All-organic superhydrophobic coatings with mechanochemical robustness and liquid impalement resistance

Subjects

Abstract

Superhydrophobicity is a remarkable evolutionary adaption manifested by several natural surfaces. Artificial superhydrophobic coatings with good mechanical robustness, substrate adhesion and chemical robustness have been achieved separately. However, a simultaneous demonstration of these features along with resistance to liquid impalement via high-speed drop/jet impact is challenging. Here, we describe all-organic, flexible superhydrophobic nanocomposite coatings that demonstrate strong mechanical robustness under cyclic tape peels and Taber abrasion, sustain exposure to highly corrosive media, namely aqua regia and sodium hydroxide solutions, and can be applied to surfaces through scalable techniques such as spraying and brushing. In addition, the mechanical flexibility of our coatings enables impalement resistance to high-speed drops and turbulent jets at least up to ~35 m s−1 and a Weber number of ~43,000. With multifaceted robustness and scalability, these coatings should find potential usage in harsh chemical engineering as well as infrastructure, transport vehicles and communication equipment.

Access options

Rent or Buy article

Get time limited or full article access on ReadCube.

from$8.99

All prices are NET prices.

Fig. 1: An illustration of the multi-fluorination strategy for the all-organic nanocomposite coating.
Fig. 2: Mechanical robustness of water-repellent PKFE coatings.
Fig. 3: Chemical resistance of the water-repellent PKFE coating.
Fig. 4: Robustness of the superhydrophobic PKFE coating following high-speed water droplet and jet impact.

References

  1. 1.

    Feng, X. J. & Jiang, L. Design and creation of superwetting/antiwetting surfaces. Adv. Mater. 18, 3063–3078 (2006).

    Article  Google Scholar 

  2. 2.

    Zheng, Y., Gao, X. & Jiang, L. Directional adhesion of superhydrophobic butterfly wings. Soft Matter 3, 178–182 (2007).

    Article  Google Scholar 

  3. 3.

    Blossey, R. Self-cleaning surfaces—virtual realities. Nat. Mater. 2, 301–306 (2003).

    Article  Google Scholar 

  4. 4.

    Jung, S., Tiwari, M. K., Doan, N. V. & Poulikakos, D. Mechanism of supercooled droplet freezing on surfaces. Nat. Commun. 3, 615 (2012).

    Article  Google Scholar 

  5. 5.

    Genzer, J. & Efimenko, K. Recent developments in superhydrophobic surfaces and their relevance to marinefouling: a review. Biofouling 22, 339–360 (2006).

    Article  Google Scholar 

  6. 6.

    Cottin-Bizonne, C., Barrat, J. L., Bocquet, L. & Charlaix, E. Low-friction flows of liquid at nanopatterned interfaces. Nat. Mater. 2, 237–240 (2003).

    Article  Google Scholar 

  7. 7.

    Xue, Z. et al. A novel superhydrophilic and underwater superoleophobic hydrogel-coated mesh for oil/water separation. Adv. Mater. 23, 4270–4273 (2011).

    Article  Google Scholar 

  8. 8.

    Darmanin, T., Taffin de Givenchy, E., Amigoni, S. & Guittard, F. Superhydrophobic surfaces by electrochemical processes. Adv. Mater. 25, 1378–1394 (2013).

    Article  Google Scholar 

  9. 9.

    Tesler, A. B. et al. Extremely durable biofouling-resistant metallic surfaces based on electrodeposited nanoporous tungstite films on steel. Nat. Commun. 6, 8649 (2015).

    Article  Google Scholar 

  10. 10.

    Mates, J. E., Bayer, I. S., Palumbo, J. M., Carroll, P. J. & Megaridis, C. M. Extremely stretchable and conductive water-repellent coatings for low-cost ultra-flexible electronics. Nat. Commun. 6, 8874 (2015).

    Article  Google Scholar 

  11. 11.

    Yang, H. et al. Lotus leaf inspired robust superhydrophobic coating from strawberry-like Janus particles. NPG Asia Mater. 7, e176 (2015).

    Article  Google Scholar 

  12. 12.

    Lu, Y. et al. Robust self-cleaning surfaces that function when exposed to either air or oil. Science 347, 1132–1135 (2015).

    Article  Google Scholar 

  13. 13.

    Steele, A., Bayer, I. & Loth, E. Adhesion strength and superhydrophobicity of polyurethane/organoclay nanocomposite coatings. J. Appl. Polym. Sci. 125, E445–E452 (2012).

    Article  Google Scholar 

  14. 14.

    Deng, X., Mammen, L., Butt, H.-J. & Vollmer, D. Candle soot as a template for a transparent robust superamphiphobic coating. Science 335, 5 (2012).

    Google Scholar 

  15. 15.

    Azimi, G., Dhiman, R., Kwon, H. M., Paxson, A. T. & Varanasi, K. K. Hydrophobicity of rare-earth oxide ceramics. Nat. Mater. 12, 315–320 (2013).

    Article  Google Scholar 

  16. 16.

    Feng, L. et al. Superhydrophobicity of nanostructured carbon films in a wide range of pH values. Angew. Chem. Int. Ed. 115, 4217–4220 (2003).

    Article  Google Scholar 

  17. 17.

    Wang, C.-F. et al. Stable superhydrophobic polybenzoxazine surfaces over a wide pH range. Langmuir 22, 8289–8292 (2006).

    Article  Google Scholar 

  18. 18.

    Lafuma, A. & Quere, D. Superhydrophobic states. Nat. Mater. 2, 457–460 (2003).

    Article  Google Scholar 

  19. 19.

    Tiwari, M. K., Bayer, I. S., Jursich, G. M., Schutzius, T. M. & Megaridis, C. M. Highly liquid-repellent, large-area, nanostructured poly(vinylidene fluoride)/poly(ethyl 2-cyanoacrylate) composite coatings: particle filler effects. ACS Appl. Mater. Inter. 2, 1114–1119 (2010).

    Article  Google Scholar 

  20. 20.

    Neinhuis, C., Koch, K. & Barthlott, W. Movement and regeneration of epicuticular waxes through plant cuticles. Planta 213, 427–434 (2001).

    Article  Google Scholar 

  21. 21.

    Li, Y., Li, L. & Sun, J. Q. Bioinspired self-healing superhydrophobic coatings. Angew. Chem. Int. Ed. 49, 6129–6133 (2010).

    Article  Google Scholar 

  22. 22.

    Ahn, B. K., Lee, D. W., Israelachvili, J. N. & Waite, J. H. Surface-initiated self-healing of polymers in aqueous media. Nat. Mater. 13, 867–872 (2014).

    Article  Google Scholar 

  23. 23.

    Asthana, A., Maitra, T., Buchel, R., Tiwari, M. K. & Poulikakos, D. Multifunctional superhydrophobic polymer/carbon nanocomposites: graphene, carbon nanotubes, or carbon black? ACS Appl. Mater. Inter. 6, 8859–8867 (2014).

    Article  Google Scholar 

  24. 24.

    Das, I. & De, G. Zirconia based superhydrophobic coatings on cotton fabrics exhibiting excellent durability for versatile use. Sci. Rep. 5, 18503 (2015).

    Article  Google Scholar 

  25. 25.

    Bird, J. C., Dhiman, R., Kwon, H. M. & Varanasi, K. K. Reducing the contact time of a bouncing drop. Nature 503, 385–388 (2013).

    Article  Google Scholar 

  26. 26.

    Liu, Y. H. et al. Pancake bouncing on superhydrophobic surfaces. Nat. Phys. 10, 515–519 (2014).

    Article  Google Scholar 

  27. 27.

    Richard, D., Clanet, C. & Quere, D. Surface phenomena: Contact time of a bouncing drop. Nature 417, 811–811 (2002).

    Article  Google Scholar 

  28. 28.

    Tsai, P. C., van der Veen, R. C. A., van de Raa, M. & Lohse, D. How micropatterns and air pressure affect splashing on surfaces. Langmuir 26, 16090–16095 (2010).

    Article  Google Scholar 

  29. 29.

    Maitra, T. et al. On the nanoengineering of superhydrophobic and impalement resistant surface textures below the freezing temperature. Nano Lett. 14, 172–182 (2014).

    Article  Google Scholar 

  30. 30.

    Ellinas, K., Chatzipetrou, M., Zergioti, I., Tserepi, A. & Gogolides, E. Superamphiphobic polymeric surfaces sustaining ultrahigh impact pressures of aqueous high- and low-surface-tension mixtures, tested with laser-induced forward transfer of drops. Adv. Mater. 27, 2231–2235 (2015).

    Article  Google Scholar 

  31. 31.

    Maitra, T. et al. Superhydrophobicity vs. ice adhesion: The quandary of robust icephobic surface design. Adv. Mater. Inter. 2, 330–330 (2015).

    Article  Google Scholar 

  32. 32.

    Wong, T. S. et al. Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity. Nature 477, 443–447 (2011).

    Article  Google Scholar 

  33. 33.

    Smith, J. D. et al Droplet mobility on lubricant-impregnated surfaces. Soft Matter 9, 1772–1780 (2013).

    Article  Google Scholar 

Download references

Acknowledgements

The work was partially supported by M.K.T.’s EPSRC First Grant (EP/N006577/1) and from the European Research Council (ERC) under the European Uninon's Horizon 2020 research and innovation programme under grant agreement no. 714712. The authors also thank D. Cripps from Blade Dynamic Company (UK) for supplying the carbon fibre fabrics and epoxy resin. We also acknowledge helpful discussions with F. Fang, S. Zhang and P. Kelly in setting up the wettability experiments; J. Davy for scanning electron microscopy and P. Hayes for Fourier transform infrared spectroscopy measurements.

Author information

Affiliations

Authors

Contributions

C.P. and M.K.T. conceived the idea of the robust superhydrophobic coatings presented. M.K.T. guided the work. C.P. and M.K.T. planned the experiments. C.P. executed all of the experiments, with support from Z.C. on paper revision experiments, jet impact and contact angle measurements and scanning electron microscopy. C.P. and M.K.T. wrote the paper and interpreted the results, with comments from all authors.

Corresponding author

Correspondence to Manish K. Tiwari.

Ethics declarations

Competing interests

M.K.T. is involved in commercialization efforts for advanced-materials-based coatings that are being explored by UCL Business.

Additional information

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

Supplementary information

Supplementary Information

Supplementary Movies 1–8 legends, Supplementary Methods, Supplementary Figures 1–14, Supplementary Notes 1–8, Supplementary References.

Supplementary Movie 1

Water droplets bouncing off the PKFE coating at different velocities. At higher speed, the water droplets atomize upon impact and spend much less time on the substrate compared to the drops impacting at lower speed

Supplementary Movie 2

Fine water jets (diameter ~0.25 mm) impacting on the PKFE coating vertically with different speeds. The videos show the corresponding jet velocities, and the Weber numbers for liquid (Wel=ρlV2d/γLG) and gas (Weg=ρgV2d/γLG). The jets are indicated as laminar, transitional and turbulent jets based on standard jet atomization thresholds1. At low speed we observe a liquid accumulation at the point of impact, without any impalement. At high speeds (> 10 m s–1) the jets atomize upon impacting the substrate

Supplementary Movie 3

Thick water jets (diameter ~2.5 mm) impacting on the PKFE coating vertically with different speeds. The videos show the corresponding jet velocities, and the Weber numbers for liquid (Wel=ρlV2d/γLG) and gas (Weg=ρgV2d/γLG). The jets are indicated as laminar, transitional and turbulent jets based on standard jet atomization thresholds1. These thick jets do not show atomization at the point of substrate impact, rather a stagnation point flow characterised by axisymmetric bending of incoming jet is observed. However, the liquid did not impale into the coating texture (tested by drop contact and sliding angle measurements at the point of impact) right after jet impact tests

Supplementary Movie 4

Fine water jets (diameter ~0.25 mm) impacting at different speeds on the PKFE coating inclined at 45°

Supplementary Movie 5

Thick water jets (diameter ~2.5 mm) impacting at different speeds on the PKFE coating inclined at 45°

Supplementary Movie 6

A turbulent water jet impacting on the PKFE coating with ~35 m s–1, corresponding to a Wel ~43,000. The video demonstrates the excellent impalement resistance of the nanocomposite coating and its ability to sustain high speed liquid impact. After jet impact test, the left over water droplets from the nozzle bounced or rolled right off from the impact spot. This substantiates the fact that the PKFE coating retains superhydrophobicity after high speed jet impact

Supplementary Movie 7

Demonstration of good adhesion and mechanical flexibility of the PKFE coatings. PKFE coating on A4 paper maintains superhydrophobicity after rolling, folding and crumpling randomly. Minimum bending radius was less than 2 mm

Supplementary Movie 8

Water droplets roll-off much faster on the PKFE coating than on the Krytox oil infused PKFE nanocomposite. The mechanical flexibility and low water adhesion are key novel features of our PKFE coatings underpinning their excellent water impalement resistance during high speed impacts

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Peng, C., Chen, Z. & Tiwari, M.K. All-organic superhydrophobic coatings with mechanochemical robustness and liquid impalement resistance. Nature Mater 17, 355–360 (2018). https://doi.org/10.1038/s41563-018-0044-2

Download citation

Further reading