Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers

Handle URI:
http://hdl.handle.net/10754/623857
Title:
Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers
Authors:
Misichronis, Konstantinos ( 0000-0002-2620-1738 ) ; Chen, Jihua; Imel, Adam; Kumar, Rajeev ( 0000-0001-9494-3488 ) ; Thostenson, James; Hong, Kunlun ( 0000-0002-2852-5111 ) ; Dadmun, Mark ( 0000-0003-4304-6087 ) ; Sumpter, Bobby G. ( 0000-0001-6341-0355 ) ; Kennemur, Justin G.; Hadjichristidis, Nikolaos ( 0000-0003-1442-1714 ) ; Mays, Jimmy W.; Avgeropoulos, Apostolos ( 0000-0002-6203-9942 )
Abstract:
A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (TODT), for the first time for PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χeff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. These copolymers exhibit well-ordered structures even at high temperatures (∼260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Polymer Synthesis Laboratory
Citation:
Misichronis K, Chen J, Imel A, Kumar R, Thostenson J, et al. (2017) Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers. Macromolecules 50: 2354–2363. Available: http://dx.doi.org/10.1021/acs.macromol.7b00104.
Publisher:
American Chemical Society (ACS)
Journal:
Macromolecules
Issue Date:
15-Mar-2017
DOI:
10.1021/acs.macromol.7b00104
Type:
Article
ISSN:
0024-9297; 1520-5835
Sponsors:
This work was supported by the Materials Science and Engineering Division, U.S. Department of Energy (DoE), Office of Basic Energy Sciences (BES), LLC, at Oak Ridge National Laboratory (ORNL). Part of the research was done at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. A.A. also thanks the Nuclear Magnetic Resonance Spectroscopy Facility and the Electron Microscopy Unit of the University of Ioannina. J.G.K. thanks the FSU Materials and Energy Hiring Initiative and the Donors of the American Chemical Society Petroleum Research Fund (55378-DNI7) for partial support during the preparation of this manuscript. N.H. acknowledges the support of King Abdullah University of Science and Technology (KAUST).
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.macromol.7b00104
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorMisichronis, Konstantinosen
dc.contributor.authorChen, Jihuaen
dc.contributor.authorImel, Adamen
dc.contributor.authorKumar, Rajeeven
dc.contributor.authorThostenson, Jamesen
dc.contributor.authorHong, Kunlunen
dc.contributor.authorDadmun, Marken
dc.contributor.authorSumpter, Bobby G.en
dc.contributor.authorKennemur, Justin G.en
dc.contributor.authorHadjichristidis, Nikolaosen
dc.contributor.authorMays, Jimmy W.en
dc.contributor.authorAvgeropoulos, Apostolosen
dc.date.accessioned2017-05-31T11:23:10Z-
dc.date.available2017-05-31T11:23:10Z-
dc.date.issued2017-03-15en
dc.identifier.citationMisichronis K, Chen J, Imel A, Kumar R, Thostenson J, et al. (2017) Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers. Macromolecules 50: 2354–2363. Available: http://dx.doi.org/10.1021/acs.macromol.7b00104.en
dc.identifier.issn0024-9297en
dc.identifier.issn1520-5835en
dc.identifier.doi10.1021/acs.macromol.7b00104en
dc.identifier.urihttp://hdl.handle.net/10754/623857-
dc.description.abstractA series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (TODT), for the first time for PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χeff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. These copolymers exhibit well-ordered structures even at high temperatures (∼260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.en
dc.description.sponsorshipThis work was supported by the Materials Science and Engineering Division, U.S. Department of Energy (DoE), Office of Basic Energy Sciences (BES), LLC, at Oak Ridge National Laboratory (ORNL). Part of the research was done at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility. A.A. also thanks the Nuclear Magnetic Resonance Spectroscopy Facility and the Electron Microscopy Unit of the University of Ioannina. J.G.K. thanks the FSU Materials and Energy Hiring Initiative and the Donors of the American Chemical Society Petroleum Research Fund (55378-DNI7) for partial support during the preparation of this manuscript. N.H. acknowledges the support of King Abdullah University of Science and Technology (KAUST).en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.macromol.7b00104en
dc.titleInvestigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymersen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentPolymer Synthesis Laboratoryen
dc.identifier.journalMacromoleculesen
dc.contributor.institutionChemical Sciences Divisionen
dc.contributor.institutionDepartment of Chemistry, University of Tennessee, Knoxville, Tennessee 37996, United Statesen
dc.contributor.institutionDepartment of Materials Science and Engineering, University of Ioannina, University Campus-Dourouti, 45110 Ioannina, Greeceen
dc.contributor.institutionCenter for Nanophase Materials Sciencesen
dc.contributor.institutionComputer Science and Mathematics Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United Statesen
dc.contributor.institutionShared Materials Instrumentation Facility, Duke University, Durham, North Carolina 27708, United Statesen
dc.contributor.institutionDepartment of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United Statesen
kaust.authorHadjichristidis, Nikolaosen
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