高分子熔体的空间密度关联

doi:10.7503/cjcu20180626

高等学校化学学报 ›› 2018, Vol. 39 ›› Issue (12): 2693.doi: 10.7503/cjcu20180626

高分子熔体的空间密度关联

潘登^1,², 孙昭艳^1,^2,³()

1. 中国科学院长春应用化学研究所, 高分子物理与化学国家重点实验室, 长春 130022
2. 中国科学院大学, 北京 100039
3. 伊犁师范学院物理科学与技术学院, 新疆凝聚态相变与微结构实验室, 伊宁 835000

收稿日期:2018-09-10 出版日期:2018-12-03 发布日期:2018-11-05
作者简介:
联系人简介: 孙昭艳, 女, 博士, 研究员, 博士生导师, 主要从事高分子物理研究. E-mail: zysun@ciac. ac. cn
基金资助:
国家自然科学基金(批准号: 21833008, 21474111, 21790340)和中国科学院前沿科学重点研究项目(批准号: QYZDY-SSW-SLH027)资助.

Spatial Density Correlation in Polymer Melts^†

PAN Deng^1,², SUN Zhaoyan^1,^2,^3,^*()

1. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China
2. University of Chinese Academy of Sciences, Beijing 100039, China
3. Xinjiang Laboratory of Phase Transitions and Microstructures in Condensed Matters,College of Physical Science and Technology, Yili Normal University, Yining 835000, China

Received:2018-09-10 Online:2018-12-03 Published:2018-11-05
Contact: SUN Zhaoyan E-mail:zysun@ciac. ac. cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21833008, 21474111, 21790340) and the Key Research Program of Frontier Sciences, Chinese Academy of Sciences, China(No.QYZDY-SSW-SLH027).

摘要/Abstract

摘要：

利用分子动力学模拟方法, 以不同链结构的高分子熔体为对象, 研究了高分子熔体的空间密度关联. 链节的局域结构性质通过Voronoi分割方法得到. 结果表明, 链端链节的平均局域体积更大, 运动能力也更强; 不同构造及链不同部位链节的局域体积大小具有统一的分布规律, 表明在链节尺度上, 熔体具有相似的无定形结构. 通过局域体积来划分疏堆积和密堆积链节, 2种链节均倾向于形成团簇. 疏堆积链节形成的团簇更大, 并且团簇大小的温度依赖性也更显著. 模拟结果表明疏堆积链节的空间关联更强.

关键词: 空间密度关联, 高分子玻璃前体, 分子动力学模拟

Abstract:

The spatial density correlation in glass-forming polymer melt with different chain architectures was investigated using molecular dynamics simulation. The local environment of each bead was identified. Using the Voronoi construction, the results indicate that the chain ends have more local volume in the average level and the mobility of chain ends is higher. Moreover, the distributions of local volume become narrow when decreasing temperature and the rescaled distributions follow a master curve, implying that the melts have qualitatively similar amorphous structure for different chain architectures. The loosely and densely packed particles were identified according to their local volume. Both loosely and densely packed particles tend to form clusters, and the loosely packed particles was larger than that by densely packed particles. The simulation results demonstrate the spatial correlation of loosely packed particles is stronger, which might help to understand the glass forming behavior of polymer melts.

Key words: Spatial density correlation, Glass-forming polymer melt, Molecular dynamics simulation

中图分类号:

O641
O631

TrendMD:

潘登, 孙昭艳. 高分子熔体的空间密度关联. 高等学校化学学报, 2018, 39(12): 2693.

PAN Deng,SUN Zhaoyan. Spatial Density Correlation in Polymer Melts^†. Chem. J. Chinese Universities, 2018, 39(12): 2693.

图/表 8

Fig.1 Schematic picture of polymers with different chain architectureGreen beads represent the branched points. The total number of beads in each chain is 22. There are 7 beads in each arm of the star polymer(3-Arm star). The H-shaped polymer(H-shape) consists of five identical linear polymer chains with lengths 4 and 2 branched beads.

Fig.2 Coherent intermediate scattering functions at q*=7.15 for different T of the star polymer(A) and the α relaxation time of different polymer architectures(the solid lines are the VFT fitting curves)(B)

Table 1 VFT fitting parameters

Architecture	D	T₀
Ring	4.64	0.301
Linear	4.50	0.309
3-Arm star	4.53	0.310
H-shape	4.42	0.314

Fig.3 Mean squared displacement of all beads, chain ends and branched beads of H-shaped polymer melts at T=0.48

Fig.4 Distribution of Voronoi cell volumes of branched beads, all beads and chain ends of H-shaped polymer melts at T=0.48

Fig.5 Temperature dependence of the mean Voronoi cell volumes of chain ends(A), ordinary beads(B) and branched beads(C)

Fig.6 Distribution of Voronoi cell volumes of star polymer at different temperature(A) and rescaled distribution of Voronoi cell volumes of all beads, chain ends and branched beads at all state points(B)

Fig.7 Temperature dependence of the number averaged cluster size which consists of beads with large Voronoi cell volume, i. e., loosely packed particles(A) and beads with small Voronoi cell volume, i. e., densely packed particles(B)a. Ring; b. linear; c. 3-Arm star; d. H-shape.

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高分子熔体的空间密度关联

Spatial Density Correlation in Polymer Melts^†

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高分子熔体的空间密度关联

Spatial Density Correlation in Polymer Melts†

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Spatial Density Correlation in Polymer Melts^†