Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies

Lewis, III, Ronald M.; Beech, Haley K.; Jackson, Grayson L.; Maher, Michael J.; Kim, Kyungtae; Narayanan, Suresh; Lodge, Timothy P.; Mahanthappa, Mahesh K.; Bates, Frank S.

doi:10.1021/acsmacrolett.8b00740

Title: Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies

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Abstract

Here, we report the dynamic behavior of a sphere-forming poly(styrene)-block-poly(1,4-butadiene) (PS–PB) diblock copolymer comprising 20 vol % PB below the order–disorder transition temperature (T_ODT = 153 °C) using dynamic mechanical spectroscopy (DMS) and X-ray photon correlation spectroscopy (XPCS). A time–temperature transformation diagram was constructed by monitoring the elasticity of the sample as a function of time following rapid quenches of the disordered melt to various temperatures T < T_ODT. Isothermal frequency spectra acquired prior to nucleation of the ordered BCC phase were time–temperature superposed, and the shift factors were fit using the Williams–Landel–Ferry (WLF) equation. For comparison, XPCS measurements were used to extract relaxation times from the supercooled liquid as a function of the quench temperature. Alignment of the temperature dependence of the XPCS-based relaxation times with that of the WLF shift factors in the range T = 125–140 °C indicates that both techniques probe the fluctuating mesomorphic micelle dynamics mediated by the relaxation modes of individual chains, including interparticle chain exchange. For deeper quench temperatures, T_ODT – T ≥ 28 °C, departure of the XPCS time constant from WLF behavior is consistent with a jamming transition, analogous to that encountered in concentrated colloidal systems. We postulate that the dominantmore »« less

Authors:

^[1]; Beech, Haley K. ^[1];

^[2];

^[1]; Kim, Kyungtae ^[1]; Narayanan, Suresh ^[3];

^[1];

^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Univ. of Wisconsin-Madison, Madison, WI (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Publication Date:: Tue Dec 04 00:00:00 EST 2018

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1494305

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: ACS Macro Letters

Additional Journal Information:: Journal Volume: 7; Journal Issue: 12; Journal ID: ISSN 2161-1653

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Lewis, III, Ronald M., Beech, Haley K., Jackson, Grayson L., Maher, Michael J., Kim, Kyungtae, Narayanan, Suresh, Lodge, Timothy P., Mahanthappa, Mahesh K., and Bates, Frank S. Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies.  United States: N. p., 2018. 
Web.  doi:10.1021/acsmacrolett.8b00740.

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                    Lewis, III, Ronald M., Beech, Haley K., Jackson, Grayson L., Maher, Michael J., Kim, Kyungtae, Narayanan, Suresh, Lodge, Timothy P., Mahanthappa, Mahesh K., & Bates, Frank S. Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies.  United States.  https://doi.org/10.1021/acsmacrolett.8b00740

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                    Lewis, III, Ronald M., Beech, Haley K., Jackson, Grayson L., Maher, Michael J., Kim, Kyungtae, Narayanan, Suresh, Lodge, Timothy P., Mahanthappa, Mahesh K., and Bates, Frank S. Tue .  
"Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies".  United States.  https://doi.org/10.1021/acsmacrolett.8b00740.  https://www.osti.gov/servlets/purl/1494305.

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@article{osti_1494305,

  title        = {Dynamics of a Supercooled Disordered Sphere-Forming Diblock Copolymer as Determined by X-ray Photon Correlation and Dynamic Mechanical Spectroscopies},

  author       = {Lewis, III, Ronald M. and Beech, Haley K. and Jackson, Grayson L. and Maher, Michael J. and Kim, Kyungtae and Narayanan, Suresh and Lodge, Timothy P. and Mahanthappa, Mahesh K. and Bates, Frank S.},

  abstractNote = {Here, we report the dynamic behavior of a sphere-forming poly(styrene)-block-poly(1,4-butadiene) (PS–PB) diblock copolymer comprising 20 vol % PB below the order–disorder transition temperature (TODT = 153 °C) using dynamic mechanical spectroscopy (DMS) and X-ray photon correlation spectroscopy (XPCS). A time–temperature transformation diagram was constructed by monitoring the elasticity of the sample as a function of time following rapid quenches of the disordered melt to various temperatures T < TODT. Isothermal frequency spectra acquired prior to nucleation of the ordered BCC phase were time–temperature superposed, and the shift factors were fit using the Williams–Landel–Ferry (WLF) equation. For comparison, XPCS measurements were used to extract relaxation times from the supercooled liquid as a function of the quench temperature. Alignment of the temperature dependence of the XPCS-based relaxation times with that of the WLF shift factors in the range T = 125–140 °C indicates that both techniques probe the fluctuating mesomorphic micelle dynamics mediated by the relaxation modes of individual chains, including interparticle chain exchange. For deeper quench temperatures, TODT – T ≥ 28 °C, departure of the XPCS time constant from WLF behavior is consistent with a jamming transition, analogous to that encountered in concentrated colloidal systems. We postulate that the dominant relaxation mode in the supercooled disordered liquid transitions from ergodic dynamics governed by chain exchange to a nonergodic regime dominated by local rearrangement of micellar particles at T ≈ Terg, where Terg denotes the ergodicity temperature.},

  doi          = {10.1021/acsmacrolett.8b00740},

  journal      = {ACS Macro Letters},

  number       = 12,

  volume       = 7,

  place        = {United States},

  year         = {Tue Dec 04 00:00:00 EST 2018},

  month        = {Tue Dec 04 00:00:00 EST 2018}

}

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