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S Pispas

Publications and source records attributed to S Pispas.

4 recordsLinked to original sources

Micelles of poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) terpolymers in aqueous media and their interaction with surfactants.

Well-defined poly(isoprene-b-2-vinylpyridine-b-ethylene oxide) (PI-P2VP-PEO) triblock terpolymers were synthesized by anionic polymerization high-vacuum techniques. The terpolymers formed spherical three-layer (onion-type) micelles in neutral and acidic pH aqueous media as evidenced by static and dynamic light scattering. In pure water, kinetically frozen micelles with a core composed of a soft PI inner part and a hard P2VP outer shell and protected by a neutral PEO corona were formed. In acidic media the core was formed by the soft PI hydrophobic segment, whereas the corona consisted of an inner cationic polyelectrolyte P2VPH+ part and an outer PEO shell. The aggregation numbers were found to be high in all cases, due to the high hydrophobicity of the core-forming blocks. In the latter case an increase in size was observed due to the electrostatic repulsions between the P2VPH+ chains in the inner part of the corona, which is also responsible for the lower aggregation numbers observed in the acidic solutions. The interaction of these onion-type micelles with cationic (DTMAB) and anionic (SDS) surfactants led to the formation of mixed polymer/surfactant aggregates. Their structural characteristics could be varied by combining changes in surfactant type and concentration, solution pH and type of electrostatic interaction, leading to interesting, block-copolymer-based, environmentally responsive colloidal systems.

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Pattern formation in homogeneous polymer solutions induced by a continuous-wave visible laser.

We report an unexpected nonphotothermal material organization induced by continuous-wave visible laser light at low power levels. This effect is observed along the laser beam propagation direction in fully transparent entangled solutions of common homopolymers featuring sufficiently high molecular mass and optical anisotropy along the chain backbone. The resulting formation of long-lived stringlike or dotlike patterns on the micrometer scale, probed by dark-field coherent imaging, depends on the molecular mass, architecture, solvent nature, and polymer concentration. Electrostrictive and alignment forces as well as chain cooperativity are responsible for the osmotic compression of the polymer solute. Subsequent waveguiding effects induce autoamplification and "pattern writing" upon prolonged illumination. This wave-medium coupling could potentially lead to photorefractive, microoptics, and nanotechnology applications.

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Dynamics of Polymer Interdiffusion: The Ripple Experiment.

We explore the interdiffusion of oppositely labeled triblock polystyrene chains, HDH/DHD, during welding in the melt using dynamic secondary ion mass spectroscopy (DSIMS) and specular neutron reflectivity (SNR). The HDH chains have the central portion of the chain deuterated (D) approximately 50% while the two ends (H) each have approximately 25% protonation; the DHD is oppositely labeled, but each set of chains contains about 50% deuteration. During welding, the deuterium depth profile exhibits "ripples" whose characteristic features, such as the time and molecular weight dependent shape, amplitude, and position, are very sensitive to the microscopic details of the polymer dynamics. The ripple experiment is especially sensitive to the presence, or absence, of topological constraints and anisotropic motion of chains. The current work significantly extends the molecular weight range up to 400 000. This allows greater separation of the six key ripple features used in deciphering the correct polymer dynamics model at the polymer-polymer interface. The DSIMS and SNR experimental results are compared to theoretical predictions and ripple simulations for Rouse, polymer mode-coupling, reptation (with and without tube broadening), and other phenomenological dynamics models. The six ripple characteristics were found to be perfectly correlated and convincingly consistent with the predictions of the reptation dynamics model. The ripple results are in significant disagreement with the polymer mode-coupling model proposed by Schweizer and other tubeless models. We conclude that the reptation model, proposed by DeGennes in 1971 with parallel developments by Edwards, is the correct model to describe the dynamics of polymer interdiffusion.

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