Advances in Colloid and Interface Science 137 (2008) 57 – 81

www.elsevier.com/locate/cis

The role of particles in stabilising foams and emulsions

Timothy N. Hunter a , Robert J. Pugh b,⁎, George V. Franks c , Graeme J. Jameson a
a
Centre for Multiphase Processes, The University of Newcastle, Callaghan, N.S.W. 2308, Australia
b
Institute for Surface Chemistry (YKI), Stockholm SE11486, Sweden
c
Department of Chemical & Biomolecular Engineering, University of Melbourne, Melbourne, VIC 3010, Australia
Available online 7 August 2007

Abstract

The use of particles as foam and emulsion stabilising species, with or without surfactants, has received great interest in recent years. The
majority of work has studied the effects of particles as stabilisers in emulsion systems, but recent successes has widened consideration into foams,
where industries such as flotation and food processing have encountered the effects of particle stabilisation for many years. This review seeks to
clarify studies into emulsions, highlighting new research in this area, and relate similarities and differences to foam systems. Past research has
focused on defining the interaction mechanisms of stability, such as principles of attachment energies, particle–particle forces at the interface and
changes to the interfilm, with a view to ascertain conditions giving optimum stability. Studied conditions include effects of particle contact angle,
aggregation formations, concentration, size and interactions of other species (i.e. surfactant). Mechanisms can be complex, but overall the
principle of particles creating a steric barrier to coalescence, is a straitforward basis of interaction. Much research in emulsions can be applied to
foam systems, however evidence would suggest foam systems are under a number of additional constraints, and the stability ‘window’ for particles
is smaller, in terms of size and contact angle ranges. Also, because of increased density differences and interfilm perturbations in foam systems,
retardation of drainage is often as important to stability as inhibiting coalescence.
© 2007 Published by Elsevier B.V.

Keywords: Foams; Froths; Emulsions; Stabilized by particles; Mechanisms; Surfactant free; Thin films interactions; Bubbles; Oil droplets

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
1.1. Basic chemistry of foams and emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
1.2. Particles in emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
1.3. Particles in foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2. Stabilisation mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.1. Particle–interface interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.1.1. Particle detachment energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.1.2. Maximum capillary pressure of coalescence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
2.2. Particle–particle Interactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
2.2.1. Air–water interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.2.2. Oil–water interface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
3. Investigations into particle stabilised systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.1. Emulsion systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.1.1. Particle network structure and droplet surface coverage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
3.1.2. Droplet–droplet particle bridging . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
3.1.3. Surfactant addition and synergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

⁎ Corresponding author.
E-mail address: bob.pugh@surfchem.kth.se (R.J. Pugh).

0001-8686/$ - see front matter © 2007 Published by Elsevier B.V.

doi:10.1016/j.cis.2007.07.007
58 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81

3.2.Foam systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.2.1. Density effects and disproportionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.2.2. Non-adsorbing Inter-film stabilisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3.2.3. Particle effects on surface tension . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
3.2.4. Particles as foam stabilisers and destabilisers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
3.2.5. Particles in metal foams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80

1. Introduction
1.1. Basic chemistry of foams and emulsions
Foams and emulsions are practically important to many che-
mical and engineering fields, and as such, investigations into the
stability, interaction and structural relationships are of great sig-
nificance. Liquid and solid foams are encountered extensively in
the food and beverage industries (e.g. cake and beer), dermato-
logy and personal care industries (e.g. shampoo), textile indus-
tries, fire retardants, general polymers/plastics, oil recovery and
mineral flotation processing [1]. Emulsions are also heavily used
in the food industry, cosmetics and paints, the pharmaceutical
industry, agricultural products and the petroleum industry [2,3].
Emulsions are typically categorized as oil-in-water (denoted O/
W), such as milk dairy emulsions, or water-in-oil (W/O), such as
oil based skin creams [4]. General pure liquid foams can be
considered a highly concentrated “emulsion” of, say, air and water
(denoted A/W). Hence there are many similarities between the
mechanisms and underlying physical principles of stable
emulsions and foams; so the inclusive study of both fields can
yield results significant for a spectrum of industrial and practical
applications. An example of a general similarity is the high
surface area per volume of the interface.
There are also some differences that play a key role in observed
behaviour. Firstly, most gas in liquid foams are formed with
bubbles up to 103 times as large as emulsion droplets, mainly the
result of the increased gas solubility in water. Also, gas bubbles
are about 105 times as compressible as oil droplets, meaning they
are easily deformed, which changes foam structure from an
individual ‘bubble’ type to typically a polyhedral type structure
[5,6]. These are not observed for emulsions, except in some cases
where the disperse phase is highly concentrated. Other significant
differences, such as the higher disproportionation of gas bubbles,
the higher Hamaker constants of gas–water systems (i.e. stronger
van der Waals attractive force), the different surfactant systems
required for stability and of course the differences in particle
stabilised systems is given in Table 1 below. These features will be
discussed throughout this review.
Foams, like pure liquid-in-liquid macroemulsions (emulsions
where droplet size ranges from 1 to 100 μm) can be considered
thermodynamically unstable, as their decay results in a decrease of
the free energy [15]. However, kinetic mechanisms involved with
breakdown can be so slow that the foams or emulsions can be
thought of as at least metastable for their applications [4]. The
primary processes for instability in foams and emulsions are crea-
ming and sedimentation (for O/W and W/O emulsions respective-
ly), analogous to drainage in foams, coalescence and flocculation

Table 1
Similarities and differences between emulsions and foams
Interaction Foam and emulsion differences
Size of dispersed phase Foams have large gas bubbles, up to 103 times as large as oil/water emulsions, due to increased gas solubility compared to oil droplets [5]
Deformability of Bubbles are much more compressible and are easily deformed into polyhedral structures [6]
dispersed phase Only very concentrated emulsions can form polyhedral structures [7]
Main forms of instability Foam instability occurs by thin film drainage, coalescence and rupture [6]. Emulsion instability also occurs by creaming and
sedimentation and kinetics are usually slower [5]
Effects of diffusion Disproportionation in foams occurs by gas diffusion leading to coarsening of bubble size [8]
Diffusion in emulsions occurs by Ostwald Ripening which is controlled by molecular solubility, and is generally significant only in
droplets b0.1um [9]
Non-ionic surfactant Foams are generally stabilized by low HLB surface active agents (b10) [10]
effect Emulsions of O/W form are stabilized by high HLB agents (N10), while emulsions of W/O form, like foams, are stabilised by low
HLB agents [11]
Hamaker constants Aqueous foam Hamaker constant (a controlling factor in the destabilising van der Waals force) normally taken as air–water–air
A(0) = 3.6 ⁎ 10− 20 Nm [12]
Emulsion Hamaker constants are smaller, generally around 1 ⁎ 10− 20 Nm. (eg. Toluene–water–toluene A(0) = 8.6 ⁎ 10− 21 Nm) [12]
Particle stabilised Foams stabilised by particles with θ b 90° (often θcrit ∼ 70°), and are susceptible to piercing from non uniform particles [13]. Particles
systems can strongly inhibit drainage by residing in bubble interfilm, as well as form a steric barrier at the interface [8]
Particles of a greater θ range (below and above 90°) can stabilise emulsions. Emulsions more stable to piercing, and have lower natural
drainage. Hence significant stability mainly from interfacial steric barrier [14]
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
[5,16]. Creaming and sedimentation are gravity induced move-
ments, caused by the difference in density of the oil and water
phases. Creaming involves the rising of oil in an O/W emulsion,
whereas sedimentation involves the settling of water in a W/O
emulsion [5]. Because gravity induced movement is increased as
differences in density become more pronounced, water drainage
(and gas “creaming”) is most significant in foams. In fact, interfilm
drainage is the basic driving force forming the ‘dry’ polyhedral
type structures in foam systems, which in turn heightens conditions
for bubble coalescence [6,15]. Coalescence involves the irrevers-
ible binding of two or more foam bubbles (or emulsion droplets),
where the interfacial film drains and is eventually ruptured forming
a single larger bubble, and is generally the most severe form of
instability [17]. Flocculation involves interaction between emul-
sion droplets (and can also be observed in ‘dilute’ foam systems,
such as the initial bubble zone of a flotation column) where the free
energy minimum is appreciably low for the droplets to interact.
Unlike coalescence, the interfacial film wall does not drain to
rupture, and the droplets remain held together as ‘clusters’[5].
In foam systems, another form of instability that is important is
disproportionation. Disproportionation is the process whereby air
molecules diffuse through the disperse phase, between bubbles.
Because of the increased Laplace pressure of smaller bubbles, the
diffusion flux generally results in the shrinking of smaller, and the
growth of larger gas bubbles [5]. Coarsening of the bubble size
distribution from disproportionation, can also lead to increased
drainage and coalescence [8]. This diffusion process is also
present in emulsion systems; termed ‘Ostwald ripening’. As it is
controlled by molecular solubility, it is negligible for immiscible
fluids, such as most oil and water emulsions, and is usually only
significant for droplets under 0.1 μm [9,17].
To help stabilise foams or emulsions of pure components, it is
normally necessary to add an additional third component, a
foaming/emulsifying agent. In, say, a traditional air–water
system, foaming agents are required to first produce conditions
that will create a foam, as well as stabilise it for required time
periods, as simply, “clean” air bubbles passed through water will
burst immediately on drainage [15]. Foamers/emulsifiers are
classically molecular surfactants (e.g. fatty acids or alcohols [18]),
polymers or larger protein type agents (e.g. egg albumen) [19].
Molecular surfactants generally contain a polar (hydrophilic)
head group and a non-polar (hydrophobic) chain tail. Surfactants
therefore preferentially adsorb to the air/oil–water interface. This
reduces the free energy involved with producing a high surface
area interface, and as a result, reduces the interfacial surface
tension [4]. Polymers and proteins cause stability largely through
electric and steric repulsion, controlled by the extent of unfolding
(or ‘denaturing’ as unfolded proteins are known) and conforma-
tional layer structure on droplets [20,21]. ‘Semi-dilute’ polymers
and larger ‘globular’ proteins, which do not denature to the same
extent, can further cause stability through changes to the rhe-
ological properties of the dispersion medium (namely through
increase in viscosity) [5]. This may also be achieved through
addition of agents such as glycerine [18]. Of course, many natu-
rally occurring emulsions and foams will contain a variety of
types of agents, leading to potentially very complex interactions
giving overall characteristics.
59
1.2. Particles in emulsions
Particles are naturally present in many types of emulsions, yet
despite this, the pointed use of particles either solely, or in addition
to other traditional surfactants as emulsion stabilisers, has only
been recently (in the last 20 years) given extensive attention. In
addition to the many recent developments, published study of
particles in emulsions has been documented for 100 years. The
person credited with first investigating particle stabilisation in
emulsions is Pickering, who in 1907 (using work documented
four years earlier by Ramsden [22]) noted that particles more
wetted by water than oil, stabilised O/W emulsions by residing at
the interface [23]. From this report, the term ‘Pickering emulsions’
has been given to emulsions stabilised by solid particles.
The role of particle wettability and emulsion stability was
discussed further by Finkle et al [24], who considered that
particles at an interface in an emulsion would most likely pre-
ferentially reside in one of the liquids, and this would become the
disperse phase. This was considered in line with resulting
emulsions from surfactant adsorption. It was not until the work
of Schulman and Leja [25], that particle wettability and interface
contact angle was comprehensively investigated. Using barium
sulphate crystals and surfactant, they found that conditions
giving particle contact angles (θ measured through the aqueous
phase) slightly below 90° resulted in O/W emulsions, and for
conditions giving θ slightly above 90°, W/O emulsions were
formed. Interestingly, conditions giving extreme contact angles
(close to 0° or 180°) no stable emulsions were formed.
The wetting behaviour of solid particles is generally
considered a key descriptive rule for particle emulsion beha-
viour. Consider a particle at an oil–water interface. For a θ
measured through the aqueous phase of below 90°, the particle is
preferentially wetted by the water (i.e. it is preferentially hydro-
philic in nature). For a particle θ of above 90°, it is preferentially
wetted by the oil (i.e. hydrophobic). For a contact angle of 90°, it
is equally wetted by both phases, and is considered at the point of
inversion [14]. Similar to surfactant behaviour, the preferentially
wetting phase becomes the disperse phase, as the particles
minimise energy by curving round the inhibited phase, forming
stable emulsion droplets [26,27]. For particles with contact
angles near 90°, whether O/W or W/O emulsions result depends
on the particle and solution properties such as concentration
[28,29]. Fig. 1 shows how the bending behaviour of droplets
coated in particles may dictate emulsion formation.
There have been a number of different particle types used as
stabilisers in both O/W and W/O emulsions, including silica, latex
particles, metal oxides and sulphates, clays and carbon. The
effectiveness of a specific particle type in stabilising an emulsion,
depends on the emulsion medium, the particle shape and size,
particle wettability and inter-particle interactions [14]. Particles
impart stability on emulsions primarily through a steric barrier,
created at the interface. With a certain concentration of particles, a
close packed network is generally formed, which further increases
stability. It is also thought that a certain level of particle
flocculation is advantageous for stability [30]. In addition, at
certain concentrations, particles may affect the rheological pro-
perties of the disperse medium (much like free-proteins), and
60 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 1. Bending behaviour of emulsion droplets coated in particles.
particles such as clays, can also act to increase stability by for-
mation of inter-droplet networks [31–33]. Unlike surfactants,
particles do not affect emulsion stability by significantly reducing
the oil–water surface tension [34].
There is a large size range of particles that can be used to
stabilise emulsions. For successful stabilisation, it is necessary
that the particles be approximately orders of size smaller than the
droplets, for the particles to be properly located around the
droplets [2]. The actual size of particles that can be used ranges
from small nanometre [35] to micrometer [36] to successfully
stabilise emulsions. The size of the particles does correlate to the
size of the droplets formed in stable emulsions, with even droplets
of up to millimetre having been found stable to coalescence,
something not easily possible with surfactants [14]. Generally the
overall stability is inversely proportional to particle size, with
smaller particles giving a higher packing efficiency, and so
producing a more homogenous layer [16,35,37].
Because of the extensive attention particle stabilised emul-
sions have gained in recent years, behaviour has previously
been well studied and documented, as evidenced from reviews
by Binks, Aveyard and co-workers, from the University of Hull
[14,26] and a recent book covering this topic edited by Binks &
Horozov [38] . Because of this, an effort will be made to focus
on presenting recent work on the subject of particles in emul-
sions, while maintaining required continuity. The second and
major focus of this report is to link well detailed emulsions
behaviour, to the study of particles in foams, a subject that has
been less extensively investigated, but currently is an area of
increasing interest.
1.3. Particles in foams
As with particles in emulsions, the phenomena of particle
stabilisation of foams, has only recently been given pointed
attention, and interest is largely the result of successes in emulsions.
Yet, it is well known that finely dispersed particles play an
important role in the stabilisation of many different types of foams.
For example, particles in the absence of surfactant are known to
cause foaming in rivers, treatment of radioactive wastes, dispersed
sludges, distillation towers, oil-well drilling, pulping in the paper
industry, fabrication of cellular metal foams and the preparation of
foods, etc. In the oil industry, obnoxious foams are produced in
boilers and various stages of distillation and are thought to be
stabilised by asphaltene particles [39,40]. In waste water, foams are
stabilised by colloidal particles such as bacteria, soil and viruses. In
other cases, heterogeneous nucleation of insoluble precipitates
(hydrolysed cations such as iron hydroxides) at the air/water
surface can also cause foaming in waste water or rivers. Many other
everyday processed products frequently involve particle stabilised
foam systems, which ensure long-term stability. In food and drink
production (bread and beer have foam like structure) and in the
dairy industry when whipping cream, partially crystalline ‘solid’
oil droplets accumulate at the interface and stabilise the foam [5].
It is also important to note that the adsorption of particles at
bubble interfaces is the basic driving mechanism in many
dynamic foaming processes, such as dissolved air flotation to
treat waste water, effluent treatment and froth flotation [41]. In
the froth flotation process, which is widely used as a particle
separation method for minerals, the attachment of particles to
bubbles occurs when the particles are dispersed in the liquid
pulp [42]. The bubble/particle aggregates then ascend to the
interface where the behaviour of the particles has a critical
influence on the stability of the thin films in the froth. It is of
interest that much early work on particles as foam stabilisers has
occurred, from a perspective of mineral processing and flo-
tation. Throughout industry, there are many examples of particle
stabilised foaming processes in both aqueous and non aqueous
environments, with and without surfactant addition. For exam-
ple, during the boiling of radioactive sludge suspensions, foam-
ing has been reported to frequently occur [43].
There has been published material, in which the role of particles
as stabilising species in foams has been noted, dating back to 1913,
where Hoffmann suggested finely divided particles had a role to
play in stabilisation of foams or froth, specifically in mineral
frothers and ore flotation ([44] as cited in [18]). In 1925, Bartsch
found partially hydrophobic particles stabilised froths, whereas
completely wetted particles had no effect on the stability [45].
Similarly Hausen found stable three phase froths formed with
various metal oxide and clay particles [46], and Lekki and
Laskowski found that particles could enhance the stabilisation
power of frothers such as diacetone and ethyl acetal [47]. Ottewill
et al., in a non-aqueous system, reported increased foam stability in
systems of alkali metal carbonates, that was attributed to increase in
bulk viscosity of the dispersion with solid particles [48]. More
recently, Tang [49] showed that fine silica particles enhanced
stability of an SDS foam, and that stability was proportional to
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
particle concentration, and inversely proportional to particle size
(much like emulsion systems).
This initial evidence would signify that many similarities lay
in the stabilisation mechanism of particles in foams and emul-
sions. The reliance on particles to create a steric barrier to coal-
escence is again a major contribution to foam stabilisation, and as
with emulsions, smaller particles in high concentrations that form
a more complete layer gives the most effective barrier. Because of
the increased effects of drainage in foam systems, the affect of
particles on the interfilm (for example, causing retardation of
drainage and increasing maximum capillary pressure) is also sig-
nificant in some systems, and generally is a more important
mechanism than in emulsions. Bridging of particles between
bubbles is also a very important process, because of the high
forced contact area in foam phases, as they become dryer [6]. Fig. 2
shows how particles may stabilise polyhedral type foam.
Hydrophobic particles (of contact angle greater than 90°)
should not work as effective stabilisers in foams, obviously as
foams will break (collapse), upon opposing bending energies, as
there is no ability for foams to ‘invert’ (although, recent evidence
suggests so-called free-flowing liquid marbles and powders
containing numerous water drops, termed ‘dry water’, may be
formed [50]). In fact, hydrophobic particles can pointedly be used
as foam breakers, further destabilising the foam from bridging
drainage, as comprehensively investigated by Dippenaar [51–
53]. Also, because of the deformability and the ‘delicate’ nature
of foams, they can be subject to foam destruction from particle
piercing, especially in the case of larger, non uniform, particles
(an environment often encountered flotation). Further, because of
the weak affect on surface tension without the use of other
Fig. 2. Particle stabilised foam.
61
frothers, it is difficult to first establish frothing conditions in clean
particle–water systems. So collectively, the increased bubble–
bubble contact area from drainage drying, deformability, and
inhibitive effects of hydrophobic particles means particle
stabilised foams are under a number of additional constraints
when compared to emulsions.
Further research into the finite stabilisation mechanism of
particles in foams may possibly yield results of great significance,
and is in some ways, a more complex proposal than in emulsions.
Overcoming the constraints of stable foam behaviour may lead to
many potentially profitable investigations, using particles in
addition to, or as a way of completely removing surfactants from
a foaming process. Particles can prove both economically and
environmentally attractive to industry. This is because particles
may cause stability over and above generally used surfactants
and also because of the benefits of reducing dependence on
potentially harmful organics. Knowledge of the stabilisation
process is especially important to the flotation industry, where
accurate prediction of mineral yields is a difficult prospect, and
the great range of particles often encountered leads to many
possibilities in overall foam structure and so flotation potential.
2. Stabilisation mechanisms
2.1. Particle–interface interactions
2.1.1. Particle detachment energy
A useful factor that theoretically links how well particles of
different contact angles stabilise emulsions and foams is the
particle detachment energy. This detachment energy is related to
the free energies involved in removing an adsorbed particle from
an interface (either oil–water or air–water). As particles create a
steric barrier to coalescence, it is obvious that strong particle
detachment energy will result in more force being required to
disrupt the particle layers and allow coalescence [54]. The
detachment energy becomes higher, as generally an area of great
line tension (oil/air water interface) is lost due to particle
adsorption, where the energy is influenced most significantly by
the area (i.e. its radius ‘R’) and immersion of the particle at the
interface (i.e. θ) and the initial surface tension γow/γaw [26].
Consider a single spherical particle moved to an air/oil–water
interface (Fig. 3), with an equilibrium immersion depth and
contact angle θ [54].
The energy required to move the particle from this equili-
brium into the bulk water can be calculated from fundamental
principles (if buoyancy/gravity effects are neglected) [16,27].
Taking into account the area and depth of immersion, and
respective surface tensions, this detachment energy (ΔGremove)
is shown.
DGremove ¼ pR2 gOW=AW ð1FcoshÞ2 ð1Þ
This energy is considerably large (in the order of 103 kT for a
10 nm particle) at angles of around 90°, but falls quite rapidly as
the particle contact angle decreases or increases. At θ b 30° or
θ N 150°, the contact energy is essentially negligible, suggesting
that in principle these particles would not create stable emulsions
62 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
or foams. Another important consequence of the large energy of
attachment, is that once at an interface, a particle can be thought
of as irreversibly absorbed, a behaviour unlike surfactants,
which are generally thought to be in a state of dynamic equili-
brium, absorbing and desorbing on a fast timescale [26]. The
energy of attachment is important, especially in determining
overall stability relationships, but many factors lead to it being
useful generally only in a qualitative sense. A significant
mitigating factor in quantitatively assessing the relationship in
real systems is the great difficulty in accurately determining
particle contact angles, especially for particles in the nanometre
size range. Other problems, such as particular contact angle
hysteresis in certain phases, and effects of irregular meniscus and
surface roughness on clean particle wetting, make very accurate
assessments almost impossible.
A theoretical comparison can be made between the
detachment energy of uniform particles, with that of true am-
phiphilic particles. It is possible to partially treat particles,
creating both a hydrophobic (apolar) section, and a hydrophilic
(polar) section on the particles. This more truly mirrors attributes
of molecular surfactants, which are naturally amphiphilic in
character [55]. These types of particles have been termed ‘Janus’
particles, a description originally coined to denote particles with
equal parts hydrophilic and hydrophobic surface [56], yet, with
modern synthesis techniques, the fractional distribution of the
polar and apolar sections can be varied [57]. Amphiphilic parti-
cles can also exist naturally in some systems, such as radioactive
waste sludge, which consists of noble metal oxides and hy-
droxides of broad chemical composition that are often bi-philic.
These particles are problematic, as they create very stable,
unwanted boiling foams [43].
As with uniform particles, theoretical attachment energies can
be related to contact angles. Binks and Fletcher [55], using the
work of Ondarcuhu et al. [58], considered the energy rela-
tionships for amphiphilic Janus particles. The detachment energy
is increased significantly with increasing amphiphilic behavior,
and is as much as three times that of a homogeneous uniform
particle. Janus particles could therefore lead to marked increases
in particle stabilised emulsion and foam performance. With the
many recent developments in chemical manufacture, there has
been extensive recent interest in the production and use of
amphiphilic type particles. Modern methods allow production
Fig. 3. Particle at an air/oil–water interface.
via a number of pathways, from chemical grafting [59], seed
polymerization [60], to methods building particles of hydropho-
bic cores and hydrophilic shells [61], and the use of composite
materials [62]. The manufacture and use of these particles in
various systems, for example, in cosmetic emulsions, has pro-
duced a number of patents, and there is little doubt, interest in the
properties of amphiphilic particles will continue.
2.1.2. Maximum capillary pressure of coalescence
Although detachment energy theory can explain much of the
overall stability phenomena observed in emulsions, it is often
found that in foam systems (as described in detail in Section 3.2),
the contact angles for maximum stability occur below 90°, and
particularly in the region of 60–70°. One mechanism that may
explain this behavior is the affect of particles on the capillary
pressure between two bubbles. Thus, instead of looking at how a
particle is attached to a single interface, one considers how
particles residing between two interfaces affect stability by
reducing the thinning of the draining interfilm. In particular we
consider the pressing force required to bring two bubbles to
coalescence (i.e. to reduce bubble-bubble distance to approxi-
mately zero) with particles holding them apart. This pressing
force is described as the capillary pressure, or the pressure
gradient between the bubbles (P1) and the interfilm fluid (P2)
(analogous to the ‘disjoining’ pressure) [63].
For different arrangements of particles (if it's assumed they
remain embedded and stationary between the enclosing bubbles)
it is possible to calculate a theoretical maximum capillary pres-
sure sustainable by a given system. A higher maximum capillary
pressure (Pcmax) indicates a more stable system. Ivanov and co-
workers were the first to consider such as system [64], and
models have been further developed by others including Nush-
taeva & Kruglyakov [65] and Kaptay [66]. A recent review by
Kaptay [67] has brought this mechanism back into focus, and it
will be briefly surmised here.
Kaptay [67], derived an analysis for a single hexagonal layer
of particles between two bubbles (or droplets); in a continuation
of the work of Visschers and co-workers [68]. Here particles
with a zero contact angle (and radius R) that are completely
resting in the interfilm, lie between the two droplets as shown in
Fig. 4. For this system, if the capillary pressure is zero (i.e. no
net ‘sucking’ pressure between the droplets) then the contact
line between the particle and bubbles is flat (irregular meniscus
profiles are not considered). As drainage occurs, the bubbles
form a meniscus around the particles as shown. The curvature of
the meniscus is given from an assumed sphere radius ‘r’. This
increases the capillary pressure between the bubbles. The con-
tact angle between the meniscus profile and particle tangent is
given by Θ, while the contact area is derived from the angle α.
As drainage increases, the meniscus profile continues to
curve around the particles, and the overall separation of the
bubbles ‘H’ decreases. As the capillary pressure continues to
increase accordingly, the bubbles will eventually touch, as H
decreases to zero, and the pressure associated with this coale-
scence event is given as Pcmax. The basic equation of maximum
capillary pressure can be resolved by equating this system to the
Laplace equation, and combining the various parameters
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 4. Particles residing in a droplet–droplet interfilm effecting Pcmax for coalescence [67].
associated with the changing structure of the interface. This is
given by Kapkay [67] as shown in Eq. (2).
2gAW=OW
Pcmax ¼ FP cosh
R
Here, as with particle detachment energy, a positive value
relates to bubble and O/W systems, while a negative value relates
to W/O systems. The factor ‘P’ is a theoretical packing parameter,
which by various approaches is used to associate the influence of
particle concentration and structure on the capillary pressure. The
other important implications of this equation are firstly that
particle size ‘R is directly and inversely proportional to Pcmax,
showing smaller particles with higher curvature and smaller
interparticle packing are more effective ‘blockers’. Secondly the
maximum capillary pressure is directly affected by contact angle.
This predicts highest Pcmax values for contact angles close to
zero, and lowest values (or lowest stability) at contact angles
around 90°. This is an opposing trend to detachment energy, but
here makes sense as obviously the more a particle resides in the
interfilm, the more the liquid film has to drain around it (and H
reduce) until coalescence. In fact, Kaptay has looked at the
combined effect of detachment energy and capillary pressure on
calculating contact angles of high stability. Assuming a relative
change in energy for each competing mechanism, he associated
the combined relationship as shown in Fig. 5 for a single layer of
particles between two bubbles [67].
This relationship highlights the potentially significant role
that capillary pressure can have on a given systems stability
performance. Most interesting however, was how the contact
angle for maximum stability theoretically changes when a
system of two particle layers is considered (two completely
coated emulsion droplets coming into contact). Here, Kaptay
found the contact angle of maximum stability was located at 85°
[67], well within the region found often with emulsions [14],
where these types of high concentration systems are encounted.
In terms of foams, often lower concentrations of particles are
encountered (especially in flotation [41]) so this relationship
may be even more critical. Also, the increased drainage in foams
will add to its relevancy. Because of the high contact between
63
interfaces in drying polyhedral foams, occasions where laterally
static interfaces are bridged by particles is more common than in
emulsions, and the proposed capillary mechanism more aptly
applies.
ð2Þ There are some general shortcomings to the theory of
capillary pressure however. Perhaps most important is that
particles are themselves assumed to be statically located and not
influenced by fluid drainage or flow. In effect, even particles
with almost no adsorption are not assumed to be ‘washed away’
from the contact area by liquid drainage. Also, the effect of
particle–particle interactions is important. Kruglyakov et al. [69]
and Slobozhanin et al. [70] found in experimental studies, that
Pcmax values followed the general stability trend, but were much
lower than theoretically predicted. The flocculated nature or
incomplete structure of particle networks was assumed to be a
key mitigating factor, highlighting the importance of categoriz-
ing such mechanisms, and why generally, equating system
stability to only particle–interface interactions often only gives
half the picture.
2.2. Particle–particle Interactions
The theoretical understanding of particle–particle interactions
at interfaces are complex, and still leave unexplained much
phenomena observed experimentally [14]. However, the princi-
ple of particle network structures generating a steric barrier is
Fig. 5. Combined effects of Pcmax and ΔGremove on the relative energy of particle
stabilised systems versus particle contact angle [67].
64 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
simple, and can be surmised in terms of the nominal steps in
droplet coalescence. For coalescence to occur, film drainage and
thinning must occur between bubbles (or emulsion droplets). In
the final stages of film thinning, dark spots (or holes) are formed,
which expand until the film becomes unstable and ruptures [27].
If a droplet or bubble surface is well covered in a stabilising
species, an energy barrier must be overcome to form a critical
sized hole in the film wall. Thus the rate of coalescence can be
considered in line with the energy required for hole formation
[17]. Because of the high free energies involved with strongly
adsorbed particles [54,71] (as discussed in Section 2.1.1), they
are far more likely to be laterally moved along the contact
interface, rather than expulsed into the open medium during film
thinning [33]. Hence, particle–particle forces such as electric
double layer repulsion and dipole–dipole repulsion, as well as
van der Waals attraction and capillary forces are of utmost
importance to overall stability of foams and emulsions, and may
dominate interactions over particle–interface attachment.
2.2.1. Air–water interface
Equating the role of various forces in interface systems is a
complex proposal, but may be achieved by breaking down the
overall interaction potential into a number of defined mechan-
isms and their related activities. Firstly, once a particle is attached
to an air–water interface, particle–particle DLVO repulsion
works through the aqueous phase, and augmented van der Waals
attraction working through the aqueous and air phases [72,73].
So, as in bulk colloidal conditions, effects of surface change and
salt counter ions can increase repulsion or cause interfacial
coagulation. Levine, from the theoretical considerations, deter-
mined that double layer repulsion was the most significant
repulsive force, and dipole–dipole repulsive energies were small
(in the range of ∼ 0.8 kT) [54,71]. However, Levine also felt that
an additional force was required as a thermodynamic equilibrium
balance with the single particle energy well. Further, current
consensus points to interactions, such as dipole–dipole repul-
sion, becoming significant in systems where particles contain
ionisable surface groups and a medium of low dielectric constant
is used (i.e. air) [74,75].
Dipole–dipole forces were first proposed by Pieranski [76],
who determined that dipoles are produced, by asymmetrical
charge distribution on particles, as the portions of particles in the
aqueous phase become ionized [54,76]. In effect, for particles
with ionisable surface groups (e.g. latex or silica), the part of the
particle immersed in the aqueous phase will become charged,
creating asymmetric charge distribution on the particle, and
causing a dipole perpendicular to the interface [75,76]. The
asymmetrically charged particles undergo partial neutralisation,
from counter-ions in the aqueous phase. Particles with smaller
aqueous immersion, will attract a lower concentration of dis-
solved counter ions, and the dipole will work normally through
the air phase, causing repulsion between particles [75]. The
dipole–dipole forces are considered to work in association with
DLVO double layer repulsion through the aqueous phase (see
Fig. 6). Also, as charge neutralisation is controlled by the extent
of aqueous immersion, more hydrophobic particles will attain
stronger dipole–dipole interactions.
There has been some conjecture on the role of dipole–dipole
repulsion forces in air–water systems. Abdel-Fattah and El-Genk
[72,73], and Williams and Berg [77] called into question the
strength of dipole–dipole forces, with work on particle adsorption
to air–water interfaces. Both found that at even moderately low
salt concentrations, conditions led to extensive particle aggrega-
tion on the surface, at salt levels up to two orders of magnitude
below bulk conditions [77], and below concentrations expected if
significant dipole–dipole repulsions were evident. Aveyard and
co-workers also found unexpected aggregation of particles at air–
water surfaces [78], but especially in this case, very low particle–
water contact angles (close to 0°) may have lead to the observed
trends (as particle–interface contact energy was therefore
minimal).
Other workers, using more hydrophobic particles have found
surprising stability of particles at air–water interfaces, and have
established that dipole–dipole forces are indeed significant
[79,80]. Further, any observed aggregation can be accounted for
without disregarding such repulsions, by equating other attractive
forces [80–84]. Robinson and Earnshaw [79], showed that by
decreasing particle contact angles (rendering particles more
hydrophilic) dipole–dipole forces were reduced in line with
increased counter ion screening, and aggregation was increased.
Ghezzi, et al. [80] further showed that by applying charge to the
air interface, aggregation was induced by retarding dipoles
through counter ion screening in the air phase. They also found
that under certain conditions, particles aggregated into complex
chain and meso-structures, an interesting result they attributed to a
secondary energy minimum (attraction force) at long-range
distances (beyond possible van de Waals attraction) [80]. This
secondary long-range attractive force was also independently
established by Ruiz-Garcia and co-workers [81,82].
The origin of this secondary attractive force is debatable.
Ghezzi [80] felt that the secondary minimum was caused by
inhomogeneous charge distributions around the particles,
leading to certain particle alignments, whereas Ruiz-Garcia et
al [81] and Meija-Rosales et al [84] felt that the secondary
minimum could be predicted even with isotropically charged
particles, by taking into account interaction potential oscillations
with particle distance, from the dipole–dipole repulsions.
Stamou and Duschel, considered the secondary minimum to
be caused by capillary attraction [85], and this is currently the
most popular theory. It was felt that particle surface roughness
could lead to irregular shaped surface meniscus around particles,
Fig. 6. Dipole–dipole formation on particles at an interface.
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 7. Possible causes of meniscus deformations and resulting capillary attraction [92].
which could lead to an attractive capillary interaction, from
particle re-alignments forced by complex meniscus associations.
Whatever the attraction basis, it has been shown through film
balance and computation analysis, the secondary minimum
cannot be attributed to DLVO interactions or hydrophobic
attraction [83,86].
It is perhaps pertinent at this point, to more fully assess the
origins and strength of general capillary interactions in
interface systems. The capillary force at work is a lateral
interaction force. It is present in any systems where the particles
cause surface deformations (menisci), and generally (depend-
ing on shape) the overlap of menisci between two close
particles causes an attraction [87]. The origin of the initial
deformations is dependent on particle size. For larger particles,
the deformation of the menisci is produced from gravitational
effects, but for particles below 5 μm, gravity effects are
negligible, and behaviour cannot be accounted for in this way
[88]. Nikolaides [89] considered that small particle meniscus
deformations were caused by electric field induced fluctuations
to the interface, from the potential differences between the
aqueous and non aqueous phases, resulting in a net long-ranged
attractive force. Questioning work from Foret and Wurger [90],
and Megans and Aizenberg [91] suggested electric field
differences could only result in a small negative (repulsive)
perturbation, and could not be the cause of any capillary
attraction in small particles. It must be noted that in a reply,
Nikolaides, stated that potential fluctuations may still lead to
capillary attraction, if trapped ions evidenced in O/W interfaces
are present [91]. Again, this could not be a potential cause in
air–water systems, where such trapped ions do not occur (see
Section 2.2.2).
The general interaction phenomenon of capillary attraction
has been a focus of research for Kralchevsky and co-workers
[88,92,93]. They have detailed two possible causes of required
meniscus deformations in small particles. Firstly, immersion in
three phase systems (i.e. thin film studies on flat plates)
meniscus deformations, and resulting capillary attraction, can
be formed from restricted surface wetting. They also
65
considered, along the lines of Stamou and Duschel [85] that
irregular particle wetting was possibly the major cause of
meniscus associations in most systems [92]. Fig. 7, shows
these potential origins of capillary attraction for both large and
small particles.
The basis of an irregular meniscus on small particles for a
capillary interaction was first proposed by Lucassen [94]. He
modelled the effects of a small particle, with a sinusoidal edge
disturbance (undulated contact line), and showed there could
be significant interaction with neighbouring particles. The
interaction is based on the minimization of the total surface
area, and could result in a capillary force, acting over distances
of the order of the sine wavelength, and magnitudes pro-
portional to the square of the amplitude. The model showed
that, in cases where there is a difference in amplitude or
wavelength, or when the sines are out of phase, an attraction at
large distances resulted, which changed into repulsion as
particles approached on another. This theory wa further de-
veloped by Stamou and Duchel [85] and by Kralchevsky [92].
Here it was assumed that irregular wetting causes changes to
the fractional area affected by charge neutralisation, which
causes further asymmetric charge distributions. In effect the
particles dipoles augment to form a quadrupolar type charge
distribution, and can then align themselves according to the
placement of the quadrupoles (Fig. 8), in an attempt to mi-
nimise energy. This could account for the particle rearrange-
ments, and meso chain like structures evidenced by Ghezzi
[80].
From the quadrupolar theoretical basis, it has been shown
that surface irregularities can cause remarkable strong attrac-
tions relative to kT [85,92,94]. Other authors have also
assessed the aggregation patterns of particles subjected to
quadrupolar capillary interaction. Brown et al used a novel
etching technique to produce various particle types with noble
metals and silica dioxide [95]. Using disk shaped particles,
with both a hydrophilic and hydrophobic face, surface
deformations and cluster formations were studied, and
generally could be approximated by considering quadrupolar
66 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 8. a) Quadrupolar charge on particles with an undulated contact line, b) resultant particle realignment in reduced energy conformations [92].
analysis. The conformations were successfully modelled,
calculating energy relationships, in terms of two and many-
body interactions by Fournier and Galatola [96].
2.2.2. Oil–water interface
Forces at work in oil–water systems show many of the
same characteristics to air–water interfaces, but with a small
number of important differences. As with air systems, DLVO
forces will again work through the aqueous phase, and
strength is dependent on the extent of particle immersion.
However, the weaker Hamaker constants present in most oil
Fig. 9. Aggregation patterns of A) ellipsoidal silica (scale bar 22 μm) and
B) ellipsoidal PS (scale bar 33 μm) at O/W interface [97].
and water systems [12] may account for some reduction in
attractive aggregation. The same principles of dipole–dipole
repulsion are also evident, working through the oil phase.
Capillary attraction is still evidenced in certain systems, as
observed by Kralchevsky and co-workers, finding both
theoretical and experimental evidence of a capillary force
sufficiently strong enough to cause partial aggregation at O/W
interfaces [87,93]. Further, Loudet et al used a model O/W
interface to study the importance of particle shape on capillary
attraction, by looking at ellipsoidal silica and latex particles
[97]. In such cases it seems the capillary attraction is enhanced
along the quadrupolar lines, producing very long-range
particle chains. Also, chaining conformation was proven to
be a direct result of particle hydrophobicity, with ellipsoidal
silica chaining almost exclusively side to side, while lenticular
latex particles formed end to end chains (see Fig. 9). The
strength of such capillary attraction is in fact remarkable for
latex spheres, considering the repulsive forces at work in oil
systems.
In many systems of very hydrophobic particles, capillary
attraction is greatly reduced, or at least is dominated by a
further force in oil–water systems. Apart from short range
double layer and long-range dipole–dipole forces, there is also
evidence for an additional ultra-long-range repulsive force.
Aveyard and workers [78] observed that latex particles in an
octane-water interface produced extremely stable networks,
even at high electrolyte concentration. This stability could
therefore not be fully attributed to dipole–dipole forces, as
these are thought to decrease significantly at high electrolyte
concentration (from increased neutralisation from counterions)
[78]. From the experimental evidence, they deduced that the
origin of this repulsive force lies in charge–charge repulsion
from the surface sulphate groups. It is thought that a small
percentage of the surface charge groups are trapped by surface
water molecules in rough surface pores, and in the oil phase act
in unscreened charge–charge repulsions [98]. Molecular
surface dynamics simulations were also fitted successfully to
models including this charge–charge force [99], and further
studies with hydrophobic silica produced similar ultra-high
order packing (from trapped hydroxide ions) [100]. In
addition, there is no evidence of these ‘ultra-long-range’
repulsive forces in air–water interfaces. This confirmed the
idea that water-trapped charged ions are the cause of the
repulsion, as these groups would not remain trapped in an air–
water system [78].
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81 67

3. Investigations into particle stabilised systems detachment energy. Major differences in packing structure
were observed between hydrophilic and hydrophobic silica,
3.1. Emulsion systems seen under freeze fracture SEM (Fig. 10). Hydrophilic silica
bonded to the interface as individual particles (no evidence of
Previous research has focused on particle emulsion sta- pre-flocculation); whereas the hydrophobic silica produced
bilisation with a view to ascertaining the inherent mechanism highly flocculated mono and multi-layers, even at salt
of stabilisation, including determination of the structure of concentrations orders of magnitude below bulk flocculation.
interparticle networks at the interface, conditions that give This would show either evidence of an additional hydrophobic
optimum emulsion stabilisation and also ways to augment attraction working through the bulk phase [17], or that because
emulsions for specific purposes. Work has been undertaken to of the increased particle attraction to the interface, closer
investigate aspects such as determination of particle to droplet interparticle distance on contact (in relation to the bulk) leads
size relationships, comparing particle types and performance, to increased flocculation.
mixtures of particles and resultant effects, oil phase polarity Horozov and Aveyards work on aggregation at static
and type, optimum percentage droplet coverage, and inversion particle interfaces found opposite trends [100]. Using silica of
principles. These systems were comprehensively studied in varying hydrophobicities, they found more hydrophilic silica
the review by Aveyard [14]. The focus here will be on produced disordered aggregated networks, and very hydro-
important areas that can be compared to foam systems, and phobic silica produced a well ordered hexagonal network, in
areas highlighting the complex questions remaining in particle line with the apparent charge–charge repulsive force.
emulsion behaviour. However, there were a number of important differences
between experimental situations. Firstly, Horozov and Ave-
3.1.1. Particle network structure and droplet surface coverage yard found the well-ordered networks were formed at
The types of singular and flocculated network structures that
can be observed in emulsions (and indeed foams, although less
studied) is vast, and very hard to categorise. The role of
particle–particle interactions can give a key indication of
expected structures, however the great energies involved in
emulsion formation may counterbalance this in some systems.
Insight has been gained from both the study of static network
interfaces, where detailed observations and analysis can be
made to degrees not possible with dynamic systems, and
emulsion interfaces (where often information can only be
gained from TEM/SEM data).
Stancik et al investigated the strength of close packed
particle networks, by subjecting particle coated surfaces to
extensional flow [75]. It was found that networks resisted
conformational changes, but under certain flow, elongated into
rhombic structures. Under the studied close-packed conditions,
the networks produced significant stability, yet with a finite
limit. Aveyard et al also found similar rhombic conformational
changes with particle networks in a Langmuir trough subjected
to compression, and showed that particle systems would ‘fold,’
when a certain collapse pressure is reached, holding arrayed
structures (particles remained at the interface, not expelled into
the open medium), indicating again significant particle
network stability [78,100,101].
Simovic and Prestidge have completed a number of studies
into the structure and behaviour of particle networks,
subjected to a series of conditions, and described a number
of differences between hydrophilic and weakly hydrophobic
silica in terms of stabilisation characteristics [30,102]. Model
polydimethylsiloxane (PDMS) oil droplets were used, which
could be synthesised to high monodispersity (and extent of
droplet cross-linking manipulated). As expected, for both
particle types, increased salt concentration lead to increased
packing (in line with decreased DLVO repulsion forces Fig. 10. A) SEM (high magnification) of hydrophilic silica on PDMS droplets;
between particles) and hydrophilic particles performed poorly, B) SEM (low magnification) of hydrophobic silica on PDMS droplets, both with
in line with the very low contact angle and attributed 10− 3 M NaCl [102,103].
68 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
hydrophobicities above those studied by Simovic and
Prestidge (contact angles above 118°). Also, differences
between a static interface and real emulsion systems (studied
by Simovic and Prestidge) cannot be discounted, as energies
involved in emulsion formation would introduce far more
particles to the oil interface, possibly causing additional
aggregation for even particles in strong networks. These types
of effects may be a mitigating factor in the general science of
equating interface systems to real emulsion and foam systems.
Effects of changes in oil phases and salt conditions could have
further led to the apparent structural differences.
Midmore discovered interesting structural packing differ-
ences between systems of silica and poly-ethylene oxide (PEO)
or hydroxypropyl cellulose (HPC) surfactants [104,105]. In
PEO-silica systems, silica networked at the oil drop interface to
coverage of approximately 72% monomer layer, an average
packing efficiency, and expected for stabilised emulsions. With
HPC-silica systems, packing of only 30% was observed for
stable systems, a figure far below a hard packed layer
considered necessary for strong steric repulsion. It was
suggested that free HPC could be adsorbed at the droplet
interface, also inhibiting coalescence, so less silica was
required for stabilisation. It was also thought that although
actual coverage was only 30%, it consisted of long range
partially flocculated networks, giving strong lateral support.
Others who have considered the effect of low coverage
stabilisation are Vignati and Piazza [34]. They investigated
systems where the silica concentration was only 15% of a
packed monolayer, and excitingly found that it could still
impart substantial stabilising power in this range. Observations
of fluorescent core silica under an electron microscope showed
that there was strong evidence of individual particles ex-
Fig. 11. Concentration specific network structures of polymer particles
(∼ 770 nm) on octanol emulsion droplet: A) dense layer B) Colloidal ‘clumps’
C) individual ‘loose’ particles D) homogenous HCP layer [34].
hibiting Brownian motion while trapped at the oil interface.
This would further suggest that below concentrations causing
packed networking, individual particles can easily move
laterally around the droplet surface. There was also evidence
of particle clustering, attributed to capillary attraction forces at
the interface. Fig. 11 shows the range of network behaviour
seen for different particle concentrations. Most surprisingly,
they discovered that when two oil droplets were brought into
contact, particles would collect around the drop-drop contact
region, thus still imposing a significant steric barrier (i.e. the
particle distribution was non-homogeneous, and was affected
by neighbouring droplets).
The range of structures observed with low concentration
systems pulls into focus the general problem of defining
particle networks. In many emulsions, and also in foams (see
Section 3.2) many authors have noted potential aggregated
‘clumps’, small flocs, long range lateral flocculated networks,
or coagulated systems. These are very difficult to categorise
distinctly, because of the great difficulty in directly observing
their nature at a nano level. The range of networks is greatest in
low to moderate concentrations of particles, where they may
either adsorb as individuals, or in small multi-particle units, or
possibly progressively acuminate and grow from a ‘seed’ type
aggregate.
Fig. 12 illustrates four basic categorised network struc-
tures, which may form under different bulk and interfacial
conditions in emulsions and foams. Condition (A) shows
a classical hexagonally close-packed (HCP) monolayer,
where particle–particle interactions dominate, and balanced
repulsive and attractive forces hold the network in place.
Condition (B) shows partially-flocculated or coagulated
‘islands’, where particles are initially flocculated into small
networks in the bulk prior to interface adsorption, where they
may undergo further rearrangement. Condition (C) is another
form of partial flocculation, where capillary attraction forces
small networks together into meso or chain like structures at
the interface (thus giving strong lateral stability in low con-
centration ranges, as envisaged by Midmore [104]). Finally a
high concentration flocculation is shown (D), where signif-
icant multilayer aggregation occurs, and forces are domi-
nated by particle–interface attraction or bulk hydrophobic
attraction rather than particle–particle repulsion forces. These
mechanisms may help explain some of the range of network
behaviour.
3.1.2. Droplet–droplet particle bridging
A stability mechanism that can be associated with a specific
low-particle-concentration interaction is particle bridging.
Here, if oil droplets have an incomplete coating, particles
adsorbed onto one droplet can directly interact with a
neighbouring droplet interface (much like in constricted foam
systems), causing stable droplet flocs. Gosa and Uricanu in
their work with PEO polymer surfactants and particle mixtures
[106] considered that polymer chains could bridge from the
silica between oil droplets, causing clustering, but increased
overall stability from additional hindrance to film drainage.
This type of cluster stabilisation was also considered by Vignati
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 12. Framework of possible particle network structures at oil or air interfaces: A) HCP layer B) Low concentration island ‘clumps’ C) low concentration long-range
lateral meso chains D) High concentration multilayer aggregation.
and Piazza to help stabilisation in their droplet systems of low
particle coverage [34]. Here, even clean particles (without
bridging polymers) could cross the inter-film region and bond
to both oil droplets.
Stancik et al have also found evidence of particle bridging
across droplet interfaces [74,107]. They used droplets mounted
at the ends of capillary tubes, which were contacted with a flat
interface, using both oil and water. As particle coated droplets
were brought into contact with the surface, particles arranged
themselves into ring structures around the outer contact area,
thus showing the lateral movement necessary to produce a
‘clean’ drop-drop interface, required for coalescence. However,
the droplets would only partially coalesce, and when removed,
resisted, but were cleanly separated.
In follow up work, both Stancik and Fuller [108] and
Horozov et al. [109] found that interfaces in close contact could
undergo long-range particle bridging, called ‘particle zips’.
Under certain circumstances, when two networked particle laden
interfaces come into contact, the two interfaces will ‘zip’ to form
one tightly networked monolayer [108] (Fig. 13), and remark-
ably this monolayer would continue to ‘zip’ nearby particles in
both layers, growing outwards from the initial point of contact,
compressing the particles to a finite distance, analogous to
crystal formation [109]. Horozov, using a vertical dual interface
(where the interlayer liquid film could be withdrawn and
69
replaced) not only found that these ‘zips’ resisted interfilm
changes, but when interfilm liquid was replaced to a point that
could eventually spit the zip, the two interfaces returned to
strong individual networked monolayers [109].
3.1.3. Surfactant addition and synergy
Masliyah, Wang and co-workers, through investigations on
petroleum emulsions, looked at the effect of negatively-
charged kaolinite clay particles on emulsion stability, with
addition of anionic palmitic acid and cationic dodecyl amine
(DDA) surfactants [36]. The addition of DDA to O/W
emulsions stabilised by kaolinite caused a significant drop in
interfacial surface tension, dependent on the amount of
kaolinite in the system. It was thought that particles at the O/
W interface surface attracted the oppositely charged DDA
surfactant molecules, which then adsorbed onto the oil–water
interface, to a greater extent than if no particles were present.
Attraction of kaolinite particles to DDA was great enough for
DDA molecules to be attracted through the oil onto particles in
the water.
In a similar approach, Tambe and Sharma focused on
idealised systems of naturally occurring oil-brine emulsions,
using barium sulphate, calcium carbonate and silica [2,32,33].
Stearic acid was used as a surfactant emulsifier. Although not
focusing on surface tension, it was found that surfactant
70 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81

addition to particle mixtures led to emulsion stability far greater

than found with either particles or surfactant alone (Fig. 14).
This synergy was attributed to the surfactant's ability to
increase the particle contact angle on adsorption. For highly
hydrophilic particles, surfactant addition caused the contact
angle to increase in parallel with stability to angles of 90°, and
for certain particle systems, they were able to induce emulsion
inversion from O/W to W/O by increasing the relative contact
angle from below to above 90°. At high surfactant particle
ratios, emulsion behaviour similar to surfactant only systems,
as surfactant molecules began to compete for active sites on the
oil–water surface, thus inhibiting particle adsorption.
In a similar finding Gosa and Uricanu found that systems of
silica and PEO–PPO–PEO block copolymers caused synergis-
tic stability [106]. Again, systems of low surfactant to particle
ratios created optimum conditions, and that increased surfactant
concentration lead to site competition between the particles and
surfactant molecules, leading to an overall stability decrease.
They attributed the synergy to principally increased flocculation
of silica with surfactant adsorption. It was thought that co-
polymer bridging mechanisms would lead to small oligomeric
silica flocs, which when adsorbed onto the oil–water interface
would cause stronger networks, increasing hindrance to lateral Fig. 14. Half life of emulsions stabilised by stearic acid with (open squares) and
movement (the main form of instability). without (closed squares) calcium carbonate particles [2].
Midmore furthered these findings, in systems of silica and both
PEO [110] and HPC [104,105] surfactants. Again clear synergy
was found between silica and each of surfactants, with stabili- continued to gain experimental backing. Very recently Binks and
sation initially increasing and then decreasing, once surfactant co-workers looked at the synergy between moderate concentra-
concentration was heightened to compete for the oil–water tions of nanosilica (20 nm) and non-ionic PEO type surfactants
interface. PEO polymers of greater chain length gave enhanced [111]. For systems with high stability clear evidence of small
results, because of their preference to adsorb onto silica, and aggregate formation was present, confirmed with bulk rheology
hindered preferential absorption onto the oil–water interface. In tests showing increases in viscosity linked to this flocculation.
terms of synergic action, there was evidence for increased Interestingly, they found that the interfacial surface tension was
flocculation of silica with surfactant addition, and increased con- negatively affected (increased) by particle addition. This was
tact angle. Again a likely scenario was that upon emulsion balanced by changes in the particle contact angle, which overall
agitation, silica flocs initially formed would be broken into small produced a net increase in the theoretical detachment energy (i.e.
oligomeric and monomeric flocs that underwent further network- increased stability) for moderate concentrations of both species.
ing on the oil–water surface (See Fig. 15). In terms of flocculation stability, questions remain as to how
The hypothesis that synergistic stability is caused by unique particle–surfactant species can intrinsically aid stability of
flocculation mechanisms between particles and surfactant has emulsions and foams. From bulk rheology tests, it is not hard to
judge how partial flocculation may impose more significant
bulk viscosity and so inhibit drainage. However, for agglom-
erates adsorbed at the interface, it is not immediately obvious
how these particle–surfactant clusters could hinder coalescence
more than, say, a strong HCP layer of individual particles. In
fact pre-flocculated clusters should not undergo the same
network rearrangement as individual particles, and so may not
produce such homogenous steric layers.
The key to understanding the synergy between particles and
surfactant may in fact lie in how their joint arrangements at an
interface could change interfacial rheology properties. It is
hypothesised here that surfactant–particle mixtures may
increase interfacial elasticity and cohesiveness over particles
or surfactant acting alone. In effect, interlocking surfactant
Fig. 13. Formation of particle zips: A) interfaces initially brought into contact chains between particles may act as elastic ‘springs’ in the layer.
B) particles conform to bond to interstitial sights on the opposing interface Also, combined effects could impart significant changes the
C) monolayer ‘zip’ is formed, expanding out from initial contact point [108]. interfacial viscosities (essentially the intrinsic hydrodynamic
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 15. Partial flocculation characteristics of particle–PEO surfactant
aggregates on a O/W emulsion droplet (TEM) [110].
resistance to flow of the layer), much like increases to the bulk
viscosity. Given in Fig. 16 is a possible ‘elastic’ arrangement of
particles and surfactant at an interface.
It can be generally surmised that there is a possibility for
surfactants to have three synergistic effects on particle–interface
stabilisation. Surfactant–particle mixtures may firstly decrease
the interfacial tension (or at least greatly alter it, as further
discussed in Section 3.2.3). Secondly surfactant adsorption acts
to change particle contact angle (and so alter stabilisation
energies). Lastly, surfactants may help promote partial particle
flocculation and network rearrangements at the interface,
perhaps observable through changes interfacial rheology. This
last topic is an area not well researched, but is one of increasing
interest. The best indicators can be found in studies of proteins in
food systems, where changes to hydrophobicity, and addition of
surfactant have led to differences in measured viscous elastic
moduli [112]. One of the first papers to directly study dilatational
changes to particles and particle–surfactant mixtures is work by
Ravera et al [113]. Here, aqueous drops containing nanosized
silica and CTAB, allowed dynamic monitoring of changes in
network structure under harmonic perturbations. The measured
dilatational modulus was markedly higher for droplets with
CTAB–particle mixtures than CTAB alone, indicating the
potential for high stability emulsion and foam systems.
3.2. Foam systems
When compared with their effect in emulsions, the action of
particles in the stabilization of foams are inherently more com-
plicated. Of particular importance are the effect of larger density
differences between the respective phases in air–water mediums,
the increased effects of disproportionation and the pointed ability
of hydrophobic particles to act as foam de-stabilisers [8]. The
study of particles in foam systems still remains a very challenging
and important prospect, because of the potential consequences for
related industrial fields such as particle flotation [26] and the
metal foam industry.
71
3.2.1. Density effects and disproportionation
The effect of increased density difference between air–water
foams over oil–water emulsions is evidenced simply by an
increased rate of film drainage [7]. Arditty and co-workers
highlighted these differences in work with bi-liquid foams. The
bi-liquid foams generated were essentially condensed O/W type
emulsions, where the water-continuous phase was withdrawn to
only 10%, leading to condensed partially coalesced oil ‘bubbles’.
These foam like droplets held strong structure and stability far
beyond what would be considered for gas–water type systems,
because of the decreased effects of gravity induced drainage
[7,114,115].
It would seem that the most difficult de-stabilising influence
to overcome is that of molecular diffusion, or disproportionation,
as even a highly packed steric barrier (such as proteins or
particles) would leave holes at a molecular level [8]. In fact
Dickinson, in and extensive investigation into foam stabilisation
by proteins, found for a range molecules that augmented inter-
facial viscosities and elasticity, stabilities were similar, and
disproportionation could be decreased no more than 2–3 orders
of magnitude [116]. It seems in response to disproportionation,
greater retardation can occur if interface particles have a high
degree of inter-networking, as evidenced by Martin (using
proteins) [117], and this is backed up by the view that proteins
can only create a truly stable foam, if the species undergoes
coagulation or aggregation at the interface, creating a strong
lateral network [118]. This would suggest that particles that
undergo partial coagulation/flocculation may be perfect candi-
dates for foam stabilisers. It must also noted here that affects of
disproportionation are most evident in systems using gases of
high molecular solubility, such as CO2 [5]. As such, dispropor-
tionation is commonly a problem encountered in the food
industry (i.e. with carbonated beverages) and is not as significant
in most air–water foams (although still an important mitigating
mechanism).
3.2.2. Non-adsorbing Inter-film stabilisation
As well as studies relating to particles as attached stabilisers,
there has been work into the mechanism by which non-adsorbing
particles may stabilise foams, specifically the phenomena of
Fig. 16. Possible joint network of particles and surfactant at an interface.
72 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
‘stratification’ (or stepwise film thinning). Stratification occurs
when particles (or particle type species) are contained within a
thinning inter-bubble film, and are forced into ordered layers of
particles, that are expelled out of the film surface into the Plateau
boarders in a stepwise manner, with each step relating to a specific
concentration of ordered species [15]. This stratification process
increases stability, through an additional contribution to the
capillary disjoining pressure [15]. In terms of foam stability,
stratification has been shown in systems containing micelles and
globular proteins [119–122].
Sethumadhavan, Wasan and co workers, have completed
extensive research into the stratifying behaviour of non-adsorbing
silica nanoparticles in thin film air–water systems [123,124]. It
was found that indeed silica produced strong stratifying
behaviour, with the number of thinning layers increasing with
concentration as expected. Stratifying behaviour was attributed to
the existence of a gradient in the chemical potential of the par-
ticles, or an osmotic pressure gradient, where particles leave the
film and vacancies appear in their place. Smaller particles pro-
duced lower rates of black spot formation, and overall produced
films more stable to rupture, indicating the importance of particle
size. There was also evidence for an order-disorder transition of
the particle layers, as the particles approached monolayer co-
verage [124], from a distinctive increase in packing efficiency,
leading to greater film stability. Basheva found similar well
ordered colloidal structure, in studies with latex suspensions, and
calculated the effective dynamic viscosity as being approximately
100 times larger than pure solvent viscosity [125]. In terms of
general packing structures, Basheva used interference methods to
study the structure of stratified latex particles [126]. It was
observed that the particles form hexagonal close packed structures
exclusively, with no evidence of tetragonal type packing.
Sethumadhavan et al considered the changes to stratifying
behaviour, in systems containing non-uniform particles [127].
The stratifying behaviour was seen to reduce markedly upon the
polydispersity of particles being increased. This behaviour was
observed, because of the degradation of ordered particle layers
with size variation in particles, and was even more apparent in bi-
disperse systems; giving systems of very low film stability (see
Fig. 17).
Velikov and Velev looked into the inter-film behaviour of
latex particles, with various surfactants, rendering the particle
behaviour either adsorbing or non-absorbing [128]. With anionic
surfactant, the particles became fully dispersed in the aqueous
phase, and were expelled between the film surfaces in a step wise
(stratifying) manner. With particle adsorption of protein, there
was some observed aggregation of particles between the film
surfaces, because of decreased mobility with protein coating,
and long-range capillary attraction. With cationic surfactant, the
latex hydrophobicity was increased, and the particles adsorbed
onto the film walls in a bridging manner similar to that observed
with emulsions.
3.2.3. Particle effects on surface tension
An interesting approach that has not been comprehensively
studied, is the ability of particles to affect interfacial surface
tension. However, if one relates back to surfactant systems [19]
the surface tension is a critical factor in defining stability. There
have been a number of interesting effects reported for certain
types of particle only systems, in addition to the synergic action
often reported with surfactants. Nushteava and Kruglayakov
[129] found similar surface tension behaviour to Masliyah and
Wang [36]. They observed a dramatic drop in the surface tension
of an oil–water interface, when particles were introduced to a
CTAB surfactant system. It was concluded that the surfactant
adsorbed onto the particles, increasing agglomeration and
attachment at the interface, in line with results and theory
presented by Tang at an air–water interface [49]. Recently some
more foam based behaviour has shown the same distinct
reductions in surface tension. Gonzenbach and Gauker have
observed surface tension decreases for nanosized aluminium
oxide and a range of short-chain fatty-acid surfactants [130]. The
greatest decreases were seen in surfactant ranges over a critical
concentration (where adsorption was maximised) (Fig. 18). It is
theorised that the particles disrupt the natural equilibrium of the
surfactant. Firstly adsorption onto particles will remove free
surfactant, but secondly the hydrophobised particles move to the
interface as surfactant carriers. Here, the action of the
surfactant–aluminium particles may collectively bring more
surfactant to the interface than a free equilibrium of surfactant
only. However, the extremely high concentration of particles
used in this system (35%) makes comparison of this phenom-
enon with other experimental systems difficult. It is also poten-
tially a very complex interfacial system, and the free energies
involved with particle, surfactant and mixture adsorption are
difficult to associate directly. There is still room for better
understanding of this process, and the combined effect of
particles on surface tension show very wide ranging outcomes,
as evidenced by other authors.
An interesting study of surface tension changes with surfactant
and particle systems was conducted by Marquez and Grady,
studying polystyrene (PS) latex and SDS structure with a
Langmiur-Blodgett trough [131]. Correlations were found
between surface tension and particle structure (Fig. 19). For
SDS/PS, the cmc is shifted to higher SDS concentrations, but a
sharp increase in surface tension occurs between 0.5–2 wt. SDS.
The relative flat plateau region (dotted circles) corresponds to the
range of surfactant concentrations at which ordered monolayers of
latex spheres form on the surface. Above this plateau, the surface
tension returns to values near the SDS solution, and this is
reflected in latex cluster formation and possible phase separation.
For nonionic surfactant addition, no ordered structure was found,
consistent with no appearance of the unique feature in surface
tension results. It was concluded that the tensiometer can be used
to determine the conditions under which well ordered latex films
form on substrates.
Okubo used surface tension measurements to study the
distribution and ordering of colloid spheres in deionized water
at interfaces (without surfactant addition) [132]. Two kinds of
colloidal systems were studied: monodispersed polystyrene
latex particles (strongly hydrophobic surface) and silica (polar
surface). A total of 19 kinds of colloidal systems were
investigated in the size range of 6–460 nm. In the case of the
colloidal silica suspensions (for size ranges 10–200 nm)
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81 73

Fig. 17. Black Spot expansion vs. film diameter, mono-disperse and bi-disperse silica [127].

relatively minor reduction in surface tension from that of water
values (− 2 MN/m) suggested very weak surface activity. On the
other hand, with polystyrene spheres the surface activity was
unusually high for spheres of a particular critical size range
diameter of 100 to 200 nm, and resulted in surface tension
reduction by values as great as 20 mN/m, at relatively high
particle concentrations (10–20%).
From the surface energy data, the ordering of the particles at
the interface was described in terms of crystal-like, liquid-like
and gas-like. To explain the differences in surface activity, it
was firstly considered a result of the hydrophobicity of the latex,
and also that the surface tension of interfacial crystal-like
suspensions was lower than that of liquid-like and gas-like
suspensions. The importance of particle size in determining
surface activity was a significant finding (Fig. 20), and it was
concluded that the critical size range corresponded to sizes,
which led to crystalline structures in bulk conditions, again
indicating the importance of structure on surface activity.
More recent studies by Dong and Johnson, using charged
stabilised (and hydrophilic) TiO2 dispersions, demonstrated the
influence of bulk particle size and concentrations on the surface
tension [133,134]. The surface tension first decreases to a
minimum at around 5–7% mass solids, before rising back to
initial values with very high particle concentrations of around
10% (Fig. 21). It was suggested that at lower concentrations, the
movement of particles to the interface decreased the total free
energy of the system, which caused a decrease in surface tension.
At higher particle concentrations, in a situation similar to the
immersion of thin films, the capillary force due to the wetting of
the particles becomes significant. The strong capillary forces
between particles will resist interfacial deformation and increase
local effective surface tension. Results with silica micro-
particles showed a weaker, but still distinct effect [135]. In line
with Okubo [132], they also felt that particle size was a
significant factor in behaviour differences [135].
These reports highlight the complexity involved in the
relationship between surface tension fluctuations and particles at
or near the interface. One may make the interpretation that partial
crystallisation and aggregation of particles in certain size ranges
can lead to a decrease in surface tension, especially for hydro-
phobic particles. Marquez and Grady's work [131] would also
suggest certain particle structuring may lead to surface tension
increases. The role of surfactant is also unclear. Indeed, it seems
conditions producing bulk decreases in surface tension may be
very specific, as a great deal of other work has shown the
depletion of free surfactant by particles dominates surface beha-
viour and results in an increased surface tension [113,136,137].
As indicated by Ravera and workers, the behaviour could be a
dynamic result of surfactant depletion, surfactant transport to the
interface by attached particles, and as a consequence, particle–
surfactant rearrangements at the interface [113]. It is obvious the
hydrophobicity of particles and surfactant-particle species is
critical in determining overall performance. The role of capillary
attraction in changing surface activity (as theorised by Dong
Fig. 18. Surface tension of butyric acid with (closed) and without (open) 35%
alumina suspensions [130].
74 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 19. Surface tension changes with polystyrene (PS) and SDS addition [131].
[134]) may also be an important regulating factor in overall
effect. Capillary influence was further observed by Casson and
Johnson, with suspended latex particles in a dish [138]. Here
capillary attraction between particles caused random initial ag-
gregation, leading to fluctuations in the local surface tension, to
such an extent to cause tension-gradient driven particle flow.
3.2.4. Particles as foam stabilisers and destabilisers
The use of particles as foam stabilisers is more complicated
than their use in emulsions; primarily because hydrophobic
particles can act as foam de-stabilisers. The antifoam action of
hydrophobic particles is caused by heightened capillary de-
wetting action, from the extenuated water receding angle
[15,139]. Given a smooth particle where θ N 90° for particles
that bridge between bubble films, the receding contact angle will
cause de-wetting of the interface film. This drainage is propelled
by a positive Laplace pressure in the film adjacent to the particle
[15]. For particles where θ b 90°, the drainage stops as the Laplace
pressure difference reduces to zero and the film becomes
essentially planer, when the two air interfaces attain steady
contact angles with the particle (assuming both air interfaces are
similar and give θ b 90°) [15]. In fact, in hydrophilic particle
bridging systems, any further drainage will cause the Laplace
pressure to draw liquid back into the particle film, creating a stable
bridging mechanism. For hydrophobic particles, as both air
surfaces will try to attain a steady contact angle above 90°, de-
wetting will accelerate until the inter-film is completely drained
(Fig. 22). Particles can further be used in conjunction with various
non spreading oils as very effective foam breakers, where the
particles protrude to create an unstable asymmetric air–water-oil
interface, allowing the entry of oil globules, that rupture the foam
through dewetting bridging & stretching mechanisms [15,140].
Although these wetting mechanisms imply that particles with
any contact angle below 90° should act as foam stabilisers, much
research has shown that particles can begin to act as de-foamers
with contact angles much lower. This is partly from the effects of
meniscus formation and surface roughness, leading to ‘non-
equilibrium’ wetting characteristics. However, it may also be a
result of the relatively low concentration and high interaction
between particles and adjoining gas-liquid interfaces, causing
changes to the maximum capillary pressure of coalescence [67]
(as stated in Section 2.1.2). Most research in this area has been
concerned with particle flotation, with a focus on the effect of
particle hydrophobicity on mineral recovery, highlighting the
practical importance of producing stable froths.
Van Der Zon et al., using a moving bubble column, found as
expected, the use of hydrophobic coal particles in flotation caused
extensive froth coalescence, and the most hydrophobic coals
produced the weakest froths [141]. Pugh and Johansson
considered the effects of the hydrophobicity of quartz particles,
in regards to mineral processing [13]. They found particles with
θ b 40° gave no effect, whereas particles with contact angle
around 65° gave optimum froth stability. More hydrophobic
particles lead to collapsing froth, with contact angles still below
90°. For particles at the optimum contact angle, froth stability was
shown clearly to exceed stability for surfactant alone (Fig. 23). As
well as this, results indicated that smaller particles worked better
at stabilising froths, and particle mixtures of hydrophobic and
hydrophilic particles lead to no increase in stability. It was thought
that even small concentrations of hydrophobic particles lead to
dominating de-wetting interactions, although instability could be
also due to changes to capillary action, as hypothesized in mixed
emulsions [17].
Schwarz found similarly that optimum particle contact angles
for stability occurred around 63° [142], and Jameson and Ata, in
experiments using froth columns to selectively separate
hydrophilic and hydrophobic particles, found particles of around
66° contact angle gave optimum stability conditions [143,144].
In both cases, increasing particle hydrophobicity led to dry
partially coalesced froths, because of increased film drainage.
Ata and Jameson also looked at mixtures of hydrophobic and
hydrophilic particles (in terms of selective flotation perfor-
mance) and found that hydrophobic particles dominated inter-
actions, and through bridge film drainage, entrapped water wet
Fig. 20. Surface tension measurements of silica (X) and latex (O), with
increasing diameter (mass fraction 0.2) [132].
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 21. Surface tension changes due to TiO2 particle suspension [134].
hydrophilic particles, inhibiting separation [144]. Along with the
work of Aveyard [139], it can be generally surmised that the
range of contact angles in which particles stabilise foams is
small, and there is a sudden drop, in line with the critical rece-
ding angle, from where particles begin to work as de-stabilisers.
This signifies that particle stabilised foam systems are far
more susceptible to conditional changes than particle–emulsion
systems.
Kaptay looked at general forces governing stability in foams
[66]. Unsurprisingly he found that particles could stabilise foams
under different conditions in a range of contact angles, in all
cases between 20° and 90°. Structurally, in line with network
formations on emulsions, particles could form loose monolayers
to packed multilayers on bubble surfaces. He also determined a
dimensionless factor PR/γ (where P = pressure destabilising
foam, R = particle radius, γ = liquid surface tension) for calcu-
lating potential foam stability. It was theorised that PR/γ b 40 is
Fig. 22. Bridging particle behaviour in a foam. A) hydrophilic, B) hydrophobic particle [139].
75
required for particles to potentially stabilise foams, indicating
that particles above 3 μm would probably not be effective
stabilisers. This is significant, because it shows foam systems
rely more critically on particle size than emulsions. Whereas in
emulsions, larger particles will tend to form larger emulsion
droplets, large particles in foam systems will tend to pierce and
break foam systems. Another factor important to stability is the
shape of particles, especially relevant to the flotation industry,
which regularly encounters larger, non-symmetrical particles.
Dippenaar, in investigations [51,52], established that ‘flaky’ flat
type particles generally result in more stable three-phase froths
from as a result of lateral alignment along the contact region.
Square (or ‘rhombic’ type particles, such as galena) can align
either laterally or diagonally, resulting in differentiating stability
profiles. In further examples, rounded or spherical particles
accomplished thinning and rupture of a liquid film in
approximately 0.1 s, whereas sharp-edged particles ruptured
the liquid film in only 0.02 s.
Despite the extensive research into particle foam stability in
terms of flotation, there has been relatively little work done on
the establishment of stabilising mechanisms of pure foam and
particle systems (without the surfactants and frothers used in
flotation). Of note is the largely unpublished work of Wilson
[145] (see Binks [26]). Using froths stabilised by latex particles,
Wilson found that the most stable froths were made, if conditions
were developed close to bulk particle coagulation conditions
(either through salt addition, pH changes, or surfactant addition).
This is again in line with the theory that for particles to work
effectively as stabilisers in pure systems, partial coagulation is
necessary [118]. Wilson also found that the optimum contact
76 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81

conditions by Murray and co-workers (see Fig. 25) [152]. Foam

stability is seen to drop more significantly at NaCl levels below
1 mol l− 1, relating to a ‘minimum’ salt concentration needed for
strong stability This was not only due to the coagulation and
gelling characteristics (shown by rheological measurements),
but also because salt screening increased the contact angle of
adsorbed particles. Interestingly almost no stability was seen in
systems without salt.
The apparent high stability to disproportionation is a most
significant result, as even considering the coagulated nature of
the particles; diffusion should still be possible on a molecular
level. This was considered by Subramanian et al., who modelled
the effects of gas diffusion on bubbles with an arbitrary number
of partially wet spheres [153]. Modelling showed that if the
local particle laden interface could be approximated to a flat
surface, it is stable to slight perturbations caused by fluctuations
in the gas volume, as any gas diffusion would cause changes to
Fig. 23. MIBC froth stability, with (filled) and without (open) 2 wt.% 26–44 μm
quarts [13].
the curvature restoring equilibrium.
These studies point to a few general rules guiding foam
stability in the presence of particles. It would seem that foam
angle for stability was closer to 85o, a value higher than gene- stabilisation is increased if a high concentration of small
rally found in flotation type systems. (nanosized) particles of moderate hydrophobicity (generally
Armes and co-workers [146,147] have furthered Wilson's 60–70°) are used, and de-stabilisation is increased with the use
research into latex stabilised foams, and have revealed some
interesting possible differences to emulsions. They firstly found
that particle stability increased with decrease in particle size only
to a point. In fact a minimum size of 260 nm was needed to
produce stable foam [146], which is about an order of magnitude
above the stable size range in emulsions [37]. However, they
also found the stability was linked strongly with the polymer-
ization and initiator species, and that (for the latexes tested) the
smaller particles were more polydisperse, with interface net-
works of smaller lateral ordering. This shows the polydispersity
of a system can be more important in forming homogenous
intrinsically strong networks than simply the given size of a
particle. Most importantly, SEM micrographs (Fig. 24) show in
all stable systems, strong ordered hexagonal networks with no
evidence of flocculated aggregates.
This is quite different to the surmised behaviour of silica
systems that Dickinson and co-workers have detailed in com-
parisons with protein stabilisation [148,149]. Silica nanopar-
ticles (of around 20 nm) could impart outstanding stability
in foams, especially in respect to disproportionation and bub-
ble shrinkage, giving results far above those achieved with
proteins. Interestingly (in line with Wilson [145]) although foam
stability was high, it was initially quite difficult to generate the
foams in clean systems [148]. This fact was also noted by Bindal
and Sethumadhavan, who found even a small degree of poly-
dispersity drastically reduced silica suspension foaminess [150].
Dickinson determined that in terms of overall stability, silica
nanoparticles should also be partially coagulated at the interface
[149], where salt concentration should be at a point to form small
oligomeric flocs (upon system sonication), which would
undergo further networking at the interface. This conclusion
was also found by Binks in similar systems of nanosilica foams
[151]. The importance of salt and electrolyte screening was Fig. 24. SEM of a latex foam fraction (A) and (B) a close up SEM of latex
furthered from research into particle behaviour in high salt bubble packing, both with 1.14 μm latex particles [146].
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
of even a small concentration of larger more hydrophobic
particles. Also, as with emulsions, partial coagulation of particle
networks on the surfaces of the bubbles is found to be advan-
tageous for stability, especially in silica systems of low to
moderate contact angles. The role of salt coagulants may also be
complicated by a possible effect on particle contact angle, and
specific ion effects [152]. One other generality is that the ability
of particles to stabilise foams is not necessarily associated with a
given particles ability to generate a foam, and because of this,
the role of co-surfactants or foamers maybe even more critical
than in emulsion systems.
3.2.5. Particles in metal foams
An interesting comparison can be made with particle stabi-
lising behaviour in metal foams. Cellular metals are a novel
class of lightweight material with unique mechanical, thermal
and electrical properties. They have potential applications as
heat exchangers, in fuel cell systems, steam generation, in the
automotive industry (car bodies) and for light-weight structural
elements in building [154]. In addition, since they have the
ability to absorb large amounts of energy at almost constant
pressure without generating high peak stresses, they can be used
as crash absorbers and sound isolation elements (as in tunnels)
[154]. Today, although several methods of fabrication of metal
foams exist, it is still difficult to achieve homogenous structure
with uniform properties. The manufacture of metal foams is
very challenging since it involves the simultaneous occurrence
of solid, liquid and gaseous phases at varying temperatures and
the morphology of the solidified foam is quite complex [155].
Several metals and metal alloys can be foamed (Al, Zn, Mg, Pb,
Fe), and among these, aluminium is the most important for
applications. Several routes and competing manufacturing tech-
nologies for foamed metals are now known. Melts can be
foamed directly by gas injection, or by indirect foaming from
metal power compacts [156]. Fig. 26 shows an example of
‘direct injected’ aluminium metal foam.
There are a number of characteristic foam types and trade
names, all with different potential properties and uses. Examples
include the European ALULIGHT, produced by compacting
metal and alloy powders with gas releasing TiH2 particles [157].
The foams develop during baking of this precursor, which
contains nanometre-sized resident oxide particles from the
former surfaces of powder mix. The Japanese ALPORAS is
Fig. 25. Comparison of foam fraction (F) with increasing time for 20 nm silanated
silica and salt. Filled diamonds, 3 mol l− 1 NaCl; open squares, 2 mol l− 1 NaCl;
closed triangles, 1 mol l− 1 NaCl; open triangles, 0.5 mol l− 1 NaCl [152].
77
Fig. 26. Examples of “METCOMB” aluminium foam [155].
produced by firstly adding calcium to an aluminium melt in the
presence of air to aid oxidation. Then TiH2 particles are admixed
to instigate foaming [157,158]. These inner oxide particles
(films) are in the submicron range. With the CYMAT and
METCOMB processes, liquid metals reinforced with micron-
sized ceramic particle (eg. SiC and Al2O3) are foamed by direct
gas injection [155,157]. These latter techniques represent the
most promising, and offer the highest quality foams and superior
technology to produced foamed parts. Generally however, a
larger fraction of particles is added in direct injection systems,
and problems occur when trying to disperse submicron sized
particles in these processes [155], a problem, which if overcome,
could lead to dramatic improvements in stability and economy.
In all manufacturing routes known up to now, foam stability is
achieved by solid particles with particle sizes ranging from
30 nm to 20 μm. As a rule, smaller stabilizing particles require a
lower volume content of such particles. Metal foams actually
give one of the clearest and significant proofs of the potential for
particle-stabilising species. Yet, even here (partly extenuated
because of differences in the various manufacturing systems) the
nature of action of these particles is still under dispute. There is
conflicting evidence of whether a particle's major contribution
lies in the inter-film layer with consequential effects on rheology
and drainage, or whether (as is most evident in, say, emulsions) a
particle–interface steric barrier is the major component. Gergely
and Clyne stated that high particle concentration could increase
viscosity, and inhibit liquid drainage [159]. Ip suggested
particles that were attached to the interface caused a flattening
of the bubble curvatures around the Plateau border, reducing the
capillary pressure, and retarding drainage [160]. Babcsan and
co-workers found that additionally, Al2O3 particles in liquid
aluminium alloy suspensions reduced the surface tension sig-
nificantly at high concentrations, highlighting another potential
basis of stability [156].
The many possible stabilisation mechanisms observed in metal
films were recently categorised by Hailbel and workers [161],
seen in Fig. 27. Here (a) represents a clean foam interfilm, with a
pressure difference between the bubbles and the interfilm and also
the plateau boarder causing drainage. Possibility (b) highlights a
single layer of particles of low absorptivity increasing the
maximum capillary pressure of coalescence. Mechanism (c)
78 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
suggests that small particles of low-to-moderate adsorbance at
interfaces can alter the capillary curvature of the surface, and so
reduce the capillary flow between interfilm and plateau border. (d)
Indicates particles flocculated in the bulk may bridge between
bubbles as aggregates, while (e) highlights how non adsorbing
particles may affect bulk viscosity. No apparent bridging between
either aggregates or individual particle layers, were found in their
experiments, as interfilm thicknesses were quite large. They
therefore concluded that stability mainly came from adsorption
based steric repulsion, with a few non-adsorbing particles trapped
in the interfilm region (seen as mechanism (f)).
However, the majority of evidence does seem to indicate that
particles can still significantly reduce capillary flow and drainage
[158], as many systems with low particle absorbance still show
increased stability. A further complicating factor is the high
concentrations of particles often used, where static repulsion and
also bulk viscosity changes should be even more apparent. Ip
[160], found that in direct injection systems, a minimum particle
coverage of 50% was required, while Babcsan et al. [162]
concluded that optimum packing of SiC and Al2O3 particles was
45% in nitrogen gas foaming systems. Both Lietlmeier et al. [163]
and Ip [160] suggested that for particle sizes of around 10 μm, a
mass fraction of at least 10% was required for long-term stability
(generally mass fractions can range from 10–20% [157]). Ip also
showed that an increase in system temperature led to reduced
system stability, attributed to a decrease in bulk viscosity, in line
with the proposal of Gergely and Clyne [159].
The effects of particle wetting are a complicated matter,
owing to general kinetically-controlled changes of substrate
wetting on molten metals (reactive wetting), often causing shifts
with temperature, time or with parameters such as drop volume
[164]. Some trends are consistent, with those in non-metal
foams. Ip [160] found a critical wetting angle of around 75° gave
optimum performance, values close to flotation air–water
foams. Kennedy and Asayayisitchai [165] looked at the effects
of TiB2 particles on indirect power-compact Al foams, which
contain large amounts of oxides. The oxides inhibited TiB2
particle wetting, giving low TiB2 particle contact angles, a
reason stated for the low long term foam stability. It was also
found that despite the low long term foam stability, the particles
Fig. 27. Mechanisms of particle stabilisation in metal foams: (A) clean bubble interfilm, (B) stabilisation from bridging particles altering Pcmax, (C) weakly adsorbing
particles reducing capillary flow through meniscus alterations in curvature, (D) bridging flocs transmitting mechanical ‘disjoining’ force, (E) non-adsorbing particles
altering viscosity, (F) strongly adsorbing particles creating steric barrier, with added trapped particles inhibiting drainage and bulk rheology [161].
did yield significant improvements in initial gas expansion of the
foamed melt. Bubbles/pores had smaller average diameters, with
smaller interfilm thicknesses. Optical micrographs (Fig. 28)
clearly show the TiB2 particles of the composite film residing
mainly in the interfilm (i.e. non-adsorbing). Stabilisation in this
manner could simply be a result of particles impeding film
drainage, as changes to capillary curvature are not immediately
evident.
Another factor in equating the dominating stability interac-
tion from particle addition is the effects of particle size. First
considered in line with volume fraction by Jin et al [166], and as
revised by Kaptay [66], there are some well grounded
conclusions. Generally, cell walls will rupture at larger minimum
thicknesses in metal foams than traditional aqueous foams, and
the diameters of the stabilising particles, have a direct affect on
the attainable minimum cell thickness. Larger particles will give
weaker films that rupture at greater interparticle thicknesses
[167]. The direct affect of particle size on cell wall thickness
supports the concept of interfilm stabilisation (eg. capillary
pressure interactions); yet particle size relationships are also
indicative of a steric barrier, as smaller particles can naturally
form a more complete, well ordered layer. Esmaeelzadeh et al
[168] and Ip [160] have experimentally shown the affect of
different particle sizes on metal foam stability. Ip produced clear
and direct support for a strait inverse relationship between
particle size and stability (Fig. 29) [160], which is also present in
emulsions [37] and aqueous foams [49].
The evidence suggests that the high level of stability in metal
foams can be gained from both drainage and coalescence
retardation. Difficulties in defining the major contributor in a
particular situation could hinder future progress. Despite the
improvement in quality over the past 10 years, metal foams still
suffer from non-uniformities and other deficiencies. In order to
improve the cellular structure of the materials, and also to make
the production technologies more reliable and reproducible, the
stability of liquid metal foams needs further investigation,
particularly aimed at avoidance of rupture and the control of
liquid drainage. In addition, the high content of stabilising
ceramic particles makes direct injection foams such as MET-
COMB difficult to cut. A strong research effort in this field is
 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81
Fig. 28. Al Foam inter-film A without and B with TiB2 nanoparticles [165].
needed to achieve a break-through in economical production
technology. In order to implement these goals, synergies between
different scientific disciplines such as chemistry, physics, physical
metallurgy, materials science and engineering have to be
established, but it can be generally stated that advances in metal
foams is generating possibilities for a whole range of foaming
systems.
4. Conclusions
The recent interest in particle-stabilised foams and emulsions
has identified the major factors affecting the stability of respective
systems. It should now be possible equate rules governing the
effect of particle size, concentration, aggregated nature and
contact angle to help improve the performance of a given system.
However, great complexities arise from the fact that these
structures attain equilibrium as a result of colloidal forces acting
on the particles and bubbles in the bulk (such as the effects of
salts) as well as interfacial forces. Difficulties also arise in
associating characteristics with the method of preparation and the
energies involved in emulsion and foam formation. A related
problem is the possible differences in aggregation kinetics,
between static interfaces and real bubbles & droplets. There are
79
still questions relating to whether the long-range meso structures
shown at static interfaces, are present in many droplet/bubble
systems. It may be thought that the large energies involved in
interface formation, and effects of other factors such as salt and
surfactants, may produce more small ranged coagulated networks
(not complex capillary induced structures). Conclusive evidence
of network formation is unfortunately inherently difficult in real
emulsion or foam systems at a nanoscale level. This kind of
information is critical however in determining the reasons for
stability, especially with low concentrations of particles
In both emulsion and foam systems, work with surfactants
warrants attention. Because of the great range of surfactants,
polymers and other absorbing species available, the range of
possible interaction mechanisms is quite extensive. It is known
that surfactants may help to promote particle emulsion stability
by increasing particle contact angle, by partial flocculation of
particle–interface networks and also by lowering surface
tension. It is not clear which of these processes will dominate
in a particular situation, particularly the effect on surface tension.
The overall stability for any given system is a delicate balance of
particle–interface, surfactant-interface and particle–surfactant
interactions. Categorising these interactions and their affect on
stability is an area of important future research. There could be
potential benefits in synergistic action, which could improve the
formulation of a wide range of naturally occurring systems (such
as in food colloids, cosmetics and flotation) where a number of
different species work (and compete) together. A largely unan-
swered question is how solid particles act with other species,
such as proteins. Such large steric molecules are more perma-
nently adsorbed at interfaces, so it could be presumed that
particles would not preferentially adsorb to the same extent, as
with dynamic surfactant systems. This may mean that particles
will adsorb onto the proteins at the interface, and not the
interface itself, possibly changing stabilisation dynamics.
The successes with particle-stabilised emulsions have contin-
ued to lead to benefits in a number of fields. The principles of O/W
emulsion stabilisation is being used in many other systems, such
as the use in stabilisation of liquid CO2 and water emulsions
[169]. In terms of foam stability performance, probably the most
Fig. 29. Relationship between particle size and Al metal foam life [160].
80 T.N. Hunter et al. / Advances in Colloid and Interface Science 137 (2008) 57–81

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