Current Opinion in Colloid & Interface Science 7 Ž2002.

21᎐41

Particles as surfactants ᎏsimilarities and differences

Bernard P. BinksU
Surfactant & Colloid Group, Department of Chemistry, Uni¨ ersity of Hull, Hull HU6 7RX, UK

Abstract

Colloidal particles act in many ways like surfactant molecules, particularly if adsorbed to a fluid᎐fluid interface. Just as the
water or oil-liking tendency of a surfactant is quantified in terms of the hydrophile᎐lipophile balance ŽHLB. number, so can
that of a spherical particle be described in terms of its wettability via contact angle. Important differences exist, however,
between the two types of surface-active material, due in part to the fact that particles are strongly held at interfaces. This
review attempts to correlate the behaviour observed in systems containing either particles or surfactant molecules in the areas
of adsorption to interfaces, partitioning between phases and solid-stabilised emulsions and foams. 䊚 2002 Elsevier Science
Ltd. All rights reserved.

Keywords: Particle wettability; Particulate monolayers; Contact angles; Partitioning of particles; Solid-stabilised emulsions and foams

1. Introduction of particles at interfaces Žboth planar and curved..

It is well known that low molar mass surfactants
and surface-active polymers are used to aid dispersion
of powdered materials in a liquid, can form a variety
of aggregated structures in aqueous or non-aqueous
media Žincluding microemulsions in their mixtures.
and are commonly employed as emulsifiers in the
preparation of emulsions and as stabilisers in the
production of foams. Much less well appreciated is
that solid particles Žnano- or micro-. can function in
similar ways to surfactants but certain differences in
behaviour are inevitable, e.g. individual particles do
not assemble to give aggregates in the same way that
surfactant molecules form micelles and hence solubil-
isation phenomena are absent in the particle case.
Partly as a result of the current activity in nanoparti-
cle technology for producing new materials w1,2x, there
has been a resurgence of interest recently in the field
U
Tel.: q44-1482-465450 fax: q44-1482-466410.
E-mail address: b.p.binks@hull.ac.uk ŽB.P. Binks..
This review aims to highlight the similarities and
differences in the behaviour of surfactants and parti-
cles and includes their adsorption to interfaces, their
partitioning between immiscible liquids and their abil-
ity to stabilise emulsions and foams. Since this area
represents a new perspective, references to existing
older literature are included which serve as relevant
background and maintain continuity.
For surfactants present in oil q water mixtures, the
system HLB is the most important variable in de-
termining whether aggregated surfactant Žmicelles or
microemulsion droplets. resides in either water, oil or
a third phase. It has been shown that the packing
parameter of the surfactant in situ at the oil-water
interface determines the tendency of the surfactant
monolayer to curve towards water or oil or remain
effectively planar w3x. This in turn is set by the geome-
try of the surfactant molecules, hydrated by water on
one side of the monolayer and solvated by oil on the
other. Thus, for hydrophilic surfactants Žionics in the
absence of salt or non-ionics with a high degree of

1359-0294r02r$ - see front matter 䊚 2002 Elsevier Science Ltd. All rights reserved.
PII: S 1 3 5 9 - 0 2 9 4 Ž 0 2 . 0 0 0 0 8 - 0
22 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 1. ŽUpper. Position of a small spherical particle at a planar
fluid᎐water interface for a contact angle Žmeasured through the
aqueous phase. less than 90⬚ Žleft., equal to 90⬚ Žcentre. and
greater than 90⬚ Žright.. ŽLower. Corresponding probable position-
ing of particles at a curved fluid᎐water interface. For ␪ - 90⬚,
solid-stabilised aqueous foams or orw emulsions may form Žleft..
For ␪ ) 90⬚, solid-stabilised aerosols or wro emulsions may form
Žright..
ethoxylation., the area per head group is larger than
that of the chain and the monolayers curve around oil
resulting in oil-in-water Žorw. micro- and macroemul-
sions. For more lipophilic surfactants Žionics in the
presence of sufficient salt or nonionics with low de-
grees of ethoxylation., the area per chain exceeds that
of the head group and water becomes the dispersed
phase in water-in-oil Žwro. micro- and macroemul-
sions. For conditions in which the head group and
chain areas are similar, monolayers have a net curva-
ture of zero and new aggregates form including lamel-
lar phases and bicontinuous microemulsions. The se-
quence of transitions for multiphase microemulsion
systems ŽWinsor I᎐Winsor III᎐Winsor II. and the
corresponding emulsion inversion can be achieved by
changes in salt concentration, oil type or temperature
and by addition of cosurfactant, and is reasonably well
understood w4x.
In the case of spherical particles which adsorb to
interfaces Žwater᎐air or water᎐oil., the relevant
parameter is thought to be the contact angle ␪ which
the particle makes with the interface. For hydrophilic
particles, e.g. metal oxides, ␪ measured into the aque-
ous phase is normally - 90⬚ and a larger fraction of
the particle surface resides in water than in the non-
polar phase. For hydrophobic particles, e.g. suitably
treated silica, ␪ is generally greater than 90⬚ and the
particle resides more in air or oil than in water. By
analogy with surfactant molecules, the monolayers
will curve such that the larger area of the particle
surface remains on the external side, giving rise to air
or oil-in-water when ␪ - 90⬚ and water-in-air or oil
when ␪ ) 90⬚ ŽFig. 1.. The former include aqueous
foams and orw emulsions, respectively, whilst the
latter include aerosols and wro emulsions.
2. Adsorption to interfaces
There are now many methods to synthesise small,
monodisperse particles of different shape and surface
coating. If the coating, e.g. alkylsilane or fluorocar-
bon, is homogeneous over the particle surface fol-
lowing, say, reaction in the vapour phase, such parti-
cles are surface-active but, unlike surfactants, are not
amphiphilic. If, however, the coating can be restricted
to a particular area of the surface only, heteroge-
neous or ‘Janus’ particles result which are both sur-
face-active and amphiphilic, i.e. the particle has a
specific area which is oil-liking and a specific area
which is water-liking. It is important to understand
why hydrophobic or hydrophilic particles are strongly
attached to fluid Ž ␣ . ᎐fluid Ž␤ . interfaces. Consider a
spherical particle Žs. of radius r which is initially
totally in phase ␣ and is subsequently adsorbed to the
␣␤ interface. The interfaces s␣ , s␤ and ␣␤ have
interfacial tensions ␥ associated with them. Ignoring
the line tension ␶ acting at the three-phase Ž ␣␤s.
contact line, adsorption of the particle at the interface
results in an area of the s␣ interface being lost but
being replaced by an equal area of the s␤ interface.
More importantly however, an area of the planar ␣␤
interface Žnormally of high tension. is also lost due to
the presence of the particle, and this area depends on
␪. The energy of attachment of a particle to a
fluid᎐fluid interface is related not only to the contact
angle but also to the tension of the interface ␥␣ ␤ .
Assuming the particle is small enough Žtypically less
than a few microns in diameter. so that the effect of
gravity is negligible, the energy E required to remove
the particle from the interface is given by
2
Es ␲ r 2 ␥␣ ␤ Ž 1 " cos␪ . Ž1.
in which the sign inside the bracket is negative for
removal into the water phase, and positive for re-
moval into the air or oil phase. Inspection of Eq. Ž1.
for given r s 10y8 m Žcharacteristic of fumed silica,
later. and ␥␣ ␤ s 0.036 N my1 Žtoluene᎐water. shows
that the particle is most strongly held in the interface
for ␪ s 90⬚ with E being 2750 kT. Either side of 90⬚,
E falls rapidly such that for ␪ between 0 and 20⬚ or
between 160 and 180⬚ this energy is relatively small
Ž- 10 kT.. It will be shown later that this extreme
variation of E with wettability has a major influence
on the ability of particles of different hydrophobicity
to stabilise emulsions. For angles - 90⬚ the particle is
more easily removed into water than into air or oil,
i.e. the particle is relatively hydrophilic and for ␪ ) 90⬚
the reverse is true, i.e. the particle is relatively hy-
drophobic.
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 2. Variation of the energy required to detach a single spherical
particle exhibiting a contact angle of 90⬚ from a planar oil᎐water
interface Žof interfacial tension 50 mN my1 . with particle radius at
298 K. Note the low energies for radii - 0.5 nm Žsimilar to surfac-
tant molecules..
One consequence of the very high energy of attach-
ment of particles to interfaces, relative to the thermal
energy kT, is that particles once at interfaces can be
thought of as effectively irreversibly adsorbed. This is
in sharp contrast to surfactant molecules which ad-
sorb and desorb on a relatively fast timescale. Since E
depends on the square of the particle radius, it de-
creases markedly for smaller and smaller particles.
Fig. 2 shows the variation in the detachment energy
for spherical particles of different radius for ␪ s 90⬚
and ␥␣ ␤ s 50 mN my1 Žtypical of an alkane᎐water
interface .. Clearly, very small particles Ž- 0.5 nm in
radius. of the size comparable to most surfactant
molecules are easily detached Žseveral kT. and and
may not be too effective as stabilisers.
2.1. Liquid᎐¨ apour surface
It is surprising to note that Okubo w5x appears to be
the only author reporting the air᎐water surface ten-
sions of deionised colloidal suspensions. His interest
arose from work on colloidal crystal formation in
aqueous dispersions of charged particles, which is due
to the electrostatic repulsion between particles with
expanded electrical double layers. For spherical
polystyrene particles, the lowering of surface tension
from the value of the pure solvent depends on the
particle volume fraction Ž ␾ p . and on particle size. At
low particle concentration Ž ␾ p - 0.005., for which the
suspensions are turbid and milky and termed gas- or
liquid-like, the tension is not significantly reduced. At
higher concentrations Ž ␾ p ) 0.005., for which the sus-
pensions form crystal-like structures including bril-
23
liant iridescent colours arising from Bragg diffraction,
the tension falls continuously with concentration. Us-
ing 12 types of latex particles of different size and
charge density, it is concluded that surface activity is
only high for surfaces between air and crystal-like
structured suspensions. At a constant high ␾ p Ž0.02.,
the surface tension passes through a sharp minimum
for particle diameters of approximately 100 nm, the
lowering being as much as 20 mN my1 . By contrast,
the surface tension of aqueous suspensions of spheri-
cal silica particles ranging in diameter from 6 to 184
nm either remained constant or increased slightly
with concentration. Most of the suspensions were
either gas or liquid-like however. For those that dis-
played crystal-like structures in bulk, the tension did
decrease but only by as much as 2 mN my1 .
Colloidal crystal formation occurs when the effec-
tive diameter of the particles Žequal to twice the
Debye length plus particle diameter. is equal to or
greater than the mean inter-particle distance. The
inter-particle distance in the two-dimensional crystal
at the surface is likely to be less than that in bulk due
to the thinner double layers at a surface. The differ-
ence in surface activity between polystyrene and silica
suspensions is attributed to the surface nature of the
particles, i.e. hydrophobic for polystyrene and polar
and hydrophilic for silica, implying that the contact
angle Žthrough water. is higher in the former case.
Unfortunately, the excess concentration of particles
at the air᎐water surface could not be calculated using
the Gibbs equation since the variation of the mean
activity of the spheres with sphere concentration,
which is very sensitive to the degree of dissociation,
was unknown.
Clearly, adsorption of particles to interfaces is ex-
pected to be slow compared with surfactant molecules
and the above study represents a special case. It is
more common to investigate spread or insoluble par-
ticle layers at interfaces using a Langmuir trough
equipped with a microscope. Typically, the surface
pressure Ž ⌸ .- surface area Ž A. isotherms for particle
monolayers are determined and the aggregate mor-
phology and fractal dimensions have been reported.
The studies include, inter alia, the use of micron sized
polystyrene w6 ,7x, or glass w8x particles and nanometre
䢇
sized silica w9x, magnetic maghemite w10x and silver
w11 x particles. In general, the forces responsible for
䢇
the interactions between particles in bulk are also
operative in particulate monolayers. Pieranski w12x
noted, however, that for charged particles at an inter-
face between water and a medium of low dielectric
constant Žair or oil., electrostatic repulsion is en-
hanced over that operating in the bulk aqueous phase
particularly at large particle separations. The reason
is that the interfacial particle has an asymmetric
distribution of counterions resulting in a dipole mo-
24 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
ment normal to the water surface. Repulsive interac-
tions between the dipoles due to neighbouring parti-
cles occurs through the phase of low dielectric con-
stant, whereas repulsion through the aqueous phase is
screened by free ions in solution. It has been shown
theoretically that the interaction energy between
charged particles near an air᎐water surface decays
inversely with the cube of the separation between the
dipoles and is inversely proportional to the electrolyte
concentration w13x.
The air᎐water surface has proved the most popular
´ ¨
choice of interface. Horvolgyi et al. have investigated
monolayers of silanised glass spheres Ž75 ␮m in di-
ameter. using both a Langmuir w14x and a Wilhelmy
w8x film balance. The advantages of using relatively
large particles are that their behaviour on the water
surface can be readily visualised and in situ contact
angle determinations can be conveniently performed.
By changing the extent of silylation the hydrophobic-
ity of the particles can be altered easily. Using a
combination of combustion gas analysis, infra-red
spectroscopy, krypton adsorption and contact angle
measurements, Fuji et al. w15x showed that for glass
beads coated with trimethylsilyl ŽTMS. groups the
air᎐water contact angle dependence on TMS surface
coverage was S-shaped, changing markedly at approxi-
mately 50% monolayer coverage. From the monolayer
studies using particles which were weakly Ž ␪ s 55⬚.,
moderately Ž ␪ s 72⬚. and highly Ž ␪ s 90⬚. hy-
drophobic, hexagonal packing of the particles was
observed in all cases at high compression w14x. How-
ever, the degree of particle attachment to the surface
varied with hydrophobicity with the most hydrophilic
particles being pushed irreversibly into the water
phase, and the most hydrophobic particles collapsing
to form a whitish multilayer. Particles of intermediate
hydrophobicity were most stable and further compres-
sion resulted in creasing of the monolayer without
particle expulsion. On the assumption that the col-
lapse pressure ⌸ c can be equated with the energy
required to remove particles, in unit area, out of the
monolayers into the more ‘wetting’ phase, the visual
observations were consistent with the influence of
contact angle on this energy. In a similar study, how-
ever w8x, there was little agreement between the con-
tact angles determined from the isotherms Žvia ⌸ c .
and those measured microscopically for a series of
increasingly hydrophobic glass spheres. The conclu-
sion is that the proposed method for the determina-
tion of ␪ from collapse pressures is suspect and this is
reinforced later.
In addition to the appearance of ordered arrays of
micron-sized charged particles, the spontaneous for-
mation of mesostructures or loosely bound internally
ordered aggregates of particles at air᎐water surfaces
has been reported. In a study utilising polystyrene
latex particles Ž0.95 and 2.84 ␮m in diameter., Ghezzi
et al. w16 x show a whole array of patterns formed in
䢇
monolayers subjected to various kinds of external
influence, including ionisation of the air phase, apply-
ing an electric current and exposing the layer to UV
light. Depending on the perturbation applied, the
lattice-like structure formed fractal aggregates, clus-
ters, striations and loops. It is argued that the charge
of the particles is neutralised for a number of reasons
and that such particles are forced into the secondary
minimum of the potential energy-particle separation
curve, of approximately kT in depth. This would help
explain the observation of the metastability of
monolayers when mesostructures can be present im-
mediately after spreading. An interesting study aimed
at investigating Langmuir monolayers of magnetic
nanoparticles was reported by Lefebure et al. w10x.
The particles were maghemite grains Ž ␥-Fe 2 O 3 . ren-
dered partially hydrophobic using lauric acid, and
were monodisperse of three diameters: 7.5, 11 and
15.5 nm. For the smallest particles, the isotherm
displays a zero pressure plateau followed by a rapid
increase in pressure when ArA o ( 1 Žwhere A o is the
area per particle in an ideal close-packed lattice .. For
the larger particles, the monolayers are less compress-
ible and the isotherms are shifted to higher areas.
Electron microscopy of deposited monolayers re-
vealed that dense, circular, compact domains form
from the smallest particles, whereas the largest parti-
cles are organised in long chains and form digitated
aggregates. In this system, the attractive interactions
between particles are van der Waals and anisotropic
magnetic dipolar ones, both of which increase with
particle size. It is at first sight surprising then to
observe that a film made of small particles appears
more compressible than one made of larger particles,
since the latter constitute a more attractive system
and so should be more compressible. The apparent
contradiction is resolved if one considers that the
isotherms reflect the behaviour of particle domains
and not of isolated particles. It turns out that the
ratio of the magnitude of the magnetic and van der
Waals interactions is ) 1 for particles larger than 12
nm in diameter, and when dipole᎐dipole interactions
are strong enough, chained and rather compressible
aggregates with aligned dipoles are predicted to form,
as opposed to more compact aggregates when isotropic
interactions are dominant. The effect of an external
magnetic field on the structure within the particle
monolayer would be an interesting extension.
The behaviour of non-spherical particles at a water
surface has been investigated by Brown et al. w17 x. 䢇
Using the technique of photolithography, particles
including gold diamonds and rectangles, Nichromer
gold crosses and disks and silicon dioxide diamonds
were prepared. By evaporating two different materi-
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
als, curved particles Ždisks. were synthesised such that
one material is on one face and the other material on
the opposite face. Such particles at an interface intro-
duce a new form of capillary force that arises from
distortions in the surface of water induced by the
chemical or physical anisotropy of the particles. For
such disks of 5 ␮m diameter, the particles aggregated
to give small clusters which ‘coalesced’ with each
other upon surface compression. Eighteen percent of
the particles had their Nichrome surface upward whilst
82% had their gold surface upward. This is not sur-
prising given that a gold surface is hydrophobic Ž ␪ ;
90⬚. and Nichrome is hydrophilic Ž ␪ ; 5⬚.. Long chains
containing over 20 particles were also observed in
which the particles were connected along their axis of
curvature. Such anisotropic forces in two dimensions
have not been studied previously on a colloidal length
scale and extend the field of control of particles at
interfaces. In contrast, Nakahama et al. w18x have
developed an alternative novel way of preparing parti-
cles possessing surface regions of differing wettabili-
ties by first forming a particle monolayer on water
and then spreading a reactive polymer material on the
surface during particle transfer to a substrate. The
part of the particle attached to the solid remains
uncoated whilst that exposed to the polymer during
transfer becomes coated. In a theoretical study, Binks
and Fletcher w19x considered the difference in the
adsorption of a spherical particle to an interface
between particles possessing a homogeneous surface
of uniform wettability and so-called Janus particles.
For Janus particles, calculations are presented which
show how the particle amphiphilicity, tuned by varia-
tion of either the relative surface areas or the differ-
ent wettabilities of the two surface regions on the
particles, influences the strength of particle attach-
ment. Increasing the amphiphilicity of the particles
produces a maximum of a 3-fold increase in surface
activity compared with homogeneously coated parti-
cles for average contact angles around 90⬚. In addi-
tion, it was shown that, unlike particles of homoge-
neous surface coating, Janus particles remain strongly
surface active for average contact angles approaching
either 0 or 180⬚.
The structure and evolution of monolayers of
monodisperse silica particles of 2 ␮m in diameter at
various liquid᎐vapour interfaces has been reported by
Hansen et al. w20,21x. In the first study, the particles
were alkoxylated using octanol or octadecanol and
their behaviour at the toluene᎐air surface was visu-
alised using video-enhanced microscopy and image
analysis. The choice of the non-aqueous liquid
minimises the influence of electrostatic phenomena,
and the alkyl coating permits the short range particle
interactions to be varied in two ways; firstly by varying
the range of the steric repulsion by means of the
25
thickness of the coating, and secondly by controlling
the magnitude of the van der Waals interaction
through changes in the contact angle. Immediately
after spreading, the particles formed a 2-D film with
substantial long range order with a tendency towards
hexagonal packing. With time the particles begin to
diffuse over larger distances and clusters start to
form. These grow in size until eventually a large
particle network is formed. The octyl system displayed
a diffusion limited cluster aggregation ŽDLCA.-like
structure of fractal dimension Df s 1.45, whereas the
octadecyl system realised a more dense structure with
Df s 1.55. This difference is consistent with the mag-
nitude of the attractive energy at contact of y30 kT
for the thinner coating and y15 kT for the thicker
one w20x. The temporal evolution of the cluster mass
´
distribution displayed a transition between a regime
of slower DLCA to a faster convection limited cluster
aggregation. In a subsequent study w21x, the silica
particles were reacted with either octyl- or octadecyl-
trichlorosilane and investigated at the surfaces of
either benzene, toluene, 1,4-dioxane, 2-meth-
oxyethanol, 1,2-dichloroethane or water. As a result
of the different contact angles for the different liq-
uids, it was found that the extent of the hexagonally
ordered particle domains Žor packing density. de-
creased exponentially with an increase in the attrac-
tive energy between the particles at contact, driven
mainly by an increase in the contact angle measured
into the liquid.
2.2. Liquid᎐liquid interface
Monolayers of charged polystyrene latex particles
Ž2.6 ␮m in diameter. have also been formed at
alkane᎐water interfaces using a modified trough de-
sign w6 ,7x, and provide new features. When an alkane
䢇
is layered onto a particle layer spread initially at the
air᎐water surface, the original disordered monolayer
rapidly becomes a highly ordered hexagonal array at
the oil᎐water interface. The monolayer retains a high
degree of order even in the presence of 0.1 M NaCl in
the aqueous phase, which is sufficient to cause con-
siderable particle aggregation at the air᎐water sur-
face. The finding points to the possibility that there
are strong long-range repulsive forces operating over
several microns at the oil᎐water interface which are
absent at the air᎐water surface. An example of such
an ordered monolayer is given in Fig. 3. The ⌸᎐A
isotherm at the oil᎐water interface is unchanged by
the addition of salt to the water phase, as is the
monolayer structure. It is concluded that the repul-
sion acts through the oil phase, since the presence of
electrolyte is expected to shield electrostatic repulsion
in the aqueous phase. The enhanced lateral repulsion
between particles at the oil᎐water interface is at-
26 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 3. Optical microscopy image Žfrom a laser tweezer instrument .
of an ordered monolayer of charged polystyrene latex particles of
diameter 2.6 ␮ m at a planar decanerundecane᎐water interface at
293 K. The centre-to-centre separation is 5.8 ␮ m. Obtained during
work described by Aveyard et al. w22 䢇 x.
tributed to the existence of residual surface charges at
the particle᎐oil surface. Such charge could easily arise
as a result of the presence of trapped or hydration
water between particles and oil. Using a model which
describes the electrostatic interaction between adsor-
bed particles and the effect of image forces Žacting
across the oil᎐water interface ., the calculated surface
charge required to account for the observed repulsion
is approximately 1% of the total possible charge
Žnumber of sulfate groups. on the particle surface
w6 x. A very recent experiment using a laser tweezer
䢇
instrument has succeeded in determining the repul-
sive force as a function of separation between two
identical latex particles at a non-polar oil᎐water in-
terface w22 x. At large separations Ž6᎐12 ␮m between
䢇
particle centres . the force is found to decay with
distance to the power minus 4, consistent with the
asymptotic form expected for a charge-dipole interac-
tion.
Even at large separation between particle surfaces
Žlow surface pressures. hexagonal packing is created
in structured monolayers w7x. Upon compression, the
monolayer structure becomes distorted to give a
rhombohedral array, probably because the compres-
sion is anisotropic. Further compression beyond ⌸ c
leads first to a gentle folding of the monolayer and, at
high compression, the monolayer becomes corrugated
of wavelength ; 100 ␮m and amplitude ; 30 ␮m.
Importantly, particle expulsion Žeither singly or as
aggregates. is not observed experimentally. The study
by Aveyard et al. also focused on the relationship
between the monolayer collapse pressure and the
interfacial tension in the absence of a particle
monolayer. The latter was varied in the range 50᎐4
mN my1 by addition of surfactants, to the aqueous
phase, over a range of concentration. Within error,
⌸ c is equal to the bare tension ␥ow in all cases. The
correspondence is explained by the fact that the sur-
face pressure exerted by the repulsive particles tends
to cause expansion of the monolayer-covered inter-
face, whereas the oil᎐water tension of the interface
between the particles tends to cause contraction. At
collapse the two opposing effects become equal. The
observed behaviour of micron-sized particles is similar
to that found by molecular dynamics simulations for
nanoparticulates w23,24x, suggesting that the repulsion
and buckling may be general features of particle
arrays w25x.
The surface behaviour of silver colloids located at
the interface between water and dichloromethane
represents a study bridging the gap between nano-
and micron-sized particle films w11 x. The particles are
䢇
prepared in situ at the oil᎐water interface and the
films consist of ‘soft’ flocs of silver nanoparticles ap-
proximately 1 ␮m in size. Both ⌸᎐A isotherms and
UV-visible absorption-reflection spectra were ac-
quired simultaneously. Upon compression, the
monolayer, which appears smooth and shiny at large
areas, suddenly loses its metallic luster and develops
creases parallel to the moving barrier. Further com-
pression beyond collapse results in the creases be-
coming more pronounced with the distance between
them remaining constant. As before, the buckling
occurs at surface pressures close to the bare interfa-
cial tension Ž23 mN my1 . and is reversible. Analysis
of the spectra yields the silver particle radius Ž1.06
nm. in the flocs in agreement with their true size.
Identical buckling of the interfacial film is also
observed in beakers by simply dispersing excess col-
loid at the oil᎐water interface. Patches of parallel
straight folding lines are visible with exactly the same
crease spacing as that in the trough. Using the model
of Milner et al. w26x for the buckling of two-dimen-
sional systems at zero interfacial tension, the bending
constant ␬ of the monolayer can be derived. The
value for the silver films is of the order of 5 = 10 4 kT,
which is much larger than that of monolayers of
soluble surfactant molecules Žtypically kT, w27x.. It is
worth pointing out, however, that values for monolay-
ers of insoluble surfactant molecules Žbehenic acid.
on water can be as high as 200 kT at high surface
pressure w28x. The difference probably arises from the
much more condensed nature of an insoluble
monolayer compared with that of a soluble surfactant.
Monolayers of nanoparticles of silica, coated to dif-
ferent extents with dichlorodimethylsilane, formed at
the octane᎐water interface also fold above ⌸ c w9x. It
is found that very hydrophilic or very hydrophobic
particles are lost from the monolayer upon compres-
sion, presumably to the aqueous and oil phases, re-
spectively. Particles of intermediate hydrophobicity
remain in the surface.
For particles or surfactant molecules at an inter-
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41 27

face, the Volmer equation of state which takes into

account the finite size of a particle but assumes all
lateral interactions are absent reads

⌸ Ž A y A o . s kT Ž2.

where A o is the co-area of a particle Žtaken as ␲ r 2 .

and k is Boltzmann’s constant. Rearranging the equa-
tion and plotting ⌸ vs. reduced area Ž A r A o ., Fig. 4a
depicts the effect of particle radius Žaffecting A o . on
the isotherms. Only for relatively large particles Ž10
nm in radius, lowest curve. should the isotherms
exhibit virtually zero pressure until hard-sphere be-
haviour sets in at A r A o equal to unity. This has
rarely been observed experimentally. Upon decreas-
ing the particle radius, the curves become more ex-
panded and shift to higher areas. The shape for a
particle of radius 0.4 nm is typical of that measured
for small surfactant molecules like myristic acid. It is
clear from this that in order to reproduce the kinds of
isotherms measured for large particles, an alternative
equation of state is required. When lateral interac-
tions within the monolayer become significant, the
two-dimensional equivalent of the van der Waals
equation can be taken

ž ⌸ q A␣ / Ž A y A . s kT
2 o
Ž3.

where ␣ is a two-dimensional van der Waals constant

which allows for lateral interactions. Positive values of
␣ signify attraction whereas negative values signify
repulsion within the monolayers. The curves in Fig. 4b
for a particle of 1 nm in radius move to higher areas
and become more expanded as the magnitude of the
repulsive term is increased; the shape is reminiscent
of that observed experimentally for repulsive particles
within monolayers w6 ,11 ,14x.
䢇 䢇
Fig. 4. Ža. Calculated surface pressure-reduced area per particle
isotherms at 298 K following the Volmer equation of state for
different particle radii. The radii Žin nm. from top to bottom are
0.25, 0.4, 1, 2 and 10. Žb. Calculated surface pressure-reduced area
per particle isotherms at 298 K following the equivalent van der
Waals equation of state for a particle of 1 nm in radius. The values
of the constant ␣ Žin J m2r10y36 . from top to bottom are ᎐1,
y0.5, y0.2, 0 and q0.05.

2.3. Determination of contact angles of particles with

interfaces area. from a hexagonal close-packed array in the
interface the contact angle is given by
As will be apparent working with spherical particles
at interfaces, a knowledge of the contact angle they ⌸ c 2'3
make with the interface and how different variables
alter it is essential in interpreting some of the pheno-
cos␪ s "
ž( ␲ ␥␣ ␤
y1
/ Ž4.

mena. In addition to direct horizontal microscopic

observation when the particles are large enough Ž) 2
␮m., three methods for determining ␪ have become
available but have their own drawbacks and deficien-
cies. The first suggested by Clint and Taylor w29x
makes use of Langmuir trough studies of particle
monolayers at liquid surfaces. By equating ⌸ c with
the work required to remove the particles Žin a unit
where the choice of sign depends on whether particles
are squeezed out of the interface into phase ␣ or
phase ␤. The method was exemplified using hy-
drophobic calcium carbonate particles 5 nm in diame-
ter spread on a pure water surface. Subsequently,
good agreement was shown between contact angles
determined this way and those measured using the
28 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
sessile drop technique for surfactant solutions on
planar substrates, in the case of hydrophobic silica
particles of 2.5 ␮m in diameter w30x. In this case,
particle expulsion was confirmed by the appearance of
either particles sinking through water Žlow ␪. or
building up as a thick multilayer on the surface Žhigh
␪.. The method requires that particles are monodis-
perse and spherical and must be small enough not to
cause curving of the interface close to the contact line
with them. However, as seen above for polystyrene
particles w7x, it appears that the assumption of particle
expulsion from the surface at collapse is inappropri-
ate. The trough method, therefore, should not be
used indiscriminately for the determination of contact
angles.
An alternative approach developed by Butt and
colleagues w31,32 x involves attaching a single particle
䢇
to the cantilever of an atomic force microscope. The
cantilever is then moved gradually in an aqueous
medium towards an air bubble Žuntil contact., where
deflection of the cantilever and position of the bubble
are measured. From the force vs. position data the
contact angle can be calculated. The initial study
involved measurement of the force between a particle
Ž4.4 ␮m diameter silica coated to different extents
with gold᎐alkylthiol monolayers. and an air bubble in
water, from which the receding air᎐water contact
angle Ž30᎐90⬚. was calculated. A systematic difference
between angles measured using particles and on pla-
nar surfaces was observed and discussed in terms of
the line tension acting at the three phase contact line.
If the influence of line tension is responsible for the
difference, its magnitude increased with the hy-
drophobicity of the particle. For ␪ ; 90⬚ the line
tension ranges from q2 to 8 = 10y8 N. A second
study included determining both the advancing
air᎐water contact angle by approaching a particle
towards a water drop in air, and the oil᎐water contact
angle by bringing a particle near a water drop in
hexadecane w32 x. Micron-sized polystyrene particles
䢇
of three diameters were employed and hysteresis in
contact angle was noted at the air᎐water surface. The
angles decreased with increasing particle diameter
from which a line tension in this system of y0.3=
10y6 N was derived. This negative value for angles
- 90⬚ means that the true angle is less than that in
the presence of line tension, i.e. the particle behaves
more hydrophobically as a result. For an 8.76-␮m
diameter latex particle, the air᎐water angle was 75⬚
compared with that at the oil᎐water interface of 145⬚.
The method is obviously unsuitable for sub-micron
particles whose size is below the limit of resolution of
an optical microscope. A completely different method
suitable for determining the contact angles of
nanoparticles with interfaces uses heat flow immer-
sion microcalorimetry w33x. The enthalpy of immer-
sion is defined as the energy released or absorbed
when a clean solid is immersed into a liquid and
depends on the particle wettability and the liquid
surface tension. Recent developments in the design of
microcalorimeters have made it possible to measure
very small changes in thermal energy for low energy
surfaces with reasonable accuracy. For fumed silica
powders of different hydrophobicity Žprimary particle
diameter s 12 nm., the enthalpies of mixing in sepa-
rate particle᎐water᎐air systems and particle᎐toluene᎐
air systems yielded the contact angles at the air᎐water
and air᎐oil interfaces, respectively. Using thermody-
namic arguments, the contact angle at the oil᎐water
interface was calculated using both aforementioned
angles and measured values of the partition coeffi-
cient of particles between oil and water. These angles
were in the range 0᎐96⬚ for a series of six silica
samples.
3. Partitioning of particles between phases
The rules are reasonably well established now for
describing the partitioning of both monomeric and
aggregated surfactant molecules between oil and
water phases. Thus, most ionic surfactants partition
exclusively in favour of water as monomers whereas
nonionic surfactant molecules containing ethylenoxy
groups partition into both phases as monomer, with
the distribution normally heavily in favour of the oil
phase. Micelles or microemulsion droplets occur in
only one of the phases at any overall composition but
changes in temperature, electrolyte concentration or
concentration of cosurfactant can induce complete
transfer of aggregates from one phase to the other
accompanied by a change in type, e.g. from oil droplets
in water to water droplets in oil. The behaviour of
colloidal particles and macromolecules in two-phase
immiscible liquid mixtures is a topic of long term
interest and of considerable practical importance,
particularly for separating biological cells w34x. Due to
the small size of the particles present in the liquid
mixture, Brownian motion is efficient in re-distrib-
uting the particles to an equilibrium configuration
with the lowest total free energy. Consequently, there
can be a partition of the majority of particles into a
preferred phase where the particle᎐liquid interaction
is most favourable, or alternatively, onto the interface
between the two phases where, due to the reduction
in the free liquid᎐liquid area, the total surface energy
is effectively reduced. Simple thermodynamic models
based on arguments of this kind have been developed
and extended to include effects of gravity, particle
shape and particular features of the particle᎐liquid
interaction w35x.
The free energy change on transferring a small
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
spherical particle from water to oil is simply given by
the product of the particle surface area and the
interfacial energy difference for the particle in both
phases, i.e. 4 ␲ r 2 Ž ␥so ᎐␥sw . where s, o and w denote
solid, oil and water, respectively. The term in brackets
is related to the contact angle ␪ and the tension of
the oil᎐water interface ␥ow through Young’s equation
␥so y ␥sw s ␥ow cos␪ Ž5.
If the entropies of mixing of particles with water
and oil are neglected, the free energy of transfer is
then 4 ␲ r 2 ␥ow cos␪. This is equivalent to ᎐kT ln K,
where K is the partition coefficient defined as Žpar-
ticle concentration in oil.rŽparticle concentration in
water.. From this, the fraction of the total number of
particles present in the water phase, f w , can be writ-
ten as Ž1r1 q K .. Fig. 5 shows the calculated variation
of f w with contact angle for particles of radius 10 nm
partitioned between water and oil for two values of
␥ow . For a tension of 36 mN my1 Žtoluene᎐water., the
distribution changes in a stepwise manner at a contact
angle of 90⬚, i.e. hydrophilic particles are partitioned
more or less exclusively to water and hydrophobic
particles are partitioned exclusively to oil. For low
tension interfaces Ž0.05 mN my1 . such as those in the
presence of certain surfactants, it can be seen that the
distribution of particles changes in a more gradual
manner with ␪. For larger particles, partitioning typi-
cally takes place between one of the phases and the
interface and the treatment above becomes more
complicated.
3.1. Partially miscible liquids
The partitioning of polystyrene latex particles
between critical mixtures of water and 2,6-lutidine
Ždimethylpyridine. has been investigated at tempera-
Fig. 5. Fraction of particles present in water in two-phase systems
containing oil as a function of the contact angle the particles make
with the interface Žmeasured through water.. The particle radius is
10 nm and the curves are for ␥ow s 36 Žfull. and 0.05 Ždashed. mN
my1 at 298 K.
29
tures where the liquid mixture separates into two
immiscible phases, and is closely linked to wetting
phenomena w36 x. This system has the advantage of
䢇䢇
exhibiting very low interfacial tensions just above the
critical temperature, Tc Ž33.8 ⬚C.. Lutidine and water
mixtures display a lower consolute temperature curve
above which two phases form. Using different latex
particles originally dispersed in water and varying
separately in diameter Ž0.4᎐1.5 ␮m. and in surface
charge density, ␴ Ž0.4᎐5.8 ␮C cmy2 ., three types of
behaviour are observed for critical mixtures. For tem-
peratures approximately 0.1 K above Tc partitioning
of the majority of particles into one of the two bulk
phases occurred, as detected by light scattering, in
which the interfaces were ‘clean’ and devoid of parti-
cles. The preferred or wetting phase was sensitive to
the surface charge density of the particles and inde-
pendent of their size or concentration. Particles of
high ␴ preferred the water-rich phase, whereas those
of low ␴ preferred the phase rich in lutidine. At
sufficiently high overall particle concentrations, the
particle concentration in both phases was determined
reasonably accurately yielding the partition coefficient
K. For particles of 0.55 ␮m diameter, K is 2300 in
favour of the preferred aqueous phase. It is expected
that K approaches unity at the critical temperature
where the two phases are identical.
In addition to the partitioning of particles between
bulk phases, a striking temperature dependence of
the concentration of particles at the liquid᎐liquid
interface was seen which is reversible. Beginning
abruptly at a temperature called the particle wetting
temperature, Tw , the onset of preferential adsorption
of particles at the interface occurs. The interface
becomes increasingly cloudy and of non-uniform re-
flectivity. The adsorption of particles at the interface
increases between 0.1 and 0.5 K above Tc , until the
´
onset of the third temperature regime with the ap-
pearance of highly concentrated islands of particles at
the interface. As the temperature increases further
from Tc , these islands grow in size until all of the
available interfacial area is occupied. By extending
the model describing the behaviour of particles in an
immiscible liquid mixture to include the temperature
dependence Žvia K ., the crossover from partition into
a bulk phase near Tc to preferential adsorption at the
interface further from Tc is predicted, in excellent
qualitative agreement with experiment. Diffraction of
laser light from the concentrated particle layer at the
interface indicated crystalline order which extended
over 60 particle diameters, probably arising from di-
rect Coulomb interactions between neighbouring par-
ticles at spacings less than the Debye length. These
findings are no doubt linked to the effect of tempera-
ture on the interfacial tension influencing the energy
of attachment of particles at the interface. The ten-
30 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
sion is very low close to Tc Ž0.001 mN my1 . where
detachment is easy but increases to 0.017 mN my1 at
Tc q 0.5 K allowing stronger attachment. Very inter-
esting kinetic effects were also mentioned including
the formation of metastable emulsion films. They
appeared at temperatures where the population of
the interface was high and phase separation was slow.
During separation, particles find the many interfaces
present and the rate of drop coalescence is reduced as
a result. Emulsion films of lutidine᎐water᎐lutidine, in
which the water layers contained high concentrations
of particles, were embedded in the upper lutidine-rich
phase and remained stable for several days before
finally rupturing. Interestingly, the opposite type of
film was rarely observed presumably because of its
inherent instability.
3.2. Immiscible liquids
In addition to determining the partitioning of parti-
cles between phases it is also important to be able to
effect transfer of particles from one phase to another.
Developing means for directing nanoparticles into
specific environments is an essential pre-requisite for
their arrangement into micro-assemblies for produc-
ing novel materials including electronic and electro-
optical devices. Two papers describe methods for
transferring either gold or silver colloidal particles
from water to oil phases, retaining their integrity and
state of dispersion. In one w37x, an orw emulsion Ž1:1.
is prepared from an aqueous dispersion of gold parti-
cles in water Ždiameter s 14 nm. and an alkane phase
containing a low concentration of sodium oleate sur-
factant. Upon addition of aqueous electrolyte with
stirring, breaking of the emulsion occurs leaving an
upper layer coloured red being the gold dispersion in
oil and a lower colourless aqueous layer. In the
absence of salt, separation also occurred but without
particle transfer. Divalent electrolytes like MgCl 2 were
more effective than monovalent ones ŽNaCl. in pro-
moting transfer. The authors suggested that salt addi-
tion causes the formation of Žsay. magnesium oleate
which adsorbs onto the surfaces of the gold particles
via its C⫽C bond. This in turn renders the particles
more hydrophobic so that they prefer oil rather than
water. An alternative explanation is that the initially
hydrophilic particles help stabilise the orw emulsion
but a change in their wettability due to oleate adsorp-
tion causes the preferred emulsion to be wro with
instability to coalescence ensuing during inversion. In
the second study w38x, monodisperse nanometre-sized
silver particles were prepared in water in the presence
of sodium oleate. Transfer of the colloid to an organic
phase is induced by addition of a low concentration of
orthophosphoric acid or sodium perchlorate with an
efficiency of ; 60%. The non-aqueous colloids are
stable and, after solvent evaporation, the particles can
be re-dispersed in a variety of other solvents. On the
basis of IR spectroscopy measurements, it is con-
cluded that the oleate chain adsorbs onto the parti-
cles via the C⫽C bond leaving the dissociated car-
boxylate group interacting with water Žhydrosol.,
whereas following rearrangement the carboxylate
group serves to anchor the surfactant to the surface in
the organosol such that the hydrophobic chain is
directed towards the oil. The importance of a double
bond within the molecule is emphasised since use of
other surfactants like sodium stearate or sodium do-
decyl sulfate does not result in particle transfer to the
oil phase. It remains, however, to elucidate the role of
the transfer agent ŽH 3 PO4 or NaH 2 PO4 . in this
process.
Very few studies exist in which the partitioning of
particles between completely immiscible liquids has
been determined in the absence of surfactant. Yan
and Masliyah w39 x measured in detail the partition-
䢇
ing of a range of suitably treated kaolinite clay parti-
cles Ždiameter 0.2 ␮m. between drop surfaces in an
orw emulsion stabilised by them and the continuous
aqueous phase. They found that the ratio of the
particle concentration at oil drop interfaces to that in
bulk water depended strongly on both the clay con-
centration in water and the contact angle of particles
at the oil᎐water interface, and related this to the
influence of ␪ on the strength of attachment of parti-
cles. An alternative way to effect migration of parti-
cles from one phase to another is to change in situ the
hydrophobicity and hence wettability of the particles.
This can be achieved, say, by an increase in aqueous
phase pH in systems containing particles possessing
ionisable surface groups. It was known for some time
that a chargeable surface is maximally hydrophobic at
conditions near its point of zero charge w40x. Two
quite different studies have demonstrated that this
line of thought appears reasonable. The first by Henry
et al. w41x is linked to what happens during the re-
moval of particles from hydrocarbon suspensions when
water is added. Removing mineral matter from coal-
derived liquids can often be a limiting process, and
addition of water to a solidrliquid suspension pro-
moting separation of the dispersed particulate phase
is more economic than conventional processes such as
filtration or centrifugation. Typically, a surfactant is
added to the particleroil slurry and water is then
dispersed into the oil phase. Electrically-induced
coalescence, used to break the resulting wro emul-
sion, separates the aqueous phase containing the min-
eral matter from the mineral depleted oil phase. The
process is analogous in many ways to that of froth
flotation, except that particles collect at oil᎐water
interfaces as opposed to air bubble᎐water surfaces.
Many of the minerals present in coal-derived liquids
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
are originally hydrophilic Žfrom clays, rocks, soils., but
these particles obtain a hydrophobic coating during
the coal liquefaction process. Experiments were con-
ducted in which the coal-derived liquid containing
such particles Ž1᎐10 ␮m. was equilibrated with water
of different pH values in a simple system in the
absence of surfactant. Using gravimetric analysis, the
percentage loss of particles from oil to water was
determined, alongwith measurement of the contact
angle of a water drop under oil on a compressed disk
of the coated mineral particles. A very nice correla-
tion between the transfer of particles from oil to
water and a decrease in ␪ ow from 120 to 30⬚ was seen
as pH was raised from 3 to 10.3. Thus, particles
initially hydrophobic at low pH are rendered increas-
ingly hydrophilic on adding base and subsequently
partition in favour of the aqueous phase. The likely
cause of this effect is the ionisation with increasing
pH of the zwitterionic asphaltene molecules adsorbed
onto the mineral particles.
In a similar vain, Binks and Lumsdon w42 x showed
䢇䢇
how changes in pH affect the partitioning of nanome-
tre-sized, partially hydrophobic silica particles between
toluene and water. At low pH Ž- 9., virtually all the
particles distributed in favour of oil, whereas at suf-
ficiently high pH Ž) 12.5. they distributed in favour of
water. At intermediate pH, particles were present in
both oil and water in addition to a third phase formed
at the interface. The particles, possessing residual
silanol ŽSiOH. groups on their surface, become in-
creasingly charged through dissociation ŽSiOy. in-
creasing their wettability by water. The findings al-
lowed the first verification of Bancroft’s rule in solid-
stabilised emulsions prepared from equilibrium multi-
phase systems. As predicted, emulsions were wro at
low pH and phase inverted to orw at high pH. As in
most surfactant-stabilised emulsions, the continuous
phase of the emulsion is the one containing the
highest concentration of particles.
4. Emulsions stabilised by particles
The fact that finely divided solid particles can act as
the stabiliser in emulsions has been known since the
beginning of the last century. The credit is usually
given to Pickering w43x, hence the term ‘Pickering
emulsions’, who noted that particles which were wet-
ted more by water than by oil acted as emulsifiers for
orw emulsions by residing at the interface. However,
in a paper 4 years earlier and cited by Pickering,
Ramsden w44x described the formation of a membrane
of solid particles enveloping both air bubbles in water
and oil drops in water, giving rise sometimes to ‘per-
sistently deformed sharply angular and grotesque
shapes of the emulsified globules’! It was not until the
31
work of Finkle et al. w45x that the relationship between
the type of solid and emulsion type Žorw or wro. was
recognised. They stated that in an emulsion contain-
ing solid particles, one of the liquids will probably wet
the solid more than the other liquid, with the more
poorly wetting liquid becoming the dispersed phase.
The importance of the wettability of the particles at
the oil᎐water interface, quantified by the contact an-
gle ␪ that the particle makes with it, was therefore
noted. Thus, water-wet particles, e.g. silica, should
stabilise orw emulsions and oil-wet particles, e.g.
carbon black, should stabilise wro emulsions. These
ideas were given strong support by the experiments of
Schulman and Leja w46x using barium sulfate
crystalsrpowders and surfactant, measuring the rele-
vant contact angles and determining the emulsion
type and stability. For conditions such that ␪ Žmea-
sured through the aqueous phase. was slightly - 90⬚,
particles stabilised orw emulsions, but for ␪ ) 90⬚
particles were still held at the interface but now
stabilised wro emulsions. However, if the particles
were either too hydrophilic Žlow ␪. or too hy-
drophobic Žhigh ␪. they tended to remain dispersed in
either the aqueous or oil phase respectively, giving
rise to very unstable emulsions.
4.1. Simple emulsions
It is surprising that, since the early studies men-
tioned above, little work in this area appeared in the
open literature until quite recently. Clues and under-
standing can be gained from the food science area
however, since it has been known for some time that
in many food emulsions Žand foams. stabilised primar-
ily by phospholipids or proteins, particles are neces-
sary for the required stabilisation, e.g. ice crystals in
ice cream and fat particles in whipping cream. The
precise role of the particles is gradually being unrav-
elled and a recent review by Rousseau w47 x discusses
䢇
the effect of fat crystal wettability and microstructure
on emulsion stability, interfacial rheology and particle
location in food systems. Further, the importance of
fat crystal concentration on the stability of water-in-
triglyceride emulsions stabilised by monoglycerides
was emphasised by Johansson et al. w48x. At low
concentrations, flocculation and eventual coalescence
of the water drops were induced, whilst at higher
concentrations both were inhibited. The results were
explained by a crossover in the mode of action of the
crystals, in which they behaved as bridging particles
between drops when dilute Ždestabilisation . but
formed a protective layer around drops when concen-
trated Žstabilisation .. A wide variety of solid particles
has been used as stabilisers of either orw or wro
emulsions including iron oxide, hydroxides, metal sul-
fates, silica, clays and carbon. The effectiveness of the
32 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
solid in stabilising emulsions depends, inter alia, on
particle size, particle shape, particle concentration,
particle wettability and on the interactions between
particles. Particle wettability may be altered by ad-
sorption of suitable surfactants, in some cases leading
to emulsion phase inversion. Several studies conclude
that stable emulsions can only be formed if the parti-
cles are weakly flocculated to some extent, achieved
by addition of salt for orw w49x or by surfactant for
wro emulsions w50x. Much less stable emulsions re-
sulted when the particles were completely flocculated.
Depending on the exact system, there are at least
two mechanisms by which colloidal particles stabilise
emulsions. In the first, the particles are required to
adsorb at the oil᎐water interface and remain there
forming a dense film Žmonolayer or multilayer. around
the dispersed drops impeding coalescence. In the sec-
ond, additional stabilisation arises when the
particle᎐particle interactions are such that a three-di-
mensional network of particles develops in the contin-
uous phase surrounding the drops. This has been
invoked particularly in clay-containing systems in
which the oil drops become captured and more or less
immobilised in the array of clay platelets in water
w51 ,52x. The enhanced viscosity of the continuous
䢇
phase reduces the rate and extent of creaming.
Amongst the teams involved in this field, Tambe and
Sharma w53x, Masliyah and colleagues w39 x, Zhai and
䢇
Efrima w54x, Midmore w55 ,56x and Lagaly and col-
䢇
leagues w51 ,52x have made particularly important
䢇
contributions recently to the understanding of parti-
cle-stabilised emulsions. Even millimetre-sized drops,
coated by particles, are shown to be extremely stable
to coalescence w54x ᎏa situation which has never been
realised in the case of surfactant-stabilised emulsions.
Such large drops are seen to roll over each other
without deformation in just the same way that true
solid spheres behave. The potential for exploiting
such stability at these length scales is high.
In a recent series of papers, Binks and colleagues
have systematically investigated the formation, stabil-
ity and structure of emulsions stabilised entirely by
solid particles in an attempt to elucidate unambigu-
ously the role of the particles in such systems
w42 ,49,57᎐64 x. Such surfactant-free emulsions
䢇䢇 䢇䢇
represent a novel alternative to conventional ones
and may prove to be more advantageous too. It is
significant that at least two patents, assigned to
Beiersdorf, have been published recently describing
the properties of both stable orw w65x and wro w66x
emulsions using particles alone for cosmetic and der-
matological applications. In the work of Binks and
colleagues w42 x and w57᎐64 x, the particle types
䢇䢇 䢇䢇
were silica, Laponite clay and polystyrene latex, and a
range of oils were used including alkanes, silicones,
alcohols and esters. Simple emulsions of both types
are possible but their stability is crucially dependent
on the wettability of the particles in situ at the
oil᎐water interface. A major objective of part of the
work was to investigate and understand the relation-
ship, if any, between the properties of the particle
dispersions before emulsification and the ensuing
emulsion characteristics. A new method for preparing
monodisperse solid-stabilised emulsions has also been
described involving the sequential replacement of sur-
factant by particles at drop interfaces, using dialysis
w63x. Such emulsions are more amenable to study and
treat using theoretical models than the more common
polydisperse ones.
For emulsions stabilised by silica particles, the ef-
fect of particle hydrophobicity has been explored since
a series of particles of the same size distribution but
increasing coating extent was synthesised specially.
Although the primary particle diameter varies between
10 and 30 nm, silica particles easily aggregate or fuse
completely forming larger structures of non-spherical
shape. The hydrophobicity of the particles is de-
scribed in terms of the percentage of silanol ŽSiOH.
groups on their surface. Thus, raw hydrophilic silica
possesses 100% SiOH and the most hydrophobic has
14% SiOH. Particles are rendered hydrophobic by
reaction of native silica with dichlorodimethylsilane in
the vapour phase. As a result, the coating is assumed
to be homogeneous over the particle surface. More
hydrophilic particles Ž) 65% SiOH. can be dispersed
in water, whereas more hydrophobic ones are easily
dispersed in oil. Preferred emulsions, i.e. those formed
at an oilrwater volume ratio of unity, are orw for the
hydrophilic silicas and wro for the hydrophobic ones
w57 x, in line with previous findings w67x. However, in
䢇
one and the same system, emulsions of both types can
be prepared depending on the oil:water ratio. In the
example given in Fig. 6a, emulsions are of low con-
ductivity and disperse in oil at low ␾ w Žwro. but
become highly conducting dispersing in water at high
␾ w Žorw.. Importantly, for particles of intermediate
hydrophobicity, both emulsion types are stable to
coalescence for periods in excess of 3 years, despite
being of very different average drop diameter, namely
1 and 100 ␮m. The ability to make both orw and wro
emulsions with the same kind of particles represents a
significant advantage compared with single surfactant
systems which do not invert at extremes of volume
fraction but which form gel emulsions instead. The
catastrophic inversion brought about by changing the
oil:water ratio occurs without hysteresis Žincreasing or
decreasing ␾ w . in the particle case, in contrast to
surfactant systems where the hysteresis can be as
much as 0.3 in volume fraction. In addition, emulsions
are most stable at conditions near inversion w57 x, 䢇
unlike those of surfactants which are notoriously very
unstable. The different behaviour is linked to the very
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 6. Ža. Conductivity of water᎐toluene emulsions stabilised by
hydrophobic silica particles Ž50% SiOH. as a function of the
volume fraction of water at 298 K. Oil contained 2 wt.% particles;
water added sequentially to oil Žopen points. or oil added sequen-
tially to water Žfilled points.. Results from drop tests included
ŽRe-drawn from earlier work w57 䢇 x.. Žb. Conductivity of
water᎐toluene emulsions Ž ␾ w s 0.5. containing 2.5 wt.% total silica
particles as a function of the weight fraction of hydrophobic parti-
cles Ž50% SiOH, initially in oil. at 298 K. Hydrophilic particles
Ž100% SiOH. are initially in water. Results from drop tests in-
cluded Žredrawn from earlier work w58x..
high energies of attachment of particles to interfaces.
It is found that the value of ␾ w at inversion increases
progressively with particle hydrophobicity, varying
from 0.35 to over 0.8. However, it remains to under-
stand why both types of emulsion occur in systems
containing the same three components.
Another type of emulsion phase transformation,
known as transitional inversion, is brought about in
surfactant systems by changing the system HLB in
some way at fixed oil:water ratio, e.g. by increasing
the concentration of hydrophobic co-surfactant in
monolayers of hydrophilic surfactant. Using mixtures
of particles of different hydrophobicity, one of which
prefers orw emulsions and the other wro emulsions,
33
offers the possibility of effecting this inversion by
changing the average wettability of the particles at the
drop interfaces. Three ways of achieving this are by
the addition of hydrophilic silica to wro emulsions
stabilised by hydrophobic silica, by addition of hy-
drophobic silica to orw emulsions of hydrophilic silica
and by varying the weight fraction of one of the
particle types at constant particle concentration w58x.
An example demonstrating this principle is seen in
Fig. 6b in which emulsions invert from orw to wro
upon increasing the weight fraction of hydrophobic
silica. As the fraction of hydrophobic silica particles
increases in the mixed particle monolayers, the aver-
age wettability of the particles changes from mainly
water wettable to mainly oil wettable accompanying
inversion.
In a detailed study into the effect of particle hy-
drophobicity on the type and stability of toluene-con-
taining emulsions w59 x, it was shown that predic-
䢇䢇
tions based on considerations of the energy of attach-
ment of a single particle to the oil᎐water interface
wEq. Ž1.x relate directly to the stability of emulsions.
Emulsions stabilised by very hydrophilic or very hy-
drophobic particles contain large drops ŽG 100 ␮m.
and are unstable to coalescence, presumably as a
result of their facile displacement from interfaces
during drop collisions. Those with particles of inter-
mediate hydrophobicity, in which particles are held
strongly at interfaces, contain sub-micron sized drops
and are stable to coalescence indefinitely. Unlike
coalescence that either occurs or does not within the
particle series, the stability to gravity-induced separa-
tion Žcreaming for orw and sedimentation for wro.
passes through a sharp maximum upon increasing the
particle hydrophobicity. In line with this, the average
emulsion drop size passes through a minimum. This
correspondence is shown to be universal and indepen-
dent of both ␾ w and the type of emulsion formed.
The effect of oil type on emulsions stabilised by
partially hydrophobic silica particles Ž67% SiOH. was
combined with measurements of the contact angles of
water drops under oil phases on hydrophobised glass
plates w42 x. Since the energy of attachment of parti-
䢇䢇
cles anchored at interfaces depends on both ␪ and the
oil᎐water tension, ␥ow , the influence of both parame-
ters on emulsion behaviour could be assessed. The
oils ranged from non-polar hydrocarbons of relatively
high ␥ow to polar alcohols and esters of relatively low
␥ow . It turns out that particles are more hydrophobic
Žhigher ␪. at polar oil᎐water interfaces preferring
wro emulsions, and are more hydrophilic Žlower ␪. at
non-polar oil᎐water interfaces with preferred emul-
sion type being orw. The combination of a low ten-
sion Ž9.5 mN my1 . and high contact angle Ž160⬚. in
the case of undecanol as oil leads to an unusual
phenomenon in which wro emulsions destabilise
34 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 7. Calculated Žordinate. and experimental Žabscissa . contact
angles of water drops under different oils on a partially hy-
drophobised glass substrate at 298 K. The diagonal line represents
agreement between theory and experiment Žredrawn from earlier
work w62 䢇 x..
completely into the parent liquid phases with time.
The breaking of the emulsion is such that it contracts
via coalescence in a way that maintains the shape of
the vessel. A recent theoretical treatment has been
developed to shed light on these findings w62 x. It 䢇
involves using surface energy considerations to inter-
pret the interactions between the solid and the two
liquid phases, and hence to predict ␪ow in the cases
mentioned above. Calculated oil᎐water contact angles
for a solid of given hydrophobicity with a range of oils
of different polarity show good agreement with exper-
imental data, as seen in Fig. 7. The approach is also
used to show that to effect inversion Ž ␪ow to pass
through 90⬚., silica surfaces of increasing hydrophilic-
ity require oils of increasing polarity. A strength of
the simple approach is that the type of emulsion,
stabilised only by solid particles of known surface
energy components, as judged by ␪ ow , can be pre-
dicted knowing only the surface tension of the oil in
air and its interfacial tension with water.
Being of intermediate hydrophobicity, particles
containing 67% SiOH groups can be dispersed sepa-
rately in either oil or water phases using ultrasound.
It is then of interest to investigate the effect of initial
location of particles on emulsion type w42 x. Since 䢇䢇
particles are significantly larger than surfactant
molecules, the question arises whether they equili-
brate between the bulk phases and interface to the
same extent in both situations. It was found that for
particles originally dispersed in toluene, the preferred
emulsions at ␾ w s 0.5 were wro, compared with orw
when dispersed in water. The continuous phase of the
emulsion thus becomes that in which particles are
first dispersed. It was also established that preferred
emulsions were composed of smaller drops and were
more stable than non-preferred emulsions Žorw if
starting in oil and wro if starting in water.. An
important conclusion arising from this is that maxi-
mum stability can be obtained for either emulsion
type simply by changing the initial particle location.
In contrast, evidence was given that emulsion type is
independent of initial location for surfactant-stabi-
lised systems due to the faster distribution of surfac-
tant between phases occurring during formation. An-
other expected difference between particles and sur-
factant molecules as emulsifiers lies in what happens
during the course of Ostwald ripening w60x. The latter
is the result of the solubility differences of Žsay. oil
contained in drops of different sizes. As a conse-
quence of its increased solubility, oil contained within
smaller drops tends to diffuse through the aqueous
phase and re-condense onto larger drops. The accom-
panying decrease in interfacial area provides the driv-
ing force for the growth of the drops. Unlike surfac-
tant molecules which are reversibly adsorbed at inter-
faces, certain types of particles are effectively irre-
versibly adsorbed. Thus, in the initial stages, it is
expected that diffusion of oil from small drops results
in compression of the adsorbed particle layer until it
either buckles or resists further area reduction, so
halting ripening. As larger drops swell, excess parti-
cles present in either the dispersed or continuous
phase may adsorb to maintain overall stability to
coalescence. For toluene-in-water emulsions stabilised
by disc-shaped clay particles and stable to coales-
cence, the initial increase in average drop diameter
with time was attributed to Ostwald ripening w60x.
However, in agreement with predictions, the process
ceased after 3 days as the emulsion reached a quasi-
equilibrium state. Another difference between the
two systems is that surfactant micelles, if present in
the continuous phase, can act as carriers of oil
between drops leading to an enhancement in the
ripening rate. No such aggregates can form in the
case of particles however.
Since sub-micron sized particles adsorbed at emul-
sion drop interfaces cannot be visualised using optical
microscopy, the technique of freeze fracture scanning
electron microscopy ŽSEM. has been applied to these
systems w64x. For wro emulsions stabilised by
polystyrene latex particles, a monolayer of close-
packed particles was observed. This contrasts with
their more dilute arrangement at planar oil᎐water
interfaces Žearlier., implying that particle᎐particle re-
pulsions can be overcome with the input of energy
during emulsification. In the case of silica, the ar-
rangement of particles at drop interfaces was either in
the form of flocs of particles separated by particle-free
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 8. Freeze fracture SEM image from a triglyceride-in-water
emulsion stabilised by silica particles Ž76% SiOH.. The close-packed
arrangement of particles on the external surface of a drop is viewed
from the continuous phase. Scale bar represents 100 nm Žredrawn
from earlier work w64x..
regions or close-packed particle layers over the entire
surface, depending on the oil. An example given in
Fig. 8 shows the external surface of a triglyceride oil
drop viewed from the continuous aqueous phase. The
absence of any holes in the particle layer is most
likely due to the polydispersity in size and to the
different shapes of the particles leading to very effi-
cient packing. It should be noted however that the
average ‘size’ of the individual particles Ž60᎐80 nm. is
larger than the primary particle diameter Ž20 nm.
suggesting fusion has taken place between particles in
close proximity. This is a common occurrence with
fumed silica particles either in the vapour phase or in
liquid dispersions. These preliminary micrographs of
particles at curved emulsion drop interfaces raise
many questions which remain to be answered.
4.2. Multiple emulsions
In addition to acting as emulsifiers in simple emul-
sions, the possibility exists that particles may be ef-
fective in the stabilisation of multiple or double emul-
sions. In the surfactant case, two different surfactants
are normally required in order to prepare such emul-
sions, one of which adsorbs primarily at the interface
of inner drops whilst the other adsorbs mainly at the
outer globule interface. Since the curvatures of the
two types of monolayer are opposite, a mixture of a
hydrophilic and a hydrophobic surfactant is used to
satisfy this requirement. Tween Žhigh HLB number.
and Span Žlow HLB number. surfactants are popular
choices in this respect. Thus, for oil-in-water-in-oil
Žorwro. emulsions, it is common practice to prepare
an orw emulsion with the hydrophilic surfactant which
is then re-emulsified gently into an oil phase contain-
ing dissolved hydrophobic surfactant. One of the main
35
problems associated with surfactant-stabilised multi-
ple emulsions is their inherent instability as a result
of coalescence leading ultimately to the formation of
a simple emulsion. Various attempts have been made
at improving the shelf-life stability of multiple emul-
sions by incorporating small solid particles into the
surfactant formulation. The idea, as before, is that
particles act as a mechanical barrier to coalescence if
adsorbed at interfaces. Oza and Frank w68 x were the
䢇
first to develop this by using colloidal microcrystalline
cellulose ŽMCC. as the water-soluble emulsifier in
wrorw emulsions containing oil-soluble Span surfac-
tants. Emulsions, stable for up to 1 month, were
shown to have a network of MCC adsorbed at the
outer oil᎐water interface. Garti et al. w69x added sub-
micron crystalline fat particles as a co-stabiliser of the
inner interface of water-in-soybean oil-in-water emul-
sions, good stability to coalescence and release of
electrolyte ensuing. A similar enhancement in stabil-
ity was reported by Sekine et al. w70x but for orwro
emulsions in which the external wro interface was
partially coated with a layer of hydrophobically modi-
fied clay particles causing it to become rigid. The
organoclay particles also caused gelling of the outer
oil phase preventing sedimentation of the water
globules. More relevant to what follows is the paper
by Midmore and Herrington w71x on both wrorw and
orwro emulsions stabilised by a mixture of polymer,
surfactant and colloidal silica particles Žhydrophilic
and hydrophobic.. Both drops and globules were stable
to coalescence over a 6-month period.
Unlike the previous studies outlined above in which
both surfactants and particles have been employed in
combination, work described by Binks et al. w72 x 䢇䢇
was aimed at preparing and stabilising multiple emul-
sions using particles alone as emulsifier. Since it has
been shown that many similarities exist between sur-
factant molecules and particles with respect to emul-
sion stabilisation, it is predicted that multiple emul-
sions should form in oil q water mixtures containing
two types of particles differing only in their hy-
drophobicity. This turns out in practice to be the case
and extremely stable multiple emulsions of both types
can be prepared using a mixture of silica particles
differing by only 25% in SiOH content. The micro-
graph in Fig. 9 is of an orwro emulsion, in which
inner oil drops are stabilised by hydrophilic silica
particles and outer water globules are stabilised by
hydrophobic particles. Despite the close proximity of
the oil drops to each other and to the globule inter-
face, they are completely stable due to the adsorbed
particle layer around them. The effects of inner and
outer particle concentration, drop and globule volume
fractions and oil type have been investigated and the
results correlated with the properties of the simple
emulsions stabilised by either type of particle alone.
36 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 9. Optical microscopy image of an orwro multiple emulsion
stabilised by two types of silica particles. The system contains
toluene and both hydrophilic Ž80% SiOH. and hydrophobic silica
Ž51% SiOH.. Inner oil drops are approximately 4 ␮ m in diameter.
The scale bar represents 20 ␮ m Žobtained during work described
earlier w72 䢇 䢇 x..
Since the migration of particles from inner to outer
interfaces or vice versa is expected to be minimal
after emulsion formation, the major cause of instabil-
ity occurring in surfactant emulsions is removed and
these emulsions are stable to coalescence for over 1
year. The kinetics of release of electrolyte from inner
drops to the outer aqueous phase has also been
determined in the wrorw emulsions of toluene. A
model in which the diffusion of salt through the oil
phase including its partitioning between water and oil
has been put forward. This new class of multiple
emulsions should prove of great benefit in the phar-
maceutical field.
5. Solid-stabilised foams
Solid particles have been incorporated into surfac-
tant-stabilised aqueous foams for many years, and
their influence on the formation and stability of the
foam is very dependent on the surfactant type, parti-
cle size and concentration w73,74x. In some cases,
particularly if the particles are fairly hydrophilic, foam
stability is enhanced since particles present in the
aqueous phase of the foam films collect in their
Plateau borders slowing down film drainage. In other
cases, hydrophobic particles enter the air᎐water sur-
faces of the foam and cause destabilisation via the
so-called bridging-dewetting mechanism. This is
thought to be the mode of action of particles Žfre-
quently in the presence of oil drops. contained within
traditional antifoam formulations. It is worth pointing
out that some of the principles involved in the use of
particles in antifoams and in the process of froth
flotation are similar. A recent study by Ip et al. w75x
describes the effect of particle concentration, size and
hydrophobicity on the stability of both aqueous and
molten aluminium foams, both in the presence of
surfactant. Metallic foams are designed to possess
special properties and are produced by introducing air
into molten aluminium containing finely dispersed
silicon carbide particles. The foam so produced is very
stable and can be manipulated and solidified to form
a slab of aluminium foam. For the aqueous system
utilising silica particles ŽG 45 ␮m., only particles of
the correct wettability Žvaried by adsorption of cationic
surfactant . were found to stabilise the foam, and
foam stability increased with decreasing particle size
and increasing concentration. Partially wetted parti-
cles were shown to accumulate at bubble surfaces,
providing a barrier preventing rupture and coales-
cence. In the high temperature aluminium system,
extremely stable foams were formed above a critical
concentration of SiC particles Ž10 ␮m., and high
quality SEM micrographs confirmed the presence of
particles at air᎐liquid surfaces both in planar films
and in Plateau borders, in addition to being present in
the bulk aluminium phase.
The literature concerned with the ability of parti-
cles to act as foam stabilisers in the absence of any
other surface-active material is very sparse w76 ,77x.
䢇䢇
However, work by Wilson w76 x, not yet published
䢇䢇
fully, is worthy of comment. The thesis was aimed at
determining the important factors involved in the
formation of particle-stabilised aqueous foams. Using
a combination of foaming experiments, contact angle
measurements, zeta potential determinations and thin
film studies, a relatively simple picture emerges in
these systems. The particles were those of polystyrene
latex containing charged sulfate groups at their sur-
face. When dispersed in pure water, such particles do
not cause foaming. Particulate foams were only
formed when the dispersion approached the condi-
tions required for coagulation in bulk. This was ef-
fected by addition of either electrolyte reducing re-
pulsion between particles or cationic surfactant which
changes their hydrophobicity through adsorption. As
an illustration, a variety of results have been collected
for one particular system, that of particles of diameter
3.88 ␮m and surface charge density Žin water. 0.059 C
my2 . In the foaming experiments, 5 cm3 of concen-
trated latex dispersion was shaken with 5 cm3 of
aqueous salt solution Žor surfactant . in a reproducible
manner at 20 ⬚C. The type of foam produced was
described in the following way: no foamᎏif formed,
bubbles collapsed within 2 s; slight foamᎏcollapsed
within 3 min; good foamᎏdefinite volume of foam
stable for 5 min; ¨ ery good foamᎏhigh ratio of foam
to liquid volume stable for 12 h. The zeta potentials
of dilute dispersions were measured using elec-
 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
Fig. 10. Effect of salt concentration on the foaming of aqueous
dispersions of polystyrene latices of diameter s 3.88 ␮ m, concen-
tration s 6.7 wt.% Ž䢇, left hand ordinate. and on the contact angle
of a particle at the air᎐water surface ŽI, right hand ordinate. at
293 K. Values of the zeta potential of particles in water are given
on the upper abscissa above the particular salt concentration, and
the dotted line signifies the transition between dispersed Žleft. and
coagulated Žright. systems in bulk. The foaming scale refers to: 0
ᎏno foam; 33ᎏslight foam; 67ᎏgood foam; 100ᎏvery good foam
Žsee text. Ždata taken from Wilson w76 䢇 䢇 x..
trophoresis and the contact angles of particles with
the air᎐water surface were determined using the tilt-
ing plate method. As seen in Fig. 10, addition of
sodium chloride to the dispersions causes a progres-
sive increase in the quality and stability of foam
formed Žfilled points., alongside a decrease in the
charge on the particles Župper numbers. and an in-
crease in contact angle Žopen points.. The vertical
dotted line represents the salt concentration beyond
which dispersions become coagulated in bulk. The
close correspondence between particle hydrophobicity
and foaming is clear; very good foams are possible
once the contact angle reaches above ; 85⬚. The
combination of particles of low charge and of rela-
tively high hydrophobicity seems an essential require-
ment for making it energetically favourable for them
to be situated at the air᎐water surface compared with
bulk.
The same conclusion was reached when the charge
on the particles was reduced by lowering the pH, in
the absence of salt. Very good foams could be pre-
pared around pH 1, again close to the condition at
which bulk coagulation occurred. Particle charge can
also be modified by addition of cationic surfactant
ŽDTAB. capable of adsorption. At low concentrations,
no foam was formed but at concentrations corre-
sponding to charge neutralisation and bulk coagula-
tion, a very good foam appeared of greater volume
37
and stability than that formed in the presence of
surfactant alone. Further increase in surfactant con-
centration resulted in a decrease in foam quality as
particles re-dispersed in bulk on acquiring a net posi-
tive charge. The structure of the foam films was
confirmed by light diffraction as being composed of a
bilayer of particles separated by water, with particles
in each monolayer arranged in a hexagonally close-
packed array. The monolayers were found to be rigid
and solid-like in character. The above findings may be
linked to earlier work by Heller and de Lauder w78x
on the phenomenon of ‘surface coagulation’, in which
an otherwise stable colloidal dispersion of particles of
low charge density was caused to coagulate at an
air᎐water surface. The destabilisation was brought
about by addition of electrolyte and by bubbling N2
gas through the liquid. The critical amount of salt
required to force particles to bubble surfaces was
found to be less than that needed for bulk coagula-
tion in dispersions at rest.
Over the last 10 years a number of non-DLVO
surface forces have been discovered experimentally.
One of them, the oscillatory structural force, appears
during the thinning of thin liquid films containing
colloidal ‘particles’, e.g. surfactant micelles, macro-
molecules or solid particles w79x. This force affects the
stability of foam Žvapour᎐liquid᎐vapour. and emul-
sion Žliquid᎐liquid᎐liquid. films. At high particle con-
centrations this force stabilises the films, whereas at
lower concentrations it degenerates into the depletion
force which is found to destabilise films. One way to
measure directly the structural force is provided by
the phenomenon of stratification, in which thinning
films stabilised by surfactant change thickness in a
regular, stepwise manner before a final stable state is
reached. The height of the steps corresponds to the
effective diameter of the particles contained within
the film. Stratification is universal and has been
observed with particle diameters varying between a
few nm Žanionic micelle, silica particles. and 2 ␮m
Žlatex.. It is due to the formation of a crystal-like
structure within the film and a layer-by-layer thinning
of such an ordered structure. This ordering occurs
because charged particles are mutually repulsive but
are forced into the restricted volume of the thinning
film.
Until recently, all of the studies of film stratifica-
tion involved particles Žmicelles or solid. which did
not adsorb on either side of the film but remained
confined within w79x. A couple of papers, however,
report on foam film behaviour in cases where solid
particles become attached to the film surfaces. Ve-
likov et al. w80x investigated the influence of the
film-forming surfactant on the dynamics of film thin-
ning in the presence of negatively charged polystyrene
latex particles Ž7 ␮m.. For plane parallel films
38 B.P. Binks r Current Opinion in Colloid & Interface Science 7 (2002) 21᎐41
stabilised by the anionic surfactant SDS, all of the
Žhydrophilic. particles were expelled from the film
interior into the surrounding meniscus due to their
repulsion with the film surfaces. For cationic surfac-
tant-stabilised films ŽCTAB. however, the same parti-
cles become partially hydrophobic due to the coupling
between the surface and the positively charged head-
groups. Following opening and closing of the films a
few times, a layer of particles simultaneously adsor-
bed at the two film surfaces is formed, sterically
inhibiting any further film opening and thinning. The
particles within this bridging monolayer displayed ex-
cellent hexagonal ordering over large distances with
almost no defects. An increase in surfactant concen-
tration led to a lower quality of the particle arrays
due to some lateral coagulation of the particles, but
to a higher rigidity and resistance to further manipu-
lation. Capillary attraction between the particles con-
fined within the film was shown to account for such
two-dimensional crystallisation.
In contrast to the above, the stability of curved
foam films containing small monodisperse particles
alone in the absence of surfactant has been investi-
gated w81x. Spherical, hydrophilic silica particles of
diameter between 8 and 39 nm and dispersed in pure
water are shown to stabilise thin films by a layering
mechanism within the film since none of the particles
adsorb to the film surfaces. The number of stepwise
transitions increases with the volume fraction of parti-
cles within the film. Eventually a black spot appears
indicative of a part of the film containing no particles.
The subsequent growth of the spot with time leading
to film rupture can be explained using the diffusive
osmotic model which takes into account the diffusion
of particles from the film to the meniscus leaving
behind vacancies. The rate of film thinning was found
to be high when the particle concentration was low
and when both the particle size and film diameter
were large. Monte Carlo simulations showed that at
high particle concentrations the energy needed to
withdraw a particle from the film is high, due to the
improved in-layer structure, thus inhibiting particle
diffusion and enhancing film stability. This is an im-
portant result and could have significant practical
implications in the stabilisation of foams and emul-
sions using colloidal particles. It would be very inter-
esting to continue this kind of work using small parti-
cles of increasing hydrophobicity Žas used in emul-
sions above. in order to study the influence of adsor-
bed particles on the thinning and eventual stability of
the particle- stabilised foam films.
6. Conclusions
There are many similarities in the behaviour of
small particles and surfactant molecules at fluid᎐fluid
interfaces and in various kinds of dispersions. Impor-
tant differences however also exist. The field of parti-
cles at interfaces, both flat and curved, is an exciting
one and is beginning to form part of the research of
many groups. Future challenges include designing a
method for measuring the contact angles sub-micron
sized spherical particles make with interfaces and
synthesising and studying particles of different shapes.
The high stability encountered in solid-stabilised
emulsions is of great advantage in terms of the shelf-
life of formulations including them. Their rheology
and deposition characteristics on surfaces, e.g. skin,
need to be investigated. Such emulsions may act as
templates for the ordering of particles into new struc-
tures following evaporation of the liquid components.
Acknowledgements
It is a pleasure to thank Dr Herbert Barthel of
Wacker-Chemie GmbH, Burghausen ŽGermany. for
the continued supply of fumed silica powders of vary-
ing hydrophobicity, without which some of our work
on solid-stabilised emulsions would not have been
possible. I also thank Prof. P.D.I. Fletcher for useful
discussions.
References and recommended reading
䢇 of special interest
䢇䢇 of outstanding interest
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5:56᎐63.
w2x Yin Y, Gates B, Xia Y. Growth of large crystals of monodis-
persed spherical colloids in fluidic cells fabricated using non-
photolithographic methods. Langmuir 2001;17:6344᎐6350.
w3x Aveyard R, Binks BP, Mead J. Interfacial tension minima in
oil᎐water-surfactant systems. J Chem Soc Faraday Trans 1
1986;82:1755᎐1770.
w4x Kabalnov A, Wennerstrom ¨ H. Macroemulsion stability: the
oriented wedge theory revisited. Langmuir 1996;12:276᎐292.
w5x Okubo T. Surface tension of structured colloidal suspensions
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w6x Aveyard R, Clint JH, Nees D, Paunov VN. Compression and
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and octanerwater interfaces. Langmuir 2000;16:1969᎐1979.
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through the oil phase.
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41
conditions necessary to achieve foam stabilisation using latex parti-
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