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Effects of protonation on foaming properties of

dodecyldimethylamine oxide solutions: a pH-
Cite this: Soft Matter, 2015, 11, 561
study†
Kathrin Schellmann,a Natalie Preisig,a Per Claessonb and Cosima Stubenrauch*a

Received 7th November 2014
Accepted 17th November 2014
DOI: 10.1039/c4sm02476a
www.rsc.org/softmatter
The critical micelle concentration (cmc), the surface excess (G), as well as the micelle aggregation number
(m) of the surfactant dodecyldimethylamine oxide (C12DMAO) have been reported to strongly depend on
the pH-value of the aqueous surfactant solution. At high ionic strength, the cmc displays a minimum,
while both G and m have a maximum at a pH-value close to the pKa of the surfactant. These
experimental observations have been explained as being due to specific hydrogen bonds between the
head groups, which are formed once the surfactant is partly or fully protonated. This investigation
addresses the question of whether the pH also affects the foaming properties of C12DMAO solutions. To
answer this question we measured the foamability and the foam stability of C12DMAO solutions at a fixed
C12DMAO concentration of 5 cmc for five different pH-values, namely pH ¼ 2, 3, 5, 8, and 10. We found
that the foamability is hardly affected by the pH-value, while the foam stability strongly depends on the
pH. As is the case for the above mentioned properties, the foam stability also displays an extremum in
the studied pH-range, namely a maximum at pH ¼ 5. We discuss our results in terms of the hydrogen
bond hypothesis and show that this hypothesis indeed is in line with the observed trend for the foam
stability. Moreover, we discuss that hydrogen bond formation may rationalize how the molecular
structure of a surfactant affects foam stability.

surfactant mixture consisting of cationic and non-ionic species.

1. Introduction
The surfactant dodecyldimethylamine oxide (C12DMAO) is
predominantly non-ionic in aqueous alkaline solutions (ref. 1
and references therein). A decrease of the pH-value leads to
protonation of the oxygen and thus renders the surfactant
cationic (C12DMAOH+). Since the protonated and the uncharged
molecules are in equilibrium, both species are present over a
large pH-range. This equilibrium is shied towards the
protonated form with decreasing pH-value. Since the chemical
structure of the head group is almost identical for the cationic
and the non-ionic species, the effect of the charge (here: of the
protonation) on typical surfactant properties can be studied
systematically without being inuenced by other parameters
such as different head group sizes and compositions.
Changing the pH-value of a dodecyldimethylamine oxide
solution has the same effect as changing the ratio of a
a
Universität Stuttgart, Institut für Physikalische Chemie, Pfaffenwaldring 55, 70569
Stuttgart, Germany. E-mail: cosima.stubenrauch@ipc.uni-stuttgart.de; Tel:
+49-711-685-64470
b
KTH Royal Institute of Technology, School of Chemical Science and Engineering,
Department of Chemistry, Division of Surface and Corrosion Science, Drottning
Kristinas väg 51, Stockholm, SE-100 44 Sweden
† Electronic supplementary information (ESI) available. See
10.1039/c4sm02476a
Thus, we can consider the pH-dependent properties of
C12DMAO in the same way as properties of surfactant mixtures
which are of great importance in all surfactant-related elds.2 It
has been found that typical surfactant properties such as the
critical micelle concentration (cmc), the maximum surface
concentration (Gmax) and the plateau value of the surface
tension (scmc) change as a function of the mixing ratio. On the
assumption of ideal mixing, which is almost always a reason-
able approximation for mixtures of classical low molecular
weight surfactants, the cmc-values and the scmc-values change
continuously from the values of surfactant 1 to those of
surfactant 2 (see e.g. data in ref. 3–5 by way of example). For the
Gmax-values a clear trend is normally not observed. In contrast,
the pH-dependence of these characteristic properties for
C12DMAO is different and the above mentioned properties have
an extremum close to where 50% of the surfactant is proton-
ated. This extremum is a minimum in the case of cmc and scmc,
while it is a maximum in the case of Gmax.1 Note that this
behaviour is only found when the ionic strength is 0.1 M (or
higher) and constant. At a low ionic strength electrostatic forces
predominate and in this case the cmc decreases with increasing
pH, i.e. with increasing abundance of the cationic species.6
To explain these extrema Maeda et al. suggested attractive
DOI:
hydrogen bonds between non-ionic and cationic species as well
as between two cationic species.1,7,8 The presence of such

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Soft Matter
hydrogen bonds appear to explain the pH-dependence of the
surface properties observed for C12DMAO in literature1,7–9 and
in the study at hand. The main idea is that with decreasing pH-
value repulsive and attractive interactions act simultaneously.
The repulsion is due to the charges and is thus of electrostatic
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nature, while the attraction is a result of hydrogen bonds
between the molecules, for which, in turn, protonation of a
fraction of the head groups is the prerequisite. These two
counteracting forces lead to a maximum in surface excess at
around 50% protonation (pH  4.6): from pH ¼ 10 down to pH
¼ 5 the attraction created by the hydrogen bonds increases
until, at pH < 5, the electrostatic repulsion becomes increasingly
important.
Motivated by the strong pH-effect on the surface properties
of C12DMAO in aqueous solutions we endeavoured to investi-
gate whether the foaming properties are also pH-dependent. If
so, would the foamability and the foam stability pass through
an extremum at 50% ionization? The answer to this question is
not straightforward since there are no direct correlations
between the surface properties mentioned above and foaming
properties. A prominent example of this lack of correlation is
the foaming behaviour of the two non-ionic surfactants n-
dodecyl-b-D-maltoside (b-C12G2) and hexaethyleneglycol mono-
dodecyl ether (C12E6).10–13 Although C12E6 has a lower cmc and a
lower scmc-value compared to b-C12G2, the stability of foams
stabilized by C12E6 is several orders of magnitude lower
compared to that of foams stabilized by b-C12G2. Furthermore,
we know from foam studies on this non-ionic mixture as well as
on mixtures of non-ionic and cationic surfactants that some
foam properties are unaffected by the mixing ratio while others
change continuously as a function of the composition.10,13–15‡
Again, this continuous change is not necessarily connected with
the surface properties. The only direct correlation between
surface and foam properties that has been observed up to now is
between surface elasticity (or surface rigidity) and foam
stability, where a few systematic studies have shown that the
higher the surface elasticity (or surface rigidity) the better the
foam stability.11–13
The question this paper addresses is whether or not the pH-
value has an effect on the foaming properties of aqueous
C12DMAO solutions. In case it has an effect, how does it affect
foamability and foam stability? To answer this question we rst
measured the foamability and the initial liquid fractions 30 of
foams which were generated with aqueous solutions of
C12DMAO at a concentration of c ¼ 5 cmc for ve different pH-
values, namely pH ¼ 2, 3, 5, 8, and 10. Aer the foams were
generated, we investigated the time evolution of the foam
volume, of the liquid fraction, and of the bubble size distribu-
tion. From these measurements we extracted pieces of infor-
mation on the foam stability and on the crucial destabilizing
‡ To the best of our knowledge there is only one study where one foam property,
namely the foam stability, runs through a maximum if one changes the mixing
ratio.14 In this particular case charge neutralisation leads to the formation of a
Newton black lm, which is a sign of high lm stability and thus of high foam
stability.
562 | Soft Matter, 2015, 11, 561–571
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processes, which we discuss in the light of the hydrogen bond
hypothesis suggested by Maeda et al.
2. Experimental section
2.1. Materials and cleaning procedure
The dodecyldimethylamine oxide (C12DMAO) was purchased
from Sigma Aldrich and puried by recrystallization three times
from pure acetone (p.a. 99.9%, from VWR). Sodium chloride
(NaCl) was obtained from Merck and roasted at 500  C over
night to drive off organic contaminants. 1 M HCl and 0.1 M
NaOH aqueous solutions from Scharr and Merck, respectively,
were used as received to adjust the pH-values of the C12DMAO
solutions. The pH adjustments of the C12DMAO solutions were
monitored with a pH-Meter pH 197 s from WTW with 0.05
accuracy. The pH-values were controlled before and aer
experiments. Please note that under atmospheric conditions pH
values higher than 6 are no equilibrium values. The dissolution
of CO2 in the aqueous solution leads to a continuous decrease
of the pH value down to 6 as a function of time. For example,
the value of pH ¼ 10 decreased down to pH ¼ 8.95 in 3 h. This
difficulty is not addressed in Maeda's work which is why the
data reported for pH > 6 should be looked at carefully. How we
dealt with this point is explained in Section 2.2 and 2.3,
respectively. All solutions were prepared with double distilled
water and contained 0.1 M NaCl to minimize the change of the
ionic strength of the solution with varying pH. All glassware was
cleaned before use with deconex UNIVERSAL 11 from Borer
Chemie and rinsed several times with distilled water to remove
impurities.
2.2. Surface tension measurements
In order to discuss our results in the light of already published
data we remeasured the surface tension isotherms at 22  C at
ve different pH-values utilizing the Du Noüy ring method and a
STA1 tensiometer from Sinterface Technologies. For each pH-
value a 100 mL ask of a stock solution with 0.1 M NaCl and a
C12DMAO concentration above the cmc was prepared. Each
time at least 5 mL solution for washing the glassware and 10 mL
solution for a measurement was used. Aer each measurement
the ask was lled up with 0.1 M NaCl solution with the same
pH-value and the diluted solution was used for the next
measurement.
In Fig. 1 the surface tensions s of all C12DMAO solutions in
the presence of 0.1 M NaCl are presented as a function of the
total surfactant concentration c for pH ¼ 2, 3, 5, 8, and 10.
Measuring the pH values before and aer the experiments
revealed that the drop of the pH due to dissolution of CO2 can
be neglected in case of pH ¼ 8. However, this was not the case
for pH ¼ 10 which is why we measured the surface tension only
down to a surfactant concentration of c ¼ 3.5  104 mol L1.
The lower the surfactant concentration the longer it takes to
reach the equilibrium value. For pH ¼ 10 we observed a
decrease, a plateau and a further decrease of the s-value which
told us that the surface tension decreases because of surfactant
adsorption and a drop of the pH. We thus stopped measuring at
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Fig. 1Surface tensions s of C12DMAO solutions in presence of 0.1 M NaCl as function of the total surfactant concentration c for five different
pH-values, namely pH ¼ 2, 3, 5, 8, and 10. Solid lines represent second order polynomial fits of the experimental data.
the lowest concentration at which we still observed a plateau
value before the decrease of the pH comes into play and further
decreases s. The solid lines in Fig. 1 represent second order
polynomial ts of the experimental s(c)-data. From these ts we
calculated the surface concentration according to


1 ds
G¼ : (1)
RT d ln c p;T
The surfactant was treated as being non-ionic for the calcu-
lation of G, which is appropriate since, due to the presence of
0.1 M NaCl, the concentration of the surfactant counterion [Cl]
remains essentially constant as the surfactant concentration is
increased.1
In Fig. 2 we summarize the main outcome of the surface
tension measurements and of the respective calculations. A
comparison with the data published by Maeda et al.1 shows the
same overall trend but slight deviations as regards the absolute
values of the cmc and of Gmax, while the scmc-values are in
perfect agreement. As regards the cmc, the differences can be
explained by the total number of experimental data points,
which are much less in Maeda's work (see e.g. Fig. 3 in ref. 7)
compared to ours. Moreover, we extracted the cmc from the
crossover point between the scmc-value and the polynomial,
while Maeda et al. most likely extracted it visually from the s(c)-
curve. The discrepancies for the Gmax-values can be explained by
the way they are calculated: we calculated them from the poly-
nomial (gray squares ( ) in Fig. 2) since this is more accurate,
while Maeda et al. most likely used the maximum slope of the
s(c)-curve drawn between two subsequent measuring points.§
That this assumption is very likely can been seen if one looks at
the data we obtained by using the maximum slope (open
squares ( ) in Fig. 2) which are in perfect agreement with
Maeda's values. Finally, Maeda et al. did overlook the pH drop
for pH values larger than 6.
§ Note that neither the way they determined the cmc-value nor the way they
calculated the Gmax-value is explicitly mentioned in any of Maeda's papers.
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2.3. Foam measurements
The foams generated from the C12DMAO solutions were studied
using the commercially available FoamScan device from TECLIS
(France, http://www.teclis.eu). Since the foams are generated
with N2 we assumed that the pH does not change signicantly
during the foam measurements (see Section 2.1 for the further
details). The FoamScan uses conductivity measurements and
image analysis to monitor the volume and the liquid fraction of
the foam. Additionally, the bubble sizes and bubble size
distributions can be analyzed with the cell size analysis (CSA)
function. For that purpose, the number and size of bubbles
found in an area of 20 mm2 were determined and the poly-
dispersity index PI, i.e. the normalized standard deviation, was
determined according to
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2
hr2 i  hri
PI ¼ ; (2)
hri
where hri is the arithmetic mean bubble radius.
A detailed description of the FoamScan method can be
found in ref. 5, 13, 16 and 17. Briey, the FoamScan device
consists of a rectangular glass column with (a) ve pairs of
electrodes to measure the foam conductance and (b) four glass
prisms where pictures of the foam can be taken using one of the
two CCD cameras. To generate the same foam volume Vfoam,
nitrogen is sparged at a constant gas ow rate Q through a
porous disk (pore sizes ¼ 41–100 mm) which is located at the
bottom of the glass column. The column contains an initial
solution volume Vinitial from which the foam is generated. Aer
stopping the gas input, which will be referred to as t ¼ 0 s in the
following, the foam conductance at xed positions along the
column is measured. From these values the liquid fraction 3 in
the foam is determined according to Feitosa's equation.18 The
changes of the foam volume are detected with the second CCD
camera.
In all our foam measurements a foam volume Vfoam of 80 mL
was generated from an initial solution volume Vinitial of 40 mL.
To study the foamability of the C12DMAO solutions the gas ow
rate Q was varied from 20 to 200 mL min1, while a constant gas
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Fig. 2 Critical micelle concentration cmc (top), plateau values of the
surface tension scmc (middle) and the maximum surface excess Gmax
(bottom) as a function of the pH in presence of 0.1 M NaCl. Data are
taken from ref. 1 ( ) and from this work ( , ). The grey squares
represent values calculated from the derivative of the polynomial fit
and the open squares are values obtained by a straight line fit between
the two last points prior to cmc.
ow rate of 50 mL min1 was used to produce foam for the foam
stability measurements. The conductivity measurements and
cell size analysis determination of the bubble size and bubble
size distribution were carried out simultaneously at xed posi-
tions along the glass column, namely, at the second electrode
and the second prism of the CCD camera at heights of Helec2 ¼
564 | Soft Matter, 2015, 11, 561–571
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Fig. 3 Foamability (top) and initial liquid fraction 30 (bottom) as a
function of the N2 flow rate Q at five different pH-values, namely pH ¼
2, pH ¼ 3, pH ¼ 5, pH ¼ 8, and pH ¼ 10. The solid line (top) is calculated
according to t ¼ V/Q.
85 mm (25 mm above the liquid level) and Hprism ¼ 105 mm
(45 mm above the liquid level), respectively.
All presented foam measurements were reproduced two
times. For the sake of clarity, only one experiment is shown in
the Result section, while both measurements are plotted in
Fig. S1–S5 of the Section ESI† to illustrate the reproducibility of
the FoamScan method. All measurements were performed at
room temperature (22  C). The freeware program ImageJ was
used to treat the foam pictures before using the cell size analysis
(CSA) function as described in ref. 13 and 17.
3. Results
We systematically studied the inuence of the pH-value on the
properties of foams stabilized by C12DMAO at a surfactant
concentration of c ¼ 5 cmc. All measurements were carried out
at ve different pH-values, namely 2, 3, 5, 8, and 10. Firstly, the
foam generation was investigated by varying the N2 gas ow rate
Q over a broad range. For that purpose, we measured the
foamability and the initial liquid fraction 30 as a function of Q
for the ve pH-values (Section 3.1). Secondly, we monitored the
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time evolution of both the foam volume and the liquid fraction
to gain information on the foam destabilizing processes in
general and about drainage in particular (Section 3.2). Finally,
the time evolution of the bubble sizes and the bubble size
distributions were investigated, which allowed us to identify
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In conclusion one can say that at moderate ow rates up to
100 mL min1 neither the foamability nor the initial liquid
fraction are strongly affected by the pH-value in a range from pH
¼ 2–8. For pH ¼ 10, however, we found a slightly lower foam-
ability and – connected with this – lower 30-values for all ow

coalescence events (Section 3.3). rates.

3.2. Time evolution of foam volume and liquid fraction

3.1. Foamability and initial liquid fraction Aer having studied the foam generation process, we investi-
gated the time evolution of the foam volume and of the liquid
In order to examine the inuence of the gas ow rate on
fraction aer turning off the gas ow. For these studies, the
foamability,{ the time required to produce a foam volume of V
foams were always generated with the same constant N2 gas
¼ 80 mL from a given surfactant solution was measured at
ow rate of Q ¼ 50 mL min1. In Fig. 4 (le) the foam volume V
different N2 ow rates Q (20–200 mL min1) at a surfactant
is shown as a function of time t. The time t ¼ 0 s is the time at
concentration of c ¼ 5 cmc. The results are shown in Fig. 3 (top).
which the preset foam volume of 80 mL was reached and where
On the assumption that all the injected N2 gas remains trapped
the N2 ow was stopped. Thus, for t < 0 s foam generation takes
in the foam and that the liquid content of the foam is negligibly
place. As can be seen, the V(t)-curves are very different except for
small, one can approximate the time t it takes to generate a
the two curves measured at pH ¼ 8 and 10 which are hardly
foam volume V as t ¼ V/Q. This relation is a mass balance for the
distinguishable. The volume of the foams generated at pH ¼ 2,
gas, and it is shown as a solid line in Fig. 3 (top). The agreement
3 and 5 decreases only slightly over a certain period of time
between the theoretical curve and the measured points allows
before it starts decaying quickly at t  1200 s for pH ¼ 2, at t 
us to conclude that close to all the N2 indeed is located in the
1500 s for pH ¼ 3 and at t  1800 s for pH ¼ 5. On the contrary,
foam bubbles.k Looking at the data more closely one sees that
the volume of the foams generated at pH ¼ 8 and pH ¼ 10,
the foamability at pH ¼ 2, 3, 5, and 8 is the same except at the
respectively, already decays very quickly aer some tens of
lowest ow rate of Q ¼ 20 mL min1 where it can be clearly seen
seconds and the foams are completely destroyed aer t  600 s.
that the foamability increases in the following order: pH ¼ 8 <
The corresponding time evolution of the foam's liquid frac-
pH ¼ 2 < pH ¼ 3 < pH ¼ 5 (the time it took to generate 80 mL
tion 3 is shown in Fig. 4 (right). As discussed in relation to Fig. 3,
decreases in this order).** However, the foamability of the
the foams generated at pH ¼ 2, 3, 5, and 8 have similar initial
solution with pH ¼ 10 turned out to be lower than those of the
liquid fractions of 30  0.06–0.09, while for pH ¼ 10 the initial
other solutions at all ow rates. For the following discussion we
liquid fraction is considerable lower (30  0.04). The resulting
will only refer to the data obtained for Q ¼ 50 mL min1 and will
3(t)-curves reect the differences observed for the V(t)-curves.
regard the foamability to be independent on the pH in a range
For pH ¼ 2, 3, and 5 the liquid drains out continuously during
from pH ¼ 2 to pH ¼ 8 and to be slightly lower at pH ¼ 10.
the rst 1800 s (30 min), which leads to a continuous decrease
To gain further insight into the foam generation the initial
of the liquid fraction from 30  0.09 to 3  0.01. For pH ¼ 8 and
liquid fraction 30 was determined at the second electrode
10, however, a continuous drainage is observed only up to 250 s
(middle of the 80 mL foam) and plotted as a function of the ow
aer which the foam collapses so that one no longer can speak
rate Q in Fig. 3 (bottom). As expected the initial liquid fraction 30
of drainage.
increases with increasing ow rate from around 3% (for Q ¼ 20
In conclusion one can say that the combination of the V(t)-
mL min1) to 24% (for Q ¼ 200 mL min1). This is due to foam
curves and the 3(t)-curves allows us to conclude that the foam
drainage during its generation. The slower the foam is gener-
stability decreases in the following order: pH ¼ 5 > pH ¼ 3 > pH
ated, the more time it has to drain before the predetermined
¼ 2 [ pH ¼ 8  pH ¼ 10. These differences are mainly due to
nal foam volume is reached and the liquid fraction is
coalescence which increases in this order and which is much
measured. The 30(Q)-curves measured at pH ¼ 2, 3, 5, and 8 are
more pronounced at pH ¼ 8 and 10 compared to the other pH
essentially the same if one takes into account the huge scatter of
values as will be shown in the following Section.
the data. However, for pH ¼ 10 a lower initial liquid fraction was
found at all ow rates which is in line with the lower foam-
ability. In other words, the foam is more difficult to generate 3.3. Time evolution of bubble size and bubble size
since it is very unstable, which, in turn, explains the lower distribution
capacity for water uptake. Although this point is oen overlooked, all foam properties
depend on the bubble size and the bubble size distribu-
{ Foamability describes the ability of a surfactant solution to produce a certain tion.13,17,19 However, reliable and straightforward determination
foam volume in a given period of time and is therefore an important foam of bubble sizes represents an on-going challenge. Our way to
property.
measure the bubble size and the respective distribution is
k Note that the relation t ¼ V/Q also describes the results at the highest ow rate
explained in ref. 13 and 17. The results for foams stabilized by
although the initial liquid fraction at this Q is as high as 24% and thus no longer
negligible. C12DMAO at the ve different pH-values are shown in Fig. 5 and
** At low gas ow rates the error bars are larger due to the partial foam collapse Table 1 as a function of time. The pictures in Fig. 5 clearly reect
that occurs during foam generation. the decrease of the amount of liquid (black parts) with time

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Fig. 4 Time evolution of the foam volume V (left) and of the liquid fraction 3 (right) at five different pH-values, namely pH ¼ 2, pH ¼ 3, pH ¼ 5, pH
¼ 8, and pH ¼ 10. The gas flow rate used for foam generation was Q ¼ 50 mL min1.
caused by drainage (see Section 3.2) and they are consistent
with the V(t)- and the 3(t)-curves discussed in Section 3.2. The
foams generated at pH ¼ 2, 3, and 5 evolve in the same way up to
400 s, while the foams generated at pH ¼ 8 and 10 start
collapsing via coalescence already aer 200 s. The images
shown in Fig. 5 directly visualize the results seen in Fig. 4,
namely the drainage behavior as well as the sudden foam
collapse.
In Table 1 we report the arithmetic mean bubble radius hri
and the polydispersity index PI for the ve pH-values at three
different times t. It can be seen that at t ¼ 0 s the mean radii hri
for all foams are approximately the same. Recalling that the
initial liquid fraction 30 is also comparable (except for pH ¼ 10)
one can conclude that at the outset of the experiments the
structure of the foams generated at pH ¼ 2, 3, 5 and 8 is very
similar. The mean radii hri and the polydispersity index PI
increase for pH ¼ 2, 3, and 5 within the rst 400 s. This
observation indicates that drainage and coalescence events (for
coarsening the time scale is too short) take place simulta-
neously with drainage being the dominant mechanism up to t 
1200–1800 s. A comparison with the foams generated at pH ¼ 8
and 10 shows that the latter are very unstable. According to the
data in Table 1 the PI increases signicantly in the rst 200 s
while the average bubble size remains the same. The data
shown in Fig. 4 and the pictures seen in Fig. 5 reveal that foam
collapse is also due to both drainage and coalescence but here
coalescence becomes the dominant mechanism as early as 200 s
aer foam generation.
The main results of our foam study can be summarized as
follows: foams generated with an aqueous solution of C12DMAO
at a concentration of 5 cmc and at ve different pH-values,
namely pH ¼ 2, 3, 5, 8, and 10
(a) Have comparable foamabilities at moderate ow rates (up
to 100 mL min1) at pH ¼ 2, 3, 5 and 8, while the foamability at
pH ¼ 10 is slightly lower.
(b) Have comparable initial liquid fractions 30 at pH ¼ 2, 3, 5
and 8, while the initial liquid fraction at pH ¼ 10 is lower.
(c) Evolve differently as a function of time as regards the
foam volume.
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(d) Show the same drainage behaviour for pH ¼ 2, 3, 5 and a
different one for pH ¼ 8 and 10.
(e) Have very different stabilities at pH ¼ 2, 3, 5 and 8, while
the stability at pH ¼ 10 is the same as that observed for pH ¼ 8.
4. Discussion
4.1. Effect of pH-value on foaming properties of aqueous
C12DMAO solutions
Let us rst recall the main question this paper addresses before
we discuss whether our experimental data help to answer this
question. Does the pH-value have an effect on the foaming
properties of aqueous C12DMAO solutions? The answer to this
question depends on the range of pH-values and on the foam
property investigated. We thus analysed the effect of the pH on
(a) foamability, (b) drainage, and (c) foam stability.
(a) We found that the foamabilities at moderate ow rates
(up to 100 mL min1) are comparable at pH ¼ 2, 3, 5 and 8,
while the foamability at pH ¼ 10 is slightly lower. However, the
differences are small as reected in the fact that the measured
data points all fall close to the same theoretical curve (see
Fig. 3). In other words, all foams are stable during foam
generation. An example of signicant differences in foamability
is presented in one of our previous work (Fig. 3 in ref. 13). The
reason for the observation that the pH-value has no signicant
inuence on the foamability is the fact that foamability is
mainly affected by the diffusion rate of surfactant molecules to
the surface, which, in turn, depends on the molecular weight
and on the concentration of the surfactant. These two quanti-
ties do not change signicantly with pH so very similar foam-
abilities are expected. In general, foamabilities of low molecular
weight surfactants do not differ very much if the generated foam
remains stable during the generation process, which is the case
for the foams generated in this study.††
†† If the generated foam is very unstable, i.e. if it collapses partly or completely
during generation, the foamability becomes much lower compared to a more
stable counterpart (see Fig. 3 in ref. 13 by way of example) and can no longer be
described with the theoretical model.
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Fig. 5 Time evolution of the bubble sizes and the bubble size distribution at five different pH-values, namely pH ¼ 2, 3, 5, 8, and 10. The gas flow
rate used for foam generation was Q ¼ 50 mL min1.
(b) As regards drainage, we observe that the drainage rates
(i.e. loss of liquid per time) are similar for pH ¼ 2, 3, and 5,
while the foams generated at pH ¼ 8 and 10 drain faster. For the
drainage rate h ¼ D(ln 3)/D(ln t) we obtained values of around h
¼ 0.26  0.02 for pH ¼ 2, 3, and 5, while we found h ¼ 0.32 
0.02 for pH ¼ 8 and 10. Drainage is predominantly affected by
the viscosity of the bulk solution and the surface rigidity: the
lower the viscosity and the lower the surface rigidity the faster
the drainage rate.20,21 Since the viscosities correspond to those
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Soft Matter
of pure water for all pH-values,‡‡ we speculate that the surfaces
of the foams generated at pH ¼ 8 and 10, respectively, have a
lower rigidity and thus a lower elasticity compared to the
surfaces of the foams generated at pH ¼ 2, 3, and 5. Unfortu-
nately, surface rheological parameters cannot be measured. At
the high surfactant concentrations (5 cmc ¼ 5  103–9  103
‡‡ Water (20  C) ¼ 1.00 mPa s; water (25  C) ¼ 0.891 mPa s; C12DMAO solution at
22  C and pH of 2 ¼ 1.09  0.05 mPa s; C12DMAO solution at 22  C and pH of 5
¼ 0.97  0.02 mPa s.
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Soft Matter Paper

Table 1 Arithmetic mean radius (hri), total bubble number in an area of has been investigated theoretically, and it has been shown that
20 mm2 (ntotal) and polydispersity index (PI) of the foam bubbles at the hydrogen bond formed between water and the amine oxide
three different times t for the foams generated at five different pH-
group is stronger than between two water molecules. Moreover,
values
even the water–water hydrogen bond strength is increased in
pH t¼0s t ¼ 200 s t ¼ 400 s close proximity to the amine oxide head group.24 No similar
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theoretical study has been performed to elucidate the interac-

2 hri/mm 0.152 0.158 0.176 tion between the protonated form of the head group and water,
ntotal 164 142 106
PI 0.224 0.321 0.423
and likewise no theoretical study has investigated the strength
3 hri/mm 0.154 0.145 0.163 of hydrogen bonds formed directly between a charged and an
ntotal 159 158 108 uncharged amine oxide head group.
PI 0.206 0.402 0.527 From the discussion above it seems clear that hydrogen
5 hri/mm 0.139 0.131 0.177 bonding is of great importance for the properties of an
ntotal 191 173 93
PI 0.237 0.537 0.528
interface carrying an adsorbed layer of amine oxide surfac-
8 hri/mm 0.177 0.166 — tants. One expects strong hydrogen bonds between the head
ntotal 119 103 — group and water as well as between two head groups. Spec-
PI 0.229 0.463 — troscopic studies of the hydration water, as reported for other
10 hri/mm 0.167 0.158 — non-ionic surfactants,25,26 could provide additional informa-
ntotal 135 137 —
tion, particularly if combined with theoretical calculations.
PI 0.238 0.333 —
However, as yet such data is lacking and thus we refer to the
hydrogen bond model suggested by Maeda et al.1,7,8 The key
assumption in this model is that repulsive electrostatic
Table 2 Degree of ionization in bulk solution (a)1, maximum surface
concentration (Gmax), minimum surface areas (Amin), average N–N interactions compete with attractive hydrogen bonds
distance between two molecules (Daverage), and fraction of hydrogen between the surfactant head groups, for which, in turn,
bonds (p) of C12DMAO in 0.1 M NaCl solution at different pH-values protonation of some head groups is the prerequisite. The
hydrogen bond model rationalizes why the surface properties
pH a Gmax/106 mol m2 Amin/Å2 Daverage/Å p
pass an extremum when the pH is changed (see Introduc-
2 1 4.27  0.10 38.92  0.99 6.24  0.07 0–0.07 tion). In addition, it explains why the scmc-values/Gmax-value
3 0.9 4.40  0.10 37.71  0.88 6.14  0.07 0.01–0.18 of the cationic species C12DMAOH+ are unusually low/high
5 0.44 4.89  0.10 33.97  0.71 5.83  0.06 0.41–0.55 compared to those of the non-ionic species C12DMAO.
8 0.07 4.37  0.10 37.96  0.89 6.16  0.07 0–0.15 Generally speaking, the scmc-values/Gmax-value of the
10 0 4.29  0.10 38.73  0.92 6.22  0.07 0
cationic species C12DMAOH+ are expected to be much higher/
lower than those of C12DMAO since the cationic species repel
each other at the surface. However, inspection of the data
M depending on the pH) required for the foam study the provided in Fig. 2 and Table 2 of the present work as well as
diffusion of surfactant to the surface is very fast. Since the those provided in Maeda's studies1,7,8 shows that this is not
available techniques allow measuring only in a limited range of the case – the scmc- and Gmax-values of the two species are very
frequencies the measurements would all lead to the same value, similar. These results strongly support the presence of a non-
namely to an elastic modulus of 0. electrostatic attraction between the cationic species or
(c) The foam stability, just as the drainage rate, depends on between a cationic and a non-ionic species at low and
the pH-value. Here, however, the differences are much more medium pH-values. As already mentioned in the Introduc-
pronounced. In addition, the foam stability passes a tion, Maeda et al. suggest that this attraction is the result of
pronounced extremum at around pH ¼ 5 and thus follows the hydrogen bonds between two neighbouring surfactant
trends observed for the cmc, the scmc-values, and the Gmax- molecules.1,7,8 More specically, Maeda speaks of “hydrogen
values. We will discuss and explain the pH-dependence of the bonded dimers” which he expects “to behave as if they are
foam stability using the hydrogen bond model suggested by double-chain amphiphiles”.7
Maeda et al. Since this model is not very well known and never
has been used to explain foam properties, we will rst recapit-
ulate the basic ideas (Section 4.2) before we use the model to
explain the different foam stabilities (Section 4.3).

4.2. Hydration and the hydrogen bond model

The N–O bond in the uncharged amine oxide head group is very
polar due to charge transfer from the nitrogen atom to the
oxygen atom. This results in strong interactions between water
and the amine oxide head group which results in signicant
repulsive forces between bilayers of C12DMAO.22,23 The interac-
tion between water and the uncharged amine oxide head group
Fig. 6 Schematic representation of the proposed hydrogen bonds
between a non-ionic and a cationic head group that leads to the
formation of a “hydrogen bonded dimer”.7 The length of the N–O
bond is taken from ref. 24, while the one of the hydrogen bond is taken
from ref. 27.

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We rened the drawing provided in ref. 7 by adding the bond
lengths and showing the tetrahedral arrangement around the
central N-atom. In Fig. 6 hydrogen bonding between a non-ionic
and a cationic species is shown by way of example (the distances
for two cationic species are the same). The gure illustrates that
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direct hydrogen bonding between the head groups is sterically
possible and may result in the formation of a dimer, while this
dimer cannot form hydrogen bonds to additional surfactants.
Note that the drawing provided by Maeda et al. for the two
cationic species in ref. 7 (Fig. 4b) is misleading since it suggests
that one molecule can form hydrogen bonds to two neighbours,
which is impossible for steric reasons and not in line with his
idea of “hydrogen bonded dimers”. The authors corrected this
drawing in ref. 8 (Fig. 1).
Let us now assume that hydrogen bonded dimers indeed
are formed and that they consist either of a non-ionic and a
cationic species or of two cationic species depending on the
pH. Next, we calculated the average distance between two
molecules in a dimer. According to the drawing in Fig. 6 the
N–N distance in the hydrogen bonded dimer is Ddimer ¼ 2(1.4
Å sin 109 ) + 2.8 Å ¼ 5.4 Å. The average distance between non-
ionic amine oxide molecules, Dmonomer, not participating in
hydrogen bonding can be calculated from the surface excess
at high pH to be 6.22 Å. Based on this idea and on the surface
excesses Gmax calculated from the surface tension curves, one
can quantify the number of hydrogen bonds and thus the
number of dimers at a given pH. From the Gmax-value we
calculated the respective Amin-value the square route of which
is the average N–N distance Daverage between two molecules
(see Table 2). Since the N–N distance calculated from the
Gmax-values is an average over all distances, it holds in a
simple two-state model that
Daverage ¼ pDdimer + (1  p)Dmonomer
where p is the fraction of molecules that form dimers which can
be calculated according to
Daverage  Dmonomer
p¼ : (4)
Ddimer  Dmonomer
In Table 2 we provide the calculated values for p at the
various pH-values. The table reads as follows: at pH ¼ 2 a
maximum of 7% of the molecules at the surface form dimers, at
pH ¼ 5 it is up to 55% and at pH ¼ 10 no dimers are formed. In
other words, the number of hydrogen bonded dimers displays a
maximum at pH  5. The lower tendency to form dimers at low
pH-values is due to the electrostatic repulsion, which counter-
acts close proximity of the head groups and thus hydrogen bond
formation, while the lower tendency to form dimers at high pH-
values is due to the low fraction of protonated head groups.
What is of importance for the following discussion is the fact
that the values calculated for pH ¼ 2, 3, 8 and 10 are very
similar. In view of the large uncertainties of these numbers a
quantitative analysis, unfortunately, is not possible which is
why we will discuss the data qualitatively in the following
Section.
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4.3. Hydrogen bonding and foam stability
Having recapitulated the hydrogen bond model and having
estimated the fraction of molecules that form dimers at the
respective pH, we now discuss whether this model can explain
the pH-dependence of the foam stability observed for
C12DMAO. Our discussion will be based on three thoughts: (a)
the degree of ionization decreases continuously from 100% at
pH ¼ 2 to 0 at pH ¼ 10 (see Fig. S6, ESI†), (b) the number of
hydrogen bonded dimers displays a maximum at pH  5 (see
Table 2) and thus does not reect the continuous change of the
degree of ionization, (c) the presence of hydrogen bonds
between head groups enhances the stability of a foam.
The two key experimental observations are as follows: (1) the
foam stabilities at pH ¼ 8 and 10 are signicantly lower
compared to those at lower pH; (2) the foam stabilities pass a
maximum at pH ¼ 5. Looking at Table 2 one sees that there are
no (or only very few) dimers at pH ¼ 2, 8, and 10. The higher
foam stability at pH ¼ 2 compared to pH ¼ 8 and 10 must thus
be due to the presence of charges and thus of electrostatic
repulsion between two approaching surfaces (note that we now
refer to electrostatic repulsion between two surfactant layers
and not between neighbouring molecules in the same layer).
This repulsion slows down drainage and coalescence and thus
increases the lifetime of the foam. At pH ¼ 3 the number of
dimers is larger compared to pH ¼ 2 which is why the foam
stability is higher. Finally, at pH ¼ 5 the attractive hydrogen
bonds and the repulsive electrostatic interactions are counter-
balanced in an optimum way resulting in the highest foam
stability.
With these results in mind we want to recall that charges are
not necessarily needed to stabilize foams. For example, foams
generated in presence of C12TAB (see Fig. 3 in ref. 14) or sodium
dodecyl sulfate (SDS)28 are much less stable compared to foams
(3)
stabilized by a mixture of C12DMAOH+ and C12DMAO at pH ¼ 5.
On the other hand, the stability of foams stabilized by the non-
ionic surfactant b-C12G2 ref. 13 can be compared to that of
foams generated at pH ¼ 5 in the study at hand (see Fig. 7
below). Thus the lower foam stabilities observed at pH ¼ 8 and
10 cannot be explained as a consequence of reduced electro-
static interactions. This is a very important conclusion since it is
just the opposite of what was argued about 35 years ago.29 Tsujii
and Arai measured the stability of foams generated with
C12DMAO solutions containing 0.1 M NaCl at different
concentrations as a function of the pH which varied from 5.5 <
pH # 7. Note that they only studied the average lifetime of
foams generated via the Bikerman method and that they did not
provide any additional information about the foamability of
their solutions, the liquid content of the foams, and the bubble
sizes. Moreover, they did not determine any other properties of
their solutions so that one can hardly draw any conclusions
from this work. Nevertheless, looking at Fig. 1 in ref. 29, one
sees that the average lifetime s of foams generated with a
C12DMAO solution of c ¼ 4 mM (4 cmc) increases from s  400
s at pH ¼ 7 to s  1700 s at pH ¼ 6.3, which is in perfect
agreement with our results (see Fig. 4). Tsujii and Arai argued
that it is the formation of ionic species that stabilizes the foam
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Soft Matter
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Fig. 7 Time evolution of the foam volume V for foams stabilized by
four different surfactants, namely C12DMAO at 5 cmc, 0.1 M NaCl, pH
¼ 5 ( ), C12E3I1 at 5 cmc, 0.1 M NaCl ( ), C12E6 at 10 cmc, 0.01 M NaCl
( ), and b-C12G2 at 10 cmc, 0.01 M NaCl ( ). The data for C12E6 and b-
C12G2 are taken from ref. 13. The gas flow rate used for foam gener-
ation was in all cases Q ¼ 50 mL min1.
due to increasing repulsive interactions between the mono-
layers of the foam lms. These repulsive interactions indeed
explain the higher stability at low compared to high pH but not
the maximum stability at pH ¼ 5, which brings us back to our
hypothesis, namely that foam stability is directly correlated with
the number of hydrogen bonds.
With the hypothesis in mind that hydrogen bonds between
head groups enhance the stability of a foam we searched for
further foam data of surfactants with a C12-chain but different
head groups. Foams stabilized by aqueous solutions of C12E6
ref. 13 and C12DMPO14 are also much less stable than the foams
generated at pH ¼ 5 in this study. The fact that C12TAB, SDS,
C12E6, and C12DMPO are not capable of forming hydrogen
bonds between the head groups supports our hypothesis. On
the other hand, foams stabilized by b-C12G2 are much more
stable compared to those stabilized by the above mentioned
surfactants, which, in turn, can be explained with hydrogen
bonds between the sugar head groups. To further test our
hypothesis we carried out a preliminary study with the non-
ionic surfactant 1-O-(3,6,9-trioxa-henicosanyl)-myo-inositol
(C12E3I1). The head group of this surfactant consists of an
ethoxylated inositol the synthesis and properties of which are
explained in ref. 30 and 31. What is signicant for the paper at
hand is the fact that the inositol head group has ve OH-groups
and is thus also capable of forming hydrogen bonds between
two neighbouring molecules. Based on our hypothesis we thus
expected foams generated in the presence of C12E3I1 to be more
stable compared to foams stabilized by C12E6 or by C12DMAO at
pH s 5 and to have a similar stability as foams stabilized by b-
C12G2 or by C12DMAO at pH ¼ 5. Comparing Fig. 7 with Fig. 4
(le), one clearly sees that this is indeed the case.
570 | Soft Matter, 2015, 11, 561–571
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Paper
5. Conclusions & outlook
We conclude by repeating our two key ndings. (1) Foams
stabilized by aqueous solutions of C12DMAO show a maximum
in the foam stability at pH ¼ 5. (2) The stabilities of foams
generated at low pH-values are signicantly higher compared to
those generated at high pH. The higher stability at low
compared to high pH-values is indeed due to the presence of
electrostatic repulsion between two opposing surfactant layers.
The maximum stability, however, cannot be explained by
changes in the electrostatic repulsion since this repulsion
decreases with increasing pH and does not pass a maximum.
Thus the maximum stability is linked to the possibility of
forming hydrogen bonds between the surfactant head groups at
moderate and low pH. Indeed, looking at foam stability data for
other surfactants with C12 alkyl chains, one nds that stable
foams are only observed when hydrogen bonds can be formed
between the head groups. Thus stable foams are observed for
surfactants with sugar head groups,13 but not with head groups
consisting of ethylene oxide,13 phosphine oxide,14 trimethyl
ammonium14 or sulphate.28 These observations suggest that
hydrogen bonds between neighbouring molecules at the surface
enhance the foam stability of C12 surfactants. Formation of
hydrogen bonds between surfactant head groups gives rise to a
short-range attractive interaction1,7,8 that may render the
surfactant layer more rigid (in the sense that the mobility of the
molecules is restricted) and more elastic (in the sense that
deformations can be counteracted), which explains the pH-
dependence of the drainage rate and of the foam stability
observed in this study. Our hypothesis of the importance of
hydrogen bonds for foam stability will be challenged by col-
lecting spectroscopic data on hydrogen bonding at the
aqueous–surfactant–air interface e.g. with sum frequency
generation spectroscopy. Theoretical investigations of interac-
tions between surfactant head groups in the presence of water
molecules also have the potential to further increase our
understanding.
Acknowledgements
We would like to thank the German Research Foundation (DFG)
for nancial support.
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