1997 年度実績報告書

高純度高分子の結晶化の分子量依存性による核生成・成長機構の実体的解明

研究課題

研究課題/領域番号	09450364
研究機関	広島大学
研究代表者	彦坂正道広島大学, 総合科学部, 教授 (60087103)
研究分担者	戸田昭彦広島大学, 総合科学部, 助教授 (70201655)
キーワード	高分子 / 分子量 / 結晶化 / 核生成 / 熱測定 / 拡散
研究概要	高分別で同一純度のポリエチレン(PE)数種類を特別に調整して、折りたたみ鎖結晶(Folded chain crystal,FCC)と伸びきりの鎖結晶(Extended chain crystal,ECC)の分子量依存性を、本補助金により購入した光学顕微鏡とホットステージを用いて直接観察した。その結果「一次核生成速度と沿面成長速度が分子量(M)のべき乗に比例して減少する」という事実を初めて見いだし、“核生成速度と成長速度のべき乗則"と命名した。また、両速度の二つの因子の中で、拡散項のみが分子量依存性を示し、もう一つの因子である臨界核生成の確率は分子量依存性を示さないことを初めて見いだした。こうした事実から「分子鎖が固・液界面において絡み合いを解きつつ、核の中を滑り拡散して、臨界核のサイズよりも十分大きなサイズに成長する過程が、核生成の実体である」という“核生成の滑り拡散モデル"を提唱し、“核生成速度と成長速度のべき乗則"を説明することに成功した。結晶化の初期過程と成長過程における熱容量と潜熱とを、温度変調型の走査型示差熱量計を用いた熱測定法によって分離評価し、結晶化過程を定量評価する新理論を提唱した。新理論による評価法を、ポリスチレンの結晶化の顕微鏡的測定との対応によって検討した結果、十分な信頼性を持つことが確かめられ、結晶化に関する新しい角度からの情報が得られることがわかり、結晶化メカニズムの研究に有効であることがわかった。

研究成果
(21件)

すべてその他

すべて文献書誌 (21件)

[文献書誌] T.Hattori: "The high-pressure crystallization behaviors and piezoeleetricity of extended chain lamellar crystals of VF trifluorocthylene copolymers with high molar content of VF." Polymer. 38. 3505-3511 (1997)
[文献書誌] S.K.Ghosh: "Phase transiton between microemulsion and lamellar phase in C12E5/water/n-octane amphilic system" J.Appl.Crystallography. (印刷中).
[文献書誌] S.K.Ghosh: "Structural Changes and interaction parameters in amphilic system C12E5/water/n-octznc" Progress Colloid and Polymer Science. 106. 91-97 (1997)
[文献書誌] S.K.Ghosh: "Structure funcitions and Interfacial curvatues in a ternary amphilic system C12E5/water/n-octznc" Progress Colloid and Polymer Science. 106. 98-103 (1997)
[文献書誌] M.Hikosaka: "Lamellar Thickening Growth of an Extended Chain Single Crystal of PE(I)---Pointers to a New Crystallization Mechanism of Polymers---" Macromolecules. 30. 2067-2074 (1997)
[文献書誌] M.Nagao: "Pressure-induced phase transition from discordered microemulsion to lamellar structure in a wter/AOT/n-decane system" Progress Colloid and Polymer Science. 106. 86-90 (1997)
[文献書誌] K.Yamada: "Isotacticity dependence of spherultic morphology of isotactic polypropylene" Polymer. (印刷中).
[文献書誌] K.Nozaki: "Rotator Phase Transition through an Intermediate State in Odd n-Alkanes : In Situ Optical Osbservation Study" Jpn.J.Appl.Phys.36. L146-149 (1997)
[文献書誌] M.Nishi: "Molecular wieght dependence of lateral growth rate of polyethylene(1)---an extended chain single crystal" Polymer. 39. 1591-1596 (1998)
[文献書誌] M.Okada: "Molecular wieght dependence of lateral growth rate of polyethylene(2)---folded chain crystals" Polymer. (印刷中). (1998)
[文献書誌] K.Nozaki: "Energy Consideration of Molecular Layer stacking in n-Alkane Crystal" J.Phys.Soc.Jpn.66. 3333-3336 (1997)
[文献書誌] J.Radhakrishnan: "Nearly pure α2 Crystals obtained by Melt Crystallization of High Tacticity isotactic Polypropylene" Polymer Communications. (印刷中).
[文献書誌] M.Nagao: "A small angle neutron scattering study of a pressure effect on structures in a ternary microemulsion system." Physic B. (印刷中).
[文献書誌] A.Toda et al.: "Kinetics of irreversible melting of polyethylene crystals revealed by Temperature Modulated DSC" Thermochimica Acta,. (印刷中).
[文献書誌] A.Toda et al.: "Melting of polymer crystals observed by Temperature Modulated DSC and its kinetic modelling" Polymer. (印刷中).
[文献書誌] A.Toda et al.: "Temperature Modulated DSC study of poly(ethylene terephthalate)crystallization II:" Polymer. 39. 1439-1443 (1998)
[文献書誌] A.Toda et al.: "A Temperature Modulated DSC study of glass transition in poly(ethylene terephthalate)" Prog.Theor.Phys.Suppl.126. 103-106 (1997)
[文献書誌] A.Toda et al.: "A new analyzing method of Temperature Modulated DSC of exo-or endothermic process : Application to polyethylene crystallization" Thermochim.Acta. 293. 47-64 (1997)
[文献書誌] A.Toda et al.: "An application of Temperature Modulated DSC to the exothermic process of poly(ethylene terephthalate)crystallization" Polymer. 38. 2849-2852 (1997)
[文献書誌] A.Toda et al.: "A new method of analyzing transformation kinetics with temperature modulated DSC : Application to polymer crystal growth" Polymer. 38. 231-233 (1997)
[文献書誌] A.Keller et al.: "Polymer crystllization : role of metastablity and the confluence of thermodynamic and kinetic factors" 124. 57-81 (1997)

1997 年度 実績報告書

高純度高分子の結晶化の分子量依存性による核生成・成長機構の実体的解明

研究代表者

彦坂 正道 広島大学, 総合科学部, 教授 (60087103)

研究成果

[文献書誌] T.Hattori: "The high-pressure crystallization behaviors and piezoeleetricity of extended chain lamellar crystals of VF trifluorocthylene copolymers with high molar content of VF." Polymer. 38. 3505-3511 (1997)

[文献書誌] S.K.Ghosh: "Phase transiton between microemulsion and lamellar phase in C12E5/water/n-octane amphilic system" J.Appl.Crystallography. (印刷中).

[文献書誌] S.K.Ghosh: "Structural Changes and interaction parameters in amphilic system C12E5/water/n-octznc" Progress Colloid and Polymer Science. 106. 91-97 (1997)

[文献書誌] S.K.Ghosh: "Structure funcitions and Interfacial curvatues in a ternary amphilic system C12E5/water/n-octznc" Progress Colloid and Polymer Science. 106. 98-103 (1997)

[文献書誌] M.Hikosaka: "Lamellar Thickening Growth of an Extended Chain Single Crystal of PE(I)---Pointers to a New Crystallization Mechanism of Polymers---" Macromolecules. 30. 2067-2074 (1997)

[文献書誌] M.Nagao: "Pressure-induced phase transition from discordered microemulsion to lamellar structure in a wter/AOT/n-decane system" Progress Colloid and Polymer Science. 106. 86-90 (1997)

[文献書誌] K.Yamada: "Isotacticity dependence of spherultic morphology of isotactic polypropylene" Polymer. (印刷中).

[文献書誌] K.Nozaki: "Rotator Phase Transition through an Intermediate State in Odd n-Alkanes : In Situ Optical Osbservation Study" Jpn.J.Appl.Phys.36. L146-149 (1997)

[文献書誌] M.Nishi: "Molecular wieght dependence of lateral growth rate of polyethylene(1)---an extended chain single crystal" Polymer. 39. 1591-1596 (1998)

[文献書誌] M.Okada: "Molecular wieght dependence of lateral growth rate of polyethylene(2)---folded chain crystals" Polymer. (印刷中). (1998)

[文献書誌] K.Nozaki: "Energy Consideration of Molecular Layer stacking in n-Alkane Crystal" J.Phys.Soc.Jpn.66. 3333-3336 (1997)

[文献書誌] J.Radhakrishnan: "Nearly pure α2 Crystals obtained by Melt Crystallization of High Tacticity isotactic Polypropylene" Polymer Communications. (印刷中).

[文献書誌] M.Nagao: "A small angle neutron scattering study of a pressure effect on structures in a ternary microemulsion system." Physic B. (印刷中).

[文献書誌] A.Toda et al.: "Kinetics of irreversible melting of polyethylene crystals revealed by Temperature Modulated DSC" Thermochimica Acta,. (印刷中).

[文献書誌] A.Toda et al.: "Melting of polymer crystals observed by Temperature Modulated DSC and its kinetic modelling" Polymer. (印刷中).

[文献書誌] A.Toda et al.: "Temperature Modulated DSC study of poly(ethylene terephthalate)crystallization II:" Polymer. 39. 1439-1443 (1998)

[文献書誌] A.Toda et al.: "A Temperature Modulated DSC study of glass transition in poly(ethylene terephthalate)" Prog.Theor.Phys.Suppl.126. 103-106 (1997)

[文献書誌] A.Toda et al.: "A new analyzing method of Temperature Modulated DSC of exo-or endothermic process : Application to polyethylene crystallization" Thermochim.Acta. 293. 47-64 (1997)

[文献書誌] A.Toda et al.: "An application of Temperature Modulated DSC to the exothermic process of poly(ethylene terephthalate)crystallization" Polymer. 38. 2849-2852 (1997)

[文献書誌] A.Toda et al.: "A new method of analyzing transformation kinetics with temperature modulated DSC : Application to polymer crystal growth" Polymer. 38. 231-233 (1997)

[文献書誌] A.Keller et al.: "Polymer crystllization : role of metastablity and the confluence of thermodynamic and kinetic factors" 124. 57-81 (1997)

1997 年度実績報告書

彦坂正道広島大学, 総合科学部, 教授 (60087103)