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Current Opinion in Colloid & Interface Science 9 (2004) 178 – 184

www.elsevier.com/locate/cocis

Review
Bubble coalescence and specific-ion effects
Vincent S.J. Craig *
Department of Applied Mathematics, Research School of Physical Sciences and Engineering, Australian National University,
Canberra ACT 0200, Australia

Abstract

Major recent advances: Recent advances that contribute to our understanding of specific-ion effects in bubble coalescence include new
theoretical and simulation efforts to determine the arrangement of ions at interfaces and a clearer recognition that specific-ion effects in
bubble coalescence are related to many other phenomena that exhibit ion specificity.
D 2004 Elsevier Ltd. All rights reserved.

Keywords: Bubble coalescence; Specific-ion effects; Electrolytes; Thin film stability; Hydrophobic; Hofmeister; Nanobubbles

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
2. The importance of ion specificity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
3. Bubble – bubble coalescence in the presence of surfactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
4. Films between two bubbles in the absence of surfactant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
5. Films formed between bubbles and solid surfaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
6. Specific-ion effects and bubble stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183

1. Introduction 2. The importance of ion specificity

Perhaps, one of the most surprising and easily ob- The Derjaguin, Landau, Verwey and Overbeek (DLVO)
served examples of a macroscopic effect of ion specificity theory of colloidal interactions has been the dominant
is the influence that dissolved electrolytes have on bubble paradigm for 50 years. This theory generally works well
coalescence in aqueous solutions. Above a certain con- under the circumstances for which it was intended, low salt,
centration, which is dependent on the particular salt inert surfaces and interactions at separations greater than a
chosen (typically f 0.1 M), many common electrolytes few nanometers. Under these conditions, the charge on an
inhibit the coalescence of bubbles, whereas others have no ion, rather than the particular type of ion, is important.
influence on bubble coalescence [1,2..]. This simple Therefore, the theory explicitly excludes specific-ion effects
observation is not understood. Here, we will attempt to and can largely be seen as a ‘‘chemistry-free’’ regime.
determine if the ions influence coalescence by action at However, since the work of Hofmeister in the 19th century,
the interface or in bulk and investigate their possible it has been known that the nature of an ion can have a very
influences on film rupture. great influence on the stability of a colloidal dispersion,
particularly at high salt concentrations. At concentrations
exceeding 0.1 M, the range of the electrostatic interactions is
greatly reduced, and specific-ion effects dominate. There-
* Tel.: +61-2-6125-3359; fax: +61-2-6125-0732. fore, interactions in biological systems [3.], as well as
E-mail address: vince.craig@anu.edu.au (V.S.J. Craig). complex fluids [4] and slurries [5], often cannot be under-

1359-0294/$ - see front matter D 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.cocis.2004.06.002
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178–184 179

stood within the DLVO framework, but rather, the specific classes; a anions, h anions, a cations and h cations. We
nature of the ions is important. Our understanding of ion should expect a fundamental difference between a and h
specificity has barely progressed from the empirical work of anions and, similarly, between the a and h cations. How-
Hofmeister more than 100 years ago, with the terms ‘‘ion ever, the labeling does not necessarily mean that a cations
size’’ and ‘‘polarisability’’ giving names to our ignorance, in and a anions or h anions and h cations share a common-
the absence of an ion-specific theory. Without theoretical ality, although this is possible. The combining rules tell us
predictions, molecular recognition, drug design, formula- that it is not the absolute behavior of a single ion that
tions science and protein crystallization will remain largely matters but the combination of ions. In my opinion, this is
empirical arts. an important and significant point that has often been
Whilst there are a great number of systems that overlooked. The behavior is inherently nonlinear and spe-
exhibit ion specificity, attempts to investigate these cific to both ions present. Therefore, any suitable description
effects are challenging. Currently, short-range interactions must identify a property or properties that separates the a
cannot be adequately measured for most systems, par- from the h ions and describe a means by which this property
ticularly when soft surfaces are involved. Therefore, or properties, in combination, can switch the coalescence
efforts necessarily concentrate on indirect methods. Stud- inhibition on or off. Ideally, in time, our ignorance will pass,
ies in protein solubility, complex fluids, enzyme action, and the terms a and h will be replaced by terms that
surface tension, pH and bubble coalescence have pro- describe the appropriate property. Clearly, the combining
vided a great deal of evidence against which theories rules provide a very strong test of any theory.
can be tested. The challenges for theoreticians are
extensive, requiring recognition of the granularity and
chemical nature of the solvent, the geometry and nature 3. Bubble – bubble coalescence in the presence of
of the surfaces, inherent nonlinearity and an appropriate surfactant
description of the ion, which may include ion size,
polarisability, solvent interactions and ion geometry, At this stage, we still do not have a clear understanding
amongst other descriptors. Simulation studies must con- of the influence of electrolytes on bubble coalescence.
tend with all this and find means to deal effectively Indeed, our ignorance is deeper than it first appears, as we
with a range of length scales that extend from the do not fully understand the coalescence process that takes
classical down to the quantum regime. Underlying all place when two air bubbles collide in pure water. In the
this is a belief that a theory of ion specificity should be following, I will examine what is known of this process.
able to describe all of the very diverse specific-ion During the collision of two bubbles, a film of liquid is
effects, such as Hofmeister, anti-Hofmeister behavior, formed between the two gaseous phases. The propensity of
strong co-ion influences and competition between ions. the film to drain and rupture ultimately determines the
Therefore, a theoretical description that is adequate in one outcome of the collision process, and whilst it is obvious
system may lead to an increased understanding of other that these two processes are not independent, they are often
systems, even if they do not exhibit the same ion-specific treated separately for convenience, with the acknowledg-
effects. If this is true, the apparently simple system of ment that once the film has drained below a certain
two bubbles colliding in an aqueous electrolyte solution thickness, then film rupture is possible, and at another
may be useful in elucidating the nature of short-range thinner film dimension, film rupture is often assured.
interactions. Drainage is often treated within the Reynolds model of
Over a decade ago, we described simple combining rules two circular parallel plates separated by a fluid, although
that predict the bubble coalescence behavior of electrolytes under some conditions, it is known that dimpling of the
based on assigned properties of the ions that make up the interfaces occurs [7. – 9..]. Additionally, the influence of
electrolytes [1,2..]. Ions were empirically assigned a type, a interfacial forces must be taken into account.
or h and the combination of ions present in the added The case of a thin film stabilized by a surface active
electrolyte determined, if the solution would inhibit bubble agent is relatively well understood. For films that are
coalescence. Bubble coalescence was inhibited relative to electrostatically stabilized, the double-layer repulsive sur-
pure water with an aa or hh combination and unchanged face forces act to provide a disjoining pressure that slows or
when an ah or ha combination was employed (see Fig. 1). prevents film drainage. The film thickness increases with
As yet, no exceptions have been found to these rules, the range and magnitude of the repulsive force, as does its
although it has been claimed that NaClO4 inhibits bubble stability to rupture. Addition of electrolyte screens the
coalescence at very high concentrations [6]. However, at repulsive force and allows a thinner film to form. As
such high concentrations, the level of contaminant ions is drainage proceeds, the film becomes sufficiently thin, such
likely to be sufficient to produce coalescence inhibition that the rupture of the film becomes likely. Thermal dis-
independently. turbances cause surface waves that can grow under the
What does the existence of these combining rules indi- action of attractive Van der Waals forces. If these waves
cate? Primarily, it enables us to separate the ions into four grow sufficiently, the liquid film will be pinched off, and
180 V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178–184

Fig. 1. Table depicting the effect of a range of electrolytes on bubble coalescence. A tick indicates that the salt inhibits bubble coalescence. A cross indicates
that no bubble coalescence inhibition has been observed. The properties a and h have been assigned empirically and can be used with the combining rules to
predict the bubble coalescence behavior of an anion – cation combination. aa or hh combinations correspond to bubble coalescence inhibition and ah or ha
combinations, no inhibition. No exceptions have been found.

film rupture will occur [10]. The growth of surface waves and the rate of film thinning has not been arrested at the
can be responsible for film rupture at thicknesses exceeding point of rupture. Clearly, the description of film rupture by
100 nm given sufficient time to develop [11.]. For surfactant capillary waves applied to films formed in the presence of
films, rupture times exceed 10 s and often exceed 100 s, and surfactants cannot be applied here. The lifetimes of these
agreement with theory is not complete but is generally good, films is shorter than the characteristic time required for the
supporting a capillary wave rupture mechanism [11.,12]. Van der Waals forces to rupture the films via capillary waves
Films may also rupture by a nucleation mechanism [8..,9..], [11.]. A description of film rupture in these cases therefore
where a hole in the film forms spontaneously. The likeli- requires a modification to the capillary wave approach or an
hood of nucleation rupture is much greater as the film thins, alternative means of film rupture, such as nucleation of
hence, film rupture by this mechanism is also closely related holes.
to film drainage. The absence of surface-active material at the interface
results in an increase in surface mobility. This will lead to a
considerable increase in the drainage rate and film thinning
4. Films between two bubbles in the absence of times comparable with the film lifetimes measured in clean
surfactant systems [14.,15.], although the mobility of the interfaces,
important in these calculations, is not truly known. Capillary
It is commonly observed that even mildly stable films waves will also grow more rapidly if the attraction between
cannot be formed in pure water (or any pure fluid); however, the gaseous phases is increased, such as in the presence of a
the addition of certain salts in sufficient amounts permits a long-range hydrophobic attraction.
metastable aqueous film to be formed. The increased sta-
bility of the film is sufficient to prevent the coalescence of
bubbles that collide in bulk or are brought together during 5. Films formed between bubbles and solid surfaces
the production process at a frit. Cain and Lee [13..]
investigated the coalescence of captive bubbles in aqueous Studies of bubbles approaching solid surfaces can be
KCl solutions and found an increase in film stability with categorized depending on the wettability of the solid mate-
increasing salt concentration. As the electrolyte concentra- rial [7.,16. – 18]. When the material is hydrophilic, a stable
tion increased, the film lifetime increased, but in all cases, film is formed, and the film thickness is well described by
was less than 1 s. Films could not be produced in 0.1 M DLVO theory. An increase in salt concentration results in a
KCl; films formed in 0.5 M KCl were found to rupture at decrease in equilibrium film thickness, and this thickness is
separations of between 75 and 95 nm, and in 1.0 M KCl, directly related to the Debye length. However, when a
films drained to thicknesses of between 55 and 75 nm before hydrophobic surface is employed, the film ruptures rapidly
rupture. In surfactant films, a decrease in the thickness of a and at large separations [16.,18] (typically >100 nm), and
stable film is observed as the electrical double layer is the addition of salt prolongs the stability of the film, such
compressed upon the addition of electrolyte. There are that the drainage process proceeds further and rupture
important differences when surfactant is absent, the film occurs at smaller separations [16.,19..]. This is true even
thickness is not related to the Debye length of the solution if the hydrophobic surface bears the same surface charge as
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178–184 181

the hydrophilic system [19..] does and therefore cannot be bubbles was assured by AFM examination. In the absence
explained by a reduction in electrical double layer repulsion. of nanobubbles, the long-range attraction measured can be
The degree of surface hydrophobicity need not be great; considered the true long-range hydrophobic attraction.
generally, a contact angle in excess of 45j is sufficient to Mahnke et al. [8..,9..] have elegantly demonstrated that
lead to an unstable film [8..]. Clearly the hydrophobicity of the film separating a bubble and a hydrophobic surface
the surface plays an important role in the film stability, ruptures at separations exceeding 40 nm in the absence of
although a direct correlation with the contact angle has not nanobubbles. They attribute this to the action of hydropho-
been shown [8..]. bic forces. There is also evidence that the drainage rate is
Films formed between a bubble and a hydrophilic solid faster on a hydrophobic surface [7.], suggesting that an
surface act similarly to films formed between two bubbles additional attraction may be present, providing further
formed from surfactant solution. Their behavior is well evidence for a hydrophobic attraction between a bubble
understood in both cases. Films formed between a bubble and a hydrophobic surface.
and a hydrophobic solid surface are unstable, unless Some time ago, we suggested that the hydrophobic
electrolyte is added, as is the case for films formed attraction may be operating between colliding bubbles to
between two bubbles in the absence of surface-active produce coalescence [1,2..]. Let us examine this in more
material. In this case, our understanding is poor, but detail. If a hydrophobic attraction (of unclear origin) that is
given the similarity of behavior, it is reasonable to suggest considerably larger than the Van der Waals interaction is
that the same destabilisation mechanism is operating in acting between bubble surfaces, this may play a role in the
both cases. The evidence suggests that the hydrophobicity destabilization of the aqueous film. First, we will consider
of the substrate is important to film rupture. Previously the capillary wave mechanism. Calculations reveal [11.] that
[1,2..], we have proposed that an uncontaminated air – the range at which films rupture is consistent with capillary
water interface is a strongly hydrophobic surface, and this waves, but the measured time of rupture is not sufficient if
has been supported in later studies [20]. Therefore, it is the interfaces are considered immobile. However, the pres-
reasonable to assume that a film separating two bubbles ence of an attractive force much larger in magnitude and
will act similarly to a film confined between a bubble and range than the Van der Waals interaction will lead to more
a hydrophobic solid surface. rapid growth of capillary waves and a large decrease in
Direct force measurements between hydrophobic surfa- rupture time. Therefore, the capillary wave mechanism of
ces are often characterized by a strong, long-range attractive film rupture driven by the hydrophobic attraction may be
interaction. The range of the measured force varies consid- valid in the pure water system.
erably and appears to be strongly dependent upon the Let us consider nucleation as a rupture mechanism.
surface preparation method employed rather than the contact The nucleation of a vapor phase between two nonwetting
angle at the surface. This suggests that the hydrophobicity of surfaces at separations below 500 nm is energetically
the interface is not the determining factor in the magnitude favourable, and in the presence of dissolved gas, the
of the interaction. Many theories have been proposed to range at which nucleation is possible is extended consid-
explain the interaction, but none are completely satisfactory erably [25.]. However, there is a large activation barrier
in terms of explaining its range and magnitude. An extensive to nucleation of a gas phase between hydrophobic surfa-
review by Christenson [21.] is recommended to the inter- ces, unless the surfaces are at a very small separation.
ested reader. When the hydrophobic surface is itself a bubble, the gas
In many systems where a hydrophobic attraction is within the bubble is able to enter the film, and this
measured, it can be argued that ‘‘nanobubbles’’ are present should reduce the barrier to nucleation. The amount of
on the surface and that these nanobubbles play an important gas entering the liquid film could be increased by a
role in the attraction and often give a false impression of the strongly attractive force; therefore, it is feasible that the
range of the attraction. The separation is determined exper- hydrophobic attraction could increase the range and
imentally as the solid –solid separation distance, when, in probability of film rupture through nucleation. Further-
fact, the solid – nanobubble or nanobubble –nanobubble sep- more, the origin of the hydrophobic attraction may be
aration may be considerably less, depending on the size of related to the metastability of the intervening film, but
the nanobubbles. There is clear evidence of the existence of until the mechanism of the attraction is understood, any
nanobubbles on some hydrophobic surfaces [22 –24]. In the relationship is speculative.
opinion of the author, many published measurements can be If one accepts a role for the long-range hydrophobic
attributed to the presence of nanobubbles, but there exist attraction in bubble coalescence in aqueous systems, a
several measurements between hydrophobic surfaces that similar force must be proposed in other pure liquids, as
exhibit a hydrophobic attraction in circumstances where stable films cannot be produced in any pure liquid. Meas-
nanobubbles are absent. For example, Ishida et al. [23.] urements have revealed a similar, long-range interaction in
measured an attraction larger than is expected based on Van other liquids [26]; however, these forces were attributed to
der Waals forces, between hydrophobic surfaces that had the presence of nanobubbles, and other liquids studied did
never been exposed to air and where the absence of nano- not exhibit a long-range attraction.
182 V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178–184

In the absence of solute, Gibbs Elasticity will be absent quantity of material per unit area of the film. The Gibbs
and Marangoni effects minimised. One could therefore Elasticity is also written in the form [31],
argue that capillary waves could grow undisturbed or
 2
mechanical disturbances could have catastrophic effects on dc
film stability; however, the considerable film stability ob- 4c dc
served between bubbles and hydrophilic substrates in pure E¼ ð2Þ
kB TD
water are strong evidence that this is not the case. We have
already indicated that if the interface is mobile, film thinning where c is the concentration, c is the surface tension, kB is
progresses more rapidly and this can lead to short rupture Boltzmanns constant, T is temperature and D is a poorly
times. A highly mobile bubble – aqueous interface could be defined measure of thickness. Note that surface elasticity is
invoked to explain the short rupture times of films between often interpreted as arising from an increase in surface tension
a bubble and a hydrophobic surface. However, films formed when an expansion of the interface leads to a reduction in the
between a bubble and a hydrophilic surface are stable for amount of adsorbed material at the interface in the presence of
long periods. In both systems, the bubble – aqueous interface a surface-active component. However, it equally applies
is identical and equally mobile, hence, this is clearly not the when the solute is depleted from the interface, as is the case
dominant influence. Therefore, the rupture of films between with many electrolytes (surface tension increases with con-
a bubble and solid surface or between two bubbles in pure centration); thus, the mechanism giving rise to elasticity is not
water remains unresolved. a local increase in surface tension, as is often described.
Inspection of Eq. (2) reveals that the magnitude of the surface
tension change with concentration of solute is important, but
6. Specific-ion effects and bubble stability not the sign. Indeed, a correlation between the transition
concentration at which bubble coalescence is prevented and
Any discussion of the role of electrolytes in bubble the magnitude of the surface tension gradient has long been
stability is going to be speculative given our lack of recognized [31 –34..], suggesting that the elasticity of the
understanding of the coalescence process in pure water. film during rapid stretching associated with film thinning, or
Electrolytes have only a little [27] influence on bubble capillary waves, is crucial in the prevention of bubble
coalescence up to the transition concentration (typically coalescence. However Stoyanov and Benkov [29.] argues
f 0.1 M for a 1:1 salt). Therefore, the electrostatic that the Gibbs Elasticity disappears from the equations that
double layer is highly compressed at the concentrations describe the drainage and hydrodynamic stability of thin
that concern us. The challenge then is to resolve how films and that surface diffusion dominates the behavior. Like
the short-range effect of electrolyte can influence the the Gibbs Elasticity, the drainage velocity determined using
bubble coalescence process that occurs at separations of the surface diffusion approach [29.] is also approximately
approximately 100 nm. We must determine if the in- proportional to (dc/dc)2. Thus, the observed experimental
fluence of electrolyte is at the interface or if it is a bulk correlation with (dc/dc)2 may arise from the diffusion of
phenomenon. solute in the thin film rather than from Gibbs Elasticity. The
In the past, we have proposed that electrolyte may reduce correlation with (dc/dc)2 also includes electrolytes that have
the range of the hydrophobic attraction between two bubbles no influence on bubble coalescence, as they generally have
sufficiently to prevent film instability [1,2..]. However, lower values of (dc/dc)2 [31]. Values of (dc/dc)2 below f 1.0
subsequent measurements of the hydrophobic attraction in (mN2 m 2 M 2) indicate no bubble coalescence inhibition.
concentrated salt solutions showed that the attraction is not Large values of (dc/dc)2 may dampen capillary waves and
reduced by the addition of salt [28]. Therefore, we can reduce film thinning and rupture. However, the coalescence
abandon this hypothesis. Two other possibilities will be inhibition of some salts is not described by their influence on
investigated here: the possible damping of the growth of surface tension. The tetramethylammonium acetate electro-
capillary waves by electrolyte, thereby preventing film lyte is a strong test of the validity of the combing rules, as it is
rupture, and film rupture by nucleation being reduced in a hh salt and bubble coalescence is prevented. However, the
the presence of electrolyte. (dc/dc)2 value of 0.25 predicts that it will have no effect on
Both surface elasticity and surface diffusion [29.] will bubble coalescence. Sodium acetate has a (dc/dc)2 value of
oppose the growth of surface waves. Gibbs [30] has defined 2.1, yet, has no significant influence on bubble coalescence;
the surface elasticity as thus, the value of this term as a true indicator of the role of
  electrolyte must questioned.
dl2 Perhaps then, electrolytes inhibit rupture by preventing
E¼ 4C22ð1Þ ð1Þ
dM2 M1
nucleation in the film separating bubbles. It is known that
most electrolytes have an electrorestrictive influence on
where E is the Gibbs Elasticity, the suffixes 1 and 2 indicate water, causing a contraction in the volume occupied by
components of the film, the latter being in excess, C is the water upon the addition of ions. It is possible that electro-
surface excess, l is the chemical potential and M is the total restriction is accompanied by an increase in the cohesiveness
V.S.J. Craig / Current Opinion in Colloid & Interface Science 9 (2004) 178–184 183

of water. However, no reasonable correlation can be found ion effects will again be important, but due to the different
with electrorestriction. A reduction of gas concentration in properties of the interface, the influence of ion combinations
the film could reduce the probability of rupture. Indeed, a may be very different from one system to the next. Such a
possible influence of dissolved gas on bubble coalescence study may see ion-specific behavior relevant to biological
has been raised [1,2..,33.,34..]. Ions are known to ‘‘salt systems.
out’’ dissolved gas, and the electrolytes that more strongly
salt out gas are known to effect bubble coalescence inhibition
at lower concentrations [20,33.,34..]. The diffusivity of the Acknowledgements
sparging gas has also been related to the amount of electro-
lyte required to prevent coalescence [35]. However, suffi- Discussions with Barry Ninham, Stjepan Marcelja,
cient data on a complete series of electrolytes are lacking to Håkan Wennerström and Pavel Jungwirth have been
fully test these correlations. These data would be useful, as it illuminating. The assistance of Chiara Neto and Mika
is possible that a reduction in the amount and ease with Kohonen in the preparation of this manuscript is appreci-
which gas enters the aqueous film separating bubbles could ated. I would like to acknowledge the support of the
inhibit nucleation and film rupture. A possible mechanism Australian Research Council, through the provision of a
for rupture in the absence of electrolyte is the migration of research fellowship.
gas molecules into the liquid film under action of an
attractive force. If electrolyte prevents or reduces this mi-
gration, film rupture could be arrested. References and recommended reading

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