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Mechanism of Polymer Crystallization and Control of Fine Structure under Molecular Orientation

Research Project

Project/Area Number 12127202
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionTokyo Institute of Technology

Principal Investigator

OKUI Norimasa  Tokyo Institute of technology, Department of Orgaic and Polymeric Materials, Professor, 大学院・理工学研究科, 教授 (20111651)

Co-Investigator(Kenkyū-buntansha) ITO Hitoshi  Tokyo Institute of Technology, Department of Organic and Polymeric Materials, Assistant Professor, 大学院・理工学研究科, 助手 (20259807)
UMEMOTO Susumu  Tokyo Institute of Technology, Department of Organic and Polymeric Materials, Assistant Professor, 大学院・理工学研究科, 助手 (90168758)
KIKUTANI Takeshi  Tokyo Institute of Technology, Department of Organic and Polymeric Materials, Professor, 大学院・理工学研究科, 教授 (70153046)
SAITO Hiromu  Tokyo University of Agriculture and Technology, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90196006)
Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥31,000,000 (Direct Cost: ¥31,000,000)
Fiscal Year 2002: ¥12,800,000 (Direct Cost: ¥12,800,000)
Fiscal Year 2001: ¥18,200,000 (Direct Cost: ¥18,200,000)
KeywordsOrdered Structure / Light Scattering / High Speed Melt Spinning / Orientation Crystallization / Birefringence / Relaxation of Molecular Orientation / Crystallization Rate / Nucleation Rate / 高分子 / 結晶化 / 高次構造 / 分子配向 / 高速紡糸 / 溶融紡糸 / 拡散
Research Abstract

Molecular weight (MW) dependence of physical properties is one-of the most common characteristics in polymeric materials. For example, melt viscosity of polymer shows remarkable MW dependence and can be scaled and expressed as a 3.4 power of MW for entangled polymer chains. Also the influence of MW on polymer crystallization rate has been the most interesting subject. We studied on molecular weight dependence of crystal nucleation rate (I) and crystal growth rate for various polymers. The temperature dependence of I and G showed bell-shaped curves showing clear maximum points of Imax and Gmax. Imax and Gmax showed remarkable MW dependence. The plots of the reduced growth rate (G/Gmax) and the reduced nucleation rate (Inmax) showed a single master curve without MW dependence. Imax and Gmax are characteristic references to nucleation and crystal growth rate behaviors, respectively. The MW dependence of Imax and Gmax are scaled and expressed as I and -0.5 power of MW, respectively for a c … More hain folding crystallization.
Crystallization rate of Poly(carbonate) (PC) in general is very slow, however its rate is accelerated by polymer blending with poly(ethylene oxide) (PEO). The crystallization of PC in the PC/PEO blends is completed within several seconds. During crystallization of the blends, spinodal decomposition was observed and spherulite of PC was observed in PC rich phase. The crystallization of PC was controlled by up-hill diffusion during liquid-liquid phase separation in the polymer blends.
Bi-and uni-axial drawing of poly(ethylene terephthalate) (PET) and poly(ethylene 2,6 naphthalene dicarboxylate) (PEN) were performed at various strain rates and temperatures. On-line measurements of drawing stress and birefringence were carried out under several drawing conditions. The stress-optical rule (SOR) was applicable at low birefringence, and the stress-optical coefficient obtained for drawing process was similar to the reported values. Flow drawings of PET and PEN were caused at relatively high drawing temperature and low strain rate. The SOR was also applicable in flow drawing conditions. To analyze the network structure of each sample that has low crystallinity and low birefringence, the entanglement density Nc of drawn films was analyzed from the measurement of heat shrinkage and shrinkage stress applying the rubber elasticity theory for Gaussian chain. In the drawing of PEN. Nc value of drawn sample was lower when the drawing temperature was higher and strain rate was lower.
Structure formation of stereo complex (racemate) polylactides fibers by high-speed melt spinning and subsequent drawing and annealing process was investigated. Distinct crystalline reflections appeared in WAXD patterns of as-spun fibers above 4 km/min. The crystal modification was co-existence of alpha-form and stereo complex crystals, and reflection intensity of stereo complex crystal increased with an increase in the take-up velocity and a decrease in the throughput rate and spinning temperature. The crystalline reflections of annealed high-speed spun fibers showed higher orientation and richer stereo complex crystallites than the fibers obtained by drawing and annealing low-speed spun fibers. From the diameter profile measurement of the spin-line, it was found that higher crystallization temperature in the spinning process leads to the preferred formation of stereo complex crystals. Less

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (57 results)

All Other

All Publications (57 results)

  • [Publications] S.Umemoto: "Master curve of crystal growth rate and its corresponding state in polymeric materials"Polymer. 43. 1423-1427 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S.Umemoto: "Molecular weight dependence of crystal growth rate and its degree of super cooling effect"J.Macromolecular Sci., Phys.Ed. B41. 923-938 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 三浦慶子: "超臨界法による高分子の高次構造制御とセルロースへの応用の可能性"Cellulose Communications. 9・3. 155-159 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] 奥居徳昌: "高分子鎖の折りたたみ構造の発見-Kellerによる発見の旅"高分子. 52. 90-92 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Kikutani: "Formation and Structure of High Mechanical Performance Fibers II. Flexible Polymers"J.Appl.Polym.Sci.. 83. 559-571 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Kikutani: "Dynamics and Evolution of Structure in Fiber Extrusion"J.Appl.Polym.Sci.. 83. 539-558 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Kawashima: "Morphological changes in flat-on and edge-on lamellae of PESU crystallized from molten thin films"J.Macromolecular Sci.. B42. 889-899 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S.Umemoto: "Molecular weight dependence of primary nucleation rate of PESU"J.Macromolecular Sci.. B42. 421-430 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Takasaki: "Structure development of ployactides with various d-lactide contents in the high speed melt spinning process"J.Macromolecular Sci.. B42. 59-75 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Takasaki: "Development of stereocomplex crystal of polylactide in high speed melt spinning and subsequent drawing and annealing process"J.Macromolecular Sci.. B42. 403-420 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] J.Shimizu: "Dynamics and evolution of structure in fiber extrusion"J.Appl.Polym.Sci., Appl.Polym.Symp.. 83. 539-558 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] T.Kikutani: "Formation and Structure of High Mechanical Performance Fibers II. Flexible Polymers"J.Appl.Polyrn.Sci., Appl.Polym.Symp.. 83. 559-571 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Okui: "Polymer Crystallization Chapter 9 343-365 (Ed. J.U.Sommer, G.Reiter, Springer-Verlag)"Maximum crystal growth rate and its corresponding state it polymeric materials. 23 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] K.Kawashima, R.Kawano, T.Miyagi, S.Umemoto, N.Okui: "Morphological changes in flat-on and edge-on lamellae of PESU crystallized from molten thin films"J.Macromol.Sci.. B42. 889-899 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S.Umemoto, R.Hayashi, R.Kawano, T.Kikutani, N.Okui: "Molecular weight dependence of primary nucleation rate of PESU"J. Macromol. Sci.. B42. 421-430 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] N.Okui, S.Umemoto: "Maximum crystal growth rate and its corresponding state in polymeric materials"Polymer Crystallization Chapter Ed. J.U.Sommer, G.Reiter, Springer-Verlag. 9. 343-365 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Takasaki, H.Ito, T.Kikutani: "Structure development of polyactides with various d-lactide contents in the high speed melt spinning process"J. Macromol.Sci.. B42. 59-75 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] M.Takasaki, H.Ito, T.Kikutani: "Development of stereocomplex crystal of polylactide in high speed melt spinning and subsequent drawing and annealing process"J. Macromol. Sci.. B42. 403-420 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] J.Shimizu, T.Kikutani: "Dynamics and evolution of structure in fiber extrusion"J.Appl. Polym. Sci., Appl. Polym. Symp.. 83. 539-558 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S.Umemoto, N.Okui: "Molecular weight dependence of crystal growth rate and its degree of supper-cooling effect"J. Macromoo. Sci.. B41. 923-938 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S.Umemoto, N.Okui: "Master curve of crystal growth rate and its corresponding state in polymeric materials"Polymer. 43. 1423-1427 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] S.Umemoto: "Master curve of crystal growth rate and its corresponding state in polymeric materials"Polymer. 43. 1423-1427 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] S.Umemoto: "Molecular weight dependence of crystal growth rate and its degree of super cooling effect"J.Macromolecular Sci., Phys.Ed. B41. 923-938 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] A.Kubono: "Adsorption characteristics of organic long chain molecules during physical vapor deposition"Applied surface science. 193. 195-203 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 奥居徳昌: "高分子鎖の折りたたみ構造の発見-Kellerによる発見の旅-"高分子. 52. 90-92 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Kikutani: "Formation and Structure of High Mechanical Performance Fibers. II. Flexible Polymers"J.Appl.Polym.Sci.. 83. 559-571 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] T.Kikutani: "Dynamics and Evolution of Structure in Fiber Extrusion"J.Appl.Polym.Sci.. 83. 539-558 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 熊沢: "交互積層構造を有する干渉発色繊維の変角反射特性"繊維学会誌. 58・6. 195-201 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Kawahara: "Permagnetic Etching of Poly(ethylene terephthalate) Fibers"Sen'i Gakkaishi. 58・7. 268-272 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 河原: "顕微レーザーラマン分光法によるPET繊維の構造解析"繊維学会誌. 58・9. 342-345 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 北山: "PP/PP同種異形態複合材料の力学特性"成形加工. 14・7. 663-670 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] M.Takasaki: "Structure Development of Polyactides with Various D-Lactide Contents in the High-Speed Melt Spinning Process"J.Macromol.Sci., Part B-Physics. 42・1. 59-75 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] 三浦慶子: "超臨界法による高分子の高次構造制御とセルロースへの応用の可能性"Cellulose Communications. 9・3. 155-159 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 斎藤拓: "非晶構造解析"成形加工. 13. 34-38 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] W.Takarada: "Studies on High-Speed Melt Spinning of Noncircular Cross-Section Fibers, Structural Analysis of As-spun Fibers"J. Appl. Polym. Sci.. 80. 1575-1581 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] W.Takarada: "Studies on High-speed Melt Spinning of Noncircular Cross-Section Fibers, II. On-Line Measurements of the Spin Line, Including Change in Cross-sectional Shape"J. Appl. Polym. Sci.. 80. 1582-1588 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] W.Takarada: "Studies on High-speed Melt Spinning of Noncircular Cross-Section Fibers, III. Modeling of Melt Spinning Process Incorporating Change in Cross-sectional Shape"J. Appl. Polym. Sci.. 80. 1589-1600 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] A.Nagai: "Quadrople aliphatic polyamide systeMs prepared by a layer-by-layer alternating vapor deposition method"High Performance Polymers. 13. 169-179 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] S.Umemoto: "Master curve of crystal growth rate and its corresponding state in polymeric materials"Polymer. 43. 1423-1427 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 奥居徳昌: "高分子の結晶化と各種の転移温度との相関"高分子加工. 50. 486-492 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Shiraishi: "The Application of an Integral Type Constitutive Equation to Numerical Flow Analyses of Viscoelastic Fluid in Unsteady Flow"Polym. Eng. & Sci.. 41・10. 1695-1704 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Kawahara: "Dyeing Behavior of High-speed Spun Poly (ethylene terephthalate) Fibers in Supercritical Carbon Dioxide"J. Macromol. Sci. -Phys. B40. 189-197 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] Y.Kawahara: "Dyeing Behaviour of Poly(ethylene terephthalate) Fibres in Supereritical Carbon Dioxide"Color. Tech.. 117. 266-269 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 河原豊: "超臨界二酸化炭素処理したポリエチレンテレフタレート繊維の構造"繊維学会誌. 57・7. 220-223 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 鞠谷雄士: "高強度繊維への挑戦-ポリエステル繊維の高強度化は可能か-"高分子. 50・12. 830-833 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 鞠谷雄士: "プラスチック成形品の高次構造解析(12)-絡み合い構造解析-"成形加工. 13・3. 167-171 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 斎藤拓: "ABCハンドブック(分担)ABの結晶化と構造形成"エヌ・ティー・エス. 135-144 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 斎藤拓: "高分子の長寿命化(分担)高分子の物理的劣化と安定化機構"シーエムシー. 105-116 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] T.Kikutani: "Encyclopedia of Materials : Science and Technology"Elsevier Science Ltd.. 10387 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 伊藤浩志: "プラスチック成形加工データブック(第2版)第3章成形加工特性"日刊工業新聞社. 353 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] E.Giza,H.Ito,T.Kikutani and N.Okui: "Fiber Structure Formation in High-speed Melt Spinning of Polyamide 6/Clay Hybrid Nanocomposite"J.Macromol.Sci.,Phys. B39(4). 545-559 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] E.Giza,H.Ito,T.Kikutani and N.Okui: "Structural Control of Polyamide 6/Clay Nanocomposite Fibers by In-Line Drawing Process"J.Polym.Eng. 20. 403-425 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.H.Cho,K.H.Kim,Y.A.Kang,H.Ito,and T.Kikutani: "Fine-Structure and Physical Properties of Polyethylene/Poly (ethylene terephthalate) Bicomponent Fibers in High-Speed Spinning I Polyethylene Sheath/Poly (ethylene terephthalate) Core Fibers"J.Appl.Polym.Sci. 77. 2254-2266 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.H.Cho,K.H.Kim,Y.A.Kang,H.Ito,and T.Kikutani,: "Fine-Structure and Physical Properties of Polyethylene/Poly (ethylene terephthalate) Bicomponent Fibers in High-Speed Spinning II Poly (ethylene terephthalate) Sheath/Polyethylene Core Fibers,"J.Appl.Polym.Sci.. 77. 2267-2277 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.H.Cho,K.H.Kim,H.Ito and T.Kikutani: "Fine-Structure and Physical Properties of Polyethylene Fibers in High-Speed Spinning I Effect of Melt-Flow Rate in the High-Density Polyethylene"J.Appl.Polym.Sci.. 77. 1182-1194 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.H.Cho,K.H.Kim,H.Ito and T.Kikutani: "Fine-Structure and Physical Properties of Polyethylene Fibers in High-Speed Spinning II Effect of Catalyst Systems in Linear Low-Density Polyethylene"J.Appl.Polym.Sci.. 77. 1195-1206 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 占部宏生,伊藤浩志,鞠谷雄士,奥居徳昌: "ポリプロピレンの高速溶融紡糸過程における分子配向形成のオンライン計測"成形加工. 12(11). 729-735 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 2001-04-01   Modified: 2018-03-28  

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