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and results in a 3-order dependence of Rp on [M]. This initiation is probably best considered 2 as an example of redox initiation (Sec. 3-4b). Other exceptions to the rst-order dependence of the polymerization rate on the monomer concentration occur when termination is not by bimolecular reaction of propagating radicals. Second-order dependence of Rp on [M] occurs for primary termination (Eq. 3-33a) and certain redox-initiated polymerizations (Sec. 3-4b-2). Less than rst-order dependence of Rp on [M] has been observed for polymerizations (Sec. 9-8a-2) taking place inside a solid under conditions where monomer diffusion into the solid is slower than the normal propagation rate [Odian et al., 1980] and also in some redox polymerizations (Sec. 3-4b-2) [MapundaVlckova and Barton, 1978].

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Many oxidation reduction reactions produce radicals that can be used to initiate polymerization [Sarac, 1999]. This type of initiation is referred to as redox initiation, redox catalysis, or redox activation. A prime advantage of redox initiation is that radical production occurs at reasonable rates over a very wide range of temperatures, depending on the particular redox system, including initiation at moderate temperatures of 0 50 C and even lower. This allows a greater freedom of choice of the polymerization temperature than is possible with the thermal homolysis of initiators. Some redox polymerizations can be initiated photolytically as well as thermally. A wide range of redox reactions, including both inorganic and organic components either wholly or in part, may be employed for this purpose. Some redox systems involve direct electron transfer between reductant and oxidant, while others involve the intermediate formation of reductant-oxidant complexes; the latter are charge-transfer complexes in some cases. 3-4b-1 Types of Redox Initiators

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1. Peroxides in combination with a reducing agent are a common source of radicals; for example, the reaction of hydrogen peroxide with ferrous ion

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Effective frequency of ion-neutral collisions can be presented as [4,6 8] nim b0 Nm Ti Tm 1=2 im 7:4

Ferrous ion also promotes the decomposition of a variety of other compounds including various types of organic peroxides [Bamford, 1988].

where the coef cient b0 accounts the difference of masses of different molecules, im effects of nonelastic interaction between particles, polarization, and recharge of molecules (see details in References [4,6 8]). Furthermore, to analyze the effects of ambient magnetic eld on charged particles, hyromagnetic frequencies of electrons, oH , and ions, OH , are also introduced to estimate effects of charged particles magnetization. As was investigated in References [9,10], at altitudes of the lower ionosphere (z < 120 150 km) oH > nem , but OH ( nim , that is electrons are magnetized and ions are not. Hence, the degree of magnetization of ionospheric plasma, which is de ned by OH oH ) nim nem, is very small, whereas in the upper ionosphere at altitudes more than 150 km, oH ) nem and OH > nim , that is, both electrons and ions, and hence, ionospheric plasma are fully magnetized. For actual ionospheric applications in radio communications and radars, another parameter of ionization is usually used [8 12, 46 48], p nei =nem , instead of the earlier de ned parameter N=Nm. As was mentioned in References [8,9], it can be done in spite of the fact that the ionospheric plasma has mainly low temperature (from 200 K at 80 90 km to 2500 2800 K at the 500 600 km). In such conditions the cross-sections of collisions between electrons and ions are much greater than the cross-sections of collisions of electrons with neutrals. So, the peculiarity of the real ionospheric plasma consists of the fact that even N=Nm ( 1, the parameter p nei =nem becomes more than the unit. Therefore, electron-ion interactions are an essential part of the transport processes in the ionospheric plasma. Figure 7.4 presents the parameter ionization p for diurnal and nocturnal middle latitude

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Other reductants such as Cr , V , Ti , Co , and Cu can be employed in place of ferrous ion in many instances. Most of these redox systems are aqueous or emulsion systems. Redox initiation with acyl peroxides can be carried out in organic media by using amines as the reductant [Morsi et al., 1977; O Driscoll et al., 1965]. An interesting system is the combination of benzoyl peroxide and an N,N-dialkylaniline. The difference in the rates of decomposition between such a redox system and the simple thermal homolysis of the peroxide alone is striking. The decomposition rate constant kd for benzoyl peroxide in styrene polymerization is 1:33 10 4 s 1 at 90 C, while that for the benzoyl peroxide-N, N-diethylaniline redox system is 1:25 10 2 L mol 1 s 1 at 60 C and 2:29 10 3 L mol 1 s 1 at 30 C. The redox system has a much larger decomposition rate. Radical production in this redox system appears to proceed via an initial ionic displacement by the nitrogen of the aniline on the peroxide linkage

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