ANTIMICROBIAL CUPROUS OXIDE-CONTAINING COATINGS
20240334938 ยท 2024-10-10
Assignee
Inventors
Cpc classification
A01N25/24
HUMAN NECESSITIES
International classification
Abstract
A coated article having an antimicrobial coating is provided. The coated article includes a substrate and at least one adhesion layer disposed over the substrate. The at least one adhesion layer includes a component selected from the group consisting of a copper oxide, a zirconium oxide, and combinations thereof. Advantageously, an antimicrobial copper suboxide layer disposed over the at least one adhesion layer.
Claims
1. A coated article comprising: a substrate; at least one adhesion layer disposed over the substrate, the at least one adhesion layer including a component selected from the group consisting of a copper oxide, a zirconium oxide, and combinations thereof; and an antimicrobial copper suboxide layer disposed over the at least one adhesion layer wherein the antimicrobial copper suboxide layer is at least 5 times thicker than the at least one adhesion layer.
2. The coated article of claim 1, wherein the antimicrobial copper suboxide layer includes a compound having formula Cu.sub.zO where z is from 2.2 to 1.1.
3. The coated article of claim 1, wherein the antimicrobial copper suboxide layer includes cuprous oxide.
4. The coated article of claim 1, wherein the at least one adhesion layer includes a compound having formula Cu.sub.xO where x is from 2.2 to 0.6.
5. The coated article of claim 1, wherein the at least one adhesion layer includes a compound having formula Zr.sub.yO.sub.2 where y is from 3 to 0.6.
6. The coated article of claim 1, wherein the antimicrobial copper suboxide layer has a uniform stoichiometry to within 20 mole % throughout the antimicrobial copper suboxide layer.
7. The coated article of claim 1, wherein a copper atom percent in the antimicrobial copper suboxide layer decreases at increasing distances from the substrate.
8. The coated article of claim 1, wherein the antimicrobial copper suboxide layer has a thickness greater than 0.5 microns.
9. The coated article of claim 1, wherein the antimicrobial copper suboxide layer has a thickness from about 0.5 microns to about 10 microns.
10. The coated article of claim 1, wherein the antimicrobial copper suboxide layer has a gray non-iridescent color.
11. The coated article of claim 1, wherein the at least one adhesion layer has a thickness less than about 250 nm.
12. The coated article of claim 1, wherein the at least one adhesion layer has a thickness from about 10 nm to about 200 nm.
13. The coated article of claim 1, wherein the antimicrobial copper suboxide layer includes a plurality of crystalline columns extending from the substrate.
14. The coated article of claim 1, wherein the antimicrobial copper suboxide layer has color space coordinates L* from 35 to 55, a* from ?5 to 5, and b* from ?10 to ?4 for illuminants D65.
15. The coated article of claim 1 further comprising a transparent metal oxide layer disposed over the antimicrobial copper suboxide layer.
16. The coated article of claim 1 further comprising an antimicrobial silane-containing layer disposed over the antimicrobial copper suboxide layer.
17. The coated article of claim 16, wherein the antimicrobial silane-containing layer comprises: a microbial inhibition material comprising: a first silane compound; and a metal ion; wherein the first silane compound comprises a functional group bound to the metal ion.
18. The coated article of claim 17, the first silane compound is described by Formula (I): ##STR00003## wherein: R.sub.1 is selected from the group consisting of C.sub.1-C.sub.x+1 alkyl-S(R.sub.3).sub.y(M), C.sub.2-C.sub.x+2 alkenyl-S(R.sub.3).sub.y(M), C.sub.3-C.sub.x+3alkynyl-S(R.sub.3).sub.y(M), C.sub.1-C.sub.x alkyl-N(R.sub.3).sub.y(M), C.sub.2-C.sub.x alkenyl-N(R.sup.3).sub.y(M), C.sub.3-C.sub.x alkynyl-N(R.sub.3).sub.y(M), C.sub.1-C.sub.x+1 alkyl-P(R.sub.3).sub.y(M), C.sub.2-C.sub.x+2 alkenyl-P(R.sub.3).sub.y(M), C.sub.3-C.sub.x+3 alkynyl-P(R.sub.3).sub.y(M); each R.sub.2 is the same or different and is a bond to another Si atom of a repeating structure, or is selected from the group consisting of hydrogen, C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl; n is a positive integer; x is a positive integer: y is a positive integer; and M is a metal ion or metal.
19. The coated article of claim 17, wherein the antimicrobial silane-containing layer further includes a fingerprint inhibition material.
20. A coated article comprising: a substrate; an adhesion layer disposed over the substrate, the adhesion layer including a copper oxide; and an antimicrobial copper suboxide layer disposed over the adhesion layer wherein the antimicrobial copper suboxide layer is at least 5 times thicker than the adhesion layer and wherein the combination of the adhesion layer and the antimicrobial copper suboxide layer are substantially free of other metals other than copper.
21. The coated article of claim 20, wherein the antimicrobial copper suboxide layer includes a compound having formula Cu.sub.zO where z is from 2.2 to 1.1.
22. The coated article of claim 20, wherein the antimicrobial copper suboxide layer includes cuprous oxide.
23. The coated article of claim 20, wherein the adhesion layer includes a compound having formula Cu.sub.xO where x is from 2.2 to 0.6.
24. The coated article of claim 20, wherein a copper atom percent in the antimicrobial copper suboxide layer decrease at increasing distances from the substrate.
25. The coated article of claim 20, wherein the antimicrobial copper suboxide layer has a thickness greater than 0.5 microns.
26. The coated article of claim 20, wherein the antimicrobial copper suboxide layer has a thickness from about 0.5 microns to about 10 microns.
27. The coated article of claim 20, wherein the antimicrobial copper suboxide layer has a gray non-iridescent color.
28. The coated article of claim 20, wherein the adhesion layer has a thickness less than about 250 nm.
29. The coated article of claim 20, wherein the adhesion layer has a thickness from about 10 nm to about 200 nm.
30. The coated article of claim 20, wherein the antimicrobial copper suboxide layer includes a plurality of crystalline columns extending from the substrate.
31. The coated article of claim 20, wherein the antimicrobial copper suboxide layer has color space coordinates L* from 35 to 55, a* from ?5 to 5, and b* from ?10 to ?4 for illuminants D65.
32. The coated article of claim 20 further comprising an antimicrobial silane-containing layer disposed over the antimicrobial copper suboxide layer.
33. The coated article of claim 32, wherein the antimicrobial silane-containing layer comprising: a microbial inhibition material comprising: a first silane compound; and a metal ion; wherein the first silane compound comprises a functional group bound to the metal ion.
34. The coated article of claim 33, the first silane compound is described by Formula (I): ##STR00004## wherein: R.sub.1 is selected from the group consisting of C.sub.1-C.sub.x+1 alkyl-S(R.sub.3).sub.y(M), C.sub.2-C.sub.x+2 alkenyl-S(R.sub.3).sub.y(M), C.sub.3-C.sub.x+3 alkynyl-S(R.sub.3).sub.y(M), C.sub.1-C.sub.x alkyl-N(R.sub.3).sub.y(M), C.sub.2-C.sub.x alkenyl-N(R.sub.3).sub.y(M), C.sub.3-C.sub.x alkynyl-N(R.sub.3).sub.y(M), C.sub.1-C.sub.x+1 alkyl-P(R.sub.3).sub.y(M), C.sub.2-C.sub.x+2 alkenyl-P(R.sub.3).sub.y(M), C.sub.3-C.sub.x+3 alkynyl-P(R.sub.3).sub.y(M); each R.sub.2 is the same or different and is a bond to another Si atom of a repeating structure, or is selected from the group consisting of hydrogen, C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl; n is a positive integer; x is a positive integer; y is a positive integer; and M is a metal ion or metal.
35. The coated article of claim 33, wherein the antimicrobial silane-containing layer further includes a fingerprint inhibition material.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] For a further understanding of the nature, objects, and advantages of the present disclosure, reference should be had to the following detailed description, read in conjunction with the following drawings, wherein like reference numerals denote like elements and wherein:
[0011]
[0012]
[0013]
[0014]
[0015]
DETAILED DESCRIPTION
[0016] Reference will now be made in detail to presently preferred compositions, embodiments and methods of the present invention, which constitute the best modes of practicing the invention presently known to the inventors. The Figures are not necessarily to scale. However, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. Therefore, specific details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for any aspect of the invention and/or as a representative basis for teaching one skilled in the art to variously employ the present invention.
[0017] Except in the examples, or where otherwise expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word about in describing the broadest scope of the invention. Practice within the numerical limits stated is generally preferred. Also, unless expressly stated to the contrary: percent, parts of, and ratio values are by weight; molecular weights provided for any polymers refers to 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 invention implies that mixtures of any two or more of the members of the group or class are equally suitable or preferred; description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among the constituents of a mixture once mixed; the first 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 initially defined abbreviation; and, unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
[0018] It is also to be understood that this invention is not limited to the specific embodiments and methods described below, as specific components and/or conditions may, of course, vary. Furthermore, the terminology used herein is used only for the purpose of describing particular embodiments of the present invention and is not intended to be limiting in any way.
[0019] It must also be noted that, as used in the specification and the appended claims, the singular form a, an, and the comprise plural referents unless the context clearly indicates otherwise. For example, reference to a component in the singular is intended to comprise a plurality of components.
[0020] 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.
[0021] The phrase consisting of excludes any element, step, or ingredient not specified in the claim. When this phrase appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
[0022] 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 characteristic(s) of the claimed subject matter.
[0023] With respect to the terms comprising, consisting of, and consisting essentially of, where one of these three terms is used herein, the presently disclosed and claimed subject matter can include the use of either of the other two terms.
[0024] It should also be appreciated that integer ranges explicitly include all intervening integers. For example, the integer range 1-10 explicitly 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 called for, intervening numbers that are increments of the difference between the upper limit and the lower limit divided by 10 can be taken 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 lower or upper limits. In the specific examples set forth herein, concentrations, temperature, and reaction conditions (e.g. pressure, pH, etc.) can be practiced with plus or minus 50 percent of the values indicated rounded to three significant figures. In a refinement, concentrations, temperature, and reaction conditions (e.g., pressure, pH, etc.) can be practiced with plus or minus 30 percent of the values indicated rounded to three significant figures of the value provided in the examples. In another refinement, concentrations, temperature, and reaction conditions (e.g., pH, etc.) can be practiced with plus or minus 10 percent of the values indicated rounded to three significant figures of the value provided in the examples.
[0025] The term copper suboxide means a copper oxide having a higher copper to oxygen atom ratio greater than the copper to oxygen ratio in cupric oxide (CuO). Therefore, the copper to oxygen ratio is greater than 1:1. For example, cuprous oxide (Cu.sub.2O) is considered a copper suboxide.
[0026] The term a copper oxide means a compound having formula Cu.sub.xO where x is from 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.
[0027] The term a zirconium oxide means a compound having formula Zr.sub.yO.sub.2 where y is from 3 to 0.6.
Abbreviations
[0028] EDS means Energy-dispersive X-ray spectroscopy.
[0029] SEM means scanning electron microscopy.
[0030] Referring to
[0031] In another aspect, top layer 20 is a transparent metal oxide layer 20 such as a layer including a zirconium oxide.
[0032] In another aspect, top layer 20 is an antimicrobial silane-containing layer as disclosed in US Pat. Pub. No. 2022/0235232; the entire disclosure of which is hereby incorporated by reference. In this regard, the antimicrobial silane-containing layer can include a microbial inhibition material having a first silane compound and a metal ion wherein the first silane compound includes a functional group bound to the metal ion. For example, the antimicrobial silane-containing layer can include an antimicrobial material. In particular, the antimicrobial silane-containing layer includes a first silane compound and a metal ion. Characteristically, the silane compound includes a functional group bound to the metal ion. In a further refinement, the antimicrobial silane-containing layer further includes a fingerprint inhibition material, which comprises a silane compound (e.g., a second silane compound) that may be preferably hydrophobic.
[0033] In another aspect, the first silane compound is described by Formula (I):
##STR00001##
wherein: [0034] R.sub.1 is selected from the group consisting of C.sub.1-C.sub.x+1 alkyl-S(R.sub.3).sub.y(M), C.sub.2-C.sub.x+2 alkenyl-S(R.sub.3).sub.y(M), C.sub.3-C.sub.x+3alkynyl-S(R.sub.3).sub.y(M), C.sub.1-C.sub.x alkyl-N(R.sub.3).sub.y(M), C.sub.2-C.sub.x alkenyl-N(R.sub.3).sub.y(M), C.sub.3-C.sub.x alkynyl-N(R.sub.3).sub.y(M), C.sub.1-C.sub.x+1 alkyl-P(R.sub.3).sub.y(M), C.sub.2-C.sub.x+2 alkenyl-P(R.sub.3).sub.y(M), and C.sub.3-C.sub.x+3 alkynyl-P(R.sub.3).sub.y(M); [0035] each R.sub.2 is the same or different and is a bond to another Si atom of a repeating structure, or is selected from the group consisting of hydrogen, C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl; [0036] n is a positive integer (e.g., from 1 to 500 or greater); [0037] x is a positive integer (e.g., from 1 to 20 or greater); [0038] y is a positive integer (e.g., from 1 to 4 or greater); and [0039] M is a metal ion or metal.
[0040] In another aspect, n is a positive integer greater than or equal to 1, 2, 10, 20, 50, 100, 200, 300, 400, or 450. In a refinement, n is a positive integer less than or equal to 500, 450, 400, 300, 200, 100, 50, 20, 10, 5, or 2. Combinations of the above-referenced ranges are also contemplated.
[0041] In another aspect, x is a positive integer greater than or equal to 1, 2, 4, 6, 8, 10, 12, 14, 16, or 18. In a refinement, x is a positive integer less than or equal to 20, 18, 16, 14, 12, less than or equal to 10, 8, 6, 4, or 2. Combinations of the above-referenced ranges are also contemplated.
[0042] In another aspect, y is a positive integer greater than or equal to 1, 2, 3. In a refinement, y is less than or equal to 4, 3, or 2. Combinations of the above-referenced ranges are also contemplated.
[0043] In a refinement, M is a metal ions selected from the group consisting of copper ions (e.g., Cu.sup.+, Cu.sup.2+), titanium ions (e.g., Ti.sup.3+, Ti.sup.4+), vanadium ions (e.g., V.sup.2+, V.sup.3+), chromium ions (e.g., Cr.sup.2+, Cr.sup.3+), manganese ions (e.g., Mn.sup.2+, Mn.sup.4+), iron ions (e.g., Fe.sup.2+, Fe.sup.3+), cobalt ions (e.g., Co.sup.2+, Co.sup.3+), nickel ions (e.g., Ni.sup.2+), zinc ions (e.g., Zn.sup.2+), zirconium ions (e.g., Zr.sup.2+), palladium ions (e.g., Pd.sup.2+), cadmium ions (e.g., Cd.sup.2+), platinum ions (e.g., Pt.sup.2+, Pt.sup.4+), gold ions (e.g., Au.sup.+, Au.sup.3+), mercury ions (e.g., Hg.sup.2+), terbium ions (e.g., Tb.sup.3+), tungsten ions (e.g., W.sup.4+), aluminum ions (e.g., Al.sup.3+), gallium ions (e.g., Ga.sup.3+), germanium ions (e.g., Ge.sup.2+), arsenic ions (e.g., As.sup.3+), selenium ions (e.g., Se.sup.2+) tin ions (e.g., Sn.sup.2+), antimony ions (e.g., Sb.sup.3+), tellurium ions (e.g., Te.sup.2+), lead ions (e.g., Pb.sup.4+), bismuth ions (e.g., Bi.sup.3+), and/or combinations thereof. In another refinement, M is a metal selected from the group consisting of Ag, Cu, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Zr, Pd, Cd, Pt, Au, Hg, W, Al, Ga, Ge, Tb, As, Se, Sn, Sb, Te, Pb, and Bi.
[0044] In some refinements, each R.sub.2 is the same or different and is a bond to another Si atom of a repeating structure, or is selected from the group consisting of hydrogen, C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.3-C.sub.10alkynyl.
[0045] In a refinement, each carbon atom and/or hydrogen atom in R.sub.1 and R.sub.2 is independently optionally substituted with deuterium, halogen. OH, CN, OR.sub.3, CO.sub.2H, C(O)O R.sub.3, C(O)NH.sub.2, C(O)NH(C.sub.1-C.sub.10alkyl), C(O)N(C.sub.1-C.sub.10alkyl).sub.2, SC.sub.1-C.sub.10alkyl, S(O)C.sub.1-C.sub.10alkyl, S(O).sub.2C.sub.1-C.sub.10alkyl, S(O)NH(C.sub.1-C.sub.10alkyl), S(O).sub.2NH(C.sub.1-C.sub.10alkyl), S(O)N(C.sub.1C.sub.10alkyl).sub.2, S(O).sub.2N(C.sub.1-C.sub.10alkyl).sub.2, NR.sub.3, NH.sub.2, C.sub.2H.sub.8N.sub.2, NH(C.sub.1-C.sub.10alkyl), P(C.sub.1-C.sub.10alkyl).sub.2, P(O)(C.sub.1-C.sub.10alkyl).sub.2, PO.sub.3H.sub.2, or Si(OC.sub.1-C.sub.10alkyl).sub.3.
[0046] In a refinement, each R.sub.3 is selected from the group consisting of a bond, hydrogen, deuterium, C.sub.1-C.sub.10alkyl, C.sub.1-C.sub.10alkenyl, C.sub.2-C.sub.10alkynyl, C.sub.3-C.sub.10cycloalkyl, and C.sub.1-C.sub.10alkyl-(O)C.sub.1-C.sub.10alkyl, optionally substituted and n is a positive integer.
[0047] In some variations, the first silane compound is immobilized on a substrate. The first silane compound can be chemically bound to the substrate by covalent bonds and/or non-covalent bonds.
[0048] The antimicrobial silane-containing layer is not limited by the amount of the microbial inhibition material. For example, the microbial inhibition material can be present in an amount from about 0.1 wt. %, to about 100 wt. %.
[0049] In a variation, the antimicrobial silane-containing layer further includes a fingerprint inhibition material. The fingerprint inhibition material includes a second silane compound. The second silane compound can provide hydrophobic properties. In a refinement, the fingerprint inhibition material includes an invisible fingerprint material that is hydrophobic and oleophilic and/or an anti-fingerprint material that is hydrophobic and oleophobic. In a variation, the second silane compound is described by structure (II):
##STR00002##
wherein: [0050] R.sub.1 is selected from the group consisting of C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, and C.sub.3-C.sub.20alkynyl, any of which may be optionally at least partially halogenated (e.g., fluorinated); and [0051] R.sub.2 is the same or different and is a linkage to a substrate, or is selected from the group consisting of hydrogen, C.sub.1-C.sub.10 alkyl. C.sub.2-C.sub.10 alkenyl, and C.sub.3-C.sub.10 alkynyl. In a refinement. R.sub.1 and R.sub.1 can be the same as set forth above for R.sub.1 and R.sub.2 respectively.
[0052] The antimicrobial silane-containing layer is not limited by the amount of fingerprint inhibition material. For example, the microbial inhibition material can be present in an amount from about 0.1 wt. %, to about 100 wt. %.
[0053] In a variation, each carbon atom and/or hydrogen atom in R.sub.1 and R.sub.2 is independently optionally substituted with deuterium, halogen, OH, CN, OR.sub.3, CO.sub.2H, C(O)O R.sub.3, C(O)NH.sub.2, C(O)NH(C.sub.1-C.sub.10alkyl), C(O)N(C.sub.1-C.sub.10alkyl).sub.2, SC.sub.1-C.sub.10alkyl, S(O)C.sub.1-C.sub.10alkyl, S(O).sub.2C.sub.1-C.sub.10alkyl, S(O)NH(C.sub.1-C.sub.10alkyl), S(O).sub.2NH(C.sub.1-C.sub.10alkyl), S(O)N(C.sub.1C.sub.10alkyl).sub.2, S(O).sub.2N(C.sub.1-C.sub.10alkyl).sub.2, NR.sub.3, NH.sub.2, C.sub.2H.sub.8N.sub.2, NH(C.sub.1-C.sub.10alkyl), P(C.sub.1-C.sub.10alkyl).sub.2, P(O)(C.sub.1-C.sub.10 alkyl).sub.2, PO.sub.3H.sub.2, or Si(OC.sub.1-C.sub.10 alkyl).sub.3; and each R.sub.3 is selected from the group consisting of hydrogen, deuterium, C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.2-C.sub.10alkynyl, C.sub.3-C.sub.10cycloalkyl, and C.sub.1-C.sub.10 alkyl-OC.sub.1-C.sub.10 alkyl, optionally substituted.
[0054] In one variation, the at least one adhesion layer includes a copper oxide layer composed of a copper oxide that is different than the antimicrobial copper suboxide layer. The copper oxide can be described by the formula Cu.sub.xO where x is from 2.2 to 0.6. In a refinement, x is at least 0.6, 0.7, 0.9, 0.9, or 0.95 and at most 2.2, 2.0, 1.8, 1.6, 1.4 or 1.2. In a refinement, the at least one adhesion layer is a cupric oxide (i.e., Cu(II)O) layer. In a refinement, the copper oxide layer has a thickness from about 10 to 200 nm. In a further refinement, the copper oxide layer has a thickness of at least 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, or 50 nm and a thickness of at most 300 nm, 250 nm, 2000 nm, 180 nm, 150 nm, 120 nm, or 100 nm.
[0055] In another variation, the at least one adhesion layer includes a zirconium oxide layer that is composed of a zirconium oxide. The zirconium oxide can be described by the formula Zr.sub.yO.sub.2 where y is from 3 to 0.6. In a refinement, y is at least 0.6, 0.7, 0.8, 0.9, or 0.95 and at most 3, 2.5, 2.0, 1.8, 1.6, 1.4 or 1.2. In another refinement, y is about 1 and the at least one adhesion layer includes a zirconia layer (ZrO.sub.2). In a refinement, the zirconium oxide layer has a thickness from about 10 to 300 nm. In a further refinement, the zirconium oxide layer has a thickness of at least 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, or 80 nm and a thickness of at most 400 nm, 300 nm, 250 nm, 2000 nm, 180 nm, 150 nm, 120 nm, or 100 nm.
[0056] In another variation, the at least one adhesion layer is a bilayer that includes a zirconium oxide layer and cupric oxide layer. For example, as depicted in
[0057] In a variation, the copper suboxide layer 18 is composed of a compound having formula Cu.sub.zO where z is from 3 to 1.1. In a refinement, z is at least 1.1, 1.3, 1.5, 1.6, 1.7, or 1.8 and at most 3, 2.7, 2.5, 2.4, 2.3, 2.2, or 2.1. In a refinement, the copper suboxide layer includes cuprous oxide (Cu.sub.2O).
[0058] In a variation, the copper suboxide layer 18 has a uniform stoichiometry to within 20 mole % throughout the thickness of the copper suboxide layer. In a refinement, the copper suboxide layer has a uniform stoichiometry to within 10 mole % throughout the thickness of the copper suboxide layer. In another variation, the copper atom percent in the copper suboxide layer decreases at increasing distances from the substrate. In other words, the ratio of copper to oxygen decrease at increasing distances from the substrate.
[0059] In a variation, the copper suboxide layer 18 has a dark gray non-iridescent color. In accessing color, copper suboxide layer 18 can be characterized by Lab color space coordinates L*, a*, and b* relative to a CIE standard illuminant such as F2, L2, D65, and D50. In a refinement, copper suboxide layer 18 has color space coordinates L* from 35 to 55, a* from ?5 to 5, and b* from ?10 to ?4 CIE standard illuminant D65.
[0060] In a variation, the copper suboxide layer includes a plurality of crystalline columns extending from the substrate. In a refinement, the columns expand (i.e., the cross section of the columns increase) along a direction perpendicular to the substrate.
[0061] In a variation, the adhesion layer includes a copper oxide with an antimicrobial copper suboxide layer disposed over the adhesion layer. As set forth above, the antimicrobial copper suboxide layer is at least 5 times thicker than the adhesion layer. Advantageous, the combination of the adhesion layer and the antimicrobial copper suboxide layer are free of other metals other than copper. In this context, free means that both the adhesion layer and the antimicrobial copper suboxide layer independently include less than 1 mole percent of other metals.
[0062] Table 1 provides properties of the antimicrobial copper suboxide layer (e.g., cuprous oxide). Table 2 provides properties of an adhesion layer that includes a copper oxide (e.g., a cupric oxide layer). Table 3 provides properties of an adhesion layer that includes a zirconium oxide (e.g., a zirconium oxide layer).
TABLE-US-00001 TABLE 1 Antimicrobial copper suboxide layer properties Bulk (cuprous oxide) layer Max Min Nominal Notes color range (55, 5, 5) (35, ?5, ?10) (43, 0, ?4) CIELAB, 0/10 (L*, a*, b*) geometry, D65 source, SPI mode thickness 10 0.5 2 (microns) grain size 0.5 0.05 0.2 (microns) composition 80 50 67 (at % Cu) composition 50 20 33 (at % O) Phase copper cupric cuprous Orientations (2, 0, 0), (1, 1, 1), (3, 1, 1) no obviously preferred orientation
TABLE-US-00002 TABLE 2 Cupric oxide layer properties Adhesion (cupric oxide) layer Max Min Nominal thickness (microns) 0.5 0.01 0.05 composition (at % Cu) 67 40 50 composition (at % O) 60 33 50
TABLE-US-00003 TABLE 3 A zirconium-containing layer properties Adhesion (zirconia) layer [Optional] Max Min Nominal thickness (microns) 0.5 0.01 0.15 composition (at % Zr) 100 33 33 composition (at % O) 67 0 67
[0063] Table 4 provides the color properties for a stainless steel substrate coated
TABLE-US-00004 TABLE 4 Color properties of a coated article Data Name L*(F2) a*(F2) b*(F2) L*(D65) a*(D65) b*(D65) Gloss (Calc) Example 1 43.33 0.34 ?4.83 43.56 0.63 ?4.72 0.9649 Example 2 43.33 0.33 ?4.84 43.56 0.63 ?4.72 0.9649 Example 3 43.25 0.65 ?4.32 43.5 0.96 ?4.13 0.9658 Example 4 43.92 ?1.04 ?5.87 44.47 ?1.36 ?4.83 0.9225 Example 5 42.74 2.47 ?2.32 43.09 3.33 ?1.76 0.9101 min 42.74 ?1.04 ?5.87 43.09 ?1.36 ?4.83 0.9101 max 43.92 2.47 ?2.32 44.47 3.33 ?1.76 0.9658
[0064] Table 5 provides examples of a multilayer coating on a stainless steel substrate.
TABLE-US-00005 TABLE 5 Examples of a multilayered coating Layer1 Layer2 Layer3 approx. approx. approx. Sample thickness thickness thickness ID material (nm) material (nm) material (nm) Exam- copper 50 copper 1200 none ple 6 oxide oxide Exam- copper 50 copper 1200 ple 7 oxide oxide Exam- zirconia 100 copper 1200 zirconia 50 ple 8 oxide
[0065] While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention.