On the role of methyl groups in the molecular architectures of mesophase pitches

Annamraju, Aparna; Jung, Gang Seob; Bhagia, Samarthya; Damron, Joshua T.; Ryder, Matthew R.; Arnould, Mark A.; Cakmak, Ercan; Vautard, Frederic; Paul, Ryan M.; Irle, Stephan; Gallego, Nidia C.; Curzio, Edgar Lara

doi:10.1016/j.fuel.2023.129976

Title: On the role of methyl groups in the molecular architectures of mesophase pitches

Journal Article · Sat Oct 07 00:00:00 EDT 2023 · Fuel

DOI:https://doi.org/10.1016/j.fuel.2023.129976· OSTI ID:2203829

Annamraju, Aparna ^[1]; Jung, Gang Seob ^[1];

^[1]; Damron, Joshua T. ^[1];

^[1]; Arnould, Mark A. ^[2]; Cakmak, Ercan ^[1]; Vautard, Frederic ^[1]; Paul, Ryan M. ^[1]; Irle, Stephan ^[1];

^[1]; Curzio, Edgar Lara ^[1]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

The role of methyl groups on the liquid–crystal structure of mesophase pitches was investigated by combining experimental characterizations and atomic-scale computational modeling, using three pitches synthesized from different precursors. Of the three pitches, C-9 alkyl benzene and naphthalene-based pitches have 13 and 7 methyl groups per average polyaromatic hydrocarbon, respectively. By contrast, mesophase produced from a coal-tar pitch has about one methyl group. The coal tar–based mesophase pitch is hydrogen deficient or more aromatic compared with C-9 alkyl benzene- and naphthalene-based pitches. Additionally, X-ray diffraction data showed that average coherent domain sizes of C-9 alkyl benzene (3.7 nm) and naphthalene-based (3.6 nm) pitches with more methyl groups are larger than that of coal tar–based mesophase (2.4 nm). Based on the identified features, the influence of the methyl group on the layering structures was investigated via molecular dynamics simulations. The results revealed that methyl groups are critical in mesophase layering in C-9 alkyl benzene- and naphthalene-based pitches, by reducing CH-π interaction. However, similar alignment could be achieved without the same degree of methyl substitutions for the coal tar-based pitch because of stronger π-π interaction than the other precursors. The insights from this study contribute to our understanding of the formation of conventional mesophase pitch and have implications for the processing of coal-derived materials. In conclusion, this knowledge is vital to produce valuable products like carbon fiber and graphite from pitches.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Fossil Energy and Carbon Management (FECM); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2203829

Journal Information:: Fuel, Vol. 357, Issue C; ISSN 0016-2361

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: On the role of methyl groups in the molecular architectures of mesophase pitches

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