Gradient radical

Under most circumstances the equiUbtium shape of silicon crystals is octahedral, ie, the slowest-growing faces are (111). However, external conditions can radically alter that shape. For example, when growth is from the vapor, concentration gradients in the gas stream may affect the shape, and when growth is from the melt, the shape is primarily determined by thermal gradients in the melt. 

The grafting through approach involves copolymerization of macromonomers. NMP, ATRP and RAFT have each been used in this context. The polymerizations are subject to the same constraints as conventional radical polymerizations that involve macromonomers (Section 7.6.5). However, living radical copolymerization offers greater product uniformity and the possibility of blocks, gradients and other architectures. 

Recombination reactions between two different macroradicals are readily observable in the condensed state where molecular mobility is restricted and the concentration of radicals is high. Its role in flow-induced degradation is probably negligible at the polymer concentration normally used in these experiments (< 100 ppm), the rate of radical formation is extremely small and the radicals are immediately separated by the velocity gradient at the very moment of their formation. Thus there is no cage effect, which otherwise could enhance the recombination efficiency. 

Whereas other experimental methods have been used to obtain values of kti no other method provides values of k-t or equilibrium data. There are, however, several important limitations of our method. First, the method is restricted to relatively fast hole transport processes that can compete with charge recombination of the Sa -G+ radical ion pair (Fig. 6). This precludes the use of strong acceptors which can oxidize A as well as G (Fig. 2a). We find that hole transport cannot compete with charge recombination in such systems, even when a charge gradient is constructed which should favor hole transport [35]. Second, the method is unable to resolve the dynamics of systems in which return hole transport, k t, is very slow (<104 s-1) or systems in which multiple hole transport processes occur. Third, since the guanine cation radical cannot be detected by transient spectroscopy, the method is dependent upon the analysis of the behavior of Sa-. In section 3.4 we de-... 

Figure 6 Simulated ESR spectra of nitroxides (a) in the absence of magnetic field gradient (b) ID image for a homogenous radical distribution (in the presence of a gradient) and (c) ID image for radicals present only in thin layers near both surfaces of the plaque (in the presence of a gradient).

The theory of particle diffusion was first advanced in 1934 by Lewis and von Elbe [5] in dealing with the ozone reaction. Tanford and Pease [6] carried this concept further by postulating that it is the diffusion of radicals that is all important, not the temperature gradient as required by the thermal theories. They proposed a diffusion theory that was quite different in physical concept from the thermal theory. However, one should recall that the equations that govern mass diffusion are the same as those that govern thermal diffusion. 

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