Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition
Abstract
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.
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
- Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering & Materials Sciences
- 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:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1336911
- Report Number(s):
- LBNL-1006901
Journal ID: ISSN 1520-6106; ir:1006901
- Grant/Contract Number:
- AC02-05CH11231
- Resource 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
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
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., 2016.
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. https://doi.org/10.1021/acs.jpcb.6b09925
Kortright, Jeffrey Barrett, Sun, Jing, Spencer, Ryan K., Jiang, Xi, and Zuckermann, Ronald N. Wed .
"Oxygen K edge scattering from bulk comb diblock copolymer reveals extended, ordered backbones above lamellar order-disorder transition". United States. https://doi.org/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 = {Wed Dec 14 00:00:00 EST 2016},
month = {Wed Dec 14 00:00:00 EST 2016}
}
Web of Science