Clarification of Order Structure Peculiar to the Near-surface Region of Crystalline Polymer Films and Dynamics on their Structural Formation

结晶聚合物薄膜近表面区域特有的有序结构的澄清及其结构形成的动力学

• 批准号: 15550109
• 负责人: SASAKI Sono
• 金额: $ 2.37万
• 依托单位: Japan Synchrotron Radiation Research Institute (JASRI/SPring-8) (2004-2005)Kyushu University (2003)
• 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-15550109/
• 关键词: Crystallization polymer films; SR-GIXD method; SR-GISAXS method; SPring-8, the large synchrotron radiation facility; Paracrystalline lattice distortion; Lamellar stacking structure; Higher-order structure; Annealing Effect; SR-GISAXS法; 高密度ポリエチレン

We have successfully investigated chain and lamellar packing structures peculiar to crystalline polymers confined to narrow space, such as the surface and the thin film, by synchrotron grazing-incidence X-ray diffraction (SR-GIXD) and grazing-incidence small-angle X-ray scattering (SR-GISAXS) measurements. Thin films with a thickness of ca. 400 nm were prepared on silicon wafers from a p-xylene solution of high-density polyethylene (HDPE) by a dip-coating method. The dip-coated films and HDPE bulk samples were isothermally crystallized from the melt or annealed at various temperatures under nitrogen atmosphere.In order to detect Bragg diffractions from the near-surface and bulk regions of the thin films, in-plane GIXD measurements were carried out at incident angles (α_i) of X-rays smaller and lager than the critical angle (α_c) at the BL13XU beamline of SPring-8 (Hyogo, Japan). It was revealed that the lattice constants a and b of orthorhombic unit cell in the near-surface region of t … More he thin film were smaller than those in the bulk region but larger than those of the bulk samples. This implied that the unit cell especially in the interfacial region between PE and silicon was distorted during sample preparation due to large mismatching between their thermal expansion coefficients. On the other hand, pracrystalline lattice analysis for the thin films indicated that long and short-range lattice distortion was larger in the near-surface region than in the bulk region. This might be related with the surface free energy of the film and/or releasing the latent heat from the surface.SR-GISAXS measurements were carried out at α_i of X-rays smaller and lager than the α_c at the BL40B2 beamline of SPring-8. The 2D-GISAXS patterns from the films placed in a vacuum cell were detected at 300K with an imaging intensifier and a CCD detector or an imaging plate. Strong scattering in the in-plane direction near Yoneda peak were detected for all of the films. From the peak position of the scattering, it was found that the long period, the average distance between stacked crystalline lamellae, was ca.25-30 nm. From the GIXD data, it was implied that chains were relatively oriented parallel to the surface in the lamellae. Combination of GIXD and GISAXS data indicated that relatively edge-on oriented lamellae were stacked in the parallel direction to the surface. By annealing, partial melting and recrystallization might occur remarkably in the near-surface region. Less

我们已经成功地研究了限制在狭窄空间的晶体聚合物（例如表面和薄膜）的链和层状堆积结构，通过同步射剂X射线X射线衍射（SR-GIXD）和绘制绘制的小型X射线X射线散射（SR-Gisaxs）测量。薄膜的厚度为ca。从高密度聚乙烯（HDPE）的P- Xylene溶液中制备400 nm，通过浸入式涂层方法制备。 The dip-coated films and HDPE bulk samples were isothermally crystallized from the melt or annealed at various temperatures under nitrogen atmosphere.In order to detect Bragg diffractions from the near-surface and bulk regions of the thin films, in-plane GIXD measurements were carried out at incident angles (α_i) of X-rays smaller and lager than the critical angle (α_c)在Spring-8的BL13XU光束线上（日本Hyogo）。据透露，在t的近表面区域的正晶单位细胞的晶格常数A和B。他的薄膜多于散装区域的薄膜小，但比散装样品的薄膜小。这意味着，由于其热膨胀系数之间的不匹配，在样品制备过程中，在样品制备过程中尤其是在PE和硅之间的界面区域。另一方面，对薄膜的Pracrystalline晶格分析表明，近地面区域的长且短距离的晶格失真大于散装区域。这可能与膜的表面自由能和/或从表面释放潜热。SR-GISAXS测量是在Spring-8的BL40B2光束线上小于X射线和lager的X射线的α_i和lager的α_i。通过成像增强剂和CCD检测器或成像板检测到位于真空电池中的膜中的2D-GISAXS模式。对于所有薄膜，检测到在Yoneda峰附近的平面方向上的强散射。从散射的峰位置，可以发现长时间（堆叠结晶层之间的平均距离）为25-30 nm。从GixD数据中，暗示链相对平行于薄片中的表面。 GIXD和GISAXS数据的组合表明，相对边缘方向的薄片被沿平行方向堆叠到表面。通过退火，在近乎表面的区域可能会明显发生部分熔化和重结晶。较少的

项目成果

Paracrystalline lattice distortion in the near-surface region of melt-crystallized polyethylene films evaluated by synchrotron-sourced grazing-incidence X-ray diffraction

• DOI: 10.1021/ma034526q
• 发表时间: 2003-07
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Hirohiko Yakabe;S. Sasaki;O. Sakata;A. Takahara;T. Kajiyama

H.Yakabe, S.Sasaki, O.Sakata, A.Takahara, T.Kajiyama: "Paracrystalline Lattice Distortion in the Near-Surface Region of Melt-Crystallized Polyethylene Films Evaluated by Synchrotron-Sourced Grazing-Incidence X-ray Diffraction"Macromolecule. 36(16). 5905-5

H.Yakabe、S.Sasaki、O.Sakata、A.Takahara、T.Kajiyama：“通过同步加速器源掠入射 X 射线衍射评估熔融结晶聚乙烯薄膜近表面区域的准晶格畸变”高分子

Microscopic lamellar organization in high-density polyethylene banded spherulites studied by scanning probe microscopy

• DOI: 10.1016/s0032-3861(02)00158-1
• 发表时间: 2002-06-01
• 期刊: POLYMER
• 影响因子: 4.6
• 作者: Sasaki, S;Sakaki, Y;Kajiyama, T
• 通讯作者: Kajiyama, T

高分子辞典(第3版)高分子学会編

高分子科学技术学会主编《高分子词典》（第3版）

• 发表时间: 2005
• 作者: S.Sasaki;Y.Sakaki;A.Takahara;T.Kajiyama;佐々木 園(共著);Sono Sasaki (coauthor);佐々木園(共著)
• 通讯作者: 佐々木園(共著)

Crystal Structure in the Near-Surface Region of Melt-Crystallized Polyethylene Films by Grazing-Incidence X-ray Diffraction

通过掠入射 X 射线衍射研究熔融结晶聚乙烯薄膜近表面区域的晶体结构

• 发表时间: 2004
• 期刊: Trans.Mater.Res.Soc.Jpn Vol.29(1)
• 作者: H.Yakabe;S.Sasaki;O.Sakata;A.Takahara;T.Kajiyama
• 通讯作者: T.Kajiyama