Abstract
Bulk films of random, block and gradient copolymer systems were studied using ellipsometry to demonstrate the applicability of the numerical differentiation technique pioneered by Kawana and Jones for studying the glass transition temperature (T g) behavior and thermal expansivities of copolymers possessing different architectures and different levels of nanoheterogeneity. In a series of styrene/n -butyl methacrylate (S/nBMA) random copolymers, T g breadths were observed to increase from ∼ 17° C in styrene-rich cases to almost 30° C in nBMA-rich cases, reflecting previous observations of significant nanoheterogeneity in PnBMA homopolymers. The derivative technique also revealed for the first time a substantial increase in glassy-state expansivity with increasing nBMA content in S/nBMA random copolymers, from 1.4×10-4 K-1 in PS to 3.5×10-4 K-1 in PnBMA. The first characterization of block copolymer T g ’s and T g breadths by ellipsometry is given, examining the impact of nanophase-segregated copolymer structure on ellipsometric measurements of glass transition. The results show that, while the technique is effective in detecting the two T g ’s expected in certain block copolymer systems, the details of the glass transition can become suppressed in ellipsometry measurements of a rubbery minor phase under conditions where the matrix is glassy; meanwhile, both transitions are easily discernible by differential scanning calorimetry. Finally, broad glass transition regions were measured in gradient copolymers, yielding in some cases extraordinary T g breadths of 69- 71° C , factors of 4-5 larger than the T g breadths of related homopolymers and random copolymers. Surprisingly, one gradient copolymer demonstrated a slightly narrower T g breadth than the S/nBMA random copolymers with the highest nBMA content. This highlights the fact that nanoheterogeneity relevant to the glass transition response in selected statistical copolymers can be comparable to or exceed that observed in moderately phase-segregated gradient copolymers.
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References
G.E. Jellison jr., F.A. Modine, in Handbook of Ellipso\-metry, edited by H.G. Tompkins, E.A. Irene (William Andrew, New York, 2005)
G. Beaucage, R. Composto, R.S. Stein, J. Polym. Sci. Part B: Polym. Phys. 31, 319 (1993)
J.L. Keddie, R.A.L. Jones, R.A. Cory, Europhys. Lett. 27, 59 (1994)
J.L. Keddie, R.A.L. Jones, R.A. Cory, Faraday Discuss. 98, 219 (1994)
J.A. Forrest, K. Dalnoki-Veress, J.R. Dutcher, Phys. Rev. E 56, 5705 (1997)
J.A. Forrest, J. Mattsson, Phys. Rev. E 61, R53 (2000)
O.K.C. Tsui, T.P. Russell, C.J. Hawker, Macromolecules 34, 5535 (2001)
D.S. Fryer, R.D. Peters, E.J. Kim, J.E. Tomaszewski, J.J. de Pablo, P.F. Nealey, C.C. White, W.L. Wu, Macromolecules 34, 5627 (2001)
S. Kawana, R.A.L. Jones, Phys. Rev. E 63, 021501 (2001)
R.S. Tate, D.S. Fryer, S. Pasqualini, M.F. Montague, J.J. de Pablo, P.F. Nealey, J. Chem. Phys. 115, 9982 (2001)
Y. Grohens, L. Hamon, G. Reiter, A. Soldera, Y. Holl, Eur. Phys. J. E 8, 217 (2002)
J.S. Sharp, J.A. Forrest, Phys. Rev. Lett. 91, 235701 (2003)
Y. Grohens, R.M. Papaleo, L. Hamon, Eur. Phys. J. E 12, S81 (2003)
C.H. Park, J.H. Kim, M. Ree, B.H. Sohn, J.C. Jung, W.C. Zin, Polymer 45, 4507 (2004)
Z. Fakhraai, J.A. Forrest, Phys. Rev. Lett. 95, 025701 (2005)
R. Seemann, S. Herminghaus, C. Neto, S. Schlagowski, D. Podzimek, R. Konrad, H. Mantz, K. Jacobs, J. Phys.: Condens. Matter 17, S267 (2005)
C.B. Roth, A. Pound, S.W. Kamp, C.A. Murray, J.R. Dutcher, Eur. Phys. J. E 20, 441 (2006)
M. Campoy-Quiles, M. Sims, P.G. Etchegoin, D.D.C. Bradley, Macromolecules 39, 7673 (2006)
C.G. Campbell, B.D. Vogt, Polymer 48, 7169 (2007)
H. Yang, J.S. Sharp, Macromolecules 41, 4811 (2008)
M.Y. Efremov, A.V. Kiyanova, P.F. Nealey, Macromolecules 41, 5978 (2008)
X.X. Li, B.D. Vogt, Macromolecules 41, 9306 (2008)
A.N. Raegen, M.V. Massa, J.A. Forrest, K. Dalnoki-Veress, Eur. Phys. J. E 27, 375 (2008)
S. Kim, S.A. Hewlett, C.B. Roth, J.M. Torkelson, Eur. Phys. J. E. 30, 83 (2009)
J.Q. Pham, P.F. Green, Macromolecules 36, 1665 (2003)
D.B. Hall, P. Underhill, J.M. Torkelson, Polym. Eng. Sci. 38, 2039 (1998)
S. Kawana, R.A.L. Jones, Eur. Phys. J. E 10, 223 (2003)
C.J. Ellison, J.M. Torkelson, Nat. Mater. 2, 695 (2003)
J.Q. Pham, C.A. Mitchell, J.L. Bahr, J.M. Tour, R. Krishnamoorti, P.F. Green, J. Polym. Sci. Part B: Polym. Phys. 41, 3339 (2003)
P. Rittigstein, J.M. Torkelson, J. Polym. Sci. Part B: Polym. Phys. 44, 2935 (2006)
P. Rittigstein, R.D. Priestley, L.J. Broadbelt, J.M. Torkelson, Nat. Mater. 6, 278 (2007)
R. Greiner, F.R. Schwarzl, Rheol. Acta 23, 378 (1984)
D.W. Van Krevelen, K. te Nijenhuis, Properties of Polymers: Their Correlation with Chemical Structure
M. Campoy-Quiles, P.G. Etchegoin, D.D.C. Bradley, Synth. Met. 155, 279 (2005)
S. Kahle, J. Korus, E. Hempel, R. Unger, S. Horing, K. Schroter, E. Donth, Macromolecules 30, 7214 (1997)
G.P. Simon, C.L. Beatty, S.R. Andrews, S. Shinton, G. Williams, Polymer 39, 5929 (1998)
G.O.R.A. van Ekenstein, R. Meyboom, G. ten Brinke, O. Ikkala, Macromolecules 33, 3752 (2000)
T. Pakula, K. Matyjaszewski, Macromol. Theor. Simul. 5, 987 (1996)
K. Matyjaszewski, M.J. Ziegler, S.V. Arehart, D. Greszta, T. Pakula, J. Phys. Org. Chem. 13, 775 (2000)
M.D. Lefebvre, M. Olvera de la Cruz, K.R. Shull, Macromolecules 37, 1118 (2004)
M.K. Gray, H.Y. Zhou, S.T. Nguyen, J.M. Torkelson, Macromolecules 37, 5586 (2004)
J. Kim, M.K. Gray, H.Y. Zhou, S.T. Nguyen, J.M. Torkelson, Macromolecules 38, 1037 (2005)
J. Kim, M.M. Mok, R.W. Sandoval, D.J. Woo, J.M. Torkelson, Macromolecules 39, 6152 (2006)
C.L.H. Wong, J. Kim, J.M. Torkelson, J. Polym. Sci. Part B: Polym. Phys. 45, 2842 (2007)
M.M. Mok, J. Kim, J.M. Torkelson, J. Polym. Sci. Part B: Polym. Phys. 46, 48 (2008)
M.M. Mok, S. Pujari, W.R. Burghardt, C.M. Dettmer, S.T. Nguyen, C.J. Ellison, J.M. Torkelson, Macromolecules 41, 5818 (2008)
M.M. Mok, J. Kim, C.L.H. Wong, S.R. Marrou, D.J. Woo, C.M. Dettmer, S.T. Nguyen, C.J. Ellison, K.R. Shull, J.M. Torkelson, Macromolecules 42, 7863 (2009)
K. Karaky, E. Pe, Soft Matter 2, 770 (2006)
K. Karaky, L. Billon, C. Pouchan, J. Desbri\`e, Macromolecules 40, 458 (2007)
S. Jouenne, J.A. Gonza, Macromolecules 40, 2432 (2007)
Y. Fu, M.F. Cunningham, R.A. Hutchinson, Macromol. Symp. 259, 151 (2007)
R. Paris, J.L. De la Fuente, J. Polym. Sci. Part B: Polym. Phys. 45, 1845 (2007)
X.Y. Sun, Y.W. Luo, R. Wang, B.G. Li, B. Liu, S.P. Zhu, Macromolecules 40, 849 (2007)
K. Karaky, G. Clisson, G. Reiter, L. Billon, Macromol. Chem. Phys. 209, 715 (2008)
K.I. Seno, I. Tsujimoto, S. Kanaoka, S. Aoshima, J. Polym. Sci. Part A: Polym. Chem. 46, 6444 (2008)
W. Jakubowski, A. Juhari, A. Best, K. Koynov, T. Pakula, K. Matyjaszewski, Polymer 49, 1567 (2008)
R. Jiang, Q.H. Jin, B.H. Li, D.T. Ding, R.A. Wickham, A.C. Shi, Macromolecules 41, 5457 (2008)
J. Nicolas, A.V. Ruzette, C. Farcet, P. Ge, Macromolecules 48, 7029 (2007)
D. Rana, K. Bag, S.N. Bhattacharyya, B.M. Mandal, J. Polym. Sci. Part B: Polym. Phys. 38, 369 (2000)
B.D. Edgecombe, J.A. Stein, J.M.J. Frechet, Z.H. Xu, E.J. Kramer, Macromolecules 31, 1292 (1998)
C.B. Roth, K.L. McNerny, W.F. Jager, J.M. Torkelson, Macromolecules 40, 2568 (2007)
R.D. Priestley, M.K. Mundra, N.J. Barnett, L.J. Broadbelt, J.M. Torkelson, Aust. J. Chem. 60, 765 (2007)
J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd edition (J. Wiley, New York, 1989)
S. Wi, N. Senthilkumar, S.W. Rhee, J. Mater. Sci.: Mater. Electron. 19, 45 (2008)
E. Penzel, J. Rieger, H.A. Schneider, Polymer 38, 325 (1997)
M. Beiner, K. Schröter, E. Hempel, S. Reissig, E. Donth, Macromolecules 32, 6278 (1999)
J.J. Fitzgerald, T.D. Binga, L.J. Sorriero, J.M. O’Reilly, Macromolecules 28, 7401 (1995)
K.J. Zhu, T.K. Kwei, E.M. Pearce, J. Appl. Polym. Sci. 37, 573 (1989)
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Mok, M.M., Kim, J., Marrou, S.R. et al. Ellipsometry measurements of glass transition breadth in bulk films of random, block, and gradient copolymers. Eur. Phys. J. E 31, 239–252 (2010). https://doi.org/10.1140/epje/i2010-10569-3
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DOI: https://doi.org/10.1140/epje/i2010-10569-3