C Vashisth1, C Whitby2, D Fornasiero3 and J Ralston4

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

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


10 SEPTEMBER 2010 408 . AUSTRALIA / 6 . The particle contact angle (θ) is nominally 23o at the air- water interface and 60o at the toluene-water interface. QLD. The zeta potentials of the particles are -38 mV in 0. The BET surface area is 190 +/. fitted with a CT1500 HR Low Temperature Cryo system. 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. 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). Ravera and co-workers (2006. The emulsions were fractured and etched at -95°C for 60 seconds.2 MΩ cm) were sonicated in an ultrasound bath (Soniclean 160T. XXV INTERNATIONAL MINERAL PROCESSING CONGRESS (IMPC) 2010 PROCEEDINGS / BRISBANE. Sigma Aldrich. The interactions between sodium dodecyl sulfate (SDS. 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. 2008) found that rearrangements in mixed layers of particles and surfactant at the interface affect the viscoelastic response of the interface. 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). A 10 mm head or an 18 mm head was used in the mixer. Preparation of particle-stabilised emulsions Emulsions were prepared by homogenising dodecane (Sigma Aldrich. Cryo-Scanning Electron Microscopy (cryo-SEM) images of the interfacial structure were obtained using a Philips XL30 Field Emission Scanning Electron Microscope. ~ 44 kHz operating frequency) for 30 minutes. Johansson and Tornell (1989) linked improvements in emulsion stability to changes in the extent of particle flocculation after surfactant addition. M. 1 mbar Argon). 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. Drop size distributions were characterised by light scattering (Mastersizer 2000) and optical microscopy (Olympus BH2 Research microscope). by Degussa (Aerosil R816). we address the question of how surfactant molecules affect particles already attached to oil-water interfaces. The dispersions were then left to stand in a water bath at 23°C. 70 W power. 105 seconds. Binks and co-workers (2007a. C VASHISTH et al Hildebrand. instead. 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. passed though chromatographic alumina twice to remove polar impurities) with aqueous particle dispersions using a rotor-stator mixer (Ingenieubüro CAT X1030D. The macroscopic and microscopic changes to emulsion structure are characterised. The volumes of foam and sedimenting particles were monitored over time. Lucassen-Reynders and van den Tempel (1963) and Hassander.20 m2 g-1. Emulsion characterisation The emulsions were stored in screw cap vials in a water bath at 23°C. 99 per cent. Binks and Lumsdon.8 (measured by laser Doppler velocimetry using a Malvern Zetasizer Nano). 99 per cent) in water (ultrapure with a resistivity not less than 18. 1923.1 M NaCl at pH 5.001 M NaCl and -13 mV in 0. The emulsions could be diluted in water and are therefore water continuous. 2000). Vigorous mixing enables competitive adsorption of the surfactant molecules at the oil-water interface and particle detachment from the oil-water interface. Exposing particle-stabilised oil-in-water drops to high concentrations of surfactant causes attractive interactions.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. Particle dispersions in solutions of sodium chloride (Chem Supply. Zipperer GmbH) operated at 13000 rpm for 2 minutes. Here. The emulsions rapidly separate into a concentrated layer of drops and a dilute aqueous phase. The separation of the emulsion into layers was monitored over time. The fractured surface was coated in platinum (10 mA. TEM images revealed that the powder broke down into 20 to 50 nm size particles.

however. The increase in the sodium chloride concentration screens the negative surface charges on the particles. 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. The concentration of the excess particles is low. This means that the volume of the cream increases with the sodium chloride concentration.1 M. dramatically alters the rate of creaming. Optical microscopy imaging revealed that the drops are not close packed in the emulsion creams (shown later). the total concentration of ions (due to dissociation of the salt and the ionic surfactant) in the aqueous phase increases dramatically. Figure 1a shows that the total proportion of water released overnight by the emulsions varies with the sodium chloride concentration.EFFECT OF ANIONIC SURFACTANT ON SILICA PARTICLE ATTACHMENT AT THE OIL-WATER INTERFACE RESULTS For these experiments. Mixing the particle-stabilised emulsions together with SDS solutions involved gentle dilution and then mechanical mixing. It takes several days for a slight amount of sediment to appear. 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 total proportion of water released gradually decreases as the concentration of sodium chloride increases. 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. Effect of diluting emulsions in surfactant solutions Gently adding SDS at low concentrations does not significantly alter the creaming behaviour of the emulsions. oil-in-water emulsions were prepared by mechanically homogenising dodecane with aqueous dispersions of partially hydrophobic silica. Addition of surfactant at concentrations ≥ 0. Light scattering XXV INTERNATIONAL MINERAL PROCESSING CONGRESS (IMPC) 2010 PROCEEDINGS / BRISBANE. On dilution. These emulsions are effectively binary mixtures of particle-stabilised drops and excess (unattached) particles. Addition of divalent ions. The fraction of the aqueous phase released is about 0. Creaming takes several hours to complete. 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). The drop size and polydispersity does not vary with the salt concentration. This enhances particle aggregation with the drops. The influence of the ionic strength on emulsion stability is discussed first. Within 10 minutes of standing. It is important to distinguish between the effects of salt and surfactant. 2009). So the creaming behaviour reflects the aggregation in these binary mixtures of particle-stabilised drops and excess particles. The increase in particle attachment to the drops coincides with an increase in the volume of the emulsion cream. The emulsions release water and particles at about the same rate as emulsions diluted in sodium chloride alone. This suggests that an open network structure of particle-stabilised drops and particles form in the cream (Whitby. the initial rate at which the aqueous phase is released decreases as the salt concentration increases. This indicates that the excess particles are entrapped in the cream layer. Flocs of particles are also present in the aqueous phase. At low sodium chloride concentrations (< 0. the emulsion separates into an upper layer of concentrated drops and a slightly less turbid lower layer. The emulsions release only clear water at higher sodium chloride concentrations. Electron microscopy imaging revealed that the drops are coated by several layers of particles (shown later).004 M). In emulsions at rest. 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. causes the release of only clear water from the emulsions. such as sodium chloride. the oil volume fraction and the particle concentration were reduced by one third. QLD.10 SEPTEMBER 2010 409 . oil drops rise to the top to form a concentrated layer of drops (cream). Fornasiero and Ralston. The drop size distributions measured by light scattering are log normal distributions. corresponding to a single population of drops. the released water is turbid due to the presence of excess particles. AUSTRALIA / 6 . With the addition of a monovalent salt. such as calcium ion at concentrations ranging from 10-4 to 0.01 M.67. The emulsions do not coalesce for several months. 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. Depending on the surfactant concentration. The salt concentration in the aqueous phase controls the extent of drop-particle heteroaggregation (discussed shortly).

The scale bar corresponds to 100 μm. particles are released at concentrations sufficient for a layer of sedimented particles to form at the bottom of the emulsion within 24 hours. AUSTRALIA / 6 . QLD. emulsion drop size population shifts to smaller sizes. the average drop size does not change XXV INTERNATIONAL MINERAL PROCESSING CONGRESS (IMPC) 2010 PROCEEDINGS / BRISBANE. the drops are so closely packed that a slight deformation of the drops occurs. 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. with the surfactant concentration. as shown in Figure 1(d). (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. The lines are shown simply to guide the eye. Figure 2a shows how the average drop size varies with the concentration of surfactant added to the emulsion. however. measurements confirmed that diluting the emulsions in surfactant solutions did not alter the emulsion drop size distribution.5 wt per cent partially hydrophobised silica particles in the aqueous phase with the concentration of sodium chloride in the aqueous phase.10 SEPTEMBER 2010 410 . the drops in the cream are clustered together but not closely packed. At low surfactant concentrations.03 M SDS.(a) Variation in the fraction of the aqueous phase (faq) released overnight by 10 vol per cent dodecane-in-water emulsions stabilised by 0. It is possible to re-disperse the drops in fresh sodium chloride solutions. At high surfactant concentrations. At surfactant concentrations above the SDS critical micelle concentration. As the surfactant concentration increases. The release of the particles does not cause coalescence. At the highest sodium chloride concentration studied (0. The packing of the drops in the cream layers that form while allowing the emulsions to stand varies dramatically. Optical micrographs of diluted emulsions where the aqueous phase contains (c) 10−4 M SDS and (d) and 0. as shown in Figure 1c. C VASHISTH et al FIG 1 .1 M).

The scale bar corresponds to 2 μm. Figure 3a illustrates how the mass of displaced particles varies with the surfactant concentration. The line is shown to guide the eye. Figure 3a shows that for emulsions with a high concentration of NaCl (0. the attached particle layer at the drop surfaces is “patchy”. The inset (Figure 3b) is a photo of an emulsion after sedimentation is complete. In contrast. AUSTRALIA / 6 .10 SEPTEMBER 2010 411 .(a) Variation in the average drop diameter (D(4. significantly and is comparable to the average drop size of emulsions stabilised by surfactant alone (13 μm). The foamability of the particle-stabilised emulsions gradually increases with the surfactant concentration. The remaining particles are trapped in the emulsion creams. The long term stability of the foams is similar to that of foams generated during the formation of surfactant-stabilised emulsions. Figure 2b shows that the oil-water interface in particle-stabilised emulsions is densely coated with particles.EFFECT OF ANIONIC SURFACTANT ON SILICA PARTICLE ATTACHMENT AT THE OIL-WATER INTERFACE FIG 2 . The drops do not penetrate and rupture the air-water interface. where the average drop size in the emulsion is minimised. Energy Dispersive X-ray analysis indicated that the elemental composition of the particulate material is silicon and oxygen. The lamellae and Plateau borders are white due to the presence of oil drops in the foams.1 M. At lower salt concentrations (not shown) the mass of displaced particles increases gradually with the surfactant concentration. So oil drops stabilised by particles or surfactant accumulate in the thin aqueous films that form between bubbles as the water drains out. The air bubbles in the foams are millimetres in size. Regions on the drop XXV INTERNATIONAL MINERAL PROCESSING CONGRESS (IMPC) 2010 PROCEEDINGS / BRISBANE. The concentration of salt in the aqueous phase affects the particle release. Particles sediment out of the foamy emulsions over time. The foams completely destabilise over 24 hours. the emulsified oil drops present in the foam are easily displaced as the water drains out. as expected for silica particles. About three quarters of the particles present in the emulsions are released.1 M) in the aqueous phase. At intermediate surfactant concentrations. (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. In all cases. QLD.3)) of emulsions after mixing with SDS solutions as a function of the concentration of SDS. the mass of displaced particles increases abruptly near the surfactant concentration. in the presence of surfactant alone foaming only occurs at surfactant concentrations near the cmc.

DISCUSSION Figure 4 summarises the effects of adding anionic surfactant on the structure of silica particle- stabilised emulsions. C VASHISTH et al FIG 3 . Figure 2c shows that the interface between the oil drops and aqueous phase appears white at high surfactant concentrations. QLD. (b) Photo of emulsion after mixing at an SDS concentration of 0. Drop flocculation is enhanced at high SDS concentrations. however. Diluting the emulsions in surfactant solutions does not alter the bulk emulsion structure.(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. AUSTRALIA / 6 . there are about six times as many particles available as required to coat the drops with a single layer. In contrast. Comparing Figures 2b and 2c show that the particles become slightly larger in size as the surfactant concentration increases. So the freezing process may have contributed to some of the features observed in the electron microscopy imaging. mechanically mixing FIG 4 . consistent with the release of particle aggregates from the bulk emulsions. The line is shown to guide the eye. There is no evidence of particles attached to the drop surfaces. These observations are. Assuming that the average radius of the particles attached to the drop surfaces (R) was 15 nm. XXV INTERNATIONAL MINERAL PROCESSING CONGRESS (IMPC) 2010 PROCEEDINGS / BRISBANE. 2000). Ice crystal formation in particle systems tends to cause artefacts (Mikula and Munoz. Particles are also observed in the continuous aqueous phase exposed in the frozen emulsion samples.1 M and then standing for several days. suggesting aggregation of the excess particles.10 SEPTEMBER 2010 412 .Schematic representation of the effects of adding SDS to particle-stabilised emulsions. surfaces coated with close-packed particles are separated by particle-free regions.

In the future we will use rheological techniques to gain further insights into shear- induced destabilisation of 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. confirming the complete displacement of particles by surfactant molecules. The decrease in drop size indicates that surfactant molecules adsorb at the oil-water interface. effectively increasing the surface charge on the particles. The lower phase consisted of a low concentration of dispersed drops. During mixing. surfactant-stabilised drops form and the particles sediment out from the emulsions. The results shown here indicate that the addition of anionic surfactant can alter the stability of silica particle-stabilised emulsions (Whitby. 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. no change in the drop size after dilution. 2009). the (now) weakly attached particles readily detach. QLD. Staples. The unusual creaming behaviour observed on dilution at SDS concentrations above the cmc (Figure 4) is likely due to depletion of surfactant micelles. measurement of the emulsion drop sizes by light scattering and optical microscopy and electron microscopy imaging of the interfacial structure of the emulsions. 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.10 SEPTEMBER 2010 413 . presumably particles remain attached to the interface. the particles redisperse. At higher SDS concentrations. There is little evidence for surfactant adsorption onto the particle surfaces. It is important to note that surfactant concentrations above the cmc are required to stabilise drops in the absence of particles. 2000). Roux and Nallet (1991) found that surfactant-stabilised oil-in-water emulsions formed two phases at SDS concentrations above the cmc. Since the drops do not coalesce at low surfactant concentrations. Surfactant molecules adsorb at the fresh interface created by drop deformation. reducing the interfacial tension and enabling drops fragmentation. 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. This is due to competitive adsorption of the surfactant at the interface. In the presence of particles alone. At surfactant concentrations above the cmc. XXV INTERNATIONAL MINERAL PROCESSING CONGRESS (IMPC) 2010 PROCEEDINGS / BRISBANE. SDS readily adsorbs at pristine alkane-water interfaces (Cockbain. Due to the reduction in the Laplace pressure of the drops.EFFECT OF ANIONIC SURFACTANT ON SILICA PARTICLE ATTACHMENT AT THE OIL-WATER INTERFACE emulsions with dilute SDS solutions causes drop fragmentation. 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. The formation of a distinct cream layer could be reversed by gentle mixing. Presumably the attached particles hinder surfactant adsorption at the oil-water interface. the stress needed to deform and fragment drops decreases. The upper phase was a dense phase of aggregated drops. Presumably the surfactant molecules adsorb in conformations which expose the anionic head group to the aqueous solution. Bibette. Thus the enhanced flocculation of the particle-stabilised drops is not linked to surfactant adsorption at the emulsion interfaces. however. 2003). Bibette. The energy required to detach a particle. the interfacial tension decreases to about 10 mN m-1 at the cmc. 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. however. AUSTRALIA / 6 . In the presence of SDS. This suggests there is some adsorption of the surfactant at high surfactant concentrations (and also higher ionic strength). 1989) is about 103 times the typical Brownian thermal energy. There is. 1954. Fornasiero and Ralston. Mixing particle-stabilised emulsions at SDS concentrations above the cmc causes particles to displace from the oil-water interface (Figure 4). Penfold and Tucker. the interfacial tension is 51 mN m-1. which is given by πR2γow(1-cosθ)2 (Levine. Bowen and Partridge. Characterisation of these effects was achieved by visual inspection of bulk emulsion and foam stability. Thus drops are fragmented at low surfactant concentrations (Figure 4). After mixing at high surfactant concentrations particles were not observed at the interface. which exposes the particle- stabilised drops to the anionic surfactant. 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.

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