Articles comprising durable water repellent, icephobic and/or biocidal coatings

Abstract

Articles including durable and icephobic and/or biocidal polymeric coatings are disclosed. The polymeric coatings can include a bonding layer which may contain a substantially fully cured polymeric resin providing excellent adhesion to metallic or polymer substrates. The polymeric coating further includes an outer surface layer which is smooth, hydrophobic, biocidal and icephobic and, in addition to a substantially fully cured resin, contains silicone comprising additives near the exposed outer surface. The anisotropic polymeric coatings are particularly suited for strong and lightweight parts required in aerospace, automotive and sporting goods applications. A process for making the articles is disclosed as well.

Claims

1. A non-isotropic article comprising: a substrate formed of a metallic material or a polymeric material; a cured polymeric coating compositionally graded or layered to be anisotropic in a deposition direction and thus not homogenous in the deposition direction, having a total thickness of at least 10 microns, and applied to at least a part of an outer surface of the substrate, wherein the cured polymeric coating includes a first chemical composition, and a second chemical composition having a different chemical composition than the first chemical composition, wherein the first chemical composition includes a first polymeric resin and is arranged at an interface between the cured polymeric coating and the substrate, wherein the second chemical composition forms an exposed outer surface of the cured polymeric coating and of the non-isotropic article, extends at least 2.5 microns in depth from the exposed outer surface, and after curing: (i) contains an icephobic material addition composed entirely of solids representing up to 25% by weight of the second chemical composition, (ii) contains at least one biocidal powder addition of a metallic material and/or a metal compound comprising a metal selected from the group consisting of Ag, Co, Cu, Ni, Sn, and Zn, said biocidal powder addition representing up to 75% per weight of the second chemical composition, (iii) has a Shore D-Scale Hardness of at least 40, (iv) has a contact angle for water greater than 90 degrees, (v) has an ice adhesion of less than 500 kPa as prepared and after 5 icing/deicing cycles when measured according to ERDC/CRREL Technical Note 03-4, and (vi) contains a second polymeric resin, wherein said non-isotropic article has a pull-off strength between the substrate and the exposed outer surface of the cured polymeric coating, according to standard ASTM 4541D, of at least 500 psi, and wherein said non-isotropic article after 24 hours at 37° C. displays a radius of no growth on a zone inhibition test for microorganisms of at least 0.1 mm.

2. The non-isotropic article according to claim 1, wherein the exposed outer surface of the cured polymeric coating after 24 hours at 37° C. displays a radius of no growth on a zone inhibition test for salmonella or listeria of between 0.1 and 50 mm.

3. The non-isotropic article according to claim 1, wherein the substrate is formed of a metallic material layer having a total thickness of at least 25 microns and comprising at least one metal selected from the group consisting of Al, Co, Cu, Fe, Ni, Sn, Ti and Zn.

4. The non-isotropic article according to claim 3, wherein at least part of said metallic material layer is grain-refined comprising an average grain size between 2 nm and 1,000 nm and/or amorphous.

5. The non-isotropic article according to claim 1, wherein an average particle size of the biocidal powder addition is between 0.5 and 25 microns.

6. The non-isotropic article according to claim 1, wherein the second chemical composition further comprises at least one carbon based additive selected from the group consisting of carbon, carbon fibers, graphite, graphite fibers, carbon nanotubes and graphene.

7. The non-isotropic article according to claim 1, wherein the biocidal powder addition is a metallic powder and at least part of the metallic powder is grain-refined comprising an average grain size between 2 nm and 500 nm.

8. The non-isotropic article according to claim 1, wherein the biocidal powder addition is a metallic powder and at least part of the metallic powder is grain-refined comprising an average grain size between 5 nm and 50 nm.

9. The non-isotropic article according to claim 1, wherein said non-isotropic article forms part of an automotive, an aircraft, a spacecraft, a sporting good, or a personal protective equipment.

10. The non-isotropic article according to claim 9, wherein said non-isotropic article forms part of a face mask.

11. The non-isotropic article according to claim 1, wherein said icephobic material addition comprises a polysiloxane.

12. The non-isotropic article according to claim 11, wherein the polysiloxane comprises an epoxy modified silicone.

13. A non-isotropic article comprising: at least one metallic material layer having a total thickness of at least 25 microns comprising at least one metal selected from the group consisting of Al, Co, Cu, Fe, Ni, Sn, Ti and Zn; a cured polymeric coating compositionally graded or layered to be anisotropic in a deposition direction and thus not homogenous in the deposition direction, having a total thickness of at least 10 microns, and applied to at least part of an outer surface of the metallic material layer, wherein the cured polymeric coating includes a first chemical composition, and a second chemical composition having a different chemical composition than the first chemical composition, wherein the first chemical composition includes a first polymeric resin and is arranged at an interface between the cured polymeric coating and the substrate, wherein the second chemical composition forms an exposed outer surface of the cured polymeric coating and of the non-isotropic article, extends at least 2.5 microns in depth from the exposed outer surface, and after curing: (i) contains an icephobic material addition composed entirely of solids representing up to 25% by weight of the second chemical composition, (ii) contains at least one biocidal powder addition representing up to 75% by weight of the second chemical composition, (iii) has a Shore D-Scale Hardness of at least 20, (iv) has a sand erosion value according to standard ASTM G76 at an impingement angle of 90 degrees of less than 10 mm.sup.3/kg, (v) is hydrophobic, and (vi) has an ice adhesion of less than 400 kPa as prepared and after 5 icing/deicing cycles when measured according to ERDC/CRREL Technical Note 03-4, and (vi) contains a second polymeric resin, wherein said non-isotropic article exhibits no failure after being exposed to at least one temperature cycle according to ASTM B553-71 service condition 1, wherein said non-isotropic article has a pull-off strength between the metallic material layer and the exposed outer surface of the cured polymeric coating, according to standard ASTM 4541 D, of at least 500 psi, and wherein said non-isotropic article after 24 hours at 37° C. displays a radius of no growth on a zone inhibition test for microorganisms of at least 0.1 mm.

14. The non-isotropic article according to claim 13, wherein the biocidal powder addition is of a metallic material and/or a metal compound comprising at least one metal selected from the group consisting of Ag, Co, Cu, Ni, Sn, and Zn.

15. The non-isotropic article according to claim 14, wherein an average particle size of the biocidal powder addition is between 0.5 and 25 microns.

16. The non-isotropic article according to claim 14, wherein the biocidal powder addition is a metallic powder and at least part of the metallic powder is grain-refined comprising an average grain size between 5 nm and 50 nm.

17. The non-isotropic article according to claim 13, wherein the second chemical composition further comprises at least one carbon based additive selected from the group consisting of carbon, carbon fibers, graphite, graphite fibers, carbon nanotubes and graphene.

18. The non-isotropic article according to claim 13, wherein said icephobic material addition comprises a polysiloxane comprising an epoxy modified silicone.

19. A non-isotropic article comprising: a substrate formed of a metallic material or a polymeric material; a cured polymeric coating compositionally graded or layered to be anisotropic in a deposition direction and thus not homogenous in the deposition direction, having a total thickness of at least 10 microns, and applied to at least a part of an outer surface of the substrate, wherein the cured polymeric coating includes a first chemical composition, and a second chemical composition having a different chemical composition than the first chemical composition, wherein the first chemical composition includes a first polymeric resin and is arranged at an interface between the cured polymeric coating and the substrate, wherein the second chemical composition forms an exposed outer surface of the cured polymeric coating and of the non-isotropic article, extends at least 2.5 microns in depth from the exposed outer surface, and after curing: (i) contains an icephobic material addition composed entirely of solids representing up to 25% by weight of the second chemical composition, (ii) contains at least one biocidal powder addition of a metallic material and/or a metal compound comprising a metal selected from the group consisting of Ag, Co, Cu, Ni, Sn, and Zn, said biocidal powder addition representing up to 75% per weight of the second chemical composition, (iii) has a Shore D-Scale Hardness of at least 40, (iv) has a contact angle for water greater than 90 degrees, (v) has an ice adhesion of less than 500 kPa as prepared and after 5 icing/deicing cycles when measured according to ERDC/CRREL Technical Note 03-4, and (vi) contains a second polymeric resin.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The features and advantages of the invention will be appreciated upon reference to the following drawings, in which:

(2) FIGS. 1 and 3 are graphs showing the wetting angle, ice adhesion, Shore D hardness as well as the sand erosion properties for impingement angles of 90° and 30° for various polymeric coatings.

(3) FIGS. 2 and 4 are graphs showing the pull-off adhesion strength of selected polymeric coatings applied to various substrates.

(4) FIG. 5 is a perspective view of a reusable, self-sterilizing facemask according to one of the preferred embodiments.

(5) FIG. 6 is an exploded perspective view of FIG. 5.

DETAILED DESCRIPTION OF THE INVENTION

(6) It is well known that the formation, adhesion, and accumulation of ice, snow, frost, glaze, rime, or their mixtures can cause severe problems for solar panels, wind turbines, aircrafts, heat pumps, power lines, telecommunication equipment, as well as land vehicles and marine vessels. These problems generate safety hazards and can result in failure. To address these issues, the fundamentals of interfaces between gases, liquids and solids and solid surfaces at low temperatures need to be taken into account and various approaches to form “icephobic” (pagophobic) surfaces have been proposed. As the person skilled in the art knows different properties may be required to prevent the formation and adhesion of ice, snow, glaze, rime, and frost.

(7) Icephobicity is the ability of a solid surface to repel ice or prevent ice formation due to a certain topographical structure and/or chemical composition of the surface. Icephobic surfaces in this specification are defined by an ice adhesion strength of typically <600 kPa, preferably <500 kPa, preferably <350 kPa, preferably <300 kPa, and more preferably <200 kPa. Slippery, liquid infused porous surfaces (SLIPS) have been proposed for reducing ice adhesion to values as low as 10 kPa, however, after a few icing-deicing cycles, ice adhesion gradually increases to over 200 kPa. Furthermore, the mechanical durability of SLIPS surfaces is typically poor. Many other approaches have been proposed as well which are capable of reducing the icephobicity, however, achieving and maintaining both icephobcity and long-term durability remains a challenge.

(8) In order to enhance icephobicity, the exposed surface needs to generally exhibit poor adhesion characteristics, however, in most of the commercial applications the icephobic material layer is applied as a homogeneous coating onto a suitable substrate. As a consequence, the “inner surface” of such icephobic coatings, e.g., the surface contacting the underlying substrate, exhibits poor adhesion particularly when containing liquid icephobic additives. Delamination and flaking of the polymeric coating at the interface with the underlying substrate frequently limits its durability even if the coating is formulated to be hard and strong.

(9) In this specification, in one preferred embodiment, therefore the inventors of the present disclosure propose to form anisotropic, icephobic coatings by minimizing adhesion on the exposed outer surface while maximizing adhesion on the inner surface to achieve a good bond at the interface with the underlying substrate. This is achieved by modifying the composition of the icephobic material coating in the deposition direction through layering and/or gradually modulating the chemical composition. In its simplest form the coating contains two layers of different composition.

(10) Similarly, it is well known that selected metallic coatings applied to touch-surfaces can significantly reduce the spread of diseases. The inventive polymeric coatings provide biocidal properties while being highly resistant to abrasive and/or sliding wear, scuffing and scratching. This invention relates to articles coated with polymeric layers containing grain-refined and/or amorphous, biocidal, metallic materials or metallic material compounds, preferably in the form of fine powders, which exhibit anti-microbial, antibacterial, anti-fungal and/or anti-viral behavior for extended periods of time while exhibiting enhanced mechanical durability. It is one aspect of the present invention that the metallic polycrystalline material exhibits bulk ionic dissolution characteristics providing enhanced biocidal efficacy.

(11) One characteristic of a metallic material is related to the stored internal energy of its microstructure. Metallic materials which are sufficiently disordered so that the bulk microstructure is prone to release metal ions in biocidal effective concentrations from the outer surface are desired. This property is intrinsic to a material that possesses a high energy microstructure. As an example, cold working (e.g. rolling) of a fully annealed metal is a common method to increase the concentration of structural defects, in this case dislocations, throughout the microstructure of the metal. The presence of these defects, in turn, increases the stored internal energy of the cold worked metal relative to the same material in the fully annealed, equilibrium state. Another way to increase the internal stored energy of a metal is to refine the size of its constituent crystals or grains. Atoms located at the grain boundary and triple junction (intersection of three grain boundaries) regions are well-known to possess much higher stored energy values compared to those atoms situated within the well-ordered crystal.

(12) When the grain size of the material is decreased, the volume fraction of the material's constituent atoms that are located at intercrystalline sites rises proportionately and, at an average grain size below approximately 300 nm, the stored internal energy contribution of the interfacial atoms becomes discernible. This manifests itself in a tendency for the fine-grained metallic material to exhibit an enhanced ionic dissolution rate relative to its chemically equivalent coarse-grained counterpart. Hence, grain refinement is an effective means to promote the sustained dissolution of metallic material at concentrations that result in enhanced biocidal efficacy. This approach allows the use of powder additions not requiring minimizing the particle size to maximize biocidal efficacy reducing/eliminating the adverse health effects of handling fine powders when preparing and/or applying the coating.

(13) Articles or coatings according to the invention can be formed by incorporating suitable metallic compositions and/or metal compounds in the form of particulates, including, but not limited to, powders, fibers, and shavings, into polymeric coatings which are applied onto permanent or temporary substrates. Suitable permanent substrates include a variety of metal substrates, carbon-based materials selected from the group of graphite, graphite fibers and carbon nanotubes, and polymer substrates, commonly referred to as “plastics”.

(14) In addition to improving biocidal efficacy, grain size reduction/grain refinement is known to increase the hardness, strength, abrasive wear, scuff, and scratch wear resistance of fully-dense metallic materials. Depending on the mechanical properties desired the grain size is suitably reduced to a level required to achieve the desired hardness, strength, abrasive wear, scuff, and/or scratch resistance.

(15) While the addition of metallic materials and/or metal compounds to the polymeric coating typically lowers the contact angle for water and increases the ice adhesion strength, the inventors have surprisingly discovered that sufficient amounts of biocidal powder can be incorporated into the polymeric coating to render the coating biocidal while still maintaining hydrophobic properties and acceptable icephobicity. It also has been surprisingly observed that the ice adhesion strength of polymeric coatings containing metallic material powders frequently decreases with increasing icing/deicing cycles while typically the ice adhesion strength without metallic material additions increases with increasing icing/deicing cycles. In addition it has also been surprisingly discovered that incorporating biocidal powder into the polymeric coating improves adhesion and increases the pull-off strength to all substrates of interest thereby reducing the need for using multilayered coatings.

(16) As highlighted before there are numerous applications and products which greatly benefit from durable coatings which are water and ice repellent, while providing biocidal properties. Applications include reusable face mask housings/shells containing a suitable air filter and sealing the mouth and nose from direct exposure to ambient, unfiltered, air which are worn in all ambient conditions and can be exposed to various form of water from the elements as well as moisture from exhaling, sweat etc. and can become a breeding ground for microorganisms.

(17) FIG. 5 and FIG. 6 depict such a reusable, biocidal face mask 10 for filtering air. The face mask 10 generally comprises an outer shell 12, typically produced from a polymeric material by injection or compression molding, which is reasonably rigid to maintain its shape, provide a protective enclosure and is perforated by holes and/or slits 18 so air can pass in and out relatively unimpeded. The outer shell 12 attaches to a support frame 16, optionally containing a one-way exhale vent 26. A replaceable filter element 14 is secured between the outer shell 12 and the support frame 16. The filter element 14 is designed to capture pollutants and airborne contaminants including, but not limited to carbon monoxide, nitrous oxides, ozone, airborne microorganisms and viruses as well as pollen. The filter element 14 may be conveniently shaped so it does not cover the exhale vent 26 to minimize the air pressure upon exhaling. The support frame 16 supports the filter element 14 and maintains it shape in the face mask 10 while the front shell 12 protects the filter element 14 and inner components of the face mask 10. The face mask 10 includes a head strap 28 attached to the front shell 12 for holding the face mask 10 in place on a user's head. The face mask 10 includes a face seal 24 typically attached to the support frame 16 for providing a flexible and air-tight seal around the nose and mouth of the user. The face seal 24 provides a snug seal to the user's face and prevents air from passing through thereby forcing the air to exclusively be drawn into the face mask 10 through the replaceable filter element 14. The flexible seal 24 can be made of medical grade silicone. To prevent buildup of water condensation and, at subzero centigrade ambient temperatures, possibly ice from plugging the holes/slits 18 in the outer shell 12 and keep the mask free from mold, bacteria and viruses, at least part of the outer shell 12 and the support frame 16 are coated with at least a 2.5 microns thick layer of the durable, water-repellent and icephobic, biocidal coating, according to the present invention. Preferably the outer shell 12 and the support frame 16 are totally encapsulated with the biocidal coating of the present invention.

(18) Epoxies are known for achieving excellent adhesion to a number of substrates including metals due to their polar nature and their ability to create chemical bonds to the surface upon cure. Hard and strong due to high crosslinking, cured epoxies can bear loads and resist wear caused by abrasion over the long term. This good mechanical strength, however, at high crosslink density flexibility decreases and epoxies are known for cracking due to their brittleness and inability to dissipate stresses. Cured epoxies layers require the addition of icephobic material additives to notably reduce ice-adhesion strength and the addition of biocidal materials to destroy undesired microorganisms, bacteria and viruses.

(19) Similarly, polyurethanes are commonly employed as coatings for preventing corrosion of metal articles and to make a variety of materials more durable. Polyurethanes are extremely resilient substances and their mechanical properties can be easily manipulated by optimizing their compositions.

(20) Silicones exhibit high elongation and flexibility that enable the dissipation of stresses and applied energy. Their strong Si—O bond and high surface energy make silicones resistant to atmospheric or chemical attack and less susceptible to degradation from sunlight, water uptake and ultraviolet (UV) light, thereby providing hydrophobic and icephobic properties for extended periods of time.

(21) The inventors of the present disclosure have discovered that combining the adhesion, abrasion resistance and mechanical strength of epoxies with the thermal stability, flexibility and icephobicity of silicones in hybrid systems yields strong and flexible materials with higher resistance to cracking in harsh environments while providing hydrophobic and icephobic properties. Starting out at the metallic or polymeric substrate surface representing the inner coating surface by applying a polymeric coating with a high epoxy content, preferably being substantially free of silicones or having a low silicone content assures a good bond between the polymeric coating and the underlying substrate. Then, as the thickness of the polymeric coating increases, the silicone contents in the deposition direction towards the outer exposed surface can be gradually or stepwise increased. Consequently a polymeric coating is formed ending up with the highest silicone content at the outer, exposed surface, thus providing for an anisotropic polymeric coating which maintains excellent adhesion to the substrate surface while being icephobic on the exposed, outer surface. In one preferred embodiment the same epoxy resin is used throughout the coating, i.e., in both the bonding and the icephobic layer.

(22) Similarly, substituting polyurethanes based coatings for epoxies using otherwise the same approach can yield durable coatings with excellent icephobic properties and high adhesion to the underlying substrates.

(23) This invention relates to articles comprising durable, icephobic coatings. In its broadest aspect the present invention relates to article of manufacture comprising: (i) a substrate comprising a metallic or polymeric material having an outer surface in direct contact with (ii) an anisotropic polymeric coating which (a) on the interface between said polymeric coating and said substrate contains a substantially fully cured organic resin and is substantially free of icephobic additives; and (b) on its exposed outer surface contains the same substantially fully cured organic resin and furthermore contains one or more solid icephobic additives.

(24) In one preferred embodiment the substrate comprises a metallic material. Examples of suitable metallic materials include metals and alloys of aluminum, cobalt, magnesium, steel, nickel and titanium. The substrate can be an isotropic, layered or graded metallic construct comprising one or more continuous metal layers wherein at least one of the continuous metal layers is a microcrystalline and/or amorphous metal layer or a grain-refined layer having a grain size below 5,000 nm.

(25) In another preferred embodiment the substrate comprises a polymer or polymer composite. Suitable polymers include any known thermoplastic or thermoset. Suitable polymer composites can contain a material selected from the group consisting of carbon, carbon fibers, graphite, graphite fibers, carbon nanotubes and graphene. Other additions such as glass, glass fibers, as well as inorganic and organic fibers or biocidal materials selected from the group of biocidally active metal or compounds are contemplated as well.

(26) The polymeric coating applied to the substrate is anisotropic in the deposition direction, e.g., layered or compositionally graded. The composition of the polymeric coating in contact with the substrate and near the interface with the substrate is chosen to maximize the adhesion strength between the polymeric coating and the substrate. In contrast, the composition of the exposed outer surface of the polymeric coating is chosen to maximize erosion performance and icephobic properties. The transition of the composition of the polymeric coating from the “bonding surface” to the “icephobic surface” and/or “biocidal” surface can be gradual, e.g., by changing the chemical composition from an epoxy or polyurethane rich and silicone and biocidal agent free to an epoxy or polyurethane and silicone and/or biocidal additive containing outer surface providing a graded polymer layer. Alternatively, distinct layers of various compositions can be applied to transition from an epoxy or polyurethane rich, silicone-free and biocidal agent free to an epoxy or polyurethane and silicone and/or biocidal agent containing outer surface. In the case of layering, at a minimum, two distinct polymer layers are applied; however, a multilayer laminate with a total of up to 100 sublayers can be applied. Combination of layered and graded sublayers is also included in the scope of this invention.

(27) In an alternative embodiment the anisotropic polymeric coating is not directly applied to the substrate but formed independently and provided with an adhesive film or an adhesive tape in contact with the bonding layer and the exposed adhesive film is protected by a release liner. Before use, the release liner is removed and the coating is applied to the substrate in a way that the adhesive film forms an intermediate layer between the substrate and the anisotropic polymeric coating. The adhesive film can be epoxy based providing high adhesive strength and preferably cures at or near room temperature. Other options include rubber-, silicone- or acrylic-based adhesive tapes which can also be pressure sensitive adhesives. In one preferred embodiment the adhesive layer replaces the bonding layer and is applied directly onto the icephobic and/or biocidal layer. Such an approach can be used to apply the icephobic and/or biocidal coating conveniently onto any part to render it icephobic and/or biocidal, it is particularly suitable for use in repair and overhaul, e.g., where there is a requirement to patch eroded or deteriorated sections of the coating.

(28) The present invention is based on the discovery that, in the case of applying an icephobic and/or biocidal organic coating to a metallic or polymeric substrate surface, an isotropic coating does not readily achieve the desired overall performance as either adhesion to the underlying substrate or icephobic properties or both are unduly compromised which can have a significant effect on performance and durability. Monolithic coatings optimized for icephobicity and/or biocidal properties were found to have rather poor adhesion to the substrate materials of interest and perform poorly on extended durability tests such as sand or rain erosion frequently resulting in part or the entire coating flaking off the underlying substrate surface resulting in premature failure.

(29) Typically, the polymeric coating according to this invention uses the same ingredients throughout, e.g., the same curable epoxy or polyurethane resin, the same curing agent formulation etc. termed “basic coating formulation”. The main difference in the chemical formulations near the “bonding surface” when compared to near the “icephobic surface” and/or “biocidal surface” is, that, in the case of the “near bonding layer surface” the coating comprises merely the “basic coating formulation” with the optional addition of adhesion promoters, and elastomers. In contrast, “near the outer icephobic and/or biocidal surface” the coating comprises the “basic coating formulation” with the addition of between 1 and 20 weight % of an “icephobic additive” and/or between 5 and 90 weight % of an biocidal additive with the optional addition of other additives, including, but not limited to, abrasive materials to enhance the hardness and erosion resistance of outer and near-outer surface and pigments to achieve any desired color. Consequently, the chemical composition throughout the polymeric coating is similar assuring excellent adhesion of sublayers, if any, to each other and excellent overall cohesive strength of the entire coating. This approach is far superior to, e.g., applying a distinct polymer primer to the substrate followed by the deposition of a distinct and unrelated, icephobic polymeric coating, which can lead to delamination of the “unrelated” polymer layers during use.

(30) Accordingly, the polymeric coating applied to the metallic or polymeric material substrate is anisotropic and comprises, on the surface in contact with the substrate material, a “bonding layer” comprising a curable resin preferably free of silicones and, on the exposed outer surface an “icephobic layer” which, in addition to the same curable resin, contains at least 1 and up to 25 weight percent of a modified silicone. In the case the exposed outer surface is also rendered biocidal a “biocidal layer” which, in addition to the same curable resin, contains at least 5 and up to 95 weight percent of a biocidal additive.

(31) Both, the bonding layer and the outer icephobic and/or biocidal layer have a thickness of at least 5 microns, preferably at least 25 microns and more preferably at least 50 microns.

(32) The bonding layer is deposited directly onto the substrate material and subsequently typically at least partially cured and another cure is performed after the icephobic top coat is applied. Depending on the number of sublayers the total number of curing steps involved is at least 2 but as many as 10+ curing cycles can be used, depending on the number of sublayers applied and the final properties desired.

(33) In another aspect the invention provides a process for coating an article, said process comprising the steps of: providing an article of manufacture having an outer surface, or a predetermined portion thereof, comprised of a metallic or polymeric substrate material; coating the outer surface of the substrate material, or a predetermined portion thereof, with a curable polymeric resin of a first composition; substantially partially or fully curing the curable polymeric resin of the first composition to form a bonding layer; coating the outer surface of the bonding layer with a polymeric resin of a second composition comprising an icephobic additive; substantially fully curing the curable polymeric resin of the second composition to form a durable icephobic exposed outer surface;

(34) In another aspect the invention provides a process for applying a prepreg coating to an article, said process comprising the steps of: providing an article of manufacture having an outer surface, or a predetermined portion thereof, comprised of a metallic or polymeric substrate material; independently forming and substantially partially or fully curing a curable polymeric resin of the second composition comprising an icephobic and/or biocidal additive to form a durable icephobic and/or biocidal exposed outer surface; optionally applying onto the second composition layer a curable polymeric resin of a first composition and optionally partially or fully curing the curable polymeric resin of the first composition; applying onto the first composition layer, if present, an adhesive layer and optionally partially or fully curing the multilayer construct; optionally applying onto the adhesive layer a release liner; upon use removing the optional release liner from the multilayer construct and applying it to the metallic or polymeric substrate material so that the icephobic and/or biocidal layer of the second composition becomes the exposed outer surface.

(35) As highlighted above, under certain conditions, the use of a bonding layer can be eliminated and an acceptable adhesion can be achieved while still providing water and ice repellent outer surfaces. Such processes results in achieving a very strong bond between the outer exposed coating surface and the underlying core substrate and the processes can be used to manufacture articles in which strong adhesion between the exposed polymeric coating and the underlying substrate is desired or necessary. In addition, the organic coating sublayers are formulated and/or processed to maximize cohesive strength within the polymeric coating sublayers themselves while achieving excellent adhesion between the sublayers as well. The processes are particularly suited for the manufacture of durable articles that require high water repellency, icephobicity, biocidal properties as well as abrasion resistance and flexural, tensile, torsional, impact and/or fatigue strength, such as required for sporting goods, automotive parts, aircraft components, building materials, industrials components exposed to the elements; and the like. It is desirable to pretreat the substrate surface before it receives the polymer coating. The pretreatment can comprise mechanical abrasion and/or etching. Etching can be, e.g., accomplished with permanganate or sulfochromic chemical etch, or with a plasma etch.

(36) The compositions comprising the curable resin can, for example, be applied by spraying. For this purpose the composition desirably uses a solvent in a sufficient amount to obtain the viscosity suitable for spraying. It has been found that preferred solvents have a boiling point of less than 150° C., preferably less than 100° C. The importance of the boiling point of the solvent is related to the need to have the film substantially fully cured. It is important that, after curing, the polymeric coating has substantially no dissolved solvents and does not contain any liquids.

(37) When applied by spraying, both the bonding layer and the icephobic layer are generally applied at about 3 to 20 mg/cm.sup.2, preferably from 5 to 15 mg/cm.sup.2. Depending on the thickness desired, it may be advantageous to apply each composition in two or more sprayed layers, with a partial curing (for example 30 minutes at 140° C. or 90° C.) between applications.

(38) After applying the bonding layer and prior to depositing the icephobic outer layer, the bonding layer can be partially or fully cured as well as suitably pretreated. This pretreatment can comprise mechanically roughening and/or etching. Suitable etching processes include chemical etching processes and/or plasma etching.

(39) When applying the icephobic layer, the spraying process described for applying the bonding layer is essentially replicated. Alternative processes can be used as well including, but not limited to, painting, doctor blading and screen printing.

(40) While building up the entire polymeric coating, various curing steps can be performed and repeated, alternatively partial curing steps can be employed or the curing step can be deferred until the entire coating has been deposited.

(41) As the person skilled in the art of organic coatings would appreciate, the organic coating can be applied to the core substrate in an automated production line where, e.g., the substrate to be coated passes from one spray booth to the next with optional partial or total curing and/or surface treatments in between. A multilayer laminate coating can be produced, e.g., changing the composition of the “paint” in each spray station to achieve a “stepwise” transition from the bonding layer composition to the icephobic surface composition. While the organic coating of this invention relies on at least two distinct layers, a multitude of layers, such as 5, or 10 or even more transitional layers can be incorporated between the inner surface (in contact with the substrate) and the outer (exposed) surface of the organic coating. Similarly, rather than having a multilayer laminate with distinct chemical compositions, a gradual change in the composition can be affected in the coating deposition direction and combinations of layered and graded layers are within the scope of this invention as well.

(42) It is also possible to provide the icephobic and/or biocidal polymer layer in freestanding form or supported such as a “pre-preg” as described above. The bonding layer film or pre-preg used in this process can be fabricated from the liquid epoxy formulation using standard industry practices used for fabricating thin film polymeric adhesive films and pre-pregs from solvent bearing formulations. The release liner protecting the adhesive film/transfer tape is removed before use and the anisotropic polymeric coating comprising an icephobic layer, a bonding layer and an additional adhesive layer or, alternatively, the adhesive layer is replacing the bonding layer altogether, is then applied to the substrate. For instance, the icephobic and/or biocidal layer can be applied, e.g., sprayed onto the exposed surface of an adhesive tape which may have a release liner on the opposite side.

(43) Articles or coatings made according to the process of this invention find use in a variety of applications requiring improved durability while retaining enhanced hydrophobic, icephobic and biocidal properties.

EXAMPLES

(44) The following is a description of Working Examples illustrating the benefits of the present disclosure, specifically the formulation of various polymeric coatings and methods of applying and curing the coatings as well as selected properties including the icephobic properties (Working Example I and III) as well as adhesion properties using a variety of substrates (Working Example II and IV). Working Examples V and VI show the benefits of incorporating metal powders into icephobic coating formulations when eliminating the bonding layer.

Example I: Icephobic Epoxy (EP) Coating Formulations, Application and Selected Properties

(45) Various coating formulations were investigated as follows: Nusil™, a commercial product (two-part silicone elastomer dispersed in xylene) available from NuSil™ Technology LLC, Carpinteria, Calif. 93013, USA, which is widely recognized for its icephobic properties as indicated above, was applied to selected substrates by doctor blade whereas the various inventive epoxy-based coatings were applied to the substrates by spraying using a gravity feed type, HVLP (high volume-low pressure) epoxy spray gun operated at 60 psi. In-house paint formulations are provided in Table 2 below. The coated substrates were subsequently cured in a furnace at 140° C. for 2 hours, except for Nusil™, which was cured according to the manufacturer's specifications using four temperatures and durations as follows: RT/30 min, 75° C./45 min, and 150° C./135 min. Total target loading for each sample was 8-12 mg/cm.sup.2 (thickness: 75-100 microns). If multiple layers were applied, e.g., an icephobic layer on top of the bonding layer, the thickness and loading for each layer was reduced to maintain the overall coating thickness/loading target and a curing step was performed after each layer. After curing, the exposed surface of all samples was smooth and had a surface roughness R.sub.a<1 μm.

(46) Cured coating samples produced were characterized as indicated in Table 3. For ease of comparison, the data of the various tests depicted in Table 3 are also shown in FIG. 1, namely the wetting angle, the ice adhesion according to the test described by the U.S. Army Engineer Research and Development Center, Hanover, N.H., USA, in the ERDC/CRREL Technical Note 03-4 (October 2003), the sand erosion value at impingement angles of 90° and 30° according to ASTM G76, and the Shore D hardness.

(47) TABLE-US-00002 TABLE 2 In-house Epoxy (EP) Paint Formulations Investigated. Epoxy Resin Icephobic Epoxy Bonding Layer Resin Top Layer Formulation [g] Formulation [g] Epoxy Resin (EEW = 550) 100 100 Elastomer 60 0 Curing Agent 5 5 Adhesion Promoter 8 0 Additives 15 0 Icephobic Additive: Epoxide 0 7.5 Functional Silicone Pre-Polymer Silicone Oil 0 0 Solvent 240 120

(48) The results indicate that all coating surfaces are hydrophobic, that an icephobic additive such as a silicone is required to achieve a low icephobicity value on the first cycle (Nusil™ and silicone top layer containing coatings) and that, after repeated icing/deicing cycles seven times, the ice adhesion of the samples containing the solid silicone remain largely unchanged (modified silicone top layer containing coatings).

(49) The data also reveal that the sand erosion values at 90° impingement with icephobic additions increase compared to the additive free formulation of the bonding layer, however, the erosion values at an impingement angle of 30° experience similar mass losses for all samples. In addition, the Shore D hardness values of the coatings containing epoxy resins are significantly higher than the one for Nusil™.

(50) TABLE-US-00003 TABLE 3 Selected Coating Properties Two-Layers Single/Homogenous Layer Elastomer-Free 6.7% Silicone Bonding Layer Containing Silicone Free plus Outer Epoxy Layer Epoxy Layer Exposed Surface Nusil ™ (Icephobic Layer) (Bonding Layer) Icephobic Layer Exposed Surface <1 <1 <1 <1 Roughness, R.sub.a [μm] Wetting Angle [°] 119 123 115 123 Cycle 1: 150 110 472 110 Ice Adhesion [kPa] Cycle 7: 305 110 691 110 Ice Adhesion [kPa] Sand Erosion Rate 4.1 4.9 1.9 4.9 @ 90° [mm.sup.3/kg] Sand Erosion Rate 2.1 1.8 1.9 1.8 @ 30° [mm.sup.3/kg] Shore Hardness 40 (scale A) 70-75 (scale D) 70-75 (scale D) 70-75 (scale D)  0 (scale D)

Example II: Icephobic Epoxy Article Characterization

(51) A number of substrates were selected (4×4 inch panels) for this investigation, namely Al, Ti, stainless steel, carbon fiber reinforced composite and Nylon. The smooth substrates (R.sub.a<1 μm) were mechanically abraded with ultra-fine (500 grit) sand paper to a uniform finish, then cleaned and degreased by wiping with a suitable solvent and various coatings described in EXAMPLE I were applied as follows: (i) Nusil™, (ii) an epoxy based, silicone-free, bonding layer, (iii) an epoxy based icephobic layer and (iv) a two layer coating comprising the epoxy based bonding layer on the substrate followed by the epoxy based icephobic outer exposed layer.

(52) TABLE-US-00004 TABLE 4 Adhesion Property Evaluation 2-Layers Single/Homogenous Layer Elastomer-Free 6.7% Silicone Bonding Layer Containing Silicone Free plus Outer Epoxy Layer Epoxy Layer Exposed Surface Nusil ™ (Icephobic Layer) (Bonding Layer) Icephobic Layer Pull Off Adhesion 228 750 1322 1239 Strength from Titanium [psi] Pull Off Adhesion 213 691 1344 1337 Strength from Aluminum [psi] Pull Off Adhesion 201 471 1411 1420 Strength from Stainless Steel Grade 304 [psi] Pull Off Adhesion 210 872 1846 1887 Strength from Carbon Fiber Composite [psi] Pull Off Adhesion 247 428 942 945 Strength from Nylon [psi]

(53) The adhesion between the top/exposed surface of any coating and the base substrate was measured by the “pull-off strength” according to standard ASTM 4541D. For ease of comparison, the data of the various samples are depicted in Table 4 are also shown in FIG. 2. The data reveal that layers with the icephobic additive (Nusil™ and icephobic layer) applied directly to the varies substrates have the lowest bond strength, whereas the icephobic additive-free bonding layer and the two-layer structure comprising a bonding layer in direct contact with the substrate and an outer, exposed icephobic layer results in an overall pull-off strength, at times, that exceeded 800 psi as well as 1,000 psi. Articles containing the Nusil™ coating, in all instances, delaminated at the interface of the substrate and the coating. Articles containing a bonding layer in contact with the various substrates, in all instances, showed both signs of delamination as well as cohesive failure, revealing the impressive strength of these samples.

(54) These results indicate that an anisotropic coating (bonding layer+icephobic layer) provides a superior article with excellent durability, bond strength and long lasting icephobic properties.

Example III: Icephobic Polyurethane (PU) Coating Formulations, Application and Selected Properties

(55) A thermoset polyurethane formulation which cures at room temperature with and without the addition of a modified silicone were applied to various substrates by spraying using a gravity feed type, HVLP (high volume-low pressure) spray gun operated at 60 psi and compared to the Nusil™ commercial product described above. In-house paint formulations are provided in Table 5 below. Total target loading for each sample was 8-12 mg/cm.sup.2 (thickness: 75-100 microns). After curing, the exposed surface of all samples was smooth and had a surface roughness R.sub.a<1 μm.

(56) Cured coating samples produced were characterized as indicated in Table 6. For ease of comparison, the data of the various tests depicted in Table 6 are also shown in FIG. 3, namely the wetting angle, the ice adhesion according to the test described by the U.S. Army Engineer Research and Development Center, Hanover, N.H., USA, in the ERDC/CRREL Technical Note 03-4 (October 2003), the sand erosion value at impingement angles of 90° and 30° according to ASTM G76, and the Shore D hardness.

(57) TABLE-US-00005 TABLE 5 In-house Polyurethane (PU) Paint Formulations Investigated. Icephobic PU PU Bonding Layer Resin Top Layer Formulation [g] Formulation [g] Thermoset Polyurethane 100 100 Elastomer 0 0 Curing Agent 100 100 Adhesion Promoter 0 0 Additives 0 0 Icephobic Additive: Epoxide 0 10 Functional Silicone Pre-Polymer Silicone Oil 0 0 Solvent 200 200

(58) TABLE-US-00006 TABLE 6 Selected Coating Properties Two-Layers Single/Homogenous Layer PU Bonding 4.8% Silicone Layer plus Containing Silicone Free Outer Exposed PU Layer PU Layer Surface Icephobic Nusil ™ (Icephobic Layer) (Bonding Layer) PU Layer Exposed Surface <1 <1 <1 <1 Roughness, R.sub.a [μm] Wetting Angle [°] 119 120 120 120 Cycle 1: 150 137 363 137 Ice Adhesion [kPa] Cycle 5: 305 532 133 Ice Adhesion [kPa] Sand Erosion Rate 4.1 4.4 4.4 4.4 @ 90° [mm.sup.3/kg] *.sup.) Sand Erosion Rate 3.3 3.3 3.3 3.5 @ 45° [mm.sup.3/kg] Sand Erosion Rate 2.1 2.1 2.1 2.1 @ 30° [mm.sup.3/kg] Shore Hardness 40 (scale A) 20 (scale D) 20 (scale D) 20 (scale D)  0 (scale D) *.sup.) As reference the sand erosion rate for Al @ 90° is 9.0 mm.sup.3/kg.

(59) The results indicate that all coating surfaces are hydrophobic, that an icephobic additive such as a silicone is required to achieve a low icephobicity value on the first cycle (Nusil™ and silicone top layer containing coatings) and that, after repeated icing/deicing cycles five times, the ice adhesion of the samples containing the solid silicone remain largely unchanged (modified silicone top layer containing coatings).

(60) The data also reveal that the sand erosion at all angles of impingement with are similar for all samples. In addition, the Shore D hardness values of the coatings containing PU resins are significantly higher than the one for Nusil™.

Example IV: Icephobic Polyurethane Article Characterization

(61) A number of substrates were selected (4×4 inch panels) for this investigation, namely Al, Ti, stainless steel, carbon fiber reinforced composite and Nylon. The smooth substrates (R.sub.a<1 μm) were mechanically abraded with ultra-fine (500 grit) sand paper to a uniform finish, then cleaned and degreased by wiping with a suitable solvent and various coatings described in EXAMPLE III were applied as follows: (i) Nusil™, (ii) a thermoset polyurethane based, silicone-free, bonding layer, (iii) an thermoset polyurethane based icephobic layer and (iv) a two layer coating comprising the thermoset polyurethane based bonding layer on the substrate followed by the thermoset polyurethane based icephobic outer exposed layer.

(62) The adhesion between the top/exposed surface of any coating and the base substrate was measured by the “pull-off strength” according to standard ASTM 4541D. For ease of comparison, the data of the various samples are depicted in Table 7 are also shown in FIG. 4. The data reveal that layers with the icephobic additive (Nusil™ and icephobic layer) applied directly to the varies substrates have the lowest bond strength, whereas the icephobic additive-free bonding layer and the two-layer structure comprising a bonding layer in direct contact with the substrate and an outer, exposed icephobic layer results in an overall pull-off strength that exceeded 1,000 psi. Articles containing the Nusil™ coating, in all instances, delaminated at the interface of the substrate and the coating. Articles containing a bonding layer in contact with the various substrates, in all instances, showed both signs of delamination as well as cohesive failure, revealing the impressive strength of these samples.

(63) These results indicate that an anisotropic coating (bonding layer+icephobic layer) provides a superior article with excellent durability, bond strength and long lasting icephobic properties.

(64) TABLE-US-00007 TABLE 7 Adhesion Property Evaluation 2-Layers Single/Homogenous Layer PU Bonding 4.8% Silicone Layer plus Containing Silicone Free Outer Exposed PU Layer PU Layer Surface Icephobic Nusil ™ (Icephobic Layer) (Bonding Layer) PU Layer Pull Off Adhesion 228 1315 1423 1425 Strength from Titanium [psi] Pull Off Adhesion 213 1298 1455 1420 Strength from Aluminum [psi] Pull Off Adhesion 201 1024 1224 1210 Strength from Stainless Steel Grade 304 [psi] Pull Off Adhesion 210 1677 1685 1650 Strength from Carbon Fiber Composite [psi] Pull Off Adhesion 247 892 1192 1200 Strength from Nylon [psi]

Example V: Icephobic and Biocidal Epoxy Property Characterization

(65) In this example, 4×4 inch mild steel panels were used as substrate. The smooth substrates (R.sub.a<1 μm) were mechanically abraded with ultra-fine (500 grit) sand paper to a uniform finish, then cleaned and degreased by wiping with a suitable solvent and various single layer coatings as described in Table 2 (EXAMPLE I) “icephobic epoxy resin top layer” were applied with the addition of various amounts of powder additions. The copper powder used had an average particle size of 1 microns and >99% purity. The brass powder (50Cu/50Zn) used had an average particle size of 1 microns and >99% purity. Vulcan XC 72R was used as the carbon powder addition. The top layer was applied directly to the steel substrate without the use of a bonding layer.

(66) Cured coated samples were characterized as in the previous examples and are illustrated in Table 8.

(67) TABLE-US-00008 TABLE 8 Selected Epoxy Coating Properties. 25% 14% 10% 25% 50% 75% copper + 4% 2% brass, 7% copper copper copper copper carbon brass carbon in EP in EP in EP in EP in EP in EP in EP Exposed Surface <1 <1 <1 1.2 <1 <1 <1 Roughness, R.sub.a [μm] Wetting Angle [°]*.sup.) 102 93 98 93 94 115 99 Cycle 1: 217 256 394 634 320 79 349 Ice Adhesion [kPa] Cycle 5: 189 259 302 800 129 224 267 Ice Adhesion [kPa] Average of 5 Ice 186 253 336 783 180 182 309 Adhesion Cycles [kPa] Sand Erosion Rate 4.9 4.9 5 5.3 4.9 4.9 4.8 @ 90° [mm.sup.3/kg] Pull Off Adhesion 1139 1249 1693 1379 997 1100 808 Strength from Stainless Steel grade 304 [psi] Shore Hardness (Scale D) 75-80 75-80 80-90 80-90 75-80 75-80 75-80 *.sup.)The contact angle for pure Cu-foil was determined to be 75°

(68) Similar pull-off adhesion results were obtained for metal substrates other than steel or polymeric substrates as illustrated in the previous examples.

Example VI: Icephobic and Biocidal Polyurethane Property Characterization

(69) In this example, 4×4 inch mild steel panels were used as substrate. The smooth substrates (R.sub.a<1 μm) were mechanically abraded with ultra-fine (500 grit) sand paper to a uniform finish, then cleaned and degreased by wiping with a suitable solvent and various single layer coatings as described in Table 5 (EXAMPLE III) “icephobic PU resin top layer” were applied with the addition of various amounts of powder additions. The copper powder used had an average particle size of 1 microns and >99% purity. The brass powder (50Cu/50Zn) used had an average particle size of 1 microns and >99% purity. Vulcan XC 72R was used as the carbon powder addition. The top layer was applied directly to the steel substrate without the use of a bonding layer.

(70) Cured coating samples were characterized as in the previous examples and are illustrated in Table 9.

(71) TABLE-US-00009 TABLE 9 Selected Polyurethane Coating Properties. 10% 25% 50% 75% copper copper copper copper in PU in PU in PU in PU Exposed Surface <1 <1 <1 <1 Roughness, R.sub.a [μm] Wetting Angle [°]*.sup.) 102 93 98 93 Cycle 1: 286 297 150 266 Ice Adhesion [kPa] Cycle 5: 158 185 191 189 Ice Adhesion [kPa] Average of 5 Ice Adhesion 224 250 163 253 Cycles [kPa] Sand Erosion Rate 4.6 4.7 4.6 4.9 @ 90° [mm.sup.3/kg] Pull Off Adhesion Strength from 1103 1260 1549 1712 Stainless Steel grade 304 [psi] Shore Hardness (Scale D) 20 20 20 20 *.sup.)The contact angle for pure Cu-foil was determined to be 75°

(72) Similar pull-off adhesion results were obtained for metal substrates other than steel or polymeric substrates as illustrated in earlier examples.

(73) Variations

(74) The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be so limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of the invention.