Pickering emulsions stabilized by hydrophilic nanoparticles: in situ surface modification by oil

We propose a novel route for the stabilization of oil-in-water Pickering emulsions using inherently hydrophilic nanoparticles. In the case of dialkyl adipate oils, in situ hydrophobisation of the particles by dissolved oil molecules in the aqueous phase enables stable emulsions to be formed. Emulsion stability is enhanced upon decreasing the chain length of the oil due to its increased solubility in the precursor aqueous phase. The oil thus acts like a surfactant in this respect in which hydrogen bonds form between the carbonyl group of the ester oil and the hydroxyl group on particle surfaces. The particles chosen include both fumed and precipitated anionic silica and cationic zirconia. Complementary experiments including relevant oil–water–solid contact angles and infra-red analysis of dried particles after contact with oil support the proposed mechanism

Collodial particles at a range of fluid-fluid particles

The study of solid particles residing at fluid-fluid interfaces has become an established area in surface and colloid science recently experiencing a renaissance since around 2000. Particles at interfaces arise in many industrial products and processes like anti-foam formulations, crude oil emulsions, aerated foodstuffs and flotation. Although they act in many ways like traditional surfactant molecules, they offer distinct advantages also and the area is now multi-disciplinary involving research in the fundamental science and potential applications. In this Feature Article, a flavour of some of this interest is given based on recent work from our own group and includes the behaviour of particles at oil-water, air-water, oil-oil, air-oil and water-water interfaces. The materials capable of being prepared by assembling various kinds of particles at fluid interfaces include particle-stabilised emulsions, particle-stabilised aqueous and oil foams, dry liquids, liquid marbles and powdered emulsions

Ultra-stable self-foaming oils

This paper is concerned with the foaming of a range of fats in the absence of added foaming agent/emulsifier. By controlling the temperature on warming from the solid or cooling from the melt, crystals of high melting triglycerides form in a continuous phase of low melting triglycerides. Such crystal dispersions in oil can be aerated to produce whipped oils of high foamability and extremely high stability. The foams do not exhibit drainage and bubbles neither coarsen nor coalesce as they become coated with solid crystals. The majority of the findings relate to coconut oil but the same phenomenon occurs in shea butter, cocoa butter and palm kernel stearin. For each fat, there exists an optimum temperature for foaming at which the solid fat content reaches up to around 30%. We demonstrate that the oil foams are temperature-responsive and foam collapse can be controllably triggered by warming the foam to around the melting point of the crystals. Our hypothesis is given credence in the case of the pure system of tristearin crystals in liquid tricaprylin

Whipped oil stabilised by surfactant crystals

We describe a protocol for preparing very stable air-in-oil foams starting with a one-phase oil solution of a fatty acid (myristic acid) in high oleic sunflower oil at high temperature. Upon cooling below the solubility limit, a two-phase mixture consisting of fatty acid crystals (length around 50 μm) dispersed in an oil solution at its solubility is formed which, after whipping, coat air bubbles in the foam. Foams which do not drain, coalesce or coarsen may be produced either by increasing the fatty acid concentration at fixed temperature or aerating the mixtures at different temperatures at constant concentration. We prove that molecular fatty acid is not surface-active as no foam is possible in the one-phase region. Once the two-phase region is reached, fatty acid crystals are shown to be surface-active enabling foam formation, and excess crystals serve to gel the continuous oil phase enhancing foam stability. A combination of rheology, X-ray diffraction and pulsed nuclear magnetic resonance is used to characterise the crystals and oil gels formed before aeration. The crystal-stabilised foams are temperature-sensitive, being rendered completely unstable on heating around the melting temperature of the crystals. The findings are extended to a range of vegetable oil foams stabilised by a combination of adsorbed crystals and gelling of the oil phase, which destabilise at different temperatures depending on the composition and type of fatty acid chains in the triglyceride molecules

pH-responsive gas–water–solid interface for multiphase catalysis

© 2015 American Chemical Society. Despite their wide utility in laboratory synthesis and industrial fabrication, gas-water-solid multiphase catalysis reactions often suffer from low reaction efficiency because of the low solubility of gases in water. Using a surface-modification protocol, interface-active silica nanoparticles were synthesized. Such nanoparticles can assemble at the gas-water interface, stabilizing micrometer-sized gas bubbles in water, and disassemble by tuning of the aqueous phase pH. The ability to stabilize gas microbubbles can be finely tuned through variation of the surface-modification protocol. As proof of this concept, Pd and Au were deposited on these silica nanoparticles, leading to interface-active catalysts for aqueous hydrogenation and oxidation, respectively. With such catalysts, conventional gas-water-solid multiphase reactions can be transformed to H 2 or O 2 microbubble reaction systems. The resultant microbubble reaction systems exhibit significant catalysis efficiency enhancement effects compared with conventional multiphase reactions. The significant improvement is attributed to the pronounced increase in reaction interface area that allows for the direct contact of gas, water, and solid phases. At the end of reaction, the microbubbles can be removed from the reaction systems through changing the pH, allowing product separation and catalyst recycling. Interestingly, the alcohol oxidation activation energy for the microbubble systems is much lower than that for the conventional multiphase reaction, also indicating that the developed microbubble system may be a valuable platform to design innovative multiphase catalysis reactions

Pickering emulsions responsive to CO₂/N₂ and light dual stimuli at ambient temperature

A dual stimulus-responsive n-octane-in-water Pickering emulsion with CO₂/N₂ and light triggers is prepared using negatively charged silica nanoparticles in combination with a trace amount of dual switchable surfactant, 4-butyl-4-(4-N,N-dimethylbutoxyamine) azobenzene bicarbonate (AZO-B₄) as stabilizers. On one hand, the emulsion can be transformed between stable and unstable at ambient temperature rapidly via the N₂/CO₂ trigger, and on the other hand a change in droplet size of the emulsion can occur upon light irradiation/re-homogenization cycles without changing the particle/surfactant concentration. The dual responsiveness thus allows for a precise control of emulsion properties. Compared with emulsions stabilised by specially synthesized stimuli-responsive particles or by stimuli-responsive surfactants, the method reported here is much easier and requires relatively low concentration of surfactant (≈1/10 cmc), which is important for potential applications

Food-grade Pickering stabilisation of foams by in situ hydrophobisation of calcium carbonate particles

© 2016 Elsevier Ltd The aim of this study was to investigate the possibility of stabilising foam bubbles in water by adsorption of calcium carbonate (CaCO 3 ) particles. Because CaCO 3 is hydrophilic and not surface-active, particles were hydrophobised in situ with several emulsifiers. The used emulsifiers were food-grade and negatively charged at the pH employed. The effect of particle addition on foamability and foam stability of solutions containing either β-lactoglobulin, sodium caseinate, Quillaja, sodium dodecanoate (SD) or sodium stearoyl-2-lactylate (SSL) was studied. It was found that the ability of the emulsifiers to induce surface activity such that the particles are able to adsorb to the air-water interface is related to their structure. The structure needs to consist of a well-defined hydrophobic part and a charged part. Large emulsifiers with a complex structure, such as β-lactoglobulin, sodium caseinate and Quillaja, were able to partially hydrophobise the particles but were not able to act synergistically with the particles to increase the foam stability. Low molecular weight emulsifiers, however, consisting of a single tail with one charged group, such as SD and SSL, adsorbed at the particle surface rendering the particles partially hydrophobic such that they adsorb to the air-water interface. In a subsequent investigation, the pH was changed to a value typical for food products (pH 6–7) and the addition of milk salts on the foamability and foam stability was assessed. Based on these results, the use of food-grade CaCO 3 particles hydrophobised in situ with food-grade surfactants (SD or SSL) to prepare ultra-stable aqueous foams is demonstrated

Aqueous foams in the presence of surfactant crystals

Aqueous foams are used extensively in many fields and anionic surfactants are commonly used foaming agents. However, potential trouble may arise when they are utilized in hard water areas and/or at low temperatures. Anionic surfactants, like sodium dodecyl sulfate (SDS), may precipitate in the form of crystals when the concentration of divalent counterions such as Mg2+ exceeds a certain limit. In an attempt to prepare ultrastable foams containing precipitated crystals, the behavior of SDS in water was systematically investigated as a function of surfactant concentration at different concentrations of Mg(NO3)2 prior to a study of their foam properties. We quantitatively study the conversion of surfactant micelles to crystals and the redissolution of crystals into micelles. It was found that the presence of surfactant crystals reduced the initial foam volume and foam half-life but greatly improved the long-term stability of foams. Foam studies were also conducted for the supernatant and sediment isolated from crystal dispersions so that the importance of surfactant crystals to foam stability could be established. Despite the foamability of a sediment being low, an order of magnitude increase in foam half-life was related to the coverage of bubble surfaces by surfactant crystals. Both rapid cooling and ultrasonication were shown to influence the surfactant crystal shape and size with an impact on foam properties

Mechanical compression to characterize the robustness of liquid marbles

In this work, we have devised a new approach to measure the critical pressure that a liquid marble can withstand. A liquid marble is gradually squeezed under a mechanical compression applied by two parallel plates. It ruptures at a sufficiently large applied pressure. Combining the force measurement and the high-speed imaging, we can determine the critical pressure that ruptures the liquid marble. This critical pressure, which reflects the mechanical robustness of liquid marbles, depends on the type and size of the stabilizing particles as well as the chemical nature of the liquid droplet. By investigating the surface of the liquid marble, we attribute its rupture under the critical pressure to the low surface coverage of particles when highly stretched. Moreover, the applied pressure can be reflected by the inner Laplace pressure of the liquid marble considering the squeezing test is a quasi-static process. By analyzing the Laplace pressure upon rupture of the liquid marble, we predict the dependence of the critical pressure on the size of the liquid marble, which agrees well with experimental results

Coalescence of electrically charged liquid marbles

© The Royal Society of Chemistry. In this work, we investigated the coalescence of liquid water marbles driven by a DC electric field. We have found that two contacting liquid marbles can be forced to coalesce when they are charged by a sufficiently high voltage. The threshold voltage leading to the electro-coalescence sensitively depends on the stabilizing particles as well as the surface tension of the aqueous phase. By evaluating the electric stress and surface tension effect, we attribute such coalescence to the formation of a connecting bridge driven by the electric stress. This liquid bridge subsequently grows and leads to the merging of the marbles. Our interpretation is confirmed by the scaling relation between the electric stress and the restoring capillary pressure. In addition, multiple marbles in a chain can be driven to coalesce by a sufficiently high threshold voltage that increases linearly with the number of the marbles. We have further proposed a simple model to predict the relationship between the threshold voltage and the number of liquid marbles, which agrees well with the experimental results. The concept of electro-coalescence of liquid marbles can be potentially useful in their use as containers for chemical and biomedical reactions involving multiple reagents