Ellipsometry measurements of glass transition breadth in bulk films of random, block, and gradient copolymers

M. M. Mok, J. Kim, S. R. Marrou, John M Torkelson

Research output: Contribution to journalArticlepeer-review

24 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)239-252
Number of pages14
JournalEuropean Physical Journal E
Issue number3
StatePublished - Mar 1 2010

ASJC Scopus subject areas

  • Biotechnology
  • Biophysics
  • Chemistry(all)
  • Materials Science(all)
  • Surfaces and Interfaces


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