respectively) and residence time. The reactor was directly adhered to
(usually 200 ~ 1000 W and 2 ~ 30 min), which do not directly couple the transducer with ultrasonic transmission glue. The resonant fre­
the microchannel and vibrator. Besides emulsion preparation, USMRs quency of 20.68 kHz was precisely determined using an impedance
have also been applied in chemical engineering and process intensifi­ analyzer (PV70A, Beijing Band Era, China). Ultrasound activation was
cation, such as extraction, crystallization and reaction [16,23,24]. achieved by connecting the USMR to a signal generator (AFG-2105,
Another important application of USMR is that it can serve as an ideal Gwinstek) and a power amplifier (AG1016, T&C Power Conversion).
platform to investigate the cavitation-induced emulsification due to the This setup generates a sine wave at the desired frequency and input load
convenience for cavitation manipulation and high-speed imaging. In our power.
previous studies [18,23], a novel mechanism of bubble shuttling The above designed USMR addressed two key concerns of emulsion
through the water/oil interface was found, which could generate fine production: uniform sound wave radiation and excellent temperature
droplets with 1–3 μm in a time scale of only milliseconds. Zhao et al.[25] control. To verify the design, a simulation with COMSOL software was
investigated the characteristics of cavitation-induced emulsification in performed to illustrate the vibration displacement (Fig. 1c). It can be
liquid–liquid Taylor flow and revealed the effects of channel material on seen that the transducer can effectively drive the USMR to vibrate and
the cavitation. The above knowledge supplement the classical two-stage the main body of the serpentine has the maximum vibration displace­
mechanism[26,27] and greatly enrich the understanding over ultrasonic ment, as well as the stress. The acoustic power density (Pth, W/mL) was
emulsification. But overall, the mechanism study in USMR is just in its determined by the standard calorimetric method, which measures the
infant stage [3]. The detailed scenario on how cavitation bubble oscil­ temperature rise of water during ultrasonic operation (Pth = CmΔT/t). As
lates in coarse emulsion in USMR remains unknown. The effects of a result, it was a linear function of the load power (Pth/[WmL− 1] =
operating parameters on the emulsification and energy efficiency are not 0.005P/[W]). Fig. 2 displays the ability over temperature of the USMR.
investigated. Therefore, persistent research in this area is still needed to When there was no circulating cooling water (20℃, CC-4008SM, Lab­
provide a more comprehensive perspective and knowledge. temp), the temperature could increase by 20℃ in 5 min under a load
In this work, a novel USMR was designed, which shows excellent power of 30 W. However, with the circulating cooling water, the tem­
ability to temperature control and emulsion production. The oscillation perature rise could be controlled to be under 0.5℃, under the power
of cavitation bubbles in coarse emulsion was observed, in both the range of 5–50 W. These results demonstrate that the USMR can both
reactor scale and bubble scale. Then the influences of various parame­ provide high energy efficiency and rapid heat transfer, to meet the re­
ters, such as fluid viscosities and oil content were investigated. A semi- quirements during emulsion production.

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L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

Fig. 1. (a) The configuration of the ultrasonic microreactor (USMR) (b) the structure of channel at the microreactor plane (c) vibration displacement from COM­
SOL simulation.

Fig. 3. 10 × Magnified image (from the inverted biological microscope) of the

Fig. 2. The temperature rise during vibration of the USMR with and without prepared emulsions (a) coarse emulsion and (b-d) treated with the USMR at
circulating cooling water. different powers. Conditions: water-octane system, oil content of 10 %.

2.3. Emulsion characterization could be captured by the current microscope. The exact size distribution
could be determined by the DLS method. As shown in Fig. 4, the dis­
The size distribution of the emulsions was qualitatively and quanti­ tribution became unimodal distribution when the ultrasound power was
tatively characterized by an inverted biological microscope (IX73, larger than 10 W. The average size also decreased with the increase in
Olympus) and Zetasizer Nano ZS (MAL1027964, Malvern Instruments the ultrasound power.
Ltd.), equipped with dynamic light scattering (DLS) technology. For
each emulsion, a sample was dropped onto a cover glass and observed 3. Results and discussion
with the microscope, which could give a direct observation of the con­
tent of large oil droplets in the sample. The Zetasizer Nano ZS could 3.1. Oscillation of cavitation bubbles in coarse emulsion
analyze the size distribution and PDI of the emulsion samples. Typical
images of the prepared emulsions were displayed in Fig. 3. As can be It has been shown that the transient cavitation involving extensive
seen, there were many droplets as large as several to tens of microns bubble oscillation and explode, as well as the accompanying liquid jet
remaining in the coarse emulsion, in consistent with the DLS result and shock wave, is responsible for the emulsion generation [3]. Gener­
displayed in Fig. 4. Apparently, the size distribution of the emulsion had ally, emulsion generation contains two stages in an ultrasonic device.
multi peaks. When the coarse emulsion was refined with the USMR, the The first stage produces primary oil droplets, which are further dis­
amount of large droplets gradually diminished as the ultrasound power rupted into finer droplets in the second stage. Currently, the mechanism
increased. At the power larger than 20 W, there was no large droplet that studies are nearly all focused on the first stage and only implement flat
water–oil interface or single droplet, since generated droplets and

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L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

Fig. 4. Droplet size distribution of the prepared emulsion measured with the
Zetasizer Nano ZS. Conditions: water-octane system, oil content of 10%.

cavitation bubbles would blur the fluids, making it extremely difficult to

observe [29]. Literature studies have made a lot efforts in revealing how
the bubble oscillation interacts with the droplet or the water–oil inter­
face, and how the parameters (e.g., bubble size, jetting strength and
direction, fluid properties) influences the droplet rupture [29–33]. The
bubble explosion and shock wave are also observed in an ultrasound-
assisted microchannels [21]. In addition, Zhao et al. [23] and Liu
et al. [34] found a novel mechanism that cavitation bubbles shuttle
across the interface of a large droplet, take an oil film coated on the
bubble surface and break the film into fine oil droplets (0.5–3 μm) in the
continuous phase. Fig. 5. Visualization of oscillation in emulsion fluids (a) bubble array in a
Due to the thin liquid layer in microchannels, it enables to observe straight channel (b) a cavitation zone with strong oscillating bubble cloud.
the flow and bubble oscillation behavior in the opaque white coarse
emulsion. During the propagation of ultrasound, the cavitation bubbles production of high-quality emulsions with uniform droplet size distri­
and container wall would reflect the wave, generating a complex sec­ bution. The distance between neighboring arrayed bubbles was in the
ondary ultrasound field. The narrow size of microchannels also leads to range of 0.5–3 mm, suggesting that there was some long-range effects of
an important wall confinement effect that influences the onset and the secondary ultrasound field, besides the Bjerknes force and secondary
strength of cavitation [35]. Several researches also reported interesting Bjerknes force [37]. The effects of operating parameters were investi­
phenomenon caused by the secondary ultrasound field, such as jetting gated. Generally, they were the same as in pure liquids. Increasing the
and atomization in gas–liquid Taylor flow, and bubble arrays power density and reducing the flow rate can lead to more bubbles in the
[17,18,28,36]. The oscillation behavior can be compared to these reactor. In addition, the distance between the neighboring bubbles was
findings, hence revealing the emulsification mechanism in the second reduced, and the bubble size increased.
stage. Fig. 5b shows the oscillation phenomenon in the meandering chan­
In this work, the oscillation of cavitation bubbles in the fluids in the nel. Because the meandering structure made it impossible to record the
USMR was characterized with a high-speed camera (Phantom M310, flow in the horizontal direction, the oscillation was recorded with a
Vision Research). As the USMR was not transparent, another two USMRs vertical light source, of which the light was reflected by the channel
reported in our previous studies [34,35] were applied. The first one bottom. As can be seen, there was a stagnant cavitation zone (bright area
composed of a glass tube (ID 1.0 mm) that was directly coupled to a marked by the red circle) with much stronger oscillation. From the video
transducer. Because of the transparent tube, we were able to record the (See the supplementary file), it can be seen that the bright area was
cavitation bubbles throughout the entire tube (Fig. 5a) and the bubble actually a strong vibrating “bubble cloud” that stayed nearly stagnantly
oscillation characteristics (Figs. 6 and 7). The second one composed of a and did not move downstream, suggesting there was a secondary ul­
stainless chip fabricated with a serpentine microchannel, which was trasound field that may be caused by the corner. Since similar phe­
used to record the acoustic phenomenon in the meandering corner nomenon was not observed in pure liquids [35,38], its formation was
(Fig. 5b). The stainless chip was sealed by gluing a transparent PC also related to the presence of the surfactant. This extensive oscillation,
membrane to the surface of the chip. Both the two USMRs did not as well as the accompanying jetting and shock wave, enabled a faster
contain cooling parts. reduction of the droplet size during the emulsion production.
Fig. 5 displayed two important and distinct oscillation phenomena In our previous work, it has been shown that a single bubble may
observed in the present work. Fig. 5a indicated that there was bubble undergo three typical oscillation modes, namely the volume oscillation,
array (or bubble cluster array) in the straight channel. Such bubble array shape oscillation and transient oscillation [3,19]. The three modes are
has been reported in anti-solvent processes in our previous studies characterized by bubble volume expanding-shrinking periodically,
[18,28]. The bubbles danced upward and downward periodically, and shape oscillation with surface distortion and violent collapse of bubbles,
moved downstream at a speed much smaller than the superficial fluid respectively. The transition of these modes has been revealed to depend
velocity. This uniform distribution of the cavitation bubbles enabled the on the competition between the acoustic pressure and surface tension.

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L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

Fig. 6. Oscillation characteristics of single bubble cluster under (a) shape oscillation and (b) transient oscillation.

deviated a lot from previous studies without surfactant. In those studies,

the oscillation of single bubbles, with size ranging from 10 to 300 μm,
can be clearly observed [3,19]. However, with surfactant present, there
were only fine bubbles that formed bubble clusters and oscillated as
whole. Hence, the bubbles shown in Fig. 5 were actually mainly bubble
clusters (at very low ultrasound power, they were still bubbles).
Regarding a single bubble cluster, two oscillation modes similar to shape
oscillation and transient oscillation were observed. As shown in Fig. 6a,
the cluster was distorted into various shapes including polygonal and
elliptical shapes. For the transient oscillation, finer bubbles were teared
off from the cluster as shown in Fig. 6b. The basic characteristics of the
cluster under the two modes were almost identical to that of bubbles
[3,19]. However, there were also several obvious differences, which
should also be caused by the presence of the surfactant. First, it was very
difficult to occur (or observe) the volume oscillation. Even for very small
clusters (<30 μm), they were easily driven to occur elliptical deforma­
tion. This is because the cluster was a loose set of fine bubbles and could
not provide enough interfacial tension as in a single bubble. For a single
bubble, small distortions on the bubble surface excited by low ultrasonic
propagation can be easily smoothed out by the strong interfacial tension,
which then lead to delayed transition to shape oscillation than a cluster.
For the same reason, the deformation of the cluster in the transient mode
was more exaggerated, as can be seen in Fig. 7. Moreover, the ruptured
filaments would not coalesce again as in most of the cases in pure
liquids.
By mapping the oscillation modes with the power density and the
cluster radius (Fig. 8), the transition from the shape mode to the tran­
sient mode can be revealed and compared to previous studies [18,39]
involving pure water and octane, where the driving frequency was also
Fig. 7. Comparison between the morphologies of the bubble in octane[18] and about 20 kHz. Note, in pure liquids the radius R is the bubble radius. The
bubble cluster in emulsion under different oscillation mode. radius R of the cluster was measured with the same method for oscil­
lation bubble [35], which included a pulse turn-off and turn-on of the
The transition lines have also been proposed accordingly [18,35]. ultrasound excitation and can capture the cluster diameter (i.e., 0 μs in
However, in these studies, there is no surfactant present in the fluid Fig. 6). It can be seen that the transition from the shape mode to the
systems. In emulsion, as there is significant amount of surfactants, the transient mode occurred near the linear resonance size of microbubble,
oscillation behavior of cavitation bubbles may have distinct character­ which was calculated based on the Minnaert theory [40,41]. This is
istics. In this work, the oscillation of bubbles in the emulsion fluids was reasonable since the oscillation strength is the largest when the bubble/
recorded in the glass reactor and the applicability of previous transition cluster size reaches this resonance size.
lines was discussed. The previous studies revealed that the transition between the two
Fig. 6 shows that the oscillation behavior in the emulsion fluids modes can be well predicted by the following correlation, which de

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L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

Fig. 8. Distribution map of the bubble oscillation mode as a function of the

power density and bubble size.

scribes the competition between interfacial tension and acoustic pres­

sure.
( )2.35
σ PA
3 2
= 0.0088 (1)
ρ R1 ω P0

As illustrated in Fig. 8, the transition line was shifted to larger cluster

size at low Pth while it approached the prediction of Eq.1 at higher Pth. In
other words, it was easier to generate transient mode for the cluster
under low power density. The reason could also be attributed to the
loose set of fine bubbles. However, this effect became negligible when
the power density increased to about 0.15 W/mL. The exact reason is
unknown yet and needs further investigation.

3.2. Characteristics of emulsification

For the emulsification process, the energy exerted into the fluid is the
key factor that significantly influences the emulsion size, as well as the
emulsion stability. In ultrasonic devices, the energy exerted is dependent
of both the ultrasonic power and processing time (residence time in
continuous system). Fig. 9 shows the effects of the two parameters on the
emulsion size for different processing volume. As can be expected,
increasing either the ultrasonic power or the residence time can reduce
the emulsion size. The emulsion size rapidly decreased for all the resi­
dence times when the ultrasonic power increased from 5 to about 40 W.
Further increasing the ultrasonic power, the effect on the emulsion size
was relatively small. Such phenomenon has been widely observed dur­
ing ultrasonic emulsion in conventional devices [3,42]. This is usually
explained by the acoustic shielding effect at high ultrasonic power [42],
namely the denser microbubbles near the horn surface restricting the
transmission of acoustic energy into the liquid medium. Generally, to
occur the acoustic shielding effect, the energy density should be at as
large as more than 100 J/mL [12]. However, the energy density in the
present work was always smaller than 10 J/mL. Thus, the phenomenon
discussed above was not likely to be caused by the acoustic shielding
effect. A possible reason maybe that the increased collision and coales­ Fig. 9. The effect of ultrasonic power and residence time on the average
cence of droplets at high power levels [43] prevented further reduction emulsion size for different processing volume (a) 88.7 (b) 233.6 and (c) 312.3
in emulsion size due to the relatively low content of surfactant (about 2 μL. octane-water system with octane content of 10 %.
%) and high oil content (10 % octane) in the present work.
At fixed ultrasonic power, the emulsion size decreased with the in­
crease in the residence time (τ). But it can be seen that at low ultrasonic
power (i.e., < 5 W), the effect of residence time can be neglected. This
agrees well with our previously finding that under such conditions the

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vibration of bubbles was dominated by the stable oscillation, namely soybean oil system due to its higher viscosity, the power index was
experiencing volume and shape oscillation. Under stable oscillation, the nearly the same. This suggests that the ultrasonic microreactor used in
disturbance caused by the bubble was very small and extensive shock the present work has consistent scaling laws for different fluid systems.
wave hardly occurred. As a result, increasing the residence time did not It should be noted that although the plotted points can be well fitted by
help to reduce the emulsion size at low ultrasonic power. From Fig. 9a, it Eq.2 on the whole, better fitting performance was achieved only Ev
can also be seen that when the residence time was smaller than 7 s, the when reached a certain value. This phenomenon can be further observed
effect of ultrasonic power was very small too. This is because it needs a in the following text. The reason is actually in agreement with the dis­
few seconds to reach the steady state of oscillation in the reactor [18]. If cussion relevant to Fig. 9. Because Ev equals to Pth × τ, either smaller Pth
the residence time was too small, the fluid flowed out of the reactor or τ will affect the droplet rupture. For smaller Pth, only shape oscillation
before the oscillation was fully developed. Then the energy of ultra­ occurred and the size reduction rate was slowed. For smaller τ, the
sound could not be transferred into the fluid medium nor be applied to received energy could be also small despite strong oscillation. The
break the droplet. Therefore, it is necessary to keep the residence time critical Ev depends on various factors and could not be precisely
larger than a critical value (e.g., 7 s in the present work). revealed by the present data. A larger value exceeding 106 Jm− 3 is
As both the ultrasonic power and residence time are important pa­ suggested for more effective operation.
rameters, the energy density (Ev, J/m3) is commonly used to correlate In Fig. 10b, the results in the present work are also compared to
the emulsion size. Karbstein and Schubert[44] proposed that the several other studies involving ultrasonic methods [12,45–47]. It should
average emulsion size can be described by a simple exponential be noted that it is impossible to simply figure out which device is better
relationship: since the emulsion systems are totally different. But by comparing the
exponential laws, the characteristics of the various devices can be
dav = C × Ev− b
(2)
illustrated. First, the energy density here with the present design was
about one or two orders of magnitude smaller than other devices with
Fig. 10a shows that this relationship well describes the results, which
ultrasonic horns, while nano-sized emulsion can still be obtained. It is
included the data obtained from the octane-water system for all the
very interesting that the correlations for the ultrasonic microreactor are
three different processing volumes and from the soybean oil–water
very close to the work of Leong et al.[41] (y = 97.7x-0.371), which also
system for 312.3 μL. Although the emulsion size was much larger in the
induced small channels in the ultrasonic horns. This may suggest some
synergy (i.e., a power index b around 0.3–0.4) in ultrasonic micro­
channels, which needs further verification.
The influence of oil content is a very complex problem. It involves
both the distribution of energy and surfactant loaded to the numerous
fine oil droplets. One may intuitively expect an increase in the emulsion
size when the oil content increases. However, different observations
have been frequently reported [45,48–50]. For example, Vankova et al.
[48] found that when viscous oil phase was used, the emulsion size may
decrease with the increase in its content. Leong et al. [45] reported a
first decrease in emulsion size when the oil content increased from 1 %
to 2.5 %, and then an increase in emulsion size when further increasing
the oil content. The exact reason is still not known yet. In the present
work, the effect of the oil content for both octane-water and soybean
oil–water was investigated. The results are displayed in Figs. 11 and 12.
As can be seen, the emulsion size was obviously affected by the oil
content under experimental conditions, though the size of the original
coarse emulsion slightly differed from each other. A monotonic increase
of emulsion size with the oil content was observed. As shown in Fig. 11,
for the content of 2 %, the size of the coarse emulsion was the largest, but
it decreased to 0.22 μm when the ultrasonic power increased to 50 W.
The effect of octane content seemed to be negligible between 8 % and 10
% since nearly the same emulsion size was obtained when the ultrasonic
power was larger than 20 W. For the soybean system, the effect of the oil
content was always obvious under experimental range, as shown in
Fig. 12. From the two figures, it can also be seen that the oil content did
not change the power index of the exponential relationship with energy
density (Eq.2). The influence of the oil content was mainly expressed by
the change of the pre-factor.
According to the classical turbulence theory, the increase in the
viscosity of the continuous phase (μC) leads to larger size of the smallest
turbulent eddies, which then results in smaller droplet size during tur­
bulent emulsification[3,48]. However, in ultrasonic emulsification, the
μC also significantly influence the oscillation intensity in the fluids.
Increasing μC can rapidly reduce the oscillation intensity [35], which is
not beneficial for the emulsion production. In this work, the μC was
changed by adding glycerol into the aqueous phase to investigate its
influence in the present ultrasonic microreactor. As shown in Figs. 13
and 14, different phenomena were observed regarding the octane-water
system and the soybean oil–water system. For the octane-water system,
Fig. 10. (a) The emulsion size as a function of the energy density and (b) the emulsion size was rarely influenced by μC. For the soybean oil–water
comparison to other studies with ultrasonic methods. system, there was obvious effect of μC on the emulsion size, especially

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L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

Fig. 11. The effect of the oil content on the emulsion size for the octane-water Fig. 12. The effect of the oil content on the emulsion size for the soybean
[Link] as a function of (a) power and (b) energy density. oil–water system. Plotting as a function of (a) power and (b) energy density.

when the glycerol content from 0 to 10 %. In addition, the power index 3.3. Correlation and comparison to literature studies
also varied largely at different glycerol contents, suggesting the scaling
mechanism had been deviated. Since the μC has opposite effects on the From the above parametric study on the ultrasonic emulsification, it
oscillation and turbulent eddy size, the present results may be resulted can be seen that although the simple exponential relationship between
from the different competition between the two factors. A possible the droplet size and energy (Eq.2) can be applied to fit the experimental
reason is given as following. In our previous studies on the cavitation data, it is not able to reflect the influences of different parameters. The
phenomenon, it was found that cavitation nuclei first occurred in the oil reason is that it was originated from conventional equipments such as
phase with smaller viscosity and surface tension during liquid–liquid high pressure homogenizers and ultrasonic devices, in which high input
two phase flow [35]. For the octane-water system, the low viscosity and energy density (ε) is required (e.g., 103 ~ 108 W/kg) [6,51]. Besides the
surface tension of octane, as well as the high solubility of gas, made it simple exponential relationship, a lot of researches have been dedicated
serve as the main source for the cavitation. When glycerol was added in to developing general theories to predict the emulsion size. The basic
the aqueous phase, the negative effect of μC on the cavitation was not too idea of these theories is quantifying the local shear at the droplet
significant, and could be well compensated by the positive effect of μC in interface to overcome the interfacial stress. For large droplets, the
the turbulent eddies. As a result, an overall negligible effect on the classical theory of Taylor [52], which describes a minimum shear of
emulsion size was observed. In the contrast, the aqueous phase served as laminar flow on a single droplet (Fig. 15a, τ ~ μCṙ) below which the
the main cavitation source for the soybean oil–water system, as the droplet will not break, suggests the final droplet in an emulsion scales as
viscosity of the oil was as large as 42 mpa•s. The addition of glycerol
Cacrit σ
lead to obvious inhibition in the cavitation, which then resulted in sig­ d= (3)
μC ṙ
nificant increase in the droplet size. According to the result and dis­
cussion, it is suggested that if viscous oil phase is applied, the viscosity of where μC is the dynamic viscosity of the continuous phase, ṙis the shear
the aqueous phase should not be larger than water. rate, Cacrit is the corresponding critical capillary number and σ is the
interfacial tension.
Under turbulent shear conditions, Hinze developed a theory[53] that

8
L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

Fig. 13. The effect of μC (glycerol content in the water) on the emulsion size.
Octane-water system. The octane content was 10%. Plotting as a function of (a) Fig. 14. The effect of μC (glycerol content in the water) on the emulsion size for
power and (b) energy density. the soybean oil–water system. The soybean oil content was 1%. Plotting as a
function of (a) power and (b) energy density.
involves a critical Weber number (Wecrit) below which the droplet will
not break (Fig. 15b). The Weber number originates from the description definitely can not reflect the condition of the present work as discussed
of the local eddy shear τ as the inertial stress ρCu2C, where uC is the tur­ previously. Because the Oh number ranged from 0.2 to 3.5 and the
bulent velocity of the eddy in the surrounding continuous phase. uC can viscosity strongly affected the cavitation, it is necessary to develop new
be described as 20.5(εd)1/3 based on the classical turbulence theory. models or correlations to predict such effects. In this work, the model of
Then the following expression can be achieved: Gupta et al. [54] was adopted for reference, which considers both the
( )3/5 viscous stress inside the droplets and the scale over the droplet rupture
d=
1
We3/5
σ 3/5 −
) ε 2/5
(4) (Fig. 15c). This enables the capture of both the effects of μC and μD.
crit (
2 ρC Briefly, the model assumes the droplet rupture time scales as ~ μD/
This scaling has been widely applied to correlate the emulsion size (ρDu2d) ~ du-1 -1
d Red , i.e., the diffusive time scale. At the moment of rupture,

and power density [6,54]. Eq.2 proposed by Karbstein and Schubert δ ~ dRed , a ~ dRe-0.5
-1
d and ua ~ udRe-0.5
d for Oh > 1. A critical Weber
[44] actually also resulted from this theory. The index of the power number is defined for the filament that forms a daughter droplet,
density is 0.4, which is very close to the present study and other studies ρD u2a a
(See Fig. 10). Realizing that the theory cannot indicate the effect of Wecrit,a = (5)
σ
properties of the droplet phase, Hinze [53] proposed a scaling of Wecrit
= C2 (1 + f(Oh)), where Oh is the Ohnesorge number (=μD/(ρDσ d)0.5) Substituting all these parameters into Eq.5, a correlation is obtained:
and governs the visco-capillary effect of the dispersed phase. However, a
Wecrit,d = Wecrit,a Re−d 0.5 = C3 Oh2/5 (6)
specific expression of f(Oh) was not given, and many studies have been
dedicated to this issue for practical usage [6,7,55].
If the droplet size is smaller or comparable to the Kolmogorov’s length
The above theory also neglects the effect of the viscous shear of the
scale (e.g., about 300–600 nm for typical high energy devices), the local
continuous phase since the formation regime of the emulsion droplets is
shear stress surrounding the droplet τapplied ~ (μCρCε)0.5 can be applied
the inertial turbulent regime [48]. The effect of the viscosity of the
to estimate Wecrit,d as (μCρCε)0.5d/σ . Substituting it into Eq.6, it results in
continuous phase is only incorporated into the power density, which

9
L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

in a convenient and intuitive way. As shown in Fig. 16, the data from the
octane and soybean oil systems can be well superimposed together when
the continuous phase was the same. Note, as the viscosities of the
continuous phases with 10 % and 20 % of glycerol were very close, the
data points were not classified. Hence, the model can predict our results
to a relatively great extent. However, as the model cannot describe the
effect of the viscosities on the cavitation in the ultrasonic microreactor,
the results of different μC deviated a lot from each other. In Fig. 16, it can
also be seen that the index of the power density deviated more from
− 0.4 when μC increased. This may be caused by a stronger effect of μC on
the cavitation.
To predict the droplet size in the ultrasonic microreactor, an
empirical correlation was proposed based on the above theories. The
parameters of the oil fraction (φD) and the viscosities were incorporated.
By fitting the experimental data, the following two correlations were
obtained. The first one was applied when the transformed droplet size
was larger than 0.6 μm while the second one was applied for smaller
than 0.6 μm. The detailed reason of the transition at this critical size is
not known yet, which may be related to the Kolmogorov’s length scale.
As shown in Fig. 17, the correlations provided excellent prediction
performance.

dμ0.4 0.33
C /μD = 11.1E−V 0.214 ((1 − φD )/μC )− 0.367
(φD /μD )− 0.088 − 0.186
μ D (8)

Fig. 15. Schematic of the mechanism for emulsion formation (a) laminor shear
dμ0.4 0.33
C /μD = 11.1E−V 0.193 ((1 − φD )/μC )− 0.726
(φD /μD )0.098 μ0.0423 (9)
(b)turbulent shear (c) turbulent shear with droplet size smaller than the Kol­ D

mogorov’s length scale.

Since dμ0.4
C / μD
0.33
(μm) is not a parameter with actual physical meaning,
the dimensions of the parameters in the two equations should be spec­
the following correlation.
ified as d (μm), Ev (J/m− 3) and μ (mpa•s)
σ5/6 μ1/3 The energy consumption and efficiency are key factors for emulsion
d = C3 D
(7) production, as well as process intensification in chemical engineering.
(ρD σ ) (μC ρC ε)5/12
1/6
There are already a lot of studies showing that ultrasonic devices are
This model is suitable for the present study since both the shear in­ very efficient in producing emulsion [56–58], regarding various issues
side and outside the droplet contributed to the rupture by the cavitation such as energy efficiency, emulsion size and product quality. Abismal
bubbles. In our previous studies, besides the shocking wave, small et al. [11] found that the coefficient (C2) from the Hinze theory being
cavitation bubbles shuttling across the droplet interface was observed about 7 × 10-3 in a ultrasonic devices, which suggests a much higher
[23,34]. Such behavior also helps to rupture the droplet and generate efficiency than in mechanical agitation devices (C2 ranges 0.036 ~ 1)
finer droplets, which accords with the model description of shear inside [48,53]. In our recent review [3] a rough comparison of energy effi­
droplets. Because the densities and interfacial tension of the fluids in the ciency between different devices was provided and predicted that in
present work did not change significantly, a transform of the droplet size ultrasonic micro-devices the energy efficiency can be further elevated.
(dμ0.4 0.33
C /μD ) was proposed to check the validity of the model. This In this study, the results were compared to other studies with similar
treatment is inspired from Eq.7 that roughly scales d ~ μ-0.4 1/3
C μD . working conditions, in a detailed manner. The results are displayed in
Accordingly, dμ0.4
C / μ 0.33
D should scale with ~ ε -0.4
, and should be inde­ Fig. 18 and Table 1. The energy efficiency was estimated by calculating
pendent of the fluid viscosity. Theoretically, it can also be applied to the theoretical energy (Etheo = ΔAσ = 6φDσ/d-6φDσ/d0) to form the final
compare the performance of different devices besides ultrasonic devices,

Fig. 17. Comparison between predicted and experimental transformed

Fig. 16. The transformed droplet size as a function of the energy density. droplet size.

10
L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

Walstra et al. [46] only provided data without figuring out the mea­
surement method. Table 2.

4. Conclusion

The oscillation of cavitation bubbles and emulsion preparation pro­

cess were investigated in a novel 3D printed ultrasonic microreactor
(USMR). The oscillation behavior in emulsion was first investigated by
high-speed imaging. The results show that there were bubble clusters
vibrating as whole, which is different from oscillation in pure liquids.
The vibration characteristics of a single cluster were similar to that of a
single bubble. There were also two distinct modes of shape oscillation
and transient oscillation. But the transition from shape to transient
oscillation of the bubble cluster was easier than that of a bubble. Due to
the uniform sound intensity and unique environment for bubble vibra­
tion, it generated secondary sound field, which then lead to cluster array
in the straight part and relatively stagnant zone with shocking wave in
the corner part of the microreactor. These phenomena contributed to the
rapid reduction of emulsion size.
Fig. 18. Comparison of the energy efficiency between different emulsifica­ The effects of processing volume, residence time, fluid viscosity and
tion devices. oil content on the prepared emulsion were investigated and discussed. It
was shown that the emulsion size could be reduced to 200–600 nm in a
very short of 7–30 s. Under experimental conditions, the energy input
Table 1 (Ev, J/m3) varied in the range of 105-107 J/m3, which was much smaller
Physical properties of the fluids used to prepare emulsion.
than conventional ultrasonic devices. The droplet size could be well
Fluid μ (mpa•s) ρ (kg/m3) σ (mN/m) described by an exponential law with the energy input. Traditional
octane 0.55 703
predicting theories do not take the effect of cavitation, hence cannot
soybean oil 5.02 927 fully describe the effects of the operating parameters. Based on the
water 0.89 998 5.37a 5.12b parametric study, a semi-empirical correlation was proposed and
10 wt% glycerol in water 1.48 1021 5.28a 5.06b
showed excellent predicting performance. Finally, the results were
20 wt% glycerol in water 2.28 1042 5.09a 4.99b
40 wt% glycerol in water 4.74 1090 5.06a 4.90b compared to literature studies with close operating conditions,
regarding the energy efficiency. Due to the controlled sound field and
a: interfacial tension with octane; b: interfacial tension with soybean oil.
cavitation bubbles of the USMR, the energy efficiency ranged from 0.03
to 2.77 %, which was at least one order of magnitude higher than con­
emulsion. The influence of coarse emulsion has been taken into account. ventional ultrasonic devices.
It can be seen that besides the droplet size the oil content can signifi­
cantly influence the energy efficiency. This well agreed with our results, CRediT authorship contribution statement
as shown in Fig. 18. Although we only displayed the results of the oil-in-
water systems, the range of results with glycerol solutions were in the Li Ding: Investigation, Writing – original draft. Shuainan Zhao:
same and the effect of μC was relatively small. The energy efficiency of Investigation. Lixue Liu: Methodology. Wei Wang: Data curation,
the present work ranged from 0.03 to 2.77 %, which was obviously Validation. Chaoqun Yao: Conceptualization, Supervision, Writing –
higher (actually at least one magnitude of order) than other studies with review & editing. Guangwen Chen: Project administration, Supervi­
values smaller than 0.1 %. The latter range was actually in the range of sion, Writing – review & editing.
the analysis of Tadros et al.[5]. The result of Leong et al. [45] was very
close to the extrapolation of the present work. This is reasonable since Declaration of competing interest
their work also fabricated mini channels (3 mm) inside the ultrasonic
horns for the fluid to pass through. However, the surfactant concentra­ The authors declare that they have no known competing financial
tion was more than doubled than other studies listed in Table 1. It should interests or personal relationships that could have appeared to influence
be noted that in the study of Behrend et al.[59,60], Li et al. [12] and the work reported in this paper.
Leong et al. [45], the energy density was measured with the standard
calorimetric calibration while the study of Zwieten et al.[47] and

Table 2
Comparison of emulsification performance between different researches.
Operation Emulsion system φD/% surfactant d/ um Ev/(J⋅m− 3) Energy efficiency/%

Behrend et al.[59] Ultrasonic batch Vegetable oil-in-water 20 SDS 0.42–1.9 107-108 0.02–0.08
Behrend et al.[60] Ultrasonic batch Vegetable oil-in-water 1 2 % SDS 0.42–1.0 107-108 0.002–0.005
Li et al.[12] Ultrasonic batch canola oil-in-water 1 5 mM SDS 0.11–7.0 107-109 0.0004–0.001
Li et al. [12] Ultrasonic continuous canola oil-in-water 1 5 mM SDS 0.11–7.0 107-109 0.0001–0.0004
Li et al. [12] homogenizer canola oil-in-water 1 5 mM SDS 0.11–7.0 107-109 0.001–0.0015
Zwieten et al.[47] Ultrasonic bag Hexadecane-in-water 10 1 % SDS 0.49–0.83 107-108 0.01–0.015
Leong et al.[45] Ultrasonic continuous Sunflower oil-in-water 15 5.6 % SDS + 13.6 % PEG 0.04–0.13 107-109 0.06–0.12
Leong et al.[45] Ultrasonic continuous Sunflower oil-in-water 15 5.6 % Tween 80 0.04–0.13 107-109 0.01–0.05
Walstra et al.[46] Ultrasonic continuous dilute paraffin 1 3 % Tween 20 0.82–1.9 106-108 0.0008–0.02
Oil-in-water
Present work Ultrasonic microreactor Octane-in-water 1–10 1.8 % Tween 20 + 0.2 % Span 80 0.22–1.21 105-107 0.03–2.77
Soybean oil-in-water

11
L. Ding et al. Chemical Engineering Journal 484 (2024) 149462

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