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Merging of Soap Bubbles

Merging of Soap Bubbles and Why Surfactant Matters


Patricia Pfeiffer,1 Qingyun Zeng,2 Beng Hau Tan,3 and Claus-Dieter Ohl1
1) Institute for Physics, Otto von Guericke University Magdeburg, Magdeburg 39106, Germanya)
2) Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang
Technological University,
637371 Singapore, Singapore
3) Low Energy Electronic Systems, Singapore-MIT Alliance for Research and Technology, Singapore 138602,
Singapore
(Dated: 23 January 2020)
The merging of two soap bubbles is a fundamental fluid mechanical process in foam formation. In the present exper-
imental study the liquid films from two soap bubbles are brought together. Once the liquid layers initially separated
arXiv:1911.03175v2 [physics.flu-dyn] 22 Jan 2020

by a gas sheet are bridged on a single spot the rapid merging of the two liquid films proceed. Thereby the connecting
rim is rapidly accelerated into the separating gas layer. We show that due to the dimple formation the velocity is not
uniform and the high acceleration causes initially a Rayleigh-Taylor instability of the liquid rim. At later times, the rim
takes heals into a circular shape. However for sufficient high concentrations of the surfactant the unstable rim pinches
off microbubbles resulting in a fractal dendritic structure after coalescence.

The coalescence of two soap bubbles is a fundamental pro- Soap bubbles, which merge with a flat film show a cascade
cess in the production of foams and is thus crucial for many of partial coalescence. This means a smaller bubble remains
industrial processes such as waste water treatment1 or foam after the contact between bubble and film14 .
separation2. Despite the importance of the soap bubble co- Here, we report about the merging of two soap bubbles at
alescence process for the growth, structure and microscopic low approach velocity. Then a dimple forms, its shape just be-
properties of foams very few studies have addressed the fluid fore coalescence is revealed through interferometry. Once the
mechanics of two merging thin filmed bubbles. two films connect on a point-like liquid bridge, surface ten-
When two soap bubbles approach each other, their films sion accelerates a rim connecting the two films radially out-
deform slightly by the pressure built up from the entrapped ward. This process is studied with high-speed photography
gas. Once this gas sheet is sufficiently thin attractive van-der- and an instability observed. While surfactants are important
Waals forces create a liquid bridge connecting the two liq- to stabilize the bubbles, we also demonstrate that they play a
uid films. This may occur at the closest distance of the de- crucial part in the hydrodynamic merging process.
formed soap films. The connecting bridge driven by surface The soap bubbles are created by dipping tip of the syringes
tension quickly spreads radially out thereby merging the two (Soft-Ject Insulin syringes with Luer connection, Henke-Sass,
films3 . The coalescence of the two bubbles involves the de- Wolf GmbH Germany) into a soap solution and inflating the
formation of the liquid films, static surface forces, rheology, flat film formed by pressing on the plunger. A bubble attached
and hydrodynamics4–6 . to the syringe tip is inflated to about 12 mm in diameter. Once
After the coalescence of the bubbles, they share a sin- two soap bubbles are created this way they are brought to-
gle film that over time drains and eventually ruptures. The gether. One of the bubbles is stationary and the second bub-
drainage and the stability of the foam film are governed by in- ble is moved slowly towards the first with a translation stage
termolecular forces and surface rheology. Additionally, in the (M1 micromanipulator, Helmut Saur Laborbedarf, Germany)
presence of spatially varying concentration of surface active at an approach velocity of ≈ 1 cm/s. During this approach
molecules Marangoni flows effect the film drainage7. Once the bubbles suddenly coalesce by forming a single soap film
the liquid film is below a critical thickness van-der-Waals connecting the two bubbles (cf. supplementary material for
forces lead to the rupture of the shared film3 . Real liquid films a sketch of the experimental setup and Fig. 1). The dy-
contain impurities such as electrolytes, which affect the coa- namics of coalescence is observed with a high-speed camera
lescence of bubbles8,9 , too. (Photron AX200) at 22,500 or 67,500 frames/s (exposure time
Besides the liquid properties, also the speed under 1/900,000 s) and illuminated with either a white light source
which the bubbles approach each other affects the merging (Sugar Cube Ultra, USHIO AMERICA, INC., USA) or a co-
process9–11 . This can lead to a pimple, wimple, dimple, or herent light source (CW532-04 Series, Roithner Lasertechnik
ripple deformation of the liquid films10,11 . A pimple results GmbH, Austria, CW laser, wavelength λ = 532 nm, intensity
from a very slow approaching speed and a negative disjoining ≈ 2 mW/cm2 ). To avoid electric charging of the two bubbles
pressure such that the film surfaces attract each other10,12 . A during the inflation at nozzle of the plastic syringe15 we con-
wimple shows a varying film thickness. The central region is nect both wetted tips of the syringes with a copper wire that is
the thinnest and thickens radially10,13 . Ripples are interfaces held on a fixed electric potential.
called where a gap between the bubbles or a bubble and a sub- The bubbles are made of an aqueous solution of the anionic
strate varies in thickness with multiple maxima and minima. surfactant sodium dodecyl sulfate (Sigma-Aldrich, BioXtra
≥99.0% (GC), critical micelle concentration (cmc) 7-10 mM
at 20-25 ◦ C). Two concentrations are used, namely 5 and
10 mM and their coefficient of surface tension has been mea-
a) Electronic mail: patricia.pfeiffer@ovgu.de sured with the capillary rise method to be σ = 25 ± 2 mN/m
Merging of Soap Bubbles 2

2 mm (a) (b)
k=0
k=0
k=5
k=5
k=5
k=0
k=0

r r
4 mm
-44 µs -44 µs 44 µs 200 µm
(c)
1.2
before coalescence
after coalescence
0.8

d [µm]
0.4

178 µs 311 µs 444 µs 1067 µs 1511 µs 2489 µs 0.0

-400 -300 -200 -100 0 100 200 300 400


FIG. 1. Inclined side view of two merging soap bubbles. In the r [µm]
magnified view at t = −44 µs fringes can be observed in the area,
(d)
where the bubbles touch each other. Time t = 0 corresponds to the
start of the liquid bridge formation. The dashed circle at t = 44 µs
surrounds the the area where the merging started. After coalescence
air d D air air
the two bubbles share one film.

and σ = 27 ± 2 mN/m for a 5 and 10 mM SDS solution, re-


spectively. We measured their kinematic viscosity using an
Ubbelohde viscometer, from which we calculated the dy- FIG. 2. (a) Interference fringes in the soap film preceding the coa-
lescence and (b) in the frame after the coalescence (frame interval
namic viscosity, which is 1.01 ± 0.02 mPa s for both solutions.
∆t = 44 µs).(c) From the fringes the spatial varying height of the air
Figure 1 is composed of selected snapshots from a high- film can be calculated and is shown before (black squares) and after
speed imaging sequence showing the process of two bubbles coalescence (red circles). (d) A sketch of the overall shape of the
merging. At the top of the first frame the syringe tips and dimple. Note that the vertical scale is strongly stretched.
the copper wire are visible. The bottom of this frame shows
a darker area that is caused by liquid draining due to grav-
ity. The first snapshot (t = −44 µs) is taken shortly before
the bridging occurs. A weak fringe pattern is visible just be- the measurements are performed in transmission, the shortest
fore the two bubbles merge. The dashed circle at t = 44 µs distance has a bright fringe. That location is indicated in Fig.
indicates the point where the liquid bridge has connected the 2a with an arrow and is the zeroth order fringe (k = 0). The
two films. Between t = 44 µs and t = 2489 µs the two bubbles distance between bright fringes of λ /2n (n is the refractive
merge. A compound bubble is formed through the sharing of a index of the soap solution: n = 1.33) allows converting the
liquid film. The merged film will grow until the angle between line drawn in Figs. 2a and 2b into a height map of the air gap
the two bubbles becomes 120 ◦ . The concentric structure after before and just after coalescence, see Fig. 2c. The position
t = 1067 µs occurs due to thickness differences in the film. of the fringes are determined by taking the mean gray values
We are concerned with the initial process of film merging. along several lines through the fringe pattern. The maximum
For this we first want to understand the shape of the air gap thickness of the air film is 1.0 ± 0.1 µm. Repeating the exper-
separating the soap films. The interference fringes forming iment 50 times we find dimple heights between 0.4 µm and
prior to the coalescence event are observed in Figure 2a with 1.0 µm at the moment of coalescence. The overall shape of
an illumination of a continuous wave laser at λ = 532 nm the gap between the two films is sketched in Fig. 2d. Please
wavelength. We observe in a magnified view the two films note that the vertical axis is strongly magnified.
with a spatial resolution of 22 µm/pixel. Unfortunately, the We now discuss the growth of the merged films starting
quality of the interference pattern is affected by the imaging from the location where the two films are bridged. Figure 3a
and illumination through two soap films. Nevertheless, we shows a typical example of this merging dynamics. The dim-
observe concentric and mildly distorted circles where the dis- pled region just before coalescence is indicated with a blue
tances between two fringes is decreasing towards the center, dotted circle and the arrow indicates the location of the liq-
which is consistent with the presence of entrapped air between uid bridge. Bridging always happens on the crest of the dim-
the two soap films. Figure 2b just after coalescence demon- pled region as shown in Fig. 2. We see the rim expanding
strates that the two films bridge between the crests of the dim- radially from the point of contact. Interestingly, that part of
ple which is the shortest distance between the two films. Since the rim which travels through the dimpled region has a dis-
Merging of Soap Bubbles 3

(a) (b) (c) top view spreading rim


fringes

1 mm
-40 µs 0 µs 40 µs r
500 µm 1
0 µs 44 µs 89 µs
side view merging point
80 µs 160 µs 240 µs air
air
soap film air
v
rim v
dimple

280 µs 340 µs 400 µs 133 µs 222 µs 1067 µs t

FIG. 3. Spreading of the merged films during the coalescence of two soap bubbles (a) with a concentration of [SDS]=5 mM and (b) with
[SDS]=10 mM. The dark circle (blue dotted) in the first snapshot represents the fringe pattern. The films merge at t = 0 in (a) at the location
indicated by the arrow and in (b) at the lower left side of the fringes. In (b) at t = 44 and 89 µs the smooth rim and the liquid bridge indicated
with a blue circle and a red cross, respectively. The modulated rim that connects the two films propagates fastest through the dimpled region.
(c) Sketch of the spreading rim from top and in side view. The rim propagates faster within the regime of the dimple (dashed blue circle) due
to the higher curvature. In the side view the region which is already merged consists only of a singe film, whereas still two separate films exist
ahead of the rim.

torted and fuzzy front, while the part that travels outside is tia with the pressure gradient from surface tension, i. e.
smooth and circular. Figure 3b shows a similar case with the
only difference that the concentration of surfactant was dou- Du 1 2σ
G= = − ∇p ≈ − , (1)
bled to [SDS]=10 mM. The liquid bridge forms on the lower Dt ρH ρ H D2
left part of the dimpled region, again on a crest and the rim
spreads circularly. In contrast the rim traveling through the where u is the velocity of the fluid particle in the rim, ρH is
dimpled region reveals an instability or modulation with a the density of the liquid and ∇p the pressure gradient. The
length scale of 44 µm at t = 89 µs after bridging. Small dark latter we estimate with the Laplace pressure in the cylindrical
structures pinch-off from the modulated rim leaving behind rim of cross-section D and radius of curvature of ≈ D/2. In-
radial streaks. These streaks of round objects emanate from serting suitable values for σ = 0.025 N/m, ρ = 103 kg/m3 and
the slower parts of the modulated rim. Even after the rim has D = 1.6 · 10−6 m we obtain a high values for the acceleration
left the field of view at t = 1067 µs in Fig. 3b, radial pointing with G = 2 · 107 m/s2 . While viscosity counteracts this ac-
structures remain on the merged film. Figure 3c sketches the celeration we nevertheless expect this acceleration to act until
process of film merging within the dimple (right) and outside viscosity has diffused. This picture has been confirmed with
the dimple (left). The part of the rim with a radial modulation Volume of Fluid simulations in axisymmetry (cf. supplemen-
has a non-uniform radial velocity. As a consequence the two tary material for details to the simulations). Figure 4 depicts a
films cannot merge simultaneously at a distance r from the liq- simulation result for the parameters similar to the experiment
uid bridge. Instead pockets of gas become entrapped during and accounting for viscous and compressible effects (solver
their merging. This is consisted with the observation that the Interfoam from the OpenFOAM framework). Within 0.5 µs
round objects in Fig. 3b are formed between the slowest trav- the rim accelerates from 0 to a velocity of about 4.0 m/s.
eling parts and the fastest parts of the rim. Connecting these Now we argue that this extreme acceleration of the rim
clues we suggest that the objects are microscopic bubbles en- from the liquid into the gas phase destabilizes the rim due
to the Rayleigh-Taylor instability 16,17 . The most amplified
trapped by the non-homogeneous merging of film. A close-up √
wavelength is 3λc with λc = σ /(GρH ), see Ref.18 . Typ-
p
of the structured process is depicted in Fig. 3b at t = 44 and
89 µs where the rim traveling to the left is marked with a blue ical experimental values lie between 44 µm (as in Fig. 3b at
circle centered around the location of the liquid bridge (red t = 89 µs) and 150 µm. Since the rim expands and hence the
cross). Comparing the radius of the circle and the radius of length-scale of the instability, the most unstable mode (i. e.
the modulated rim, it is clearly visible that the velocity in the how many lobes the rim has as a result of the instability) is
dimpled regime is higher, i. e. 3.0±0.2 m/s, whereas the ve- taken as a quantitative measure. We obtain values for the un-
locity of the smooth rim is 2.5±0.2 m/s. The difference in the stable mode between 12 (as in Fig. 3a) and 44. Perturbations
velocity can be attributed to the varying curvature of the of the below a critical wavelength λc are stabilized by surface ten-
soap film inside and outside the dimple. Outside the two free sion. The critical wavelength can be calculated as18
soap films separate more rapidly than within the dimple. p
λc = σ /G(ρH − ρL ), (2)

We now address the mechanism destabilizing the rim’s cir- where ρH and ρL are the densities of the heavier (water) and
cular shape. For this we estimate the acceleration G of rim lighter (air) fluids, respectively. Since ρH ≫ ρL , we can ne-
due to surface tension σ . Ignoring viscosity we balance iner- glect ρL in equation (2).
Merging of Soap Bubbles 4

10 The applied potential on the bubbles ensures reproducible


results, however, a simple connection between the bubbles
r [µm]
(i. e. a wire to exchange electric charges) yields the same re-
5 sults. In experiments without this potential, a deformation of
the rim is only observed by chance. We speculate that the
bubbles are charged by inflating them. A similar effect was
0 -3 investigated by Choi et al.15 , who observed that droplets be-
10 10-2 10-1 100
5.0 come charged during conventional pipetting.
The closure of the distorted rim depends strongly on the
u [m/s]

SDS concentration: with increasing amount of SDS more bub-


2.5 ble pinch-off events are seen. However, when reaching the
critical micelle concentration, a further increase of the bub-
ble formation does not occur. The detachment of tiny soap
0 -3 bubbles from the rim is only possible, because more surface
10 10-2 10-1 100 active molecules are available than necessary for the current
7
5.0 X 10 surface. So the excess molecules can be used to create and
stabilize a new surface in a much shorter time, which leads to
G [m/s2]

the pearling of the droplets. The pearling is more pronounced


2.5 directly after the formation of the liquid bridge than further
away from the bridging point, since the distance of the films
increases with distance from the bridging point and thus the
0 -3 closure dynamics slows down.
10 10-2 10-1 100 The measured wavelength of the indentation agrees with an
t [µs]
impulsively acting Rayleigh-Taylor instability and growth by
radial expansion. The high acceleration of the liquid within
FIG. 4. Numerical simulations of the development of the rim radius
over time (top row) and reaches a velocity of 4.0 m/s (center row). the first 50 ns after the coalescence, which is confirmed by
The rim accelerates within 0.5 µs to a velocity of 4.0 m/s, i. e. that simulations, induces the instability. Since the instability al-
results in an acceleration of 5·107 m/s2 (bottom row). Dimple height: ready occurs during bridging the instability timescale is con-
1.6 µm, film thickness: 5.5 µm. sistent with the claim that the acceleration of the liquid is caus-
ing the instability25–27 .
Structures similar to those described in the current work
The acceleration G governs the dominant wavelength at the were already found in similar systems at the receding rim of
rim, which strongly depends on the dimple height. With an bursting fluid films28,29 or during the impact of a droplet on
acceleration of G = 2 · 107 m/s2 λc is ≈ 0.7 µm. a fluid surface30 . Another work was provided by Thoraval et
The instability already occurs during bridging, and thus a al., who investigated an impacting droplet on a liquid layer
diameter of the √ liquid bridge of 7 µm with the initial wave- and found a formation of bubble rings in the impact region31.
length of λc / 3 = 0.4 µm would lead to a wavelength of Despite these structures look similar to those described in the
44 µm at a circumference of the rim of 2.4 mm. Thus, λc ≈ current work, the mechanism of their formation differs.
0.7 µm seems an appropriate value. In this work the coalescence of soap bubbles is studied.
The Rayleigh-Taylor instability leads to a pearling of tiny Prior to their coalescence the bubbles form a dimple and en-
soap bubbles from the rim if the indentation is sufficiently trap a tiny volume of air. Upon merging, the rim of the spread-
large. The indentation leads locally to a higher curvature of ing film is accelerated for a brief moment, simulations predict
the rim and thus a higher propagation velocity of the highly less than 1 µs. During that time a Rayleigh-Taylor instability
curved parts. The curvature decreases due to the reunion of sets in resulting in an instability of the rim front. The velocity
the water columns and thus the velocity decreases. The rim of the rim is higher in the area of the dimple, due to a higher
becomes smooth after the propagation through the dimpled curvature in that regime and hence the velocity of the rim is
area and remains circular. faster. Depending on the surfactant concentration the entrap-
Upon the approach of two merging bubbles a dimple is ment of gas pockets is possible with increasing SDS concen-
formed between them. This is a general phenomenon when tration. However above the cmc no further effect of the SDS
bubbles or droplets approach either each other19–21 or a concentration on the instability of the rim is observed.
substrate22–24 . The computed height of the dimple calculated See supplementary material for a sketch of the experimental
using the Bragg equation agrees very well with the height in setup, details and snapshots of the simulations.
other experiments23,24 . The distance between the bubbles is The Deutsche Forschungsgemeinschaft, DFG, is acknowl-
shortest at the rim of the dimple and the film thickness at edged for support within project DA 2108/1-1.
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Merging of Soap Bubbles 5

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