Emulsions droplet size distributions

Dickinson, E., Galazka, V. B., and Anderson, D. M. W. (1991a). Emulsifying behavior of gum arabic. Part I. Effect of the nature of the oil phase on the emulsion droplet-size distribution. Carbohydr. Polym. 14 373-383 Part II. Effect of the gum molecular weight on the emulsion droplet-size distribution. Carbohydr. Polym. 14 385-392. 

Droplet size depends on a number of factors such as the type of oil, brine composition, interfacial properties of the oil-water system, surface-active agents present (added or naturally occurring), flow velocity, and nature of porous material. For the study of OAV emulsions, McAuliffe (9) varied emulsion droplet sizes and size distributions by increasing the sodium hydroxide concentration in the aqueous phase, as shown in Figure 10. Higher NaOH concentration neutralizes more of the surface-active acids in the crude oil and produces an emulsion that has droplets of smaller diameters and is also more stable. Emulsion droplet size distribution can also be varied by varying the concentration of a surfactant added to the crude oil, as shown in Figure 11. 

Droplet diameters of emulsions stored for 12 months show smaller dmean values than droplets of fresh emulsions in the case of acrylate variation (Fig. 5). For SE47-01-05-17 and SE47-10-05-17 the difference in dmean is approx. 1 p.m, whereas emulsions with concentrations between 0.3 and 0.9 wt. % acrylate have dmsm values which are 0.5 p.m smaller compared to dmsm from fresh emulsions. Droplet size distributions of aged emulsions are less broad than... 

Emulsion A has a droplet size distribution that obeys the ordinary Gaussian error curve. The most probable droplet size is 5 iim. Make a plot of p/p(max), where p(max) is the maximum probability, versus size if the width at p/p(max) = j corresponds to... 

As an example figure B 1.14.13 shows the droplet size distribution of oil drops in the cream layer of a decane-in-water emulsion as determined by PFG [45]. Each curve represents the distribution at a different height in the cream with large drops at the top of the cream. The inset shows the PFG echo decay trains as a fiinction of... 

Figure Bl.14.13. Derivation of the droplet size distribution in a cream layer of a decane/water emulsion from PGSE data. The inset shows the signal attenuation as a fiinction of the gradient strength for diflfiision weighting recorded at each position (top trace = bottom of cream). A Stokes-based velocity model (solid lines) was fitted to the experimental data (solid circles). The curious horizontal trace in the centre of the plot is due to partial volume filling at the water/cream interface. The droplet size distribution of the emulsion was calculated as a fiinction of height from these NMR data. The most intense narrowest distribution occurs at the base of the cream and the curves proceed logically up tlirough the cream in steps of 0.041 cm. It is concluded from these data that the biggest droplets are found at the top and the smallest at the bottom of tlie cream.

MoDonald P J, Ciampi E, Keddie J L, Fleidenreioh M and Kimmioh R, Magnetio resonanoe determination of the spatial dependenoe of the droplet size distribution in the oream layer of oil-in-water emulsions evidenoe for the effeots of depletion floooulation Rhys. Rev. E, submitted... 

A Malvern Mastersizer (Malvern Instruments Ltd, Malvern, UK) with optical parameters defined by the manufacturer s presentation code 0505 was used to determine the droplet size distribution. The measurement was made in triplicate at room temperature. Water was used to disperse the emulsion droplets. 

In terms of measuring emulsion microstructure, ultrasonics is complementary to NMRI in that it is sensitive to droplet flocculation [54], which is the aggregation of droplets into clusters, or floes, without the occurrence of droplet fusion, or coalescence, as described earlier. Flocculation is an emulsion destabilization mechanism because it disrupts the uniform dispersion of discrete droplets. Furthermore, flocculation promotes creaming in the emulsion, as large clusters of droplets separate rapidly from the continuous phase, and also promotes coalescence, because droplets inside the clusters are in close contact for long periods of time. Ideally, a full characterization of an emulsion would include NMRI measurements of droplet size distributions, which only depend on the interior dimensions of the droplets and therefore are independent of flocculation, and also ultrasonic spectroscopy, which can characterize flocculation properties. 

Figure 4.5.8 shows the spatially-resolved droplet size distribution of a fully creamed isooctane-in-water emulsion obtained using the PGSTE pulse sequence shown in Figure 4.5.5(b). It can be seen that this method is able to provide droplet size distributions with spatial resolution. 

Studies of flow-induced coalescence are possible with the methods described here. Effects of flow conditions and emulsion properties, such as shear rate, initial droplet size, viscosity and type of surfactant can be investigated in detail. Recently developed, fast (3-10 s) [82, 83] PFG NMR methods of measuring droplet size distributions have provided nearly real-time droplet distribution curves during evolving flows such as emulsification [83], Studies of other destabilization mechanisms in emulsions such as creaming and flocculation can also be performed. 

Spatially-resolved measurement of the droplet size distribution can be accomplished by the implementation of velocity compensated pulse sequences, such as the double PGSTE [81] in a spatially resolved imaging sequence. Accurate measurements of spatially resolved droplet size distributions during flow and mixing of emulsions would provide truly unique information regarding flow effects on the spatial distribution of droplets. 

G. J. W. Goudappel, J. P. M. van Duyn-hoven, M. M. W. Mooren 2001, (Measurement of oil droplet size distributions in food oil/water emulsions by time domain pulsed field gradient NMR), /. Colloid Interface Sci. 239, 535. 

M. Heidenreich, R. Kimmich 1999, (Magnetic-resonance determination of the spatial dependence of the droplet size distribution in the cream layer of oil-in-water emulsions Evidence for the effects of depletion flocculation) Phys. Rev. E 59, 874. 

K. J. Packer, C. Rees 1972, (Pulsed NMR studies of restricted diffusion. 1. Droplet size distributions in emulsions),/. Colloid Interface Sci. 40, 206. 

Techniques of emulsification of pharmaceutical products have been reviewed by Block [27]. The location of the emulsifier, the method of incorporation of the phases, the rates of addition, the temperature of each phase, and the rate of cooling after mixing of the phases considerably affect the droplet size distribution, viscosity, and stability of the final emulsion. Roughly four emulsification methods can be distinguished ... 

Rheological Property Determination. The rheology of an emulsion is often an important factor in determining its stability. Any variation in droplet size distribution, degree of flocculation, or phase separation frequently results in viscosity changes. Since most emulsions are non-Newtonian, the cone-plate type device should be used to determine their viscosity rather than the capillary viscometer. 

J. Floury, A. Desrumaux, and J. Lardieres Effect of High-Pressure Homogenization on Droplet Size Distributions and Rheological Properties of Model Oil-in-Water Emulsions. hmovat. Food Sci. Emergi. Technol. 1, 127 (2000). 

Figure 5.13. Evolution of the droplet size distribution with time for an OAV emulsion containing 90 wt% oU and 24.4 mg of sUica particles. (Reproduced from [46], with permission.)...

It is probable that numerous interfacial parameters are involved (surface tension, spontaneous curvature, Gibbs elasticity, surface forces) and differ from one system to the other, according the nature of the surfactants and of the dispersed phase. Only systematic measurements of > will allow going beyond empirics. Besides the numerous fundamental questions, it is also necessary to measure practical reason, which is predicting the emulsion lifetime. This remains a serious challenge for anyone working in the field of emulsions because of the polydisperse and complex evolution of the droplet size distribution. Finally, it is clear that the mean-field approaches adopted to measure > are acceptable as long as the droplet polydispersity remains quite low (P < 50%) and that more elaborate models are required for very polydisperse systems to account for the spatial fiuctuations in the droplet distribution. 

Other pharmaceutical applications have seen the SdFFF applied successfully to monitor droplet size distributions in emulsions, together with their physical state or stability. Some examples are fluorocarbon emulsions, safflower oil emulsions, soybean oil emulsions, octane-in-water emulsions, and fat emulsions. SdFFF is also able to monitor changes in emulsion caused by aging or by the addition of electrolytes. SdFFF has been used to sort liposomes, as unilamellar vesicles or much larger multilamellar vesicles, the cubosom, and polylactate nanoparticles used as drug delivery systems [41]. 

The absorption of ozone from the gas occurred simultaneously with the reaction of the PAH inside the oil droplets. In order to prove that the mass transfer rates of ozone were not limiting in this case, the mass transfer gas/water was optimized and the influence of the mass transfer water/oil was studied by ozonating various oil/water-emulsions with defined oil droplet size distributions. No influence of the mean droplet diameter (1.2 15 pm) on the reaction rate of PAH was observed, consequently the chemical reaction was not controlled by mass transfer at the water/oil interface or diffusion inside the oil droplets. Therefore, a microkinetic description was possible by a first order reaction with regard to the PAH concentration (Kornmuller et al., 1997 a). The effects of pH variation and addition of scavengers indicated a selective direct reaction mechanism of PAH inside the oil droplets... 

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