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Colloids and Surfaces A: Physicochem. Eng.

Aspects 441 (2014) 4350


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Colloids and Surfaces A: Physicochemical and
Engineering Aspects
j our nal home page: www. el sevi er . com/ l ocat e/ col sur f a
Effect of interfacial dilational rheology on the breakage of dispersed
droplets in a dilute oilwater emulsion
Wei Wang

, Kai Li, Pengyu Wang, Shuai Hao, Jing Gong


Beijing Key Laboratory of Urban Oil & Gas Distribution Technology, Department of Mechanical and Transportation Engineering, China University of
Petroleum, 18 no. Fuxue Road, Changping District, 102249 Beijing, China
h i g h l i g h t s

Interfacial dilational properties are


introduced to explain for drop break-
age in stirred vessels.

Chord length distributions measured


with a FBRM instrument are com-
pared.

Strong relationship between interfa-


cial dilational elasticity and dispers-
ing modality is demonstrated.
g r a p h i c a l a b s t r a c t
a r t i c l e i n f o
Article history:
Received 25 August 2013
Accepted 29 August 2013
Available online xxx
Keywords:
Interfacial dilational modulus
Breakage
Chord length
Square weighted mean diameter
a b s t r a c t
Surfactants reduce the interfacial tension of oilwater and hence favor emulsication; however, attention
has rarely been focused on the effect of interfacial dilational rheology on drop breakage. The aimof this
work is to rheologically characterize the interfacial properties of oilwater droplets and the effect on
drop breakage during emulsication. The dispersed holdups are xed indilute dispersion where breakage
dominates during mixing. The total number of droplets, the square weighted (sqr-wt) mean diameter and
the chord length distribution (CLD) are measured online using the focus beam reectance method (FBRM).
Variations in the dispersed droplets are further analyzed with the interfacial dilational modulus. For
emulsions with surfactant concentrations below the critical micelle concentration (CMC), the interfacial
tension decreases as the surfactant concentration increases, whereas the mean drop diameter initially
shows an increasing trend and then decreases. However, for concentrations above the CMC, the interfacial
tension rarely decreases, whereas the mean diameter of the dispersed phase continues to decrease, and
thetotal number of droplets increases as the concentration of Span 80continues to increase. This indicates
that the interfacial dilational elasticity is a key factor that inuences the pure breakage emulsication
process and the related dispersed modality.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Oilwater dispersions play a signicant role in petroleum pro-
ductionprocesses where twoimmiscible liquids are mixed, andone
Abbreviations: Sqr-wt, square weighted; CLD, chord length distribution; FBRM,
focus beam reectance method; CMC, critical micelle concentration; RPM, revolu-
tions per minute; mM, mmol/L.

Corresponding author. Tel.: +86 10 8973 3804.


E-mail addresses: w.wang@cup.edu.cn (W. Wang), ydgj@cup.edu.cn (J. Gong).
phase is dispersed into the other phase. In mature oilelds, oil is
often obtained mixed with water that was injected into the well to
improve oil recovery. Oil produced fromreservoirs always contains
certain quantities of asphaltenes, resins and polymers, which are
acknowledged as surface active components, or surfactants. When
sheared in a turbulent multiphase ow, a stable oilwater emul-
sion is formed due to the major contribution of such surfactants.
The emulsication process of oilwater dispersions has been the
subject of many studies, due to its importance to several industries
including petroleum, cosmetics, pharmacy, and food production.
Much attention has been paid to the phenomenology and modeling
0927-7757/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.08.075
44 W. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 4350
of droplet breakage and coalescence processes [14]. Al-Wahaibi
[5] studied the CLD of horizontal oilwater ows and developed
correlations for drop breakage in a turbulent ow eld. Birouks
work[6] investigatedtheeffects of liquidviscosityandcross airow
velocities on the primary break-up mechanisms of a viscous liquid
jet. In regard to the breakage of droplets in emulsions, however,
the inuence of surfactants adsorbed onto the oilwater interface
must be considered.
Surfactants reduce the interfacial tension and facilitate emul-
sication of such dispersions [79]. This can be explained by the
reducedGibbs freeenergyduetothesurfactant molecules adsorbed
onto the oilwater interfaces. Tcholakova et al. [10] studied the
effects of oil viscosity, oil volume fraction, and interfacial tension
on the dispersing modality of high volume fraction O/W emul-
sions. The reduced interfacial tension is not the only explanation
for the stability of an emulsion. Emulsions of certain lower paraf-
n hydrocarbons do not remain stable even when the interfacial
tension is extremely low. Additionally, emulsions stabilized by
large molecule surfactants, such as asphaltenes and resins, can
remain stable for years and have interfacial tensions as high as
3040mN/m[11].
Recently, the importance of interfacial dilational rheology on
emulsion stability has been widely recognized [1215]. Work by
many researchers [1619] demonstrates that the surface rheolo-
gical properties of the adsorption layers are the most important
factor for determining the stability of emulsions. The equilibriums
and dynamic properties of surfactants at uid interfaces, which
modify the dilational viscoelasticity and hence the stability of
emulsions, have been explored [2023]. However, work has rarely
been focused on the effect of interfacial dilational rheology dur-
ing emulsion formation, which is where drop breakage mainly
occurs. Work by Bak et al. [24] has investigated the role of the non-
ionic surfactants Tween 20 and Tween 80 on drop breakage in an
oilwater dispersion. The inuence of surfactants on drop break-
age is taken into consideration with the idea of reduced interfacial
tension. However, this is insufcient to give a proper explanation
for the case of certain stably formed emulsions with relatively high
interfacial tensions. Hence, we argue that the factors that affect
emulsication include the interfacial dilational properties, espe-
cially the dilational elasticity. If this holds, then a correlation could
be demonstrated between the interfacial dilational properties and
the dispersing modality of the emulsion.
To prove the above hypothesis, a set of experiments on interfa-
cial properties and oilwater mixing processes were conducted to
ndanexplicit relationshipbetweenthe interfacial dilational prop-
erties andthe dropsize distributionof the dispersion. The dispersed
hold-ups were restricted to less than 10% in dilute dispersions to
eliminate the inuence of drop coalescence, so that the inuences
of interfacial properties would be mainly on drop breakage.
2. Theoretical background
2.1. Droplet breakage mechanisms
The breakage of droplets experiencingturbulentlyshearing ow
is discussed extensively in the literature, and several mechanisms
have been proposed. Liao [3] reviewed most of the mechanisms
of uid particle breakup and classied them into four categories
including:
(1) Breakup due to turbulent uctuation and collision: Drop
shape is balanced between the turbulent pressure of the surround-
ing uid and interfacial interactions. It is characterized by Weber
number We, whichis theratioof dynamic pressuretosurfacestress;
(2) Breakup due to the viscous shear forces: It is the viscous shear
forces that cause velocity gradient near the surface and deformthe
droplet. The capillary number Ca is proposed as a judgment. (3)
Breakupdue tothe shearing-off process: The shearing-off process is
a result of the velocity difference across the interface, whichis com-
mon for foams with bubbles dispersed in bulk liquid. (4) Breakup
due to interfacial instability.
Despite the fact that the mechanisms mentioned above vary
from each other and the conditions may differ, they are strongly
related to the ability of an interface to resist deformation. Thus,
drop breakage is essentially demanded to be studied fromthe per-
spective of interfacial dilational rheology.
2.2. Interfacial dilational rheology
Interfacial dilational rheology manifests the ability of an inter-
face to resist changes in the interface area and is described by
the interfacial dilational modulus () [25]. The interfacial dilational
modulus is dened as the surface tension increase after a small
increase in area of a surface element [12] and is expressed by
=
d
dln /
= || exp

i0

(1)
where is the interfacial tension, Ais the interface area, and 0 is the
phase angle, which indicates a hysteresis of interface deformation
response to the change in interfacial stress.
Once surfactant molecules are introduced into the dispersion,
they will transfer from the bulk onto the interface to maximally
reduce the Gibbs free energy of the system. When adsorption
equilibrium is reached, the interface shows some content of vis-
coelasticity. This property means that when the interfacial area
undergoes a periodic change, relaxation processes, including dif-
fusion exchange between the surface layers, will occur, and the
interfacial dilational modulus can be divided into two parts, with
the real part representing the elastic/storage modulus and the
imaginary part representing the viscous/loss modulus [26,27],
=

+i

=
d
+iq
d
(2)
where is the frequency of the oscillations, and q
d
is the interfacial
dilational viscosity.
The phase angle can be obtained by
tan0 =
q
d

d
(3)
The elasticity or rigidity of the interface lmleads to high emul-
sionstability[28] becauseit dampens breakageandthecoalescence
of the dispersed droplets. This observation can be explained by the
Marangoni effect, which is induced by the interfacial tension gra-
dient generated in the process of mass transfer or heat exchange
[29]. Surfactant molecules contribute in two aspects: First, when
equilibrated at low bulk surfactant concentration, molecules tend
to adsorb homogeneously onto the surface, as is shown in the
left picture of Fig. 1. When the surface is elongated, a concentra-
tion gradient occurs, and molecules rearrange due to the resulting
interfacial tension gradient; thus, the surface restores its deforma-
tion. Second, when saturated adsorption is reached, the diffusion
of excess molecules in the bulk to the depleted region (see the
right picture of Fig. 1) will take charge of the process, result-
ing in a weakened Marangoni effect. The above mechanism was
further conrmed by Wang [30], who explored the interfacial dila-
tional properties of surface-active fractions at oilwater interfaces.
A highly elastic interface resists deformation and produces a larger
driving force for surfactants to diffuse to the depletedregion, which
decreases the lm compressibility and increases the resistance to
the change in surface area that occurs in drop breakage or coales-
cence [31]. This may further explain the emulsication process and
the related drop size distribution in a turbulently stirred vessel.
W. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 4350 45
Fig. 1. Schematic diagram of surfactant molecule absorption and rearrange-
ment/diffusion during drop deformation.
Table 1
Properties of test uids (at 20

C) fraction.
Exxsol D80 oil Deionized water
Density (kg/m
3
) 792.6 992.8
Viscosity (mPa s) 1.78 0.93
Interfacial tension (mN/m)
a
42.87
a
Measured interfacial tension between Exxsol D80 oil and deionized water by
spinning drop method.
3. Experimental facility
3.1. Fluid properties
The experiment is conducted in a 400mL beaker
(width=80mm, height =110mm). A four pitched blade impeller
is used (diameter D=50mm, width 7.5mm, height 5.0mm, incli-
nation angle 45

). The height of the impeller is xed at 8mm


from the bottom of the beaker. The temperature is maintained at
200.5

C. Deionized water and Exxsol D80 oil are used as the test
uids; their properties are shown in Table 1.
Deionized water is used as the second phase of the dispersion,
and its surface tension is checked before the experiment to assure
a high purity. The surfactant used is sorbitan monooleate (Span
80), which is oil soluble. The molecular formula is C
24
H
44
O
6
, and
the molecular weight is 428.6g/mol. The molecule structure of
the surfactant is shown in Fig. 2. The density used for Span 80 is
1.068g/cm
3
. The surfactant is dissolved in D80 oil before being
mixed together with water for seven different concentrations.
McClements [32] proposed an equation concerning the minimum
amount requiredtoprepare a stable emulsion, however, it is unnec-
essarytodecide whether this minimumvalue is reachedor not here
since the aim is to discuss the correlation between drop break-
age and interfacial properties. Hence a wide range of concentration
from0.00037 to 0.556mM (mmol/L) is elaborately selected.
Note that the current work particularly focuses on the drop
breakage process during mixing instead of the stability of emul-
sions, Span 80 is introduced as the surface active component
Fig. 2. Molecule structure of Span 80.
betweenoil andwater interfaceandnomoreemulsier or stabilizer
is used.
3.2. Interfacial properties
The investigation of interfacial tension and interfacial dilational
rheological properties is performed with spinning drop tensiome-
ter (Data physics SVT20N). The spinning drop method determines
the interfacial properties by analyzing the size and prole of the
dispersed drop being elongated by a high-speed rotating motor.
A camera was used to obtain the curvature radii of the elon-
gated drop and interfacial tension could be calculated according
to YoungLaplace equation [33]:

1
R
1
+
1
R
2

=
2
R
0
+^
2
z
2
(4)
where R
0
is the sphere radius and R
1
, R
2
represent the two ortho-
gonal maximum curvature radii of the elongated drop, is the
angular velocity of the motor and z is the potential distance.
Elastic/viscous modulus is determined by applying a sinusoidal
speed oscillation to the motor, with the base speed of the motor
being 10,000rpmand the amplitude being 3000rpm. The frequen-
cies of the oscillations are 0.05, 0.1, or 0.2Hz according to the
measurement conditions of the tensiometer.
3.3. Chord length measurement
The chord length distribution is measured in-situ with the
focus beam reectance method (FBRM D600L, Mettler Toledo).
The probe is placed 30mm under the liquid surface and 20mm
away from the vertical middle line of the vessel. The probe
can detect a minimum drop size of approximately 397.5nm and
measures the time the beam is reected and determines the
chord length by the product of the time and the laser scan
speed.
The number of chord lengths obtained is subjected to a moving-
average lter, which averages a specied number of J
max
past
measurements by giving equal weight to each measurement. The
moving-average lter can be expressed as
Y
t
=
1
j
t

z=tj+1
X
j
(5)
where J is the number of past data points available. At the beginning
of the measurement or when restarting the averaging, J is set to 1
because there is only one past measurement available. With each
new measurement, J increases until it reaches J
max
. In the present
research, J
max
is set to 10.
D80 oil, water and surfactant are prepared at the experimen-
tal temperature in a beaker. The total volume of the dispersion is
300mL, with the dispersed oil phase volume fraction making up
approximately 0.510% of the dispersion. Emulsication is initi-
ated with a stirring rate of 500 rpmfor all the experiments, which
generates a fully developed turbulent ow (Re =20,833). The mix-
ing time is xed at 30min to allowa nearly stabilized chord length
distribution.
To make sure that the dispersions are O/W, conductivity is
measured. As the water phase is deionized, the measured con-
ductivity of the dispersion is limited, with a value of about
0.9s/cm, indicating that with oil holdup low enough (no more
than 10%), O/W dispersion is obtained. This is also validated
by the fact that as the volume fraction of oil phase exceeds
70%, the conductivity of the system becomes zero and stays
unchangedas the oil holdupcontinues to increase, indicating a W/O
dispersion.
46 W. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 4350
Fig. 3. O/Wequilibriuminterfacial tension versus Span 80 concentration.
4. Results and discussion
4.1. Interfacial dilational properties
To investigate the inuence of surfactants on the emulsication
process of dilute D80 oil/water dispersions, the interfacial prop-
erties including interfacial tension and dilational modulus were
determined.
Fig. 3 shows the equilibrium interfacial tension between D80
oil and water phases at different Span 80 concentrations. Without
surfactant the interfacial tension measured between oil and water
phases is 42.87mN/m at 200.5

C. With a surfactant concentra-


tion below the CMC, the interfacial tension decreases signicantly
as the Span 80 concentration increases. When the Span 80 concen-
tration exceeds the CMC, the interfacial tension remains stable at
a value of 5.67mN/m. It can be concluded fromthe gure that the
CMC for the studied systemis about 0.4mM.
Figs. 46 show the interfacial dilational total modulus, the
elastic modulus and the phase angle as a function of surfac-
tant concentrationat different oscillationfrequencies, respectively.
The total modulus and the elastic modulus rst increase to a
peak and then decrease as the surfactant concentration increases
for all three oscillation frequencies. The maximum is obtained
with a concentration of approximately 10
3
10
2
mM. This can
be explained by two exclusive relaxation processes: molecular
rearrangements within the surface layer or diffusion exchange
Fig. 4. Interfacial dilatational modulus E as a function of surfactant concentration
at different frequencies.
Fig. 5. Interfacial dilatational elastic modulus E

as a function of surfactant concen-


tration at different frequencies.
of molecules between the surface layer and the bulk solution.
At low surfactant concentrations, the unsaturated adsorption of
molecules on the interface increases, and molecular rearrange-
ments dominate as the concentration increases, which reects an
increased Gibbs elasticity of the interface due to the strength-
ened Marangoni effect. Simultaneously, the diffusion exchange
of molecules between the surface layer and the bulk solution is
strengthenedas theconcentrationcontinues toincrease, whichbal-
ances the interfacial tensiongradient andweakens the ability of the
interface to resist deformation. Thus, the total and elastic modulus
initially increases and then decreases with continuously increasing
surfactant concentration. For surfactant concentrations above the
CMC, saturated adsorption on the interface is reached, and micelles
exist in the bulk oil phase. Further increasing the bulk concentra-
tion only inuences the diffusion exchange and results in a limited
decreaseof theelastic modulus. Thegures alsoshowthat themod-
ulus increases as the oscillation frequencies increases. Phase angle
for each concentration shown in Fig. 6 is a relative ratio of vis-
cous modulus to elastic modulus. The data shows a non-monotone
increasing trend while the sudden decrement for 0.05Hz may be
attributed to the formation of micelle as surfactant concentration
reaches CMC.
Fig. 6. Interfacial dilatational phase angle as a function of surfactant concentration
at different frequencies.
W. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 4350 47
Fig. 7. Square weighted mean diameter versus surfactant concentration at different
oil volume fractions.
4.2. Inuence on the dispersed modality
Square-weighted mean diameter, Sauter mean diameter,
counted chord length and total counts are parameters chosen to
characterize the dispersed modality of oilwater mixing system.
Detail information about the above four parameters could be found
fromWang et al. [34].
The measured sqr-wt mean diameters (chord length) at differ-
ent surfactant concentrations are shown in Fig. 7, with oil phase
volume fractions of 0.5%, 1%, 2.5%, 5% and 10%, respectively. At
such lowdispersed hold-ups, drop breakage dominates during the
stirring process, and the inuence of coalescence can be ignored,
whichprovides a clearer perspective for discussingthe role of inter-
facial dilational elasticity on pure breakage. The measured mean
diameter is square weighted according to the following equation:
y
i
= w
i
n
i
(6)
where y
i
is the weighted channels, n
i
is the corresponding counts,
and w
i
is the weights obtained fromthe channel midpoints M
i
via
w
i
=
M
2
i

N
j=1
M
2
j
N (7)
The sqr-wt mean diameter, a surface average property mainly
for adsorption experiments, is used because interfacial dilation
properties are planar, and they affect the emulsication process
through changes in the surface area. The mean diameters are cal-
culated and plotted in Fig. 7 based on an average value of 40 points
gathered at 30min after the end of stirring. The sqr-wt diameters
experience a rst increase then decrease trend with the increment
of surfactant concentration in Fig. 7, with a maximum reached
between 10
3
and 10
2
mM. Frompure systemto surfactant con-
centrations of 0.00037 and 0.0037mM, as shown in Fig. 7, the
increase trend of sqr-wt diameter is not in accordance with the
result of IFT in Fig. 4 which suffers a mono decreasing trend, where
the elongation and breakage of dispersed drop becomes enhanced
at lowIFT. Instead, the increase of dilational elastic modulus in the
commented concentrations in Fig. 5 is correlated with the sqr-wt
diameters change in Fig. 7.
The trend of molecular rearrangement dominates at surfac-
tant concentrations below the peak point of 3.7110
3
mM. The
increased dilational elasticity reects a strengthened resistance to
drop deformation and a counteractive effect for droplet breakage.
Thus, the mean diameter rst increases as the surfactant con-
centration increases, despite the fact that the interfacial tension
Fig. 8. Sauter meandiameter versus surfactant concentrationat different oil volume
fractions.
decreases. When the concentration of the surfactant exceeds the
peak value in Fig. 4, the resistance to deformation is reduced due
to the gradually dominated molecular diffusion effect from the
bulk phase, which in turn results in a decreasing mean diameter.
When the concentration increases over the CMC, both the inter-
facial tension and the elastic modulus of the interface are lower,
which favors deformation, and droplets are further broken to even
smaller droplets. In Fig. 7, the mean diameters showa rising trend
as the dispersed hold-ups increases.
The Sauter mean diameter (chord length), d
32
, sampled after
30min of mixing is compared in Fig. 8, where the diame-
ter is found to be nearly stable. Sauter mean diameter, d
32
=

k
i=1
n
i
d
3
i
]

k
i=1
n
i
d
2
i
, which links the area of dispersed phase to
its volume, is widely used in the characterization of liquidliquid
dispersions. According to Leng [35] and Pacek [36], the equilibrium
size of the largest stable droplet, d
max
, is proportional to the Sauter
mean diameter, which gives d
max
d
32
. A maximum is observed
at the 3.7110
3
mM surfactant concentration, which manifests a
strong Marangoni effect and stabilization characteristics. A similar
trend of d
32
is observed in the measured sqr-wt mean diameter,
which further manifests the inuence of interfacial elasticity on
emulsication.
Comparing the variations of sqr-wt mean diameter in Fig. 7 and
the d
32
in Fig. 8 with the interfacial tension change in Fig. 3 and
the elastic modulus variation in Fig. 5, it can be seen that although
the interfacial tension remains constant above the CMC, the diame-
ters decrease as the surfactant concentrationincreases. The slightly
decreased elasticity in Fig. 5 provides an insight into the decreasing
diameters.
The measured number density of the chord length further
demonstrates the above nding. Data from the 0.5%, 1%, 2.5%, 5%,
and 10% oil holdups are obtained and compared; only that of the
0.5% is chosen for detailed demonstration, and a set of comparisons
of droplet number counts per secondat various chordlengthscopes
are shown in Fig. 9(ae). The number counts of the small chord
length scopes (i.e., <10m and 1050m) initially decreases as
the surfactant concentration increases below the CMC, indicating
that it becomes harder for drops to be broken into smaller ones
due to the strengthened surface elasticity resisting drop break-
age.
The number counts of larger chord lengths (150300m and
3001000m) increase as a result of enhanced stability. The dis-
persion with a surfactant concentration of 3.7110
3
mM has the
fewest small droplets and the greatest number of large droplets,
48 W. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 4350
Fig. 9. Comparison of droplet counts per second at various chord length scopes for different surfactant concentrations, 0.5% oil volume fraction.
which corresponds to the maximum elastic modulus shown in
Fig. 5.
As thesurfactant concentrationcontinues toincrease, thecounts
of small chordlengthbegintoincrease andthe counts of large chord
lengthdecrease. Withsurfactant concentrations abovetheCMC, the
counts of small drops continue to increase, and the number counts
for large drops are nearly zero, which indicates that the interface of
large drops is not stable when undergoing an external deformation
effect, breaking the drops into smaller ones. This agrees with the
evolutionof the interfacial dilational modulus, especiallythe elastic
modulus.
In Figs. 10 and 11, the total counts per second of all seven
concentrations are compared, with oil holdups of 2.5% and 5%,
respectively. The numerical counts at each time point vary, but
general trends can be observed. The two gures show that the
dispersions with a 3.7110
3
mM surfactant concentration have
the least total counts per second and that the 5.56mM surfactant
dispersions have the most total counts per second. This suggests
W. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 441 (2014) 4350 49
Fig. 10. Comparison of total droplet counts per second for different surfactant con-
centrations, 2.5% oil volume fraction.
Fig. 11. Comparison of total droplet counts per second for different surfactant con-
centrations, 5% oil volume fraction.
that the droplets of dispersions with smaller elastic modulus could
break easily, which results in the system having the most droplet
counts.
The dispersing modality of emulsions with surfactant concen-
trations above the CMC is to be discussed further based on the
experimental data shown in Figs. 711 because it differs fromthat
of concentrations below the CMC as a result of micelle formation.
Researchonemulsionstabilitypresentedstabilizedemulsions with
surfactant concentrations far above the CMC. This is explained by
the effect of the adsorbed surfactant, which hinders droplet coales-
cence. The interfacial dilational elastic modulus is greatly reduced
at these higher concentrations; large droplets could still be broken
into smaller ones, but the steric repulsion force will strongly resist
the Laplace pressure due to drop deformation and prevent the lm
drainage process and coalescence of smaller one. The more uni-
formand stabilized drop size distributions at these concentrations
further demonstrates the effect of the interfacial dilational elastic
modulus on droplet breakage in emulsions.
5. Conclusions
Surfactant added into oilwater dispersions is believed to pro-
mote the emulsication process, and the inuence of surfactants
on drop breakage is caused mainly by the reduced interfacial ten-
sion. However, the interfacial dilational properties, especially the
dilational elastic modulus, are responsible for the droplet breakage
process because they are important parameters for characterizing
the stability of emulsions. A set of experiments are conducted to
ndanexplicit relationshipbetweenthe interfacial dilational prop-
erties andthe dropsize distributionof the dispersions, witha broad
range of surfactant concentrations.
The experimental results for the interfacial dilational rheo-
logical properties indicate that as the surfactant concentration
increases, the elasticity of the oilwater interface initially increases
due to the dominant rearrangement relaxation of the surfac-
tant molecules adsorbed onto the interface; thus, the ability of
the droplet to resist deformation strengthens. The diffusion of
molecules between the bulk and the interface then takes charge,
and the dilational modulus decreases as the concentration contin-
ues to increase, which results in a weakened droplet stability.
The sqr-wt mean diameter, Sauter mean diameter, counted
chordlength, andtotal counts are determinedto examine the effect
of the interfacial dilational modulus on drop breakage during the
mixing process. The dispersing modality are in consistent with the
trends observed in the interfacial dilational modulus, which sug-
gests that as the elasticity of the interface increases, the ability
of the dispersed droplets to resist deformation is strengthened,
whereas interfaces with low dilational elasticity are broken rela-
tivelyeasily. These results verifythe argument that the mainfactors
effecting emulsication include the interfacial dilational proper-
ties, especially dilational elasticity.
Acknowledgments
The authors wish to thank the National Natural Science Founda-
tion of China (51104167), the Program for New Century Excellent
Talents in University (NCET), the Foundation for the Author of
National Excellent Doctoral Dissertationof PRChina (FANEDD), and
the Science Foundation of China University of PetroleumBeijing
(BJ-2011-02) for providing support for this work.
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