banner
Home / Blog / Scalable production of critically thin polyethylene films via multistep stretching | Nature Chemical Engineering
Blog

Scalable production of critically thin polyethylene films via multistep stretching | Nature Chemical Engineering

Nov 03, 2024Nov 03, 2024

Nature Chemical Engineering (2024)Cite this article

24 Accesses

Metrics details

Plastic films are among the most used materials. In many applications, both high strength and low thickness are required. The thickness of free-standing plastic films has recently been reduced to micrometres, 200 nm and even 60 nm. Pushing this boundary further faces considerable challenges, as processability conflicts with stability at the ‘ultrathin’ scale (below ~100–200 nm). Here, to overcome this trade-off, we modulated the entanglement density of plastic chains to identify a maximum stretching processing window. Then, relaxation was introduced during stretching to kinetically stabilize the ultrathin film. Combined, polyethylene film thicknesses were reduced to ~12 nm, near its critical thickness. This critically thin polyethylene reveals physical properties different from its bulk counterparts, such as high mechanical strength (113.9 GPa (g cm–3)–1), abnormal interfacial properties and a high aspect ratio near 108. Potential applications of these films include nuclear fusion ignition support and thin breathable epidermal sensors. Our work reveals advanced processing strategies, distinctive properties and broader applications of plastic films near the processing limit.

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

Subscribe to this journal

Receive 12 digital issues and online access to articles

$119.00 per year

only $9.92 per issue

Buy this article

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

All data are available in the article or its Supplementary Information. Source data are provided with this paper. Any other relevant data are available from the corresponding author upon request.

Jiao, K. et al. Designing the next generation of proton-exchange membrane fuel cells. Nature 595, 361–369 (2021).

Article CAS PubMed Google Scholar

Li, J. et al. Flexible ultrastrong 100-nm polyethylene membranes with polygonal pore structures. Preprint at https://arxiv.org/abs/1901.07952 (2019).

Sun, W. et al. Ultrahigh molecular weight polyethylene lamellar-thin framework on square meter scale. Adv. Mater. 34, 2107941 (2022).

Article CAS Google Scholar

Gee, G. Polymerisation in monolayers. Trans. Faraday Soc. 32, 187–195 (1936).

Article CAS Google Scholar

Schlüter, A. D., Payamyar, P. & Öttinger, H. C. How the world changes by going from one- to two-dimensional polymers in solution. Macromol. Rapid Commun. 37, 1638–1650 (2016).

Article PubMed Google Scholar

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

Article PubMed Google Scholar

Wang, G. et al. Mechanical size effect of freestanding nanoconfined polymer films. Macromolecules 55, 1248–1259 (2022).

Article CAS Google Scholar

Li, X. & McKenna, G. B. Ultrathin polymer films: rubbery stiffening, fragility, and Tg reduction. Macromolecules 48, 6329–6336 (2015).

Article CAS Google Scholar

Ishikawa, K., Miyasaka, K. & Maeda, M. Drawing of single-crystal mats of linear polyethylene. J. Polym. Sci. A-2 Polym. Phys. 7, 2029–2041 (1969).

Article CAS Google Scholar

Kanamoto, T., Tsuruta, A., Tanaka, K., Takeda, M. & Porter, S. R. On ultra-high tensile modulus by drawing single crystal mats of high molecular weight polyethylene. Polym. J. 15, 327–329 (1983).

Article CAS Google Scholar

Holdsworth, P. J. & Keller, A. Ductile behavior of single crystal mats of an ethylene–propylene copolymer. J. Polym. Sci. A-2 Polym. Phys. 6, 707–712 (1968).

Article CAS Google Scholar

Ziabicki, A. Fundamentals of Fibre Formation: The Science of Fibre Spinning and Drawing (Wiley, 1976).

Keller, A. & O’Connor, A. Large periods in polyethylene: the origin of low-angle X-ray scattering. Nature 180, 1289–1290 (1957).

Article CAS Google Scholar

González-Mijangos, J. A., Lima, E., Guerra-González, R., Ramírez-Zavaleta, F. I. & Rivera, J. L. Critical thickness of free-standing nanothin films made of melted polyethylene chains via molecular dynamics. Polymers 13, 3515 (2021).

Article PubMed PubMed Central Google Scholar

Chen, L., Pan, Z. & Hu, G.-H. Residence time distribution in screw extruders. AIChE Journal 39, 1455–1464 (1993).

Article CAS Google Scholar

Zhang, X.-M., Feng, L.-F., Chen, W.-X. & Hu, G.-H. Numerical simulation and experimental validation of mixing performance of kneading discs in a twin screw extruder. Polym. Eng. Sci. 49, 1772–1783 (2009).

Article CAS Google Scholar

Yin, L., Chen, J., Yang, X. & Zhou, E. Structure image of single crystal of polyethylene. Polymer 44, 6489–6493 (2003).

Article CAS Google Scholar

Jandt, K. D., Buhk, M., Miles, M. J. & Petermann, J. Shish-kebab crystals in polyethylene investigated by scanning force microscopy. Polymer 35, 2458–2462 (1994).

Article CAS Google Scholar

Statton, W. O. & Geil, P. H. Recrystallization of polyethylene during annealing. J. Appl. Polym. Sci. 3, 357–361 (1960).

Article CAS Google Scholar

Halmo, P. M. et al. Thin battery separators and methods. US patent 9,666,847 (2024).

Wang, Z. et al. Structure and properties of biaxial stretched submicron thin UHMWPE membranes. Polymer 285, 126393 (2023).

Article CAS Google Scholar

Wang, B. et al. Camphor-enabled transfer and mechanical testing of centimeter-scale ultrathin films. Adv. Mater. 30, 1800888 (2018).

Article Google Scholar

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

Article CAS PubMed Google Scholar

Galuska, L. A. et al. SMART transfer method to directly compare the mechanical response of water-supported and free-standing ultrathin polymeric films. Nat. Commun. 12, 2347 (2021).

Article CAS PubMed PubMed Central Google Scholar

Tashiro, K., Kobayashi, M. & Tadokoro, H. Calculation of three-dimensional elastic constants of polymer crystals. 2. Application to orthorhombic polyethylene and poly(vinyl alcohol). Macromolecules 11, 914–918 (1978).

Article CAS Google Scholar

Kanamoto, T., Tsuruta, A., Tanaka, K., Takeda, M. & Porter, R. S. Super-drawing of ultrahigh molecular weight polyethylene. 1. Effect of techniques on drawing of single crystal mats. Macromolecules 21, 470–477 (1988).

Article CAS Google Scholar

Kim, J., Zhang, G., Shi, M. & Suo, Z. Fracture, fatigue, and friction of polymers in which entanglements greatly outnumber cross-links. Science 374, 212–216 (2021).

Article CAS PubMed Google Scholar

Belton, P. S. Mini review: on the elasticity of wheat gluten. J. Cereal Sci. 29, 103–107 (1999).

Article CAS Google Scholar

Yin, J. et al. Recyclable sericin/nanocellulose aerogel with high adsorption capacity for tetrabromobisphenol A in water: insight from DFT calculations. Chem. Eng. J. 474, 145695 (2023).

Article CAS Google Scholar

Missale, E., Frasconi, M. & Pantano, M. F. Ultrathin organic membranes: can they sustain the quest for mechanically robust device applications? iScience 26, 105924 (2023).

Article CAS PubMed PubMed Central Google Scholar

Espinosa-Loza, F. et al. Modeling the mechanical properties of ultra-thin polymer films. High Pow. Laser Sci. Eng. 5, e27 (2017).

Article Google Scholar

Baxamusa, S. H. et al. Enhanced delamination of ultrathin free-standing polymer films via self-limiting surface modification. Langmuir 30, 5126–5132 (2014).

Article CAS PubMed Google Scholar

Nagel, S. R. et al. Effect of the mounting membrane on shape in inertial confinement fusion implosions. Phys. Plasmas 22, 22704 (2015).

Article Google Scholar

Hammel, B. A. et al. Simulations and experiments of the growth of the ‘tent’ perturbation in NIF ignition implosions. J. Phys.: Conf. Ser. 717, 12021 (2016).

Google Scholar

Download references

Q.F. and R.L. acknowledge support from the National Natural Science Foundation of China (grant nos. 52233002, 52103042 and 22341304), State Key Laboratory of Polymer Materials Engineering grant (no. sklpme2022-3-09) and the Provincial Natural Science Foundation of Sichuan (grant no. 24NSFSC6554). We also thank B. Tee and Z. Wang for help with the fabrication of conformation sweat sensors. We thank B. Zhang for help with the in situ AFM during heating. We thank Q. Huang for the elongational rheology experiments. We thank K. Zhang for help in several characterizations and Z. Su for his generous support in the cryo-EM observations.

These authors contributed equally: Runlai Li, Zirui Wang.

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, China

Runlai Li, Zirui Wang, Weilong Sun, He Zhang, Hua Deng & Qiang Fu

State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science, Fudan University, Shanghai, China

Yuwen Zeng

School of Materials Science and Engineering, Peking University, Beijing, China

Xiaoxu Zhao

State Key Lab of Coordination Chemistry, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China

Wenbing Hu

Department of Chemistry, National University of Singapore, Singapore, Singapore

Kian Ping Loh

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

You can also search for this author in PubMed Google Scholar

Q.F. conceived the idea and guided the project. R.L., Z.W., W.S. and H.Z. prepared the C-PE and performed the characterizations. K.P.L. designed the sweat sensor demonstration and assisted in the C-PE preparation. Y.Z. contributed the indentation tests, and X.Z. performed the HRTEM tests. W.H. and H.D. assisted in the data visualization. Q.F., R.L. and Z.W. co-wrote the paper. All the authors analysed the data, commented on the paper and agreed with the paper.

Correspondence to Qiang Fu.

The authors declare no competing interests.

Nature Chemical Engineering thanks Mukerrem Cakmak, Phil Coates, Guo-Hua Hu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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

a, Photographs of C-PE films to demonstrate transparency. b, Scanning-electron-miscropscopy images of C-PE films displaying a library of fibrous crystalline structures.

a-c, Mw-Conc diagrams on the thickness, stretch ratios and tensile moduli of prepared C-PE. d, The definition of C-PE processing window, the FQ isorheic line and the FQ line deviation index (FQ-DI). e, Conc-Mw phase diagram on FQ-DI. f, Classification of four regions based on the diagram in (e) according to the processability of precursors.

Source data

a, Scheme of FCP supporting nuclear fuel capsule inside the hohlraum during fusion ignition. b, C-PE’s stable adherence to the wrist was maintained even after one-minute exposure to intense tap water flushing. The upper inset captures C-PE post-flushing, while the lower inset provides a microscopic view of the C-PE boundary on a skin replica, with C-PE parts pseudo-colored in blue. Scale bar: 400 µm. c, A four-channel sweat sensor is integrated on C-PE with self-conformability. Inset, the schema of C-PE-based sweat sensor spontaneously conformed on human skin, detecting Na+, K+, Ca2+ ions, glucose and temperature.

Supplementary Sections 1–10, Figs. 1–86, Tables 1 and 2, and discussion.

Statistical source data.

Statistical source data.

Statistical source data.

Statistical source data.

Statistical source data.

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

Li, R., Wang, Z., Sun, W. et al. Scalable production of critically thin polyethylene films via multistep stretching. Nat Chem Eng (2024). https://doi.org/10.1038/s44286-024-00139-w

Download citation

Received: 01 March 2024

Accepted: 04 October 2024

Published: 01 November 2024

DOI: https://doi.org/10.1038/s44286-024-00139-w

Anyone you share the following link with will be able to read this content:

Sorry, a shareable link is not currently available for this article.

Provided by the Springer Nature SharedIt content-sharing initiative