Method of forming an article coated with an antimicrobial coating and coated article

Abstract

A method for forming an article coated with an antimicrobial coating includes the step of depositing a mixed metal layer on a substrate. Characteristically, the mixed metal layer comprises copper and an oxidizable metal. Oxidizing the mixed metal layer: oxidizing at least a portion of the mixed metal layer to form an antimicrobial copper-containing layer by anodizing in an electrolyte solution or by applying a sufficient voltage to the surface of the mixed metal layer sufficient to form an electrical discharge, the antimicrobial copper-containing layer comprises a mixture of copper and an oxide of an oxidizable metal. The present application also relates to a coated article.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

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

[0002] In at least one aspect, the present invention is directed to antimicrobial coatings, and articles coated with such coatings and antimicrobial oxidative surfaces. Background Art

[0003] Coatings with bioactive properties can be used for various purposes. Bioactivity refers to materials that have biological or physiological effects on organisms. For example, bioactive materials include materials that cause changes in the normal biological functions or physiological mechanisms of organisms. As used herein, bioactivity includes beneficial and harmful effects on microorganisms or changes in the normal functions of microorganisms. A common bioactive material is an antimicrobial substance. Antimicrobial coatings have many uses. Antimicrobial coatings usually inhibit the growth of microorganisms (like viruses, bacteria or fungal organisms) or kill them. A particularly relevant example includes preventing the spread of communicable diseases by using antimicrobial materials. Antimicrobial materials can also be used for sanitary purposes. The desire to prevent the spread of disease and enhance hygiene has led to significant efforts in the development of antimicrobial materials. The use of antimicrobial materials in healthcare facilities and health treatments can provide significant benefits. Healthcare facilities (such as hospitals) present a unique environment that combines high concentrations of germs and individuals with fragile immunity. Therefore, facilities (such as hospitals) benefit greatly from antimicrobial surfaces. Antimicrobial materials used in medical equipment can reduce the burden of disinfection and prevent the spread of disease. In addition, affordable antimicrobial surfaces can present benefits on any surface that comes into contact with organisms. For example, surfaces involved in cooking or commonly touched surfaces like door handles can greatly benefit from antimicrobial properties. Even surfaces that are primarily decorative, if affordable, can benefit from antimicrobial properties and help inhibit the spread and growth of harmful or undesirable antimicrobial organisms.

[0004] Antimicrobial materials can be difficult and expensive to produce. In addition, antimicrobial properties can have other undesirable properties. For example, some antimicrobial materials can be too soft. Other antimicrobial materials can have poor wear resistance. is an antimicrobial coating comprising silver particles dispersed in an organic matrix. Antimicrobial coatings involving organic matrices may have a painted aesthetic appearance. In some applications, the painted appearance may be undesirable. Some antimicrobial coatings may use nanoparticle vapor deposition to deposit nanoparticles having antimicrobial properties on the surface of the coating. For example, Protec Antimicrobial coatings are those that use nanoparticles. However, using nanoparticles can be complex and expensive. In addition, such coatings can have a brittle surface or poor wear resistance. Another example of an antimicrobial material includes various metals. For example, silver is known to have antimicrobial properties. However, as mentioned above, silver can be expensive, and its properties may not be suitable for many applications. For example, the appearance or wear resistance of silver may not be suitable for certain applications.

[0005] Therefore, there is a need for an antimicrobial coating that addresses one or more of these problems or provides an alternative to existing antimicrobial materials. Summary of the invention

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

[0007] In another aspect, a coated article is provided. The coated article comprises a substrate composed 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 composed of an oxidizable metal. Advantageously, the antimicrobial copper-containing layer comprises a mixture of oxides of copper and oxidizable metals.

[0008] In another aspect, a coated article is provided. The coated article comprises a substrate composed 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 comprises copper and an oxidizable metal. Advantageously, the antimicrobial copper-containing layer comprises a mixture of oxides of copper and an oxidizable metal.

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

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

[0011] Figure 1A . A flow chart depicting a method for forming an article coated with an antimicrobial coating.

[0012] Figure 1B . A flow chart depicting a method for forming an article coated with an antimicrobial coating.

[0013] Figure 2A . Schematic diagram of the coated article.

[0014] Figure 2B . Schematic diagram of the coated article. DETAILED DESCRIPTION

[0015] Reference will now be made in detail to the currently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the present invention currently known to the inventors. The accompanying drawings are not necessarily drawn to scale. However, it should be understood that the disclosed embodiments are merely examples of the present invention, which can be implemented in different and alternative forms. Therefore, the specific details disclosed herein should not be interpreted as limiting, but only as representative benchmarks for any aspect of the present invention and / or as representative benchmarks for teaching those skilled in the art to use the present invention in a variety of ways.

[0016] Except in the examples or otherwise explicitly stated, all numerical quantities in this specification indicating the amount of material or reaction and / or use conditions should be understood as being modified by the word "about" when describing the broadest scope of the invention. Practice within the stated numerical limits is generally preferred. And, unless expressly stated to the contrary: percentages, "parts of..." and ratios are by weight; unless otherwise stated, the molecular weight provided for any polymer refers to the weight average molecular weight; the description of a group or class of materials suitable or preferred for a given object in conjunction with the present invention means that any mixture of two or more of the members of the group or class is equally suitable or preferred; the description of ingredients in chemical terms refers to the ingredients when added to any combination specified in this specification, and does not necessarily exclude chemical interactions that occur among the ingredients of the mixture once mixed; the first definition of an acronym or other abbreviation applies to all subsequent uses of the same abbreviation in this article, and applies to normal expression variants of the initially defined abbreviation with necessary modifications; and, unless expressly stated to the contrary, the measurement of the same property is determined by the same technique for reference to the property before and after.

[0017] It should also be understood that the present invention is not limited to the specific embodiments and methods described below, as specific components and / or conditions may of course vary. In addition, the terminology used herein is only for the purpose of describing specific embodiments of the present invention, and is not intended to be limiting in any way.

[0018] It must 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, a component mentioned in the singular is intended to include plural components.

[0019] 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.

[0020] The phrase "consisting of" excludes any element, step, or ingredient not specified in the claim. When the phrase appears in a clause of the body of a claim, rather than immediately following the preamble, it is limited only to the elements set forth in that clause; other elements are not excluded from the claim as a whole.

[0021] The phrase "consisting essentially of" limits the scope of a claim to the specified materials or steps, plus those that do not materially affect the basic and novel characteristics of the claimed subject matter.

[0022] With respect 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 the use of either of the other two terms.

[0023] The phrase “composed of” means “comprising” or “including.” Typically, the phrase is used to indicate that an object is formed from a material.

[0024] It should also be understood that the integer range clearly includes all intermediate integers. For example, the integer range 1-10 clearly includes 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. Similarly, the range 1 to 100 includes 1, 2, 3, 4 ... 97, 98, 99, 100. Similarly, when any range is needed, the difference between the upper limit and the lower limit can be divided by the intermediate digit of the increment of 10 as an alternative upper limit or lower limit. For example, if the scope 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 limit or upper limit. In the specific examples listed in this article, concentration, temperature and reaction conditions (such as pressure, pH, etc.) can be expressed as a value rounded to three significant figures plus or minus 50% to implement. In a refinement, the concentration, temperature, and reaction conditions (e.g., pressure, pH, etc.) may be implemented with values ​​expressed as rounding the values ​​provided in the examples to three significant figures plus or minus 30%. In another refinement, the concentration, temperature, and reaction conditions (e.g., pH, etc.) may be implemented with values ​​expressed as rounding the values ​​provided in the examples to three significant figures plus or minus 10%.

[0025] The term "copper oxide" means a compound having the chemical formula Cu x O, wherein x is 2.2 to 0.6. 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.

[0026] The term "zirconium oxide" means a compound having the chemical formula ZrO y A compound wherein y is 1.7 to 2.3. An example of zirconium oxide is ZrO2.

[0027] The term "titanium oxide" means a substance having the chemical formula TiO z In a modified embodiment, titanium oxide refers to a compound having a chemical formula of TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiOz In another refinement, titanium oxide refers to a compound having a chemical formula of TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z In another refinement, titanium oxide refers to a compound having the chemical formula TiO z A compound wherein z is from 1.9 to 2.3. An example of titanium oxide is TiO2.

[0028] The term "aluminum oxide" means a substance having the chemical formula Al2O w In a modified embodiment, aluminum oxide refers to the compound Al2O w , wherein w is 2.7 to 2.9. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 2.8 to 3.0. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 2.9 to 3.1. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 3.0 to 3.2. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 3.1 to 3.3. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 2.7 to 3.0. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 2.8 to 3.1. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 2.9 to 3.2. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 3.0 to 3.3. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 2.7 to 3.1. In another refinement, aluminum oxide refers to the compound Al2O w, wherein w is 2.8 to 3.2. In another refinement, aluminum oxide refers to the compound Al2O w , wherein w is 2.9 to 3.3. An example of aluminum oxide is Al2O3.

[0029] The term "niobium oxide" means a niobium oxide having the chemical formula NO w wherein w is 0.8 to 2.3. In a refinement, niobium oxide means a compound having a chemical formula of NO w In another refinement, the niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, the niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w In another refinement, niobium oxide refers to a compound having a chemical formula of NO w wherein w is 2.1 to 2.3. Examples of niobium oxides are NbO, NbO2 and NbO2.

[0030] The term "standard electrode potential" means the potential (i.e., the voltage generated) of a reversible electrode under standard conditions where the effective concentration of the solute is 1 mol / L, the activity of each pure solid, pure liquid, or water (solvent) is 1, the pressure of each gaseous reagent is 1 atm., and the temperature is 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) under standard temperature, pressure, and ion concentration conditions (e.g., 25°C, 1 atm, and 1 M concentration).

[0031] The term "antimicrobial" means a material or surface of a material that kills or inhibits the growth of bacteria, viruses, and / or fungi.

[0032] abbreviation:

[0033] "MAO" means micro-arc oxidation.

[0034] "PEO" means plasma electrolytic oxidation.

[0035] refer to Figure 1A and 1B , a flow chart depicting a method for forming an article coated with an antimicrobial coating is provided. 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, a sufficient voltage is applied to the surface of the mixed metal layer to form a discharge, so that at least a portion of the mixed metal layer is oxidized to form an antimicrobial copper-containing layer 14, which comprises a mixture of copper and oxidizable metal oxides. In a modified embodiment, the mixed metal layer 10 is substantially completely oxidized. The applied voltage can vary according to the specific requirements of the process. For example, the oxide of the oxidizable metal can be niobium oxide, zirconium oxide, aluminum oxide and / or titanium oxide. The copper oxide can oxidize copper. In one aspect, the antimicrobial copper-containing layer 14 can be regarded as dispersed in a metal oxide matrix of the oxide of the oxidizable metal. This provides better control over the amount and is expected to have excellent durability. In addition, it will be able to be applied to a variety of substrate materials.

[0036] Figure 1A A variation is depicted in which the mixed metal layer 10 is oxidized for a sufficient period of time so that a portion of the substrate is oxidized to a metal oxide layer 16 to form a coated article 18. In a refinement, the mixed metal layer 10 is substantially fully oxidized. In a refinement, the substrate is comprised of an oxidizable metal or an alloy containing an oxidizable metal. In a further refinement, the oxidizable metal is Mg, Ti, Al, Zr, or Nb.

[0037] Figure 1BA variation is depicted where the mixed metal layer 10 is oxidized for a sufficient period of time so that a portion of the mixed metal layer remains unoxidized as a mixed metal interlayer 20 to form a coated article 22. In a refinement, the substrate is composed of an oxidation resistant metal or metal alloy. For metal alloys, examples of oxidation resistant metals include stainless steel. In another refinement, the substrate is composed of an oxidizable metal or an alloy containing an oxidizable metal. In another refinement, the oxidizable metal is Mg, Ti, Al, Zr, or Nb. In another refinement, the substrate is chrome plated.

[0038] 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 typically contains an oxidant (e.g., sulfuric acid or chromic acid) to promote the formation of an oxide layer. The positive terminal of a DC power supply is connected to the metal substrate to form the oxide layer.

[0039] On the other hand, 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. The useful range of high voltage is 300V to 800V.

[0040] On the other hand, 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 for producing an oxide coating on a metal (such as aluminum, magnesium, titanium and its alloys). The 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 an anode and is immersed in an electrolyte solution. In an improved scheme, the electrolyte can include an alkaline substance, such as potassium hydroxide (KOH) or sodium silicate (Na2SiO3). A high voltage (hundreds to several thousand volts) is applied between the anode (workpiece) and the cathode (counter electrode), which is significantly higher than the voltage used in the conventional anodizing process. For example, the high voltage is typically greater than 1000V. The useful range of the high voltage is 10kV to 30kV. In micro-arc oxidation, the voltage can be applied in a short-time high-intensity pulse. Under high voltage, the oxide layer undergoes dielectric breakdown, resulting in the formation of microdischarges or plasma arcs on the metal surface. These microdischarges generate localized high temperatures and high pressures. The high-energy microdischarges cause the metal to react with the electrolyte, forming a thick, dense oxide layer. The oxide layer grows inward and outward from the original metal surface.

[0041] As explained above, the mixed metal layer 10 can be composed of an oxidizable metal. Similarly, the substrate can be composed of an oxidizable metal. In an improved scheme, the oxidizable metal has a standard electrode potential of less than 0V. In some improved schemes, the oxidizable metal has a standard electrode potential of less than 0V, -0.2V, -0.5V, -0.8V, -1.0V, or -1.2V. Examples of oxidizable metals include Mg, Ti, Al, Zr, or Nb.

[0042] In a variant, the antimicrobial copper-containing layer comprises copper oxide. In a refinement, the antimicrobial copper-containing layer comprises a z O, wherein z is 2.2 to 0.8. In a refinement, the antimicrobial copper-containing layer comprises copper oxide (ie, CuO). In another refinement, the antimicrobial copper-containing layer comprises cuprous oxide (ie, Cu2O).

[0043] In a 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 of about 0.5 microns to about 2 microns.

[0044] refer to Figure 2A , a schematic diagram of a coated article is provided. The coated article 18 includes a substrate 12 composed of an oxidizable metal, a metal oxide layer 16 disposed on the substrate and optionally in contact with the substrate, and an antimicrobial copper-containing layer 14 disposed on the metal oxide layer and optionally in contact with the metal oxide layer. Characteristically, the metal oxide layer is composed of an oxidizable metal. Advantageously, the antimicrobial copper-containing layer comprises a mixture of oxides of copper and oxidizable metals.

[0045] refer to Figure 2B , a schematic diagram of a coated article is provided. The coated article 22 includes a substrate 12 composed of 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 comprises copper and an oxidizable metal. 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.

[0046] Although exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in this specification are words of description rather than limitation, and it should be understood that various changes can be made without departing from the spirit and scope of the 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. A method for forming an article coated with an antimicrobial coating, the method comprising: depositing a mixed metal layer on a substrate, the mixed metal layer comprising copper and an oxidizable metal; as well as At least a portion of the mixed metal layer is oxidized to form an antimicrobial copper-containing layer comprising a mixture of oxidizable metal and copper oxides by anodizing or oxidizing the mixed metal layer in an electrolyte solution by applying a sufficient voltage to the surface of the mixed metal layer sufficient to form a discharge.

2. The method of claim 1, wherein: The mixed metal layer is oxidized for a sufficient time such 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 containing 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 cause a portion of the substrate to be oxidized.

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

7. The method of claim 6, wherein: The oxidation resistant metal or the 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 0V.

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

13. The method of claim 1, wherein: The antimicrobial copper-containing layer comprises a layer having a chemical formula of Cu z O, wherein z is from 2.2 to 0.

6.

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

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

16. 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 coated article comprising: a substrate composed of an oxidizable metal; a metal oxide layer disposed on the substrate, the metal oxide layer being composed of the oxidizable metal; as well as An antimicrobial copper-containing layer is disposed on the metal oxide layer, the antimicrobial copper-containing layer comprising a mixture of the oxidizable metal and an oxide of copper.

19. 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 -1.0V.

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

23. The coated article of claim 18, wherein: The antimicrobial copper-containing layer comprises a layer having a chemical formula of Cu z O, wherein z is from 2.2 to 0.

6.

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

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

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

27. 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 coated article comprising: A substrate composed of metal or metal alloy; a mixed metal layer disposed on the substrate, the mixed metal layer comprising copper and an oxidizable metal; as well as An antimicrobial copper-containing layer is disposed on the mixed metal layer, the antimicrobial copper-containing layer comprising a mixture of the oxidizable metal and an oxide of copper.

29. The coated article of claim 28, wherein The substrate is composed of the oxidizable metal or an alloy containing the oxidizable metal.

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

31. The coated article of claim 28, wherein: The substrate is made of an oxidation-resistant metal or metal alloy.

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

33. The coated article of claim 28, wherein: The antimicrobial copper-containing layer comprises a layer having a chemical formula of Cu z O, wherein z is from 2.2 to 0.

6.

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

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

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

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

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