Skip to main content

Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

  • Original Article
  • Published:

Thermal stabilities of a molecularly stepped PMMA substrate prepared by thermal nanoimprinting and isolated PMMA chains deposited on it evaluated by high-temperature atomic force microscopy

Abstract

Polymer surfaces are believed to have high mobility, and the glass transition temperature (Tg) of these surfaces is significantly decreased compared to that of the bulk. In this study, we prepared a molecularly stepped poly(methyl methacrylate) (PMMA) substrate by thermally nanoimprinting a PMMA plate with an atomically stepped sapphire substrate and PMMA isolated chains deposited on it by the Langmuir-Blodgett technique. The imprinted PMMA surface with a step height of ~0.2 nm and isolated PMMA chains deposited on it could be observed at the molecular level up to the PMMA bulk Tg by in situ high-temperature atomic force microscopy, indicating that the PMMA surface and the PMMA chains deposited on it have thermal stability close to the bulk PMMA Tg and that no significant decrease in Tg was observed. The significant thermal stability of the surface of the imprinted PMMA substrate and deposited PMMA chains is unexpected and differs from the results based on our present understanding of the polymer surfaces.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. Jones RAL, Richards RW, editors. Polymers at surfaces and interfaces. New York: Cambridge University Press; 1999.

  2. Forrest JA, Dalnoki-Veress K. The grass transition in thin polymer films. Adv Colloid Int Sci. 2001;94:167–96.

    Article  CAS  Google Scholar 

  3. Ediger MD, Forrest JA. Dynamics near free surfaces and the glass transition in thin polymer films: A view to the future. Macromolecules. 2014;47:471–8.

    Article  CAS  Google Scholar 

  4. Russell TP, Chai Y. 50th Anniversary perspective: putting the squeeze on polymers: a perspective on polymer thin films and interfaces. Macromolecules. 2017;50:4597–609.

    Article  CAS  Google Scholar 

  5. Keddie JL, Jones RAL, Cory RA. Size-dependent depression of the glass transition temperature in polymer films. Europhys Lett. 1994;27:59–64.

    Article  CAS  Google Scholar 

  6. Keddie JL, Jones RAL, Cory RA. Interface and surface effects on the glass-transition temperature in thin polymer films. Faraday Discuss. 1994;98:219–30.

    Article  CAS  Google Scholar 

  7. Ellison CJ, Torkelson JM. The distribution of glass-transition temperatures in nanoscopically confined glass formers. Nat Mater. 2003;2:695–700.

    Article  CAS  Google Scholar 

  8. Inoue R, Kawashima K, Matsui K, Kanaya T, Nishide K, Matsuba G, et al. Distributions of glass-transition temperature and thermal expansivity in multilayered polystyrene thin films studies by neutron reflectivity. Phys. Rev. E 2011;83:021801-1-7.

  9. Inoue R, Nakamura M, Matsui K, Kanaya T, Nishida K, Hino M. Distribution of glass transition temperature in multilayered poly(methyl methacrylate) thin film supported on a Si substrate as studied by neutron reflectivity. Phys Rev E. 2013;88:032601.

    Article  Google Scholar 

  10. Paeng K, Ediger MD. Molecular motion in free-standing thin films of poly(methyl methacrylate), poly(4-tert-butylstyrene), poly(α-methylstyrene), and poly(2-vinylpyridine). Macromolecules. 2011;44:7031–42.

    Article  Google Scholar 

  11. Tanaka K, Takahara A, Kajiyama T. Rheological analysis of surface relaxation process of monodisperse polystyrene films. Macromolecules. 2000;33:7588–593.

    Article  CAS  Google Scholar 

  12. Fujii Y, Akabori K-I, Tanaka K, Nagamura T. Chain conformation effects on molecular motions at the surface of poly(methyl methcrylate) films. Polym J. 2007;39:928–34.

    Article  CAS  Google Scholar 

  13. Fujii Y, Nagamura T, Tanaka K. Relaxation behavior of poly(methyl methacrylate) at a water interface. J Phys Chem B. 2010;114:3457–60.

    Article  CAS  Google Scholar 

  14. Qi D, Ilton M, Forrest JA. Measuring surface and bulk relaxation in glassy polymers. Eur Phys J E. 2011;34:56.

    Article  CAS  Google Scholar 

  15. Fakhraai Z, Forrest JA. Measuring the surface dynamics of glassy polymers. Science. 2008;319:600–4.

    Article  CAS  Google Scholar 

  16. Fakhraai Z, Forrest JA. Substrate and chain size dependence of near surface dynamics of glassy polymers. Phys Rev Lett. 2008;101:096101.

    Article  Google Scholar 

  17. Paeng K, Ediger MD. Molecular motion in free-standing thin films of poly(methyl methacrylate), poly(4-tert-buylstyrene), poly(α-methylstyrene), and poly(2-vinylphyridine). Macromolecules. 2011;44:7034–42.

  18. Paeng K, Richert R, Ediger MD. Molecular mobility in supported thin films of polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) proved by dye reorientation. Soft Matter. 2012;8:819–26.

    Article  CAS  Google Scholar 

  19. Serghei A, Huth H, Schick C, Kremer F. Glassy dynamics in thin polymer layers having a free upper interface. Macromolecules. 2008;41:3636–9.

    Article  CAS  Google Scholar 

  20. Tress M, Mapesa EU, Kossack W, Kipnusu WK, Reiche M, Kremer F. Glassy dynamics in condensed isolated polymer chains. Science. 2013;341:1371–4.

    Article  CAS  Google Scholar 

  21. Liu Y, Russell TP, Samant MG, Stöht J, Brown HR, Cossy-Favre A, et al. Surface relaxations in polymers. Macromolecules. 1997;30:7768–71.

    Article  CAS  Google Scholar 

  22. Tan G, Inoue N, Funabasama T, Mita M, Okuda N, Mori J, et al. Formation of 0.3-nm-high stepped polymer surface by thermal nanoimprinting. Appl Phys Esp. 2014;7:055202.

    CAS  Google Scholar 

  23. Tan G, Nozawa Y, Funabasama T, Koyama K, Mita M, Kaneko S, et al. Atomic-scale thermal behavior of nanoimprinted 0.3-nm-high step patterns on PMMA polymer sheets. Polym J. 2016;48:225–7.

    Article  CAS  Google Scholar 

  24. Umetsu R, Kumaki J. Fabrication of a polymer molecularly flat substrate by thermal nanoimprinting and AFM observation of polymer chains deposited on it. Macromolecules. 2019;52:6555–65.

    Article  CAS  Google Scholar 

  25. Yoshimoto M, Maeda T, Ohnishi T, Koinuma H, Ishiyama O, Shinohara M, et al. Atomic-scale formation of ultrasmooth surfaces on sapphire substrates for high-quality thin-film fabrication. Appl Phys Lett. 1995;67:2615–7.

    Article  CAS  Google Scholar 

  26. McKinstry HA. Thermal expansion of clay minerals. Am Mineral. 1965;50:212–22.

    CAS  Google Scholar 

  27. Wen G, Sun Z, Shi T, Yang J, Jiang W, An L, et al. Thermodynamics of PMMA/SAN blends: application of the Sanchez-Lacombe lattice fluid theory. Macromolecules. 2001;34:6291–6.

    Article  CAS  Google Scholar 

  28. Wen G, An L. Pressure-dependent glass-transition temperatures of poly(methyl methacrylate)/poly(styrene-co-acrylonitrile) blends. J. Appl. Polym. Sci. 200;90:959–62.

Download references

Acknowledgements

We sincerely appreciate Dr. Goon Tan, Kobe University, for instruction in the nanoimprinting technique. We also thank Dr. Yoshihiro Uozu, Mr. Kazuhiko Nakagawa, Mitsubishi Chemical Corporation, for providing the PMMA plates. This work was supported by JSPS KAKENHI Grant Numbers JP15H03861, JP17K19147, JP18H02025, JP20H05201, and JP21H01993.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Jiro Kumaki.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Umetsu, R., Kumaki, J. Thermal stabilities of a molecularly stepped PMMA substrate prepared by thermal nanoimprinting and isolated PMMA chains deposited on it evaluated by high-temperature atomic force microscopy. Polym J 53, 1111–1121 (2021). https://doi.org/10.1038/s41428-021-00508-9

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/s41428-021-00508-9

Search

Quick links