Direct Observation of Early-Stage Polymer Crystallization Driven by Surface Wrinkling and Compressive Stress in Thin Films

Peng Zhang; Stephan V. Roth; Peter Müller-Buschbaum; Tian-Bai He

doi:10.1007/s10118-025-3264-3

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Direct Observation of Early-Stage Polymer Crystallization Driven by Surface Wrinkling and Compressive Stress in Thin Films

RESEARCH ARTICLE | Updated：2025-01-23

- Direct Observation of Early-Stage Polymer Crystallization Driven by Surface Wrinkling and Compressive Stress in Thin Films
- Chinese Journal of Polymer Science Vol. 43, Issue 2, Pages: 360-367(2025)
- Affiliations：
  
  a.School of Materials Science and Engineering, Key Laboratory for Polymeric Composite and Functional Materials of Ministry of Education, Institute of Green Chemistry and Molecular Engineering, Sun Yat-sen University, Guangzhou 510275, China
  b.Deutsches Elektronen-Synchrotron (DESY), Notkestrasse 85, 22607 Hamburg, Germany
  c.Department of Fibre and Polymer Technology, KTH Royal Institute of Technology, Teknikringen 56–58, Stockholm SE-100 44, Sweden
  d.Technical University of Munich, TUM School of Natural Sciences, Department of Physics, Chair for Functional Materials, James-Franck-Str. 1, Garching 85748, Germany
  e.Heinz Maier-Leibnitz-Zentrum (MLZ), Technical University of Munich, Lichtenbergstr. 1, Garching 85748, Germany
  f.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Graduate University of Chinese Academy of Sciences, Chinese Academy of Sciences, Changchun 130022, China
- Author bio：
  
  zhangpeng3@mail.sysu.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3264-3
  CLC：
- Received：19 August 2024，
  
  Revised：2024-10-19，
  
  Accepted：11 November 2024，
  
  Online First：18 January 2025，
  
  Published：01 February 2025
- Accepted：
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Zhang, P.; Roth, S. V.; Müller-Buschbaum, P.; He, T. B. Direct observation of early-stage polymer crystallization driven by surface wrinkling and compressive stress in thin films. Chinese J. Polym. Sci. 2025, 43, 360–367

Peng Zhang, Stephan V. Roth, Peter Müller-Buschbaum, et al. Direct Observation of Early-Stage Polymer Crystallization Driven by Surface Wrinkling and Compressive Stress in Thin Films[J]. Chinese Journal of Polymer Science, 2025, 43(2): 360-367.
Zhang, P.; Roth, S. V.; Müller-Buschbaum, P.; He, T. B. Direct observation of early-stage polymer crystallization driven by surface wrinkling and compressive stress in thin films. Chinese J. Polym. Sci. 2025, 43, 360–367 DOI： 10.1007/s10118-025-3264-3.

Peng Zhang, Stephan V. Roth, Peter Müller-Buschbaum, et al. Direct Observation of Early-Stage Polymer Crystallization Driven by Surface Wrinkling and Compressive Stress in Thin Films[J]. Chinese Journal of Polymer Science, 2025, 43(2): 360-367. DOI： 10.1007/s10118-025-3264-3.

摘要

Surface wrinkling precedes nucleation and crystal growth in the semicrystalline deblock copolymer thin film

as demonstrated for the first time by in situ atomic force microscopy and synchrotron radiation X-ray scattering data.

Abstract

The early stages of crystallization and occurrence of surface wrinkling were investigated using poly(butadiene)-block-poly(

-caprolactone) with an ordered lamellar structure. Direct evidence has demonstrated that surface wrinkling precedes nucleation and crystal growth. This study examined the relationship between surface wrinkling

nucleation

and the formation of crystalline supramolecular structures using atomic force microscopy (AFM) and X-ray scattering measurements. Surface wrinkling is attributed to curving induced by accumulated stresses

including residual stress from the sample preparation and thermal stress during cooling. These stresses cause large-scale material flow and corresponding changes in the molecular conformations

potentially reducing the nucleation barrier. This hypothesis is supported by the rapid crystal growth observed following the spread of surface wrinkles. Additionally

the surface curving of the polymer thin film creates local minima of the free energy

facilitating nucleation. The nuclei subsequently grow into crystalline supramolecular structures by incorporating polymer molecules from the melt. This mechanism highlights the role of localized structural inhomogeneity in the early stages of crystallization and provides new insights into structure formation processes.

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references

Sheng, J. F.; Chen, W.; Cui, K. P.; Li, L. B. Polymer crystallization under external flow. Rep. Prog. Phys. 2022 , 85 , 036601..

Liu, Y. X.; Chen, E. Q. Polymer crystallization of ultrathinfilms on solid substrates. Coordin. Chem. Rev. 2010 , 254 , 1011−1037..

Yue, K.; Liu, G.; Feng, X.; Li, L.; Lotz, B.; Cheng, S. Z. D. A few rediscovered and challenging topics in polymer crystals and crystallization. Polym. Cryst. 2018 , 1 , e10053..

Hu, W. B. Polymer features in crystallizat ion. Chinese J. Polym. Sci. 2022 , 40 , 545−555..

Ungar, G.; Zeng, K. B. Learning polymer crystallization with the aid of linear, branched and cyclic model compounds. Chem. Rev. 2001 , 101 , 4157−4188..

Zhang, M. C.; Guo, B. H.; Xu, J. A review on polymer crystallization theories. Crystals 2017 , 7 , 1−37..

Ming, Y.; Hao, T.; Zhou, Z.; Zhang, S.; Nie, Y. Study on the crystallization behavior of polymer thin films with a substrate by computer simulation. Cryst. Growth Des. 2023 , 23 , 7653−7661..

Carvalho, J. L.; Dalnoki-Veress, K. Homogeneous bulk, surface, and edge nucleation in crystalline nanodroplets. Phys. Rev. Lett. 2010 , 105 , 237801..

Löhmann, A. K.; Henze, T.; Thurn-Albrecht, T. Direct observation of prefreezing at the interface melt–solid in polymer crystallization. Proc. Natl. Acad. Sci. U. S. A. 2014 , 111 , 17368−17372..

Frank, C. W.; Rao, V.; Despotopoulou, M. M.; Pease, R. F. W.; Hinsberg, W. D.; Miller, R. D.; Rabolt, J. F. Structure in thin and ultrathin spin-cast polymer films. Science 1996 , 273 , 912−915..

Reiter, G. Some unique features of polymer crystallisation. Chem. Soc. Rev. 2014 , 43 , 2055−2065..

Luo, C.; Sommer, J. U. Frozen topology: entanglements control nucleation and crystallization in polymers. Phys. Rev. Lett. 2014 , 112 , 195702..

Chandran, S.; Reiter, G. Transient cooperative processes in dewetting polymer melts. Phys. Rev. Lett. 2016 , 116 , 088301..

Gránásy, L.; Tóth, G. I. Colloidal suspense. Nat. Phys. 2014 , 10 , 12−13..

Li, M.; Chen, Y.; Tanaka, H.; Tan, P. Revealing roles of competing local structural orderings in crystallization of polymorphic systems. Sci. Adv. 2020 , 6 , 1−9..

Lupulescu, A. I.; Rimer, J. D. In situ imaging of silicalite-1 surface growth reveals the mechanism of crystallization. Science 2014, 344 , 729-732..

Baumgartner, J.; Dey, A.; Bomans, P. H. H.; Le Coadou, C.; Fratzl, P.; Sommerdijk, N. A. J. M.; Faivre, D. Nucleation and growth of magnetite from solution. Nat. Mater. 2013 , 12 , 310−314..

Green, P. F.; Limary, R. Block copolymer thin films: pattern formation and phase behavior. Adv. Colloid Interface Sci. 2001 , 94 , 53−81..

Zhang, P.; Huang, H.; He, T.; Hu, Z. Long-range ordered crystallization structure in the micromolded diblock copolymer thin film. ACS Macro Lett. 2012 , 1 , 1007−1011..

Zhang, P.; Wang, Z.; Huang, H.; He, T. Direct observation of the relief structure formation in the nearly symmetric poly(styrene)-block-poly( ε -caprolactone) diblock copolymer thin film. Macromolecules 2012 , 45 , 9139−9146..

Nojima, S.; Kato, K.; Yamamoto, S.; Ashida, T. Crystallization of block copolymers. 1. Small-angle X-ray scattering study of a .jpgilon.-caprolactone-butadiene diblock copolymer. Macromolecules 1992 , 25 , 2237−2242..

Yang, Y.; Tian, H.; Napolitano, S.; Zuo, B. Crystallization in thin films of polymer glasses: the role of free surfaces, solid interfaces and their competition. Prog. Polym. Sci. 2023 , 144 , 101725..

Michell, R. M.; Müller, A. J. Confined crystallization of polymeric materials. Prog. Polym. Sci. 2016 , 54−55 , 183−213..

Horcas, I.; Fernández, R.; Gómez-Rodríguez, J. M.; Colchero, J.; Gómez-Herrero, J.; Baro, A. M. WSXM: A software for scanning probe microscopy and a tool for nanotechnology. Rev. Sci. Instrum. 2007 , 78 , 013705..

Buffet, A.; Rothkirch, A.; Döhrmann, R.; Körstgens, V.; Kashem, M. M. A.; Perlich, J.; Herzog, G.; Schwartzkopf, M.; Gehrke, R.; Müller-Buschbaum, P.; Roth, S. V. P03, the microfocus and nanofocus X-ray scattering (MiNaXS) beamline of the PETRA III storage ring: the microfocus endstation. J. Synchrotron. Radiat. 2012 , 19 , 647−653..

Benecke, G.; Wagermaier, W.; Li, C. H.; Schwartzkopf, M.; Flucke, G.; Hoerth, R.; Zizak, I.; Burghammer, M.; Metwalli, E.; Müller-Buschbaum, P.; Trebbin, M.; Förster, S.; Paris, O.; Roth, S. V.; Fratzl, P. A customizable software for fast reduction and analysis of large X-ray scattering data sets: applications of the new package to small-angle X-ray scattering and grazing-incidence small-angle X-ray scattering. J. Appl. Crystallogr. 2014 , 47 , 1797−1803..

Zhang, P.; Huang, H.; Yan, D.; He, T. In situ study of the breakout crystallization in the poly(butadiene)-block-poly(ε-caprolactone) thin film. Langmuir 2012, 28 , 6419-6427..

Segalman, R. A. Patterning with block copolymer thin films. Mater. Sci. Eng. R: Rep. 2005 , 48 , 191−226..

Mareau, V. H.; Prud'homme, R. E. In-situ hot stage atomic force microscopy study of poly( ε -caprolactone) crystal growth in ultrathin films. Macromolecules 2005, 38 , 398-408..

Xu, J.; Reiter, G.; Alamo, R. G. Concepts of nucleation in polymer crystallization. Crystals 2021 , 11 , 304..

Wang, W.; Buzzi, S.; Fenni, S. E.; Carmeli, E.; Wang, B.; Liu, G.; Müller, A. J.; Cavallo, D. Surface nucleation of dispersed droplets in double semicrystalline immiscible blends with different matrices. Macromol. Chem. Phys. 2022 , 223 , 2200202..

Liu, G.; Müller, A. J.; Wang, D. Confined crystallization of polymers within nanopores. Acc. Chem. Res. 2021 , 54 , 3028−3038..

Murphy, J. G.; Raybin, J. G.; Ansay, G. E.; Sibener, S. J. Spatiotemporal mapping of hole nucleation and growth during block copolymer terracing with high-speed atomic force microscopy. ACS Nano 2023 , 17 , 5644−5652..

Reiter, G.; Hamieh, M.; Damman, P.; Sclavons, S.; Gabriele, S.; Vilmin, T.; Raphaël, E. Residual stresses in thin polymer films cause rupture and dominate early stages of dewetting. Nat. Mater. 2005 , 4 , 754−758..

Reiter, G.; Castelein, G.; So mmer, J. U. Liquidlike morphological transformations in monolamellar polymer crystals. Phys. Rev. Lett. 2001 , 86 , 5918−5921..

Irvine, W. T. M.; Vitelli, V.; Chaikin, P. M. Pleats in crystals on curved surfaces. Nature 2010 , 468 , 947−951..

Gómez, L. R.; García, N. A.; Vitelli, V.; Lorenzana, J.; Vega, D. A. Phase nucleation in curved space. Nat. Commun. 2015 , 6 , 6856..

Flieger, A. K.; Schulz, M.; Thurn-Albrecht, T. Interface-induced crystallization of polycaprolactone on graphite via first-order prewetting of the crystalline phase. Macromolecules 2018 , 51 , 189−194..

Mamun, A. Retardation of the growth rate of the basal and overgrown lamellar crystals of PCL/PVME miscible binary blends with thickness confinement. Polym. J. 2022 , 54 , 653−665..

Zhang, P.; Huang, H.-y.; Chen, Y.; Yu, S.; Krywka, C.; Vayalil, S. K.; Roth, S. V.; He, T.-b. Preparation of long-range ordered nanostructures in semicrystalline diblock copolymer thin films using micromolding. Chinese J. Polym. Sci. 2014 , 32 , 1188−1198..

Müller-Buschbaum, P. Grazing incidence small-angle X-ray scattering: an advanced scattering technique for the investigation of nanostructured polymer films. Anal. Bioanal. Chem. 2003 , 376 , 3−10..

Smilgies, D. M. GISAXS: A versatile tool to assess structure and self-assembly kinetics in block copolymer thin films. J. Polym. Sci. 2022 , 60 , 1023−1041..

Papadakis, C. M.; Darko, C.; Di, Z.; Troll, K.; Metwalli, E.; Timmann, A.; Reiter, G.; Förster, S. Surface-induced breakout crystallization in cylinder-forming P(I- b -EO) diblock copolymer thin films. Eur. Phys. J. E 2011 , 34 , 7..

de Boer, D. K. G.; Leenaers, A. J. G.; van den Hoogenhof, W. W. Glancing-incidence X-ray analysis of thin-layered materials: a review. X-Ray Spectrom. 1995 , 24 , 91−102..

Galeski, A.; Piorkowska, E.; Koenczoel, L.; Baer, E. Acoustic emission during crystallization of polymers. J. Polym. Sci., Part B: Polym. Phys. 1990 , 28 , 1171−1186..

Chung, J. Y.; Chastek, T. Q.; Fasolka, M. J.; Ro, H. W.; Stafford, C. M. Quantifying residual stress in nanoscale thin polymer films via surface wrinkling. ACS Nano 2009 , 3 , 844−852..

Sharp, J. S.; Vader, D.; Forrest, J. A.; Smith, M. I.; Khomenko, M.; Dalnoki-Veress, K. Spinodal wrinkling in thin-film poly(ethylene oxide)/polystyrene bilayers. Eur. Phys. J. E 2006 , 19 , 423−432..

Bowden, N.; Brittain, S.; Evans, A. G.; Hutchinson, J. W.; Whitesides, G. M. Spontaneous formation of ordered structures in thin films of metals supported on an elastomeric polymer. Nature 1998 , 393 , 146−149..

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