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.

Hydrophobicity of rare-earth oxide ceramics

Nature Materials volume 12, pages 315–320 (2013)Cite this article

Subjects

Abstract

Hydrophobic materials that are robust to harsh environments are needed in a broad range of applications1,2,3. Although durable materials such as metals and ceramics, which are generally hydrophilic, can be rendered hydrophobic by polymeric modifiers4, these deteriorate in harsh environments. Here we show that a class of ceramics comprising the entire lanthanide oxide series, ranging from ceria to lutecia, is intrinsically hydrophobic. We attribute their hydrophobicity to their unique electronic structure, which inhibits hydrogen bonding with interfacial water molecules. We also show with surface-energy measurements that polar interactions are minimized at these surfaces and with Fourier transform infrared/grazing-angle attenuated total reflection that interfacial water molecules are oriented in the hydrophobic hydration structure. Moreover, we demonstrate that these ceramic materials promote dropwise condensation, repel impinging water droplets, and sustain hydrophobicity even after exposure to harsh environments. Rare-earth oxide ceramics should find widespread applicability as robust hydrophobic surfaces.

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

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Prices vary by article type

from$1.95

to$39.95

Learn more

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

Figure 1: Schematic of the orientation of water molecules and the associated wetting properties of a surface.
Figure 2: Surface characterization and wetting properties of sintered REOs.
Figure 3: Steam condensation and water repellency on smooth REO substrates.
Figure 4: Thermal stability, abrasive-wear resistance and sustained hydrophobicity.
Figure 5: Superhydrophobicity and water repellency of REO-coated textured surfaces.

References

  1. Quéré, D. Non-sticking drops. Rep. Prog. Phys. 68, 2495–2532 (2005).

    Article  Google Scholar 

  2. Bocquet, L. & Lauga, E. A smooth future? Nature Mater. 10, 334–337 (2011).

    Article  CAS  Google Scholar 

  3. Quéré, D. Wetting and roughness. Annu. Rev. Mater. Res. 38, 71–99 (2008).

    Article  Google Scholar 

  4. Liu, K. & Jiang, L. Metallic surfaces with special wettability. Nanoscale 3, 825–838 (2011).

    Article  CAS  Google Scholar 

  5. Zhang, X., Zhu, Y. & Granick, S. Hydrophobicity at a Janus interface. Science 295, 663–666 (2002).

    Article  CAS  Google Scholar 

  6. Chandler, D. Interfaces and the driving force of hydrophobic assembly. Nature 437, 640–647 (2005).

    Article  CAS  Google Scholar 

  7. Giovambattista, N., Debenedetti, P. G. & Rossky, P. J. Enhanced surface hydrophobicity by coupling of surface polarity and topography. Proc. Natl Acad. Sci. USA 106, 15181–15185 (2009).

    Article  CAS  Google Scholar 

  8. Kuna, J. J. et al. The effect of nanometer-scale structure on interfacial energy. Nature Mater. 8, 837–842 (2009).

    Article  CAS  Google Scholar 

  9. Giovambattista, N., Debenedetti, P. G. & Rossky, P. J. Effect of surface polarity on water contact angle and interfacial hydration structure. J. Phys. Chem. B 111, 9581–9587 (2007).

    Article  CAS  Google Scholar 

  10. Kung, H. H. Transition Metal Oxides: Surface Chemistry and Catalysis Ch. 4 (Elsevier, 1989).

    Google Scholar 

  11. Drzymala, J. Hydrophobicity and collectorless flotation of inorganic materials. Adv. Colloid Interface Sci. 50, 143–185 (1994).

    Article  CAS  Google Scholar 

  12. Hass, K. C., Schneider, W. F., Curioni, A. & Andreoni, W. The chemistry of water on alumina surfaces: reaction dynamics from first principles. Science 282, 265–268 (1998).

    Article  CAS  Google Scholar 

  13. Argyris, D., Ashby, P. D. & Striolo, A. Structure and orientation of interfacial water determine atomic force microscopy results: Insights from molecular dynamics simulations. ACS Nano 5, 2215–2223 (2011).

    Article  CAS  Google Scholar 

  14. Stirnemann, G., Rossky, P. J., Hynes, J. T. & Laage, D. Water reorientation, hydrogen-bond dynamics and 2D-IR spectroscopy next to an extended hydrophobic surface. Faraday Discuss. 146, 263–281 (2010).

    Article  CAS  Google Scholar 

  15. Adachi, G., Imanaka, N. & Kang, Z. C. Binary Rare Earth Oxides Ch. 2 (Kluwer Academic, 2004).

    Google Scholar 

  16. Topp, N. E. The Chemistry of The Rare Earth Elements Ch. 1 (Elsevier, 1965).

    Google Scholar 

  17. Cheng, E., Cole, M. W., Saam, W. F. & Treiner, J. Helium prewetting and nonwetting on weak-binding substrates. Phys. Rev. Lett. 67, 1007–1010 (1991).

    Article  CAS  Google Scholar 

  18. Nasher, P. J. & Dupont-Roc, J. Experimental evidence for nonwetting with superfluid helium. Phys. Rev. Lett. 67, 2966–2969 (1991).

    Article  Google Scholar 

  19. Yalamanchili, M. R., Atia, A. A. & Miller, J. D. Analysis of interfacial water at a hydrophilic silicon surface by in-situ FTIR/internal reflection spectroscopy. Langmuir 12, 4176–4184 (1996).

    Article  CAS  Google Scholar 

  20. Scatena, L. F., Brown, M. G. & Richmond, G. L. Water at hydrophobic surfaces: Weak hydrogen bonding and strong orientation effects. Science 292, 908–912 (2001).

    Article  CAS  Google Scholar 

  21. Du, Q., Freysz, E. & Shen, R. Surface vibrational spectroscopic studies of hydrogen bonding and hydrophobicity. Science 264, 826–828 (1994).

    Article  CAS  Google Scholar 

  22. Good, R. J. Contact angle, wetting, and adhesion: A critical review. J. Adhes. Sci. Technol. 6, 1269–1302 (1992).

    Article  CAS  Google Scholar 

  23. Martínez, L. et al. Surface study of cerium oxide based coatings obtained by cathodic electrodeposition on zinc. Appl. Surf. Sci. 257, 6202–6207 (2011).

    Article  Google Scholar 

  24. Jiang, K. Fabrication and Catalytic Property of Cerium Oxide Nanomaterials Ch. 2 (Univ. Nebraska, 2011).

    Google Scholar 

  25. Boreyko, J. B. & Chen, C. H. Self-propelled dropwise condensate on superhydrophobic surfaces. Phys. Rev. Lett. 103, 184501 (2009).

    Article  Google Scholar 

  26. Rose, J. W. Dropwise condensation theory and experiment: A review. Proc. Inst. Mech. Eng. A 216, 115–128 (2002).

    Article  CAS  Google Scholar 

  27. Neumann, A. W., Abdelmessih, A. H. & Hameed, A. The role of contact angles and contact angle hysteresis in dropwise condensation heat transfer. Int. J. Heat Mass Transfer 21, 947–953 (1978).

    Article  Google Scholar 

  28. Merte, H. & Yamali, C. Profile and departure size of condensation drops on vertical surfaces. Wärme - und Stoffübertragung 17, 171–180 (1983).

    Article  Google Scholar 

  29. Lewis, J. A. Colloidal processing of ceramics. J. Am. Ceram. Soc. 83, 2341–2359 (2000).

    Article  CAS  Google Scholar 

Download references

Acknowledgements

We are grateful for support from the NSF Career Award (0952564), Dupont-MIT Alliance, MIT Energy Initiative, and DARPA Young Faculty Award. We thank S. Speakman from CMSE at MIT for supporting XRD characterizations and K. Broderick from MTL at MIT for help with sputtering. We thank R. Cohen of MIT for carefully reading and commenting on the manuscript.

Author information

Authors and Affiliations

  1. Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Gisele Azimi, Rajeev Dhiman, Hyuk-Min Kwon, Adam T. Paxson & Kripa K. Varanasi

Authors
  1. Gisele Azimi
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Rajeev Dhiman
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Hyuk-Min Kwon
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Adam T. Paxson
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Kripa K. Varanasi
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

K.K.V. and G.A. conceived the research. K.K.V. supervised the research. G.A. fabricated the sintered pellets and coated substrates, carried out surface wettability and surface-energy characterization, and performed SEM, XPS, XRD and FTIR-GATR characterizations. A.T.P. and G.A. conducted steam condensation experiments. H-M.K. fabricated textured surfaces and prepared the Supplementary Movies. R.D. and G.A. carried out drop impact tests. G.A. carried out the high-temperature stability and abrasive-wear tests and measured the materials’ hardness. All authors contributed to writing and revising the manuscript.

Corresponding author

Correspondence to Kripa K. Varanasi.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

Supplementary Information (PDF 1814 kb)

Supplementary Information

Supplementary Movie S1 (MOV 11683 kb)

Supplementary Information

Supplementary Movie S2 (MOV 4529 kb)

Supplementary Information

Supplementary Movie S3 (MOV 4407 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Azimi, G., Dhiman, R., Kwon, HM. et al. Hydrophobicity of rare-earth oxide ceramics. Nature Mater 12, 315–320 (2013). https://doi.org/10.1038/nmat3545

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat3545

This article is cited by

Search

Advanced search

Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing