3626 Langmuir 2007, 23, 3626-3636

Synergistic Interaction in Emulsions Stabilized by a Mixture of

Silica Nanoparticles and Cationic Surfactant
Bernard P. Binks* and Jhonny A. Rodrigues
Surfactant and Colloid Group, Department of Chemistry, UniVersity of Hull, Hull,
HU6 7RX United Kingdom

William J. Frith
UnileVer Research, Colworth, Colworth House, Sharnbrook, Bedfordshire, MK44 1LQ United Kingdom

ReceiVed NoVember 28, 2006. In Final Form: January 9, 2007

Using a range of complementary experiments, a detailed investigation into the behavior of dodecane-water emulsions
stabilized by a mixture of silica nanoparticles and pure cationic surfactant has been made. Both emulsifiers prefer
to stabilize o/w emulsions. At high pH, particles are ineffective emulsifiers, whereas surfactant-stabilized emulsions
become increasingly stable to coalescence with concentration. In mixtures, no emulsion phase inversion occurs although
synergism between the emulsifiers leads to enhanced stability at either fixed surfactant concentration or fixed particle
concentration. Emulsions are most stable under conditions where particles have negligible charge and are most flocculated.
Freeze fracture scanning electron microscopy confirms the presence of particle flocs at drop interfaces. At low pH,
particles and surfactant are good emulsifiers alone. Synergism is also displayed in these mixtures, with the extent of
creaming being minimum when particles are most flocculated. Experiments have been undertaken in order to offer
an explanation for the latter synergy. By determining the adsorption isotherm of surfactant on particles in water, we
show that surfactant addition initially leads to particle flocculation followed by re-dispersion. Using suitable contact
angle measurements at oil-water-solid interfaces, we show that silica surfaces initially become increasingly hydrophobic
upon surfactant addition, as well as surfactant adsorption lowering the oil-water interfacial tension. A competition
exists between the influence of surfactant on the contact angle and the tension in the attachment energy of a particle
to the interface.

Introduction with surfactants being cationic, anionic, or polymeric. If surfactant

Much is known about the behavior of emulsions stabilized by
surfactant molecules1 and, more recently, those stabilized solely
by surface-active solid particles.2 Since many commercial
emulsion formulations contain a mixture of both surfactant and
particles, e.g., suspoemulsions,3 it is of interest to study emulsions
stabilized by such mixtures from a fundamental point of view.
The hydrophile-lipophile balance number of surfactant molecules
is one parameter which determines both the type and stability
of emulsions using them.1 Likewise, the wettability of particles
at the oil-water interface has been shown to be crucial in
optimizing the stability of solid-stabilized emulsions.4 Addition
of surfactant to particle systems or vice versa in relation to wetting
and emulsification is not new, with reports on model systems,5-10
crude oil emulsions,11,12 and food emulsions.13 Particle types
have included silica, clay, alumina, barium sulfate, and carbon
* To whom correspondence should be addressed. E-mail: b.p.binks@
hull.ac.uk.
(1) Binks, B. P., Ed.; Modern Aspects of Emulsion Science; The Royal Society
of Chemistry: Cambridge, U.K., 1998.
(2) Binks, B. P., Horozov, T. S., Eds.; Colloidal Particles at Liquid Interfaces;
Cambridge University Press: Cambridge, U.K., 2006.
(3) Mulqueen, P. AdV. Colloid Interface Sci. 2003, 106, 83.
(4) Binks, B. P. Curr. Opin. Colloid Interface Sci. 2002, 7, 21.
(5) Gelot, A.; Friesen, W.; Hamza, H. A. Colloids Surf. 1984, 12, 271.
(6) Hassander, H.; Johansson, B.; Törnell, B. Colloids Surf. 1989, 40, 93.
(7) Tambe, D. E.; Sharma, M. M. J. Colloid Interface Sci. 1993, 157, 244.
(8) Lagaly, G.; Reese, M.; Abend, S. Appl. Clay Sci. 1999, 14, 83.
(9) Gosa, K-L.; Uricanu, V. Colloids Surf. A 2002, 197, 257.
(10) Legrand, J.; Chamerois, M.; Placin, F.; Poirier, J. E.; Bibette, J.; Leal-
Calderon, F. Langmuir 2005, 21, 64.
(11) Menon, V. B.; Wasan, D. T. Colloids Surf. 1986, 19, 89.
(12) Sullivan, A. P.; Kilpatrick, P. K. Ind. Eng. Chem. Res. 2002, 41, 3389.
(13) Johansson, D.; Bergenståhl, B.; Lundgren, E. J. Am. Oil. Chem. Soc.
1995, 72, 921.
adsorbs on particle surfaces, their wettability is modified which
affects their efficiency as emulsifiers, either improving or reducing
it. This adsorption can also lead to particle aggregation which
may or may not be advantageous to emulsion stability. If surfactant
does not adsorb on particles, e.g., they are of the same charge
sign, the possibility exists that both species will compete for the
oil-water interface, but one may dominate.
Schulman and Leja14 linked the changes in the contact angle
of oil-water-solid systems with the preferred emulsion type.
Thus, addition of BaSO4 powder to water-in-oil (w/o) emulsions
of oleic acid caused phase inversion to oil-in-water (o/w)
emulsions as hydrophilic coated particles adsorbed at droplet
interfaces. In contrast, o/w emulsions stabilized by sodium dodecyl
sulfate could be phase inverted to w/o by adding BaSO4 as
hydrophobic coated particles adsorbed. Similarly, Tambe and
Sharma7 demonstrated inversion from o/w to w/o for emulsions
stabilized by calcium carbonate particles on increasing the
concentration of stearic acid as surfactant. In some cases, e.g.,
addition of cetyltrimethylammonium bromide to Ludox silica-
stabilized emulsions,6 surfactant adsorption onto particles is
followed by particle agglomeration, and such agglomerates adsorb
at the oil-water interface yielding fine emulsions of excellent
long-term stability. Addition of particles to surfactant systems
does not always lead to emulsion stabilization however, and
Legrand et al.10 showed how adding hydrophilic silica particles
to the continuous phase of a bitumen-in-water emulsion stabilized
by cationic surfactant led to flocculation of the drops and partial
coalescence under applied shear. In connection with liquid-
liquid extraction of fine particles from aqueous suspensions, an
(14) Schulman, J. H.; Leja, J. Trans. Faraday Soc. 1954, 50, 598.

10.1021/la0634600 CCC: $37.00 © 2007 American Chemical Society

Published on Web 02/23/2007
Synergistic Interaction in Emulsions
Figure 1. Ludox HS-30 particles in water at pH ) 9.5. (a) TEM
image at 0.1 wt %, scale bar ) 50 nm, (b) particle size distribution
at 2 wt % determined using ZetaSizer HS-3000.
old paper by Lai and Fuerstenau15 deserves a mention. They
showed how adsorption of alkyl sulfonate anionic surfactants
onto positively charged alumina particles in water increased their
hydrophobicity allowing transfer of particles from water to oil
and subsequent emulsion stabilization. The adsorption isotherms
of surfactant onto particles were determined alongwith the contact
angles of oil drops under water on single crystals of sapphire;
effects of surfactant concentration, surfactant chain length, and
pH were investigated. Longer chain lengths and lower pH gave
conditions where the contact angle through water was >90° and
highest extraction occurred.
Despite some activity in this area, systematic studies of the
behavior and properties of emulsions in mixtures of surfactant
and surface-active particles are lacking. Do the two emulsifiers
act synergistically or antagonistically with respect to emulsion
stabilization? What is the influence of the mixing protocol on
the final emulsion? As a model system, we investigate here the
type and stability of emulsions stabilized by either pure cationic
(15) Lai, R. W. M.; Fuerstenau, D. W. Trans. Soc. Miner. Eng. 1968, 241, 549.
Langmuir, Vol. 23, No. 7, 2007 3627
Figure 2. (a) Photograph of vessels after 24 h containing aqueous
dispersions of Ludox HS-30 particles (2 wt %) at pH ) 9.5 as a
function of CTAB concentration (given in M) at 30 °C. (b) Sediment
height after 24 h versus CTAB concentration for system in (a).
surfactant, hydrophilic silica particles, or their mixture. Additional
experiments have been conducted to shed light on the findings
including determination of the adsorption of surfactant onto silica,
zeta potentials of particle dispersions, equilibrium oil-water
interfacial tensions, and contact angles. Since surfactant adsorbs
on particle surfaces, we have investigated the behavior at extremes
of pH, one corresponding to a highly charged surface and the
other close to its isoelectric point.
Experimental Section
Materials. Water was first passed through an Elga reverse osmosis
unit and then a Milli-Q reagent water system. Its surface tension at
25 °C was 71.9 mN m-1, in excellent agreement with literature
values. Hydrochloric acid (Fisher, 99%) and sodium hydroxide (BDH,
99%) were used to effect the aqueous phase pH. The oil used was
n-dodecane (Aldrich, >99%). It was columned twice through
chromatographic alumina before use. The pure cationic surfactant
hexadecyltrimethylammonium bromide, CTAB, was purchased from
Fluka with a purity of 99%. The critical micelle concentration, cmc,
in water at 30 °C is 0.9 mM. The silica particles were those of Ludox
HS-30 (Grace Davison), received as a 31.6 wt.% aqueous dispersion
at pH ) 9.8. As seen in the transmission electron micrograph, TEM,
in Figure 1a, the particles are spherical and relatively monodisperse
with an average diameter of approximately 15 nm and a specific
surface area of 220 m2 g-1. The particle size distribution determined
by dynamic light scattering using a Malvern Zetasizer HS-3000
instrument is shown in Figure 1b, yielding an average particle
diameter of 13 nm, in agreement with that quoted by the manufacturer
of 12 nm. The fraction of the population with diameters >30 nm
have a size representative of particle aggregates, which are visible
in Figure 1a.
3628 Langmuir, Vol. 23, No. 7, 2007
Methods. (a) Preparation and Characterization of Aqueous
Dispersions. We have investigated silica particle dispersions in water
(2 wt.%) in the presence of CTAB surfactant at two pH values. At
pH ) 9.5, aliquots of aqueous CTAB were added to a volume of
diluted, as-received dispersion at this pH. For high CTAB concen-
trations, concentrated NaOH was added subsequently to adjust the
pH to 9.5. For pH ) 3.0, CTAB was added first and then the pH
was lowered from 9.5 to 3.0 by addition of concentrated HCl with
stirring. The extent of sedimentation of dispersions was determined
by measuring the height of the sediment as a function of time. The
zeta potentials of 1 cm3 of a 2 wt.% particle dispersion at low and
high pH in the presence of increasing amounts of CTAB were
determined using a Malvern Zetasizer HS-3000 instrument employing
a dip cell, using the Smoluchowski equation for converting measured
mobilities. At least two separate measurements were made for each
surfactant concentration. For dispersions which sediment, the
supernatant was taken for these measurements. For TEM, an
aqueous particle dispersion was evaporated on a carbon coated copper
grid and imaged using a JEOL-2010 microscope. For scanning
electron microscopy, SEM, a homogeneous sample of the aqueous
particle dispersion was left to evaporate overnight in a 1 cm wide
glass strip and then coated with a 2 nm layer of Au-Pd alloy using
a Polaron sputter coater to enhance conductivity. A Zeiss EVO 60
microscope was used at low (100) and high (200 keV) magnification,
respectively.
(b) Preparation and Characterization of Emulsions. For systems
containing either surfactant or particles alone, emulsions of equal
volumes of oil and water (total 10 cm3) were prepared in glass
vessels using a Janke and Kunkel Ultra-Turrax T25 homogenizer
with a 1 cm head operating at 11 000 rpm for 2 min. Both particles
and surfactant originate in water. For systems containing a mixture
of surfactant and particles, surfactant was added to a particle
dispersion in water and left 30 min to equilibrate. Emulsification
was the same as described above. Immediately after homogenization,
the conductivity of the emulsions was determined using a Jenway
4310 digital conductivity meter with Pt/Pt black electrodes. Emulsion
type was also confirmed using the “drop” test. The stability of
emulsions to creaming and coalescence was assessed by monitoring
the positions of the water-emulsion and emulsion-oil interfaces,
respectively, with time. Photographs of the vessels were taken with
a Canon IXUS 55 digital camera. Drop size distributions were
determined using a Malvern MasterSizer 2000 light diffraction
instrument. A drop (0.5 cm3) of emulsion was diluted into 100 cm3
of either water (for particle-only systems) or aqueous surfactant
solution at its cmc, (for all other systems) in the presentation unit.
The volume weighted median of the distribution, d(V, 0.5), is quoted.
A Nikon Labophot microscope equipped with a QICAM 12-bit Mono
Fast 1394 camera (QImaging) was used to observe emulsion samples.
A drop of emulsion was diluted in its continuous phase on a
microscope slide and gently covered with a cover slip. The images
were processed using Image-Pro Plus 5.1 software (Media Cyber-
netics). Freeze fracture SEM measurements were carried out on
selected emulsion samples in the following way. A small volume
of fresh emulsion was mounted onto a 0.1 cm diameter brass rivet
and plunged into nitrogen slush. The frozen sample was transferred
to a Gatan Alto 2500 cryo preparation system, fractured with a
scalpel blade at - 97 °C, etched for 2 min, cooled to -110 °C, and
coated with 2 nm of Pt/Pd. Examination was done at -150 °C using
a Jeol 6301F field emission SEM as described elsewhere.16
(c) Determination of Adsorption Isotherm of Surfactant on Silica
in Water. The method employed to determine the adsorption of
CTAB surfactant onto Ludox HS-30 silica particles dispersed in
water at pH ) 9.5 was via surface tension, in which the air-water
surface tension of surfactant solutions in the absence and presence
of silica particles was determined. Loss of surfactant monomer to
particle surfaces leads to an increase in surface tension. The surface
tensions were measured using a Krüss K12 apparatus with a du
Noüy ring and appropriate correction. All vessels were rinsed in
alcoholic KOH and then Milli-Q water. The surface tension of pure
(16) Binks, B. P.; Kirkland, M. Phys. Chem. Chem. Phys. 2002, 4, 3727.
Binks et al.
water (or aqueous dispersions of 2 wt % silica) is measured first,
and then an aliquot of a stock surfactant solution is added to increase
the surfactant concentration, and the mixture is left to equilibrate
for 5 min. This continuous-like protocol was repeated. In addition,
the tensions were determined for batch samples of surfactant plus
particles. The tensions were measured three times for each sample,
with the accuracy being ( 0.2 mN m-1.
(d) Equilibrium Oil-Water Interfacial Tensions and Oil-Water-
Silica Contact Angles. Equal volumes of aqueous surfactant solution
at pH ) 9.5 and dodecane were gently stirred for at least 24 h
without emulsification. The equilibrium aqueous phase was loaded
into the Hamilton syringe of a Krüss DSA 10 drop shape analyzer
instrument, and a drop (typically 10 µL) was formed in the equilibrium
oil phase contained in a glass cuvette. The oil-water interfacial
tension is determined by fitting the Young-Laplace equation to the
drop profile after allowing 10 min for stability. At least four separate
samples of oil and water at each surfactant concentration were used
to determine the tension. The same equilibrated oil and water phases
were used to determine the contact angle of both an aqueous surfactant
solution drop under oil and of an oil drop in water on a planar silicon
wafer substrate. Silicon wafers (Plasmos, 1.6 × 1.6 cm) were treated
with concentrated nitric acid and rinsed with water before use
rendering them hydrophilic. For sessile water drops, the oil phase
contacted the substrate first in a Hellma glass cuvette and then a
10 µL aqueous drop was formed on the wafer. For captive oil drops,
the water phase contacted the substrate first in an inverted
arrangement. Advancing angles were determined. A mean contact
angle of at least four drops was taken for each surfactant concentration.
All measurements were carried out at 30 °C using a Grant LTD-6
thermostat, to avoid problems with surfactant crystallization at the
Krafft point of 26 °C.
Results and Discussion
We first describe the effect of adding CTAB surfactant to
aqueous dispersions of Ludox HS-30 particles at high pH (where
silica is most charged) and the subsequent emulsification of these
mixed dispersions. A limited equivalent data set is then presented
for a low pH, in which silica is initially only slightly charged,
for comparison.
(a) Aqueous Dispersions of Silica Particles and Cationic
Surfactant at pH ) 9.5. Since the isoelectric point for silica
particles is between pH ) 2 and 3, at pH ) 9.5, particle surfaces
are appreciably negatively charged due to dissociation of surface
silanol SiOH groups. Addition of oppositely charged cationic
surfactant like CTAB leads to electrostatic adsorption of surfactant
monomer onto particle surfaces. As a monolayer forms, particles
become increasingly hydrophobic (alkyl chains exposed to
solution). Further adsorption of surfactant can occur via chain-
chain interaction resulting in a bilayer, now with headgroups
exposed to the solution rendering the particles more hydrophilic
again.17 Such changes in the wettability of coated particles could
be sufficient to induce inversion of emulsions stabilized by them,
since hydrophilic particles tend to stabilize o/w emulsions,
whereas hydrophobic ones prefer w/o emulsions.2 At fixed particle
concentration of 2 wt %, addition of CTAB leads to a dramatic
change in the stability of the dispersions. In Figure 2a, it can be
seen that the initial stable dispersion begins to sediment
increasingly up to 10-2 M CTAB (10 times the cmc), after which
the sedimentation falls. This is reversible. The sedimentation is
complete after 24 h, and Figure 2b shows the height of the
sediment (relative to the total volume) as a function of CTAB
concentration. Between 10-5 and 10-4 M CTAB, dispersions are
stable and bluish since surfactant adsorption is low and repulsion
between particles dominates. At intermediate concentrations
between 5 × 10-4 and 10-2 M CTAB, coagulation of particles
(17) Fuerstenau, D. W.; Jia, R. Colloids Surf. A 2004, 250, 223.
Synergistic Interaction in Emulsions
Figure 3. SEM images of dried aqueous dispersions of Ludox HS-30 particles (2 wt%) at pH ) 9.5 in the presence of (a) 0, (b) 10-4, (c)
10-3, and (d) 10-2 M CTAB. Scale bars ) 500 nm.
resulting in their sedimentation occurs progressively as van der
Waals attraction between alkyl chains on neighboring particles
dominates. Above 10-2 M CTAB, the sedimentation extent
decreases again and a fraction of the particles are re-stabilized
as a surfactant bilayer forms on their surfaces leading to charge
repulsion. It is likely that the flocculation observed here at high
surfactant concentration is due to depletion of micelles between
particles on close approach. This was reported recently for CTAB
addition to negatively charged polystyrene latex particles.18
Samples of the dispersions were taken for SEM analysis and
the images are shown in Figure 3. In the absence of surfactant,
(a), discrete particles are visible (white). For 10-4 M CTAB, (b),
particles are more attractive forming small chains, although the
degree of coagulation is not sufficient to induce sedimentation.
By 10-3 M CTAB, (c and d), extensive flocculation has occurred
leading to large flocs of micron size dimension. Do such flocs
adsorb to oil-water interfaces on addition of oil?
The adsorption of cationic surfactants on silica surfaces has
been investigated by others using ellipsometry,19 atomic force
microscopy,20,21 depletion from solution,17,22-24 spectroscopy,25
and combined streaming potential/optical reflectometry.26 In
(18) Furusawa, K.; Sato, A.; Shirai, J.; Nashima, T. J. Colloid Interface Sci.
2002, 253, 273.
(19) Wängnerud, P.; Olofsson, G. J. Colloid Interface Sci. 1992, 153, 392.
(20) Velegol, S. B.; Fleming, B. D.; Biggs, S. R.; Wanless, E. J.; Tilton,
R. D. Langmuir 2000, 16, 2548.
Langmuir, Vol. 23, No. 7, 2007 3629
order to quantify the extent of surfactant adsorption on silica
particles in water, we have determined the adsorption isotherm
using a surface tension method. This involves measuring the
air-water tension as a function of the initial bulk surfactant
concentration in the presence and absence of silica particles. The
raw data is plotted in Figure 4a, where the curve for the silica-
containing system is shifted to higher surfactant concentrations,
since a fraction of the surfactant adsorbs on the particles and is
not available to adsorb at the liquid surface. The surface tension
of the silica dispersion without surfactant was the same as that
of pure water, indicating the absence of surface-active contami-
nants associated with the particles. For the same surface tension,
the difference in concentration between the curves allows us to
calculate the amount of surfactant adsorbed on silica. The
drawback of the method is that once the surface tension of the
particle-containing system reaches that of the particle-free system
at its cmc, no analysis is possible. The isotherm derived from
(21) Atkin, R.; Craig, V. S. J.; Biggs, S. Langmuir 2001, 17, 6155.
(22) Goloub, T. P.; Koopal, L. K.; Bijsterbosch, B. H.; Sidorova, M. P. Langmuir
1996, 12, 3188.
(23) Szekeres, M.; Dékánya, I.; de Keizer, A. Colloids Surf. A 1998, 141, 327.
(24) Koopal, L. K.; Goloub, T.; de Keizer, A.; Sidorova, M. P. Colloids Surf.
A 1999, 151, 15.
(25) Wang, W.; Gu, B.; Liang, L.; Hamilton, W. A. J. Phys. Chem. B 2004,
108, 17477.
(26) Theodoly, O.; Cascão-Pereira, L.; Bergeron, V.; C. J. Radke Langmuir
2005, 21, 10127.
3630 Langmuir, Vol. 23, No. 7, 2007 Binks et al.

Figure 5. Variation of zeta potential of aqueous Ludox HS-30

dispersions (2 wt %) with CTAB concentration at pH ) 3.0 (open
circles) and 9.5 (filled circles).

Figure 4. (a) Variation of air-water surface tension at 30 °C with

CTAB concentration at pH ) 9.5 with (open circles) and without
(filled circles) 2 wt % Ludox HS-30 particles. (b) Adsorption isotherm
of CTAB on Ludox HS-30 particles derived from data in (a).

such data is given in Figure 4b. There is a gentle increase in

adsorbed amount initially followed by a more significant increase
at higher concentrations, ending at the cmc. In a detailed study
of similar cationic surfactants (alkylpyridinium chloride) on quartz
particles, Fuerstenau and Jia17 describe four regions in their
isotherms. In region I, surfactant ions adsorb individually with
their headgroups down. In region II, adsorbed ions associate into
patches or hemimicelles on the surface through chain-chain
interaction. This results in an adsorbed monolayer. In region III,
a second layer begins to adsorb on the first through hydrophobic
interactions of the chains. In region IV occurring close to the
cmc, the bilayer is complete and the adsorbed amount reaches
a plateau value. The last point on the isotherm corresponds to
an area per CTAB molecule on particle surfaces equal to 0.60
nm2. This is to be compared with that measured at the air-water
surface of 0.55 nm2 calculated from the data in Figure 4a.
Since the zeta potential of particles directly reflects adsorption
in the Stern plane, electrophoretic measurements were conducted
with Ludox HS-30 dispersions as a function of CTAB concen-
tration and are given in Figure 5 (filled points). In the absence
Figure 6. Photograph of vessels containing emulsions of dodecane
and water (1:1) at pH ) 9.5 and 30 °C stabilized by (a) Ludox HS-30
particles alone at concentrations of 0.1, 0.5, 1.0, and 2.0 wt % and
(b) CTAB surfactant alone at concentrations of 10-4, 10-3, 10-2,
and 10-1 M (left to right).
of surfactant at this high pH, the zeta potential is -40 mV.
Addition of CTAB gradually decreases the magnitude of the
potential up to 10-2 M after which there is a sudden reversal of
the sign and magnitude to yield positively charged particles of
appreciable charge, as reported by Wang et al.25 for neutral pH.
The initial CTAB concentration at which particles possess a zeta
potential of zero corresponds to an equilibrium (free) concentra-
Synergistic Interaction in Emulsions
Figure 7. Field emission cryo-SEM images of dodecane-in-water emulsions (1:1) at pH ) 9.5 stabilized by (a and b) 10-2 M CTAB alone;
a mixture of 2 wt % Ludox HS-30 particles and (c) 10-3, (d and e) 5 × 10-3, and (f) 10-1 M CTAB.
tion of ≈ 7.8 × 10-4 M, which is in the second increase in the
isotherm amd close to the cmc. The picture emerging is that, on
addition of CTAB, initially hydrophilic and negatively charged
particles become hydrophobic and uncharged leading to floc-
culation and then positively charged and hydrophilic again. We
now describe the type and stability of emulsions prepared from
these different particle-surfactant dispersions.
(b) Emulsions Stabilized by a Mixture of Surfactant and
Particles at pH ) 9.5. In order to understand emulsions stabilized
by a mixture of particles and surfactant, we have investigated
preferred emulsions (1:1) with dodecane in systems containing
silica or CTAB alone. At pH ) 9.5, Ludox HS-30 particles are
poor emulsifiers at any concentration up to 2 wt %, as illustrated
in Figure 6a. Although the emulsion type is o/w, complete phase
separation occurs within 5 min of ceasing homogenization. This
Langmuir, Vol. 23, No. 7, 2007 3631
is most likely due to the very hydrophilic nature of these charged
particles and the corresponding low energy of their attachment
to the oil-water interface, as observed previously with fumed
silica nanoparticles.2 By contrast, Figure 6b illustrates that CTAB
is a good emulsifier at high enough concentration. Its emulsions
were o/w with the stability to coalescence increasing with
concentration. No coalescence was observed above 10-2 M
CTAB, although creaming with separation of water ensues. The
progressive increase in stability is due to an increase in the
adsorption of surfactant to the oil-water interface up to the cmc,
after which an adsorbed monolayer around drops impedes
coalescence. Freeze fracture SEM images for the surfactant-
stabilized emulsion (10-2 M) shown in Figure 7, panels a and
b, reveal a sharp contrast between the frozen oil drops and the
3632 Langmuir, Vol. 23, No. 7, 2007
Figure 8. (a) Photograph of vessels containing emulsions of
dodecane-in-water at pH ) 9.5 and 30 °C stabilized by a fixed
concentration of Ludox HS-30 particles (2 wt %) and increasing
concentrations of CTAB given in M (left to right). (b) Percentage
of oil (open circles) and water (filled circles) separated after 24 h
from the emulsions in (a).
continuous aqueous phase, seen as a white interphase. The aqueous
phase is featureless, and the external surface of a drop is irregular.
The appearance of emulsions prepared from aqueous disper-
sions of a fixed concentration of particles (2 wt %) and increasing
CTAB concentration 24 h after preparation is shown in Figure
8a. All emulsions were o/w but their stability to both creaming
and coalescence depends critically on surfactant concentration.
Thus, whatever the initial increase in particle hydrophobicity
following surfactant adsorption discussed above, it is not sufficient
to induce inversion from o/w to w/o emulsions. It is readily seen
that a synergism exists between particles and surfactant enhancing
emulsion stability, since the emulsion with 10-4 M CTAB (far
left) is now moderately stable in contrast to complete instability
for emulsions with particles or surfactant alone. Creaming is
least at intermediate CTAB concentrations, for which the resolved
aqueous phase is clear implying that all of the particles are
associated with the creamed emulsion. The extent of creaming
(water separated) and coalescence (oil released) is plotted against
CTAB concentration in Figure 8b. Coalescence stability increases
up to 10-3 M CTAB (around the cmc), after which all emulsions
are completely stable. A marked maximum in stability to creaming
occurs at 10-2 M CTAB, where it will be recalled flocculation
of particles in water was maximum. The correlation means that
the most stable emulsions are formed from the most unstable
dispersions. This is a common finding in particle-stabilized
Binks et al.
Figure 9. Median diameter of drops in dodecane-in-water emulsions
as a function of CTAB concentration with (filled circles) and without
(open circles) 2 wt % Ludox HS-30 particles at pH ) 9.5.
Figure 10. Variation of dodecane-water interfacial tension (triangles,
left ordinate) and contact angle measured through water (right
ordinate) of a water drop under dodecane (filled circles) and of an
oil drop under water (open circles) on a silicon wafer both at
pH ) 9.5 as a function of CTAB concentration in water.
emulsions and was reported earlier by, inter alia, Binks and
Lumsdon27 where fumed silica particles were flocculated in that
case by addition of electrolyte. It is not clear whether electrostatic
adsorption of surfactant onto particles in water is sufficiently
strong to remain during rotor-stator mixing with oil during
emulsification. We therefore repeated the above scan with more
gentle hand shaking of the mixtures (20 times in 8 s) but the
trend was exactly the same even for the larger oil drops, suggesting
that surfactant remains adsorbed.
The arrangement of particles around oil drops in these mixed
emulsions has been probed using freeze fracture SEM (Figure
7). In panel c, for 10-3 M CTAB, part of the external surface
of an oil drop is seen in the bottom right corner in which particles
are close-packed. In addition, small stringy particle aggregates
of size below 1 µm are seen in the aqueous phase in the top left
(27) Binks, B. P.; Lumsdon, S. O. Phys. Chem. Chem. Phys. 1999, 1, 3007.
Synergistic Interaction in Emulsions
Figure 11. Photograph of vessels after 24 h containing emulsions
of dodecane and water (1:1) stabilized by a fixed concentration of
CTAB (10-4 M) and increasing concentrations of Ludox HS-30
particles (given in wt %) at pH ) 9.5 and 30 °C. The far right vessel
(*) contains no CTAB.
Figure 12. Effect of CTAB concentration on the sediment height
after 24 h of 2 wt % aqueous Ludox HS-30 dispersions at pH ) 3.0
and 30 °C.
corner. At 5 × 10-3 M CTAB (and 10-2 M not shown), flocs
of particles are visible both in the aqueous phase (size up to
several µm) and at the interface around drops, (d and e), aiding
their resistance to coalescence. At 5 × 10-2 M (not shown) and
10-1 M CTAB, particles are close packed on the drop interface,
(f), but aggregates are not present at the interface. Instead, small
aggregates (<0.1 µm) exist in the continuous phase. The images
provide confirmatory evidence of the scenario put forward above.
Creaming stability depends on both the size of the oil drops
and the viscosity of the continuous aqueous phase. The median
drop diameters determined from light diffraction are plotted as
a function of CTAB concentration in Figure 9, for emulsions
with and without particles. Without particles (open points), the
drop size decreases from over 60 µm at low concentration where
significant coalescence occurs to 15 µm for emulsions stable to
coalescence, in line with the observations in Figure 6b. Increasing
the surfactant concentration up to the cmc lowers the oil-water
interfacial tension facilitating drop breakup during emulsification.
On adding 2 wt % of particles (filled points), the drop size falls
continuously with CTAB concentration until reaching the same
limit by 6 × 10-2 M. However, drops are nearly always larger
in the mixed system than in the surfactant-only emulsions. This
is because loss of surfactant to particle surfaces reduces the free
surfactant concentration responsible for adsorption at the oil-
water interface and lowering of its tension. The fraction of
adsorbed surfactant compared with the initial amount is highest
Langmuir, Vol. 23, No. 7, 2007 3633
Figure 13. (a) Photograph of vessels after 24 h containing dodecane
and aqueous Ludox HS-30 (1:1) at pH ) 3.0 and 30 °C for different
particle concentrations (given in wt %). (b) Field emission cryo-
SEM images of dodecane-in-water emulsion stabilized by 2 wt %
Ludox HS-30 particles alone at pH ) 3.0. The upper image shows
water (left), interface (center) and oil drop (right). The lower image
shows the interface only containing close packed particles.
at low surfactant levels, where the difference in drop size is
largest. Several effects may be responsible for the decrease in
drop size with surfactant concentration in mixtures. Monomeric
surfactant, surfactant-coated particles, or their mixture can all
potentially adsorb at the oil-water interface. For particle
adsorption alone, previous work showed that the oil drop size
decreased with particle concentration up to a limit as finer drops
were stabilized at higher particle content.28 Linking this to the
present system, on adding CTAB, particles become increasingly
hydrophobic promoting their adsorption to the drop interface,
akin to increasing their overall concentration. We do not know
the exact composition of the emulsion drop interfaces but expect
a high surface concentration of coated particles.
(28) Binks, B. P.; Philip, J.; Rodrigues, J. A. Langmuir 2005, 21, 3296.
3634 Langmuir, Vol. 23, No. 7, 2007
Figure 14. (a) Percentage of oil (open circles) and water (filled
circles) separated after 24 h from dodecane-in-water (1:1) emulsions
stabilized by a mixture of Ludox HS-30 particles (2 wt %) and
CTAB at pH ) 3.0 and 30 °C. (b) Effect of CTAB concentration
on the mean drop diameter of the emulsions in (a).
Regarding viscosity, we noticed visually that emulsions were
increasingly viscous up to 10-2 M CTAB where they were gelled,
above which they were relatively fluid. The minimum creaming
extent at 10-2 M originates from both a small drop size and a
thickened aqueous phase retarding upward movement of the drops.
We have sought to determine the change in the wettability of
hydrophilic silica surfaces following surfactant adsorption in
oil + water systems, in addition to monitoring the change of the
oil-water interfacial tension. These measurements have been
performed on pre-equilibrated oil and aqueous phases. Both
monomeric and aggregated CTAB partition exclusively into the
water phase in the presence of dodecane. In Figure 10, the
advancing contact angles through water of equilibrated aqueous
phases at pH ) 9.5 in the presence of equilibrated oil phases on
a hydrophilic silicon wafer (possessing a surface silica layer
akin to Ludox HS-30 particles), θow are plotted as a function of
the initial concentration of surfactant in the water phase. The
importance of the protocol is highlighted. If oil contacts the
substrate first and a sessile water drop forms (filled circles), the
Binks et al.
contact angle first increases from 34° without surfactant to over
145° at 3 × 10-3 M CTAB (monolayer) and then decreases to
80° at higher concentrations (bilayer). The changes in the
wettability of the surface result from the changes in the surface
energies of the oil-water, solid-water, and solid-oil interfaces
with surfactant concentration. Since the contact angle greatly
exceeds 90° at intermediate concentrations, it is predicted that
emulsions should invert in this system, which they do not.
However, the emulsions are prepared by contacting water with
the solid particle surfaces first and then adding oil. With this
protocol and using captive oil drops (open circles), the contact
angles pass slightly above 90° initially and then fall to zero (oil
drop repelled from substrate under water) at and above the cmc,
in line with all emulsions being o/w and particles remaining
relatively hydrophilic. The difference between the two data sets
is due to the difference in the stability of the thin liquid film
between the drop and the substrate; in the first case, the water
drop breaks through any oil film to make contact with the substrate,
whereas in the second case, the aqueous film adsorbed on the
substrate at and above 10-3 M CTAB is too stable for the oil drop
to penetrate. We discussed previously the impact of which phase
contacts the particles first in relation to the preferred emulsion
type.29 There are several reasons why the contact angles
determined here may not be directly applicable to those pertaining
to the particles themselves including differences in surface
chemistry (silicon vs silica), surface roughness, and heterogeneity.
We believe however that the angles measured in the second
protocol are more representative of those attained in the emulsions,
and their magnitude is reflected in the aqueous phase continuity
of all emulsions.
The corresponding oil-water interfacial tensions γow of pre-
equilibrated phases are also shown in Figure 10 (triangles). The
tension decreases from 51 mN m-1 in the absence of surfactant
to a value of 5 mN m-1 at the cmc, after which it decreases
slightly as the ionic strength increases. The free energy of
adsorption of a single, spherical silica nanoparticle to the oil-
water interface E has been shown to be related to the stability
of emulsions containing adsorbed particles;30 that is, as E
increases, the stability to coalescence increases. For contact angles
θow < 90°, this energy E is given by2
E ) πr2γow(1 - cos θow)2 (1)
in which r is the particle radius (7 nm). Inspection of eq 1 reveals
that lowering the value of γow should decrease E, whereas
increasing the value of θow should increase E. There is thus a
competing effect of the tension and the contact angle on the
magnitude of E upon initially increasing the surfactant concen-
tration. We also investigated the effect of increasing the particle
concentration on emulsions at fixed, low surfactant concentration
(below the cmc). All aqueous dispersions were stable to
sedimentation in this case. The appearance of the vessels
containing the emulsions after 24 h is seen in Figure 11, where
the synergy between both emulsifier types is again evident. The
vessels on the far left and far right are those with surfactant only
and particles only (at 31.6 wt.%), respectively, where no stable
emulsion forms. In mixtures however, o/w emulsions form which
cream with time and, at and above 0.5 wt % particles, are stable
to coalescence. At 30.0 wt % particles and only 10-4 M CTAB,
knowing the adsorption isotherm we calculate that approximately
20 surfactant molecules adsorb per particle, sufficient to render
(29) Binks, B. P.; Lumsdon, S. O. Phys. Chem. Chem. Phys. 2000, 2, 2959.
(30) Binks, B. P.; Lumsdon, S. O. Langmuir 2000, 16, 8622.
Synergistic Interaction in Emulsions Langmuir, Vol. 23, No. 7, 2007 3635

Figure 15. Optical microscopy images of dodecane-in-water emulsions (1:1) prepared at pH ) 3.0 and 30 °C stabilized by (a) 10-1 M CTAB
alone, (b) 2 wt % Ludox HS-30 alone and mixtures of 2 wt % particles, and (c) 10-4, (d) 10-3, (e) 10-2, and (f) 10-1 M CTAB. Scale
bars ) 100 µm.

them suitably hydrophobic for adsorption at the oil-water
interface. Stable emulsions can thus be prepared at low overall
emulsifier concentration, Viz. 0.504 wt.% of particles plus
surfactant.
(c) Aqueous Dispersions and Emulsions Prepared at
pH ) 3.0. Since the surface charge density of silica decreases
on lowering the pH as charged SiO- groups become protonated,
we were interested in seeing if the concomitant reduction in the
adsorption of surfactant to particle surfaces influenced the
emulsion behavior. Aqueous dispersions of Ludox HS-30 particles
were prepared at pH ) 3.0 in the presence of CTAB at different
concentrations. Their stability to sedimentation, as a direct result
of CTAB adsorption, passes through a maximum with CTAB
concentration as before but the maximum occurs at lower
concentration, Figure 12, being 2.5 × 10-3 M instead of 10-2
M. This is because less surfactant is required to reach the optimum
hydrophobicity due to the reduced number of charged sites.
However, initially negatively charged particles become positively
charged as before around 1 × 10-3 M CTAB, as evidenced by
the zeta potential changes in Figure 5 (open points).
3636 Langmuir, Vol. 23, No. 7, 2007
In contrast to the results at pH ) 9.5, emulsions of dodecane
and water at pH ) 3.0 with particles alone are o/w and relatively
stable to coalescence. As seen in Figure 13a, as little as 0.5 wt
% particles is required, although they cream and release a small
volume of oil through coalescence with time. The decrease in
the charge on the particles at low pH results in an increase in
their hydrophobicity promoting their adsorption and attachment
to the oil-water interface. Freeze fracture SEM images of these
emulsions are given in Figure 13b. At low magnification, small
particle aggregates of different shape and size (<1 µm) are visible
in the continuous aqueous phase (left) and a particle layer is seen
at the drop interface (center). At high magnification and focusing
only at the interface, discrete particles of approximately 10-20
nm in diameter form a very close packed layer at the drop interface.
The findings using CTAB alone as emulsifier at pH ) 3.0
were similar to those at higher pH (not shown). In particle-
surfactant mixtures, Figure 14a plots the percentage of water or
oil separated after 24 h as a function of CTAB concentration at
fixed particle content of 2 wt %. All emulsions are water
continuous showing no signs of coalescence. Again, their stability
to creaming passes through a maximum at the same CTAB
concentration as that in which dispersions were most flocculated
and sedimented the fastest. The median diameter of oil drops in
emulsion mixtures decreases continuously on adding CTAB as
seen in Figure 14b. They are all smaller than those of emulsions
prepared at pH ) 9.5, reflecting the fact that the uncoated particles
adsorb at drop interfaces alone at low pH facilitating emulsifica-
tion. This is in addition to the adsorption of surfactant and
concomitant lowering of the interfacial tension. Optical micros-
copy images of emulsions in this series are given in Figure 15,
for the separate emulsifiers alone, (a and b), and their mixtures,
(c-f). All drops are spherical and discrete, apart from the emulsion
containing 10-2 M CTAB. Here, extensive aggregation of oil
drops is visible in which aggregated particles adsorbed as flocs
to drop interfaces extending into the continuous aqueous phase
serve as bridges between neighboring drops to form a three-
dimensional network aiding stability. The decrease in drop size
with surfactant concentration is clearly seen and in line with the
data in Figure 14b.
Binks et al.
Conclusions
A detailed investigation into the behavior of dodecane-water
emulsions stabilized by a mixture of Ludox HS-30 silica
nanoparticles and CTAB cationic surfactant has been made. Both
emulsifiers prefer to stabilize o/w emulsions. At high pH, particles
are ineffective emulsifiers, whereas surfactant-stabilized emul-
sions become increasingly stable to coalescence with concentra-
tion. In mixtures, synergism between the emulsifiers leads to
enhanced emulsion stability at either fixed surfactant concentration
or fixed particle concentration. At low pH, particles and surfactant
are good emulsifiers alone. Synergism is also displayed in
mixtures, with the extent of creaming being minimum when
particles are most flocculated. Complementary experiments have
been undertaken in order to offer an explanation for the latter
synergy. By determining the adsorption isotherm of surfactant
on particles in water, we show that surfactant addition initially
leads to particle flocculation followed by re-dispersion. Emulsions
are most stable when prepared from flocculated dispersions, with
a maximum viscosity appearing in both at intermediate surfactant
concentrations. From cryo-SEM, particle flocs are shown to
adsorb at drop interfaces. Using suitable contact angle measure-
ments at oil-water-solid interfaces, we show that silica surfaces
become increasingly hydrophobic initially upon surfactant
addition as well as surfactant adsorption lowering the oil-water
interfacial tension. A competition exists between the influence
of surfactant on θow and γow in the attachment energy of a particle
to the interface.
Acknowledgment. The authors thank Unilever Corporate
Research for the provision of a postdoctoral grant to J.A.R. They
also thank S.I. Lamble, E.L. Sharp and K.D. Simila of the
University of Hull for obtaining the data at pH ) 3.0, and Mr.
M. Kirkland, Unilever Colworth, for carrying out the freeze
fracture SEM measurements.
LA0634600