Skip to main content

Thank you for visiting 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.

Robust Hydrophobic Surfaces from Suspension HVOF Thermal Sprayed Rare-Earth Oxide Ceramics Coatings


This study has presented an efficient coating method, namely suspension high velocity oxy-fuel (SHVOF) thermal spraying, to produce large super-hydrophobic ceramic surfaces with a unique micro- and nano-scale hierarchical structures to mimic natural super-hydrophobic surfaces. CeO2 was selected as coatings material, one of a group of rare-earth oxide (REO) ceramics that have recently been found to exhibit intrinsic hydrophobicity, even after exposure to high temperatures and abrasive wear. Robust hydrophobic REO ceramic surfaces were obtained from the deposition of thin CeO2 coatings (3–5 μm) using an aqueous suspension with a solid concentration of 30 wt.% sub-micron CeO2 particles (50–200 nm) on a selection of metallic substrates. It was found that the coatings’ hydrophobicity, microstructure, surface morphology, and deposition efficiency were all determined by the metallic substrates underneath. More importantly, it was demonstrated that the near super-hydrophobicity of SHVOF sprayed CeO2 coatings was achieved not only by the intrinsic hydrophobicity of REO but also their unique hierarchically structure. In addition, the coatings’ surface hydrophobicity was sensitive to the O/Ce ratio, which could explain the ‘delayed’ hydrophobicity of REO coatings.


Rare-earth oxide (REO) ceramics have received increasing attention during the last few years owing to their intrinsic hydrophobicity and robustness to harsh environment1,2. The intrinsic hydrophobicity of REOs arises from the unique electronic structure of the RE metals atoms where the unfilled 4f orbitals are shielded from interactions by the filled 5s2p6 outer shell1. This extraordinary feature makes REOs stand out from the common metals and ceramics which are generally hydrophilic with contact angle (CA) less than 90°. More importantly, unlike polymeric modifiers, e.g. polytetrafluoroethylene (PTFE, or Teflon®), which are used as conventional hydrophobic coatings, REOs exhibited sustained hydrophobicity after high temperature exposure to up to 1000 °C for 2 h and abrasive-wear test1. Accordingly, these robust hydrophobic surfaces obtained from REOs ceramics are seen to be incredibly useful for a wide range of applications including anti-icing3,4,5,6, anti-corrosion7,8,9, drag reduction10,11,12, and dropwise condensation13,14,15,16, etc. So far, many known techniques have been applied to deposit thin-films of REOs for hydrophobic applications, including atomic layer deposition (ALD)17, sputtering18,19, and cathodic electrodeposition20,21, etc. REO ceramics have also been used to fabricate super-hydrophobic surfaces (CA > 150°) by incorporating micro and nanoscale hierarchical surface textures by depositing a thin layer of REOs onto a textured surface (e.g. nanograss-covered cubical microposts)1 or directly texturing the hydrophobic REOs by laser machining22. This approach faces the challenges of machining brittle ceramics and fragile silicon substrates.

In 2016, Cai et al.23 first manufactured super-hydrophobic REO coatings with hierarchically structured topography using precursor solutions as feedstock in a plasma spray deposition process, which is also known as solution precursor plasma spray (SPPS). After vacuum treatment at 1 Pa for 48 hours, the as-sprayed coatings showed a CA value up to 65% higher than on bulk REO surfaces. A recently developed technology, namely suspension high velocity oxy-fuel thermal spraying (SHVOF) was first introduced for the preparation of super-hydrophobic hierarchically-textured TiO2/hexagonal boron nitride (h-BN) composite coatings on stainless steel by Zhang et al.24. Although TiO2 is widely known as intrinsically hydrophilic, the resultant TiO2/h-BN coatings exhibited super-hydrophobic behaviour when the addition of h-BN reaches 10 wt. % due to the presence of hierarchical nano-texture on the surface. SHVOF also offers a rapid and economical method to produce large hydrophobic surface areas on a variety of substrates. SHVOF uses suspensions as feedstocks instead of solution precursor, which enables the use of submicron and nano-powders to form unique nano-structured coatings with higher deposition efficiency25,26,27. In addition, during spraying, particle injection is directly inside the combustion chamber and thus a considerably good heat transfer of the particles can be realised, which enables complete melting and homogenisation of feedstock powders. Lastly, SHVOF torches can reach very high gas velocities (>2000 m/s)28, and the substrates are typically cooled with compressed air jets, which all contribute to rapid cooling of the molten droplets. This results in a significantly high nucleation rate as well as a negligibly low growth rate of crystallites as inhibited by the short residence time due to rapid acceleration in the flame and rapid cooling upon impact, all of which contribute to the formation of nano-crystallized coatings with significant improvement in density, strength and durability29,30,31.

In this study, SHVOF was used to deposit REO coatings with intrinsic hydrophobicity and hierarchically structured surface topography on a selection of commonly used metallic substrates, i.e. aluminium, stainless steel and nickel-based alloys, which can be found in various applications but differ significantly in hardness. CeO2 (ceria) has been chosen for study as it is one of the most extensively studied REO materials and also an important product for catalytic application32. A schematic drawing of the SHVOF system is shown in Fig. 1 and the CeO2 particles dried from the suspension feedstock exhibit granular shapes. It has a particle size range of around 50–200 nm with a d50 of 0.280 μm in the suspension feedstock. Detailed characterizations of the as-sprayed coatings were undertaken with main focuses on coatings’ surface topography, microstructure phase, crystallite size and surface hydrophobicity using field emission gun scanning electron microscopy (FEG-SEM), surface profilometry, x-ray diffraction (XRD) with Rietveld Refinement and contact angle (CA) measurement. We aim not only to demonstrate the potential of SHVOF technique for industrial preparation of robust water-repellent REO coatings on various metallic components; but also find out the mechanism for the improvement in surface hydrophobicity of SHVOF sprayed REO coatings.

Figure 1

An overview of the suspension HVOF process for spraying CeO2 coatings on metallic substrates from suspension feedstock containing CeO2 sub-micron particles.


Surface hydrophobicity

Figure 2 shows the contact angle (CA) measurement of the as-sprayed CeO2 coatings on the three substrates with an inset photo showing the non-wetting water droplets on the CeO2 coated SS. All three coatings exhibited superior surface hydrophobicity with average CA values over 130–140°. Although the static CA measurement with conventional sessile-drop method coupled with the tangent line entails unavoidable errors in determining the air-solid base line due to the smoothness problem and substrate tilting33, it has been clearly seen that the CA results in this study are comparable to those in the literatures23,24 that reported super-hydrophobicity with CA values of over 150°. More importantly, the CA values on the SHVOF sprayed CeO2 coatings are 30–40% higher than those measured on the sintered CeO2 pellets with smoother surface1. The significant increase of CA values was believed to be attributed to the hierarchically structured surface topography as obtained from the plasma/thermal spraying23,24. SEM images on the right show typical surface morphology of the CeO2 coatings under high magnifications. A lamellae structure with fully deformed molten droplets is observed on the CeO2 coatings showing well-merged and sintered particles with significantly reduced surface area. The formation of these nano-sized or micro-sized features from thermal spray is mainly caused by differing particle trajectories in the flame and by various droplet sizes being formed from the disintegration of primary droplets of suspension24. Moreover, the coatings’ surface morphology is found to be dependent on the substrates even though all coatings are sprayed under the same condition, which leads to a variation in surface hydrophobicity.

Figure 2

CA measurements on the CeO2 coatings on Al, SS and Ni substrates and SEM images showing the typical surface morphology of the CeO2 coatings under high magnifications.

Surface morphology

Figure 3 shows the quantitative characterization of the surface morphology of the as-sprayed CeO2 coatings on the three substrates including the 3D views, 2D views and Abbott-Firestone curves. The unique surface morphology of the SHVOF coatings can be described by the surface roughness (i.e. Sa, Sq) and surface texture (i.e. Ssk, Sku) according to the distribution of surface heights and the spatial distribution of peaks and valleys across the surface as listed in Table 1. With the highest CA values, the CeO2 (SS) coatings have the lowest Sq and Sa values indicating the smoothest surface, in combination with the strongest surface texture owing to the highest Sku indicating a ‘spiky’ surface and the lowest Ssk indicating the least symmetrical distribution of heights. While the other two coatings have rougher surfaces and weaker surface texture, which could be described as relating to a ‘bumpy’ surface. It is worth noting that the surface slopes in 2D and 3D views appear much steeper than they really are due to the different magnifications used to represent the dataset in the horizontal and vertical directions. The formation of the distinctive surface morphology is affected by the mechanical properties of the substrates upon the impact of the molten droplets with high kinetic energy during spraying. More detailed characterization results of the as-sprayed CeO2 coatings on the three substrates including the FEG-SEM images showing the surface and cross-sectional microstructure, XRD analysis of the phases and crystallize sizes, and discussions on the spraying mechanism can be found in the Supplement Information (See Figures S1S3).

Figure 3

Quantitative characterization of the surface morphology of the CeO2 coatings on Al, SS and Ni substrates with 3D views, 2D views and amplitude density function.

Table 1 Quantitative characterization of the coatings surface and contact angle measurements.

Surface effect

A series of experiments were also conducted to examine the effect of the unique surface of SHVOF thermal sprayed CeO2 coatings on their surface hydrophobicity as shown in Fig. 4. A precisely controlled Iridium nano-sputter was used to apply a thin Iridium coating on the same coating surface with a highly sensitive film thickness monitor. Iridium provides fine grains (sub-nanometer) films that are more favourable for FEG-SEM high resolution imaging analysis than the others. The aim was not only to rule out the effect of REO material on the surface hydrophobicity by applying a different material with higher surface energy (hydrophilic metal), but also retain the delicate surface morphology of SHVOF coatings. Figure 4(c,d) shows the XPS spectra of the Iridium coated surface with inset figures of the high-resolution XPS spectrum of Ce 3d indicating the full coverage of Iridium over CeO2 coatings. With the deposition of over 5 nm of Iridium, the existence of Ce is nearly undetectable. In Fig. 4(a), the CA values drops to around 130° when the thickness of Iridium is 5 nm but no significant change was observed with thicker Iridium coatings. The effect of the REO underneath should be ruled out by the replacement of Iridium, and the CA value of 125–130° could then be considered as the sole contribution of the hierarchical microstructure on the surface. For comparison, Iridium coatings were applied on the mirror-polished SS as shown in Fig. 4(b), and the CA measurements show constant values at around 80°. It demonstrates that the unique hierarchical structure of SHVOF coatings has significantly improved the surface hydrophobicity by contributing to an over 50% increase of CA. These results confirmed that the near-super-hydrophobicity of the SHVOF REO coatings was contributed by both the intrinsic hydrophobic property of REO and the unique hierarchical structure from thermal spraying.

Figure 4

CA measurements on Iridium coated surface of the (a) CeO2 coated SS; and (b) mirror polished SS to examine the effect of the surface morphology of REO coatings on their hydrophobicity, in combination with XPS analysis on the Iridium coated surface with a thickness of (c) 5 nm and (d) 10 nm to confirm that Iridium has fully covered the CeO2 underneath.

Surface chemistry

Despite the unique hierarchically structured surface that would contribute to the improvement in surface hydrophobicity of REO coatings, there is another important issue that should not be over looked, i.e. the “delayed” hydrophobicity of the plasma/thermal sprayed REO coatings. This phenomenon was first reported by Cai et al.23 on the SPPS sprayed REOs coatings, that the as-sprayed coating surface was initially hydrophilic (CA ≈ 0°), but after vacuum treatment at 1 Pa for 48 hours the CA value increased dramatically to over 150°. We have observed similar phenomenon that the coatings immediately after spray were hydrophilic with low CA values (<90°) but then increased to over 130° after 4 weeks left in the ambient air. This transition is believed to be largely dependent on the surface oxygen-to-metal (e.g. O/Ce) ratio, which was proved by Khan et al.19,34 through rigorous investigations on the wettability of sputtered CeO2 surface as a dependency of O/Ce ratios using X-ray Photoelectron Spectroscopy (XPS) in a ultra-high vacuum (UHV) environment. Khan19 reported that an O/Ce ratio higher than 2.0 can negatively affect the hydrophobicity as it provides more sites for hydrogen bonding with water. Figure 5 shows the full XPS spectrum and high-resolution spectrum of Ce 3d with detailed deconvolutions into constituent satellite peaks and identified using the nomenclature proposed by Burroughs et al.35. The XPS peaks were associated with the Ce4+ or the Ce3+ oxidation state. Peaks v, v″, v″′, u, u″ and u″′ were associated with the Ce4+ state, while v0, v′, u0 and u′ were associated with the Ce3+ state. The relative concentrations of Ce4+ and Ce3+ were determined using the following equations36.

$${\boldsymbol{A}}({\boldsymbol{C}}{{\boldsymbol{e}}}^{3+})={\boldsymbol{A}}({{\boldsymbol{v}}}_{0})+{\boldsymbol{A}}({\boldsymbol{v}}^{\prime} )+{\boldsymbol{A}}({{\boldsymbol{u}}}_{0})+{\boldsymbol{A}}({\boldsymbol{u}}^{\prime} )$$
$${\boldsymbol{A}}({\boldsymbol{C}}{{\boldsymbol{e}}}^{4+})={\boldsymbol{A}}({\boldsymbol{v}})+{\boldsymbol{A}}({\boldsymbol{v}}^{\prime\prime} )+{\boldsymbol{A}}({\boldsymbol{v}}\prime\prime\prime )+{\boldsymbol{A}}({\boldsymbol{u}})+{\boldsymbol{A}}({\boldsymbol{u}}^{\prime\prime} )+{\boldsymbol{A}}({\boldsymbol{u}}\prime\prime\prime )$$
$$\begin{array}{cc} \% \,{\boldsymbol{C}}{{\boldsymbol{e}}}^{{\boldsymbol{y}}+}=\frac{{\boldsymbol{A}}({\boldsymbol{C}}{{\boldsymbol{e}}}^{{\boldsymbol{y}}+})}{{\boldsymbol{A}}({\boldsymbol{C}}{{\boldsymbol{e}}}^{3+})+{\boldsymbol{A}}({\boldsymbol{C}}{{\boldsymbol{e}}}^{4+})}\times 100 & ({\boldsymbol{y}}={\bf{3}},{\bf{4}})\end{array}$$

A(x) above refers to the peak area (and corresponding peak intensity) as determined from the XPS spectra. As calculated, there is 78% Ce4+ and 22% Ce3+, corresponding to a lattice O/Ce ratio of 1.89 based on the conservation of valence state. This is lower than the stoichiometric value indicating a deficient oxygen and less tendency to form hydrogen bonds with interfacial water and hence a better surface hydrophobicity. The “delayed” hydrophobicity is believed to be caused by the partial reduction in state from Ce4+ to Ce3+ with time, which is consistent with previous observations19,37,38. It was observed by Khan19 that the Ce4+ contribution decreased from 89.8% to 72.8% after overnight relaxation in UHV which directly led to an increase of CA values from 15° to 104°. Therefore, in view of all these observations, it can be concluded that the change in cerium’s chemical state caused an overall decrease in the surface O/Ce ratio, which ultimately affected the surface hydrophobicity of REO coatings.

Figure 5

(a) XPS survey scan on the as-sprayed CeO2 coatings; and (b) High-resolution XPS spectrum of Ce 3d peaks with detailed peak deconvolutions and quantification results.

To conclude, robust hydrophobic surfaces on a selection of metallic substrates (namely Al, SS and Ni) were obtained from the deposition of thin CeO2 coatings (3–5 μm) by SHVOF thermal spraying using an aqueous suspension with a solid concentration of 30 wt.% sub-micron CeO2 particles (50–200 nm). Several important conclusions can be drawn as follows,

  1. (1)

    Near super-hydrophobicity was observed with 30–40% increase of CA than that of smooth surface. The use of thin Iridium deposition (5–15 nm) on the surface clearly demonstrated that the improvement was achieved mainly by their unique surfaces with hierarchical structure.

  2. (2)

    The substrates determined the coatings’ hydrophobicity, microstructure, surface morphology, and deposition efficiency, etc. The coatings on SS performed the best among the three with the highest contact angle, smoothest surface and strongest surface texture.

  3. (3)

    The coatings’ surface hydrophobicity was also sensitive to the O/Ce ratio and the ‘delayed’ hydrophobicity of CeO2 coatings was caused by the partial reduction in state from Ce4+ to Ce3+ with time, which ultimately led to a slow transition from hydrophilic to hydrophobic.

Materials and Methods

Suspension and sample preparation

A water-based CeO2 suspension (MilliDyne, Finland) with a solid concentration of 30 wt.% was used in this study. Particle size distribution was measured using laser diffractometer (LS13320, Beckman-Coulter, USA). Suspension was mixed for 90 mins using a mechanical stirrer at a speed of 940 rpm to achieve a homogeneous suspension. The suspension was sprayed onto 3 different types of substrates with a dimension of 60 × 25 × 2 mm3 including (1) Aluminium alloy (1050A), (2) stainless steel (AISI 304) and (3) Nickel Alloy (NIMONIC C263), which are referred to as Al, SS, and Ni, respectively (See Table 2). Substrates were grit blasted with F100 brown alumina particles (0.125–0.149 mm) under 3 bar pressure, and cleaned by an ultrasonic acetone bath to remove any embedded alumina particles.

Table 2 Composition and properties of the metallic substrates*.

SHVOF Thermal spraying

A modified UTP/Miller Thermal HVOF system with a direct injection at the centre of the gas-mixing block was used to spray the suspension. The suspension injector had a diameter of 0.3 mm to inject the suspension into the centre of the combustion chamber. A 22 mm long combustion chamber with 100 mm long barrel nozzle was used in this study. The suspension was fed using a pressurised 2 L vessel equipped with a mechanical stirrer to ensure uniform dispersion of the nano-particles in solution and consistent flow onto the substrate without clogging the nozzle. The pressure of the feeding system was fixed at 5 bar during the spray. The gun was mounted on a z-axis traverse unit in front of the rotating carousel and it was set to a stand-off distance from the surface of the substrate of 85 mm. The substrates were mounted onto a carousel rotating at 73 rpm with a vertical axis of rotation. The substrates were cooled using compressed air jets during and after the spray. The flame heat power was 110 kW with a hydrogen fuel flow rate of 1650 scfh (equals to 775 L/min) and oxygen flow rate of 715 scfh (equals to 336 L/min). Hydrogen was used as the combustion fuel to achieve a cleaner flame and to reduce any hydrocarbon combustion products in the resulting coating, as any contamination might affect the hydrophobic behaviour of coatings. The theoretical flame heat power for each spray was calculated using standard combustion formulae.

Characterizations methods

SEM with JEOL in-lens Schottky field emissions source (FEG-SEM, JEOL 7100F, USA) was used to examine the morphology of the feedstock powder dried from the suspension, as well as the surface morphology and cross-sectional microstructure of the as-sprayed coatings. The coating thickness was analysed by Image Pro-Plus (6.0, Media Cybernetics, Rockville, USA) software. Hydrophobicity of the surfaces was characterized using a contact angle goniometer (FTA200, First Ten Angstroms, Inc., Portsmouth, VA, USA) with pumping out rate of 1 µL/s. Quantitative characterization of the coatings surface was carried out using an Alicona InfiniteFocus G5 focus variation microscopy (FVM) with 20x objective lens (vertical resolution 50 nm). Data was further analysed using MountainsMap® Premium software version 7 (Digital Surf, Besançon, France) to generate 3D views, 2D views, and detailed surface roughness and texture results. Surface roughness were measured by stylus surface profilometry (Talysurf CLI 1000 Profilometer, Leicester, U.K.) with a resolution of 40 nm. Quorum 150T S turbomolecular-pumped coating system (Quorum Technologies, UK) was used to sputter-coat samples with iridium, and the coating thickness was precisely controlled by a Film Thickness Monitor at a deposition rate of 3 nm/min. XRD analysis was conducted using a Siemens D500 (Germany) with Cu produced at 40 kV and 25 mA. The 2θ diffraction angle range was from 10° to 90° with step width of 0.05° and time per step of 2 seconds. Quantitative Rietveld refinement (TOPAS V5 software package) was employed to determine the crystallite size based on the principles of whole powder pattern modelling (WPPM)39. The penetration depth of the X-ray through CeO2 was calculated according to the literature40. The surface chemistry of the coating samples was analysed using a Kratos AXIS Supra X-ray photoelectron spectroscopy (XPS, Kratos Analytical Limited, UK) equipped with a GCIS (Kratos minibeam 6), and Al Kα X-ray source (1486.6 eV). The settings for the GCIS were the same for all experiments, 10 kV Ar+1000 with rastered areas of 1 mm2. The photoelectron acquisition was performed on each sample at three positions with a wide survey scan and high-resolution scans: O 1s, C 1s, Ce 3d and Ir 4f. The data analysis was carried out by the CasaXPS software (Version 2.3.18PR1.0) with Kratos sensitivity factors (RSFs) to determine relative atomic concentrations from the peak areas. The energy scale of the spectra was corrected for sample charging.


  1. 1.

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

    ADS  CAS  Article  PubMed  Google Scholar 

  2. 2.

    Tian, Y. & Jiang, L. Wetting: Intrinsically robust hydrophobicity. Nature materials 12, 291–292 (2013).

    ADS  CAS  Article  PubMed  Google Scholar 

  3. 3.

    Lv, J., Song, Y., Jiang, L. & Wang, J. Bio-Inspired Strategies for Anti-Icing. Acs Nano 8, 3152–3169 (2014).

    CAS  Article  PubMed  Google Scholar 

  4. 4.

    Eberle, P., Tiwari, M. K., Maitra, T. & Poulikakos, D. Rational nanostructuring of surfaces for extraordinary icephobicity. Nanoscale 6, 4874–4881 (2014).

    ADS  CAS  Article  PubMed  Google Scholar 

  5. 5.

    Maitra, T. et al. On the Nanoengineering of Superhydrophobic and Impalement Resistant Surface Textures below the Freezing Temperature. Nano Letters 14, 172–182 (2014).

    ADS  CAS  Article  PubMed  Google Scholar 

  6. 6.

    Meuler, A. J. et al. Relationships between Water Wettability and Ice Adhesion. Acs Appl Mater Inter 2, 3100–3110 (2010).

    CAS  Article  Google Scholar 

  7. 7.

    Zhang, D., Wang, L., Qian, H. & Li, X. Superhydrophobic surfaces for corrosion protection: a review of recent progresses and future directions. Journal of Coatings Technology and Research 13, 11–29 (2016).

    CAS  Article  Google Scholar 

  8. 8.

    Mohamed, A. M. A., Abdullah, A. M. & Younan, N. A. Corrosion behavior of superhydrophobic surfaces: A review. Arabian Journal of Chemistry 8, 749–765 (2015).

    CAS  Article  Google Scholar 

  9. 9.

    Ishizaki, T., Masuda, Y. & Sakamoto, M. Corrosion Resistance and Durability of Superhydrophobic Surface Formed on Magnesium Alloy Coated with Nanostructured Cerium Oxide Film and Fluoroalkylsilane Molecules in Corrosive NaCl Aqueous Solution. Langmuir 27, 4780–4788 (2011).

    CAS  Article  PubMed  Google Scholar 

  10. 10.

    Bhushan, B. Biomimetics inspired surfaces for drag reduction and oleophobicity/philicity. Beilstein Journal of Nanotechnology 2, 66–84 (2011).

    ADS  CAS  Article  PubMed  PubMed Central  Google Scholar 

  11. 11.

    Srinivasan, S. et al. Drag reduction for viscous laminar flow on spray-coated non-wetting surfaces. Soft Matter 9, 5691–5702 (2013).

    ADS  CAS  Article  Google Scholar 

  12. 12.

    Solomon, B. R., Khalil, K. S. & Varanasi, K. K. Drag Reduction using Lubricant-Impregnated Surfaces in Viscous Laminar Flow. Langmuir 30, 10970–10976 (2014).

    CAS  Article  PubMed  Google Scholar 

  13. 13.

    Ghosh, A., Beaini, S., Zhang, B. J., Ganguly, R. & Megaridis, C. M. Enhancing Dropwise Condensation through Bioinspired Wettability Patterning. Langmuir 30, 13103–13115 (2014).

    CAS  Article  PubMed  Google Scholar 

  14. 14.

    Patankar, N. A. Supernucleating surfaces for nucleate boiling and dropwise condensation heat transfer. Soft Matter 6, 1613–1620 (2010).

    ADS  MathSciNet  CAS  Article  Google Scholar 

  15. 15.

    Anderson, D. M. et al. Using Amphiphilic Nanostructures To Enable Long-Range Ensemble Coalescence and Surface Rejuvenation in Dropwise Condensation. Acs Nano 6, 3262–3268 (2012).

    CAS  Article  PubMed  Google Scholar 

  16. 16.

    Dietz, C., Rykaczewski, K., Fedorov, A. G. & Joshi, Y. Visualization of droplet departure on a superhydrophobic surface and implications to heat transfer enhancement during dropwise condensation. Appl Phys Lett 97, 033104 (2010).

    ADS  Article  Google Scholar 

  17. 17.

    Oh, I.-K. et al. Hydrophobicity of rare earth oxides grown by atomic layer deposition. Chemistry of Materials 27, 148–156 (2014).

    Article  Google Scholar 

  18. 18.

    Zenkin, S., Kos, Š. & Musil, J. Hydrophobicity of Thin Films of Compounds of Low‐Electronegativity Metals. J Am Ceram Soc 97, 2713–2717 (2014).

    CAS  Article  Google Scholar 

  19. 19.

    Khan, S., Azimi, G., Yildiz, B. & Varanasi, K. K. Role of surface oxygen-to-metal ratio on the wettability of rare-earth oxides. Appl Phys Lett 106, 061601 (2015).

    ADS  Article  Google Scholar 

  20. 20.

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

    ADS  Article  Google Scholar 

  21. 21.

    Pedraza, F., Mahadik, S. & Bouchaud, B. Synthesis of ceria based superhydrophobic coating on Ni20Cr substrate via cathodic electrodeposition. Phys Chem Chem Phys 17, 31750–31757 (2015).

    CAS  Article  PubMed  Google Scholar 

  22. 22.

    Azimi, G., Kwon, H.-M. & Varanasi, K. K. Superhydrophobic surfaces by laser ablation of rare-earth oxide ceramics. MRS Communications 4, 95–99 (2014).

    CAS  Google Scholar 

  23. 23.

    Cai, Y., Coyle, T. W., Azimi, G. & Mostaghimi, J. Superhydrophobic Ceramic Coatings by Solution Precursor Plasma Spray. Sci Rep 6, 24670 (2016).

    ADS  CAS  Article  PubMed  PubMed Central  Google Scholar 

  24. 24.

    Zhang, F., Robinson, B. W., de Villiers-Lovelock, H., Wood, R. J. & Wang, S. C. Wettability of hierarchically-textured ceramic coatings produced by suspension HVOF spraying. Journal of Materials Chemistry A 3, 13864–13873 (2015).

    CAS  Article  Google Scholar 

  25. 25.

    Killinger, A. et al. Review of new developments in suspension and solution precursor thermal spray processes. Journal of Thermal Spray Technology 20, 677–695 (2011).

    ADS  Article  Google Scholar 

  26. 26.

    Müller, P., Killinger, A. & Gadow, R. Comparison Between High-Velocity Suspension Flame Spraying and Suspension Plasma Spraying of Alumina. Journal of Thermal Spray Technology 21, 1120–1127 (2012).

    ADS  Article  Google Scholar 

  27. 27.

    Ganvir, A., Curry, N., Markocsan, N., Nylén, P. & Toma, F.-L. Comparative study of suspension plasma sprayed and suspension high velocity oxy -fuel sprayed YSZ thermal barrier coatings. Surface and Coatings Technology 268, 70–76 (2015).

    CAS  Article  Google Scholar 

  28. 28.

    Killinger, A., Müller, P. & Gadow, R. What Do We Know, What are the Current Limitations of Suspension HVOF Spraying? Journal of Thermal Spray Technology 24, 1130–1142 (2015).

    ADS  Article  Google Scholar 

  29. 29.

    Pala, Z., Shaw, E., Murray, J., Senin, N. & Hussain, T. Suspension high velocity oxy-fuel spraying of TiO2: A quantitative approach to phase composition. Journal of the European Ceramic Society 37, 801–810 (2017).

    CAS  Article  Google Scholar 

  30. 30.

    Bai, M., Maher, H., Pala, Z. & Hussain, T. Microstructure and phase stability of suspension high velocity oxy-fuel sprayed yttria stabilised zirconia coatings from aqueous and ethanol based suspensions. Journal of the European Ceramic Society 38, 1878–1887 (2018).

    CAS  Article  Google Scholar 

  31. 31.

    Bai, M., Khammas, R., Guan, L., Murray, J. W. & Hussain, T. Suspension high velocity oxy-fuel spraying of a rutile TiO2 feedstock: Microstructure, phase evolution and photocatalytic behaviour. Ceram Int 43, 15288–15295 (2017).

    CAS  Article  Google Scholar 

  32. 32.

    Da Silva, J. L., Ganduglia-Pirovano, M. V., Sauer, J., Bayer, V. & Kresse, G. Hybrid functionals applied to rare-earth oxides: The example of ceria. Phys Rev B 75, 045121 (2007).

    ADS  Article  Google Scholar 

  33. 33.

    Hung, Y.-L., Chang, Y.-Y., Wang, M.-J. & Lin, S.-Y. A simple method for measuring the superhydrophobic contact angle with high accuracy. Rev Sci Instrum 81, 065105 (2010).

    ADS  Article  PubMed  Google Scholar 

  34. 34.

    Khan, S. Hydrophobicity of rare-earth oxide ceramics and their application in promoting sustained drop-wise condensation, Massachusetts Institute of Technology (2016).

  35. 35.

    Burroughs, P., Hamnett, A., Orchard, A. F. & Thornton, G. Satellite structure in the X-ray photoelectron spectra of some binary and mixed oxides of lanthanum and cerium. Journal of the Chemical Society, Dalton Transactions, 1686–1698 (1976).

  36. 36.

    Paparazzo, E. On the curve-fitting of XPS Ce (3d) spectra of cerium oxides. Materials Research Bulletin 46, 323–326 (2011).

    CAS  Article  Google Scholar 

  37. 37.

    Preisler, E., Marsh, O., Beach, R. & McGill, T. Stability of cerium oxide on silicon studied by x-ray photoelectron spectroscopy. Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures Processing, Measurement, and Phenomena 19, 1611–1618 (2001).

    ADS  CAS  Article  Google Scholar 

  38. 38.

    Zhang, F., Wang, P., Koberstein, J., Khalid, S. & Chan, S.-W. Cerium oxidation state in ceria nanoparticles studied with X-ray photoelectron spectroscopy and absorption near edge spectroscopy. Surface Science 563, 74–82 (2004).

    ADS  CAS  Article  Google Scholar 

  39. 39.

    Scardi, P. & Leoni, M. Whole powder pattern modelling. Acta Crystallographica Section A: Foundations of Crystallography 58, 190–200 (2002).

    CAS  Google Scholar 

  40. 40.

    Li, C. et al. Precise strain profile measurement as a function of depth in thermal barrier coatings using high energy synchrotron X-rays. Scripta Materialia 113, 122–126 (2016).

    CAS  Article  Google Scholar 

Download references


This work was supported by the Engineering and Physical Sciences Research Council [grant number EP/M01536X/1, EP/L022494/1, EP/K005138/1] and University of Nottingham. The authors thank the Nanoscale and Microscale Research Centre (nmRC) for providing access to instrumentation and Dr. Karen Alvey, Mr. Martin J. Roe, Ms. Nicola J. Weston and Dr. Emily F. Smith for technical assistance. Ms. Hafsah Kazi would like to thank the financial support from the Nottingham Summer Engineering Research Programme and BP P.L.C. The authors would also like to acknowledge Mr. Rory Screaton for the experimental assistance in thermal spray, Dr. James W. Murray, Dr. Zhirong Liao and Dr. Wahyudin P. Syam from the Advanced Manufacturing Technology Research Group for the quantitative surface analysis.

Author information




M. Bai designed and performed the experiments, analysed data, and wrote the manuscript; H. Kazi, X. Zhang and J. Liu supported the experiments and assisted in data analysis. T. Hussain supervised the projects, interpreted data and reviewed the manuscript.

Corresponding author

Correspondence to T. Hussain.

Ethics declarations

Competing Interests

The authors declare no competing interests.

Additional information

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

Electronic supplementary material

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Bai, M., Kazi, H., Zhang, X. et al. Robust Hydrophobic Surfaces from Suspension HVOF Thermal Sprayed Rare-Earth Oxide Ceramics Coatings. Sci Rep 8, 6973 (2018).

Download citation

Further reading


By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.


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