Durable Low Adhesion Hydrophobic and Superhydrophobic Reinforced

Fluoropolymer Coatings

Dr. Alexander Titomirov, Chairman/CEO

Alarnia LLC: Proprietary and Confidential. 2019-2029. All Rights Reserved.

PROPOSED TECHNOLOGY

We propose a low surface energy hydrophobic and superhydrophobic coatings based on reinforced
fluoropolymers (RFP). Such RFP coatings can be used on a variety of materials including metals, alloys
and composites.

Hydrophobic and superhydrophobic:

Some micro/nanopatterned surfaces utilizing the “Lotus Effect” can be superhydrophobic and water
repellent. According to the common definition, a surface is called superhydrophobic if the water contact
angle (CA) on that surface is greater than 150° and it also has low CA hysteresis (i.e., the difference
between the maximum or advancing and the minimum or receding CA).

The proposed RFP coating combines the hierarchical controlled surface roughness with micro and
submicron-scale details of self-assembled morphology. The hierarchical structure is formed by
reinforcing particles and fibers embedded into the coating and protruding to the surface. Furthermore,
hydrophobic micro/nanoparticles with optional additional coating can be used.

The proposed RFP coatings can also demonstrate a potential for icephobic surfaces, for which ice
adhesion strength was reduced by an order of magnitude. The mechanism of icephobicity combines low
adhesion of water droplets due to superhydrophobicity, freezing delay, and easy ice detachment from
the substrate due to inherent voids (composite or Cassie interface).

ANTICIPATED BENEFITS/POTENTIAL COMMERCIAL APPLICATIONS

It is anticipated that novel durable low surface energy hydrophobic and superhydrophobic RFP coatings
will be used in the number of applications such as ships, bridges, aircraft etc. RFP coatings can reduce
the cost of maintenance such as repainting or cleaning during the lifetime of the structures.

Additional benefits: drag reduction and icephobic (ice-repellent) properties.

Drag reduction: shark skin effect [2]

The proposed RFP coatings provide an autonomous, robust, sustainable, and durable ability to prevent
ice formation, and thus can operate in cold climate conditions, such as the Arctic or Antarctic regions.
The proposed solution is also environmentally benign as it does not involve any toxic or otherwise
hazardous components.

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Existing Solutions

The phenomenon of surface roughness-induced superhydrophobicity (extreme water-repellency) has

been actively investigated during the past decade. A typical superhydrophobic surface is rough and
covered with posts of high asperities with a typical size and pitch distance in the range between 100 nm
to 0.1 mm (Figure 1). When such a surface is wetted by water, an air layer or air pockets usually develop
between the solid and the water droplets (Figure 1).

Figure 1. The Superhydrophobic Surfaces

Conventional superhydrophobic products (e.g. Neverwet, Nanopool) achieve high contact angle surfaces
by nanoparticle coating. Different nanoparticles are used in these coatings: nano- SiO2, nano-Al2O3,
nano-ZrO2, as well as nanoparticles of gold and silver. The application technique involves the spraying
the sol-gel form of these nanoparticles onto specially prepared surfaces. The principal idea of
nanoparticle coating is well-known. The performance of such nanoparticle coatings vs. conventional
materials is quite exceptional; however, nanoparticle coating cannot provide long-term abrasion
resistance and, therefore, durable superhydrophobic modification of surfaces.

Further Advancement of the State of the Art

The use of nano-sized particles, fibers and platelets and engineering of superhydrophobic paints and
coatings with hierarchical surface roughness based on proposed RFP technology is a further
breakthrough in the field.

Ultra-durable RFP coatings on metallic, ceramic and composite materials can better satisfy the need for
wear-resistant superhydrophobicity [3]. To achieve the goal of superhydrophobic modification of
surfaces, we combined the results of recent advances in the field of biomimetic microstructured
surfaces, nano-object deposition with paint and surface coating technology [4-6]. The Lotus leaf has
extremely water-repellent (superhydrophobic) properties due to a hierarchical composition of its
surface, consisting of microscale bumps (papillae), on tops of which smaller nanoscale bumps are found.
Geckos can control adhesion (having it very high when they climb on a wall or low when they have to
detach) due the hierarchical structure of the surface of their toes. Many breakthroughs have been made
in the last 10 years in synthesizing artificial surfaces mimicking the lotus leaf and gecko toe.
However, we suggest, for the first time, to apply these advances to paint and surface coating
technologies.
The proposed RFP coatings are based on the application of hierarchically designed particles with micro-
and nano-scale bumps on the surface (Figure 3). Such approach allows for complete reproduction of
“Lotus Effect,” creating durable multi-scale surface roughness and so more effective superhydrophobic
modification of surfaces. Furthermore, the proposed concept is extended to provide shark- and sailfish-
skin like structure in order to achieve superior self-cleaning, antifouling properties and lower hydro-
/aero- dynamical resistance. This approach was used to create superhydrophobic coatings on

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ceramic/metals and can be very useful for the composite, plastic, and paint and varnish materials and
multifunctional coatings. Multifunctional nanoparticles (including doped) can also be applied to the
surface of polymeric materials with embedded microparticles. The hydrophobization of multifunctional
coatings is realized by treatment with siloxanes, PDMS, SiCl4 and fluorination.

(a) (b) (c)

Figure 3. The mechanism for formation of random wear-resistant superhydrophobic hierarchical surfaces: (a) the
formation of wear-resistant patterns on a fractured/eroded surface and self-deposition and “welding” of
hydrophobic micro-/nano- particles, (b) water droplets on fiber-reinforced composite and (c) ice droplets on
surface on steel protected by durable RFP coating

The proposed superhydrophobic modification include RFP coatings reinforced with high-strength
micro/nano fibers (e.g., Al2O3, glass, PVA) and siloxane-based hydrophobic liquids with small quantities
of super-fine, submicro- or nanosized materials such as nanosilica, nanoclay additives or SiO2-rich
reactive powders.
The follow-up hydrophobization of multifunctional coatings is realized by treatment with siloxanes,
PDMS, SiCl4 and fluorination. This composition, when added to material, provides hydrophobic and
superhydrophobic hybridization enhancing anti-drag, anti-icing and de-icing properties.
We anticipate the proposed concept will produce a new generation of coating materials with anti-icing
and de-icing properties and significantly improved durability and corrosion resistance as required for
critical components of structural elements, ships, vessels, aircraft, equipment, armor, and navigation
tools.
The following are characteristics of proposed RFP project:
a) By introducing hydrophobic fibers, particles and nanoparticles with properly selected parameters
(size, geometry, volume fraction) the hydrophobic/superhydrophobic RFP coating with enhanced
performance is created.
b) The hydrophobic/superhydrophobic surfaces are wear-resistant.
c) The hydrophobic/superhydrophobic coatings repel water and ice and thus will enhance the
durability and performance of structural elements, ships, vessels, aircraft, equipment, armor, and
navigation tools.
Fluoropolymer / FEVE

Different types of coating compositions including fluoropolymer have been used on steel and concrete
for more than 40 years (US Patent 3,895,029 by Ward, etc). Due to strong chemical bonds between
carbon and fluorine atoms, fluoropolymer (e.g. fluoro-olefin vinyl ether copolymers, FEVE) coatings

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provide excellent performance in respect to durability, UV radiation, heat, wear and chemical resistance
(when compared with conventional polymers like acrylics). The FEVE polymer structure consists almost
entirely of regularly alternating fluoro-ethylene and vinyl ether segments [1]. While the most
fluoropolymers are solvent based resins cross-linked with isocyanate hardener and cured at a room
temperature, there are also water-based solvent-free fluoropolymer products.

FEVE polymer structure [1]

Examples: solvent-soluble fluoropolymer LUMIFLON® developed by AGC Chemicals Europe

Fluorosurfactants, or fluorinated surfactants, are synthetic organofluorine chemical compounds that

have multiple fluorine atoms. They can be polyfluorinated or fluorocarbon-based (perfluorinated)

Polydimethylsiloxane (PDMS) belongs to a group of polymeric organosilicon compounds that are

commonly referred to as silicones.[1] PDMS is the most widely used silicon-based organic polymer

The structure of PDMS

Nanofibers are defined as fibers with diameters less than 100 nanometers.[1] These can be produced by
interfacial polymerization and electrospinning.[3] Carbon nanofibers are graphitized fibers produced by
catalytic synthesis. Nanofiber composition can be titanium dioxide (TiO2), silicon dioxide (SiO2),
zirconium dioxide (ZrO2), aluminum oxide (Al2O3), lithium titanate (Li4Ti5O12), titanium nitride (TiN),
platinum (Pt), polymeric or organometallic compounds.

Metal, dielectric, and semiconductor (quantum dots), as well as hybrid structures (core–shell)
nanoparticles with the size of less than 100 nanometers were developed for different applications. The
surface coating (functionalization) of nanoparticles is crucial to determining their properties. In
particular, the surface coating can regulate stability, solubility, and compatibility with matrices. Zinc
oxide particles have been found to have superior UV blocking and anti-corrosive properties. Clay
nanoparticles when incorporated into polymer matrices result in stronger plastics.

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Application
3 coat system on steel:
1) zinc-rich primer
2) epoxy midcoat
3) fluoro-urethane topcoat

Claims
1. The durable coating composition comprising the combination of:
a) about 1 to about 99% by weight of fluoropolymer resin;
b) cross-linking agent in a range from zero to required volume to realize the cross-liking and optimal
mechanical performance;
c) about 0.01 to about 25% by weight of reinforcing nanoparticles;
d) about 0.01 to about 25% by weight of reinforcing nanofibers;
e) about 1 to about 99% by weight of solvent.
2. The coating composition in accordance with Claim 1 wherein said fluoropolymer resin has a molecular
weight of from about 1,500 to 1,500,000
3. The coating composition in accordance with Claim 1 wherein said cross-linking agent is selected from
the group.
4. The coating composition in accordance with Claim 1 wherein said reinforcing nanoparticles between 1
and 100 nanometers in size are selected from the group of silicon dioxide (SiO2), aluminum oxide
(Al2O3), titanium dioxide (TiO2), iron dioxide (Al2O3), zirconium dioxide (ZrO2), zinc oxide (ZnO), cerium
oxide (CeO2), nano silver, clay nanoparticles
5. The coating composition in accordance with Claim 1 wherein said reinforcing nanofibers are selected
from the group of nanofibers composed of titanium dioxide (TiO2), silicon dioxide (SiO2), zirconium
dioxide (ZrO2), aluminum oxide (Al2O3), lithium titanate (Li4Ti5O12), titanium nitride (TiN), platinum
(Pt), carbon (nanotubes and grapheme), polymeric or organometallic compounds.
6. The coating composition in accordance with Claim 1 wherein said solvent is selected from the group
of _____ or water (for zero-solvent applications).
7. The recess/method of formation the surfaces with hierarchical roughness based on consequent
application of the layers of different composition in accordance with Claims 1-6.
Use of micro- and mezo- particles (e.g., glass, basalt, mica, quartz, silica fume, micro silica, metakaolin,
clay)
Use of high-strength micro- and mezo- fibers (e.g., glass, HDPE, PET, PVA)
Use hollow-core fibers/particles micro-, mezo-, nano-sized and saturated with silane/siloxane-based
hydrophobic liquids
Use of silane/siloxane-based hydrophobic liquids: polydimethylsiloxane (PDMS), SiCl4 and fluorination
Use of Fluorosurfactants
Use of epoxy, acrylate, polyurethane, chitosan, PVA in the composition of matrix
Use of emulsifying agents (PVA, etc) for water-based RFP.