纳米限域效应下聚合物薄膜力学性能的研究

肖雨寒; 柏培; 郭云龙

doi:10.14028/j.cnki.1003-3726.2024.24.211

您当前的位置：

首页 >

文章列表页 >

纳米限域效应下聚合物薄膜力学性能的研究

专论 | 更新时间：2025-01-23

- 纳米限域效应下聚合物薄膜力学性能的研究
- Studies on Mechanical Properties of Polymer Films under Nanoconfinement Effect
- 高分子通报 2025年38卷第2期页码：183-193
- 作者机构：
  
  上海交通大学密西根学院，上海 200240
- 作者简介：
  
  *郭云龙，E-mail: yunlong.guo@sjtu.edu.cn
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2024.24.211
  中图分类号：
- 收稿日期：2024-07-19，
  
  录用日期：2024-09-25，
  
  网络出版日期：2024-11-07，
  
  纸质出版日期：2025-02-20
- 稿件说明：
移动端阅览
肖雨寒, 柏培, 郭云龙. 纳米限域效应下聚合物薄膜力学性能的研究. 高分子通报, 2025, 38(2), 183–193.

Xiao, Y. H.; Bai, P.; Guo, Y. L. Studies on mechanical properties of polymer films under nanoconfinement effect. Polym. Bull. (in Chinese), 2025, 38(2), 183–193.
肖雨寒, 柏培, 郭云龙. 纳米限域效应下聚合物薄膜力学性能的研究. 高分子通报, 2025, 38(2), 183–193. DOI： 10.14028/j.cnki.1003-3726.2024.24.211.

Xiao, Y. H.; Bai, P.; Guo, Y. L. Studies on mechanical properties of polymer films under nanoconfinement effect. Polym. Bull. (in Chinese), 2025, 38(2), 183–193. DOI： 10.14028/j.cnki.1003-3726.2024.24.211.

摘要

准确掌握纳米尺度下聚合物的力学性能，对于其在纳米器件中作为功能材料或在微纳加工中作为结构模板等应用至关重要。研究发现，纳米限域作用下的聚合物力学性能相较于本体材料存在显著差异。传统测试仪器无法适用于纳米级聚合物材料，因此全面掌握纳米限域下的复杂黏弹性力学及其作用机理存在不小的挑战。近年来，我们通过搭建一套压力和温度可控的基于气压作用和高速摄影的力学测试系统，实现了对自支撑高分子纳米薄膜力学性能的直接观测。运用此系统，我们对100 nm以下厚度的橡胶弹性体和热塑性薄膜在受限于空气或聚合物界面时的力学性能(包括弹性、黏弹性和黏塑性等)进行了较深入的研究，结果揭示了纳米限域下聚合物薄膜力学性能的一些新奇特征。本专论文章简要综述了高分子纳米限域黏弹性力学领域的研究现状和最新成果，并展望了其未来发展趋势。

Abstract

Accurate comprehension of the mechanical properties of polymers at the nanoscale is essential for their application as functional materials or structural templates in nanodevices. Previous research has identified significant disparities in the mechanical properties of nanoscale polymers compared to bulk materials due to the nanoconfinement effect. However

conventional commercial testing instruments are often inadequate for evaluating nanoscale polymer materials

which poses a considerable challenge to fu

lly grasp the complex viscoelastic mechanics and its underlying mechanism under nanoconfinement. In recent years

we have realized the direct observation of the mechanical properties of supported polymer nanofilms by constructing a pressure- and temperature-controllable mechanical testing system based on pneumatic pressure action and high-speed photography. Using this system

the authors’ group has conducted a deeper study of the mechanical properties (including elasticity

viscoelasticity

and viscoplasticity

etc.

) of both rubber elastomers and thermoplastic films with thicknesses of less than 100 nm when confined to the air or polymer interface. The results reveal novel features of the mechanical properties of polymer films under the nanoconfinement effect. This monograph article briefly summarizes the current research status and recent results in the field of viscoelastic properties of the nanoconfined polymers and looks forward to the future development trend.

关键词

Keywords

references

Jones, R. A. L . Glasses with liquid-like surfaces . Nat. Mater. , 2003 , 2 , 645 − 646 .

Xu, J. ; Wang, S. H. ; Wang, G. J N. ; Zhu, C. X. ; Luo, S. C. ; Jin, L. H. ; Gu, X. D. ; Chen, S. C. ; Feig, V. R. ; To, J. W. F. ; Rondeau-Gagné, S. ; Park, J. ; Schroeder, B. C. ; Lu, C. E. ; Oh, J. Y. ; Wang, Y. M. ; Kim, Y. H. ; Yan, H. ; Sinclair, R. ; Zhou, D. S. ; Xue, G. ; Murmann, B. ; Linder, C. ; Cai, W. ; Tok, J. B. H. ; Chung, J. W. ; Bao, Z. N . Highly stretchable polymer semiconductor films through the nanoconfinement effect . Science , 2017 , 355 ( 6320 ), 59 − 64 .

Zhao, C. ; Zhang, P. ; Zhou, J. ; Qi, S. ; Yamauchi, Y. ; Shi, R. ; Fang, R. ; Ishida, Y. ; Wang, S. ; Tomsia, A. P . Layered nanocomposites by shear-flow-induced alignment of nanosheets . Nature , 2020 , 580 ( 7802 ), 210 − 215 .

Tavakkoli K G, A. ; Gotrik, K. W. ; Hannon, A. F. ; Alexander-Katz, A. ; Ross, C. A. ; Berggren, K. K . Templating three-dimensional self-assembled structures in bilayer block copolymer films . Science , 2012 , 336 ( 6086 ), 1294 − 1298 .

Keddie, J. L. ; Jones, R. A. L. ; Cory, R. A . Size-dependent depression of the glass transition temperature in polymer films . Europhys. Lett. , 1994 , 27 ( 1 ), 59 − 64 .

Stafford, C. M. ; Harrison, C. ; Beers, K. L. ; Karim, A. ; Amis, E. J. ; VanLandingham, M. R. ; Kim, H. C. ; Volksen, W. ; Miller, R. D. ; Simonyi, E. E . A buckling-based metrology for measuring the elastic moduli of polymeric thin films . Nat. Mater. , 2004 , 3 ( 8 ), 545 − 550 .

Liu, Y. J. ; Chen, Y. C. ; Hutchens, S. ; Lawrence, J. ; Emrick, T. ; Crosby, A. J . Directly measuring the complete stress-strain response of ultrathin polymer films . Macromolecules , 2015 , 48 ( 18 ), 6534 − 6540 .

Huang, J. S. ; Juszkiewicz, M. ; de Jeu, W. H. ; Cerda, E. ; Emrick, T. ; Menon, N. ; Russell, T. P . Capillary wrinkling of floating thin polymer films . Science , 2007 , 317 ( 5838 ), 650 − 653 .

O’Connell, P. A. ; McKenna, G. B . Rheological measurements of the thermoviscoelastic response of ultrathin polymer films . Science , 2005 , 307 ( 5716 ), 1760 − 1763 .

Chang, J. ; Toga, K. B. ; Paulsen, J. D. ; Menon, N. ; Russell, T. P . Thickness dependence of the Young's modulus of polymer thin films . Macromolecules , 2018 , 51 ( 17 ), 6764 − 6770 .

Lee, J. H. ; Chung, J. Y. ; Stafford, C. M . Effect of confinement on stiffness and fracture of thin amorphous polymer films . ACS Macro Lett. , 2012 , 1 ( 1 ), 122 − 126 .

Stafford, C. M. ; Vogt, B. D. ; Harrison, C. ; Julthongpiput, D. ; Huang, R . Elastic moduli of ultrathin amorphous polymer films . Macromolecules , 2006 , 39 ( 15 ), 5095 − 5099 .

Yoon, H. ; McKenna, G. B . “Rubbery stiffening” and rupture behavior of freely standing nanometric thin PIB films . Macromolecules , 2017 , 50 ( 24 ), 9821 − 9830 .

Song, R. Q. ; Schrickx, H. ; Balar, N. ; Siddika, S. ; Sheikh, N. ; O’Connor, B. T . Unveiling the stress-strain behavior of conjugated polymer thin films for stretchable device applications . Macromolecules , 2020 , 53 ( 6 ), 1988 − 1997 .

O’Connell, P. A. ; Hutcheson, S. A. ; McKenna, G. B . Creep behavior of ultra-thin polymer films . J. Polym. Sci. Part B Polym. Phys. , 2008 , 46 ( 18 ), 1952 − 1965 .

O’Connell, P. A. ; Wang, J. ; Ishola, T. A. ; McKenna, G. B . Exceptional property changes in ultrathin films of polycarbonate: glass temperature, rubbery stiffening, and flow . Macromolecules , 2012 , 45 ( 5 ), 2453 − 2459 .

Bay, R. K. ; Crosby, A. J . Uniaxial extension of ultrathin freestanding polymer films . ACS Macro Lett. , 2019 , 8 ( 9 ), 1080 − 1085 .

Galuska, L. A. ; Muckley, E. S. ; Cao, Z. Q. ; Ehlenberg, D. F. ; Qian, Z. Y. ; Zhang, S. ; Rondeau-Gagné, S. ; Phan, M. D. ; Ankner, J. F. ; Ivanov, I. N. ; Gu, X. D . Smart transfer method to directly compare the mechanical response of water-supported and free-standing ultrathin polymeric films . Nat. Commun. , 2021 , 12 ( 1 ), 2347 .

Chung, P. C. ; Glynos, E. ; Green, P. F . The elastic mechanical response of supported thin polymer films . Langmuir , 2014 , 30 ( 50 ), 15200 − 15205 .

Oommen, B. ; Van Vliet, K. J . Effects of nanoscale thickness and elastic nonlinearity on measured mechanical properties of polymeric films . Thin Solid Films , 2006 , 513 ( 1-2 ), 235 − 242 .

Li, L. ; Encarnacao, L. M. ; Brown, K. A . Polymer nanomechanics: separating the size effect from the substrate effect in nanoindentation . Appl. Phys. Lett. , 2017 , 110 ( 4 ), 043105 .

Chung, P. C. ; Glynos, E. ; Sakellariou, G. ; Green, P. F . Elastic mechanical response of thin supported star-shaped polymer films . ACS Macro Lett. , 2016 , 5 ( 4 ), 439 − 443 .

Wang, J. H. ; McKenna, G. B . Viscoelastic and glass transition properties of ultrathin polystyrene films by dewetting from liquid glycerol . Macromolecules , 2013 , 46 ( 6 ), 2485 − 2495 .

Yiu, P. M. ; Yuan, H. L. ; Gu, Q. ; Gao, P. ; Tsui, O. K. C . Strain rate and thickness dependences of elastic modulus of free-standing polymer nanometer films . ACS Macro Lett. , 2020 , 9 ( 11 ), 1521 − 1526 .

Bai, P. ; Xiao, Y. H. ; Yang, W. Q. ; Duan, M. B. ; Guo, Y. L . A micro-vibration apparatus for dynamic mechanical analysis of ultrathin polymer films . Rev. Sci. Instrum. , 2021 , 92 ( 10 ), 103904 .

Xiao, Y. H. ; Bai, P. ; Zhang, Z. Y. ; Guo, Y. L . Direct measurement and modeling of viscoelastic-viscoplastic properties of freely standing thin polystyrene films . J. Chem. Phys. , 2023 , 159 ( 21 ), 214903 .

Bai, P. ; Ma, M. C. ; Sui, L. ; Guo, Y. L . Nanoconfinement controls mechanical properties of elastomeric thin films . J. Phys. Chem. Lett. , 2021 , 12 ( 33 ), 8072 − 8079 .

Zhang, Z. Y. ; Bai, P. ; Xiao, Y. H. ; Guo, Y. L. ; Wang, Y. M . Conformation-Induced stiffening effect of crosslinked polymer thin films . Commun. Phys. , 2023 , 6 , 332 .

Schapery, R. A . On the characterization of nonlinear viscoelastic materials . Polym. Eng. Sci. , 1969 , 9 ( 4 ), 295 − 310 .

Perzyna, P . Fundamental problems in viscoplasticity . Adv. Appl. Mech. , 1966 , 9 , 243 − 377 .

Ngai, K. L. ; Prevosto, D. ; Grassia, L . Viscoelasticity of nanobubble-inflated ultrathin polymer films: justification by the coupling model . J. Polym. Sci. Part B Polym. Phys. , 2013 , 51 ( 3 ), 214 − 224 .

Hohlfelder, R. J . Bulge and blister testing of thin films and their interfaces . Ph.D. Thesis , Stanford University , Stanford, California, USA , 1999 .

Lin, P . The in-situ measurement of mechanical properties of multi-layer coatings . Ph.D. Thesis , Massachusetts Institute of Technology , Cambridge, MA, USA , 1990 .

Paeng, K. ; Swallen, S. F. ; Ediger, M . Direct measurement of molecular motion in freestanding polystyrene thin films . J. Am. Chem. Soc . 2011 , 133 ( 22 ), 8444 − 8447 .

Baglay, R. R. ; Roth, C. B . Local glass transition temperature T g ( z ) of polystyrene next to different polymers: hard vs . soft confinement . J. Chem. Phys. , 2017 , 146 ( 20 ), 203307 .

Kasavan, B. L. ; Baglay, R. R. ; Roth, C. B . Local glass transition temperature T g ( z ) profile in polystyrene next to polybutadiene with and without plasticization effects . Macromol. Chem. Phys. , 2018 , 219 ( 3 ), 1700328 .

Gagnon, Y. J. ; Roth, C. B . Local glass transition temperature T g ( z ) within polystyrene is strongly impacted by the modulus of the neighboring PDMS domain . ACS Macro Lett. , 2020 , 9 ( 11 ), 1625 − 1631 .

Gagnon, Y. J. ; Burton, J. C. ; Roth, C. B . Development of broad modulus profile upon polymer-polymer interface formation between immiscible glassy-rubbery domains . Proc. Natl. Acad. Sci. USA , 2024 , 121 ( 1 ), e2312533120 .

Xiao, Y. H. ; Bai, P. ; Guo, Y. L . Modulus alteration of thin polystyrene films by their neighboring PDMS: soft and hard confinement . J. Chem. Phys. , 2024 , 160 ( 21 ), 211105 .

Zuo, B. ; Liu, Y. J. ; Wang, L. ; Zhu, Y. M. ; Wang, Y. F. ; Wang, X. P . Depth profile of the segmental dynamics at a poly(methyl methacrylate) film surface . Soft Matter , 2013 , 9 ( 39 ), 9376 − 9384 .

Yuan, H. L. ; Yan, J. S. ; Gao, P. ; Kumar, S. K. ; Tsui, O. K. C . Microscale mobile surface double layer in a glassy polymer . Sci. Adv. , 2022 , 8 ( 45 ), eabq5295 .

浏览量

104

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

支化高分子熔体流变本构模型的研究进展

氧化石墨烯改性聚乙烯醇缩丁醛透明高分子薄膜研究

聚对苯二甲酸-己二酸丁二酯/聚3-羟基丁酸酯4-羟基丁酸酯共混材料的制备及性能表征

PHB与PHBV的β晶结构及其与力学和降解性能关系的研究进展