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Observation of Dynamic Fluctuation at Phase Changes and Study on the Mechanism

Research Project

Project/Area Number 19H02671
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 32010:Fundamental physical chemistry-related
Research InstitutionToyota Physical and Chemical Research Institute

Principal Investigator

Nishikawa Keiko  公益財団法人豊田理化学研究所, フェロー事業部門, フェロー (60080470)

Co-Investigator(Kenkyū-buntansha) 桝 飛雄真  千葉大学, 大学院工学研究院, 准教授 (80412394)
森田 剛  千葉大学, 大学院理学研究院, 准教授 (80332633)
Project Period (FY) 2019-04-01 – 2023-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000)
Fiscal Year 2022: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2021: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2020: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2019: ¥15,340,000 (Direct Cost: ¥11,800,000、Indirect Cost: ¥3,540,000)
Keywords動的ゆらぎ / 相転移 / イオン液体 / 表面融解 / 緩和時間 / 柔粘性結晶 / 回転運動 / 並進運動 / 静的ゆらぎ / 柔粘性イオン結晶 / 核磁気共鳴 / スピン-格子緩和時間 / スピン-スピン緩和時間 / 混合状態 / 溶液 / 超臨界水 / イオン性柔粘性結晶 / rotational disorder / 超高感度熱測定 / ダイナミクス / 相変化 / 超高感度熱量測定 / 同時測定
Outline of Research at the Start

研究の概要
相転移によって引き起こされる挙動を動的ゆらぎと位置付け、ミクロ・メゾ・マクロの視点で直接観測し、多角的・複眼的観点から相転移ダイナミクスを議論する。具体的には、比較的遅い相転移を示すイオン液体を試料として、以下の「4つの問い」に解答を与える実験(超高感度熱量測定、Raman散乱と熱量の同時測定、NMRによる緩和時間測定)を行う。
(1) 相転移を引き起こすトリガーは?;
(2) 局所的相転移場での熱エネルギーの出入りは?;
(3) 相転移時の構成分子やイオンの構造変化は?;
(4) 変化の時間スケールは?

Outline of Final Research Achievements

We have developed experimental methods to capture various phenomena during phase transitions, in which dynamic fluctuations become apparent, and applied it to several systems. The samples are ionic liquids, which are characterized by relatively slow phase transitions.
We succeeded in capturing the surface melting and its crystallization by using a laboratory-made ultra-sensitive calorimeter and a Raman scattering system that can measure simultaneously with the calorimeter. In this sample, it was found that the phase transition is triggered by the conformational change of the constituent ions and that the surface melting occurs to relieve the structural stress of the complex ionic configuration. NMR relaxation time measurements were performed on another sample with a plastic crystal phase. It was clarified how the rotational and translational motions of the ions are involved in the phase transitions.

Academic Significance and Societal Importance of the Research Achievements

相転移時に起こっている様々な現象を実験的に直接捉えることに成功した。感度が良く、掃引時間を転移の速度に合わせることができる装置では、熱測定といえども相変化の詳細を追うことができることを示した。また、イオン液体を試料として相転移現象を観察する場合、NMRの緩和時間が丁度マッチした時間スケールであり、新しい観点での相転移現象を観測した。
試料として取り上げた柔粘性結晶(PC)相を有するイオン液体は、今、固体燃料電池の電解質をしての利用が期待されている。PC相でのイオンのダイナミクスを定量的に測定できることを示すことができたので、実用化を目指す研究者にも有意義な情報を提供できることになる。

Report

(5 results)
  • 2022 Annual Research Report   Final Research Report ( PDF )
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • Research Products

    (27 results)

All 2023 2022 2021 2020 2019 Other

All Int'l Joint Research (3 results) Journal Article (13 results) (of which Int'l Joint Research: 3 results,  Peer Reviewed: 11 results,  Open Access: 4 results) Presentation (7 results) (of which Invited: 1 results) Book (1 results) Remarks (3 results)

  • [Int'l Joint Research] The University of British Columbia(カナダ)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] Technical University of Denmark(デンマーク)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] The University of British Columbia(カナダ)

    • Related Report
      2019 Annual Research Report
  • [Journal Article] A method for determining the density fluctuations of supercritical fluids absolutely based on small-angle scattering experiments and application to supercritical methanol2023

    • Author(s)
      Morita Takeshi、Kadota Teruki、Kusano Kouhei、Tanaka Yoshitada、Nishikawa Keiko
    • Journal Title

      Japanese Journal of Applied Physics

      Volume: 62 Issue: 1 Pages: 016504-016504

    • DOI

      10.35848/1347-4065/aca854

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 乱れを科学する-ゆらぎの研究2023

    • Author(s)
      西川惠子
    • Journal Title

      イオン液体研究会サーキュラー

      Volume: 20 Pages: 1-12

    • Related Report
      2022 Annual Research Report
    • Open Access
  • [Journal Article] A study combining magic-angle spinning NMR and small-angle X-ray scattering on the interaction in the mixture of poly(benzyl methacrylate) and ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide2022

    • Author(s)
      Morita Takeshi、Okada Hitomi、Yamada Taisei、Hidaka Ryo、Ueki Takeshi、Niitsuma Kazuyuki、Kitazawa Yuzo、Watanabe Masayoshi、Nishikawa Keiko、Higashi Kenjirou
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 24 Issue: 43 Pages: 26575-26582

    • DOI

      10.1039/d2cp02207a

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Free ionic rotators on crystal lattice points - Structures of ionic plastic crystals-2022

    • Author(s)
      Nishikawa Keiko、Fujii Kozo、Yamada Taisei、Yoshizawa-Fujita Masahiro、Matsumoto Kazuhiko
    • Journal Title

      Chemical Physics Letters

      Volume: 803 Pages: 139771-139771

    • DOI

      10.1016/j.cplett.2022.139771

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structure disorder observation of fluoropolymers composed of vinylidene fluoride and tetrafluoroethylene in supercritical CO2 using time-resolved small- and wide-angle X-ray scattering2022

    • Author(s)
      Yamanoi Kohei、Shibuta Satoshi、Shiro Atsushi、Noumi Masao、Empizo Melvin John F.、Cadatal-Raduban Marilou、Sarukura Nobuhiko、Nishikawa Keiko、Morita Takeshi
    • Journal Title

      The Journal of Supercritical Fluids

      Volume: 184 Pages: 105555-105555

    • DOI

      10.1016/j.supflu.2022.105555

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] 柔粘性イオン結晶の構造研究2022

    • Author(s)
      西川惠子
    • Journal Title

      ケミカルタイムス

      Volume: 265 Pages: 2-7

    • Related Report
      2022 Annual Research Report
    • Open Access
  • [Journal Article] Structure of Solution Probed via Fluctuations: Direct Description of Inhomogeneity in Mixing2021

    • Author(s)
      西川惠子
    • Journal Title

      Nihon Kessho Gakkaishi

      Volume: 63 Issue: 3 Pages: 197-207

    • DOI

      10.5940/jcrsj.63.197

    • NAID

      130008083576

    • ISSN
      0369-4585, 1884-5576
    • Year and Date
      2021-08-31
    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Two different regimes in alcohol-induced coil?helix transition: effects of 2,2,2-trifluoroethanol on proteins being either independent of or enhanced by solvent structural fluctuations2021

    • Author(s)
      Ohgi Hiroyo、Imamura Hiroshi、Sumi Tomonari、Nishikawa Keiko、Koga Yoshikata、Westh Peter、Morita Takeshi
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 23 Issue: 10 Pages: 5760-5772

    • DOI

      10.1039/d0cp05103a

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Formulation of Diffraction Intensity of Ionic Plastic Crystal and Its Application to Trimethylethylammonium Bis(fluorosulfonyl)amide2021

    • Author(s)
      Nishikawa Keiko、Yamada Taisei、Fujii Kozo、Masu Hyuma、Tozaki Ken-ichi、Endo Takatsugu
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 94 Issue: 8 Pages: 2011-2018

    • DOI

      10.1246/bcsj.20210159

    • NAID

      130008087860

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The Solution Chemistry of Mixing States Probed via Fluctuations: a Direct Description of Inhomogeneity in Mixing2021

    • Author(s)
      Nishikawa Keiko
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 94 Issue: 9 Pages: 2170-2186

    • DOI

      10.1246/bcsj.20210205

    • NAID

      130008103631

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Structure and Properties of Supercritical Water: Experimental and Theoretical Characterizations2021

    • Author(s)
      Yoshida Norio、Matsugami Masaru、Harano Yuichi、Nishikawa Keiko、Hirata Fumio
    • Journal Title

      J

      Volume: 4 Issue: 4 Pages: 698-726

    • DOI

      10.3390/j4040049

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Unique Phase Behavior of a Room-Temperature Ionic Liquid, Trimethylpropylammonium Bis(fluorosulfonyl)amide: Surface Melting and its Crystallization2020

    • Author(s)
      K. Nishikawa, K. Fujii, Y. Hashimoto, K. Tozaki
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 22 Issue: 36 Pages: 20634-20642

    • DOI

      10.1039/d0cp03073b

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Characterization of [P4444]CF3COO in water by the 1-propanol probing methodology2020

    • Author(s)
      Matsushita Midori、Morita Takeshi、Nishikawa Keiko、Koga Yoshikata
    • Journal Title

      Journal of Molecular Liquids

      Volume: 302 Pages: 112560-112560

    • DOI

      10.1016/j.molliq.2020.112560

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] 複雑凝集系を対象としたゆらぎの構造科学2020

    • Author(s)
      西川惠子
    • Organizer
      日本結晶学会
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 柔粘性結晶状態を持つ短鎖アンモニウム系イオン液体における相挙動2020

    • Author(s)
      山田大誠、藤井幸造、東崎健一、桝飛雄真、遠藤太佳嗣、森田剛、西川惠子
    • Organizer
      イオン液体討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] イオン液体中に存在する複数ドメインからの並列結晶化2019

    • Author(s)
      西川惠子,藤井幸造,西里健太,橋本佑介,東崎健一
    • Organizer
      分子科学会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 微分熱力学的手法を用いたイオン液体[P4,4,4,4]CF3COOの疎水性/親水性2019

    • Author(s)
      松下碧,西川恵子,古賀精方,森田剛
    • Organizer
      分子科学会
    • Related Report
      2019 Annual Research Report
  • [Presentation] NMRで観るアンモニウム系イオン液体のダイナミクスと相挙動の相関2019

    • Author(s)
      西里健太,藤井幸造,遠藤太佳嗣,西川惠子
    • Organizer
      分子科学会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 柔軟な構造を持つアンモニウム系イオン液体の特徴的な融解挙動2019

    • Author(s)
      西里健太,藤井幸造,森田剛,遠藤太佳嗣,桝飛雄馬,西川恵子
    • Organizer
      イオン液体討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] テトラブチルホスホニウム系イオン液体の親水性/疎水性2019

    • Author(s)
      松下碧,西川恵子,古賀精方,森田剛
    • Organizer
      イオン液体討論会
    • Related Report
      2019 Annual Research Report
  • [Book] イオン液体2021

    • Author(s)
      日本化学会、西川 惠子、伊藤 敏幸、大野 弘幸
    • Total Pages
      178
    • Publisher
      共立出版
    • ISBN
      9784320044784
    • Related Report
      2020 Annual Research Report
  • [Remarks] 豊田理化学研究所研究報告

    • URL

      https://www.toyotariken.jp/research-report/

    • Related Report
      2022 Annual Research Report
  • [Remarks]

    • URL

      https://www.toyotariken.jp/prg/fellow

    • Related Report
      2020 Annual Research Report
  • [Remarks] 豊田理化学研究所/常勤フェロー/西川惠子

    • URL

      https://www.toyotariken.jp/fellow/keiko-nishikawa

    • Related Report
      2019 Annual Research Report

URL: 

Published: 2019-04-18   Modified: 2024-01-30  

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