Propagation particle size

When initiator is first added the reaction medium remains clear while particles 10 to 20 nm in diameter are formed. As the reaction proceeds the particle size increases, giving the reaction medium a white milky appearance. When a thermal initiator, such as AIBN or benzoyl peroxide, is used the reaction is autocatalytic. This contrasts sharply with normal homogeneous polymerizations in which the rate of polymerization decreases monotonicaHy with time. Studies show that three propagation reactions occur simultaneously to account for the anomalous auto acceleration (17). These are chain growth in the continuous monomer phase chain growth of radicals that have precipitated from solution onto the particle surface and chain growth of radicals within the polymer particles (13,18). 

Copolymers with butadiene, ie, those containing at least 60 wt % butadiene, are an important family of mbbers. In addition to synthetic mbber, these compositions have extensive uses as paper coatings, water-based paints, and carpet backing. Because of unfavorable reaction kinetics in a mass system, these copolymers are made in an emulsion polymerization system, which favors chain propagation but not termination (199). The result is economically acceptable rates with desirable chain lengths. Usually such processes are mn batchwise in order to achieve satisfactory particle size distribution. 

Many finely divided metal powders in suspension in air are potential e] losion hazards, and causes for ignition of such dust clouds are numerous [Hartmann and Greenwald, Min. MetalL, 26, 331 (1945)]. Concentration of the dust in air and its particle size are important fac tors that determine explosibility. Below a lower Umit of concentration, no explosion can result because the heat of combustion is insufficient to propagate it. Above a maximum limiting concentration, an explosion cannot be produced because insufficient oxygen is available. The finer the particles, the more easily is ignition accomplished and the more rapid is the rate of combustion. This is illustrated in Fig. 20-7. 

This is the probability that failure will occur due to the propagation of one tip of the initial defect c under stress o, where is the critical stress intensity factor of the filler particle and a is the filler particle size. 

Even though the chemical reactions are the same (i.e. combination, disproportionation), the effects of compartmentalization are such that, in emulsion polymerization, particle phase termination rates can be substantially different to those observed in corresponding solution or bulk polymerizations. A critical parameter is n, the average number of propagating species per particle. The value of h depends on the particle size and the rates of entry and exit. 

Many emulsion polymerizations can be described by so-called zero-one kinetics. These systems are characterized by particle sizes that are sufficiently small dial entry of a radical into a particle already containing a propagating radical always causes instantaneous termination. Thus, a particle may contain either zero or one propagating radical. The value of n will usually be less than 0.4. In these systems, radical-radical termination is by definition not rate determining. Rates of polymerization are determined by the rates or particle entry and exit rather than by rates of initiation and termination. The main mechanism for exit is thought to be chain transfer to monomer. It follows that radical-radical termination, when it occurs in the particle phase, will usually be between a short species (one that lias just entered) and a long species. 

A recent review relating the pyrotechnic reaction mechanism, particle size, stoichiometry, temp and compaction density to burning rate is Ref 66, and a study of the effect of multidimensional heat transfer on the rate of flame propagation is Ref 120, which showed that the material of the delay body has no effect on the performance of most delay compns, a finding which agrees with test data... 

An influence of particle size on the kinetics of COads electro-oxidation has been shown by Maillard and co-workers with FTIR spectroscopy. It has been suggested that the reaction starts on the terraces of large (> 3 nm) particles, and then propagates to the particle edges. Electro-oxidation of COads on small (<2nm) particles commences at more positive potentials, when COads on large particles is oxidized. 

The conditions in the reaction zone determine the release rate of the N-precursors HCN and NH3 [11], Among these conditions are the properties of the fuel (e.g., N-content and particle size), parameters related to the combustion front (temperature and propagation velocity) and the gas composition in and directly above the combustion front. As the prediction of the mass fractions of the N-precursors is important for the final goal of this research, i.e., the prediction of NO formation of the complete furnace, a model is needed in which all these conditions are represented. 

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