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In situ atomic force microscopy observation of crystallization of isolated polymer chains

Research Project

Project/Area Number 21H01993
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 35020:Polymer materials-related
Research InstitutionYamagata University

Principal Investigator

Kumaki Jiro  山形大学, 大学院有機材料システム研究科, 客員教授 (00500290)

Project Period (FY) 2021-04-01 – 2024-03-31
Project Status Completed (Fiscal Year 2023)
Budget Amount *help
¥17,550,000 (Direct Cost: ¥13,500,000、Indirect Cost: ¥4,050,000)
Fiscal Year 2023: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2022: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2021: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
Keywords高分子結晶構造 / 原子間力顕微鏡 / 折り畳み鎖結晶 / 孤立鎖 / 結晶化メカニズム / 高分子超薄膜 / 高分子構造・物性 / Langmuir-Blodgett膜 / 結晶化挙動 / 折りたたみ鎖結晶 / 高分子孤立鎖 / 原子間力顕微鏡(AFM) / Langmuir-Blodgett film / 原子間力顕微鏡(AFM)
Outline of Research at the Start

高分子は長くてフレキシブルなひも状の分子であり、それが、一般に折りたたまれて折りたたみ鎖結晶を形成する。その過程は複雑であり、現在でも不明な点が多い。もし、最も単純な高分子1分子が結晶化する過程を分子レベルで直接観察できれば、結晶化過程の理解が飛躍的に進むと考えられるが、今日まで観察に成功した例はない。本研究では、高分子1分子を結晶化しないマトリックス単分子膜中に孤立した状態で分散させたサンプルを用い、高湿度下での結晶化過程を原子間力顕微鏡(AFM)を用いて分子レベルで直接実像観察する。結晶構造は、力学特性等に大きな影響を与えるため、結晶化過程を解明、制御することは実用的にも極めて重要である。

Outline of Final Research Achievements

The crystallization process of a single isolated polymer chain into a folded-chain crystal (FCC) was visualized at the molecular level in situ and in real time by atomic force microscopy (AFM). The sample was a single Langmuir monolayer deposited on mica, in which isotactic poly(methyl methacrylate) (it-PMMA) was solubilized as isolated chains in an it-oligo(MMA) monolayer. The nucleation occurred at any point of the chain and the crystal grew by winding the residual part of the amorphous chain. The growth of a crystal formed at the end of an amorphous chain was observed. Unexpectedly, the crystal grew not only on the side where the amorphous chain was attached but also significantly on the opposite side where no amorphous chain was attached, indicating that the chains significantly slipped inside the folded crystal and crystallized on the opposite side. The crystallization behavior of a single isolated chain provides new insight in understanding the polymer crystallization process.

Academic Significance and Societal Importance of the Research Achievements

折りたたみ鎖結晶は高分子の最も一般的な結晶形態であるが、構造が複雑でその結晶化過程は不明な点が多い。本研究では、高分子一分子鎖を孤立させた状態で結晶化させ、孤立鎖の結晶化過程を初めて実時間で原子間力顕微鏡観察することに成功した。高分子鎖の任意の位置で結晶化が開始すること、折りたたみ鎖結晶化の際に、分子鎖が結晶内部を顕著に滑って結晶化していることなど、孤立鎖の結晶挙動を観察することで初めて明らかになった。

Report

(4 results)
  • 2023 Annual Research Report   Final Research Report ( PDF )
  • 2022 Annual Research Report
  • 2021 Annual Research Report
  • Research Products

    (28 results)

All 2024 2023 2022 2021 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Open Access: 2 results) Presentation (18 results) (of which Int'l Joint Research: 6 results,  Invited: 9 results) Remarks (2 results)

  • [Journal Article] In Situ AFM Observation of Folded-Chain Crystallization of Single Isolated Isotactic Poly(methyl methacrylate) Chains in Langmuir-Blodgett Monolayers2024

    • Author(s)
      Yusaku Takahashi, Jiro Kumaki
    • Journal Title

      Macromolecules

      Volume: 57 Issue: 3 Pages: 1147-1158

    • DOI

      10.1021/acs.macromol.3c02274

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] In situ Real-Time Atomic Force Microscopy Observations of Chain Mobility at the Polymer/Water Interfaces of Poly(methyl methacrylate), Poly(2-hydroxyethyl methacrylate), and Poly(2-methoxyethyl methacrylate) Films in Water2024

    • Author(s)
      Jiro Kumaki
    • Journal Title

      Langmuir

      Volume: 40 Issue: 10 Pages: 5270-5277

    • DOI

      10.1021/acs.langmuir.3c03699

    • Related Report
      2023 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Crystallization of Star-Shaped Poly(L-lactide)s with Arm Chains Aligned in the Same Direction in Two-Dimensional Crystals in a Langmuir Monolayer2023

    • Author(s)
      Yamazaki Shota、Harada Mahoko、Watanabe Yuya、Lang Rongjian、Kato Takashi、Haba Osamu、Fukushima Kazuki、Kumaki Jiro
    • Journal Title

      Langmuir

      Volume: 39 Issue: 15 Pages: 5486-5494

    • DOI

      10.1021/acs.langmuir.3c00199

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chain Movements at the Topmost Surface of Poly(methyl methacrylate) and Polystyrene Films Directly Evaluated by In Situ High-Temperature Atomic Force Microscopy2022

    • Author(s)
      Koike Kouki、Kumaki Jiro
    • Journal Title

      Langmuir

      Volume: 38 Issue: 45 Pages: 13707-13719

    • DOI

      10.1021/acs.langmuir.2c01788

    • Related Report
      2022 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Chain Movements of a Molecularly Flat PMMA Substrate Surface Prepared by Thermal Imprinting with Mica and Isolated PMMA Chains Deposited on the PMMA Substrate Observed by AFM around the Bulk Tg2022

    • Author(s)
      Jin Ohkawa, Jiro Kumaki
    • Journal Title

      Polym. J.

      Volume: 54 Issue: 3 Pages: 281-292

    • DOI

      10.1038/s41428-021-00600-0

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Solubilization of Poly(styrene)(PS)-b-Poly(methyl methacrylate)(PMMA)-b-PS in Poly(n-nonyl acrylate) and PMMA Monolayers as Isolated Chains with Both PS Blocks Forming Separated Single-Block Particles2022

    • Author(s)
      Fumiki Honma, Jiro Kumaki
    • Journal Title

      Polym. J

      Volume: 54 Issue: 5 Pages: 687-696

    • DOI

      10.1038/s41428-022-00614-2

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Thermal Stabilities of a Molecularly Stepped PMMA Substrate Prepared by Thermal Nanoimprinting and Isolated PMMA Chains Deposited on It Evaluated by High-Temperature Atomic Force Microscopy2021

    • Author(s)
      Ryota Umetsu, Jiro Kumaki
    • Journal Title

      Polym. J.

      Volume: 53 Issue: 10 Pages: 1111-1121

    • DOI

      10.1038/s41428-021-00508-9

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Molecular Combing of Various Poly(n-alkyl acrylate) Chains on Mica by the Dipping Method2021

    • Author(s)
      Akihiro Ohmatsuzawa, Moriya Kikuchi, Seigou Kawaguchi, Jiro Kumaki
    • Journal Title

      Langmuir

      Volume: 37 Issue: 24 Pages: 7556-7564

    • DOI

      10.1021/acs.langmuir.1c01054

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Presentation] 高分子鎖構造のin-situ AFM観察 -結晶化過程、固体表面分子運動―2024

    • Author(s)
      熊木治郎
    • Organizer
      公益社団法人日本顕微鏡学会 SPM研究会2023
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] Chain movements at the topmost surface of polymer films at high temperatures or under water directly evaluated by in-situ real-time AFM in the tapping mode2024

    • Author(s)
      Koike, Yuto Kashiwaya, Jiro Kumaki
    • Organizer
      2024 March Meeting, American Physical Society
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] In-Situ Real-Time AFM Observation of Folded-Chain Crystallization of Single Isolated Isotactic Poly(methyl methacrylate) Chains in a Langmuir-Blodgett Monolayer at the Molecular Level2024

    • Author(s)
      Yusaku Takahashi, Jiro Kumaki
    • Organizer
      2024 March Meeting, American Physical Society
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research
  • [Presentation] In Situ AFM Observation of Folded-Chain Crystallization of Single Isolated Isotactic PMMA Chains2024

    • Author(s)
      Yusaku Takahashi, Jiro Kumaki
    • Organizer
      International Discussion Meeting on Polymer Crystallization 2024 (IDMPC 2024)
    • Related Report
      2023 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 単分子膜中のPLA伸び切り鎖2次元結晶の融解挙動AFM観察2023

    • Author(s)
      田中翔、熊木治郎
    • Organizer
      第72回高分子学会年次大会
    • Related Report
      2023 Annual Research Report
  • [Presentation] 高分子鎖構造の原子間力顕微鏡観察 -孤立鎖、結晶から固体表面まで-2023

    • Author(s)
      熊木治郎
    • Organizer
      公益社団法人日本顕微鏡学会第79回学術講演会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] 高分子鎖構造の高分解能原子間力顕微鏡観察2023

    • Author(s)
      熊木治郎
    • Organizer
      産業技術総合研究所講演会
    • Related Report
      2023 Annual Research Report
    • Invited
  • [Presentation] AFM Observation of Polymer Structures at the Molecular Level2022

    • Author(s)
      Jiro Kumaki
    • Organizer
      Virtual Royal Microscopical Society (RMS) AFM & SPM Meeting 2022
    • Related Report
      2022 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 高分子鎖構造の高分解能原子間力顕微鏡観察2022

    • Author(s)
      熊木治郎
    • Organizer
      龍谷大学学術講演会
    • Related Report
      2022 Annual Research Report
    • Invited
  • [Presentation] ポリ乳酸伸び切り鎖結晶の結晶化過程in-situ AFM観察2022

    • Author(s)
      大友和也、熊木治郎
    • Organizer
      第71回高分子討論会
    • Related Report
      2022 Annual Research Report
  • [Presentation] AFM Observation of Polymer Structures at the Molecular Level2022

    • Author(s)
      Jiro Kumaki
    • Organizer
      The Japan-Taiwan Bilateral Polymer Symposium 2022 (JTBPS2022)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 単分子膜中におけるit-PMMA折りたたみ鎖結晶の結晶化過程高分解能in-situ AFM観察2021

    • Author(s)
      小野裕貴、熊木治郎
    • Organizer
      第70回高分子学会年次大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 原子間力顕微鏡による高分子の高倍観察2021

    • Author(s)
      熊木治郎
    • Organizer
      光ナノサイエンス特別講義(奈良先端科学技術大学院大学)
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 星型ポリ乳酸の分子鎖方向を識別した結晶化挙動2021

    • Author(s)
      山﨑翔太、原田真帆子、羽場修、福島和樹、熊木治郎
    • Organizer
      第70回高分子討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ポリ乳酸伸び切り鎖結晶の結晶化過程in-situ AFM観察2021

    • Author(s)
      大友和也、熊木治郎
    • Organizer
      第70回高分子討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] it-PMMA孤立鎖の結晶化挙動観察2021

    • Author(s)
      高橋佑朔、熊木治郎
    • Organizer
      第70回高分子討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 星型ポリ乳酸の分子鎖方向を識別した結晶化挙動2021

    • Author(s)
      山﨑翔太、原田真帆子、羽場修、福島和樹、熊木治郎
    • Organizer
      2021高分子学会東北支部研究発表会
    • Related Report
      2021 Annual Research Report
  • [Presentation] In Situ Real-Time Observations of isotactic Poly(methyl methacrylate)(it-PMMA) Crystallization in Langmuir Monolayers by AFM2021

    • Author(s)
      Jiro Kumaki
    • Organizer
      Sakura Science
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research / Invited
  • [Remarks] 山形大学熊木研究室

    • URL

      https://kumaki-lab.yz.yamagata-u.ac.jp/index.html

    • Related Report
      2022 Annual Research Report 2021 Annual Research Report
  • [Remarks] 山形大学教員情報

    • URL

      https://yudb.kj.yamagata-u.ac.jp/html/100000173_ja.html

    • Related Report
      2022 Annual Research Report 2021 Annual Research Report

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Published: 2021-04-28   Modified: 2025-01-30  

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