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Ultrasound Emulsification—An Overview

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DOI: 10.1080/01932690208984209

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Ultrasound Emulsification—An Overview

a a a a
J. P. Canselier , H. Delmas , A. M. Wilhelm & B. Abismaïl
a
Laboratoire de Génie Chimique (UMR CNRS 5503 INPT-UPS), Ecole Nationale
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To cite this article: J. P. Canselier, H. Delmas, A. M. Wilhelm & B. Abismaïl (2002): Ultrasound Emulsification—An
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 1. Dispersion Science and Technology, 23(1-3 ), 333-349 (2002)

Ultrasound Emulsification-An Overview

Downloaded by [Institut National Polytechnique de Toulouse ] at 04:48 23 October 2012

J. P. Canselier, * H. Delmas, A. M. Wilhelm,

and B. Ablsrnail
Laboratoire de Genic Chimique (UMR CNRS 5503 INPT-UPS),
Ecole Nationale Superieure des Ingenieurs en Arts Chimiques
et Technolog iques, 118 route de Narbonne , F31077 Toulouse,
Cedex 4, France

ABSTRACT

Fundamentals and applications of ultrasound emulsification are reviewed. The

importance of cavitation is stressed, as also is power input to the multiphase
fluid. The influence ofsurfactants, polym eric stabilizers, temperature, pressure, and
ultrasonic parameters such as frequency, residence time, acoustic intensity, and
energy density are described. The effects ofother physicochemical parameters such
as emulsifier concentration, disperse phase volume F action, and viscosity are
discussed. Applications to both water-in-oil and oil-in-water emulsions are
discussed.

ULTRASOUND PRODUCTION
Fundamentals
The Ultrasonic Domain
The audible acoustic spectrum extends from 16 Hz to
16 kHz. Below and above this audio-frequency range,
vibrations belong to the infrasonic and ultrasonic
domain s, respectively. Within the ultrasound range, the
power available varies inversely with the frequency
(Figure I) and only powerfu l ultrasound (16- 100 kHz,
and, to a lesser extent, 100 kHz-I MHz) is able to interact
with matter, producing physica l and chemical chang es,
essentially by cavitation phenomena. On the contrary,
higher frequency ultrasound goes through solid or liquid
media without affecting their structure and is used as
non-destructive characterization or diagnosis tools e.g. in
analysis, physical measurements and medical imaging
(1,2).

*Corresponding author. E-mail: jeanpaul. canselier@ensiacet.fr

333

Copyright © 2002 by Marcel Dekker, Inc. www.dekker.com

 334
Audible
Infrasound
Sound
120 kHz I It()() kIlz I
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Figure I. Ultrasound frequency range .
Power Ultrasound Emission and Propagation
The displacement, a, around its equilibrium position
of a planar surface vibrating at a frequency f with a
maximum amplitude A (of the order of 111m) is:
a = A sin(2rrft) (I)
An almost planar, longitudinal wave of wavelength i.
propagates in the surrounding liquid medium with a
velocity c (i. = c/f) and produces alternate regions of
compression and depression (the local pressure being the
sum of the external pressure, Po, and the acoustic
pressure, P~.) , which generates variations of the density,
p, of the medium (3). P" and I, the wave intensity (power
per surface area unit) are functions of the acoustic
impedance of the medium, Z (Z = pc):
PA = AZ 2rrf (2a)
1= P;' /2Z (2b)
For instance, Z is 1.5 x 106 kg m- 2 s- I in water, ten
times less than in glass but nearly 4000 times higher than
In air.
Across any medium, ultrasonic waves undergo
absorption, characterized by the coefficient ':I.. The term
lY. /f 2 , constant for a given medium, mainly depends on its
viscosity and thermal conductivity. This means that part
of (and eventually all) the acoustic energy is degraded
into heat under the effect of viscous friction . At a
distance x from the source:
A = Ao exp( - 1Y..x) (3)
At an interface, especially if the impedances of the two
media are very different, reflection is likely to exceed
Canselier et al.
Low
Power Diagnostic
Hypersound
Ultrasound
11 MHz 110 MHzl
transmission. Stationary waves then occur, with a
distance of i./ 2 between two nodes (or antinodes).
The effective ultrasonic power transferred to a liquid is
not exactly the electrical input or output power to or from
the ultrasound generator. So, since the whole acoustic
energy is eventually converted into heat, calorimetric
measurements are more significant. The effects of
temperature, static pressure, vibration amplitude and
medium viscosity on the ultrasonic power actually avail-
able have been discussed in detail elsewhere (4).
Cavitation
Cavitation is the main phenomenon responsible for
ultrasonically induced effects. Although not a purely
specific effect of ultrasound waves, since cavitation is
also observed in high-pressure homogenizers and, to a
lesser extent, in vessels stirred vigorously with rotor-
stator devices. Hydrodynamic cavitation, normally
avoided in reactor design and operation (2), and often
unlikely to become a desirable phenomenon in large-
scale chemical and physicochemical processes, may be
turned to good use in some cases (5). On the other hand,
acoustic cavitation, associated with power dissipation, is
considered the driving force in sonochemical processing
(6,7) and, in particular, the essential mechanism of
droplet breakup occurring during ultrasound emulsifi-
cation (8). In depression zones, if intensity exceeds a
certain threshold, the cohesion of the liquid is reduced
and rather stable or transient micro-bubbles, containing
dissolved gas and/or vapor of the continuous phase,
appear, oscillate, then implode (Figure 2).
 Ultrasound Emulsification
Pa = f(Time)
o
- P,\
o ° °~
Gas
° )Oor
Rectified
microbubble
diffusion
Downloaded by [Institut National Polytechnique de Toulouse ] at 04:48 23 October 2012
Figure 2. Evolution of a cavitation bubble.
Cavitation bubbles originate from nuclei, i.e. micro-
bubbles in the bulk of the liquid, on dust particles or on
the walls. Through those bubbles, acting as "hotspots",
temperatures of about 4000 K and pressures in excess of
100 MPa can be generated (2,9). Cavitation threshold and
shock wave intensity show the same trend with respect to
a number of parameters. For instance, cavitation thresh-
old increases with ultrasound frequency, hydrostatic
pressure, liquid purity, viscosity, gas content and surface
tension. The influence of temperature is not so straight-
forward, at least resulting in a combination of the last
three parameters (6). On the other hand, above the
corresponding threshold, cavitation phenomena become
stronger for higher external pressure and acoustic inten-
sity values as well as in more viscous liquids (more
violent bubble collapse) (4) or in the presence of low
conductivity, high heat capacity ratio (')' = Cp/ Cv ) gases.
As regards the temperature effect, when the vapor pres-
sure of the continuous medium increases, the cavitation
bubble contains more vapor, and implosion is then
inhibited or at least delayed. Moreover, cavitation is a
rather short-range phenomenon with respect to the loca-
tion of the ultrasonic probe.
At low acoustic intensity, bubbles oscillate with a
small amplitude for several vibrational cycles (stable
cavitation), whereas, at high intensity, unstable cavitation
occurs, that is bubbles more than double their size during
a lifetime shorter than one cycle. Anyway, the main
condition for efficient cavitation is that resonance is
allowed by matching ultrasound frequency with the
proper oscillation frequency of the bubble, associated
with its radius (e.g. 100 11m at 20 kHz and a few 11m at
335
Time
Implosion Fragmentation
(P '" 1000 bar) (E '" 1011 V1m)
(T '" :1000 K)
500 kHz). To describe the behavior of stable bubbles,
Lorimer and Mason's dynamic model (6) leads to an
expression of the bubble radius vs. time. Full mathema-
tical modeling of cavitation phenomena has not been
achieved yet, and most published papers are related to
experimental studies (10,11).
Most of the mechanical effects of power ultrasound,
namely cleaning, dispersion, grinding and emulsification,
originate from cavitation. They are related to surface
erosion, interface breaking, transferenhancement through
liquid mixing near an interface, and are favored at low
frequenc ies. The 20-50 kHz range is the most efficient.
Chemical and engineering aspects of sonochemistry
have been the subject of recent reviews (2,7, 12, 13). It does
not seem to be the case for ultrasound emulsification.
Technology
Ultrasound Generation
Ultrasound can be generated either mechanically
(whistle, siren) or electrically (reverse piezoelectric
effect or magnetostrictive transducers) (7,14). The whis-
tle is a rather old device in which a liquidjet, accelerated
through a small hole, hits a thin metal plate whose
resonance frequency may be reached by varying the
pressure, the liquid speed and the hole-plate distance.
This device is currently used, e.g. in the manufacture of
food emulsions and skin creams. Magnetostrictive trans-
ducers induce ferromagnetic materials to shrink under the
effect of a magnetic field and to return to their normal
size when the field is removed. Cobalt/iron, aluminum/
iron and even more recently, terbium/dysprosium/iron
 336 Canselier et al.

Fluid output ! Generator

jl;
~avity Con verter
Fluid input

a)

Vibration node
Vibrating plate
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Tip

Insonated medium

Figure 4. Insonation equipment with sonotrode.

Blocki ng
capacity

Altema tive
current
- (Terfinol-D) alloys tend to replace the former nickel
alloys, but are electrica lly less efficient. All these magneto-
c) strictive materials have an upper frequency limitation at
ca. 70 kHz . In the third, most widel y used, type of
Self
DQQO apparatus,' a high-frequency oscillati ng elec tric field is
Tran sduce r
Direct + converted : into mechanical vibrat ions of the same
current
I freque ncy : thanks to a piezoelectric (quartz, ceramics
such as lead zirco nate-titanate or baryum niobates or
titanates) material. This kind of dev ice covers the entire
High density material '
(e.g. steel) range of ultrason ic frequencies. " 1-3 Co mposite " piezo-
ceramic arrays provide transducers in the form of flexible
sheets, ens uring much better acoustic transmission into
Assembling bolt
aqueo us systems (7).

Probes and Reactors

Piezoelectric In batch operation, ultrasound is emitted by transdu-
blocks
cers fixed on the outside wall of the vessel or by
cyli ndrical sonotrodes, or horns, imme rsed in the
liquid. With sonotrodes the local acoustic power may
be a hundred times higher than in an ultraso nic bath.
d) Low density material
(e.g aluminum ) However, the coresponding energy is only available just
near the vibrating tip.
Figure 3. Ultrasound devices: (a) whistle; (b) siren (from In conti nuous operation the circulating fluid may enter
Ref. 3 with permission); (c) electric generator for magnetos- and leave a small reactor equi ppe d with a probe; other-
trictive transducer; (d) reverse piezoelectric effect transducer wise , one or several transducers are located inside the
(sandwic h type),
tubing, unless the tubin g itself is vibrating.
 Ultrasoun d Emulsification 337

EMULSIFICATION BY ULTRASOU ND longer times can yield submic ron ic emulsions, they
propose a two-step mechan ism (Figure 5) :
Principles and Operation
- the first step involves a combination of interfacial
Emu lsification, i.e. intim ate mixing of two imm iscible
waves and Rayleigh-Taylor instability, leading to the
liqu ids (15) was one of the first applications of powerful
eruption of dispersed phase dropl ets into the
ultra sound ( 16) and the first related patent was taken out
co ntinuous phase;
more than fifty yea rs ago ( 17). Bond y and Sollner were
- the seco nd step consists of breaking dropl ets up
ab le to link aco ustic emulsifica tion to fluid dynamics
through cavita tion near the interface; the intense
through cavitation phenomena (8), but Ned uzhii ( 18),
effect (dis ruption and mixing) of shock waves
then Li and Fogler (19,20) elaborated mo re comprehen-
exp lains the very small dropl et size , and the mos t
sive theories.
influent ial parameters are those affec ting cavitation
According to Neduzhii ( 18), the cavitation threshold is
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phenomena.
reached for a min imum aco ustic intensity allowing
nucl eus form ation (10- 5 to 10- 3 em in radiu s) and
Start ing from two separa te phases, ultrasound can be
development. In particular, the cavitation pressure thresh-
used directly, but since breaking a planar interface
old in a liqu id increases with its viscos ity. During an
requires a large amo unt of energy, it may be more
indu ction ("i nertial") time lag, only nuclei large enough
advisab le to first prepare a coarse emulsion (e.g. by
grow to the size required for cavitation . By analogy
gentle stirring) before applying aco ustic power. It is
between cavitation and emulsification processes, the
also possible to add the seco nd liqu id (dispersed phase)
author assumes that:
to the first prog ress ively or to feed a cont inuous reactor
with both phases. A lot of papers have been devoted to
- liquid mixing is due to local perturbation s of the
ultrasound-made a / W emulsions but a much smaller
interface;
number to W/ 0 emulsions. Experim ent s on the parti-
- bubbl e implosion is much faster than dilation.
cularly unfavorable formation of mercu ry-in-water
emulsions led the authors to the co nclusion that the
Generally, the less visco us liquid (e.g. water) under-
latter process could be different from oil-in-water emul-
goes cavitation more eas ily (6) and become s the
sification (21). In some cases, ultrasound can also act as a
emulsion continuous phase (oil-in-wate r, O/W, or
demulsifying techn ique.
direct, em ulsio n). But , if a seco nd, higher thresho ld
ultrason ic intensity is reached, a reverse emulsion Results
(water-in-oi l, W/ 0 , type) may be obt ained.
Effect of Ultrasound on the Emulsifier (Surfactant or
On the other hand, Li and Fogler (19,20) consider the
Polymer)
irradiation time is the key parameter in ultrasound
emulsification: since very short times (a few seconds) Very high local temperature and pressure values (e.g.
provide coarse emulsions (e.g. 70 urn droplets), whereas T '" 5000 K, p ", 1000 bar, with dT / dt '" I 0 I 0 K/ s) (22)

Step
l SI

increa sing time

----..
~

o o

• 0 .~)O o ~
eP°
o

Figure 5. Acoustic emulsification: droplet formation and breakup.

 338
result from the quasi-adiabatic bubble compression
when they implode. Those conditions are able to break
chemical bonds, give rise to sonoluminescence
phenomena (22,23) and produce highly reactive free
radicals (especially 'OH and H' from the thermal
decomposition of water) (24,25). The collapse of cavita-
tion bubbles is so powerful that the shear forces produced
are able of breaking bonds in any polymeric material
(26). Degradation of various chemicals (small molecules
or polymers) under ultrasonic irradiation is more efficient
at higher frequencies (27-30). Unfortunately, due to their
tendency to accumulate at the interface of cavitating
bubbles, surfactants should be easily degraded (31,32).
Downloaded by [Institut National Polytechnique de Toulouse ] at 04:48 23 October 2012
However, the extent of degradation becomes noticeable
only for rather long irradiation times and, for instance, at
low frequency (20 kHz) the loss of active matter for
sodium dodecylsulfate has been shown negligible after
30 s, a period of time of the order of that required for
emulsification (33) . For the sake of comparison, Alegria
et al.'s experiments lasted about 15 min (31). Eventually,
organic solvents ("oils") are also degraded on sonication
(2), but, here again, this process may be assumed to be
very slow with respect to emulsification rates.
o/ W Emulsions: Effect of Various Parameters on
Properties (Drop Size and Drop Size Distribution)
Cavitational collapse at or near the interface produces
very efficient droplet disruption, so that, on the whole,
ultrasound is known to allow formation of very fine
emulsions, much appreciated in various formulations
(e.g . drugs, cosmetic products, etc.) as well as in chemi-
cal synthesis in liquid-liquid media (emulsion polymer-
ization (6), alkaline hydrolysis of waxes (34)). Let us
consider the influence of some parameters on emulsion
properties, and especially on drop size and drop size
distribution, since physical stability, rheological behavior
and many other properties largely depend on drop size
(35). The drop size will be expressed as the Sauter
diameter (average surface diameter), d32 :
d 7 = Linjdf = 6Y- (4)
3_ " d2
L.j n, i
A
where n., dj,V and A the number and diameter of droplets
belonging to the ith class, and the total volume and area
of the dispersed phase, respectively.
Temperature and Pressure
Temperature. Obviously, a temperature rise reduces the
viscosities of both phases, making their intimate mixing
Canselier et al.
easier, especially because of weaker viscous forces in the
continuous phase. It also lowers the interfacial tension, I'i,
thereby reducing the minimum thermodynamic surface
free energy (~GS rv YjA ) necessary for emulsification,
and above all the Laplace pressure (P = 2yJr) between
a drop of radius r and the continuous medium. Those
trends are favorable to all emulsification processes.
However, the complex effect of temperature on cavitation
may be detrimental (6,8): the number of nuclei giving
rise to cavitation increases with temperature, but so does
the vapor pressure inside the bubble, producing a damp-
ing of the shock wave and a lowering of the maximum
pressure reached at the implosion. All other things being
equal (formulation variables, ultrasonic power), no signif-
icant effect on d 32 was observed between room tempera-
ture and 50°C (33).
Hydrostatic pressure. Hydrostatic pressure is known to
affect both the onset and intensity of cavitation. On the
one hand, an increase of the ambient pressure shifts the
threshold pressure amplitude to higher values, thus
reducing the regions where the local pressure falls
below the critical (cohesive) pressure of the system,
therefore suppressing cavitation partially. On the other
hand, with increasing ambient pressure, shock waves get
stronger, giving rise to higher peak values of the local
power density. It is therefore relevant to learn the influ-
ence of this parameter on the emulsification process.
Now, an optimum in emulsification efficiency had
been found by Bondy and Soliner (8) at an absolute
pressure of about two atmospheres. More recently, in
continuous process, a shift towards larger droplets with
increasing pressure at constant flow rate has been
noticed. If indeed this effect may be due to partial
suppression of cavitation, it must be kept in mind that
the power dissipated by the ultrasound device depends on
the hydrostatic pressure. Thus , at constant energy dissi-
pation per unit volume, practically no effect of the
hydrostatic pressure on emulsion quality (droplet size)
was observed (36).
Ultrasonic Parameters
Frequen cy. Only ultrasound frequencies ranging
between 20 kHz and a few MHz produce cavitation. If
there is a theoretical relationship between frequency and
emulsion drop size, the trend should be a drop size
reduction with increasing frequency (20). However, a
greater amount of energy is required for emulsification at
higher frequency (the cavitation threshold increases)
(18). Since other authors mention no effect of the
ultrasound frequency on emulsion properties (37), a
 Ultrasound Emulsification 339

check, performed with a cuphom at 533 kHz (P (electric

power) = 40 W), showed the following results (33):
lOA
A
MI
US
- firstly, these ultrasonic waves were unable to
disperse kerosene in water directly in the presence
of polyethoxylated sorbitan monostearate;
- secondly, no change in the medium was observed
after moderate stirring;
- thirdly, the above system, emulsified with a sono- ••
t *-,
trode (f = 20 kHz, t = 60 s, d = 0.3 11m) was not 80 100 120 140 160
modified by insonation at 533 kHz during 15 min. I'c(W)

Finally, the best results in terms of dispersion effi- Figure 6. Effect of the consumed power on d32 : AM,
Downloaded by [Institut National Polytechnique de Toulouse ] at 04:48 23 October 2012

ciency and emulsion fineness are obtained at low mechanical agitation; US, ultrasound with gentle mechanical
frequency, say between 20 and 40 kHz, the conventional pre-emulsification (Montanox 60, 10 giL, r/J = 0.25, to = 30 s).
power ultrasound domain also used in classical sono-
chemistry (2).

Insonation time. residence time. It makes sense that, at
least up to a certain limit, longer insonation times
produce finer emulsions, since a greater amount of
energy is provided to the medium. Let us recall that,
according to Li and Fogler, irradiation time is "a key
variable to understanding the acoustic emulsification
mechanism". It is then relevant to follow the evolution
of d32 as a function of time. Abismail et al.'s results show
that, in batch process, with 20 kHz power ultrasound,
very small droplet sizes can be reached even within a few
seconds and that, after a seemingly exponential decrease,
the minimum diameter (ca. 0.3 urn), smaller than with a
classical rotor-stator device, is attained after about 30 s
insonation (38,40). In this size domain, no abrupt slope
change is observed . As a matter of fact, for continuous
processes, the Sauter diameter can be expressed in the
form of a power law involving the power density, Pv e
(power dissipated per unit volume of emulsion) and the
residence time, t, in the dispersing zone (36):
d3_) = p-v b l cr b2 (5)
If both exponents are quite similar, and if the two
parameters may be treated as a single variable, this
product represents the concept of energy density
(detailed below).
Acoustic intensity and pOWCI: The effect of the acoustic
intensity, I, is the most clear-cut: this intensity must reach
a threshold value to allow emulsion formation (8,18) and
physical and chemical effects of ultrasound increase with
I. The effective power density provided to the medium,
equivalent to I, is the measured parameter. For instance,
working in well defined conditions and with a given
system, Neduzhii needed at least 0.5 W/ cm' to make
an O/W emulsion and 1.5 W / cm2 to make a W/ 0
emulsion (39).
A comparison of the relative efficiencies of mech-
anical agitation ("Ultra-Turrax" T45 rotor-stator device ,
10000 rpm) and insonation ("Misonix Sonicator
XL2020" sonotrode, 0 = 13 mm, f = 20 kHz) showed
that: i) with both techniques, increased dissipated
power yields finer kerosene-in-water emulsions, ii) inso-
nated emulsions are finer than agitated ones, iii) a
minimum acoustic power of 90 W is necessary to emul-
sify the mixture, unless a coarse emulsion (Rushton
turbine, 250 rpm, d32 rv 10011m) has been previously
made (Figure 6) (33,40). In fact, even at low power,
very small drop size can be achieved with ultrasound
provided that a pre-emulsification is effected by simple
mechanical agitation.
It is a common misconception that the higher the power,
the better the efficiency of the process. There is generally
an optimum power for maximum effect (7,9,41). Beyond
this optimum, coalescence may become predominant: this
is perhaps due to excessive cavitation phenomena.
Energy density. The energy dissipated per unit volume
(or mass) of the processed mixture, I-; seems to be the
determining parameter: it has been shown that, as with
mechanical stirring, the average drop size varies as 1-; - 0 ,4
(42):
d = CI-;-OA y? ,6p-;O,6 if I-; is the energy per
unit mass (6)
d = CI-;,-OA y?,6 p-;O,2 if 1-;' is the energy per
unit volume (6')
 340
10
05
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-05-L----,-------,---"'-------j
1.5
_ log P (MJ m- 3 )
Figure 7. Average dropl et size vs. net energy input P for dilut ed paraffin oil-in-water emul sion s produced in various machin es (from
Ref. 42 with permission) .
where Yj and Pc are the interfacial tension and the density
of the continuous phase, respectively.
Figure 7 shows the variations of the average volume
diameter, d 43 , or X43 (d43 = l:nidf/l:njdf ) vs. net energy
input, P, (42,43) for OjW emulsions produced in different
device s, and Figure 8 represents the evolution of d 32 as a
function of G (ultrason ic power, or energy, per unit mass)
(33) . All other things being equal, the same curve has
been drawn for other values of ¢ (0.25) and the exposure
time (30 s) (44). The effects of power in ultrasound
emulsification and in mechanical turbulent isotropic
regime are therefore similar, but the correlation constants
in Eq. (5) are quite different: 7 x 10- 3 for ultrasound
against 37 x 10- 3 for mechanical agitation. This means
that, for a given system and at a constant power (energy)
density , insonation, yielding smaller droplets, is
much more efficient than stirring with a rotor-stator
apparatus (44) .
The phenomena are not different in continuous emulsi-
fication (36 ,44) . A small reactor volume ensures that high
energy is provided efficiently to the fluid mixture (no dead
Canselier et al.
20 50
0.5
2
volume). The effect of the residence time is evidenced by
the increase of d32 with flowrate (Figure 9).
But a more important result is shown in Figure 10. In
fact, whether the insonation time is varied at constant
power or the reverse in a batch process, or the flowrate
(therefore the residence time) varies in a continuous
process, the experimental points are almo st located on
the same curve, emphasizing the importance of the
energy density parameter.
Physicochemical Parameters
Gas content. The effect of the gas phase on cavitation
and emulsification has been studied for a long time
(45). Dissolved or dispersed gases are indispensable for
the onset of cavitation since they give rise to nuclei
growing to microbubbles. There must not be a too high
gas-to-vapor ratio, because, acting as a buffer, the gas
reduces the shock wave intensity and is therefore
detrimental to emulsion formation (36,46 ,47) . Dega s-
sing then allows a higher maximum ratio of disperse
 Ultrasound Emulsification 341

d32 (urn) from the specific adsorption of OH - ions, always present

0.7 in water, at the oil-water interface. However, unsuccessful
0.6 • attempts of stabilization of emulsifier-free kerosene-in-
0.5 water emulsions are reported by Abismail (33). Even
004
0.3
0.2
•
• -- . • • dexp
with progressive introduction of kerosene vapor into the
insonated aqueous phase, less than 2% of the organic
could be temporarily dispersed, giving rise to a rapid
0.1 -corOA
creaming phenomenon.
o - 1-'-
To the best of our knowledge, the effect of the nature
o 1000 2000 3000 4000 of the emulsifier on the properties of insonated emulsions
E (W/kg)
has not been studied systematically. In addition to the
charge of the amphiphile polar head and its equilibrium
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Figure 8. Variation of d 32 vs. acoustic power: experimental
points and solid line for /;0.4 (Montanox 60. 10 giL. ¢ = 0.375.
t, = 60 s).
phase to be incorporated. On the other hand, Abismail
did not find any significant effect of degassing on the
droplet size of a kerosene/water emulsion (33), and
Behrend and Schubert observed no clear effect of gas
content on droplet disruption at constant energy density.
The highest energy densities were obtained neither for
degassed nor for gas-saturated systems (36).
Emulsifier. Reddy and Fogler claim to have prepared
stable oil-in-water emulsions with low volume fraction of
dispersed phase without emulsifier (48). This particular
stability of ultrasound-made emulsions could originate
adsorption properties, its adsorption rate is likely to play
a major part, especially in continuous processes, and
should be considered. Abismail et a1. (40) chose nonionic
surfactants to minimize the role of Coulombic interac-
tions; nevertheless, the value of the measured ( potential
was -18 mV with a polyethoxylated sorbitan monostea-
rate (MONTANOX 60, gift from SEPPIC). The replace-
ment of this surfactant by a smaller molecule (pilot-plant
manufactured alcohol ethoxylate, C'2Eg, SEPPIC)
reduces the droplet size ( '" 0.2 11m instead of 0.3 urn),
may be due to interfacial tension lowering
(Figure II) (33).
The droplet size is reduced when the surfactant
concentration increases until a plateau is reached. For
instance, in fixed conditions, above 10 gil MONTA-
NOX 60 (i.e. about 100 times its erne), d 32 remains
constant (Figure 12) (40). All other things being equal,

... <1>=0.50

• <1>=0.25

• <1>=0.05

I :
400 600 800 1000 1200 1400

flowrate (mL/mn)

Figure 9. Variation of d32 vs. flowrate for different values of ¢ (Montanox 33 giL, P, = 170 W).
 342 Can selier et al.

d'2 (11m) 6
1.4
.. batch (te)
5
1.2 .. • batch (Pe)
• contin uous (f1owrate)
4
1.0
E
2: 3
0.8

0.6 . ..
••
... .
2

0.4
I
• •• o,
0.2
o 5 10 15
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o C (gi L )
o 20000 40000 60000 80000 100000

Figure 12. Variations of d 3 2 vs. surfactant (Montanox 60 )

Fig ure 10. Variation o f d 32 vs. energy density (E/V = I: . concentration : AM , mech anical agitation ; US. ultra sound
¢ = 0.25) ; legend in the box , top to bottom : varying emulsi- ((P = 0.25. t, = 30 S . PAM = 170 W. Pus = 130 W) (from Ref. 40
fication time (P, = 130 W). varying power (t, = 30 s) ; vary ing with permission).
flowrate (P, = 170 W ).

the surfactant amount needed in ultrasound em ulsifica- mass balance calcul ation yields an expression of d 32 vs.
tion is always lower than with a rotor-stator dev ice. In surfactant concentration :
other words, at a fixed surfactant concentration. inson ated
em ulsions are finer than agitated one s. Although , at first (7)
sig ht, this fact is qu ite unexpected, it may be due to a
rather important foam formation in the cas e of classical
Even without taking into account the amount of micel-
mechan ical agitation with respect to insonation.
lized surfactant (C t - cmc - Cm;c'" Ct ) this relation is
With classica l hypotheses (surfactant so luble in the
fairly we ll obeyed. As a matter of fact, this purely
continuous phase and preferably adsorbed at the
geometrical mod el should be complemented by also
liquid-liquid interface as a monolayer, coalescence
con sidering turbu lence phenomen a, so that the minimum
much slower than film formation , surfactant con centra-
droplet diam eter at the plate au level after a sufficiently
tion in the continuous phase higher than its cmc) a simple
long emulsification tim e cou ld read:

d 32 = max I o.6.
C II. ,0I 6 1',- OA ! Jc '

-+-Tween 60
0. 1
__ C12E08

0.08 A-- - - I'Ii= 4.5 mN/m 1 Moreover, narrower drop size distributions are observed
for insonated emulsions, compared with agitated ones,
~ 0 .06
~
>
I'li=9,5 mN/M I with smaller standard deviations for lower surfactant
concentration in both cases (40).
0 .04 1
I Volume fra ction of disperse phas e. Gradua lly increas-
0 .02
I
ing the volume fraction of disperse phase, ¢, leads
eventually to catastrophic phase inversion. Such
0
a phenomenon has been observed by conductivity
0.01 0.1 10 100 1000 measurements aro und 0.5 for a kerosene-in-wa ter
di (1-IIn ) emulsion stabi lized by a non ionic emulsifier (40) .
Figure 9 shows that the higher the disperse phase
Figure 11. Drop size distribution for two nonionic surfactants. volume fraction , the larger the droplet size and a plo t
 Ultrasound Emulsification 343

25
4 ~
20
3.5 ~
~ 15 -O--1g/LAM 3
o
2.5
~ 10 ---...- 19/L US E

.g=-
2

5 1,5
0

o ~_ ...~....
0,01 0,1 10 100
0,5
0
... * 1 -
di (urn) 0 0.2 0,4 0,6 0,8
$ /( I-¢)
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Figure 14. Variations of d32 vs. ¢ I(I - ¢).

8
7
6
found between continuous phase viscosity and droplet
~ 5 -0-- 15g/L AM size. Behrend et al. observed smaller droplets in the
~4 ---...- 15g/L US
o presence of stabilizer (glycerol or polyethyleneglycol)
:> 3
with sodium dodec ylsulfate as an emulsifier (35) ,
2
wherea s Abismail notic ed that , with a nonionic
1
O +----4lt\lI~:...-,-~ .... emulsifier, only for a glycerol-rich (83%) aqueous
0,01 0,1 10 100 phase, d 32 reached 0.6 urn, with a multimodal distribu-
tion, instead of ca. 0.3 11m for pure water
di (urn)
or less concentrated water- glycerol mixtures (up to
Figure 13. Volum e drop size distribution at low (top) and 50%) (33).
high (bottom) surfactant concentrat ions. As regards the viscosity of the disperse pha se, Eq. (6)
or (6') are not in agreement with experiments, since a plot
of d43 vs. log lid gives a straight line with positi ve slope :
the droplets are larger for a more viscous disperse
of d 32 vs. </J / (I - </J) yield s a stra ight line , in agree- phase (43).
ment with Eq . (7) (33 ,40) .

Viscosities ojcontinuous phase or disperse phase. Ultra-

sound prop agation can be visualized in high viscosity
media (Figure 15) and longer emu lsification times are
required. Eq. (6) or (6') predicts no change in droplet size
with viscos ity of the continuous phase or disp erse phase ,
li e or li d, respecti vely. In fact, no correlation has been
w10 Emulsions
To the best of our knowledge, W10 emul sions
preparation by ultrasound have been only very rarely
reported (35). In fact, in this case, a combination of
gentle mechanical stirring and insonation is necessary,
otherwise the two type s of emul sions are obtained

Figure 15. Ultrasound propagation in a high viscous medium .

 344
15
10
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05
0 -
-C 5 ' \ ,.....- - - - - - ...,---
05 10
Figure 16. Effect of viscos ity of disperse phase (I/ o. in mPa.s) on d43 (J..I m): circ les, turbomixer; crosses, ultrasonic generator: other
symbols, homo genizers (from Ref. 43 with permission ),
simultaneously (33) . Drop size analysis is also less
straightforward than wit h O/W emulsions. Polarizatio n
intensity differential scattering combined with laser
di ffraction (Coulter LS 230) (35) or back-scattering
intensity measurement s (Turbisca n on-line) (33) are
preferred to classical laser drop size distribution analy-
zers. In optimiz ed co nditio ns, minimum average droplet
sizes of the order of 0.3 urn are obtained, as for O/W
emulsions.
Th e influence of the viscosity of the cont inuous phase,
lie. on the dropl et size of W / 0 emulsio ns has been
studied by vary ing the nature of the o il. At low vo lume
fract ion of water (¢ = I %) and co nstant energy density,
almo st no change in dropl et size was found for oil
viscos ities ranging between 2.6 and 1850 mPa s at
20°e. Therefore. cavitat ion occ urs read ily even in
highly visco us liquids. Aga in, the mean droplet size
varies inversely with energy den sity (Figure 17). But , at
Canselie r et a1.
- - - - - - - - - - - -,-- - - -'
1.5 20
lo g '10
highe r water cont ent, drop lets get slightly larger wit h
more viscous oils. This is prob ab ly related to a higher
coa lesce nce frequ ency, due to slower stabilization by the
emulsifier (35 ).
Stability of Insonated Emulsions
T he Turbiscan series is a tool of cho ice for studying
the stability of co ncen trated dispersion s, for it does not
require any dilution process before analysis (49). Th e
co mparison of drop sizes of ag itated (rotor-stator device)
and insonated emulsio ns tend s to predi ct a higher stabi-
lity of the latter. Smaller drop size is related to higher
interfacial area, imp lying a higher amo unt of adso rbed
surfactant, therefore a lower micellized amount, which
co uld weaken the dep letion interaction. On the other
hand, better mon odi spersity will limit Ostwald ripening.
This is always confirmed by performing analyses with the
 Ultrasound Emul sification 345

10
E
I
::1. w/o
- 0

-
Veloc ite 3

veg. oil

~
'-
• 0 Nuto 220

E
CIS
'0 1
,...
~
• Nuto 460

Q) M 10- 1 q>= 1 %
0..
e •
"0
c
CIS
0.3
0 'i. ri......
a~-
Q)
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0. 1
5'10 6

energy density Ev / J·m· 3

Figure 17. Influence of'le on d 32 in relat ion to energy density (W/ 0 emul sion, ¢ = I %, emulsifier PGPR 90; oil viscosities, in
mPa. s at 200 e; velocity 3, 2.6, vegetable oil, 64, Nuto 220, 798, Nuto 460, 1850) (from Ref. 35 with permi ssion) .

Turbiscan MA 1000. This device is able to detect
creami ng, sedimentation, clarification and coalescence
phenomena at their very beginning. Figure 18 shows
the comparative behavior of rather concentrated O/W
emulsions (33). Important decreases of back-scattering
occurring at the top and at the bottom of the agitated
sample indicate clarification at both ends. Therefore, a
phase separation (oil at the top, water at the bottom) has
begun, whereas the insonated sample appears more stable
with only a slight clarification at the top and almost no
change at the bottom. For less concentrated emulsions,
the classica l behavior consists of creaming at the top and
clarification at the bottom, both phenomena being
more pronounced with agitation than with insonated
emulsions.
Figure 19 represents the destabilization rate of O/W
emulsions at the top of the sample as a function of ¢
showing the evolution from creaming to clarification
(40). The same ultrasound process has been applied
successfu lly to some practical examp les, namely a
model of O/W sun lotion emulsion and a few models
of veterinary vaccines (W /0 or W/ O/ W emulsions)
(33,50).
Scaling-up
Unless a number of ultrasound probes, located at
selected places in the bath, lie at one's disposa l, the
drawback of large vessels resides in the inhomogeneity of
the acoustic field. Sound waves are strong ly absorbed by
the liquid-liquid medium and progressive but rapid
attenuation of the acoustic vibrations while moving
away from the emitting source means that the cavitation
region is limited to the neighborhood of the probe.
Continuous flow systems where the insonated zone is
rather small, therefore almost homogeneous, will then
be preferred . The scaling-up parameter is the energy
density, f; (14).
CONCLUS IONS
Insonation of two-phase media can yield very fine,
highly stable emulsions. Ultrasound processing is a very
efficient emulsification technique with respect to others,
namely mechanical agitation, and can be compared with
high pressure homogenization or membrane systems.
The amount of surfactant required to give a stable
emulsion is generally lower than with other techniques
(low foam formation). In addition to quick droplet
rupture due to cavitation, this phenomenon is said to
favor the formation of electric charges able to adsorb
onto the interface and playing a role in emulsion
stabilization .
To summa rize the advantages and limitations of
the use of acoustic frequenc ies (ultrasound) for
 346 Canselier et al.

Agitation mecanlque 50% (25106197 11:17)

Delta Retrodiffusion 0:00

5% ----+---~---- -.--- - - -------.-.. ---t--------- ~

il ---- -------j 0 :02

I j 0 :04
j 1

jj I r ,I
0 :06

0 :08
I ' ··'1.',i 0:10
!j ' 1:\
l
'~t
0 :12
-5% - - --- ·- -- - ·- -- - f-- -- - ---'- - - - - - +-- - - - - - 'Il;
I 0 :14

I '.1 0:16
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0:18
10%
0:20

0:22

15% f·- - - -·--·-·- - -·-··- - ··--- - ··- -1-- -- - - - -- -.- -.-- --. - .-- .. - ..- ---------- -'! 0:24

0:26

0:28

20% '---:=--'-------=::-'------=~-----=_''--------' I 0:30

10mm 30mm 40mm

Ultrasons 50% (25/06/97 11:27)

Delta Retrodllfusion 0 :00

5% 0:02

0 :04

0 :06
0% J
0 :08
f !
,~

~
0 :10

0 :12
-5%
0:14

0 :16

0:18
10%
0 :20

0 :22

0 :24
15% .-
0 :26

0 :28

0:30
20%
10mm 20mm 30mm 40mm 50mm

Figure 18. Back-scattering variations in the Turbiscan sample tube for agitated (top) and insonated (bottom) emulsions
(Montano x 60, 10 g / L, ¢ = 0.50, t, = 30 s, PAM= 170 W, Pus = 130 W).
 Ultrasound Emulsification 347

Destabilization rate (L\ back scattering/hr.)

8 ·r -- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - --,
6 t-- r -l-- - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - --!
4

6.25%
-2 - - - .

-4 -.-- .- - -.-..- - - ..
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-6 f---- - - - - - - - - - - .
o Mechanical agitation
-8 1- - - - - - - - - - -- - - - - - - - - - -- - - - - - - - -

-10 . - - - - --.-..--- - . - -.... 0 Ultrasound - -- ·-- · . - ----------.---- ..-.-.------- ---.-- .- - -

-12 ·j- - - - - - -- - - - - - - - -- - - - - - - - - - - - - - - - + - - 1 - - ---+

-14 - - - -- _ .. __ __._------
.•.. -- - - - - - - _.._-

-16 . - - - - -- ----

-18 +-- - - - - - - - - - - - - - - - -- - - - - - - - -- - -- - - - - 1

-20 1- - - - - ·- - - - - - - - - - -

-22

Volume percent oil (100 lP)

Figure 19. Destabilization rate of agitated and insonated kerosene-in-water emulsions observed at the top of the samples vs. oil
volume percent (from Ref. 40 with permission).

emulsification, let us stress that ultrasound techniques 5. Gogate, P. R.; Pandit, A.B. Hydrodynamic Cavitation
deliver a high power output in a small volume, near the Reactors: A State of the Art Review. Rev. Chern. Eng.
emitting surface of the probe. Since the range of action of 2001 , 17 ( I), 1- 85.
acoustic vibrations is rather short, this process often 6. Lorimer, 1.P. ; Mason, TJ. Sonochemistry. Part I - The
Physical Aspects. Chern. Soc. Rev. 1987, 16 (2),
needs a mechanical pre-emulsification and is particularly
237-274.
well-suited for continuous operation.
7. Mason, TJ . Large Scale Sonoche mical Processing:
Aspiration and Actuality. Ultrasonics Sonochem. 2000,
7, 145-149.
8. Bondy, c.; Si:illner, K. On the Mechanism of Emulsifica-
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12. Ashokk umar, M; Griese r, F. Ultrasound Assisted Chemi-
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 Ultrasound Emulsification 349

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Received: November 15, 200 I

Accepted: December 13, 200 I
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