WO2012003004A2 - Superhydrophobic and anti-icing coating and method for making same - Google Patents

Superhydrophobic and anti-icing coating and method for making same Download PDF

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Publication number
WO2012003004A2
WO2012003004A2 PCT/US2011/001172 US2011001172W WO2012003004A2 WO 2012003004 A2 WO2012003004 A2 WO 2012003004A2 US 2011001172 W US2011001172 W US 2011001172W WO 2012003004 A2 WO2012003004 A2 WO 2012003004A2
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superhydrophobic
anti
particles
coating according
ranging
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PCT/US2011/001172
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French (fr)
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WO2012003004A3 (en )
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Di Gao
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University Of Pittsburgh-Of The Commonwealth System Of Higher Education
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1656Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662Synthetic film-forming substance
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1681Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1687Use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00Inorganic fillers
    • B05D2601/20Inorganic fillers used for non-pigmentation effect
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING LIQUIDS OR OTHER FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00Inorganic fillers
    • B05D2601/20Inorganic fillers used for non-pigmentation effect
    • B05D2601/22Silica

Abstract

Superhydrophobic and anti-icing coating composed of resin, clustered particles, a solvent, and/ or a surfactant. The clustered particles, ranging in diameter from 0.2 to 5 micrometers, are formed from small individual particles ranging in diameter from 2 to 200 nm that are aggregated into, agglomerated into, assembled into clusters or attached onto larger micrometer- sized particles. The surface of the clustered particles is hydrophobic. The surfactant diffuses to the surface of the resin during the curing of the resin when added to improve the water repellency of the original resin that binds the nanoparticles to a substrate. The coatings made through this method have superior water-repellency and anti-icing properties.

Description

SUPERHYDROPHOBIC AND ANTI-ICING COATING AND METHOD FOR

MAKING SAME

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a Non-provisional Application of U.S. Provisional Application No: 61 /360,618, titled: SUPERHYDROPHOBIC COATING AND METHOD FOR MAKING SAME, filed on July 1 , 2010, herein incorporated by reference.

FIELD OF THE INVENTION

[0002] The present invention is related generally to the composition and method of making superhydrophobic and anti-icing coatings, and in particular to resin with clustered particles to form the superhydrophobic and anti-icing coatings.

SUMMARY OF THE INVENTION

[0003] The present invention is a superhydrophobic and anti-icing coating composed of a resin (such as polyurethane, polyacrylate, or silicone based coatings) and clustered particles. The clustered particles are formed from small individual particles ranging in diameter from 2 to 200 nm aggregated into, agglomerated into, or assembled into clusters. The clustered particles range in diameter from 0.2 to 5 micrometers either before or after being added to the resin. Alternatively, the clustered particles can be made by attaching or growing small particles ranging in diameter from 2 to 200 nm onto larger particles ranging in diameter from 0.2 to 5 micrometers. Typically, the clustered particles have a flower-like or raspberry- like morphology, with a surface roughness in the nanometer scale as a result of packing or clustering the smaller nanometer-sized particles. The surface of the finished coating typically has a two-tier roughness— the first tier in the micrometer scale corresponding to the size of the larger particles and the second tier in the nanometer scale corresponding to the size of the smaller nanoparticles. Solvent can be added to dilute the mixture to reduce the viscosity. When the hydrophobicity of the polyurethane, polyacrylate, or silicone resin is not high enough (i.e. the water contact angle of the resin is less than 90°) to make the final finished coating superhydrophobic, a surfactant can be added to the coating mixture. The surfactant is able to diffuse to the surface of the resin during the curing of the resin, which improves the water repellency of the original resin that binds the nanoparticles to a substrate. The coatings made through this method have superior water-repellency and are anti-icing.

BRIEF DESCRIPTION OF THE DRAWINGS

[0004] For the present invention to be easily understood and readily practiced, the invention will now be described, for the purposes of illustration and not limitation, in conjunction with the following figures, wherein:

[0005] FIG. 1 is a schematic for making silica nanoparticles attached onto a bigger micrometer- sized silica particle by chemical synthesis;

[0006] FIG. 2 is a representative scanning electron microscopy (SEM) image of silica nanoparticles attached to a larger micrometer-sized particle. Scale bar, 500 nm;

[0007] FIGS. 3a-c illustrate flower-like Fe2O3 particles: FIG. 3a is a SEM image of a particle, showing its flower-like morphology; FIG. 3b) is a transmission electron microscopy (TEM) image of two Fe2O3 particles, showing that they are spheres of 1 -2 micrometer in diameter with 40-60 nm thick distorted plates on the surface; and FIG.3c is a TEM image taken at the edge of a plate, showing that the thin plate is composed of interconnected crystals of about 5 nm in diameter;

[0008] FIGS. 4a-b show images of 100 - 300 nm Fe3O4 particles in a raspberry-like shape which are assemblies of 10 - 20 nm Fe3O4 crystals: FIG. 4a is a SEM image of raspberry-like Fe3O4 particles of 100 - 300 nm in diameter; FIG 4b is a TEM image which shows that each Fe3O4 particle is an assembly of smaller Fe3O4 crystals with diameters varying from 10 to 20 nm; [0009] FIGS. 5a-d present micrometer- and submicrometer- sized organocopper particles in varied shapes that consist of assemblies of nanometer-sized particles. The particles are prepared with (a) 9 mM, (b) 20 mM„ (c) 36 mM, and (d) 1 10 mM Cu(CH3COO)2, respectively. The circular openings on the outer shell of the particles are indicated by white arrows in (d); and

[0010] FIGS. 6a-b present SEM and TEM images of micrometer-sized CuO particles in a doughnut-like shape composed of assemblies of less than 10 nm CuO crystals: FIG 6a is an SEM image; FIG 6b is an TEM image.

DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention is a superhydrophobic coating composed of (i) resin, (ii) micrometer or submicrometer- sized particles as assemblies or clusters of nanometer-sized particles, (iii) one or more solvents, as required, and (iv) one or more surfactants, as required.

[0012] (i) Resin

[0013] The resin can be any commercially available resin or resin contained in commercial coatings, such as polyure thane, poly aery late, or silicone coatings, from coating companies such as PPG, Valspar, Minwax and/ or chemical suppliers such as Bayer Material Science, BASF, DuPont, Dow Corning. These coatings are typically formulated for specific applications (e.g. marine coatings, automobile coatings, aircraft coatings, indoor or outdoor furniture coatings, etc.) and for specific substrates (metal, ceramic, wood, glass, etc.). The weight percentage of resin in the final superhydrophobic coating ranges from about 5 to about 95 weight percentage. In another embodiment of the present invention, the weight percentage of the resin varies between 10 to 90. Yet in another embodiment of the present invention, the weight percentage of the resin varies between 25 to 75. Yet in another embodiment of the present invention, the weight percentage of the resin is about 50. [0014] (ii) Clustered Particles

[0015] In one embodiment of the present invention, the clustered particles incorporated into the coatings range in diametral size from 0.2 to 5 micrometers. The clustered particles are formed by individual particles or crystals in the size of 2 to 200 nm aggregating into, agglomerating into, or assembling into clusters. The individual particles may assemble into clustered particles before they are dispersed into the coatings, e.g. by physical attachment or aggregation, chemical synthesis, chemical assembly, or electrostatic interaction. The individual particles may also assemble or agglomerate into clustered particles after dispersed into the coatings during the curing of the polymer resin, such as during the crosslinking of the polymer resin, in situ polymerization of the resin, or evaporation of the solvent. Alternatively, the clustered particles can be made by attaching or growing small particles ranging in diameter from 2 to 200 nm onto larger particles ranging in diameter from 0.2 to 5 micrometers before they are mixed with the resin.

[0016] Typically, the assembled or clustered particles have a flower-like or raspberry-like morphology, with a surface roughness in the nanometer scale as a result of packing or clustering the smaller nanometer-sized particles into one large particle. The surface of the finished coating typically has a two-tier roughness— the first tier in the micrometer scale with a root mean square (RMS) roughness ranging from 0.2 to 5 micrometers corresponding to the size of the larger particles and the second tier in the nanometer scale with a RMS roughness ranging from 2 to 200 nm corresponding to the size of the smaller nanoparticles. The roughness in both tiers is important to induce the superhydrophobicity of the final coating.

[0017] The major chemical composition of the particles may be chosen from a group, including but not limited to oxides (such as silicon oxide, titanium oxide, aluminum oxide, iron oxide, magnesium oxide, manganese oxide, copper oxide, and zinc oxide), metals (such as iron, aluminum, copper, silver, and gold), and polymers (such as polytetrafluoroethylene and polyvinylidenefluoride). The native surface of the assembled particles may be either hydrophobic (such as polytetrafluoroethylene and polyvinylidenefluoride particles) or hydrophilic (such as metal oxide particles). If the native surface of the assembled particles is hydrophilic, then the surface of the particles needs to be modified with chemicals that render hydrophobicity to the particles. Such chemicals may be selected from a group of molecules, whose end group can be either -CF3 [such as n- C6Fi3CH2CH2Si(CH3CH20)3] , -CF2H, -CH2F, or -CH3. The chemicals may be attached to the particle surface by covalent chemical bonds, electrostatic interaction, or Van der Waals force. Methods for coating particles with such chemicals have been well established. Alternatively, the hydrophilic particles may also be made hydrophobic by attaching components of a hydrophobic resin in the base coatings to the particle surface during the crosslinking of the polymer resin or in situ polymerization of the resin.

[0018] Another embodiment of the present invention includes nanoparticles having a diameter about 100 nm or less. Yet another embodiment of the present invention includes nanoparticles having a diameter about 20-50 nm. The weight percentage of the nanoparticles varies between 1 to 20% in the wet coating mixture, and between 1 to 80% in the cured dry coating.

[0019] (iii) Solvents

[0020] If the assembled or clustered particles are hydrophilic and the base coating is water soluble, then the clustered particles can be dispersed in the base coating in aqueous solution (such as water, acid, or base aqueous solution). If the assembled or clustered particles are hydrophobic, then dispersion of the hydrophobic clustered particles in aqueous solution becomes difficult, and a mixture of organic solvents may be used. The organic solvents can be selected from a group of commercially available solvents (such as acetone, toluene, heptane, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, Eastman PM acetate, isopropyl acetate, ethanol, solvent Naphtha, Stoddard solvent, xylene, etc.) and can be a mixture of several different solvents. The weight percentage of the solvent varies between 5 to 95.

[0021] (iv) Surfactant

[0022] Another embodiment of the present invention includes surfactants mixed into the coating system where the polyure thane, polyacrylate, or silicone base coatings do not possess high enough hydrophobicity (water contact angle in less than 90 degrees) to make the final coating superhydrophobic (even after they are mixed with hydrophobic particles). The function of the surfactant is to improve the hydrophobicity of the polyurethane, polyacrylate, or silicone base coatings. If the coating system is in aqueous solution, the surfactant needs to be soluble in water; whereas if the coating system uses organic solvent (or oil-based), the surfactant needs to be soluble in oil-based vehicles and solvents. One embodiment of the surfactant is that it is able to diffuse to the surface of the coating during the curing of the coating, so that only a small percentage (0. 1-2.0 weight percentage) of surfactant is needed. Such surfactants may also be selected from a group of commercial products including, but not limited to, fluorinated polymers produced by DuPont with Tradenames of Zonyl® or Capstone®.

[0023] The following examples of making clustered particles that are formed by small particles being aggregated into, agglomerated into, assembled into, or attached onto larger particles, and examples of making superhydrophobic and anti-icing coatings using such clustered particles are intended to illustrate the invention and should not be construed as limiting the invention in any way.

[0024] Example 1. Method for making silica particles with a primary size of about 50 nm attached to a micrometer-sized particle

[0025] Now turning to Figure 1 illustrating a chemical synthesis process for making silica nanoparticles attached onto a bigger micrometer- sized silica particle. Silica nanoparticles with a primary size of about 50 nm attached to a micrometer-sized particle are made by the following procedure. 20 mg silica particles with a diameter of about 1 micrometer (purchased from Sigma-Aldrich) are mixed with 20 ml ethanol in a beaker or flask. The mixture is sonicated for 30 min.; 5 mL 25 weight percentage aqueous ammonia is added to the mixture under stirring. The mixture is stirred for another 30 min before 160 μΐ tetraethylorthosilicate (TEOS) was added under stirring. The mixture is then stirred for 3 hours, during which silica nanoparticles are synthesized on the surface of the micrometer-sized silica particles via the Stober reaction. Afterwards, the product is washed with ethanol, centrifuged, and collected. The washing step may be repeated by redispersing the product in ethanol if necessary. After the final washing step, the product is dried in oven and calcinated at 550 °C for 4 h. Figure 2 shows a typical scanning electron microscopy (SEM) image of the final product of silica nanoparticles attached to a larger micrometer-sized particle. Scale bar, 500 nm.

[0026] Both the synthesized silica nanoparticles and the micrometer- sized particles that they are attached to can be functionalized by molecules having an end group of -CF3, -CF2H, -CH2F, or -CH3 to render hydrophobicity to the particles. The following describes a specific procedure as an example to functionalize the particles with (tridecafluoro- 1 , 1,2,2, -tetrahydrooctyl) trichlorosilane.

[0027] Step 1 : 0.5 mM (tridecafluoro- 1 , 1 , 2,2, -tetrahydrooctyl) trichlorosilane (n-CeF CI-teCI-bSiCh, >95%, purchased from Gelest Inc.) is dissolved into a 4: 1 (v/v) mixture of hexadecane and chloroform.

[0028] Step 2: The silica nanoparticles are dispersed into the mixture.

[0029] Step 3: The mixture is stirred for 15 min and then centrifuged.

[0030] Step 4: The silica nanoparticles were collected and then rinsed with isooctane and isopropanol in sequence by centrifugation-redispersion cycles. [0031] Step 5: The particles are finally dried in oven at 60 °C.

[0032] Example 2. Method for making flower-like Fe2O3 particles that comprise of nanometer particles attached to micrometer-sized particles.

[0033] The flower-like Fe2O3 particles are synthesized by using an ethylene glycol (EG)-mediated reaction. In a typical synthesis process, approximately 0.7 g Fe( Os)3 (Fisher Scientific) and approximately 0.7 g urea [CO(NH2)2, Sigmar-Aldrich] are added into approximately 60 mL ethylene glycol (C2H6O2, J.T. Baker) to form a cloudy mixture. The mixture is then stirred with a magnetic stirrer bar and heated to about 170°C. The cloudy mixture turns clear in approximately 10 minutes and becomes opaque again after approximately 20 minutes, indicating the formation of iron oxide precursor. The products are collected by centrifugation-redispersion cycles with alcohol. The collected products are then calcinated in air at about 450°C for approximately 3 hours in a tube furnace (Lindberg) to obtain Fe203 particles.

[0034] SEM and TEM images of the synthesized particles are shown in Figs. 3a and 3b, respectively. These particles are spheres of 1-2 micrometer in diameter. They have a rough surface consisting of 40-60 nm thick distorted plates, which resemble the shape of petals of a flower. Figure 3c shows a TEM image taken at the edge of a plate on the surface of the particle, which indicates that the thin plate is composed of interconnected crystals of about 5 nm in diameter.

[0035] The synthesized Fe2O3 particles can be functionalized by molecules having an end group of -CF3, -CF2H, -CH2F, or -CH3. The following describes a specific procedure as an example to functionalize the particles with (Tridecafluoro- l, l ,2,2,-tetrahydrooctyl) trichlorosilane.

[0036] STEP 1 : 0.5 mM (Tridecafluoro- l , l ,2,2,-tetrahydrooctyl) trichlorosilane (n-CeF^CI-^Cl^SiC , >95%, purchased from Gelest Inc.) is dissolved into a 4: 1 (v/v) mixture of hexadecane and chloroform. [0037] Step 2: The Fe2O3 nanoparticles are dispersed into the mixture.

[0038] Step 3: The mixture is stirred for approximately 15 minutes and then centrifuged.

[0039] Step 4: The Fe2O3 nanoparticles are collected by centrifugation and then rinsed with isooctane and isopropanol in sequence by centrifugation-redispersion cycles.

[0040] Step 5: The particles are finally dried in oven at about 60 °C.

[0041] Example 3. Method for making raspberry-like Fe3O4 particles that comprise of nanometer particles assembled to micrometer- sized particles.

[0042] In a typical synthesis process, 0.82 g FeC.3 is dissolved in 40 ml ethylene glycol with vigorous stirring. When the solution become clears, 3.6 g NaAc is added with continuous stirring for 30 min. The mixture is then transferred into a 50 ml teflon-lined stainless-steel autoclave and reacted at 200°C for 12 h. After the reaction is completed, the autoclave is cooled to room temperature. The product in a black color is collected, rinsed with ethanol for several times, and dried at 60°C.

[0043] Figure 4a shows an SEM image of 100 - 300 nm Fe304 particles in a raspberry-like shape made by this method. Figure 4b is a TEM image of these particles which shows that each Fe304 particle is an assembly of smaller Fe3O4 crystals with diameters varying from 10 to 20 nm.

[0044] Example 4. Methods for making organocopper particles in varied shapes, including microplates, doughnut-like structures, and multi-layer microspheres, that comprise of nanometer particles assembled to micrometer- sized particles.

[0045] In a typical synthesis process, copper acetate [Cu(CH3COO)2] (Sigma- Aldrich) was added into 30 mL ethylene glycol (J. T. Baker) to a final concentration of 3-200 nM. The mixture forms a cloudy solution and is stirred with a magnetic stirrer bar and heated to 150 °C. The cloudy mixture turns clear in 10 min and becomes opaque again after another 20 min, indicating the formation of organocopper particles. The product is collected after another 10 min by centrifugation-redispersion cycles with alcohol. If it is needed, this product can be calcinated at 400 °C for 2 h to obtain crystalline copper oxide.

[0046] The morphology of the organocopper particles could be gradually regulated by tuning the initial concentration of Cu(CH3COO)2 in the reaction system. A series of samples are synthesized by varying the initial concentration of Cu(CH3COO)2 while keeping other process parameters constant as described above. When the initial Cu(CH3COO)2 concentration is 9 mM, a plate-like structure is produced. As shown in Figure 5a, these plates are uniform in shape with the diameter around 1 pm and thickness around 200 nm. A higher magnification of a representative plate (inset of Figure 5a) shows that the surface of the plate is rough and tends to twist. When the initial concentration of Cu(CH3COO)2 is 20 mM, such tendency of surface twist becomes more apparent. As a result, a doughnut-like structure is formed as shown in Figure 5b. These particles are uniform in shape and size with the diameter around 2 pm and height about 1 pm. Each particle has convex surfaces with concaved holes on its both sides, giving the whole structure a "doughnut-like" morphology. When the initial concentration of Cu(CH3COO)2 is increased to 36 mM, the concaved holes are partially filled as shown in Figure 5c. Consequently, the particles tend to be rounded. When the initial concentration of Cu(CH3COO)2 is further increased to 1 10 mM, spherical particles are formed with an average diameter of about 10 μπι (Figure Id) . Incomplete shells with circle openings are found on the outer side of some particles (as indicated by the white arrows in Figure 5d), suggesting that these microspheres are grown in a layer-by-layer mode.

[0047] CuO particles may be prepared by calcinating the organocopper particles as synthesized by the abovementioned methods at 400 °C in air for 2 h. The various morphologies of the organocopper particles shown in Figure 5 are not significantly changed by the calcination process. Figures 6a and 6b present representative SEM and TEM images, respectively, of the sample made by calcinating the doughnut-like organocopper particles shown in Figure 5b, showing the preservation of the doughnut-like morphologies. A high-magnification TEM image taken at the edge of the CuO particle reveals that the particle consists of interconnected crystallites of less than 10 nm in size.

[0048] Example 5. Method for converting a commercial coating product PPG DC3000 to a superhydrophobic and anti-icing coating:

[0049] This example describes the procedure to convert a commercial coating product PPG DC3000 to a superhydrophobic and anti-icing coating.

[0050] 1. A polyurethane or polyacrylate coating used in this example is PPG DC3000 with a hardener PPG DCH3070. PPG DC3000, a clear coat currently used for automobile industry, is typically sold with a hardener (such as DCH 3070), which is mixed with DC3000 before application. The hardener acts as a crosslinker and is essential to obtain a coating with a high hardness. Material Safety Data Sheets were published by PPG for DC3000 on November 12, 2009 and for DCH3070 on December 19, 2009.

[0051] 2. Silica particles as synthesized in example 1 are used. Alternatively, Fe2O3 particles as synthesized in example 2, Fe3O4 particles as synthesized in example 3, organocopper or CuO particles as synthesized in example 4 may be used.

[0052] 3. Acetone is used as the solvent.

[0053] 4. A fluorinated polymer, purchased from DuPont with a trade name Zonyl® or Capstone®, is the surfactant.

[0054] The coating is made by mixing the above components contemporaneously in any order at room temperature at the following weight percentages: DC3000 (20-40%), DCH3070 (7- 12%), silica or Fe2O3 particles (2- 10%), the fluorinated surfactant (0. 1-2%) , and acetone (40-60%) . [0055] The coating cures at room temperature in approximately 12 hours. The cured coating has superior water repellency since the static water contact angle of the cured coating is measured to be greater than about 160°.

[0056] The process also imparts anti-icing properties to the final product, as indicated by the following static ice accumulation test. Nine aluminum beams (172 x 38.5 x 3 mm) coated with the product are compared to nine bare aluminum beams. Three panels of each sample are placed on a support at angles of 0, 45, and 80 degrees to the horizontal. All 18 samples are iced at - 1°C with a fine vertical water spray equivalent to freezing drizzle at a rate of 7.0 ± 0.5 mm/h for 30 minutes. The amount of ice accumulated was determined from the difference in weight before and after icing. Ice accumulation reduction factor (IARF) is measured, which is defined by the following equation:

[0057] Ice Accumulation Reduction Factor (IARF) = (Mean ice mass on bare aluminum) / (Mean ice mass on the coated aluminum)

[0058] IARF is measured to be 2-3 at 0° tilting angles, 4-5 at 45° tilting angles and 4-5 at 80° tilting angles.

[0059] It should be noted in the case that the commercial polyurethane, polyacrylate, or silicone coatings possess a high enough hydrophobicity, indicated by a static water contact angle of greater than 90°, the use of the surfactant is not necessary but may further improve the water-repellency and anti-icing properties of the coating.

[0060] It should also be noted that silica nanoparticles with a primary size of about 50 nm and functionalized with -CH3 terminated molecules may be purchased from commercial suppliers such as PPG. Due to nonspecific interactions between the particles, these silica nanoparticles may be agglomerated into larger particles with a diameter in the order of 0.2 to 5 micrometers as received. In such cases, these commercially available particles may be used to replace the synthesized silica or Fe2O3 particles in this example.

[0061] While the disclosure has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the embodiments. Thus, it is intended that the present disclosure cover the modifications and variations of this disclosure provided they come within the scope of the appended claims and their equivalents.

Claims

What is claimed is:
1. A superhydrophobic and anti-icing coating comprising: a resin; and a plurality of individual particles ranging in diametrial size from 2 to 200 nm clustered together to form a plurality of clustered particles ranging in diametrial size from 0.2 to 5 micrometers, wherein a surface of the coating has a two-tier roughness.
2. The superhydrophobic and anti-icing coating according to Claim 1 , wherein the resin is selected from a group consisting of a polyure thane, a polycrylate, and a silicone based coating;
3. The superhydrophobic and anti-icing coating according to Claim 1 , further comprising one or more solvents.
4. The superhydrophobic and anti-icing coating according to Claim 1 , wherein the two-tier roughness comprises a first tier roughness in the micrometer scale with a root mean square (RMS) roughness ranging from 0.2 to 5 micrometers and a second tier roughness in the nanometer scale with a RMS roughness ranging from 2 to 200 nm.
5. The superhydrophobic and anti-icing coating according to Claim 1 , further comprising a surfactant to increase hydrophobicity of the polyure thane, polyacrylate, or silicone base coating, wherein a static water contact angle of the polyure thane polyacrylate, or silicone base coating is 90° or less.
6. The superhydrophobic and anti-icing coating according to Claim 1, wherein the resin ranges from about 5 to about 95 weight percentage.
7. The superhydrophobic and anti-icing coating according to Claim 1, wherein the solvent from about 5 to about 95 weight percentage.
8. The superhydrophobic and anti-icing coating according to Claim 5, the surfactant ranging from about 0.1 to about 2.0 weight percentage.
9. The superhydrophobic and anti-icing coating according to Claim 1, wherein each individual particle of the plurality of individual particles range in diametrial size from 2 to 200 nm clustered together to form the plurality of clustered particle ranging in diametrial size from 0.2 to 5 micrometers.
10. The superhydrophobic and anti-icing coating according to Claim 1 , wherein each individual particle of the plurality of individual particles range in diametrial size from about 100 nm or less.
1 1. The superhydrophobic and anti-icing coating according to Claim 1 , wherein each individual particle of the plurality of individual particles range in diametrial size from about 20 nm to about 50 nm.
12. The superhydrophobic and anti-icing coating according to Claim 1 , wherein weight percentage of the plurality of clustered particles varies between 1 to 20% in the wet coating mixture, and between 1 to 80% in the cured dry coating.
13. The superhydrophobic and anti-icing coating according to Claim 1 , wherein the resin ranges from about 10 to about 90 weight percentage.
14. The superhydrophobic and anti-icing coating according to Claim 1 , wherein the resin ranges from about 25 to about 75 weight percentage.
15. The superhydrophobic and anti-icing coating according to Claim 1 , wherein the resin is about 50 weight percentage.
16 A superhydrophobic and anti-icing coating comprising: a resin ranging from about 5 to about 95 weight percentage; and clustered particles ranging from about 1 to about 20 weight percentage.
17. The superhydrophobic and anti-icing coating according to Claim 16, wherein the resin is selected from a group consisting of a polyure thane, a polyacrylate, and a silicone base coating.
18. The superhydrophobic and anti-icing coating according to Claim 16, further comprising a solvent ranging from about 5 to about 95 weight percentage.
19. The superhydrophobic and anti-icing coating according to Claim 16, further comprising a surfactant ranging from about 0.1 to about 2.0 weight percentage.
20. The superhydrophobic and anti-icing coating according to Claim 16, wherein the clustered particles range in diametrial size from 0.2 to 5 micrometers.
21. The superhydrophobic and anti-icing coating according to Claim 16, wherein the clustered particles are formed by a plurality of particles ranging in diametrial size from 2 to 200 nm.
22 A method to manufacturing a superhydrophobic and anti-icing coating comprising the steps of: mixing a resin and clustered particles formed by small particles aggregating into, agglomerating into, assembling into, or attaching onto large particles, wherein the small particles and the large particles are selected from a group consisting in range in diametral size from 2 to 200 nm; applying the mixture onto a substrate by brush, spray, roller, or dip coating; and curing the coating.
23. The superhydrophobic and an ti- icing coating according to Claim 22, wherein the resin is selected from a group consisting of a polyurethane, a polyacrylate, and a silicone base coating.
24. The superhydrophobic and anti-icing coating according to Claim 22, further comprising a solvent ranging from about 5 to about 95 weight percentage.
25. The superhydrophobic and anti-icing coating according to Claim 22, further comprises a surfactant ranging from about 0.1 to about 2.0 weight percentage.
26 A method to manufacturing a superhydrophobic and anti-icing coating comprising the steps of: mixing a resin and particles ranging in diametral size from 2 to 200 nm; applying the mixture onto a substrate by brush, spray, roller, or dip coating; and curing the coating, wherein the particles aggregate into, agglomerate into, assemble into, or attached onto each other to form a plurality of clustered particles ranging in diametrial size from 0.2 to 5 micrometers during the curing step.
27. The superhydrophobic and anti-icing coating according to Claim 26, further comprising a solvent ranging from about 5 to about 95 weight percentage.
28. The superhydrophobic and anti-icing coating according to Claim 26, further comprises a surfactant ranging from about 0. 1 to about 2.0 weight percentage.
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