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DOI 10.1007/s00397-006-0089-z
ORIGINA L CONTRIBUTION
Julien Mougel
Oscar Alvarez
Christophe Baravian
Franois Caton
Philippe Marchal
Marie-Jos Stb
Lionel Choplin
Introduction
Long time stability of concentrated emulsion is a widely
studied and complex field of investigation (e.g., Princen
and Kiss 1986; Bibette et al. 1999; Langevin 1998; Taylor
1995). Indeed, three main mechanisms were shown to lead
to droplet coalescence. Firstly, the Schmoluchowski model
(see, for example, Langevin 1998) is built on the hypothesis that two droplets in contact coalesce. The main
consequence is that the number N of droplets in volume
unit decreases during time leading to a complete phase
separation. This evolution is given by dN =dt / N 2 and
implies that the droplet radius follows R t 1=3 :
556
557
0.01
100
10
0.1
R0 (m)
30
R (m)
95%
20
93.5%
92%
Coalescence
10
93.5% (stabilized)
(1)
1000
71%
0
1
10
100
t-t0 (hours)
95%
0.1
93.5%
800
600
85%
0.01
(m3/s)
G (Pa)
92%
78%
400
200
0.001
0
1
10
100
t-t0 (hours)
Fig. 1 Evolution of the samples elastic modulus G0 at various
volume fractions. For clarity reason, not all the data are plotted
0.0001
0.7
0.8
0.9
Volume fraction
Fig. 3 Variation of the coalescence rate ! with the volume fraction
558
Slope -2
92%
6.5
Ln G (Pa)
85%
6
95%
75%
5.5
90%
73%
93.5%
78%
Slope -1
4.5
1.5
2.5
3.5
Ln R (m)
Elastic modulus
Figure 4 shows the elastic modulus (G0 ) dependence with
the average droplet radius R for different volume fractions.
This figure is obtained from Figs. 1 and 2. It is clear that the
well-known Princen and Kiss (1986) model does not apply
to our experimental data because G0 does not vary like 1=R
(the corresponding slope 1 is plotted on Fig. 4). Indeed,
we find that G0 is better correlated to 1=R2 (see slope 2
on Figs. 4 and 5), especially for volume fractions greater
Present work
Pals experiments
/(c )
Princen for the present work
G' R
2 AD0
10
1
0.8
W
V
Vf / R3
0.7
G0
(2)
100
0.9
Volume fraction
1
:
(3)
559
AH R
;
12D
(4)
(5)
2D0
:
R2 1
(6)
2AD0
;
R2 c
(7)
Conclusion
The steady light transport technique allows the simultaneous measurement of the temporal evolution of the
sample shear elastic modulus G0 and droplet average radius
R for samples at various volume fractions .
We find that the coalescence law R t 1=3 applies in our
system for the whole range of volume fractions. The
coalescence rate shows different domains in relation with
the clustering of droplets.
The relation that we found between G0, R, and (Eq. 7)
differs from Princen and Kiss (1986) model, probably due
to the use of a nonionic surfactant (Span80) in the
preparation of our samples. Based on dominant van der
Waals interactions, a tentative model is built up. This model
also describes other results obtained with another nonionic
surfactant for an o/w emulsion (Pal 1999).
Further investigations with other nonionic surfactants
have to be performed to verify if this behavior is only valid
in some particular cases or if it is a more general one.
Acknowledgement We thank Daniel Quemada for useful remarks
and comments.
References
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concentrated water-in-oil emulsions:
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Sci 159:134149
Baravian C, Caton F, Dillet J (2004) Steady
light diffusion application to rheology:
a new tool for the characterization of
concentrated suspensions. Rheol Acta
43:427432
Baravian C, Caton F, Dillet J, Mougel J
(2005) Steady light transport under
flow: characterization of evolving
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(066603)
560