Fourier Transform Rheology as a universal non-linear mechanical characterization

of droplet size and interfacial tension of dilute monodisperse emulsions

Kathrin Reinheimer
a
, Massimiliano Grosso
b
, Manfred Wilhelm
a,
a
Karlsruher Institut fr Technologie (KIT), Technische Chemie und Polymerchemie, Engesserstr. 18, D-76131 Karlsruhe, Germany
b
Universit degli Studi di Cagliari, Dipartimento di Ingegneria Chimica e Materiali, Piazza dArmi, I-09123 Cagliari, Italy
a r t i c l e i n f o
Article history:
Received 24 January 2011
Accepted 2 May 2011
Available online 9 May 2011
Keywords:
Fourier Transform Rheology
Emulsion
Ellipsoidal model
Droplet size
Interfacial tension
a b s t r a c t
A new protocol to gain interfacial tension and droplet size of dilute monodisperse emulsions from Fourier
Transform Rheology (FTR), is proposed. Specically, a universal dimensionless quantity E was found at
small strain amplitudes to correlate with the droplet size of the emulsion where E is inversely related
to the square of the capillary number Ca and directly proportional to the relative intensities of the fth
and third harmonics, I
5
/I
3
. The limiting value E
0
at small strain deformations can be used as a universal
parameter to calculate different emulsion properties. Different morphological constitutive models for
emulsions were used to establish the universality of the parameter E
0
. Preliminary analysis on experi-
mental data conrms the validity of this approach for the characterization of emulsion properties, includ-
ing the estimation of interfacial tension and droplet radius.
2011 Elsevier Inc. All rights reserved.
1. Introduction
Emulsions (and blends in general) are a class of materials where
two or more uids or viscous constituents are blended together to
create a new composite material. Blends can be broadly divided
into three categories: miscible, partially miscible and immiscible
blends where immiscible blends are by far the most common
group and are ubiquitous in the polymer, food processing, pharma-
cology and cosmetics industries e.g. [15] to name prominent
examples. For dilute emulsions, the typical microstructure of an
immiscible blend at rest consists of spherical droplets immersed
in a continuous matrix. As the size and size distribution of these
globular domains strongly affect both the processing and the
mechanical properties of the nal products, signicant efforts were
made in the last decades to quantitatively measure and control the
morphology of blends using non-invasive measurement tech-
niques such as direct optical microscopy, light scattering and rhe-
ological methods [69]. For rheological experiments the interest
has been primarily focused on establishing protocols to determine
the morphological properties of emulsions from rheological mea-
surements (for a review on this topic see e.g. [5,1013] and the ref-
erences therein). It is important to note that these experiments
typically used either dynamic Small Amplitude Oscillatory Shear
(SAOS) ows or steady shear ows and analyzed the mechanical
linear or steady state response, e.g. G
0
(x), G
00
(x) or g _ c.
Most rheological models of dilute emulsions are based on ellip-
soidal deformation models where the morphology of the included
phase is assumed to be globular and a single droplet is modeled as
an ellipsoid under deformation. When dealing with neutrally-
buoyant Newtonian droplets dispersed in a Newtonian uid at
low Reynolds numbers, the relevant physical parameters under
periodic shear ow conditions include the external uid viscosity
g
m
, the droplet viscosity g
d
, the interfacial tension C, the radius
of the undistorted spherical droplet R and the maximum shear rate
of the macroscopic ow _ c
max
c
0
x
1
, where x
1
/2p is the excitation
frequency and c
0
is the strain amplitude. Two dimensionless num-
bers are dened using these quantities, the capillary number
Ca g
m
_ c R=C and the viscosity ratio k g
d
=g
m
. The capillary
number describes the relative importance of viscous and interfacial
forces which directly affect the degree of droplet deformation un-
der shear as the interfacial tension resists the applied shear stress
to preserve the original droplet shape.
The fact that there is a clear connection between the morphol-
ogy of the emulsions (i.e. the shape of the droplets and their orien-
tation in ow) and their rheological behavior has been previously
established [1622]. For example, solving the equations of motion
for the single droplet problem under shear ow leads to a very
accurate prediction. There are also numerical simulations based
on the boundary element technique [14,15] which also give very
accurate answers, but are unfortunately very time consuming
and require signicant computational resources. Several analytical
models for droplet deformation have been proposed in the litera-
ture as an adequate and simple way to describe droplet dynamics
under generic ow conditions [1620]. One particularly effective
0021-9797/$ - see front matter 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.05.002

Corresponding author. Fax: +49 721 608 43153.

E-mail address: Manfred.Wilhelm@kit.edu (M. Wilhelm).
Journal of Colloid and Interface Science 360 (2011) 818825
Contents lists available at ScienceDirect
Journal of Colloid and Interface Science
www. el sevi er . com/ l ocat e/ j ci s
phenomenological model introduced by Maffettone and Minale
[16], hereafter referred to as the MM model, was proven to give
quantitative agreement with experimental results up to Ca values
slightly larger than unity [21]. The MM model is also a valuable
tool to infer emulsion properties such as the average droplet radius
of the emulsion under these conditions [22].
For the situation where Small Amplitude Oscillatory Shear
(SAOS) is applied, Palierne proposed a mathematical solution for
the deformation and orientation of liquid droplets in ow that is
suitable for the linear range of periodic oscillations [7,2325]. In
these studies, the dependence of the viscoelastic properties of
emulsions on parameters such as matrix viscosity, interfacial ten-
sion and the radius of the systemand its oscillation frequency were
investigated in detail. The Palierne model led to a robust procedure
that could relate the linear viscoelastic properties of polymer
blends to their chemicalphysical properties. For example, the
model could estimate the volume-average droplet radius of a blend
[26] or, alternatively, its interfacial tension [2729]. The Palierne
model has been subsequently extended to estimate a nite volume
fraction [7,8], to calculate a droplet size distribution instead of an
averaged mean value [30] and to include the effect of surfactants
on the interfacial tension and the droplet deformation [31]. The
impact of the surfactant concentration at the interface on the
resulting droplet deformation is of great interest, for example, in
food science applications [32]. The Palierne model can also be ex-
tended to predict the dynamic viscoelastic behavior of multiple
emulsions [33].
In general, most of the models mentioned above are valid only
in the linear regime, meaning that a Small Amplitude Oscillatory
Shear is applied to the sample under investigation and G
0
(x),
G
00
(x) or g _ c are analyzed. However, in this work, the focus is on
extending the characterization of emulsions into the non-linear re-
gime using Large Amplitude Oscillatory Shear (LAOS) ow instead.
In the literature, this type of analysis is often referred to as Fourier
Transform Rheology (FTR) [34] because the stress response is usu-
ally analyzed in the Fourier domain. FTR is useful because it con-
verts the measured stress data in the time domain into a
frequency dependent spectrum that can detect even very weak
nonlinearities in the stress response. In addition, both the intensi-
ties and phases of the higher harmonics in the power spectrum
provide valuable information about the sample being evaluated.
FT-Rheology methodology has been applied to many types of com-
plex uids and can, for example, distinguish between linear and
branched polymers [3537] and infer the droplet morphologies
in polymer blends [38,39]. The importance of FT-Rheology for the
characterization of dispersions of colloidal particles is shown in a
recent study [40] where the non-linear standard steady shear
experiments cannot distinguish between two different aqueous
polymeric dispersions, but differences between these samples are
clearly seen in the nonlinear oscillatory experiments.
The purpose of this work is to establish for emulsions a new
non-linear mechanical coefcient, E, where E is proportional to
the ratio of the 5th harmonic intensity to the 3rd harmonic inten-
sity scaled by c
2
0
respectively Ca
2
. This proposed E coefcient quan-
ties the nonlinearities arising from the interfacial stress
contribution, which is, after all, mainly responsible for the non-
Newtonian behavior of the emulsions under investigation.
In this paper, the mathematical model used (Section 2.1) and
the main principles of FT-Rheology (Section 2.2) are presented in
the Methods section. Afterwards, Sections 2.32.6 summarize the
denition and development of E as a function of the capillary num-
ber Ca and the viscosity ratio between the two emulsion compo-
nents k g
d
=g
m
: The experimental setup used to validate this
model is then introduced (Section 2.7). Results are given in Section
3 starting with a description of how the highest achieved values of
E can be used to calculate the characteristic properties of an emul-
sion or blend. In the conclusion, the effectiveness of this new emul-
sion quantity, E, as a novel approach to characterize emulsions and
its experimental validation are summarized.
2. Theory and experiment
2.1. The model
Since FT-Rheology will be used in this study for determining
emulsion characteristics such as the droplet size (or, alternatively,
its interfacial tension) the LAOS experiments in FTR analysis must
be compared with the relevant theoretical predictions.
To make this comparison, a theoretical model based on a dilute
system consisting of buoyancy free droplets of a single Newtonian
liquid dispersed in a different, but also Newtonian, matrix is con-
sidered. The deformation forces acting on the isolated droplets un-
der oscillatory shear are balanced by the restoring effects caused
by the interfacial tension. In this scenario, break-up of the droplets
is excluded due to the high viscosity ratio and coalescence can also
be neglected because of the assumption of diluteness. As a conse-
quence of this assumption, the droplet volume distribution re-
mains unchanged under shear ow and is not time dependent.
The measured shear stress is therefore a linear superposition of
the matrix contribution and the contributions originating from
each droplet [38,39], as predicted by Batchelor [41]:
rt pI
..
isotropic term
g
m
rv rv
T

..
external contribution

g
m
V
_
A
nu undA
..
viscous part

C
V
_
A
nn
1
3
I
_ _
dA
..
elastic part
..
interfacial contribution
1
In Eq. (1), C is the interfacial tension, p is the pressure, rv is the
undisturbed velocity gradient tensor and rv
T
its transpose, g
m
is
the viscosity of the continuous phase, V is the total volume of the
system, n is the unit vector orthogonal to the interface between
the two phases, u is the velocity at the interface, dA is the area of
an interfacial element and the integrals are evaluated over the
whole interfacial area of the system, A. The unit vectors n and u
are orthogonal to the interface and computed with the MM model.
The MM model uses a second rank, symmetric and positive denite
tensor S to describe the time dependent shape behavior of an ellip-
soid under non-linear oscillatory shearing, Eq. (2) [16,42]:
dS
dt
f
1
k S
3
II
I
_ _
f
2
k; CatD S S D X S S X
f
1
k
40k1
2k319k16
f
2
k
5
2k3

3Ca
2
26Ca
2
2
With the use of the emulsion time s = g
m
R/C, where R is the ra-
dius, Eq. (2) is made dimensionless. In Eq. (2), I is the second rank
unit tensor, D and Xare the deformation rate and the vorticity ten-
sors, respectively, and II is the second scalar invariant of tensor S,
see also [16]. At rest, the droplet is spherical with S I. Please note
that droplet break-up will not occur under oscillatory shear ow as
long as the ratio of the viscosities is greater than or equal to 2.5, i.e.
that k
g
d
g
m
P2:5 [43].
The MM model was proven to quantitatively describe the non-
linear response of emulsions up to Ca values slightly higher than
unity [21]. Therefore, the highest capillary number Ca experienced
by the largest radius R
max
of the droplet population using LAOS
conditions is given by Ca
max

x
1
c
0
g
m
Rmax
C
where _ c
max
c
0
x
1
. If the
K. Reinheimer et al. / Journal of Colloid and Interface Science 360 (2011) 818825 819
strain amplitude of the oscillating experiment varies between
c
0
= 0.0110 and the excitation frequency is chosen such that
x
1
/2p = 0.011 Hz a coverage of ve decades of experimental
excitation for the droplet behavior under LAOS can be compared
where the predictions from the MM model are still valid. A maxi-
mum capillary number Ca
max
of about 1.3 is achieved when the
maximum droplet radius is estimated to be R
max
= 20 lm (using
g
m
= 31 Pa s and C = 3 mN/m for these experiments, see below). If
n and u are known, Eq. (1) can be used to predict the shear stress
even under non-linear excitation. The prediction of the non-linear
response for LAOS excitation is based on the interfacial contribu-
tion as described in the Batchelor theory. In this analysis, the
viscous and elastic shear stress are referred to as the interfacial
shear stress r
I
. Further details can be found in the literature detail-
ing the use of the MM model when combined with the Batchelor
theory [38,39]. From here on, the mathematical model formed by
combining the MM model, Eq. (2), with the Batchelor stress formu-
lation, Eq. (1), will be referred to as the MM-B model. As a rst
approximation, the viscous part of the interfacial contribution in
Eq. (1) will be neglected.
2.2. FT-Rheology
LAOS data were analyzed according to the relevant FTR proto-
cols [34,44,45]. The imposed sinusoidal deformation is given by
c(t) = c
0
sin (x
1
t) where x
1
= 2pm
1
= 2p/T is the characteristic
angular frequency with T the oscillation period and c
0
the strain
amplitude. The stress response r(t) retains the periodicity of the
exciting strain e.g. r(t) = r(t + T), but at large strain amplitudes
the stress can no longer be represented by a simple, single sinusoi-
dal waveform. The measured shear stress signal is therefore ex-
pressed in the Fourier domain as a superposition of higher
harmonics, since they fulll the r(t) = r(t + T) side constrain:
rt ()
FT
~ rx
_
1
1
rt expixtdt

j1
j1
odd j
c
j
dxjx
1
:
3
In Eq. (3), d(x jx
1
) is the Dirac delta located at x = jx
1
(j = 1, 2, 3, . . .), i is the imaginary unit and c
j
is the (complex) coef-
cient of the jth harmonic. Since the tangential stress is an odd
function of the imposed strain, only odd terms of the Fourier series
can, in principle, be included in Eq. (3) [34]. The relationship be-
tween the applied strain deformation, the measured or simulated
shear stress and the related FT parameters is already explained
in detail in several references and leads to the result given in Eq.
(4) [44,46,47]:
rt

1
j1
odd
c
j
x
1
expijx
1
t

1
j1
odd
c
jR
x
1
cosjx
1
t c
jI
x
1
sinjx
1
t:
4
where i is the imaginary unit, c
j
(x
1
) = c
jR
+ ic
jI
is the complex coef-
cient of the jth harmonic in the Fourier domain and c
jR
(x
1
) and
c
jI
(x
1
) are, respectively, the real and imaginary part of c
j
(x
1
). The
condition c
j
x
1
c

j
x
1
(with denoting the complex conju-
gate) guarantees that the original time series r(t) is real valued.
In addition, the absolute values I
j
of the c
j
coefcients were previ-
ously found to give useful information and are calculated from:
I
j
absc
j

c
2
jR
c
2
ji
_
jc
j
j: 5
As I
j
(j > 1) reaches appreciable values, i.e. for
I
3
I
1
: I
3=1
> 10
4
,
this marks at the state of the art experimentally the point where
the onset of nonlinearities in the stress response begins. Therefore,
FT-Rheology is demonstrated to be a powerful tool to detect and
quantify nonlinearities that are otherwise not observed in tradi-
tional linear rheological measurements [44,4749].
In addition, it should be noted that, at small amplitudes, the
scaling of the normalized intensity of the nth harmonic to the fun-
damental peak,
In
I
1
I
n=1
, is a function of strain as shown in the
following constitutive equations thus far investigated [48,51,52]:
I
n=1
/ c
n1
0
as a consequence a new quantity can be dened:
n
Q :
I
n=1
c
n1
0
lim
c
0
!0
n
Q :
n
Q
0
: 6
This allows for the denition of scalars based on the relative
intensities of the harmonics of the stress response, which can then
be used to infer inherent non-linear material properties of the sam-
ple. One example of this, that was used to evaluate polymer melts,
is the non-linear mechanical coefcient of the third harmonic
3
Q : Q [52] with:
3
Q
I
3
I
1
1
c
2
0
: Q: 7
According to Eqs. (6) and (7), the zero-strain non-linear coef-
cient Q
0
is a constant value, also described as the intrinsic nonlin-
earity of a material at relatively small strain amplitudes
lim
c
0
!0
Q Q
0
_ _
. This denition of Q
0
allows for the introduction
and measurement of Q
0
(x) spectra over a wide range of frequen-
cies and material properties, allowing for quantitative comparisons
between experiments and simulations under non-linear oscillatory
shear conditions [52,53]. For emulsions, it was previously demon-
strated that the appearance of higher harmonics in the magnitude
spectrum is associated with the droplet size and interfacial tension
properties of the included phase in a straightforward manner [39].
To be more precise, the higher harmonics are easily evaluated by
taking into consideration only the non-linear elastic contribution,
which is valid because the other terms in Eq. (1) are either nil
(the Newtonian external force and the isotropic pressure terms)
or, like the viscous part in the interfacial contribution Eq. (1), con-
sidered negligible. Therefore,
I
k
R
2p
T
_
T
r
I
t expjkx
1
tdt

2p
T
_
T
C
V
_
AR
nn
1
3
I
_ _
dA
_ _
..
elastic contribution
expjkx
1
tdt: 8
Due to the non-linear nature of the interface deformation,
attention can be focused mainly on the behavior of the higher coef-
cients of the magnitude spectrum, namely I
3
and I
5
, therefore
being not inuenced by the Newtonian response of the dispersed
phase or matrix viscosity:
I
3
abs
1
T
_
t
0
T
to
r
I
t expi3x
1
tdt
_ _
; T
2p
x
1
with k > 1; odd
I
5
abs
1
T
_
t
0
T
to
r
I
t expi5x
1
tdt
_ _
; T
2p
x
1
with k > 1; odd:
9
For the following analysis, it is important torst dene a quantity
E for emulsions that represents the non-linear ratio
I
5
I
3
: I
5=3
and to
note that E originates purely frominterfacial contributions. It is also
important to note that this non-linear coefcient does not involve
the fundamental harmonic I
1
and that this is justied by the hypoth-
esis [38] that, for dilute emulsions formed by two Newtonian com-
ponents, the fundamental harmonic I
1
in the magnitude spectrum
is mainly dominated by properties of the neat Newtonian matrix,
i.e. the viscosity of the single phase. The information deduced from
820 K. Reinheimer et al. / Journal of Colloid and Interface Science 360 (2011) 818825
I
1
and the phase information results in G
0
(x) and G
00
(x). As a conse-
quence the Palierne model only analyses the fundamental harmonic
while FTR relates to the higher harmonic contribution. In contrast
the higher harmonics are affected solely by the interfacial stress,
whichinturndepends upon(i) the interfacial tension, (ii) thedroplet
size and (iii) the viscosity ratio, among other factors. This scenario
has been previously conrmed by experiments [39], thus the I
5/3
ratio appears to be a useful tool for ltering out the linear part of
the experimental signal to focus only on the non-linear contribu-
tions caused by the deformed interface. As a consequence of Eq.
(6), a quadratic dependence on the strain deformation is expected
for I
5=3
/ c
2
0
as c
0
tends to zero.
2.3. Derivation of a universal behavior, preliminary denitions
The physical parameters that mainly affect the rheological
behavior of a dilute Newtonian dispersed phase in a Newtonian
matrix are: the viscosities of the matrix and the dispersed phase,
interfacial tension, the mean droplet diameter and the droplet size
distribution. For the sake of simplicity, only monodisperse blends
will be considered in the present study and the rst goal of this
work is to generate a universal dependency which can relate the
dimensionless quantities identied in the model, i.e. the capillary
number Ca
c
0
x
1
g
m
R
C
and the ratio of the dispersed phase and ma-
trix viscosities k g
d
=g
m
. A universal function E(Ca, k) would have
the advantage that once such function is established via simula-
tions, it can then be used for every experimental emulsion. There-
fore, the amount of data needed to characterize the droplet size or
interfacial tension of an emulsion is reduced to a minimum.
It is possible to use FT-rheological analysis of the shear stress to
evaluate I
3
and I
5
in the resulting spectra as different physical
parameters are varied in experiment and simulation. Fig. 1 repre-
sents the values I
3/1
and I
5/1
as a function of c
0
computed by the
MM-B model. The strain deformation c
0
is the logarithmic x-axis
and normalization to the fundamental peak I
1
is done to gain
experimentally an intense quantity. The inuence of I
1
and, there-
fore, the contribution of the Newtonian pure phases is lost by sub-
sequently establishing the ratio I
5/3
. The physical parameters of the
model used in the simulation are x
1
/2p = 0.1 Hz, g
m
= 60 Pa s,
R = 10 lm, C = 3 mN/m and k 3. As previously noted for low
strain amplitudes, the expected dependencies I
3=1
/ c
2
0
and
I
5=1
/ c
4
0
are seen, conrming the asymptotic behavior predicted
in other constitutive models [47,50]. The insets in Fig. 1 show
the derivation of the higher harmonics at the strain amplitude of
c
0
= 3.135 used to generate this data. The unexpected occurrence
of a weak peak at 2x
1
in the experiment is also clearly seen in
the inset. Although even harmonics are not predicted by the simple
theory, they are still frequently encountered in LAOS experiments.
Several explanations for the presence of even overtones in the
spectra have been proposed in the literature including wall-slip
phenomena [45,54] and time-dependent memory effects in the
system [34]. Recently [39], it was also proposed that these over-
tones originate from the instrument itself and might be unrelated
to the measured sample. They do not seem to give in the here pre-
sented case any information on the material itself and were there-
fore not studied further, especially as the intensity of the overtones
is so weak, i.e. the intensity of I
2
is about a factor of 50 smaller than
that for I
3
.
The scalar quantity I
5=3
=c
2
0
is thus a constant as c
0
tends to zero.
However, of great interest is the fact that this limiting value con-
stant is a function of the emulsion properties g
m
, R, C and the exci-
tation frequency x
1
/2p over a wide range of parameter values.
2.4. Derivation of E as a function of capillary number
In starting this derivation, the viscosity ratio k is held constant
for the reasons mentioned previously. Fig. 2a displays a selection of
simulated curves showing the intrinsic non-linear ratio I
5=3
=c
2
0
for
different emulsion characteristics and for k 3. By varying the
parameters c
0
, x
1
, g
m
, R and C over a wide range and numerous
combinations of values, the following dependencies were found:
I
5=3
c
2
0
/
x
2
1
g
2
m
R
2
C
2

Ca
2
c
2
0
: 10
Taking into account the denition of the capillary number
Ca
c
0
x
1
g
m
R
C
, the value for I
5/3
is clearly seen to be proportional to
the square of Ca. A superposition of all the curves shown in
Fig. 1. Normalized I
3/1
and I
5/1
as a function of strain amplitude for the MM-B
model. The physical parameters used in the simulation are x1=2p 0:1 Hz;
g
m
60 Pa s; R 10 lm; C 3 mN=m and k 3. The insets show the time and
frequency data to gain the higher harmonics at x1=2p 0:1 Hz and a strain
amplitude of c
0
= 3.135 for real experimental data.
Fig. 2. (a) Simulated ratio I5=3=c
2
0
as a function of strain amplitude. Each variation in
an emulsion property results in a new curve with different plateau values for small
c
0
. The simulation conditions are, if not listed otherwise: x1=2p 0:1 Hz;
g
m
1 Pa s; R 10 lm; C 10 mN=m. (b) The coefcient Ek I5=3=Ca
2
as a func-
tion of Ca. A universal curve Ek is described in direct analogy to a Carreau like model,
Ek
I5=3
Ca
2

E
0
k
1b Ca
c (where E
0
k3
3:93; b 2:8 and c 1:88) for a viscosity ratio
k 3.
K. Reinheimer et al. / Journal of Colloid and Interface Science 360 (2011) 818825 821
Fig. 2a is achieved by plotting the quantity E
k

I
5=3
Ca
2
as a function of
Ca, which leads to the creation of a single curve, as shown in Fig. 2b
where the simulation conditions are: x
1
/2p = 0.1 Hz, g
m
= 1
Pa s, R = 10 lm and C = 10 mN/m. Similar to a Carreau model [4],
a three parameter model quanties the dependence of E
k
on Ca
for the shear rate dependent viscosity:
E
k

E
0
k
1 bCa
c
: 11
It can be easily demonstrated that the limiting behavior of E
k
is
similar to that of Q
0
[52] in that:
lim
Ca!0
E
k
E
0
k
:
As an example, for k 3, the parameters of Eq. (11) are esti-
mated by the least square method where it was found that
E
0
k3
3:93 (plateau value), b = 2.8 (representing the onset of
decreasing values at Ca = 1/b = 0.36) and c = 1.88 (describing the
slope of the curve at high Ca values).
First, it is important to emphasize that E
k
is dimensionless as it
is the ratio of two dimensionless quantities. Furthermore, the sub-
script k is an important reminder that E
k
depends on the viscosity
ratio and, therefore, that different values of E
k
(and E
0
k
) will be ob-
served as k varies.
2.5. Inuence of the viscosity ratio k
The viscosity ratio k includes the temperature dependence of
the viscosity and this causes, therefore, shifts in the plateau values
of E
0
k
with variable k, see Fig. 3, for emulsions under non-linear
shear. The MM-B model is a suitable choice to describe emulsions
with viscosity ratios k > 2:5. At lower values of k, droplet breakup
becomes signicant and the MM-B model is less able to describe
the experiments. Using this simulation, it was also found that the
plateau value E
0
k
increases with increasing viscosity ratio.
The dependency of the plateau value E
0
k
on the viscosity ratio is
modeled in terms of a power law dependency:
E
0
k
E
0
k
p
: 12
The parameters E
0
and p in Eq. (12) were estimated by the pla-
teau values of E
0
k
evaluated from Eq. (11) at different k values using
a non-linear regression. With this approach, it was found that
E
0
= 0.64 0.01 and p = 1.63 0.02. The excellent agreement be-
tween E
0
k
values and the power law is shown in Fig. 3. In addition,
considering that the condence intervals are very small and that
the adjusted R-square statistics (R
2
a
) [55] of the regression was esti-
mated to be R
2
a
0:99885, this further corroborates the appropri-
ateness of the power law assumption formulated in Eq. (12).
Thus, a new non-linear, dimensionless coefcient E can be nal-
ly introduced and is given by the following relation:
E
E
k
k
p

I
5=3
Ca
2
1
k
p
: 13
It should be noted that this dimensionless coefcient is univer-
sally applicable as it now includes an explicit dependence on the k
parameter.
With Eq. (13), a superposition of all factors into a single curve is
possible by plotting E as a function of Ca k
0:82
, see Fig. 4.
At low Ca k
0:82
(or equivalently c
0
) values, it is possible to esti-
mate the limiting value E
0
for the E coefcient:
lim
Ca!0
E lim
Ca!0
E
k
k
p

E
0
k
k
p

E
0
k
p
k
p
E
0
: 14
A crucial point is that this estimated E
0
value, determined via
the MM-B model, should be universal for all dilute, monodisperse,
NewtonianNewtonian emulsions and can therefore be used to
determine the physical properties C or R. In fact, the following
relationship for the dimensional quantities implicitly appearing in
Eq. (13) can be written as:
I
5=3
c
2
0
x
2
1
E
0
k
p
g
2
m
R
2
C
2
And, taking into account the above results:
I
5=3
c
2
0
x
2
1
0:64k
1:63
g
2
m
R
2
C
2
15
It is important to note that the left side of Eq. (15) can be eval-
uated from LAOS experiments using FT-Rheology analysis. With
knowledge of the matrix viscosity g
m
and the viscosity ratio k,
the plateau value E
0
is a useful tool to calculate the droplet size
R when the interfacial tension C is known or vice versa. Thus,
the following course of action is proposed: (i) perform LAOS expe-
riences at (relatively) small amplitude values; (ii) detect a strain
amplitude interval where I
3
and I
5
clearly evidence power law
behavior with respect to c
0
; (iii) evaluate the related
3
Q
0
and
5
Q
0
coefcients as dened in Eq. (6); (iv) calculate the droplet size R
by exploiting the knowledge of C or vice versa through Eq. (15).
In the Results section, an illustrative example is given where the
average droplet radius is estimated from a known value of the
interfacial tension. Alternatively, it is possible to estimate the
interfacial tension once the droplet distribution is determined
from, for example, optical measurements [56].
As will be later shown, one benet of the proposed procedure is
that a few experiments are sufcient to estimate E
0
(and, thus, R or,
Fig. 3. Computed E
0
k
values as a function of the viscosity ratio k (black squares)
reported with the power law t E0 E
0
k
k
p
(solid line) with E
0
= 0.64 0.01 and
p = 1.63 0.02.
Fig. 4. Mastercurve E I5=3=Ca
2
k
1:63
as a function of Ca k
0:82
for different viscosity
ratios k.
822 K. Reinheimer et al. / Journal of Colloid and Interface Science 360 (2011) 818825
alternatively, C), which requires, in principle, less effort than the
traditional frequency sweep measurements.
Obviously, the methodology introduced here is limited to
emulsions fulllingthe assumptions of the adoptedmodel, i.e. emul-
sions that are monodisperse, dilute and with two Newtonian
components. However, this technique could be extended to cover
polydisperse samples and non-Newtonian compounds if the proper
constitutive equations are taken into account.
Finally, it should be noted that the results obtained with the
MM-B model are quantitatively conrmed by a second ellipsoidal
model proposed by Yu et al. [57] as reported in detail in the Appen-
dix, see also Fig. 6.
2.6. Experiments: materials and sample preparation
The model emulsions consisted of a matrix of poly(isobutylene)
(PIB) purchased from Ineos (Indopol H300) and a droplet phase of
poly(dimethylsiloxane) (PDMS) supplied by Rhone-Poulenc (Rho-
dorsil 47V200000). Relevant physical properties of the polymers
are listed in Table 1. Both PIB and PDMS exhibited pure Newtonian
behavior with a constant viscosity in the investigated shear rate
range at the temperatures used in this investigation (LAOS typically
c
0
x
1
< 6 s
1
and steady shear _ c < 10 s
1
were utilized). The viscos-
ity ratio is equal to 3.5, which is a large enough value to avoid sig-
nicant droplet break-up phenomena under pure shear ow.
Buoyancy effects are negligible in viewof the almost identical poly-
mer densities and their high viscosities. All the experiments were
carried out with a volumetric fraction / of the dispersed phase xed
at 0.1, which creates the desired globular morphology. This value of
/ is still small enough to neglect effects caused by droplet coales-
cence. Accordingly, the emulsion is assumed to be stable meaning
that its microstructure does not signicantly vary during the exper-
iments (i.e. negligible droplet breakup and coalescence). Typically,
30 mL samples were prepared by mixing the two phases with a stir-
rer at 135 rpm in a 100 mL beaker until a homogeneous white
emulsion was obtained. Air entrapped during stirring was then re-
moved by allowing the blend to sit under vacuum overnight. The
rheological experiments were carried out at 30 C on samples that
were not subjected to any pretreatment or particular ow history.
The interfacial tension between PDMS and PIB was measured using
the pendant drop method fromDataphysics (OCA 15EC) which gave
a value for the interfacial tension C = 3.54 mN/m at 23 C. With the
temperature coefcient differential dC/dt approximated by
0.03 mN/m/K, which is the upper limit for immiscible homopoly-
mer blends [58], an interfacial tension of C = 3.33 mN/m was
estimated for 30 C. This result is in good agreement with other
estimations previously reported in the literature for this system
[59].
With a linear frequency sweep measurement in the range of x
1
/
2p = 0.110 Hz, the characteristic relaxation time s
rel
of the emul-
sion was determined to be s
rel
= 0.404 s [24]. According to the
Palierne model [24], the volume average droplet radius of the sys-
tem can then be obtained from Eq. (16):
hRi
V

4Cs
rel
g
m
10k 1 2/5k 2
19k 162k 3 2/k 1
16
which results in hRi
V
= 9.4 lm.
2.7. LAOS experimental setup
The FT-Rheology experimental setup is based on a Rheometrics
Scientic Advanced Rheometer (ARES G2), which is a strain con-
trolled rotational rheometer using a separate motor and transducer
technology. The motor is an air bearing supported, brushless DC
motor, where position and rate are measured with an optical
encoder including a position feed-back loop. The benets of this
motor are a non-invasive motor current, inertia and friction on
sinusoidal strain controlled rheological measurements [47]. The
new generation of rheometers from TA Instrument already in-
cludes a setup for FT-Rheology that is based on the published work
of Wilhelm [44,46]. For the ARES G2 software TRIOS, there are two
possible methods to analyze the LAOS response. The rst one is a
real time correlation to determine the magnitude and phase of
the fundamental frequency as well as the contribution of odd high-
er harmonics as a function of experimental time. A second possibil-
ity is the post processing of the acquired raw strain and stress data
in the time domain detected via TRIOS software using a discrete
Fourier Transformation with a specially written Matlab

routine.
As rst introduced by Wilhelm [34], the higher harmonic intensi-
ties are typically presented as the ratio of the magnitude of the
nth harmonic to the magnitude of the fundamental peak
In
I
1

Inx
1

Ix
1

I
n=1
with n = odd and n > 1. To reduce mechanical noise,
a rigid and mechanically stable environment was ensured by using
a heavy stone table with carpet sheets under the legs. Within the
applied frequency domain, the maximum signal to noise ratio for
the prominent rst harmonic is typically S/N = I
1
/N 10
5
.
The rheometer consists of a Force Rebalance Transducer (FRT),
which is suitable for measuring torques between 50 nN m and
200 mN mas specied by the manufacturer. The installed brushless
DCmotor withjewelledair bearings is capable of applyingrotational
angular velocities from 10
6
rad/s to 300 rad/s and deformation
amplitudes of 1 lradto anunlimitedmaximum. The appliedoscilla-
tion frequency can be varied between 10
7
rad/s and 628 rad/s.
Measurements were performed in a 50 mm cone plate xture
from TA Instruments with an angle of a = 0.02, which is the largest
diameter cone and plate xture available from TA Instrument. This
was selected to maximize the contact surface between the sample
and test xture and, consequently, maximize the torque signal. The
temperature control was set to 30 C with a force convected oven.
The excitation frequency was set to x
1
/2p = 0.1 Hz and the defor-
mation amplitude varied in the range of c
0
2 [0.1; 10] in absolute
values. A comparison of the post processing of detected time cycles
of the shear stress with the real time correlation of the higher har-
monics from the ARES G2 resulted in a perfect overlay of the curves
for I
n/1
(c
0
). The two softwares calculated a value for the relative
higher harmonic contribution that varied only by a factor of
I
5=3
TRIOS
I
5=3
Matlab
1:007. Therefore, as the online detection is the faster
procedure, this was preferred. Droplet breakup can be considered
to be negligible due to the low capillary numbers used (Ca
max
1).
A frequency sweep test performed at both the beginning and end
of the LAOS measurements monitored the stability of the emulsion
morphology. An overlap of G
0
(x) and G
00
(x) at these two stages
(before and after) was considered proof of the stability of the emul-
sion microstructure [39].
3. Results
3.1. Calculation of droplet size
In the previous section, the concept of a universal emulsion
curve ECa k
0:82
and its limiting value E
0
as Ca tends to zero
Table 1
Main physical properties of the PDMS/PIB system.
Polymer Formula Molecular
weight
(g/mol)
Density
(g/cm
3
)
at 23 C
Viscosity
(Pa s)
at 30 C
Interfacial
tension (mN/m)
at 30 C
PDMS [Si(CH
3
)
2
O]
n
200,000 0.896 110 3.33
PIB [CH
2
C(CH
3
)
2
]
n
1300 0.973 31
K. Reinheimer et al. / Journal of Colloid and Interface Science 360 (2011) 818825 823
was introduced as a general description for emulsions. An illustra-
tive experiment will now be presented to conrm the usefulness of
this emulsion curve E for evaluating the droplet radius or, alterna-
tively, the interfacial tension.
For these experiments, the range of strain amplitudes that can be
used has a lower limit due to the fact that nonlinear behavior only
starts at a certain minimum strain amplitude and also has an upper
limit caused by the onset of measurement artifacts such as loss of
sample volume. Using the correct frequency of x
1
/2p = 0.1 Hz, re-
sulted in curves where the predicted strain amplitude dependencies
of c
2
0
and c
4
0
for, respectively, I
3/1
and I
5/1
were measured [51] as re-
ported in Fig. 5. Fig. 5a shows in detail the measured I
3/1
and I
5/1
val-
ues as a function of strain amplitude c
0
(lled symbols). For a given
range of c
0
values, both the power law relationships I
3=1
/ c
2
0
and
I
5=1
/ c
4
0
are observed, whereas this dependence is lost at lower
strain rates due to experimental noise. The torque L at the minimum
value for I
3/1
= 5.74 10
4
is L = 863 10
6
N m and reects I
1
.
Therefore, I
3
has a torque of I
3/1
L = 495 nN m. The torque of I
5
at
the minimum value for I
5/1
= 9.3 10
5
is calculated using
L = I
1
= 1850 10
6
N m resulting in a value of 172 nN m, which is
close to the measurement limit of the current rheometer specied
at 50 nN m by the manufacturer. The measured I
3/1
and I
5/1
are
capped three points below the minimum measured torque for I
3
and I
5
. In this light, it should be remarked that the power lawbehav-
ior observed at intermediate strain rates is experimentally repro-
ducible, while the irregular values observed for I
3/1
and I
5/1
at
smaller strain rates are dominated by noise. These experiments,
therefore, allow for a reasonable estimation of the coefcients
3
Q
0
and
5
Q
0
introduced in Eq. (6). It should also be noted that the onsets
of power law behavior are seen for the two higher harmonics at
different c
0
values. Specically, for I
3
it was found at c
0
< 1 whereas
I
5
exhibits power lawbehavior only at slightly larger values of strain
deformation (c
0
< 3). Thus, the scalar
5/3
Q
0
=
5
Q
0
/
3
Q
0
can be evalu-
ated later with ease. For sake of clarity, the extrapolated curves at
small strain deformations are also reported in Fig. 5. Conversely,
Fig. 5b compares the measured (lled symbols) and extrapolated
(open symbols) curves of E together with the universal emulsion
curve obtained with the MM-B model simulation. To calculate the
droplet radius, Eq. (15) can be transformed leading to the following
explicit relationship for the droplet radius:
R

5=3
Q
0
E
0

C
x
1
g
m
1
k
p=2
17
The terms on the right hand side are known from experiments
using various strain amplitudes: the measured plateau value of
the intrinsic non-linear ratio is
5/3
Q
0
= 0.013, x
1
/2p = 0.1 Hz,
k 3:5, g
m
= 31 Pa s and C = 3.33 mN/m, E
0
= 0.64 and p/2 = 0.82.
Using these values, the droplet size radius is thus estimated to be
R = 8.8 lm. This value is remarkably close to the droplet radius esti-
mated via the Palierne model, hRi
V
= 9.4 lm, conrming the good
agreement between these two procedures. One reason that the
agreement is not even better is that the calculation for droplet
radius via an estimation of E
0
is based on simulations for monodis-
perse emulsions, however, the actual sample is likely to exhibit
some polydispersity.
It is also interesting to note that there is a reasonable agreement
between the model simulations (solid line) and experiments (black
points) even at higher strain rate deformations, as shown in Fig. 5b
for Ca k
0:82
> 0:8, thus conrming the validity of the MM-B model
even at higher strain rates.
4. Conclusions
A new approach to characterize emulsions towards droplet size
and interfacial tension based on FT-rheological measurements is
presented. The non-linear behavior of monodisperse dilute emul-
sions, subjected to LAOS conditions is investigated for emulsions
composed of two Newtonian constituents. In this case, the nonlin-
earity of the response under LAOS is thought to originate exclu-
sively from the presence of the polymerpolymer interface. The
Maffettone and Minale constitutive model coupled with Batchelor
theory (MM-B) was selected for the analysis and investigated in
the Fourier domain at LAOS conditions.
Via numerical simulations using the MM-B model, a general
function E for emulsions could be established as a universal corre-
lation among (i) the ratio of the higher harmonics I
5/3
, (ii) the cap-
illary number Ca and (iii) the viscosity ratio k. Its limiting value E
0
Fig. 5. (a) Measured I
3/1
and I
5/1
values as a function of strain amplitude c
0
(lled
symbols). (b) Measured (lled symbols) and extrapolated (open symbols) curves of
I5=3
Ca
2
k
1:63
together with the universal emulsion curve of the simulation made using the
MM-B model.
Fig. 6. Comparison of the universal emulsion curve E simulated either with MM-B
model (line) and Yu and Bousmina model (symbol).
824 K. Reinheimer et al. / Journal of Colloid and Interface Science 360 (2011) 818825
as the strain deformation tends to zero is universal and holds for
any dilute emulsion with two Newtonian constituents. This univer-
sal value is useful for inferring blend properties such as the droplet
radius or, alternatively, the interfacial tension between the two
emulsion components.
Preliminary experimental results on a model blend (PDMS 10%
in PIB 90%) conrm the validity of this approach in that the average
droplet radius estimated with E
0
agrees well with the average
droplet radius estimated from traditional linear rheological meth-
odologies (i.e. Palierne method), excluding effects caused by
polydispersity.
In conclusion, the non-linear dimensionless quantity E appears
to be a promising parameter to characterize blend properties such
as droplet size and interfacial tension and this procedure can be also
extended in the future to other mathematical models to take into
account, for example, the presence of non-Newtonian components
and/or concentrated emulsions. With respect to this a general func-
tion E is a comprehensive value in combination with FT-rheological
experiments to analyze emulsions towards radius or interfacial ten-
sion in a few steps.
Acknowledgments
The authors would like to thank Ivanka Koleva from the group
of Professor Rehage at the Technical University Dortmund (Ger-
many) for measuring the interfacial tension. Furthermore, the
authors would like to thank Ineos and Rhone-Poulenc for the dona-
tion of PIB and PDMS, respectively. Finally, we wish to acknowl-
edge the input from the referees who helped to improve this
article and stimulated future work as well as Mrs. Kbel for her
improvements as a native English speaker.
Appendix A
A.1. Comparison with the Model of Yu and Bousmina
As mentioned previously, the concept introduced here uses
ubiquitous quantities, which are not specic to any given model.
Therefore, other approaches can also be compared with the results
here. For example, the model of Yu et al. uses the Maffettone and
Minale model to simulate the droplet shape behavior, but calcu-
lates the shear stress with the following equation [57] instead of
using the Batchelor theory:
r
I

2f
2
K
II
I S S S
2
3
III 18
where S is the non-dimensional droplet shape tensor, I the unit ten-
sor, I and II the rst and second scalar invariant of S, respectively,
and K
6 C
5 R

k12k3 /
5k15k2 /
. The dependency of E as a function of Ca
with these two different models shows quantitative agreement, as
shown in Fig. 6. Finally, it should be noted that this result supports
the assumption made in the calculation of the interfacial shear
stress that only the elastic contribution must be considered, see
Eq. (1), and that any viscous contribution to the interfacial contribu-
tion can be neglected in the rst approximation using the MM-B
model.
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