Pickering emulsions stabilized by surface-modified Fe3O4 nanoparticles

Unmodified Fe(3)O(4) nanoparticles do not stabilize Pickering emulsions of a polar oil like butyl butyrate. In order to obtain stable emulsions, the Fe(3)O(4) nanoparticles were modified by either carboxylic acid (RCOOH) or silane coupling agents (RSi(OC(2)H(5))(3)) to increase their hydrophobicity. The influence of such surface modification on the stability of the resultant Pickering emulsions was investigated in detail for both a non-polar oil (dodecane) and butyl butyrate in mixtures with water. The stability of dodecane-in-water emulsions in the presence of carboxylic acid-coated particles decreases as the length of the alkyl group (R) and the coating extent increase. However, such particles are incapable of stabilizing butyl butyrate-water emulsions even when the carboxylic acid length is decreased to two. However, the silane-coated Fe(3)O(4) nanoparticles can stabilize butyl butyrate-in-water emulsions, and they also increase the stability of dodecane-in-water emulsions. Thermal gravimetric analysis indicates that the molar quantity of silane reagent is much higher than that of carboxylic acid on nanoparticle surfaces after modification, raising their hydrophobicity and enabling enhanced stability of the resultant polar oil-water emulsions.     

Multiple phase inversion of emulsions stabilized by in situ surface activation of CaCO3 nanoparticles via adsorption of fatty acids

The in situ surface activation of raw CaCO(3) nanoparticles by interaction with a series of sodium carboxylates of chain length between 6 and 12 as well as sodium 2-ethylhexylsulfosuccinate (AOT) was studied, and the impact of this on the stabilization and phase inversion of toluene-water emulsions was assessed. By using complementary experiments including measurement of particle zeta potentials, adsorption isotherms of amphiphile, and relevant contact angles, the mechanism of this activation was revealed. The results show that hydrophilic CaCO(3) nanoparticles can be surface activated by interaction with sodium carboxylates and AOT even if they are not surface-active themselves. Both the electrostatic interaction between the positive charges on particle surfaces and the negative charges of anionic amphiphile headgroups and the chain-chain interactions of the amphiphile result in monolayer adsorption of the amphiphile at the particle-water interface. This transforms the particles from hydrophilic to partially hydrophobic such that they become surface-active and stabilize oil-in-water O/W(1) emulsions and induce O/W(1) → water-in-oil W/O phase inversion, depending on the chain length of the carboxylate molecules. At high amphiphile concentration, bilayer or hemimicelle adsorption may occur at the particle-water surface, rendering particles hydrophilic again and causing their desorption from the oil-water interface. A second phase inversion, W/O → O/W(2), may occur depending on the surface activity of the amphiphile. CaCO(3) nanoparticles can therefore be made good stabilizers of both O/W and W/O emulsions once surface activated by mixing with traces of suitable anionic amphiphile.     

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 effect of silica nanoparticles and charged surfactants in the formation and stability of submicron oil-in-water emulsions

The influence of hydrophilic silica nanoparticles on the emulsification of a triglyceride oil (Miglyol812) in the presence of charged surfactants (lecithin or oleylamine) and the long term stability of the resultant oil-in-water emulsions are reported. A synergistic effect of nanoparticles and surfactants in improving emulsification and stability to coalescence is evident only when the silica nanoparticles are initially added to the oil phase. When nanoparticles are included from the water phase, no synergistic stabilisation was observed due to electrostatic bridging or unfavourable attachment due to the repulsive electrostatic and hydration forces. Free energies of adsorption for silica nanoparticles at the oil-water interface calculated from experimentally determined interfacial tensions and three phase contact angles can be correlated to long-term emulsion stability only when silica is added from oil phase.     

颗粒乳化剂的研究及应用

近年来,颗粒乳化剂因其在食品、采油、化妆品、医药、催化以及功能纳米材料制备等领域具有潜在应用前景而备受关注。本文综述了近来颗粒乳化剂的研究进展,归纳了颗粒乳化剂的种类,包括:无机纳米粒子、表面改性或杂化的无机粒子、有机纳米粒子以及特殊的颗粒乳化剂Janus粒子;并对颗粒乳化剂能够在油水界面稳定吸附的热力学机理和动力学行为进行了阐述,颗粒乳化剂在油水界面接触角以及粒径大小是其在界面稳定吸附的关键参数,而颗粒在油水界面的排布方式则主要受粒子之间相互作用的影响。重点介绍了颗粒乳化剂的热点应用,包括:(1)利用颗粒乳化剂制备Pickering乳液,以及通过对颗粒乳化剂的功能化,使得Pickering乳液具备环境响应性(即pH、盐浓度、温度、紫外光、磁场敏感响应性);(2)以颗粒乳化剂为构筑基元、以Pickering乳液为模板制备Janus颗粒、Colloidosome、具有多级结构的粒子或膜,以及多孔结构材料;(3) Janus粒子在催化领域的应用。     

Amphiphilic polymers facilitated solid-phase extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry for direct extraction and analysis of zearalenone and zearalanone in corn juice samples

In this work, amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions are demonstrated to be capable of direct extracting zearalenone and zearalanone in samples consisting of an oil-water emulsion system. Under optimal conditions, the maximum adsorption capacities for zearalenone and zearalanone are 17.27 and 13.26 mg/g. The adsorption is mainly attributed to π-π interaction, hydrophobic interaction, and hydrogen-bonding interaction for zearalenone and zearalanone. The adsorption isotherms reveal that the adsorption of zearalenone and zearalanone on amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions follows Freundlich model with multilayer and heterogeneous adsorption due to the presence of multiple kinds of adsorption sites. The relative recoveries of the spiked zearalenone and zearalanone in corn juice samples range from 85% to 93% with relative standard deviations lower than 3.52%. The results manifest the high efficiency of amphiphilic polymers synthesized from carboxylated carbon nanotubes stabilized high internal phase emulsions for the adsorption and separation of analytes in the oil-water emulsion system. This study provides a new perspective on adsorbent engineering for the adsorption application in heterogeneous media.     

Macroporous polymers obtained in highly concentrated emulsions stabilized solely with magnetic nanoparticles

Magnetic macroporous polymers have been successfully prepared using Pickering high internal phase ratio emulsions (HIPEs) as templates. To stabilize the HIPEs, two types of oleic acid-modified iron oxide nanoparticles (NPs) were used as emulsifiers. The results revealed that partially hydrophobic NPs could stabilize W/O HIPEs with an internal phase above 90%. Depending upon the oleic acid content, the nanoparticles showed either an arrangement at the oil-water interface or a partial dispersion into the oil phase. Such different abilities to migrate to the interface had significant effects on the maximum internal phase fraction achievable and the droplet size distribution of the emulsions. Highly macroporous composite polymers were obtained by polymerization in the external phase of these emulsions. The density, porosity, pore morphology and magnetic properties were characterized as a function of the oleic acid content, concentration of NPs, and internal phase volume of the initial HIPEs. SEM imaging indicated that a close-cell structure was obtained. Furthermore, the composite materials showed superparamagnetic behavior and a relatively high magnetic moment.     

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.     

Symmetric and asymmetric adsorption of pH-responsive gold nanoparticles onto microgel particles and dispersion characterisation

The interaction between carboxylic acid-stabilised gold nanoparticles (AuNP) and pH-responsive microgels is shown. The microgel particles are a copolymer of N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) and N-isopropylacrylamide (NIPAM). The microgel properties are presented by their hydrodynamic diameter and electrophoretic mobility in response to pH. These microgel particles are pH-responsive under neutral conditions decreasing in diameter beyond pH 7. The dispersion characteristics of AuNP adsorbed onto the microgel network are shown with respect to adsorbed amount and the pH-responsive properties of the AuNP. This data is presented between pH 3 and 6 where the microgel properties remain constant. Asymmetric adsorption of AuNP onto poly(DMAPMA-co-NIPAM) microgels is achieved by adsorption of nanoparticles, from the aqueous phase, onto microgel-stabilised oil-in-water emulsions. These asymmetrically modified microgels display very different dispersion behaviour, in response to pH, due to their dipolar nature.     

Interactions of hydrophilic silica nanoparticles and classical surfactants at non-polar oil-water interface

The interfacial and bulk properties of submicron oil-in-water emulsions simultaneously stabilised with a conventional surfactant (either lecithin or oleylamine) and hydrophilic silica nanoparticles (Aerosil?380) were investigated and compared with emulsions stabilised by either stabiliser. Emulsions solely stabilised with lecithin or oleylamine showed poor physical stability, i.e., sedimentation and the release of pure oil was observed within 3 months storage. The formation and long-term stability of silica nanoparticle-coated emulsions was investigated as a function of the surfactant type, charge, and concentration; the oil phase polarity (Miglyol?812 versus liquid paraffin); and loading phase of nanoparticles, either oil or water. Highly stable emulsions with long-term resistance to coalescence and creaming were formulated even at low lecithin concentrations in the presence of optimum levels of silica nanoparticles. The attachment energy of silica nanoparticles at the non-polar oil-water interface in the presence of lecithin was significantly higher compared to oleylamine in line with good long-term stability of the former compared to the sedimentation and release of oil in the latter. The attachment energy of silica nanoparticles at the polar oil-water interface especially in the presence of oleylamine was up to five-times higher compared to the non-polar liquid paraffin. The interfacial layer structure of nanoparticles (close-packed layer of particle aggregates or scattered particle flocs) directly related to the free energy of nanoparticle adsorption at both MCT oil and liquid paraffin-water interfaces.     

SANS and SAXS analysis of charged nanoparticle adsorption at oil-water interfaces

A systematic study of the adsorption of charged nanoparticles at dispersed oil-in-water emulsion interfaces is presented. The interaction potentials for negatively charged hexadecane droplets with anionic polystyrene latex particles or cationic gold particles are calculated using DLVO theory. Calculations demonstrate that increased ionic strength decreases the decay length of the electrostatic repulsion leading to enhanced particle adsorption. For the case of anionic PS latex particles, the energy barrier for particle adsorption is also reduced when the surface charge is neutralized through changes in pH. Complementary small-angle scattering experiments show that the highest particle adsorption for PS latex occurs at moderate ionic strength and low pH. For cationic gold particles, simple DLVO calculations also explain scattering results showing that the highest particle adsorption occurs at neutral pH due to the electrostatic attraction between oppositely charged surfaces. This work demonstrates that surface charges of particles and oil droplets are critical parameters to consider when engineering particle-stabilized emulsions.     

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.     

On the thermodynamics of particle-stabilized emulsions: curvature effects and catastrophic phase inversion

The flexural properties of a particle adsorption monolayer are investigated theoretically. If the particles are not densely packed, the interfacial bending moment and the spontaneous curvature (due to the particles) are equal to zero. The situation changes if the particles are closely packed. Then the particle adsorption monolayer possesses a significant bending moment, and the interfacial energies of bending and dilatation become comparable. In this case, the bending energy can either stabilize or destabilize the Pickering emulsion, depending on whether the particle contact angle is smaller or greater than 90 degrees . Theoretical expressions are derived for the bending moment, for the curvature elastic modulus, and for the work of interfacial deformation and emulsification. The latter is dominated by the work for creation of a new oil-water interface and by the work for particle adsorption. The curvature effects give a contribution of second order, which is significant only for emulsification at 50:50 water/oil volume fractions. A thermodynamic criterion for the type of the formed emulsion is proposed. It predicts the existence of a catastrophic phase inversion in particle-stabilized emulsions, in agreement with the experimental observations. The derived theoretical expressions could find application for interpretation of experimental data on production and stability of Pickering emulsions.     

纳米SiO2与阳离子表面活性剂的相互作用及其诱导的正辛烷-水乳状液的双重相转变

研究了3种不同结构的水溶性阳离子表面活性剂对纳米二氧化硅颗粒的原位表面活性化作用, 它们分别是单头单尾的十六烷基三甲基溴化铵(CTAB)、单头双尾的双十二烷基二甲基溴化铵(di-C12DMAB)和双头双尾的Gemini型阳离子三亚甲基-二(十四酰氧乙基溴化铵)(II-14-3), 并通过测定Zeta电位、吸附等温线及接触角等参数对相关机理进行了阐述. 结果表明, 阳离子表面活性剂吸附到颗粒/水界面形成以疏水基朝向水的单分子层, 从而增强了颗粒表面的疏水性是原位表面活性化的基础. 通过吸附CTAB和II-14-3, 颗粒的疏水性适当增强, 能吸附到正辛烷/水界面稳定O/W(1)型乳状液; 而通过吸附di-C12DMAB所形成的单分子层更加致密, 颗粒的疏水性进一步增强, 进而使乳状液从O/W(1)型转变为W/O型; 当表面活性剂浓度较高时, 由于链-链相互作用, 表面活性剂分子将在颗粒/水界面形成双层吸附, 使颗粒表面变得亲水而失去活性, 但此时体系中游离表面活性剂的浓度已增加到足以单独稳定O/W(2)型乳状液的程度. 因此当采用纳米二氧化硅和di-C12DMAB的混合物作乳化剂时, 通过增加di-C12DMAB的浓度即可诱导乳状液发生O/W(1)→W/O→O/W(2)双重相转变.     

Magnetic Pickering emulsions stabilized by Fe3O4 nanoparticles

Superparamagnetic Fe(3)O(4) nanoparticles prepared by a classical coprecipitation method were used as the stabilizer to prepare magnetic Pickering emulsions, and the effects of particle concentration, oil/water volume ratio, and oil polarity on the type, stability, composition, and morphology of these functional emulsions were investigated. The three-phase contact angle (θ(ow)) of the Fe(3)O(4) nanoparticles at the oil-water interface was evaluated using the Washburn method, and the results showed that for nonpolar and weakly polar oils of dodecane and silicone, θ(ow) is close to 90°, whereas for strongly polar oils of butyl butyrate and 1-decanol, θ(ow) is far below 90°. Inherently hydrophilic Fe(3)O(4) nanoparticles can be used to prepare stable dodecane-water and silicone-water emulsions, but they cannot stabilize butyl butyrate-water and decanol-water mixtures with macroscopic phase separation occurring, which is in good agreement with the contact angle data. Emulsions are of the oil-in-water type for both dodecane and silicone oil, and the average droplet size increases with an increase in the oil volume fraction. For stable emulsions, not all of the particles are adsorbed to drop interfaces; the fraction adsorbed decreases with an increase in the initial oil volume fraction. Changes in the particle concentration have no obvious influence on the stability of these emulsions, even though the droplet size decreases with concentration.     

Conformational changes of α-lactalbumin adsorbed at oil-water interfaces: interplay between protein structure and emulsion stability

The conformation and structural dimensions of α-lactalbumin (α-La) both in solution and adsorbed at oil-water interfaces of emulsions were investigated using synchrotron radiation circular dichroism (SRCD) spectroscopy, front-face tryptophan fluorescence (FFTF) spectroscopy, and dual polarization interferometry (DPI). The near-UV SRCD and the FFTF results demonstrated that the hydrophobic environment of the aromatic residues located in the hydrophobic core of native α-La was significantly altered upon adsorption, indicating the unfolding of the hydrophobic core of α-La upon adsorption. The far-UV SRCD results showed that adsorption of α-La at oil-water interfaces created a new non-native secondary structure that was more stable to thermally induced conformational changes. Specifically, the α-helical conformation increased from 29.9% in solution to 45.8% at the tricaprylin-water interface and to 58.5% at the hexadecane-water interface. However, the β-sheet structure decreased from 18.0% in solution to less than 10% at both oil-water interfaces. The DPI study showed that adsorption of α-La to a hydrophobic C18-water surface caused a change in the dimensions of α-La from the native globule-like shape (2.5-3.7 nm) to a compact/dense layer approximately 1.1 nm thick. Analysis of the colloidal stability of α-La stabilized emulsions showed that these emulsions were physically stable against droplet flocculation at elevated temperatures both in the absence and in the presence of 120 mM NaCl. In the absence of salt, the thermal stability of emulsions was due to the strong electrostatic repulsion provided by the adsorbed α-La layer, which was formed after the adsorption and structural rearrangement. In the presence of salt, although the electrostatic repulsion was reduced via electrostatic screening, heating did not induce strong and permanent droplet flocculation. The thermal stability of α-La stabilized emulsions in the presence of salt is a combined effect of the electrostatic repulsion and the lack of covalent disulfide interchange reactions. This study reports new information on the secondary and tertiary structural changes of α-La upon adsorption to oil-water interfaces. It also presents new results on the physical stability of α-La stabilized emulsions during heating and at moderate ionic strength (120 mM NaCl). The results broaden our understanding of the factors controlling protein structural change at emulsion interfaces and how this affects emulsion stability.     

Oil-in-water emulsions stabilized by hydrophobically modified hydroxyethyl cellulose: adsorption and thickening effect

The preparation and stability of oil-in-water emulsions stabilized by hydrophobically modified hydroxyethyl cellulose (HMHEC) were investigated. The rheological measurements of aqueous HMHEC were studied. It was found that HMHEC showed much better thickening ability than the parent (HEC) from which it was derived, which is caused by the association of the hydrophobic alkyl chains, which are absent in HEC. The oscillatory experimental results of the emulsions showed that at higher concentrations, HMHEC could form an elastic gel, which has good thixotropic properties. The stability and droplet size distribution were investigated by visual observation, photomicrograph and a laser-scattering particle size distribution analyzer. The adsorption of HMHEC at the oil-water interface and the surface of emulsion droplets due to the penetration of the alkyl chains in HMHEC into the oil phase were confirmed by visual observation, the interfacial tension method and an in situ environmental scanning electron microscope (ESEM). The stability of emulsions prepared using HMHEC is based on both an associative thickening mechanism caused by alkyl chains in HMHEC and the adsorption of HMHEC at the oil-water interface, which can form a solid film preventing coalescence of the droplets.     

Structural rearrangement of β-lactoglobulin at different oil-water interfaces and its effect on emulsion stability

Understanding the factors that control protein structure and stability at the oil-water interface continues to be a major focus to optimize the formulation of protein-stabilized emulsions. In this study, a combination of synchrotron radiation circular dichroism spectroscopy, front-face fluorescence spectroscopy, and dual polarization interferometry (DPI) was used to characterize the conformation and geometric structure of β-lactoglobulin (β-Lg) upon adsorption to two oil-water interfaces: a hexadecane-water interface and a tricaprylin-water interface. The results show that, upon adsorption to both oil-water interfaces, β-Lg went through a β-sheet to α-helix transition with a corresponding loss of its globular tertiary structure. The degree of conformational change was also a function of the oil phase polarity. The hexadecane oil induced a much higher degree of non-native α-helix compared to the tricaprylin oil. In contrast to the β-Lg conformation in solution, the non-native α-helical-rich conformation of β-Lg at the interface was resistant to further conformational change upon heating. DPI measurements suggest that β-Lg formed a thin dense layer at emulsion droplet surfaces. The effects of high temperature and the presence of salt on these β-Lg emulsions were then investigated by monitoring changes in the ζ-potential and particle size. In the absence of salt, high electrostatic repulsion meant β-Lg-stabilized emulsions were resistant to heating to 90 °C. Adding salt (120 mM NaCl) before or after heating led to emulsion flocculation due to the screening of the electrostatic repulsion between colloidal particles. This study has provided insight into the structural properties of proteins adsorbed at the oil-water interface and has implications in the formulation and production of emulsions stabilized by globular proteins.     

Simple, reversible emulsion system switched by pH on the basis of chitosan without any hydrophobic modification

Chitosan without hydrophobic modification is not a good emulsifier itself. However, it has a pH-tunable sol-gel transition due to free amino groups along its backbone. In the present work, a simple reversible Pickering emulsion system based on the pH-tunable sol-gel transition of chitosan was developed. At pH > 6.0, as adjusted by NaOH, chitosan was insoluble in water. Chitosan nanoparticles or micrometer-sized floccular precipitates were formed in situ. These chitosan aggregates could adsorb at the interface of oil and water to stabilize the o/w emulsions, so-called Pickering emulsions. At pH < 6.0, as adjusted by HCl, chitosan was soluble in water. Demulsification happened. Four organic solvents (liquid paraffin, n-hexane, toluene, and dichloromethane) were chosen as the oil phase. Reversible emulsions were formed for all four oils. Chitosan-based Pickering emulsions could undergo five cycles of emulsification-demulsification with only a slight increase in the emulsion droplet size. They also had good long-term stability for more than 2 months. Herein, we give an example of chitosan without any hydrophobic modification to act as an effective emulsifier for various oil-water systems. From the results, we have determined that natural polymers with a stimulus-responsive sol-gel transition should be a good particulate emulsifier. The method for in situ formation of pH-responsive Pickering emulsions based on chitosan will open up a new route to the preparation of a wide range of reversible emulsions.     

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.