EP3694809A1 - Revêtements hydrophobes destinés à des métaux incorporant des oxydes anodiques et des oxydes de terres rares et leurs procédés d'application - Google Patents

Revêtements hydrophobes destinés à des métaux incorporant des oxydes anodiques et des oxydes de terres rares et leurs procédés d'application

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Publication number
EP3694809A1
EP3694809A1 EP17928201.7A EP17928201A EP3694809A1 EP 3694809 A1 EP3694809 A1 EP 3694809A1 EP 17928201 A EP17928201 A EP 17928201A EP 3694809 A1 EP3694809 A1 EP 3694809A1
Authority
EP
European Patent Office
Prior art keywords
substrate
hydrophobic
cathodizing
anodizing
yttrium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17928201.7A
Other languages
German (de)
English (en)
Other versions
EP3694809A4 (fr
Inventor
Christopher Rankin
Marlowe Moncur
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GKN Aerospace Transparency Systems Inc
Original Assignee
GKN Aerospace Transparency Systems Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GKN Aerospace Transparency Systems Inc filed Critical GKN Aerospace Transparency Systems Inc
Publication of EP3694809A1 publication Critical patent/EP3694809A1/fr
Publication of EP3694809A4 publication Critical patent/EP3694809A4/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting

Definitions

  • This invention relates generally to hydrophobic coatings and, more particularly, to a hydrophobic coating comprising anodic and rare-earth oxides and methods of applying such a coating to a surface of a metallic substrate.
  • Aircraft, automotive, and other transparency applications provide additional challenges.
  • a hydrophobic coating should maintain high hardness and resistance to attack by acids and bases.
  • these applications can involve metallic substrates, with thermal expansion coefficients and elastic moduli that are incompatible with many existing hydrophobic coatings.
  • the coating should be robust to environmental degradation, mechanical abrasion, and repeated stress, while exhibiting inherently low surface energy without additional surface patterning.
  • the coating should maintain hardness and resistance to attack by acids and bases, while also maintaining a permanent bond to the metallic surface as the surface thermally expands and contracts.
  • the present invention is embodied in a method of applying a hydrophobic coating to a surface of a metallic substrate, as well as in the hydrophobic coating formed by the method.
  • the method includes anodizing a nanoporous layer of anodic metal oxide on the surface; applying a hydrophobic ceramic coating composition to the surface, after anodizing the surface, by an application method selected from the group consisting of: flowing, dipping, and spraying; and heating the coated surface at a cure temperature from about 150° C to about 300° C for at least 2 hours.
  • the method further includes the step of cathodizing yttrium oxide nanoparticles onto the before applying the hydrophobic ceramic coating composition to the surface.
  • Each feature or concept is independent, but can be combined with any other feature of concept disclosed in this application.
  • the method includes anodizing a nanoporous layer of anodic metal oxide on the surface, and cathodizing yttrium oxide nanoparticles onto the surface after anodizing the surface.
  • the method further includes the steps of applying a hydrophobic ceramic coating composition to the surface, after cathodizing the surface, by an application method selected from the group consisting of: flowing, dipping, and spraying; and heating the coated surface at a cure temperature from about 150° C to about 300° C for at least 2 hours.
  • an application method selected from the group consisting of: flowing, dipping, and spraying; and heating the coated surface at a cure temperature from about 150° C to about 300° C for at least 2 hours.
  • the method can further include the step of cleaning surface of the metallic substrate with acetone before the anodizing step.
  • the anodic metal oxide can comprises anodic aluminum oxide.
  • the anodizing step can comprise anodizing the surface in an acidic solution having a concentration from about 0.1 M to about 0.3 M, at an anodizing voltage from about 8 V to about 12 V for an anodizing time from about 20 minutes to about 90 minutes.
  • the acidic solution can have a pH less than about 5.
  • the acidic solution can comprise an acid selected from the group consisting of: acetic acid, citric acid, hydrogen chloride, nitric acid, and sulfuric acid.
  • the acid can comprise sulfuric acid.
  • the concentration can be about 0.2 M.
  • the anodizing voltage can be about 10 V.
  • the anodizing time can be from about 30 minutes to about 60 minutes.
  • the cathodizing step can comprise cathodizing the surface in a colloidal dispersion of yttrium oxide nanoparticles, at a cathodizing voltage from about 8 V to about 12 V, and a current from about 0.05 mA to about 0.15 mA, for a cathodizing time from about 30 minutes to about 90 minutes.
  • the yttrium oxide nanoparticles can have a mean particle size of about 10 nm and can be in an amount ranging from about 2% to about 10% by weight of the colloidal dispersion.
  • the amount of yttrium oxide nanoparticles can be about 5% by weight of the colloidal dispersion.
  • the cathodizing voltage can be about 10 V and the current can be about 0.1 mA.
  • the cathodizing time can be about 60 minutes.
  • the method can further include the step of removing excess nanoparticles from the surface after cathodizing the surface.
  • the removing step can include wiping the surface with isopropanol.
  • the method can further include the step of drying the coating composition on the surface of the substrate for about 1 hour.
  • the method can include heating the coated surface at a cure temperature of about 200° C.
  • the hydrophobic ceramic coating composition can comprise a yttrium compound, a dispersion of yttrium oxide nanoparticles, a water-soluble polymer, and a solvent solution of de- ionized water and a water-soluble alcohol.
  • the yttrium compound can comprise yttrium acetate
  • the dispersion of yttrium oxide nanoparticles can be in an amount ranging from about 0.5% to about 1% by weight of the coating composition
  • the water-soluble polymer can comprise polyvinyl alcohol in an amount from about 1% to about 5% by weight of the coating composition
  • the water-soluble alcohol can comprise isopropyl alcohol
  • the de- ionized water and water-soluble alcohol can be present in the solvent solution in a ratio of about 2: 1.
  • the metallic substrate can comprises a metal selected from the group consisting of: aluminum, titanium, and stainless steel.
  • the metal can comprise aluminum.
  • the present invention is also embodied in a hydrophobic, coated substrate.
  • the substrate can include a metallic substrate having a surface, a nanoporous layer of anodic metal oxide formed on the surface, and a hydrophobic ceramic coating bonded to the nanoporous layer.
  • the substrate can further include yttrium oxide nanoparticles embedded in the nanoporous layer.
  • the hydrophobic, coated substrate can include a metallic substrate having a surface, a nanoporous layer of anodic metal oxide formed on the surface, and yttrium oxide nanoparticles embedded in the nanoporous layer.
  • the substrate can further include a hydrophobic ceramic coating bonded to the nanoporous layer.
  • the nanoporous layer of anodic metal oxide can include nanopipettes.
  • the nanopipettes can have an average diameter from about 10 nm to about 100 nm.
  • the nanopipettes can have an average diameter from about 20 nm to about 50 nm.
  • the nanopipettes can have a minimum diameter of about 10 nm and a maximum diameter of about 100 nm.
  • the nanopipettes can have an average length from about 100 nm to about 10 ⁇ .
  • the nanopipettes can have an average length from about 1.5 ⁇ to about 8 ⁇ .
  • the nanopipettes can have a minimum length of about 100 nm and a maximum length of about 10 ⁇ .
  • the yttrium oxide nanoparticles can have a mean particle size of about 10 nm.
  • the yttrium oxide nanoparticles can be embedded in the nanopipettes.
  • the hydrophobic ceramic coating can comprise yttrium acetate.
  • the metallic substrate can comprise a metal selected from the group consisting of: aluminum, titanium, and stainless steel.
  • the metal can comprise aluminum.
  • the anodic metal oxide can comprise anodic aluminum oxide.
  • Each feature or concept is independent, but can be combined with any other feature of concept disclosed in this application.
  • Figures 1A-1C are flow diagrams showing methods of applying a hydrophobic coating in accordance with some embodiments of the invention.
  • Figure 2A is a cross-sectional illustration of a nanoporous layer of anodic metal oxide formed on the surface of a metallic substrate, in accordance with one embodiment of the invention.
  • Figure 2B is a top-view illustration of a nanoporous layer of anodic metal oxide formed on the surface of a metallic substrate, in accordance with one embodiment of the invention.
  • Figure 3A is a cross-sectional illustration of a hydrophobic, coated substrate, in accordance with one embodiment of the invention.
  • Figure 3B is a cross-sectional illustration of a hydrophobic, coated substrate, in accordance with one embodiment of the invention.
  • Figure 3C is a cross-sectional illustration of a hydrophobic, coated substrate, in accordance with one embodiment of the invention.
  • Figure 4 is a cross-sectional illustration of a hydrophobic ceramic coating applied to an aluminum substrate having a native aluminum oxide layer.
  • Figure 5 is a scanning electron micrograph of an anodized aluminum oxide nanopipette layer, in accordance with one embodiment of the invention.
  • Figure 6 is a photograph of a water droplet on an aluminum surface having a yttrium-oxide-nanoparticle-enhanced hydrophobic, ceramic coating, in accordance with one embodiment of the invention.
  • the method can include a step 110 of anodizing a nanoporous layer of anodic metal oxide on the surface; a step 120 of cathodizing yttrium oxide nanoparticles onto the surface; a step 130 of applying a hydrophobic ceramic coating composition to the surface; and a step 140 of heating the coated surface.
  • the method can omit one or more of these steps.
  • the method can include the step 110 of anodizing a nanoporous layer of anodic metal oxide on the surface, the step 130 of applying a hydrophobic ceramic coating to the surface, and the step 140 of heating the coated surface.
  • the method can include the step 110 of anodizing a nanoporous layer of anodic metal oxide on the surface, and the step 120 of cathodizing yttrium oxide nanoparticles onto the surface.
  • the metallic substrate can comprise a metal selected from the group consisting of: aluminum, titanium, and stainless steel.
  • the metal can comprise aluminum.
  • Anodization is an electro-chemical process that changes the surface chemistry of a metal, via oxidation, to produce an anodic oxide layer.
  • the nanoporous layer of anodic metal oxide formed on the surface by step 110 can serve to create a permanent bond between sol gel coatings, such as a hydrophobic ceramic coating, and the surface of the metallic substrate.
  • the anodizing step 110 can comprise anodizing the surface in an acidic solution.
  • the acidic solution can have a pH less than about 5.
  • the acidic solution can comprise an acid selected from the group consisting of: acetic acid, citric acid, hydrogen chloride, nitric acid, and sulfuric acid.
  • the acid can comprise sulfuric acid.
  • the acidic solution can have a concentration from about 0.1 M to about 0.3 M. In another embodiment, the concentration can be about 0.2 M.
  • the step 110 can be performed with an anodizing voltage from about 8 V to about 12 V for an anodizing time from about 20 minutes to about 90 minutes. In an additional embodiment, the anodizing voltage can be about 10 V. In yet another embodiment, the anodizing time can be from about 30 minutes to about 60 minutes.
  • anodic metal oxide 210 such as anodic aluminum oxide
  • the anodization parameters described above can produce a nanoporous layer of anodic metal oxide 210 having an ordered array of cylindrical pores, or nanopipettes 215.
  • the pore diameters D, periodicity, and density distribution of the nanopipettes 215 can be controlled by adjusting the anodization parameters described above. Adjustments to the anodization parameters can be made to control both the diameter D and length L of the nanopipettes 215, independently.
  • the nanopipettes 215 can have an average diameter D from about 10 nm to about 100 nm. In another embodiment, the nanopipettes 215 can have an average diameter D from about 20 nm to about 50 nm. In a further embodiment, the nanopipettes 215 can have a minimum diameter D of about 10 nm and a maximum diameter of about 100 nm.
  • the nanopipettes 215 can have a minimum diameter D of about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, or about 100 nm.
  • the nanopipettes 215 can have a maximum diameter D of about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, or about 100 nm.
  • the nanopipettes 215 can have an average length L from about 100 nm to about 10 ⁇ . In another embodiment, the nanopipettes 215 can have an average length L from about 1.5 ⁇ to about 8 ⁇ . In a further embodiment, the nanopipettes 215 can have a minimum length L of about 100 nm and a maximum length L of about 10 ⁇ . [0038] In one embodiment, the nanopipettes 215 can have a minimum length L of about
  • the nanopipettes 215 can have a maximum length L of about 100 nm, about 500 nm, about 1 ⁇ , about 1.5 ⁇ , about 2 ⁇ , about 2.5 ⁇ , about 3 ⁇ , about 3.5 ⁇ , about 4 ⁇ , about 4.5 ⁇ , about 5 ⁇ , about 5.5 ⁇ m, about 6 ⁇ , about 6.5 ⁇ , about 7 ⁇ m, about 7.5 ⁇ , about 8 ⁇ m, about 8.5 ⁇ , about 9 ⁇ , about 9.5 ⁇ m, or about 10 ⁇ .
  • This nanoporous layer of anodic metal oxide 210 can enhance material interpenetration and increase the strength of the mechanical and chemical bond between the surface 205 and, for example, embedded yttrium oxide nanoparticles 220 (Figure 3C) a hydrophobic ceramic coating 230 (Figure 3B), or both ( Figure 3 A).
  • the cathodizing step 120 can comprise cathodizing the surface in a colloidal dispersion of yttrium oxide nanoparticles.
  • the yttrium oxide nanoparticles can have a mean particle size of about 10 nm and can be in an amount ranging from about 2% to about 10% by weight of the colloidal dispersion. In a further embodiment, the amount of yttrium oxide nanoparticles can be about 5% by weight of the colloidal dispersion.
  • the cathodizing step 120 comprises electrically connecting the metallic substrate to the negative (cathodic) terminal in an electrodeposition assembly (not shown).
  • the surface of the metallic substrate is cathodized with a cathodizing voltage from about 8 V to about 12 V, and a current from about 0.05 mA to about 0.15 mA, for a time from about 30 minutes to about 90 minutes.
  • the cathodizing voltage can be about 10 V and the current can be about 0.1 mA.
  • the cathodizing time can be about 60 minutes.
  • the cathodizing step 120 can further include the step of removing excess nanoparticles from the surface after it has been cathodized.
  • the removing step can include wiping the cathodized surface with isopropanol.
  • embodiments of this method can result in a hydrophobic, coated substrate 200 as illustrated in Figure 3C.
  • the hydrophobic, coated substrate 200 can include the metallic substrate having the surface 205, the nanoporous layer of anodic metal oxide 210 formed on the surface 205, and yttrium oxide nanoparticles 220 embedded in the nanoporous layer 210.
  • the yttrium oxide nanoparticles 220 can have a mean particle size of about 10 nm.
  • the yttrium oxide nanoparticles 220 can be embedded in the nanopipettes 215.
  • These embedded yttrium oxide nanoparticles 220 can improve the hydrophobicity of the surface 205 while also providing robust performance against surface abrasion and deformation.
  • a ceramic coating such as the ceramic coating discussed below, the nanoparticles 220 can allow the ceramic coating to cure at a lower temperature, which mitigates atomic migration and other changes to the mechanical properties of the metallic substrate.
  • the coating composition can be applied to the surface, in step 130, by an application method selected from the group consisting of flowing, dipping, and spraying.
  • an application method selected from the group consisting of flowing, dipping, and spraying.
  • the selection of the appropriate method, or combination of methods, is commonly understood by one of ordinary skill in the art.
  • a flow or spray coating may be appropriate for large parts or complex shapes, or when two different coatings are required.
  • Dip coating may be appropriate, for example, where an entire part is to be coated.
  • the coating composition can include a yttrium compound; an additive selected from the group consisting of a cerium compound and a dispersion of yttrium oxide nanoparticles; a water-soluble polymer; and a solvent solution of de-ionized water and a water-soluble alcohol.
  • the yttrium is selected from the group consisting of yttrium acetate, yttrium carbonate, yttrium chloride, yttrium fluoride, yttrium hydroxide, yttrium metal, yttrium nitrate, yttrium oxalate, and yttrium sulfate.
  • the yttrium is yttrium acetate.
  • the cerium compound is water-soluble.
  • water- soluble cerium compounds include cerium bromide, cerium chloride, and cerium nitrate.
  • the cerium compound is sparingly water-soluble. Examples of sparingly water-soluble cerium compounds include cerium acetate and cerium sulfate.
  • the coating composition comprises an additive of a dispersion of yttrium oxide nanoparticles.
  • the dispersion of yttrium oxide nanoparticles is preferably compatible with the coating composition and can therefore be added at high levels without precipitation.
  • the dispersion of yttrium oxide nanoparticles is in an amount ranging from about 0.1% to about 5% by weight of the coating composition. In a preferred embodiment, the amount of the dispersion of yttrium oxide nanoparticles is from about 0.5% to about 1%) by weight of the coating composition.
  • a preferred embodiment of the coating composition further comprises a water- soluble polymer.
  • This water-soluble polymer component acts to increase the thickness of the final hydrophobic coating.
  • the hydrophobic nature of the coating composition without the water-soluble polymer makes it resistant to generating high thickness.
  • the addition of a water- soluble polymer to the coating composition increases the final coating thickness to over about 50 nm, over about 75 nm, over about 100 nm, over about 125 nm, over about 150 nm, over about 200 nm, over about 225 nm, or over about 250 nm.
  • the water-soluble polymer is selected from the group consisting of poly(n-vinylpyrrolidone), poly(vinylamine) hydrochloride, polymethacrylamide, polyvinyl alcohol, polyacrylamide, poly(ethylene oxide-b -propylene oxide), poly(methacrylic acid), poly(ethylene oxide), poly(n-iso-propylacrylamide), and poly(2-vinylpyridine).
  • the water-soluble polymer is polyvinyl alcohol.
  • the water-soluble polymer is in an amount ranging from about 1% to about 10% by weight of the coating composition. In yet another embodiment, the amount of the water-soluble polymer is from about 1% to about 5% by weight of the coating composition.
  • a preferred embodiment of the coating composition further comprises a solvent solution of de-ionized water and a water-soluble alcohol.
  • the water-soluble alcohol is selected from the group consisting of isopropyl alcohol, methanol, ethanol, propanol, and butanol.
  • the table below provides the chemical formulas and the water solubility levels of some water-soluble alcohols, but any other water-soluble alcohol may be used.
  • the de-ionized water and water-soluble alcohol are present in the solvent solution in a ratio of about 2: 1.
  • the method includes the step of allowing the coating composition on the surface of the substrate to dry before the heating step 140.
  • the method can comprise the step of drying the coating composition on the surface of the substrate before heating 140.
  • the coating composition can be allowed to dry for about 1 hour, about 2 hours, about 3 hours, or until the coating composition is in the "green state.”
  • the method can comprise the step 140 of heating the coated surface at a cure temperature from about 150°C to about 300°C for a cure time of at least 2 hours.
  • the cure time can be from about 2 hours to about 24 hours.
  • the cure temperature can be about 200°C and the cure time can be at least 2 hours.
  • the substrate can include a metallic substrate having a surface 205, a nanoporous layer of anodic metal oxide 210 formed on the surface 205, yttrium oxide nanoparticles 220 embedded in the nanoporous layer 210, and a hydrophobic ceramic coating 230 bonded to the nanoporous layer 210.
  • the hydrophobic, coated substrate 200 depicted in Figure 3A can be made by the method outlined in Figure 1 A.
  • the hydrophobic, coated substrate 200 can omit one or more of these elements.
  • the hydrophobic, coated substrate 200 can include the metallic substrate having the surface 205, the nanoporous layer of anodic metal oxide 210 formed on the surface 205, and the hydrophobic ceramic coating 230 bonded to the nanoporous layer 210.
  • This hydrophobic, coated substrate 200 can be made by the method outlined in Figure IB.
  • the hydrophobic, coated substrate 200 can include the metallic substrate having the surface 205, the nanoporous layer of anodic metal oxide 210 formed on the surface 205, and the yttrium oxide nanoparticles 220 embedded in the nanoporous layer 210.
  • This hydrophobic, coated substrate 200 can be made by the method outlined in Figure 1C.
  • the nanoporous layer of anodic metal oxide 210 can include nanopipettes 215.
  • the nanopipettes 215 can have an average diameter D from about 10 nm to about 100 nm.
  • the nanopipettes 215 can have an average diameter D from about 20 nm to about 50 nm.
  • the nanopipettes 215 can have a minimum diameter D of about 10 nm and a maximum diameter D of about 100 nm.
  • the nanopipettes 215 can have a minimum diameter D of about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, or about 100 nm.
  • the nanopipettes 215 can have a maximum diameter D of about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, or about 100 nm.
  • the nanopipettes 215 can have an average length L from about 100 nm to about 10 ⁇ . In another embodiment, the nanopipettes 215 can have an average length L of about 1.5 ⁇ to about 8 ⁇ . In a further embodiment, the nanopipettes 215 can have a minimum length L of about 100 nm and a maximum length L of about 10 ⁇ .
  • the nanopipettes 215 can have a minimum length L of about
  • the nanopipettes 215 can have a maximum length L of about 100 nm, about 500 nm, about 1 ⁇ , about 1.5 ⁇ , about 2 ⁇ , about 2.5 ⁇ , about 3 ⁇ , about 3.5 ⁇ , about 4 ⁇ , about 4.5 ⁇ , about 5 ⁇ , about 5.5 ⁇ , about 6 ⁇ , about 6.5 ⁇ , about 7 ⁇ , about 7.5 ⁇ , about 8 ⁇ , about 8.5 ⁇ , about 9 ⁇ , about 9.5 ⁇ , or about 10 ⁇ .
  • the yttrium oxide nanoparticles 220 can have a mean particle size of about 10 nm. In an additional embodiment, the yttrium oxide nanoparticles 220 can be embedded in the nanopipettes 215. In yet another embodiment, the hydrophobic ceramic coating 230 can comprise yttrium acetate.
  • These embedded yttrium oxide nanoparticles 220 can improve the hydrophobicity of the surface 205 while also providing robust performance against surface abrasion and deformation.
  • the nanoparticles 220 can allow the ceramic coating 230 to cure at a lower temperature, which mitigates atomic migration and other changes to the mechanical properties of the metallic substrate.
  • the resulting hydrophobic, coated substrate 200 will exhibit water-contact angles greater than about 90°, greater than about 95°, greater than about 100°, or greater than about 105°.
  • the hydrophobic coating will have a thickness of over about 50 nm, over about 75 nm, over about 100 nm, over about 125 nm, over about 150 nm, over about 200 nm, over about 225 nm, or over about 250 nm.
  • the hydrophobic coating will be robust to environmental degradation, mechanical abrasion, and repeated stress. For example, in some embodiments, the hydrophobic coating will exhibit high hardness and resistance to attack by acids and bases.
  • the present invention provides a scalable method of applying a hydrophobic coating that exhibits environmentally robust hydrophobicity. Coatings produced by these methods are hydrophobic and resistant to environmental degradation, mechanical abrasion, repeated stress, and attack by acids and bases. In addition, the coatings are thick enough for robust performance and the cure temperature is low enough to mitigate atomic migration and other changes to the mechanical properties of the metallic substrate. For all of these reasons, the methods described in this application, and the resulting coatings, are ideal for aircraft and automotive transparency applications.
  • hydrophobic means lacking an affinity for water, and a surface considered hydrophobic when the water contact angle is at least about 80 degrees.
  • water-soluble means the compound is infinitely soluble in water, very soluble in water, freely soluble in water, or soluble in water, as these terms are commonly understood.
  • a material is generally considered “very soluble” if about 1 gram of material requires about 1 milliliter or less of solute to dissolve.
  • a material is generally considered “freely soluble” if about 1 gram of material requires about 1 milliliter to about 10 milliliters of solute to dissolve.
  • a material is generally considered “soluble” if about 1 gram of material requires about 10 milliliters to 30 milliliters of solute to dissolve.
  • a material is generally considered “sparingly soluble” if about 1 gram of material requires about 30 milliliters to about 100 milliliters of solute to dissolve.
  • a first sample series was prepared using aluminum coupons, which had been cleaned with acetone.
  • a ceramic coating was applied to the aluminum substrates by flow or spray coating.
  • the ceramic coating composition included a yttrium compound, a dispersion of yttrium oxide nanoparticles, a water-soluble polymer, and a solvent solution of de-ionized water and a water-soluble alcohol.
  • the coated substrate was thermally treated at about 300°C for about 2 hours in ambient atmosphere.
  • An illustration of the first sample series is shown in Figure 4, which depicts the ceramic coating 230 on a native aluminum oxide layer 206 formed on the surface 205 of the aluminum substrate.
  • a second sample series was prepared using aluminum coupons, which had been cleaned with acetone.
  • the second sample series was subjected to an anodization process in an acidic solution of 0.2 M sulfuric acid.
  • the aluminum coupons were attached to the anode and a constant voltage of 10 V was applied for about 30 minutes.
  • a nanoporous layer of anodized aluminum oxide was developed on the aluminum surface.
  • the nanoporous structure included nanopipettes having an average diameter from about 20 nm and an average length of about 1.5 ⁇ .
  • a third sample series was prepared under the same conditions as the second sample series, except the voltage was applied for about 5 hours. Under these anodization conditions, a nanoporous layer of anodized aluminum oxide was developed on the aluminum surface, and the structure included nanopipettes having an average diameter from about 20 nm and an average length of about 8 ⁇ .
  • a fourth sample series was prepared under the same conditions as the second sample series, except the acidic solution comprised 0.2 M hydrochloric acid. Under these anodization conditions, a nanoporous layer of anodized aluminum oxide was developed on the aluminum surface, and the structure included nanopipettes having an average diameter from about 50 nm and an average length of about 500 nm.
  • the resulting anodized layers (for the second, third, and fourth samples) exhibited a low water contact angle, which is consistent with aluminum oxide.
  • the layers were abrasion resistant, as measured by steel wool hand abrasion tests.
  • cross-sectional scanning electron microscopy reveals an extremely fine structure.
  • the anodized layer (zone 1) comprises high aspect-ratio aluminum oxide crystalline grains, which are oriented perpendicular to the substrate, and which have an average diameter of about 20 nm and an average length of about 8 ⁇ .
  • the ceramic coating was applied to the aluminum substrates, in the second sample series, by flow or spray coating, and the coated substrates were thermally treated at about 300°C for about 2 hours in ambient atmosphere.
  • An illustration of the second sample series is shown in Figure 3B, which depicts the nanoporous layer of anodic metal oxide 210 formed on the surface 205, and the hydrophobic ceramic coating 230 bonded to the nanoporous layer 210.
  • the first sample series which was coated on the native aluminum surface, was compared to the anodized aluminum oxide buffered coatings from the second sample series.
  • the table below illustrates the results.
  • the hydrophobic ceramic coatings applied directly to the native aluminum surface displayed variable quality in surface finish and hydrophobicity.
  • the ceramic coatings that were applied without the anodized layer were easily removed with hand pressure.
  • the second sample series had a smooth, hydrophobic surface and exhibited significant abrasion resistance.
  • the fifth and sixth series were compared and the table below illustrates the results.
  • initial testing of the nanoparticle-enhanced coatings indicated significant abrasion resistance.
  • the surfaces were hydrophobic, with water contact angles measuring between about 80° and about 90°, which is a reduction from that of the hydrophobic ceramic coating from the second sample series. This is presumably due to incomplete coverage of the surface with yttrium oxide.
  • the coated coupons showed extremely robust performance against surface abrasion and deformation, sustaining greater than 5% deformation with no reduction in water contact angle.
  • aluminum coupons were prepared in an identical configuration to the seventh sample series, but with a reduced 200°C cure.
  • aluminum coupons were prepared in an identical configuration to the eight sample series. However, before the hydrophobic ceramic coating was applied, the anodized coupons were cathodized in a colloidal dispersion of yttrium oxide nanoparticles, as described above in connection with the sixth sample series.
  • FIG. 3A An illustration of the ninth sample series is shown in Figure 3A, which depicts the nanoporous layer of anodic metal oxide 210 formed on the surface 205, the yttrium oxide nanoparticles 220 embedded in the nanoporous layer 210, and the hydrophobic ceramic coating 230 bonded to the nanoporous layer 210.
  • the ninth sample series exhibited a water contact angle greater than or equal to about 90°.
  • the seventh, eighth, and ninth series were compared and the table below illustrates the results.
  • the nanoparticle-enhanced ninth sample series displayed improved cosmetic quality and higher water contact angles compared to the version without the yttrium oxide nanoparticles (eight series) cured at the same temperature.
  • the data show high concentrations of yttrium oxide nanoparticles in the anodic aluminum oxide pores causes enhanced nucleation under the surface and crystallization temperature suppression.
  • the seventh and ninth sample series had smooth, high quality coatings, which exhibited robust hydrophobicity. Therefore, the nanoparticle-embedded anodic aluminum oxide buffer layer allows for a lower temperature cure to achieve similar desirable properties, The lower cure temperature mitigates atomic migration and other changes to the mechanical properties of the metallic substrate.

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Abstract

L'invention concerne un revêtement hydrophobe et un procédé d'application d'un tel revêtement sur la surface d'un substrat métallique. Le procédé peut comprendre l'anodisation d'une couche nanoporeuse d'oxyde métallique anodique sur la surface ; la cathodisation de nanoparticules d'oxyde d'yttrium sur la surface ; l'application d'une composition de revêtement céramique hydrophobe sur la surface par un procédé d'application sélectionné dans le groupe constitué par : l'écoulement, l'immersion et la pulvérisation ; et le chauffage de la surface revêtue à une température de durcissement d'environ 150 °C à environ 300 °C pendant au moins 2 heures.
EP17928201.7A 2017-10-09 2017-10-09 Revêtements hydrophobes destinés à des métaux incorporant des oxydes anodiques et des oxydes de terres rares et leurs procédés d'application Pending EP3694809A4 (fr)

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US7780786B2 (en) 2002-11-28 2010-08-24 Tokyo Electron Limited Internal member of a plasma processing vessel
US7695767B2 (en) * 2005-01-06 2010-04-13 The Boeing Company Self-cleaning superhydrophobic surface
US20130251942A1 (en) * 2012-03-23 2013-09-26 Gisele Azimi Hydrophobic Materials Incorporating Rare Earth Elements and Methods of Manufacture
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EP2904132A1 (fr) * 2012-10-08 2015-08-12 Süddeutsche Aluminium Manufaktur GmbH Procédé de production d'un revêtement sol-gel sur une surface à revêtir d'un composant et composant correspondant
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US10519063B2 (en) 2016-08-19 2019-12-31 GKN Aerospace Transparency Systems, Inc. Transparent hydrophobic mixed oxide coatings and methods
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JP2021508004A (ja) 2021-02-25
EP3694809A4 (fr) 2021-07-07
WO2019074482A1 (fr) 2019-04-18
BR112020006656B1 (pt) 2023-04-25
BR112020006656A2 (pt) 2020-09-24

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