非溶剂诱导聚苯乙烯超薄膜去润湿过程中不同有序表面形貌的形成

doi:10.7503/cjcu20150553

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (1): 174.doi: 10.7503/cjcu20150553

非溶剂诱导聚苯乙烯超薄膜去润湿过程中不同有序表面形貌的形成

徐林¹(), 张欢欢^2,³, 石彤非²

1. 贵州师范学院表面物理与化学实验室, 贵阳 550018
2. 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
3. 中国科学院大学, 北京 100049

收稿日期:2015-07-14 出版日期:2016-01-10 发布日期:2015-12-20
基金资助:
国家自然科学基金(批准号: 21234007, 51473168, 51503048)和国家“九七三”计划项目(批准号: 2010CB631100)资助

Morphology Evolution of Thin Polystyrene Film During the Non-solvent Driven Dewetting Process^†

XU Lin^1,^*(), ZHANG Huanhuan^2,³, SHI Tongfei^2,^*

1. Laboratory of Surface Physics and Chemistry, Guizhou Normal College, Guiyang 550018, China
2. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
3. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2015-07-14 Online:2016-01-10 Published:2015-12-20
Contact: XU Lin,SHI Tongfei E-mail:tfshi@ciac.ac.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21234007, 51473168, 51503048) and the National Basic Research Program of China(No.2010CB631100)

摘要/Abstract

摘要：

利用原子力显微镜研究了带有自然氧化层硅基底上聚苯乙烯薄膜在不同非溶剂诱导下的去润湿过程. 研究发现, 非溶剂是通过渗透取代机理诱导高分子薄膜发生去润湿. 薄膜的形貌取决于成孔过程与孔增长过程的相对速度. 当聚苯乙烯(PS)薄膜厚度为15 nm时, 随着溶剂烷基链的增长, 成孔数显著降低; 然而孔开始合并时孔径明显地增加. 当PS薄膜厚度增加到25 nm时, 随着溶剂烷基链的增长, 成孔数略有降低, 薄膜形貌形成长程有序的双连续的结构. 当PS膜厚为35 nm时, 与其它2个膜厚相比, 成孔数大幅下降. 此外, 温度和分子量能进一步降低去润湿过程中的成孔数, 从而形成分形结构形貌.

关键词: 高分子薄膜, 去润湿机理, 非溶剂诱导去润湿, 表面形貌

Abstract:

We investigated the dewetting process of thin polystyrene(PS) film induced by different non-solvents via atomic force microscope(AFM). It is found that the non-solvent induced dewetting of thin PS film is via the penetration-replacement mechanism. The morphology of thin PS film depends on the relative velocity of the hole forming process and the hole growth process. When the thickness of PS film is 15 nm, with the increase of the alkyl chain of solvents, the number of holes significantly decreased, while the size of the holes obviously increased. When the thickness of PS film increased to 25 nm, with the increase of the alkyl chain of solvents, the formation of the number of holes is slightly low and the film morphology is a long-range ordered double continuous structure. When the PS film thickness is 35 nm, the number of holes decreased significantly comparing with the other two films. In addition, temperature and molecular weight can further reduce the number of holes in the process of dewetting and form fractal morphology.

Key words: Thin polymer film, Dewetting mechanism, Non-solvent induced dewetting, Surface morphology

中图分类号:

O631

TrendMD:

徐林, 张欢欢, 石彤非. 非溶剂诱导聚苯乙烯超薄膜去润湿过程中不同有序表面形貌的形成. 高等学校化学学报, 2016, 37(1): 174.

XU Lin, ZHANG Huanhuan, SHI Tongfei. Morphology Evolution of Thin Polystyrene Film During the Non-solvent Driven Dewetting Process^†. Chem. J. Chinese Universities, 2016, 37(1): 174.

图/表 5

Scheme 1 Schematic of experimental apparatus

Fig.1 AFM height images of thin PS film(Mw=2500, h=15 nm) as a function of exposure time(ta) to methyl alcohol vapor at 35 ℃^ta/s: (A) 15; (B) 30; (C) 60; (D) 140.

Fig.2 AFM height images of thin PS film(Mw=2500) as a function of exposure time during the dewetting process induced by different solvents at 35 ℃^(A) h=15 nm, methyl alcohol, ta=60 s; (B) h=15 nm, ethyl alcohol, ta=60 s; (C) h=15 nm, n-butyl alcohol, ta=30 s; (D) h=26 nm, methyl alcohol, ta=7 min; (E) h=26 nm, ethyl alcohol, ta=5 min; (F) h=26 nm, n-butyl alcohol, ta=2.5 min; (G) h=34 nm, methyl alcohol, ta=50 min; (H) h=34 nm, ethyl alcohol, ta=20 min; (I) h=34 nm, n-butyl alcohol, ta=5 min.Inset: 2D FFT images.

Fig.3 AFM height images of PS film(Mw=2500, h=15 nm) as a function of exposure time during the dewetting process induced by different solvents at 15 ℃^ (A) Methyl alcohol, ta=60 h; (B) ethyl alcohol, ta=150 min; (C) n-butyl alcohol, ta=30 min.

Fig.4 AFM height images of PS film(Mw=5400, h=26 nm) with different exposure time during the dewetting process induced by different solvent at 35 ℃^ (A) Methyl alcohol, ta=60 h; (B) ethyl alcohol, ta=16 h; (C) n-butyl alcohol, ta=12 h.

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非溶剂诱导聚苯乙烯超薄膜去润湿过程中不同有序表面形貌的形成

Morphology Evolution of Thin Polystyrene Film During the Non-solvent Driven Dewetting Process^†

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非溶剂诱导聚苯乙烯超薄膜去润湿过程中不同有序表面形貌的形成

Morphology Evolution of Thin Polystyrene Film During the Non-solvent Driven Dewetting Process†

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Morphology Evolution of Thin Polystyrene Film During the Non-solvent Driven Dewetting Process^†