Abstract
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.
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Amelar S, Eastman CE, Morris RL, Smeltzly MA, Lodge TP, von Meerwall ED (1991) Macromolecules 24:3505
Anastasiadis SH, Fytas G, Vogt S, Gerharz B, Fischer EW (1993) Europhys Lett 22:619
Bates FS (1984) Macromolecules 17:2607
Bates FS, Rosedale JH, Fredrickson GH (1990) J Chem Phys 92:6255
Bates FS, Schulz MF, Kandpur AK, Förster S, Rosedale JH, Almdal K, Mortensen K (1994) J Chem Soc, Faraday Disc 98:7
Brazovskii SA (1975) Sov Phys JETP 41:85
Chung CI, Gale JC (1976) J Polym Sci, Polym Phys Ed 14:1149
Colby RH (1996) Current Opinion Coll Sci 1:454
Dalvi MC, Lodge TP (1994) Macromolecules 27:3487
Eastman CE, Lodge TP (1994) Macromolecules 27:5591
Ferry JD (1980) Viscoelastic properties of polymers, 3rd ed. Wiley, New York
Fredrickson GH (1986) J Chem Phys 85:5306
Fredrickson GH, Helfand E (1987) J Chem Phys 87:697
Fredrickson GH, Larson RG (1987) J Chem Phys 86:1553
Fredrickson GH, Helfand E (1988) J Chem Phys 89:5890
Fredrickson GH, Leibler L (1989) Macromolecules 22:1238
Fredrickson GH, Bates FS (1996) Annu Rev Mater Sci 26:503
Gouinlock EV, Porter RS (1977) Polym Eng Sci 17:535
Hadziioannou G, Mathis A, Skoulios A (1979) Colloid Polym Sci 257:136
Hamley IW, Koppi KA, Rosedale JH, Baltes FS, Almdal K, Mortensen K (1993) Macromolecules 26:5959
Han CD, Kim J (1987) J Polym Sci, Polym Phys Ed 25:1741
Holzer B, Lehmann A, Stuhn B, Kowalski M (1991) Polymer 32:1935
Hong KM, Noolandi J (1983) Macromolecules 16:1083
Jian T, Anastasiadis SH, Fytas G, Adachi K, Kotaka T (1993) Macromolecules 26:4706
Jian T, Anastasiadis SH, Semenov AN, Fytas G, Adachi K, Kotaka T (1994) Macromolecules 27:4762
Jian T, Semenov AN, Anastasiadis SH, Fytas G, Yeh F-J, Chu B, Vogt S, Wang F, Roovers JEL (1994) J Chem Phys 100:3286
Jin X, Lodge TP, manuscript in preparation
Kannan RM, Kornfield JA (1994) Macromolecules 27:1177
Keller A, Odell A (1985) In: Folkes MJ (ed) Processing, structure and properties of block copolymers. Applied Science, New York
Koppi KA, Tirrell M, Bates FS, Almdal K, Colby RH (1992) J Phys II France 2:1941
Landry CJT (1985) Ph. D. Thesis, Wisconsin
Leibler L (1980) Macromolecules 13:1602
Lodge TP (1993) J Phys Chem 97:1480
Lodge TP, Schrag JL (1982) Macromolecules 15:1376
Lodge TP, Dalvi MC (1995) Phys Rev Lett 75:657
Lodge TP, Pan C, Jin X, Liu Z, Zhao J, Maurer WW, Bates FS (1995) J Polym Sci, Polym Phys Ed 33:2289
Morrison FA, Winter HH (1989) Macromolecules 22:3533
Olvera de la Cruz M (1989) J Chem Phys 90:1995
Pan C, Maurer W, Liu Z, Lodge TP, Stepanek P, von Meerwall ED, Watanabe H (1995) Macromolecules 28:1643
Patel SS, Takahashi KM (1992) Macromolecules 25:4382
Rosedale JH, Bates FS (1990) Macromolecules 23:2329
Sahouani H, Lodge TP (1992) Macromolecules 25:5632
Schrag JL, Stokich TM, Strand DA, Merchak PA, Landry CJT, Radtke DR, Man VE, Lodge TP, Morris RL, Hermann KC, Amelar S, Eastman CE, Smeltzly MA (1991) J Non-Cryst Solids 131–133:537
Schweizer KS, Szamel G (1995) Transport Theory & Statistical Physics 24:947
Stepanek P, Lodge TP (1996) Macromolecules 29:1244
Stühn B, Stickel F (1992) Macromolecules 25:5306
Vogt S, Anastasiadis SH, Fytas G, Fischer EW (1994) Macromolecules 27:4335
Whitmore MD, Noolandi J (1990) J Chem Phys 93:2946
Widmaier JM, Meyer GC (1980) J Polym Sci, Polym Phys Ed 18:2217
Winey KI, Patel SS, Larson RG, Watanabe H (1993) Macromolecules 26:2542
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Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.
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Jin, X., Lodge, T.P. Fluctuation regime in the viscoelastic properties of block copolymer solutions. Rheola Acta 36, 229–238 (1997). https://doi.org/10.1007/BF00366663
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DOI: https://doi.org/10.1007/BF00366663