Super hydrophobic Coatings

There is a high level of interest in the practical applications

of superhydrophobic surfaces. Effective practical applications have been identif
ied in a variety of applications including corrosion inhibition, anti-icing, sel
f-cleaning surfaces, anti-fouling, and in microfluidic applications [1, 2]. A su
perhydrophobic surface is defined as having a contact angle of greater than 150
degrees and a small contact hysteresis (Figure 1) [3]. In nature these character
istics can be found in the lotus leaf (Figure 2), which has played a significant
role in aiding researchers and scientists in the discovery and understanding of
super hydrophobicitys mechanisms. In the cross section of the lotus leaf (figure
3) the nanostructure appears to have hairy little fingers protruding outward fr
om the surface. Between these nanoscale fingers and hairs, air is trapped. When
water, which has a high surface energy of around 72 mN/m, lands on the surface i
t maintains its spherical shape which produces a contact angle greater than 150
degrees. The air between the hairs aids in maintaining this high contact angle b
ecause it does not allow the water to effectively wet the surface of the leaf. T
he important piece to the puzzle is the ability of the lotus leaf to trap air be
neath the water. Other nanostructure surface morphologies have been syntheticall
y developed to accomplish this same air trapping phenomena as the lotus (figure
4).
Examples of Potential Practical Applications
Thin films and coatings have been shown to be effective at synth
etically creating these superhydrophobic surfaces on various materials, includin
g metals and cement. Research has shown that superhydrophobic coatings can funct
ion as corrosion inhibitors when applied to metals. Barkhudarov et al. have show
n that the application of thin nano-porous films to aluminum can act as a good c
orrosion inhibitor when exposed to immersion testing in 5 wt% NaCl salt water [5
]. This particular application utilized an aerogel thin film which requires curi
ng in an oven. (Figure 5) shows that the superhydrophobic coating significantly
stunted the corrosion of the aluminum in comparison to films with contact angles
of 0 degrees [5]. Flores-Vivian et al. found that super hydrophobic coatings ca
n be effectively applied on various cement formulations. The coating was applied
to dried cement and was found to possess contact angles in excess of 150 degree
and roll off angles below 10 degrees (figure 6). The coating surface morphology
was formulated by employing siloxane oil and either metakaolin (MK) or silica f
ume (SF) to produce a nanoscale polyvinyl alcohol (PVA) surface (figure 7) [6].
Again, we can see from figure 7 that air will be trapped between the surface of
the concrete and the water to create a high contact angle.
Discussion, opinions, experiment
For any technology to find a practical application it needs to b
e economically viable, and superhydrophobic coatings are no exception. Larsen ex
plains that superhydrophobic coatings could be a potentially multi-billion dolla
r solution to a number of marine corrosion and fouling issues ranging from offsh
ore oil rigs to marine vehicles such as submarines [7]. The savings could be see
n not only in extended life of the marine vehicle but also in reduced maintenanc
e costs [7]. I would also venture to believe the superhydrophobic coating could
also save money on fuel by reducing drag on marine vehicles such as a submarine,
effectively making it more efficient, thus saving even more money. Less down ti
me for an oil rig: a simple equation equaling more up time thus increasing the r
eturn on investment. In the case of superhydrophobic cement, the financial poten
tial is in the trillions. According to the American Society of Civil Engineers 3
.6 trillion dollars will be needed over the next 6 years to protect Americas infr
astructure. If a superhydrophobic coating can be used to prolong the life of bri
dges and highways from the detrimental freeze- thaw cycle the economic viability
could be easily met. Even if the superhydrophobic coating needs to be replaced
on these support structures every few years the economic impact would be minimal
in comparison to new construction. The same holds true for metal corrosion. The
basic math makes sense, but just how durable is a superhydrophobic coating agai
nst oceanic salt water? How does it hold up to UV rays in direct sunlight? How d
oes the coating hold up against abrasion? Is erosion an issue? Does the coating

need to be cured at elevated temperatures? All of these questions could pose pot
ential problems for some of the applications listed above. To get a better under
standing I tested out Rustoleum Neverwet. The Neverwet is a 2 part, superhydroph
obic, aerosol spray system that is cured at room temperature. The substrate I us
ed was a polish cold rolled steel panel. The coating was relatively easy to set
up and when tested under running water (figure 8) the water could not adhere to
the surface. I took a picture of a side view angle of approximately a 3 L water d
roplet (figure 9) and it is clear to see a high contact angle was present. I tes
ted the abrasion with the use of my finger nail to scratch the coating surface (
for lack of a better test procedure). In the area I scratched the super hydropho
bicity was lost and the water readily adhered to the surface of the panel. The l
oss of super hydrophobicity is concern for practical applications like roadways
and oceanic uses, and while the Neverwet coating was never intended for use in t
hese potentially harsh environments I remain skeptical. In conclusion, I think s
uperhydrophobic coatings has enormous potential but for some of the biggest nove
l applications some development is needed in making the coating more practical g
iven in this article and the basic experiment conducted.
[1]
H. M Shang, Y. Wang, K. Takahashi, Z. Cao, Nanostructured superhy
drophobic surfaces, Journal of Material Science: 2005, 40, 3587-3591
[2]
L. Feng, S. Li, Y. Li, H. Li, L. Zhang, J. Zhai, Y. Song, B. Liu,
L. Jiang, D. Zhu, Super-hydrophobic surfaces: from natural to artificial, Adv.
Mater. 2002, 14, No. 24, Dec 17, 1857-1860
[3]
V. Hejazi, M. Nosonovsky, Contact angle hysteresis in multiphase
systems, Colloid Polym. Sci., 2013, 291: 329-338
[4]
O. Velev, Contact angle, wetting, and capillary phenomena, Lecture
3, North Carolina State University, Fall 2014, Lecture
[5]
P. M. Barkhudarov, P. B. Shah, E. B. Watkins, D. A. Doshi, C. J.
Brinker, J. Majewski, Corrosion inhibition using superhydrophobic films, Corrosi
on Sci., 2008, 50:3, 897-902
[6]
I. Flores-Vivian, V. Hejazi, M. I. Kozhukhova, M. Nosonovsky, K.
Sobolev, Self-assembling particle- siloxane coatings for superhydrophobic concre
te, ACS Appl. Mater. Interfaces 2013, 5(24), 13284-13294
[7]
K.R. Larsen, "Superhydrophobic Coating Prevents Corrosion on Mari
ne Structures", Materials Performance, 2011 vol. 50, no. 10, pp. 6.
Figure 1: contact angle hysteresis: for super hydrophobicity the difference betw
een the advancing contact angle and the receding contact angle should be small.
[3]
Figure 2: Lotus Leaf with a water droplet on the surface. [4]
Figure 3: Schematic cross section of a Lotus Leaf surface. [3]
Figure 4. Schematic of various synthetic surface morphologies that produce a sup
erhydrophobic surface. [1]
Figure 5 SH film (superhydrophobic) has a contact angle of 160 degrees, and is c
ompared to a film of 0 degrees contact angle and film of 134 degree contact angl
e. The test occurred in a 5 wt% NaCl Salt water immersion which is an accelerate
d aging test focused on simulating oceanic environments. [5]
Figure 6 Here we see that both Mk2- MK5 and the Mk2- SF5 show superhydrophobic c
haracteristics. The Mk2- MK5 meaning: mk2 stands for what is represented by figure
7 (called shell theory surface morphology) and the MK5 means metakaolin 5% was adde
d to the emulsion prior to application. For the Mk2 SF5: shell theory was also u
sed and SF5 - silica fume 5% was added to the emulsion. The chart shows that the

metakaolin proved to be a better additive and that 5% is necessary to reach sup

erhydrophobicity. The article did not experiment with >5% MK or SF and it would
be interesting to see how significant the amount of MK or SF is on the superhydr
ophobicity of the coating. Application was made by immersion of the concrete int
o the emulsion at room temperature and a spatula was used to remove excess. [6]
Figure 7 A visual representation of the Mk2 Shell theory nanostructure. PVA stands
for polyvinyl alcohol. [6]
Figure 8 This is a picture of a steel panel I coated with Rustoleum Neverwet und
er a faucet. You can see that the water runs right off of the panel. [photo was
taken myself]
Figure 9 This is a side view picture of approximately a 3 L water droplet balanci
ng on the surface of the superhydrophobic panel I coated. Even with just a basic
camera, it is clear that there is a high contact angle present. [photo was take
n myself]