Stimuli-responsive polyelectrolyte surfactant complexes for the reversible control of solution viscosity.

Interactions of polyelectrolytes with oppositely charged surfactants can give rise to a large variety of self-assembled structures. Some of these systems cause a drastic increase in solution viscosity, which is related to the surfactant forming aggregates interconnecting several polyelectrolyte chains. For these aggregates to form, the surfactant needs to be sufficiently hydrophobic. Here, we present a system consisting of the anionic surfactant sodium monododecyl phosphate and the cationic cellulose-based polyelectrolyte JR 400. The hydrophobicity of the surfactant can be controlled by the solution's pH. At pH > 12, the surfactant headgroup bears two charges. As a consequence, the solution viscosity decreases drastically by up to two orders of magnitude, while it can be as high as 10 Pa s at lower pH. In this paper, we investigate the changes of the mesoscopic structure of the system which lead to such drastic changes in viscosity using small angle neutron scattering and neutron spin-echo spectroscopy. Such systems are potentially interesting as they allow for a modular design where stimuli responsiveness is introduced by relatively small amounts of surfactant reusing the same simple polyelectrolyte.

On the Mechanism of Shear-Thinning in Viscous Oppositely Charged Polyelectrolyte Surfactant Complexes (PESCs).

Semidilute mixtures of the cationically modified cellulose-based polyelectrolyte JR 400 and the anionic surfactant sodium dodecyl sulfate (SDS) form highly viscous solutions if a slight excess of charges from the polyelectrolyte is present. The reason for this is the formation of mixed rodlike aggregates in which the surfactant cross-links several polyelectrolyte chains. The same solutions also show shear-thinning behavior. In this paper, we use rheoSANS to investigate the structural evolution of the rodlike aggregates under steady shear and thereby elucidate the mechanism of shear-thinning in these viscous oppositely charged polyelectrolyte surfactant complexes.

Non Monotonous Effects of Noncovalently Functionalized Graphene Addition on the Structure and Sound Absorption Properties of Polyvinylpyrrolidone (1300 kDa) Electrospun Mats.

Graphene is an attractive component for high-performance stimuli-responsive or 'smart' materials, shape memory materials, photomechanical actuators, piezoelectric materials and flexible strain sensors. Nanocomposite fibres were produced by electrospinning high molecular weight Polyvinylpyrrolidone (PVP-1300 kDa) in the presence of noncovalently functionalised graphene obtained through tip sonication of graphite alcoholic suspensions in the presence of PVP (10 kDa). Bending instability of electrospun jet appears to progressively increase at low graphene concentrations with the result of greater fibre stretching that leads to lower fibre diameter and possibly conformational changes of PVP. Further increase of graphene content seams having the opposite effect leading to greater fibre diameter and Raman spectra similar to the pure PVP electrospun mats. All this has been interpreted on the basis of currently accepted model for bending instability of electrospun jets. The graphene addition does not lower the very high sound absorption coefficient, α, close to unity, of the electrospun PVP mats in the frequency range 200⁻800 Hz. The graphene addition affects, in a non-monotonous manner, the bell shaped curves of α versus frequency curves becoming sharper and moving to higher frequency at the lower graphene addition. The opposite is observed when the graphene content is further increased.