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

Konstantinos Misichronis; Jihua Chen; Adam Imel; Rajeev Kumar; James Thostenson; Kunlun Hong; Mark Dadmun; Bobby G. Sumpter; Justin G. Kennemur; Nikos Hadjichristidis; Jimmy W. Mays; Apostolos Avgeropoulos

doi:10.1021/acs.macromol.7b00104

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

Konstantinos Misichronis, Jihua Chen, Adam Imel, Rajeev Kumar, James Thostenson, Kunlun Hong, Mark Dadmun, Bobby G. Sumpter, Justin G. Kennemur, Nikos Hadjichristidis, Jimmy W. Mays, Apostolos Avgeropoulos

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6 Scopus citations

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.

Original language	English (US)
Pages (from-to)	2354-2363
Number of pages	10
Journal	Macromolecules
Volume	50
Issue number	6
DOIs	https://doi.org/10.1021/acs.macromol.7b00104
State	Published - Mar 15 2017

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: 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).

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Misichronis, K., Chen, J., Imel, A., Kumar, R., Thostenson, J., Hong, K., Dadmun, M., Sumpter, B. G., Kennemur, J. G., Hadjichristidis, N., Mays, J. W., & Avgeropoulos, A. (2017). Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers. Macromolecules, 50(6), 2354-2363. https://doi.org/10.1021/acs.macromol.7b00104

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

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.",

author = "Konstantinos Misichronis and Jihua Chen and Adam Imel and Rajeev Kumar and James Thostenson and Kunlun Hong and Mark Dadmun and Sumpter, {Bobby G.} and Kennemur, {Justin G.} and Nikos Hadjichristidis and Mays, {Jimmy W.} and Apostolos Avgeropoulos",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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).",

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doi = "10.1021/acs.macromol.7b00104",

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T1 - Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers

AU - Misichronis, Konstantinos

AU - Chen, Jihua

AU - Imel, Adam

AU - Kumar, Rajeev

AU - Thostenson, James

AU - Hong, Kunlun

AU - Dadmun, Mark

AU - Sumpter, Bobby G.

AU - Kennemur, Justin G.

AU - Hadjichristidis, Nikos

AU - Mays, Jimmy W.

AU - Avgeropoulos, Apostolos

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: 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).

PY - 2017/3/15

Y1 - 2017/3/15

N2 - 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.

AB - 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.

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UR - http://pubs.acs.org/doi/full/10.1021/acs.macromol.7b00104

UR - http://www.scopus.com/inward/record.url?scp=85016413178&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.7b00104

DO - 10.1021/acs.macromol.7b00104

M3 - Article

SN - 0024-9297

VL - 50

SP - 2354

EP - 2363

JO - Macromolecules

JF - Macromolecules

IS - 6

ER -

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

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