The surface composition of a sterically-stabilized polypyrrole
colloid has been examined by X-ray
photoelectron spectroscopy (XPS). The sulfur atom of the
polyelectrolyte stabilizer poly(potassium
3-sulfopropyl methacrylate) [PKSPM] and the nitrogen atom of the
polypyrrole were used as unique elemental
markers for each component. The S/N atomic ratio at the particle
surface determined using XPS was found
to be significantly higher than the corresponding ‘macroscopic' S/N
atomic ratio calculated from elemental
microanalyses. This is the first direct evidence for the presence
of a stabilizer-rich layer at the surface
of sterically-stabilized conducting polymer particles. Changing to
a lower energy X-ray source (Mg Kα)
did not lead to an increase in the surface S/N ratio; thus, the
stabilizer layer is probably ‘patchy' rather
than a continuous coating. XPS also revealed that the surface
concentrations of the K+ and Cl-
counterions
in the colloid were substantially depleted relative to those found in
the PKSPM stabilizer and chloride-doped polypyrrole ‘bulk powder'. Moreover, the surface dopant
level of the polypyrrole particles calculated
on the basis of the remaining chloride ions was unusually low (Cl/N =
0.07). More realistic surface dopant
levels were obtained if it was assumed that some of the sulfonate
groups of the polyelectrolyte stabilizer
acted as dopant anions for the conducting polymer component. It
was concluded that the PKSPM stabilizer
is adsorbed onto the surface of the polypyrrole particles as a
polymeric dopant anion, with the concomitant
expulsion of KCl. Finally, there is some evidence that this
stabilizer is present as a polymeric dopant in
the interior of the particles as well.
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