Emulsion solid particles

As it is well known, the contacts between drops (in emulsions), solid particles (in suspensions) and gas bubbles (in foams) are accomplished by films of different thickness. These films, as already discussed, can thin, reaching very small thickness. Observed under a microscope these films reflect very little light and appear black when their thickness is below 20 nm. Therefore, they can be called nano foam films. IUPAC nomenclature (1994) distinguishes two equilibrium states of black films common black films (CBF) and Newton black films (NBF). It will be shown that there is a pronounced transition between them, i.e. CBFs can transform into NBFs (or the reverse). The latter are bilayer formations without a free aqueous core between the two layers of surfactant molecules. Thus, the contact between droplets, particles and bubbles in disperse systems can be achieved by bilayers from amphiphile molecules. 

The cleaning process proceeds by one of three primary mechanisms solubilization, emulsification, and roll-up [229]. In solubilization the oily phase partitions into surfactant micelles that desorb from the solid surface and diffuse into the bulk. As mentioned above, there is a body of theoretical work on solubilization [146, 147] and numerous experimental studies by a variety of spectroscopic techniques [143-145,230]. Emulsification involves the formation and removal of an emulsion at the oil-water interface the removal step may involve hydrodynamic as well as surface chemical forces. Emulsion formation is covered in Chapter XIV. In roll-up the surfactant reduces the contact angle of the liquid soil or the surface free energy of a solid particle aiding its detachment and subsequent removal by hydrodynamic forces. Adam and Stevenson s beautiful photographs illustrate roll-up of lanoline on wood fibers [231]. In order to achieve roll-up, one requires the surface free energies for soil detachment illustrated in Fig. XIII-14 to obey... 

It was pointed out in Section XIII-4A that if the contact angle between a solid particle and two liquid phases is finite, a stable position for the particle is at the liquid-liquid interface. Coalescence is inhibited because it takes work to displace the particle from the interface. In addition, one can account for the type of emulsion that is formed, 0/W or W/O, simply in terms of the contact angle value. As illustrated in Fig. XIV-7, the bulk of the particle will lie in that liquid that most nearly wets it, and by what seems to be a correct application of the early oriented wedge" principle (see Ref. 48), this liquid should then constitute the outer phase. Furthermore, the action of surfactants should be predictable in terms of their effect on the contact angle. This was, indeed, found to be the case in a study by Schulman and Leja [49] on the stabilization of emulsions by barium sulfate. 

In the emulsion polymerization of vinyl chloride (VC) initiated with type II MAI composed of PDMS, block efficiency was as high as 95-97%, and solid particles with a narrow range of particle size, 0.1-50 microns, were obtained in high yield [15]. 

The bubbles play the role of the gas phase. The role of the liquid is played by an emulsion phase that consists of solid particles and suspending gas in a configuration similar to that at incipient fluidization. The quasi-phases are in cocurrent flow, with mass transfer between the phases and with a solid-catalyzed reaction occurring only in the emulsion phase. The downward flow of solids that occurs near the walls is not explicitly considered in this simplified model. 

A solids-stabilized water-in-oil emulsion may be used either as a drive fluid for displacing hydrocarbons from the formation or to produce a barrier for diverting the flow of fluids in the formation. The solid particles may be formation solid particles or nonformation solid particles, obtained from outside the formation (e.g., clays, quartz, feldspar, gypsum, coal dust, asphaltenes, polymers) [228,229]. 

The number of the constituent phases of a disperse system can be higher than two. Many commercial multiphase pharmaceutical products cannot be categorized easily and should be classified as complex disperse systems. Examples include various types of multiple emulsions and suspensions in which solid particles are dispersed within an emulsion base. These complexities influence the physicochemical properties of the system, which, in turn, determine the overall characteristics of the dosage forms with which the formulators are concerned. 

Finely divided solid particles that are wetted to some degree by both oil and water can also act as emulsifying agents. This results from the fact that they can form a particulate film around dispersed droplets, preventing coalescence. Powders that are wetted preferentially by water form O/W emulsions, whereas those more easily wetted by oil form W/O emulsions. The compounds most frequently used in pharmacy are colloidal clays, such as bentonite (aluminum silicate) and veegum (magnesium aluminum silicate). These compounds tend to be adsorbed at the interface and also increase the viscosity of the aqueous phase. They are frequently used in conjunction with a surfactant for external purposes, such as lotions or creams. 

An emulsion separation method using hydrocyclones. The emulsion comprises a continuous phase, a discontinuous phase and fine solid particles. In the first step, the original emulsion is separated into an overflow emulsion and an underflow emulsion, in a first hydrocyclone. The overflow emulsion comprises portions of the continuous phase, the discontinuous phase and the fine solid particles. The overflow emulsion is inverted in which the continuous phase of the overflow emulsion is now a second discontinuous phase and the original discontinuous phase becomes a second continuous phase. Then, the inverted emulsion is directed to one or more subsequent hydrocyclones and the second continuous and discontinuous phases are collected. The fine solid particles remain in the second discontinuous phase. 

Each bubble drags a wake of solid particles up with it (Rowe and Partridge, 1965). This forms an additional region, and the movement creates recirculation of particles in the bed upward behind the bubbles and downward elsewhere in the emulsion region. 

It should be highlighted that equation (47) holds for solid particles. In the case of liquid particles, e.g. with emulsions, the convective diffusion process is very different due to interfacial momentum transfer which gives rise to a different velocity profile. Consequently, convective diffusion to/from a liquid particle is more effective than that for a solid particle. Starting again from equation (43),... 

Colloidal suspensions, emulsions and solid dispersions are produced by means of colloid mills or dispersion mills. Droplets or particles of sizes less than 1 (im may be formed, and solids suspensions consisting of discrete solid particles are obtainable with feed material of approximately 100-mesh or 50 p,m in size. 

Aerosols. A suspension of liquid or solid particles in a gas. Aerosols generally refer to a packaging technique for gaseous products in sealed, pressurized containers. Aerosols consist of product, propellant, and the package. The contained product may be in the form of solution, emulsion, or suspension, and can be dispersed by merely opening a valve. Propellants are typically CO2, N2O, and N2. Typical uses include hair sprays, shaving soaps, pairits, insect sprays, and deodorants. 

In solid-stabilized emulsions, the droplet surface can be regarded as a compact 2-D network of solid particles with strong lateral attractive interactions. The surface... 

FIGURE 9.6 Stable emulsion formation by polymers. Polymer molecules adsorb (on solid particles) and penetrate (on liquid drops). 

Another important emulsion stabilization is achieved by using polymers. The large polymer molecules adsorbed on solid particles (Figure 9.6) will exhibit repulsion at the surface of the particles. The charged polymers also will give additional charge-charge repulsion. Polymers are used in many pharmaceutical, cosmetics, and other systems (milk). Obviously, the choice of a suitable polymer is specific to each system. 

Colloid chemistry investigates substance mixtures. These substance mixtures can be heterogenous, such as emulsions (in which tiny droplets of one liquid are dispersed in another), suspensions (consisting of a fine dispersion of solid particles in a liquid volume phase), and aerosols (in which liquid droplets are dispersed in the gas phase). However, there are also homogenous mixtures in which the solute is present in larger, supermolecular aggregates. These homogenous mixtures include micellar solutions and liquid crystalline... 

Phenomena at Liquid Interfaces. The area of contact between two phases is called the interface three phases can have only a line of contact, and only a point of mutual contact is possible between four or more phases. Combinations of phases encountered in surfactant systems are L—G, L—L—G, L—S—G, L—S—S—G, L—L, L—L—L, L—S—S, L—L—S—S—G, L—S, L—L—S, and L—L—S—G, where G = gas, L = liquid, and S = solid. An example of an L—L—S—G system is an aqueous surfactant solution containing an emulsified oil, suspended solid, and entrained air (see Emulsions Foams). This embodies several conditions common to practical surfactant systems. First, because the surface area of a phase increases as particle size decreases, the emulsion, suspension, and entrained gas each have large areas of contact with the surfactant solution. Next, because interfaces can only exist between two phases, analysis of phenomena in the L—L—S—G system breaks down into a series of analyses, ie, surfactant solution to the emulsion, solid, and gas. It is also apparent that the surfactant must be stabilizing the system by preventing contact between the emulsified oil and dispersed solid. Finally, the dispersed phases are in equilibrium with each other through their common equilibrium with the surfactant solution. 

In the simplest emulsions just described, the linal separation is into two liquid phases upon deslahilizalinn. The majority of emulsions tire of this kind, but in some cases the emulsion is divided into more Ilian two phases. One ubvious reason lor such a behavior is the presence of it material thal does not dissolve in the oil or the water. One such case is Ihe presence of solid particles, which is common in emulsions lor food, pharmaceuticals, and cosmetics. Another less trivial reason is that the surfactant associates w ith the water and/or Ihe oil to form a colloidal structure that spontaneously separates from the two liquid phases. This colloidal structure may be an isotropic liquid or may he a. semisnlid phase, a liquid crystal, with long-range order. 

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