Ultrasonics Sonochemistry 6 (1999) 75–83

Emulsification by ultrasound: drop size distribution

and stability
B. Abismaı̈l, J.P. Canselier*, A.M. Wilhelm, H. Delmas, C. Gourdon
Laboratoire de Génie Chimique (UMR CNRS 5503 INPT/UPS), Ecole Nationale Supérieure d’Ingénieurs de Génie Chimique, 18 chemin de la loge,
F31078 Toulouse, France

Abstract

The aim of this work is to compare the oil-in-water emulsions produced by mechanical agitation ( Ultra-Turrax, 10 000 rpm,
P=170 W ) or power ultrasound (ultrasound horn, 20 kHz, 130 W ) using the same model system : water/kerosene/polyethoxylated
(20 EO) sorbitan monostearate. The following parameters were varied : emulsification time, surfactant concentration, consumed
power and volume fraction of oil. With ultrasound, the drop size (Sauter diameter, d ) is much smaller than that given by
32
mechanical agitation under the same conditions, which makes insonated emulsions more stable. For a given drop size (d ), less
32
surfactant is required. © 1999 Elsevier Science B.V. All rights reserved.

Keywords: Emulsification; Emulsion stabililty; Power ultrasound

1. Introduction surfactants reduce the surface free energy required to

According to P. Becher, an emulsion is ‘‘a hetero-
geneous system, consisting of at least one immiscible
liquid intimately dispersed in another in the form of
droplets, whose diameters, in general, exceed 0.1 mm.
Such systems possess a minimal stability, which may be
accentuated by such additives as surface-active agents,
finely divided solids, etc.’’ [1]. In this respect, surfactants
may be present as monolayers or liquid crystals; poly-
mers are another class of emulsifiers. Those thermody-
namically unstable (i.e., only kinetically stable) liquid–
liquid dispersions possess a high interfacial area. The
type of simple emulsion (water-in-oil or oil-in-water,
commonly abbreviated as w/o or o/w) is decided mainly
by the volume ratio of the two liquids, their order of
addition and the nature of the emulsifier [2], charac-
terized, for instance, along the HLB scale [3]. Emulsions
are common in a large range of technologies [4] and
their preparation should be carefully but easily con-
trolled when scaled up to commercial production.
Except in special cases where spontaneous emulsifica-
tion can occur [1,5], energy must be supplied to produce
such metastable mixtures. Thermodynamically speaking,
* Corresponding author. Tel.: +5-62-25-23-31;
fax: +5-61-25-23-18.
increase any interfacial area (DG=cDA), by lowering
the interfacial tension, c, and allow finely dispersed
media to be created easily. In fact, a much higher
amount of energy, with respect to this thermodynamic
part, is necessary, since comminution of large droplets
into smaller ones involves additional shear forces, so
that the viscous resistance during agitation absorbs most
of the energy [2,6 ]. The excess energy is dissipated as
heat. Energy may be provided through various means,
namely mechanical agitation (stirrer, colloid mill, mixer,
valve homogenizer, …) or ultrasound generation. High-
power ultrasound must be used, low-intensity acoustic
waves leaving the medium unchanged. High-frequency
vibrations applied to a diphasic liquid system provide a
different means of breaking and dispersing a bulk phase:
large drops (ca. 80 mm), produced by the instability of
interfacial waves, are broken into smaller ones by acous-
tic cavitation [7,8]. Ultrasound emulsification was
reported for the first time by Wood and Loomis [9].The
first patent was granted in 1944 in Switzerland [10].
Since then, many scientists and industrialists have used
different types of ultrasound devices (whistle, horn) to
make emulsions [1,11]. Beal and Skauen have studied
the influence of exposure time and sample geometry on
the quality of emulsion [12]. Higgins et al. have observed
that, in general, for short exposure times, higher power

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76 B. Abismaı̈l et al. / Ultrasonics Sonochemistry 6 (1999) 75–83
Fig. 1. Destabilization phenomena in emulsions.
setting produces higher specific surface area, but an
optimum amount of energy seems to exist in order to
produce a maximum interfacial area [13]. Above this
optimum, degradation of the surfactant may occur. In
fact, it has been observed by Alegria et al. [14] that the
surfactant accumulates at the interface of cavitation
bubbles, where it can be chemically degraded by H•
and •OH radicals produced by the thermal decomposi-
tion of water [15,16 ].
The ultrasound device has been found to produce
o/w emulsion with very small particle sizes, more stable
than those prepared, for instance, with the Eppenback
Homomixer or other mechanical devices [17]. The best
emulsions were prepared at optimum surfactant levels,
optimum HLB [3] and high power. In the emulsions
studied, the effects of HLB and surfactant parameters
appear to be more important than those of the power
parameters [13]. Besides, Reddy and Fogler [18] claim
to have prepared very stable ‘acoustic’ o/w emulsions
(however, at very low volume fraction of oil ) without
any surfactant: they invoke electrostatic stabilization
due to preferential adsorption of OH− ions at the
oil/water interface.
Emulsions may remain practically unchanged to the
naked eye for several months, but will eventually return
to their stable state, that is, a phase-separated system.
In emulsion breaking, two kinds of phenomena can be
discriminated (Fig. 1): those, generally reversible,
involving particle aggregation and migration and those,
irreversible, related to particle size modification. On the
one hand, reversible flocculation of droplets can be
followed by creaming or sedimentation, according to
the respective densities of dispersed and continuous
phases. The migration rate of the particles of the dis-
persed phase is given by Stoke’s law. On the other hand,
irreversible changes, through Ostwald ripening and
coalescence, lead to formation of larger drops, therefore
to less and less stable emulsions and eventually to phase
separation. Phase inversion can occur with temperature
or composition change. To summarize, emulsion sta-
bility depends on:
$ droplet size,
$ density difference between dispersed and continuous
phases,
$ viscosity of the contiuous phase, and
$ above all, electrostatic and/or steric repulsion between
droplets (for which the surfactant plays a major role).
Ultrasound emulsification is thus an already known
phenomenon [19], but in this work our goal was to
undertake a systematic phenomenological study compar-
ing the performances of ultrasound energy with those
of classical mechanical agitation, all other things being
 B. Abismaı̈l et al. / Ultrasonics Sonochemistry 6 (1999) 75–83
equal. Our main interests lie in the average size of
droplets as well as their size distribution, and in emulsion
stability.
2. Experimental
In the present work, parallel studies on batch emulsi-
fication processes were conducted through mechanical
agitation and power ultrasound. An Ultra-Turrax
(10 000 rpm, 170 W ) and an ultrasound horn (Misonix
Sonicator XL 2020, 20 kHz, 130 W ) were used,
respectively.
Two series of experiments were then carried out with
a model o/w emulsion system. The oil was kerosene
(CAS Registry No. [8008-20-6 ], required HLB = 12)
[19] and the surfactant a polyethoxylated (20 EO) sorbi-
tan monostearate (CAS [9005-67-8], as Tween 60 or
Montanox 60, kindly supplied by ICI and SEPPIC,
respectively). Its cmc in pure water (8.10−5 M at 25°C,
with c =35 mN/m), was determined by surface ten-
cmc
sion measurements. The measured micelle size was ca.
4 nm (MALVERN Zetasizer 3000). Surfactant HLB is
14.9 [19,20] and cloud point 69°C [21], according to
NFT 73-403 annex [22]. Although Tween 60 is a non-
ionic surfactant, the f potential of the droplets amounts
to −18 mV and the conductivity of the aqueous phase
is not zero, either of which may be due to residual
electrolyte coming from ethoxylation catalyst. Above
surfactant cmc, the interfacial tension of the Tween
60–H O/kerosene system is 9.5 mN/m. Since the behavi-
2 32
our of metastable systems depends on the conditions of
preparation of the final mixture, the procedure must be
rigorously the same for all experiments. A fixed volume
of emulsion (V=80 mL) was prepared at room temper-
ature, the surfactant being first dissolved in distilled
water; oil was then added and energy supplied over a
controlled period of time.
The average drop size, expressed as the Sauter diame-
ter (d =S n d3 /S n d2, representing a surface average
32 i i i i
value), and the drop size distribution, were both
obtained by means of a laser diffractometer (Malvern
MasterSizer S) according to the Mie theory.
Emulsion stability was studied by visual inspection
and with the help of the Turbiscan MA 1000
(Formulaction) [23]. This is a recently designed auto-
mated optical device, working in the near-infrared region
with a double detection mode: transmission and back-
scattering (turbidity range from 0 to 50 000 NTU ). It
carries out step-by-step vertical scans of a tube (flat-
bottomed cylindrical cell ) containing a sample of a
concentrated dispersion (such as emulsion, suspension
or foam) and converts the macroscopic aspect of the
mixture into graphics. Designed to work in the kinetic
mode, it allows very early visualization of flocculation,
sedimentation, creaming and coalescence phenomena.
77
Samples of 6 mL of each emulsion were observed in the
Turbiscan (back-scattering mode) at 35°C for only
25 min.
3. Results and discussion
The parameters studied were the time of emulsifica-
tion, the surfactant concentration, the power supplied
and the volume fraction of oil. It is important to note
that there was no sonochemical degradation of sodium
dodecylsulfate, a model surfactant, under our working
conditions. Therefore, we conclude that over the very
short time of exposure to the power source, the surfac-
tant used in our experiments was not decomposed either.
3.1. Variations of d versus exposure time
32
With a volume fraction of oil (w) of 0.25 and a
surfactant concentration (c) of 10 g/L, the variations of
the Sauter diameter, d , as a function of the exposure
32
time are presented in Fig. 2. In both cases, d decreases
32
with the exposure time, but the most severe influence is
observed during the first 15 s. After 30 s, the slopes
approach zero. Anyway, the ultrasound technique
always gives smaller droplet sizes and, after 30 s, the
diameter is three times smaller with ultrasound than
with mechanical agitation. In the following, the emulsi-
fication time was fixed to 30 s.
3.2. Variations of d versus surfactant concentration
The next experiment describes the variation of d vs.
32
surfactant concentration, all other parameters being the
same as previously (Fig. 3). The Sauter diameter
decreases while the surfactant concentration increases
up to ca.10 g/L. This follows a rather general observa-
tion, which makes sense, since the amount of surfactant
available to form an adsorbed monolayer onto the
emulsion droplets controls the interfacial surface area
produced. At low surfactant concentration, the tempo-
rary interface is not completely covered, therefore drops
coalesce and give rise to higher values of d . In fact,
32
knowing the area per polar head of the amphiphilic
species from the slope of the Gibbs adsorption isotherm
(A~115 Å2) should allow a check on the conditions of
total coverage of the interface by surfactant molecules
with the monolayer hypothesis.
Two further comments may be added. Firstly, the cmc
value does not seem to play a role in the variation of
d vs. c: it has already been observed that, with non-
32
ionic surfactants, droplet size is further reduced above
the cmc, perhaps because of the solubility of the non-
ionic in both phases [2]. Secondly, Fig. 3 shows that
much less surfactant is required with ultrasound for a
desired average drop size.
78 B. Abismaı̈l et al. / Ultrasonics Sonochemistry 6 (1999) 75–83

Fig. 2. Variations of d as a function of the exposure time (MA: mechanical agitation; US: power ultrasound ) (c=10 g/L, w=0.25,
32
P =170 W, P =130 W ).
MA US

Fig. 3. Variations of d as a function of the surfactant concentration (MA: mechanical agitation, US: power ultrasound ) (t=30 s, w=0.25,
32
P =170 W, P =130 W ).
MA US

3.3. Drop size distributions
Let us now consider the possible relation between the
surfactant concentration, the emulsification mode and
the volume drop size distribution. The results are pre-
sented in Figs. 4 and 5. Two types of comparisons may
be made. Firstly, if the effect of surfactant concentration
is considered, in both cases (ultrasound and agitation)
volume drop size distributions flatten with higher surfac-
tant concentrations. In the case of ultrasound, we
observe: a peaked distribution at low surfactant concen-
trations (c=1 g/L, standard deviation s =0.737) but a
v
 B. Abismaı̈l et al. / Ultrasonics Sonochemistry 6 (1999) 75–83
Fig. 4. Volume drop size distribution of o/w emulsions at various surfactant concentrations: (a) mechanical agitation, (b) power ultrasound.
Fig. 5. Volume drop size distribution: (a) low surfactant concentration, (b) high surfactant concentration.
flattened distribution at higher surfactant concentrations
(c=15 g/L, s =1.16). The same tendency is observed
v
in the case of mechanical agitation, with respective s
v
values of 4.802 and 10.535. The number drop size
distribution would show the reverse trend with respect
to the concentration scale (s small for high surfactant
n
concentration). Secondly, if the two techniques are
compared, the standard deviation values, s and s , as
v n
well as the d values, are always much lower with the
32
ultrasound technique.
3.4. Variations of d versus power supplied
32
For an oil volume fraction of 0.25 and with 10 g/L
surfactant, mechanical agitation always gives complete
emulsification in 30 s, whatever the power involved. On
the contrary, with the ultrasound device, a minimum
power of 90 W is necessary to emulsify the mixture
completely. In fact, in the particularly unfavourable
cases of mercury-in-water and analogous liquid metal-
in-water emulsion systems (very high density differ-
ences), no emulsification occurs below the threshold of
cavitation [24]. Now, cavitation is produced above only
2 W/cm2. This means that, in our experimental condi-
tions (geometrical features of the equipment, rather
large volume of emulsion and volume fraction of oil ),
79
the sole ultrasound energy does not allow efficient
breaking of the bulk oil phase into primary large drops.
This is likely to be due to insufficient acoustic streaming
under the horn. Gentle stirring in batch operation or
continuous flow process should easily improve this first
step. Anyway, between 90 and 130 W, the Sauter diame-
ter values are about four times smaller with ultrasound
( Fig. 6).
The reported power P for mechanical agitation is in
fact the difference of power consumption between the
loaded and unloaded states at various rotation speeds.
Now, let us try to determine the quantity of heat (Q)
absorbed by water per unit of time at the starting of the
process. The well-known calorimetric formula reads:
Q=m C (dT/dt) ,
p t=0
where m is the mass of the system, C its heat capacity,
p
T the absolute temperature and t the time.
The measurement supposes that all ultrasound energy
that propagates in the liquid is converted into heat: the
loss of energy by thermal exchange at the liquid–liquid
interface and at the walls of the vessel is therefore
neglected.This is verified on the initial straight part of
T vs. t curves, whose slopes yield values of Q to be
compared with the corresponding electrical inlet power
values. According to this approach through very simple
80 B. Abismaı̈l et al. / Ultrasonics Sonochemistry 6 (1999) 75–83
Fig. 6. Variations of d as a function of the power (t=30 s, c=10 g/L, w=0.25 ).
32
experiments involving pure water, a much lower dissi-
pated energy has been evidenced in the case of ultra-
sound generation ( Table 1). Therefore, ultrasound,
although providing less energy, affords better emulsifi-
cation performances.
3.5. Variations of d versus volume fraction of oil
32
Finally, let us consider the effect of w on d .
32
Surfactant concentration is now constant with respect
to aqueous phase and not to the total sample volume
As expected, we then get the reverse trend: in both
cases, the Sauter diameter increases with w ( Fig. 7).
Since emulsification is not always complete at high w
values, the other purpose of this experiment is to deter-
mine the dispersive power of the two techniques towards
kerosene. Here again, ultrasound appears as more effi-
cient than agitation, all other things being equal.
Besides, phase inversion, water then becoming the
dispersed phase, occurs around equal volumes of both
phases. The observed phenomenon can be illustrated by
a simplified scheme (Fig. 8). On the whole, ultrasound
yields more complete and finer dispersions.
Table 1
Electrical power (P) and evolved heat flux (Q) values
P (W)
Mechanical agitation 170
Ultrasound 130
3.6. Compared stability of emulsions
Simple visual inspection shows longer stability of
ultrasound-made emulsions. For instance, the same
extent of creaming appears 6 days after insonation vs.
1 day after mechanical emulsification. The Turbiscan
MA 1000 [23] shortens the period of observation
required to draw a conclusion, somewhat predicting the
future behaviour of an apparently stable emulsion. A
parallel study, carried out with this apparatus, shows
the following types of back-scattering intensity varia-
tions (DI ):
$ a drop of DI at the bottom of all samples, due to
clarification of the mixture,
$ an increase of DI at the top of the less-concentrated
samples, with a typical isosbestic point, associated to
creaming (particle migration),
$ a drop of DI at the top of the more-concentrated
samples, without isosbestic point, coming from clari-
fication (drop size increase followed by oil phase
separation).
Reporting back-scattering intensity data for agitated
and insonated emulsions at 35°C for 25 min, Fig. 9
shows increasing creaming as a function of time, but
the main difference lies in the larger extent of clarifica-
tion at the bottom of the tube for an Ultra-Turrax-
Q (W) made emulsion, compared with the insonated sample.
Since the continuous and dispersed phases are immisci-
120
ble, Ostwald ripening can be neglected and destabiliza-
53
tion originates only in coalescence. Fig. 10 summarizes
 B. Abismaı̈l et al. / Ultrasonics Sonochemistry 6 (1999) 75–83 81

Fig. 7. Variation of d as a function of oil fraction (t=30 s, c=10 g/L, P =170 W, P =130 W ).
32 MA US

Fig. 8. General behaviour of agitated (AG) and utrasound-made ( US ) o/w emulsions as a function of oil volume fraction (w).

Fig. 9. Back-scattering variations in the Turbiscan sample tube for agitated ( left) and insonated (right) kerosene-in-water emulsions.
82 B. Abismaı̈l et al. / Ultrasonics Sonochemistry 6 (1999) 75–83
Fig. 10. Destabilization of agitated and insonated kerosene-in-water emulsions observed at the top of the samples as a function of oil volume percent.
the behaviour of kerosene emulsions as a function of
oil volume fraction. The bars represent the initial desta-
bilization rates, as differences in back-scattered inten-
sities per hour at the top of the samples. Below 25% oil,
both emulsions are rather stable, with some creaming.
Above this value, agitated and insonated emulsions
behave differently: clarification of the medium, reflecting
phase separation, is much faster after mechanical agita-
tion and increases with higher oil volume fraction. It
appears that, under those conditions, mechanical and
ultrasound emulsification are efficient up to about 25%
and 37.5% oil phase, respectively.
Consistently with the droplet size differences, the first
results regarding the stability of emulsions obtained by
both techniques therefore indicate a much higher sta-
bility of ultrasound-made emulsions.
Moreover, at constant overall surfactant concen-
tration, a higher interfacial area implies a higher amount
of adsorbed surfactant, therefore a lower amount of
micellized surfactant. Then, the depletion interaction
(attraction between droplets associated with the presence
of micelles) could be weakened, which would enhance
emulsion stability.
4. Conclusion
With our simple, three-component, model system, the
comparison of two types of emulsification processes, the
first one using mechanical agitation and the second one
involving power ultrasound at low frequency (20 kHz),
affords several interesting results in favour of the ultra-
sound technique:
$ smaller average drop sizes d (down to 0.3 mm) can
32
be obtained,
$ for a given desired diameter, the surfactant amount
required is reduced,
$ energy consumption (through heat loss) is lower,
$ ultrasound-made emulsions are less polydispersed
and more stable.
Hopefully, those first results will be further explained
thanks to a better knowledge of cavitation phenomena.
An extension of this work would require the direct
measurement of acoustic bubble size and their distribu-
tion as a function of the working parameters.
Acknowledgements
The authors thank Formulaction S.A., and especially
K. Puech, for performing the stability study with their
specific equipment ( Turbiscan MA1000).
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