Glass transition of polymer-molecular liquid mixtures studied by broadband dielectric spectroscopy

通过宽带介电谱研究聚合物分子液体混合物的玻璃化转变

• 批准号: 15540396
• 负责人: SHINYASHIKI Naoki
• 金额: $ 2.37万
• 依托单位: Tokai University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15540396/
• 关键词: Broadband; Dielectric spectroscopy; Polymer; Molecular liquid; Alcohol; Solution; Glass transition; Relaxation

In order to make clear the dynamics of polymer and molecular liquid in polymer solutions, broadband dielectric spectroscopy of the mixtures with polar polymer and solvent were measured in the frequency range of 30 GHz - 1μHz.1. Dielectric relaxation of PVP-alcohol mixturesBDS measurements were carried out for poly(vinyl pyrrolidone)(PVP)-alcohol mixtures with mono- and poly-hydroxyl alcohols at 25℃. The dielectric relaxation processes due to the molecular motions of alcohol and local chain motion PVP were observed in the frequency ranges of 2 GHz - 100 MHz and 10 MHz - 10 kHz, respectively. The relaxation times of mono-hydroxyl alcohols were determined by the density of hydrogen-bond, ρ_<HB>. On the other hand, the relaxation times of poly-hydroxyl alcohols were not determined by ρ_<HB>. These results imply that the mechanism which determines the relaxation time of mono-hydroxyl alcohols is different from that of the poly-hydroxyl alcohols. The relaxation time of PVP increases with the PVP concentration, since the increase of the interactions among the polymer chain makes the relaxation time larger. The relaxation time at the infinite dilution of PVP is proportional to the viscosity of poly-alcohol and proportional to 1.3 powers of that of mono-alcohols.2. Dielectric relaxation of EGO-water mixtures on liquid to glassBDS measurements of 65 wt% ethylene glycol oligomer (EGO)-water mixtures for various repeat units of EGO were carried out in the frequency range of 10 mHz - 10 GHz in the temperature range of 128 - 298K. According to these experimental results, the shape of dielectric loss peak observed in the liquid state is related to the cooperativity between water and EGO molecules and the separation scenario of the α- and β-processes in low temperature range close to the glass transition temperature.

为了明确聚合物溶液中聚合物和分子液体的动力学行为，在30 GHz～1μHz频率范围内测量了极性聚合物和溶剂混合物的宽带介电谱。1． PVP-醇混合物的介电弛豫在25℃下对聚(乙烯基吡咯烷酮)(PVP)-醇混合物与一元醇和多元醇进行BDS测量。分别在 2 GHz - 100 MHz 和 10 MHz - 10 kHz 频率范围内观察到由于醇分子运动和局部链运动 PVP 引起的介电弛豫过程。一元醇的弛豫时间由氢键密度ρ_<HB>确定。另一方面，多元醇的弛豫时间不是由ρ_<HB>决定的。这些结果表明，决定一元醇弛豫时间的机制与多元醇不同。 PVP的弛豫时间随着PVP浓度的增加而增加，因为聚合物链间相互作用的增加使得弛豫时间变大。 PVP无限稀释时的弛豫时间与多元醇的粘度成正比，与一元醇的粘度的1.3次方成正比。 2． EGO-水混合物在液体到玻璃上的介电弛豫在 10 mHz - 10 GHz 的频率范围内，在 128 - 298K 的温度范围内，对 65 wt% 乙二醇低聚物 (EGO)-水混合物的各种 EGO 重复单元进行了 BDS 测量。根据这些实验结果，在液态下观察到的介电损耗峰的形状与水和EGO分子之间的协同作用以及接近玻璃化转变温度的低温范围内α-和β-过程的分离情况有关。

项目成果

Dielectric study of the α and β processes in supercooled ethylene glycol oligomer–water mixtures

• DOI: 10.1063/1.1796232
• 发表时间: 2004-10
• 期刊: Journal of Chemical Physics
• 影响因子: 4.4
• 作者: S. Sudo;S. Tsubotani;Mayumi Shimomura;N. Shinyashiki;S. Yagihara

S.Tsubotani: "Broadband dielectric study on dynamics of Poly (vinyl pyrrolidone)- Poly (ethylene glycol)blend"Proceedings of The 3^<rd> International Symposium on Slow Dynamics in Complex Systems (AIP conference proceedings). 印刷中.

S. Tsubotani：“聚（乙烯基吡咯烷酮）-聚（乙二醇）混合物动力学的宽带介电研究”第三届复杂系统慢动力学国际研讨会论文集（AIP 会议论文集）。

Broadband Dielectric Study on Alpha- and Beta-Process for Poly (Ethylene Glycol)-Water Mixtures

聚乙二醇-水混合物的α和β过程的宽带介电研究

• 发表时间: 2004
• 期刊: AIP conference proceedings 708
• 作者: S.Yagihara;M.Oyama;N.Shinyashiki;S.Yagihara;S.Yagihara;S.Yagihara;Shin Yagihara;Kazuya Furusawa;八木原 晋;S.Sudo;S.Sudo;S.Tsubotani;N.Shinyashiki;D.Imoto;S.Yagihara;S.Sudo;S.Sudo;S.Tsubotani;D.Imoto;S.Sudo;N.Shinyashiki
• 通讯作者: N.Shinyashiki

Structural and kinetic modification of aqueous hydroxypropyl- methylcellulose (HPMC) induced by electron beam irradiation

电子束辐照诱导的水性羟丙基甲基纤维素（HPMC）的结构和动力学改性

• 发表时间: 2005
• 期刊: Physica A 353
• 作者: S.Sudo;S.Sudo;M.Shinohara;N.Shinyashiki;S.Sudo;N.Shinyashiki;K.Furusawa;S.Yagihara;K.Furusawa
• 通讯作者: K.Furusawa

Dynamics of Water Structure in Biological System and Broadband Dielectric Spectroscopy

生物系统中水结构的动力学与宽带介电谱

• 发表时间: 2004
• 期刊: SEIBUTSU BUTSURI 44-1
• 作者: S.Sudo;S.Sudo;M.Shinohara;N.Shinyashiki;S.Sudo;N.Shinyashiki;K.Furusawa;S.Yagihara;K.Furusawa;S.Yagihara;K.Furusawa;八木原 晋;S.Sudo;N.Shinyashiki;S.Tsubotani;D.Imoto;S.Sudo;S.Yagihara
• 通讯作者: S.Yagihara