Dilational rheology of monolayers of a miscible polymer blend: from good- to poor-solvent conditions.
The viscoelastic moduli (elasticity and dilational viscosity) of monolayers of PVAc + P4HS has been studied over a broad frequency range (0.1 mHz-200 kHz) using a combination of relaxation and capillary-waves techniques. The analysis of the surface pressure, the elasticity and the viscosity on the semidilute regime show that the air-water interface is a good solvent for the monolayers of PVAc-rich blends, and a poor (near-Theta) solvent for the monolayers of P4HS-rich blends. The solvent quality changes continuously over a broad concentration range. The results of viscoelastic moduli show that there is a broad relaxation process in the low-frequency range (omega < 1 Hz). While for PVAc-rich monolayers this relaxation process follows the reptation-like behavior described by Noskov, for P4HS-rich monolayers the model does not describe the amplitudes of the different relaxation modes. For PVAc-rich monolayers two processes are clearly distinguished at higher frequencies: one centered at around 500 Hz and another one at around 40 kHz. However, for P4HS-rich monolayers only one broad relaxation mode is found below 1 kHz. The crossover from one type of behavior to the other one takes place in a very narrow blend-composition range, and is not clearly related to the crossover from good- to poor-solvent condition.
Rivillon
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Departamento Química Física I, Facultad de Química, Universidad Complutense, E-28040 Madrid, Spain.
Monroy
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Ortega
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Rubio
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