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EFFECT OF ANIONIC SURFACTANT ON SILICA

PARTICLE ATTACHMENT AT THE OIL-WATER
INTERFACE
C Vashisth1, C Whitby2, D Fornasiero3 and J Ralston4

ABSTRACT
Controlling particle attachment is crucial where powdered solids come into contact with oil and
water. Particles are trapped in a deep energy well at the oil-water interface, stabilising emulsions.
Here it is shown that adding anionic surfactant causes dramatic changes to the bulk and interfacial
structure of silica particle-stabilised oil-in-water emulsions. Exposing particle-stabilised drops to
surfactant concentrations above the critical micelle concentration enhances the rate and extent of
creaming and flocculation. Mixing particle-stabilised emulsions with surfactant solutions causes
drop fragmentation. As the surfactant concentration increases, the average drop size decreases and
particles are displaced from the interface during the mixing process.
Keywords: particle-stabilised emulsions, Pickering emulsions, depletion, competitive adsorption,
detachment, destabilisation

INTRODUCTION
Emulsion formation is a critical step in oil recovery, solvent extraction, water remediation and
leaching processes. Finely divided solids in contact with mixtures of water and oil can attach to
the oil-water interface (Binks, 2002). A potential method for removing dense non-aqueous phase
liquid contaminants from groundwater, for example, involves using particles to encapsulate the
contaminants (Roy-Perreault, Kueper and Rawson, 2005; Torres et al, 2008). Particles are trapped
at the oil-water interface, providing there are attractive interactions between the particles and drops
(Ralston, Fornasiero and Hayes, 1999).
Low molecular weight surfactants adsorbed at interfaces are in dynamic equilibrium. Physical
stresses (shear, electrical fields) or chemical demulsifiers can break surfactant-stabilised emulsions.
In contrast, trapped particles form compact networks due to strong lateral attractions, making the
drop surfaces rigid and resistant to coalescence (Arditty et al, 2005). This can be highly detrimental.
Formation of particle-stabilised emulsions generates waste disposal problems during bitumen
extraction from oil sands or the separation of salts and fine solids from shale oil (Yan, Kurbis and
Masliyah, 1997; Sullivan and Kilpatrick, 2002). Phase separation in solvent extractions can be
completely arrested by the formation of particle-stabilised emulsions (Zhou et al, 2009).
Controlling particle attachment is crucial in aqueous processing routes where powdered solids come
into contact with oil and water. In this paper, we focus on routes for altering the stability of unwanted
particle-stabilised emulsions. These involve the addition of a surfactant, which is negatively charged,
like the particles used to stabilise the drops. Surfactant adsorption at the oil-water interface, rather
than onto the particles, is favoured.
Typically, surfactant is added during emulsion formation and adsorbs onto the particle surfaces.
Changing the particle contact angle alters the subsequent attachment processes. The particle contact
angle at the oil-water interface controls the position of particles attached to fluid interfaces (Schulze,
1977; Levine Bowen and Partridge, 1989) and hence the interfacial curvature (Finkle, Draper and

1. Visiting Intern Student, Ian Wark Research Institute, University of South Australia, Mawson Lakes SA 5095, Australia.
2. Research Fellow (AMSRI), Ian Wark Research Institute, University of South Australia, Mawson Lakes SA 5095, Australia. Email: Catherine.Whitby@unisa.edu.au
3. Associate Research Professor, Ian Wark Research Institute, University of South Australia, Mawson Lakes SA 5095, Australia. Email: Daniel.Fornasiero@unisa.edu.au
4. Laureate Professor and Director, Ian Wark Research Institute, University of South Australia, Mawson Lakes SA 5095, Australia. Email: John.Ralston@unisa.edu.au

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Hildebrand, 1923; Binks and Lumsdon, 2000). Schulman and Leja (1954) and Tambe and Sharma
(1993) linked the type of emulsion stabilised to the influence of surfactant adsorption on the
particle contact angle. Lucassen-Reynders and van den Tempel (1963) and Hassander, Johansson
and Tornell (1989) linked improvements in emulsion stability to changes in the extent of particle
flocculation after surfactant addition. Binks and co-workers (2007a,b) showed that the synergistic
stabilization of emulsions by silica particles and cationic surfactant is linked to the increase in particle
hydrophobicity and particle flocculation with surfactant adsorption onto the particles. Ravera and
co-workers (2006, 2008) found that rearrangements in mixed layers of particles and surfactant at
the interface affect the viscoelastic response of the interface.
Here, instead, we address the question of how surfactant molecules affect particles already
attached to oil-water interfaces. The macroscopic and microscopic changes to emulsion structure are
characterised. Exposing particle-stabilised oil-in-water drops to high concentrations of surfactant
causes attractive interactions. The emulsions rapidly separate into a concentrated layer of drops and
a dilute aqueous phase. Vigorous mixing enables competitive adsorption of the surfactant molecules
at the oil-water interface and particle detachment from the oil-water interface.

EXPERIMENTAL SECTION
Preparation and characterisation of particle dispersions
Ultrafine silica particles (12 nm in diameter) modified by reaction with hexadecylsilane were supplied
as a powder, by Degussa (Aerosil R816). The particle contact angle () is nominally 23o at the air-
water interface and 60o at the toluene-water interface. The BET surface area is 190 +/- 20 m2 g-1.
Particle dispersions in solutions of sodium chloride (Chem Supply, 99 per cent) in water (ultrapure
with a resistivity not less than 18.2 M cm) were sonicated in an ultrasound bath (Soniclean 160T,
70 W power, ~ 44 kHz operating frequency) for 30 minutes. TEM images revealed that the powder
broke down into 20 to 50 nm size particles. The zeta potentials of the particles are -38 mV in 0.001 M
NaCl and -13 mV in 0.1 M NaCl at pH 5.8 (measured by laser Doppler velocimetry using a Malvern
Zetasizer Nano).
The interactions between sodium dodecyl sulfate (SDS, Sigma Aldrich, 99 per cent) and the particles
were investigated by diluting or mixing particle dispersions with SDS solutions in a similar fashion
to the emulsions (see below). The dispersions were then left to stand in a water bath at 23C. The
volumes of foam and sedimenting particles were monitored over time. Air-water surface tensions
of the supernatants of the particle dispersions were measured by the pendant drop method using a
Contact Angle System OCAH 200 (DataPhysics Instruments).
Preparation of particle-stabilised emulsions
Emulsions were prepared by homogenising dodecane (Sigma Aldrich, 99 per cent, passed though
chromatographic alumina twice to remove polar impurities) with aqueous particle dispersions using
a rotor-stator mixer (Ingenieubro CAT X1030D, M. Zipperer GmbH) operated at 13000 rpm for 2
minutes. A 10 mm head or an 18 mm head was used in the mixer. The emulsions could be diluted in
water and are therefore water continuous.
Mixing emulsions and surfactant solutions
Samples of the emulsion diluted in solutions of sodium chloride and SDS were stored in screw cap
vials and tumbled end-over-end on a Ratek suspension rotary mixer at about 6 rpm for 4 hours.
Emulsions were mechanically mixed with aqueous solutions of SDS using the rotor stator mixer with
a 10 mm head operated at 13000 rpm for 2 minutes.
Emulsion characterisation
The emulsions were stored in screw cap vials in a water bath at 23C. The separation of the emulsion
into layers was monitored over time. Drop size distributions were characterised by light scattering
(Mastersizer 2000) and optical microscopy (Olympus BH2 Research microscope). Cryo-Scanning
Electron Microscopy (cryo-SEM) images of the interfacial structure were obtained using a Philips
XL30 Field Emission Scanning Electron Microscope, fitted with a CT1500 HR Low Temperature
Cryo system. The emulsions were fractured and etched at -95C for 60 seconds. The fractured surface
was coated in platinum (10 mA, 105 seconds, 1 mbar Argon).

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RESULTS
For these experiments, oil-in-water emulsions were prepared by mechanically homogenising
dodecane with aqueous dispersions of partially hydrophobic silica. The emulsions do not coalesce for
several months. The drop size distributions measured by light scattering are log normal distributions,
corresponding to a single population of drops. Electron microscopy imaging revealed that the
drops are coated by several layers of particles (shown later). Flocs of particles are also present in
the aqueous phase. These emulsions are effectively binary mixtures of particle-stabilised drops and
excess (unattached) particles. The salt concentration in the aqueous phase controls the extent of
drop-particle heteroaggregation (discussed shortly).
Mixing the particle-stabilised emulsions together with SDS solutions involved gentle dilution and
then mechanical mixing. On dilution, the oil volume fraction and the particle concentration were
reduced by one third. Depending on the surfactant concentration, the total concentration of ions
(due to dissociation of the salt and the ionic surfactant) in the aqueous phase increases dramatically.
It is important to distinguish between the effects of salt and surfactant. The influence of the ionic
strength on emulsion stability is discussed first.
Effect of diluting emulsions in salt solutions
The concentration and charge of the cation in the salt added to the aqueous phase affects drop
flocculation and hence emulsion creaming. In emulsions at rest, oil drops rise to the top to form
a concentrated layer of drops (cream). Figure 1a shows that the total proportion of water released
overnight by the emulsions varies with the sodium chloride concentration. Creaming takes several
hours to complete. With the addition of a monovalent salt, such as sodium chloride, the initial rate
at which the aqueous phase is released decreases as the salt concentration increases. The total
proportion of water released gradually decreases as the concentration of sodium chloride increases.
This means that the volume of the cream increases with the sodium chloride concentration.
At low sodium chloride concentrations (< 0.004 M), the released water is turbid due to the presence
of excess particles. The concentration of the excess particles is low. It takes several days for a slight
amount of sediment to appear. The emulsions release only clear water at higher sodium chloride
concentrations. This indicates that the excess particles are entrapped in the cream layer.
Addition of divalent ions, such as calcium ion at concentrations ranging from 10-4 to 0.1 M, causes
the release of only clear water from the emulsions. The fraction of the aqueous phase released is
about 0.67. This is comparable to the fraction of aqueous phase released by emulsions at sodium
chloride concentrations where the drops completely aggregate with the excess particles.
The drop size and polydispersity does not vary with the salt concentration. So the creaming
behaviour reflects the aggregation in these binary mixtures of particle-stabilised drops and excess
particles. The increase in the sodium chloride concentration screens the negative surface charges
on the particles. This enhances particle aggregation with the drops. Lower concentrations of the
divalent calcium ions are required to reduce the surface charge of the particles and cause complete
aggregation of the excess particles with the drops. The increase in particle attachment to the drops
coincides with an increase in the volume of the emulsion cream. Optical microscopy imaging revealed
that the drops are not close packed in the emulsion creams (shown later). This suggests that an open
network structure of particle-stabilised drops and particles form in the cream (Whitby, Fornasiero
and Ralston, 2009).
Effect of diluting emulsions in surfactant solutions
Gently adding SDS at low concentrations does not significantly alter the creaming behaviour of the
emulsions. The emulsions release water and particles at about the same rate as emulsions diluted in
sodium chloride alone. Figure 1b shows that the fraction of water released does not depend on the
surfactant concentration at SDS concentrations less than the critical micelle concentration (cmc).
Addition of surfactant at concentrations 0.01 M, however, dramatically alters the rate of creaming.
Within 10 minutes of standing, the emulsion separates into an upper layer of concentrated drops
and a slightly less turbid lower layer. Figure 1b shows that the proportion of water released at SDS
concentrations above the cmc is over 90 per cent of the total aqueous phase in the emulsions.
Inspection of the drops directly after mixing emulsions with surfactant solutions did not reveal
changes to the drop size or extent of flocculation with surfactant concentration. Light scattering

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FIG 1 - (a) Variation in the fraction of the aqueous phase (faq) released overnight by 10 vol per cent dodecane-in-water emulsions stabilised
by 0.5 wt per cent partially hydrophobised silica particles in the aqueous phase with the concentration of sodium chloride in the aqueous phase.
(b) Variation in the fraction of the aqueous phase released overnight by emulsions diluted in SDS solutions with the concentration of SDS
in the aqueous phase. Optical micrographs of diluted emulsions where the aqueous phase contains (c) 104 M SDS and (d) and 0.03 M SDS.
The scale bar corresponds to 100 m. The lines are shown simply to guide the eye.

measurements confirmed that diluting the emulsions in surfactant solutions did not alter the
emulsion drop size distribution. The packing of the drops in the cream layers that form while
allowing the emulsions to stand varies dramatically, however, with the surfactant concentration. At
low surfactant concentrations, the drops in the cream are clustered together but not closely packed,
as shown in Figure 1c. At high surfactant concentrations, the drops are so closely packed that a slight
deformation of the drops occurs, as shown in Figure 1(d).
At the highest sodium chloride concentration studied (0.1 M), particles are released at concentrations
sufficient for a layer of sedimented particles to form at the bottom of the emulsion within 24 hours.
The release of the particles does not cause coalescence. It is possible to re-disperse the drops in fresh
sodium chloride solutions.
Effect of mixing emulsions with surfactant solutions
Vigorously mixing the particle-stabilised emulsions with solutions of SDS reduces the average drop
size in the emulsions and causes foam generation and the release of particles. Figure 2a shows how
the average drop size varies with the concentration of surfactant added to the emulsion. As the
surfactant concentration increases, emulsion drop size population shifts to smaller sizes. At surfactant
concentrations above the SDS critical micelle concentration, the average drop size does not change

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EFFECT OF ANIONIC SURFACTANT ON SILICA PARTICLE ATTACHMENT AT THE OIL-WATER INTERFACE

FIG 2 - (a) Variation in the average drop diameter (D(4,3)) of emulsions after mixing with SDS solutions as a function of the concentration of SDS.
The line is shown to guide the eye. (b) Examples of freeze fracture SEM images of the structure at the water-oil interface in emulsions after mixing
with SDS solutions at SDS concentrations of (b) 0 M and (c) 0.1 M. The scale bar corresponds to 2 m.

significantly and is comparable to the average drop size of emulsions stabilised by surfactant alone
(13 m).
The foamability of the particle-stabilised emulsions gradually increases with the surfactant
concentration. In contrast, in the presence of surfactant alone foaming only occurs at surfactant
concentrations near the cmc. The air bubbles in the foams are millimetres in size. The lamellae and
Plateau borders are white due to the presence of oil drops in the foams. So oil drops stabilised by
particles or surfactant accumulate in the thin aqueous films that form between bubbles as the water
drains out. The drops do not penetrate and rupture the air-water interface.
The long term stability of the foams is similar to that of foams generated during the formation of
surfactant-stabilised emulsions. In all cases, the emulsified oil drops present in the foam are easily
displaced as the water drains out. The foams completely destabilise over 24 hours.
Particles sediment out of the foamy emulsions over time. Figure 3a illustrates how the mass of
displaced particles varies with the surfactant concentration. The inset (Figure 3b) is a photo of an
emulsion after sedimentation is complete. The concentration of salt in the aqueous phase affects the
particle release. Figure 3a shows that for emulsions with a high concentration of NaCl (0.1 M) in the
aqueous phase, the mass of displaced particles increases abruptly near the surfactant concentration,
where the average drop size in the emulsion is minimised. About three quarters of the particles
present in the emulsions are released. The remaining particles are trapped in the emulsion creams.
At lower salt concentrations (not shown) the mass of displaced particles increases gradually with the
surfactant concentration.
Figure 2b shows that the oil-water interface in particle-stabilised emulsions is densely coated
with particles. Energy Dispersive X-ray analysis indicated that the elemental composition of the
particulate material is silicon and oxygen, as expected for silica particles. At intermediate surfactant
concentrations, the attached particle layer at the drop surfaces is patchy. Regions on the drop

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FIG 3 - (a) Variation in the percentage of particles (mp) released from emusions mixed with SDS solutions as a function of the concentration of SDS
in the aqueous phase for a background salt concentration of 0.1 M NaCl. The line is shown to guide the eye. (b) Photo of emulsion after mixing at
an SDS concentration of 0.1 M and then standing for several days.

surfaces coated with close-packed particles are separated by particle-free regions. Figure 2c shows
that the interface between the oil drops and aqueous phase appears white at high surfactant
concentrations. There is no evidence of particles attached to the drop surfaces.
Particles are also observed in the continuous aqueous phase exposed in the frozen emulsion
samples. Assuming that the average radius of the particles attached to the drop surfaces (R) was
15 nm, there are about six times as many particles available as required to coat the drops with a
single layer. Comparing Figures 2b and 2c show that the particles become slightly larger in size as
the surfactant concentration increases, suggesting aggregation of the excess particles. Ice crystal
formation in particle systems tends to cause artefacts (Mikula and Munoz, 2000). So the freezing
process may have contributed to some of the features observed in the electron microscopy imaging.
These observations are, however, consistent with the release of particle aggregates from the bulk
emulsions.

DISCUSSION
Figure 4 summarises the effects of adding anionic surfactant on the structure of silica particle-
stabilised emulsions. Diluting the emulsions in surfactant solutions does not alter the bulk emulsion
structure. Drop flocculation is enhanced at high SDS concentrations. In contrast, mechanically mixing

FIG 4 - Schematic representation of the effects of adding SDS to particle-stabilised emulsions.

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emulsions with dilute SDS solutions causes drop fragmentation. At higher SDS concentrations,
surfactant-stabilised drops form and the particles sediment out from the emulsions.
Rationalising the changes to emulsion structure on surfactant addition requires considering the
interactions of the surfactant molecules with the different interfaces present in the emulsions.
There is little evidence for surfactant adsorption onto the particle surfaces. The surface tension of
the supernatant in particle dispersions containing surfactant is comparable to the surface tension
of a pure surfactant solution at the same concentration as that in the dispersion. At surfactant
concentrations above the cmc, the particles redisperse. This suggests there is some adsorption of
the surfactant at high surfactant concentrations (and also higher ionic strength). Presumably the
surfactant molecules adsorb in conformations which expose the anionic head group to the aqueous
solution, effectively increasing the surface charge on the particles. These results are consistent with
observations that adsorption of SDS on silanised silica surfaces is inhibited by the negative charge of
the silica surfaces (Atkin et al, 2003).
SDS readily adsorbs at pristine alkane-water interfaces (Cockbain, 1954; Staples, Penfold and
Tucker, 2000). There is, however, no change in the drop size after dilution, which exposes the particle-
stabilised drops to the anionic surfactant. Presumably the attached particles hinder surfactant
adsorption at the oil-water interface. Thus the enhanced flocculation of the particle-stabilised drops
is not linked to surfactant adsorption at the emulsion interfaces.
The unusual creaming behaviour observed on dilution at SDS concentrations above the cmc (Figure 4)
is likely due to depletion of surfactant micelles. Fairhurst et al (1983) first observed similarities
between the flocculation of latex particles by free (non-adsorbed) polymer and the flocculation of
surfactant-stabilised emulsions induced by excess surfactant. Bibette, Roux and Nallet (1991) found
that surfactant-stabilised oil-in-water emulsions formed two phases at SDS concentrations above
the cmc. The upper phase was a dense phase of aggregated drops. The lower phase consisted of a
low concentration of dispersed drops. Bibette, Roux and Nallet (1991) argued that the creaming
behaviour was related to a fluid-solid phase transition due to attraction interactions between the
drops being induced by depeletion of surfactant micelles. Koh et al (2000) showed that addition of
cationic surfactant to emulsions stabilised by non-ionic surfactant induced depletion flocculation at
surfactant concentrations above the cmc. The formation of a distinct cream layer could be reversed
by gentle mixing. The results shown here indicate that the addition of anionic surfactant can alter the
stability of silica particle-stabilised emulsions (Whitby, Fornasiero and Ralston, 2009).
Mixing particle-stabilised emulsions at SDS concentrations above the cmc causes particles to
displace from the oil-water interface (Figure 4). This is due to competitive adsorption of the surfactant
at the interface. The decrease in drop size indicates that surfactant molecules adsorb at the oil-water
interface, reducing the interfacial tension and enabling drops fragmentation. It is important to
note that surfactant concentrations above the cmc are required to stabilise drops in the absence of
particles. Since the drops do not coalesce at low surfactant concentrations, presumably particles
remain attached to the interface. After mixing at high surfactant concentrations particles were not
observed at the interface, however, confirming the complete displacement of particles by surfactant
molecules.
Analysis of particle partitioning between water and a planar dodecane-water interface indicates
that an isolated spherical silica particle is trapped in a deep energy well. In the presence of particles
alone, the interfacial tension is 51 mN m-1. The energy required to detach a particle, which is given
by R2ow(1-cos)2 (Levine, Bowen and Partridge, 1989) is about 103 times the typical Brownian
thermal energy. In the presence of SDS, the interfacial tension decreases to about 10 mN m-1 at the
cmc. Due to the reduction in the Laplace pressure of the drops, the stress needed to deform and
fragment drops decreases. Thus drops are fragmented at low surfactant concentrations (Figure 4).
During mixing, the (now) weakly attached particles readily detach. Surfactant molecules adsorb at
the fresh interface created by drop deformation. Characterisation of these effects was achieved by
visual inspection of bulk emulsion and foam stability, measurement of the emulsion drop sizes by
light scattering and optical microscopy and electron microscopy imaging of the interfacial structure
of the emulsions. In the future we will use rheological techniques to gain further insights into shear-
induced destabilisation of emulsions.

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CONCLUSIONS
We have demonstrated that the stability and structure of unwanted silica-particle-stabilised
emulsions can be altered by the addition of anionic surfactant. Surfactant adsorption at the oil-water
interface is energetically favourable. Under gentle mixing conditions, however, it is hindered by the
attached layer of particles. Particle-stabilised drops exposed to high concentrations of surfactant
flocculate strongly due to depletion interactions caused by the non-adsorbed surfactant. Vigorous
mixing of the emulsions with surfactant solutions enables surfactant adsorption to occur. As a result,
particles are displaced from the interface. It should be possible to then apply one of the common
routes used to break surfactant-stabilised emulsions, if it is necessary to separate the oil and water
phases.

ACKNOWLEDGEMENTS
The particles used in these experiments were kindly supplied by Evonik Degussa. We thank Dr P. Self
(Adelaide Microscopy, The University of Adelaide) for his help with the cryo-SEM experiments. The
financial support of the Australian Research Council Linkage Scheme, AMIRA International, and
State Governments of South Australia and Victoria, is gratefully acknowledged.

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