Abstract
The influence of morphology on the viscoelastic properties of melts of microphase-separated polystyrene-block-polyisoprene (PS-b-PI) diblock copolymers was investigated in oscillatory shear and creep recovery experiments. By means of anionic polymerization, three PS-b-PI diblock copolymers with a narrow molecular weight distribution and different types of morphology (spherical, cylindrical and lamellar microstructure) were prepared. Linear viscoelastic shear oscillations and creep recovery experiments in shear were performed in order to determine the elastic and viscous properties of the diblock copolymers in the melt at small and large time scales. Our analysis reveals that melts of diblock copolymers are characterized by a pronounced elastic behavior leading to a relatively large recoverable deformation in creep recovery experiments. The elasticity of the diblock copolymers is also revealed by the appearance of the creep-ringing effect. Morphological investigations were carried out to establish relations between microstructure and melt elasticity. Since ordering phenomena take place in melts of diblock copolymers until an equilibrium morphology is achieved, the storage modulus G′ of diblock copolymer melts increases with time up to a steady-state value.
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References
Abetz, V. and A. Boschetti-de-Fierro, 2012, Block copolymers in the condensed state, Polymer science: a comprehensive reference 7, 3–44.
Adams, J.L., D.J. Quiram, W.W. Graessley, R.A. Register, and G.R. Marchand, 1996, Ordering Dynamics of Compositionally Asymmetric StyreneIsoprene Block Copolymers, Macromolecules 29, 2929–2938.
Bates, F.S. and G.H. Fredrickson, 1990, Block Copolymer Thermodynamics: Theory and Experiment, Ann. Rev. Phys. Chem. 41, 525–557.
Bates, F.S. and G.H. Fredrickson, 1999, Block Copolymers—Designer Soft Materials, Phys.Today 52, 32–38.
Breiner, U., U. Krappe, T. Jakob, V. Abetz, and R. Stadler, 1998, Spheres on spheres — a novel spherical multiphase morphology in polystyrene-block-polybutadiene-block-poly(methyl methacrylate) triblock copolymers, Polym. Bull. 40, 219–226.
Buzza, D.M.A., A.H. Fzea, J.B. Allgaier, R.N. Young, R.J. Hawkins, I.W. Hamley, T.C.B. McLeish, and T.P. Lodge, 2000, Linear Melt Rheology and Small-Angle X-ray Scattering of AB Diblocks vs A2B2 Four Arm Star Block Copolymers, Macromolecules 33, 8399–8414.
Cogswell, F.N., 1981, Polymer Melt Rheology: A Guide for Industrial Practice, Elsevier Science
Ewoldt, R.H. and G.H. McKinley, 2007, Creep ringing in rheometry or how to deal with oft-discarded data in step stress tests!, Rheol. Bull. 76, 22–24.
Ferry, J.D., 1980, Viscoelastic Properties of Polymers, Wiley
Fetters, L.J., D.J. Lohse, S.T. Milner, and W.W. Graessley, 1999, Packing Length Influence in Linear Polymer Melts on the Entanglement, Critical, and Reptation Molecular Weights, Macromolecules 32, 6847–6851.
Förster, S., A.K. Khandpur, J. Zhao, F.S. Bates, I.W. Hamley, A.J. Ryan, and W. Bras, 1994, Complex Phase Behavior of Polyisoprene-Polystyrene Diblock Copolymers Near the Order-Disorder Transition, Macromolecules 27, 6922–6935.
Graessley, W.W., 1980, Some phenomenological consequences of the Doi–Edwards theory of viscoelasticity, J. Polym. Sci. Pol. Phys. 18, 27–34.
Han, C.D., D.M. Baek, J.K. Kim, T. Ogawa, N. Sakamoto, and T. Hashimoto, 1995, Effect of volume fraction on the orderdisorder transition in low molecular weight polystyrene-blockpolyisoprene copolymers. 1. Order-disorder transition temperature determined by rheological measurements, Macromolecules 28, 5043–5062.
Harrison, C., D.H. Adamson, Z. Cheng, J.M. Sebastian, S. Sethuraman, D.A. Huse, R.A. Register, and P.M. Chaikin, 2000, Mechanisms of Ordering in Striped Patterns, Science 290, 1558–1560.
Hashimoto, T., K. Kowsaka, M. Shibayama, and H. Kawai, 1986, Time-resolved small-angle x-ray scattering studies on the kinetics of the order-disorder transition of block polymers. 2. Concentration and temperature dependence, Macromolecules 19, 754–762.
Helfand, E. and Z.R. Wasserman, 1976, Block Copolymer Theory. 4. Narrow Interphase Approximation, Macromolecules 9, 879–888.
Helfand, E. and Z.R. Wasserman, 1978, Block Copolymer Theory. 5. Spherical Domains, Macromolecules 11, 960–966.
Helfand, E. and Z.R. Wasserman, 1980, Block Copolymer Theory. 6. Cylindrical Domains, Macromolecules 13, 994–998.
Honerkamp, J. and J. Weese, 1993, A note on estimating mastercurves, Rheol. Acta 32, 57–64.
Jung, A., S. Rangou, C. Abetz, V. Filiz, and V. Abetz, 2012, Structure Formation of Integral Asymmetric Composite Membranes of Polystyrene-block-Poly(2-vinylpyridine) on a Nonwoven, Macromol. Mater. Eng. 297, 790–798.
Kaneko, T., K. Suda, K. Satoh, M. Kamigaito, T. Kato, T. Ono, E. Nakamura, T. Nishi, and H. Jinnai, 2006, A “ladder” Morphology in an ABC Triblock Copolymer, Macromol. Symp. 242, 80–86.
Keller, A., E. Pedemonte, and F.M. Willmouth, 1970, Macro lattice from segregated amorphous phases of a three block copolymer, Kolloid-Z.u.Z.Polymere 238, 385–389.
Khandpur, A.K., S. Förster, F.S. Bates, I.W. Hamley, A.J. Ryan, W. Bras, K. Almdal, and K. Mortensen, 1995, Polyisoprene-Polystyrene Diblock Copolymer Phase Diagram near the Order-Disorder Transition, Macromolecules 28, 8796–8806.
Koppi, K.A., M. Tirrell, F.S. Bates, K. Almdal, and R.H. Colby, 1992, Lamellae orientation in dynamically sheared diblock copolymer melts, J. Phys. II France 2, 1941–1959.
Krappe, U., R. Stadler, and I. Voigt-Martin, 1995, Chiral Assembly in Amorphous ABC Triblock Copolymers. Formation of a Helical Morphology in Polystyrene-block-polybutadieneblock-poly(methyl methacrylate) Block Copolymers, Macromolecules 28, 4558–4561.
Kryder, M.H., 1992, Magnetic thin films for data storage, Thin Solid Films 216, 174–180.
Larson, R.G., K.I. Winey, S.S. Patel, H. Watanabe, and R. Bruinsma, 1993, The rheology of layered liquids: lamellar block copolymers and smectic liquid crystals, Rheol. Acta 32, 245–253.
Leibler, L., 1980, Theory of Microphase Separation in Block Copolymers, Macromolecules 13, 1602–1617.
Matsen, M.W. and F.S. Bates, 1997, Block copolymer microstructures in the intermediate-segregation regime, J. Chem. Phys. 106, 2436–2448.
Mori, K., H. Hasegawa, and T. Hashimoto, 1985, Small-angle Xray scattering from bulk block polymers in disordered state. Estimation of X-values from accidental thermal fluctuations, Polymer J. 17, 799–806.
Morrison, F.A. and H.H. Winter, 1989, The effect of unidirectional shear on the structure of triblock copolymers. I. Polystyrene-polybutadiene-polystyrene, Macromolecules 22, 3533–3540.
Münstedt, H., 2014, Rheological experiments at constant stress as efficient method to characterize polymeric materials, J. Rheol. 58, 565–587.
Münstedt, H., N. Katsikis, and J. Kaschta, 2008, Rheological Properties of Poly(methyl methacrylate)/Nanoclay Composites As Investigated by Creep Recovery in Shear, Macromolecules 41, 9777–9783.
Pakula, T., K. Saijo, H. Kawai, and T. Hashimoto, 1985, Deformation behavior of styrene-butadiene-styrene triblock copolymer with cylindrical morphology, Macromolecules 18, 1294–1302.
Park, C., J. Yoon, and E.L. Thomas, 2003, Enabling nanotechnology with self assembled block copolymer patterns, Polymer 44, 6725–6760.
Patel, S.S., R.G. Larson, K.I. Winey, and H. Watanabe, 1995, Shear Orientation and Rheology of a Lamellar Polystyrene-Polyisoprene Block Copolymer, Macromolecules 28, 4313–4318.
Rieger, J., 1996, The glass transition temperature of polystyrene, J. Therm. Anal. Calorim. 46, 965–972.
Ryu, C.Y., M.S. Lee, D.A. Hajduk, and T.P. Lodge, 1997, Structure and viscoelasticity of matched asymmetric diblock and triblock copolymers in the cylinder and sphere microstructures, J. Polym. Sci. Pol. Phys. 35, 2811–2823.
Scott, D.B., A.J. Waddon, Y.G. Lin, F.E. Karasz, and H.H. Winter, 1992, Shear-induced orientation transitions in triblock copolymer styrene-butadiene-styrene with cylindrical domain morphology, Macromolecules 25, 4175–4181.
Sebastian, J.M., C. Lai, W.W. Graessley, and R.A. Register, 2002a, Steady-Shear Rheology of Block Copolymer Melts and Concentrated Solutions: Disordering Stress in Body-Centered-Cubic Systems, Macromolecules 35, 2707–2713.
Sebastian, J.M., C. Lai, W.W. Graessley, R.A. Register, and G.R. Marchand, 2002b, Steady-Shear Rheology of Block Copolymer Melts: Zero-Shear Viscosity and Shear Disordering in Body-Centered-Cubic Systems, Macromolecules 35, 2700–2706.
Winter, H.H., D.B. Scott, W. Gronski, S. Okamoto, and T. Hashimoto, 1993, Ordering by flow near the disorder-order transition of a triblock copolymer styrene-isoprene-styrene, Macromolecules 26, 7236–7244.
Zhang, Y. and U. Wiesner, 1998, Rheology of lamellar polystyrene-block-polyisoprene diblock copolymers, Macromol. Chem. and Phys. 199, 1771–1784.
Zhao, J., B. Majumdar, M.F. Schulz, F.S. Bates, K. Almdal, K. Mortensen, D.A. Hajduk, and S.M. Gruner, 1996, Phase Behavior of Pure Diblocks and Binary Diblock Blends of Poly(ethylene)Poly(ethylethylene), Macromolecules 29, 1204–1215.
Zott, H. and H. Heusinger, 1975, Electron Spin Resonance Investigations of Radicals and Trapped Electrons in ã-Irradiated 3,4-Polyisoprene and 1,2-Polybutadiene, Macromolecules 8, 182–185.
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Haenelt, T.G., Georgopanos, P., Abetz, C. et al. Morphology and elasticity of polystyrene-block-polyisoprene diblock copolymers in the melt. Korea-Aust. Rheol. J. 26, 263–275 (2014). https://doi.org/10.1007/s13367-014-0031-3
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DOI: https://doi.org/10.1007/s13367-014-0031-3