Langmuir 2001, 17, 2647-2655 2647

Coalescence in Surfactant-Stabilized Emulsions Subjected

to Shear Flow
Arup Nandi, D. V. Khakhar, and Anurag Mehra*
Department of Chemical Engineering, Indian Institute of TechnologysBombay,
Powai, Bombay-400076, India

Received October 20, 2000. In Final Form: January 29, 2001

Experiments were carried out to study the coalescence dynamics of a neutrally buoyant liquid-liquid
emulsion subjected to a simple shear flow in a Couette device. The effect of shear rate and dispersed phase
holdup were studied. The surfactant-stabilized emulsions were prepared in a stirred tank at high shear
rates which were applied for long times so as to obtain reproducible equilibrium drop size distributions.
Low shear rates were used in the Couette device to prevent drop breakup. Sufficiently large drops and
density matching ensured that coalescence due to Brownian motion and creaming was negligible and thus
the change in drop size distribution with time was entirely due to shear-induced coalescence. The evolving
volume density distributions were measured using optical microscopy and image analysis. A population
balance model based on Smoluchowski’s result for the rate of shear-induced coalescence and an empirical
form for the coalescence efficiency was used to describe the system. Shearing results in stabilization of
the emulsion, and the coalescence rate reduces with increasing shear rates. The stabilizing effect due to
shearing is greater for higher holdups. The drop size distribution for high values of the holdup becomes
bimodal at long times. The coalescence efficiency, back-calculated from experimental data, is independent
of drop size for low holdups but is size dependent for higher holdups. This work demonstrates a simple
experimental method for evaluating the coalescence efficiency for emulsions with high holdups where
theoretical models are not available.

Introduction the drops to “collide” (interfaces approach within some

Liquid-liquid emulsions constitute a wide variety of
products and are formed in many processes of industrial
relevance. Most lubricants, paints, and cosmetics and
many food products are emulsions.1 Processes such as
liquid-liquid extraction, petroleum refining, and many
areas of polymer processing involve handling and convey-
ing of emulsions.1-3 During these operations the emulsion
drops are subjected to flow fields which may cause them
to break or coalesce. The simultaneous occurrence of the
two phenomena controls the drop size distribution, which
in turn has a significant effect on the processing conditions
and characteristics of the product. Most emulsions contain
surface active impurities or added surfactants, which act
as emulsion stabilizers. Thus, a fundamental understand-
ing of the phenomena of drop coalescence and breakage
in surfactant-stabilized emulsions is of wide interest.
This work explores the effect of shear rate and dispersed
phase holdup on the coalescence kinetics of a surfactant-
stabilized emulsion subjected to a simple shear flow. The
shear rates used are small enough such that no drop
breakup occurs.4,5 The drops in the emulsions used are
large enough so that coalescence due to Brownian motion
is negligible. Also, the densities of the drops and the
continuous phase are matched so that creaming-induced
coalescence is insignificant. Thus, the evolution of the drop
size distribution in the system occurs due to shear-induced
coalescence alone.
Consider the physical processes during the interaction
of a pair of drops in a shear flow. The shear flow causes
* Corresponding author. E-mail: mehra@che.iitb.ernet.in.
(1) Venugopal, B. V.; Wasan, D. T. In Encyclopedia of Emulsion
Technology; Becher, P., Ed.; Marcel Dekker: New York, 1983; Vol. 2.
(2) Mana-Zloczower, I. In Mixing and Compounding of Polymers-
Theory and Practice; Mana-Zloczower, I., Tadmor, Z., Eds.; Hanser
Publishers: Munich, 1994; p 5.
(3) Ottino, J. M.; et al. Adv. Chem. Eng. 1999, 25, 105.
(4) Grace, H. P. Chem. Eng. Commun. 1982, 14, 225.
(5) Khakhar, D. V.; Ottino, J. M. J. Fluid Mech. 1986, 166, 265.
specified small length) as a result of the velocity gradient
(Figure 1). The drops form a doublet and rotate in a plane
that is coplanar to the drop relative velocity vector (u)
and the line joining their centers (e). The interfacial film
between the drops thins initially, and it may deform due
to the pressure within the film. The process of film thinning
continues until the following condition is satisfied
u‚e e 0 (1)
Beyond this time the drops move apart and the film begins
to thicken. If the film has achieved the critical thickness
within this time, it may rupture, leading to coalescence.
Otherwise, the drops continue their respective motions
with the bulk flow (Figure 1). A review of previous studies
related to this process is given below.
The simplest model for coalescence of drops in an
emulsion subjected to a simple shear flow is based on
Smoluchowski’s theory,6 with the coalescence rate given
by
γ
Cs(ν,ν′) ) [ν1/3 + ν′1/3]3n(ν) n(ν′) (2)
π
where ν and ν′ are the volumes of the coalescing drops,
γ is the shear rate, and n(ν) is the number density of the
drops. Smoluchowski’s equation is based on the assump-
tion that the drops move along the flow streamlines and
hence does not account for hydrodynamic interactions.
The effects of physicochemical parameters affecting in-
terdrop film stability are also unaccounted for in the
theory. Inclusion of such effects generally results in a
coalescence rate that is lower than the Smoluchowski
collision rate and is typically expressed as
C(ν,ν′) ) Cs(ν,ν′) (3)

10.1021/la001473m CCC: $20.00 © 2001 American Chemical Society

Published on Web 04/05/2001
2648 Langmuir, Vol. 17, No. 9, 2001
Figure 1. Schematic view of the stages of the collision between
two drops in a shear flow where u is the relative velocity vector
and e is the unit vector along the line joining the centers.
where  is the coalescence efficiency, defined as the fraction
of collisions which result in coalescence.
The drainage of the film between closely spaced drops,
which may determine coalescence efficiency, has been
studied in several works, and a review is given by
Chesters.7 Expressions for the coalescence efficiency based
on models for the rate of thinning of films for fully mobile,
partially mobile, and immobile drop interfaces are de-
rived.7 An assumption of the models is that films below
a critical thickness rupture, thereby leading to coalescence.
Several more recent works focus on the details of film
thinning between drops.
Davis et al.8 carried out a lubrication analysis of film
thinning for nondeformable drops pressed together by a
constant force. Hartland et al.9 considered both the viscous
and inertial components for a flat circular interface with
partially mobile interfaces. Later work by Jeelani and
Hartland10 included the effect of van der Waals forces on
the interfacial film thinning rate during the axisymmetric
motion of a pair of equal-sized liquid drops pressed together
by a constant force. Abid and Chesters11 carried out
detailed calculations of the film thinning rate for a pair
of deformable drops with partially mobile interfaces. Their
results are close to the rates predicted by the model of
Chesters7 for the same case. Hartland and Jeelani12 also
studied the effect of interfacial tension gradients on the
rate of thinning of the intervening film.
Computations of the coalescence efficiency, taking into
account the detailed hydrodynamics around a pair of drops,
have been carried out in a few works. Zeichner and
Schowalter13 studied the coagulation of equal-sized rigid
particles with immobile interfaces in shear and extensional
flow taking into account van der Waals forces. Particles
which approach closer than a critical distance form a
permanent doublet (coagulate) as a result of van der Waals
forces. This work was extended by Feke and Schowalter14
to include the case of particles with different diameters.
Wang et al.15 calculated the coalescence efficiency for rigid
drops with partially mobile interfaces under the action of
a simple shear and uniaxial extensional flow. Their results
indicate that the highest probability of coalescence exists
for drops which are of the same size. For a given emulsion
system, their results predict a critical drop diameter ratio
(smaller drop diameter to larger drop diameter) below
which there is no coalescence. The value of this critical
(6) Smoluchowski, M. V. Z. Phys. Chem. 1917, 92, 129.
(7) Chesters, A. K. Trans. Inst. Chem. Eng. 1991, 69, 259.
(8) Davis, R. H.; Schonberg, J. A.; Rallison, J. M. Phys. Fluids A
1989, 1, 77.
(9) Hartland, S.; Jeelani, S. A. K.; Suter, A. Chem. Eng. Sci. 1989,
44, 387.
(10) Jeelani, S. A. K.; Hartland, S. J. Colloid Interface Sci. 1993, 156,
467.
(11) Abid, S.; Chesters, A. K. Int. J. Multiphase Flow 1994, 20, 613.
(12) Hartland, S.; Jeelani, S. A. K. Colloids Surf., A 1994, 88, 289.
(13) Zeichner, G. R.; Schowalter, W. R. AIChE J. 1977, 23, 243.
(14) Feke, D. L.; Schowalter, W. R. J. Fluid Mech. 1983, 133, 17.
(15) Wang, H.; Zinchenko, A. Z.; Davis, R. H. J. Fluid Mech. 1994,
265, 161.
Nandi et al.
diameter ratio becomes smaller with decreasing viscosity
ratio (µd/µc), where µd is the viscosity of the dispersed phase
and µc that of the continuous phase.
Only relatively few experimental studies of coalescence
in emulsions subjected to a laminar shear flow have been
previously reported. Hazlett and Schechter16 subjected
an emulsion of methyl methacrylate in a mixture of
methanol and water to tangential Couette flow. The
coalescence efficiency, calculated using a population
balance model, was studied at temperatures close to the
critical point of the emulsion. Their results indicate that
there is no variation of the coalescence efficiency at
temperatures near the critical point. Vinckier et al.17
studied shear-induced coalescence in a polymer blend
produced at a shear rate higher than that at which the
emulsion was broken. Their results, obtained from mea-
sured average drop diameters, matched the coalescence
efficiency model for partially mobile interfaces given by
Chesters.7 Experiments at high dispersed phase holdups
gave a coalescence efficiency which increased with dis-
persed phase holdup. This was explained on the basis of
an increased critical film thickness for coalescence at
higher holdups. Mishra et al.18 subjected a surfactant-
free emulsion of pentadecane in an aqueous solution of
NaCl to a simple shear flow using a concentric cylinder
apparatus. The evolving drop size was measured using
laser Doppler anemometry. Their results follow the hard
sphere predictions of Zeichner and Schowalter13 and Feke
and Schowalter.14 They also found the drop size distribu-
tion to be self-similar, in agreement with the analysis of
Swift and Friedlander,19 for systems with a constant
coalescence efficiency. The coalescence rate was found to
increase with shear rate as well as with electrolyte
concentration.
Shear-induced coalescence in the presence of surfactant
was studied by Mousa and van de Ven.20 An emulsion of
silicone oil in water, stabilized by SDS (sodium dodecyl
sulfate) was sheared between rotating circular plates. The
coalescence efficiency was back-calculated using the
population balance equation incorporating an assumed
functionality for the coalescence efficiency given by
{
[ 4q
]
5.0
R0 , if ν and ν′ < νc
) (1 + q)2 (4)
if ν or ν′ > νc
0,
In the above equation, q ) (ν/ν′)1/3 is the ratio of the
diameter of the colliding drops, and νc is the maximum
volume a drop can attain due to coalescence with other
drops. The index value (5.0) was selected on the basis of
phenomenological arguments. Experiments were carried
out at a dispersed-phase holdup of 0.2%, and the volume-
averaged diameters of the coalescing emulsion were found
from the transmitted light intensity measurements. Their
results indicate that for a surfactant-free emulsion the
coalescence efficiency term (R0) first decreased with shear
rate and then showed an abrupt increase beyond a certain
value of the shear rate. A similar qualitative behavior
was reported earlier in the theoretical study by van de
Ven and Mason.21 The addition of salts such as KCl and
AlCl3 resulted in a rise in the coefficient R0 with shear
(16) Hazlett, R. D.; Schechter, R. S. Colloid Surf. 1988, 29, 71.
(17) Vinckier, I.; et al. AIChE J. 1998, 44, 951.
(18) Mishra, V.; Kresta, S. M.; Masliyah, J. H. J. Colloid Interface
Sci. 1998, 197, 57.
(19) Swift, D. L.; Friedlander, S. K. J. Colloid Sci. 1964, 19, 621.
(20) Mousa, H.; van de Ven, T. G. M. Colloids Surf., A 1991, 60, 39.
(21) van de Ven, T. G. M.; Mason, S. G. Colloid Polym. Sci. 1977, 255,
468.
Coalescence in Surfactant-Stabilized Emulsions
rate and then a drop beyond a critical value. The addition
of sodium dodecyl sulfate (SDS) to the emulsion gave a
similar result. Schokker and Dalgleish22 reported floc-
culation of drops in an oil-in-water emulsion stabilized by
sodium casseinate. Their experiments were conducted in
a tangential Couette device at very high shear rates (670-
740 s-1). They showed that the coalescence rate was
strongly influenced by the storage time as well as by the
apparatus used for making the emulsion.
We have recently studied coalescence in a neutrally
buoyant, surfactant-stabilized emulsion subjected to a
simple shear flow in a Couette device.23 The experiments
were done for a low dispersed phase holdup (1%) at which
multidrop collisions are negligibly small. The coalescence
efficiency was determined by fitting the theoretically
obtained drop size distribution profile to the experimental
data and found to be independent of colliding drop sizes.
The model of Chesters7 was found to overpredict the rate
of coalescence by 2 orders of magnitude. A model for the
computation of coalescence efficiency, based on the
stochastic nature of film rupture, gave good agreement
with experimental data.
The stability of the film between flat interfaces was
studied by Nikolov and Wasan;24 they found that the
coalescence time in the presence of a surfactant was much
higher than that for the corresponding surfactant-free
system as well as the value predicted by models for film
thinning. Coalescence times for identical drops were
distributed over a range of values, and the stability of the
interface was found to be more important than the fluid
mechanics governing the thinning of the film. Dreher et
al.25 conducted a similar study in a surfactant-free system
and found that the coalescence time was log-normally
distributed. Ghosh26 has demonstrated similar results for
surfactant loaded systems using different surfactants.
The objective of the current work is to study the effect
of shear rate on surfactant-stabilized emulsions at high
dispersed-phase holdups. Despite the practical importance
of emulsions with high holdup, no theoretical or experi-
mental work for the case of well-defined laminar flows
has been previously reported. We present here the results
of an experimental study of the evolution of the drop size
distribution in a neutrally buoyant, surfactant-stabilized
emulsion subjected to a shear flow. The evolving drop size
distributions obtained from a population balance model
simulation are fitted to the experimentally obtained drop
size distributions to back-calculate the coalescence ef-
ficiency. Experimental details are given in the next section
followed by a description of the model and computational
procedures used.
Experimental Section
Materials and Method. Monochlorobenzene (analytical
grade, Glaxo Chemicals, India) was dispersed in a mixture of
glycerol (LR grade, Merck, India), double-distilled water, and
sodium chloride (Loba Chemie, India), using TWEEN-80 (spec-
troscopic grade, SD Fine Chemicals, India) as the surfactant.
Emulsions were prepared in a 1 L beaker fitted with stainless
steel baffles. A shrouded turbine impeller was used for emul-
sification. The beaker was covered in order to avoid dust
contamination as well as to minimize the evaporation of
chlorobenzene. To avoid gravity-driven motion of the drops, the
specific gravity of the continuous phase was adjusted, by varying
(22) Schokker, E. P.; Dalgleish, D. G. Colloids Surf., A 1998, 145, 61.
(23) Nandi, A.; Mehra, A.; Khakhar, D. V. Phys. Rev. Lett. 1999, 83,
2461.
(24) Nikolov, A. D.; Wasan, D. T. Ind. Eng. Chem. Res. 1996, 34,
3653.
(25) Dreher, T. M.; et al. AIChE J. 1999, 45, 1182.
(26) Ghosh. Ph.D. Thesis, I. I. T.sBombay.
Langmuir, Vol. 17, No. 9, 2001 2649
Figure 2. Initial volume density distributions for all three
holdups.
Table 1. Time of Stirring (ts) and Rotation Speed (ωs) for
Making the Emulsion and Resulting Volume-Average
h ) for the Starting Emulsions for the Three
Diameters (D
Holdups (O), Together with the Interfacial Tension
Values (σ)
φ ts (h) ωs (rpm) h (µm)
D σ (mN/m)
1% 2.5 2090 ( 40 8.41 ( 0.09 16.99 ( 0.01
5% 5.5 2200 ( 50 8.07 ( 0.24 16.95 ( 0.05
15% 8.5 2450 ( 40 8.83 ( 0.28 16.92 ( 0.12
the ratio of glycerol to water, to match that of the dispersed
phase to an accuracy of (0.005 g/cm3. All experiments were
conducted at room temperature, which was maintained at 25 (
1 °C. The continuous-phase constituted 0.525 L of glycerol and
10 g of sodium chloride (0.1131 M) dissolved in 1 L of double-
distilled water. The addition of sodium chloride masks the trace
ionic impurities and suppresses the electric double layer, resulting
in a characteristic Debye-Huckel length of 3.35 × 10-2 µm.27
The surfactant was initially dissolved in the dispersed phase,
and a surfactant concentration of 0.85% (w/w) of the dispersed
phase was used in all the emulsions.
Preparation of Emulsion. Emulsions were stirred for long
times to achieve a dynamic equilibrium between drop breakup
and coalescence and thus to obtain a steady state for the drop
size distribution. This ensured reproducibility of the starting
drop size distributions in the shear flow experiments. Further,
the impeller rotation speed was adjusted to obtain nearly similar
drop size distributions for the different cases. The emulsion-
making conditions for the various holdups are summarized in
Table 1, where φ is the volume fraction of the dispersed phase,
ts is the time of stirring, and ωs is the impeller rotational speed.
The interfacial tension (σ) between the two phases was measured
using a drop volume tensiometer after equilibrating the two
phases (oil and aqueous) for 36 h. The values of the interfacial
tensions are quite close to each other (Table 1) for the three
holdups.
The initial volume average diameters (D h ) 〈D3〉1/3) are highly
reproducible and are quite close for all three holdups (Table 1).
Figure 2 shows the initial drop size distributions for the three
holdups, which are very similar. The distributions are shown on
a volume basis with (πD3/6)f(D) dD being the volume fraction of
drops in the size range (D, D + dD). The distributions are
normalized by the total volume fraction (φ) for comparison. The
error bars, which indicate the standard deviation over a minimum
of three runs, are small and show the reproducibility of the initial
distributions.
(27) Stokes, R. J.; Evans, D. F. Advances in Interfacial Engineering:
Wiley-VCH: New York, 1997.
2650 Langmuir, Vol. 17, No. 9, 2001 Nandi et al.

Figure 3. Schematic diagram of the tangential Couette flow

assembly.

Figure 5. Schematic diagram showing a rectangular cavity

made using cover slips for viewing the emulsion sample in the
microscope. The typical height of the rectangular cavity varied
Figure 4. Plot of the volume-average diameter versus the from 270 to 300 µm, which was significantly higher than the
number of drops counted. diameter of the largest drop in the experiments.
Shear Flow Apparatus. The emulsion was sheared in a
tangential Couette flow apparatus with the inner cylinder
rotating. A schematic view of the apparatus along with dimen-
sions is shown in Figure 3. The rotation of the inner cylinder
generates a shear flow in the gap between the cylinders which
is small compared to the diameter of the cylinders to ensure a
uniform shear rate. The ratio of the width of the gap to the length
of the cylinder was >20, which resulted in minimization of
longitudinal instabilities28 and negligible end effects. The
cylinders were made of brass to obtain a smooth surface and to
prevent corrosion. The bottom surface of the lower cylinder was
cut in the form of a cone with an angle of 6° to ensure a uniform
shear rate at the bottom. The inner cylinder was powered by an
ac motor, through a set of gears with a high reduction ratio, so
that small fluctuations in the shaft speed resulted in minimal
changes of the rotation speed of the inner cylinder ((0.5 rpm).
The critical angular speed of the inner cylinder for transition
from simple shear flow to Taylor vortices is given by29

[3390(d22 - d12)
]
0.5
Ωc ) ν 2 4
(5)
4d1 (d2 - d1)

where d1 and d2 are the diameters of the outer and the inner
cylinders, respectively (Figure 3). The critical angular velocity
calculated using the kinematic viscosity (ν) of the continuous
phase is 5.0 rad s-1 (48 rpm).
Measurement of Drop Size Distribution. The drop size
distribution was obtained by using an Image analysis system
consisting of a CCD camera (SONY 94C) mounted on an optical
microscope (Olympus BX60). Various combinations of objective
lenses were used to accurately measure drops of diameter between
2 and 200 µm. The emulsion samples were diluted to prevent
overlap of drops during viewing in the microscope and to control
agglomeration as well as coalescence of the drops during
microscopy. The diluent used was the pure continuous phase,
equilibrated with chlorobenzene, and containing 1% (w/w of the
continuous phase) surfactant. The large quantity of surfactant
present prevented the drops from coalescing during storage on
the slide. A drop of the diluted emulsion was placed on a glass
slide with spacers, and a cover slip was carefully placed over it.
Thus, the emulsion sample was enclosed in a rectangular cavity,
as shown in Figure 4. This procedure ensures that the top cover
slip does not press the drops and deform them. Nor does the
emulsion flow out due to the weight of the cover slip. To ensure
that all drops are within the same plane of focus, the specific
(28) Snyder, H. D. Phys. Fluids 1968, 11, 1599.
(29) Chandrashekhar, S. In Hydrodynamic and hydromagnetic
stability; Dover publications: New York, 1981; pp 272-339.
Figure 6. Volume density distribution of the same emulsion
sample taken separately on two different slides: (A) measure-
ment made 8 min after sampling and again after 2.5 h; (B)
measurement made 8 min after sampling from the same
emulsion stock from which A was withdrawn.
gravity of the diluting phase was maintained around 0.4%-0.6%
higher than that of the dispersed phase. This resulted in all the
drops rising and resting lightly against the top cover slip, and
consequently, all drops were in the plane of focus of the objective
lens. Each image typically contained 80-200 drops, and several
nonoverlapping images (at least 156) were taken to capture a
sufficiently large number of drops.
Consistency Tests. Several tests were performed to check
the consistency and accuracy of the experimental procedure. The
minimum number of drops to be counted in order to obtain a
good description of the drop size distribution was examined by
counting an increasing number of drops. Figure 5 shows the
variation of volume-average diameter with the number of drops
counted for an emulsion sample. The value of the volume-average
diameter becomes nearly constant beyond 15 000 drops, and
beyond this limit reasonably smooth distributions were obtained
as well. Hence, in all the reported data, the number of drops
counted was in excess of 15 000. The stability of the emulsion,
withdrawn for making drop size measurements, after dilution
was tested as follows. Two samples (samples A and B) were taken
Coalescence in Surfactant-Stabilized Emulsions
Figure 7. Volume density distribution of emulsion samples
taken from the top sampling port and the bottom of the Couette
apparatus after 2.5 h of shearing at 10 rpm, for holdup φ ) 1%.
from the same emulsion stock and then diluted separately. The
volume density distribution was measured first for sample A
within 8 min of sampling and then again after it had been left
standing for 2.5 h, while sample B was assessed for the drop size
distribution only once, after 8 min of sampling. The distributions
are shown in Figure 6 and are nearly identical. This indicates
the consistency of the sampling method as well as the stability
of the emulsion after it has been diluted and transferred to the
slide. The third test consisted of shearing an emulsion of 1%
holdup in the tangential Couette flow apparatus for a period of
2.5 h. Samples were then withdrawn from the sampling port and
also from the top and bottom of the apparatus. The volume density
distributions for each of the samples were found to be nearly the
same (Figure 7). This shows that the shear rate along the length
of the cylinder is uniform and that creaming and settling of the
drops during the course of the experiment are negligible.
Theoretical Analysis
The time evolution of the drop size distribution for a
purely coalescing system is given by the population balance
equation
∂n 1
)
∂t 2 ∫0νCs(ν,ν-ν′) dν′ - ∫0∞Cs(ν,ν′) dν′ (6)
where n(ν) is the number density of drops of volume ν and
Cs is the Smoluchowski coalescence rate given by eq 1 for
drops of size ν and ν′. An assumption in the above equation
is that only pairwise collisions are considered. If all
collisions result in coalescence,  ) 1. However, as will be
seen below, the experimental results indicate that  , 1
and the efficiency values also depend on the sizes of the
colliding drops. Here we assume the following expression
for the coalescence efficiency, which is a generalization of
that proposed by Mousa and van de Ven,20
[ ][ ( )] [ ( )]
C Di 2 -m Dj 2 -m
4q
 ) R0 1+ 1- 1+ 1-
(1 + q)2 Dc Dc
(7)
The first two terms on the right-hand side of the expression
are the same as those assumed by Mousa and van de Ven.20
The second term captures the dependence of the coales-
cence efficiency on the ratio of the diameters (q ) Di/Dj)
of the colliding drops. The value of the exponent C indicates
the strength of the dependence of the coalescence efficiency
Langmuir, Vol. 17, No. 9, 2001 2651
on the size ratio. The last two terms account for the fact
that there may be a critical drop diameter (Dc) at which
the coalescence efficiency is maximum or minimum,
depending on the value of m. The prefactor R0 is an overall
coalescence efficiency term which is assumed to depend
only on the shear rate and holdup. The parameters of the
model (R0, C, m, and Dc) are obtained by a regression
procedure applied to the experimental drop size distribu-
tions as described below.
The population balance equation (eq 6) along with the
coalescence efficiency (eq 7) was solved using a 4th-order
Runge-Kutta method with a variable time step. The
experimentally obtained initial drop size distribution was
used as the initial condition in the computations. There-
after, at each integration time step, the error (E) between
the theoretical and the experimental distributions was
calculated using
N
E) ∑
i)0
[(Di3n(Di)|theor - Di3n(Di)|exp)∆Di]2 (8)
Computations were carried out for fixed values of m, C,
and Dc, and the value of R0 was obtained at which the
error was minimum for an experimental drop size
distribution corresponding to a particular time. The
parameters m, C, and Dc were varied in the ranges C ∈
[-4.0,4.0] in steps of 0.5, m ∈ [-1.0,2.5] in steps of 0.5, and
Dc ∈ [3.0,81] µm in steps of 3.0 µm, and the set of values
at which the error is a minimum was obtained for the
distribution. This was repeated for each experimental
distribution in a run and for all runs corresponding to
various shear rates (for a fixed holdup). The arithmetic
averages of the values obtained for all samples for a
particular holdup were used as the final values of C, m,
and Dc. Thereafter, the computation was repeated with
these average values of m, C, and Dc and the value of R0
was recalculated. For a given shear rate, the average R0
was the mean of the values obtained (for constant m, C,
and Dc corresponding to that particular holdup) calculated
over the four samples for that particular shear rate and
holdup.
Results and Discussions
We first present the experimental results and discuss
the significant qualitative features of the data. The model
predictions and their implications are discussed next.
The time evolution of the drop size distributions for the
three holdups studied are shown in Figures 8-10, and
the volume-averaged drop diameters for all three holdups
are shown in Figure 11. Each figure shows data for three
different rotational speeds used. Some trends are common
to all the cases, and we list these first. The peak in the
drop size distributions falls and the tail lengthens with
increasing time of shearing. The rate of coalescence
decreases with increasing shear rate, and the coalescence
rate is highest at the lowest shear rate. Both features are
evident from the extent of change of the distributions with
time for the different shear rates as well as from the slopes
of the average diameter versus time curves.
There are also significant differences in the results for
the different volume holdups studied. From Figure 10 it
can be seen that the most significant difference is the
formation of the second peak at larger drop sizes in the
high-holdup case (φ ) 15%) whereas at φ ) 5% (Figure 9)
just a shoulder appears. At, φ ) 1% there is simply a
smooth tail. The rate of coalescence also increases with
holdup, and this is most clearly evident from the time
variation of the average diameters. However, the rate of
2652 Langmuir, Vol. 17, No. 9, 2001
Figure 8. Time variation of the volume density distributions
for various shear rates at 1% holdup: (symbols) experimental
data, error bars show standard deviation over 3 runs; (solid
lines) predictions of the population balance model using
parameters given in Table 2 and Figure 14.
increase is not proportional to φ2 (as predicted by Smolu-
chowski6 theory) but slower. Thus, the coalescence ef-
ficiency decreases with increasing holdup. Finally, from
Figure 11 it can be observed that the nature of the average
diameter versus time curves are different. For φ ) 1%,
the variation is almost linear with time, and this is
indicative of a coalescence efficiency that is independent
of the sizes of the colliding drops, as shown in Nandi et
al.23 However, at φ ) 5%, the rate initially rises with time
and then slows down toward the end. For the dispersed-
phase holdup φ ) 15%, the rate of coalescence goes up
with time for the entire period of the experiment. This is
evident from the increasing slope of the plot showing the
nondimensionalized volume-average diameter with time.
These two cases indicate a dependence of the coalescence
efficiency upon the diameters of the colliding drops.
A reduction in the coalescence rate at later times (as
seen from the 5% holdup) was also observed by Mishra et
al.18 in their experimental results with a surfactant-free
emulsion system. The slowing was attributed to the
flattening of the surfaces of the colliding drops, resulting
in a slow rate of film thinning.7 This does not occur during
the initial stages of the process when drops are small,
since interfacial tension prevents significant flattening.
A similar effect could be active in the present system as
well. Possible reasons why this effect is not seen in the
lower and higher holdup systems are as follows. In the 1%
holdup system the drops never become large enough. In
the 15% holdup case, chaining of drops due to shear flow
may provide the extra force to overcome the additional
resistance to thinning of the film due to flattening of the
larger drops. More detailed drop-level studies, however,
are required to confirm these explanations.
The drop size distributions for the case with φ ) 1%
Nandi et al.
Figure 9. Time variation of the volume density distributions
for various shear rates at 5% holdup: (symbols) experimental
data, error bars show standard deviation over 3 runs; (solid
lines) predictions of the population balance model using
parameters given in Table 2 and Figure 14.
were scaled using the analysis of Swift and Friedlander.19
A plot of the cumulative oversize number fraction (1 -
Nνi/NT) versus the normalized drop volume (νi/〈ν〉) for φ )
1% and for three rotation speeds is shown in Figure 12
along with that for φ ) 15% for the lowest shear rate.
∞
Here, Nν ) ∑k)1i
nk, NT ) ∑i)1 ni, and 〈ν〉 ) NT/φ. For the
lowest holdup (φ ) 1%) the scaled distributions at different
times of shearing superimpose (Figure 12a-c), showing
that the distributions are self-similar and that the
coalescence efficiency is independent of drop size. However,
the curves for φ ) 15% and γ ) 10.8 s-1 (Figure 12d) do
not scale, indicating that the coalescence efficiency in this
case is dependent on drop size.
The solid lines in Figures 8-10 are the model predictions
obtained using the fitted parameters. The predictions
match the experimental distributions within the limits of
experimental error. Note that the development of the
shoulder for the 5% emulsions and the formation of the
second peak for the 15% holdup are well-described by the
model. The prediction of the variation of the volume-
average drop diameter with time also matches well with
experimental data for all cases except for the 5% holdup
at long times.
The values of the fitted parameters (C, DC, and m) along
with the standard deviations for each value of the
dispersed-phase holdup are given in Table 2. The values
of these parameters obtained from fitting the model to
the experimental distributions at different time steps
(during any single run) were nearly the same. The values
were also found to be nearly independent of shear rate at
a particular holdup. The parameter values provide an
insight into the coalescence at the scale of individual drops.
At the lowest volume holdup, C ) 0 and m ) 0, implying
that the coalescence efficiency is independent of the sizes
Coalescence in Surfactant-Stabilized Emulsions
Figure 10. Time variation of the volume density distributions
for various shear rates at 15% holdup: (symbols) experimental
data, error bars show standard deviation over 3 runs; (solid
lines) predictions of the population balance model using
parameters given in Table 2 and Figure 14.
of the colliding drops and depends only on the shear rate,
as reported earlier.23 With increasing holdup, the pa-
rameter C decreases while m increases. The critical drop
diameter is found to be about 18 µm for both 5% and 15%
holdup. A lower value of C indicates a higher probability
of coalescence for drops of unequal sizes. The coalescence
efficiency attains a maximum (since m is positive) at the
critical diameter (Dc). However, coalescence efficiency is
a product of these two terms, and the variation of the
coalescence efficiency with the diameters of the colliding
drops is shown in Figure 13 for the highest dispersed-
phase holdup. This figure shows that coalescence is most
likely when one of the pair of colliding drops is close to the
critical diameter and the other is small (∼2.0 µm). While
the existence of an optimal drop size for coalescence has
been proposed earlier,30 it is not clear whether the same
effects are applicable here. We speculate that the observed
maximum could be the result of long-lived clusters of one
large and several small drops which eventually coalesce.
The clusters comprising 18 µm and several 2 µm drops
are perhaps the most stable under shear flow. We note
that a bimodal distribution is not produced if m ) 0 (which
corresponds to the model of Mousa and van de Ven20), for
any value of the exponent C. Thus, the existence of a critical
diameter seems essential to explain this feature of the
results.
The shear rate dependence of the coalescence rate is
given by the product of R0 with the shear rate (γ) (eq 3).
Figure 14 shows that the coalescence rate decreases
monotonically with shear rate, indicating that coalescence
efficiency decreases faster than the inverse of the shear
(30) Kumar, S.; Kumar, R.; Gandhi, K. S. Chem. Eng. Sci. 1993, 48,
2025.
Langmuir, Vol. 17, No. 9, 2001 2653
Figure 11. Variation of the nondimensionalized volume-
averaged diameters with time for various shear rates (corre-
sponding to each holdup as shown in Figures 8-10).
rate. Further, R0γ decreases with increasing holdup,
indicating that the probability of coalescence is lower in
the case of higher holdups. Thus, the coalescence rate
increases with holdup but at a rate that is lower than the
φ2 proportionality, as suggested by Smoluchowski’s theory.6
The magnitude of coalescence efficiency obtained is 2
orders of magnitude lower than that predicted by Ches-
ters’7 model.
Experiments were also performed in which the emulsion
was kept standing in a beaker and samples were with-
drawn at specified times and the size distributions
analyzed. For the case of 1% holdup, the extent of increase
of the volume-averaged diameter was slightly higher (D h /D
h0
) 1.337 after standing for 4.5 h) than that at the lowest
shear rate studied. For the holdup of 5%, the dimensionless
volume-averaged diameter increased to 3.7 after standing
for 4.5 h, which is much larger than the result for the
lowest shear rate. In the 15% holdup case, the emulsion
separated into two distinct layers on standing for 0.5 h,
the bottom layer being the dispersed phase, as its specific
gravity was higher than that of the continuous phase by
0.003 g/cm3. The high coalescence rate in standing
emulsions is due to the formation of long-lived aggregates
of drops. The thin films in these aggregates have sufficient
time to rupture. Weak Brownian motion and small flow
currents generated due to handling cause the drops to
collide and form aggregates which can be seen under the
microscope if a sample is carefully taken. Formation of
such aggregates was reported by Bibette et al.31
The reduction in the coalescence efficiency is primarily
due to the fact that, with higher shear rates, the interdrop
contact time (tc) goes down approximately as the inverse
of the shear rate.7 As a result of this, the time available
for the film between two drops to rupture is reduced as
(31) Bibette, J.; et al. Phys. Rev. Lett. 1992, 69, 981.
2654 Langmuir, Vol. 17, No. 9, 2001 Nandi et al.

Figure 14. Variation of R0γ with shear rate (γ) for different
holdup emulsions: (symbols) values back-calculated from
experimental distributions; (solid line) prediction of eq 10.

Table 3. Back-calculated Dimensionless Contact Times

(γtc) for Colliding Drops Based on the Results Given in
Figure 14
φ γ ) 10.8 s-1 γ ) 21.5 s-1 γ ) 43.0 s-1
1% 1.00 1.00 1.00
5% 0.61 0.75 1.04
15% 0.54 0.64 0.83
Figure 12. Scaled cumulative oversize distribution for different
shear rates and holdups. The distributions are self-similar for be stochastically distributed, with a log-normal distribu-
the emulsion having φ ) 1% tion25,26
.

( [
1 ln tb - µb
])
2
1
P(ln tb) ) exp - (9)
σx2π 2 σb

Assuming that the interdrop contact time is tc ) 1/γ7 for

dilute emulsions (φ ) 1%), the coalescence efficiency is
given by

R0 ) ∫-∞ln t
c
P(ln tb) d ln tb )
1
2
erfc
{
µb + ln γ
x2σb } (10)

The above equation was fitted to the values of R0 obtained

for φ ) 1% emulsions and for different shear rates to yield
µb ) 4.35 and σb ) 1.99. The solid line in Figure 14 shows
Figure 13. Variation of the normalized coalescence efficiency that the model adequately describes the experimental
(/R0) with diameters of the colliding drops (Di,Dj) obtained from data. In the case of high holdups, although film stability
eq 7 for the 15% emulsion (Table 2). may be well-described by the log-normal probability
density (eq 9), the average contact time is difficult to
estimate independently. Fitting eq 10 to the data for R0
Table 2. Fitted Values of the Parameters C, m and Dc for
the Three Holdups Studied (Refer to Eq 7) and Standard given in Figure 14 for the higher holdups yields estimates
Deviations of Each of the Parameters over the Three of the average contact times (tc). The results obtained for
Shear Rates for Each Holdup different shear rates are given in Table 3. The increased
φ C M Dc (µm)
stabilization (compared to that for the lower holdups) may
be due to multidrop collisions which reduce the contact
1% 0.0 0.0 times as shown in Table 3. A quantitative understanding
5% -1.5 ( 0.43 0.5 ( 0.5 18.75 ( 2.54 of such phenomena is complicated, and as yet models to
15% -2.0 ( 0.90 1.75 ( 0.66 18.00 ( 3.5
calculate parameters such as average contact time are
unavailable in the literature.
The lack of dependence of the coalescence efficiency on
the shear rate is increased and thus the probability of the sizes of the colliding droplets, for the case of a
coalescence is also reduced. A model based on this dispersed-phase holdup of 1%, can be explained from the
mechanism was presented in ref 23. The time (tb) for model of Chesters7 for droplets with immobile interfaces.
which the film between the drops survives is assumed to Calculations show that, on reducing the critical thickness
Coalescence in Surfactant-Stabilized Emulsions
at which the film can rupture, the coalescence efficiency
becomes weakly dependent on the sizes of the colliding
species. In the case of our emulsion system, the critical
thickness for the rupture of the film is low, since the film
is stabilized by the presence of surfactant. Further, only
“near head-on” collisions give contact times long enough
to allow for film rupture and coalescence. The contact time
may be divided into two regimes. Initially, the film thins
rapidly, and thereafter, the film thinning becomes very
slow. The second part may be termed as the “drop rest
time”. For near head-on collisions, the period for the drop
rest time is significantly higher than the time for which
the film thins. The rate of film thinning is dependent on
the sizes of the colliding species, however, the drop rest
time is not. Thus, for collisions in which the time of
thinning is small compared to the drop rest time, the
dependence of the coalescence efficiency on the drop sizes
becomes insignificant. At higher dispersed-phase holdups,
hydrodynamic, multibody interactions are likely to affect
the interdroplet contact times and the situation of a size
independent coalescence efficiency will therefore not hold,
as has been observed in this work.
Conclusions
A neutrally buoyant emulsion, stabilized by surfactant
and containing an electrolyte, was subjected to a tangential
Couette flow in the simple shear regime. The drop size
distributions were measured using optical microscopy and
image analysis. Studies were conducted for varying shear
rates and holdups. An increasing shear rate was found to
stabilize the emulsion in all the cases. Increasing the
dispersed-phase holdup gave rise to a bimodal distribution,
unlike in the case of the lowest holdup (1%), where the
drop size distribution curves showed an elongating tail
with time and a diminishing peak. On scaling the
experimental distributions, it was noted that the distri-
butions of samples withdrawn at various times for the
case of 1% holdup showed self-similarity, indicating that
the coalescence efficiency was independent of drop size.
A similar graph for the case with 15% holdup showed a
wide difference between the scaled distributions, indicat-
Langmuir, Vol. 17, No. 9, 2001 2655
ing the dependence of the coalescence efficiency on the
size of the coalescing droplets.
A population balance model was used to describe
transient evolution of the experimentally obtained drop
size distribution and to back-calculate the coalescence
efficiency. The coalescence efficiency was found to decrease
with increasing shear rate in all the cases. At low holdup
(1%) the coalescence efficiency was found to be independent
of drop size, in agreement with the scaling result. At high
holdups the coalescence efficiency exhibited dependence
on colliding drop sizes and the highest efficiency was
obtained for a pair of drops with one drop size being about
18 µm and the other approximately 2 µm. The coalescence
efficiency was found to reduce significantly with increased
holdup. Thus, the coalescence rate increases at a rate
slower than φ2.
An estimate of the coalescence efficiency was obtained
considering the process of film rupture to be controlling
and assuming a log-normal distribution of the rupture
time. The analysis gave a good description of the variation
of coalescence efficiency with shear rate at low holdups.
With increasing holdups, the drop-drop contact times
were found to decrease, indicating the importance of
interdrop interactions.
This work demonstrates an experimental method for
back-calculating the shear-induced coalescence efficiency
for emulsions, for which quantitative models are as yet
unavailable. The experimental results and analysis
provide a qualitative insight into drop level processes
during shear-induced coalescence. More detailed models
and computations including multidrop interactions are
perhaps required to obtain a quantitative description of
the process.
Acknowledgment. The financial support of the BRNS
through Project No. 36/7/94/R&D-II is gratefully acknowl-
edged. D.V.K. acknowledges the financial support from
DST, India, through the Swarnajayanti fellowship. The
authors thank Dr. B. K. Das and Dr. P. D. Sawant of the
Alchemie Research Center, Bombay, for the help in
measuring the interfacial tension values.
LA001473M