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

dc.contributor.authorKumar, Rajeev Senthil
dc.contributor.authorSides, Scott W.
dc.contributor.authorGoswami, Monojoy
dc.contributor.authorSumpter, Bobby G.
dc.contributor.authorHong, Kunlun
dc.contributor.authorWu, Xiaodong
dc.contributor.authorRussell, Thomas P.
dc.contributor.authorGido, Samuel P.
dc.contributor.authorMisichronis, Konstantinos
dc.contributor.authorRangou, Sofia
dc.contributor.authorAvgeropoulos, Apostolos
dc.contributor.authorTsoukatos, Thodoris
dc.contributor.authorHadjichristidis, Nikos
dc.contributor.authorBeyer, Frederick L.
dc.contributor.authorMays, Jimmy Wayne
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Division
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.contributor.departmentPolymer Synthesis Laboratory
dc.contributor.institutionNational Center for Computational Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United States
dc.contributor.institutionTech-X Corporation, Boulder, CO 80303, United States
dc.contributor.institutionComputer Sciences and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United States
dc.contributor.institutionCenter for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN 37831, United States
dc.contributor.institutionPolymer Science and Engineering Department, University of Massachusetts, Amherst, MA 01003, United States
dc.contributor.institutionDepartment of Materials Science and Engineering, University of Ioannina, University Campus, Dourouti, 45110 Ioannina, Greece
dc.contributor.institutionDepartment of Chemistry, University of Athens Panepistimiopolis, Zografou, 15771 Athens, Greece
dc.contributor.institutionU.S. Army Research Laboratory, Aberdeen Proving Ground, MD 21005-5069, United States
dc.contributor.institutionDepartment of Chemistry, University of Tennessee, Knoxville, TN 37996, United States
dc.date.accessioned2015-08-03T10:59:52Z
dc.date.available2015-08-03T10:59:52Z
dc.date.issued2013-01-31
dc.date.published-online2013-01-31
dc.date.published-print2013-02-12
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.
dc.identifier.citationKumar, R., Sides, S. W., Goswami, M., Sumpter, B. G., Hong, K., Wu, X., … Mays, J. W. (2013). Morphologies of ABC Triblock Terpolymer Melts Containing Poly(Cyclohexadiene): Effects of Conformational Asymmetry. Langmuir, 29(6), 1995–2006. doi:10.1021/la304576c
dc.identifier.doi10.1021/la304576c
dc.identifier.issn07437463
dc.identifier.journalLangmuir
dc.identifier.urihttp://hdl.handle.net/10754/562652
dc.publisherAmerican Chemical Society (ACS)
dc.titleMorphologies of ABC triblock terpolymer melts containing poly(Cyclohexadiene): Effects of conformational asymmetry
dc.typeArticle
display.details.left<span><h5>Type</h5>Article<br><br><h5>Authors</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Kumar, Rajeev Senthil,equals">Kumar, Rajeev Senthil</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Sides, Scott W.,equals">Sides, Scott W.</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Goswami, Monojoy,equals">Goswami, Monojoy</a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0001-6341-0355&spc.sf=dc.date.issued&spc.sd=DESC">Sumpter, Bobby G.</a> <a href="https://orcid.org/0000-0001-6341-0355" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-2852-5111&spc.sf=dc.date.issued&spc.sd=DESC">Hong, Kunlun</a> <a href="https://orcid.org/0000-0002-2852-5111" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Wu, Xiaodong,equals">Wu, Xiaodong</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Russell, Thomas P.,equals">Russell, Thomas P.</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Gido, Samuel P.,equals">Gido, Samuel P.</a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-2620-1738&spc.sf=dc.date.issued&spc.sd=DESC">Misichronis, Konstantinos</a> <a href="https://orcid.org/0000-0002-2620-1738" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Rangou, Sofia,equals">Rangou, Sofia</a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0002-6203-9942&spc.sf=dc.date.issued&spc.sd=DESC">Avgeropoulos, Apostolos</a> <a href="https://orcid.org/0000-0002-6203-9942" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Tsoukatos, Thodoris,equals">Tsoukatos, Thodoris</a><br><a href="https://repository.kaust.edu.sa/search?query=orcid.id:0000-0003-1442-1714&spc.sf=dc.date.issued&spc.sd=DESC">Hadjichristidis, Nikos</a> <a href="https://orcid.org/0000-0003-1442-1714" target="_blank"><img src="https://repository.kaust.edu.sa/server/api/core/bitstreams/82a625b4-ed4b-40c8-865a-d6a5225a26a4/content" width="16" height="16"/></a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Beyer, Frederick L.,equals">Beyer, Frederick L.</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.author=Mays, Jimmy Wayne,equals">Mays, Jimmy Wayne</a><br><br><h5>KAUST Department</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Biological and Environmental Sciences and Engineering (BESE) Division,equals">Biological and Environmental Sciences and Engineering (BESE) Division</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Chemical Science Program,equals">Chemical Science Program</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=KAUST Catalysis Center (KCC),equals">KAUST Catalysis Center (KCC)</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Physical Science and Engineering (PSE) Division,equals">Physical Science and Engineering (PSE) Division</a><br><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.department=Polymer Synthesis Laboratory,equals">Polymer Synthesis Laboratory</a><br><br><h5>Online Publication Date</h5>2013-01-31<br><br><h5>Print Publication Date</h5>2013-02-12<br><br><h5>Date</h5>2013-01-31</span>
display.details.right<span><h5>Abstract</h5>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.<br><br><h5>Citation</h5>Kumar, R., Sides, S. W., Goswami, M., Sumpter, B. G., Hong, K., Wu, X., … Mays, J. W. (2013). Morphologies of ABC Triblock Terpolymer Melts Containing Poly(Cyclohexadiene): Effects of Conformational Asymmetry. Langmuir, 29(6), 1995–2006. doi:10.1021/la304576c<br><br><h5>Publisher</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.publisher=American Chemical Society (ACS),equals">American Chemical Society (ACS)</a><br><br><h5>Journal</h5><a href="https://repository.kaust.edu.sa/search?spc.sf=dc.date.issued&spc.sd=DESC&f.journal=Langmuir,equals">Langmuir</a><br><br><h5>DOI</h5><a href="https://doi.org/10.1021/la304576c">10.1021/la304576c</a></span>
kaust.personHadjichristidis, Nikos
orcid.authorKumar, Rajeev Senthil
orcid.authorSides, Scott W.
orcid.authorGoswami, Monojoy
orcid.authorSumpter, Bobby G.::0000-0001-6341-0355
orcid.authorHong, Kunlun::0000-0002-2852-5111
orcid.authorWu, Xiaodong
orcid.authorRussell, Thomas P.
orcid.authorGido, Samuel P.
orcid.authorMisichronis, Konstantinos::0000-0002-2620-1738
orcid.authorRangou, Sofia
orcid.authorAvgeropoulos, Apostolos::0000-0002-6203-9942
orcid.authorTsoukatos, Thodoris
orcid.authorHadjichristidis, Nikos::0000-0003-1442-1714
orcid.authorBeyer, Frederick L.
orcid.authorMays, Jimmy Wayne
orcid.id0000-0003-1442-1714
orcid.id0000-0002-6203-9942
orcid.id0000-0002-2620-1738
orcid.id0000-0002-2852-5111
orcid.id0000-0001-6341-0355
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