Nanoparticle adsorption and stabilisation of surfactant-free emulsions

The formation of particle-stabilised emulsions by adding partially hydrophobised silica particles to surfactant-free oil-in-water emulsions (average drop diameter approximately 700 nm) stabilised by hydroxide ions adsorbed at the oil-water 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 flocculated 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.     

Synergistic stabilization of emulsions by a mixture of surface-active nanoparticles and surfactant

The stability and rheology of tricaprylin oil-in-water emulsions containing a mixture of surface-active hydrophilic silica nanoparticles and pure nonionic surfactant molecules are reported and compared with those of emulsions stabilized by each emulsifier alone. The importance of the preparation protocol is highlighted. Addition of particles to a surfactant-stabilized emulsion results in the appearance of a small population of large drops due to coalescence, possibly by bridging of adsorbed particles. Addition of surfactant to a particle-stabilized emulsion surprisingly led to increased coalescence too, although the resistance to creaming increased mainly due to an increase in viscosity. Simultaneous emulsification of particles and surfactant led to synergistic stabilization at intermediate concentrations of surfactant; emulsions completely stable to both creaming and coalescence exist at low overall emulsifier concentration. Using the adsorption isotherm of surfactant on particles and the viscosity and optical density of aqueous particle dispersions, we show that the most stable emulsions are formed from dispersions of flocculated, partially hydrophobic particles. From equilibrium contact angle and oil-water interfacial tension measurements, the calculated free energy of adsorption E of a silica particle to the oil-water interface passes through a maximum with respect to surfactant concentration, in line with the emulsion stability optimum. This results from a competition between the influence of particle hydrophobicity and interfacial tension on the magnitude of E.     

Synergistic interaction in emulsions stabilized by a mixture of silica nanoparticles and cationic surfactant

Using a range of complementary experiments, a detailed investigation into the behavior of dodecane-water emulsions stabilized by a mixture of silica nanoparticles and pure cationic surfactant has been made. Both emulsifiers prefer to stabilize o/w emulsions. At high pH, particles are ineffective emulsifiers, whereas surfactant-stabilized emulsions become increasingly stable to coalescence with concentration. In mixtures, no emulsion phase inversion occurs although synergism between the emulsifiers leads to enhanced stability at either fixed surfactant concentration or fixed particle concentration. Emulsions are most stable under conditions where particles have negligible charge and are most flocculated. Freeze fracture scanning electron microscopy confirms the presence of particle flocs at drop interfaces. At low pH, particles and surfactant are good emulsifiers alone. Synergism is also displayed in these mixtures, with the extent of creaming being minimum when particles are most flocculated. Experiments have been undertaken in order to offer an explanation for the latter synergy. By determining the adsorption isotherm of surfactant on particles in water, we show that surfactant addition initially leads to particle flocculation followed by re-dispersion. Using suitable contact angle measurements at oil-water-solid interfaces, we show that silica surfaces initially become increasingly hydrophobic upon surfactant addition, as well as surfactant adsorption lowering the oil-water interfacial tension. A competition exists between the influence of surfactant on the contact angle and the tension in the attachment energy of a particle to the interface.     

Effects of pH and salt concentration on oil-in-water emulsions stabilized solely by nanocomposite microgel particles

Aqueous dispersions of lightly cross-linked poly(4-vinylpyridine)/silica nanocomposite microgel particles are used as a sole emulsifier of methyl myristate and water (1:1 by volume) at various pH values and salt concentrations at 20 degrees C. These particles become swollen at low pH with the hydrodynamic diameter increasing from 250 nm at pH 8.8 to 630 nm at pH 2.7. For batch emulsions prepared at pH 3.4, oil-in-water (o/w) emulsions are formed that are stable to coalescence but exhibit creaming. Below pH 3.3, however, these emulsions are very unstable to coalescence and rapid phase separation occurs just after homogenization (pH-dependent). The pH for 50% ionization of the pyridine groups in the particles in the bulk (pK(a)) was determined to be 3.4 by acid titration measurements of the aqueous dispersion. Thus, the charged swollen particles no longer adsorb at the oil-water interface. For continuous emulsions (prepared at high pH with the pH then decreased abruptly or progressively), demulsification takes place rapidly below pH 3.3, implying that particles adsorbed at the oil-water interface can become charged (protonated) and detached from the interface in situ (pH-responsive). Furthermore, at a fixed pH of 4.0, addition of sodium chloride to the aqueous dispersion increases the degree of ionization of the particles and batch emulsions are significantly unstable to coalescence at a salt concentration of 0.24 mol kg(-1). The degree of ionization of such microgel particles is a critical factor in controlling the coalescence stability of o/w emulsions stabilized by them.     

Interfacial properties of emulsions stabilized with surfactant and nonsurfactant coated boehmite nanoparticles

The properties of emulsions stabilized with surface-modified boehmite particles of 26 and 8 nm in diameter have been investigated. The surface-modified particles were prepared by mixing aqueous dispersions of cationic boehmite particles with aqueous solutions of the surfactant p-dodecylbenzenesulfonic acid (DBSA) or the nonsurfactant p-toluenesulfonic acid (TSA). For the 26 nm particles, interfacial tension measurements indicate that p-dodecylbenzenesulfonic acid partitions between the particle surface and the oil-water interface, while p-toluenesulfonic acid remains on the particle surface. The partitioning of p-dodecylbenzenesulfonic acid supports the formation of emulsions, although in the absence of the particles the same surfactant concentration is not sufficient for emulsion stabilization. Due to the fast exchange kinetics, p-dodecylbenzenesulfonic acid is gradually replaced by particles. At equilibrium, the interfacial tension in the presence of the surface-modified particles is between the values for the pure particles and the pure surfactant solutions. However, the interfacial tension is independent of the surfactant concentration used in the preparation of the particles. Reducing the particle size to 8 nm leads to increased emulsion stability, and thus, the minimum particle concentration required to prepare stable emulsions was reduced to 0.1 g/L. However, above approximately 3.5 mmol/L of the sulfonic acids, the small particles dissolve slowly, and the emulsion stability is lost. This mechanism can be used to trigger the collapse of the emulsions.     

固体粒子稳定的乳状液研究进展

综述了固体粒子对乳状液稳定性影响的有关研究进展。微细不溶的固体粒子构成重要的一类乳化剂,被水相和油相部分润湿的固体粒子能够有效地稳定乳状液。固体粒子稳定乳状液的效果取决于以下因素:粒子大小、粒子间相互作用和粒子的润湿性质。固体粒子存在的油-水界面表现出粘弹行为,这种粘弹界面膜可大大地提高空间位阻,减缓乳状液液珠间液膜变薄的速率,从而提高乳状液地稳定性。原油中的粘土、胶质、沥青质和石蜡等胶体粒子被证明对乳状液的稳定性起很大的作用。     

Synergetic Effect of Reactive Surfactants and Clay Particles on Stabilization of Nonaqueous Oil-in-Oil (o/o) Emulsions

Although surfactants and particles are often used together in stabilization of aqueous emulsions, the contribution of each species to such stabilization at the oil-water interface is poorly understood. The situation becomes more complicated if we consider the nonaqueous oil-oil interface, i.e, the stabilization of nonaqueous oil-in-oil (o/o) emulsions by solid particles and reactive surfactants which, to our knowledge, has not been studied before. We have prepared Pickering nonaqueous simple (o/o) emulsions stabilized by a combination of kaolinite particles and a nonionic polymerizable surfactant Noigen RN10 (polyoxyethylene alkylphenyl ether). Different pairs of immiscible oils were used which gave different emulsion stabilities. Using kaolinite with equal volumes of paraffin oil/formamide system gave no stable emulsions at all concentrations while the addition of Noigen RN10 enhanced the emulsion stability. In contrast, addition of Noigen RN10 surfactant to silicon oil-in-glycerin emulsions stabilized by kaolinite resulted in destabilization of the system at all concentrations. For all systems studied here, no phase inversion in simple emulsion was observed by altering the volume fraction of the dispersed phase as compared to the known water-based simple Pickering emulsions.      

A stable AKD-in-water emulsion: Stabilized by MSG-modified laponite nanoparticle

Alkyl ketene dimmer (AKD) is widely used in papermaking industry, which is applied in form of o/w emulsion to increase paper water-resistance. In this paper, AKD-in-water emulsions were prepared by monosodium glutamate (MSG)-modified laponite. The aggregation, surface charge, and hydrophobicity of the laponite particles in aqueous dispersion were changed by the MSG and the properties of the as-prepared emulsions were varied correspondingly. When the MSG concentration is 2?mmol/g, AKD emulsion with small droplet size, high storage stability, and high sizing efficiency is obtained. The morphology, droplet diameter and distribution, storage stability and sizing efficiency of the AKD-in-water emulsion were investigated.     

Latex-particle-stabilized emulsions of anti-Bancroft type

Here, we investigate water-in-oil (W/O) emulsions that are stabilized by polystyrene latex particles with sulfate surface groups. The particles, which play the role of emulsifier, are initially contained in the disperse (water) phase. The existence of such emulsions formally contradicts the empirical Bancroft rule. Theoretical considerations predict that the drop diameter has to be inversely proportional to the particle concentration, but should be independent of the volume fraction of water. In addition, there should be a second emulsification regime, in which the drop diameter is determined by the input mechanical energy during the homogenization. The existence of these two regimes has been experimentally confirmed, and the obtained data agree well with the theoretical model. Stable W/O emulsions have been produced with hexadecane and tetradecane, while, in the case of more viscous and polar oils (soybean and silicone oil), the particles enter into the oily phase, and Pickering emulsions cannot be obtained. The formation of stable emulsions demands the presence of a relatively high concentration of electrolyte that lowers the electrostatic barrier to particle adsorption at the oil-water interface. Because the attachment of particles at the drop surfaces represents a kind of coagulation, it turns out that the Schulze-Hardy rule for the critical concentration of coagulation is applicable also to emulsification, which has been confirmed with suspensions containing Na(+), Mg(2+), and Al(3+) counterions. The increase of the particle and electrolyte concentrations and the decrease of the volume fraction of water are other factors that facilitate emulsification in the investigated system. To quantify the combined action of these factors, an experimental stability-instability diagram has been obtained.     

Comparison of alkenyl succinic anhydride emulsions stabilized by laponite modified with ethylamine,diethylamine and triethylamine

The modifications of laponite particles with three short amines, that is, ethylamine, diethylamine and triethylamine, were compared and the amine-modified laponites were used to stabilize alkenyl succinic anhydride emulsions. The results show that the emulsion stability can be improved while the emulsion droplet size can be reduced by using the amines to modify laponite particles. Among the three amines, the diethylamine exerts the largest while the triethylamine exerts the smallest effects on the zeta potential of laponite, the turbidity of laponite aqueous dispersion and the emulsion stability and morphology. The emulsion with the smallest droplet size shows the highest sizing performance.     

Pickering emulsions stabilized solely by layered double hydroxides particles: the effect of salt on emulsion formation and stability

The formation and stability of liquid paraffin-in-water emulsions stabilized solely by positively charged plate-like layered double hydroxides (LDHs) particles were described here. The effects of adding salt into LDHs dispersions on particle zeta potential, particle contact angle, particle adsorption at the oil-water interface and the structure strength of dispersions were studied. It was found that the zeta potential of particles gradually decreased with the increase of salt concentration, but the variation of contact angle with salt concentration was very small. The adsorption of particles at the oil-water interface occurred due to the reduction of particle zeta potential. The structural strength of LDHs dispersions was strengthened with the increase of salt and particle concentrations. The effects of particle concentration, salt concentration and oil phase volume fraction on the formation, stability and type of emulsions were investigated and discussed in relation to the adsorption of particles at the oil-water interface and the structural strength of LDHs dispersions. Finally, the possible stabilization mechanisms of emulsions were put forward: the decrease of particle zeta potential leads to particle adsorption at the oil-water interface and the formation of a network of particles at the interface, both of which are crucial for emulsion formation and stability; the structural strength of LDHs dispersions is responsible for emulsion stability, but is not necessary for emulsion formation.     

Effect of charged colloidal particles on adsorption of surfactants at oil-water interface

A change of oil/water interfacial tension in the presence of cationic or anionic surfactants in an organic phase was observed due to the addition of charged fine solids in the aqueous phase. The charged fine solids in the aqueous phase adsorb surfactants diffused from the oil phase, thereby causing an increase in the bulk equilibrium surfactant concentration in the aqueous phase, governed by the Stern-Grahame equation. Consequently, surfactant adsorption at the oil-water interface increases, which was demonstrated from the measured reduction of the oil-water interfacial tension. The increased surfactant partition in the aqueous phase in the presence of the charged particles was confirmed by the measured decrease in the surface tension for the collected aqueous solution after solids removal, as compared with the cases without solids addition.     

Effect of electrolyte in silicone oil-in-water emulsions stabilised by fumed silica particles

Partially hydrophobised fumed silica particles are used to make silicone oil-in-water emulsions at natural pH of the aqueous phase. The stability and rheological properties of the emulsions and suspensions are studied at NaCl concentrations in the range 0-100 mM. It is found that all emulsions are very stable to coalescence irrespective of the NaCl concentration. However, a strong effect of electrolyte on the creaming and rheological properties is observed and linked to the particle interactions in aqueous suspensions. The creaming rate and extent are large at low electrolyte concentrations but both abruptly decrease at salt concentrations exceeding the critical flocculation concentration of the suspension (approximately 1 mM NaCl). The drastic improvement of the stability to creaming is attributed to the formation of a visco-elastic three-dimensional network of interconnected particles and emulsion droplets.     

Ion partitioning at the oil-water interface as a source of tunable electrostatic effects in emulsions with colloids

We present a combined experimental and theoretical investigation of the surprisingly strong electrostatic effects that can occur in mixtures of low- and high-polar liquids (e.g. oil-water emulsions), here in the presence of colloidal particles. For our experiments, we used confocal microscopy imaging, supplemented with electrophoresis and conductivity measurements. Theoretically, we studied our systems by means of a modified Poisson-Boltzmann theory, which takes into account image charge effects and the electrostatic self-energies of the micro-ions in the different dielectric media. Our results show that the unequal partitioning of micro-ions between the two liquid phases is the common driving force behind most of the observed electrostatic effects. The structural signatures of these effects typically develop on a time scale of hours to days and are qualitatively well-described by our theory. We demonstrate how the partitioning process and its associated phenomena can be controlled by shifting the balance of the interlocked ionic dissociation and partitioning equilibria. Moreover, we present strong experimental proof that the two-dimensional colloidal crystals at the oil-water interface are due to long-ranged Coulombic repulsion through the oil phase. The acquired insight in the role of electrostatics in oil-water emulsions is important for understanding the interactions in particle-stabilized ('Pickering') and charge-stabilized emulsions, emulsion production, encapsulation and self-assembly.     

Effects of Surface Properties on Rheological and Interfacial Properties of Pickering Emulsions Prepared by Fumed Silica Suspensions Pre-Adsorbed Poly(N-Isopropylacrylamide)

The hydrophobic fumed silica suspensions physically pre-adsorbed poly(N-isopropylacrylamide) (PNIPAM) in water could prepare oil dispersed in water (O/W) Pickering emulsion by mixing of silicone oil. The resulting Pickering emulsions were characterized by the measurements of volume factions of emulsified silicone oil, adsorbed amounts of the silica suspensions, oil droplet size, and some rheological responses, such as stress-strain sweep curve and dynamic viscoelastic moduli as a function of the added amount of PNIPAM. Moreover, their characteristics were compared with those of the O/W Pickering emulsions prepared by the hydrophilic fumed silica suspensions pre-adsorbed PNIPAM. For the emulsions prepared by the hydrophobic silica suspensions, an increase in the added amount of PNIPAM led to (1) a decrease in the volume fraction of the emulsified oil in the emulsified phase, (2) both the size of oil droplets and the adsorbed amount of the corresponding silica suspensions being almost constant, except for the higher added amounts, and (3) both the storage modulus (G′) and the yield shear strain being constant. The term of 1 is the same for the emulsions prepared by the hydrophilic silica suspensions, whereas both the adsorbed amount of the corresponding silica suspension and the G′ value increase and both the droplet size and the yield shear strain decrease with an increase in the added amount of PNIPAM. The differences between the rheological properties of the emulsions prepared by the hydrophilic silica suspensions and those by the hydrophobic ones are attributed to the hydrophobic interactions of the flocculated silica particles in the Pickering emulsions.     

Hydroxyapatite nanoparticles as stimulus-responsive particulate emulsifiers and building block for porous materials

Hydroxyapatite (HAp) nanoparticles with spherical, rod-shaped or fiber-shaped morphologies were synthesized by wet chemical method in aqueous media. Scanning electron microscopy, dynamic light scattering, helium pycnometry, and aqueous electrophoresis techniques were used to characterize the nanoparticles in terms of their particle size and morphology, density and zeta potential, respectively. Stable "Pickering-type" emulsions were prepared using the HAp nanoparticles as a particulate emulsifier and methyl myristate as an oil phase above pH 7.7, but not below pH 6.1. These emulsions were characterized in terms of their emulsion type, mean droplet diameter and morphology using electrical conductivity, light diffraction and optical microscopy. Rapid demulsification could be induced by lowering the solution pH: addition of acid led to dissolution of the HAp nanoparticles attached on oil-water interface and the emulsion was destabilized. HAp nanoparticles precipitated by addition of base to the aqueous phase after demulsification and the HAp particles precipitated worked as an effective particulate emulsifier. This emulsification-demulsification cycle was reversible. Sintering of methyl myristate-in-water emulsion stabilized with the HAp nanoparticles led to a porous HAp material.     

Microstructure of beta-lactoglobulin-stabilized emulsions containing non-ionic surfactant and excess free protein: influence of heating

The influence of the non-ionic surfactant Tween 20 on the microstructure of beta-lactoglobulin-stabilized emulsions with substantial excess free protein present was investigated via confocal microscopy. The separate distributions of oil droplets and protein were determined using two different fluorescent dyes. In the emulsion at ambient temperature the excess protein and protein-coated oil droplets were associated together in a reversibly flocculated state. The pore-size distribution of the initial flocculated emulsion was found to depend on the surfactant/protein ratio R, and at higher values of R the system became more inhomogeneous due to areas of local phase separation. Evidence for competitive displacement of protein from the oil-water interface by surfactant was obtained only on heating (from 25 to 85 degrees C) during the process of formation of a heat-set emulsion gel. By measuring fluorescence intensities of the protein dye inside and outside of the oil-droplet-rich areas, we have been able to quantify the evolving protein distribution during the thermal processing. The results are discussed in relation to previous work on the competitive adsorption of proteins and surfactants in emulsions and the effect of emulsion droplets on the rheology of heat-set protein gels.     

Stabilization of oil-in-water emulsions by colloidal particles modified with short amphiphiles

Emulsions stabilized through the adsorption of colloidal particles at the liquid-liquid interface have long been used and investigated in a number of different applications. The interfacial adsorption of particles can be induced by adjusting the particle wetting behavior in the liquid media. Here, we report a new approach to prepare stable oil-in-water emulsions by tailoring the wetting behavior of colloidal particles in water using short amphiphilic molecules. We illustrate the method using hydrophilic metal oxide particles initially dispersed in the aqueous phase. The wettability of such particles in water is reduced by an in situ surface hydrophobization that induces particle adsorption at oil-water interfaces. We evaluate the conditions required for particle adsorption at the liquid-liquid interface and discuss the effect of the emulsion initial composition on the final microstructure of oil-water mixtures containing high concentrations of alumina particles modified with short carboxylic acids. This new approach for emulsion preparation can be easily applied to a variety of other metal oxide particles.     

Naturally occurring spore particles at planar fluid interfaces and in emulsions

We have investigated the potential of utilizing naturally occurring spore particles of Lycopodium clavatum as sole emulsifiers of oil and water mixtures. The preferred emulsions, prepared from either oil-borne or aqueous-borne dispersions of the monodispersed particles of diameter 30 microm, are oil-in-water. The particles act as efficient stabilizers for oils of different polarity. Droplets as large as several millimeters are stable to coalescence indefinitely, despite the low coverage of interfaces by particles observed microscopically. Consistent with the emulsion findings, we discover that particles spontaneously adsorb to bare oil-water interfaces of single drops from oil dispersions, whereas adsorption is less spontaneous and extensive from aqueous dispersions. Monolayers of the spore particles at both air-water and oil-water planar interfaces contain particles in an aggregated state forming clusters and chains. The influence of particle concentration, oil/water ratio, and additives in the aqueous phase is studied.     

Influence of microgel architecture and oil polarity on stabilization of emulsions by stimuli-sensitive core-shell poly(N-isopropylacrylamide-co-methacrylic acid) microgels: Mickering versus Pickering behavior?

Charged poly(N-isopropylacrylamide-co-methacrylic acid) [P(NiPAM-co-MAA)] microgels can stabilize thermo- and pH-sensitive emulsions. By placing charged units at different locations in the microgels and comparing the emulsion properties, we demonstrate that their behaviors as emulsion stabilizers are very different from molecular surfactants and rigid Pickering stabilizers. The results show that the stabilization of the emulsions is independent of electrostatic repulsion although the presence and location of charges are relevant. Apparently, the charges facilitate emulsion stabilization via the extent of swelling and deformability of the microgels. The stabilization of these emulsions is linked to the swelling and structure of the microgels at the oil-water interface, which depends not only on the presence of charged moieties and on solvent polarity but also on the microgel (core-shell) morphology. Therefore, the internal soft and porous structure of microgels is important, and these features make microgel-stabilized emulsions characteristically different from classical, rigid-particle-stabilized Pickering emulsions, the stability of which depends on the surface properties of the particles.