Patent Description:
Accumulation of frost, ice, or snow on aircraft changes airflow over aircraft wings, reducing lift and increasing drag. The accumulations also add to the total weight, increasing lift required for takeoff. Accordingly, frost, ice, or snow is normally removed prior to take-off. While in flight, hot engine bleed air, electric blankets, mechanical boots, or combinations thereof may be used to keep ice off exterior surfaces of aircraft. These measures, however, consume energy, add weight to the aircraft, and reduce fuel economy.

On the ground, anti-icing and de-icing fluids in the form of hot glycol sprays are used. While effective, such fluids generate an added expense and may cause gate delays from additional application time. As a result, new options for removing ice from aircraft are desirable.

Fluoropolymers can be coated onto a surface to reduce or prevent ice accumulation. However, conventional methods, such as conventional spray coating methods, for forming coatings, such as fluoropolymer coatings, provide coatings having voids which can limit the mechanical properties and/or smoothness of the outer surface of the coating which can limit resistance to sand and rain at high speed (e.g., <NUM> mph - <NUM> mph; <NUM> kph - <NUM> kph). Furthermore, conventional methods for fluoropolymer deposition provide fluoropolymer coatings having a maximum thickness of about <NUM> mils (about <NUM>), e.g. over a curved surface of the aircraft part because of creep/flow of the deposited coating. In addition, if a fluoropolymer is mixed with a substantial amount of another component, conventional methods for fluoropolymer deposition promote "waxing out" of the fluoropolymer from the deposited layer.

<CIT>, in accordance with its abstract, states the present disclosure provides methods for forming a fluoropolymer coated component, such as a metal component, comprising applying an adhesion promoter onto a surface of the component; applying an organic material onto the adhesion promoter; and applying a mixture comprising a fluoropolymer and a solvent selected from a furan or a fluorinated solvent onto the organic material. Aspects of the present disclosure further provide fluoropolymer coatings having a thickness of from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>) on a component, an average porosity of from about <NUM>% to about <NUM>% based on the total volume of the layer, and a void density of from about <NUM><NUM> to about <NUM><NUM> voids per cm<NUM>.

<CIT>, in accordance with its abstract, states this invention provides durable, low-ice-adhesion coatings with excellent performance in terms of ice-adhesion reduction. Some variations provide a low-ice-adhesion coating comprising a microstructure with a first-material phase and a second-material phase that are microphase-separated on an average length scale of phase inhomogeneity from <NUM> micron to <NUM> microns. Some variations provide a low-ice-adhesion material comprising a continuous matrix containing a first component; and a plurality of discrete inclusions containing a second component, wherein the inclusions are dispersed within the matrix to form a phase-separated microstructure that is inhomogeneous on an average length scale from <NUM> micron to <NUM> microns, wherein one of the first component or the second component is a low-surface-energy polymer, and the other is a hygroscopic material. The coatings are characterized by an AMIL Centrifuge Ice Adhesion Reduction Factor up to <NUM> or more. These coatings are useful for aerospace surfaces and other applications.

<CIT>, in accordance with its abstract, states disclosed are materials that possess both low adhesion and the ability to absorb water. The material passively absorbs water from the atmosphere and then expels this water upon impact with debris, to create a self-cleaning layer. The lubrication reduces friction and surface adhesion of the debris (such as an insect), which may then slide off the surface. The invention provides a material comprising a continuous matrix including a polymer having a low surface energy (less than <NUM> mJ/m<NUM>) and a plurality of inclusions, dispersed within the matrix, each comprising a hygroscopic material. The continuous matrix and the inclusions form a lubricating surface layer in the presence of humidity. The material optionally contains porous nanostructures that inject water back onto the surface after an impact, absorbing water under pressure and then releasing water when the pressure is removed. The material may be a coating or a surface, for example.

<CIT>, in accordance with its abstract, states variations of this invention provide durable, impact-resistant structural coatings that have both dewetting and anti-icing properties. The coatings in some embodiments possess a self-similar structure that combines a low-cost matrix with two feature sizes that are tuned to affect the wetting of water and freezing of water on the surface. Dewetting and anti-icing performance is simultaneously achieved in a structural coating comprising multiple layers, wherein each layer includes (a) a continuous matrix; (b) discrete templates dispersed that promote surface roughness to inhibit wetting of water; and (c) nanoparticles that inhibit heterogeneous nucleation of water. These structural coatings utilize low-cost, lightweight, and environmentally benign materials that can be rapidly sprayed over large areas using convenient coating processes. The presence of multiple layers means that if the surface is damaged during use, freshly exposed surface will expose a coating identical to that which was removed, for extended lifetime.

There is a need for methods for forming smooth void-free icephobic coatings.

Aspects of the present disclosure provide coatings and methods for depositing coatings onto surfaces.

In one aspect, a coating includes the reaction product of a first polymer, a second polymer that is a fluoropolymer, an isocyanate, and a curative (e.g., polyol or polyamine curative) having a molecular weight less than the molecular weight of the first polymer. The coating has a thickness of from about <NUM> mils to about <NUM> mils (about <NUM> to about <NUM>) and a void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>; wherein the first polymer is selected from poly(acrylic acid), polyethylene glycol), poly(<NUM>-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(<NUM>-methyl-<NUM>-oxazoline), poly(<NUM>-ethyl-<NUM>-oxazoline), poly(vinylpyrolidone), cellulose, modified cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydrogels, PEG diacryalate, PEG polyacrylates, or combinations thereof; or wherein the first polymer is selected from poly(oxymethylene), polyethylene glycol), polypropylene glycol), poly(tetrahydrofuran), poly(glycolic acid), poly(caprolactone), polyethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), or combinations thereof.

Aspects of the present disclosure further provide a method for forming a coating, the method including applying a composition to a surface of a component, the composition comprising a first polymer, a second polymer that is a fluoropolymer, an isocyanate, a curative; and solvent having a boiling point of from about <NUM> to about <NUM>. The first polymer is selected from poly(acrylic acid), polyethylene glycol), poly(<NUM>-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(<NUM>-methyl-<NUM>-oxazoline), poly(<NUM>-ethyl-<NUM>-oxazoline), poly(vinylpyrolidone), cellulose, modified cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydrogels, PEG diacryalate, PEG polyacrylates, or combinations thereof; or from poly(oxymethylene), polyethylene glycol), polypropylene glycol), poly(tetrahydrofuran), poly(glycolic acid), poly(caprolactone), poly(ethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), or combinations thereof. The method includes curing the composition at a first temperature of about <NUM> or greater; and increasing the first temperature to a second temperature of about <NUM> or greater. The method includes obtaining a coating disposed on the surface of the component, the coating having a thickness of from about <NUM> mils to about <NUM> mils (about <NUM> to about <NUM>) and a void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>.

Aspects of the present disclosure further provide an airfoil including: a root section having a first surface; an intermediate section having a first surface and coupled with the root section at a first end; a tip section having a first surface and coupled at a first end with a second end of the intermediate section; and a coating adjacent at least one of the first surface of the root section, the first surface of the intermediate section, and the first surface of the tip section. The coating includes the reaction product of a first polymer, a second polymer that is a fluoropolymer, an isocyanate, and a curative (e.g., a polyol or polyamine having a molecular weight less than the molecular weight of the first polymer). The coating has a thickness of from about <NUM> mils to about <NUM> mils (about <NUM> to about <NUM>) and a void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>.

So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to aspects, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical aspects of this present disclosure and are therefore not to be considered limiting of its scope.

It is contemplated that elements and features of one aspect may be beneficially incorporated in other aspects without further recitation.

Aspects of the present disclosure provide coatings and methods for depositing coatings onto surfaces. Methods can include applying a composition to a surface of a component, the composition including a first polymer, a second polymer that is a fluoropolymer, an isocyanate, and a curative (e.g., a polyol or a polyamine having a molecular weight less than the molecular weight of the first polymer). Methods can include curing the mixture at a first temperature of about <NUM> or greater and increasing the first temperature to a second temperature of about <NUM> or greater. The second temperature can be increased to a third temperature of about <NUM> or greater. Methods of the present disclosure can provide coatings having a thickness of from about <NUM> mils to about <NUM> mils (about <NUM> to about <NUM>) and a void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>, providing smooth icephobic coatings on surfaces, such as vehicle surfaces, with improved rain and sand erosion resistance.

<FIG> is a method <NUM> for manufacturing surfaces having smooth icephobic coatings disposed thereon. In at least one aspect, as shown in <FIG>, a surface, such as a surface of a component, can be abraded and/or washed with a solvent (block <NUM>). A component can be a part of a wind turbine, satellite, or a vehicle such as a car, a train, a boat, and the like. A vehicle component is a component of a vehicle, such as a structural component, such as an engine inlet lip, an airfoil, a wing, landing gear(s), a panel, or joint, of an aircraft. Examples of a vehicle component include an engine inlet lip, an airfoil (such as a rotor blade), an auxiliary power unit, a nose of an aircraft, a fuel tank, a tail cone, a panel, a coated lap joint between two or more panels, a wing-to-fuselage assembly, a structural aircraft composite, a fuselage body-joint, a wing rib-to-skin joint, and/or other internal component. In at least one aspect, a surface is abraded with an abrasion pad to provide an exposed surface. For example, an aluminum surface is abraded to remove oxidized aluminum and expose an elemental aluminum surface. In at least one aspect, an abrasion pad has an about <NUM> grit surface to about <NUM>,<NUM> grit, such as about <NUM> grit to about <NUM> grit. Suitable abrasion pads include Scotch-Brite™ abrasion pads available from <NUM> Corporation. An abraded surface can be washed with soap and water with scrubbing to remove any loose surface material or debris. After washing, the surface (such as a surface of a vehicle component) can be introduced into an alkaline solution containing a detergent. Additionally or alternatively, an alkaline solution containing a detergent can be sprayed on the surface. The alkaline solution can be aqueous sodium hydroxide, sodium bicarbonate, potassium carbonate, or sodium carbonate. A detergent can be Micro-<NUM>® detergent (which includes surfactants and chelators) available from International Products Corporation of Burlington, New Jersey. The pH of the alkaline solution containing a detergent can be from about <NUM> to about <NUM>, such as about <NUM>. The surface (such as a surface of a vehicle component) present in the alkaline solution having a detergent can be sonicated for about <NUM> minute to about <NUM> hour, such as about <NUM> minutes. The alkaline solution having a detergent provides additional removal of oxidation on the surface. The surface (such as a surface of a vehicle component) can then be removed from the solution, washed with water, and introduced into an acetone bath. The surface present in the acetone bath can be sonicated for about <NUM> minute to about <NUM> hour, such as about <NUM> minutes. The surface is removed from the acetone bath and dried. The surface can be stored under an inert atmosphere, such as nitrogen or argon, until further use.

A coating of the present disclosure can be applied to the abraded surface directly (for example, in the manner described below) or the abraded surface can undergo further surface preparation, for example, as described below.

In at least one aspect, as shown in <FIG>, a metal adhesion promoter is applied to the surface (block <NUM>) to enhance the bond of an organic material to the surface. The method includes applying an adhesion promoter that is the reaction product of acetic acid, zirconium tetra-n-propoxide, and (<NUM>-glycidyloxypropyl)trimethoxysilane. An adhesion promoter can be Boegel®, such as <NUM> Surface Pre-Treatment AC-<NUM> CB. The <NUM>% AC-<NUM> kit can be obtained from <NUM> Corporation. The adhesion promoter can be a layer on the surface. The <NUM>% AC-<NUM> is a non-chromate conversion coating and is typically disposed on aluminum, nickel, stainless steel, magnesium, and titanium alloys. AC-<NUM> has a Part A, which is an aqueous mixture of glacial acetic acid (GAA) and zirconium tetra-n-propoxide (TPOZ) and a Part B, which is (<NUM>-glycidyloxypropyl)trimethoxysilane (GTMS). The two components are mixed together (Part A + Part B) and the molar ratio of silicon to zirconium in the mixture is <NUM>:<NUM>. A molar ratio of acetic acid to TPOZ in Part A is <NUM>:<NUM>. The measured volumes of GAA and TPOZ can be mixed vigorously for about <NUM> minutes and then added to the Part A from the AC-<NUM> kit. The premixed Part A solution can then be added to a measured volume of the Part B solution from the AC-<NUM> kit and stirred followed by a <NUM> minute induction period. This solution is then disposed on the surface (such as a surface of a vehicle component) by spraying, immersing, brushing, and/or wiping. For example, suitable forms of spraying include spraying with a spray gun, high-volume, low-pressure spray gun, and/or hand pump sprayer. The solution is then cured (at room temperature or elevated temperature) to form a sol-gel. In at least one aspect, a curing temperature is from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>. Curing can be performed for a time period of from about <NUM> minutes to about <NUM> hours. An adhesion promoter layer can have a thickness of from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>).

As shown in <FIG>, an organic material is deposited onto the adhesion promoter (block <NUM>). The organic material can be a layer on the adjesion promoter. Organic material can include a primer such as an epoxy, a polyurethane, a primer material such as an epoxy or urethane primer, or a fiber-reinforced plastic. Depositing can include painting, spraying, immersing, contacting, adhering, and/or bonding sol-gel with the organic material to form an organic material layer. An organic material layer can have a thickness of from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>).

As shown in <FIG>, a coating is deposited or disposed onto the adhesion promoter layer or the organic material layer or surface (e.g., metal surface) (block <NUM>).

A coating of the present disclosure can be formed by applying a composition to a surface of a component (e.g., the organic material layer disposed on a vehicle component). As used herein, the term "composition" can include the components of the composition and/or the reaction product(s) of two or more components of the composition. As used herein, the term "mixture" can include the components of the mixture and/or the reaction product(s) of two or more components of the mixture.

Compositions of the present disclosure can include a first polymer, a second polymer that is a fluoropolymer, an isocyanate, optional filler, and a curative (a polyol or a polyamine) having a molecular weight less than the molecular weight of the first polymer.

For example, a composition can be formed by mixing a first polymer and an isocyanate and heating the mixture (e.g., at a temperature of from about <NUM> to about <NUM>, such as about <NUM>) with stirring. A molar ratio of first polymer to isocyanate can be from about <NUM>:<NUM> to about <NUM>:<NUM>, such as about <NUM>:<NUM>. To the mixture, a tin catalyst can be added and stirred at the elevated temperature for from about <NUM> minutes to about <NUM> hours, such as about <NUM> hour. A tin catalyst can be any suitable catalyst configured to promote bonding of the first polymer with an isocyanate, such as any known organo tin catalyst for polyurethane synthesis. In at least one aspect, a tin catalyst is dibutyltin dilaurate.

An isocyanate can be one or more of <NUM>,<NUM>'-methylenebis(cyclohexyl isocyanate), hexamethylene diisocyanate, cycloalkyl-based diisocyanates, tolylene-<NUM>,<NUM>-diisocyanate, <NUM>,<NUM>'-methylenebis(phenyl isocyanate), or isophorone diisocyanate. In at least one aspect, a first polymer is a polyester, a polyether, a siloxane, or a combination thereof. For example, a siloxane can be polydimethylsiloxane. In one example, a first polymer is selected from poly(oxymethylene), polyethylene glycol), polypropylene glycol), poly(tetrahydrofuran), poly(glycolic acid), poly(caprolactone), polyethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), or combinations thereof. Alternatively, a first polymer can be selected from poly(acrylic acid), polyethylene glycol), poly(<NUM>-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(<NUM>-methyl-<NUM>-oxazoline), poly(<NUM>-ethyl-<NUM>-oxazoline), poly(vinylpyrolidone), cellulose, modified cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydrogels, polyethylene glycol) (aka, PEG) diacryalate, or polyethylene glycol) (aka, PEG) polyacrylates (e.g., triacrylates or greater), or combinations thereof. The first polymer can be a polyester or a polyether, in examples. In examples, the first polymer is polyethylene glycol).

To the mixture containing tin catalyst, a second polymer that is a fluoropolymer is added. A molar ratio of first polymer to second polymer can be from about <NUM>:<NUM> to about <NUM>:<NUM>, such as about <NUM>:<NUM>. The mixture containing the second polymer can be heated (e.g., at a temperature of from about <NUM> to about <NUM>, such as about <NUM>) with stirring for from about <NUM> minute to about <NUM> hours, such as about <NUM> hour. A fluoropolymer can include a polyfluoroether, a perfluoropolyether, a polyfluoroacrylate, a polyfluorosiloxane, a polytetrafluoroethylene, a polyvinylidene difluoride, a polyvinylfluoride, a polychlorotrifluoroethylene, a copolymer of ethylene and trifluoroethylene, a copolymer of ethylene and chlorotrifluoroethylene, or combinations thereof. In examples, the fluoropolymer is a perfluoropolyether. In at least one example, a fluoropolymer has a number average molecular weight of from about <NUM>/mol to about <NUM>,<NUM>/mol, such as from about <NUM>,<NUM>/mol to about <NUM>,<NUM>/mol. Fluoropolymers having a number average molecular weight of from about <NUM>/mol to about <NUM>,<NUM>/mol can provide sufficiently polar and large enough polymers to form a multiphasic composition in the presence of first polymer.

In at least one example, a fluoropolymer is represented by Formula (I):
<CHM>
wherein:.

The mixture containing the fluoropolymer, first polymer, and isocyanate can then be allowed to cool, e.g. to about <NUM> to about <NUM>. A solvent and a curative are added to the fluoropolymer mixture after or during the cooling such that the mixture, after addition of solvent and curative (e.g., polyol, polyamine, or a mixture thereof), includes from about <NUM> wt% to about <NUM> wt% solvent, such as from about <NUM> wt% to about <NUM> wt%, based on the total weight of the mixture. A molar ratio of curative to second polymer can be from about <NUM>:<NUM> to about <NUM>:<NUM>, such as about <NUM>:<NUM>.

The solvent and curative can be added to the mixture (fluoropolymer, first polymer, and isocyanate) sequentially or as a mixture of solvent and curative. The mixture containing fluoropolymer, first polymer, isocyanate, solvent, and curative can be stirred for from about <NUM> seconds to about <NUM> hour, such as from about <NUM> seconds to about <NUM> minute. The mixture containing first polymer, fluoropolymer, isocyanate, solvent, and curative is applied to a surface of a component (e.g., the organic material layer disposed on a vehicle component). Because of the low amounts of solvent used, the mixture containing first polymer, fluoropolymer, isocyanate, solvent, and curative can have a viscosity from about <NUM> Pa*s to about <NUM> Pa*s at <NUM>, such as from about <NUM> Pa*s to about <NUM> Pa*s at <NUM> as determined by ASTM D445 - 17a. A mixture containing first polymer, fluoropolymer, isocyanate, solvent, and curative can provide a viscosity sufficiently high, such as <NUM> Pa*s or greater, to coat non-flat surfaces, such as non-flat metal surfaces, conformally (e.g., conformal deposition onto a curved surface of a vehicle component). The conformal coating can have a substantially uniform thickness across the surface. After a stage-wise curing of the present disclosure, the conformal coating can also have a low void content because of one or more of the low solvent content, high boiling point of the solvent, and stage-wise curing.

A solvent can be a hydrocarbon solvent, an ester solvent, or a fluorinated solvent. A solvent has a boiling point of from about <NUM> to about <NUM>. Ester solvents can include ethyl acetate, n-butyl acetate, or a mixture thereof. Hydrocarbon solvents can include toluene or xylenes. Fluorinated solvents can include <NUM>-chlorobenzotrifluoride, <NUM>,<NUM>-bis(trifluoromethyl)benzene, or a mixture thereof. Solvents of the present disclosure can provide dissolution of the components of the mixture in addition to having a boiling point that (in combination with the stage-wise curing described below) provides coatings having little or no voids.

A curative (e.g., a polyol or a polyamine) of the present disclosure can have a molecular weight less than the molecular weight of the first polymer. A polyol can have a molecular weight of <NUM>,<NUM>/mol or less. A polyol can be selected from <NUM>,<NUM>-butanediol, <NUM>,<NUM>-propanediol, <NUM>,<NUM>-ethanediol, glycerol, trimethylolpropane, or a mixture thereof. A polyamine can have a molecular weight of <NUM>,<NUM>/mol or less. A polyamine can be selected from ethylenediamine, isophoronediamine, or diaminocyclohexane. Without being bound by theory, it is believed that a curative (e.g., a polyol or a polyamine) of the present disclosure can provide crosslinking of first polymer phases with second polymer phases to provide added strength to a multiphasic system.

In addition, a composition of the present disclosure can optionally further include one or more particulate fillers, a pigment, a dye, a plasticizer, a flame retardant, a flattening agent, and a substrate adhesion promoter. A particulate filler may be selected from silica, alumina, silicates, talc, aluminosilicates, barium sulfate, mica, diatomite, calcium carbonate, calcium sulfate, carbon, wollastonite, or combinations thereof. For example, a filler can be introduced to the composition before or while the first polymer and the isocyanate are being mixed.

The mixture containing first polymer, second polymer, isocyanate, solvent, and curative (and optional filler) can be applied to a surface of a component (e.g., the organic material layer) and cured. The mixture can be applied to a surface of a component by spray coating, dip coating, doctor-blade coating, spin coating, air knife coating, curtain coating, single and multilayer slide coating, gap coating, knife-over-roll coating, metering rod (Meyer bar) coating, reverse roll coating, rotary screen coating, extrusion coating, casting, or printing.

For example, a mixture containing first polymer, second polymer, isocyanate, solvent, and curative can be poured onto the adhesion promoter layer or the organic material layer and drawn out across a surface of the adhesion promoter layer or the organic material layer with a doctor blade, draw down bar, direct or reverse gravure, offset gravure, Precision Slot Die, or Meyer rod to form a layer. The mixture can be drawn out at line speed of from <NUM> fpm to about <NUM> fpm at a coating web width of from about <NUM>" wide to about <NUM>" wide (about <NUM> to about <NUM>). The mixture can be drawn out in an inert atmosphere, e.g. nitrogen or argon. The layer can have a thickness of about <NUM> mils (about <NUM>) or greater. The drawn out mixture (layer) can be cured in a stage-wise process, as described in more detail below. In at least one aspect, the mixture is poured onto the adhesion promoter layer or the organic material layer through a gap, such as a slot die.

Alternatively, a mixture containing first polymer, second polymer, isocyanate, solvent, and curative can be sprayed onto the adhesion promoter layer or the organic material layer using any suitable spray apparatus, such as an airbrush. In at least one aspect, during spraying, a nozzle of the spray apparatus is separated from the surface of the adhesion promoter layer or the organic material layer at a distance of from about <NUM> inch to about <NUM> inches (about <NUM> to about <NUM>), such as from about <NUM> inches to about <NUM> inches (about <NUM> to about <NUM>), such as from about <NUM> inches to about <NUM> inches (about <NUM> to about <NUM>), which is a distance sufficiently close to the surface to provide spraying at a controlled location of the surface. In at least one aspect, the mixture containing first polymer, second polymer, isocyanate, solvent, and curative is sprayed onto the adhesion promoter layer or the organic material layer at a pressure of from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa), such as from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa). Other sprayer/pressure options can include: HVLP/LVLP from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa); Air brushes from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa); Hydraulic sprayers from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa); Robotic sprayers from about <NUM> to about <NUM> psi (about <NUM> kpa to about <NUM> kpa).

The nozzle of the spray apparatus is moved parallel to the surface of the adhesion promoter layer or the organic material layer. Two full movements of the nozzle parallel to the surface ("there and back") of the adhesion promoter layer or the organic material layer is referred to as one "pass". One pass can deposit the mixture onto the surface at a thickness of from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as about <NUM> mil (about <NUM>). A time period from one pass to a subsequent pass can be from about <NUM> minute to about <NUM> minutes, such as from about <NUM> minute to about <NUM> minutes, such as from about <NUM> minute to about <NUM> minutes. Providing time in between passes promotes solvent removal from layers deposited by individual passes. Furthermore, stage-wise curing of the present disclosure, after one or more of the passes, can promote removal of solvent from the layer of the pass to further reduce void content of compositions of the present disclosure.

After several passes, a mixture (as a layer) is formed having a thickness of from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>). It has been discovered that curing the mixture (layer) in a stage-wise process provides reduced void content of a cured composition (layer) of the present disclosure, which can provide smooth icephobic coatings on the surfaces of components, such as vehicle components. Curing further promotes removal of solvent from a composition (as a layer). Stage-wise curing further provides reduced "waxing out" of the fluoropolymer from the deposited layer.

For example, a mixture (layer) of the present disclosure can be cured at a first temperature, such as a first temperature of about <NUM> or greater, such as from about <NUM> to about <NUM>, such as from <NUM> to about <NUM>, such as from about <NUM> to about <NUM>. Curing the mixture at the first temperature can be performed for from about <NUM> minutes to about <NUM> hours (a "dwell time").

After a dwell time, the first temperature can be increased to a second temperature, such as a second temperature of about <NUM> or greater, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>. Increasing the first temperature to the second temperature can be performed at a ramp rate of about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min. Curing the mixture at the second temperature can be performed for from about <NUM> minutes to about <NUM> hours, such as from about <NUM> minutes to about <NUM> hours (dwell time).

After a dwell time, the second temperature can be increased to a third temperature, such as a third temperature of about <NUM> or greater, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>. Increasing the second temperature to the third temperature can be performed at a ramp rate of about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min. Curing the mixture at the third temperature can be performed for from about <NUM> minutes to about <NUM> hours, such as from about <NUM> minutes to about <NUM> hours (dwell time).

After a dwell time, the third temperature can be increased to a fourth temperature, such as a fourth temperature of about <NUM> or greater, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>. Increasing the third temperature to the fourth temperature can be performed at a ramp rate of about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min. Curing the mixture at the fourth temperature can be performed for from about <NUM> minutes to about <NUM> hours, such as from about <NUM> minutes to about <NUM> hours (dwell time).

After a dwell time, the fourth temperature can be increased to a fifth temperature, such as a fifth temperature of about <NUM> or greater, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>. Increasing the fourth temperature to the fifth temperature can be performed at a ramp rate of about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min, such as from about <NUM>/min to about <NUM>/min. Curing the mixture at the fifth temperature can be performed for from about <NUM> minutes to about <NUM> hours, such as from about <NUM> minutes to about <NUM> hours (dwell time).

The temperature of the mixture during a curing stage can be determined by any suitable thermocouple contacting the surface, such as a Type K or Type J thermocouple. Heating a mixture can be performed using light exposure (e.g., ultraviolet light) of a surface. The light can be infrared (IR) or ultraviolet (UV). Exposing a mixture to light (and heating) can be performed using a FUSION UV curing unit fitted with a H+ bulb with a maximum emmittance at <NUM>. In at least one aspect, the bulb of the UV/IR curing unit is oriented about <NUM>° relative to the flow direction of material flowing from the nozzle of the spray apparatus. In at least one aspect, the bulb of the UV/IR curing unit is separated from the surface at a distance of from about <NUM> inches to about <NUM> feet (about <NUM> to about <NUM>), such as about <NUM> inches to about <NUM> feet (about <NUM> about <NUM>). An IR curing unit, for example, provides a smooth surface texture of the coating which might otherwise have a more rippled effect, providing improved durability of the surface against rain and sand erosion.

Furthermore, in examples where the first polymer and the second polymer (fluoropolymer) substantially differ in polarity, a composition of the present disclosure may be multiphasic such that the first polymer is a first phase and the second polymer is a second phase within the first phase. Alternatively, the first phase can be within the second phase simply by increasing the molar ratio of second polymer to first polymer during the preparation of the composition, as described above, e.g. a molar excess of second polymer to first polymer. A fluoropolymer can provide a non-stick surface (for water/ice) while a first polymer, such as polyethylene glycol, can provide freezing point suppression for ice.

For example, a first polymer of the present disclosure can have a polarity that is sufficiently different than the second polymer (fluoropolymer) such that a composition is multiphasic (e.g., biphasic) having a major phase (continuous phase) of first polymer (or second polymer) and a minor phase (having islands ("inclusions")) of second polymer (or first polymer). An average distance between inclusions can be from about <NUM> microns to about <NUM> microns, such as from about <NUM> micron to about <NUM> microns. Multiphase compositions of the present disclosure can provide improved ice-adhesion properties.

In at least one aspect, a composition of the present disclosure has an average void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>, such as less than <NUM> void of size <NUM> or greater per cm<NUM>, as determined by optical microscopy, which can provide a smooth, conformal surface of the composition. In at least one aspect, a composition of the present disclosure has a surface roughness of less than about <NUM> microinches (about <NUM>), such as less than about <NUM> microinches (about <NUM>), such as less than about <NUM> microinches (about <NUM>), such as less than about <NUM> microinches (about <NUM>), such as from about <NUM> microinches to about <NUM> microinches (about <NUM> to about <NUM>), such as from about <NUM> microinches to about <NUM> microinches (about <NUM> to about <NUM>), as determined by ASTM D7127-<NUM> (Standard Test Method for Measurement of Surface Roughness of Abrasive Blast Cleaned Metal Surfaces Using a Portable Stylus Instrument).

The smooth compositions (layers) of the present disclosure can provide stable laminar flow of water over the composition for reduced rain erosion as compared to conventional fluoropolymer layers. For example, a composition of the present disclosure can have a coating rain erosion rate of <NUM> mil/<NUM> mins (<NUM>/<NUM> mins) or less at <NUM> mph (<NUM> kph), such as <NUM> mil/<NUM> mins (<NUM>/<NUM> mins) or less, as determined using the University of Dayton Research Institute method described herein. A composition of the present disclosure can have a sand loading erosion of <NUM>/cm<NUM> or greater at a <NUM> mil (<NUM>) thickness at <NUM> mph (<NUM> kph) at an impact angle of <NUM> degrees, such as <NUM>/cm<NUM> or greater, such as <NUM>/cm<NUM> or greater, as determined using the University of Dayton Research Institute method described herein.

The compositions (layers) of the present disclosure can provide mechanical properties. For example, a composition of the present disclosure can have an elongation of from about <NUM>% to about <NUM>,<NUM>%, such as from about <NUM>% to about <NUM>%, as determined by ASTM D412 (suitably ASTM D412-<NUM>). A composition of the present disclosure can have a tensile strength of from about <NUM> MPa to about <NUM> MPa, such as from about <NUM> MPa to about <NUM> MPa, as determined by ASTM D412 (suitably ASTM D412-<NUM>).

Because compositions of the present disclosure can be icephobic, a composition can have an ice adhesion reduction factor of about <NUM> or more, such as about <NUM> or more, such as about <NUM> or more, such as about <NUM> or more, such as about <NUM> or more, as determined by the Anti-Icing Materials International Laboratory (AMIL) test. AMIL is the Anti-icing Materials International Laboratory located at the Universit6 du Québec à Chicoutimi in Chicoutimi, Quebec, Canada. The icephobic character of a coating can be evaluated by measuring the ice adhesion reduction effect of a candidate coating compared to an uncoated surface. AMIL can evaluate icephobic coatings in many different atmospheric conditions (wind and temperature) with glaze or rime accreted ice obtained with a simulation of freezing precipitation.

A single "Centrifuge Adhesion Test" by AMIL consists of the ice adhesion measurement of <NUM> or <NUM> small aluminum beams covered with the candidate product, compared with <NUM> or <NUM> bare beams. The extremity of the sample beams are iced simultaneously with freezing precipitation on about <NUM><NUM> surface to a thickness of about <NUM>. Each sample beam is rotated and balanced in the centrifuge apparatus. The rotation speed increases with a constant acceleration rate until the centrifugal force resulting from rotation reaches the adhesion stress of ice, detaching the ice. This detachment is picked up by a piezoelectric cell (sensitive to vibrations) which relays signals in real time to a computer. Finally, the adhesion stress is calculated using detachment speed, the mass of ice, and the beam length.

The Adhesion Reduction Factor, ARF is calculated using the average stress measured on the coated beams compared to the average stress measured on the three bare (control) beams. In particular, from the centrifugal force the stress is determined as F=mr ω2 where F=centrifugal force [N], m=mass of ice [kg], r=radius of the beam [m], and ω=speed of rotation [rad/s]. The Adhesion Reduction Factor (AMIL ARF) is then calculated using the average stress measured on the three coated beams compared to the average stress measured on the three bare beams: ARF=τbare/τcoated where τbare=average stress measured on three simultaneously iced bare beams [Pa] and τcoated=average stress measured on three simultaneously iced beams with candidate icephobic coating [Pa]. The web site www. ca/amil/en/icephobiccoatings/centrifuge, as retrieved on the filing date hereof.

An ARF value of <NUM> means there is no icephobic effect. An ARF value greater than <NUM> means there is an ice-adhesion reduction (icephobic effect); the higher the value, the more icephobic (low ice adhesion) the coating.

In at least one aspect, the spray apparatus for depositing the composition, the second fluoropolymer, the adhesion promoter, and/or the organic material is a robotic sprayer. <FIG> is a robotic sprayer. As shown in <FIG>, a material (such as a mixture of first polymer, second polymer, isocyante, curative and solvent) is charged to a pressure pot <NUM> with a disposable polyethylene liner. The lid <NUM> is installed and clamped pressure tight. A fluid delivery hose <NUM> is connected to the pickup tube <NUM> inside the pressure pot. Pressure regulated nitrogen or dry air is injected through line <NUM> to pressurize the pot and force material into the pickup tube and line. The pressure pot has pressure relief valves to prevent over pressurization and to bleed pressure from the pot for removing or adding the material. A regulator is located near the gun <NUM> to control the fluid pressure being delivered. Controlling the fluid pressure at the gun controls the volumetric flow rate through the gun's spray nozzle. Installing the regulator near the gun eliminates any pressure drop influence from hose length, hose diameter, or robot arm height. Nozzle control is also desired to control flow rates. Slight manufacturing variances in the nozzle orifice can result in different liquid flow rates. Nozzle control and fluid pressure regulation at the gun work in conjunction to give consistent and repeatable volumetric flow rates through the nozzle. The air assist atomization pressure through line <NUM> also is regulated and controlled to give consistent spray dispersion from the nozzle.

The robot <NUM> carries the gun and is programmed to traverse across the surface of the component with a constant offset from the surface <NUM> (which can be a non-flat surface) and a controlled velocity. The spray from the nozzle typically has a flat fan pattern. Most of the spray material is deposited at the center of the fan with tapering amounts delivered at the fan edges. To compensate for this nonuniform distribution in the spray fan, the robot is programmed to overlap adjacent passes to even out the distribution. Typical pass indexing is ¼ fan width.

In at least one aspect, as shown in <FIG>, method <NUM> includes heating the surface (such as a surface of a vehicle component) before, during, and/or after depositing fluoropolymer onto the surface (block <NUM>). For example, heating the surface while depositing the fluoropolymer composition onto the surface can provide in-situ solvent removal and increased viscosity of the mixture containing first polymer, second polymer, isocyanate, curative, and solvent, providing conformal deposition onto a curved (non-flat) surface of a vehicle component. Heating the surface while depositing the composition onto the surface can provide additional uniform composition layers to achieve an overall thicker coating (e.g., <NUM> mil to <NUM> mil; <NUM> to <NUM>) with reduced or eliminated voids caused by trapped solvent because some or all of the solvent has been removed. Heating the surface while depositing composition onto the surface further provides smoother layers as compared to room temperature cured layers. The conformal coating has a substantially uniform thickness across the surface. During heating, a surface (such as a surface of a vehicle component) can have a temperature of from about <NUM> to about <NUM>, such as from about <NUM> to about <NUM>, as determined by any suitable thermocouple contacting the surface, such as a Type K or Type J thermocouple. Heating a surface can be performed using light exposure (e.g., ultraviolet light) of a surface. The light can be infrared (IR) or ultraviolet (UV). Exposing a surface to light (and heating) can be performed using a FUSION UV curing unit fitted with a H+ bulb with a maximum emmittance at <NUM>. In at least one aspect, the bulb of the UV/IR curing unit is oriented about <NUM>° relative to the flow direction of material flowing from the nozzle of the spray apparatus. In at least one aspect, the bulb of the UV/IR curing unit is separated from the surface at a distance of from about <NUM> inches to about <NUM> feet (about <NUM> to about <NUM>), such as about <NUM> inches to about <NUM> feet (about <NUM> to about <NUM>). An IR curing unit, for example, provides a smooth surface texture of the coating which would otherwise have a more rippled effect, providing improved durability of the surface against rain and sand erosion.

<FIG> is a flow diagram of a method <NUM> for manufacturing surfaces having smooth icephobic coatings disposed thereon, according to one aspect. Method <NUM> includes applying <NUM> a composition to a surface of a component, the composition including a first polymer, a second polymer that is a fluoropolymer, an isocyanate, and a curative. Method <NUM> includes curing <NUM> the mixture at a first temperature of about <NUM> or greater and increasing <NUM> the first temperature to a second temperature of about <NUM> or greater. Method <NUM> includes obtaining <NUM> a coating disposed on the surface of the component, the coating having a thickness of from about <NUM> mils to about <NUM> mils (about <NUM> to about <NUM>) and a void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>.

As shown in <FIG>, method <NUM> includes forming a free standing composition film (block <NUM>). A mixture of first polymer, second polymer, isocyante, curative and solvent, as described above, is sprayed or deposited (as described above) onto the a mylar sheet, such as silanized mylar.

For example, a mixture containing first polymer, second polymer, isocyanate, solvent, and curative can be poured onto the mylar sheet and drawn out across a surface of the mylar sheet with a doctor blade, draw down bar, direct or reverse gravure, offset gravure, Precision Slot Die, or Meyer rod to form a layer. The mixture can be drawn out at line speed of from <NUM> fpm to about <NUM> fpm at a coating web width of from about <NUM>" wide to about <NUM>" wide (about <NUM> to about <NUM>). The mixture can be drawn out in an inert atmosphere, e.g. nitrogen or argon. The layer can have a thickness of about <NUM> mils (about <NUM>) or greater. The drawn out mixture (layer) can be cured in a stage-wise process, as described above. In at least one aspect, the mixture is poured onto the mylar sheet through a gap, such as a slot die.

In at least one aspect, during spraying, a nozzle of the spray apparatus is separated from a surface of the mylar sheet at a distance of from about <NUM> inch to about <NUM> inches (about <NUM> to about <NUM>), such as from about <NUM> inches to about <NUM> inches (about <NUM> to about <NUM>), such as from about <NUM> inches to about <NUM> inches (about <NUM> to about <NUM>). In at least one aspect, the mixture is sprayed onto the mylar sheet at a pressure of from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa), such as from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa). Other sprayer/pressure options can include: HVLP/LVLP from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa); Air brushes from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa); Hydraulic sprayers from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa); Robotic sprayers from about <NUM> to about <NUM> psi (about <NUM> kpa about <NUM> kpa). The nozzle of the spray apparatus is moved parallel to the surface of the mylar sheet. Two full movements of the nozzle parallel to the surface ("there and back") of the mylar sheet is referred to as one "pass". One pass can deposit the mixture onto the surface at a thickness of from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as from about <NUM> mil to about <NUM> mil (about <NUM> to about <NUM>), such as about <NUM> mil (about <NUM>). A time period from one pass to a subsequent pass can be from about <NUM> minute to about <NUM> minutes, such as from about <NUM> minute to about <NUM> minutes, such as from about <NUM> minute to about <NUM> minutes. Providing time in between passes promotes solvent removal from layers deposited by individual passes. Furthermore, the deposited mixture can be cured in a stage-wise process as described above. Stage-wise curing of the present disclosure, after one or more of the passes, can promote removal of solvent from the layer of the pass to further reduce void content of compositions of the present disclosure.

The free-standing film can be hot pressed at a temperature of from about <NUM> to about <NUM>, such as about <NUM>. In at least one aspect, two platens are heated to the desired temperature (e.g., <NUM>). The free-standing film is placed between two release layers (e.g., silanized mylar) and placed in between the hot platens. The hot platens are then closed providing pressure and heat on the film. The thermoplastic will flow and the thickness of the film can be controlled with the use of shims. The platens are then cooled down before pressure is removed. The temperature chosen for hot pressing is dependent on the thermoplastic or polymer film. In at least one aspect, the temperature of the platens is above the Tg (glass transition temperature) of the polymer but below the decomposition temperature.

As shown in <FIG>, method <NUM> includes bonding the free standing film to the composition coated surface (block <NUM>). The composition is the composition formed from the first polymer, second polymer, isocyanate, and curative, as described above. An adhesive can be applied to one or both of an exposed (e.g., outer) composition surface of the free standing film or an exposed (e.g., outer) composition surface of the composition coated component. The adhesive can be pressed with pressure onto one or both of the fluoropolymer surface of the free standing film or the composition surface of the composition coated component to reduce or eliminate air content between the adhesive and the applied surface. Adhesives include any suitable adhesive such as an epoxy, such as AF163-<NUM> obtained from <NUM> Corporation. If the adhesive is applied to the fluoropolymer surface of the free standing film, a protective liner on the opposite surface of the adhesive is then removed and positioned over the composition surface of the composition coated component and then pressed with pressure onto the composition surface of the composition coated component. If the adhesive is applied to the composition surface of the composition coated component, a protective liner on the opposite surface of the adhesive is then removed and positioned over the composition surface of the free standing film and then pressed with pressure onto the composition surface of the free standing film.

The entire (pressed) assembly is then sealed in a vacuum bag. <FIG> is a perspective view of a vacuum bag apparatus <NUM>. As shown in <FIG>, vacuum hose <NUM> is connected to vacuum seal <NUM>. Vacuum seal <NUM> is connected to vacuum bag <NUM>. Vacuum bag <NUM> is disposed on metal plate <NUM> and two assemblies shown at locations 410a and 410b. Metal plate <NUM> provides improved vacuum efficiency. The metal plate can be a flat metal plate and can comprise aluminium or stainless steel. It has been discovered that without the metal plate coupled to the vacuum bag, the vacuum bag wraps freely around the assembly creating voids and/or creases in the bag which, depending on the location of the creases and/or pleats, can affect the coating texture on the assembly.

A vacuum is applied to bag <NUM> ensuring contact with the free standing film to the composition coated metal of the assembly. A pressure inside bag <NUM> during a vacuum bagging process can be from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa), such as from about <NUM> psi to about <NUM> psi (about <NUM> kpa to about <NUM> kpa). Once air is substantially or completely removed from the bond line between the free standing film and the composition coated metal of the assembly, the bagged assembly is transferred to an oven to cure the adhesive (of the pressed assembly), bring the composition to the <NUM> baseline temperature, and proceed with curing the composition in a stage-wise manner as described above, e.g. by incrementally increasing the temperature of the oven to control temperature increases and dwell times. After curing, excess film (if present) can be trimmed from the edges of the component. The vacuum bag can contain one or more breather materials, such as a porous cotton material, disposed within the vacuum bag. Breather material provides connection of the vacuum to the assembly surface.

After a vacuum bagging procedure, the assembly can have a composition (layer) of the present disclosure, as described above. For example, the composition can have a thickness of from about <NUM> mils to about <NUM> mils (about <NUM> to about <NUM>) and an average void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>, such as less than <NUM> void of size <NUM> or greater per cm<NUM>, as determined by optical microscopy, which can provide a smooth, conformal surface of the composition. In at least one aspect, the composition can have a surface roughness of less than about <NUM> microinches (about <NUM>), such as less than about <NUM> microinches (about <NUM>), such as less than about <NUM> microinches (about <NUM>), such as less than about <NUM> microinches (about <NUM>), such as from about <NUM> microinches to about <NUM> microinches (about <NUM> to about <NUM>), such as from about <NUM> microinches to about <NUM> microinches (about <NUM> to about <NUM>), as determined by ASTM D7127-<NUM> (Standard Test Method for Measurement of Surface Roughness of Abrasive Blast Cleaned Metal Surfaces Using a Portable Stylus Instrument). The smooth composition layers of the present disclosure can provide stable laminar flow of water over the fluoropolymer layer, for improved rain erosion and sand erosion.

While adding additives to paints and coatings is common knowledge in the industry, it is important to retain the anti-ice performance of the coating. Many additives can be used to produce smoother finishes, better wetting of the surface being coated and better resistance to environmental effects and conditions such as moisture, heat and UV exposure. Some of these additives work by modifying the surface energy of the coating composition which can alter the microstructure of any incompatible chemistry composition. The microstructure and phase separation of the incompatible chemistries is important to having high anti-ice performance and should not be altered significantly. These additives may also migrate to the surface of the coating which can change how ice interacts with the surface of the coating which can also effect freezing delays and ice adhesion.

The chemical nature of the components in the coating technology readily absorb moisture from the environment, which may cause premature curing of the coating and the production of carbon dioxide. To mitigate this issue, moisture scavengers (e.g. oxazolidines such Incozol-<NUM>) can be added to the mixtures of first polymer, second polymer, isocyanate, curative, and/or solvent of the present disclosure. To improve surface wetting and spreading of the coating on the component, a wetting agent (e.g., block copolymers such as Disperbyk-<NUM> which is a high molecular weight block copolymer with pigment affinic groups) and/or defoamer (e.g. BYK-051N, which is a silicone-free defoamer) can be included in a mixture of first polymer, second polymer, isocyanate, curative, and/or solvent of the present disclosure. These additives are not particulates, but are small molecule additives. They are moisture scavengers or reduce void formation. Lower amount of voids promotes the integrity/strength of the film. Voids can be observed macroscopically using microscopy.

Additives of the present disclosure include any suitable moisture scavenger, wetting agent, and/or defoamer. Moisture scavengers can include isophorone diisocyanate (IPDI) and oxazolidines (such as <NUM>-Ethyl-<NUM>-methyl-<NUM>-(<NUM>-methylbutyl)-<NUM>,<NUM>-oxazolidine). Wetting agents can include polyamides, polyamides having long chain fatty acid moieties, and p-Dodecylbenzenesulfonic acid (DDBSA). Defoamers can include poly(dimethylsiloxane) fluids, poly(octyl acrylates), SiO<NUM>, siloxanes with a polyether terminal group, and potassium tripolyphosphate.

Due to the enhancements in processing fluoropolymer coatings of the present disclosure, it has been discovered that the amount of these additives can be reduced or eliminated from the coatings of the present disclosure as compared to fluoropolymer coatings prepared using conventional deposition and curing methodology. In at least one aspect, a fluoropolymer layer of the present disclosure has an additive content of less than about <NUM> wt%, such as less than about <NUM> wt%, which saves manufacturing time and cost as compared to higher additive contents of conventional anti-ice layers; and is an amount sufficiently low to reduce or prevent accumulation of the additives at the composition surface ("waxing out").

As used herein, "airfoil" comprises a substrate in the shape of a wing or a blade (of a propeller, rotor, or turbine). Airfoils may include rotor blades, static wing surfaces of rotorcraft or fixed wing aircraft, or blades of a wind turbine. Airfoils, such as rotor blades, comprise one or more surfaces, such as an outer surface, and one or more components as described in more detail below. As described herein, "airfoil component" comprises any suitable structure adapted, in combination with one or more other airfoil components, to form an airfoil.

Airfoil components of the present disclosure that are rotor blades comprise one or more rotor blade components. As described herein, "rotor blade component" comprises any suitable structure adapted, in combination with one or more other rotor blade components, to form a rotor blade. <FIG> is a perspective view of a rotor blade, according to some aspects of the present disclosure. As shown in <FIG>, rotor blade <NUM> of a main rotor assembly (not shown) is made of a root section <NUM>, an intermediate section <NUM>, and a tip section <NUM>. Each of sections <NUM>, <NUM>, <NUM> is any suitable geometry to tailor rotor blade aerodynamics to the velocity increase along the rotor blade span. Rotor blade tip section <NUM> comprises an angled geometry such as anhedral, cathedral, gull, and bent, among others. Rotor blade sections <NUM>, <NUM>, <NUM> define a span of rotor blade <NUM> between the axis of rotation A and a distal end <NUM> of tip section <NUM> along a longitudinal axis P between a first edge <NUM> and a second edge <NUM>. Compositions of the present disclosure can be disposed on one or more components of a rotor blade, such as rotor blade <NUM>.

One improvement over prior techniques was to shift from heavily diluting the resin and spray coating to adding a modest amount of solvent (less than or equal to <NUM> wt% with respect to solids) to maintain a flowable resin viscosity and casting onto a film surface. The solvent used for dilution and casting with these sytems was n-butyl acetate. Surfaces used were most commonly non-stick surfaces, such as a silanized Mylar film. Some other non-stick release surfaces that would be acceptable include fluorinated surfaces such as Teflon aka poly(tetrafluoroethylene), PVDF aka poly(vinyldifluoride), and Tedlar aka poly(vinyl fluoride). Films were cast onto Mylar using a doctor blad with film thickness set for <NUM> mils (<NUM>).

The viscous resin was promptly poured from the reaction vessel after curative addition onto a surface where the film thickness was controlled through techniques such as a draw down bar used with shims, a doctor blade or a Meyer rod. Larger scale continuous processes can be envisioned where resin is dispensed through a gap such as a slot die onto a continuously fed roll to roll film.

Following the drawing out of a film of a controlled thickness, the film was then placed in an oven or heated chamber to both evolve solvent and effect cure of the material. Inert gas environments were preferred but were not necessary. The cure profile was designed to produce a graceful evolution of the solvent from the film thus avoiding void formation. The goal was to steadily evaporate solvent to concentrate the film down to <NUM>% solids but not so fast that solvent was trapped underneath the surface upon gelation/solidification of the film leading to voids as with conventional spray techniques. A significant contribution to the success in this respect was the boiling point or vapor pressure of solvent with respect to the surrounding temperature of the film. Earlier examples with spray coating and tetrahydrofuran (boiling point <NUM>) as solvent were found to be too volatile even at room temperature and prone to forming voids. High boiling point solvents such as n-butyl acetate (<NUM>) were found to be much less prone to void formation even under elevated temperature conditions in addition to being able to mix with the high fluoropolymer resin.

The cure profile was also found to be important to a graceful evolution of solvent from the coating during cure. The goal was to elevate the temperature in order to help drive curing at a reasonable rate but not so aggressively that it caused solvent to boil or flash off so rapidly in the coating leading to void formation in the coating. Staged curing profiles given below in the two examples are representative of exemplary cure schedules.

Upon curing, the films were removed from the non-stick release layer and able to be handled as free standing films. Films were then bonded to surfaces using a variety of bonding strategies including.

In certain cases such as that of the film adhesives, vacuum bag techniques are desired to apply pressure on the substrate during heating and curing which was found to effect a high quality bond.

In certain cases where bonding to heavily fluorinated surfaces such as these is insufficient for a desired purpose, a surface pretreatment can be carried out by expose of the film surface to a Sodium Napthalide based etchant (Fluoroetch, Acton Technologies).

Materials: Poly(ethylene glycol) <NUM> (PEG Mn = <NUM>/mol), <NUM>,<NUM>'-methylenebis(cyclohyxyl isocyanate) mixture of isomers (HMDI), <NUM>,<NUM>-butanediol (BD), and dibutyltin dilaurate (DBTDL) were obtained from Sigma Aldrich. PEG was freeze-dried. Fluorolink D4000 (E10-H Mn = <NUM>/mol) was obtained from Solvay and dried in vacuum oven at ~<NUM>-<NUM> for <NUM> hours under nitrogen. n-Butyl acetate (nBA) was obtained from Sigma Aldrich and dried over molecular sieves prior to use.

Stoichiometry: PEG/HMDI/D4000/BD in a <NUM>/<NUM>/<NUM>/<NUM> molar ratio, with 200ppm DBTBL as the catalyst.

Procedure: A <NUM> two-neck or <NUM> <NUM>-neck round-bottom flask was heated in <NUM> oven for at least one hour to drive off residual water and then cooled under inert gas (Ar or N<NUM>). PEG (<NUM>, <NUM> mmole) and HMDI (<NUM>, <NUM> mmole) are added to flask and brought to <NUM> in silicone oil bath while stirred at approximately <NUM> rpm. After the PEG had melted (approximately <NUM> minutes), DBTBL was added and the reaction was left to proceed for <NUM> hour at <NUM> rpm stir rate. After the <NUM> hour, D4000 (<NUM>, <NUM> mmole) was added and left to react for <NUM> hour. The BD (<NUM>, <NUM> mmole) was weighed in a jar, drawn up in syringe and the jar is flushed with ~<NUM> nBA (for <NUM>-<NUM> BD systems). The reaction was removed from heat and allowed to cool to approx. <NUM>-<NUM>. Approximately <NUM> phr or <NUM> wt% of nBA was slowly added <NUM> at a time as the reaction flask cooled. The <NUM> nBA/BD flush was added to the flask followed by the BD. The reaction was left to stir at <NUM> rpm for ~ <NUM> seconds and then cast onto silanized Mylar affixed to a glass plate and drawn down with glass rod. The cast film was then placed in <NUM> oven under nitrogen and ramped using the following cure schedule:
Cure Schedule: The film was added to a preheated <NUM> oven and underwent the following:.

Mechanicals: Mechanical properties of the films (n=<NUM>) were tested on an Instron <NUM> using a crosshead speed of <NUM>/min. Results: Elongation <NUM> ± <NUM>% and Tensile Strength <NUM> ± <NUM> MPa.

Materials: Poly(ethylene glycol) <NUM> (PEG Mn = <NUM>/mol), <NUM>,<NUM>'-methylenebis(cyclohyxyl isocyanate) mixture of isomers (HMDI), <NUM>,<NUM>-butanediol (BD), and dibutyltin dilaurate (DBTDL) were obtained from Sigma Aldrich. PEG was freeze-dried using LABCONCO freeze dryer equipment at < <NUM> Papressure and < -<NUM> temperature for <NUM>+ hours. Fluorolink E10-H (E10-H Mn = <NUM>/mol) was obtained from Solvay and dried in vacuum oven at ~<NUM> for <NUM> hours under nitrogen. n-Butyl acetate (nBA) was obtained from Sigma Aldrich and dried over molecular sieves prior to use.

Stoichiometry: PEG/HMDI/E10H/BD in a <NUM>/<NUM>/<NUM>/<NUM> ratio, with 200ppm DBTBL as the catalyst. The following chart can be used for ease of calculation based off PEG mass:.

Procedure: A <NUM> two-neck round-bottom flask was heated in <NUM> oven for approximately an hour to drive off residual water and then cooled under inert gas (Ar or N<NUM>). PEG (<NUM>, <NUM> mmole) an HMDI (<NUM>, <NUM> mmole) were added to the flask and brought to <NUM> in silicone oil bath while stirred at 30rpm. After the PEG had melted (approximately <NUM> minutes), DBTBL was added and the reaction was left to proceed for <NUM> hour at <NUM> rpm stir rate. After the <NUM> hour, E10-H (<NUM>, <NUM> mmole) was added and left for <NUM> hours. The BD (<NUM>, <NUM> mmole) is weighed in jar, drawn up in syringe and the jar was flushed with ~<NUM> nBA (for <NUM>-<NUM> BD systems). The reaction was removed from heat and allowed to cool to approx. The <NUM> nBA/BD flush is added to the flask followed by the BD. The reaction was left to stir at <NUM> rpm for <NUM> minute and then cast onto silanized mylar. The cast film was then placed in <NUM> oven under nitrogen and ramped using the following cure schedule:
Cure Schedule: The film was added to a preheated <NUM> oven and underwent the following:.

A primary benefit of creating icephobic coatings with excellent mechanical properties is their resistance to high speed sand and rain. In order to fully test this, small airfoils were coated and sent to the University of Dayton Research Institute for testing on their Particle Erosion Test Rig (PETR) and Rain Rig.

Description of UDRI Rain rig: The "rain rig" is an <NUM>-foot (<NUM>)-diameter rotating arm and <NUM> calibrated needles are used to simulate flight in a <NUM> inch (<NUM>) per hour rainfall. Coupon specimens are tested at speeds up to <NUM> mph (<NUM> kph). Real-time video is monitored and recorded, allowing "time to failure" testing.

<FIG> is a graph illustrating rain erosion testing (coating erosion rate) performed at <NUM> mph (<NUM> kph). All samples were Sample #<NUM> with Test sample #<NUM> sprayed and bonded with <NUM> AF163 film adhesive. Test sample #<NUM> was cast and bonded with <NUM> AF163 film adhesive. Finally, Test sample #<NUM> was bonded with <NUM> <NUM> double sided pressure sensitive adhesive. Rain erosion performance was compared against <NUM> <NUM> leading edge erosion protection tape.

Sand erosion: "Dust rig": The "dust rig" was designed and developed in <NUM> to simulate erosion effects on aircraft surfaces subjected and has been recently upgraded to test the larger mass loading seen by helicopter rotors. Typically, crushed silica (e.g., angular quartz) in sizes ranging from <NUM> microns to <NUM> microns (known as "golf sand") is used as the test media. Specimens are translated in front of an oscillating nozzle. The <NUM>-inch (<NUM>) square test area is uniformly covered with a pre-determined mass of particles of a known size at a measured speed up to <NUM> mph (<NUM> kph). Impact angles from normal to <NUM> degrees (<NUM> degrees angle of incidence) can be tested, and many specimen configurations are possible. A calibrated screw feed in a plenum tank and an electronic pressure controller ensure correct mass delivery and stability, and a laser Doppler anemometry system is used to determine a delivery pressure for the required velocity.

<FIG> is a graph illustrating <NUM> mph (<NUM> kph) sand impacted onto <NUM> mil (<NUM>) thick coated airfoils and reduction in coating thickness measured at specific mass loading levels of impacted sand. <NUM> <NUM> and <NUM> leading edge erosion protection tapes were run as controls and failed based on coating breakthrough at <NUM> and <NUM>/cm<NUM> respectively. Samples #<NUM> and #<NUM> failed at <NUM>/cm<NUM> and <NUM>/cm<NUM> respectively, losing thickness in a graceful controlled manner reflective of tough durable coatings.

Overall, methods of the present disclosure provide smooth icephobic coatings on surfaces with improved rain and sand erosion resistance. Although generally discussed in the context of aviation use, other possible uses of methods of the present disclosure are contemplated, such as on wind turbine blades, in non-aerospace transportation, and in communications, including satellite dishes.

The term "alkyl" includes a substituted or unsubstituted, linear or branched acyclic alkyl radical containing from <NUM> to about <NUM> carbon atoms. In at least one aspect, alkyl is a C<NUM>-<NUM>alkyl, C<NUM>-<NUM>alkyl or C<NUM>-<NUM>alkyl. Examples of alkyl include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and structural isomers thereof.

The term "cycloalkyl" includes a substituted or unsubstituted, cyclic alkyl radical containing from <NUM> to about <NUM> carbon atoms.

The term "hydroxy" and "hydroxyl" each refers to -OH.

The term "amine" or "amino" refers to a primary, secondary or tertiary amine-containing radical. An example of an amino radical is -NH<NUM>. An amino radical may be substituted with R<NUM> or R<NUM> (e.g.,
<CHM>
), where R<NUM> may be, for example, cyano, haloacyl, alkenylcarbonyl, hydroxyalkenylcarbonyl, aminoalkenylcarbonyl, monoalkylaminoalkenylcarbonyl, dialkylaminoalkenylcarbonyl, haloalkenylcarbonyl, cyanoalkenylcarbonyl, alkoxycarbonylalkenylcarbonyl, alkynylcarbonyl, hydroxyalkynylcarbonyl, alkylcarbonylalkenylcarbonyl, cycloalkylcarbonylalkenylcarbonyl, arylcarbonylalkenylcarbonyl, aminocarbonylalkenylcarbonyl, monoalkylaminocarbonylalkenylcarbonyl, dialkylaminocarbonylalkenylcarbonyl or alkenylsulfonyl; and R<NUM> may be, for example, H, alkyl or cycloalkyl.

Compounds of the present disclosure include tautomeric, geometric or stereoisomeric forms of the compounds. Ester, oxime, onium, hydrate, solvate and N-oxide forms of a compound are also embraced by the present disclosure. The present disclosure considers all such compounds, including cis- and trans-geometric isomers (Z- and E- geometric isomers), R- and S-enantiomers, diastereomers, d-isomers, I-isomers, atropisomers, epimers, conformers, rotamers, mixtures of isomers and racemates thereof are embraced by the present disclosure.

Number average molecular weight may suitably be measured by quantification of end-groups using nuclear magnetic resonance spectroscopy for polymers having a molecular mass of up to <NUM> daltons, or by gel permeation chromatography for polymers having a molecular mass over <NUM> daltons.

Claim 1:
A coating disposed on a surface, the coating comprising a reaction product of:
a first polymer;
a second polymer that is a fluoropolymer;
an isocyanate; and
a curative, the coating having a thickness of from about <NUM> mils to about <NUM> mils (about <NUM> to about <NUM>) and a void density of less than <NUM> voids of size <NUM> or greater per cm<NUM>;
wherein the first polymer is selected from poly(acrylic acid), poly(ethylene glycol), poly(<NUM>-hydroxyethyl methacrylate), poly(vinyl imidazole), poly(<NUM>-methyl-<NUM>-oxazoline), poly(<NUM>-ethyl-<NUM>-oxazoline), poly(vinylpyrolidone), cellulose, modified cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, hydrogels, PEG diacryalate, PEG polyacrylates, or combinations thereof; or
wherein the first polymer is selected from poly(oxymethylene), polyethylene glycol), polypropylene glycol), poly(tetrahydrofuran), poly(glycolic acid), poly(caprolactone), polyethylene adipate), poly(hydroxybutyrate), poly(hydroxyalkanoate), or combinations thereof.