Martin Varga

Polypyrrole–silver composites prepared by the reduction of silver ions with polypyrrole nanotubes

Polypyrrole nanotubes were prepared by the oxidation of pyrrole with iron(III) chloride in the presence of methyl orange. They were subsequently used for the reduction of silver ions to silver nanoparticles. The nanotubular form of polypyrrole is compared with the classical globular morphology in its ability to reduce silver ions. Both polypyrrole salts and bases were used in the experiments. The content of metallic silver in the resulting composite, determined by thermogravimetric analysis, was 21–31 wt%. Elemental composition is also discussed on the basis of energy-dispersive X-ray spectroscopy. Contrary to the expectation, the conductivity of polypyrrole nanotubes in salt form, 35.7 S cm−1, was reduced to 20.9 S cm−1 after the incorporation of silver. The presence of silver had generally little effect on the conductivity. The temperature dependence of conductivity reveals that the composites maintain the semiconducting character of polypyrrole and their conductivity increased with increasing temperature. The conductivity of the composites surprisingly increased when the samples were placed in vacuo.

Polypyrrole salts and bases: superior conductivity of nanotubes and their stability towards the loss of conductivity by deprotonation

Polypyrrole nanotubes exhibit conductivity of tens S cm−1 which is one of the highest among the current conducting polymers. They are thus superior to the common globular form with the conductivity of units of S cm−1 or lower. The conductivity of both forms is reduced after treatment with alkalis but still remains high, units of S cm−1 and 10−2 S cm−1, respectively. The deprotonation, which is responsible for conductivity reduction, is discussed on the basis of salt–base transition in polypyrrole. It is not fully reversible, and the reprotonation with acids recovers the conductivity only in part. The role of methyl orange, which was used to support the formation of nanotubes, is proposed to be similar to that of surfactants. FTIR and Raman spectroscopies prove that methyl orange is strongly bound to polypyrrole in its acid form, and an “insertion” mechanism is proposed to explain the resistance towards the deprotonation of nanotubes. The spectra also illustrate that the molecular structure of nanotubular polypyrrole is preserved even under highly alkaline conditions at a pH close to 14, where the globular form becomes damaged. Polypyrrole, especially in its nanotubular form, is of promise in applications requiring electrical conduction even under neutral or alkaline conditions, where other conducting polymers, such as polyaniline, lose their exploitable conductivity.

The influence of compression pressure on transport properties of polyaniline

The transport of charge carriers and the thermal diffusivity were studied on a set of polyaniline (emeraldine) samples that were compressed at various pressures, 50–1000 MPa. Marked correlations between the plots of compression pressure dependence of the electrical resistivity, the thermal diffusivity and the sample density were observed. This study has demonstrated that in order to obtain comparable data on samples prepared by compression of polymeric powders it is necessary to use sufficiently high pressure. In the case of polyaniline powder the pressure should be higher than 400 MPa. The values of the thermal diffusivity measured on polyaniline salt and its respective base indicate that charge carriers are not dominant in a heat-transport mechanism; only less than ten per cent of the thermal diffusion in pressed polyaniline samples can be eventually attributed to charge carriers.

Dye-stimulated control of conducting polypyrrole morphology

Azo dyes represent important structure-guiding agents which exhibit non-covalent interactions of various types (ionic and hydrogen bonding, π–π stacking, hydrophobic interactions, etc.) allowing for their self-assembly in aqueous solutions and the subsequent formation of seeds or templates for the preparation of supramolecular structures of conducting polymers, especially polypyrrole (PPy). Three azo dyes (Acid Red 1, Orange G and Sunset Yellow FCF) bearing hydrophilic functional groups, with mutually different positions on a hydrophobic naphthylphenyldiazene skeleton, were used as structure-guiding agents in the synthesis of highly organized supramolecular structures of PPy in aqueous media. The synthesized polymers were studied by scanning electron microscopy, energy dispersive X-ray, and Fourier-transform infrared and Raman spectroscopies. Measurement of the conductivity revealed a moderate value of conductivity (around units of S cm−1) and reduced stability indicated by relatively fast conductivity decay. Infrared spectroscopy indicated a lower doping level of all PPy prepared in the presence of tested dyes compared to that of standard globular PPy. In contrast, Raman spectroscopy, which is a surface-sensitive method, indicated a slightly higher protonation level compared to that of standard globular PPy or nanotubular PPy synthesized in the presence of the well-known structure-guiding agent methyl orange. This discrepancy in the obtained doping levels is discussed and some consequences between the doping level of PPy and its conductivity are also pointed out.