Morphology polypyrrole

E. Chainet and M. Billon, In situ study of polypyrrole morphology by STM effect of the doping state. J. Electroanal. Chem., 451, 273 (1998). 

A number of approaches are available to improve the morphology and homogeneity of electrochemically deposited conducting polymer films. Priming of the electrode surface with a monolayer of adsorbed or covalently bonded monomer leads to more compact deposits of polyaniline,87,88 poly thiophene,80 and polypyrrole.89,90 Electrode rotation has been shown to inhibit the deposition of powdery overlayers during poly(3-methylthiophene) deposition.81... 

Glatzhofer et al.1281 describe the reduction of conductivity of polypyrrole films, doped with poly(styrene-p-sulfonate), as increasing concentrations of dioxane are added to the aqueous electrolyte. They claim that the solvent induces a conformational change in the counterion, which modifies the film morphology. 

Comparable to thiophene, pyrrole is a five-membered heterocycle, yet the ring nitrogen results in a molecule with distinctly different behavior and a far greater tendency to polymerize oxidatively. The first report of the synthesis of polypyrrole (PPy) 62 that alluded to its electrically conductive nature was published in 1968 [263]. This early material was obtained via electrochemical polymerization and was carried out in 0.1 N sulfuric acid to produce a black film. Since then, a number of improvements, which have resulted from in-depth solvent and electrolyte studies, have made the electrochemical synthesis of PPy the most widely employed method [264-266]. The properties of electrosynthesized PPy are quite sensitive to the electrochemical environment in which it is obtained. The use of various electrolytes yield materials with pronounced differences in conductivity, film morphology, and overall performance [267-270]. Furthermore, the water solubility of pyrrole allows aqueous electrochemistry [271], which is of prime importance for biological applications [272]. 

As mentioned in the introduction, the electrical conductivity upon doping is one of the most important physical properties of conjugated polymers. The conductivity ranges from lOOOOOS/cm for iodine-doped polyacetylene [41], 1000 S/cm for doped and stretched polypyrrole [42], to 500 S/cm for doped PPP [43], 150 S/cm for hydrochloric acid doped and stretched polyaniline [44], and 100 S/cm for sulfuric acid doped PPV [45] to 50 S/cm for iodine-doped poly thiophene [46]. The above listed conductivities refer to the unsubstituted polymers other substitution patterns can lead to different film morphologies and thus to a different electrical conductivity for the same class of conjugated polymer in the doped state. 

Composites of polypyrrole and poly(vinyl chloride) have been prepared by several groups (64-67). Polythiophene-poly(vinyl chloride) composites have also been prepared (68). The electropolymerization of pyrrole on poly(vinyl chloride)-coated electrodes yielded composites with mechanical properties (tensile strength, percent elongation at break, percent elongation at yield) similar to poly(vinyl chloride) (65) but with a conductivity of 5-50 S/cm, which is only slightly inferior to polypyrrole (30-60 S/cm) prepared under similar conditions. In addition, the environmental stability was enhanced. Morphological studies (69) showed that the polypyrrole was not uniformly distributed in the film and had polypyrrole-rich layers next to the electrode. Similarly, poly(vinyl alcohol) (70) poly[(vinylidine chloride)-co-(trifluoroethylene)] (69) and brominated poly(vinyl carbazole) (71) have been used as the matrix polymers. The chemical polymerization of pyrrole in a poly(vinyl alcohol) matrix by ferric chloride and potassium ferricyanide also yielded conducting composites with conductivities of 10 S/cm (72-74). 

The him morphology of electrochemically prepared polythiophene has been shown in numerous studies to be almost identical to that commonly observed for polypyrrole (described in Chapter 2). A nodular surface is observed for both unsubstituted and 3-alkyl substituted thiophenes.92 As with PPy, the electrochemical preparation of PTh at higher current densities produced rougher surface morphologies. The similarity in morphologies suggest a similar growth mechanism for electrochemically polymerized PPy and PTh. 

A. D. W. Carswell, E. A. O Rear, and B. P. Grady, Adsorbed surfactants as templates for the synthesis of morphologically controlled polyaniUne and polypyrrole nanostructures on flat surfaces from spheres to wires to flat films, J. Aon. Chem. Soc., 125, 14793-14800 (2003). 

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