PAN-oxides

The anodic peak observed during the electrochemical doping is always followed by a large capacitive current as was the case for PAn and PPy [162,178]. This large residual current observed beyond the anodic peak has been clearly shown to arise from capacitance currents in the case of PAn oxidation by the derivative cyclic voltabsorptometry experiment (see below) [179]. This residual current, however, was also interpreted as a continuous distribution of redox states with different oxidation potentials [180]. The cathodic currents usually have more than one peak, neither of which is as sharp as their anodic counterparts. This was attributed to differences in redox potentials due to the different interactions with charged states as in the case of hydroxide or other anion-doped PPy [172] and differences in structural relaxation and conformational changes [181]. 

This picture is consistent with spectroelectrochemical observations, conductivity data, and chemistry following the second oxidation of PAn films. Very similar spectra were reported by Jiang et al. who conducted a photothermal spectroscopic study on PAn oxidation [195]. 

Greszczuk et al. [252] employed the a.c. impedance measurements to study the ionic transport during PAn oxidation. Equivalent circuits of the conducting polymer-electrolyte interfaces are made of resistance R, capacitance C, and various distributed circuit elements. The latter consist of a constant phase element Q, a finite transmission line T, and a Warburg element W. The general expression for the admittance response of the CPE, Tcpr, is [253]... 

Fig. 1. The stmcture of Dow EDF fiber. EDF = elongatable Dow fiber OPF = oxidized PAN fiber.

Process. Any standard precursor material can be used, but the preferred material is wet spun Courtaulds special acrylic fiber (SAF), oxidized by RK Carbon Fibers Co. to form 6K Panox B oxidized polyacrylonitrile (PAN) fiber (OPF). This OPF is treated ia a nitrogen atmosphere at 450—750°C, preferably 525—595°C, to give fibers having between 69—70% C, 19% N density less than 2.5 g/mL and a specific resistivity under 10 ° ohm-cm. If crimp is desired, the fibers are first knit iato a sock before heat treating and then de-knit. Controlled carbonization of precursor filaments results ia a linear Dow fiber (LDF), whereas controlled carbonization of knit precursor fibers results ia a curly carbonaceous fiber (EDF). At higher carbonizing temperatures of 1000—1400°C the fibers become electrically conductive (22). 

In the older method, still used in some CIS and East European tar refineries, the naphthalene oil is cooled to ambient temperatures in pans, the residual oil is separated from the crystals, and the cmde drained naphthalene is macerated and centrifuged. The so-called whizzed naphthalene crystallizes at ca 72—76°C. This product is subjected to 35 MPa (350 atm) at 60—70°C for several minutes in a mechanical press. The lower melting layers of the crystals ate expressed as Hquid, giving a product crystallizing at 78—78.5°C (95.5—96.5% pure). This grade, satisfactory for oxidation to phthaHc anhydride, is referred to as hot-pressed or phthaHc-grade naphthalene. 

There are two mechanisms of PAN-based carbon fiber oxidation dependent on oxidation temperature ((67,68). At temperatures below 400°C, oxygen diffuses into the fiber and attacks at pores resulting in significantly increased fiber surface area. At higher temperatures impurities catalyze the oxidation reaction. 

The burden must have a definite sohdification temperature to assure proper pickup from the feed pan. This limitation can be overcome by side feeding through an auxiliary rotating spreader roll. Apphcation hmits are further extended by special feed devices for burdens having oxidation-sensitive and/or supercoohng characteristics. The standard double-drum model turns downward, with adjustable roll spacing to control sheet thickness. The newer twin-drum model (Fig. ll-55b) turns upward and, though subject to variable cake thickness, handles viscous and indefinite solidification-temperature-point burden materials well. 

The as-spun acrylic fibers must be thermally stabilized in order to preserve the molecular structure generated as the fibers are drawn. This is typically performed in air at temperatures between 200 and 400°C [8]. Control of the heating rate is essential, since the stabilization reactions are highly exothermic. Therefore, the time required to adequately stabilize PAN fibers can be several hours, but will depend on the size of the fibers, as well as on the composition of the oxidizing atmosphere. Their are numerous reactions that occur during this stabilization process, including oxidation, nitrile cyclization, and saturated carbon bond dehydration [7]. A summary of several fimctional groups which appear in stabilized PAN fiber can be seen in Fig. 3. 

The pollutants most strongly damaging to human, animal, and sometimes plant health include ozone, fine particulate matter, lead, nitrogen oxides (NO ), sulfur oxides (SOJ, and carbon monoxide. Many other chemicals found in polluted air can cause lesser health impacts (such as eye irritation). VOC compounds comprise the bulk of such chemicals. Formaldehyde is one commonly mentioned pollutant of this sort, as is PAN (peroxyacyl nitrate). Such... 

Figure 1. Temperature variation of the conductivity for a cross-section of polymer electrolytes. PESc, poly (ethylene succinate) PEO, polyethylene oxide) PPO, polypropylene oxide) PEI, poly(ethyleneimine) MEEP, poly(methoxyethoxy-ethoxyphosphazene) aPEO, amorphous methoxy-linked PEO PAN, polyacrylonitrile PC, propylene carbonate EC, ethylene carbonate.

PCSs obtained by dehydrochlorination of poly(2-dilorovinyl methyl ketones) catalyze the processes of oxidation and dehydrogenation of alcohols, and the toluene oxidation207. The products of the thermal transformation of PAN are also catalysts for the decomposition of nitrous oxide, for the dehydrogenation of alcohols and cyclohexene274, and for the cis-tnms isomerization of olefins275. Catalytic activity in the decomposition reactions of hydrazine, formic acid, and hydrogen peroxide is also manifested by the products of FVC dehydrochlorination... 

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