Glass transition and dynamics in thin polymer films

• Project/Area Number: 19H01865
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Review Section: Basic Section 13040:Biophysics, chemical physics and soft matter physics-related
• Research Institution: Ritsumeikan University
• Principal Investigator: Fukao Koji 立命館大学, 理工学部, 教授 (50189908)
• Co-Investigator(Kenkyū-buntansha): 吉岡 潤 立命館大学, 理工学部, 助教 (50708542)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000); Fiscal Year 2021: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2020: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2019: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000)
• Keywords: 高分子薄膜 / ガラス転移温度 / α過程 / 遅い過程 / 中性子反射率測定 / 誘電緩和測定 / X線小角・広角散乱 / エイジング / 液体状態 / ガラス状態 / アレニウス過程 / ガラス転移 / 特性長 / 高分子積層膜 / ポリフマル酸 / アダマンチルアクリレート / 誘電緩和 / ポリスチレン積層膜 / 中性子反射率 / 相互拡散 / 膜厚依存性 / 界面ダイナミクス / 散乱長密度 / 積層膜 / 移動度 / 重水素化 / ダイナミクス / 界面相互作用 / 拘束条件下

Outline of Research at the Start

高分子薄膜で観測されるガラス転移温度のバルクからのずれの原因を明らかにし，さらには，ガラス転移温度の制御を最終的な目的として，高分子単層膜，高分子積層膜のダイナミクスと界面構造の変化を誘電緩和測定と中性子反射率測定を用いて調べる．誘電緩和測定からは，高分子薄膜のガラス転移に関係したα過程の緩和時間の温度依存性，中性子反射率測定からは界面のラフネスと各層の膜厚が得られる。これらの物理量の温度，アニール時間依存性を評価することにより，ガラス転移の本質に迫る．

Outline of Final Research Achievements

Dynamics of polymer chains at the interface between deuterated polymer (d-PMMA) and protonated polymer (h-PMMA) in the two-layered polymer films have been investigated under the isothermal annealing process by the neutron reflectivity measurements. From such measurements, we could evaluate quantitatively the mobility due to the mutual diffusion of polymer segment at the interface. For nanocomposites between polymer P2VP and nanoparticle OAPS, we have elucidated how the dynamics of P2VP such as the alpha-process and the slower process change with the increase in the fraction of nanoparticle OAPS.

Academic Significance and Societal Importance of the Research Achievements

本研究では、積層膜界面、ナノ粒子と高分子のナノコンポジット、細孔内部に拘束された液体でのダイナミクスを系統的に明らかにすることができた。これらの成果を応用することにより、様々な拘束条件下での鎖状分子のダイナミクスをコントロールするための指標が明確となった。このことは学術的な意義に留まらず、高分子のマテリアルとしての応用に重要な意義を有すると言える。

Research Products

• [Int'l Joint Research] マサチューセッツ大学(米国)
• [Int'l Joint Research] マサチューセッツ大学(米国)
• [Int'l Joint Research] CNRS(フランス)
• [Journal Article] Crystallization with Nodular Aggregation near the Glass Transition Temperature for Syndiotactic Polypropylene (2023)
  • Author(s): Takashi Konishi, Ken Taguchi, Koji Fukao, Noriaki Takagi, and Yoshihisa Miyamoto
  • Journal Title: ACS Macro Letters Volume: 12 Issue: 2 Pages: 208-214
  • DOI: 10.1021/acsmacrolett.2c00666
  • Peer Reviewed
• [Journal Article] Lamellar crystallization of poly(trimethylene terephthalate) (2023)
  • Author(s): Daisuke Tadokoro, Takashi Konishi, Koji Fukao, and Yoshihisa Miyamoto
  • Journal Title: Polymer Journal Volume: - Issue: 7 Pages: 775-783
  • DOI: 10.1038/s41428-023-00777-6
  • Peer Reviewed
• [Journal Article] Crystallization and Transformation Behavior of Triacylglycerol Binary Mixtures Forming Molecular Compounds of POP/OPO, POP/rac-PPO, and POP/sn-PPO (2023)
  • Author(s): Bayes-Garcia Laura、Fukao Koji、Konishi Takashi、Sato Kiyotaka、Taguchi Ken
  • Journal Title: Crystal Growth & Design Volume: 23 Issue: 4 Pages: 2870-2881
  • DOI: 10.1021/acs.cgd.3c00038
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Ideal Glass Transitions from the View Point of Fragility in Polymer-Dimer Mixture (2022)
  • Author(s): 辰巳 創一、菊本 元気、八尾 晴彦、猿山 靖夫、深尾 浩次
  • Journal Title: Netsu Sokutei Volume: 49 Issue: 3 Pages: 102-107
  • DOI: 10.11311/jscta.49.3_102
  • ISSN: 0386-2615, 1884-1899
  • Year and Date: 2022-07-25
  • Peer Reviewed
• [Journal Article] A Hidden Relaxation Process in Poly(2-vinylpyridine) Homopolymers, Copolymers, and Nanocomposites (2022)
  • Author(s): Young Walter W.、Tabuchi Hiromu、Iguchi Ryo、Konishi Takashi、Fukao Koji、Katsumata Reika
  • Journal Title: Macromolecules Volume: 55 Issue: 15 Pages: 6590-6597
  • DOI: 10.1021/acs.macromol.2c00789
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Marangoni convection driven by temperature gradient near an isotropic-nematic phase transition point (2022)
  • Author(s): Jun Yoshioka, Tasuku Sakikawa, Yuki Ito, and Koji Fukao
  • Journal Title: Physical Review E Volume: 105 Issue: 1
  • DOI: 10.1103/physreve.105.l012701
  • Peer Reviewed
• [Journal Article] Dielectric relaxation and glassy dynamics in poly(diisopropyl fumarate) and its copolymers with acrylate segments (2022)
  • Author(s): Kairi Miyata, Jun Yoshioka, Koji Fukao, Yasuhito Suzuki, Akikazu Matsumoto
  • Journal Title: Polymer Volume: 245 Pages: 124671-124671
  • DOI: 10.1016/j.polymer.2022.124671
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Kinetics of Polymer Crystallization with Aggregating Small Crystallites (2022)
  • Author(s): Takashi Konishi, Daisuke Okamoto, Daisuke Tadokoro, Yoshitaka Kawahara, Koji Fukao, and Yoshihisa Miyamoto
  • Journal Title: Physical Review Letters Volume: 128 Issue: 10 Pages: 107801-107801
  • DOI: 10.1103/physrevlett.128.107801
  • Peer Reviewed
• [Journal Article] Polymerization-Induced Vitrification and Kinetic Heterogenization at the Onset of the Trommsdorff Effect (2021)
  • Author(s): Suzuki Yasuhito、Shinagawa Yuya、Kato Eri、Mishima Ryutaro、Fukao Koji、Matsumoto Akikazu
  • Journal Title: Macromolecules Volume: 54 Issue: 7 Pages: 3293-3303
  • DOI: 10.1021/acs.macromol.0c02260
  • Peer Reviewed
• [Journal Article] Characteristic Features of α and β Relaxations of Poly(diethyl fumarate) as the Poly(substituted methylene) (2021)
  • Author(s): Yasuhito Suzuki, Nagisa Tsuji, Kairi Miyata, Takahito Kano, Koji Fukao, Akikazu Matsumoto
  • Journal Title: Macromolecular Chemistry and Phyiscs Volume: 222 Issue: 16 Pages: 2100124-2100124
  • DOI: 10.1002/macp.202100124
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Self-excited oscillation of the director field in cholesteric liquid crystalline droplets under a temperature gradient (2020)
  • Author(s): Jun Yoshioka, Koji Fukao
  • Journal Title: J. Phys.: Condens. Matter Volume: 32 Issue: 32 Pages: 325102-325102
  • DOI: 10.1088/1361-648x/ab83b1
  • Peer Reviewed
• [Journal Article] Relaxation behavior of poly(diisopropyl fumarate) including no methylene spacer in the main chain (2020)
  • Author(s): Yasuhito Suzuki, Kairi Miyata, Masashi Sato, Nagisa Tsuji, Koji Fukao, Akikazu Matsumoto
  • Journal Title: Polymer Volume: 196 Pages: 122479-122479
  • DOI: 10.1016/j.polymer.2020.122479
  • Peer Reviewed
• [Journal Article] Horizontal Transportation of a Maltese Cross Pattern in Nematic Liquid Crystalline Droplets under a Direct-Current Electric Field (2020)
  • Author(s): Yoshioka Jun、Fukao Koji
  • Journal Title: Journal of the Physical Society of Japan Volume: 89 Issue: 9 Pages: 094401-094401
  • DOI: 10.7566/jpsj.89.094401
  • NAID: 40022344798
  • Peer Reviewed
• [Journal Article] Spectroscopic analysis in molecular simulations with discretized Wiener-Khinchin theorem for Fourier-Laplace transformation (2020)
  • Author(s): Koyama Akira、Nicholson David A.、Andreev Marat、Rutledge Gregory C.、Fukao Koji、Yamamoto Takashi
  • Journal Title: Physical Review E Volume: 102 Issue: 6 Pages: 063302-063302
  • DOI: 10.1103/physreve.102.063302
  • Peer Reviewed
• [Journal Article] Direct observation of mobility of thin polymer layers via asymmetric interdiffusion using neutron reflectivity measurements (2019)
  • Author(s): Megumi Ooe, Kairi Miyata, Jun Yoshioka, Koji Fukao, Fumiya Nemoto, and Norifumi L. Yamada
  • Journal Title: Journal of Chemical Physics Volume: 151 Issue: 24 Pages: 244905-244905
  • DOI: 10.1063/1.5132768
  • Peer Reviewed
• [Journal Article] Processing Pathways Decide Polymer Properties at the Molecular Level (2019)
  • Author(s): S. Chandran, J. Baschnagel, D. Cangialosi, K. Fukao, E. Glynos, L.M.C. Janssen, M. Mueller, M. Muthukumar, U. Steiner, J. Xu, S. Napolitano, G. Reiter
  • Journal Title: Macromolecules Volume: 52, Issue: 19 Pages: 7146-7156
  • DOI: 10.1021/acs.macromol.9b01195
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Dielectric study of relaxation process in nanocomposites of poly(2-vinylpyridine) and small particles (2023)
  • Author(s): K. Fukao, H. Nobori, H. Tabuchi, W. Young, R. Katsumata
  • Organizer: American Chemical Society March Meeting 2023, Indianapolis
  • Int'l Joint Research
• [Presentation] Phase transitions and structural changes of ionic liquid crystals in nanopores (2023)
  • Author(s): Hiroki Nobori, Daisuke Fujimoto, Jun Yoshioka, Koji Fukao
  • Organizer: American Physical Society March Meeting 2023, Las Vegas
  • Int'l Joint Research
• [Presentation] Marangoni convection driven by temperature gradient in cyanobiphenyl liquid crystals (2023)
  • Author(s): Yuki Ito, Jun Yoshioka, Koji Fukao
  • Organizer: American Physical Society March Meeting 2023, Las Vegas
  • Int'l Joint Research
• [Presentation] A hidden relaxation process under DC conductivity in poly(2- vinylpyridine) and nano-composites (2022)
  • Author(s): Koji Fukao, Walter Young, Hiromu Tabuchi, Ryo Iguchi, Takashi Konishi, Reika Katsumata
  • Organizer: 11th Conference on Broadband Dielectric Spectroscopy and its Applications
  • Int'l Joint Research / Invited
• [Presentation] Rotational Phenomenon Driven by Temperature Gradient in a Cholesteric Droplet with Air Interface (2022)
  • Author(s): J. Yoshioka, K. Fukao
  • Organizer: 28th International Liquid Crystal Conference
  • Int'l Joint Research
• [Presentation] Interdiffusion and glass transition in thin polymer films (2020)
  • Author(s): K.Fukao, M.Ooe, T.Hayashi, K.Miyata, J.Yoshioka, F.Nemoto, N.L.Yamada
  • Organizer: Princeton center conference: Polymers at the Nanoscale: Phase transition and dynamics
  • Int'l Joint Research / Invited