Core-shell-structured silica/polyacrylate particles prepared by Pickering emulsion: influence of the nucleation model on particle interfacial organization and emulsion stability
© Ji et al.; licensee Springer. 2014
Received: 21 August 2014
Accepted: 20 September 2014
Published: 29 September 2014
This work reports a new evidence of the versatility of silica sol as a stabilizer for Pickering emulsions. The organization of silica particles at the oil-water interface is a function of the nucleation model. The present results show that nucleation model, together with monomer hydrophobicity, can be used as a trigger to modify the packing density of silica particles at the oil-water interface: Less hydrophobic methylmethacrylate, more wettable with silica particles, favors the formation of core-shell-structured composite when the composite particles are prepared by miniemulsion polymerization in which monomers are fed in batch (droplet nucleation). By contrast, hydrophobic butylacrylate promotes the encapsulating efficiency of silica when monomers are fed dropwise (homogeneous nucleation). The morphologies of polyacrylate-nano-SiO2 composites prepared from different feed ratio of methylmethacrylate/butylacrylate (with different hydrophobicity) and by different feed processes are characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques. The results from SEM and TEM show that the morphologies of the as-prepared polyacrylate/nano-SiO2 composite can be a core-shell structure or a bare acrylic sphere. The stability of resulting emulsions composed of these composite particles is strongly dependent on the surface coverage of silica particles. The emulsion stability is improved by densely silica-packed composite particles.
Since the emulsion stabilized by only fine solid particles, as described in 1907 , these so-called Pickering emulsions have been obtained with a wide variety of organic or mineral powders [2–12]. Very strong anchoring energy and specific interparticle interactions at interfaces are at the origin of peculiar properties of solid stabilized emulsions. Some general rules concerning solid-stabilized emulsions arise from different studies reported in the literatures [13, 14]. Energy of attachment of a particle to a liquid-liquid interface is related to the interfacial tension ΥOW and the particle contact angle θ at the interface. The energy needed to remove a particle of radius b from this interface is estimated using E = πb2ΥOW (1 ± cos(θ))2, where b is the particle radius, γ is the interfacial tension, and ϑ is the contact angle measured across the aqueous phase . The minus sign is for removal into the water phase and the plus sign is for removal into the oil phase. The maximum stability of particles at the oil-water interface is attained at 90°. To adsorb at an interface, particles need to be partly wetted by both phases. The relative balance between hydrophilic and lipophilic properties of these particles is considered to be the most important parameter governing the creation and stabilization of such emulsions [13, 14].
Obviously, the affinity between inorganic (silica particle) and organic (polymers) components plays an important role in combining silica and polymeric particles, and it can be improved by modifying the surface of silica particles with coupling agents or by utilizing electrostatic attractions and/or an acid-base interaction [16–22]. To avoid the supplementary modifying stage made for silica particles, some previous experiments used unmodified solid particles to stabilize the emulsion under carefully controlled conditions. Arditty et al.  indicated that the surface coverage of particles increased with the increasing of the mixing intensity. Furthermore, they used different oils, with the viscosities ranging from 10 to 350 cP, to prepare the solid-stabilized emulsions, but found no apparent effect of o/w ratio on the generation of the emulsions. Hey  further proposed that the stability of o/w Pickering emulsion using highly viscous oils was closely related to the processing time. Since the viscous force within the oil droplets can create resistance to particle penetration into the interface, the viscosity of dispersed phase acts as a damping factor for a particle anchoring at the o/w interface and plays an important role during the emulsification process . M. J. Percy and S. P. Armes [26–28] employed three different ultrafine alcoholic silica sols, with neither surface pretreatments nor auxiliary comonomers required, to successfully prepare colloidally stable inorganic/organic hybrid particles. R.F.A. Teixeira  discussed the hybrid ‘soft’ polymer latexes armored with Laponite XLS clay discs. The experiment showed that although the use of monomers that had high water solubility and was prone to hydrolyze under basic conditions would result in complete microcoagulation, the use of small amounts of methacrylic acid as auxiliary monomer promoted clay adhesion to the surface of the particles in the Pickering emulsion (co)polymerization of hydrophobic monomers.
Actually, if the preparing conditions (such as the viscosity of dispersed phase , the relative balance between hydrophilic and lipophilic properties of these particles [30–32], the polar compatibility  between dispersed and dispersing phases, the pH values of aqueous solutions , etc.) are right, untreated inorganic particles can be thermodynamically adsorbed to and anchored in the surface of the polymer particles, thus forming the core-shell-structured composite particles.
Inspired by the works of Hey , we investigate the effects of the glass-transition temperature Tg (i.e., viscosity of the growing particles) of growing polymer particles and the monomer mixture hydrophobicity on the anchorage of silica particles in the polymer by varying the mass ratio of MMA/BA. It is found that the effect of wetting ability of acrylic monomers on silica adsorption is not always consistent with the model  proposed by Hey and S. Levine for solid-stabilized emulsions. The anchorage of silica particles in the polymer also depends on the feeding processes of monomers. In the Pickering emulsion polymerization, the feeding process, dropwise or in batch, determines the types of initially prepared emulsion (i.e., the emulsion of a colloidal suspension of latex particles or of a colloidal suspension of monomer droplets), which thereby forms a conventional emulsion or a miniemulsion, respectively. The droplets in a miniemulsion are typically in the range of 100 ~ 500 nm in diameter, which are depended on the intensity of ultrasonication. The small droplet size and the consequent large droplet surface area result in most of the silica particles being adsorbed to the monomer droplets. As no surfactant is available to form micelles and stabilize aqueous phase particle nucleation, there is little or no micellar or homogeneous nucleation [33, 34]. In contrast to the homogeneous nucleation of the conventional emulsion, the monomer droplets become the primary locus of particle nucleation, and droplet nucleation is predominant in miniemulsion. Different nucleation models may lead to different behaviors in viscosity of the growing particles and in hydrophobicity of monomers during the polymerization processes. Consequently, the characteristics of the final composite particles may be affected by the nucleation models. In this paper, we not only discuss the effects of feed mass ratios of MMA/BA (with varied monomer hydrophobicity) on the formation of the core-shell structure of the resulting composite particles, but also explain why the effect of wetting ability of acrylic monomers on silica adsorption is not always consistent with the model proposed by Hey and S. Levine from the nucleation mechanism perspective. Finally, we discuss how the morphologies of the composite particles influence the stability of emulsions. Understanding this mechanism is fundamental in designing composite emulsions with desired properties.
Silica sol, obtained from Beijing Xingdaxin Corporation, is 10 ~ 20-nm silica nanoparticles dispersed in an aqueous solution. The silica concentration is 30% by weight. Anionic initiator potassium peroxydisulfate (KPS) and acrylate monomer: methyl merthacrylate (MMA), butyl acrylate (BA) were purchased from Sinopharm Chemical Reagent Co., Ltd. All materials were used as received.
Synthesis of polyacrylate-silica composite particles
Polyacrylate-silica composite emulsion was prepared by two different methods, which were adopted as follows: 1) the mixture of water and aqueous silica sol were agitated mechanically for 20 min, and subsequently, the solution was degassed with nitrogen gas and kept in nitrogen atmosphere. When the temperature was raised to 78°C, monomers were added dropwise into the system, and the initiator solution was added to initiate the polymerization simultaneously. 2) The nano-SiO2 sol mixed with acrylic monomers was ultrasonically dispersed into water for 60 min in the ice bath to produce a stable Pickering or miniemulsion, in which there was a colloidal suspension of monomer droplets stabilized by silica particles. The resultant Pickering emulsion was poured into a 100-ml three-neck flask equipped with a nitrogen inlet and a reflux condenser. The emulsion was agitated mildly and polymerized at 78°C for 8 h. The dropwise and in-bulk feeding ways of monomers were also designated as method 1 and method 2, respectively. Before characterization, samples were diluted with water for transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The emulsion sample was centrifuged at 12,000 rpm for 5 min, and the sediment was isolated from supernatant for thermogravimetric (TG) measurement.
Characterizations and contact angle measurements
A FE-JSM-6701 F SEM (JEOL, Akishima-shi, Japan) and TEM (Hitachi H-800, Hitachi, Tokyo, Japan) were used to observe the morphologies of polyacrylate/silica composite particles. The average particle diameter and the particle size distribution were measured using the dynamic light scattering technique (DLS) (Nano ZS90, Malvern, Worcestershire, UK). Before TG measurement, the samples were placed in vacuum for 24 h at 60°C and then purged by nitrogen gas.
Mixtures of MMA and BA, their mass ratios ranging from 3/1 to 1/3, were used for contact angle measurements. Liquid monomer droplets were dripped carefully onto the sample surface which was covered by a membrane derived from silica sol, and the average value of five measurements, made at different positions of the same sample, was adopted as the average values of contact angles of the substrates. The error of the mean contact angle values, calculated as the standard deviation, did not exceed 2° and 3°. Tilt angle was measured using a contact angle goniometer (JC-2000C2 China).
Results and discussion
Since the surface of unmodified silica is hydrophilic, it is expected to stabilize the oil/water emulsion polymerization. According to the following relationship: E = πb2ΥOW (1 ± cos (θ))2, 90° is the angle corresponding to the maximum energy value necessary to move the particle in which it is preferably wetted . As MMA is more hydrophilic than BA, the acrylic oligomers prepared should become more compatible with hydrophilic silica with the increase of mass ratio of MMA/BA. Thus, more silica particles are expected to be incorporated in the composite particles according to the above model .
However, the compatibility of hydrophilic silica with acrylic monomers varies with the types of initially prepared emulsion (i.e., an emulsion of a colloidal suspension of latex particles or of a colloidal suspension of monomer droplets) which result from different feed processes. It is expected that the packing density of the silica particles at the oil-water interface can be controlled by the feeding process.
The summary of different acrylate/silica nanocomposite synthesis
Feed of SiO2(wt.%)
Solid content (%)
Stability of emulsion
Contact angle (θ)c
Effect of the MMA/BA on the polymer’s affinity with the silica
MMA/BA (mass ratio)
Content of silica (%)
As indicated above, the adsorption of silica particles is at the polymer-water interface, and the composite emulsion is a colloidal suspension of latex particles stabilized by silica particles. Therefore, besides the silica's affinity with polyacrylate segment, the intrinsic viscoelasticity of the latex particles is another influencing factor on the anchorage of silica particles.
The polymer particles prepared with different mass ratios of MMA/BA have varied glass transition temperature (Tg). As the mass ratio of MMA/BA is increased, the Tg of the dispersed phase (aggregation of primary particles) increases due to more MMA incorporated therein, and the as-prepared polymer particle behaves like a rigid solid. This leads to believe that the viscosity of polymer particles or viscous forces within the growing particles can create resistance to silica particle penetration into the growing polymeric particles. When the mass ratio of MMA/BA is increased to 2/1, the viscosity of polymer particles, acting as a damping factor to silica particle penetration, is up to a point where it will eventually become a barrier to silica particle penetration. Furthermore, the active precursors or primary particles of MMA/BA of 2/1 are more hydrophilic and more compatible with aqueous system, and they can be stabilized by themselves rather than by silica particles. Therefore, it is not necessary for polyacrylic particles to absorb silica particles for their stability. In this case, the adsorption is ruled by the intrinsic viscous forces within the growing particles rather than the hydrophobicity of the polymeric segments.
Stability of polyacrylate latex, composite latex, and polyacrylate/12% SiO 2 blend latex
MMA/BA (mass ratio)
Blend of acrylic emulsionb and silica sol
In summary, core-polyacrylate/shell-silica nanocomposite particles are synthesized by simple soap-free emulsion polymerization employing negatively charged silica sol. It is found that the formation of polyacrylate (core)-silica (shell)-structured composite particles is obviously influenced by either the wettability of acrylic monomers or the viscosity of the dispersed phase (i.e., polymeric particles in growth), and their impacts on the morphologies of composite particles depend on the nucleation models of polymer which is also determined by feeding processes of monomers. Less hydrophobic MMA favors the formation of core-shell structures when prepared by way of feeding in bulk (droplet nucleation). By contrast, the hydrophobic monomer BA incorporated improves the encapsulation of silica particles due to the lower Tg thus lowering the resistance to penetration of the silica particles when the monomers are fed dropwise (homogeneous nucleation). The results derived from TEM and SEM technologies show that the morphologies of the as-prepared acrylate/nano-SiO2 composites of different feed ratio of MA/BA change from core-shell structure to bare acrylic spheres as the increase of feed ratio of MMA/BA. It can be concluded that the oil-water interfacial tension, contact angle and the viscosity of disperse phase provide criteria for the formation of core-shell structure. The composite emulsion with well core-shell-structured particles is stable. The control of the organization of silica particles at the interface can modify emulsion end-use properties.
This work is supported by the National Natural Science Funds (Grant Nos. 51273016 and 51125007).
- Pickering SU: Emulsions. J Chem Soc Trans 1907, 91: 2001–2021.View ArticleGoogle Scholar
- Kaewsaneh C, Tangboriboonrat P, Polpanich D, Eissa M, Elaissari A: Preparation of Janus colloidal particles via Pickering emulsion: an overview. Colloids Surf A Physicochem Eng Asp 2013, 439: 35–42.View ArticleGoogle Scholar
- Sauzedde F, Elaissari A, Pichot C: Hydrophilic magnetic polymer latexes. 1-Adsorption of magnetic iron oxide nanoparticles onto various cationic latexes. Colloid Polym Sci 1999, 277: 846–855. 10.1007/s003960050461View ArticleGoogle Scholar
- Xiao Q, Tan X, Ji L, Xue J: Preparation and characterization of polyaniline/nano-Fe3O4composites via a novel Pickering emulsion route. Synth Met 2007, 157: 784–791. 10.1016/j.synthmet.2007.08.010View ArticleGoogle Scholar
- He Y, Yu X: Preparation of silica nanoparticle-armored polyaniline microspheres in a Pickering emulsion. Mater Lett 2007, 61: 2071–2074. 10.1016/j.matlet.2006.08.018View ArticleGoogle Scholar
- Chen T, Colver PJ, Bon SAF: Organic–inorganic hybrid hollow spheres prepared from TiO2-stabilized Pickering emulsion polymerization. Adv Mater 2007, 19: 2286–2289. 10.1002/adma.200602447View ArticleGoogle Scholar
- Voorn DJ, Ming W, van Herk AM: Polymer − clay nanocomposite latex particles by inverse pickering emulsion polymerization stabilized with hydrophobic montmorillonite platelets. Macromolecules 2006, 39: 2137–2143. 10.1021/ma052539tView ArticleGoogle Scholar
- He Y: A novel emulsion route to sub-micrometer polyaniline/nano-ZnO composite fibers. Appl Surf Sci 2005, 249: 1–6. 10.1016/j.apsusc.2004.11.061View ArticleGoogle Scholar
- Sullivan AP, Kilpatrick PK: The effects of inorganic solid particles on water and crude oil emulsion stability. Ind Eng Chem Res 2002, 41: 3389–3404. 10.1021/ie010927nView ArticleGoogle Scholar
- Binks BP, Lumsdon SO: Catastrophic phase inversion of water-in-oil emulsions stabilized by hydrophobic silica. Langmuir 2000, 16: 2539–2547. 10.1021/la991081jView ArticleGoogle Scholar
- Giermanska-Kahn J, Schmitt V, Binks BP, Leal-Calderon F: A new method to prepare monodisperse pickering emulsions. Langmuir 2002, 18: 2515–2518. 10.1021/la0111809View ArticleGoogle Scholar
- He Y: Preparation of polyaniline/nano-ZnO composites via a novel Pickering emulsion route. Powder Technol 2004, 147: 59–63. 10.1016/j.powtec.2004.09.038View ArticleGoogle Scholar
- Binks BP: Particles as surfactants—similarities and differences. Colloid Interface Sci 2002, 20(7):21–41.View ArticleGoogle Scholar
- Aveyard R, Binks BP, Clint JH: Emulsions stabilised solely by colloidal particles. Adv Colloid Interface Sci 2003, 100: 503–546.View ArticleGoogle Scholar
- Levine S, Bowen BD, Partridge SJ: Stabilization of emulsions by fine particles. I. Partitioning of particles between continuous phase and oil/water interface. Colloids Surf A 1989, 38: 325–343. 10.1016/0166-6622(89)80271-9View ArticleGoogle Scholar
- Zhang K, Wu W, Meng H, Guo K, Chen J-F: Pickering emulsion polymerization: preparation of polystyrene/nano-SiO2 composite microspheres with core-shell structure. Powder Technol 2009, 190: 393–400. 10.1016/j.powtec.2008.08.022View ArticleGoogle Scholar
- Freris I, Cristofori D, Riello P, Benedetti A: Encapsulation of submicrometer-sized silica particles by a thin shell of poly(methyl methacrylate). J Colloid Interface Sci 2009, 311: 351.View ArticleGoogle Scholar
- Feng L: Grafting poly(methyl methacrylate) onto silica nanoparticle surfaces via a facile esterification reaction. Mater Chem Phys 2009, 16: 158–163.View ArticleGoogle Scholar
- Lee J, Chang Kook H: Synthesis of polystyrene/silica composite particles by soap-free emulsion polymerization using positively charged colloidal silica. J Colloid Interface Sci 2007, 310: 112–120. 10.1016/j.jcis.2006.11.008View ArticleGoogle Scholar
- Chen M, Limin W: A novel preparation method of raspberry-like PMMA/SiO2 hybrid microspheres. Macromolecules 2005, 38: 6411–6417. 10.1021/ma050132iView ArticleGoogle Scholar
- Percy MJ, Barthetm C, Lobb JC, Khan MA, Armes SP: Synthesis and characterization of vinyl polymer − silica colloidal nanocomposites. Langmuir 2000, 16: 6913. 10.1021/la0004294View ArticleGoogle Scholar
- Chen M, Zhou S, You B, Wu L: Synthesis of raspberry-like PMMA/SiO2 nanocomposite particles via a surfactant-free method. Macromolecules 2004, 37: 9613–9619. 10.1021/ma048431fView ArticleGoogle Scholar
- Arditty S, Whitby CP, Binks BP, Schmitt V, Leal-Calderon F: Some general features of limited coalescence in solid-stabilized emulsions. Eur Phys J E 2003, 11(3):273–281. 10.1140/epje/i2003-10018-6View ArticleGoogle Scholar
- Hey MJ, Kingston JG: Maximum stability of a single spherical particle attached to an emulsion drop. J Colloid Interface Sci 2006, 298(1):497–499. 10.1016/j.jcis.2005.12.002View ArticleGoogle Scholar
- Fournier C-O, Fradette L, Tanguy PA: Effect of dispersed phase viscosity on solid-stabilized emulsions. Chem Eng Res Des 2009, 87: 499–506. 10.1016/j.cherd.2008.11.008View ArticleGoogle Scholar
- Percy MJ, Armes SP: Surfactant-free synthesis of colloidal poly(methyl methacrylate)/silica nanocomposites in the absence of auxiliary comonomers. Langmuir 2002, 18(12):4562–4565. 10.1021/la020158sView ArticleGoogle Scholar
- Percy MJ, Amalvy JI, Randall DP, Armes SP: Synthesis of vinyl polymer − silica colloidal nanocomposites prepared using commercial alcoholic silica sols. Langmuir 2004, 20(6):2184–2190. 10.1021/la035868sView ArticleGoogle Scholar
- Fielding LA, Jeff T, Armes SP: All-acrylic film-forming colloidal polymer/silica nanocomposite particles prepared by aqueous emulsion polymerization. Langmuir 2011, 27: 11129–11144. 10.1021/la202066nView ArticleGoogle Scholar
- Teixeira RFA, McKenzie HS, Boyd AA, Bon SAF: Pickering emulsion polymerization using laponite clay as stabilizer to prepare armored “soft” polymer latexes. Macromolecules 2011, 44(18):7415–7422. 10.1021/ma201691uView ArticleGoogle Scholar
- Frelichowska J, Bolzinger MA, Chevalier Y: Pickering emulsions with bare silica. Colloids Surf A Physicochem Eng Aspects 2009, 343: 70–74. 10.1016/j.colsurfa.2009.01.031View ArticleGoogle Scholar
- Colver PJ, Colard CAL, Bon SAF: Multilayered nanocomposite polymer colloids using emulsion polymerization stabilized by solid particles. J Am Chem Soc 2008, 130(50):16850–16851. 10.1021/ja807242kView ArticleGoogle Scholar
- Colard CAL, Teixeira RFA, Bon SAF: Unraveling mechanistic events in solids-stabilized emulsion polymerization by monitoring the concentration of nanoparticles in the water phase. Langmuir 2010, 26(11):7915–7921. 10.1021/la904817fView ArticleGoogle Scholar
- Asua JM: Miniemulsion polymerization. Prog Polym Sci 2002, 27: 1283–1346. 10.1016/S0079-6700(02)00010-2View ArticleGoogle Scholar
- Schork FJ, Poehlein GW, Wang S, Reimers J, Rodrigues J, Samer C: Miniemulsion polymerization. Colloids Surf A Physiochemical Eng Aspects 1999, 153: 39–45. 10.1016/S0927-7757(98)00424-5View ArticleGoogle Scholar
- Jing J, Shi S, Feng W: Revisit to the self-assembled hybrid acrylate/silica core-shell structured particles in the presence of unmodified silica particles. Colloids Surf A Physicochem Eng Asp 2014, 5: 156–162.Google Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited.