Kinetics particle size control

A considerable amount of work has been published during the past 20 years on a wide variety of emulsion polymerization and latex problems. A list of 11, mostly recent, general reference books is included at the end of this chapter. Areas in which significant advances have been reported include reaction mechanisms and kinetics, latex characterization and analysis, copolymerization and particle morphology control, reactor mathematical modeling, control of adsorbed and bound surface groups, particle size control reactor parameters. Readers who are interested in a more in-depth study of emulsion polymerization will find extensive literature sources. 

Impeller design and geometry to explore the relative effects of flow and shear distribution in the vessel for particle size control, micromixing for fast kinetics, and so on. Geometric ratios of importance include ... 

The batch process is similar to the semibatch process except that most or all of the ingredients are added at the beginning of the reaction. Heat generation during a pure batch process makes reactor temperature control difficult, especially for high soHds latices. Seed, usually at 5—10% soHds, is routinely made via a batch process to produce a uniform particle-size distribution. Most kinetic studies and models are based on batch processes (69). 

Wagner (1961) examined theoretically the growdr kinetics of a Gaussian particle size distribution, considering two growth mechanisms. When the process is volume diffusion controlled... 

The (en) compound developed nuclei which advanced rapidly across all surfaces of the reactant crystals and thereafter penetrated the bulk more slowly. Kinetic data fitted the contracting volume equation [eqn. (7), n = 3] and values of E (67—84 kJ mole"1) varied somewhat with the particle size of the reactant and the prevailing atmosphere. Nucleus formation in the (pn) compound was largely confined to the (100) surfaces of reactant crystallites and interface advance proceeded as a contracting area process [eqn. (7), n = 2], It was concluded that layers of packed propene groups within the structure were not penetrated by water molecules and the overall reaction rate was controlled by the diffusion of H20 to (100) surfaces. 

Prior to conducting the DOE (design of experiments) described in Table 3, it was established that no reaction took place in the absence of a catalyst and that the reactions were conducted in the region where chemical kinetics controlled the reaction rate. The results indicated that operating the reactor at 1000 rpm was sufficient to minimize the external mass-transfer limitations. Pore diffusion limitations were expected to be minimal as the median catalyst particle size is <25 pm. Further, experiments conducted under identical conditions to ensure repeatability and reproducibility in the two reactors yielded results that were within 5%. 

The control of particle size by concentration indicates that particle growth is a kinetic phenomenon. It is unlikely that particle growth is reversible once a Au-Au bond is formed it would not break under these experimental conditions. In a dilute solution of atoms, the frequency of encounters would be lower. As the gold atom-solvent matrix warms, the atoms and subsequent metal particles become mobile. It is the number of encounters that occur before particle stabilization that is important. If metal concentration is high the frequency of encounters is higher and the particles become bigger. 

Intraparticle Mass Transfer. One way biofilm growth alters bioreactor performance is by changing the effectiveness factor, defined as the actual substrate conversion divided by the maximum possible conversion in the volume occupied by the particle without mass transfer limitation. An optimal biofilm thickness exists for a given particle, above or below which the particle effectiveness factor and reactor productivity decrease. As the particle size increases, the maximum effectiveness factor possible decreases (Andrews and Przezdziecki, 1986). If sufficient kinetic and physical data are available, the optimal biofilm thickness for optimal effectiveness can be determined through various models for a given particle size (Andrews, 1988 Ruggeri et al., 1994), and biofilm erosion can be controlled to maintain this thickness. The determination of the effectiveness factor for various sized particles with changing biofilm thickness is well-described in the literature (Fan, 1989 Andrews, 1988)... 

---