Spray-on anti-soiling coatings that exhibit high transparency and

mechanical durability
Daniel A. Schaeffer*a, Georgios Polizosa, D. Barton Smitha, Dominic F. Leea, Slobodan Rajica,
Panos G. Datskosa, Scott R. Huntera
a
Oak Ridge National Laboratory, 1 Bethel Valley Rd., Oak Ridge, TN, USA 37831

ABSTRACT

A superhydrophobic (SH) surface has many characteristics, one of which is its self-cleaning, anti-soiling functionality,
that are desirable across various industries. A transparent, self-cleaning surface utilizes the right combination of surface
chemistry and roughness that force water droplets to form high water contact angles (CA). This in turn allows droplets to
easily roll off and pick up dirt and debris across the surface. In theory this is simple but in practice this can be very
difficult as superhydrophobicity and optical transparency are competitive. We have developed a simple, spray-on coating
based on functionalized SiO2 nanoparticles that can easily be applied to surfaces whose application requires high
transparency including, but not limited to, optical sensors, photovoltaics, sights, and lenses. In addition, these coatings
exhibit practical mechanical and environmental durability that allow prolonged use of the coatings in harsh
environments.
Keywords: superhydrophobic, optical components, anti-corrosion, self-cleaning, nanoparticles, transparent

1. INTRODUCTION
Soiling and corrosion of both metallic and non-metallic surfaces exposed to varying environmental conditions are major
problems associated with overwhelming manufacturing and maintenance costs. Over the past decade superhydrophobic
(SH) materials have attracted increased interest due to their remarkable water repellency and are a viable approach
toward mitigating corrosion1, soiling2-4, and pertinent degradation mechanisms. There have been copious methods
proposed for fabrication of SH surfaces5-7; however, large area SH surfaces are still underutilized due to poor durability8
and the ability to be scaled cost-effectively9.
Low energy surfaces and extreme dewetting states, such as those that exhibit superhydrophobicity and/or
superoleophobicity, are interesting due to their potential and wide application areas, including self-cleaning coatings and
corrosion protection. The wetting behavior of surfaces is dominated by the surface chemistry and roughness. The SH
property is mainly due to the low surface energy that is realized from a combination of surface chemistry and
nanostructuring10-11. A nanostructured SH surface has an air-solid interface that permeates throughout the morphology of
the surface. By trapping these small-scale air pockets the fractional coverage at the solid-liquid interface is greatly
reduced and the hydrophobic properties are enhanced through reduced van der Waals forces.
There are several environments that dewetting of a surface is very desirable providing anti-corrosion, soiling, icing12-13,
and biofouling characteristics. Transparent SHs is well suited for applications and equipment requiring high optical
clarity and whose performance overtime degrades due to soiling of the surface. Sights and lenses, sensors, and solar
panels are among these that require such great optical efficiency. Having a transparent, SH surface reduces maintenance
costs and efforts drastically without compromising the performance of the equipment. This can lead to more efficient
energy conversion, improved sensing ability, and more reliable equipment for personnel.
Typically, for untreated, flat surfaces with contact angles greater than 90°, an increase in surface roughness leads to a
decrease in surface energy resulting in larger static contact angles (CA). Surfaces with a CA >90° are considered
hydrophobic while those with CA ≥150° are regarded as SH (see Figure 1). More recently, multifunctional SH surfaces
with two or more functional properties have attracted much interest due to high optical transmittance, anti-soiling (see
Figure 2), anti-fogging, and anti-reflection. In this work, we focus on SH surfaces that are optically transparent,
mechanically robust, and have an application process that is scalable to cover large surface areas (i.e., ~m2).

Sensors, and Command, Control, Communications, and Intelligence (C3I) Technologies for Homeland Security
and Homeland Defense XIII, edited by Edward M. Carapezza, Proc. of SPIE Vol. 9074, 90740C
© 2014 SPIE · CCC code: 0277-786X/14/$18 · doi: 10.1117/12.2053387

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 Figure 1. Water contact angles illustrating a superhydrophobic, hydrophilic, and hydrophobic surface.

Figure 2. Dirt particles remain on a normal surface. Water drops collect dirt on a superhydrophobic surface.

2. METHODOLOGY
Through our research efforts we have developed different types of SH materials and coatings that have the potential to
rapidly and effectively impact corrosion, soiling, and maintenance issues. Novel functionalities such as self-cleansing,
anti-icing, anti-corrosion, anti-electrical shorting, etc., have been demonstrated with these developed coatings. More
interestingly, optically transparent SH coatings have also recently been developed. Debris and obstructions such as dirt,
avian droppings, ice and snow can be self-cleansed from surfaces without notable detrimental effects.
The inspiration for the SH work is based in general from nature, and in particular from the Lotus plant of Southeast Asia.
The plant exists in a wet and dirty environment yet it always appears clean and dry. The secret of the Lotus plant is the
SH surface that is composed of micro and nano sized features covered in a very thin waxy (Teflon-like) material.
The main questions that needed to be addressed about the SH coating for these applications and beyond are adhesion on
varying substrates and the durability or lifetime of these coatings. Transparent SH coatings are even more complex and
involve obtaining the proper particle size and distribution, coating thickness, and binder-particle ratio to ensure
durability and robustness all while maintaining high optical transparency and reflectivity.
Initially, the anti-soiling work was performed on flat glass coupons of similar material for their respective applications.
Optical coatings were sprayed onto scopes and lenses that could be mounted as well as mirrors used in concentrated
solar power (CSP), photovoltaic (PV), or heliostat systems. The materials used are all commercially available and
characterization of the coatings were performed using atomic force microscopy (AFM), scanning electron microscopy
(SEM), surface profilometry, film thickness, water CA using a tensiometer, Taber abrasion, optical transmission (190
nm – 1100 nm), specular and diffuse reflectivity, and accelerated UV exposure.

3. RESULTS AND DISCUSSION

3.1 Surface Characterization
Achieving uniform coatings with evenly distributed nanoparticles is key to obtaining transparent coatings without
sacrificing its hydrophobic properties. Thermodynamically immiscible functionalized nanoparticles and solvents led to
phase separating morphologies. This coating formulation can be characterized by micron-size defects that lead to
detrimental effects on both static contact angle and mechanical durability of the coatings. By contrast, coatings
consisting of silica nanoparticles compatible solvents used for their dispersion exhibit excellent dispersion properties
over large surface areas. AFM measurements reveal the uniformity of the coatings along with well-dispersed particulates

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 (see Figure 3). These measurements indicate a surface roughness of 21 nm, which is a desirable feature size promoting
high superhydrophobicity without undermining optical transparency.

_.........ea
.00.:M. ._,r
.... -- rw I r -. r
Mr
avt rer
141..41
tiMO

Figure 3. AFM surface characterization of spray-coated SH surfaces. AFM measurements reveal evenly distributed
functionalized silica nanoparticles and uniform coatings with average roughness of 21 nm.

3.2 Optical Performance

The optical performance of a window or lens is mainly characterized by how well it lets light pass through. Optical
transmission measurements in the ultraviolet-visible spectral region (190 - 1100 nm) were performed to evaluate the
optical clarity of the coatings. Figure 4 shows optical transmission measurements of uncoated and coated soda-lime glass
substrates. The inset in Figure 4 is the difference measurement and reveals that the there is no loss in transmission for the
coating but an increase in transmission across the spectrum for.

100
93-
80
- Bare Glass
- Coating 1 92-
a> 60
U
C
f13
«_ 40 91-
E
rn - Borosilicate Slide
cD 20 -3 Layers
90- -4 Layers
H -8 Layers
o - - 9 Layers
89
400 600 800 1000 1200 400 600 800 1000
Wavelength (nm) Wavelength (nm)

Figure 4. Optical transmission spectra of a coated glass substrate in comparison with an uncoated glass substrate in the UV-
Vis spectral region (190 nm – 1100 nm). The inset is a difference measurement and reveals there is no loss in transmission
for the coating but rather an increase in transmission due to anti-reflection properties. By adding several layers of the
coating, the transmission across the spectrum can be drastically improved.

The optical performance of a solar mirror is characterized by the mirror’s ability to reflect the solar radiation incident on
its surface to the surface of a receiver located some distance from the mirror. Solar rays that are reflected from the mirror
according to the law of reflection are called specular reflections, while rays that undergo scattering are called diffuse
reflections. Diffuse reflections arise from imperfections on the mirror surface such as scratches, particulates, and
patterning. To be useful for transferring solar radiation to the receiver the specular reflections must deviate only slightly
(<12 mrad) from the angle predicted by the law of reflection.

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 A solar mirroor’s performan nce can be quanntified by meassuring its specuular reflectancee across the terrrestrial solar spectrum
s
(λ = 280 to 2500
2 mal angles θi, and
nm). The mirror is irraddiated with lighht that is incideent at near-norm a the intensiity of the
reflected lighht is measured d with a detecctor. The specuular reflectancce ρs(λ,θ,φ) is defined as thhe intensity off light at
wavelength λ and incidence angle θ that is i reflected witthin a cone of divergence
d witth half-angle φ and vertex sited at the
point of incidence. The heemispherical reeflectance ρh(λ λ,θ,π) of a mirrror is the total radiation refl flected from thhe mirror
surface, conssisting of the co
ombination of the specular annd diffuse refleected and scatteered light.
The specularr reflectance wasw calculatedd by subtractiing the diffusee reflectance from f the hem
mispherical refllectance.
Optical loss due to absorpttion was negliggibly small andd was not conssidered in calcculating the speecular reflectannce. The
angles of inccidence for thhe hemisphericcal and diffusee measurementts were 3.3° and a 0°, respectively. A Specctralon®
(polytetrafluooroethylene, orr PTFE) reflecctance standardd was used to calibrate
c the sppectrophotometter detection effficiency
and enable us
u to quote abso olute reflectance of the mirroor surfaces. Thhe Spectralon®® standard is iddentical in com
mposition
to the broadbband reflectance lining in thhe diffuse refleectance accessoory. The resullts for coated mirrors
m can bee seen in
Table 1 and

Table 1. Specular and difffuse measurements for uncoateed reference mirrrors and SH coaated mirrors. Onne mirror was cooated
with onlyy a binder solutio
on to help determ
mine the effects of
o the nanoparticcles.

SSolar-weightedd Referencce Spray-cooated Referrence Sprayy-coated Sppray-coated

reflectance Mirror 1 Mirror 1 Mirrror 2 Mirrror 2 Mirror 2
(n SH SiO2)
(no

Specular 94.8 89.00 955.4 9

90.1 88.1
Diffuse 0.60 5.655 0.551 4
4.85 4.30

nmental and Mechanical

3.3 Environ M Du
urability
In order to investigate
i thee coating degrradation mechaanisms, the cooatings were subjected to abbrading forces using a
Taber® Induustries Abraser (see Figure 5). We obtained water CA meaasurements forr SH coatings before b and afterr several
abrading cyccles. When a glass
g coupon coated
c with a single
s SH coatting layer was subjected to ~10~ cycles of abrasion
testing there was a noticeeable loss of silica
s particles and the CA decreased droopping below the t SH limit of 150°.
However, wiith multiple coaating layers, cooatings were reeduced ~10% after
a 35-40 abrrasion cycles annd remained abbove the
single layer coating
c after 10
00 abrasion cycles. This resuults in roughly a four-fold incrrease for durabbility performaance. XX
shows the ressults for Taberr abrading.

40
36
Single Abrasion Cycles

32
(@ 10% decrease in CA)

28
24
20
16

III
12
8
4
0 ME
Coatinggs
Figure 5. Mechanical durrability of coatinngs as subjected to Taber abradiing. Multilayeredd anti-soiling cooatings exhibit much
m
more abraasion resistance compared to sinngle layer coatinggs.

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 In addition to mechanical abrading the coated surfaces, several glass coupons coated with anti-soiling coatings were
subjected to simulated UV exposure. The water contact angles were monitored as a function of UV exposure time. The
accelerated UV exposures are approximately 12-17 times greater than that of normal solar UVA exposures in the field.
Figure 6 shows several coatings along with a polymeric binder with up to 700 hours of simulated UV exposure. Some
coatings still maintains their superhydrophobicity with a CA >150°. The binder-only coating follows a similar trend,
however at a significantly lower CA, as expected. Coatings based on prior formulations initially followed the same trend
as the top performing coatings but after 200 hours of UV exposure rapidly drops off and becomes marginally
hydrophobic. These simulated environmental tests results in the coatings exposure being equivalent to 8000-12000 hours
of real world solar UV exposure. This is on the order of nearly two to three years in the field, assuming 12 hours
exposure per day.

170 -

160 -

d 150
-3

- N-C6
-0-C7
f Binder 2
-1F C7.A
f C7-B
C7-C
-4-- C7-E
100 -

90
0 100 200 300 400 500 600 700
UV Exposure (hrs)

Figure 6. Simulated UV exposure results. All samples were subjected in 100-hour increments.

4. CONCLUSION
Transparent superhydrophobic coatings – based on functionalized SiO2 – possessing a sub-100 nm roughness and a high
water contact angle (>160°) have been produced. The transmittance of the superhydrophobic coating is improved due to
anti-reflection properties compared to the transmittance for uncoated (bare) glass. The as-prepared transparent
superhydrophobic coatings appear to maintain superhydrophobicity even after exposure to extreme UV conditions for
more than 12 months of simulated time. The superhydrophobic coating also has moderate to high mechanical durability
with some coatings surviving more than 30 abrasion cycles with only a 10% decrease in performance and have proven to
be more robust than coatings reported previously in the literature.
These coatings have also shown great promise and a practical path forward towards various applications including, but
not limited to, anti-corrosion, anti-biofouling, and anti-icing. The coatings can be tailored to be adherent to both metallic
and non-metallic substrates alike and provide a low cost application to large areas.

ACKNOWLEDGEMENTS

Oak Ridge National Laboratory is operated for the U.S. Department of Energy by U.T.-Battelle under Contract No. DE-
AC05-00OR22725. This work was supported by the U.S. Department of Energy, SunShot Program of the Office of

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 Energy Efficiency and Renewable Energy, and the JSSAP office. A portion of this research was conducted at the Center
for Nanophase Materials Sciences, which is sponsored at Oak Ridge National Laboratory by the Scientific User
Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy.

REFERENCES

[1] Weng, C. J. et al, “Corrosion resistance conferred by superhydrophobic fluorinated polyacrylate-silica composite
coatings on cold-rolled steel,” J. Appl. Polym. Sci. 126, E48-E55 (2012).
[2] Chen, Y. et al, “Transparent superhydrophobic/superhydrophilic coatings for self-cleaning and anti-fogging,” Appl.
Phys. Lett. 101(3), (2012).
[3] Xiu, Y. H. et al, “UV-Resistant and Superhydrophobic Self-Cleaning Surfaces Using Sol-Gel Processes,” J. Adhes.
Sci. Technol. 22(15), 1907-1917 (2008).
[4] Polizos, G. et al, “Nonfunctionalized Polydimethyl Siloxane Superhydrophobic Surfaces Based on Hydrophobic-
Hydrophilic Interactions,” Langmuir 27(6), 2953-2957 (2011).
[5] Verho, T. et al, “Mechanically Durable Superhydrophobic Surfaces,” Adv. Mater. 23(5), 673-678 (2011).
[6] Deng, X. et al “Transparent, Thermally Stable and Mechanically Robust Superhydrophobic Surfaces Made from
Porous Silica Capsules,” Adv. Mater. 23(26), 2962 (2011).
[7] Xiu Y. H. et al, “Mechanically robust superhydrophobicity on hierarchically structured Si surfaces,”
Nanotechnology 21(15), (2010).
[8] Erbil, H. Y. et al, “Transformation of a simple plastic into a superhydrophobic surface,” Science 299(5611), 1377-
1380 (2003).
[9] Polizos, G. et al, “Scalable superhydrophobic coatings based on fluorinated diatomaceous earth: Abrasion resistance
versus particle geometry,” Appl. Surf. Sci. 292, 563-569 (2014).
[10] Dorrer, C. and Ruhe, J., “Some thoughts on superhydrophobic wetting,” Soft Matter 5(1), 51-61 (2009).
[11] Park, K. C. et al, “Nanotextured silica surfaces with robust superhydrophobicity and omnidirectional broadband
supertransmissivity,” ACS Nano 6, 3789 (2012).
[12] Cao, L. L. et al, “Anti-Icing Superhydrophobic Coatings,” Langmuir 25(21), 12555-12448 (2009).
[13] Gao, X. F. et al, “The dry-style antifogging properties of mosquito compound eyes and artificial analogues prepared
by soft lithography,” Adv. Mater. 19(17), 2213 (2007).

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