Macromolecules
Article
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networks. This suggests the β relaxations are possibly related to
the cooperative motion of the entire DGEBA unit, whereas
below the β transition the ring motions have a correlation
length equal to the BPA moiety. From the study of BPA ring
motions, a picture of gradual development of molecular
motions is seen, starting with localized motions that involve
only the BPA unit, transitioning to a cooperative motion that
has a correlation length scale of a DGEBA unit, and ultimately
becoming long-range cooperative motions characteristic of the
glass transition.
The 44DDS ring motions contribute to the high temperature
part of 44A’s γ relaxation. The 44DDS diamine rings undergo
flip motions and the diamine backbones actively fluctuate and
sweep out certain molecular space, resulting in a lower
mechanical modulus for 44A. The 44DDS ring motions also
provide an additional energy dissipation mechanism giving rise
to a higher Tg of 44A. The swept-out space from the fluctuation
of the 44DDS ring axis explains the higher hole-size free
volume. 33DDS rings do not exhibit large-amplitude motions
but only undergo fast small-angle fluctuations, which results in a
decrease in the magnitude of the high temperature part of the γ
relaxation of 33A, a phenomenon often seen in the
antiplasticization process.
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ASSOCIATED CONTENT
* Supporting Information
■
S
(22) Bang, H. S.; Oh, I. H.; Lee, K. W.; Han, J. H.; Lee, C. E.; Jin, J.-I.
J. Appl. Phys. 2007, 102, 116106.
Thermal analysis, complete sets of experimental data, fitting
parameter values and step width information, side by side
comparisons of experimental data and calculated data. This
material is available free of charge via the Internet at http://
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AUTHOR INFORMATION
Corresponding Author
■
(26) Shi, J.-F.; Inglefield, P. T.; Jones, A. A.; Meadows, M. D.
Macromolecules 1996, 29, 605−609.
(27) Hansen, M. T.; Blumich, B.; Boeffel, C.; Spiess, H. W.
̈
Present Addresses
Macromolecules 1992, 25, 5542−5544.
(28) Hansen, M. T.; Boeffel, C.; Spiess, H. W. Colloid Polym. Sci.
1993, 271, 446−453.
S.J.T. and S.C.: Boeing Research and Technology, Seattle, WA.
A.R.S.: Department of Chemistry, Faculty of Science,
University of Beni Suef, Egypt.
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Notes
(30) Poliks, M. D.; Gullion, T.; Schaefer, J. Macromolecules 1990, 23,
2678−2681.
The authors declare no competing financial interest.
(31) Lee, P. L.; Schaefer, J. Macromolecules 1995, 28, 2577−2578.
(32) Hirschinger, J.; Miura, H.; Gardner, K. H.; English, A. D.
Macromolecules 1990, 23, 2153−2169.
ACKNOWLEDGMENTS
■
The authors acknowledge the following organizations and
individuals for their kind financial support and collaboration:
Boeing Research and Technology, Air Force Office of Scientific
Research (Charles Lee), Award No. FA9550-08-1-0077 and Dr.
Joycelyn Harrison Award No. FA9550-13-1-0103; Office of
Naval Research (Cliff Bedford), Award No. N00014-07-1-1057.
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