Fluctuation regime in the viscoelastic properties of block copolymer solutions

We report measurements of the dynamic shear moduli for solutions of three symmetric styrene isoprene diblock copolymers in the neutral solvent di-octyl phthalate. For each sample the concentration range was selected to extend from the disordered regime to the (lamellar) ordered state, with the emphasis placed on the intermediate regime, where large amplitude composition fluctuations are clearly evident. Temperatures from 0° to nearly 100°C were employed. The fluctuations were most clearly revealed when the data were plotted as phase angle versus reduced frequency, where the frequency axis was scaled by the longest relaxation time in the absence of fluctuations. The dynamic shear moduli and the apparent longest relaxation times, all normalized to their respective values in the absence of fluctuations, increased markedly as the order-disorder transition was approached. The rate of increase was consistent with recent theoretical predictions of Fredrickson, Larson, and Helfand, but the magnitude of the effect is larger than anticipated by theory. The onset of visible fluctuation effects depends on molecular weight in a manner that suggests that entanglements play an important role in determining the coupling of the fluctuations to the viscoelastic properties. This is consistent with previous measurements of translational diffusion, which demonstrated that entanglements severely diminish the mobility of lamellar-forming block copolymers along the interfaces between microdomains.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.