Small droplets

The derivation of Young s equation neglects the line tension x associated with the triple line where the three phases intersect. This introduces no error for larger droplets but for the case of small droplets, namely those less than one micrometer in diameter, the line tension must be considered. In this case Equation (3.5) is written dA%  

While the emulsions studied by Princen and Kiss were solid-like, or elastic, at low frequencies, dense water-in-oil emulsions studied by Pons et al. (1993) were liquid-like at low 

Pons et al. (1993) found that r increases rapidly with increasing volume fraction 0, and they suggested an equation for this dependence  

Fits to experimental data could be obtained by choosing rather large fitting values of the empirical coefficient, c 300-20,000, depending on the system. So far, no analysis of such flows, and no derivation of a scaling law for r in such emulsions, seems to be available. 

---

On a microscopic scale (the inset represents about 1 - 2mm ), even in parts of the reservoir which have been swept by water, some oil remains as residual oil. The surface tension at the oil-water interface is so high that as the water attempts to displace the oil out of the pore space through the small capillaries, the continuous phase of oil breaks up, leaving small droplets of oil (snapped off, or capillary trapped oil) in the pore space. Typical residual oil saturation (S ) is in the range 10-40 % of the pore space, and is higher in tighter sands, where the capillaries are smaller. 

As small droplets of liquid are usually still present in the gas phase, demisting secWons are required to recover the liquid mist before it is carried over" in the gas stream out of the separator. The largest liquid droplets fall out of the gas quickly under the action of gravity but smaller droplets (less than 200 microns) require more sophisticated extraction systems. 

While Eq. III-18 has been verified for small droplets, attempts to do so for liquids in capillaries (where Rm is negative and there should be a pressure reduction) have led to startling discrepancies. Potential problems include the presence of impurities leached from the capillary walls and allowance for the film of adsorbed vapor that should be present (see Chapter X). There is room for another real effect arising from structural peiturbations in the liquid induced by the vicinity of the solid capillary wall (see Chapter VI). Fisher and Israelachvili [19] review much of the literature on the verification of the Kelvin equation and report confirmatory measurements for liquid bridges between crossed mica cylinders. The situation is similar to that of the meniscus in a capillary since Rm is negative some of their results are shown in Fig. III-3. Studies in capillaries have been reviewed by Melrose [20] who concludes that the Kelvin equation is obeyed for radii at least down to 1 fim. 

An important approach to the study of nucleation of solids is the investigation of small droplets of large molecular clusters. Years ago, Turnbull showed that by studying small droplets one could eliminate impurities in all except a few droplets and study homogeneous nucleation at significant undercoolings [13]. 

For a conserved order parameter, the interface dynamics and late-stage domain growth involve the evapomtion-diffusion-condensation mechanism whereby large droplets (small curvature) grow at tlie expense of small droplets (large curvature). This is also the basis for the Lifshitz-Slyozov analysis which is discussed in section A3.3.4. 

Nebulizers can be divided into several main types. The pneumatic forms work on the principle of breaking up a stream of liquid into droplets by mechanical means the liquid stream is forced through a fine nozzle and breaks up into droplets. There may be a concentric stream of gas to aid the formation of small droplets. The liquid stream can be directed from a fine nozzle at a solid target so that, on impact, the narrow diameter stream of liquid is broken into many tiny droplets. There are variants on this approach, described in the chapter devoted to nebulizers (Chapter 19). 

The simplest desolvation chambers consist simply of a tube heated to about 150°C through which the spray of droplets passes. During passage through this heated region, solvent evaporates rapidly from the droplets and forms vapor. The mixed vapor and residual small droplets or particulates of sample matter are swept by argon through a second cooled tube, which allows vapor to... 

The various heating methods produce a vapor that is a mixture of gas, very small droplets, and small particles of solid matter (particulates). Before droplets or particulates can coalesce, the whole vapor is swept into the plasma flame for analysis. Clearly, the closer the heating source is... 

Aerosols can be produced as a spray of droplets by various means. A good example of a nebulizer is the common household hair spray, which produces fine droplets of a solution of hair lacquer by using a gas to blow the lacquer solution through a fine nozzle so that it emerges as a spray of small droplets. In use, the droplets strike the hair and settle, and the solvent evaporates to leave behind the nonvolatile lacquer. For mass spectrometry, a spray of a solution of analyte can be produced similarly or by a wide variety of other methods, many of which are discussed here. Chapters 8 ( Electrospray Ionization ) and 11 ( Thermospray and Plasmaspray Interfaces ) also contain details of droplet evaporation and formation of ions that are relevant to the discussion in this chapter. Aerosols are also produced by laser ablation for more information on this topic, see Chapters 17 and 18. 

The term nebulizer is used generally as a description for any spraying device, such as the hair spray mentioned above. It is normally applied to any means of forming an aerosol spray in which a volume of liquid is broken into a mist of vapor and small droplets and possibly even solid matter. There is a variety of nebulizer designs for transporting a solution of analyte in droplet form to a plasma torch in ICP/MS and to the inlet/ionization sources used in electrospray and mass spectrometry (ES/MS) and atmospheric-pressure chemical ionization and mass spectrometry (APCI/MS). 

Having removed the larger droplets, it may remain only to encourage natural evaporation of solvent from the remaining small droplets by use of a desolvation chamber. In this chamber, the droplets are heated to temperatures up to about 150 C, often through use of infrared heaters. The extra heat causes rapid desolvation of the droplets, which frequently dry out completely to leave the analyte as small particles that are swept by the argon flow into the flame. 

A sample to be examined by electrospray is passed as a solution in a solvent (made up separately or issuing from a liquid chromatographic column) through a capillary tube held at high electrical potential, so the solution emerges as a spray or mist of small droplets (i.e., it is nebulized). As the droplets evaporate, residual sample ions are extracted into a mass spectrometer for analysis. 

A stream of liquid issuing from a narrow tube can be broken up into a spray of small droplets by injecting helium gas just before the end of the tube. This nebulization is analogous to the action of an aerosol spray-can nozzle. 

A liquid sample must be vaporized to a gas or, more likely, to a vapor consisting of an aerosol of gas, small droplets, and even small particles of solid matter. To be examined, the aerosol is mixed with argon gas to make up the needed flow of gas into the plasma and is then swept into the flame. 

For mass spectrometric ionization and introduction into a plasma flame, the analyte needs to be separated from most of the accompanying solvent. One way to accomplish this separation is to break the solution down into small droplets using a nebulizer. 

Nebulizers convert bulk liquid into an aerosol, consisting of a mix of small droplets of various sizes and solvent vapor. Such devices are used to transfer analyte solutions into the flame of a plasma torch. 

Mechanical Aerators. Mechanical aerators are modular ia design and built usiag electric motors. This type of aerator is also known as a surface splasher because it pumps water vertically iato the air. During this process the water is broken up iato small droplets allowiag exchange of oxygen from the air to the water. One type of mechanical aerator is shown ia Figure 3e. 

Ammonia from coal gasification has been used for fertilizer production at Sasol since the beginning of operations in 1955. In 1964 a dedicated coal-based ammonia synthesis plant was brought on stream. This plant has now been deactivated, and is being replaced with a new faciUty with three times the production capacity. Nitric acid is produced by oxidation and is converted with additional ammonia into ammonium nitrate fertilizers. The products are marketed either as a Hquid or in a soHd form known as Limestone Ammonium Nitrate. Also, two types of explosives are produced from ammonium nitrate. The first is a mixture of fuel oil and porous ammonium nitrate granules. The second type is produced by emulsifying small droplets of ammonium nitrate solution in oil. 

Other. Because a foam consists of many small, trapped gas bubbles, it can be very effective as a thermal insulator. Usually soHd foams are used for insulation purposes, but there are some instances where Hquid foams also find uses for insulation (see Eoamed plastics Insulation, thermal). Eor example, it is possible to apply and remove the insulation simply by forming or coUapsing the foam, providing additional control of the insulation process. Another novel use that is being explored is the potential of absorbing much of the pressure produced by an explosion. The energy in the shock wave is first partially absorbed by breaking the bubbles into very small droplets, and then further absorbed as the droplets are evaporated (53). 

Dispersion is the process of wetting the surface of the metal, thereby penetrating the oil film. Surfactants can reduce the surface tension and interfacial tension of the cleaning solution at the metal—Hquid interface. As the cleaner undercuts and penetrates the oil, the cleaner breaks the oil into small droplets which then float to the surface. 

The second step is to disperse the core material being encapsulated in the solution of shell material. The core material usually is a hydrophobic or water-knmiscible oil, although soHd powders have been encapsulated. A suitable emulsifier is used to aid formation of the dispersion or emulsion. In the case of oil core materials, the oil phase is typically reduced to a drop size of 1—3 p.m. Once a suitable dispersion or emulsion has been prepared, it is sprayed into a heated chamber. The small droplets produced have a high surface area and are rapidly converted by desolvation in the chamber to a fine powder. Residence time in the spray-drying chamber is 30 s or less. Inlet and outlet air temperatures are important process parameters as is relative humidity of the inlet air stream. 

The solubiHty of phosphoms in water is about 3 ppm. However, process water used in phosphoms manufacture or handling often catties larger amounts of phosphoms as particulates or small droplets, depending on the water temperature. Phosphoms-contaminated water is commonly called phossy water. Phosphoms has low solubiHty in most common solvents, but is quite soluble in carbon disulfide and some other special solvents. The solubiHty in CS2 and benzene was formerly used in phosphoms analyses, but toxicity and increasing waste disposal costs have led to mote use of toluene and xylene, and mote tecentiy to the use of nonchemical turbidity measurements. 

Some concerns directly related to a tomizer operation include inadequate mixing of Hquid and gas, incomplete droplet evaporation, hydrodynamic instabiHty, formation of nonuniform sprays, uneven deposition of Hquid particles on soHd surfaces, and drifting of small droplets. Other possible problems include difficulty in achieving ignition, poor combustion efficiency, and incorrect rates of evaporation, chemical reaction, solidification, or deposition. Atomizers must also provide the desired spray angle and pattern, penetration, concentration, and particle size distribution. In certain appHcations, they must handle high viscosity or non-Newtonian fluids, or provide extremely fine sprays for rapid cooling. 

In agricultural spraying, one of the biggest concerns is the drifting of small droplets. Drifting sprays not only lead to waste and environment problems, but also could endanger other nearby crops. Droplets smaller than 150 p.m can be easily blown away from the intended target area by a cross wind. A typical herbicide atomizer produces a spray with 15—20% of the Hquid volume contained in droplets less than 150 p.m. Atomizer improvements must be made so that the spray contains a narrow droplet size distribution with Hquid volume less than 5% contributed by the smaller droplets. 

Mini-emulsion processes have been developed where the monomer is emulsified under high energy with either a long-chain alcohol or a polymer producing very small droplets. The long-chain alcohol retards the diffusion of the monomer out of the droplets (65). Polymerization takes place primarily... 

Suspension Polymerization. Suspension polymerization is carried out in small droplets of monomer suspended in water. The monomer is first finely dispersed in water by vigorous agitation. Suspension stabiUzers act to minimize coalescence of droplets by forming a coating at the monomer—water interface. The hydrophobic—hydrophilic properties of the suspension stabiLizers ate key to resin properties and grain agglomeration (89). 

A solution of sulfur trioxide [7446-11-9] dissolved in chlorosulfonic acid [7990-94-5] CISO H, has been used as a smoke (U.S. designation FS) but it is not a U.S. standard agent (see Chlorosulfuric acid Sulfuric acid and sulfur trioxide). When FS is atomized in air, the sulfur trioxide evaporates from the small droplets and reacts with atmospheric moisture to form sulfuric acid vapor. This vapor condenses into minute droplets that form a dense white cloud. FS produces its effect almost instantaneously upon mechanical atomization into the atmosphere, except at very low temperatures. At such temperatures, the small amount of moisture normally present in the atmosphere, requires that FS be thermally generated with the addition of steam to be effective. FS can be used as a fill for artillery and mortar shells and bombs and can be effectively dispersed from low performance aircraft spray tanks. FS is both corrosive and toxic in the presence of moisture, which imposes limitations on its storage, handling, and use. 

---