Abstract
Centrifugation is a common method used in many industries to reduce the time for stability studies, as the acceleration field
leads to a quicker destabilization of the system. However, correlation with real shelf life of a colloidal system can prove to be
complex, as the stress applied to the sample is far from natural forces, which can be encountered in the normal life of a
product. This paper presents some data proving the detrimental effects of centrifugation on the destabilization process, as
important segregation between small and large particles is observed after centrifugation of the dispersion and not when the
sample is left at rest.
Keywords: stability, centrifugation, suspension, dispersion, shelf life, Turbiscan.
Introduction
Many industrial products available in the market
are in the form of emulsion or suspension. These
products are often complex due to the large number
of components in the formulation and their physical
stability is a critical parameter, which has to be
controlled thoroughly. Different techniques are
available to monitor the stability of such colloidal
systems and most of them offer the possibility to
accelerate the destabilization phenomena in order
to obtain results more quickly. Two methods are
commonly used to accelerate the destabilization
process: temperature and centrifugation. The
scientific community is regularly debating whether
these methods are realistic and can be correlated to
real shelf life of a product.
In this paper, experiments show evidences that
centrifugation
causes
segregation
among
polydispersed particles, which is not observed when
the sample is left still for the stability analysis. This
effect is highlighted using simple fluorescence
imaging experiments. The mechanism involved in
this process involves the jamming properties of the
percolation network, which can be applied to most
of the gel-like structures, corresponding to many
industrial products (cosmetic creams, toothpaste,
yogurt, cheese, paint, etc.).
Gel structures are between liquid and solid
states. The gel transition, or so-called sol-gel
transition involves a percolation threshold and
jamming transition, whereby a continuous path
between particles starts to form (as in Figure 1 for
weakly interacting PMMA particles). The jamming
transition can be caused either by an increase in
particle density (concentrated emulsion or
suspension) or physico-chemical interactions
Experimental
1. Materials
The suspensions studied in this work are
composed of PMMA beads (density 1.19 g/cm3)
dispersed in a refractive index-matched fluid. The
fluid is a mixture of microscope oil immersion
(Sigma-Aldrich S150) and n-hexadecane (viscosity
25cP, density 0.88 g/cm3). The suspension is
transparent and therefore can be studied by optical
Results
1. Settling at rest of PMMA suspensions
When the suspension is left to settle at rest,
the following fluorescence images are obtained
(Figure 3).
t=0
t=3 hours
t=10 hours
t=24 hours
fluorescence
field
shows
no
significant
t=0
t = 3h
t = 24h
z (cm)
Figure 4. Small particle concentration profiles along
the vertical direction during the settling of a
bidispersed PMMA suspension. Z=0 denotes the
vertical position of the air/fluid interface.
Looking at the second system consisting of
small polydispersed PMMA beads, at 25% and 50%
volume fraction, similar results are obtained (Figure
5), showing uniform fluorescence field during
particle settling.
The Turbiscan makes scans at various preprogrammed times and overlays the profiles on one
graph in order to show the destabilisation.
=25%
t=0
t=3 days
=50%
t=0
t=3 days
s
G=0
G= 150g
z (cm)
G=
G=10g
G=150g
G=1000g
Figure 6. Fluorescence images of small labelled
particles during the settling under centrifugation of
bidispersed PMMA beads (b=0.25 and s=0.25).
s
G=0
G= 150g
G=0
G= 10g
G=150g
G= 1000g
z (cm)
Figure 9. Small particles concentration profiles
along the vertical direction during the settling of 50%
polydispersed PMMA beads (10m-40m) under
centrifugation.
z (cm)
Figure 7. Small particles concentration profiles
along the vertical direction during the settling of a
bidispersed suspension under centrifugation.
The blue curve, corresponding to 10g acceleration
show two regions : in the bottom part of the tube,
the smallest particles partly occupy the free space
between large particles (s=0.2) while the top part
3. Turbiscan analysis
The bidispersed PMMA beads suspension has
also been studied with the Turbiscan LAb at 30C
for 2 days. The following profiles are obtained in
transmission (Figure 10).
Fluid/sediment
interface layer
Clarification
Centre part of
the top layer
sediment
Discussion
The segregation phenomenon, which is
observed under centrifugation is corroborated by
microscopy analysis of samples from different layers
of the sediment (Figure 12).
Conclusion
This study proves the issue of using
centrifugation to accelerate the destabilization
process of emulsions or suspensions. Excess