Molecular origin of viscoelasticity and influence of methylation in mesophase pitch

Gang Seob Jung; Pilsun Yoo; Matthew R. Ryder; Frederic Vautard; Aparna Annamraju; Stephan Irle; Nidia C. Gallego; Edgar Lara-Curzio

doi:10.1016/j.carbon.2024.119599

Molecular origin of viscoelasticity and influence of methylation in mesophase pitch

Gang Seob Jung
, Pilsun Yoo
, Matthew R. Ryder
, Frederic Vautard
, Aparna Annamraju
, Stephan Irle
, Nidia C. Gallego
, Edgar Lara-Curzio

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

7 Scopus citations

Abstract

The viscoelastic and thermomechanical properties of pitches are responsible for their melt-spinning behavior, a critical step for manufacturing high-performance pitch-based carbon fibers. Here, we systematically explore the impact of methyl group modifications on the viscoelastic and thermal properties of mesophase pitches. We employ a range of atomistic modeling approaches, including Density Functional Theory (DFT), Density Functional Tight Binding (DFTB), and Classical Molecular Mechanics (MM), to provide detailed insights into the molecular interactions and structural changes. Our results revealed the molecular mechanisms that promote layered structures leading to the anisotropic nature of the viscoelastic behavior of mesophase pitch. Furthermore, we propose a modified molecular representation of naphthalene-based mesophase pitch based on the analysis of x-ray diffraction measurements. This study provides fundamental insights into the molecular structures of mesophase pitch and the role of methyl groups controlling its viscosity, which offer valuable insights into mesophase-based carbon fiber production.

Original language	English
Article number	119599
Journal	Carbon
Volume	230
DOIs	https://doi.org/10.1016/j.carbon.2024.119599
State	Published - Nov 2024

Funding

Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan (http://energy.gov/downloads/doe-public-access-plan).This research work was sponsored by the U.S. Department of Energy (DOE) Fossil Energy and Carbon Management Program, Advanced Coal Processing Program C4WARD project (FEAA155). This research used resources from the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725. Additionally, supercomputing resources of National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility, were employed. This work is a part of a user project at the Center for Nanophase Materials Sciences (CNMS), a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. This research work was sponsored by the U.S. Department of Energy (DOE) Fossil Energy and Carbon Management Program, Advanced Coal Processing Program C4WARD project (FEAA155). This research used resources from the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725 and National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility for access to additional supercomputing resources. This work is a part of a user project at the Center for Nanophase Materials Sciences (CNMS), a US Department of Energy, Office of Science User Facility at Oak Ridge National Laboratory. Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a nonexclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes. The Department of Energy will provide public access to these results of federally sponsored research in accordance with the DOE Public Access Plan ( http://energy.gov/downloads/doe-public-access-plan ).

Keywords

Glass transition
Mesophase pitch
Molecular dynamics
Perylene
Viscoelasticity

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10.1016/j.carbon.2024.119599

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@article{76a654a955df482eafabd080806817e6,

title = "Molecular origin of viscoelasticity and influence of methylation in mesophase pitch",

abstract = "The viscoelastic and thermomechanical properties of pitches are responsible for their melt-spinning behavior, a critical step for manufacturing high-performance pitch-based carbon fibers. Here, we systematically explore the impact of methyl group modifications on the viscoelastic and thermal properties of mesophase pitches. We employ a range of atomistic modeling approaches, including Density Functional Theory (DFT), Density Functional Tight Binding (DFTB), and Classical Molecular Mechanics (MM), to provide detailed insights into the molecular interactions and structural changes. Our results revealed the molecular mechanisms that promote layered structures leading to the anisotropic nature of the viscoelastic behavior of mesophase pitch. Furthermore, we propose a modified molecular representation of naphthalene-based mesophase pitch based on the analysis of x-ray diffraction measurements. This study provides fundamental insights into the molecular structures of mesophase pitch and the role of methyl groups controlling its viscosity, which offer valuable insights into mesophase-based carbon fiber production.",

keywords = "Glass transition, Mesophase pitch, Molecular dynamics, Perylene, Viscoelasticity",

author = "Jung, \{Gang Seob\} and Pilsun Yoo and Ryder, \{Matthew R.\} and Frederic Vautard and Aparna Annamraju and Stephan Irle and Gallego, \{Nidia C.\} and Edgar Lara-Curzio",

note = "Publisher Copyright: {\textcopyright} 2024",

year = "2024",

month = nov,

doi = "10.1016/j.carbon.2024.119599",

language = "English",

volume = "230",

journal = "Carbon",

issn = "0008-6223",

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TY - JOUR

T1 - Molecular origin of viscoelasticity and influence of methylation in mesophase pitch

AU - Jung, Gang Seob

AU - Yoo, Pilsun

AU - Ryder, Matthew R.

AU - Vautard, Frederic

AU - Annamraju, Aparna

AU - Irle, Stephan

AU - Gallego, Nidia C.

AU - Lara-Curzio, Edgar

PY - 2024/11

Y1 - 2024/11

N2 - The viscoelastic and thermomechanical properties of pitches are responsible for their melt-spinning behavior, a critical step for manufacturing high-performance pitch-based carbon fibers. Here, we systematically explore the impact of methyl group modifications on the viscoelastic and thermal properties of mesophase pitches. We employ a range of atomistic modeling approaches, including Density Functional Theory (DFT), Density Functional Tight Binding (DFTB), and Classical Molecular Mechanics (MM), to provide detailed insights into the molecular interactions and structural changes. Our results revealed the molecular mechanisms that promote layered structures leading to the anisotropic nature of the viscoelastic behavior of mesophase pitch. Furthermore, we propose a modified molecular representation of naphthalene-based mesophase pitch based on the analysis of x-ray diffraction measurements. This study provides fundamental insights into the molecular structures of mesophase pitch and the role of methyl groups controlling its viscosity, which offer valuable insights into mesophase-based carbon fiber production.

AB - The viscoelastic and thermomechanical properties of pitches are responsible for their melt-spinning behavior, a critical step for manufacturing high-performance pitch-based carbon fibers. Here, we systematically explore the impact of methyl group modifications on the viscoelastic and thermal properties of mesophase pitches. We employ a range of atomistic modeling approaches, including Density Functional Theory (DFT), Density Functional Tight Binding (DFTB), and Classical Molecular Mechanics (MM), to provide detailed insights into the molecular interactions and structural changes. Our results revealed the molecular mechanisms that promote layered structures leading to the anisotropic nature of the viscoelastic behavior of mesophase pitch. Furthermore, we propose a modified molecular representation of naphthalene-based mesophase pitch based on the analysis of x-ray diffraction measurements. This study provides fundamental insights into the molecular structures of mesophase pitch and the role of methyl groups controlling its viscosity, which offer valuable insights into mesophase-based carbon fiber production.

KW - Glass transition

KW - Mesophase pitch

KW - Molecular dynamics

KW - Perylene

KW - Viscoelasticity

UR - https://www.scopus.com/pages/publications/85203067903

U2 - 10.1016/j.carbon.2024.119599

DO - 10.1016/j.carbon.2024.119599

M3 - Article

AN - SCOPUS:85203067903

SN - 0008-6223

VL - 230

JO - Carbon

JF - Carbon

M1 - 119599

ER -

Molecular origin of viscoelasticity and influence of methylation in mesophase pitch

Abstract

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Keywords

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