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Title: Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition

The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc 12-b-pNte 21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODT corresponds to loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.
Authors:
 [1] ;  [2] ;  [3] ;  [1] ;  [4]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  3. Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering & Materials Sciences
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
Publication Date:
Report Number(s):
LBNL-1006901
Journal ID: ISSN 1520-6106; ir:1006901
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1336911

Kortright, Jeffrey Barrett, Sun, Jing, Spencer, Ryan K., Jiang, Xi, and Zuckermann, Ronald N.. Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition. United States: N. p., Web. doi:10.1021/acs.jpcb.6b09925.
Kortright, Jeffrey Barrett, Sun, Jing, Spencer, Ryan K., Jiang, Xi, & Zuckermann, Ronald N.. Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition. United States. doi:10.1021/acs.jpcb.6b09925.
Kortright, Jeffrey Barrett, Sun, Jing, Spencer, Ryan K., Jiang, Xi, and Zuckermann, Ronald N.. 2016. "Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition". United States. doi:10.1021/acs.jpcb.6b09925. https://www.osti.gov/servlets/purl/1336911.
@article{osti_1336911,
title = {Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition},
author = {Kortright, Jeffrey Barrett and Sun, Jing and Spencer, Ryan K. and Jiang, Xi and Zuckermann, Ronald N.},
abstractNote = {The evolution of molecular morphology in bulk samples of comb diblock copolymer pNdc12-b-pNte21 across the lamellar order-disorder transition (ODT) is studied using resonant x-ray scattering at the oxygen K edge, with the goal of determining whether the molecules remain extended or collapse above the ODT. The distinct spectral resonances of carbonyl oxygen on the backbone and ether oxygen in the pNte side chains combine with their different site symmetry within the molecule to yield strong differences in bulk structural sensitivity at all temperatures. Comparison with simple models for the disordered phase clearly reveals that disordering at the ODT corresponds to loss of positional order of molecules with extended backbones that retain orientational order, rather than backbone collapse into a locally isotropic disordered phase. This conclusion is facilitated directly by the distinct structural sensitivity at the two resonances. Lastly, we discuss the roles of depolarized scattering in enhancing this sensitivity, and background fluorescence in limiting dynamic range, in oxygen resonant scattering.},
doi = {10.1021/acs.jpcb.6b09925},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = ,
volume = ,
place = {United States},
year = {2016},
month = {12}
}