Dependence of emulsion stability on particle size: Relative importance of drop concentration and destabilization rate on the half lifetimes of O/W nanoemulsions

This study reports the behavior of ionic dodecane-in-water nanoemulsions in distinct salt concentrations. Systems of smaller particle size (74–285 nm) were synthesized by a sudden dilution of an equilibrated mixture. Larger size systems (384–670 nm) were obtained from a set of formerly smaller nanoemulsions that evolved unperturbed for 2 weeks. Characteristic destabilization times for flocculation, coalescence, and Ostwald ripening were evaluated. In general, it was observed that stability increases with drop size. However, this size dependence is largely the consequence of the lower particle concentration of the coarser emulsions.     

Impact of oil type on nanoemulsion formation and Ostwald ripening stability

The formation of stable transparent nanoemulsions poses two challenges: the ability to initially create an emulsion where the entire droplet size distribution is below 80 nm, and the subsequent stabilization of this emulsion against Ostwald ripening. The physical properties of the oil phase and the nature of the surfactant layer were found to have a considerable impact on nanoemulsion formation and stabilization. Nanoemulsions made with high viscosity oils, such as long chain triglycerides (LCT), were considerably larger ( D = 120 nm) than nanoemulsions prepared with low viscosity oils such as hexadecane ( D = 80 nm). The optimization of surfactant architecture, and differential viscosity eta D/eta C, has led to the formation of remarkably small nanoemulsions. With average sizes below 40 nm they are some of the smallest homogenized emulsions ever reported. What is more remarkable is that LCT nanoemulsions do not undergo Ostwald ripening and are physically stable for over 3 months. Ostwald ripening is prevented by the large molar volume of long chain triglyceride oils, which makes them insoluble in water thus providing a kinetic barrier to Ostwald ripening. Examination of the Ostwald ripening of mixed oil nanoemulsions found that the entropy gain associated with oil demixing provided a thermodynamic barrier to Ostwald ripening. Not only are the nanoemulsions created in this work some of the smallest reported, but they are also thermodynamically stable to Ostwald ripening when at least 50% of the oil phase is an insoluble triglyceride.     

Characterization of Astaxanthin Nanoemulsions Produced by Intense Fluid Shear through a Self-Throttling Nanometer Range Annular Orifice Valve-Based High-Pressure Homogenizer

Stable, oil-in-water nanoemulsions containing astaxanthin (AsX) were produced by intense fluid shear forces resulting from pumping a coarse reagent emulsion through a self-throttling annular gap valve at 300 MPa. Compared to crude emulsions prepared by conventional homogenization, a size reduction of over two orders of magnitude was observed for AsX-encapsulated oil droplets following just one pass through the annular valve. In krill oil formulations, the mean hydrodynamic diameter of lipid particles was reduced to 60 nm after only two passes through the valve and reached a minimal size of 24 nm after eight passes. Repeated processing of samples through the valve progressively decreased lipid particle size, with an inflection in the rate of particle size reduction generally observed after 2–4 passes. Krill- and argan oil-based nanoemulsions were produced using an Ultra Shear Technology™ (UST™) approach and characterized in terms of their small particle size, low polydispersity, and stability.     

Preparation of water-in-diesel oil nano-emulsion using nonionic surfactants with enhanced stability and flow properties

Formation of water-in-diesel oil (w/o) nano-emulsion has been achieved by a low-energy emulsification method by stabilizing a new combination of nonionic sorbitan esters surfactants, that is PEG20-sorbitan monostearate and sorbitan monooleate in mixed proportions. Different combinations of the surfactants (T6?+?S8) have been tested and the best possible combination of mixed surfactants is found at a surfactants ratio of 35:65 (wt/wt) for T6:S8 at hydrophile–lipophile balance (HLB)?=?8.01, which resulted in smaller droplet size of 44.87?nm. A phase diagram study is performed to identify the zones of formation of transparent, translucent, and opaque emulsions (44?nm??27?m³?·?s^?1. Comparison of Ostwald ripening rate with other sets of surfactants obtained by different authors showed the lowest rate among them, indicative of enhanced stability. A rheological study of the tested set of nano-emulsions depicts the Newtonian behavior (1.0371?≤?n?≤?1.0826) over a wider range of shear rates (10–1000?s^?1) at different temperatures (25–40°C).     

Effect of Oil Type,Aliphatic Alcohol,and Ionic Surfactants on the Formation and Stability of Ceramide-2 Enriched Nanoemulsions

Oil-in-water nanoemulsions are finding increasing use as delivery systems to encapsulate lipophilic bioactive components in personal care and pharmaceutical. The aim of this study was to optimize the composition and stability of ceramide-2 nanoemulsions. The nanoemulsions were prepared by high pressure homogenizer emulsification method using sodium dilauramidoglutamide lysine (DLGL) as surfactant. Results showed that the oil type and concentration had an appreciable impact on the particle size and stability of the ceramide-2 enriched nanoemulsions. The presence of the aliphatic alcohol altered the curvature of the surfactant molecular and increased the stability of nanoemulsions. The zeta potential of nanoemulsions decreased with the addition of cetyl trimethyl ammonium chloride (1631), which weakens the electrostatic interactions between droplets and lowers the stability of the nanoemulsions. The particle size decreased with increasing concentrations of both sodium dodecyl sulfate (SDS) and cocoamidopropyl betaine (CAB). The variation of zeta potential with SDS and CAB was insignificant, which was attributed to the high zeta potential value resulted from anionic gemini surfactant DLGL. The instability mechanism of nanoemulsions was the Ostwald ripening. This study demonstrated that the addition of aliphatic alcohol, SDS, or CAB was beneficial to the stability of ceramide-2 nanoemulsions and decreased the Ostwald ripening rate.     

Emulsion Ripening through Molecular Exchange at Droplet Contacts

Two coarsening mechanisms of emulsions are well established: droplet coalescence (fusion of two droplets) and Ostwald ripening (molecular exchange through the continuous phase). Here a third mechanism is identified, contact ripening, which operates through molecular exchange upon droplets collisions. A contrast manipulated small‐angle neutron scattering experiment was performed to isolate contact ripening from coalescence and Ostwald ripening. A kinetic study was conducted, using dynamic light scattering and monodisperse nanoemulsions, to obtain the exchange key parameters. Decreasing the concentration or adding ionic repulsions between droplets hinders contact ripening by decreasing the collision frequency. Using long surfactant chains and well‐hydrated heads inhibits contact ripening by hindering fluctuations in the film. Contact ripening can be controlled by these parameters, which is essential for both emulsion formulation and delivery of hydrophobic ingredients.     

Influence of oil polarity on droplet growth in oil-in-water emulsions stabilized by a weakly adsorbing biopolymer or a nonionic surfactant

The influence of oil type (n-hexadecane, 1-decanol, n-decane), droplet composition (hexadecane:decanol), and emulsifier type (Tween 20, gum arabic) on droplet growth in oil-in-water emulsions was studied. Droplet size distributions of emulsions were measured over time (0-120 h) by laser diffraction and ultrasonic spectroscopy. Emulsions containing oil molecules of low polarity and low water solubility (hexadecane) were stable to droplet growth, irrespective of the emulsifier used to stabilize the droplets. Emulsions containing oil molecules of low polarity and relatively high water solubility (decane) were stable to coalescence, but unstable to Ostwald ripening, irrespective of emulsifier. Droplet growth in emulsions containing oil molecules of relatively high polarity and high water solubility (decanol) depended on emulsifier type. Decanol droplets stabilized by Tween 20 were stable to droplet growth in concentrated emulsions but unstable when the emulsions were diluted. Decanol droplets stabilized by gum arabic exhibited rapid and extensive droplet growth, probably due to a combination of Ostwald ripening and coalescence. We proposed that coalescence was caused by the relatively low interfacial tension at the decanol-water boundary, which meant that the gum arabic did not absorb strongly to the droplet surfaces and therefore did not prevent the droplets from coming into close proximity.     

Preparation of calcium alginate nanoparticles using water-in-oil (W/O) nanoemulsions

A procedure for the preparation of calcium alginate nanoparticles in the aqueous phase of water-in-oil (W/O) nanoemulsions was developed. The emulsions were produced from mixtures of the nonionic surfactant tetraethylene glycol monododecyl ether (C(12)E(4)), decane, and aqueous solutions of up to 2 wt % sodium alginate by means of the phase inversion temperature (PIT) emulsification method. This method allows the preparation of finely dispersed emulsions without a large input of mechanical energy. With alginate concentrations of 1-2 wt % in the aqueous phase, emulsions showed good stability against Ostwald ripening and narrow, monomodal distributions of droplets with radii <100 nm. Gelation of the alginate was induced by the addition of aqueous CaCl(2) to the emulsions under stirring, and particles formed were collected using a simple procedure based on extraction of the surfactant on addition of excess oil. The final particles were characterized using cryo-transmission electron microscopy (cryo-TEM) and dynamic light scattering (DLS). They were found to be essentially spherical with a homogeneous interior, and their size was similar to that of the initial emulsion droplets. The herein presented "low-energy" method for preparation of biocompatible nanoparticles has the potential to be used in various applications, e.g., for the encapsulation of sensitive biomacromolecules.     

Influence of Ionic Surfactants on the Properties of Nanoemulsions Emulsified by Nonionic Surfactants Span 80/Tween 80

The instability of nanoemulsions were mainly due to Ostwald ripening. The droplet charge was influenced by the stability of nanoemulsions significantly. In this work, the properties of the shea butter oil-loaded nanoemulsions were investigated in detail with the addition of cationic surfactants (cetyl trimethyl ammonium chloride, 1631; octadecyl trimethyl ammonium chloride, 1831), anionic surfactants (alcohol ethoxysulfate, AES; dodecyl phosphate ester sodium salt, MAP), and zwitterionic surfactants (cocoamidopropyl betaine, CAB; dodecyl hydroxysulfobetaine, 20HD). By increasing the concentration of cationic surfactants, the positively charged nanoemulsions were prepared and the smallest droplets were being formed with 0.05% 1831. Upon the addition of anionic surfactants, a more negative value was obtained and the smallest droplets were being formed with 0.1% AES. The ionic surfactants by increasing the electrostatic interactions between droplets and incorporation into the oil phase improved the stability of the nanoemulsions via lowering the Ostwald ripening rate, and especially improved the high temperature stability. By increasing the concentration of zwitterionic surfactants, a less negative zeta potential was observed and the stability of the nanoemulsions did not improve. The results proved that the electrosteric repulsion had an appreciable impact on the stability of the nanoemulsions.     

Preparation and characterization of bioactive oils nanoemulsions: Effect of oil unsaturation degree,emulsifier type and concentration

The effect of formulation parameters namely oil type, emulsifier type and concentration was assessed on various properties of the nanoemulsions. All nanoemulsions yielded droplets with a desirable size ranged from 38.5 to 127.9?nm. The findings showed that emulsifier type had significant effects on the physicochemical properties of emulsions. Emulsifier concentration had a negative correlation with droplet diameter, turbidity and positive correlation with polydispersity index, viscosity and creaming stability. Nanoemulsions prepared from pomegranate seed oil were different from that of two other oils in droplet size, viscosity, creaming and turbidity because of its higher intrinsic viscosity and degree of unsaturation.     

Preparation of highly monodisperse W/O emulsions with hydrophobically modified SPG membranes

Experimental investigations on the hydrophobic modification of SPG membranes and the preparation of monodisperse W/O (water-in-oil) emulsions using the modified membranes were carried out. Effects of the osmotic pressure of disperse phase, the average pore size of membranes, emulsifier concentrations in continuous phase and the transmembrane pressure on the average size, size distribution and size dispersion coefficient of emulsions were systematically studied. The stability of W/O emulsions was also investigated. The results showed that SPG membranes took on excellent hydrophobicity through the modification by silane coupler reagent (octyltriethoxysilane) or by silicone resin (polymethylsilsesquioxane). Monodisperse W/O emulsions with size dispersion coefficient of about 0.25, which meant high monodispersity, were successfully prepared by using the hydrophobically modified SPG membranes with average pore sizes of 1.8, 2.0, 2.5, 4.8 and 11.1 microm. When the osmotic pressure was lower than 0.855 MPa, the average size of emulsions was gradually increased while the size dispersion coefficient delta gradually decreased with the osmotic pressure; when the osmotic pressure was higher than 0.855 MPa, both the coefficients kept unvarying. When kerosene was saturated with disperse phase in advance, the average size of emulsions became larger and the monodispersity of emulsions was slightly better than that prepared using unsaturated kerosene. The smaller the pore size of SPG membranes was, the better the monodispersity of the W/O emulsions. The average size and size dispersion coefficient delta were nearly independent on the emulsifier concentrations when the PGPR concentration was in the range from 0.5 to 5.0 wt%, whereas both of them slightly increased as the PGPR concentration was below 0.5 wt%. The effect of the transmembrane pressure on size distributions was slight. Both the average size and size dispersion coefficient delta slightly increased to some extent with the increase of the transmembrane pressure in the experimental range. The stability of the W/O emulsions was dependent on the storage time. The mean size of W/O emulsions decreased gradually with the increase of storage time at the first 35 days, and then kept constant; while the size dispersion coefficient of W/O emulsions was nearly not changed.     

Ostwald ripening of oil-in-water emulsions stabilized by phenoxy-substituted dextrans

The stability of oil-in-water emulsions prepared using dextran, a natural polysaccharide, hydrophobically substituted with phenoxy groups, was studied. The evolution of the emulsion droplet size was investigated as a function of polymer concentration (Cp=0.2 to 1% w/w in a water phase) and the degree of phenoxy substitution (tau=4.2 to 15.7%). For the highest tau values, emulsions, which presented submicrometer droplets, were stable over more than 4 months at room temperature. The most substituted polymers clearly showed a better efficiency to lower the surface tension at the oil/water interface. DexP did not induce real viscosification of the continuous phase. The linearity of the particle volume variation with time, and the invariability of the volume distribution function, proved that Ostwald ripening was the main destabilization mechanism of the phenoxy dextran emulsions. The nature of the oil dispersed phase drastically affected the behavior of emulsions. While the emulsions prepared with n-dodecane presented a particle growth with time, only few size variations occurred when n-hexadecane was used. Furthermore, small ratios of n-hexadecane in n-dodecane phase reduced the particle growth due to the lower solubility and lower diffusion coefficient in water of n-hexadecane, which acted as a ripening inhibitor.     

How to prepare and stabilize very small nanoemulsions

Practical and theoretical considerations that apply when aiming to formulate by ultrasonication very small nanoemulsions (particle diameter up to 150 nm) with very high stability are presented and discussed. The droplet size evolution during sonication can be described by a monoexponential function of the sonication time, the characteristic time scale depending essentially on the applied power. A unique master curve is obtained when plotting the mean diameter size evolution as a function of sonication energy. We then show that Ostwald ripening remains the main destabilization mechanism whereas coalescence can be easily prevented due to the nanometric size of droplets. The incorporation of "trapped species" within the droplet interior is able to counteract Ostwald ripening, and this concept can be extended to the membrane compartment. We finally clarify that nanoemulsions are not thermodynamically stable systems, even in the case where their composition lies very close to the demixing line of a thermodynamically stable microemulsion domain. However, as exemplified in the present work, nanoemulsion systems can present very long-term kinetic stability.     

Demulsification of water-in-oil emulsions by permeation through Shirasu-porous-glass (SPG) membranes

To investigate the effect of the droplet/pore size ratio on membrane demulsification, water-in-oil (W/O) emulsions with uniform-sized droplets was demulsified by permeation through Shirasu-porous-glass (SPG) membranes with a narrow pore size distribution at mean droplet/pore diameter ratios of 0.52–5.75. At transmembrane pressures above a critical pressure, the water droplets larger than the membrane pore size were demulsified, where the SPG membrane acted as a coalescer because the hydrophilic membrane surface had a high affinity for the water droplets. By contrast, at transmembrane pressures below the critical pressure, the larger water droplets were all retained by the membrane due to the sieving effect of the uniform-sized pores. When a W/O emulsion with a mean droplet diameter of 2.30 μm was allowed to permeate through a membrane with a mean pore diameter of 0.86 μm, the demulsification efficiency increased with increasing transmembrane pressure, to a maximum value of 91% at a transmembrane pressure of 392 kPa, and then decreased, while the transmembrane flux increased almost linearly with increasing transmembrane pressure. The demulsification efficiency was higher for higher water phase content and lower concentration of the surfactant, tetraglycerin condensed ricinoleic acid ester, in the emulsions due to the reduction of the emulsion stability.     

Ceramic membrane characterization via the bubble point technique

Porous membranes having nanometer and smaller pores challenge existing characterization methods. An easy, fast and inexpensive method to determine the maximum pore size and the pore size distribution is offered by the bubble point technique. Several methods based on similar principles have been presented in the literature. Here the original bubble point test and a liquid-liquid variation are considered. Two types of ceramic membranes with very different morphologies have been characterized with these methods in our labs. Results obtained for Anodisc^® flat disc membranes with straight, non-intersecting pores using binary and ternary probing liquid systems are in very good agreement with each other and the manufacturers characteristics. On the other hand, analysis of tubular γ-alumina membranes, i.e., Membralox^®, resulted in two phase flow within the pores, and hence information about the pore size distribution could not be extracted from these tests.     

Characteristics of spontaneously formed nanoemulsions in octane/AOT/brine systems

Nanoemulsions were formed spontaneously by diluting water-in-oil (W/O) or brine-in-oil (B/O) microemulsions of a hydrocarbon (octane), anionic surfactant (Aerosol-OT or AOT) and water or NaCl brine in varying levels of excess brine. The water-continuous nanoemulsions were characterized by interfacial tension, dynamic light scattering, electrophoresis, optical microscopy and phase-behavior studies. The mechanism of emulsification was local supersaturation and resulting nucleation of oil during inversion. For nanoemulsions formed at low salinities with Winsor I phase behavior, octane drops grew from initial diameters of 150-250nm to 480-1000nm over 24h, depending on salinity. Growth was caused by mass transfer but seemed to approach the asymptotic stage of Ostwald ripening described by the Lifshitz-Slyozov-Wagner (LSW) theory only for dilution with salt-free water. Near the higher cross-over salinity (Winsor III), the nanoemulsions showed much slower growth with droplet size consistently remaining below 200nm over 24h and reaching 250nm after 1week. Birefringence indicated the presence of liquid crystal for these conditions, which could have contributed to the slow growth rate. At even higher salinity levels in the Winsor II domain, W/O/W multiple emulsions having drops greater than 1μm in diameter were consistently recorded for the first 5-7h, after which size decreased to values below 1μm. The number and size of internal water droplets in multiple emulsion drops was found to decrease over time, suggesting coalescence of internal droplets with the continuous water phase and mass transfer of water from internal droplets to continuous phase as possible mechanisms of the observed drop shrinkage. Electrophoresis studies showed the nanoemulsions to be highly negatively charged (zeta potentials of -60mV to -120mV). The high charge on octane droplets helped assure stability to flocculation and coalescence, thereby allowing mass transfer to control growth in the Winsor I and III regions.     

Effect of Ionic Strength of Dispersed Phase on Ostwald Ripening in Water-in-Oil Emulsions

Water-in-oil emulsions with a low electrolyte content in the internal phase are unstable with respect to Ostwald ripening. The main components of the total pressure acting on the surface of internal phase droplets are considered. The equilibrium values of the diameters of dispersed phase droplets are calculated. The dependences of the difference in the osmotic and Laplace pressures on the droplet size and electrolyte concentration in the droplets are obtained. It is shown that, at the electrolyte concentration below the critical value, the number of droplets in emulsion decreases. If the concentration is above the critical value, water diffuses from small to large droplets, but their number remains unchanged. The change in NaCl concentration in the droplets of internal phase of polydisperse emulsion during the Ostwald ripening is calculated. The results of calculations correlate with the experimental data on the stability of emulsions with respect to coalescence and sedimentation.     

Optimization of Phytosterols Dispersion in an Oil/Water Emulsion Using Mixture Design Approach

Major problems related to enrichment of products with phytosterols are high melting temperature, chalky taste and low solubility in water phase. Dispersion of phytosterols in an emulsion was optimized using a mixture design with four components (phytosterols, emulsifier, soy oil, and water). It was found that the particle size of the dispersed phase decreased with the increase in emulsifier concentration. The appearance viscosity was increased with decreasing particle size. The stability of these emulsions could be correlated with the decrease in surface tension and particle size by using oil and emulsifier as components of oil phase.     

Phase ripening in particulate binary polymer blends

Particulate polymer‐in‐polymer mezodispersions show a pronounced increase in the size of the dispersed particles during melt‐phase annealing. Three ripening mechanisms have been proposed: Brownian coalescence, Ostwald ripening, and hydrodynamic coarsening. The modified Cahn–Hilliard equation predicts growth by Ostwald ripening and diffusion‐induced coalescence. Simulations of this mechanism show a self‐similar particle size distribution, but the distribution broadens with the increasing volume fraction of the minor phase. Hydrodynamic coarsening caused by concentration gradients and random Brownian forces has been simulated according to the hydrodynamic model. The simulations show that concentration‐driven hydrodynamics have little effect on the particle size distribution. Experiments have been performed to investigate the relative importance of these ripening mechanisms for polybutadiene in a polystyrene system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 603–612, 2004     

Aging of oil-in-water emulsions: the role of the oil

Controlling stability and aging of emulsions is important from commercial and scientific perspectives. Achieving such control comes through gaining an understanding of the relationship between emulsion constituents and microstructure and how these influence the kinetics and mechanism of destabilisation. We present here an investigation determining the rate of destabilisation as a function of time for a series of water/n-alkane/Triton X-100 oil-in-water emulsions. The time dependence of the emulsions was investigated using static light scattering, PFG-NMR and measurement of gross phase separation. By changing the chain length of the oil from hexane to tetradecane, an almost five orders of magnitude variation in emulsion lifetime could be achieved, while maintaining most of the other chemical and physical characteristics of the emulsions. Further, we show that while Ostwald ripening is the dominant destabilisation mechanism, two distinct regimes are evident. Initially, we observed an enhanced Ostwald ripening regime due to the presence of oil-swollen micelles in the aqueous continuum, that is a depletion flocculation mechanism is followed. The presence of oil-swollen micelles was confirmed using PFG-NMR. The micelles aid the gross oil transport between the discrete oil domains. Upon phase separation the oil-swollen micelles are predominantly removed from the emulsion along with the excess water resulting in a concomitant reduction in the ripening rate, producing the more general Ostwald ripening cubic dependence of droplet radius as a function of time for the lower molecular weight oils. The oils with higher molecular weight (decane and above), however, were observed to switch over to destabilisation via creaming. PFG-NMR was shown to be a powerful technique to fully probe emulsion microstructure as a function of time with droplet size and spacing being directly obtained from the data.