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Long-term stability of aerophilic metallic surfaces underwater

Nature Materials (2023)Cite this article

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Abstract

Aerophilic surfaces immersed underwater trap films of air known as plastrons. Plastrons have typically been considered impractical for underwater engineering applications due to their metastable performance. Here, we describe aerophilic titanium alloy (Ti) surfaces with extended plastron lifetimes that are conserved for months underwater. Long-term stability is achieved by the formation of highly rough hierarchically structured surfaces via electrochemical anodization combined with a low-surface-energy coating produced by a fluorinated surfactant. Aerophilic Ti surfaces drastically reduce blood adhesion and, when submerged in water, prevent adhesion of bacteria and marine organisms such as barnacles and mussels. Overall, we demonstrate a general strategy to achieve the long-term stability of plastrons on aerophilic surfaces for previously unattainable underwater applications.

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Fig. 1: Physicochemical characteristics of Ti-APhS.
Fig. 2: Quantifying the wetting regime of Ti-APhS.
Fig. 3: Blood repellency of Ti-APhS.
Fig. 4: Bacterial repellence of Ti-APhS.
Fig. 5: Marine anti-biofouling characteristics of Ti-APhS.

Data availability

All data are available in the main text or Supplementary Information. All relevant data are available from the corresponding authors upon reasonable request.

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Acknowledgements

We thank A. Marmur for fruitful discussions on the plastron stability of Ti-APhS. A.B.T. thanks N. Vogel and J. Harrer for help with AFM measurements and E. Alkhateeb for help with X-ray diffraction measurements. A.B.T. thanks F. Krause from Keyence Deutschland GmbH for providing a laser confocal microscope for surface roughness measurements. W.H.G. and A.B.T. are indebted to L. Nicholson (Master of Arts) for proofreading the manuscript. We acknowledge the provision of facilities and technical support by Aalto University at OtaNano’s Nanomicroscopy Center (Aalto-NMC). A.B.T., P.S., W.H.G. and B.F. thank the Deutsche Forschungsgemeinschaft (DFG; SCHM 1597/38-1 and FA 336/13-1) for their financial support. A.B.T. acknowledges the Emerging Talents Initiative (ETI) of the Friedrich-Alexander-Universität Erlangen-Nürnberg (grant agreement number 5500102). This work was funded in part by grants from the German Science Foundation (DFG; FA 336-12/1, TRR-SFB 225 Projects A01 and C02). J.V.I.T. acknowledges funding from the Academy of Finland Center of Excellence Program (2022–2029) in Life-Inspired Hybrid Materials (LIBER), project number 346112. M. Backholm acknowledges postdoctoral funding from the Academy of Finland (grant agreement number 309237). M. Bruns, B.K., H.A.N., M.L., Z.M.C., J.V.I.T. and R.H.A.R. acknowledge funding from the Academy of Finland Center of Excellence Program (2022–2029) in Life-Inspired Hybrid Materials (LIBER, project number 346109). S.S. acknowledges funding from the Office of Naval Research, US Department of Defense (grant N00014-17-1-2153). S.K. and J.A. acknowledge funding from the Office of Naval Research, US Department of Defense (grants N00014-15-1-2323 and N00014-17-1-2913) and the Department of Energy (award DE-SC0005247).

Author information

Authors and Affiliations

  1. Department of Materials Science and Engineering, Institute for Surface Science and Corrosion WW4-LKO, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany

    Alexander B. Tesler, Lucia H. Prado, Mark Bruns, Anca Mazare, Sannakaisa Virtanen & Patrik Schmuki

  2. Wyss Institute for Biologically Inspired Engineering, Harvard University, Cambridge, MA, USA

    Stefan Kolle & Joanna Aizenberg

  3. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA

    Stefan Kolle & Joanna Aizenberg

  4. Department of Physics, Biophysics Institute, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany

    Ingo Thievessen, David Böhringer, Lena Fischer, Ben Fabry & Wolfgang H. Goldmann

  5. Department of Applied Physics, School of Science, Aalto University, Espoo, Finland

    Matilda Backholm, Bhuvaneshwari Karunakaran, Heikki A. Nurmi, Mika Latikka, Zoran M. Cenev, Jaakko V. I. Timonen & Robin H. A. Ras

  6. Department of Coatings and Polymeric Materials, North Dakota State University, Fargo, ND, USA

    Shane Stafslien

  7. Advanced Institute for Materials Research (AIMR), National University Corporation Tohoku University (TU), Sendai, Japan

    Anca Mazare

  8. Department of Operative Dentistry and Periodontology, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Germany

    Ulrich Lohbauer

  9. Regional Centre of Advanced Technologies and Materials, Palacky University, Olomouc, Czech Republic

    Patrik Schmuki

  10. Department of Bioproducts and Biosystems, School of Chemical Engineering, Aalto University, Espoo, Finland

    Robin H. A. Ras

Authors
  1. Alexander B. Tesler
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Contributions

A.B.T. conceived the original idea for the project. A.B.T. developed the anodization method to form highly rough aerophilic Ti substrates with hierarchical structures and analysed the formation mechanisms. A.B.T. and S.K. screened and down-selected different coating compositions and fabrication methods, discovering the most promising designs for further study. A.M. performed XPS characterizations. A.B.T., L.H.P. and M. Bruns performed the plastron longevity characterization. A.B.T., L.H.P., M. Backholm, B.K., H.A.N. and M.L. performed the wetting characterization and analysed the experimental data. A.B.T., I.T., L.F., D.B., B.F. and W.H.G. performed the anti-blood adhesion and anti-bacterial characterizations. A.B.T., Z.M.C. and J.V.I.T. performed the SEM, TEM and confocal microscopy characterizations. U.L. carried out the optical profilometry characterization. S.K. and S.S. performed the marine anti-biofouling characterization. A.B.T., S.K., B.F., S.V. and W.H.G. wrote the manuscript. A.B.T., S.K., R.H.A.R., B.F., P.S., S.V., J.A. and W.H.G. discussed the results and revised the manuscript. All authors contributed to the manuscript.

Corresponding authors

Correspondence to Alexander B. Tesler or Wolfgang H. Goldmann.

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The authors declare no competing interests.

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Peer review information

Nature Materials thanks Björn Wickman and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–16, Tables 1 and 2 and Materials and Methods.

Supplementary Video 1

Spreading of water drops on the as-anodized (super-hydrophilic) Ti surface.

Supplementary Video 2

Adhesion of water droplets to Ti-APhS. The substrate tilt angle is ~0 degrees.

Supplementary Video 3

Measurements of the adhesive force on Ti-APhS using MFS.

Supplementary Video 4

Dynamic characteristics of air bubbles on Ti-APhS after 78 days of continuous immersion underwater.

Supplementary Video 5

Wetting properties of Ti-APhS before and after 14 and 67 days underwater at 0.5 m depth. The substrate tilt angle is 10 degrees.

Supplementary Video 6

Hot-water and cold-water jet impinging Ti-APhS. Jet pressure, 70 psi. An equivalent impinging mass is 900 grams.

Supplementary Video 7

Plastron stability under bending and twisting of Ti-APhS underwater.

Supplementary Video 8

WCA hysteresis before and after sand abrasion by 0.8 mm yttria-stabilized zirconia beads.

Supplementary Video 9

Affinity and CA hysteresis of blood to Ti-APhS.

Supplementary Video 10

Blood droplet on Ti-APhS removed by paper wipe.

Supplementary Video 11

Blood affinity to bare Ti immersed for 1 s, and Ti-APhS immersed 99 times at 1 s each.

Supplementary Video 12

Bare Ti and Ti-APhS in 1.5 M NaOH aqueous electrolyte under an applied potential of 10 V.

Supplementary Video 13

Blood droplets roll off bare Ti and off Ti-APhS immersed 99 times in the container with blood.

Supplementary Video 14

Water affinity, WCA hysteresis and blood affinity to aluminium SHS.

Supplementary Video 15

Sliding time window analysis of the bare Ti sample, super-hydrophilic Ti sample and Ti-APhS exposed to E. coli.

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Tesler, A.B., Kolle, S., Prado, L.H. et al. Long-term stability of aerophilic metallic surfaces underwater. Nat. Mater. (2023). https://doi.org/10.1038/s41563-023-01670-6

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