Antibacterial oxidized surface

Abstract

To provide an antibacterial coating that solves one or more problems associated with conventional techniques or replaces current antibacterial materials.SOLUTION: A method for forming an article coated with an antibacterial coating includes a step of depositing a mixed metal layer over a substrate. Characteristically, the mixed metal layer includes copper and oxidizable metal. The mixed metal layer is oxidized in an electrolyte solution by anodization, or by applying a sufficient voltage to the surface of the mixed metal layer to sufficiently form an electric discharge that oxidizes at least a portion of the mixed metal layer, thereby forming an antibacterial copper-containing layer including a mixture of oxides of copper and oxidizable metal.SELECTED DRAWING: Figure 1A

Description

[Technical field]

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 472,623, filed June 13, 2023, the disclosure of which is incorporated herein by reference in its entirety.

[0002] In at least one embodiment, the present invention relates to antimicrobial coatings and articles coated with such coatings. [Background technology]

[0003] Coatings with bioactive properties can be useful for a variety of purposes. Bioactive refers to materials that have a biological or physiological effect on an organism. For example, bioactive materials include materials that result in the modification of the normal biological functions or physiological mechanisms of an organism. Bioactive as used herein includes beneficial and harmful effects on microorganisms or modifications to the normal functions of microorganisms. One common bioactive material is an antimicrobial. Antimicrobial coatings serve many purposes. Generally, antimicrobial coatings inhibit the growth of or kill microorganisms such as viruses, bacteria, or fungi. One particularly relevant example includes preventing the spread of infectious diseases through the use of antimicrobial materials. Antimicrobial materials can also serve hygiene purposes. The desire to prevent the spread of disease and improve hygiene has led to significant efforts to develop antimicrobial materials. The use of antimicrobial materials in health care facilities and medical treatments can provide significant benefits. Medical facilities such as hospitals present a unique environment that combines high concentrations of bacteria with individuals with weak immune systems. Thus, facilities such as hospitals would benefit greatly from antimicrobial surfaces. Antimicrobial materials for medical devices can reduce the burden of disinfection and prevent the spread of disease. Additionally, affordable antimicrobial surfaces can be beneficial for any surface that comes into contact with living organisms. For example, surfaces involved in food preparation or commonly touched surfaces such as doorknobs can greatly benefit from antimicrobial properties. Even primarily decorative surfaces can benefit from antimicrobial properties, if affordable, to help inhibit the spread and growth of harmful or undesirable antimicrobial life.

[0004] Antimicrobial materials can be difficult and expensive to manufacture. Furthermore, antimicrobial properties may have other undesirable properties. For example, some antimicrobial materials may be too soft. Other antimicrobial materials may have insufficient abrasion resistance. Microban® is an antimicrobial coating that includes silver particles dispersed in an organic matrix. Antimicrobial coatings that include an organic matrix may have the aesthetic appearance of paint. In some applications, the appearance of paint may be undesirable. Some antimicrobial coatings may use nanoparticle deposition to deposit nanoparticles with antimicrobial properties on the surface of the coating. For example, ABACO® from Protec is an antimicrobial coating that uses nanoparticles. However, the use of nanoparticles may be complicated and expensive. Furthermore, such coatings may have delicate surfaces or insufficient abrasion resistance. Other examples of antimicrobial materials include various metals. For example, silver is known to have antimicrobial properties. However, as discussed above, silver can be expensive and its properties may not be suitable for many applications. For example, the appearance or abrasion resistance of silver may not be suitable for certain applications. Summary of the Invention [Problem to be solved by the invention]

[0005] Therefore, there is a need for an antimicrobial coating that overcomes one or more of these challenges or provides an alternative to current antimicrobial materials. [Means for solving the problem]

[0006] In at least one embodiment, a method of forming an article coated with an antimicrobial coating is provided. The method includes depositing a mixed metal layer on a substrate. Characteristically, the mixed metal layer includes copper and an oxidizable metal. The mixed metal layer is oxidized in an electrolyte solution by anodization or by applying a sufficient voltage to a surface of the mixed metal layer to create a discharge sufficient to oxidize at least a portion of the mixed metal layer to form an antimicrobial copper-containing layer that includes a mixture of oxides of copper and the oxidizable metal.

[0007] In another aspect, a coated article is provided. The coated article includes a substrate comprised of an oxidizable metal, a metal oxide layer disposed on the substrate, and an antimicrobial copper-containing layer disposed on the metal oxide layer. Characteristically, the metal oxide layer is comprised of an oxidizable metal. Advantageously, the antimicrobial copper-containing layer includes a mixture of copper and an oxide of the oxidizable metal.

[0008] In another aspect, a coated article is provided. The coated article includes a substrate comprised of a metal or metal alloy, a mixed metal layer disposed on the substrate, and an antimicrobial copper-containing layer disposed on the mixed metal layer. Characteristically, the mixed metal layer includes copper and an oxidizable metal. Advantageously, the antimicrobial copper-containing layer includes a mixture of oxides of copper and the oxidizable metal.

[0009] The foregoing summary is illustrative only and is not intended to be in any way limiting. In addition to the exemplary aspects, embodiments, and features described above, further aspects, embodiments, and features will become apparent by reference to the drawings and the following detailed description.

[0010] For a fuller understanding of the nature, objects, and advantages of the present disclosure, reference should be made to the following detailed description which should be read in conjunction with the following drawings, in which like reference numerals indicate like elements and in which: [Brief description of the drawings]

[0011] [Figure 1A]1 is a flow chart illustrating a method of forming an article coated with an antimicrobial coating. [Figure 1B] 1 is a flow chart illustrating a method of forming an article coated with an antimicrobial coating. [Figure 2A] FIG. 1 is a schematic diagram of a coated article. [Figure 2B] FIG. 1 is a schematic diagram of a coated article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Reference will now be made in detail to presently preferred configurations, embodiments and methods of the invention, which constitute the best modes of practicing the invention currently known to the inventors. The figures are not necessarily to scale. It should be understood, however, that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various and alternative forms. Thus, the specific details disclosed herein should not be construed as limiting, but merely as a representative basis for any aspect of the invention and / or for teaching one of ordinary skill in the art to variously use the invention.

[0013] Except in the examples or where otherwise expressly stated, all quantities in this description indicating amounts of materials or reaction conditions and / or conditions of use should be understood to be modified by the word "about" in describing the broadest scope of the invention. Practice within the stated numerical limits is generally preferred. Also, unless expressly stated otherwise, percent, "parts" and ratio values ​​are by weight; the molecular weight provided for any polymer refers to the weight average molecular weight unless otherwise indicated; the description of a group or class of materials as suitable or preferred for a given purpose in connection with the present invention implies that mixtures of any two or more members of the group or class are equally suitable or preferred; the description of components in chemical terms refers to the components upon addition to any combination specified in the description and does not necessarily exclude chemical interactions between the components of the mixture once mixed; the initial definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation, and applies mutatis mutandis to normal grammatical variations of the abbreviation originally defined; and unless expressly stated otherwise, measurements of properties are determined by the same techniques as previously or subsequently mentioned for the same property.

[0014] It is also to be understood that the invention is not limited to the specific embodiments and methods described below, since specific components and / or conditions can, of course, vary. Further, the terminology used herein is used only to describe particular embodiments of the invention, and is not intended to be limiting in any way.

[0015] It should also be noted that as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. For example, reference to a singular element is intended to include the plural elements.

[0016] The term "comprising" is synonymous with "including," "having," "containing," or "characterized by." These terms are inclusive and open-ended and do not exclude additional, unrecited elements or method steps.

[0017] The phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. When this phrase appears in a clause in the body of a claim rather than immediately following the preamble, it limits only the elements recited in that clause and does not exclude other elements from the claim as a whole.

[0018] The phrase "consisting essentially of" limits the scope of a claim to certain materials or steps that do not materially affect the basic and novel characteristic(s) of the claimed subject matter.

[0019] With regard to the terms "comprising," "consisting of," and "consisting essentially of," when one of these three terms is used herein, the presently disclosed and claimed subject matter may include use of either of the other two terms.

[0020] The phrase "composed of" means "including" or "comprising." Typically, this phrase is used to indicate that an object is formed from certain materials.

[0021] It should also be understood that integer ranges explicitly include all intervening integers. For example, the integer range of 1 to 10 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. Similarly, the range of 1 to 100 explicitly includes 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.···· 97, 98, 99, 100. Similarly, when any range is claimed, the intervening numbers, which are increments of the difference between the upper and lower limits divided by 10, can be considered as alternative upper or lower limits. For example, if the range is 1.1 to 2.1, the following numbers 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, and 2.0 can be selected as the lower or upper limits. In certain examples described herein, concentrations, temperatures, and reaction conditions (e.g., pressure, pH, etc.) can be performed at plus or minus 50 percent of the values ​​shown, rounded to three significant figures. In one refinement, concentrations, temperatures, and reaction conditions (e.g., pressure, pH, etc.) can be performed at plus or minus 30 percent of the values ​​shown, rounded to three significant figures, of the values ​​presented in the examples. In another refinement, concentrations, temperatures, and reaction conditions (e.g., pH, etc.) can be carried out at plus or minus 10 percent of the values ​​presented in the examples, rounded to three significant figures.

[0022] The term "copper oxide" refers to a compound of the formula Cu, where x is between 2.2 and 0.6. x O. In a refinement, z is at least 0.6, 0.7, 0.9, or 0.95 and at most 2.2, 2.0, 1.8, 1.6, 1.4, or 1.2.

[0023] The term "zirconium oxide" refers to a compound having the formula ZrO y An example of zirconium oxide is ZrO 2 It is.

[0024] The term "titanium oxide" refers to titanium dioxide having the formula TiO z In one refinement, titanium oxide refers to a compound having the formula TiO z In another refinement, titanium oxide refers to a compound having the formula TiO z In another refinement, titanium oxide refers to a compound having the formula TiO zIn another refinement, titanium oxide means a compound having the formula TiOz, where z is 2.0 to 2.2. In another refinement, titanium oxide means a compound having the formula TiOz, where z is 2.1 to 2.3. In another refinement, titanium oxide means a compound having the formula TiOz, where z is 1.7 to 2.0. In another refinement, titanium oxide means a compound having the formula TiOz, where z is 1.8 to 2.1. In another refinement, titanium oxide means a compound having the formula TiOz, where z is 1.9 to 2.2. In another refinement, titanium oxide means a compound having the formula TiOz, where z is 2.0 to 2.3. In another refinement, titanium oxide means a compound having the formula TiOz, where z is 1.7 to 2.1. In another refinement, titanium oxide means a compound having the formula TiOz, where z is 1.8 to 2.2. In another refinement, titanium oxide refers to a compound having the formula TiOz, where z is between 1.9 and 2.3. An example of a titanium oxide is TiO 2 It is.

[0025] The term "aluminum oxide" refers to a compound of the formula Al, where w is between 2.7 and 3.3. 2 O w In one refinement, the aluminum oxide is the compound Al, with w between 2.7 and 2.9. 2 O w In another refinement, the aluminum oxide is of the compound Al, where w is between 2.8 and 3.0. 2 O w In another refinement, the aluminum oxide is the compound Al, where w is between 2.9 and 3.1. 2 O w In another refinement, the aluminum oxide is a compound Al 2 O w In another refinement, the aluminum oxide is the compound Al, where w is between 3.1 and 3.3. 2 O w In another refinement, the aluminum oxide is of the compound Al, where w is between 2.7 and 3.0. 2 O wIn another refinement, the aluminum oxide is the compound Al, where w is between 2.8 and 3.1. 2 O w In another refinement, the aluminum oxide is the compound Al, where w is between 2.9 and 3.2. 2 O w In another refinement, the aluminum oxide is the compound Al, where w is between 3.0 and 3.3. 2 O w In another refinement, the aluminum oxide is the compound Al, where w is between 2.7 and 3.1. 2 O w In another refinement, the aluminum oxide is the compound Al, where w is between 2.8 and 3.2. 2 O w In another refinement, the aluminum oxide is the compound Al, where w is between 2.9 and 3.3. 2 O w An example of aluminum oxide is Al 2 O 3 It is.

[0026] The term "niobium oxide" refers to niobium oxide having the formula NO w In one refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO wIn another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w In another refinement, the niobium oxide refers to a compound having the formula NO w Examples of niobium oxide include NbO, NbO 2 , and NbO 2 It is.

[0027] The term "standard electrode potential" means the potential (i.e., the voltage developed) of a reversible electrode at standard conditions, with an effective concentration of solute of 1 mole / liter, activity of 1 for each pure solid, pure liquid, or water (solvent), pressure of 1 atm for each gaseous reagent, and temperature of 25°C. The standard electrode potential is the reduction potential. The standard electrode potential is the voltage difference between a half cell and a standard hydrogen electrode (SHE) at standard conditions of temperature, pressure, and ion concentration (e.g., 25°C, 1 atm, 1 M concentration).

[0028] The term "antimicrobial" refers to a material or surface of a material that kills or inhibits the growth of bacteria, viruses, and / or fungi.

[0029] The following abbreviations: "MAO (MAO: micro-arc oxidation)" stands for micro-arc oxidation. "PEO (plasma electrolytic oxidation)" means plasma electrolytic oxidation.

[0030] 1A and 1B, a flow chart is provided depicting a method of forming an article coated with an antimicrobial coating. In step a), a mixed metal layer 10 is deposited on a substrate 12. The mixed metal layer 10 comprises an oxidizable metal. Typically, the mixed metal layer 10 comprises copper and an oxidizable metal. In step b), the mixed metal layer 10 is oxidized in an electrolyte solution by applying a sufficient voltage to the surface of the mixed metal layer to form a sufficient discharge to oxidize at least a portion of the mixed metal layer to form an antimicrobial copper-containing layer 14 comprising a mixture of copper and oxidizable metal oxides. In one refinement, the mixed metal layer 10 is substantially completely oxidized. The applied voltage can vary depending on the specific requirements of the process. For example, the oxidizable metal oxide can be niobium oxide, zirconium oxide, aluminum oxide, and / or titanium oxide. The copper oxide can be copper oxide. In one embodiment, the antimicrobial copper-containing layer 14 can be considered to be dispersed in a metal oxide matrix of the oxidizable metal oxide. This provides better control over dosage and is believed to have better durability, plus can be applied to a variety of substrate materials.

[0031] 1A depicts a variation in which the mixed metal layer 10 is oxidized for a sufficient time to oxidize a portion of the substrate into a metal oxide layer 16 to form a coated article 18. In a refinement, the mixed metal layer 10 is substantially completely oxidized. In a refinement, the substrate is comprised of an oxidizable metal or an alloy that includes an oxidizable metal. In a further refinement, the oxidizable metal is Mg, Ti, Al, Zr, or Nb.

[0032] FIG. 1B shows a variation in which the mixed metal layer 10 is oxidized for a sufficient time that a portion of the mixed metal layer remains unoxidized as a mixed metal intermediate layer 20 to form a coated article 22. In one refinement, the substrate is comprised of an oxidation-resistant metal or metal alloy. Examples of oxidation-resistant metals for metal alloys include stainless steel. In another refinement, the substrate is comprised of an oxidizable metal or an alloy that includes an oxidizable metal. In a further refinement, the oxidizable metal is Mg, Ti, Al, Zr, or Nb. In another refinement, the substrate is chromium plated.

[0033] In one variation, the mixed metal layer is oxidized by anodization. In the anodization process, the metal substrate is contacted with an electrolyte solution (e.g., an aqueous solution) containing oxygen ions. The electrolyte solution typically contains an oxidizing agent (e.g., sulfuric acid or chromic acid) to facilitate the formation of the oxide layer. The positive terminal of a DC power source is connected to the metal substrate to form the oxide layer.

[0034] In another embodiment, the mixed metal layer is oxidized by plasma electrolytic oxidation. In the plasma electrolytic oxidation process, the metal substrate is contacted with an electrolyte solution (e.g., an aqueous solution) containing oxygen ions. A high voltage is continuously applied to the metal surface with sufficient voltage to form a plasma discharge. The high voltage is typically greater than 200V. A useful range of high voltage is between 300V and 800V.

[0035] In another embodiment, the mixed metal layer is oxidized by micro-arc oxidation. In the micro-arc oxidation process, the metal substrate is contacted with an electrolyte solution (e.g., an aqueous solution) containing oxygen ions. A high voltage is applied to the metal surface with sufficient voltage to form a series of micro-discharges. Micro-arc oxidation is an electrochemical surface treatment process used to form oxide coatings on metals such as aluminum, magnesium, titanium, and their alloys. This process can enhance the surface properties of the metal, such as hardness, wear resistance, and corrosion resistance. In micro-arc oxidation, the metal workpiece acts as the anode and is immersed in the electrolyte solution. In one refinement, the electrolyte is potassium hydroxide (KOH) or sodium silicate (Na 2 SiO 3 ), which may include alkaline substances such as nitriding agents. A high voltage (hundreds to thousands of volts), significantly higher than that used in conventional anodizing processes, is applied between the anode (work) and the cathode (counter electrode). For example, the high voltage is typically greater than 1000 V. A useful range of high voltages is 10 kV to 30 kV. In micro-arc oxidation, the voltage can be applied in short, high-intensity bursts. At high voltages, dielectric breakdown of the oxide layer occurs, resulting in the formation of micro-discharges or plasma arcs at the surface of the metal. These micro-discharges produce localized high temperatures and pressures. The high-energy micro-discharges react the metal with the electrolyte, forming a thick, dense oxide layer. The oxide layer grows both inward and outward relative to the original metal surface.

[0036] As discussed above, the mixed metal layer 10 can be comprised of an oxidizable metal. Similarly, the substrate can be comprised of an oxidizable metal. In one refinement, the oxidizable metal has a standard electrode potential of less than 0 V. In some refinements, the oxidizable metal has a standard electrode potential of less than 0 V, -0.2 V, -0.5 V, -0.8 V, -1.0 V, or -1.2 V. Examples of oxidizable metals include Mg, Ti, Al, Zr, or Nb.

[0037] In one variation, the antimicrobial copper-containing layer comprises copper oxide. In one refinement, the antimicrobial copper-containing layer has the formula Cu z In one refinement, the antimicrobial copper-containing layer comprises cupric oxide (i.e., CuO). In a further refinement, the antimicrobial copper-containing layer comprises cuprous oxide (i.e., Cu 2 O).

[0038] In one variation, the antimicrobial copper-containing layer has a thickness greater than about 0.5 microns. In a refinement, the antimicrobial copper-containing layer has a thickness between about 0.5 microns and about 2 microns.

[0039] Referring to Figure 2A, a schematic diagram of a coated article is provided. The coated article 18 includes a substrate 12 comprised of an oxidizable metal, a metal oxide layer 16 disposed on and optionally in contact with the substrate, and an antimicrobial copper-containing layer 14 disposed on and optionally in contact with the metal oxide layer. Characteristically, the metal oxide layer is comprised of an oxidizable metal. Advantageously, the antimicrobial copper-containing layer comprises a mixture of oxides of copper and the oxidizable metal.

[0040] Referring to Figure 2B, a schematic diagram of a coated article is provided. The coated article 22 includes a substrate 12 constructed from a metal or metal alloy, a mixed metal layer 20 disposed on the substrate 12, and an antimicrobial copper-containing layer 14 disposed on the mixed metal layer. Characteristically, the mixed metal layer includes copper and an oxidizable metal. Advantageously, the antimicrobial copper-containing layer includes a mixture of oxides of copper and an oxidizable metal.

[0041] Although exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the present invention. Rather, the terms used herein are terms of description rather than limitation, and it should be understood that various modifications can be made without departing from the spirit and scope of the present invention. Characteristically, the mixed metal layer comprises copper and an oxidizable metal. Advantageously, the antimicrobial copper-containing layer comprises a mixture of oxides of copper and an oxidizable metal.

Claims

1. 1. A method of forming an article coated with an antimicrobial coating, comprising: depositing a mixed metal layer on a substrate, the mixed metal layer comprising copper and an oxidizable metal; oxidizing the mixed metal layer in an electrolyte solution by anodization or by applying a sufficient voltage to a surface of the mixed metal layer to create a sufficient electrical discharge to oxidize at least a portion of the mixed metal layer to form an antimicrobial copper-containing layer comprising a mixture of copper and oxides of the oxidizable metal; A method comprising:

2. The method of claim 1 , wherein the mixed metal layer is oxidized for a sufficient period of time that a portion of the mixed metal layer remains unoxidized.

3. The method of claim 1 , wherein the substrate is composed of the oxidizable metal or an alloy including the oxidizable metal.

4. The method of claim 3 , wherein the oxidizable metal is Mg, Ti, Al, Zr, or Nb.

5. The method of claim 1 , wherein the mixed metal layer is oxidized for a sufficient time to oxidize a portion of the substrate.

6. The method of claim 1 , wherein the substrate is comprised of an oxidation-resistant metal or metal alloy.

7. The method of claim 6 , wherein the oxidation-resistant metal or metal alloy is stainless steel.

8. The method of claim 1 , wherein the substrate is chrome plated.

9. The method of claim 1 , wherein the mixed metal layer is oxidized by anodization.

10. The method of claim 1 , wherein the mixed metal layer is oxidized by micro-arc oxidation or plasma electrolytic oxidation.

11. The method of claim 1 , wherein the oxidizable metal has a standard electrode potential of less than 0 V.

12. The method of claim 1 , wherein the oxidizable metal is Mg, Ti, Al, Zr, or Nb.

13. The antibacterial copper-containing layer is a copper-containing layer having the formula Cu ｚ The method of claim 1 , comprising a compound having O.

14. The method of claim 1 , wherein the antimicrobial copper-containing layer comprises cupric oxide.

15. The method of claim 1 , wherein the antimicrobial copper-containing layer comprises cuprous oxide.

16. 10. The method of claim 1, wherein the antimicrobial copper-containing layer has a thickness greater than about 0.5 microns.

17. The method of claim 1 , wherein the antimicrobial copper-containing layer has a thickness of about 0.5 microns to about 2 microns.

18. A substrate made of an easily oxidizable metal; a metal oxide layer disposed on the substrate, the metal oxide layer being composed of the easily oxidizable metal; an antimicrobial copper-containing layer disposed on the metal oxide layer, the antimicrobial copper-containing layer comprising a mixture of copper and an oxide of the oxidizable metal; A coated article comprising:

19. 20. The coated article of claim 18, wherein the oxidizable metal has a standard electrode potential of less than 0V.

20. The coated article of claim 18, wherein the oxidizable metal has a standard electrode potential of less than -0.5V.

21. The coated article of claim 18, wherein the oxidizable metal has a standard electrode potential of less than −1.0 V.

22. 20. The coated article of claim 18, wherein the oxidizable metal is Ti, Al, Zr, or Nb.

23. The antibacterial copper-containing layer is a copper-containing layer having the formula Cu ｚ The coated article of claim 18 comprising an O-bearing compound.

24. 20. The coated article of claim 18, wherein the antimicrobial copper-containing layer comprises cupric oxide.

25. 20. The coated article of claim 18, wherein the antimicrobial copper-containing layer comprises cuprous oxide.

26. 20. The coated article of claim 18, wherein the antimicrobial copper-containing layer has a thickness greater than about 0.5 microns.

27. 20. The coated article of claim 18, wherein the antimicrobial copper-containing layer has a thickness of about 0.5 microns to about 2 microns.

28. A substrate made of a metal or metal alloy; a mixed metal layer disposed on the substrate, the mixed metal layer comprising copper and an oxidizable metal; an antimicrobial copper-containing layer disposed on the mixed metal layer, the antimicrobial copper-containing layer comprising a mixture of copper and an oxide of the oxidizable metal; A coated article comprising:

29. 30. The coated article of claim 28, wherein the substrate is comprised of the oxidizable metal or an alloy including the oxidizable metal.

30. 30. The coated article of claim 29, wherein the oxidizable metal is Ti, Al, Zr, or Nb.

31. 30. The coated article of claim 28, wherein the substrate is composed of an oxidation-resistant metal or metal alloy.

32. 32. The coated article of claim 31 , wherein the oxidation-resistant metal or metal alloy is stainless steel.

33. The antibacterial copper-containing layer is a copper-containing layer having the formula Cu ｚ 30. The coated article of claim 28 comprising an O-bearing compound.

34. 30. The coated article of claim 28, wherein the antimicrobial copper-containing layer comprises cupric oxide.

35. 30. The coated article of claim 28, wherein the antimicrobial copper-containing layer comprises cuprous oxide.

36. 30. The coated article of claim 28, wherein the antimicrobial copper-containing layer has a thickness greater than about 0.5 microns.

37. 30. The coated article of claim 28, wherein the antimicrobial copper-containing layer has a thickness of from about 0.5 microns to about 2 microns.

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