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

Particles at oil–air surfaces : powdered oil, liquid oil marbles, and oil foam

The type of material stabilized by four kinds of fluorinated particles (sericite and bentonite platelet clays and spherical zinc oxide) in air–oil mixtures has been investigated. It depends on the particle wettability and the degree of shear. Upon vigorous agitation, oil dispersions are formed in all the oils containing relatively large bentonite particles and in oils of relatively low surface tension (γla < 26 mN m⁻¹) like dodecane, 20 cS silicone, and cyclomethicone containing the other fluorinated particles. Particle-stabilized oil foams were obtained in oils having γla > 26 mN m⁻¹ where the advancing air–oil–solid contact angle θ lies between ca. 90° and 120°. Gentle shaking, however, gives oil-in-air liquid marbles with all the oil–particle systems except for cases where θ is <60°. For oils of tension >24 mN m⁻¹ with omniphobic zinc oxide and sericite particles for which advancing θ ≥ 90°, dry oil powders consisting of oil drops in air which do not leak oil could be made upon gentle agitation up to a critical oil:particle ratio (COPR). Above the COPR, catastrophic phase inversion of the dry oil powders to air-in-oil foams was observed. When sheared on a substrate, the dry oil powders containing at least 60 wt % of oil release the encapsulated oil, making these materials attractive formulations in the cosmetic and food industries

Effective surface dilatational viscosity of highly concentrated particle-laden interfaces

The effective surface dilatational viscosity is calculated of a flat interface separating two immiscible fluids laden with half-immersed monodisperse rigid spherical non-Brownian particles in the limit of high particle concentration. The derivation is based upon the facts that (i) highly concentrated particle arrays in a plane form a hexagonal structure and (ii) the dominant contribution to the viscous dissipation rate arises in the thin gaps between neighboring particles

Preparation of double emulsions using hybrid polymer/silica particles: New pickering emulsifiers with adjustable surface wettability

A facile route for the preparation of water-in-oil-in-water (w/o/w) double emulsions is described for three model oils, namely, n-dodecane, isopropyl myristate, and isononyl isononanoate, using fumed silica particles coated with poly(ethylene imine) (PEI). The surface wettability of such hybrid PEI/silica particles can be systematically adjusted by (i) increasing the adsorbed amount of PEI and (ii) addition of 1-undecanal to the oil phase prior to homogenization. In the absence of this long-chain aldehyde, PEI/silica hybrid particles (PEI/silica mass ratio = 0.50) produce o/w Pickering emulsions in all cases. In the presence of 1-undecanal, this reagent reacts with the primary and secondary amine groups on the PEI chains via Schiff base chemistry, which can render the PEI/silica hybrid particles sufficiently hydrophobic to stabilize w/o Pickering emulsions at 20 °C. Gas chromatography, 1H NMR and X-ray photoelectron spectroscopy provide compelling experimental evidence for this in situ surface reaction, while a significant increase in the water contact angle indicates markedly greater hydrophobic character for the PEI/silica hybrid particles. However, when PEI/silica hybrid particles are prepared using a relatively low adsorbed amount of PEI (PEI/silica mass ratio = 0.075) only o/w Pickering emulsions are obtained, since the extent of surface modification achieved using this Schiff base chemistry is insufficient. Fluorescence microscopy and laser diffraction studies confirm that highly stable w/o/w double emulsions can be achieved for all three model oils. This is achieved by first homogenizing the relatively hydrophobic PEI/silica hybrid particles (PEI/silica mass ratio = 0.50) with an oil containing 3% 1-undecanal to form an initial w/o emulsion, followed by further homogenization using an aqueous dispersion of relatively hydrophilic PEI/silica particles (PEI/silica mass ratio = 0.075). Dye release from the internal aqueous cores into the aqueous continuous phase was monitored by visible absorption spectroscopy. These studies indicate immediate loss of 12-18% dye during the high speed homogenization that is required for double emulsion formation, but no further dye release is observed at 20 °C for at least 15 days thereafter

Saddle-splay modulus of a particle-laden fluid interface

The scaled-particle theory equation of state for the two-dimensional hard-disk fluid on a curved surface is proposed and used to determine the saddle-splay modulus of a particle-laden fluid interface. The resulting contribution to saddle-splay modulus, which is caused by thermal motion of the adsorbed particles, is comparable in magnitude with the saddle-splay modulus of a simple fluid interface.Comment: 10 pages, 2 figure

Stability of bubbles in wax-based oleofoams: decoupling the effects of bulk oleogel rheology and interfacial rheology

Oleofoams are dispersions of gas bubbles in a continuous oil phase and can be stabilized by crystals of fatty acids or waxes adsorbing at the oil-air interface. Because excess crystals in the continuous phase form an oleogel, an effect of the bulk rheology of the continuous phase is also expected. Here, we evaluate the contributions of bulk and interfacial rheology below and above the melting point of a wax forming an oleogel in sunflower oil. We study the dissolution behaviour of single bubbles using microscopy on a temperature-controlled stage. We compare the behaviour of a bubble embedded in an oleofoam, which owes its stability to both bulk and interfacial rheology, to that of a bubble extracted from the oleofoam and resuspended in oil, for which the interfacial dilatational rheology alone provides stability. We find that below the melting point of the wax, bubbles in the oleofoam are stable whereas bubbles that are only coated with wax crystals dissolve. Both systems dissolve when heated above the melting point of the wax. These findings are rationalized through independent bulk rheological measurements of the oleogel at different temperatures, as well as measurements of the dilatational rheological properties of a wax-coated oil-air interface

Emulsification in binary liquids containing colloidal particles: a structure-factor analysis

We present a quantitative confocal-microscopy study of the transient and final microstructure of particle-stabilised emulsions formed via demixing in a binary liquid. To this end, we have developed an image-analysis method that relies on structure factors obtained from discrete Fourier transforms of individual frames in confocal image sequences. Radially averaging the squared modulus of these Fourier transforms before peak fitting allows extraction of dominant length scales over the entire temperature range of the quench. Our procedure even yields information just after droplet nucleation, when the (fluorescence) contrast between the two separating phases is scarcely discernable in the images. We find that our emulsions are stabilised on experimental time scales by interfacial particles and that they are likely to have bimodal droplet-size distributions. We attribute the latter to coalescence together with creaming being the main coarsening mechanism during the late stages of emulsification and we support this claim with (direct) confocal-microscopy observations. In addition, our results imply that the observed droplets emerge from particle-promoted nucleation, possibly followed by a free-growth regime. Finally, we argue that creaming strongly affects droplet growth during the early stages of emulsification. Future investigations could clarify the link between quench conditions and resulting microstructure, paving the way for tailor-made particle-stabilised emulsions from binary liquids.Comment: http://iopscience.iop.org/0953-8984/22/45/455102

Colloid-stabilized emulsions: behaviour as the interfacial tension is reduced

We present confocal microscopy studies of novel particle-stabilized emulsions. The novelty arises because the immiscible fluids have an accessible upper critical solution temperature. The emulsions have been created by beginning with particles dispersed in the single-fluid phase. On cooling, regions of the minority phase nucleate. While coarsening these nuclei become coated with particles due to the associated reduction in interfacial energy. The resulting emulsion is arrested, and the particle-coated interfaces have intriguing properties. Having made use of the binary-fluid phase diagram to create the emulsion we then make use of it to study the properties of the interfaces. As the emulsion is re-heated toward the single-fluid phase the interfacial tension falls and the volume of the dispersed phase drops. Crumpling, fracture or coalescence can follow. The results show that the elasticity of the interfaces has a controlling influence over the emulsion behaviour.Comment: Submitted for the proceedings of the 6th Liquid Matter Conference, held in Utrecht (NL) in July 200

CO2 capture by dry alkanolamines and an efficient microwave regeneration process

Removal of acidic gases such as H2S and CO2 is performed during the purification of raw natural gas, most commonly using amine gas treatment. However, this industrially entrenched method is limited by significant shortcomings including low operational capture efficiency, amine pipeline corrosion and a large energy penalty due to the sorbent regeneration process. To address these shortcomings, we have studied the use of perfluorinated silica-stabilized dry alkanolamines (DAf) for CO2 capture. Due to their micronized liquid domains, DAf display high operational CO2 capture efficiency. Further, to minimize energy requirements for sorbent regeneration, microwave-assisted regeneration of the spent DAf sorbent was also studied and shown to decrease the energy requirements by about ten times. In contrast to very recent work, our results show that the use of DAf exhibits extraordinary recyclability, with a negligible decrease in absorption capacity over at least ten absorption–regeneration cycles, indicating the potential of this material for gas treatment applications