EMULSIONS

published by srl Via Cesare da Sesto, 10 20123 Milano (Italy) Tel. 0039 02 83241119 Fax 0039 02 8376457 www.b5srl.com

Emulsion preparation: Theoretical notions and practical aspects

J.P. CANSELIER M. POUX

Laboratoire de Gnie Chimique (UMR CNRS 5503 ENSIACET-INPT/UPS) 5 rue Paulin Talabot, BP 1301 F-31106 Toulouse, France Tel +33-534-615254 Fax +33-534-615253 JeanPaul.Canselier@ensiacet.fr

INTRODUCTION

Firstly, some techniques for emulsion characterization (phase identification, droplet size distribution, viscosity) are briefly reviewed. The energy requirements and the main mechanisms involved in emulsification processes are then considered: the conditions of droplet formation and break-up in laminar or turbulent regime are recalled. The roles played by the emulsifier are explained and kinetic aspects are dealt with. Finally, the most frequently used emulsification equipments are described and compared.
JANUARY/FEBRUARY 2004

According to Becher, an emulsion is a heterogeneous system, consisting of at least one immiscible liquid intimately dispersed in another in the form of droplets, whose diameters, in general, exceed 0.1m. Such systems possess a minimal stability, which may be accentuated by such additives as surfaceactive agents, finely-divided solids, etc. (emulsifying agents) (1). Simple emulsions belong to two types: oil in water (O/W) and water in oil (W/O). There are also two kinds of multiple (double) emulsions: W/O/W and O/W/O. The so-called aqueous phase may contain inorganic or organic solutes and the oil phase, often a mixture of species, can be of mineral, vegetable or animal origin. In spite of their thermodynamic instability, natural emulsions are not rare (e.g. milk, rubbertree latex). Synthetic ones are more often formulated products used in extremely various fields, such as food, cosmetics, pharmacy and medicine, biotechnology, agrochemicals, fabric, leather or metal processing, pulp and paper industry, paints and lacquers, detergence, lubrication, road construction, automotive fuels, explosives, etc.. It also happens that emulsions, desirable or not, are formed temporarily during industrial processes (e.g. polymerization, oil extraction). While formulating emulsions, composition variables (nature and proportions of ingredients), temperature and process parameters have to be considered: the former, including temperature, will mainly determine the type of emulsion, whereas the latter will partly govern its stability. In fact, sooner or later, an emulsion will break and undergo Figure 1 Destabilization of an emulsion: phase separation. The observed droplet migration and droplet size alteration from Ref. 49a, with permission changes involve:

reversible phenomena flocculation, creaming or sedimentation according to Stokes law: V=!" g d2 /18 #, if particles only migrate; and irreversible phenomena (Ostwald ripening, coalescence), if particle size is altered (Figure 1). Among the properties enhancing emulsion stability, let us list: a low dispersed-phase volume fraction, a low density difference between phases, a low (but not too low) interfacial tension, a high viscosity of the continuous phase, high mechanical resistance and elasticity of the interface, a high $ potential, a high solubility of the emulsifier in the continuous phase (Bancrofts rule), a narrow droplet size distribution. Increasing temperature often accelerates emulsion breaking. The formulation, properties and stability of emulsions have been described in a number of books and reviews (1-7). As for the theoretical analysis and comparison of emulsification processes, they have given rise to some recent papers (8-15). The present work is intended to briefly summarize the state-of-the-art of emulsion

16

ABSTRACT

EMULSIONS

characterization, mechanisms of formation and emulsification equipment.

hand, for colloidal or finely-dispersed media, a log-normal distribution is considered preferably (29):

EMULSION CHARACTERIZATION
Phase Identification

The continuous and dispersed phases can

be identified by three types of tests: addition of a water-soluble dye, dilution by water and conductivity measurement. In the latter, recommended for instance by AFNOR (16), the higher conductivity of the aqueous phase, especially in the presence of added electrolyte, is turned to account. According to Maxwell (17), the conductivity of not too concentrated emulsions (spherical droplets) obeys to: ! $ !c ! $ !c = d " ! + 2! c ! d + 2! c [1]

where P is the probability of finding a droplet of diameter di, % the geometrical standard deviation and d50 the average geometrical diameter. Criteria for emulsion stability and techniques of emulsion stabilization have been detailed elsewhere (4-6,30).

Viscosity

The viscosity of very dilute emulsions

(" & 0.02) only depends on the volume fraction of the dispersed phase,according to Einsteins relation: 'r = '/'c = 1+(5/2) " [4] where ' and 'c are the shear viscosities of the emulsion and the continuous phase. This relation is obeyed provided that there is no interaction (repulsive Coulombic or attractive Van der Waals forces) between rigid, spherical droplets. If this is not the case, especially for more concentrated emulsions, an empirical, polynomial form may be used: 'r =1+ a " + b "2 + c "3 + [5] with b theoretically equal to 14.1, according to Guth, Gold and Simha (1), but found to vary between 3 and 6 experimentally. More generally, emulsion viscosity also depends on droplet size and DSD (finer, less polydisperse emulsions are more viscous)(31), oil/water interfacial tension, viscosity of both individual phases (mainly the continuous one) and interfacial rheology. Concentrated emulsions often show non-Newtonian behaviour (namely shear-thinning at low shear rate and shear-thickening at higher shear rate), with, possibly, a yield value at a minimum shear stress. Thixotropy, that is apparent viscosity decrease with time at constant shear rate, is observed in very viscous emulsions (e.g. gelemulsions)(4). Viscoelastic properties also characterize highly concentrated emulsions (" > 0,70-0,74). Recent reviews on emulsion viscosity have been published (32,33).

where !, !c and !d are emulsion, continuous phase and dispersed phase specific conductivities, respectively and " is the dispersed phase volume fraction.

Droplet Size and Droplet Size Distribution

Unless a special process is applied to make monodisperse emulsions (18-20), these systems are best characterized by their droplet size distribution (DSD), measured with a particle sizer or, possibly with a microscope or an image analysis system (21). All other things being equal, two emulsions can behave differently only because different DSD (22). However, for a monomodal, not too wide DSD, the surface average diameter (Sauter diameter, d32) is the most representative single parameter: d32 = # nidi3/# nidi2 = 6V/A [2] where ni is the number of droplets belonging to the class of average diameter di, and V and A are the volume and area of the dispersed phase, respectively. Other average diameters, di,i-1, defined similarly, are also in use. Let us notice that, among the commercial particle sizers, only that based on ultrasound velocity is able to deal with concentrated emulsions (up to " = 0.5 or even 0.8) directly (23), whereas the other apparatuses need previous dilutions (" of the order of 10-5). On the other hand, optical reflectance (24) and focussed beam reflectance devices (25) allow to extend the range of DSD techniques towards concentrated media. Besides, Turbiscan MA2000 (26) and Turbiscan on-line (27), operating by measuring back-scattered light intensity, also yield an average droplet size diameter for concentrated emulsions without dilution. The shape of the DSD curve of roughly dispersed liquid-liquid systems corresponds generally to a normal distribution function around d32, with the stirrer diameter and " as main parameters (28). On the other
EMULSIONS

term, T(Sconfig ((Gform = )(A T(Sconfig ~ )A > 0, unless ) < T(Sconfig/A, where spontaneous emulsification can occur) only accounts for about 1 of the total energy provided. For instance, the [3] magnitude of )A in the formation of an oil-in-water emulsion (" = 0,1, = 1m, therefore A/V = 3.105 m-1, ) = 10 mN/m) is 3 kJ/m3 to be compared with an actual energy expense of 3 MJ/m3 necessary to make such an emulsion. In fact, as far as emulsification mechanisms are known, the energy supply is divided between viscous dissipation and energy actually used for droplet formation and droplet break-up, that is interfacial free energy increase, and terms related to droplet deformation and involving dispersed phase viscosity, interfacial viscosity and Laplace pressure, (P: for a spherical droplet of radius r, this pressure difference across the curved interface (the pressure being higher on the concave side) is approximated by: (P =2 ) / r [6] So, (P reaches 1 bar for a droplet radius of 0,2 m and an interfacial tension of 10 mN/m. Energy is more often supplied by mechanical agitation, a more vigorous dispersive action yielding finer droplets. Finally, except )A, the whole amount of energy is dissipated as heat (13). In fact, elementary processes include at least two steps: droplet formation and droplet breaking into smaller ones. The second phenomenon is the most important one: the smaller the droplets, the more stable the emulsion. That is why coalescence must be avoided.

Mechanisms

From the hydrodynamic point of view,

emulsification can take place under laminar or turbulent flow regimes (8,9), the latter being more often turned to account. In the following, a mechanical energy supply will be first considered. We shall see later that some processes are less energy-consuming.

EMULSIFICATION PROCESSES
Energy Requirements

The enormous increase of interfacial

area ((A ~ A) involved during emulsification requires an energy input proportional to the interfacial tension, ). However, the increase of interfacial free energy, including a very small entropic

Figure 2 Instabilities of an interface: 1, capillary waves; 2 and 3, left, development of Rayleigh-Taylor instability; 2 and 3, right, combination of Kelvin-Helmholtz and Rayleigh-Taylor instabilities - from Refs. 63, with permission
JANUARY/FEBRUARY 2004

17

Figure 3 Instability of a stationary liquid cylinder - from Ref. 64, with permission

Droplet Formation Emulsification processes begin with the formation of a film of the future continuous phase around the future dispersed phase. Gibbs elasticity (E = d)/d(lnA)) best explains the phenomena, with the emulsifier concentration as the controlling parameter: with enough surfactant, the thinnest part of the film, possessing the highest E value, will be more resistant to stretching and contribute to stabilization (8). A coarse emulsion can form through the breaking of either a planar interface or a liquid cylinder. The first phenomenon is produced by turbulence, capillary waves, Rayleigh-Taylor or Kelvin-Helmholtz instabilities (14), and it is likely that drop formation results from a combination of those four mechanisms (Figure 2). For instance a low interfacial tension is favorable to overcome the Laplace pressure in turbulent regime and to increase wave amplitude, but, even for very low ) values, Rayleigh-Taylor instability will only produce rather large drops, while interfacial gradients seem to be detrimental to Kelvin-Helmholtz instability. Thin cylinders can come from spikes, produced by interfacial instabilities, or result from a liquid jet or from the stretching of a large drop. The axisymmetrical deformations of a stationary cylinder lead to breaking into droplets surrounded by satellites, especially for an optimum wavelength (Figure 3). A very wide DSD may be observed with a turbulent jet: the average diameter depends on the viscosities and densities of both phases as well as on the jet speed. On the other hand, for a thread coming from a large drop, the more intense the stretching, the smaller the resulting droplets. In a laminar flow, cylinder breaking is controlled by two opposite forces, whose ratio of the associated pressures (Laplace pressure acting against deformation and shear stress favouring deformation) is the Weber number: We = 'c G r/) [7] where 'c is the viscosity of the continuous phase and G the elongation rate (velocity gradient). If We is high enough, the cylinder will be broken by viscous forces (8,14).

Viscous forces and inertial forces play a

18
JANUARY/FEBRUARY 2004

Droplet Break-Up

role in droplet deformation and break-up. dmax = (Wecr)3/5 (+c/))-3/5 *-2/5 = The former, generating stresses tangential C1 (+c/))-3/5 *-2/5 [11] or perpendicular to the droplet surface, Experimentally, dmax has been found predominate in laminar flow, whereas the proportional to d32 (36,37): latter, producing pressure differences, are d32 = K dmax [12] essential in turbulent flow, although viscous with K ranging from 0.38 and 0.70 forces may not be negligible. The Laplace and increasing with viscosity (38,39). pressure is always associated to an internal In continuous processes, the restitution force opposing droplet dependence of the droplet diameter on the disruption. Break-up, due to shear, and residence time (tres) may be combined coalescence phenomena take place with that on power density into a simultaneously and give rise to a dynamic dependence on specific energy. On the equilibrium. other hand, in batch processes, an In laminar flow, a droplet will break up if expression analogous to [11] must include its Weber number is higher than a critical the power density, a function of tres as well value, Wecr, that is if its radius, r, is larger as a term in 'd,. (40). than the critical rcr. Under simple shear and In short, under prevailing inertial forces, for viscosity ratios (q = 'd/'c) between ca. d varies as )0.6 and often as *-0.4 (*-0.6 in a 0.02 and 2, Wecr is of the order of 1, going high-pressure homogenizer)(9), the through a minimum (slightly lower) for exponent of 'd being 0. However, when equal viscosities (9,14,34) (Figure 4). So, viscous forces are predominant, d is highly viscous drops can hardly be proportional to ), to *-0.25 and to a certain deformed. Practically, emulsification in power of 'd, laminar flow can be achieved in a capillary Beside elongational flow in laminar tube (19) or in a regime and colloid mill. The turbulence, a former, low-shear third process is mechanism efficient with both involved in rather viscous droplet phases and high disruption is " values. Energy cavitation. consumption is This low, DSD narrow, phenomenon but the resides in the emulsification formation, in time may reach low-pressure several hours. zones and not Figure 4 Droplet break-up under simple shear The turbulent very deeply in flow (Grace curve) - from Ref. 65, with permission regime is more the liquid, of efficient and more stable or commonly used; it will be supposed transitional tiny bubbles, containing isotropic. If viscous forces appear dissolved gas and/or vapour of the negligible compared with others volatile components of the continuous ('d < 10 mPa.s), droplet stability is phase. During ultrasound emulsification, related to deformation forces (turbulent cavitation takes place as the main fluctuations) and surface forces. The mechanism of droplet breakup Weber number of a moving droplet is (Figure 5), but it also plays a role in then the ratio of the corresponding high-pressure homogenization and, to a energies, *v and *s. Another hypothesis is lesser extent, with classical rotor-stator that the macro-turbulence scale is of the devices. Cavitation is inhibited by an same order of magnitude as the droplet increase of hydrostatic pressure. Energy diameter, d. Then: density (dissipated instantaneously We = *v/ *s = +c (u2d3/)d2 = per mass or volume unit) appears to be +c(u2d/) [8] the key parameter. For instance, at (u = (*.d)1/3 [9] constant energy density, drop size is not We = +c*2/3d5/3/) [10] affected by hydrostatic pressure (8,14). * is the power dissipated per mass unit and (u the fluctuation of the local velocity. Here again, it is assumed that droplets break up when We is higher than Wecr (35): their diameter is then the maximum stable Figure 5 Acoustic emulsification: droplet formation and break-up from Ref. 50, with permission diameter, dmax:
EMULSIONS

Mechanical Processes: Dispersers and Homogenizers As stated above, mechanical processes Effect of the Emulsifier often consist of two Figure 6 Multistage rotor-stator device (VMI-Rayneri model) Although it is considered as successive operations: a practically impossible to first step of mixing and obtain a stable emulsion by only mixing dispersion, leading to a coarse emulsion Kinetic Aspects two pure liquids, Reddy and Fogler (drops of ca. 100 m), is followed by a Three characteristic time scales are claim they made stable, very dilute homogenization step reducing droplet involved in emulsification processes. O/W emulsions through insonation, size and stabilizing the medium. Those The deformation time (or relaxation without using any emulsifying agent operations can be effected in vessels or time following a small deformation of a (41). They assume that their emulsions in pipes (batch or continuous processes) droplet), -def, is of the order of are stable thanks to OH- ion adsorption by means of dispersers and 0.01-0.1 ms, except for large drops in onto oil droplets. Usually, however, the homogenizers, respectively. turbulent regime (-def = 10 ms for addition of at least an emulsifier is For dispersers, the main issue is to r = 1 mm). The adsorption time, -ads, required for enhancing emulsion kinetic produce a high shear able to form and necessary to the transport of the stability. The part played by this additive break up droplets. Stronger shear forces surfactant (by convection) towards the is multiple. More often, it determines are required if the dispersion is harder to new interface, increases from 10-4 ms the emulsion type (O/W or W/O), it prepare. Radial stirrers, such as Rushton in laminar flow to 0.5 ms in turbulent lowers the interfacial tension, produces or pitched blade turbines, are well flow for large drops, and from 0.1 ms interfacial tension gradients during adapted but must ensure a good (laminar) to 6 ms (turbulent) for a emulsification and slows down or recirculation of the fluid: in fact, droplet of critical radius. As regards the prevents coalescence. coalescence is more likely to occur average time between collisions, -col, it The spectacular interfacial tension farther from the stirrer. ranges from 5.10-4 ms in turbulent lowering (from 30-50 mN/m down to a In a homogenizer, the two-phase regime to a few tenths of a ms in few mN/m with a surfactant, or even a mixture, possibly containing rather large laminar flow (8). few N/m in the presence of a drops (10-100 m) is forced to enter a The time needed for disruption is of cosurfactant) reduces the surface free confined zone (e.g. a few-millimeter the same order as -def: so, although energy change and the Laplace wide gap) where it is subjected to very disruption must be repeated many pressure considerably, but the high shear rates. Rotor-stator devices are times, emulsification should be equilibrium value is not the main issue, the most used ones: the product is complete within a second or so. Now, since adsorption times can be long, sucked into the head of the machine, practically, it takes minutes. In fact, compared with drop break-up and due to the high speed of the rotor, then some kinds of machines (colloid mills, collision times. expelled by the blades, passing through high-pressure homogenizers, ultrasound Interfacial tension gradients may the holes or slits of the stator (Figure 6). transmitters, high-speed rotor-stator generate lateral motion of the A particular type of rotor-stator devices) are able to break small interface and even interfacial system is the colloid mill, characterized droplets very quickly, but they are not instability, favourable to droplet by its truncated-cone shape and its very so suitable for the first steps of disruption. In addition, if the narrow gap (= 0.1 mm). The fluid enters emulsification. Inversely, mixers involve surfactant is dissolved in the the mill through its upper part (top of the much slower processes, especially in continuous phase (Bancrofts rule), it cone) and is strongly sheared between the final stages. Therefore, opposes droplet coalescence, thanks the smooth or rough internal surfaces of preemulsifying a mixture by stirring may to the Marangoni effect. Before the gap, at a rotation speed of 3,000 to be advantageous (smaller droplets, equilibrium is reached, while 15,000 rpm. narrower distribution). surfactant adsorption occurs, its A high-pressure homogenizer is a On the whole, emulsification time amount is less and the interfacial machine in which the mixture is forced depends on the process variables and tension higher where the film through a narrow valve slit (~ 0.1 mm). on the nature and amount of surfactant. between droplets is thinner, so that Under the effect of pressure (up to 100 For instance, as regards the supposed liquid flows towards the centre of MPa), the valve opens against a spring. dynamic equilibrium between rupture the film. This self-healing Very high liquid velocities (~200 m.s-1) and coalescence during emulsification, mechanism can only take place if and energy densities (of the order of 106 it has been shown recently that, only at the Gibbs elasticity, E, of the film is W.cm-3) may be reached (8). All other high surfactant concentration, the final high enough. On the contrary, if the things being equal, homogenizers usually DSD reflects the disruption efficiency of surfactant is dissolved in the produce finer emulsions ( ~ 0.2-1m) the device (no coalescence)(42). dispersed phase, E is low, than colloid mills, but not there is no interfacial tension so monodisperse (3). gradient and no liquid flow Various types of emulsifying inside the film: without the devices are represented in Gibbs-Marangoni effect, Figure 7. droplets would coalesce. A novel technique to Coulombic repulsions could prepare monodisperse also play a role in preventing emulsions (%/d50 ~ 0.05) coalescence. Anyway, the uses a microchannel (MC) higher the surfactant device consisting of a concentration, the slower the channel and a terrace. Figure 7 Various emulsifying devices: a) membrane, b) colloid mill, c) and d) high-pressure homogenizers - from Ref. 66, with permission coalescence rate (8,14). Because, on a smaller scale,
EMULSIONS JANUARY/FEBRUARY 2004

Process functions, such as [11], designed for emulsification, can thus provide a guide for process optimization and scaling-up (40).

Techniques and Devices

19

module with outer and inner stator classical membranes has also been applied to apparatus. The the preparation of double emulsions only drawbacks (e.g. by dispersing an aqueous phase are the rather into a vegetable oil containing a short lipophilic surfactant, then dispersing the penetration W/O emulsion into an aqueous phase length of dissolving a hydrophilic surfactant)(58). ultrasonic waves, which Less Common Processes requires preMechanical emulsification Several processes, mentioned in the Processes: Static in the case literature, are seldom used, at least on Mixers where a large scale: this is the case, for maximum example, of spontaneous Pipe flow in laminar or power is not emulsification, phase inversion turbulent regime may applied (28,50) temperature (PIT) emulsification, turn to account and the shaking, electrical techniques, aerosol constrictions and/or restriction to to liquid and condensation processes baffles. By dividing the Figure 8 Piezoceramics ultrasound products of low (8). Let us only consider a few lowflow, whose parts are transducer (sandwich type) - from viscosity. energy processes. then joined together, Ref. 50 with permission Ultrasound In spontaneous emulsification the these obstacles emulsification required energy either comes from a enhance velocity has been recently reviewed (51). chemical reaction (e.g. pouring gradients or turbulence. The fluids vegetable oil containing a few percent are circulated by means of a pump, Membrane Processes of fatty acid into an alkaline aqueous acording to the pressure drop and solution) or from redistribution of the desired flowrate (44). Membrane emulsification, using species inside the medium. Several Emulsions, with rather narrow DSD, mechanisms completely different mechanisms can contribute to this form above a speed threshold (e.g. from the usual ones (52), is well3 m/s to yield droplets smaller than adapted to shear-sensitive 1 m diameter). Static mixers can species. In the more common often replace stirred vessels of these low-shear, low-energy advantageously, because of the processes, the dispersed phase absence of moving parts and their is forced towards the perfect adaptation to continuous continuous one through the processes (45). The plug-flow pores of a microfiltration or model is quite convenient. Their ultrafiltration membrane (crossmain drawback resides in a difficult flow process) (53) (Figure 9). It cleaning. makes sense that, without stirring, ultrafiltration Injection membranes yield finer emulsions than microfiltration In the classical technique, a cylindrical membranes (54), but, in jet of the dispersed phase, entering the Figure 9 Membrane emulsification through a cross-flow addition to membrane average continuous one, is broken up into device - from Ref. 58, with permission pore size and pore size droplets. A new system involves the phenomenon: interfacial turbulence, distribution, the adsorption kinetics collision of two pre-emulsified flows diffusion and trapping of dispersed of the emulsifier onto the droplet (46). Several equations have been phase droplets in the presence of a surface also plays a role (55). A proposed to evaluate droplet size as a co-solvent with possible liquid crystal narrow pore size distribution does function of operating conditions (47). formation (e.g. addition of an not always yield a monodisperse isooctane/isooctanol mixture to an emulsion (56), whereas a mixing Insonation aqueous solution of C12E5)(59), the device on the permeate side helps Emulsification by high-power, lowproducing very disputed transitional occurrence of frequency (~ 20 kHz) smaller droplets a zero or even negative interfacial ultrasound has been with a narrower tension and the recently proposed reported for the first DSD (54). bursting of swollen bilayers, leading to time a long time ago In the more the pulverization of oil micro-droplets (48). Since then, recent dead-end into the aqueous phase (60). various types of process, a coarse Other low-energy techniques do ultrasound devices emulsion is forced not need sophisticated apparatus (1,28,49), mainly through the either. They consist, for instance in operating through membrane: producing a phase transition by cavitation, have been droplets get changing temperature or salinity. Very used. An example of smaller and a fine, blue emulsions can be prepared those is represented in high flowrate by the phase inversion temperature Figure 8. Insonation affords more (PIT) method (61) (Figure 10). Highlyrepresents a very fast, monodisperse concentrated W/O emulsions (gelefficient means of emulsions (57). emulsions) form spontaneously from making fine, therefore Figure 10 Preparation of a fine The Shirasu oil-swollen micellar solutions with an stable O/W, and even emulsion by the phase inversion Porous Glass abrupt increase in temperature (62). W/O emulsions, temperature (PIT) process - from Ref. 67, with permission technique, using a Other examples are cited in (59). compared with rotorinterfacial tension is more significant than other forces, it becomes the driving force for droplet formation. Droplet size may be varied at will according to MC dimensions (43).

20

JANUARY/FEBRUARY 2004

EMULSIONS

CONCLUSION

Although the tools for characterizing emulsions are now well developed and the mechanisms of emulsification reasonably understood, it is still difficult to predict the exact result of an emulsification process, since this is a combination of a lot of parameters, including formulation and process variables. As regards the equipment, mechanical agitation apparatuses, especially rotor-stator devices, and homogenizers will certainly continue to undergo wide use. On the other hand insonation techniques and lower energy systems, such as membranes, appear to be quite advantageous and of great interest in continuous processes.
ACKNOWLEDGEMENT

14)

15) 16)

17)

18)

19) 20)

The authors thank Dr. B. Abismal for his

contribution to this paper during his thesis.

21)

22)

REFERENCES
1) BECHER, P. Emulsions: Theory and Practice, 2nd Edn.; Rheinhold Publishing Corp.: New York, 1965 Encyclopedia of Emulsion Technology, Becher, P. Ed. Marcel Dekker: New York; 1983Vol.1, 1983; vol. 2, 1985; vol. 3, 1987; vol.4, 1996 GRIFFIN, W.C. in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edn.; Grayson M. Ed.; J. Wiley & Sons: New York, 1979; Vol.8, pp.900-930 FRIBERG, S.; JONES, S. in Kirk-Othmer Encyclopedia of Chemical Technology 4th Edn., Kroschwitz J.I. Ed.; J. Wiley & Sons: New York, 1994, Vol.9, pp.393-413 Emulsions and Emulsion Stability, Surfactant Science Series; Sjblom, J. Ed.; Marcel Dekker: New York, 1996, Vol.61 BROCHETTE, P. Techniques de lIngnieur, J2150, Paris, 1999 JOHNSON, J.C. Emulsifiers and Emulsifying Techniques; Noyes Data Corp.: Park Ridge, NJ, 1979 WALSTRA, P. in Encyclopedia of Emulsion Technology; Becher P. Ed.; Marcel Dekker: New York, 1983, Vol.1, pp.57-127 WALSTRA, P. Chem. Eng. Sci. 1993, 48, 333-349 MENDIBOURE, B.; GRACIAA, A.; LACHAISE, J.; MARION, G.; BOURREL, M.; SALAGER, J.L. Progr. Colloid Polym. Sci.1991, 84, 338-341 DICHARRY, C.; MENDIBOURE, B.; MARION, G.; SALAGER, J.L.; LACHAISE, J. Progr. Colloid Polym. Sci.1995, 98, 169- 172 LUCASSEN-REYNDERS, E.H. in Encyclopedia of Emulsion Technology; Becher P. Ed.; Marcel Dekker: New York, 1996, Vol.4, pp.63- 91 DOKIC, P.P.; DAKOVIC, L.M.; 23) 24)

2)

25) 26)

3)

27)

4)

28) 29)

5)

6) 7)

30)

31) 32) 33) 34) 35) 36)

8)

9) 10)

11)

37) 38) 39) 40)

12)

13)

RADIVOJEVIC, P.P.; SOVILJ, V.J.; SEFER, I.B. J. Disp. Sci. Technol. 1999, 20, 215-234 DALMAZZONE, C. Oil and Gas Sci. Technol. Rev. IFP 2000, 55, 281-305 CANSELIER, J.P.; POUX, M. Techniques de l'Ingnieur, Paris, 2003 (in press) Recueil de Normes Franaises: Agents de Surface, Dtergents, Savons; AFNOR: Paris-la-Dfense, 1986 ADAMSON, A.W. Physical Chemistry of Surfaces, 5th Edn.; J. Wiley & Sons: New York, 1990 BIBETTE, J. J. Colloid Interf. Sci. 1991, 147, 474-478; Act. Chim. 1996, 2-3, 23-28 MASON, T.G.; BIBETTE J. Phys. Rev. Letters 1996, 77, 3481-3484 MASON, T.G.; KRALL, A.H.; HU GANG; WEITZ, D.A.; BIBETTE, J. in Encyclopedia of Emulsion Technology; P. Becher Ed.; Marcel Dekker: New York, 1996, Vol.4, pp.299-336 TROTTIER, R.; KYE, B. in Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; Kroschwitz, J.I. Ed.; J. Wiley & Sons: New York, 1997, Vol.22, pp.2565-278 SALAGER, J.L.; RAMIREZ-GOUVEIA, M.; BULLON J. Progr. Colloid Polym. Sci. 1995, 98, 173-176 www.malvern.co.uk DANIELS, R.; KARWOTH, R. in Emulsions and Nanosuspensions for the Formulation of Poorly Soluble Drugs; Mller, R.H., Benita, S.; Bhm, B. Eds.; Medpharm: Stuttgart, 1998, pp.237-255 REVILLON, A. Spectra Analyse 1998, 200, 16-20 MENGUAL, O.; MEUNIER, G., CAYRE, I.; PUECH, K.; SNABRE, P. Talanta 1999, 50, 445-456 MENGUAL, O.; MEUNIER, G.; SNABRE, P. Rcents Progrs en Gnie des Procds 1999, 13, 69, 395-402 ABISMAL, B. Doctoral dissertation, INP Toulouse, Dec. 1999 MENDIBOURE, B.; GRACIAA, A.; LACHAISE, J.; MARION, G.; SALAGER, J.L. Progr. Colloid Polym. Sci.1989, 81, 274 WALSTRA P. in Encyclopedia of Emulsion Technology; Becher P. Ed.; Marcel Dekker: New York, 1996, Vol.4, pp.1-62 PAL, R. AIChE Journal 1996,42, 3181-3190 BARNES, H.A. Colloids and Surfaces A 1994, 91, 89-95 TADROS, Th.F. Colloids and Surfaces A 1994, 91, 39-55 GRACE, H.P. Chem. Eng. Comm. 1982, 14, 2257 HINZE, J.O. AIChE J. 1955, 1, 289 VERMEULEN, T.; WILLIAMS, G.M.; LANGLOIS, G.E. Chem. Eng. Progr. 51, 85-94 DAVIES, J.T., Chem. Eng. Sci. 1987, 42, 1671 CALABRESE, R.V.; CHANG, T.P.K.; DANG P.T. AIChE J. 1986, 32, 657-666 CALABRESE, R.V.; WANG, C.Y.; BRYER, N.P. AIChE J. 1986, 32, 677-681 SCHUCHMANN, H.P.; SCHUBERT, H. Eng. Life Sci. 2003, 3, 67-76

41) REDDY, S.R.; FOGLER, H.S. J. Phys. Chem.1980, 84, 1570-1575 42) TAISNE, L.; WALSTRA, P.; CABANE, B. In Proc. 2nd World Congress on Emulsion, Bordeaux, 1997, Vol.1, 1-2/014 43) SUGIURA, S.; NAKAJIMA, M.; SEKI, M. J. Am. Oil Chem. Soc. 2002, 79, 515-519 44) HEMRAJANI, R.R. in Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; Kroschwitz, J.I. Ed.; J. Wiley & Sons: New York, 1995, Vol.16, pp.844-887 45) POUX, M.; LE SAUZE, N.; ALBAN, B.; XUEREB, C.; CANSELIER, J.P. In Proc. (CD-ROM) 3rd World Congress on Emulsions, Lyon, 2002 46) STANG, M., KARBSTEIN, H.; SCHUBERT, H. Chem. Eng. Proc. 1994, 33, 307 47) KITAMURA, Y.; TAKAHASHI, T. Encyclopedia of Fluid Mechanics 1986, 20, 475-510 48) WOOD, R.W.; LOOMIS, A.L. Phil. Mag.1927, 4, 417 49) BROWN, P.; GOODMAN, J.E. HighIntensity Ultrasonics; Iliffe Books: London, 1965 50) ABISMAL, B.; CANSELIER, J.P.; WILHELM, A.M.; DELMAS, H., GOURDON C., Ultrasonics Sonochemistry a) 1999, 6, 75-83; b) ibid. 2000, 7, 187-192 51) CANSELIER, J.P.; DELMAS, H.; WILHELM, A.M.; ABISMAL, B. J. Disp. Sci. Technol. 2002, 23, 333-349 52) Informations Chimie, 1998, 396, March, 60-65 53) JOSCELYNE, S.M.; Trgrdh J. Membr. Sci. 2000, 169, 107-117 54) COLLINS, S.E.; BOWEN, W.R., Proc. 2nd World Congress on Emulsion, Bordeaux, 1997, vol. 1, 1-2/215 55) KANDORI, K.; KISHI, K.; ISHIKAWA, T. Colloids Surf. 1991, 55, 73-78 56) ABRAHAMSE, A.J.; VAN LIEROP, R.; VAN DER SMAN, R.G.M.; VAN DER PADT, A.; BOOM, R.M. J. Membr. Sci. 2002, 204, 125-137 57) SUZUKI, K.; FUJIKI, I.; HAGURA, Y. Food Sci. Technol. Int. Tokyo, 1998, 4, 164-167 58) KANDORI, K. in Food Processing: Recent Developments; Gaonkar, A.G. Ed.; Elsevier: Amsterdam, 1995, pp.113-142 59) ESQUENA, J.; SOLANS, C. Progr. Colloid Polym. Sci. 1998, 110, 235-239 60) SHAHIDZADEH, N.; BONN, D.; MEUNIER, J. Europhys. Letters 1997, 40, 459-464 61) SHINODA, K.; SAITO, H. J. Colloid Interf. Sci. 1969, 24, 4 62) KUNIEDA, H.; FUKUI, Y.; UCHIYAMA, H.; SOLANS C. Langmuir 1996, 12, 2136-2140 63) RAJA GOPAL, E.S. in Rheology of Emulsions; Pergamon Press: Oxford, 1963; and in Emulsion Science, Academic Press: London, 1968 64) F.D.RUMSCHEID, F.D.; MASON, S.G. J. Colloid Sci. 1962, 17, 260 65) JANSSEN, J.J.M.; et al. AIChE J., 1994, 40, 1929 66) SCHUBERT, H.; STANG, M. in Proc. 2nd World Congress on Emulsion, Bordeaux, 1997, Vol.4, pp.327-335 67) T. FRSTER, T.; et al. Int. J. Cosm. Sci., 1990, 12, 217
JANUARY/FEBRUARY 2004

EMULSIONS

21