Professional Documents
Culture Documents
Short Communication
a r t i c l e
i n f o
a b s t r a c t
We have studied the stability and structure of emulsions formed in the presence of colloidal mixtures of partially hydrophobic titania particles and hydrophilic silica particles. On their own, the titania particles attached strongly to the oilwater interface and stabilised emulsions, while the silica particles did not attach to the interface. Adding silica particles to the titania dispersions enhanced coalescence processes during emulsion formation, except under mixing conditions that favoured particle heteroaggregation. The destabilisation of the emulsions was linked to the presence of silica particles in the particle layers at the interface. 2009 Elsevier Inc. All rights reserved.
Article history: Received 14 April 2009 Accepted 27 October 2009 Available online 30 October 2009 Keywords: Pickering emulsions Nanoparticle stabiliser Binary particle mixture Coalescence Heteroaggregation
1. Introduction Small particles present at interfaces in foams [1,2], oil recovery processes [3,4] and pharmaceutical formulations [5] can dramatically alter the stability and structure of these colloidal systems. Investigations of emulsions stabilised by a single kind of particle [6,7] revealed that the contact angle the particles make with the oilwater interface (how, the particle wettability) controls the equilibrium position of particles at uid interfaces and hence the type of emulsion formed [811]. Particles of intermediate wettability attach strongly to the oilwater interface, while particles which are completely wet by one liquid phase remain dispersed in that phase and do not stabilise emulsions. Particle attachment and hence emulsion stability tend to be optimal for weakly surface charged [12] and weakly occulated [13] particles. It is not obvious, however, how mixtures of particles of different charge or wettability will interact with drops. Briggs [14] observed the antagonistic effects of mixing hydrophobic (how > 90) and hydrophilic (how < 90) particles on emulsion formation. No emulsion was formed when equal amounts of the two particle types were mixed with water and kerosene [14]. Binks and Lumsdon [15] later demonstrated that it was possible to cause transitional phase inversion of toluenewater emulsions by mixing hydrophilic and hydrophobic silica nanoparticles. The type of emulsion formed depended on the ratio of hydrophilic to hydrophobic particles in the mixture and the initial location of
* Corresponding author. Fax: +61 8 8302 3683. E-mail addresses: Catherine.Whitby@unisa.edu.au (C.P. Whitby), Daniel.Forna siero@unisa.edu.au (D. Fornasiero), John.Ralston@unisa.edu.au (J. Ralston). 0021-9797/$ - see front matter 2009 Elsevier Inc. All rights reserved. doi:10.1016/j.jcis.2009.10.068
the particles. The average wettability of the particle mixture at the oilwater interface was assumed to vary with the proportion of hydrophobic particles in the mixture [16]. Lagaly and co-workers [1719] investigated emulsions formed by mixing aqueous dispersions of bentonite and dispersions of layered double hydroxides in oil. The oppositely charged particles heteroaggregated to form a network that stabilised oil drops [19]. Binks et al. [20] investigated emulsion formation from aqueous dispersions of oppositely charged, hydrophilic particles. Emulsions were only stabilised under conditions where the particles heteroaggregated. Binks et al. [20] argued that the heteroaggregates were hydrophobic, and thus attached to the drops [20,21]. In most studies of emulsions formed in the presence of particle mixtures, both types of particles in the mixtures could, on their own, stabilise emulsions. We have investigated emulsion formation in the presence of binary particle mixtures where only one type of particle was capable of stabilising emulsions. The nal emulsion structure provided clues to the origin of the signicant destabilisation of the emulsions that resulted.
2. Experimental section 2.1. Materials Dodecane (Sigma Aldrich, 99%) was passed through chromatographic alumina twice. The dodecanewater interfacial tension (51.9 0.2 mN m1) was consistent with previous measurements [22]. Drops of dodecane in pure aqueous electrolyte rapidly creamed and coalesced. Ultrapure water (resistivity P18.2 MX cm), calcium
206
C.P. Whitby et al. / Journal of Colloid and Interface Science 342 (2010) 205209
chloride (Ajax Finechem, 99%) and sodium hydroxide (Chem Supply, 97%) were used. The titania powder (partially coated with 10% aluminium oxide and 2.5% simethicone and kindly provided by Merck) consisted of needle-shaped particles, about 10 nm wide and 100 nm long (derived from transmission electron microscopy measurements, TEM). Hydrophilic, monodisperse spherical silica particles of three different sizes dispersed in concentrated alkaline suspensions were kindly provided by Nissan. The average particle diameter was 20, 63 or 140 nm (from TEM and dynamic light scattering). 2.2. Measurements of contact angles at solidoilwater interfaces The particle wettability (how) was estimated by measuring the advancing contact angle (Contact Angle System OCAH 200, DataPhysics Instruments) of water drops (0.01 M CaCl2 at pH 9.0) on solid substrates under dodecane or of oil drops on substrates in contact with water. The titania powder was compressed into at substrates and a clean glass slide was used as a model surface for the hydrophilic silica particles. 2.3. Dispersion and emulsion preparation and characterisation Titania dispersions (1 wt.%) were prepared by sonicating titania powder with the electrolyte solution (Soniclean Bath 160T, 70 W power, $44 kHz) for 30 min. Silica dispersions (1 wt.%) were prepared by diluting the concentrated, alkaline silica suspensions in aqueous electrolyte and tumbling the diluted dispersions end over end for 30 min to ensure complete mixing. The zeta potential of dilute particle dispersions was measured using the Malvern Zetasizer Nano. Batch emulsions were prepared by homogenising together dodecane and samples of the 1 wt.% titania dispersion and of the 1 wt.% silica dispersion using a X1030D homogeniser (Ingenieurbro CAT, M. Zipperer GmbH) with a 10 mm diameter shaft operated at 1300 rpm for 2 min. The stability of the emulsions at 24 C was determined by monitoring the emulsion appearance over time. After formation, the emulsion drop size distributions were examined by optical microscopy (Olympus BH2 Research microscope) and light scattering (Mastersizer, 2000). Cryo-scanning electron microscopy (cryo-SEM) images of some emulsions were obtained using a Philips XL30 eld emission scanning electron microscope tted with a CT1500 HR Low Temperature Cryo system following a similar method to that described by Binks and Kirkland [23]. 3. Results and discussion We investigated the stability and structure of 20 vol.% dodecane-in-water (0.01 M CaCl2 at pH 9) emulsions prepared in the presence of 1 wt.% mixtures of titania particles and silica particles in the aqueous phase. First, the behaviour of dispersions of each particle type was studied. The zeta potentials of the silica particles in 0.01 M CaCl2 at pH 9 were weakly negative ($14 mV). The adsorption of calcium ions onto silica surfaces increases abruptly at alkaline pH [24]. The particles sedimented and occulated out of the dispersions. Adsorption of metal ions can increase particle hydrophobicity [25], however the silica particles were completely wet by the aqueous phase (how was $5). In previous studies, alkane-in-water emulsions were stabilised by quartz particles after addition of low concentrations of calcium ions to increase the heteroaggregation of the particles and drops [26,27]. It has been shown, however, that adding 0.01 M calcium ions to alkaline silica nanoparticle dispersions causes homoaggregation to dominate and emulsions undergo rapid phase separation [28]. Consistent with these observations, we found that emulsions prepared from the
silica dispersions in 0.01 M CaCl2 at pH 9.0 underwent complete phase separation (100% coalescence) within a few hours. In contrast, emulsions prepared in the presence of 1 wt.% titania dispersions in 0.01 M CaCl2 at pH 9 did not coalesce for several months. The emulsion stability was consistent with other observations of emulsions stabilised by these particles [29]. The zeta
Fig. 1. Variation in the proportion of oil released (%fo) due to coalescence over 24 h from 20 vol.% dodecane-in-water (0.01 M CaCl2 at pH 9) emulsions stabilised by mixtures of titania and 20 nm diameter silica particles dispersed separately () and together (}), and from emulsions stabilised by mixtures of titania and 140 nm diameter silica particles dispersed separately (N) and together (4) with the concentration of titania particles in the aqueous phase ([TiO2]). The total particle concentration in the emulsions was 1 wt.% in the aqueous phase. Also shown is the variation in the proportion of oil released due to coalescence from emulsions stabilised by titania particles alone (s) with the concentration of titania particles in the aqueous phase. The lines are shown simply to guide the eye.
Fig. 2. Variation in the mean drop diameter (D(4,3)) of emulsions stabilised by mixtures of titania and 140 nm diameter silica particles dispersed separately (N) and together (4) with the concentration of titania particles in the aqueous phase. Also shown is the variation in the mean drop diameter of emulsions stabilised by titania particles alone (s) with the concentration of titania particles in the aqueous phase. The lines are shown simply to guide the eye. The average drop sizes were only measured for emulsions that were reasonably stable to coalescence.
C.P. Whitby et al. / Journal of Colloid and Interface Science 342 (2010) 205209
207
potentials of the titania particles in 0.01 M CaCl2 at pH 9 were weakly positive ($16 mV) and the titania particles occulated strongly and sedimented out of the dispersions. The titania particles were partially hydrophobic with advancing dodecanewater contact angles of about 93. Thus, unlike the silica particles, the titania particles attach strongly to the oilwater interface and stabilise emulsions. Previous studies showed that needle-shaped crystals cause coalescence, perhaps by rupturing the thin lms between drops at close separations [30]. The titania particles were not, however, sufciently hydrophobic for rupture to occur. In the presence of 1 wt.% titania particles, the emulsions had an average drop size of 50 lm. The drops were coated with several dense close-packed layers of titania particles (shown later). Emulsion formation consisted of fragmentation of the oil and then drop coalescence until the drop surfaces were sufciently coated with particles. The average drop size increased as the titania particle concentration was reduced. Oil was released from emulsions only at titania concentrations <0.1 wt.%. We next investigated emulsion formation from mixtures of titania and 20 nm diameter silica. The stability of mixed particle dispersions to aggregation depends on the difference in colloidal stability between the particle types [31,32]. The silica and titania dispersions each aggregated and most particles sedimented out from mixed dispersions (0.01 M CaCl2 at pH 9) left standing for 30 min. Since the particles were weakly oppositely charged, heteroaggregation of the silica and titania particles as well as homoaggregation occured in mixed particle dispersions. The particles were dispersed separately and only added together prior to emulsion formation to limit the opportunities for heteroaggregation prior to emulsication. Fig. 1 shows how the proportion of oil released by the emulsions varied with the particle mixture composition, as a function of the titania concentration. There appeared to be three stability regimes. Emulsions prepared from titania-rich mixtures consisted of drops (tens of micrometres in size) that released almost no oil. In the presence of mixtures of roughly equal weights of particles, the emulsions released up to 20% of the oil phase. Emulsions prepared from silica-rich mixtures released increasing amounts of oil as the proportion of silica in the mixture increased. Fig. 1 shows that for the same concentration of titania particles, emulsions prepared in the presence of mixtures of titania and 20 nm diameter silica were less stable. So the increasing emulsion instability was due mainly to the presence of the silica particles. There are at least two ways in which the silica particles would disrupt the formation of the titania particle layers coating the drops. During mixing, the presence of silica particles may hinder the approach of titania particles to the drop surfaces. Silica particles entrained by the drops [33] may alter the drop coalescence processes which the titania-stabilised drops normally undergo until the drops are sufciently coated by particles. Assuming that the needle-shaped titania particles attached parallel to the drop surfaces, the area occupied by a titania particle ($23 m2 g1 of particles) is comparable to the area in the particle layers which could be occupied by hexagonally close packed 20 nm silica particles (32 m2 g1) [34]. Fig. 1 shows that as the silica particle size in the mixtures increased (and the area that could be occupied by a given mass of silica particles decreased), larger concentrations of the silica particles were required to enhance drop coalescence. Irrespective of the silica particle size, similar variations in emulsion stability with mixture composition were observed. In the silica-rich regime, the volume of oil released was roughly proportional to the silica particle concentration. So the disruption to the particle layers dominated emulsion formation, causing a dramatic enhancement in coalescence. Examination of the emulsion structure by microscopy and light scattering revealed the effects of the coalescence processes. In the
presence of titania particles alone, the drop size distributions were log normal, consistent with a single population of drops. As shown in Fig. 2, the average emulsion drop size increased as the titania concentration decreased and hence the total interfacial area which could be stabilised decreased [35]. In the titania-rich regime, the emulsion drops were comparable in size to drops prepared at the same concentrations of titania particles alone, as shown by the example in Fig. 2. So there were insufcient silica particles to alter drop coalescence processes during emulsion formation. There was a sharp increase in the polydispersity of the drop size distributions in the residual emulsions for emulsions prepared in the intermediate stability regime. At 20 nm diameter silica particle
Fig. 3. Examples of optical micrographs of the sub-millimetre-sized drops in emulsions stabilised by mixtures of titania and 20 nm diameter silica particles dispersed separately. The concentration of titania was 0.8 wt.% (a) and 0.4 wt.% in the aqueous phase (b and c). The circle in (b) identies a cluster of particles and drops, an example of which is shown at higher magnication in (c). The scale bars correspond to 300 lm in the (a) and (b) images and 100 lm in (c).
208
C.P. Whitby et al. / Journal of Colloid and Interface Science 342 (2010) 205209
concentrations P0.2 wt.%, for example, the emulsion cream consisted of spherical, millimetre-sized drops separated by thick layers of white material. Optical microscopy images of the material showed that it contained drops, tens of micrometres in diameter, which increased in size as the silica particle concentration increased, as shown in Fig. 3a and b. The drop size polydispersity likely reected poor mixing of the silica and titania particles at the drop surfaces causing signicant variation in the stability of the interface to coalescence. Clusters of particulate material, within which small drops were trapped, were observed as shown in the higher magnication image in Fig. 3c. Emulsions prepared from mixtures of titania and larger silica particles had similar structures. These emulsions tended to release excess silica particles which sedimented as the drops creamed. The interfacial structure was examined using cryo-scanning electron microscopy. These measurements were restricted to emulsions in the titania-rich stability regime, which best survived the freezing process. In titania particle-stabilised emulsions, the
drops were coated by dense, close-packed layers of needle-shaped particles as shown in Fig. 4a. Energy dispersive X-ray analysis conrmed that the elemental composition of the particles was consistent with titania. For emulsions stabilised by mixtures of particles, there were silica particles in the interfacial particle layers, as shown by the example in Fig. 4b. The silica and titania were not well-mixed in the layer. Segregation in attached particle layers at planar interfaces was observed previously for particles of different size [36] or shape [37]. We observed, however, segregation even where the silica and titania particle size was comparable. The silica particles tended to be in the outside layers, closer to the water than the oil, as shown in Fig. 4c. In this stability regime, there were insufcient silica particles to signicantly affect titania particle attachment at the interface and alter coalescence processes during formation. So it is not unreasonable that the silica particles were located in the outside layers in the nal emulsion structure. It could be argued that particle heteroaggregation was occurring in these emulsions although the silica and titania particles
Fig. 4. SEM images of the interfacial layer in emulsions stabilised by mixtures of titania and 140 nm diameter silica particles. The concentration of titania was 1 wt.% (a) and 0.8 wt.% (b, c and d). The particles were dispersed separately and only mixed together just prior to homogenisation (b,c) or dispersed together (d). Images (a,b and d) show the internal surface of a drop and the dark areas are holes in the particle layer. Image (c) shows the external surface of a drop. The scale bars correspond to 1 lm. The arrows (b, c and d) point towards spherical silica particles in the layer.
C.P. Whitby et al. / Journal of Colloid and Interface Science 342 (2010) 205209
209
were dispersed separately. Some mixed dispersions were prepared by sonicating titania and silica particles together in 0.01 M CaCl2 at pH 9 for 30 min. Emulsions that released almost no oil formed over a wider range of mixture compositions for the various silica particle sizes, as shown in Fig. 1. The average drop size was slightly smaller than those stabilised by the corresponding concentration of titania particles alone, as shown in Fig. 2. Some aggregation of particles and small drops was observed in emulsions prepared from mixtures of titania and 20 nm diameter silica particles (similar to that observed when the particles were dispersed separately). The emulsion drops coalesced only at very low titania concentrations. Thus heteroaggregation produced mixtures with an average wettability that was optimal for drop stabilisation. Consistent with these observations, cryo-SEM images of the emulsions showed that the silica and titania particles appeared to be better mixed in the attached particle layers on the drops (Fig. 4d). These results conrmed that particle heteroaggregation did not have a major role in emulsion formation where the titania and silica particles were dispersed separately. 4. Conclusions We have investigated the structure and stability of oil-in-water emulsions prepared from mixtures of partially hydrophobised titania particles and hydrophilic silica particles. On their own, the titania particles attached strongly to the oilwater interface, while the silica particles remained completely wet by the aqueous phase. During mixing in the presence of both particle types, silica particles were entrapped in the titania particle layer attached to the drops. At low silica concentrations, there were sufcient titania particles attached to limit coalescence. Intermediate silica concentrations disrupted the attachment of the titania particles, so highly polydisperse drops formed. High silica concentrations hindered the formation of the titania particle layers to the extent that coalescence dominated emulsion formation. These results indicate the importance of controlling aggregation and attachment in emulsion and foams containing mixtures of particles. In future experiments we will investigate the effects of aggregation in particle mixtures on dispersion and emulsion rheology and on attachment at planar interfaces. Acknowledgments The nancial support of the Australian Research Council Linkage Scheme, AMIRA International, and State Governments of South
Australia and Victoria, is gratefully acknowledged. We thank Dr. P. Self (Adelaide Microscopy, The University of Adelaide) for performing the freeze fracture-SEM experiments. CPW is grateful to R. Sedev (The University of South Australia) for useful discussions. References
[1] U.T. Gonzenbach, A.R. Studart, E. Tervoort, L.J. Gauckler, Angew. Chem., Int. Ed. 45 (2006) 3526. [2] J. Ralston, D. Fornasiero, R. Hayes, Int. J. Miner. Process. 56 (1999) 133. [3] G. Gu, Z. Zhou, Z. Xu, J.H. Masliyah, Colloids Surf. A 215 (2003) 141. [4] C. Tsamantakis, J. Masliyah, A. Yeung, T. Gentzis, J. Colloid Interface Sci. 288 (2005) 129. [5] E. Melzera, J. Kreuter, R. Daniels, Eur. J. Pharm. Biopharm. 56 (2003) 23. [6] R. Aveyard, B.P. Binks, J.H. Clint, Adv. Colloid Interface Sci. 100102 (2003) 503. [7] C. Prestidge, T. Barnes, S. Simovic, Adv. Colloid Interface Sci. 108109 (2004) 105. [8] S. Levine, B.D. Bowen, S.J. Partridge, Colloids Surf. A 38 (1989) 325. [9] P. Finkle, H.D. Draper, J.H. Hildebrand, J. Am. Chem. Soc. 45 (1923) 2780. [10] B.P. Binks, S.O. Lumsdon, Langmuir 16 (2000) 8622. [11] N. Yan, M.R. Gray, J.H. Masliyah, Colloids Surf. A 97 (2001) 193. [12] S. Simovic, C.A. Prestidge, Langmuir 19 (2003) 8364. [13] B.P. Binks, S.O. Lumsdon, Phys. Chem. Chem. Phys. 1 (1999) 3007. [14] T.R. Briggs, J. Ind. Eng. Chem. 13 (1921) 1008. [15] B.P. Binks, S.O. Lumsdon, Langmuir 16 (2001) 3748. [16] D. Diggins, L.G.J. Fokkink, J. Ralston, Colloids Surf. 44 (1990) 299. [17] S. Abend, N. Bonnke, U. Gutschner, G. Lagaly, Colloid Polym. Sci. 276 (1998) 730. [18] U. Neuhusler, A. Abend, C. Jacobsen, G. Lagaly, Colloid Polym. Sci. 277 (1999) 719. [19] S. Abend, G. Lagaly, Clay Miner. 36 (2001) 557. [20] B.P. Binks, W. Liu, J.A. Rodgrigues, Langmuir 24 (2008) 4443. [21] H.-J. Tsai, Y.-L. Lee, Langmuir 23 (2007) 12687. [22] R. Aveyard, D.A. Haydon, Trans. Faraday Soc. 61 (1965) 2255. [23] B.P. Binks, M. Kirkland, Phys. Chem. Chem. Phys. 2 (2002) 3724. [24] R.O. James, T.W. Healy, J. Colloid Interface Sci. 40 (1972) 42. [25] W. Wu, R.F. Giese, C.J. van Oss, Colloids Surf. A 89 (1994) 241. It should be noted that the measured advancing contact angles on the untreated glass powders (49.4) are unusually high. [26] E. Kusaka, Y. Nakahiro, T. Wakamatsu, Int. J. Miner. Process. 41 (1994) 257. [27] M. Cao, W. Gan, Q. Liu, J. Colloid Interface Sci. 310 (2007) 489. [28] B.P. Binks, C.P. Whitby, Colloids Surf. A 253 (2005) 105. [29] S. Stiller, H. Gers-Barlag, M. Lergenmueller, F. Pucker, J. Schulz, K.P. Wittern, R. Daniels, Colloids Surf. A 232 (2004) 261. [30] M.A.J.S. van Boekkel, P. Walstra, Colloids Surf. A 3 (1981) 109. [31] B. Vincent, C.A. Young, T.F. Tadros, Faraday Discuss. Chem. Soc. 65 (1978) 296. [32] R.H. Pugh, in: J.S. Laskowski, J. Ralston (Eds.), Colloid Chemistry in Mineral Processing, Elsevier, Amsterdam, 1992, p. 243. [33] W.J. Trahar, L.J. Warren, Int. J. Miner. Process. 3 (1976) 103. [34] A rectangular solid shape was assumed for the titania particles. Densities of 2.2 g/cm3 and 4.2 g/cm3 were assumed for the silica and titania nanoparticles, respectively. [35] S. Arditty, C.P. Whitby, B.P. Binks, V. Schmitt, F. Leal-Calderon, Eur. Phys. J. E 11 (2003) 273. [36] H. Xu, M. Lask, J. Kirkwood, G.G. Fuller, Langmuir 23 (2007) 4837. [37] M.G. Basavaraj, G.G. Fuller, J. Fransaer, J. Vermant, Langmuir 22 (2006) 6605.