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PVT Analysis of Chain Molecules Exhibited Crystal-Liquid Crystal-Isotropic Phase Transition-Orientational Order Dependence of Intramolecular Interaction Potentials and Limitation of Mean-Field Theory

Research Project

Project/Area Number 16550112
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Polymer chemistry
Research InstitutionTokyo Polytechnic University

Principal Investigator

HIEJIMA Toshihiro  Tokyo Polytechnic University, Department of Nanochemistry, Associate Professor, 工学部, 助教授 (30288112)

Project Period (FY) 2004 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 2005: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2004: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsChain Molecules / PVT analysis / Dimer compound / Mean-field theory / Intermolecular interaction potentials / Vibrational spectroscopic analysis / DFT calculation / ^2H-NMR / DFT解析 / 配向秩序度 / オキシエチレン鎖
Research Abstract

The effects of volume dependence of thermal-pressure coefficient on the estimation of constant-volume transition entropy (ΔS_m)_v were investigated by the analysis of PVT data of main-chain dimer compounds, the amount (approximately 10%) being reasonably small. The PVT analysis suggested that about 65% of the transition entropy arises from (ΔS_m)_v corresponding to the variation in the conformational distribution of the spacer. We pointed out that the order-disorder characteristics inherent in the primary structure of the flexible spacer are precisely controlled in order to develop the LC mesophase.
The intermolecular interaction potentials such as ε=-η/V^m have been widely adopted in conventional mean-field theories of liquids including molten polymers. Here η is defined as a mean-field parameter representing the strength of the interaction field and the parameter m is often set equal to unity in the conventional treatment of liquid. In the analysis of PVT data, m approaches unity only … More within a narrow range of temperature. This results suggested that the conventional form of the potential in the above-mentioned is only valid within a certain limited range of temperature and volumes in both isotropic and nematic LC phases.
Vibrational analyses were performed on dimer liquid crystals having a diethylene glycol spacer such as CN-φφ-(OCH_2CH_2)_2O-φφ-CN(CBE2). The specific IR active modes in CBE2 were found to show the frequency shift resembled in the qualitatively shape of nematic order parameter, while other vibrations remain unaltered. It is considered that the selective coupling between intramolecular vibration and the liquid crystalline order is relative to the intrinsic symmetry of the modes.
Screw-sense inversion behaviors of a-helical polyaspartate differ substantially depending on the chemical structure of the ester group at the side-chain terminals. The cause of such phenomenological difference among polymers has been investigated by constructing the phase diagram as a function of solvent composition and temperature. Less

Report

(3 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • Research Products

    (10 results)

All 2005 2004

All Journal Article (10 results)

  • [Journal Article] Stepwise Phase transition of Chain Molecules : Crystallization/Melting via a Nematic Liquid Crystalline Phase2005

    • Author(s)
      A.Abe, H.Furuya, Z.Zhou, T.Hiejima, Y.Kobayashi
    • Journal Title

      Adv.Polym. Sci. 181

      Pages: 121-152

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] screw-Sense Inversion Characteristic of a-Helical Poly(β-p-chlorobenzyl L-aspartate) and Comparison with Other Related Polyaspartates.2005

    • Author(s)
      A.Abe, K.Hiraga, Y.Imada, T.Hiejima, H.Furuya
    • Journal Title

      Biopolymer(Peptide Science) 70

      Pages: 249-257

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Stepwise Phase transition of Chain Molecules : Crystallization/Melting via a Nematic Liquid Crystalline Phase.2005

    • Author(s)
      A.Abe, H.Furuya, Z.Zhou, T.Hiejima, Y.Kobayashi
    • Journal Title

      Adv.Polym.Sci. 181

      Pages: 121-152

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Screw-Sense Inversion Characteristic of a-Helical Poly(β-p-chloro benzyl L-aspartate) and Comparison with Other Related Polyaspartates.2005

    • Author(s)
      A.Abe, K.Hiraga, Y.Imada, T.Hiejima, H.Furuya
    • Journal Title

      Biopolymer (Peptide Science) 70

      Pages: 249-257

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Stepwise Phase transition of Chain Molecules : Crystallization/Melting via a Nematic Liquid Crystalline Phase2005

    • Author(s)
      A.Abe, H.Furuya, Z.Zhou, T.Hiejima, Y.Kobayashi
    • Journal Title

      Adv.Polym.Sci., 181

      Pages: 121-152

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Screw-Sense Inversion Characteristic of a-Helical Poly(β- p-chlorobenzyl L-aspartate) and Comparison with Other Related Polyaspartates.2005

    • Author(s)
      A.Abe, K.Hiraga, Y.Imada, T.Hiejima, H.Furuya
    • Journal Title

      Biopolymer (Peptide Science) 80

      Pages: 249-257

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Stepwise Phase Transitions of Chain Molecules : Crystallization/Melting via a Nematic LC Phase.2005

    • Author(s)
      A.Abe, H.Furuya, Z.Zhou, T.Hiejima, Y.Kobayashi
    • Journal Title

      Adv.Polym.Sci (In press)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Estimation of conformational transition entropies involved in the stepwise crystallization/melting of mainchain liquid crystalline compounds.2004

    • Author(s)
      T.Hiejima, T.Kobayashi, Z.Zhou, A.Abe
    • Journal Title

      40^<th> International Symposium on Macromolecules CD-ROM

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Molecular Dynamics in Chiral Smectic Liquid-Crystalline Phases Studies by Solid State ^<13>C-NMR measurements2004

    • Author(s)
      K.Hiraoka, T.Seki, K.Miyayama, T.Hiejima, M.Kanekiyo
    • Journal Title

      Ferroelectrics 310

      Pages: 37-43

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Estimation of conformational transition entropies involved in the stepwise crystallization/melting of mainchain liquid crystalline compounds.2004

    • Author(s)
      T.Hiejima, Y.Kobayashi, Z.Zhou, A.Abe
    • Journal Title

      40^<th> International Symposium on Macromolecules (CD-ROM)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary 2004 Annual Research Report

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Published: 2004-04-01   Modified: 2016-04-21  

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