Reprinted from American Laboratory News June 2005

The Size and Rheology Characterization of Concentrated Emulsions

by Zhigang Sun, Torrey Deluca, and Kevin Mattison
A common dilemma when measuring the particle size of concentrated samples using dynamic
light scattering (DLS) is the question of
whether some sample preparation, such as dilution, is required. Many classes of samples,
emulsions, for example, usually cannot be diluted without affecting the fundamental nature
of the material; thus measurement without dilution is desirable or necessary.
Classical dynamic light scattering techniques
require that the sample be highly diluted for
measurement. New technologies, such as that
incorporated in the Zetasizer Nano series
(Malvern Instruments, Southborough, MA),
enable measurements without dilution. However, it is not possible to compensate for all particle interaction effects, and this article examines a method with which to determine
whether the results achieved are free from
these interactions.

Figure 1
Concentration dependence of the measured intensity particle size
distributions for neat and dilute emulsion mixtures, measured with a Zetasizer
Nano system and using the viscosity of water in the Stokes-Einstein calculations.

One aspect of the group of effects categorized

as particle interactions is the hydrodynamic effect, also known as restricted or hindered diffusion. Restricted diffusion is a consequence of
the proximity of particles, which limits the
space within which the particles can diffuse.
The calculation of particle size from the particle diffusion speed in dynamic light scattering
measurements uses the Stokes-Einstein relationship, and in turn this requires the input of
the continuous-phase viscosity. For Newtonian samples, empirical evidence suggests that Figure 2
Particle size distribution of the dilute emulsion sample measured
compensation for restricted diffusion effects
with a Mastersizer 2000.
can be achieved using the viscosity of the bulk
solution. The experiment described here shows the
The sample was characterized using a range of techuse of the AND SV-10 viscometer accessory for the
nologies: the Zetasizer Nano system, Mastersizer 2000,
Zetasizer Nano system to accomplish this correction
Malvern Bohlin C-VOR research-grade rheometer,
for a concentrated emulsion.
and an SV-10 viscometer suitable for the accurate viscosity measurement of Newtonian fluids (all available
from Malvern Instruments). Measurements were made
on both neat and diluted forms of the sample, with the
The sample is described as a flavored alcoholic beverdilution medium being 10 mM NaCl solution. The
age emulsion. The goal was to identify a technology
temperature was controlled and fixed in all measurethat could indicate whether or not the product was homents at 25 C.
mogeneous and had a narrow size distribution.

Experimental

of the shear rate, at all concentrations, verifying that the sample is a

Newtonian fluid.
The AND SV-10 is an oscillating
fork viscometer accessory for the Zetasizer Nano system that can be used
to measure the viscosity of samples,
with high accuracy, over a very wide
viscosity range. In theory, the viscosity measured by the viscometer
should be equivalent to the viscosity
measured by the rheometer for Newtonian fluids.
Figure 3
Concentration dependence of the absolute viscosity of the emulsion sample
measured with a Malvern Bohlin C-VOR rheometerneat (), 75% (o), 50% (), and
dilute().

The rheometer and viscometer systems were calibrated

with pure water at 25 C. For these measurements, the
rheometer used a cone and plate geometry setup in a
step-ramped constant shear measurement mode. In
comparison, the SV-10 utilizes an oscillating fork geometry. The value produced by this vibration technique needs to be divided by the solution density in
g/mL to give the viscosity.

Results
Figure 1 shows the dependence on concentration of
the particle size distributions for the emulsion sample, assuming the viscosity of water in the StokesEinstein transformation. For the neat sample, the apparent particle size is in the order of 2 m. As the
sample is diluted, the size distribution shifts toward
smaller values, with no change in either the modality
(number of peaks) or the polydispersity (peak width).
At 10% relative concentration, the concentration dependence of the size distribution is lost. The constant modality and
polydispersity suggest the influence of restricted diffusion at higher concentrations
rather than the onset of more complex interaction effects.

Figure 4 shows a comparison of the

viscosity of the emulsion sample measured with the rheometer and the SV10 viscometer, respectively. As expected, the results are in good agreement, particularly
in the lower viscosity region, where restricted diffusion
effects can dominate other particle interaction effects.
In dynamic light scattering, the transformation of the
measured diffusion coefficient to the particle size distribution is accomplished using the Stokes-Einstein
equation shown in the following expression, where
R H is the hydrodynamic radius, k is the Boltzmann
constant, T is the temperature, D is the diffusion coefficient, and is the viscosity of the medium.
kT
RH = 
6D

Under classical dilute DLS measurement conditions,

the accepted viscosity value for use in the above expression is that of the diluent10 mM NaClfor the

Additional evidence for the particle size

distribution of the dilute sample was provided by the Mastersizer 2000, a low-angle
laser diffraction system. The size distribution measured with the Mastersizer 2000
system is shown in Figure 2, which indicates
a mean of 0.2 m, consistent with the 200nm size measured on the Zetasizer Nano.
In order to establish whether or not the
sample exhibited Newtonian fluid behavior, the shear rate dependence of the absolute viscosity was examined using the
rheometer. The results, shown in Figure 3,
indicate that the viscosity is independent

Figure 4
Comparison of the viscosities measured by the Malvern Bohlin CVOR rheometer and the SV-10 viscometer, respectively.

viscosity can be used as the viscosity parameter in the Stokes-Einstein transform. However, this may only be valid if
the sample is a Newtonian fluid.
Figure 5 shows the same data as presented in Figure 1, corrected using
the viscosity of the sample measured using the SV-10 viscometer.
As seen in this figure, restricted diffusion effects are normalized by use
of the bulk viscosity value in the
Stokes-Einstein expression, yielding a mean particle size of circa 200
nm at all sample concentrations.

Conclusion
The above results verify that the primary particle interaction effect for this
emulsion is restricted diffusion, and
that the sample can be measured accurately without dilution, as long as the
Figure 5
Comparison of the particle size distributions for neat and diluted emulsions,
viscosity of the sample is used for the
showing the normalization effect of using the viscosity of the bulk solution for high concencorrection in the Stokes-Einstein relatration measurements.
tionship, rather than the viscosity of
the dispersant. The results also show
emulsion results presented here. Modern light scatterthat the SV-10 viscometer is sufficiently accurate to
ing instruments such as the Zetasizer Nano system,
measure the sample viscosity to the high precision rehowever, can measure the particle diffusion at high
quired by this technique.
sample concentrations by observing the backscattered
light, rather than relying on the transmission of light
through the turbid sample.
At moderate concentrations, it is proposed that the viscosity of the bulk solution rather than the dispersant

The authors are with Malvern Instruments Inc., 10 Southville

Rd., Southborough, MA 01772, U.S.A.; tel: 508-480-0200; fax:
508-460-9692; e-mail: kevin.mattison@malvernusa.com.