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Title: Double-Gyroid Network Morphology in Tapered Diblock Copolymers

Abstract

We report the formation of a double-gyroid network morphology in normal-tapered poly(isoprene-b-isoprene/styrene-b-styrene) [P(I-IS-S)] and inverse-tapered poly(isoprene-b-styrene/isoprene-b-styrene) [P(I-SI-S)] diblock copolymers. Our tapered diblock copolymers with overall poly(styrene) volume fractions of 0.65 (normal-tapered) and 0.67 (inverse-tapered), and tapered regions comprising 30 vol % of the total polymer, were shown to self-assemble into the double-gyroid network morphology through a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The block copolymers were synthesized by anionic polymerization, where the tapered region between the pure poly(isoprene) and poly(styrene) blocks was generated using a semibatch feed with programmed syringe pumps. The overall composition of these tapered copolymers lies within the expected network-forming region for conventional poly(isoprene-b-styrene) [P(I-S)] diblock copolymers. Dynamic mechanical analysis (DMA) clearly demonstrated that the order-disorder transition temperatures (T{sub ODT}'s) of the network-forming tapered block copolymers were depressed when compared to the T{sub ODT} of their nontapered counterpart, with the P(I-SI-S) showing the greater drop in T{sub ODT}. These results indicate that it is possible to manipulate the copolymer composition profile between blocks in a diblock copolymer, allowing significant control over the T{sub ODT}, while maintaining the ability to form complex network structures.

Authors:
; ; ; ; ;  [1]
  1. (Delaware)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
NSFINDUSTRYNIH
OSTI Identifier:
1049543
Resource Type:
Journal Article
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 44; Journal Issue: (10) ; 05, 2011
Country of Publication:
United States
Language:
ENGLISH
Subject:
59 BASIC BIOLOGICAL SCIENCES; 60 APPLIED LIFE SCIENCES; COPOLYMERS; MORPHOLOGY; POLYMERIZATION; SCATTERING; TRANSITION TEMPERATURE; TRANSMISSION ELECTRON MICROSCOPY

Citation Formats

Roy, Raghunath, Park, Jong Keun, Young, Wen-Shiue, Mastroianni, Sarah E., Tureau, Maeva S., and Epps, III, Thomas H. Double-Gyroid Network Morphology in Tapered Diblock Copolymers. United States: N. p., 2012. Web. doi:10.1021/ma1025847.
Roy, Raghunath, Park, Jong Keun, Young, Wen-Shiue, Mastroianni, Sarah E., Tureau, Maeva S., & Epps, III, Thomas H. Double-Gyroid Network Morphology in Tapered Diblock Copolymers. United States. doi:10.1021/ma1025847.
Roy, Raghunath, Park, Jong Keun, Young, Wen-Shiue, Mastroianni, Sarah E., Tureau, Maeva S., and Epps, III, Thomas H. Wed . "Double-Gyroid Network Morphology in Tapered Diblock Copolymers". United States. doi:10.1021/ma1025847.
@article{osti_1049543,
title = {Double-Gyroid Network Morphology in Tapered Diblock Copolymers},
author = {Roy, Raghunath and Park, Jong Keun and Young, Wen-Shiue and Mastroianni, Sarah E. and Tureau, Maeva S. and Epps, III, Thomas H.},
abstractNote = {We report the formation of a double-gyroid network morphology in normal-tapered poly(isoprene-b-isoprene/styrene-b-styrene) [P(I-IS-S)] and inverse-tapered poly(isoprene-b-styrene/isoprene-b-styrene) [P(I-SI-S)] diblock copolymers. Our tapered diblock copolymers with overall poly(styrene) volume fractions of 0.65 (normal-tapered) and 0.67 (inverse-tapered), and tapered regions comprising 30 vol % of the total polymer, were shown to self-assemble into the double-gyroid network morphology through a combination of small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM). The block copolymers were synthesized by anionic polymerization, where the tapered region between the pure poly(isoprene) and poly(styrene) blocks was generated using a semibatch feed with programmed syringe pumps. The overall composition of these tapered copolymers lies within the expected network-forming region for conventional poly(isoprene-b-styrene) [P(I-S)] diblock copolymers. Dynamic mechanical analysis (DMA) clearly demonstrated that the order-disorder transition temperatures (T{sub ODT}'s) of the network-forming tapered block copolymers were depressed when compared to the T{sub ODT} of their nontapered counterpart, with the P(I-SI-S) showing the greater drop in T{sub ODT}. These results indicate that it is possible to manipulate the copolymer composition profile between blocks in a diblock copolymer, allowing significant control over the T{sub ODT}, while maintaining the ability to form complex network structures.},
doi = {10.1021/ma1025847},
journal = {Macromolecules},
number = (10) ; 05, 2011,
volume = 44,
place = {United States},
year = {2012},
month = {11}
}