Origin of the Free Surface Effect of Polymers with Different Sizes of Side Groups

被引：0

作者：

Jiang, Zhenwei ^{[1
]}

Tian, Weihang ^{[1
]}

Weng, Wenwu ^{[1
]}

Zhan, Xiaozhi ^{[2
]}

Zhou, Xianjing ^{[1
]}

Xu, Jianquan ^{[1
]}

Zhu, Tao ^{[2
,3
,4
]}

Wang, Xinping ^{[1
]}

机构：

[1] Zhejiang Sci Tech Univ, Sch Chem & Chem Engn, Key Lab Surface & Interface Sci Polymer Mat Zhejia, Hangzhou 310018, Peoples R China

[2] Spallat Neutron Source Sci Ctr, Dongguan 523803, Peoples R China

[3] Chinese Acad Sci, Beijing Natl Lab Condensed Matter Phys, Beijing 100190, Peoples R China

[4] Chinese Acad Sci, Inst Phys, Beijing 100190, Peoples R China

来源：

MACROMOLECULES | 2024年 / 57卷 / 23期

基金：

中国国家自然科学基金;

关键词：

GLASS-TRANSITION TEMPERATURE; T-G; POLY(METHYL METHACRYLATE); MOLECULAR-WEIGHT; THIN-FILMS; RHEOLOGICAL PROPERTIES; CHAIN ENTANGLEMENT; POLYSTYRENE FILMS; FREE-VOLUME; DYNAMICS;

D O I：

10.1021/acs.macromol.4c01910

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

The free surface effect in nanoconfined polymer systems is important. Hence, understanding the influence of polymer structures on the free surface effect is essential. Herein, the dynamics of the free surface of polystyrene, poly(4-methylstyrene), and poly(4-tert-butylstyrene) with p-substituted methyl and tert-butyl groups in the benzene ring were investigated. An enhanced free surface effect was exhibited by polymers with large side groups and high fragility, which was attributed to the high free volume of the surface and the long distance for this unusual free volume to propagate into the bulk. This phenomenon was proven by deuterium oxide vapor penetration into the film surface via neutron reflectivity. High levels of packing frustration could be relieved on the free surface of fragile polymers during film formation; the chain packing efficiency on the surface was reduced, resulting in a large and broad free volume distribution on the free surface. This study provides a deep understanding of the relationship between the free surface effect and the chemical and physical properties of polymers.

引用

页码：11075 / 11084

页数：10

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