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Shear thickening of an emulsion stabilized with

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Shear thickening of an emulsion stabilized with hydrophilic silica particles

Bettina Wolf, Sylvie Lam, Mark Kirkland, and William J. Frith
Citation: J. Rheol. 51, 465 (2007); doi: 10.1122/1.2714642
View online: http://dx.doi.org/10.1122/1.2714642
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Shear thickening of an emulsion stabilized with

hydrophilic silica particles
Bettina Wolfa) and Sylvie Lam
Unilever Corporate Research, Colworth Science Park,
Bedford MK44 1LQ, United Kingdom
Mark Kirkland
Measurement Sciences, Colworth Science Park,
Bedford, MK44 ILQ, United Kingdom
William J. Frith
Unilever Corporate Research, Colworth Science Park,
Bedford MK44 1LQ, United Kingdom
(Received 21 September 2006; final revision received 6 February 2007
Synopsis
The flow behavior of particle stabilized oil-in-water emulsions with different dispersed volume
fractions was analyzed in steady shear on a rotational rheometer employing a coaxial cylinder
geometry. The dispersed phase of the emulsion was a mixture of equal volumes of a polar oil,
isopropyl myristate, and a nonpolar oil, dodecane. The continuous phase was an aqueous
suspension of hydrophilic colloidal silica particles of 8 nm diameter with the pH adjusted to pH2
in order to stabilize the emulsion Binks and Whitby, Colloids Surf., A 253, 105115 1995.
Droplet diameters were of the order of a few micrometers, and droplet surfaces apparently show
dense particle coverage. We show that the markedly different interfacial structure in particle
stabilized emulsions when compared to surfactant stabilized emulsions is reflected in the
rheological behavior. To illustrate these differences, the rheological behavior of a comparable
surfactant stabilized emulsion with the particles in the aqueous phase replaced by Tween 20, was
also investigated. The rheological characterization revealed a domain of shear thickening in the
particle stabilized emulsions at high droplet phase volumes that is not observed for the classical
surfactant stabilized emulsions. 2007 The Society of Rheology. DOI: 10.1122/1.2714642
I. INTRODUCTION
Emulsions are dispersions of deformable droplets normally stabilized by surfaceactive species such as surfactant molecules, amphiphilic polymers or proteins. Their
rheological behavior is typically shear thinning where, depending on the phase volume of
the internal droplet phase and the material properties of the continuous phase, a low shear
Author to whom correspondence should be addressed. Present address: Division of Food Sciences, University
of Nottingham, Sutton Bonington Campus, Loughborough LE12 5RD U.K.; electronic mail:
bettina.wolf@nottingham.ac.uk
2007 by The Society of Rheology, Inc.

J. Rheol. 513, 465-478 May/June 2007
0148-6055/2007/513/465/14/$27.00
465
466
WOLF et al.
viscosity plateau or yield behavior and, occasionally, a high shear viscosity plateau is
observed Barnes 1994; Tadros 1994. Reports of classical emulsions showing shear
thickening, or dilatancy, are scarce. In fact, there appears to be only the work by Otsubo
and Prudhomme 1994 who studied the rheology of oil-in-water emulsions. For their
emulsions, Otsubo and Prudhome varied the interfacial tension between 0.9 and
5.9 mN m1 by using different oils and surfactants. The oils were either a mixture of
tritolyl phosphate and dioctyl phthalate which was a close density match for the aqueous
phase, or paraffin oil. The surfactants were either Alipal CD-128 or Triton X-100, each
20% in the aqueous phase. Shear thickening was only observed for the one emulsion
system that was comprised of paraffin oil, which incidentally had the highest interfacial
tension of the emulsions studied, and the largest droplet size. They observed that at oil
volume fractions of 0.20.53 the viscosity initially decreased, passing through a minimum which was followed by an increasing viscosity as the shear rate increased. At the
higher volume fractions, for which this behavior was observed, a viscosity plateau was
reached upon further increase of the shear rate. The authors tentatively ascribed the
shear-thickening behavior to interfacial elasticity causing an inhibition of fluid circulation
within the drops, and hence increasing the energy dissipation within the emulsion as a
whole. The observations by Otsubo and Prudhomme 1994, however, are questioned by
Pal 1996 who, for emulsions, reported the effect of using certain measurement geometries in a rotational rheometer on the apparent rheological behavior. Pal 1996 demonstrated that creaming and sedimentation of the droplet phase of an emulsion measured in
a cone-and-plate geometry, or a plate-and-plate geometry can lead to the detection of
apparent shear-thickening and time-dependent effects which are not present when the
same sample is measured in a concentric cylinder geometry. The work by Otsubo and
Prudhomme 1994 is quoted by Pal 1996 as an example from the published literature
in which reports of shear thickening are based on rheological characterization in a coneand-plate geometry. The recommendation was to employ coaxial cylinder geometries to
ensure a negligible effect of sedimentation or creaming on the rheological data. It is
worth noting that the only system in which Otsubo and Prudhomme observed the shearthickening behavior was also the only system in which the oil phase was significantly less
dense than the aqueous phase, making creaming more likely.
As introduced in this paper, it appears, however, that emulsions can be designed such
that they exhibit true shear thickening when stabilizing the emulsion droplets with solid
particles. With reference to the above cited paper by Pal 1996, all rheological measurements reported here were conducted using coaxial cylinder geometries. Evidence of such
behavior, i.e., shear thickening or true suspension-like rheological behavior, has not been
reported previously though there are a small number of recent publications discussing
rheological data for well characterized particle stabilized emulsions Binks et al. 2005;
Arditty et al. 2005. Binks et al. 2005 studied the rheological behavior of water-in-oil
emulsions prepared from dispersions of hydrophobic clay particles in oils. Depending on
the type of oil the continuous phase fluid used, the emulsions microstructure resembled
a classical emulsion, that may or may not flocculate, or showed a network in the oil phase
continuous phase formed by the clay particles to which the droplet surfaces are largely
connected. In the former case, a rheological response, including steady shear and oscillatory shear data, that was classical for emulsions is reported. In the latter case, the
rheological behavior is more complicated and appears to be determined by the network
structure in the continuous phase in which the droplets are embedded. Rheological data
on particle stabilized emulsions have also been reported by Arditty et al. 2005. They
performed oscillatory measurements in the linear viscoelastic regime, and while the data
cannot be compared to those reported here, obtained under steady flow conditions, we
PICKERING EMULSIONS
467
quote them since they are one of the scarce sets of rheological data published for particle
stabilized emulsion. The emulsions studied by Arditty et al. 2005 were strongly flocculated and the surface coverage of the droplets with particles is reported to be below the
value expected for a densely packed layer of adsorbed particles. This is important with
regards to the interpretation of the rheological data. The authors state that the results are
reminiscent of those classically obtained for surfactant-stabilized emulsions. The presence of classical emulsion behavior is underlined by the fact that the authors succeeded in
deforming and ultimately rupturing the droplets in an emulsion initially prepared with an
average droplet diameter of 8 m by applying sufficiently high shear stresses in the
cone-and-plate gap of a rheometer. This indicates that the droplets were deformable, and,
hence, the overall system should behave like an emulsion. Taking into consideration the
fact that the authors report the surface coverage of the droplets with particles is below the
value expected for a densely packed layer, the occurrence of droplet deformation is not
too surprising. In contrast to these findings, we report on a particle stabilized emulsion
showing suspension-like rheological behavior in steady shear which is hypothesized to be
a result of dense surface coverage of the droplets with adsorbed particles. To emphasize
the unusualness of the flow behavior found here for an emulsion system, albeit a particle
stabilized emulsion, data for an equivalent surfactant stabilized emulsion prepared from
the same fluid phases are also presented.
II. EXPERIMENT
A. Materials
Particle stabilized oil-in-water emulsions were prepared from a mixture of equal volumes of isopropyl myristate IPM, 98%, Sigma Aldrich, UK and dodecane 98%, Sigma
Aldrich, UK, de-ionized water, and alkaline dispersions of silica particles Ludox SM30
ex Grace Davison, UK. All materials were used as supplied.
The pH of the aqueous phase of the emulsions containing the silica particles at
1 % w / w was adjusted to pH2 using hydrochloric acid. As reported previously by Binks
and Whitby 2005, emulsification at neutral or alkaline pH did not yield a stable emulsion. Also, the choice of mixing a nonpolar oil, dodecane, with a polar oil, IPM, is based
on the aforementioned publication. However, heptane was replaced with dodecane to
circumvent changes in the oil composition due to the volatility of heptane. The viscosity
of the oil mixture as used was 4 mPa s at 20 C.
The silica particles were used as received. Dispersions of Ludox SM30 are of pH10,
and sodium is used as the stabilizing counter ion. As given on the material data sheet, the
specific surface area of the particles was 350 m2 g1. Particle size distributions of the
Ludox particles were measured at a particle concentration of 1%w/w in aqueous suspension at pH10, pH7 and pH2 using dynamic light scattering Zetasizer Nano ex Malvern
Instruments; see Fig. 1 for the results. The corresponding particle diameters at the peak
of the distributions were 7.8, 11.1, and 14.2 nm at pH10, pH7, and pH2, respectively.
Particles were also imaged using transmission electron microscopy TEM; see Fig. 2,
whereby the sample for the imaging was taken straight from the bulk dispersion at pH10.
The increase in measured particle diameter, although not large, with decreasing pH may
indicate particle aggregation, or weak flocculation, which was previously concluded to be
a requirement for the preparation of stable particle stabilized emulsions Binks 2002.
From the TEM micrographs see Fig. 2, it appears that the primary silica particles are
mainly spherical in shape, and relatively narrow in size distribution with a minor fraction
of the particles aggregated or fused.
468
WOLF et al.
FIG. 1. Particle size distribution for silica particles Ludox SM30 as determined by dynamic light scattering.
Surfactant stabilized oil-in-water emulsions were prepared from the same mixture of
equal volumes of isopropyl myristate and dodecane as used for the particle stabilized
emulsion, and de-ionized water containing the nonionic surfactant Tween 20 Sigma
Aldrich, UK, used as supplied at 1%w/w. The choice of Tween 20 as surfactant was
solely based on the fact that it is known to be a good surfactant for oil-in-water emulsions.
B. Methods
1. Emulsion preparation and characterization
The particle stabilized emulsion was prepared at 20 % v / v oil by direct emulsification
of the oil phase and the aqueous phase in batches of 200 ml using a high speed rotary
mixer Silverson L4R, 8000 rpm for 5 min.
FIG. 2. TEM micrographs of silica particles Ludox SM30, samples taken from dispersion at pH10, scale bar
equals 100 nm on the left, and 50 nm on the right.
PICKERING EMULSIONS
469
The surfactant stabilized emulsion was prepared following the same protocol omitting
the acidification step. The same oil phase volume, V = 0.2.
The emulsions were visually inspected using a standard optical light microscope
Polyvar. Droplet size distributions were determined by static light scattering using a
Malvern Instruments Mastersizer 2000. A few drops of the emulsion were added to
de-ionized water in the small sample dispersion unit, to achieve an appropriate scattering
intensity. The results were then obtained using Fraunhoffer analysis. Care was taken to
ensure that the use of Fraunhoffer or Mie analysis using the measured RI of the oil
phase did not make any significant difference to the size distributions obtained. Additionally, values characterizing the droplet size distributions, the volume based values
d10,3, d50,3 and d90,3, as well as the volume weighted mean diameter, d4,3, and the surface
weighted mean diameter, d3,2, are provided in the results section below. The latter was
used to estimate the surface coverage of the droplets with particles.
Emulsions with an oil phase volume of less than 20% or more than 20% were prepared
from the originally processed emulsion by diluting with continuous phase fluid and concentrating via creaming, respectively. This procedure of preparing emulsions with a range
of oil phase volumes was chosen to keep the droplet size distribution in emulsions with
different oil phase volumes constant. Preparation of emulsions at different oil phase
volumes in the homogenizer would almost certainly have led to a variation in droplet size
distribution and interfacial characteristics. The procedure was as follows: The droplet
phase of the emulsions was allowed to cream followed by removal, or addition of the
appropriate amount of continuous phase fluid. The creaming process was accelerated by
centrifugation 90 min at 300 g. It was ensured that this treatment in the centrifuge did
not influence the properties of the emulsion.
2. Structure of the oil-water interface
The structure of the particle layers adsorbed at the oil-water interface was imaged by
cryogenic scanning electron microscopy JEOL 6301F field emission scanning electron
microscope with a Gatan alto2500 low temperature preparation system fitted. This technique has been applied previously for the visualization of the interfacial structure in
particle stabilized emulsions as reported by Binks and Kirkland 2002. There, however,
the particle diameters were large compared to the diameters of the particles used in this
study, and the experimental protocol was adapted as outlined below.
A drop of emulsion was frozen in a nitrogen slush and then placed in the preparation
chamber of the cryo scanning electron microscope SEM held at 90 C. The sample
was fractured and etched for 75 s followed by cooling down to 110 C in order to only
remove part of the water. At 110 C, where the sublimation was stopped, the exposed
surface area of the emulsion was coated with a thin layer 2 nm of a mixture of platinum
and palladium. The sample was then transferred onto the cold stage of the microscope
and imaged at 150 C.
3. Rheological measurements
The rheological characterization of the emulsions was conducted in a strain-rate controlled rotational rheometer ARES ex Rheometrics Scientific now available from TA
Instruments, UK. A concentric cylinder geometry with an inner diameter of 32 mm and
an outer diameter of 34 mm was used. The length of the measurement gap was 33 mm.
Shear viscosities were measured by applying a constant shear rate for 30 s followed by
application of the same shear rate in the opposite shear direction. The data recorded
correspond to an average of the last 10 s of each measurement direction. The applied
470
WOLF et al.
FIG. 3. Particle size distribution for particle stabilized emulsion left hand side and surfactant stabilized
emulsion right hand side.
shear rate was increased, and 5 measurement points per shear rate decade were recorded.
Samples showing an apparent yield stress see Results section were also analyzed in a
stress controlled rotational rheometer DSR ex Rheometrics Scientific, UK using a concentric cylinder geometry of similar dimensions. Here, each shear stress was applied for
180 s, and 5 measurement points were applied per shear stress decade. All measurements
were conducted at 20 C. There was no indication of slip in any of the results obtained.
Also, the shear history did not influence the results established by repeating measurements without changing the sample. Viscosities reported in the results section can be
assumed to be steady state viscosity values with the exception of the data that were
recorded for emulsions showing apparent yield stress behavior. Here, it might be expected that data points in the region of the apparent yield stress will show more time
dependence, and hence not represent a true steady state.
III. RESULTS
A. Bulk microstructure
In Fig. 3, the graph on the left hand side shows the droplet size distribution for the
particle stabilized emulsion as prepared at 20 % v / v oil. Also plotted is the droplet size
distribution for a second batch of base emulsion to demonstrate the reproducibility of the
emulsion preparation. The result for the surfactant stabilized emulsion as prepared at
20 % v / v oil is shown in the second graph in Fig. 3, and the values for characteristic
parameters of the droplet size distribution are provided in Table I. The disperse structure
of the two emulsions compare well, justifying a comparison of their rheological behavior.
For the particle stabilized emulsion, based on the surface weighted mean diameter,
d3,2, it was estimated that per 100 ml emulsion the total available surface area is 37.5 m2
TABLE I. Characteristic parameters of the droplet size distribution.
Sample
d10,3
m
d50,3
m
d90,3
m
d4,3
m
d3,2
m
Particle stabilized batch 1

Particle stabilized batch 2
Surfactant stabilized
2.0
1.9
1.5
3.6
3.4
2.8
6.3
6.0
5.3
3.9
3.7
3.1
3.2
3.1
2.5
PICKERING EMULSIONS
471
compared to a total cross sectional area of the silica particles present of 87.5 m2 calculated using the specific surface area of the Ludox particles as provided by the manufacturer and ignoring the fact that the contact angle at the interface is not 90 which introduces only a small error. Hence, there are more particles available than needed to fully
cover the total surface area of the droplets, in fact there are sufficient particles to fully
cover droplets of half the size with a monolayer. In the surfactant stabilized emulsions, it
is also true that there is a large excess of surfactant, and that smaller droplets could be
formed and fully coated with surfactant, while still maintaining a concentration in solution above the CMC. Hence, in these two emulsions particle and surfactant stabilized it
is likely that the droplet size is determined by the process conditions in the homogenizer,
rather than being limited by the available surfactant or particle concentrations. The
breakup process in the homogenizer is determined to a first approximation by two material parameters; namely the viscosity ratio which is the same in both emulsions and the
interfacial tension which is similar. Hence, it is not surprising that the two emulsion
types have similar size distributions, indeed, the surfactant stabilized emulsion drops are
slightly smaller, which probably arises from them having a somewhat lower surface
tension.
B. Interfacial structure of the particle stabilized emulsion
The SEM micrographs depicted in Fig. 4 appear to demonstrate that the droplet interface is close packed with particles. This is particularly evident from the bottom micrograph showing what appears to be a particle shell on the surface of a droplet fractured by
the sample preparation routine. Also visible are clusters of particles on the outside surface
of the shell. Although the resolution of the image is not sufficient to image individual
particles, it seems clear that the droplets are coated with a dense layer which is likely
composed of the Ludox particles.
C. Flow behavior in steady shear
1. Particle stabilized emulsion
The rheological behavior of the particle stabilized emulsions as measured in steady
shear is plotted in Fig. 5 as the relative viscosity
r =
s
m
versus the applied shear stress, s: viscosity of the suspension/emulsion; m: viscosity

of the suspension medium/continuous phase fluid. When calculating r, the viscosity of
the suspension medium was taken to be equal to the viscosity of water, 1 mPa s measured values for the aqueous emulsion phase prior to emulsification did not significantly
deviate from 1 mPa s. Each curve corresponds to a different oil phase volume as given
in the legend.
For a dispersed phase volume of 0.2, and below, the rheological behavior of the
emulsions is Newtonian. With increasing dispersed phase volume, however, shearthickening as well as shear-thinning regions are present in each of the viscosity curves.
This behavior is most pronounced in the emulsions with an oil phase volume of 0.5 and
0.55. For an even higher internal phase volume, see data for V = 0.6 in Fig. 5, the initial
shear-thinning region is not resolved. It is assumed that the increase in viscosity measured for shear stresses of up to roughly 10 Pa corresponds to the shear-thickening region
as detected for the emulsions with slightly smaller values of V. Further rheological
472
WOLF et al.
FIG. 4. SEM micrographs of emulsion stabilized with 1 % w / w particles with increasing magnification from top
to bottom.
measurements, also in oscillatory shear, are required to confirm this hypothesis. The
emulsion with an internal phase volume of 0.7 was characterized in a stress controlled
rheometer since this emulsion apparently exhibited yield stress-like behavior. In order to
relate the results of the two instruments, the emulsion with V = 0.6 was also analyzed in
the stress controlled rheometer; see Fig. 6. For comparison, the previous results for the
PICKERING EMULSIONS
473
FIG. 5. Relative viscosity measured for particle stabilized emulsions at different dispersed phase volumes, V;
see legend.
emulsion with V = 0.6 as measured in the strain-rate controlled instrument are re-plotted.
The sharp decline in viscosity found for the emulsion with V = 0.7 is indicative of yield
behavior.
Figure 7 illustrates the concentration dependence of the relative viscosity by plotting
the viscosity at two shear stresses 0.2 and 2 Pa as a function of the oil volume fraction.
These data were also fitted with the Krieger-Dougherty equation Krieger and Dougherty
1959; Krieger 1972
r = 1
V
V,max
V,max
for the relative viscosity of hard sphere suspensions V,max: maximum dispersed phase
volume, : intrinsic viscosity, = 2.5 for a hard sphere suspension, or an emulsion
with nondeforming droplets; see Fig. 7 for the fits at two different shear stresses. For
FIG. 6. Relative viscosity for particle stabilized emulsions with the two highest oil phase volumes, V; see
legend. Open symbols: measured with the stress controlled rheometer. Filled symbols: measured with strain-rate
controlled rheometer, data re-plotted from above.
474
WOLF et al.
FIG. 7. Krieger-Dougherty fit dashed line for data symbols at two different shear stresses.
both sets of data, the fitted value for was 3.3, and for V,max the results were 0.63 and
0.61 for the data set at 0.2 and 2 Pa, respectively. Values for 2.5 are found for
particle shapes other than spheres Barnes et al. 1989 or for perfect spheres featuring
particle/particle or particle/solvent interactions which form aggregates Yang et al.
2001. In the present sample, aggregation can in principle occur between droplets,
between particles, and between droplets and particles, so the value of 3.3 for is not
unreasonable.
The shear-thickening effect observed here is not as dramatic as sometimes found for
hard sphere suspensions, or even suspensions of deformable microspheres Otsubo
2001; Frith et al. 1996; Frith et al. 1998; Frith and Lips 1995. Despite only having
a limited set of data available, we have calculated the Peclet number
Pec =
a3 cm
kT
for the onset of shear thickening for V = 0.5 and 0.55 where c = 1.5 and 10 s1, respectively a: droplet radius, a = d3,2 / 2; c: critical shear rate for the onset of shear-thickening;
k: Boltzman constant; T: absolute temperature. For clarity, c was taken as the shear rate
corresponding to the first measured increased viscosity following the initial shearthinning region. It follows that Pec 15 and 8 for V = 0.5 and 0.55 which is in the same
order of magnitude as reported for suspensions of sterically stabilized particles Frith et
al. 1996 apparently substantiating our hypothesis that the particle stabilized emulsions
investigated here behave rheologically like suspensions. It is interesting to note, however,
that the increasing trend in Pec with V is the opposite to that observed in Frith et al.
1996. Also, the Pec values obtained here are much lower than those observed for
suspensions of starch granules and microgel particles Frith et al. 1998.
As mentioned above, the shear-thickening region is followed by a shear-thinning
domain. Attempting to interpret this finding locally on the scale of the drops, one might
assume that the observed decrease in viscosity for further increases in shear stresses
originates from deformation of the emulsion droplets. However, since we argue that the
emulsion droplets behave like rigid particles in suspensions, it appears unlikely that
droplet deformation is the origin of the observed effect. This is also demonstrated by the
following estimation, assuming that droplet deformation is not inhibited by the presence
of the particles at the interface. The deformation of individual drops can be estimated
using the classical relation by Taylor for droplet deformation in shear flow Taylor
1932
PICKERING EMULSIONS
475
d
+ 16
a
m
D=
d
16
+1
m
19
where is the interfacial tension and d: viscosity of the droplet phase fluid. The deformation parameter is defined as
D=
LB
L+B
assuming that the deformed droplet is of ellipsoidal shape L: dimension of the long axis
of the deformed droplet; B: dimension of the short axis of the deformed droplet. The
static interfacial tension between the two emulsion phases IPM/dodecane and particle
laden aqueous phase was 23 mN m1 as determined with the pendant drop technique.
The shear stress, , acting at the interface of the droplets at the beginning of the second
shear-thinning region is probably higher than the bulk shear stress since the droplets are
thought to form a transient network during shear thickening. In simulations of shearthickening polymer coated spheres, Melrose and Ball 2004b found that the hydrodynamic forces between close neighboring spheres were exponentially distributed. The
characteristic forces in the contact network dominating the thickening response scaled as
the shear stress times the diameter of the spheres squared with a pre-factor varying
between 2 and 3 up the thickening curve. With = 10 Pa, corresponding to the shear stress
at which shear-thinning postshear thickening sets in, and taking into account the cited
work by Melrose and Ball 2004b, a value of D of the order of 103 follows. This
indicates that the droplets hardly deform, hence, the origin of the second shear-thinning
region does not appear to arise from droplet deformation. The effect of a system flipping
from thickening back to thinning is also seen in polymer coated hard sphere simulations
Melrose and Ball 2004a. It is a subtle effect for which Melrose and Ball 2004a offer
an explanation based on the origin of the preceding shear-thickening region. Thickening
occurs when the shear time, which is equal to the inverse shear rate, is shorter than the
relaxation time of close particle approaches. Consequently, contacts cannot relax and
networks build up. As one moves up the shear-thickening curve to ever higher shear
stresses, the particles get ever closer in their approach, and, if the conservative spring
forces stiffen up at very close approach, the relaxation time of the contact can because
fast again, and one drops out of the thickening region. However, this can only be a
hypothesis with respect to the emulsions investigated here, since we have no knowledge
of the detailed particle interactions.
2. Comparison to surfactant stabilized emulsion
As mentioned in the Introduction, we compare the behavior of the particle stabilized

emulsion system to that of a conventional surfactant stabilized emulsion system. Figure
8 shows the relative viscosity as a function of shear stress for the surfactant stabilized
emulsions. The emulsions display near Newtonian flow behavior for oil phase volumes
up to 0.5. At an oil phase volume of 0.6, shear thinning is observed. To emphasize the
different behavior of the particle stabilized emulsions, the data for three different phase
volumes were re-plotted in Fig. 9 together with the corresponding data of the particle
stabilized emulsion. Whereas the viscosity behavior of the two emulsion types is nearly
identical for V = 0.2, differences in behavior at elevated droplet phase volume are clearly
evident. The data were also fitted with the Krieger-Dougherty relation see Fig. 10 and
476
WOLF et al.
FIG. 8. Relative viscosity measured for surfactant stabilized emulsions at different dispersed phase volumes,
V; see legend.
the fitted model parameters were = 2.5 and V,max = 0.67 indicating that the droplets in
this emulsion system follow the Einstein relation, and that they show no sign of
aggregation/flocculation. The latter is confirmed by the absence of shear thickening compared to the particle stabilized emulsions at a volume fraction of 0.6.
IV. CONCLUSIONS
The rheological behavior of particle stabilized oil-in-water emulsions with an average
droplet size of a few microns and interfacial stabilization by nanometer sized silica
particles effected by reducing the pH to pH2, and using an oil phase with a polar component, shows a domain of slight shear thickening for elevated droplet phase volumes.
The shear-thickening region is preceded and followed by a shear-thinning domain. The
presence of shear thickening indicates that the emulsion system behaves rheologically
like a suspension, though it is characterized by a slow increase in viscosity with increasing shear rate/stress compared to sharp increases reported for other types of suspensions
FIG. 9. Relative viscosity. Open symbols: particle stabilized emulsions. Filled symbols: surfactant stabilized
emulsions.
PICKERING EMULSIONS
477
FIG. 10. Krieger-Dougherty fit dashed line for data symbols.
Otsubo 2001; Frith et al. 1996; Frith and Lips 1995. The second shear-thinning
domain is likely not to originate from deformation of the individual emulsion droplets,
but might be the result of a competition between shearing time and relaxation time of
approaching droplets/particles with the latter becoming fast compared to the former at the
highest shear rates. While this study is only a first step towards understanding the
microstructure-rheology relationships for particle stabilized emulsions, it demonstrates a
novel material behavior in terms of being observed for an emulsion. Further rheological
characterization, including oscillatory shear measurements and creep tests, combined
with flow visualization and an attempt to quantify particle-particle interactions, are required to build a more complete picture of the material behavior of particle stabilized
emulsions.
ACKNOWLEDGMENTS
The authors would like to thank D. A. Adams, D. B. Farrer, J. R. Melrose, S. Furzeland, D. Rossetti, and T. Weaver for their input in the form of valuable discussions or
experimental support. J. R. Melrose in particular is acknowledged for discussing the
onset of the second shear-thinning region with us. Grace Davison U.K. is thanked for
providing the particle suspension.
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Shear thickening of an emulsion stabilized with

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Shear thickening of an emulsion stabilized with hydrophilic silica particles

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Shear thickening of an emulsion stabilized with

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TABLE I. Characteristic parameters of the droplet size distribution.

Particle stabilized batch 1

versus the applied shear stress, s: viscosity of the suspension/emulsion; m: viscosity

As mentioned in the Introduction, we compare the behavior of the particle stabilized

FIG. 10. Krieger-Dougherty fit dashed line for data symbols.

hydrophobic bentonite particles, Langmuir 21, 53075316 2005.

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