Colloids and Surfaces A: Physicochem. Eng.

Aspects 302 (2007) 439–448

Preparation of o/w emulsions stabilized by solid particles and their

characterization by oscillatory rheology
L.G. Torres a , R. Iturbe a , M.J. Snowden b , B.Z. Chowdhry b , S.A. Leharne b,∗
a
Instituto de Ingenierı́a, Coordinación de Ingenierı́a Ambiental, Grupo Tratamiento de Suelos y Acuı́feros,
Universidad Nacional Autónoma de México, Apartado Postal 70-472, Coyoacan 04510, México, D.F., Mexico
b Medway School of Science, University of Greenwich, Medway Campus, Chatham Maritime, Kent ME4 4TB, UK

Received 24 October 2006; received in revised form 19 February 2007; accepted 8 March 2007
Available online 14 March 2007

Abstract
The purpose of this investigation was to examine the preparation and characterisation of hexane-in-water emulsions stabilised by clay particles.
These emulsions, called Pickering emulsions, are characterised by the adsorption of solid particles at the oil/water (o/w) interface. The development
of an elastic film at the o/w interface following the adsorption of colloidal particles helps to promote emulsion stability. Three different solid materials
were used: silica sand, kaolin, and bentonite. Particles were added to the liquid mixtures in the range of 0.5–10 g dm−3 . Emulsions were prepared
using o/w ratios of 0.1, 0.2, 0.3, and 0.4. The effect of sodium chloride, on the stability of the prepared emulsions, was assessed in the range
of 0–0.5 mol dm−3 . In addition the use of a cationic surfactant hexadecyl-trimethylammonium bromide (CTAB) as an aid to improving emulsion
stability was assessed in the concentration range of 0–0.05% (w/v). Characterisation of emulsion stability was realised through measurements of
rheological properties including non-Newtonian viscosity, the elastic modulus, G , the loss modulus, G , and complex modulus, G*. The stability
of the emulsions was evaluated immediately after preparation and 4 weeks later.
Using the stability criteria, that for highly stable emulsions: G > G and both G and G are independent of frequency () it was concluded that
highly stable emulsions could be prepared using a bentonite concentration of 2% (or more); an o/w ratio greater than 0.2; a CTAB concentration
of 0.01%; and a salt concentration of 0.05 M or less—though salt was required.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Bentonite; Kaolin; Oscillatory rheology; Pickering emulsions; Sand

1. Introduction emulsion formation can be reduced through the use of surfactants

Emulsions are heterogeneous mixtures that consist of
droplets of a liquid dispersed in a second continuous immiscible
liquid phase. Liquid/liquid immiscibility creates an interfacial
tension at the contact area between the two liquids. As a con-
sequence emulsions are thermodynamically unstable systems
since the increase in interfacial contact area that accompanies
the dispersion of droplets of the order of several microme-
ters in diameter results in an increase in chemical potential.
In thermodynamic terms the free energy penalty of emulsi-
fication can be recovered by dispersed phase droplet/droplet
coalescence and phase separation as this reduces the extent of
unfavourable liquid/liquid contact. The free energy penalty of
∗ Corresponding author. Tel.: +44 20 8331 9565; fax: +44 20 8331 9805.
E-mail addresses: S.A.Leharne@gre.ac.uk, ls02@gre.ac.uk (S.A. Leharne).
which sufficiently reduce interfacial tension. However physi-
cally stable (as opposed to thermodynamically stable) emulsion
dispersions are most likely to be produced by creating kinetic
barriers to drop/drop coalescence.
The compositional conditions necessary to produce stable
emulsions are of considerable industrial importance. In fact the
production and use of stable emulsions has been extensively
examined in relation to the food industry, petroleum production
(drilling fluids), pharmaceutics (mainly cosmetics), and envi-
ronmental applications (e.g. aquifer remediation). More recently
there has been a surge of interest in the use of mini-emulsions
for the preparation of nano-particles [1–4]. Understanding the
conditions necessary for the formation of physically stable emul-
sions is an important area of research. It is recognised that
emulsions can be stabilised not only by surfactants, but also
by solid particles. These latter kinds of emulsions are termed
Pickering emulsions, honouring the eponymous researcher who

0927-7757/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2007.03.009
440 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448
first described these systems a century ago [5]. There has been a
considerable amount of recent interest in these emulsions, with a
number of reports appearing in the literature describing various
aspects of Pickering emulsion preparation and characterization
[6–11].
Particle wettability is primarily responsible for trapping a par-
ticle at the interface between two immiscible fluids. The depth of
the potential energy minimum encountered by the particle at the
interface is directly related to the contact angle. The Gibbs free
energy (G) required to remove a particle (of radius r) from an
o/w interface is equal to the potential energy reduction for attach-
ment of the particle at the interface, and can be expressed [12] as
G = −πr 2 γow (1 ± cos θow )2 (1)
where γ ow is the oil water interfacial tension, and θ ow is the
contact angle (measured through the water phase) the particle
makes at the o/w interface. The sign on cos θ ow is determined
by the fluid into which the particle is removed. It is negative
for removal into water. The depth of the potential energy well
for a particle of radius 250 nm held at the interface between
hexane and water (for which the interfacial tension is assumed
to be 0.051 N m−1 [13]) and at a contact angle of 90◦ – is about
−2.4 × 106 kT (k is the Boltzmann constant and T is the absolute
temperature – assumed to be 298.15 K). Such a deep potential
well indicates that thermal energy is insufficient to detach the
particles from the interface. Indeed the emulsion droplets should
be stable to coalescence because the kinetic energy of collision
between droplets will be insufficient to remove the particles.
Even for intermediate wetting states the energy needed to detach
the particles, as a prelude to droplet coalescence, is large. Only
under strong wetting conditions, that is for contact angles less
than 20◦ (strongly water wetting) or greater than 160◦ (strongly
oil wetting), will the emulsions be unstable to coalescence.
The nature of the emulsion is determined by the contact
angle made by the stabilising colloidal particles at the water-
oil-solid contact line. Contact angles less than 90◦ give rise to
o/w emulsions whereas contact angles greater than 90◦ favour
w/o emulsions [14].
The magnitude of the free energy required to remove a par-
ticle from the interface between two immiscible fluids does not
provide an insight into the stability of the emulsion [15]. Eq. (1)
does not explain why emulsions should be stable to coalescence.
Indeed for coalescence to occur, as two dispersed emulsion
droplets approach each other, the resulting film composed of the
continuous phase, between the drops, must progressively thin
and ultimately rupture. The force bringing together the drops
must, in other words, exceed the capillary pressure of the thin
film which, when the film becomes ultra-thin, is augmented by
the disjoining pressure [16]. The disjoining pressure is devel-
oped within very thin films as a result of attractive van der
Waals forces and electrostatic, steric or other repulsive forces.
A negative disjoining pressure gives rise to films that are unsta-
ble whereas a positive disjoining pressure gives rise to films
which thicken thereby preventing dispersed droplet aggrega-
tion. It is reported that the water film between two drops of
the discontinuous oil phase resists rupture if the contact angle
(θ) of the stabilising particles is in the range 15◦ < θ < 90◦ [15].
It should also be emphasised that thinning of the film separating
the two droplets is considerably inhibited if the film has vis-
coelastic properties as a result of the particle network adsorbed
at the water/oil interface [17]. In other words the development
of elastic, gel-like properties at the interface hinders drainage.
Emulsions have elastic properties. The origin of this elasticity
is the interfacial energy of the droplets. At low volume frac-
tions interfacial tension ensures that the droplets are spherical
in shape; however, at higher packing densities volumetric con-
straints force the droplet shapes to deform. Deformation results
in energy storage. The application of a shear strain to a com-
pressed emulsion causes the dispersed phase droplets to deform
further, increasing their surface area and thereby storing elastic
energy [18].
The long term physical stability of emulsions can be assessed
through the use of rheology [19]. In an authoritative review
Tadros has shown how (i) steady state shear stress-shear rate, (ii)
constant stress and (iii) oscillatory rheological measurements
can be used to assess stability to creaming, flocculation, coa-
lescence and phase inversion. The rheological properties of oil
droplets dispersed in water and stabilised by surfactants have
been extensively studied [20]. It has been shown that they exhibit
a sharp transition from a liquid to a solid behaviour when the
oil volume fraction, φ, reaches the random close packing vol-
ume fraction of hard spheres, φ* = ∼64%. When the emulsion
is dilute, it behaves as a fluid whose viscosity increases with the
oil volume fraction. Examination of how changes in emulsion
composition can improve the elastic response to shear ought to
be able to provide useful information about those compositions
which enhance the physical stability of an emulsion.
The aim of the work reported herein was, therefore, to inves-
tigate the preparation and characterization of hexane-in-water
emulsions stabilized by solid particles. Three different solids
materials were employed for this purpose, namely silica sand,
kaolin, and bentonite. The effect of particulate matter to fluid
ratio, and the o/w ratio on emulsion stability was assessed.
The effect of NaCl on the stability of the prepared emulsions
was assessed in the concentration range of 0–0.5 M. In addition
the use of a cationic surfactant (CTAB), as an aid to emulsion
stability, was assessed in the compositional range of 0–0.05%.
The emulsions were characterized using measurements of rhe-
ological properties which were subsequently used to assess the
physical stability of the emulsions, directly after preparation and
4 weeks later.
2. Experimental details
2.1. Materials
Silica sand – described by the manufacturer as low in
iron, acid washed kaolin and bentonite (40–100 mesh) were
obtained from Fisher Scientific UK Ltd., (Loughborough, UK).
Hexadecyl-trimethylammonium bromide (CTAB) was obtained
from Aldrich (Gillingham, UK). Hexane and reagent grade
sodium chloride were obtained from BDH Ltd. (Poole, UK).
Double distilled water was produced in our laboratories.
 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448
Table 1
Parameters varied during the preparation of hexane-in-water emulsions
o/w ratio Particles Particle load (% w/w)
40/60 Silica sand 0.5
30/70 Bentonite 1.0
20/80 Kaolin 2.0
10/90 3.0
5.0
2.2. Emulsion preparation
Emulsions were prepared using a Silverson L4R rotor-stator
(ex Silverson Machines Ltd., Chesham, UK). Bentonite and
water were placed in a plastic beaker followed by the addi-
tion of salt and CTAB. The rotor-stator was then placed in the
beaker and using a high speed, creosote was slowly added over a
90–120 s period. Once all the hexane was added, the mixture was
vigorously homogenized for a further 180 s. The total emulsion
preparation time was ∼300 s. Table 1 provides a compositional
overview of all the emulsions prepared.
2.3. Physical measurements
The rheology of hexane-in-water emulsions was charac-
terised by means of the CS10 Controlled Stress Rheometer. Two
different rheological measurements were made in order to char-
acterise the emulsions. First, shear rate versus shear stress runs
were applied to the emulsion samples over a shear rate range of
0.01–100 s−1 . Secondly, oscillatory rheological measurements
were made in the linear viscoelastic region, using a cone and
plate system (angle 4◦ and gap 40 mm). All measurements were
carried out at room temperature (21 ± 1 ◦ C)
Particle sizes and ␨-potential were measured using a Zeta-
sizer 3000 instrument (Malvern Instruments; Worcestershire,
UK).
The du Nöuy ring detachment technique (White Instruments,
Worcestershire, UK) was employed to measure surface tension.
All measurements were made at a temperature of 25 ± 0.5 ◦ C.
Temperature control was maintained by a circulatory water bath.
All glassware was soaked in alcoholic-KOH for 30 min and
washed with hot water, and thoroughly rinsed with copious
amounts of Milli-Pore water, then dried in a clean oven before
use. The platinum du Nöuy ring was washed using alcoholic-
KOH, rinsed in Milli-Pore water, and flamed until red-hot before
each measurement. All measurements were made sufficiently
slowly so as to ensure equilibrium conditions. The uncertainty
in the IFT measurements was no greater than 0.2 mN m−1 .
3. Results and discussion
3.1. Initial experiments
Binks and co-workers report that the stability of particle
stabilised emulsions is dependent upon particle size [11] and
particle wettability [21]. The Zeta-sizer 3000 was used to mea-
441
NaCl concentration (mM) CTAB concentration (%, w/v)
0 0
0.001 0.005
0.01 0.01
0.05 0.05
0.1
0.5
sure the size of the kaolin and bentonite particles. In the case of
silica sand it was impossible to obtain reliable results using the
zeta-sizer. This was because the particles have a size range of
150–450 ␮m and tended to sediment out in a matter of seconds.
The bentonite and kaolin samples were more amenable to stable
dispersion in the aqueous phase. Replicate measurements gave
average particle size values of 896 ± 45.2 and 498.6 ± 30.3 nm,
respectively (the uncertainty values provide the range of mea-
sured values).
In a preliminary series of experiments, emulsions with dif-
ferent solid concentrations and o/w ratios were prepared. No
sodium chloride or CTAB was added at this point. In those sys-
tems where silica sand was used, a greyish product was obtained.
The system produced a lot of foam; but there was always an
immediate separation of the dispersed hexane and water. In addi-
tion during the preparation of these emulsions it was observed
that a lot of noise and heat were produced due to the hardness
and size of the silica particles.
Emulsions prepared with kaolin had a white-creamy appear-
ance; but the emulsions were not stable. In all cases the
emulsions broke up in minutes. The emulsions prepared with
bentonite showed a slightly better performance, but were still
not good enough since they broke up in minutes.
This inability to produce stable emulsions led to an extended
examination of how aqueous phase composition can affect the
long term physical stability of oil in water emulsions. The parti-
cles used as emulsions stabilisers have a surface charge, which
provides an electrostatic repulsive force between the particles
forming the film at the water/hexane interface. Ashby and Binks
[22] reported that the addition of electrolytes reduces the elec-
trostatic repulsion between the negatively charged clay particles,
permitting the formation of a denser film around the oil drops,
thereby increasing their stability to coalescence. Midmore has
also concluded that incipiently flocculated silica particles pro-
duce more stable emulsions [23].
In this series of experiments, emulsions were prepared as
before; but this time with the addition of 0.01, 0.005, 0.1, 0.5,
and 1 M NaCl. The results obtained were quite different from
those obtained for kaolin and bentonite particles in the absence
of added salt. The emulsions obtained were more continuous
and stable, especially those emulsions prepared with less than
0.5 M NaCl (data not shown). From these data it was concluded
that the physical stability of the emulsions could be improved
by using an aqueous phase containing 0.01 M NaCl.
It was also apparent from the observations made, that even
with the addition of sodium chloride to the emulsion mixtures,
442 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448

3.2. Rheological characterisation 1: viscosity versus shear

stress plots

Emulsions can be divided into two main groups: dilute emul-

Fig. 1. Surface tension of aqueous bentonite suspensions containing 0.01%
CTAB and 0.01 M NaCl.
sions with low concentration of inner phase, which exhibit
almost ideal Newtonian viscous behaviour; and in the second
group belong concentrated emulsions with high dispersed phase
contents and non-Newtonian viscous properties [32]. A Newto-
nian fluid is characterised by a viscosity that is independent of
shear rate. On the other hand non-Newtonian fluids demonstrate
viscous behaviour that is a function of shear rate. Indeed the non-
Newtonian rheological behaviour of many polymer solutions,
biological fluids and emulsions is shown to be shear-thinning,
a process wherein the viscosity of the system decreases as
the shear rate increases. Such rheological behaviour is readily
described by the Power Law equation [19]:
η = kγ̇ n−1 (2)

where η is the viscosity (Pa s−1 ), γ̇ the strain rate (s−1 ), k the
the silica sand was still unable to help with the formation of stable
consistency index—essentially the viscosity of the system at
emulsions; and so it’s further examination was discontinued.
a strain rate of 1 s−1 and n is the Power Law index. n provides
Particle wettability is shown in Eq. (1) to be an important
information about the effects of shear on the system. Three value
parameter controlling particle trapping at the o/w interface.
ranges can be identified for n:
The wetting properties of mineral surfaces can be made more
hydrophobic by the adsorption of cationic surfactants at low
aqueous concentrations [24–26]. CTAB, as a cationic surfac- (a) n < 1 the system is shear-thinning—the lower the value of
tant, should therefore readily attach itself to negatively charged n the more shear thinning the emulsion is. Systems that are
clay surfaces via columbic attraction [24]. CTAB has a molecu- weakly flocculated or have thickeners added to them are
lar mass of 364.46 g mol−1 and a critical micelle concentration usually sear-thinning [19];
of 0.92 mM [27] (0.034% (w/v)). In this study CTAB adsorption (b) n = 1 flow in the system is Newtonian, and
to bentonite was established by examining how the presence of (c) n > 1 the system is shear-thickening.
dispersed bentonite in an aqueous solution of 0.01% CTAB and
0.01 M NaCl affects solution surface tension. Fig. 1 reveals that Fig. 2 is a log/log plot showing the effect of increasing ben-
the surface tension of these solutions increases with increas- tonite concentration upon the functional relationship between
ing fraction of bentonite. According to the Gibbs adsorption viscosity and shear rate for a range of hexane-in-water emul-
equation [28], the surface tension of a surfactant solution is sions. The concentration of bentonite varies from 1 to 5%. No
proportional to the logarithm of surfactant activity (which in data is shown for emulsions prepared with 0.5% bentonite as
dilute solutions is approximately equal to concentration) in
bulk solution. The removal of CTAB from aqueous solution
by adsorption to bentonite reduces the bulk CTAB concen-
tration and will, as a consequence, result in an increase in
surface tension. Similar interpretations of the observation that
the addition of solids to aqueous surfactant solutions results in an
increase in surface tension have been advanced by other authors
[29,30].
Additional evidence that CTAB is adsorbed to bentonite is
provided by the ␨-potential measurements. Bentonite in dis-
tilled water had a ␨-potential of −54.0 ± 0.4 mV; whereas
bentonite in a 0.001% (w/v) solution of CTAB had a ␨-
potential of −37.9 ± 0.9 mV. The data strongly suggest that
CTAB molecules are strongly adsorbed to cation exchange sites
present on the bentonite surface, which reduces the surface
charge and thus results in the resultant change in ␨-potential.
Wang and co-workers [31] have presented similar data for CTAB
adsorption to sodium kaolinite, which they too have interpreted
Fig. 2. Rheological characterisation of 30/70 hexane/water emulsions prepared
as CTAB adsorption to the mineral surface via electrostatic with () 1%; ( ) 2%; ( ) 3% and ( ) 5% bentonite, 0.01% CTAB, and
attraction. 0.01 M NaCl.
 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448
Table 2
Power Law parameters obtained from fitting the data shown in Figs. 3 and 4 to
the Power Law equation η = Kγ̇ n−1
Bentonite concentration K n
(%, w/w)
5 8.21 0.000
3 2.92 0.069
2 1.85 0.020
1 0.68 0.101
Hexane/water ratio K n
30:70 2.91 0.072
20:80 0.84 0.107
10:90 0.69 0.061
these broke in hours. The linear portions of the plots are readily
fitted to the Power Law model shown in Eq. (2) and the derived
Power Law parameters are shown in Table 2. Careful scrutiny
of the plots reveals that at high shear rates there is some dis-
cernible departure from linearity, with the curvature suggesting
the attainment of a constant viscosity at high shear rates. Such
behaviour is expected for shear-thinning systems [33]. The plots
in Fig. 3 and data in Table 2 indicate that the consistency index,
k increases as the bentonite concentration increases and the val-
ues obtained for n by model fitting are all less than 1 pointing to
shear-thinning systems.
Fig. 3 provides a graphical overview of how changing the
hexane–water composition affects the functional relationship
between viscosity and shear rate. The data clearly demonstrates
that as the level of hexane in the emulsion system is increased
there is an increase in the consistency index, K (Table 2). The data
obtained for each emulsion system can be fitted satisfactorily to
the Power Law model with the exception of the data obtained
for the 40/60 hexane water emulsion. The n values (Table 2)
obtained again indicate that these emulsions are shear-thinning
systems.
Shear-thinning behaviour in emulsions can be interpreted as
indicating the presence of weak attractive forces between the
Fig. 3. Rheological characterisation of hexane/water emulsions consisting of
() 40/60, ( ) 30/70, ( ) 20/80 and ( ) 10/90 hexane/water; 3% bentonite,
0.01% CTAB and 0.01 M NaCl.
443
Fig. 4. Rheological characterisation of 30/70 hexane/water emulsions contain-
ing 3% bentonite, 0.01% CTAB and () 0.01 M, ( ) 0.05 M and ( ) 0.1 M
NaCl.
emulsion droplets, which give rise to the formation of a weak
elastic gel-like network [33]. The application of a shear stress
causes the droplets to move away from each other. If the shear
stress is smaller in magnitude than the attractive forces the phys-
ical response of the emulsion is elastic; and the shear energy is
elastically stored as an extension of the bonds between the dis-
persed droplets. The resistance to flow provided by the network
that arises from these weak interaction forces is however readily
overcome, by the application of shear forces, in these systems.
Fig. 4 shows the effect of changing salt concentration on
emulsion rheology. There appears to be little difference between
the plots of each salt concentration. However one important
observation that can be made is that the emulsions containing
0.05 and 0.1 M NaCl appear to become even more shear thinning
at higher shear rates. The onset of this behaviour occurs at a shear
rate of 59 s−1 , for the emulsion containing 0.05 M NaCl; and at
a shear rate of 88 s−1 for the system containing 0.1 M NaCl. The
system containing 0.01 M NaCl – in contradistinction – appears
to approach a constant viscosity value. In the absence of appro-
priate experimental data we can only speculate as to why there
might be a change in the shear-thinning properties of the system
but a reasonable explanation could include the observation that
as the salt concentration increases there is a greater tendency
for the clay particles to aggregate since the stabilising repulsive
forces are weakened by the increase in electrolyte concentra-
tion. Hence at larger shear rates any clay aggregates are likely to
be disrupted. The fact that the onset of this behaviour occurs at
a higher shear rate for the highest salt concentration fits neatly
with the notion of a stronger more extensive aggregated clay
system that should arise as a result of the higher ionic strength
of the emulsion.
Fig. 5 shows the effect of CTAB on the rheological properties
of the hexane-in-water emulsions. The graph effectively indi-
cates that those systems comprising 0.01% CTAB are slightly
more viscous than those prepared with 0.005% and 0.05%
CTAB. The data already presented in figures I suggests that
CTAB is adsorbed to the surfaces of bentonite particles. This
444 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448
Fig. 5. Rheological characterization of 30/70 hexane in water emulsions pre-
pared with 3% bentonite, 0.01 M NaCl and () 0.005%, ( ) 0.01% and ( )
0.05% CTAB.
would be anticipated. The pH of the bentonite suspensions lies
between 9 and 10. At these pH values the surfaces are nega-
tively charged. CTAB as a cationic molecule is therefore readily
physisorbed to the surface. Midmore [34] in his investigation of
the synergy between silica and polyoxyethylene surfactants in
the formation of stable o/w emulsions observes that the role of
surfactant in such systems is three-fold: (a) to promote floccu-
lation in the solid particles, (b) to render the particles partially
wettable to allow adsorption at the o/w interface, and (c) to lower
the interfacial tension. The adsorption of CTAB creates a sur-
face alkyl film, which partially covers the clay surface. This has
the effect of altering the wetting properties of the particles and
thus promotes particle trapping at the hexane water interface.
The adsorption of a cationic surfactant of bentonite also has the
effect of neutralising the surface negative charges, which in turn
reduces the surface potential and thus allows the particles to get
closer to each other thereby supporting flocculation [35]. It has
also been observed that the adsorption of cationic surfactants
to mineral particles gives rise to a long range attractive force
[36]. These factors are all likely to play an important role in the
formation of an elastic film held at the oil/water interface which
promotes stability to droplet/droplet coalescence.
It is possible to apply the Herschel–Bulkeley model to silica
stabilised oil-in-water emulsions [23]. The Herschel–Bulkeley
model takes the form [37]:
τ = τ0 + kHB γ̇ α
where τ is the shear stress (Pa), τ 0 the apparent yield stress,
γ̇ the shear rate (s−1 ), and kHB as well as α are model con-
stants. The model accounts for the fact that for any system
that posses a network structure, the initial application of shear
results in distortion of the network. Once the applied stress is
greater than the yield stress then non-Newtonian flow will occur.
Fig. 6 indicates how increasing bentonite concentration affects
the functional relationship between shear stress and shear rate.
The figure also shows that the data can be adequately fitted to
the Herschel–Bulkeley model. The apparent yield stress values
Fig. 6. A plot of shear stress as a function of shear rate for 30/70 hexane/water
emulsions prepared with ( ) 1%; ( ) 2%; ( ) 3% and () 5% bentonite,
0.01% CTAB, and 0.01 M NaCl. The solid lines are the lines of best fit to the
Herschel–Bulkeley mode l [37].
for the emulsions were obtained from the fitting process and
increase as the bentonite concentration increases. These values
are shown in Table 3. The apparent yield stresses are actually
quite low compared to the ones obtained by Midmore [23]. It
should be appreciated that the true yield stress value provides an
indication of how well the emulsion can resist sedimentation or
creaming. The yield stress associated with the emulsion network
ought to be able to resist the gravitational forces acting upon the
emulsion droplet in order for the emulsion to remain physically
stable for an substantial period of time. A very low yield stress
may indicate a tendency to separation [37].
3.3. Rheological characterisation 2: oscillatory viscometry
The viscous and elastic responses of viscoelastic systems can
be quantified by undertaking dynamic oscillatory measurements.
The basis of these measurements is the application of a sinu-
soidal strain, of frequency (ω), to the viscoelastic system and
the measurement of the corresponding stress. For viscoelastic
systems the stress and strain are out of phase with each other.
The phase angle shift (δ) can be measured as the time shift (t)
between the amplitudes of the oscillating stress (τ 0 ) and strain
(γ 0 ):
δ = ωt (4)
(3)
From the amplitudes and the phase angle various viscoelas-
tic parameters may be obtained. These include the complex
Table 3
Herschel–Bulkeley parameters obtained from fitting the data shown in Fig. 8
Bentonite concentration Yield stress (Pa) kHB α
(%, w/w)
5 8.06 0.004 1.40
3 2.84 0.082 0.80
2 1.73 0.017 0.97
1 0.48 0.24 0.20
 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448
modulus (G*), the elastic (G ) and viscous components (G ) of
the complex modulus and tan δ [19]. The relationships between
these parameters are shown in Eqs. (6)–(8):
τ0
G∗ =
γ0
G = G∗ cos δ
G = G∗ sin δ
To obtain these parameters, a preliminary series of measure-
ments were undertaken to identify the linear viscoelastic region.
From this region a constant strain amplitude was selected for a
subsequent series of measurements in which the stress amplitude
was obtained as a function of changing oscillatory frequency.
These data were subsequently used to obtain the storage modulus
(G ) and loss modulus (G ) of the system.
The extent of network formation can be inferred from these
measurements since the more developed the network the more
the system demonstrates an elastic response to shear. Oscillatory
rheological measurements of storage modulus and loss modulus
can indicate whether the emulsion system is strongly or weakly
associated. In this latter category the system is essentially liquid
like. Values for δ can also be obtained, and provide information
about the nature of the viscoelastic response of the emulsion
system. In elastic networks δ is 0◦ , whereas in purely viscous
liquids δ is 90◦ . For viscoelastic systems δ takes some value in
this range. The closer δ is to 0◦ the more the emulsion system
displays an elastic response to the application of the shear stress
and thus the more developed is the gel-like colloidal network.
Two contrasting facets of the behaviour of the hexane/water
emulsions are shown in Figs. 7 and 8. The data show how the
storage modulus, G , the loss modulus G and the complex vis-
cosity η* change as a function of frequency. It is recognised that
viscoelastic behaviour, together with shear-thinning behaviour
and the observation of a yield stress are rheological parameters
Fig. 7. Exemplar graph for a frequency sweep of an emulsion system which
shows an elastic response to shear. The diagram shows the storage (G ; ) and
loss (G ; ) moduli and complex viscosity (η*, ) for an emulsion system
containing 3% bentonite, 0.01% CTAB, 0.01 M NaCl, and a hexane/water ratio
of 30/70. The insert shows how the phase angle varies with frequency.
445
(5)
(6)
(7)
Fig. 8. Exemplar graph for a frequency sweep of an emulsion system which
shows a viscous response to shear. The diagram shows the storage (G ; ) and
loss (G ; ) moduli and complex viscosity (η*, ) for an emulsion system
containing 3% bentonite, 0.01% CTAB, 0.01 M NaCl and a hexane/water ratio
of ratio of 10/90. The insert shows how the phase angle varies with frequency.
that indicate the presence of a weak elastic network structure.
In the case of polymer solutions, viscoelastic behaviour occurs
because of extensive entanglement phenomena. In the case of
emulsions such rheological behaviour arises because a network
is created between dispersed phase droplets. In those cases where
the emulsion stabilisers are colloidal particles it appears that
the adhesion of dispersed phase droplets can arise through the
sharing of the colloidal particles; and can provide an important
stabilising mechanism [8] since it impedes film drainage and
thus retards drop/drop coalescence. It must be added that the
existence of these adhesive interactions has, so far, only been
demonstrated for water droplets stabilised by latex particles in
oil [8,38]. The presence of a network structure is indicated by
measurements which show G to be greater than G and both
are independent of frequency. This behaviour is readily demon-
strated in Fig. 7. However, when G is lower or equal to G and
both are functionally dependent on frequency, then this is an indi-
cation of viscous liquid-like systems with little if any network
structure. Such behaviour is shown in Fig. 8. In this particular
case the low hexane water ratio of 10:90 makes it very difficult
for network formation to occur simply because the dispersed
phase droplets are too far from each other to be able to interact.
In both Figs. 7 and 8 an insert shows how the phase angle
δ varies with frequency. In Fig. 7 has the phase angle that is
less than 15◦ across the entire frequency range, indicating that
the system tends to show an elastic response to shear. On the
other hand in Fig. 8 the phase angle shows a more complex
behaviour with frequency. At low frequencies (at long time
scales) the response of the system is viscous. As the frequency
increases (which corresponds to increasingly shorter time scales)
the response of the system becomes more elastic. Such behaviour
is a common feature of viscoelastic systems and arises as a result
of the characteristic relaxation timescales for the network bonds.
Identification of the emulsion compositions which give rise to
an elastic response to shear over all frequencies should enable us
446 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448

Fig. 10. Elastic (G , solid symbols) and viscous (G , open symbols) moduli for
hexane/water emulsions consisting of () 10/90, ( ) 20/80, ( ) 30/70 and ( )
(G ,
Fig. 9. Elastic (G ,
solid symbols) and viscous open symbols) moduli for
40/60 hexane/water; 3% bentonite, 0.01% CTAB and 0.01 M NaCl.
30/70 hexane/water emulsions prepared with () 1%; ( ) 2%; ( ) 3% and ( )
5% bentonite, 0.01% CTAB, and 0.01 M NaCl.
emulsion compared to the others over the entire frequency range
examined. In addition the data suggests that the storage modu-
to identify the compositions necessary for producing physically lus also increases as the oil fraction increases. This is expected
stable emulsions. This implies that the compositions necessary since an increase in hexane concentration should lead to a closer
to promote the physical stability of an emulsion can be estab- packing and greater degree of interaction between the dispersed
lished using the following criteria: G > G ; and both G and G phase droplets.
are independent of frequency. We pointed out, in a preceding section, that salt was necessary
Fig. 9 shows how these critical parameters vary as a function for the formation of stable emulsions. Fig. 11 demonstrates that
of bentonite concentration. The data points to the existence of a too much salt may also lead to weakly associated emulsions. It
critical concentration of bentonite below which the hexane-in- is suggested that this arises because the 0.1 M salt concentration
water emulsion provides a viscous response to shear – which is shields the electrostatic repulsions to such an extent as to give
assumed to indicate a potentially physically unstable emulsion. rise to extensive clay aggregation, which tends to suppress the
The role bentonite plays in emulsion stability is clearly to pro- stabilising role of the clay particles.
duce a viscoelastic film at the o/w interface which hinders film The data in Fig. 12 also indicate that there is an optimal CTAB
drainage. It should also hinder coalescence by making the ther- concentration. Too little or too much CTAB creates emulsions
modynamic cost of removing the weakly water wetting particles with a poorly developed network structure. It has been noted that
from the interface into bulk water greater than the thermody- CTAB adsorption not only alters the wetting properties of the
namic gain of reducing the oil water surface contact area, which bentonite particles but it also reduces the surface charge density.
would derive from coalescence. Stancik et al. [39] however sug- The data in Fig. 12 suggest that if the CTAB concentration is too
gest that repulsive forces between similarly charged particles
may also play a pivotal role in preventing drop/drop coalescence.
Such repulsive forces can be enhanced because the charged par-
ticles held at the interface between water and a low dielectric
fluid such as an alkane. This arises because at the interface there
is an asymmetric distribution of counter-ions which creates a
dipole normal to the fluid/fluid interface [40]. Repulsive effects
occur predominantly through the low dielectric constant medium
rather than through the aqueous phase since in the aqueous phase
the interactions are shielded. Indeed the repulsive dipole/dipole
interaction is enhanced in the oil phase because the dielectric
constant is small [41].
Fig. 10 provides a summary of how G and G are affected
by changes in the o/w ratio. The data indicates that the emul-
sion prepared using the low hexane fraction (10:90) shows little
evidence of network formation; whereas the other emulsions
demonstrate the existence of weak bonding between the dis- Fig. 11. Elastic (G , solid symbols) and viscous (G , open symbols) moduli for
persed droplets. There is over an order of magnitude difference 30/70 hexane/water emulsions containing 3% of bentonite, 0.01% CTAB, and
between the storage modulus values of the 10/90 hexane water () 0.01 M, ( ) 0.05 M and ( ) 0.1 M NaCl.
 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448
Fig. 12. Elastic (G , solid symbols) and viscous (G , open symbols) moduli for
hexane/water emulsions containing 3% of bentonite, () 0.005%; ( ) 0.01%
and ( ) 0.05% CTAB, and 0.01 M NaCl.
low then either the wetting properties are inadequate for effective
particle adsorption at the interface or the reduction in surface
charge is too modest to overcome particle/particle electrostatic
repulsion; or it could be some combination of both effects. When
the CTAB concentration is too high then there is possibly too
great a reduction in surface charge and again the clay particles
form large aggregates.
3.4. Using rheology to predict emulsion stability
In this section we use the rheological characterisation out-
lined in the previous section as a means to predict compositions
which provide physically stable emulsions. We should stress
that we use the term “stability” in a kinetic sense and not in
a thermodynamic sense. To do this we recognise that a physi-
cally stable emulsion is created if the system forms an elastic
gel network [19]. Ross-Murphy [42] has noted that dilute solu-
tions are characterised by G > G and both parameters show a
marked dependency upon frequency of measurement. On the
other hand weak gels are characterised by G > G and both
parameters show little dependency upon frequency. We thus use
the following criteria to distinguish between physically stable
and unstable emulsions. An emulsion is considered stable if
G > G and both G and G are independent of frequency ()
since under these circumstances the emulsion displays gel-like
properties. An emulsion is classified as physically unstable if
G > G and G and G are dependent upon frequency since by
these criteria the emulsion exhibits the properties of a dilute solu-
tion. Using these stability criteria it is clear that physically stable
emulsions were prepared using a bentonite concentration of 2%
or more; an o/w ratio greater than 0.2; a CTAB concentration of
0.01%; and a salt concentration of 0.05 M or less—though salt
was required.
These emulsions were stored at room temperature for 4 weeks
after which period they were gently shaken and characterised
again. The rheological properties were identical indicating that
not only were they stable; but they could be stored for weeks
without loss of their original properties. For many applications
447
this is very important, since some emulsions have interesting
properties but only for short periods of time.
4. Conclusions
Physically stable hexane-in-water emulsions have been pre-
pared using bentonite as the emulsion stabiliser which has
modified by the addition of the cationic surfactant CTAB, and
dilute sodium chloride. Under appropriate compositional condi-
tions the emulsions develop an elastic network which provides
the emulsions with good long term stability to coalescence.
Acknowledgements
L. Torres wishes to thank the Royal Society (UK) and
Academia Mexicana de Ciencias (Mexico) for their support
which enabled him to work at Greenwich University, where most
of the research was developed and undertaken. He further wishes
to thank Professor John Mitchell of Medway Sciences (Green-
wich University) for his support and the provision of office and
laboratory space during his stay; Mrs. A. Raza (School of Sci-
ence) for technical support and finally the postgraduate students
of Medway Sciences who made his visit such an enjoyable one.
References
[1] S.J. Han, T. Hyeon, Chem. Commun. (1999) 1955–1956.
[2] H.P. Hentze, S.R. Raghavan, C.A. McKelvey, E.W. Kaler, Langmuir 19
(2003) 1069–1074.
[3] K. Landfester, Macromol. Rapid Commun. 22 (2001) 896–936.
[4] T. Welzel, W. Meyer-Zaika, M. Epple, Chem. Commun. (2004) 1204–
1205.
[5] S.U. Pickering, J. Chem. Soc. Trans. 91 (1907) 2001–2021.
[6] E. Vignati, R. Piazza, T.P. Lockhart, Langmuir 19 (2003) 6650–6656.
[7] S. Tarimala, L.L. Dai, Langmuir 20 (2004) 3492–3494.
[8] E.J. Stancik, G.G. Fuller, Langmuir 20 (2004) 4805–4808.
[9] J. Giermanska-Kahn, V. Schmitt, B.P. Binks, F. Leal-Calderon, Langmuir
18 (2002) 2515–2518.
[10] B.P. Binks, S.O. Lumsdon, Langmuir 16 (2000) 8622–8631.
[11] B.P. Binks, S.O. Lumsdon, Langmuir 17 (2001) 4540–4547.
[12] R. Aveyard, B.P. Binks, J.H. Clint, Adv. Colloid Interf. Sci. 100–102 (2003)
503–546.
[13] J.F. Dong, B.Z. Chowdhry, S.A. Leharne, Colloid Surf. A: Physicochem.
Eng. Aspects 212 (2003) 9–17.
[14] G. Lagaly, M. Reese, S. Abend, Appl. Clay Sci. 14 (1999) 83–103.
[15] G. Kaptay, Colloids Surf. A: Physicochem. Eng. Aspects 282–283 (2006)
387–401.
[16] N. Romero, A. Cardenas, M. Henriquez, H. Rivas, Colloid Surf. A: Physic-
ochem. Eng. Aspects 204 (2002) 271–284.
[17] B.P. Binks, J.H. Clint, C.P. Whitby, Langmuir 21 (2005) 5307–5316.
[18] M.-D. Lacasse, G.S. Grest, D. Levine, T.G. Mason, D.A. Weitz, Phys. Rev.
Lett. 76 (1996) 3448–3451.
[19] T. Tadros, Adv. Colloid Interf. Sci. 108–109 (2004) 227–258.
[20] L. Bressy, P. Hebraud, V. Schmitt, J. Bibette, Langmuir 19 (2003) 598–
604.
[21] B.P. Binks, J.H. Clint, Langmuir 18 (2002) 1270–1273.
[22] N.P. Ashby, B.P. Binks, Phys. Chem. Chem. Phys. 2 (2000) 5640–5646.
[23] B.R. Midmore, Colloids, Surf. A: Physicochem. Eng. Aspects 132 (1998)
257–265.
[24] B.H. Cipriano, S.R. Raghavan, P.M. McGuiggan, Colloid Surf. A: Physic-
ochem. Eng. Aspects 262 (2005) 8–13.
[25] A.H. Demond, F.N. Desai, K.F. Hayes, Water Resour. Res. 30 (1994)
333–342.
448 L.G. Torres et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 302 (2007) 439–448
[26] N.V. Churaev, I.P. Sergeeva, V.D. Sobolev, H.-J. Jacobasch, P. Weidenham-
mer, F.-J. Schmitt, Colloid Surf. A: Physicochem. Eng. Aspects 164 (2000)
121–129.
[27] M.J. Rosen, Surfactants and Interfacial Phenomena, 2nd ed., John Wiley
& Sons, New York, 1989.
[28] R.J. Hunter, Introduction to Modern Colloid Science, Oxford University
Press, Oxford, 1993.
[29] W.D. Hergeth, R. Zimmermann, P. Blo, K. Schmutzler, S. Wartewig, Col-
loid Surf. 56 (1991) 177–187.
[30] Z. Liu, D.A. Edwards, R.G. Luthy, Water Res. 26 (1992) 1337–1345.
[31] J. Wang, B. Han, M. Dai, H. Yan, Z. Li, R.K. Thomas, J. Colloid Interf.
Sci. 213 (1999) 596–601.
[32] K.K. Krynke, J.P. Sek, Colloid Surf. A: Physicochem. Eng. Aspects 245
(2004) 81–92.
[33] E. Dickinson, An Introduction to Food Colloids, Oxford University Press,
Oxford, 1992.
[34] B.R. Midmore, Colloid Surf. A: Physicochem. Eng. Aspects 145 (1998)
133–143.
[35] Y.-H. Shen, Water Res. 36 (2002) 1107–1114.
[36] L.G.T. Eriksson, P.M. Claesson, J.C. Eriksson, V.V. Yaminsky, J. Colloid
Interf. Sci. 181 (1996) 476–489.
[37] J.H. Prentice, Measurements in the Rheology of Foodstuffs, Elsevier
Applied Science Publishers, London, 1984.
[38] N.P. Ashby, B.P. Binks, V.N. Paunov, Chem. Commun. (2004) 436–437.
[39] E.J. Stancik, M. Kouhkan, G.G. Fuller, Langmuir 20 (2004) 90–94.
[40] R. Aveyard, J.H. Clint, D. Nees, V.N. Paunov, Langmuir 16 (2000)
1969–1979.
[41] J.N. Israelachvili, Intermolecular and Surface Forces, 2nd ed., Academic
Press, London, 1992.
[42] S.B. Ross-Murphy, Rheology of biopolymer solutions and gels, in: E. Dick-
inson (Ed.), New Physico-Chemical Techniques for the Characterisation of
Complex Food Systems, Blackie, London, 1995, pp. 139–156.