Journal of Colloid and Interface Science 301 (2006) 342345 www.elsevier.

com/locate/jcis

Note

Nanoparticle adsorption and stabilisation of surfactant-free emulsions

Catherine P. Whitby , Alex M. Djerdjev, James K. Beattie, Gregory G. Warr
School of Chemistry, University of Sydney, N.S.W. 2006, Australia Received 8 February 2006; accepted 20 April 2006 Available online 27 April 2006

Abstract The formation of particle-stabilised emulsions by adding partially hydrophobised silica particles to surfactant-free oil-in-water emulsions (average drop diameter 700 nm) stabilised by hydroxide ions adsorbed at the oilwater interface has been investigated. Nanoparticles (average particle diameter 18 nm) adsorbed onto the drops under alkaline conditions to produce particle-stabilised emulsions with the same drop size distribution as the surfactant-free emulsions. Unlike the surfactant-free emulsions, the particle-stabilised emulsions were stable even in acidic conditions. Strongly occulated nanoparticles (average particle diameter 150 nm) adsorbed onto the drop surfaces under acidic conditions where the emulsions were destabilised, forming coarser particle-stabilised emulsions with micron-sized drops. 2006 Elsevier Inc. All rights reserved.
Keywords: Particle-stabilised emulsion; Flocculation; Interface

The formation of particle-stabilised emulsions [1] has attracted considerable interest since it provides a route for the assembly of nanoparticles into, for example, capsules [2], porous solids [3] (after evaporation of the liquid phases) or networks of nanoparticle wires [4]. Typically, particle-stabilised emulsions are prepared by homogenisation of oil and water in the presence of particles. We report here an innovative stepwise approach to the formation of particle-stabilised emulsions. Dilute surfactant-free oil-in-water emulsions were prepared in the absence of particles [5]. Dispersions of nanoparticles were added to the emulsions and the particles adsorbed onto the drop surfaces. We have investigated the effect of adding weakly or strongly occulated nanoparticles on the emulsion stability to coalescence and the emulsion drop size. Adsorption of particles at the oilwater interface is thermodynamically favoured since the oilwater interfacial energy is larger than the difference between the particleoil and particle water interfacial energies [6]. Thus a particle will adsorb onto a drop if they collide with sufcient energy to cause drainage of the liquid lm between them. Particles that are preferentially wet by one liquid phase tend to adsorb less strongly than
* Corresponding author.

E-mail address: c.whitby@chem.usyd.edu.au (C.P. Whitby). 0021-9797/$ see front matter 2006 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2006.04.067

particles wet to an intermediate extent by both liquids [6]. During the preparation of particle-stabilised emulsions by the usual methods, drop formation and particle adsorption occur simultaneously. Extensive studies [1,713] have shown that the nal emulsion reects the combined effects of these processes, since drops bearing adsorbed particles may fragment, or coalesce during emulsication. The nal drop size is determined by the homogenisation power [7] and the particle concentration [810]. Although weakly occulated particles tend to stabilise emulsions more efciently [11,12], the interactions between particles at the oilwater interface can be different from those in the continuous phase and during homogenisation large ocs may fragment into smaller particles that stabilise drops [13]. The aim of this research was to investigate the effect of adsorbed nanoparticles on the structure and stability of surfactant-free emulsions. 2 vol% oil-in-aqueous 0.2 mM NaCl at pH 9 emulsions were prepared by emulsication in a high pressure homogeniser for six hours following the method described previously [5]. Milli-Q water with a conductivity of 18.2 M cm1 was used throughout. Dodecane (SigmaAldrich, 99%), hexadecane (SigmaAldrich, 99%), 1-bromododecane (SigmaAldrich, 98%) and 1-bromohexadecane (Merck, 96%) were puried by being passed through a column of chromatographic basic alumina at least twice.

C.P. Whitby et al. / Journal of Colloid and Interface Science 301 (2006) 342345

343

The dynamic mobility and size distribution of the emulsion droplets were measured in the ow-through cell of a prototype of the Colloidal Dynamics Acoustosizer-II. The size distribution of the emulsions (after dilution in alkaline water) was also measured by light scattering using a Malvern High Performance Particle Sizer 3.0. The alkane-in-water emulsions had monomodal drop size distributions. Surfactant-free emulsions prepared by agitation are usually polydisperse [14,15], however in the homogeniser the emulsion is forced through micron-sized slits under high pressure repeatedly, causing the drop size distribution to narrow since large drops are fragmented, while small drops are less affected [16]. The median drop diameter was about 740 nm for hexadecane-in-water emulsions and 650 nm for dodecane-in-water emulsions. The zeta potentials of the hexadecane drops (70 8) mV and the dodecane drops (80 10) mV at pH 9, were consistent with previous measurements [5,14]. The substantial negative charge of (nonpolar) oil drops in water is linked to the spontaneous adsorption of hydroxide ions at the oilwater interface [5,14]. When left at rest, the surfactant-free emulsions creamed very slowly. For drop volume fractions up to 0.05, the emulsions were stable to coalescence for several days due to the low frequency of drop collisions. The emulsions became unstable if the electrolyte concentration was increased above about 5 mM [5]. If the pH of the emulsions was lowered to pH 4 by the addition of a small volume of concentrated acid and the emulsions gently stirred, however, the emulsions became less turbid as the drop size increased due to coalescence. Creaming was not apparent (to the eye) as the drops became larger, however, release of oil from the emulsions was observed. The rate of destabilisation increased as the pH decreased. A layer of oil above the emulsions was observed within a few days at pH 4, while at pH 3.3 it was observed within several hours. This was reasonable since the charge generating species are hydroxide ions adsorbed from the water phase. The isoelectric point for these pristine oil drops is between pH 3 and 4 [5]. It might be assumed that at pH lower than the isoelectric point the drops would be re-stabilised, however, unlike occulation (which occurs in particle dispersions at the isoelectric point) drop coalescence is not reversible. In contrast, 2 vol% bromohexadecane (or bromododecane)in-water emulsions were unstable under alkaline conditions. Once homogenisation was halted, a small proportion of the oil phase rapidly separated from the emulsions. When left gently stirring, the remaining drops coarsened with time and more oil was released within a few days. This may be due to Ostwald ripening, as haloalkanes have higher solubilities in water than alkanes of the same chain length [17], or to coalescence, as fewer hydroxide ions may be adsorbed at the bromoalkane water interface. The effect of adding three types of silica particles to the alkaline surfactant-free emulsions, within a day of formation, was examined. A 37 vol% alkaline dispersion of silica particles treated with -glycidoxypropyltrimethoxysilane (BINDZIL CC40) was kindly provided by Peter Greenwood of Eka Chemicals. The primary particle diameter ranged from 5 to 30 nm as shown in Fig. 1a (a Philips CM120 Biolter transmission

Fig. 1. (a) TEM image of partially hydrophobised silica nanoparticles (BINDZIL CC40) as received. (b) Particle size distributions for 0.3 vol% BINDZIL CC40 () after separation of ocs, and for N20 (- - -) and SLM 160 ( ) silica particles dispersed in 0.2 mM NaCl at pH 9 from light scattering measurements.

electron microscope was used to image particles deposited on a carbon coated copper grid). The particle size distribution was bimodal (from light scattering) due to occulation. The large ocs were removed by centrifugation using a Beckman Optima L 100-XP S Ultracentrifuge with a Type 90 titanium rotor (average radius 55.4 mm) operated at 70 000 rpm for 45 min. The particles in the supernatant had a monomodal size distribution with an average diameter of 18 nm as shown in Fig. 1b. The average particle size was conrmed by Small Angle Neutron Scattering [18]. In 0.01 M NaCl at pH 8, the particles were weakly charged with a zeta potential of 26 mV. The isoelectric point of the particles was estimated to be pH 2 (from electroacoustics). Two samples of fumed silica particles (ex. Wacker Chemie) kindly provided by B.P. Binks (University of Hull) were also used, one unmodied (N20) and the other reacted with dichlorodimethylsilane to reduce the surface silanol content to 87% (SLM 160) [19]. The primary particle diameter in these samples ranged from 5 to 30 nm. Dispersions of both types of particles were formed by sonicating a known mass of powder in 0.2 mM NaCl using an ultrasonic processor (UP 200S Ultraschall prozessor, GmbH, tip diameter 7 mm) operated at 20 kHz and 20 W for 2 min while the dispersion was cooled in an icewater bath. The particles aggregated and the average aggregate diameter in the (monomodal) dispersions was about 170 nm

344

C.P. Whitby et al. / Journal of Colloid and Interface Science 301 (2006) 342345

Fig. 2. Drop size distributions for 2 vol% dodecane-in-water emulsions where the aqueous phase contained 0.2 mM NaCl and was at pH 9 () and after the pH of the aqueous phase of the emulsion had been adjusted to pH 3.5 and the emulsion left to stir for about 30 min ( ). Also shown are the drop size distributions for emulsions at pH 9 to which 0.3 vol% BINDZIL CC40 was added and the emulsion stirred overnight (- - -) and then the pH of the continuous phase was adjusted to pH 3.5 and the emulsion stirred for 4 h (- -). No peaks were observed at diameters lower than 200 nm.

(a)

for the hydrophilic (N20) particles and 150 nm for the partially hydrophobised (SLM 160) particles, as shown in Fig. 1b. Small volumes of the dispersion (<5 vol% of the emulsion) of partially hydrophobised silica nanoparticles (BINDZIL CC40) were added to the surfactant-free 2 vol% alkane-in-water emulsions and the mixtures gently stirred (at approximately 300 rpm). The electrolyte concentration in the emulsions increased to about 1 mM since the (alkaline) dispersion contained electrolyte but the emulsions remained stable. The stability of emulsions containing less than 0.2 vol% particles was similar to the surfactant-free emulsions, while at higher particle concentrations the emulsions remained stable for several weeks. This was attributed to the adsorption of particles onto drop surfaces. There would only be weak electrostatic repulsions between the particles and drops and the partially silanised particles may show anomalous instability at alkaline pH similar to hydrophillic silica particles [12]. For a particle concentration of 0.2 vol% it was calculated that there are sufcient particles for all the drops to be coated by a single layer of particles. As shown in Fig. 2, the emulsion drop size distribution was unchanged. To conrm there had been signicant particle adsorption, the pH of the emulsions was lowered to pH 3.3. Emulsions containing less than 0.2 vol% particles destabilised over about three days. The drop size in emulsions containing at least 0.2 vol% particles was unchanged, as shown in Fig. 2, and the emulsions remained stable to coalescence for a few weeks of gentle stirring. Only dilute dispersions of fumed hydrophilic (N20) and partially hydrophobised (SLM 160) silica particles could be prepared. Known volumes of the surfactant-free alkane-in-water emulsions and particle dispersions were gently mixed together so that the oil volume fraction in the emulsion was reduced (to 1 vol%). Under alkaline conditions, the emulsion stability to creaming and coalescence was not altered by the addition of the strongly occulated (hydrophilic or partially hydrophobised) particles. Separate peaks due to the particle ocs and the emulsion drops were observed in light scattering measurements, indicating that particle adsorption onto the drop surfaces was not signicant. When the pH of the emulsions was lowered to pH 3.3 and the emulsions gently stirred, they became less turbid, indicat-

(b) Fig. 3. Optical micrographs of 1 vol% dodecane-in-water emulsions containing (a) 0.3 vol% N20 and (b) 0.3 vol% SLM 160, after the pH of the aqueous phase of each emulsion (which contained 0.2 mM NaCl) had been adjusted to pH 3.3 and the mixtures left to stir gently for 3 days.

ing that the drops were coalescing together. Over time, however, the emulsions were observed to cream. Three days after acidication of emulsions containing 0.3 vol% of N20 particles, the average drop size in the emulsion was 10 m, as shown in Fig. 3a. These large drops continued to coalesce and oil was released from the emulsion. Three days after acidication of emulsions containing 0.3 vol% of SLM 160 particles, the average drop size was about 5 m and the drops were strongly occulated, as shown in Fig. 3b. The occulated drops remained stable to coalescence for several days. Clearly, once the oil drops began to coalesce, the drop size increased such that the larger ocs of particles could adsorb to a greater extent. In contrast, the addition of nanoparticles to bromohexadecane (or bromododecane)-in-water emulsions did not halt their destabilisation. Oil was released from these emulsions both in the presence and absence of particles. The addition of partially hydrophobised nanoparticles to preformed, sub-micron sized alkane-in-water emulsion drops stabilised by adsorbed hydroxide ions can enhance stability un-

C.P. Whitby et al. / Journal of Colloid and Interface Science 301 (2006) 342345

345

der some circumstances, and offers an alternate route to the preparation of particle-stabilised emulsions. Weakly occulated partially hydrophobised nanoparticles adsorbed onto the drop surfaces under alkaline conditions. Since the emulsions were only gently stirred, there was no further drop fragmentation or coalescence as the particles adsorbed and the nal drop size was not affected by the particle concentration. Above a minimum particle concentration, emulsion stability was substantially enhanced by particle adsorption. Strongly occulated nanoparticles did not readily adsorb onto the drop surfaces under alkaline conditions, due to the comparable sizes of the ocs and drops. This is consistent with observations [12] of the effect of particle occulation on emulsion formation by the usual methods. Particle adsorption only occurred after acidication allowed coarsening to a sufcient size and was presumably enhanced by weaker electrostatic repulsions between the particles and drops under acidic conditions. The adsorption of hydrophilic ocs only slowed coalescence, while adsorption of ocs of partially hydrophobised particles was sufcient to halt drop coalescence. This is consistent with ndings that particles of intermediate wettability adsorb strongly at the oilwater interface compared to hydrophilic particles [19]. Nanoparticle adsorption in surfactant-free emulsions has been studied previously in the context of polymer particle formation [20]. Those drops were formed by the base-catalysed hydrolysis and polymerisation of silanes and were electrostatically stabilised by anionically terminated siloxane chains formed during the drop synthesis [21]. In contrast, the method of emulsion formation described here is expected to be quite general as long as the oil is sparingly soluble in water so that the primary destabilisation mechanism is coalescence rather than ripening. Acknowledgments We thank D. Nguyen (University of Sydney) and R.B. Knott (ANSTO) for performing the TEM and SANS measurements,

respectively. C.P.W. acknowledges receipt of a Henry Bertie and Florence Mabel Gritton Postdoctoral Fellowship from the University of Sydney. This work was supported by the Australian Research Council. References
[1] R. Aveyard, B.P. Binks, J.H. Clint, Adv. Colloid Interface Sci. 100102 (2003) 503. [2] A.D. Dinsmore, M.F. Hsu, M.G. Nikolaides, M. Marquez, A.R. Bausch, D.A. Weitz, Science 298 (2002) 1006. [3] B.P. Binks, Adv. Mater. 14 (2002) 1824. [4] G. Ramanath, J. DArcy-Gall, T. Maddanimath, A.V. Ellis, P.G. Ganesan, R. Goswami, A. Kumar, K. Vijayamohanan, Langmuir 20 (2004) 5583. [5] J.K. Beattie, A.M. Djerdjev, Angew. Chem. Int. Ed. 43 (2004) 3568. [6] S. Levine, B.D. Bowen, S.J. Partridge, Colloids Surf. 38 (1989) 325. [7] B.P. Binks, J.A. Rodrigues, Langmuir 19 (2003) 4905. [8] R.M. Wiley, J. Colloid Sci. 9 (1954) 427. [9] B.R. Midmore, J. Colloid Interface Sci. 213 (1999) 352. [10] S. Arditty, C.P. Whitby, B.P. Binks, V. Schmitt, F. Leal-Calderon, Eur. Phys. J. E 11 (2003) 273. [11] B.R. Midmore, Colloids Surf. A 145 (1998) 133. [12] B.P. Binks, S.O. Lumsdon, Phys. Chem. Chem. Phys. 1 (1999) 3007. [13] B.P. Binks, C.P. Whitby, Langmuir 20 (2004) 1130. [14] K.G. Marinova, R.G. Alargova, N.D. Denkov, O.D. Velev, D.N. Petsev, I.B. Ivanov, R.P. Borwankar, Langmuir 12 (1996) 2045. [15] K. Kamogawa, T. Sakai, N. Momozawa, M. Shimazaki, M. Enomura, H. Sakai, M. Abe, J. Jpn. Oil Chem. Soc. 47 (1998) 159. [16] L. Kong, J.K. Beattie, R.J. Hunter, Chem. Eng. Proc. 40 (2001) 421. [17] A.L. Horvath, F.W. Getzen, J. Phys. Chem. Ref. Data 28 (1999) 649. [18] SANS measurements were performed on the AUSANS spectrometer at the Bragg Institute of the Australian Nuclear Science and Technology Organisation using neutrons with a wavelength of 3.5 and a sample to detector distance of 4.8 m, accessing a scattering angle range of 0.010.1 1 . Raw data were corrected for background and normalised to absolute values following ANSTO standard procedures. The data were analysed using National Institute for Standards and Technology SANS Analysis software. [19] B.P. Binks, S.O. Lumsdon, Langmuir 16 (2000) 8622. [20] C.A. Prestidge, T. Barnes, S. Simovic, Adv. Colloid Interface Sci. 108 109 (2004) 105. [21] T.M. Obey, B. Vincent, J. Colloid Interface Sci. 163 (1994) 454.