High Internal Phase Ratio Emulsions Research Articles

Apollonian emulsions

We have discovered the existence of extremely polydisperse High Internal-Phase-Ratio Emulsions (HIPEs) in which the internal-phase droplets, present at 95% volume fraction, remain spherical and organize themselves in the available space according to Apollonian packing rules. Such Apollonian emulsions are obtained from dispersing oil dropwise in water in the presence of very little surfactant, and allowing them to evolve at rest for at least a week. The packing structure of the droplets was confirmed through size distribution measurements that evolved spontaneously towards power laws with the known Apollonian exponents, as well as comparison of the structure factors of aged HIPEs measured by Small-Angle X-ray Scattering with that of a numerically simulated Random Apollonian Packing. Thanks to the perfect sphericity of the droplets, Apollonian emulsions were found to display Newtonian flow even at such extremely high volume fraction. We argue that these fascinating space-filling assemblies of spherical droplets are a result of coalescence and fragmentation processes obeying simple geometrical rules of conserving total volume and sphericity, and minimizing the elastic energy associated with interactions of neighbouring droplets.

Apollonian packing in polydisperse emulsions

We have discovered the existence of polydisperse high internal-phase-ratio emulsions (HIPE) in which the internal-phase droplets, present at 95% volume fraction, remain spherical and organise themselves according to Apollonian packing rules. These polydisperse HIPEs are formed by emulsifying oil dropwise in a surfactant-poor aqueous continuous phase. After stirring has ceased, their droplet size distributions begin to evolve spontaneously and continuously through coalescence towards well-defined power laws with the Apollonian exponent. Small-angle X-ray Scattering performed on aged HIPEs demonstrate that the droplet packing structure agrees with that of a numerically simulated random Apollonian packing. We argue that when such concentrated emulsions are allowed to evolve, the coalescing droplets must obey volume and sphericity conservation. This leads to a mechanism that differs from typical coalescence in dilute emulsions.

Performance, combustion, and emissions in a diesel engine operated with fuel-in-water emulsions based on lignin

Abstract We report for the first time on the use of water-continuous emulsions stabilized by a bio-based macromolecule in a compression-ignition diesel engine and compare their performance, combustion and emissions against the base fuels (diesel, biodiesel, and jet fuel). For this purpose, high internal phase ratio emulsions (70:30 fuel-to-water) were produced by mechanical emulsification using carboxymethylated wood lignin as stabilizer. Combusting experiments were performed with the engine operating at 2000 rpm under three loads (0, 1.26 and 3.26 bar brake mean effective pressure, BMEP). Engine performance, in-cylinder combustion, and exhaust emissions were monitored and compared for the fuels tested. At no load condition and when compared to the respective base (single phase) fuels, an increase in the indicated work was observed for diesel and biodiesel emulsions. Compared to the base fuels, the emulsions resulted in higher engine mechanical efficiency at 1.26 and 3.26 bar BMEP except for jet fuel emulsion at 1.26 bar. Additionally, they displayed a lower brake specific fuel consumption (BSFC), if calculated on the basis of effective fuel content discounting emulsion water, and higher brake thermal efficiency. Compared to the base fuel, the respective emulsions generally presented lower peak in-cylinder pressure, lower heat release rates, and longer ignition delays at 1.26 bar and 3.26 bar BMEP; the opposite effect was observed at no-load conditions. Remarkably, a large reduction of nitrogen oxides (NOx) emissions was noted in the combustion of the fuel emulsions, which was accompanied with a relatively higher carbon monoxide (CO) release at 1.26 and 3.26 bar (at 0 bar BMEP, the emulsions produced less CO emissions). The effect of emulsions on hydrocarbon emissions and smoke opacity depended on the fuel type and the engine load. Overall, it is concluded that while reports on fuel emulsions involve oil-continuous systems, the proposed water-continuous alternative represents an opportunity for diesel engines, whereby the fuel is dispersed as micrometric droplets for improved combustion and reduced emissions. At the same time, the fuel emulsion formulation takes advantage of the surface activity and high calorific value of widely available, inexpensive lignin stabilizers, making the proposed system a viable option towards cleaner or fully bio-based fuels.

Flow of High Internal Phase Ratio Emulsions through Pipes

The flow behavior of W/O type of HIPRE stabilized by hydrogen bonds with a sugar (sorbitol) in the aqueous phase, was studied. Two groups of experiments were done in this work: The effect of wall shear stresses were investigated in flow through pipes of different diameters. For this end, HIPREs prestirred at constant rate for the same duration were used to obtain similar drop size distributions. Existence and extent of elongational viscosity were used as a probe to elucidate the effect of drop size distribution on the flow behavior: HIPREs prestirred for the same duration at different rates were subjected to flow through converging pipes. The experimental flow curves for flow through small cylindrical pipes indicated four different stages: 1) initial increase in the flow rate at low pressure difference, 2) subsequent decrease in the flow rate due to capillary flow, 3) pressure increase after reaching the minimum flow rate and 4) slip flow after a critical pressure difference. HIPREs with sufficient external liquid phase in the plateau borders can elongate during passage through converging pipes. In the absence of liquid stored in the plateau borders, the drops rupture during extension and slip flow takes place without elongation.

Janus Emulsions from a One-Step Process; Optical Microscopy Images

The optical microscopy images of an emulsion are commonly distorted when viewed between a cover glass and a planar microscopy slide. An alternative method is to place the sample on a slide with a cavity, which in turn suffers from incomplete information for high internal phase ratio (HIPR) emulsions, due to the inevitable crowding of the drops. This problem is particularly acute for more complex emulsions, such as those with Janus drops, for which a detailed image of the drop is essential. A number of publications have recently described Janus emulsions prepared by a one-step high energy emulsification process with microscopy images obtained by the sample between a planar slide and a cover glass. The correlation to the morphology of emulsions in bulk of these images is critical, but, so far, a potential equivalence has not been established. Since the images are central in order to understand why Janus emulsions should form under such conditions, the need to ascertain any such association is urgent. With this contribution, we compare images from different microscopy methods to those of gently diluted HIPR emulsions. The results reveal that the images of the emulsion samples between a cover glass and a planar microscope slide actually present a realistic representation of the drop topology in bulk emulsions.

Highly concentrated emulsion with a cubic liquid crystal as the external phase: characterization and obtaining of meso/macroporous material

High internal phase ratio emulsions (HIPRE) or highly concentrated emulsions are characterized by their large internal phase volume.The nature and concentration of surfactant affects several features of the final emulsion, such as stability, droplet size and structure of the external phase. Therefore, an ordered external mesophase (structure of liquid crystal) can be obtained. The present work studies the influence of composition and preparation variables on the final properties of HIPRE with an external phase formed by a bicontinuous cubic liquid crystal. The studied outputs variables were droplet size, stability and rheological parameters as yield stress, viscosity at a fixed shear rate and the plateau value of the storage modulus. O/W HIPREs were prepared with a decane/brij 35/water system. Once the emulsions were characterized the meso/macroporous material was obtained. In order to prepare the materials, the emulsions were formed by incorporating the catalyst of the reaction (HCl) in the continuous phase. When the emulsions were formed, tetraethylorthosilicate (TEOS) was added as a silica source In order to optimize the production process a study of reutilization and recovery of some of the raw materials (i.e: the surfactant and the EtOH used) was done.DOI: http://dx.doi.org/10.3126/jncs.v30i0.9374Journal of Nepal Chemical Society Vol. 30, 2012 Page: 87-96 Uploaded date: 12/19/2013

Scale invariants in the preparation of reverse high internal phase ratio emulsions

Reverse high internal phase ratio emulsions (HIPRE) are prepared with the system water/Span80/dodecane to identify the influence of the process variables on droplet size and polydispersity, and to study the influence of the process scale-up. After discussing the most common scale invariants used in emulsification processes, we prepare emulsions at two different scales following a complete factorial experimental design. Using the empirical models obtained with the statistical analysis of the results, we determine the scale invariants for the system. Results from a previous study indicated that the scale invariant for the preparation of HIPRE could be the stirring rate. However, the results obtained in this work show that the scale invariant, based on droplet size, could change depending on the conditions of emulsification. Only when the stirring rate is high enough (>1500rpm), or when the surfactant-to-oil ratio is high and the total addition time low, the scale invariant is indeed the stirring rate. The elevated shear stress inside the mixer when the stirring rate is high is responsible for the small droplet size obtained on both scales. However, for other values of the process variables, the scale-invariant can be expressed as N·Dα, where 0<α<0.5, and depends on other two factors: the addition flow rate of dispersed phase or addition time, and the surfactant-to-oil ratio. We propose a methodology to determine these scale invariants and to calculate the threshold values of surfactant-to-oil ratio and addition flow rate from which the stirring rate is the scale invariant (when α→0).

New insights on the mechanisms of drug release from highly concentrated emulsions

High kinetic stability water-in-oil high internal phase ratio emulsions (W/O-HIPREs) have been obtained in a 0.5% Theophylline (TP) aqueous solution/Cremophor WO7/liquid paraffin system at 25°C. The release of TP has been studied from HIPREs with pH values of the dispersed phase ranging between 2 and 12. Although the release from aqueous solutions was not influenced by pH, the release from HIPREs depended strongly on the pH of the dispersed phase. Increasing the solubility of TP in the dispersed phase, its apparent diffusion coefficient decreased over two orders of magnitude. Two different physico-chemical models have been applied to describe the diffusion of TP, showing an excellent agreement with experiments and confirming the role of the structure of the emulsions and the solubility of the drug. It has been shown that only non-ionized species are able to cross the interfacial film. Therefore, at pH>pKa diffusion is limited by the concentration of non-ionized species inside the emulsion droplets, while at pH<pKa diffusion is determined by the interfacial film. This demonstrates that solubility of the diffusing molecule can have a higher effect on release from HIPREs than the interfacial film properties.

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.

Preparation of honeycomb scaffold with hierarchical porous structures by core-crosslinked core–corona nanoparticles

The preparation of honeycomb scaffold with hierarchical controllable porous structures is reported. The ABA three block amphiphilic copolymer PS-b-P(St-Alt-AMn)-b-PS was synthesized through reversible addition fragmentation chain transfer polymerization (RAFT) and subsequently self-assembled to core–corona nanoparticles with the middle block P(St-Alt-AMn) as the core and two side block PS as the corona. The formed core–corona nanoparticles were further crosslinked through the reaction of amino diphenyl methane with anhydride in chains. The core-crosslinked core–corona nanoparticles were used as the building block to fabricate the controllable porous scaffold with hierarchical structure. The micrometer level honeycomb mesostructures can be obtained by an inverse emulsion template method which is consisted in the formation of the high internal phase ratio emulsions (HIPRE) while the nanometer level pores are formed by the close-packed core–corona block copolymer nanoparticles. As carboxylic group is formed in the crosslink step of the core, the growth factor can be easily incorporated into the matrix in order for the growth of the cell in the tissue engineering application. This kind of hierarchical honeycomb structure is an ideal candidate for the tissue engineering and drug delivery applications.

Laminar Flow Emulsification Process to Control the Viscosity Reduction of Heavy Crude Oils

The formation of heavy crude oil in water (O/W) emulsion by a low energy laminar controlled flow has been investigated. The emulsion was prepared in an eccentric cylinder mixer. Its geometry allows the existence of chaotic flows that are able to mix well highly viscous fluids. This new mixer design is used to produce high internal phase ratio emulsions for three oils: castor oil and two heavy crude oils of different initial viscosity (Zuata and Athabasca crude oils). The influence of the stirring conditions, geometrical parameters, and water volume fraction on the rheological properties of the resulting O/W emulsion is studied.

Modelling and characterisation of diluted and concentrated water-in-crude oil emulsions: comparison with classical behaviour

Water-in-oil type emulsions can be formed during the crude oil production process. The presence of natural surfactants in oil (asphaltenes, resins) and mechanical stirring (piping/well system) produce emulsions, the stability and rheological behaviour of which depend mainly on the chemical composition of the oil and the internal phase concentration. In this work, water (brine 8 g NaCl/cm3) in oil (crude oil) emulsions were prepared and characterised by varying the internal phase concentration (5–80%). Rheological properties are discussed according to the composition of the oil and the temperature of the system. Relative viscosity was modelled following the classical models of Mooney and Krieger and Dougherty, but the best-fitting model for the experimental results was found with an exponential type equation between relative viscosity and volume fraction, as proposed by Richardson. Moreover, we observed that the plastic behaviour determined through the yield stress determination depended not only on the internal phase concentration but also on the temperature. Quantitative analysis of the emulsions’ viscoelastic parameters (storage and loss modulus) was made. In the case of concentrated emulsions (containing over 70% of internal phase), Princen’s theory of the high internal phase ratio emulsions (HIPRES) was verified.

Rheology of high internal phase ratio emulsions

The rheology of high internal phase ratio oil-in-water emulsions was investigated experimentally using a controlled-stress rheometer. Steady shear, oscillatory shear, and creep/recovery measurements were carried out on a series of highly concentrated fine (Sauter mean radius 1.28 μm), coarse (Sauter mean radius 1.95 μm), and mixed fine-and-coarse emulsions. The dispersed-phase (oil) concentration ranged from 78.55% to 94.02% by volume. All the emulsions investigated in this study possessed a yield stress. The yield stress values obtained from different experiments for the same emulsion showed good agreement with each other. Both yield stress and storage modulus of the emulsions increased with the increase in the dispersed-phase concentration and with the decrease in the average droplet size. When coarse droplets were replaced by fine droplets (keeping total volume fraction of the dispersed-phase constant), the resulting emulsion exhibited an increase in the yield stress and storage modulus due to a decrease in the average droplet size. The Princen and Kiss equations were used to interpret the yield stress and storage modulus data of this study.

Microstructure of colloidal liquid aphrons (CLAs) by freeze fracture transmission electron microscopy (FF-TEM)

Colloidal liquid aphrons (CLAs) composed of triethylene glycol monododecyl ether (C 12E 3)/ n-decane/sodium dodecyl sulphate (SDS) or Tween 80/water have been visualized by freeze fracture transmission electron microscopy (FF-TEM) and confirmed by small angle X-ray scattering (SAXS) and polarizing microscopy. The resolution achieved allows detailed inspection of the size, shape of individual micelles, as well as core-shell structure of CLAs. The microstructure of CLAs was compared with that conventional emulsions presented, particularly high internal phase ratio emulsions (HIPREs), from the viewpoint of morphology. The combined results indicate that the CLAs consist of spherical, oil droplets (oil-rich phase) of micron size separated by an aqueous “soapy shell” (water-rich phase) and there exist supramolecular structures such as reversed micelles and O/W micelles or microemulsions in oil-rich and water-rich phases, respectively. The total interfacial area of stable CLAs is consistent with that of colloidal gas aphrons (CGAs) reported previously, with an approximate thickness of 0.3–0.4 μm. It has been shown throughout this work that the overall microstructure CLAs presented here is somewhat analogous to that of HIPREs, with biphasic structure and presence of the supramolecular aggregates in these phases, which seems to support the Princen's opinion.

Polyaphrons as Templates for the Sol–Gel Synthesis of Macroporous Silica

Macroporous silica was synthesized using polyaphrons as shape-directing templates in a sol–gel hydrolysis scheme using tetraethyl orthosilicate (TEOS). Polyaphrons are a special class of high internal phase ratio emulsions (HIPRE) that can potentially be used in the continuous processing of long range ordered macroporous solids. The structures so formed were examined using a scanning electron microscope after thermal curing to 400∘C. The majority of the pores in the silica structures were in the range between 0.1 and 10 μ m. Key parameters affecting the polyaphrons template characteristics were varied and their effects on the final silica structure were studied.

In-situ control of DNAPL density using polyaphrons.

Once spilled into soils, dense nonaqueous phase liquids (DNAPLs) such as chlorinated solvents migrate deep into the subsurface because of their high density. Their downward migration typically continues until capillary forces balance gravitational forces or until essentially impermeable strata are reached. Efforts to mobilize the DNAPL for remediation purposes risks driving the contaminants deeper, which has spurred research for modifying buoyancy forces in situ. In this paper, a novel means of controlling the density of a DNAPL phase using polyaphrons is presented. Polyaphrons are a class of high internal phase ratio emulsions (HIPREs) that have unusual properties such as indefinite stability and flow properties through porous media. They provide a means of selectively delivering a light organic phase liquid to the vicinity of the DNAPL phase. Upon destabilization of the polyaphron by a polyvalent cation, the light internal phase mixes with the DNAPL to produce a nonaqueous phase of lower density than the original contaminant. The negative buoyancy of the DNAPL can thus be reversed. This approach holds great promise for manipulating DNAPL densities prior to or during remediation treatments.

Highly Concentrated Emulsions: Physicochemical Principles of Formulation

ABSTRACT This review deals with the preparation, stability, rheology and different applications of highly concentrated emulsions. These emulsions, which are known as high internal phase ratio emulsions (HIPRE), gel-emulsions, biliquid foams, etc., containing over 90% internal phase by volume, have a swollen micellar (L1 or L2) solution of nonionic or ionic surfactants as a continuous phase. These emulsions have the structure of biliquid foams and behave as gels since they present viscoelastic and plastic properties. The functional macroscopic properties of gel-emulsions are dependent on the structural parameters of the microemulsion continuous phase as well as of the interfacial properties (interfacial tension, bending modules, spontaneous curvature) of surfactant monolayers. The depletion interaction between emulsion droplets due to the non-compensated osmotic pressure of micelles is revealed as a main factor, along with surface forces, which determine the aggregative stability and the rheological properties of these emulsions. The effect of electrolyte and surfactant concentration, temperature, as well as other physicochemical parameters on the fiocculation threshold, stability, and yielding properties of highly concentrated emulsions is explained by the effect of these parameters on the critical micelle concentration (CMC) and the aggregation number of surfactants, and, consequently, on the depletion interaction. The thermodynamic theory of adhesion of fluid droplets in micellar solution and the suggested model of elasticity of gel-emulsions permit to explain the effect of mentioned physicochemical parameters on the elasticity modulus, the plastic strength and the linear deformation of these emulsions. A novel mechanism for the spontaneous formation of gel-emulsions by the phase inversion temperature (PIT) route is suggested, allows the selection of ternary systems able to yield these emulsions, and explains how the droplet size can be controlled during the PIT process. An original model for liquid film rupture is also suggested, and allows the prediction of the effect of structural parameters of micellar solutions and the interfacial properties of surfactant monolayers on the stability of gel-emulsions.

Effect of interfacial properties on the drop size distribution of high internal phase ratio emulsions

Interfacial properties of polyoxyethylene(2) oleyl ether and drop size distributions of emulsions prepared with this surfactant are investigated experimentally in this work; 80, 88 and 94% (v) internal phase ratio W/O type emulsions were prepared, where the aqueous phase was 1% sorbitol solution and the oil phase, a 1:1 v/v mixture of surfactant and paraffin oil. Experimental evidence indicated an interaction between the hydrocarbon chains of surfactant molecules and the solvent paraffin oil through van der Waals forces and between the ethoxylate groups and sorbitol, a polyalcohol, in the aqueous phase through hydrogen bonds, notably below the transition temperature. Continuous phase liquid present in the plateau borders was found to act as a reservoir of surface active agents, minimizing the effect of stretching of the film under shear. In cases where the amount of liquid hold up in plateau borders is negligible, the drop size distributions were found to be very sensitive to shearing rate. Interplay between the interfacial shear viscosity and the interfacial tension was found to control the rate of coalescence of drops less than 0.48 μm only in the case of 94% emulsions, corresponding to maximum stretching of interfacial area. In other cases, interfacial film stability seems to control the rate of coalescence.

Effect of stirring energy upon the dynamic inversion hysteresis of emulsions

The effect of stirring energy upon the characteristics of dynamic emulsion inversion is discussed on an experimental formulation–composition map for emulsions containing an anionic surfactant. It is shown that a vigorous agitation promotes the early inversion of high internal phase ratio emulsions. The hysteresis zone narrows and moves to an intermediate position within the ambivalent region that is attained for lower stirring speeds. A simple explanation based on the catastrophic inversion model is proposed to interpret these features.

Highly concentrated water-in-oil emulsions as novel reaction media for protease-catalysed kinetically controlled peptide synthesis

High-internal-phase-ratio-emulsions (HIPREs) or gel emulsions, formulated with a large amount of water (80.0–99.5% w/w), were investigated as reaction media for α-chymotrypsin-catalysed peptide synthesis under kinetic control using Ac-L-Phe-OEt and H-L-Leu-NH2 as model substrates. Both the initial reaction rate and dipeptide yield were examined as a function of the structure of the non-ionic polyoxyethylene alkyl ether type surfactant, alkyl chain length of the oil component, temperature and aqueous buffer content. Dipeptide yields of 70% were achieved in gel emulsions formulated with 90% w/w aqueous buffer. In these systems, the reaction performance was found to be independent of the gel emulsion system (i.e. surfactant and oil) and therefore of the water–oil interfacial tension. Interestingly, α-chymotrypsin showed superactivity at surfactant concentrations ranging between 0.2 and 0.8% w/w, that is, at 99.5 and 98.0% w/w water content, respectively. Furthermore, high dipeptide yields (90–94%) were achieved in the gel emulsions studied at very high substrate concentrations and thus with undissolved reactants. Under these conditions, examples of α-chymotrypsin-catalysed dipeptide synthesis on an analytical and preparative scale were conducted.