Shear-Modulated Rates of Phase Transitions in Sphere-Forming Diblock Oligomer Lyotropic Liquid Crystals

Connor S. Valentine; Ashish Jayaraman; Mahesh K. Mahanthappa; Lynn M. Walker

doi:10.1021/acsmacrolett.1c00154

Shear-Modulated Rates of Phase Transitions in Sphere-Forming Diblock Oligomer Lyotropic Liquid Crystals

Connor S. Valentine
, Ashish Jayaraman
, Mahesh K. Mahanthappa
, Lynn M. Walker

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

Hydration of the amphiphilic diblock oligomer C16H33(CH2CH2O)20OH (C16E20) leads to concentration-dependent formation of micellar body-centered cubic (BCC) and Frank-Kasper A15 lyotropic liquid crystals (LLCs). Quiescent thermal annealing of aqueous LLCs comprising 56-59 wt % C16E20 at 25 °C after quenching from high temperatures established their ability to form short-lived BCC phases, which transform into long-lived, transient Frank-Kasper σ phases en route to equilibrium A15 morphologies on a time scale of months. Here, the frequency and magnitude of applied oscillatory shear show the potential to either dynamically stabilize the metastable BCC phase at low frequencies or increase the rate of formation of the A15 to minutes at high frequencies. Time-resolved synchrotron small-angle X-ray scattering (TR-SAXS) provides in situ characterization of the structures during shear and thermal processing. This work shows that the LLC morphology and order-order phase transformation rates can be controlled by tuning the shear strain amplitude and frequency.

Original language	English (US)
Pages (from-to)	538-544
Number of pages	7
Journal	ACS Macro Letters
Volume	10
Issue number	5
DOIs	https://doi.org/10.1021/acsmacrolett.1c00154
State	Published - Apr 19 2021

Bibliographical note

Funding Information:
M.K.M. and A.J. gratefully acknowledge funding from the National Science Foundation (CHE-1807330). C.S.V. and L.M.W. gratefully acknowledge a fellowship from PPG Industries, Inc., and the Dowd Fellows Program at CMU. Preliminary SAXS analyses were performed at the Characterization Facility at the University of Minnesota, which receives partial support from NSF through the MRSEC program (DMR-2011401). Synchrotron SAXS experiments were performed at the 12-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under Contract DE-AC02-06CH11357.

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© 2021 American Chemical Society.

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@article{3ee9f3dd5ba543a98843c05a728db11d,

title = "Shear-Modulated Rates of Phase Transitions in Sphere-Forming Diblock Oligomer Lyotropic Liquid Crystals",

abstract = "Hydration of the amphiphilic diblock oligomer C16H33(CH2CH2O)20OH (C16E20) leads to concentration-dependent formation of micellar body-centered cubic (BCC) and Frank-Kasper A15 lyotropic liquid crystals (LLCs). Quiescent thermal annealing of aqueous LLCs comprising 56-59 wt \% C16E20 at 25 °C after quenching from high temperatures established their ability to form short-lived BCC phases, which transform into long-lived, transient Frank-Kasper σ phases en route to equilibrium A15 morphologies on a time scale of months. Here, the frequency and magnitude of applied oscillatory shear show the potential to either dynamically stabilize the metastable BCC phase at low frequencies or increase the rate of formation of the A15 to minutes at high frequencies. Time-resolved synchrotron small-angle X-ray scattering (TR-SAXS) provides in situ characterization of the structures during shear and thermal processing. This work shows that the LLC morphology and order-order phase transformation rates can be controlled by tuning the shear strain amplitude and frequency. ",

author = "Valentine, \{Connor S.\} and Ashish Jayaraman and Mahanthappa, \{Mahesh K.\} and Walker, \{Lynn M.\}",

note = "Funding Information: M.K.M. and A.J. gratefully acknowledge funding from the National Science Foundation (CHE-1807330). C.S.V. and L.M.W. gratefully acknowledge a fellowship from PPG Industries, Inc., and the Dowd Fellows Program at CMU. Preliminary SAXS analyses were performed at the Characterization Facility at the University of Minnesota, which receives partial support from NSF through the MRSEC program (DMR-2011401). Synchrotron SAXS experiments were performed at the 12-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under Contract DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

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AU - Walker, Lynn M.

N1 - Funding Information: M.K.M. and A.J. gratefully acknowledge funding from the National Science Foundation (CHE-1807330). C.S.V. and L.M.W. gratefully acknowledge a fellowship from PPG Industries, Inc., and the Dowd Fellows Program at CMU. Preliminary SAXS analyses were performed at the Characterization Facility at the University of Minnesota, which receives partial support from NSF through the MRSEC program (DMR-2011401). Synchrotron SAXS experiments were performed at the 12-ID-B beamline of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated by Argonne National Laboratory under Contract DE-AC02-06CH11357. Publisher Copyright: © 2021 American Chemical Society.

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N2 - Hydration of the amphiphilic diblock oligomer C16H33(CH2CH2O)20OH (C16E20) leads to concentration-dependent formation of micellar body-centered cubic (BCC) and Frank-Kasper A15 lyotropic liquid crystals (LLCs). Quiescent thermal annealing of aqueous LLCs comprising 56-59 wt % C16E20 at 25 °C after quenching from high temperatures established their ability to form short-lived BCC phases, which transform into long-lived, transient Frank-Kasper σ phases en route to equilibrium A15 morphologies on a time scale of months. Here, the frequency and magnitude of applied oscillatory shear show the potential to either dynamically stabilize the metastable BCC phase at low frequencies or increase the rate of formation of the A15 to minutes at high frequencies. Time-resolved synchrotron small-angle X-ray scattering (TR-SAXS) provides in situ characterization of the structures during shear and thermal processing. This work shows that the LLC morphology and order-order phase transformation rates can be controlled by tuning the shear strain amplitude and frequency.

AB - Hydration of the amphiphilic diblock oligomer C16H33(CH2CH2O)20OH (C16E20) leads to concentration-dependent formation of micellar body-centered cubic (BCC) and Frank-Kasper A15 lyotropic liquid crystals (LLCs). Quiescent thermal annealing of aqueous LLCs comprising 56-59 wt % C16E20 at 25 °C after quenching from high temperatures established their ability to form short-lived BCC phases, which transform into long-lived, transient Frank-Kasper σ phases en route to equilibrium A15 morphologies on a time scale of months. Here, the frequency and magnitude of applied oscillatory shear show the potential to either dynamically stabilize the metastable BCC phase at low frequencies or increase the rate of formation of the A15 to minutes at high frequencies. Time-resolved synchrotron small-angle X-ray scattering (TR-SAXS) provides in situ characterization of the structures during shear and thermal processing. This work shows that the LLC morphology and order-order phase transformation rates can be controlled by tuning the shear strain amplitude and frequency.

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Shear-Modulated Rates of Phase Transitions in Sphere-Forming Diblock Oligomer Lyotropic Liquid Crystals

Abstract

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Shear-Modulated Rates of Phase Transitions in Sphere-Forming Diblock Oligomer Lyotropic Liquid Crystals

Abstract

Bibliographical note

MRSEC Support

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