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The concentration dependence of the dielectric properties of aqueous solutions of sodium maleate copolymers with comonomers of different hydrophobicities have been investigated by means of frequency domain dielectric spectroscopy in the frequency range from 1 kHz to 2 GHz. The dielectric relaxation falling between the process at low frequencies (polarization involving the whole polymer chain) and the one at high frequencies (polarization of the bulk aqueous phase) has been analyzed in light of the scaling properties of polyelectrolyte solutions. Within this framework, the dielectric properties are governed by two characteristic lengths, the distance R(cm) between chains in the dilute regime and the correlation length xi in the semidilute regime. We find that, for both these regimes, the exponents of the scaling laws, which describe the dielectric increment Deltaepsilon and the relaxation time tau(ion) are in a reasonably good agreement with the ones experimentally observed. This analysis gives further support to the scaling approach of the dynamic behavior of polyelectrolytes, appearing very suitable to modeling our dielectric results.

We present a set of low-frequency electrical conductivity measurements of solutions of differently charged, salt-free polyelectrolytes in poor- and in good-solvent conditions, in the semidilute concentration regime. The data have been analyzed and discussed in light of the necklace model for hydrophobic polyelectrolytes recently proposed by Dobrynin et al. [Macromolecules 29, 2974 (1996)] that predicts the chains to collapse into spheroidal cores connected by narrow strings. By varying the quality of the solvent, we have measured the polyion equivalent conductance λp in an extended concentration range in the semidilute regime and have demonstrated that this parameter is influenced by the polyion chain conformation, giving further support, when the poor-solvent condition prevails, to the picture of a string of electrostatic blobs. On the contrary, in good-solvent condition, the electrical conductivity data are in reasonable good agreement with the picture of an extended chain consisting of a collection of electrostatic blobs. These electrical conductivity measurements, in light of scaling theory, furnish new experimental support for the necklace model for hydrophobic polyions in poor solvents. [ABSTRACT FROM AUTHOR]