Fluoropolymers, electrochemical carbonization

The product of the reaction (5.5.29) is, however, unstable against subsequent interchain crosslinking and insertion of supporting electrolyte cations. The electrochemical carbonization of fluoropolymers was recently reviewed by L. Kavan. 

Electrochemical corrosion processes also include a number of processes in organic chemistry, involving the reduction of various compounds by metals or metal amalgams. A typical example is the electrochemical carbonization of fluoropolymers mentioned on p. 316. These processes, that are often described as purely chemical reductions, can be explained relatively easily on the basis of diagrams of the anodic and cathodic polarization curves of the type shown in Fig. 5.54. 

Kavan, L. Electrochemical carbonization of fluoropolymers. In Chemistry and Physics of Carbon, Vol. 23, New York Marcel Dekker, 1991 69. 

The theoretical treatment presented (Eqs 4.1-4.5) is applicable also for direct wet electrochemistry on Pt cathode in aprotic electrolyte solution [12,13] (Table 4.1) and for some other chemical reductants, Rj, viz. benzoin dianion [14] and sodium dihydronaphthylide [15] (Table 4.1). Apparently, the decision between chemical and electrochemical carbonization may not be straightforward. The latter scenario requires a compact solid electrolyte with mixed electron/ion conductivity to be present at the interface. This occurs almost ideally in the reactions of solid fluoropolymers with diluted alkali metal amalgams [3]. If the interfacial layer is mechanically cracked, both electrochemical and chemical carbonization may take place, and the actual kinetics deviates from that predicted by Eq. 4.4 [10]. There is, however, another mechanism, leading to the perturbations of the Jansta and Dousek s electrochemical model (Eq. 4.4). This situation typically occurs if gaseous perfluorinated precursors react with Li-amalgam [4,5], and it will be theoretically treated in the next section. 

Characterization of Structure and Microtexture of Carbon Materials by Magnetoresistance Technique, F. Hishiyama, Y. Kaburagi, and M. Inagaki Electrochemical Carbonization of Fluoropolymers, L. Kavan Oxidation Protection of Carbon Materials, Douglas W. McKee... 

Kavan, L. Dousek, F.P. Micka, K. The role of ion transport in the electrochemical corrosion of fluoropolymers. Preparation and properties of n-doped polymeric carbon with mixed ion/electron conductivity. Solid State Ionics 1990, 38. 109-118. 

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