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Double-diffusive fingering instability of a surfactant-glycerine-water drop in water

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2001 Europhys. Lett. 55 807
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EUROPHYSICS LETTERS

15 September 2001

Europhys. Lett., 55 (6), pp. 807813 (2001)

Double-diusive ngering instability of a

surfactant-glycerine-water drop in water
tter and M. Markus
K. Ko
Max-Planck-Institut f
ur molekulare Physiologie - Postfach 500247
D-44202 Dortmund, Germany
(received 2 November 2000; accepted in nal form 28 June 2001)
PACS. 47.54.+r Pattern selection; pattern formation.
PACS. 47.20.Bp Buoyancy-driven instability.
PACS. 66.10.Cb Diusion and thermal diusion.

Abstract. We present an experimental setup that allows easy visualization of single ngers
formed by double diusive convection. This setup consists of a drop (containing water and two
solutes) that is injected at the bottom of a dish lled with water. The gravity-driven expansion
of the drop induces a toroidal bulk ow of the surrounding water. This ow straightens and
connes the ngers horizontally and quasitwo-dimensionally. An extremely low diusion coefcient of one of the two solutes (a surfactant in our case) causes unusually stable congurations.
This stability is robust within a wide range of concentrations. Wavelength measurements agree
well with theoretical estimations.

Introduction. Double-diusive convection (see reviews in [13]) results from an instability at the interface between two uid layers. These layers dier in their concentrations of
two components: a slowly diusing, gravitationally destabilizing component S and a fastly
diusing, stabilizing component T . Considering the total densities of the layers only, the
system would be stable. However, a uctuation at the interface causing a thin protrusion
from the layer with larger T into the layer with lower T may be depleted of T so fastly by
diusion, that the protrusion can grow due to its content of S. As an example, consider hot,
salty water (density 1 ) layered over colder, less salty water (density 2 > 1 ); since thermal
energy diuses much faster than salt, a thin protrusion coming downwards from the upper
layer cools down, while it still contains enough salt to sink; thus, the protrusion grows and a
so-called salt-nger is formed.
Examples of double-diusive convective systems are: the mediterranean outow over the
Atlantic [4,5], ice oating in salty water (double-diusive structures near the interface may [6,7]
or may not [8] be relevant in projects of fresh water supply via melting of icebergs towed to
warmer coastal areas), a sugar solution layered over a salt solution [9, 10], crystallisation of
multi-component melts [11] leading to nger-like distributions of impurities in cold metal,
layering of magma below the Earths crust [12], stellar atmospheres [13] leading to helium
ngers [1], deeply disposed sewage rising upwards from the bottom of the sea [3, 14], and
polymer transport [15] via cross diusion [16]. The latter phenomenon is envisaged to occur in
c EDP Sciences

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transport processes within concentrated biological systems, including the extracellular matrix
of connective tissues [17, 18]. Furthermore, a number of prototypical laboratory experiments
using aqueous solutions have been reported [13].
Fingers occurring due to double-diusive convection are preceded by the formation of cell
structures [9]. The closed-packed array of these cells makes observations dicult. In order to
solve this visualization problem, Taylor and Veronis [10] constructed a setup consisting of two
parallel glass plates separated by a 1 mm gap. Another quasitwo-dimensional connement
had been achieved by Linden [19] at the interface between two chambers containing uids
forced to ow in opposite directions. In the present work we show that a construction simpler
than those is sucient for connement into a quasitwo-dimensional region. In fact, we just
inject a drop containing S and T on the bottom of a dish lled with water; the connement
then results from the hydrodynamic ow induced in the water surrounding the drop.
An additional problem in previous investigations so far is that the formation of ngers
is overshadowed by irregular transverse distortions or plumes; evaluation and comparison
with calculations are hindered by these phenomena. In the present work we show that such
irregularities are eliminated by using a destabilizing component S with an extremely low
diusion coecient. We meet this requirement by using a surfactant, which diuses very
slowly because of the formation of large aggregates, namely micelles (see [20, 21]); thus, S
stays within the ngers during the duration of the experiments.
Experiments. Experiments are started by stirring for 12 minutes a mixture of water,
glycerin (substance T ; density T = 1.26 g/cm3 ) and an alcohol ethoxylate, i.e.
CH3 (CH2 )n1 O[CH2 CH2 O]m H (nonionic surfactant; substance S; density S =
0.95 g/cm3 ). The concentrations of S and T vary between 0.4 vol% and 10 vol%. V0 50 l
of this mixture is injected at the center of the bottom of a Petri dish containing water ( 3
mm high). The injection is performed (continuously during 20 s) with a syringe using an
HT-pump (Infusor Basel). Note that for qualitative work it is sucient to place the drop
from above with a pipette at the bottom of an ordinary dish. The density of the mixture is
higher than for pure water. We use Petri dishes with two dierent diameters
: 2 cm and
7 cm. The larger dish is used to observe the long-term development of ngers (as in g. 3).
The smaller dish is used to measure the distance between the ngers (wavelength ) over a
wide range of initial concentrations; the reason for the restriction of the dish size to
= 2 cm
is the elimination of the inuence of the gravity-driven expansion of the drop on , simply by
stopping this expansion.
In order to have an optical contrast that is independent of the concentrations, we establish
the following measuring conditions. We determine as soon as all minima of the measured
absorbed light are within 5% of the intensity measured with a void dish. We call Tem (nger
emergence time) the time at which these minima are reached after initiating the experiment.
We nd Tem to be dependent on the initial concentrations of T0 and S0 , but Tem is always
larger than the time needed for the drop to reach the wall of the dish. We determine by
two-dimensional Fourier transforms of video images; then, we average over the values obtained
from 50 such images.
We investigate all surfactants with n = 3, 4, 5 and m = 8, 10, 12, 14 and 16 (available from
SIGMA). For the initial concentrations of T0 and S0 given above, we only observe ngers
for n = 4, m = 12 or 14. This specicity is explained by the fact that the conditions for
double-diusive convection must be met; these conditions are, rstly, that the net densities
are gravitationally stable stratied, i.e. the mixture in the drop must be heavier than water,
and, secondly,
(1)
R = |T T |/S S < DT /DS = 1 ,

 tter et al.: Double-diffusive fingering of a surfactant etc.

K. Ko

a)

height [mm]

c)
D

b)

809

3
2
1
0
-0.04 -0.02

0.02 0.04

velocity [mm/s]

Fig. 1 (a) Scheme illustrating the experimental situation if a drop D of a surfactant-glycerin-water

mixture is placed in a Petri dish lled with water. The gravity-driven spreading of the drop induces a
torus-shaped bulk water ow (closed arrows). (b) The torus extends, as the drop spreads. The rising
ow causes a perimetral lifting of the mixture (P). (c) Measured velocities of the bulk water ow in
a Petri dish with diameter
= 7 cm at t = 5 min and at a distance of 12 mm from the center of the
dish.

as given in [22]. T = (T H2 O )/H2 O , S = (S H2 O )/H2 O , S = [S]/z, T =

[T ]/z. z: height. DS , DT : diusion coecients. The choice of the surfactant aects S
and DS . DS is most strongly aected by this choice because as discussed in [21] the size
and shape of the micelles (and thus their diusion coecient) is highly sensitive to the chain
lengths in the surfactant molecule. For a quantitative analysis of the micelles in the present
work (n = 4, m = 12), we perform X-ray small-angle scattering measurements (for details on
this method, see [23]).
Results and discussion. X-ray small-angle scattering shows that micelles have the
shape of long rods, as revealed by a slope 1 of the log-log plot of scattered intensity
vs. scattering vector length. The molecule length implies a rod diameter of 50
A. On
the other hand, the micelles are found to be larger than the resolution of our scattering
setup, i.e. 4000
A. (In addition, the surfactant-water mixture appears milky, so that the
micelle length should be at least of the order of the wavelength of light.) The minimum
axis-ratio P = 4000/50 implies that the diusion coecient of the micelles is at least a factor
A [23].
[(2/3)1/3 P 2/3 ]/(ln 2 0.3) 3.3 larger than that of a sphere having a diameter of 50
Since glycerin molecules have a length of 5
A and are much less elongated than the micelles,
and since the diusion coecient of spheres is inversely proportional to their diameter (Stokes
law), we obtain = DS /DT < 5/(3.3 560) = 1/33.
An arising question is whether the rod-like micelles get oriented in the solution by virtue of
non-Newtonian properties of the solution. To test this, we add elongated particles (as in [24]),
their length being 1 m through 100 m, to the solution and observe them through a light
microscope during the whole duration of our experiments. We nd no alignment of these
particles along the ow, thus discarding non-Newtonian properties of the uid (see [25]).
We inject the mixture drop at the center of the bottom of the larger Petri dish (
= 7 cm)
and observe a toroidal bulk ow of the surrounding water (g. 1a and b). We measure this
ux by mixing black pigment particles (supplied by F. Schoenfeld, D
usseldorf; mean diameter:
0.5 m) into the medium. The particle velocities are determined at dierent depths with a
microscope by adjusting its focus. The torus widens as the drop expands due to gravity
(compare g. 1a with 1b). A typical velocity prole is shown in g. 1c. We explain this ow
by shearing forces exerted by the expanding drop and acting radially outwards in the lower
water layers; the ow closes to a torus because of the conservation of mass. For t
90 s, the
microscope reveales no structuring (g. 2a). For t > 90 s, cells appear in the attened mixture

810

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a)

b)

c)

d)

Fig. 2 Development of nearly hexagonal cells out of (a) an unstructured mixture, 0.5-min, to (b) the
rst visible appearance of cells, 1.5 min, and to (c) well-organized shapes, 2.5 min. (d) 3.5 min. In
the section shown in (d) the center of the dish is at the lower left; the surfactant accumulating at the
cell vertices forms ngers that are driven radially outwards by the water current. (a, b, c, d): Dish
diameter
= 7 cm, surfactant and glycerin concentration: 3 vol%. Observations are done from
below; the surfactant appears dark because of light absorption.

(gs. 2a through c). Fingers are formed from the material accumulating at the vertices of the
cells. These ngers are driven radially outwards (away from the lower left of g. 2d) as they
follow the bulk water ow, thus behaving like the markers commonly used for visualization in
uid dynamics. The scenario of the formation of ngers, which are straightened by the ow,
is shown in g. 3. Note: the cells and ngers do not change when we change the duration
of injection of the drop at the beginning of the experiment. We impose changes in the water
ow, e.g., by blowing air on the dish or putting obstacles in the water, and found that the
ngers always follow the ow lines. The ngers have a typical width of 200 m. Moreover, we
nd that they widen to twice this thickness within t = 3055 min. In diusive systems, the
meanparticle displacement x vs. time t can be roughly approximated by the relationsship
x 6DS t. Using this relationship, we can estimate that DS 2.83.7 1012 m2 /s.
This result in compatible with the estimation performed above by X-ray scattering. In fact,
considering DT = 1010 m2 /s, we obtain now = DS /DT approximately between 1/50 and
1/27.
The extremely small value of DS leading to negligible displacement within the duration
of the experiments accounts for the long time the ngers keep their needle-like shape. In
fact, we can visualize the ngers as straight lines for times in the range 1060 min for T0 and
S0 ranging between 0.4 and 10 vol% (satisfying, in addition, condition (1) and T0 /S0  1).

 tter et al.: Double-diffusive fingering of a surfactant etc.

K. Ko

a)

c)

811

b)

d)

Fig. 3 Formation and straightening of ngers (
= 7 cm). The surfactant appears white because
light is not absorbed as in g. 2, but scattered. Surfactant and glycerin concentration: 10 vol%.
(a) Drop at 0 min. (b) 3.5 min, ngers have appeared; the circle around them corresponds to the
lifting P in g. 1b. (c) 7.5 min. (d) Close-up after 7.5 min. (Note that (a, b, c) correspond to a
dierent experiment than (d), so that the video-time inserts are not compatible.)

Using our setup, we also performed experiments with salt and sugar, injecting a drop
with coloured salt solution (salt 1.09 g/cm3 ) on the bottom of a dish containing sugar
solution (sugar 1.04 g/cm3 ). In these experiments, we observe connement of ngers in
two dimensions, as in the experiments with the surfactant. However, lateral distortions are
present already at the beginning of the horizontal nger displacement. It has been shown
(see [26]) that ngers can be straightened by using concentrations T0 and S0 , such that the
condition (1) is satised with R 1 . We check this in our setup with salt and sugar
setting salt 1.110 g/cm3 and sugar 1.037 g/cm3 , so that R = 3.0 leads to ngers almost
as straight as in our g. 3. However, the slightest change in S0 and T0 causing a change of
R in the salt/sugar experiment disrupts the ngers. This is in contrast with the extreme
robustness of stable shape of our needles on changes of S0 and T0 , as indicated in the preceding
paragraph.
Yet another advantage of the extremely low DS in our mixture is the fact that condition
(1) is fullled for a much larger range of initial concentrations T0 and S0 . In fact, if one
approximates S by S0 /z and T by T0 /z (z: initial height), then condition (1) becomes
T0 < 0.89S0 for salt and sugar, while it becomes T0 < 6.4S0 for our mixture. In the present
work, we do not take full advantage of our large range of possible T0 and S0 , but this range

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1.0

500

Tem [s]

[mm]

300

100

0.5

0.2

b)

a)
0.1

50
0.3

10

0.3

T0 [vol%]

10

T0 [vol%]

Fig. 4 (a) Finger emergence time Tem vs. initial glycerine concentration T0 (equal to the initial
surfactant concentration S0 ); straight line: scaling law Tem T00.48 (eq. (2)). (b) Wavelength vs.
T0 = S0 ; straight line: scaling law T00.34 (eq. (3)). (a, b) Measurements are shown as diamonds
with bars (standard deviation resulting from 50 video images).

can be kept in mind for future work, especially for the determination of scaling laws with
respect T0 at constant S0 , and viceversa.
Figure 4 shows our measurements of the nger emergence time Tem (dened in the section
Experiments) vs. T0 = S0 . These measurements can be tted by the scaling law
Tem T0 .

(2)

By tting this to the experimental data we obtain = 0.48 0.03. Tem aects the wavelength
due to time dependence of T . According to [22] and [27], (t) T (t)1/4 . In order to
estimate T , we assume that at t = 0 the solutes are in a at zone dened by z < h0 with an
homogeneous concentration

T0 . As time elapses, the upper border h of T rises due to diusion

approximately as h 6DT t. From mass conservation it follows that [T] h0 T0 / 6DT t,
1/4 1/4
which leads to the average gradient T (t) h0 T0 /(6DT t). This renders (t) T0
t .
Setting t = Tem and considering eq. (2) (with = 0.48 0.03) we obtain
T0 .

(3)

with = 0.37 0.01. A numerical t to the experimental data gives = 0.34 0.02, which
is compatible to the theoretically estimated result. This scaling law is plotted in g. 4b)
(straight line), agreeing well with the experimentally determined (at time Tem ) vs. T0 . Note
that is evaluated here over a much larger range of concentrations than in previous works
(e.g., in [28]). Despite the numerous approximations we make in our model, both scaling laws
are strongly supported by PDE-simulations using the governing Navier-Stokes and continuity
equations; these results will be published in a forthcoming paper. These scaling laws may be
used for good estimations of the wavelength or nger emergence time without considering the
experimentally hardly accessible gradients.
In the course of this work we found that for purely qualitative experiments it is
sucient to inject (using an ordinary pipette) a bit of non-diary coee whitener (e.g., Kr
ugers,
Cata, van Cooks or Coee-mate), stirred beforehand with water, at the bottom of a dish.
In fact, most brands contain sugar (which takes up the role of our glycerin) and among
other components surfactants which happen to have the properties required in the present
work. Using such whiteners, we observe cells and impressively straight ngers. (Note: it is
best to use a black background for better viewing with the naked eye.) Moreover, we nd a
good agreement with both scaling laws, when stirring Cata with dierent volumes of water;

 tter et al.: Double-diffusive fingering of a surfactant etc.

K. Ko

813

we obtain = 0.51 0.03 and = 0.39 0.02. As long as there is no interest in more detailed
investigations, any more complex setup is superuous for demonstration of cells and ngers.

We thank the Deutsche Forschungsgemeinschaft (Grants Ma 629/5- ) for nancial support

and R. Winter, University of Dortmund, for help with the X-ray small angle scattering. We
also thank Dr. Ferdinand (Kr
uger GmbH, Bergisch Gladbach, Germany) for revealing the
components of Kr
ugers coee-whitener to us.
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