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

我们通过同步加速器掠入射 X 射线衍射 (SR-GIXD) 和掠入射小角 X 射线衍射，成功研究了局限于狭窄空间（例如表面和薄膜）的结晶聚合物特有的链状和层状堆积结构。射线散射 (SR-GISAXS) 测量在硅片上制备了约 400 nm 的薄膜。通过浸涂法将浸涂薄膜和 HDPE 块状样品从熔体中等温结晶或在氮气气氛下在不同温度下退火。对于薄膜的体区域，面内 GIXD 测量是在小于和大于临界角 (α_c) 的 X 射线入射角 (α_i) 下进行的。 SPring-8（日本兵库县）的 BL13XU 光束线表明，薄膜近表面区域的斜方晶胞的晶格常数 a 和 b 小于块体区域的晶格常数 a 和 b。这意味着在样品制备过程中，由于热膨胀系数之间的巨大不匹配，晶胞尤其是 PE 和硅之间的界面区域发生了扭曲。薄膜的准晶格分析表明，近表面区域的长程和短程晶格畸变比块体区域更大，这可能与薄膜的表面自由能和/或释放潜热有关。 SR-GISAXS 测量是在 SPring-8 的 BL40B2 光束线上的 X 射线的 α_i 处进行的，该 α_i 小于和大于 α_c。 2D-GISAXS 图案。将放置在真空室中的所有膜用成像增强器和CCD检测器或成像板在米田峰附近的面内方向上检测强散射。 ，发现长周期，即堆叠晶体片层之间的平均距离，约为 25-30 nm。根据 GIXD 数据，这表明链相对平行于表面取向。 GIXD 和 GISAXS 数据的结合表明，通过退火，相对边缘取向的片层在近表面区域可能不常见。

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