Synchrotron Small-Angle X-Ray Scattering Studies on Phase Transitions in Block Copolymers and Crystalline Polymers under High Pressure

高压下嵌段共聚物和结晶聚合物相变的同步加速器小角 X 射线散射研究

• 批准号: 15350134
• 负责人: SAKURAI Shinichi
• 金额: $ 3.65万
• 依托单位: Kyoto Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15350134/
• 关键词: High Pressure; Block Copolymer; Crystalline Polymer; Phase Transition; Synchrotron; Small-Angle X-Ray Scattering; Nanostructure; ANBC-22; 圧力依存性; ミクロ相分離構造; 小角X線散乱; シンクロトロン; 配向制御; シリンダー構造; 自発的配向; 秩序-無秩序転移; 球構造; 規則性

In this study, we have focused on the following three topics :(1)Effects of High Pressure on Phase Transition Temperatures in Block Copolymers(2)Effects of High Pressure on Spontaneous Orientation of Microdomains in Block Copolymers(3)High Pressure Phase Transitions in Origomeric Block Copolymers (Low-Molecular Weight Liquid Crystalline Compound ANBC-22)For this purpose, high-brilliance X-rays from synchrotron radiation source at SPring-8 (Hyogo, Japan) were used and time-resolved two-dimensional small-angle X-ray scattering (2d-SAXS) measurements were conducted upon pressure jump. The results obtained are briefly summarized.(1)The order-disorder transition temperature (T^<ODT>) of sphere-forming block copolymers was determined by SAXS as a function of pressure. T^<ODT> was found to increase with an increase of pressure. According to the Clapeyron-Clausius equation, it can be concluded that the ODT is an endothermic transition, although DSC can hardly detect the endotherm upon the ODT. … More Therefore, we can show significance of studies of high pressure.(2)Effects of high pressure on the spontaneous ordering of cylindrical microdomains were investigated. It has been discovered in our previous study that slightly shear-oriented cylinders can spontaneously improve their orientation when the sample is further annealed even in the absence of shear flow. The degree of orientation exhibited an interesting behavior when the sample was subjected to continuous heating, such that the degree of orientation started to increase above a certain temperature T_L until temperature reached T_H, above which it turned to decrease rapidly down to zero (no appreciable orientation). As the pressure was increased, T_L decreased whereas T_H increased. Thus, T_L is found to have no relevance to the glass transition temperature. At a first glance, T_H can be taken as the T^<ODT> because not only orientation of cylinders but also cylinders themselves disappear above T^<ODT>. However, it has been found that T_H is lower than T^<ODT>, namely cylinder orientation spoiled without dissolution of cylinders. This is an interesting result which deserves a future problem.High pressure phase transitions and phase behaviors for low-molecular weight liquid crystalline compound ANBC-22 (4'-22-docosyloxy-3'-nitrobiphenyl-4-carboxylic acids) were studied. The reason of this study is to examine phase transition phenomena in this curious material which has an aspect of origomeric block copolymers. As a matter of fact, the ANBC-22 exhibits cubic (bicontinuous) phases with Ia3d and Im3m symmetries. Under the ambient pressure, the phase behavior is such that smectic C (SmC) to Im3m to Ia3d with increasing temperature. Note here that the block copolymer double gyroid structure also has the Ia3d cubic symmetry. Among interesting results by SAXS, the study of structural transformation from SmC to Im3m under 35 MPa in the range of 130〜175℃ is mentioned here. Upon the transformation, immatured Im3m appeared and this was co-existent with SmC for ca. 7℃ and gradually turned into a firm Im3m structure. It is interesting to point out here that the co-existing SmC phase displayed discontinuous change in peak position during the structural transformation (SmC to Im3m), indicating the spacing of the layered structure discontinuously changed. Less

在这项研究中，我们关注以下三个主题：（1）高压对块共聚物中相过渡温度的影响（2）高压对块共聚物中微型构中微型构的自发方向的影响（3）高压相变的高压相变于起源液体液体液体液体液体液体液体的同步（较低分子液体液体液体）的同步量，以下（使用春季-8（日本Hyogo）的源，并在压力跳跃时进行了时间分辨的二维小角度X射线散射（2D-SAXS）测量。简要汇总了所获得的结果。（1）由saxs确定球体形成块共聚物的阶顺序过渡温度（T^<odt>）作为压力的函数。发现T^<odt>随着压力的增加而增加。根据clapeyron-clausius方程，可以得出结论，ODT是一个吸热的过渡，尽管DSC几乎无法检测到ODT上的吸热。 ……更重要的是，我们可以显示出高压研究的重要性。（2）研究高压对圆柱微区圆柱体微区的赞助顺序的影响。在我们先前的研究中已经发现，即使在没有剪切流动的情况下，即使样品进一步退火，略微面向剪切的圆柱体也可以赞助其方向。当样品受到连续加热时，取向的程度表现出有趣的行为，使得方向的程度开始增加到一定温度T_L以上，直到达到T_H的温度达到T_H，而在其上方迅速下降至零（不值得注意的方向）。随着压力的增加，T_L降低，而T_H则增加。那就是发现T_L与玻璃过渡温度无关。乍一看，可以将T_H视为t^<odt>，因为不仅圆柱体的方向，而且还可以消失在t^<odt>之上。但是，已经发现T_H低于T^<odt>，即圆柱方向变质而不会溶解气缸。这是一个有趣的结果，值得将来有一个问题。对低分子量液晶晶体晶体化合物ANBC-22（4'-22-二氧基-3'-硝基苯基-4-苯基-4-羧酸）的高压相变和相行为。这项研究的原因是检查具有起源块共聚物方面的好奇物质中的相变现象。实际上，ANBC-22表现出具有IA3D和IM3M对称性的立方（双连续）相。在环境压力下，相位行为使得近晶型C（SMC）至IM3M至IA3D，并且温度升高。请注意，块共聚物双旋能结构也具有IA3D立方对称性。在SAXS的有趣结果中，此处提到了从SMC到IM3M的结构转化在35 MPa以下的研究范围为130-175℃。转换后，不成熟的IM3M出现，这与SMC共存。 7℃并逐渐变成了牢固的IM3M结构。有趣的是在这里指出，共存的SMC相在结构转换期间（SMC至IM3M）显示出不连续的变化，表明分层结构的间距不连续变化。较少的

项目成果

Micro-convection, Dissipative Structure and Pattern Formation in Polymer Blend Solutions under Temperature Gradients

温度梯度下聚合物共混溶液中的微对流、耗散结构和图案形成

• 发表时间: 2005
• 期刊: Faraday Discussions 128
• 作者: T.Nambu;Y.Yamauchi;T.Kushiro;S.Sakurai
• 通讯作者: S.Sakurai

Synchrotron Small-Angle X-ray Scattering Studies on Flow-Induced Gyroid to Cylinder Transition in an Elastomeric SBS Triblock Copolymer

弹性体 SBS 三嵌段共聚物中流动诱导陀螺仪到圆柱体转变的同步加速器小角 X 射线散射研究

• 发表时间: 2004
• 期刊: J.Macromol.Sci., Physics B43
• 作者: S.Sakurai;T.Kota;D.Isobe;S.Okamoto;K.Sakurai;T.Ono;K.Imaizumi;S.Nomura
• 通讯作者: S.Nomura

Mechanism of Thermally Induced Morphological Reorganization and Lamellar Orientation from the Herringbone Structure in Cross-Linked Polystyrene-block-polybutadiene-block-polystyrene Triblock Copolymers

• DOI: 10.1021/ma012259n
• 发表时间: 2003-02
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: S. Sakurai;S. Aida;S. Okamoto;K. Sakurai;S. Nomura

Crystallization in Microdomains of a Block Copolymer Comprising Semicrystalline Block Observed by Simultaneous Measurement of SAXS and WAXS with Hv-SALS or DSC

[0103] 通过用Hv-SALS或DSC同时测量SAXS和WAXS观察到的包含半结晶嵌段的嵌段共聚物的微区中的结晶

• 发表时间: 2004
• 期刊: J.Macromol.Sci., Physics B43
• 作者: S.Okamoto;K.Yamamoto;K.Nomura;S.Hara;I.Akiba;K.Sakurai;A.Koyama;M.Nomura;S.Sakurai
• 通讯作者: S.Sakurai

"Melt Behaviour of Block Copolymers" in "Developments in Block Copolymer Science and Technology" (edited by Ian W.Hamley)

《嵌段共聚物科学与技术的发展》中的“嵌段共聚物的熔体行为”（由 Ian W.Hamley 编辑）

• 发表时间: 2004
• 作者: S.Sakurai;S.Okamoto;K.Sakurai
• 通讯作者: K.Sakurai