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.     

Effect of diutan microbial polysaccharide on the stability and rheological properties of O/W nanoemulsions formed with a blend of Span20-Tween20

The stability and rheological behavior of oil-in-water (O/W) nano-emulsions formed with a blend of Span20-Tween20 have been studied with and without diutan microbial polysaccharide. It is found that there exist thresholds for the water content and emulsifier to obtain stable nano-emulsions using the emulsion inversion phase (EIP) method. The viscosity of the nano-emulsion is proportional to the emulsifier content and inversely proportional to the water content. High emulsifier content is not conducive to the thermal stability of the nano-emulsion. The addition of diutan gum with negative charge into the nano-emulsions increases the electrostatic repulsion between droplets and makes the droplet size smaller and more unifom, slowing down the coalescence and Ostwald ripening of the nano-emulsions. Due to the association of the diutan gum double helix, a three-dimensional network structure is formed in the continuous phase of nano-emulsions, which improves the stability of nano-emulsions and is also the main factor giving the nano-emulsion high viscoelasticity at high temperature. This study offers new insight into the nano-emulsion containing microbial polysaccharide and may serve as a guideline for practical applications of new nano-emulsion systems.     

Properties of water-in-oil (W/O) nano-emulsions prepared by a low-energy emulsification method

Properties of water-in-oil (W/O) nano-emulsion formed by a low-energy emulsification method are described in this work. Nano-emulsions have been formed in water/mixed non-ionic surfactant/decane. Several mixtures of Span 20, Span 80, Tween 20 and Tween 80 were studied. Phase behavior studies and stability studies allowed to determine zones where nano-emulsions can be formed. Bluish and transparent W/O nano-emulsion with droplet sizes as low as 30 nm was formed. Nano-emulsion droplet size was measured by Dynamic Light Scattering. Nano-emulsions stability was studied by multiple light scattering and by dynamic light scattering. The results showed the evolution with time of the average radius droplet. The nano-emulsions prepared showed high kinetic stability for weeks, without phase separation, sedimentation or creaming. Nevertheless, their droplet size increased slightly over time. Stability studies show that nano-emulsion breakdown could be attributed to Ostwald ripening and coalescence mechanism, depending on the water concentration.     

Modification of the stability of oil-in-water nano-emulsions by polymers with different structures

The effect of polymers (hydrolyzed polyacrylamide (HPAM) and hydrophobically modified polyacrylamide (HMPAM)) on the stability of oil-in-water nano-emulsions has been studied in paraffin oil/Span 20-Tween 20/water systems by method of phase inversion composition (PIC). The stabilization of nano-emulsions was investigated by visual observation and the change of water content induced by centrifugation. Droplet size distributions of nano-emulsions were obtained by a laser-scanner particle size distribution analyzer. The interfacial tension and charge of nano-emulsions were obtained by interfacial tension and zeta potential measurements. All the results indicate that the droplet size can be decreased by the addition of HMPAM, while almost no change could be observed when the HPAM was added. Meanwhile, HMPAM has a better effect on the stabilization of nano-emulsions than HPAM. It may conclude that the HMPAM molecules adsorbed at the oil/water interface of the nano-emulsion droplets. Therefore, the stability of nano-emulsion with the addition of HMPAM is based on both an associative thickening mechanism caused by the alkyl chains of HMPAM molecules and the adsorption of HMPAM at the oil/water interface, which can form a solid film to prevent the Ostwald ripening of nano-emulsion droplets.     

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).     

Control of Ostwald ripening by using surfactants with high surface modulus

We describe results from systematic measurements of the rate of bubble Ostwald ripening in foams with air volume fraction of 90%. Several surfactant systems, with high and low surface modulus, were used to clarify the effect of the surfactant adsorption layer on the gas permeability across the foam films. In one series of experiments, glycerol was added to the foaming solutions to clarify how changes in the composition of the aqueous phase affect the rate of bubble coarsening. The experimental results are interpreted by a new theoretical model, which allowed us to determine the overall gas permeability of the foam films in the systems studied, and to decompose the film permeability into contributions coming from the surfactant adsorption layers and from the aqueous core of the films. For verification of the theoretical model, the gas permeability determined from the experiments with bulk foams are compared with values, determined in an independent set of measurements with the diminishing bubble method (single bubble attached at large air-water interface) and reasonably good agreement between the results obtained by the two methods is found. The analysis of the experimental data showed that the rate of bubble Ostwald ripening in the studied foams depends on (1) type of used surfactant-surfactants with high surface modulus lead to much slower rate of Ostwald ripening, which is explained by the reduced gas permeability of the adsorption layers in these systems; (2) presence of glycerol which reduces the gas solubility and diffusivity in the aqueous core of the foam film (without affecting the permeability of the adsorption layers), thus also leading to slower Ostwald ripening. Direct measurements showed that the foam films in the studied systems had very similar thicknesses, thus ruling out the possible explanation that the observed differences in the Ostwald ripening are due to different film thicknesses. Experiments with the Langmuir trough were used to demonstrate that the possible differences in the surface tensions of the shrinking and expanding bubbles in a given foam are too small to strongly affect the rate of Ostwald ripening in the specific systems studied here, despite the fact that some of the surfactant solutions have rather high surface modulus. The main reason for the latter observation is that the rate of surface deformation of the coarsening bubbles is extremely low, on the order of 10(-4) s(-1), so that the relaxation of the surface tension (though also slow for the high surface modulus systems) is still able to reduce the surface tension variations down to several mN/m. Thus, we conclude that the main reason for the reduced rate of bubble Ostwald ripening in the systems with high surface modulus is the low solubility and diffusivity of the gas molecules in the respective condensed adsorption layers (which have solid rather than fluid molecular packing).     

Enhancement of Ostwald ripening by depletion flocculation

The time dependence of the dynamic mobility and the ultrasonic attenuation of octane and decane oil-in-water emulsions stabilized by sodium dodecyl sulfate (SDS) was measured. The emulsions grew to larger droplets due to Ostwald ripening. The growth rate measured by attenuation depends on the surfactant concentration and the polydispersity of the emulsion. At surfactant concentrations below the critical micelle concentration (cmc) of SDS, the growth was linear with time and the rate was dependent on the polydispersity of the drops; the rate was several times faster than that predicted on the basis of a diffusion growth mechanism. Above the cmc, however, as the droplets grew in size there was a point at which the rate of growth increased, which corresponds to the droplet size at which depletion forces due to the surfactant micelles become significant. Under these conditions both the electroacoustic dynamic mobility and the acoustic attenuation spectra displayed characteristics of flocs: a large decrease in the phase lag at higher frequencies in the dynamic mobility spectrum and a decrease in the attenuation coefficient at low-megahertz frequencies with an increase at higher frequencies. This depletion flocculation enhancement in ripening rates in the presence of SDS micelles provides another, alternative, and self-consistent mechanism for the effect of surfactant micelles on Ostwald ripening.     

Progress in understanding emulsion metastability and surface forces

We provide an overview of the most recent advances in the field of surfactant and polymer-stabilized emulsions. The article is focused on inter-droplet forces, monolayer adhesion, aggregation of emulsion droplets, emulsion gels and finally destruction through coalescence and Ostwald ripening.     

Monitoring the simultaneous ostwald ripening and solubilization of emulsions

The simultaneous Ostwald ripening of an emulsion and the solubilization of its oil droplets by added micellar surfactant solutions are monitored by measurements of time-averaged scattered intensities. A simple computer simulation model for the interpretation of the measurements is presented. Experimental data are analyzed with this model using one single parameter: an effective ratio of oil to surfactant molecules involved in the withdrawal of oil from the Ostwald ripening process by the added micelles. The fitted value of this parameter appears to be more than twice the one that can be predicted from the equilibrium solubilization of oil by the surfactant micelles, indicating that more oil is involved in the nonequilibrium exchange of oil and surfactant between micelles and droplets.     

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.     

Preparation of positively charged oil/water nano-emulsions with a sub-PIT method

The phase inversion temperature (PIT) method is generally used to prepare nonionic surfactant stabilized nano-emulsions because of its low energy and surfactant consumption. The emulsion droplets are usually negatively charged because of the selective adsorption of OH(-) onto the droplet surfaces. In this work, positively charged oil/water nano-emulsions were prepared by adding a cationic surfactant to the system. The cationic molecules change the spontaneous curvature of the surfactant layers and raise the PIT above 100 °C. The PIT can be depressed by addition of NaBr, as shown by conductivity measurements and equilibrium phase behavior. Therefore, these nano-emulsions can be prepared by the PIT method. We found that the formation of the nano-emulsions did not require a cross-PIT cycle. The mechanism of the emulsification is the formation of mixed swollen micelles that can solubilize all the oil above a "clearing boundary", followed by a stir-quench to a temperature where these droplets become metastable emulsions. The zeta potential of the emulsion droplets can be easily tuned by varying the cationic surfactant concentrations. Due to electrosteric stabilization, the resulting nano-emulsions are highly stable, thus could find significant applications in areas such as pharmaceuticals, cosmetics and food industries.     

Ostwald ripening of water-in-hydrocarbon emulsions

The purposes of this study are to determine Ostwald ripening rates in water-in-oil (W/O) emulsions and evaluate the potential application of the LSW theory to W/O emulsions. Water-in-oil emulsions were prepared by mixing water and hydrocarbon phases containing Span 83 and homogenizing. n-Heptane, n-decane, n-dodecane, and n-tetradecane were used to obtain a range of solubilities. A linear increase in the cube of the droplet size with time was observed (within the initial period of 1-2 h after emulsion preparation), supporting the LSW theory. Based on this linear relationship, Ostwald ripening rates were determined to be 3.0 x 10(-24), 2.3 x 10(-24), 1.8 x 10(-24), and 5.8 x 10(-25) m3 s(-1) for water-in-heptane, water-in-decane, water-in-dodecane, and water-in-tetradecane emulsions, respectively. These values are in agreement with theoretical predictions calculated using the LSW equation. It was observed that the ripening process gradually slowed, resulting in deviations from the LSW theory. This was attributed to the effect of the interfacial surfactant film through which the dispersed material has to diffuse during Ostwald ripening. This effect is not taken into consideration by the LSW theory. The results showed that Ostwald ripening of W/O emulsions was less sensitive to the nature of oil used and slower compared to O/W emulsions consisting of the same hydrocarbons.     

Influence of interfacial characteristics on Ostwald ripening in hydrocarbon oil-in-water emulsions

The influence of the nature of the interfacial membrane on the kinetics of droplet growth in hydrocarbon oil-in-water emulsions was investigated. Droplet growth rates were determined by measuring changes in the droplet size distribution of 1 wt % n-tetradecane or n-octadecane oil-in-water emulsions using laser diffraction. The interfacial properties of the droplets were manipulated by coating them with either an SDS layer or with an SDS-chitosan layer using an electrostatic deposition method. The emulsion containing SDS-coated octadecane droplets did not exhibit droplet growth during storage for 400 h, which showed that it was stable to Ostwald ripening because of this oils extremely low water-solubility. The emulsion containing SDS-coated n-tetradecane droplets showed a considerable increase in mean droplet size with time, which was attributed to Ostwald ripening associated with this oils appreciable water-solubility. On the other hand, an emulsion containing SDS-chitosan coated n-tetradecane droplets was stable to droplet growth, which was attributed to the ability of the interfacial membrane to resist deformation because of its elastic modulus and thickness. This study shows that the stability of emulsion droplets to Ostwald ripening can be improved by using an electrostatic deposition method to form thick elastic membranes around the droplets.     

Water Transport by Nanodispersion Droplets in a Water-in-Oil Emulsion

The mechanisms of water transport through an organic dispersion medium are considered for an emulsion during Ostwald ripening and for a three-phase system upon a contact of a water-in-oil emulsion with an external aqueous phase. Electron microscopy shows a formation of nanodispersion droplets during the diffusion of water through the organic phase of water-in-oil emulsions. The experimental water diffusion coefficient during Ostwald ripening in emulsions is 40 times smaller than the calculated molecular diffusion coefficient. The experimental diffusion coefficients are determined for rhodamine C, which solubilizes in the surfactant micelles, and for ethyl alcohol, a cosurfactant, which reduces the interfacial tension in the emulsion and promotes the formation of nanodispersion droplets. The experimental diffusion coefficients of rhodamine C and ethanol are three orders of magnitude smaller than the calculated values. The ratio between the numbers of rhodamine C and water molecules diffusing through the organic phase is 1 : 10000. The nanodispersion droplets are shown to make the main contribution to the water transport in the organic dispersion medium of the emulsions. Water can also be transported by single surfactant molecules, but this mechanism is not the predominant one.     

Solubility of fluorocarbons in water as a key parameter determining fluorocarbon emulsion stability

The kinetics of particle size growth in emulsions of 14 fluorocarbons has been studied by means of photon correlation spectroscopy. It was assumed that Ostwald ripening is the mechanism of emulsion coarsening with time; solubility of fluorocarbons in water (about 10⁻⁶-10⁻¹⁰ml/ml) being the key parameter determining fluorocarbon emulsion stabilities. The solubilities of fluorocarbons in water were calculated from the Ostwald ripening kinetics data and a solubility-fluorocarbon structure relationship was established. In a homologous series of normal chain fluorocarbons the solubility in water decreased by a factor of 8.0 for each -CF₂ - group. For a given carbon number, ring formation and branching increased water solubility of the fluorocarbons. A correlation between fluorocarbon solubility in water and solvent cavity surface area was found which allows prediction of the fluorocarbon emulsion stability from the structure of the fluorocarbon.     

Inhibition of Ostwald ripening in heptane/water miniemulsions

The Ostwald ripening has been shown to cause the degradation of model low-concentrated heptane/water miniemulsions containing, as the only stabilizer, Tween 80 (Tw), hydroxypropyl cellulose (HPC), a drug (amlodipine (Am) or felodipine (F)), or a promoter of skin permeability (glyceryl monooleate (GMO)). The efficiency of the Ostwald ripening inhibition increases in the following series: Am < Tw < GMO < HPC < F. The analysis of different mechanisms of the Ostwald ripening inhibition by the hydrophilic (Tw, HPC) and lipophilic (Am, F, GMO) surface-active stabilizers has resulted in the preparation of a stable high-concentrated miniemulsion containing F, GMO, HPC, and Tw, this emulsion being promising for pharmaceutical fields of application.     

Stabilization of carbon dioxide-in-water emulsions with silica nanoparticles

Stable carbon dioxide-in-water emulsions were formed with silica nanoparticles adsorbed at the interface. The emulsion stability and droplet size were characterized with optical microscopy, turbidimetry, and measurements of creaming rates. The increase in the emulsion stability as the silica particle hydrophilicity was decreased from 100% SiOH to 76% SiOH is described in terms of the contact angles and the resulting energies of attachment for the silica particles at the water-CO(2) interface. The emulsion stability also increased with an increase in the particle concentration, CO(2) density, and shear rate. The dominant destabilization mechanism was creaming, whereas flocculation, coalescence, and Ostwald ripening played only a minor role over the CO(2) densities investigated. The ability to stabilize these emulsions with solid particles at CO(2) densities as low as 0.739 g/mL is particularly relevant in practical applications, given the difficulty in stabilizing these emulsions with surfactants, because of the unusually weak solvation of the surfactant tails by CO(2).     

The influence of surfactant mixing ratio on nano-emulsion formation by the pit method

The formation of O/W nano-emulsions by the PIT emulsification method in water/mixed nonionic surfactant/oil systems has been studied. The hydrophilic-lipophilic properties of the surfactant were varied by mixing polyoxyethylene 4-lauryl ether (C12E4) and polyoxyethylene 6-lauryl ether (C12E6). Emulsification was performed in samples with constant oil concentration (20 wt%) by fast cooling from the corresponding HLB temperature to 25 degrees C. Nano-emulsions with droplet radius 60-70 nm and 25-30 nm were obtained at total surfactant concentrations of 4 and 8 wt%, respectively. Moreover, droplet size remained practically unchanged, independent of the surfactant mixing ratio, X(C12E6). At 4 wt% surfactant concentration, the polydispersity and instability of nano-emulsions increased with the increase in X(C12E6). However, at 8 wt% surfactant concentration, nano-emulsions with low polydispersity and high stability were obtained in a wide range of surfactant mixing ratios. Phase behavior studies showed that at 4 wt% surfactant concentration, three-liquid phases (W+D+O) coexist at the starting emulsification temperature. Furthermore, the excess oil phase with respect to the microemulsion D-phase increases with the increase in X(C12E6), which could explain the increase in instability. At 8 wt% surfactant concentration, a microemulsion D-phase is present when emulsification starts. The low droplet size and polydispersity and higher stability of these nano-emulsions have been attributed, in addition to the increase in the surface or interfacial activity, to the spontaneous emulsification produced in the microemulsion D-phase.     

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.     

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.