Droplet transformation

Figure 43. Schematic illustration of the cylinder-droplets transformation. See also Fig. 42.

The mechamsm of droplet transformation into the particle, and degree reduction of the droplet tbough tbs process, depends on different parameters. The most important parameters are temperature gradient between the surface and the center of the droplet or particle, the viscoelastic properties of the droplet (character and level of its rigidity and droplet behavior during its colhsion with other aerosol droplets and coalescence), the thermodiffusion coefficient, and permeability of the shell formed on the droplet surface during its solidification [3]. 

Droplet transformation into particles can be achieved in a different way. For example, both emulsification of a monomer mixture and polymerization can be achieved in the continuous mode in a MF reactor (or in situ), as it is done for the photoinitiated synthesis of polymer beads. Typically, this polymerization mode is used for fast polymerization process, for example, for redox-initiated or photoinitiated polymerizations. Alternatively, following emulsification and partial polymerization of the monomer mixture in the MF reactor, the droplet particles are transferred into a batch reactor and post-polymerized using, for example, thermoinitiated polymerization. This polymerization process can be used for the synthesis of, for example, polystyrene particles. 

Dispersion of a soHd or Hquid in a Hquid affects the viscosity. In many cases Newtonian flow behavior is transformed into non-Newtonian flow behavior. Shear thinning results from the abiHty of the soHd particles or Hquid droplets to come together to form network stmctures when at rest or under low shear. With increasing shear the interlinked stmcture gradually breaks down, and the resistance to flow decreases. The viscosity of a dispersed system depends on hydrodynamic interactions between particles or droplets and the Hquid, particle—particle interactions (bumping), and interparticle attractions that promote the formation of aggregates, floes, and networks. 

The final factor influencing the stabiHty of these three-phase emulsions is probably the most important one. Small changes in emulsifier concentration lead to drastic changes in the amounts of the three phases. As an example, consider the points A to C in Figure 16. At point A, with 2% emulsifier, 49% water, and 49% aqueous phase, 50% oil and 50% aqueous phase are the only phases present. At point B the emulsifier concentration has been increased to 4%. Now the oil phase constitutes 47% of the total and the aqueous phase is reduced to 29% the remaining 24% is a Hquid crystalline phase. The importance of these numbers is best perceived by a calculation of thickness of the protective layer of the emulsifier (point A) and of the Hquid crystal (point B). The added surfactant, which at 2% would add a protective film of only 0.07 p.m to emulsion droplets of 5 p.m if all of it were adsorbed, has now been transformed to 24% of a viscous phase. This phase would form a very viscous film 0.85 p.m thick. The protective coating is more than 10 times thicker than one from the surfactant alone because the thick viscous film contains only 7% emulsifier the rest is 75% water and 18% oil. At point C, the aqueous phase has now disappeared, and the entire emulsion consists of 42.3% oil and 57.5% Hquid crystalline phase. The stabilizing phase is now the principal part of the emulsion. 

Consider an alchemical transformation of a particle in water, where the particle s charge is changed from 0 to i) (e.g., neon sodium q = ). Let the transformation be performed first with the particle in a spherical water droplet of radius R (formed of explicit water molecules), and let the droplet then be transferred into bulk continuum water. From dielectric continuum theory, the transfer free energy is just the Born free energy to transfer a spherical ion of charge q and radius R into a continuum with the dielectric constant e of water ... 

The secondary source of fine particles in the atmosphere is gas-to-particle conversion processes, considered to be the more important source of particles contributing to atmospheric haze. In gas-to-particle conversion, gaseous molecules become transformed to liquid or solid particles. This phase transformation can occur by three processes absortion, nucleation, and condensation. Absorption is the process by which a gas goes into solution in a liquid phase. Absorption of a specific gas is dependent on the solubility of the gas in a particular liquid, e.g., SO2 in liquid H2O droplets. Nucleation and condensation are terms associated with aerosol dynamics. 

Finally, atmospheric chemical transformations are classified in terms of whether they occur as a gas (homogeneous), on a surface, or in a liquid droplet (heterogeneous). An example of the last is the oxidation of dissolved sulfur dioxide in a liquid droplet. Thus, chemical transformations can occur in the gas phase, forming secondary products such as NO2 and O3 in the liquid phase, such as SO2 oxidation in liquid droplets or water films and as gas-to-particle conversion, in which the oxidized product condenses to form an aerosol. 

Another process, the Barton process, is based on molten lead. The core of such a device is the "Barton reactor", a heated pot that is partly filled with molten lead. It is continuously refilled by a fine stream of molten lead. Fine droplets of lead are produced by a fast rotating paddle that is partly immersed under the surface of the molten lead within the "Barton reactor". The surface of each droplet is transformed by oxidation into a shell of PbO by an airstream that simultaneously carries away the oxidized particles if they are small enough otherwise, they fall back into the melt and the process is repeated. Thus the airstream acts as a classifier for particle size. 

Lagues et al. [17] found that the percolation theory for hard spheres could be used to describe dramatic increases in electrical conductivity in reverse microemulsions as the volume fraction of water was increased. They also showed how certain scaling theoretical tools were applicable to the analysis of such percolation phenomena. Cazabat et al. [18] also examined percolation in reverse microemulsions with increasing disperse phase volume fraction. They reasoned the percolation came about as a result of formation of clusters of reverse microemulsion droplets. They envisioned increased transport as arising from a transformation of linear droplet clusters to tubular microstructures, to form wormlike reverse microemulsion tubules. 

The topological transformations in an incompatible blend can be described by the dynamic phase diagram that is usually determined experimentally at a constant shear rate. For equal viscosities, a bicontinuous morphology is observed within a broad interval of the volume fractions. When the viscosity ratio increases, the bicontinuous region of the phase diagram shrinks. At large viscosity ratios, the droplets of a more viscous component in a continuous matrix of a less viscous component are observed practically for all allowed geometrically volume fractions. 

Both models apply the same chemical scheme of mercury transformations. It is assumed that mercury occurs in the atmosphere in two gaseous forms—gaseous elemental HgO, gaseous oxidized Hg(II) particulate oxidized Hgpart, and four aqueous forms—elemental dissolved HgO dis, mercury ion Hg2+, sulphite complex Hg(S03)2, and aggregate chloride complexes HgnClm. Physical and chemical transformations include dissolution of HgO in cloud droplets, gas-phase and aqueous-phase oxidation by ozone and chlorine, aqueous-phase formation of chloride complexes, reactions of Hg2+ reduction through the decomposition of sulphite complex, and adsorption by soot particles in droplet water. 

Fig. 11.5. Diagram illustrating the components of an ESI source. A solution from a pump or the eluent from an HPLC is introduced through a narrow gage needle (approximately 150 pm i.d.). The voltage differential (4-5 kV) between the needle and the counter electrode causes the solution to form a fine spray of small charged droplets. At elevated flow rates (greater than a few pl/min up to 1 ml/min), the formation of droplets is assisted by a high velocity flow of N2 (pneumatically assisted ESI). Once formed, the droplets diminish in size due to evaporative processes and droplet fission resulting from coulombic repulsion (the so-called coulombic explosions ). The preformed ions in the droplets remain after complete evaporation of the solvent or are ejected from the droplet surface (ion evaporation) by the same forces of coulombic repulsion that cause droplet fission. The ions are transformed into the vacuum envelope of the instrument and to the mass analyzer(s) through the heated transfer tube, one or more skimmers and a series of lenses.

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