Chem. Eng. Technol. 2009, 32, No.

7, 11071112

1107

Brigitte Braisch1
Karsten Khler1

Research Article

Heike P. Schuchmann1
Bettina Wolf2

Preparation and Flow Behaviour of

Oil-In-Water Emulsions Stabilised
by Hydrophilic Silica Particles

Food Process Engineering,

Karlsruhe University,
Karlsruhe, Germany.
Division of Food Sciences,
University of Nottingham,
Loughborough, UK.

Emulsions are a common form of material and are encountered in products including foods, cosmetics, and pharmaceuticals. Appropriate formulation and
processing ensures stability and quality. The research reported is concerned with
the use of nano-particles for interfacial stabilisation of oil-in-water (o/w) emulsions. This is a route far less often chosen by formulation engineers than interfacial stabilisation based on small molecular surfactants. Known concepts of
stabilising simple o/w emulsions with hydrophilic silica particles were applied.
The emulsion components were carefully selected in view of their application relevance in consumer goods such as foods and creams. Emulsions stable against
coalescence were formulated based on discrete 230 nm silica particles and corn
oil. The viscosity behaviour of the emulsions was characterised after suppressing
creaming through dissolution of a thickening agent in the continuous emulsion
phase. The emulsions were shear-thinning and viscosity levels were reduced after
removal of free particles. Particle stabilisation of o/w interfaces alters the product
characteristics of emulsion-based products, giving formulation engineers novel
ways to adjust product rheologies.
Keywords: Emulsions, Particle-stabilised emulsion, Pickering emulsion, Rheology,
Silica particles
Received: February 3, 2009; accepted: February 13, 2009
DOI: 10.1002/ceat.200900064

Introduction

Emulsions are a common form of material encountered in

foods, cosmetics, and pharmaceuticals. Appropriate formulation engineering will ensure stability against creaming or sedimentation, flocculation and coalescence. In liquid emulsions,
stability against coalescence is accomplished by addition of
emulsifiers. Most commonly, the formulation engineer will
choose a suitable small molecular surfactant. Alternative
classes of interfacial active materials are polymeric surfactants
and particles (nano- or micro-). This paper is concerned with
particle stabilisation of emulsion interfaces [1], first reported
about a century ago by Ramsden [2] and Pickering [3]. Unlike
small molecular surfactants, particle adsorption at interfaces is

Correspondence: Dr. B. Wolf (Bettina.Wolf@nottingham.ac.uk), Division of Food Sciences, University of Nottingham, Sutton Bonington
Campus, Loughborough LE12 5RD, UK.

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

practically irreversible, rendering emulsions very stable. Use of

particles instead of surfactants may also be of interest from a
formulation point of view, such as replacing environmentally
problematic surfactants in home and personal care products
or E-number-registered ingredients in food formulations. A
fundamental requirement for particle stabilisation is partial
wettability of the particles by both emulsion phases [4]. This
may be achieved by suitable chemical modification of the surfaces, addition of suitable surfactants [5], suitable multivalent
ions [68], and pH adjustment [9, 10].
This paper reports on the formulation and viscosity behaviour of oil-in-water (o/w) emulsions stabilised by discrete
230 nm silica particles in the aqueous emulsion phase. The
particles were rendered interfacially active through pH adjustment or addition of the multivalent ion lanthanum chloride.
Corn oil was used as oil phase, and o/w emulsions with different Sauter diameters were produced with a high-shear overhead mixer. The main objective of this paper is the investigation of the viscosity behaviour of particle-stabilised emulsions,
paying particular attention to the effect of free nano-particles
(those that had not adsorbed at the o/w interface) on the viscosity behaviour.

http://www.cet-journal.com

1108

Chem. Eng. Technol. 2009, 32, No. 7, 11071112

B. Braisch et al.

Materials and Methods

2.1

Materials

Stober silica particles with a nominal diameter of 200 nm were

purchased from Blue Helix (UK). The quality of these particles
with regard to their sphericity has previously been confirmed
[8]. The size and monodispersity of the batch obtained for this
work were measured by particle size distribution analysis using
dynamic light scattering (Nanotrac, Microtrac, USA), and
the average particle diameter was 230 nm with a standard
deviation of 7 % (measured in water de-ionised to 18.2 MX).
These values were verified by transmission electron microscopy (TEM) pictures. The silica particles were used as received.
Corn oil was used as oil phase without further treatment.
The aqueous emulsion phase consisted of water de-ionised to
18.2 MX. The solvent conditions of the aqueous phase
were manipulated using hydrochloric acid (32 M), sodium
hydroxide (3 M) and lanthanum(III) chloride heptahydrate
dissolved at 3 mM [8]. All aqueous phases contained sodium
azide at 0.05 wt % to prevent microbial spoilage. The interfacial tension at the o/w interface was 9 mN/m (at 20 C; Wilhelmy pate method, DCAT 21, DataPhysics Instruments, Germany).
For rheological characterisation, the continuous emulsion
phase was thickened with polyethylene glycol (PEG6000) by
direct dissolution of the powder into the emulsion (concentration in the aqueous phase 30 wt %, viscosity increase from
1 mPa.s to 25 mPa.s at 20 C). The droplet size spectra of the
emulsions did not change as a result of PEG addition. It
should be noted that the contact angle of the particles at the
interface as well as the particle-particle interaction potential
may have changed.

2.2

Emulsion Preparation

Initially, the silica particles were dispersed in the aqueous

emulsion phase using a high-shear rotor-stator overhead
device (Ika Yellowline-Disperser, S25KN-18G head) at
10 000 rpm for 5 min. o/w stock emulsions were then prepared by homogenisation of a total sample volume of 200 mL
for 2 min at rotor speeds between 13 000 and 24 000 rpm.
Compositions are given in Tab. 1.

The dispersed-phase volume of the emulsions was adjusted

post-processing by removal or addition of continuous-phase
fluid [8]. The droplet phase of the stock emulsion was allowed
to cream, which was accelerated by mild centrifugation.
Appropriate amounts of continuous phase were removed to
increase the droplet phase volume. To decrease the droplet
phase volume, continuous-phase fluid from the same stock
emulsion was added. The advantage of controlling the phase
volume using the procedure described is that the droplet size
distribution of the emulsions remained constant.

2.3

Droplet Size Distribution

The droplet size distributions were measured using the principle of laser light diffraction (Beckmann-Coulter LS 230,
Mastersizer S; results were independent of the instrument
used). Standard procedures for analysing o/w emulsions using
de-ionised water as solvent were applied and data analysis was
based on the Fraunhofer model.

2.4

Rheology

A rotational rheometer (Bohlin CVOR) fitted with 40-mm serrated parallel plates (1 mm gap height) was used for rheological characterisation of the PEG-thickened emulsions at 20 C.
The shear stress was increased stepwise from 0.01 to 100 Pa,
acquiring 10 logarithmically spaced data points for each decade of shear stress applied (up-curve acquisition). The time
of shear stress application prior to data acquisition was progressively decreased from 120 s at 0.01 Pa to 15 s at 100 Pa,
with a maximum data acquisition time of 10 s at each point.
Above the yield stress region, data corresponded to equilibrium data. Following shear stress increase, it was stepwise decreased using otherwise the same settings (down-curve). The
maximum stress applied was lower for emulsions with an oil
phase volume of 20 % due to their low viscosity (despite thickening). The emulsions contained free silica particles, and the
effect of these free silica particles on the viscosity behaviour
was investigated by analysing the emulsions as prepared and
after decanting off the silica particles that had formed a sediment at the bottom of the storage vial.

Table 1. Characteristics of emulsions (prepared at 24 000 rpm, 2 min) studied rheologically.

Base emulsion
Oil volume fraction

Adjusted emulsion
volume fractions

Aqueous phase composition

Sauter diameter
[lm]

0.2

pH 2; 3 wt %

16.7

0.48

0.2

pH 10; 3 mM LaCl3; 3 wt %

19.5

0.48

0.5

pH 2; 3 wt %

35.6

0.75

0.5

pH 2; 5 wt %

17.3

0.75

Emulsions that were additionally investigated after removal of the particle sediment.

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Results and Discussion

3.1

Emulsion Formation and

Stability

Initial experiments on emulsion formation were based on 0.55 wt % silica particles in an aqueous phase of
pH 2 or pH 10. The minimum particle
concentration for emulsions with 20 %
oil and a Sauter diameter of 5 lm is
0.6 wt %, assuming 74 % surface coverage (theoretical value for monolayer
coverage in tight sphere packing).

http://www.cet-journal.com

Chem. Eng. Technol. 2009, 32, No. 7, 11071112

Emulsions were prepared above minimal particle concentration (3 wt %) to avoid coalescence due to insufficient surface
coverage during processing. Kinetic limitations of particle deposition, however, cannot be overcome by increasing the particle concentration.
The oil phase volume fraction was 0.2 and the rotary speed
of the high-speed mixer was varied from 13 500 to
24 000 rpm. The comminution duration was held constant at
2 min. To form longer-term stable emulsions at pH 10, the
presence of LaCl3 was a requirement, whereas emulsions prepared at pH 2 were also stable in the absence of LaCl3 (no
change in droplet size distributions measured after 1 month).
The silica particles had negative zeta-potentials, which increased to low positive values in the presence of 3 mM LaCl3
(0 to +40 mV depending on pH).
The Sauter diameters of the emulsions rheologically characterised are plotted in Fig. 1. With increasing power input (rotary speed of the overhead mixer), the Sauter diameter decreased as predicted by droplet disruption theory [11]. The
droplets were large compared to those of emulsions stabilised
by small molecular surfactants (by a factor of 10) while the
interfacial tension is only slightly increased (by a factor of 3).
This and a slope of less than 0.4 (see Fig. 1) are indications for
coalescence during emulsification in turbulent flow [11].
It should be noted that, during storage at room temperature,
all emulsions developed a creamed droplet phase and a particle
sediment phase was clearly visible after 2 days (the droplet
size distributions remained unchanged). The droplets and the
particles could easily be redistributed by manual shaking of
the sample container, or gentle stirring of the emulsion using a
spatula. The continuous emulsion phase was clear in case of

Oil-In-Water Emulsions

1109

the emulsions prepared at pH 2 and turbid for the emulsions

prepared at pH 10, suggesting particle flocculation (at pH 10).
This is reflected in the rheological behaviour. The presence of
free particles indicates that the droplet size spectra generated
were kinetically limited. As for surfactant-stabilised emulsions
[12, 13], droplet sizes are not only determined by energy input
but also by droplet stabilisation, which in this case corresponds
to particle deposition kinetics, while emulsion stability is only
limited by particle concentration (surface coverage). The o/w
interface of the stable emulsions was closely packed with a
monolayer of particles, as the freeze fracture scanning electron
microscopy (SEM) image in Fig. 1 (inset) shows. The same
kind of interfacial microstructure has previously been shown
for similar emulsions [8] (consult reference for imaging technique).
Emulsions originally prepared at 20 % oil could reasonably
be concentrated to a 48 % oil. To obtain emulsions with 75 %
oil, an emulsion with an initial oil phase volume of 50 % was
prepared (see Tab. 1). As expected in emulsification processes
with increased coalescence rate [14], the oil droplets were bigger (Tab. 1 shows the Sauter diameters). To achieve smaller
drop diameters the particle concentration was increased to
5 wt %. Tab. 1 shows that this resulted in an emulsion with a
droplet size spectrum close to the emulsion prepared at the
lower oil content (at pH 2).

3.2

Rheology

The rheological behaviour was not affected by the presence of

PEG (being at the same concentration level in all continuous
phases), but by different droplet-droplet or droplet-particle interactions.
Fig. 2 depicts the viscosity curve for emulsions
with an aqueous phase at pH 2 originally prepared
at 20 %. The flow behaviour was independent of
shear history, as indicated by the superposition of
the up-curve and down-curve data. The measurements were highly reproducible. At 20 % oil, the
flow behaviour is Newtonian over a wide shear
stress range, with a slight deviation from this behaviour at low shear stresses. At 48 % oil phase volume, and independent of the presence or absence
of free particles, the emulsion is clearly shear-thinning, indicating flocculation. Non-flocculated
emulsions, the classical surfactant-stabilised type,
rarely show pronounced shear-thinning at volume
fractions below close packing. Removal of the particle sediment at 48 % oil leads to a shift of the
flow curve to lower viscosities.
The rheological profile of emulsions with an
aqueous phase at pH 10 containing LaCl3, originally prepared at 20 % oil, is shown in Fig. 3. Differing from the pH 2 case, this emulsion showed
time dependence at 48 % oil (see Fig. 3a). Also
Figure 1. Sauter diameters of the emulsions containing 20 % oil and 3 % silica
plotted in Fig. 3a are data obtained from repeated
particles prepared during 2 min at different rotary speeds of the overhead mixer.
analysis, i.e., the measurement cycle was re-applied
The lines were added to guide the eye. The inset shows a freeze fracture SEM of
to the emulsion without removal from the rhean emulsion with 50 % oil prepared at pH 2 containing 3 % silica particles. Comometer. Fig. 3b shows results for the same emulminution conditions: 24 000 rpm for 2 min.

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

http://www.cet-journal.com

1110

Chem. Eng. Technol. 2009, 32, No. 7, 11071112

B. Braisch et al.

a)

Figure 2. Viscosity of emulsions prepared at 20 % oil at pH 2

measured upon stepwise shear stress increase (up-curve) and
decrease (down-curve), denoted by solid and open symbols, respectively.

sion system after removal of the particle sediment. The degree

of thixotropy is much less pronounced, indicating that particle
aggregation and not droplet aggregation is the origin of the
thixotropy. The large influence of particle aggregation on the
rheological behaviour of particle-stabilised emulsions has been
reported previously [15]. However, a direct comparison between systems containing or void of free particles has so far
been absent in the literature.
The rheology data indicate that the method applied to render the hydrophilic particles interfacially active has no effect
on the viscosity behaviour of the emulsions containing 20 %
oil. At elevated oil content, however, the emulsions show an
influence of shear history. Also, the reproducibility of the data
for emulsions containing all particles originally added is not as
good as for the other samples. Independent of the presence of
free particles, down-curve data are at a lower level than upcurve data, indicating the disruption of a network formed by
the dispersed phase. Once shear has been applied, this network
appears to be permanently disrupted since data from repetition of the complete measurement cycle on the same sample
(without removal from the rheometer) superimpose on the
down-curve data of the initial measurement cycle (marked triangles versus inverted triangles in Fig. 3). It could, however, be
possible that the network recovers after a period of rest, and
further studies are required to elucidate the true nature of the
thixotropy. The results of a measurement on a new sample lie
somewhat in between, demonstrating the poorer reproducibly
of the rheological data for this emulsion due to the presence of
particles that have not adsorbed at the o/w interface.
Apparent yield behaviour was detected for emulsions with a
dispersed-phase volume below closed packing, which is normally
in the range of 0.650.8 for polydisperse emulsions. This observation suggests flocculation of the system. The extent to which
yield stress behaviour is pronounced appears to be strongly
affected by the formulation in terms of pH and added ions.
The rheological results for emulsions with an aqueous phase
at pH 2 prepared at 50 % oil are shown in Fig. 4. The viscosity

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

b)

Figure 3. Viscosity of emulsions originally prepared at 20 % oil

at pH 10 in the presence of LaCl3 measured upon stepwise
shear stress increase with corresponding down-curves (open
symbols) for the emulsion with 48 % oil (a) and for the emulsion
with 48 % oil after removal of the particle sediment (b).
** in (a) denotes a further up-curve measurement without
change of sample.

is overall slightly lower compared to the emulsions discussed

above, likely to be a result of the larger droplets in this emulsion. As expected, at 75 % oil, the yield behaviour is much
more pronounced. Increase of the particle concentration to
shift the droplet size spectrum close to the spectrum of the
emulsion prepared at 20 % oil resulted in an increase of the
viscosity level of the emulsion prepared at the higher oil content. Indeed, the viscosity level is slightly higher, which may be
caused by differences in the droplet size distribution at the
lower end of the size spectrum. It could also be argued that the
amount of free particles may be larger in the emulsion containing more particles, causing a higher degree of interaction
between the dispersed-phase entities and therefore the detection of higher viscosities. At 75 % oil, this emulsion shows limited ability to flow upon application of the same measurement
protocol. To induce flow, the maximum applied shear stress
was increased to 250 Pa, which was the maximum shear stress

http://www.cet-journal.com

Chem. Eng. Technol. 2009, 32, No. 7, 11071112

Oil-In-Water Emulsions

1111

dependence. The same was observed for

the other emulsion containing 75 % oil.
The differences between the up-curve and
down-curve data for any of the other results shown in Figs. 4 and 5 are insignificant. An exception is the low shear stress
end of the emulsion with 50 % oil and 5 %
particles. It appears that this emulsion system contains a larger amount of free particles causing this behaviour.

Conclusions

Studies on o/w emulsions stabilised with

230 nm hydrophilic silica particles were
carried out. Stabilisation was achieved by
pH adjustment of the aqueous phase, pH 2
and pH 10, whereby at pH 10 the presence
of La3+ ions was necessary to obtain stable
emulsions. As reported previously [8], the
surface of the oil droplets in these emulsions was fully covered by a particle monoFigure 4. Viscosity of emulsions prepared at 50 % oil at pH 2 measured upon stepwise
shear stress increase and decrease, denoted by solid and open symbols, respectively.
layer, whereby stabilisation of these emulData labelled 48 % oil pH 2 relate to the emulsion prepared at 20 % oil at pH 2 and are
sions at pH 2 had not been achieved
included for comparison. The droplet sizes given in the legend are the Sauter diameters
before. The rheological characterisation of
as reported in Tab. 1.
stable emulsions thickened through addition of PEG to the aqueous phase revealed
shear-thinning and apparent yield behaviour at dispersedpossible to apply without the rotating geometry spinning
phase volumes at which this behaviour is not normally obthrough. The results of this measurement are marked by inserved for comparable surfactant-stabilised emulsions. The
verted commas (see Fig. 5). Inducing a significant level of flow
type of stabilisation (pH 2 in the absence of LaCl3, pH 10 in
appears to result in a viscosity behaviour showing shear history

Figure 5. Summary plot of data on emulsions prepared at pH 2 with varying initial oil content (20, 50 %) and particle concentration
(3, 5 %). 48 % oil: 20 %/3 %particles; 50, 75 % oil: 50 %/3 % particles; see legend for the remaining three data sets). Filled symbols: upcurve data; open symbols: down-curve.

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

http://www.cet-journal.com

1112

B. Braisch et al.

the presence of LaCl3) as well as the presence or absence of free

particles affected the rheological response in terms of reproducibility and thixotropy, offering the formulation engineer
routes to adjust the material properties of particle-stabilised
emulsion systems according to requirement.

Acknowledgements
The authors thank M. Kirkland for taking the SEM images and
V. Street for proof reading of the manuscript. B.B. thanks the
Solvay Foundation, Karlsruhe, Germany, for financial support.
The authors have declared no conflict of interest.

References
[1] R. Aveyard, B. P. Binks, J. H. Clint, Adv. Colloid Interface Sci.
2003, 100, 503.
[2] W. Ramsden, Proc. R. Soc. London (18541905) 1903, 72,
156.
[3] S. U. Pickering, J. Chem. Soc. Faraday Trans. 1907, 91, 2001.

2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Chem. Eng. Technol. 2009, 32, No. 7, 11071112

[4] B. P. Binks, S. O. Lumsdon, Langmuir 2000, 16 (23), 8622.

[5] B. P. Binks, J. A. Rodrigues, W. J. Frith, Langmuir 2007, 23
(7), 3626.
[6] W. Wu, R. F. Giese, C. J. Vanoss, Colloids Surf. A Physicochem. Eng. Asp. 1994, 89 (2/3), 241.
[7] B. P. Binks, S. O. Lumsdon, Phys. Chem. Chem. Phys. 1999,
1, 3007.
[8] W. J. Frith, R. Pichot, M. Kirkland, B. Wolf, Ind. Eng. Chem.
Res. 2008, submitted.
[9] B. P. Binks, C. P. Whitby, Colloids Surf. A Physicochem. Eng.
Asp. 2005, 253 (13), 105.
[10] B. Wolf, W. J. Frith, S. Lam, M. Kirkland, J. Rheol. 2007, 51,
465.
[11] P. Walstra, P. E. A. Smulders, in Modern Aspects of Emulsion
Science (Ed: B. P. Binks), Royal Society of Chemistry, Cambridge 1998.
[12] Emulgiertechnik (Ed: H. Schubert), Behrs Verlag, Hamburg,
2005.
[13] H. P. Schuchmann, H. Schuchmann, Lebensmittelverfahrenstechnik, 1st ed., Wiley-VCH, Weinheim 2005.
[14] T. Danner, PhD Thesis, Universitt Karlsruhe (TH) 2001.
[15] P. Thareja, S. Velankar, Rheol. Acta 2008, 47 (2), 189.

http://www.cet-journal.com