Morphologies of ABC triblock terpolymer melts containing poly(Cyclohexadiene): Effects of conformational asymmetry

Handle URI:
http://hdl.handle.net/10754/562652
Title:
Morphologies of ABC triblock terpolymer melts containing poly(Cyclohexadiene): Effects of conformational asymmetry
Authors:
Kumar, Rajeev Senthil; Sides, Scott W.; Goswami, Monojoy; Sumpter, Bobby G.; Hong, Kunlun; Wu, Xiaodong; Russell, Thomas P.; Gido, Samuel P.; Misichronis, Konstantinos; Rangou, Sofia; Avgeropoulos, Apostolos; Tsoukatos, Thodoris; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Beyer, Frederick L.; Mays, Jimmy Wayne
Abstract:
We have synthesized linear ABC triblock terpolymers containing poly(1,3-cyclohexadiene), PCHD, as an end block and characterized their morphologies in the melt. Specifically, we have studied terpolymers containing polystyrene (PS), polybutadiene (PB), and polyisoprene (PI) as the other blocks. Systematically varying the ratio of 1,2- /1,4-microstructures of poly(1,3-cyclohexadiene), we have studied the effects of conformational asymmetry among the three blocks on the morphologies using transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and self-consistent field theory (SCFT) performed with PolySwift++. Our work reveals that the triblock terpolymer melts containing a high percentage of 1,2-microstructures in the PCHD block are disordered at 110 C for all the samples, independent of sequence and volume fraction of the blocks. In contrast, the triblock terpolymer melts containing a high percentage of 1,4-microstructure form regular morphologies known from the literature. The accuracy of the SCFT calculations depends on calculating the χ parameters that quantify the repulsive interactions between different monomers. Simulations using χ values obtained from solubility parameters and group contribution methods are unable to reproduce the morphologies as seen in the experiments. However, SCFT calculations accounting for the enhancement of the χ parameter with an increase in the conformational asymmetry lead to an excellent agreement between theory and experiments. These results highlight the importance of conformational asymmetry in tuning the χ parameter and, in turn, morphologies in block copolymers. © 2012 American Chemical Society.
KAUST Department:
Biological and Environmental Sciences and Engineering (BESE) Division; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Polymer Synthesis Laboratory
Publisher:
American Chemical Society
Journal:
Langmuir
Issue Date:
12-Feb-2013
DOI:
10.1021/la304576c
Type:
Article
ISSN:
07437463
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC); Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorKumar, Rajeev Senthilen
dc.contributor.authorSides, Scott W.en
dc.contributor.authorGoswami, Monojoyen
dc.contributor.authorSumpter, Bobby G.en
dc.contributor.authorHong, Kunlunen
dc.contributor.authorWu, Xiaodongen
dc.contributor.authorRussell, Thomas P.en
dc.contributor.authorGido, Samuel P.en
dc.contributor.authorMisichronis, Konstantinosen
dc.contributor.authorRangou, Sofiaen
dc.contributor.authorAvgeropoulos, Apostolosen
dc.contributor.authorTsoukatos, Thodorisen
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorBeyer, Frederick L.en
dc.contributor.authorMays, Jimmy Wayneen
dc.date.accessioned2015-08-03T10:59:52Zen
dc.date.available2015-08-03T10:59:52Zen
dc.date.issued2013-02-12en
dc.identifier.issn07437463en
dc.identifier.doi10.1021/la304576cen
dc.identifier.urihttp://hdl.handle.net/10754/562652en
dc.description.abstractWe have synthesized linear ABC triblock terpolymers containing poly(1,3-cyclohexadiene), PCHD, as an end block and characterized their morphologies in the melt. Specifically, we have studied terpolymers containing polystyrene (PS), polybutadiene (PB), and polyisoprene (PI) as the other blocks. Systematically varying the ratio of 1,2- /1,4-microstructures of poly(1,3-cyclohexadiene), we have studied the effects of conformational asymmetry among the three blocks on the morphologies using transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS), and self-consistent field theory (SCFT) performed with PolySwift++. Our work reveals that the triblock terpolymer melts containing a high percentage of 1,2-microstructures in the PCHD block are disordered at 110 C for all the samples, independent of sequence and volume fraction of the blocks. In contrast, the triblock terpolymer melts containing a high percentage of 1,4-microstructure form regular morphologies known from the literature. The accuracy of the SCFT calculations depends on calculating the χ parameters that quantify the repulsive interactions between different monomers. Simulations using χ values obtained from solubility parameters and group contribution methods are unable to reproduce the morphologies as seen in the experiments. However, SCFT calculations accounting for the enhancement of the χ parameter with an increase in the conformational asymmetry lead to an excellent agreement between theory and experiments. These results highlight the importance of conformational asymmetry in tuning the χ parameter and, in turn, morphologies in block copolymers. © 2012 American Chemical Society.en
dc.publisherAmerican Chemical Societyen
dc.titleMorphologies of ABC triblock terpolymer melts containing poly(Cyclohexadiene): Effects of conformational asymmetryen
dc.typeArticleen
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalLangmuiren
dc.contributor.institutionNational Center for Computational Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United Statesen
dc.contributor.institutionTech-X Corporation, Boulder, CO 80303, United Statesen
dc.contributor.institutionComputer Sciences and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United Statesen
dc.contributor.institutionCenter for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United Statesen
dc.contributor.institutionPolymer Science and Engineering Department, University of Massachusetts, Amherst, MA 01003, United Statesen
dc.contributor.institutionDepartment of Materials Science and Engineering, University of Ioannina, University Campus, Dourouti, 45110 Ioannina, Greeceen
dc.contributor.institutionDepartment of Chemistry, University of Athens Panepistimiopolis, Zografou, 15771 Athens, Greeceen
dc.contributor.institutionU.S. Army Research Laboratory, Aberdeen Proving Ground, MD 21005-5069, United Statesen
dc.contributor.institutionDepartment of Chemistry, University of Tennessee, Knoxville, TN 37996, United Statesen
kaust.authorHadjichristidis, Nikolaosen
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