Coated surfaces, coatings, and articles using same

Abstract

Coated surfaces and coatings are described. The coated surfaces can include surface coatings comprising an alloy layer. The alloy layer can include molybdenum or tungsten in combination with one or more of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. A process for producing the surface coating is also described.

Description

[Technical field]

[0001] Priority and Related Applications This application is related to and claims priority to and the benefit of U.S. patent application Ser. No. 63 / 212,515, filed June 18, 2021, U.S. patent application Ser. No. 63 / 223,497, filed July 19, 2021, and U.S. patent application Ser. No. 63 / 226,649, filed July 28, 2021.

[0002] Technical Field Certain configurations described herein relate to coatings, coated surfaces, and surface coatings that may be used on a variety of articles. More particularly, certain embodiments relate to surface coatings comprising an alloy layer. [Background technology]

[0003] Many different articles have components that are subjected to stresses and environments during use that can reduce the lifespan of the article and can lead to premature wear or failure of the article. Summary of the Invention [Means for solving the problem]

[0004] Particular features, aspects, embodiments and configurations of the coatings, coated surfaces and coated articles are described in more detail below. Although the exact configuration may vary, the coated surfaces typically include a surface coating comprising an alloy layer. For example, the alloy layer may include molybdenum or tungsten in combination with one or more other materials. Various particular configurations of the alloy layer on the article are described in more detail below.

[0005] In one embodiment, the coated surface includes a surface coating comprising an alloy layer comprising molybdenum or tungsten and at least one element selected from the group consisting of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

[0006] In certain embodiments, the surface coating is an exposed outer layer and is free of silver or gold, or free of all precious metals. In other embodiments, molybdenum or tungsten is present in the surface coating at 35% or less by weight based on the weight of the surface coating, or at 25% or less by weight based on the weight of the surface coating, or at 15% or less by weight based on the weight of the surface coating. In some examples, molybdenum or tungsten is present in the alloy layer at 35% or less by weight based on the weight of the alloy layer, or at 25% or less by weight based on the weight of the alloy layer, or at 15% or less by weight based on the weight of the alloy layer. In additional examples, molybdenum or tungsten is present in the surface coating at 65% or more by weight based on the weight of the surface coating, or at 75% or more by weight based on the weight of the surface coating, or at 85% or more by weight based on the weight of the surface coating. In certain embodiments, molybdenum or tungsten is present in the alloy layer at 65% or less by weight based on the weight of the alloy layer, or at 75% or less by weight based on the weight of the alloy layer, or at 85% or less by weight based on the weight of the alloy layer.

[0007] In some configurations, the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum and one of tin, phosphorus, iron, or boron, or consists essentially of nickel and tungsten, or nickel, tungsten molybdenum, and one of tin, phosphorus, iron, or boron. In certain embodiments, the coated surface is on a substrate, the substrate being carburized steel, nitrided steel, carbonitrided steel, stainless steel, carbon steel, alloy steel, titanium, copper, copper alloy. In some examples, the coated surface comprises a surface roughness Ra of less than 1 micron. In certain examples, the coated surface comprises a surface roughness Ra of 1 micron or more and less than 15 microns.

[0008] In another example, the alloy layer is an electrodeposited exposed alloy layer, and the electrodeposited exposed outer layer consists essentially of (i) molybdenum and only one of nickel, tungsten, cobalt, tin, phosphorous, iron, chromium, magnesium, or boron, or (ii) molybdenum and only two of nickel, tungsten, cobalt, tin, phosphorous, iron, chromium, magnesium, or boron, or (iii) both molybdenum and phosphorous and at least one of nickel, cobalt, tin, chromium, tungsten, iron, magnesium, or boron. (iv) consisting essentially of tungsten and one of nickel, molybdenum, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (v) consisting essentially of tungsten and two of nickel, molybdenum, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (vi) consisting essentially of both tungsten and phosphorus and at least one of nickel, molybdenum, cobalt, tin, chromium, tungsten, iron, magnesium, or boron.

[0009] In some examples, the alloy layer is an electrodeposited alloy layer and further comprises an intermediate layer below the alloy layer, the intermediate layer comprising one or more of nickel, a nickel alloy, copper, a copper alloy, a nickel-tungsten alloy, a cobalt alloy, a nickel-phosphorus alloy, an alloy of molybdenum or tungsten, or both, and at least one of nickel, cobalt, chromium, tin, phosphorus, iron, or boron.

[0010] In certain embodiments, the coated surface may comprise an additional layer formed on the alloy layer, the additional layer comprising one or more of nickel, nickel alloy, nickel-tungsten alloy, cobalt alloy, cobalt-phosphorus alloy, nickel-phosphorus alloy, molybdenum alloy, and at least one of nickel, cobalt, chromium, tin, phosphorus, iron or boron, ceramics, the ceramics comprising tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, metal nitrides, nitrides, metal carbides, carbides, boron, tungsten, tungsten carbide, chromium carbide, chromium oxide, aluminum oxide, zirconia, zirconium oxide, titania, nickel carbide, nickel oxide, nanocomposites, oxide composites, or combinations thereof. In some embodiments, the additional layer is formed on the alloy layer and comprises a ceramic. In some examples, the coated surface has a surface roughness Ra of less than 1 micron, or from 1 micron to less than 5 microns, or from 5 microns to less than 15 microns.

[0011] In one embodiment, the alloy layer further comprises one or more particles selected from the group consisting of solid nanoparticles, polymer particles, hard particles, silicon dioxide particles, silicon carbide particles, titanium dioxide particles, polytetrafluoroethylene particles, hydrophobic particles, diamond particles, particles functionalized with hydrophobic groups, solid particles, and combinations thereof. In some examples, the alloy layer is present as an exposed outer layer of the surface coating, the exposed outer layer being an electrodeposited alloy layer, the electrodeposited alloy layer excluding silver or gold, or excluding all precious metals. In certain embodiments, the exposed alloy layer further comprises particles.

[0012] In some embodiments, the surface coating comprises a first layer and a second layer, and the first layer or the second layer, or both, comprise an alloy layer. In other embodiments, the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum and one of tin, phosphorus, iron, magnesium, or boron, or consists essentially of nickel and tungsten, or consists essentially of nickel, tungsten and one of tin, phosphorus, iron, magnesium, or boron.

[0013] In some examples, each of the first layer and the second layer comprises an alloy layer, each alloy layer consisting essentially of nickel and molybdenum, or consisting essentially of nickel, molybdenum and one of tin, phosphorus, iron, magnesium, or boron, or consisting essentially of nickel and tungsten, or consisting essentially of nickel, tungsten and one of tin, phosphorus, iron, magnesium, or boron. In certain embodiments, the second layer is an alloy layer, the second layer is present as an exposed outer layer of the surface coating, the exposed outer layer is an electrodeposited alloy layer, and the electrodeposited alloy layer excludes silver or gold. In some examples, the second layer is an alloy layer, the second layer is present as an exposed outer layer of the surface coating, the exposed outer layer is an electrodeposited alloy layer, and the electrodeposited alloy layer excludes all precious metals.

[0014] In some embodiments, the alloy layer is comprised of nickel and molybdenum, or nickel, molybdenum and phosphorous, or nickel and tungsten, or nickel, tungsten and phosphorous.

[0015] In some embodiments, the alloy layer is textured. In another aspect, an article includes a substrate having a coated surface, the coated surface comprising a surface coating, the surface coating comprising an alloy layer comprising molybdenum or tungsten and at least one element selected from the group consisting of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

[0016] In some examples, the surface coating is an exposed outer layer and does not include silver or gold, or does not include any precious metals. In some embodiments, the substrate is carburized steel, nitrided steel, carbonitrided steel, stainless steel, carbon steel, alloy steel, titanium, copper, copper alloy. In some embodiments, the coated surface of the article has a surface roughness Ra of less than 1 micron. In other embodiments, the coated surface of the article has a surface roughness Ra of 1 micron or more and less than 15 microns. In some embodiments, the coated surface has a surface roughness Ra of less than 1 micron, or 1 micron or more and less than 5 microns, or 5 microns or more and less than 15 microns.

[0017] In another aspect, an article comprises a substrate having a coated surface, the coated surface comprising a surface coating, the surface coating comprising a first layer and a second layer on the first layer, the first layer or the second layer or both comprising an alloy layer comprising molybdenum and at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

[0018] In an additional aspect, an article comprises a substrate having a coated surface, the coated surface comprising a surface coating, the surface coating comprising a first layer and a second layer on the first layer, each of the first layer and the second layer comprising molybdenum, and the first layer, the second layer, or both, comprising an alloy layer comprising molybdenum or tungsten and at least one element selected from the group consisting of nickel, tungsten cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, tungsten cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

[0019] In another aspect, an article comprises a substrate having a coated surface, the coated surface comprising a surface coating, the surface coating comprising a first layer and a second layer on the first layer, the first layer or the second layer or both comprising an alloy layer comprising tungsten and at least one element selected from the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

[0020] In an additional aspect, an article comprises a substrate having a coated surface, the coated surface comprising a surface coating, the surface coating comprising a first layer and a second layer on the first layer, each of the first layer and the second layer comprising molybdenum, and the first layer, the second layer, or both, comprising an alloy layer comprising tungsten and at least one element selected from the group consisting of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, molybdenum, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

[0021] In another aspect, an article comprises a substrate having a coated surface, the coated surface comprising a surface coating, the surface coating comprising an electrodeposited alloy layer, the electrodeposited alloy layer being present as an exposed outer electrodeposited alloy layer of the surface coating, the exposed outer electrodeposited alloy layer consisting essentially of nickel and molybdenum, or consisting essentially of nickel, molybdenum and one of tin, phosphorous, iron, magnesium, or boron, the molybdenum being present in the exposed outer electrodeposited layer at 35 wt % or less based on the weight of the surface coating.

[0022] In another aspect, an article comprises a substrate having a coated surface, the coated surface comprising a surface coating, the surface coating comprising an electrodeposited alloy layer, the electrodeposited alloy layer being present as an exposed outer electrodeposited alloy layer of the surface coating, the exposed outer electrodeposited alloy layer consisting essentially of nickel and tungsten, or consisting essentially of nickel, tungsten and one of tin, phosphorous, iron, magnesium, or boron, the tungsten being present in the exposed outer electrodeposited layer at 35 weight percent or less based on the weight of the surface coating.

[0023] Additional aspects, features, embodiments and examples are described below. BRIEF DESCRIPTION OF THE DRAWINGS Certain aspects, embodiments, and configurations are described with reference to the drawings. [Brief description of the drawings]

[0024] [Figure 1] FIG. 1 is a diagram of a device including a surface coating on a substrate. [Diagram 2] FIG. 2 is a diagram of a device with two layers in a coating on a substrate. [Diagram 3] FIG. 3 is another view of a device with two layers in a coating on a substrate. [Figure 4A] FIG. 4A is a diagram of a device with a textured surface. [Figure 4B]FIG. 4B is a diagram of a device with a textured surface. [Figure 5A] FIG. 5A is a diagram of a device with two or more layers. [Figure 5B] FIG. 5B is a diagram of a device with two or more layers. [Figure 6] FIG. 6 is a diagram of the coating layers. [Figure 7] FIG. 7 is a diagram of the coating layers. [Figure 8] FIG. 8 is a diagram of the coating layers. [Figure 9] FIG. 9 is an explanatory diagram of a non-planar surface. [Figure 10] FIG. 10 is an explanatory diagram of a non-planar surface. [Figure 11] FIG. 11 is an explanatory diagram of a non-planar surface. [Figure 12] FIG. 12 is a diagram of a device having multiple coating layers. [Figure 13] FIG. 13 is a diagram of a process that can be used to produce the coated surfaces described herein. [Figure 14] FIG. 14 is a photograph showing the two coatings on different articles. [Figure 15A] FIG. 15A is a photograph showing the hard chromium coating and the electroless nickel coating. [Figure 15B] FIG. 15B is a photograph showing the hard chromium coating and the electroless nickel coating. [Figure 16A] FIG. 16A is a photograph showing the results of a salt spray test on the tested coatings. [Figure 16B] FIG. 16B is a photograph showing the results of a salt spray test on the tested coatings. [Figure 16C] FIG. 16C is a photograph showing the results of a salt spray test on the tested coatings. [Figure 16D] FIG. 16D is a photograph showing the results of a salt spray test on the tested coatings. [Figure 16E]FIG. 16E is a photograph showing the results of a salt spray test on the tested coatings. [Figure 17] FIG. 17 is a graph comparing salt spray tests. [Figure 18A] FIG. 18A is a photograph showing the salt spray test and the coating appearance after 5000 hours. [Figure 18B] FIG. 18B is a photograph showing the salt spray test and coating appearance after 5000 hours. [Figure 18C] FIG. 18C is a photograph showing the salt spray test and coating appearance after 5000 hours. [Figure 18D] FIG. 18D is a photograph showing the salt spray test and coating appearance after 5000 hours. [Figure 18E] FIG. 18E is a photograph showing the salt spray test and coating appearance after 5000 hours. [Figure 19] FIG. 19 is a photograph showing images of the notched bar before and after application of the coating. [Figure 20A] FIG. 20A is an image of the MaxShield-V2 (FIG. 20A) coating after 6% elongation. [Figure 20B] FIG. 20B is an image of the MaxShield-V1 (FIG. 20B) coating after 6% elongation. [Figure 21] FIG. 21 is a microscope image of the MaxShield-V1 coating'. [Figure 22] FIG. 22 is a diagram of an apparatus for measuring the coefficient of friction. [Figure 23] FIG. 23 is a diagram showing a crack. [Figure 24A] FIG. 24A is an image of two carbon steel bars coated with MaxShield-V1 before testing (FIG. 24A). [Figure 24B] FIG. 24B is an image of two carbon steel bars coated with MaxShield-V1 after testing (FIG. 24B). [Diagram 25] FIG. 25 is a microscope image of the steel bar of FIG. 24B. [Figure 26]FIG. 26 is a diagram of the apparatus used to polish the surface of the coating by applying a load of 1 kg to each polishing wheel. [Figure 27] FIG. 27 is a graph comparing the wear index of different coatings. [Figure 28] FIG. 28 is a graph showing coefficient of friction versus cycles. [Figure 29] FIG. 29 is a graph showing the corrosion rates of different coatings. [Figure 30A] FIG. 30A shows a magnified image of the plated and heat treated coating. [Figure 30B] FIG. 30B shows a magnified image of the plated and heat treated coating. [Figure 31A] FIG. 31A is an image showing the surface coating. [Figure 31B] FIG. 31B is an image showing the surface coating. [Figure 31C] FIG. 31C is an image showing the surface coating. [Figure 31D] FIG. 31D is an image showing the surface coating. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] In certain embodiments, the materials and methods described herein can be used to provide a coated surface on a portion of a substrate present in an article, device, or system. The coated surface comprises a surface coating. The surface coating can comprise one, two, three, or more layers. In some configurations, the surface coating comprises only one layer, or only two layers, or only three layers. As described in more detail below, the substrate can be part of a variety of different articles and devices. For ease of reference, a small cross section of a substrate that is part of a larger device or article is described with reference to Figures 1-12 below. Certain articles or devices that comprise a substrate and / or other layers are also described. The exact material or materials in the surface coating can vary. In some configurations, the surface coating comprises one or more metals. In some embodiments, the surface coating may comprise a metal alloy, for example an alloy comprising two or more metals. In some embodiments, the surface coating comprises a metal alloy comprising only two metals, or a metal and another material. In certain embodiments, the surface coating comprises a metal alloy comprising only three metals, or a metal and two other materials. In other embodiments, the surface coating may comprise only a single layer formed on a substrate. For example, the single layer may be exposed to the environment to protect the underlying substrate from degradation. In some cases, the surface coating may comprise only a first layer formed on a substrate and a second layer formed on the first layer.

[0026] In some embodiments, the alloy layer may "consist essentially of" two or more materials. The phrase "consists essentially of" or "consisting essentially of" is intended to refer to only the specified materials and trace impurities, and materials that do not substantially affect the fundamental property(ies) of the composition. The term "consisting of" refers only to materials and impurities that cannot be removed by conventional purification techniques.

[0027] In certain embodiments, the alloy layers described herein may include one, two or more Group IV transition metals, including scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper and zinc.

[0028] In other configurations, the alloy layers described herein may include one, two or more Group V metals, including yttrium, zirconium, niobium, ruthenium, rhodium, palladium, silver and cadmium.

[0029] In some configurations, the alloy layers described herein can include one, two or more Group VI metals, including non-radioactive lanthanides (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and mercury.

[0030] In other embodiments, the alloy layers described herein may include one, two or more Group VII metals, including the non-radioactive actinides (Th, Pa, U).

[0031] In some cases, the alloy layers described herein can include one or more metals from Group IV metals and one or more metals from Group V metals or Group VI metals or Group VII metals.

[0032] In other examples, the alloy layers described herein can include one or more metals from Group V metals and one or more metals from Group VI metals or Group VII metals.

[0033] In other examples, the alloy layers described herein can include one or more metals from Group VI metals and one or more metals from Group VII metals.

[0034] In some embodiments, the alloy layers described herein include only two metals, one metal from Group IV metals and another metal from Group V, Group VI, or Group VII metals.

[0035] In some embodiments, the alloy layers described herein include only two metals, one metal from a Group V metal and the other metal from a Group VI metal or a Group VII metal.

[0036] In other embodiments, the alloy layers described herein include only two metals, one metal from Group VI metals and the other metal from Group VII metals.

[0037] In some examples, the alloy layers described herein include only two metals, both of which are Group IV metals.

[0038] In some embodiments, the alloy layers described herein include only two metals, and both metals are Group V metals.

[0039] In some embodiments, the alloy layers described herein include only two metals, and both metals are Group VI metals.

[0040] In some embodiments, the alloy layers described herein include only two metals, and both metals are Group VII metals.

[0041] Optionally, the alloy layers described herein can also include Group II materials (Li, Be, B and C) or Group III materials (Na, Mg, Al, Si, P, S) in addition to or in place of other metals. These materials may be present in combination with one, two, three or more metals.

[0042] In some embodiments, the alloy layer described herein comprises molybdenum and one or more additional metals, e.g., one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises molybdenum and only one additional metal, e.g., only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises molybdenum and only two additional metals or materials, e.g., only two additional metals or materials selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II materials, and group III materials. In some embodiments, the surface coating has a monolayer formed on a substrate, the monolayer comprises molybdenum and one or more additional metals, e.g., one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the surface coating has a monolayer formed on a substrate, the monolayer comprising molybdenum and only one additional metal, e.g., only one additional metal selected from the group consisting of Group IV metals, Group V metals, Group VI metals, and Group VII metals. In some examples, the surface coating has a monolayer formed on a substrate, the monolayer comprising molybdenum and only two additional metals or materials, e.g., only two additional metals or materials selected from the group consisting of Group IV metals, Group V metals, Group VI metals, Group VII metals, Group II materials, and Group III materials.

[0043] In some embodiments, the alloy layer described herein comprises tungsten and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises tungsten and only one additional metal, such as only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises tungsten and only two additional metals or materials, such as only two additional metals or materials selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II materials, and group III materials. In some embodiments, the surface coating has a monolayer formed on the substrate, the monolayer comprises tungsten and one or more additional metals, such as one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the surface coating has a monolayer formed on a substrate, the monolayer comprising tungsten and only one additional metal, e.g., only one additional metal selected from the group consisting of Group IV metals, Group V metals, Group VI metals, and Group VII metals. In some examples, the surface coating has a monolayer formed on a substrate, the monolayer comprising tungsten and only two additional metals or materials, e.g., only two additional metals or materials selected from the group consisting of Group IV metals, Group V metals, Group VI metals, Group VII metals, Group II materials, and Group III materials.

[0044] In some embodiments, the alloy layer described herein comprises nickel and one or more additional metals, e.g., one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises nickel and only one additional metal, e.g., only one additional metal selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the metal alloy comprises nickel and only two additional metals or materials, e.g., only two additional metals or materials selected from the group consisting of group IV metals, group V metals, group VI metals, group VII metals, group II materials, and group III materials. In some embodiments, the surface coating has a monolayer formed on the substrate, the monolayer comprises nickel and one or more additional metals, e.g., one or more additional metals selected from the group consisting of group IV metals, group V metals, group VI metals, and group VII metals. In certain embodiments, the surface coating has a monolayer formed on a substrate, the monolayer comprising nickel and only one additional metal, e.g., only one additional metal selected from the group consisting of Group IV metals, Group V metals, Group VI metals, and Group VII metals. In some examples, the surface coating has a monolayer formed on a substrate, the monolayer comprising nickel and only two additional metals or materials, e.g., only two additional metals or materials selected from the group consisting of Group IV metals, Group V metals, Group VI metals, Group VII metals, Group II materials, and Group III materials.

[0045] In certain configurations, the alloy layer includes (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound including one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In certain embodiments, the alloy excludes precious metals.

[0046] In certain configurations, the alloy layers described herein include two or more of nickel, molybdenum, copper, phosphorous, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, carbon fibers, carbon nanotubes, particles, cobalt, tungsten, gold, platinum, silver, or alloys or combinations thereof.

[0047] In other embodiments, the alloy layers described herein include two or more of nickel, molybdenum, copper, phosphorous, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, carbon fibers, carbon nanotubes, particles, cobalt, tungsten, gold, platinum, silver, or alloys or combinations thereof.

[0048] In certain embodiments, the alloy layer described herein comprises an alloy of (i) molybdenum, molybdenum oxide, or other compound of molybdenum, and (ii) a transition metal, transition metal oxide, or other compound of a transition metal.

[0049] In certain embodiments, the alloy layers described herein include only two metals: (i) molybdenum, molybdenum oxide, or other compound of molybdenum, and (ii) a transition metal, transition metal oxide, or other compound of a transition metal.

[0050] In certain embodiments, the metal alloy of the layers described herein includes only two metals: (i) tungsten, tungsten oxide, or other compound of tungsten, and (ii) a transition metal, transition metal oxide, or other compound of a transition metal.

[0051] In certain embodiments, the alloy layer described herein includes only two metals: (i) nickel, nickel oxide, or other compound of nickel, and (ii) a transition metal, transition metal oxide, or other compound of a transition metal. In some embodiments, the transition metal, transition metal oxide, or other compound of a transition metal includes scandium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, technetium, silver, cadmium, lanthanum, platinum, gold, mercury, actinium, and combinations thereof. For example, the metal alloy coating can include a Ni-Mo alloy, a Ni-W alloy, or can have only a Ni-Mo alloy or a Ni-W alloy.

[0052] In certain embodiments, the metal alloy layer exhibits at least two times more corrosion resistance than a chromium coating according to the ASTM B117 salt spray corrosion test. In some embodiments, the metal alloy layer does not exhibit hydrogen embrittlement as tested according to the ASTM F519 standard.

[0053] In embodiments where the metal alloy layer includes molybdenum, molybdenum oxide, or other compounds of molybdenum, these materials may be present in the metal alloy coating at 35 wt% or less (or 25 wt% or less), based on the weight of the alloy layer or the weight of the surface coating. In some other cases where the metal alloy layer includes molybdenum, molybdenum oxide, or other compounds of molybdenum, these materials may be present in the metal alloy coating at 48 wt% or less, based on the weight of the alloy layer or the surface coating.

[0054] In some cases, the alloy layer may consist of a single layer. In other configurations, two or more layers may be present in the surface coating. As described herein, the two layers may include the same or different materials. If the material is the same, the material may be present in different amounts in the two layers, or may be deposited in the different layers using different processes.

[0055] In some embodiments, the alloy layer can include an alloy of molybdenum, such as molybdenum in combination with one or more of nickel, chromium, carbon, cobalt, tin, tungsten, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. For example, molybdenum can be present at 35% by weight or less and the other components can be present at 65% by weight or more. There can be more than two components or metals, if desired. In other embodiments, the surface coating can include an alloy of molybdenum in combination with only one other metal or material, such as nickel, chromium, carbon, cobalt, tin, tungsten, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In some embodiments, the surface coating can include an alloy of molybdenum in combination with only two other metals, such as nickel, chromium, carbon, cobalt, tin, tungsten, aluminum, vanadium, titanium, niobium, iron, boron, phosphorous, magnesium, or copper.

[0056] In some embodiments, the alloy layer can include an alloy of tungsten in combination with one or more of nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In other embodiments, the surface coating can include an alloy of tungsten in combination with only one other metal or material, such as nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In some embodiments, the surface coating can include an alloy of tungsten in combination with only two other metals, such as nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In some embodiments, the surface coating can include an alloy of tungsten, such as tungsten in combination with one or more of chromium, molybdenum, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. For example, tungsten can be present at 35% by weight or less, and other components can be present at 65% by weight or more. There can be more than two components or metals, if desired. In other embodiments, the surface coating can include an alloy of tungsten in combination with only one or two other metals or materials, such as nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper. In some embodiments, the surface coating can include an alloy of tungsten in combination with only two other metals, such as nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorous, magnesium, or copper.

[0057] In some embodiments, the surface coatings described herein may provide desirable performance criteria including, but not limited to, a specific surface roughness (Ra) as described in the ISO 4287 and ISO 4288 standards. The roughness may be measured, for example, using a profilometer. The coating thickness may also be measured using non-destructive techniques such as magnetic measurement tools, XRF, or destructive techniques such as sampling and cross-sectional analysis. The exact surface roughness (Ra) may vary, for example, and may be less than 1 micron, or may be between 0.1 micron and 1 micron. The device may also have a desired coefficient of friction (CoF). This characteristic generally depends on both the surfaces that are worn against each other and the fluid located between them. The roughness of each surface, the viscosity of the fluid, and the temperature of the test may affect the coefficient of friction measurement. The CoF may be measured, for example, according to a block-on-ring test such as those specified in ASTM G99-17 or ASTM G77-17. The coating, or one or more layers of the coating, may provide a specific hardness as tested by ASTM E384-17. For example, the coating may have a hardness of greater than 600 Vickers as measured in accordance with ASTM E384-17. If the coating comprises multiple layers, any one or more of the layers have a hardness of greater than 600 Vickers as measured in accordance with ASTM E384-17. In some embodiments, an outer layer of the coating may have a hardness of greater than 600 Vickers as measured in accordance with ASTM E384-17. In other embodiments where the coating has a hardness of 600 Vickers or greater as measured in accordance with ASTM E384-17, one of the layers, when present alone, may have a hardness of less than 600 Vickers as measured in accordance with ASTM E384-17.

[0058] Although the various layers and substrates are described below with reference to Figures 1-12 as having flat surfaces, flat surfaces are not necessary and may in some cases be undesirable. For example, the substrate (or any or both of the layers) may have a rough surface, or may be intentionally roughened, or may be intentionally smoothed as desired. As an example, the substrate may have a textured surface including a transfer texture, and a partial or complete replica of the transfer texture is to be transferred to other objects that come into contact with such a surface having the transfer texture. In one embodiment, such a surface may be part of an article or device that comes into contact with another material during use or movement. For example, a steel work roll used in a cold rolling process, where the surface of the work roll has a particular transfer texture that can be transferred to a steel sheet during the rolling process. Another example is a steel work roll as described in the previous embodiment, where the transfer texture is created using electrical discharge texturing (EDT). Another embodiment is a work roll used in a hot rolling process. In another embodiment, the transfer texture can be part of a mold designed to transfer the texture to another object. In one embodiment, the texture is transferred to metal. In one embodiment, the texture is transferred to a polymer, hi one embodiment, the texture is transferred to a molten metal that subsequently solidifies, hi one embodiment, the texture is transferred to a liquid or fluid that subsequently solidifies.

[0059] In another embodiment, the surface may have an adhesive roughness designed to enhance adhesion between such surface and another surface or coating applied thereon. In one embodiment, the adhesive texture is used to enhance adhesion of the substrate to a thermal spray coating. In another embodiment, the adhesive texture is used to enhance adhesion of a coating that includes the surface tungsten. In another embodiment, the adhesive layer is used to enhance adhesion of the coating compared to one or a combination of nitrides, nitrides, metal carbides, carbides, borides, tungsten, tungsten carbide, tungsten alloys, tungsten compounds, stainless steel, ceramics, chromium, chromium carbide, chromium oxide, chromium compounds, aluminum oxide, zirconia, titania, nickel, nickel carbide, nickel oxide, nickel alloys, cobalt compounds, cobalt alloys, cobalt phosphorus alloys, molybdenum, molybdenum compounds, nanocomposites, oxide composites.

[0060] In another embodiment, roughness is added to affect light reflection. In one embodiment, the surface roughness is modified to have a lower roughness. In one embodiment, the surface roughness Ra may be modified to less than 1 μm. In another embodiment, the surface roughness is modified to less than 0.5 um. In one embodiment, the surface with modified roughness is shiny. In another embodiment, the surface with modified roughness is exposed and requires human touch. In another embodiment, the surface reflects less light and is less shiny. In one embodiment, the contact angle of water on the surface with modified roughness is less than the original surface.

[0061] In certain embodiments, the roughness may have irregular shapes or respective patterns. In certain embodiments, the roughness Ra of the coated surface is less than 1 μm. In other embodiments, the roughness Ra of the coated surface is greater than 1 μm and less than 10 μm. In other embodiments, the roughness Ra of the coated surface is greater than 10 μm and less than 100 μm, and in other embodiments, the Ra of the surface is less than 0.7. In some embodiments, Ra is less than 0.5 μm and greater than 0.05 μm. In other embodiments, Ra is less than 0.5 μm. In other embodiments, Ra is less than 0.4 um. In other embodiments, Ra is less than 0.3 um. In other embodiments, Ra is less than 0.2 um. In other embodiments, Ra is less than 0.1 um. In another embodiment, the pattern is created using grinding, blasting, sand blasting, abrasive blasting, sand blasting, burnishing, grinding, honing, mass finishing, tumbling, barrel finishing, polishing, buffing, lapping, electrochemical etching, chemical etching, laser etching, laser patterning, or other methods. In another method, shot blasting (SB), laser beam texturing (LBT) and discharge texturing (EDT) are used to texture the surface, or electron beam texturing (EBT) is being evaluated. Discharge texturing (EDT) can be used on steel substrates to create texture. Electrochemical deposition techniques can be used to form the texture. The texture can be formed using thermal spray techniques. The cross section of the pattern can have a specific geometric shape, such as a rectangle, triangle, star, circle, or combinations thereof. The pattern can be a ridge, pillar, spiral, combinations thereof, or other shapes. Ra can be greater than 100um. The pattern can be created using cutting, milling, molding, and / or other tools.

[0062] Certain embodiments are described in more detail below with reference to coatings or layers. Coatings or layers may include a single material, a combination of materials, an alloy, a composite, or other materials and compositions described herein. In embodiments where a layer refers to a metal alloy, the metal alloy may include two or more materials, e.g., two or more metals. In some configurations, one metal may be present in the layer at 79% or more by weight, and the other material may be present in the layer at 21% or less by weight. For example, one of the layers described herein may include a molybdenum alloy, a tungsten alloy, or a nickel alloy. One material may be present in the layer at 79% or more by weight, and the other material may be present in the layer at 21% or less by weight. When the metal alloy includes molybdenum, the molybdenum may be present in the layer at 21% or less by weight, or at 79% or more by weight, and other material(s) may be present, so that the total weight percentages add up to 100% by weight. Alternatively, the other material(s) may be present in the layer at 79% or more by weight, and molybdenum may be present in the layer at 21% or less by weight. One or more of the layers may also contain another metal or metal alloy. Trace amounts of impurities may also be present that add negligible weight to the overall alloy layer or surface coating.

[0063] The exact amount of each material present may be selected to provide a layer or article with the desired performance specifications. The weight percentages may be based on the weight of the entire alloy layer or surface coating. In some embodiments, one metal in a layer is present in the layer at 35% or less by weight, for example, 34%, 33%, 32%, 31%, 30%, 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or less by weight in the layer or coating. For example, one or more of molybdenum, tungsten or cobalt can be present in the layer or coating at 35% by weight or less, for example, 25%, 24%, 23%, 33%, 31%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1% or less in the layer or coating. In other configurations, one or more layers can include a metal present in the layer at 65% or more by weight, for example, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 81% by weight, 82% by weight, 83% by weight, 84% by weight, 85% by weight, 85% by weight, 87% by weight, 88% by weight, 89% by weight, 90% by weight, 91% by weight, 92% by weight, 93% by weight, 94% by weight, 95% by weight, 96% by weight, 97% by weight, 98% by weight, 99% by weight or more by weight in the layer or coating. For example, nickel can be present in the layer or coating at 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 85% by weight, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more by weight of the alloy layer or surface coating.Alternatively, molybdenum can be present in the layer or coating at 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 85% by weight, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more by weight of the alloy layer or surface coating.

[0064] In some embodiments, the alloy layer described herein may be present without precious metals. The term "precious metal" refers to gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. For example, the alloy layer (and / or the overall surface coating) may be free of (none of) each of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. Omission of precious metals may reduce overall costs.

[0065] In certain embodiments, when nickel is present in a metal alloy layer, it can be present without tungsten or cobalt in the same layer. For example, when a layer includes a nickel alloy, the layer has neither tungsten nor cobalt, e.g., there is 0 wt.% cobalt or tungsten. The layer can also have 0 wt.% precious metal.

[0066] In certain examples, the alloy layer may include non-metallic materials and additives as desired. For example, particles, nanoparticles, nanomaterials, or other materials may be present in the metal alloy layer, including one or more of polytetrafluoroethylene (PTFE), SiC, SiO2, diamond, graphite, graphene, boron, borides, functionalized silicon particles, fluorosilicones, siloxanes, TiO2, nanotubes, and nanostructures. Additional materials are described in more detail below.

[0067] In some examples, one of the metals of the layers described herein is nickel, such as nickel, nickel alloys, nickel compounds, nickel composites, nickel-phosphorus alloys, nickel-molybdenum alloys, nickel-molybdenum-phosphorus alloys, nickel-cobalt alloys, nickel-tungsten alloys, nickel-cobalt-phosphorus alloys, nickel-tungsten-phosphorus alloys, nickel alloys containing only nickel and molybdenum, nickel alloys containing at least nickel and a transition metal, nickel alloys containing at least two metals other than a precious metal, nickel alloys containing at least nickel and a refractory metal other than a precious metal, nickel alloys containing at least nickel and a refractory metal other than tungsten, nickel alloys containing at least a few metals other than a precious metal, nickel alloys containing at least nickel and a refractory metal other than tungsten, Nickel alloys comprising at least nickel and a refractory metal excluding tungsten and any precious metal, nickel alloys comprising at least nickel and excluding cobalt and precious metals, composite alloys containing nickel and particles, composite alloys containing nickel and nanoparticles, composite alloys containing nickel and SiO2, SiC or other silicon compounds, composite alloys containing nickel and borides, bromine nitrides or other boron compounds, composite alloys containing nickel and PTFE or other fluorine compounds, composite alloys containing nickel, molybdenum and chromium, chromium carbides, chromium oxides or other chromium compounds may be present in one or more layers described herein.

[0068] In certain embodiments, one of the metals of the alloy layer described herein is molybdenum, for example, molybdenum, molybdenum alloys, molybdenum composites, molybdenum tin alloys, alloys including at least molybdenum and nickel, alloys including at least molybdenum and tin, alloys including at least molybdenum and cobalt, alloys including at least molybdenum and phosphorus, alloys including only nickel and molybdenum, alloys including only tin and molybdenum, alloys including only cobalt and molybdenum, alloys including only nickel, molybdenum and phosphorus, molybdenum alloys including at least two metals other than noble metals, molybdenum alloys including at least molybdenum and a transition metal, and alloys including at least molybdenum and a noble metal. Molybdenum alloys containing a transition metal other than molybdenum alloys, molybdenum alloys containing at least two metals excluding substances of very high concern under European legislation, composite alloys containing molybdenum and particles, composite alloys containing molybdenum and soft particles, composite alloys containing molybdenum and nanoparticles, composite alloys containing molybdenum and SiO2, SiC or other silicon compounds, composite alloys containing molybdenum and borides, bromine nitrides or other boron compounds, composite alloys containing molybdenum and PTFE or other fluorine compounds, composite alloys containing molybdenum and chromium, chromium carbides, chromium oxides or other chromium compounds may be present in one or more of the layers described herein.

[0069] In another embodiment, one of the metals of the alloy layer described herein is cobalt, for example, cobalt, cobalt alloys, cobalt compounds, cobalt composites, cobalt-phosphorus alloys, cobalt-molybdenum alloys, cobalt-molybdenum-phosphorus alloys, cobalt-tungsten alloys, cobalt-tungsten-phosphorus alloys, cobalt alloys containing only cobalt and molybdenum, cobalt alloys containing at least cobalt and a transition metal, cobalt alloys containing at least two metals excluding precious metals, cobalt alloys containing at least cobalt and a refractory metal excluding precious metals, cobalt alloys containing at least cobalt and a refractory metal excluding tungsten, at least cobalt alloys containing at least cobalt and a heat-resistant metal other than tungsten and a precious metal; cobalt alloys containing at least cobalt and nickel and a precious metal other than the cobalt; composite alloys containing cobalt and particles; composite alloys containing cobalt and nanoparticles; composite alloys containing cobalt and SiO2, SiC or other silicon compounds; composite alloys containing cobalt and a boride, bromine nitride or other boron compound; composite alloys containing cobalt and PTFE or other fluorine compounds; and composite alloys containing cobalt, molybdenum, and chromium, chromium carbide, chromium oxide or other chromium compounds.

[0070] In some embodiments, one of the metals of the alloy layer described herein is tin. For example, tin, tin alloys, tin compounds, tin composites, tin-phosphorus alloys, tin-molybdenum alloys, tin-molybdenum-phosphorus alloys, tin-tungsten alloys, tin-tungsten-phosphorus alloys, tin alloys containing only tin and molybdenum, tin alloys including at least tin and a transition metal, tin alloys including at least two metals other than precious metals, tin alloys including at least tin and a refractory metal other than precious metals, tin alloys including at least tin and a refractory metal other than tungsten ... tin alloys containing tin and a heat-resistant metal other than tin and a precious metal, tin alloys containing at least tin and excluding nickel and a precious metal, composite alloys containing tin and particles, composite alloys containing tin and nanoparticles, composite alloys containing tin and SiO2, SiC or other silicon compounds, composite alloys containing tin and a boride, bromine nitride or other boron compound, composite alloys containing tin and PTFE or other fluorine compounds, composite alloys containing tin, molybdenum and chromium, chromium carbide, chromium oxide or other chromium compounds.

[0071] In another embodiment, one of the metals of the alloy layer described herein is tungsten.For example, tungsten, tungsten alloy, tungsten compound, tungsten composite, tungsten-phosphorus alloy, tungsten-molybdenum alloy, tungsten-molybdenum-phosphorus alloy, tungsten alloy containing only tungsten and molybdenum, tungsten alloy containing at least tungsten and transition metal, tungsten alloy containing at least two metals except precious metal, tungsten alloy containing at least tungsten and refractory metal except precious metal, tungsten alloy containing at least tungsten and nickel and precious metal except, composite alloy containing tungsten and particles, composite alloy containing tungsten and nanoparticles, composite alloy containing tungsten and SiO2, SiC or other silicon compounds, composite alloy containing tungsten and boride, bromine nitride or other boron compounds, composite alloy containing tungsten and PTFE or other fluorine compounds, composite alloy containing tungsten, molybdenum and chromium, chromium carbide, chromium oxide or other chromium compounds.

[0072] In certain embodiments, one or more of the alloy layers described herein may be considered a "hard" layer. A hard layer typically has a higher Vickers hardness than the substrate and / or any underlayers. Although not required, a hard layer is usually present as an outer layer. In some embodiments, the hard layer may include one or more of nitrides, metal nitrides, carbides, metal carbides, borides, metal borides, tungsten, tungsten carbide, tungsten alloys, tungsten compounds, stainless steel, ceramics, chromium, chromium carbide, chromium oxide, chromium compounds, aluminum oxide, zirconia, titania, nickel, nickel carbide, nickel oxide, nickel alloys, cobalt compounds, cobalt alloys, cobalt phosphorus alloys, molybdenum, molybdenum compounds, nanocomposites, oxide composites, or combinations thereof.

[0073] In certain embodiments, a simplified diagram of a substrate and an alloy layer of a surface coating is shown in FIG. 1. The article or device 100 includes a substrate 105 (which is shown in cross section in FIG. 1) and a first layer 110 on a first surface 106 of the substrate 105. Although not shown, layers or coatings may also be present on surfaces 107, 108, and 109 of the substrate 105. The layer 110 is shown in FIG. 1 as a solid layer having a uniform thickness present across the surface 106 of the substrate 105. This configuration is not required, and different regions of the layer 110 may include different thicknesses or even different materials. Additionally, certain regions of the surface 106 may not include a surface coating at all. In some embodiments, the substrate 105 may be or include a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, etc.), copper, copper alloys, aluminum, aluminum alloys, chromium, chromium alloys, nickel, nickel alloys, titanium, titanium alloys, nickel-chromium superalloys, nickel-molybdenum alloys, brass, Hastelloy, Inconel, Nichrome, Monel, other substrates including at least one metal, or substrates that have been nitrided or carburized. In some embodiments, the substrate may be porous or non-porous. The layer 110 typically includes one or more metals, or two or more metals, or three or more metals or materials. For example, the layer 110 may be a metal alloy formed from two or more metals. In some embodiments, the layer 110 is an alloy layer formed from only two metals or two materials. In some examples, the layer 110 is the only layer present in the surface coating. In certain examples, layer 110 is an outer or exposed layer such that the layer can contact surrounding fluids or other materials and protect the underlying substrate 105 and any layers between layer 110 and substrate 105.

[0074] In some embodiments, one of the metals in layer 110 is nickel. In other embodiments, one of the metals in layer 110 is molybdenum. In other embodiments, one of the metals in layer 110 is tungsten. In other embodiments, one of the metals in layer 110 is cobalt. In additional embodiments, one of the metals in layer 110 is molybdenum in the form of a molybdenum alloy. In other embodiments, layer 110 can include a nickel alloy, a molybdenum alloy, a cobalt alloy, a tungsten alloy, or combinations thereof. In other examples, layer 110 can be a nickel molybdenum alloy. In certain configurations, layer 110 can be comprised of a nickel molybdenum alloy with no other materials present in layer 110. In some configurations, layer 110 can include a nickel molybdenum phosphorus alloy. In some configurations, layer 110 can be comprised of a nickel molybdenum phosphorus alloy with no other materials present in layer 110.

[0075] In some configurations, the exact thickness of layer 110 can vary from 1 micron to about 2 mm depending on the device in which it is present. For example, layer 110 can have a thickness of about 5 microns to about 1 mm, or about 7 microns to about 900 microns. If there are multiple layers in the surface coating, each layer may have a thickness of 1 micron to about 2 mm, or the total thickness of all layers may be from about 1 micron to about 2 mm.

[0076] In certain embodiments, layer 110 can also include other materials, such as particles, fibers, non-metals (e.g., phosphorus, boron, boron nitride, silicon compounds such as silicon dioxide, silicon carbide, etc.), aluminum oxide, molybdenum disulfide, carbon fibers, carbon nanotubes, cobalt, tungsten, tin, gold, platinum, silver, and combinations thereof. The particles can be soft particles, such as polymer particles, PTFE particles, fluoropolymers, and other soft particles. The particles can be hard particles, such as diamond, boron, boron nitride, etc., silicon compounds such as silicon dioxide, silicon carbide, etc. The particles can be hydrophobic or hydrophilic. Hydrophobic particles, such as PTFE particles, Teflon particles, fluoropolymers, silicon-based particles, hard particles functionalized with hydrophobic, hydrophilic, or both groups. For example, silicon dioxide or silicon carbide functionalized with fluoro compounds, molecules containing fluorine, silicon compounds, molecules containing silicon, and other polymers. Other particles such as titanium dioxide, and other catalysts can be similarly functionalized or used as is.

[0077] In other configurations, layer 110 is selected from the group consisting of nickel molybdenum alloys, nickel molybdenum alloys having a weight percent of molybdenum less than 35% by weight, nickel molybdenum phosphorus alloys having a weight percent of molybdenum less than 35% by weight, ductile alloys of refractory metals and nickel, ductile alloys of nickel and molybdenum, brittle alloys of refractory metals and nickel, ductile alloys of nickel and molybdenum, brittle alloys of transition metals and molybdenum, ductile alloys of transition metals and molybdenum, alloys of nickel and molybdenum having a hardness less than 1100 Vickers and greater than 500 Vickers, Nickel-molybdenum alloys providing a surface roughness Ra of less than 1 micrometer, nickel-molybdenum alloys with uniform and non-uniform grain size, nickel-molybdenum alloys with an average grain size of less than 2 microns, conformal nickel-molybdenum alloys, alloys of nickel, molybdenum and phosphorus, alloys of cobalt and molybdenum, alloys of cobalt, molybdenum and phosphorus, alloys of nickel, molybdenum and tungsten, alloys of nickel with materials having a lower magnetic property than nickel, alloys of molybdenum with materials having a lower hardness than molybdenum, co-alloys of refractory metals and nickel alloys, ductile alloys of nickel-molybdenum, ductile alloys of nickel-tungsten, brittle alloys of nickel-tungsten, ductile alloys of nickel-cobalt, brittle alloys of nickel-cobalt, alloys of nickel and materials more heat resistant than nickel, nickel-molybdenum alloys, which do not include heat resistant metals, precious metals, hard particles, soft particles, hydrophobic particles, hydrophilic particles, catalytic action, materials more conductive than nickel, materials more conductive than molybdenum, materials softer than nickel, materials harder than nickel but not harder than molybdenum, or phosphorus, boron, boron nitride, silicon carbide , nickel-molybdenum alloys, refractory metals, precious metals, hard particles, materials more conductive than nickel, materials more conductive than molybdenum, materials softer than nickel, or other compounds such as phosphorus, boron, boron nitride, silicon carbide, silicone oxide, aluminum oxide, molybdenum disulfide, hard particles with a HV hardness greater than 750 Vickers, and / or hard particles with a size less than 1 micron,and / or other compounds including, but not limited to, hard particles less than 1 micron in size.

[0078] In some cases, the layer 110 on the substrate 105 may include nickel tungsten alloys or nickel tungsten alloys containing a third element including, but not limited to, elements that are refractory metals, precious metals, hard particles, or other compounds such as phosphorus, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, hard particles with a hardness of HV>750, hard particles less than 500 nm in size, highly conductive particles, carbon nanotubes and / or carbon nanoparticles. Combinations of these materials may also be present in the layer 110 on the substrate 105.

[0079] In some embodiments, a simplified diagram of another device is shown in FIG. 2. In this figure, the article or device 200 includes an intermediate layer 210 between the layer 110 and the underlying substrate 105. In some examples, the intermediate layer 210 can improve adhesion, improve corrosion, brighten the coating, or any combination thereof. For example, nickel, nickel alloys, copper alloys, nickel compounds, nickel composites, nickel-phosphorus alloys, nickel-molybdenum alloys, nickel-molybdenum-phosphorus alloys, nickel-cobalt alloys, nickel-tungsten alloys, nickel-cobalt-phosphorus alloys, copper, nickel-tungsten-phosphorus alloys, copper alloys, copper composites, tin, tin alloys, tin composites, cobalt, cobalt alloys, cobalt composites, cobalt-molybdenum alloys, cobalt-tungsten alloys, cobalt-molybdenum-phosphorus alloys, cobalt-tungsten alloys, cobalt-tungsten-phosphorus alloys, molybdenum, molybdenum alloys, molybdenum composites, and other metals, except precious metals. Nickel alloys containing at least two metals, molybdenum alloys containing at least two metals excluding precious metals, molybdenum alloys containing at least molybdenum and a transition metal, molybdenum alloys containing at least molybdenum and a transition metal excluding precious metals, metallic tungsten alloys, nickel alloys containing at least nickel and a refractory metal, nickel alloys containing at least nickel and a refractory metal (excluding precious metals), molybdenum-tin alloys, tungsten alloys, tungsten composites, or other materials may be present as layer 110 between layer 210 and substrate 105 to improve adhesion between layer 210 and layer 110. Such layers may be less than 10 um, 9 um, 8 um, 7 um, 2 um, 1 um, 0.75 um, 0.5 um, or 0.25 um thick. As discussed herein, in some cases, layer 210 may be a strike layer, such as a nickel layer, added to substrate 105 to improve adhesion between substrate 105 and layer 110.

[0080] In certain configurations, layer 210 can act as a brightener to enhance the overall glossy appearance of article or device 200. A glossy or semi-glossy layer generally reflects a higher percentage of light than layer 110. For example, nickel, nickel alloys, copper alloys, nickel compounds, nickel composites, nickel-phosphorus alloys, nickel-molybdenum alloys, nickel-molybdenum-phosphorus alloys, nickel-cobalt alloys, nickel-tungsten alloys, nickel-cobalt-phosphorus alloys, copper, nickel-tungsten-phosphorus alloys, copper alloys, copper composites, tin, tin alloys, tin composites, cobalt, cobalt alloys, cobalt composites, cobalt-molybdenum alloys, cobalt-tungsten alloys, cobalt-molybdenum-phosphorus alloys, cobalt-tungsten-phosphorus alloys, molybdenum, molybdenum alloys, molybdenum composites. A metal, a nickel alloy comprising at least two metals excluding precious metals, a molybdenum alloy comprising at least two metals excluding precious metals, a molybdenum alloy comprising at least molybdenum and a transition metal, a molybdenum alloy comprising at least molybdenum and a transition metal excluding precious metals, a metallic tungsten alloy, a nickel alloy comprising at least nickel and a transition metal, a nickel alloy comprising at least nickel and a refractory metal excluding precious metals, a tungsten alloy, a tungsten composite, or other material may be present as layer 110 between layer 210 and substrate 105 to brighten the overall coating appearance.

[0081] In other configurations, layer 210 may act to increase the corrosion resistance of article or device 200 . For example, nickel, nickel alloys, copper alloys, nickel compounds, nickel composites, nickel-phosphorus alloys, nickel-molybdenum alloys, nickel-molybdenum-phosphorus alloys, nickel-cobalt alloys, nickel-tungsten alloys, nickel-cobalt-phosphorus alloys, copper, nickel-tungsten-phosphorus alloys, copper alloys, copper composites, tin, tin alloys, tin composites, cobalt, cobalt alloys, cobalt composites, cobalt-molybdenum alloys, cobalt-tungsten alloys, cobalt-molybdenum-phosphorus alloys, cobalt-tungsten alloys, cobalt-tungsten-phosphorus alloys, molybdenum, molybdenum alloys, molybdenum composites, molybdenum-tin alloys, alloys containing at least molybdenum and nickel, alloys containing at least molybdenum and tin, alloys containing at least molybdenum and cobalt, composites containing molybdenum and particles, composites containing molybdenum and soft particles, composites containing molybdenum and nanoparticles, A composite, a composite including molybdenum and hard particles, a nickel alloy including at least two metals excluding precious metals, a molybdenum alloy including at least two metals excluding precious metals, a molybdenum alloy including at least molybdenum and a transition metal, a molybdenum alloy including at least molybdenum and a transition metal excluding precious metals, a tungsten alloy, a nickel alloy including at least nickel and a transition metal, a nickel alloy including at least nickel and a refractory metal excluding precious metals, a nickel alloy including at least nickel and a refractory metal excluding tungsten, a nickel alloy including at least nickel and a refractory metal excluding tungsten and precious metals, a tungsten alloy, a tungsten composite, a tungsten alloy excluding an alloy containing both nickel and tungsten, chromium, a chromium compound, or other material may be present as layer 110 between layer 210 and substrate 105 to enhance corrosion resistance.

[0082] In some embodiments, the substrate 105 used with the intermediate layer 210 can be or include a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate can be porous or non-porous. In certain embodiments, the layer 210 can include one or more materials selected from the group consisting of Group II materials, Group III materials, Group IV metals, Group V metals, Group VI metals, and Group VII metals. In some examples, the layer 210 does not include a precious metal. In other examples, the layer 210 includes only a single metal, but may include other non-metallic materials.

[0083] In certain embodiments, the layer 110 used with the intermediate layer 210 typically includes one or more metals or two or more metals. For example, the layer 110 used with the intermediate layer 210 can include any of the materials and configurations described with reference to FIG. 1. The layer 210 used with the layer 110 is, for example, a metal alloy consisting of two or more metals. In some embodiments, one of the metals in the layer 110 used with the intermediate layer 210 is nickel. In other embodiments, one of the metals in the layer 110 used with the intermediate layer 210 is molybdenum. In additional embodiments, one of the metals in the layer 110 used with the intermediate layer 210 is tungsten. In additional embodiments, one of the metals in the layer 110 used with the intermediate layer 210 is cobalt. In additional embodiments, one of the metals in the layer 110 used with the intermediate layer 210 is chromium. In some embodiments, the layer 110 used with the layer 210 can include only two metals or two materials or three metals or three materials. For example, layer 110 used with layer 210 may include only nickel and molybdenum, or only nickel, molybdenum and phosphorous, or only nickel and tungsten, or only nickel and cobalt, or only nickel, phosphorous and iron, or only nickel and phosphorous.

[0084] In other embodiments, the layer 110 used with the intermediate layer 210 may include a nickel alloy, a molybdenum alloy, a tungsten alloy, a cobalt alloy, a chromium alloy, or a combination thereof. In other examples, the layer 110 used with the intermediate layer 210 may be a nickel-cobalt alloy, a nickel-tungsten alloy, a nickel-phosphorus alloy, a cobalt, a cobalt-molybdenum alloy, a cobalt-tungsten alloy, a cobalt-phosphorus alloy, a nickel-molybdenum-phosphorus alloy, a cobalt-molybdenum-phosphorus alloy, a cobalt-tungsten-phosphorus alloy, a chromium, a chromium alloy, a molybdenum-tin alloy, or a chromium compound. In certain configurations, the layer 110 used with the intermediate layer 210 may be comprised of a nickel-molybdenum alloy with no other materials present in the layer 110. In other configurations, the layer 110 used with the intermediate layer 210 may be comprised of a nickel-molybdenum-phosphorus alloy with no other materials present in the layer 110. In other configurations, the layer 110 used with the intermediate layer 210 may be made of a cobalt-molybdenum alloy with no other materials present in the layer 110. In other configurations, the layer 110 used with the intermediate layer 210 may be made of a cobalt-molybdenum-phosphorus alloy with no other materials present in the layer 110. In other configurations, the layer 110 used with the intermediate layer 210 may be made of a nickel alloy including at least two metals, excluding precious metals. In other configurations, the layer 110 used with the intermediate layer 210 may be made of a molybdenum alloy including at least two metals, excluding precious metals. In other configurations, the layer 110 used with the intermediate layer 210 may be made of a molybdenum alloy including at least molybdenum and a transition metal. In other configurations, the layer 110 used with the intermediate layer 210 may be made of a molybdenum alloy including at least molybdenum and a transition metal, excluding precious metals. The exact thickness of layer 110 used with intermediate layer 210 can vary from 1 micron to about 2 mm, depending on the article in which layer 110 is present. For example, layer 110 may be from about 10 microns to about 200 microns thick. Similarly, the thickness of intermediate layer 210 may be from 0.1 microns to about 2 mm, such as from about 1 micron to about 20 microns. The thickness of layer 210 may be less than the thickness of layer 110 or may be greater than the thickness of layer 110.

[0085] In another configuration, there may be two or more layers on an underlying substrate. With reference to FIG. 3, an article or device 300 is shown that includes a first layer 110 and a second layer 320 on a substrate 105. The order of layers 110, 320 may be reversed, so that layer 320 is closer to substrate 105, if desired. Layers 110, 320 may include the same or different materials, or may include similar materials deposited in different ways or under different conditions. For example, layers 110, 320 of FIG. 3 may independently be any of the materials described herein, for example, any of the materials described with reference to the layers of FIG. 1 or FIG. 2. In some configurations, layers 110, 320 may each be an alloy layer. For example, each of layers 110, 320 may include one or more of nickel, copper, molybdenum, cobalt, or tungsten. The layers may be formed in similar or different ways. For example, layer 110 may be electrodeposited under basic conditions, and layer 220 may be electrodeposited under acidic conditions. As another example, layers 110, 320 may each independently comprise nickel, copper, molybdenum, cobalt, or tungsten, but layer 110 may be electrodeposited under basic conditions and layer 220 may be deposited using physical vapor deposition techniques, chemical vapor deposition, atomic layer deposition, thermal spray techniques, or other methods. Layers 110, 320 may comprise metals other than copper, such as nickel, molybdenum, cobalt, tungsten, tin, etc., or nonmetals, or both. Different conditions may provide different overall structures for layers 110, 320, even when similar materials are present. In certain configurations, layer 110 may improve the adhesion of layer 320. In other configurations, layer 110 may "brighten" the surface of device 300, so that device 300 has a shinier overall appearance.

[0086] In some embodiments, the substrate 105 used with the layers 110, 320 can be or include a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 105 can be porous or non-porous. The layers 110, 320 typically include one or more metals or two or more metals, respectively. For example, the layers 110, 320 can be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the layers 110, 320 is nickel. In other embodiments, one of the metals in the layers 110, 320 is molybdenum. In additional embodiments, one of the metals in the layers 110, 320 is cobalt. In additional embodiments, one of the metals in the layers 110, 320 is tungsten. The layers 110, 320 need not have the same metal, and it is desirable for the metals in the layers 110, 320 to be different. In other embodiments, the layers 110, 320 can independently comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the layers 110, 320 can independently comprise a nickel-molybdenum alloy, a nickel-molybdenum-phosphorus alloy, a tungsten alloy, a nickel-tungsten alloy, or the like. In certain configurations, one or both of the layers 110, 320 can be comprised of a nickel-molybdenum alloy with no other materials present in each layer. In certain configurations, one or both of the layers 110, 320 can be comprised of a nickel-molybdenum alloy with no other materials present in each layer. In some configurations, both layers 110, 320 may be comprised of a nickel-molybdenum-phosphorus alloy with no other materials present in each layer. In other configurations, one or both of layers 110, 320 may be comprised of a nickel alloy including at least nickel and a transition metal. In other configurations, one or both of layers 110, 320 may be comprised of a nickel alloy including at least nickel and a transition metal excluding noble metals.In other configurations, one or both of layers 110, 320 may be comprised of a molybdenum alloy containing at least molybdenum and a transition metal. In other configurations, one or both of layers 110, 320 may be comprised of a molybdenum alloy containing at least molybdenum and a transition metal excluding noble metals. The exact thickness of layers 110, 320 may vary from 0.1 microns to about 2 mm depending on the device in which the coating is present, and layers 110, 320 need not be the same thickness. Layer 110 may be thicker or thinner than layer 320.

[0087] In certain configurations, an intermediate layer may be present between the first layer 110 and the second layer 320. The intermediate layer may include, for example, any of the materials described with reference to layer 210 herein. Alternatively, when the coating includes the first layer 110 and the second layer 120, an intermediate layer may be present between the substrate 105 and layer 110. In some embodiments, layer 320 may have a higher hardness than layer 110. For example, the hardness of layer 320 may be greater than 750 Vickers. In certain embodiments, layer 320 may include one or more of a nitride, a metal nitride, a carbide, a metal carbide, a boride, a metal boride, tungsten, tungsten carbide, a tungsten alloy, a tungsten compound, stainless steel, a ceramic, chromium, chromium carbide, chromium oxide, a chromium compound, aluminum oxide, zirconia, titania, nickel, nickel carbide, nickel oxide, a nickel alloy, a cobalt compound, a cobalt alloy, a cobalt phosphorus alloy, molybdenum, a molybdenum compound, a nanocomposite, an oxide composite, or a combination thereof.

[0088] In other embodiments, the surface of the substrate may be treated or may include a transferred surface that has been coated or treated with one or more other layers (e.g., carburized, nitriding, carbonitriding, induction hardening, age hardening, precipitation hardening, gas nitriding, normalizing, sub-zero treatment, annealing, shot peening, or chemically, thermally, or physically, or a combination thereof). With reference to FIG. 4A, an article or device 400 is shown that includes a transferred or treated surface 410 on a substrate 105. The article or device 400 also includes a layer 110 on the treated surface 410. The layer 110 can be any of the materials described herein with reference to layer 110 of FIGS. 1-3, 5A, 5B, and 12. If desired, a layer 420 can be present between the treated surface 410 and layer 110 of the device 450, as shown in FIG. 4B. The thickness of the layer / treated surface 410 may vary, for example, from about 0.1 microns to about 50 millimeters. The treated surface 410 may be harder than the underlying substrate 105 if desired. For example, the treated surface 410 may have a case hardness of 50-70 HRC. If the treated surface / layer 410 is a transferred surface, the substrate may be, but is not limited to, steel (low carbon steel, stainless steel, nitrided steel, alloy steel, low alloy steel, etc.) or other metal-based material. The exact results of the treatment may vary, and typically treatments may be performed to enhance adhesion, alter surface roughness, improve wear resistance, improve internal stresses, reduce internal stresses, alter hardness, alter lubricity, or for other reasons. The layer 110 may be used to protect the device 450 from corrosion, abrasion, heat, and other impacts. In some cases, the treated surface 410 may negatively reduce the resistance of the device 450 to corrosion, abrasion, a combination of corrosion and abrasion, heat, a combination of heat and abrasion, a combination of corrosion and heat, or other scenarios, and the layer 110 may be used to improve performance if desired.

[0089] In some embodiments, the substrate 105 of FIGS. 4A and 4B can be or include a metallic material, including, but not limited to, steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 105 can be porous or non-porous. The layer 110 of FIGS. 4A and 4B typically includes one or more metals or two or more metals, as described in connection with FIGS. 1-3, 5A, 5B, and 12 herein. For example, the layer 110 of FIGS. 4A and 4B can be a metal alloy formed from two or more metals. In some embodiments, one of the metals of the layer 110 of FIGS. 4A and 4B is nickel. In other embodiments, one of the metals of the layer 110 of FIGS. 4A and 4B is molybdenum. In additional embodiments, one of the metals of the layer 110 of FIGS. 4A and 4B is cobalt. In additional embodiments, one of the metals of the layer 110 of FIGS. 4A and 4B is tungsten. In additional embodiments, one of the metals of the layer 110 of FIGS. 4A and 4B is tin. In additional embodiments, one of the metals of the layer 110 of FIGS. 4A and 4B is chromium. In other embodiments, the layer 110 of FIGS. 4A and 4B can include a nickel alloy, a molybdenum alloy, or a combination thereof. In other embodiments, the layer 110 of FIGS. 4A and 4B can include a molybdenum alloy including at least two metals (optionally excluding a precious metal), a molybdenum alloy including at least molybdenum and a transition metal, or a molybdenum alloy including at least molybdenum and a transition metal excluding a precious metal. In other embodiments, layer 110 of Figures 4A and 4B can include a nickel alloy including at least two metals excluding precious metals, a nickel alloy including at least nickel and a refractory metal, a nickel alloy including at least nickel and a refractory metal excluding precious metals, etc. In other examples, layer 110 of Figures 4A and 4B can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy.4A and 4B may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy with no other materials present in layer 110. In other configurations, layer 110 may include any of the materials and combinations of materials described with reference to FIGS.

[0090] In certain embodiments, the exact thickness of layer 110 in Figures 4A and 4B may vary from 1 micron to about 2 mm depending on the article or device in which layer 110 resides, for example, the thickness may vary from about 5 microns to about 200 microns.

[0091] In certain embodiments, intermediate layer 420, when present as shown in Figure 4B, can improve adhesion between layer 110 and layer / surface 410. For example, copper, nickel, or other material may be present as a thin layer, e.g., 1 micron or less in thickness, between layer 110 and layer / surface 410. Although not shown, there may be two or more layers between layer / surface 410 and layer 110.

[0092] In certain embodiments, one or more layers may be present above the alloy layer 110. For example, a metal layer, a metal alloy layer, a layer with particles or composite materials, or a layer with other materials may be present above the layer 110. With reference to FIG. 5A, an article or device 500 is shown in which a layer 510 is present above the layer 110. If desired, an additional layer 560 may be present between the layers 510 and 110, as shown in FIG. 5B. The exact materials present in the layers 510, 560 may vary depending on the end use of the device 500.

[0093] In certain embodiments, the substrate 105 of FIGS. 5A and 5B can be or include a metallic material, including, but not limited to, steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 105 can be porous or non-porous. The layer 110 of FIGS. 5A and 5B typically includes one or more metals or two or more metals, as described in connection with FIGS. 1-4B and 12. For example, the layer 110 of FIGS. 5A and 5B can be a metal alloy formed from two or more metals. In some embodiments, one of the metals of the layer 110 of FIGS. 5A and 5B is nickel. In other embodiments, one of the metals of the layer 110 of FIGS. 5A and 5B is molybdenum. In additional embodiments, one of the metals of the layer 110 of FIGS. 5A and 5B is tungsten. In additional embodiments, one of the metals of the layer 110 of FIGS. 5A and 5B is cobalt. In additional embodiments, one of the metals of the layer 110 of FIGS. 5A and 5B is chromium. In other embodiments, the layer 110 of FIGS. 5A and 5B can include a nickel alloy, a molybdenum alloy, a cobalt alloy, a tungsten alloy, or a combination thereof. In other examples, the layer 110 of FIGS. 5A and 5B can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, the layer 110 of FIGS. 5A and 5B can be made of a nickel-molybdenum alloy, a nickel-molybdenum-phosphorus alloy, with no other materials present in the layer 110. In another example, layer 110 of Figures 5A and 5B may include a nickel-molybdenum-phosphorus alloy.In other configurations, the layer 110 of Figures 5A and 5B may be comprised of nickel-cobalt alloys, nickel-tungsten alloys, nickel-phosphorus alloys, cobalt, cobalt-molybdenum alloys, cobalt-tungsten alloys, cobalt-phosphorus alloys, nickel-molybdenum-phosphorus alloys, cobalt-molybdenum-phosphorus alloys, cobalt-tungsten-phosphorus alloys, chromium, chromium alloys, molybdenum-tin alloys, chromium compounds in the layer 110. In other configurations, the layer 110 of Figures 5A and 5B may be comprised of molybdenum alloys including at least two metals (optionally excluding precious metals), molybdenum alloys including at least molybdenum and a transition metal, molybdenum alloys including at least molybdenum and a transition metal excluding precious metals, molybdenum alloys including at least molybdenum, a transition metal, and phosphorus, molybdenum alloys including at least molybdenum, a transition metal, and tin, molybdenum alloy composites including some particles and nanoparticles. In other configurations, layer 110 of Figures 5A and 5B may be comprised of a nickel alloy comprising at least two metals excluding precious metals, a nickel alloy comprising at least nickel and a refractory metal, or a nickel alloy comprising at least nickel and a refractory metal excluding precious metals. The exact thickness of layer 110 in Figures 5A and 5B may vary from 0.1 microns to about 2 mm depending on the device in which layer 110 is present. In certain embodiments, layers 510, 560 may each independently be a nickel layer, a nickel molybdenum layer, a metal alloy, tin, chromium, or a combination of these materials. In certain embodiments, layer 510 may include nitrides, metal carbides, carbides, borides, tungsten, tungsten carbide, tungsten alloys, tungsten compounds, stainless steel, ceramics, chromium, chromium carbide, chromium oxide, chromium compounds, aluminum oxide, zirconia, titania, nickel, nickel carbide, nickel oxide, nickel alloys, cobalt compounds, cobalt alloys, cobalt phosphorus alloys, molybdenum, molybdenum compounds, nanocomposites, oxide composites, or combinations thereof. In certain embodiments, layer 510 may protect layer 110 from wear. In another embodiment, layer 110 may protect substrate 105 from corrosion.In another embodiment, layer 110 can protect layer 510 from delamination, chipping off, or abrasion, and in another embodiment, layer 110 can increase adhesion of layer 510 to substrate 105. In another embodiment, layer 110 can improve brightness, for example, by reflecting more light.

[0094] In other configurations, the article or device may comprise an outer metal layer and at least one underlying alloy layer. With reference to FIG. 6, several layers are shown, including layers 110, 610, and 620. To simplify the illustration, the substrate is intentionally omitted from FIGS. 6-8. The substrate is typically adjacent to layer 110, but may be adjacent to another layer if desired. Layer 110 of FIG. 6 typically comprises one or more metals as described with reference to FIGS. 1-5B and 12, or two or more metals or other materials described herein. For example, layer 110 of FIG. 6 may be a metal alloy of two or more metals. In some embodiments, one of the metals of layer 110 of FIG. 6 is nickel. In other embodiments, one of the metals of layer 110 of FIG. 6 is molybdenum. In other embodiments, layer 110 of FIG. 6 may comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 of FIG. 6 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, layer 110 of Figure 6 may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy with no other materials present within layer 110. The exact thickness of layer 110 of Figure 6 may vary from 1 micron to about 2 mm, for example from about 5 microns to about 200 microns, depending on the device in which layer 110 is present.

[0095] In certain embodiments, layer 610 of FIG. 6 typically includes one or more metals or metal alloys, such as, for example, nickel, copper, molybdenum, nickel-molybdenum, nickel-molybdenum-phosphorus, or combinations thereof. The thickness of layer 610 may typically be greater or less than the thickness of layer 110. For example, the thickness of layer 610 may vary from about 0.1 microns to about 1 micron. In some embodiments, the metal in layer 610 may be present in the form of an alloy with another metal. Layer 620 typically also includes one or more metals, such as, for example, nickel, copper, molybdenum, nickel-molybdenum, nickel-molybdenum-phosphorus, or combinations thereof. The metal in layer 620 may be present in the form of an alloy or non-alloy, and may be present at a thickness greater or less than the thickness of layer 610. For example, layer 620 may be present at a thickness of about 0.1 microns to about 0.5 microns. In some embodiments, layer 620 may provide increased wear resistance, increased electrical conductivity, a glossier surface, and the like. In some configurations, layers 610, 620 can include the same material, but the material may be present in different amounts. For example, each of layers 610, 620 can be a nickel-molybdenum alloy, but the amount of molybdenum in layer 610 is different from the amount of molybdenum in layer 620.

[0096] In certain embodiments, layer 110 as described herein with reference to Figures 1-6 may be present between two incompatible materials to allow the incompatible material to be present in a coating or device. The term "incompatible" generally refers to materials that do not readily bond or adhere to one another or have incompatible physical properties that make them unsuitable for use together. By including a metal alloy in layer 110, it may be possible to include certain coatings in devices having a copper substrate. For example, a Ni-Mo or Ni-Mo-P alloy layer may be present between the copper substrate and another metal layer. In certain embodiments, by including layer 110 between the metal layer (or metal alloy layer) and the substrate, the overall wear resistance of the outer metal layer may be increased as well.

[0097] In certain embodiments, one or more of the layers shown in Figures 1-6 may include tin (Sn). For example, tin may provide some corrosion resistance. Referring to Figure 7, several layers are shown, including layers 110, 710, and 720. A substrate (not shown) is typically adjacent to layer 110, but may be adjacent to layer 72 if desired. Layer 110 of Figure 7 typically includes one or more metals as described with reference to Figures 1-6 and 12, or two or more metals, or other materials described herein. For example, layer 110 of Figure 7 may be a metal alloy of two or more metals. In some embodiments, one of the metals of layer 110 of Figure 7 is nickel. In other embodiments, one of the metals of layer 110 of Figure 7 is molybdenum. In other embodiments, layer 110 of Figure 7 may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 of Figure 7 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, layer 110 of Figure 7 may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy with no other materials present within layer 110. The exact thickness of layer 110 of Figure 7 may vary from 1 micron to about 2 mm, such as from about 5 microns to about 200 microns, depending on the article or device in which layer 110 resides.

[0098] In certain embodiments, layer 710 of FIG. 7 typically comprises one or more metals or metal alloys or combinations thereof. The thickness of layer 710 may be thicker or thinner than the thickness of layer 110. For example, the thickness of layer 710 may vary from about 0.1 microns to about 1 micron. In some embodiments, the metal in layer 710 may be present in the form of an alloy with another material, for example another metal. Layer 720 may comprise, for example, tin or a tin alloy, etc. The exact thickness of layer 720 may vary and may be thicker or thinner than the thickness of layer 710. For example, layer 720 may be present at a thickness of more than 5 microns, for example 10-300 microns or 10-100 microns. In some embodiments, layer 720 may be present to help keep the surface clean, may increase wear resistance, may increase electrical conductivity, may provide a shinier surface, may withstand hydraulic fluids, etc. In some configurations, layers 710, 720 may comprise the same material, but the materials may be present in different amounts. For example, each of layers 710 , 720 can be a tin alloy, but the amount of tin in layer 710 is different from the amount of tin in layer 720 .

[0099] In certain embodiments, the tin or tin alloy layer may be directly on the metal or metal alloy layer, as shown in FIG. 8. Several layers are shown, including layers 110 and 720. There are no layers between layers 110 and 720. A substrate (not shown) is typically attached to layer 110. Layer 110 of FIG. 8 typically includes one or more metals as described with reference to FIG. 1, FIG. 2, or FIG. 3, or two or more metals or other materials described herein. For example, layer 110 of FIG. 8 may be a metal alloy of two or more metals. In some embodiments, one of the metals of layer 110 of FIG. 8 is nickel. In other embodiments, one of the metals of layer 110 of FIG. 8 is molybdenum. In other embodiments, layer 110 of FIG. 8 may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 of FIG. 8 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, layer 110 of FIG. 8 may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy with no other materials present within layer 110. The exact thickness of layer 110 of FIG. 8 may vary from 1 micron to about 2 mm, for example 5 microns to 200 microns, depending on the article or device in which layer 110 is present with typical thicknesses ranging from 10 microns or less or 5 microns or less. Layer 720 may include, for example, tin or a tin alloy, etc. The exact thickness of layer 720 may vary and is typically thicker than layer 710. For example, layer 720 may be present at a thickness greater than 5 microns, for example 10 to 500 microns or 10 to 200 microns. In some embodiments, layer 720 may be present to help keep the surface clean, may increase wear resistance, may increase electrical conductivity, may provide a shinier surface.

[0100] In certain embodiments, the tin layer described with reference to Figures 7 and 8 can be replaced with a chromium layer. For example, chromium can be used to increase hardness and can also be used in a decorative layer to improve the appearance of an article or device. One or both of layers 710, 720 can be a chromium layer or a layer that includes chromium.

[0101] Referring to FIG. 9, a diagram is shown including a substrate 905 and a first layer 912. The surface of the substrate is shown as rough for illustrative purposes, and the layer 912 generally conforms to the various peaks and valleys on the surface. The thickness of the layer 912 may be the same or may be different in different areas. In some embodiments, the substrate 905 may be or may include a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 905 may be porous or non-porous. For example, the coating 912 may be a metal alloy formed from two or more metals as described with reference to layer 110 of FIGS. 1-8 and 12 or other materials described herein. In some embodiments, one of the metals in coating 912 is nickel. In other embodiments, one of the metals in coating 912 is molybdenum. In other examples, coating 912 may be a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy. In certain configurations, coating 912 may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy with no other materials present in coating 912. The exact thickness of coating 912 may vary from 1 micron to about 2 mm, such as from about 5 microns to about 200 microns, depending on the article or device in which coating 912 is present. The exact function of layer 912 may vary, but as will be further described below, the roughened surface of layer 912 and substrate 905 may provide a texture that makes the surface more likely to scatter light or less likely to exhibit fingerprints.

[0102] In certain embodiments, there may be one or more layers between the substrate 905 and the layer 912. For example, there may be one or more intermediate layers between the substrate 905 and the layer 912. In some cases, the intermediate layer may improve adhesion between the layer 912 and the substrate 905. For example, copper, nickel, or other materials may be present as a thin layer, for example, 1 micron or less in thickness, between the coating 912 and the substrate 905. In certain configurations, the intermediate layer(s) may function as a brightener to increase the overall glossy appearance of the article or device surface. In other configurations, the intermediate layer may act to increase the corrosion resistance of the coating. In some embodiments, the substrate 905 used with the intermediate layer may be or may include a metallic material, including, but not limited to, steel (carbon steel, tool steel, stainless steel, etc.), copper, copper alloys, aluminum, aluminum alloys, chromium, chromium alloys, nickel, nickel alloys, titanium, titanium alloys, nickel-chromium superalloys, nickel-molybdenum alloys, brass, plastics, polymers, or combinations thereof. The coating 912 used with the intermediate layer typically includes one or more metals or two or more metals. For example, the coating 912 used with the intermediate layer may be a metal alloy formed from two or more metals as described with reference to layer 110 of FIGS. 1-8 and 12 or other materials described herein. In some embodiments, one of the metals in the coating 912 used with the intermediate layer(s) is nickel. In other embodiments, one of the metals in the coating 912 used with the intermediate layer(s) is molybdenum. In other embodiments, the coating 912 used with the intermediate layer(s) may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 912 used with the intermediate layer(s) may be a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy. In certain configurations, the coating 912 used with the intermediate layer(s) may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy with no other materials present in the coating 912.The exact thickness of the coating 912 used in conjunction with the intermediate layer can vary from 1 micron to about 2 mm, for example from about 5 microns to about 200 microns, depending on the article or device in which the coating 912 resides.

[0103] In certain embodiments, it may be desirable to have a roughened surface layer. Referring to FIG. 10, an article or device is shown that includes a substrate 105 and a roughened surface layer 1012. The roughened surface layer 1012 can include any of the materials described in connection with layer 110. In this figure, the substrate 105 is generally smooth, and the layer 1012 may be subjected to a post-deposition process to roughen the surface layer 1012. The thickness of the layer 1012 is different in different regions. In some embodiments, the substrate 105 shown in FIG. 10 can be or include a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or non-porous. The coating 1012 typically includes one or more metals as described with reference to layer 110 of Figures 1-8 and 12, or two or more metals, or other materials described herein. For example, the coating 1012 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the coating 1012 is nickel. In other embodiments, one of the metals in the coating 1012 is molybdenum. In other embodiments, the coating 1012 may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1012 may be a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy. In certain configurations, the coating 1012 may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy with no other materials present in the coating 1012. The exact thickness of the coating 1012 may vary from 0.1 microns to about 2 mm, for example, from about 5 microns to about 200 microns, depending on the article or device in which the coating 1012 is present.The exact function of layer 1012 may vary, but as explained further below, layer 1012 may provide a texture that makes the surface more likely to scatter light or less likely to show fingerprints.

[0104] In certain embodiments, one or more layers may be present between the substrate 105 and the layer 1012. For example, one or more intermediate layers may be present between the substrate 105 and the layer 1012. In some cases, the intermediate layer may improve adhesion between the layer 1012 and the substrate 105. For example, copper, nickel, or other materials may be present as a thin layer, e.g., 1 micron or less in thickness, between the coating 1012 and the substrate 105. In certain configurations, the intermediate layer(s) may function as a brightener to increase the overall glossy appearance of the article or device. In other configurations, the intermediate layer(s) may act to increase the corrosion resistance of the article or device. In some embodiments, the substrate 105 used with the intermediate layer may be or include a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or non-porous. The coating 1012 used with the intermediate layer(s) typically includes one or more metals as described with reference to layer 110 of Figures 1-8 and 12 or two or more metals or other materials described herein. For example, the coating 1012 used with the intermediate layer(s) may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the coating 1012 used with the intermediate layer(s) is nickel. In other embodiments, one of the metals in the coating 1012 used with the intermediate layer(s) is molybdenum. In other embodiments, the coating 1012 used with the intermediate layer(s) can include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1012 used with the intermediate layer(s) can be a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy.In certain configurations, the coating 1012 used with the intermediate layer(s) may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy with no other materials present in the coating 1012. The exact thickness of the coating 1012 used with the intermediate layer may vary from 1 micron to about 2 mm, for example from about 10 microns to about 200 microns, depending on the article or device in which the coating 1012 is present.

[0105] In certain embodiments, a surface coating can be applied to the roughened surface to provide an overall smooth surface. In FIG. 11, a roughened substrate 905 is shown including a layer 1110 that fills in the peaks and valleys and provides a generally smoother outer surface. The surface layer 1110 can include any of the materials described in connection with layer 110 of FIGS. 1-8 and 12 or other materials described herein. In this illustration, the substrate 905 may be subjected to a roughening process, and the layer 1110 may be subjected to a post-deposition step, such as shot peening or other process, to smooth the surface layer 1110 if it is not smooth after deposition. The thickness of the layer 1110 is different in different areas to fill in the peaks and valleys. In some embodiments, the substrate 905 can be or include a metallic material, including, but not limited to, steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 905 can be porous or non-porous. The coating 1110 typically includes one or more metals or two or more metals as described herein in connection with the layer 110. For example, the coating 1110 can be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the coating 1110 is nickel. In other embodiments, one of the metals in the coating 1110 is molybdenum. In other embodiments, the coating 1110 can include a nickel alloy, a molybdenum alloy, or combinations thereof. In other examples, the coating 1110 may be a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy. In certain configurations, the coating 1110 may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy with no other materials present in the coating 1110.The exact thickness of coating 1110 can vary from 1 micron to about 2 mm, such as from about 5 microns to about 200 microns, depending on the article or device in which coating 1110 is present. The exact function of layer 1110 can vary, but as described further below, layer 1110 can provide a smoother or glossier surface that is more aesthetically pleasing.

[0106] In certain embodiments, one or more layers may be present between the substrate 905 and the layer 1110. For example, one or more intermediate layers may be present between the substrate 905 and the layer 1110. In some cases, the intermediate layer may improve adhesion between the layer 1110 and the substrate 905. For example, copper, nickel, or other materials may be present as a thin layer, e.g., 1 micron or less in thickness, between the coating 1110 and the substrate 905. In certain configurations, the intermediate layer(s) may function as a brightener to increase the overall glossy appearance of the article or device. In other configurations, the intermediate layer may act to increase the corrosion resistance of the coating. In some embodiments, the substrate 105 used with the intermediate layer may be or include a metallic material, including but not limited to steel (carbon steel, tool steel, stainless steel, alloy steel, low alloy steel, etc.), copper, copper alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, molybdenum, molybdenum alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, bronze, superalloy, Hastelloy, Inconel, Nichrome, Monel, or combinations thereof. In some embodiments, the substrate 105 may be porous or non-porous. The coating 1110 used with the intermediate layer typically includes one or more metals or two or more metals. For example, the coating 1110 used with the intermediate layer may be a metal alloy formed from two or more metals as described with reference to the layer 110 of Figures 1-8 and 12 or other materials described herein. In some embodiments, one of the metals in the coating 1110 used with the intermediate layer(s) is nickel. In other embodiments, one of the metals in the coating 1110 used with the intermediate layer(s) is molybdenum. In other embodiments, the coating 1110 used with the intermediate layer(s) can include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1110 used with the intermediate layer(s) can be a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy.In certain configurations, the coating 1110 used with the intermediate layer(s) may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum phosphorus alloy with no other materials present in the coating 1012. The exact thickness of the coating 1110 used with the intermediate layer(s) may vary from 0.1 microns to about 2 mm, such as from about 5 microns to about 200 microns, depending on the article or device in which the coating 1110 is present.

[0107] In certain embodiments, the devices or articles described herein may include coating a first layer, a second layer, and a third layer on a surface of a substrate. Referring to FIG. 12, an article or device 1200 includes a substrate 105, a first layer 110, a second layer 320, and a third layer 1230. Each of the layers 110, 320, and 1230 may include any of the materials described in connection with layers 110 and 320 above. In some embodiments, the layer 1230 may be a polymer coating, or a metal or non-metal based coating. The layer 110 is typically a metal alloy layer including two or more metals as described in connection with layer 110 of FIGS. 1-8 or other materials described herein.

[0108] In certain configurations, the articles and devices described herein can include a substrate having a coated surface, the coated surface comprising a surface coating. The surface coating may comprise two or more layers. For example, an alloy layer as described in connection with layer 110 may be on the surface of substrate 105, and a second layer may be on alloy layer 110. In some examples, the alloy layer may include molybdenum as described herein, e.g., molybdenum in combination with one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. The second layer is on the alloy layer and may include a ceramic or alloy, or any material that may be harder than the underlayer including molybdenum. In other examples, the alloy layer including molybdenum may be harder than the second layer, depending on the intended use of the article or device. In some embodiments, the second layer may include one or more of tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, or combinations thereof. The ceramic composite may include metal nitrides, nitrides, metal carbides, carbides, borides, tungsten, tungsten carbide, tungsten alloys, tungsten compounds, stainless steel, ceramics, chromium, chromium carbide, chromium oxide, chromium compounds, aluminum oxide, zirconia, zirconium oxide, titania, nickel, nickel carbide, nickel oxide, nickel alloys, cobalt compounds, cobalt alloys, cobalt phosphorus alloys, molybdenum, molybdenum compounds, nanocomposites, oxide composites, or combinations thereof. In some cases, the second layer may have a Vickers hardness of 600 Vickers or greater.

[0109] In other configurations, the articles or devices described herein can include a material that provides a lubricating alloy layer. For example, a substrate can include a coated surface having a smooth alloy layer. In some embodiments, the alloy layer can be formed on the substrate and can include molybdenum or other materials as described in connection with layer 110 of the figure. The weight percentage of molybdenum or other metal can be 35% by weight or less. The surface roughness Ra of the lubricating alloy layer can be less than 1 micron. In some cases, the alloy layer can also include one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some embodiments, the surface coating can include two or more layers. For example, a base layer can be present with the alloy layer formed or added to the base layer. The base layer can be an intermediate layer between the substrate and the alloy layer, or can be a free-standing layer that is self-supporting and not present on any substrate. In some examples, the base layer can include one or more of a nickel layer, a copper layer, a nickel-phosphorus layer, a nickel-molybdenum layer, or other materials. The coating on the base layer may include one or more of molybdenum, nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some cases, the alloy layer may be an exposed outer layer or may not include a precious metal. If desired, particles may also be present in one or more layers. Exemplary particles are described herein.

[0110] In certain embodiments, a surface coating comprising two or more layers comprising the same material may be present on the article described herein. Alternatively, one of the layers may be a free-standing layer that is self-supporting and not present on any substrate. For example, a first alloy layer comprising nickel and molybdenum may be present in combination with a second alloy layer comprising nickel and molybdenum. The amount of material in the different layers may be different, or the different layers may have different additives, such as different particles or other materials. In some cases, one of the layers may be rougher than the other layer by varying the amount of material in one of the layers. For example, the weight percentage of molybdenum in the second alloy layer may be less than 30% by weight, and the roughness of the entire surface coating may be less than 1 um Ra. Each of the two layers may independently comprise one or more of molybdenum, nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some cases, one of the alloy layers may not comprise a precious metal. In other examples, each of the alloy layers does not comprise a precious metal. Optionally, particles may also be present in one or more of the alloy layers. Exemplary particles are described herein.

[0111] In certain embodiments, the article can include a surface coating having an alloy layer as described herein with a chromium layer on the alloy layer. The alloy layer can include molybdenum and one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. The chromium layer can be an alloy including other metals or materials. In some examples, the chromium layer does not include a precious metal. In other examples, each of the alloy layer and the chromium layer does not include a precious metal.

[0112] In another configuration, the surface coating may include a nickel-molybdenum phosphorus (Ni-Mo-P) alloy layer. In some cases, one or more other materials may be present in the nickel-molybdenum phosphorus alloy layer. For example, one or more of tungsten, cobalt, chromium, tin, iron, magnesium, or boron may be present. Particles may also be present, if desired. The Ni-Mo-P alloy layer may contain up to 35 wt. % molybdenum in the alloy layer or in the surface coating.

[0113] In certain examples, the coating layers described herein can be applied to a substrate using any suitable method, including, but not limited to, vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel (HVOF) coating, thermal spraying, or other suitable methods.

[0114] In certain examples, one or more coating layers may be deposited using vacuum deposition. In certain embodiments, vacuum deposition generally deposits a layer of material on the surface of a substrate, either atom by atom or molecule by molecule. The vacuum deposition process can be used to deposit one or more materials having a thickness ranging from one or more atoms to several millimeters.

[0115] In certain embodiments, one or more coating layers described herein can be deposited using physical vapor deposition (PVD), a type of vacuum deposition. PVD generally uses vapors of a material to produce a thin coating on a substrate. The coatings described herein can be, for example, sputtered onto the surface of the substrate or applied onto the surface of the substrate using vapor deposition PVD. In other embodiments, one or more coating layers can be produced on the substrate using chemical vapor deposition (CVD). CVD generally involves exposing the substrate to one or more materials that react and / or decompose on the substrate's surface to provide the desired coating layer on the substrate. In other configurations, plasma deposition (PD), such as plasma accelerated chemical vapor deposition or plasma assisted chemical vapor deposition, can be used to provide a coating layer on the substrate. PD generally involves generating a plasma discharge from a reactive gas that includes the material to be deposited and / or subjecting an already deposited material to ions in the plasma gas to modify the coating layer. In another example, atomic layer deposition (ALD) can be used to provide a coating layer on a surface. In ALD, the substrate surface is exposed to repeated doses of precursors that can react with the surface of the material to build up the coating layer.

[0116] In other examples, one or more coating layers described herein can be deposited on the surface of the substrate using brushing, spin coating, spray coating, dip coating, electrodeposition (e.g., electroplating, cathodic electrodeposition, anodic electrodeposition, etc.), electroless plating, electrocoating, electrophoretic deposition, or other techniques. When an electric current is used to deposit the coating layer on the substrate, the electric current can be continuous, pulsed, or a combination of continuous and pulsed current. Certain electrodeposition techniques are described in more detail below.

[0117] In some configurations, one or more layers of the coating can be applied using electrodeposition. In general, electrodeposition uses a voltage applied to a substrate placed in a bath to form a coating on a charged substrate. For example, ionic species present in a solution can be reduced using an applied voltage to deposit the ionic species in solid form on a surface (or all surfaces) of the substrate. As described in more detail below, the ionic species can be deposited to provide a metal coating, a metal alloy coating, or a combination thereof. Depending on the exact ionic species used and the electrodeposition conditions and techniques, the resulting properties of the formed electrodeposited coating can be selected or tailored to provide a desired result.

[0118] In certain embodiments in which electrodeposition is used, the ionic species may be dissolved or solvated in an aqueous solution or water. The aqueous solution may contain suitable dissolved salts, inorganic species, or organic species to facilitate the electrodeposition of the coating layer(s) on the substrate. In other embodiments in which electrodeposition is used, the liquid used in the electrodeposition bath may be generally non-aqueous, for example, may contain more than 50% by volume of non-aqueous species, and may include hydrocarbons, alcohols, liquefied gases, amines, aromatics, and other non-aqueous materials.

[0119] Generally, an electrodeposition bath includes a species that is deposited as a coating on a substrate. For example, if nickel is deposited on the substrate, the bath can include ionic nickel or solvated nickel. If molybdenum is deposited in the substrate, the bath can include ionic molybdenum or solvated molybdenum. If an alloy is deposited on the substrate, the bath can include multiple species, for example, the bath can include ionic nickel and ionic molybdenum that are co-electrodeposited to form a nickel-molybdenum alloy as a coating layer on the substrate. The exact form of the material added to the bath to provide the ionic or solvated species can vary. For example, the species may be added to the bath as metal halides, metal fluorides, metal chlorides, metal carbonates, metal hydroxides, metal acetates, metal sulfates, metal nitrates, metal nitrites, metal chromates, metal dichromates, metal permanganates, metal platinates, metal cobalt nitrites, metal hexachloroplatinates, metal citrates, ammonium salts of metals, metal cyanides, metal oxides, metal phosphates, metal monobasic sodium phosphates, metal dibasic sodium phosphates, metal tribasic sodium phosphates, sodium salts of metals, potassium salts of metals, metal sulfamates, metal nitrites, and combinations thereof. In some instances, a single material containing both of the metal species to be deposited may be dissolved in the electrodeposition bath, e.g., a metal alloy salt may be dissolved in a suitable solution prior to electrodeposition. The particular material used in the electrodeposition bath will depend on the particular alloy layer to be deposited. Exemplary materials include, but are not limited to, nickel sulfate, nickel sulfamate, nickel chloride, sodium tungstate, tungsten chloride, sodium molybdate, ammonium molybdate, cobalt sulfate, cobalt chloride, chromium sulfate, chromium chloride, chromic acid, stannous sulfate, sodium stannate, hypophosphorous acid, sulfuric acid, nickel carbonate, nickel hydroxide, potassium carbonate, ammonium hydroxide, hydrochloric acid, or other materials.

[0120] In certain embodiments, the exact amount or concentration of the species electrodeposited on the substrate may vary. For example, the concentration of the species may vary from about 1 gram / liter to about 400 grams / liter. If necessary, as the ionic species is depleted as a result of the formation of the coating on the substrate, additional material may be added to the bath to increase the amount of the species available for electrodeposition. In some cases, the concentration of the deposited species may be maintained at a substantially constant level during electrodeposition by continuously adding material to the bath.

[0121] In certain embodiments, the pH of the electrodeposition bath may vary depending on the particular ionic species present in the bath. For example, the pH may range from 1 to about 13, although in certain cases the pH may be less than 1, or less than 0, or greater than 13, or even greater than 14. When the metal species is deposited on the substrate as a metal alloy, the pH may range from 4 to about 12, in certain instances. However, it will be appreciated that the pH may vary depending on the particular voltage and electrodeposition conditions selected for use. Several pH adjusters and buffers may be added to the bath. Examples of pH adjusters include, but are not limited to, boric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, glycine, sodium acetate, buffered saline, cacodylate buffer, citrate buffer, phosphate buffer, phosphate-citrate buffer, barbital buffer, TRIS buffer, glycine-NaOH buffer, and any combination thereof.

[0122] In certain embodiments, the alloy plating can use a complexing agent. For example, the main role of a complexing agent in the alloy deposition process is to complex different metal ions. Thus, without a suitable complexing agent, the simultaneous deposition and alloy formation of nickel and molybdenum will not occur. Examples of complexing agents include, but are not limited to, phosphates, phosphonates, polycarboxylates, zeolites, citrates, ammonium hydroxide, ammonium salts, citric acid, ethylenediaminetetraacetic acid, diethylene-triaminepentaacetic acid, aminopolycarboxylates, nitrilotriacetic acid, IDS (N-(1,2-dicarboxyethyl)-D,L-aspartic acid (iminodisuccinic acid), DS (polyaspartic acid), EDDS (N,N'-ethylenediaminedisuccinic acid), GLDA (N,N-bis(carboxylmethyl)-L-glutamic acid), and MGDA (methylglycine diacetate), hexamine cobalt(III) chloride, ethylene glycol-bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA), ferrocene, cyclodextrin, cholic acid, polymers, and any combination thereof.

[0123] In some examples, appropriate voltages can be applied to the cathode and anode of the electrodeposition bath to promote the formation of the layer(s) described herein on the substrate. In some embodiments, direct current (DC) voltages can be used. In other examples, alternating current (AC), optionally in combination with current pulses, can be used to electrodeposit the layer. For example, AC electrodeposition can be performed with AC voltage waveforms, typically sinusoidal, square, triangular, etc. High voltages and current densities can be used to promote tunneling of electrons through the oxide-based layer, which can form on the substrate. Additionally, the base layer can be conducted in the direction of the cathode, which promotes the deposition of material and avoids reoxidation during the oxidant half cycle.

[0124] In certain embodiments, an exemplary current density range that can be used for electrodeposition is 1 mA / cm 2 DC~about 600mA / cm 2 DC, more specifically, about 1 mA / cm2 DC~approx.300mA / cm 2 In some examples, the current density is 5 mA / cm 2 DC~approx.300mA / cm 2 DC, 20mA / cm 2 DC~approx. 100mA / cm 2 DC, 100mA / cm 2 DC~about 400mA / cm 2 The current may vary from about 10 seconds to several days, more specifically from about 40 seconds to about 2 hours. If desired, a pulsed current may be applied instead of a direct current.

[0125] In some instances, electrodeposition can use pulsed current or pulsed reverse current during electrodeposition of the alloy layer. In pulsed electrodeposition (PED), the potential or current is rapidly alternating between two different values. This results in a series of pulses of equal amplitude, duration and polarity, separated by zero current. Each pulse consists of an on-time (TON) during which potential and / or current is applied, and an off-time (TOFF) during which zero current is applied. By adjusting the pulse amplitude and width, it is possible to control the composition and thickness of the deposited film in atomic order. They favor the initiation of grain nuclei, greatly increasing the number of grains per unit area, resulting in finer grained deposits with better properties than conventional plated coatings.

[0126] In examples where the coating includes two or more layers, the first and second layers of the coating may be applied using the same or different electrodeposition baths. For example, the first layer may be applied using a first aqueous solution in the electrodeposition bath. After applying a voltage for a period of time sufficient to deposit the first layer, the voltage may be reduced to zero, the first solution may be removed from the bath, and a second aqueous solution containing a different material may be added to the bath. The voltage may then be reapplied to electrodeposit the second layer. In other examples, two separate baths may be used, for example a reel-to-reel process may be used, where a first bath is used to electrodeposit the first layer and a second, different bath is used to deposit the second layer.

[0127] In some cases, the individual articles may be connected such that they can be sequentially exposed to separate electrodeposition baths, such as in a reel-to-reel process. For example, the articles may be connected to a common conductive substrate (e.g., a strip). In some embodiments, each of the electrodeposition baths may be associated with a separate anode, and the interconnected individual articles may be commonly connected to a cathode.

[0128] While the exact materials used in the electroplating process can vary, exemplary materials include cations of one or more of the following metals: nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or combinations thereof. The exact anion forms of these metals can vary from chloride, acetate, sulfate, nitrate, nitrite, chromate, dichromate, permanganate, platinate, cobalt nitrite, hexachloroplatinate, citrate, cyanide, oxide, phosphate, sodium phosphate monobasic, sodium phosphate dibasic, sodium phosphate tribasic, and combinations thereof.

[0129] In another example, the electrodeposition process can be designed to apply an alloy layer comprising molybdenum and at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some embodiments, the resulting alloy layer may be free of precious metals.

[0130] In some embodiments, there may be no intervening or intermediate layer between the coating layer 110 and the substrate 105. For example, the coating layer 110 may be deposited directly on the substrate surface 105 without an intervening layer therebetween. In other examples, there may be an intermediate layer between the coating layer 110 and the surface 106 of the substrate 105. The intermediate layer may be formed using the same method used to form the coating layer 110 or a different method used to form the coating layer 110. In some embodiments, the intermediate layer may include one or more of copper, copper alloys, nickel, nickel alloys, nickel-phosphorus alloys, hard particles or nickel-phosphorus alloys with other compounds such as phosphorus, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, hard particles with a hardness of HV>1000, hard particles less than 500 nm in size, highly conductive particles, carbon nanotubes, and / or carbon nanoparticles. In other examples, the intermediate layer may include an alloy of nickel that is less magnetic than nickel alone. In some cases, the intermediate layer may be substantially smaller than the coating layer 110 and may be used to enhance adhesion of the coating layer 110 to the substrate 105. For example, the intermediate layer may be 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, or 10% thinner than the thickness of the coating layer 110. In certain embodiments, the layer between the substrate and the alloy layer may be a "nickel strike" layer, as is commonly known in the electroplating art.

[0131] In some embodiments, one or more of the materials of the coating layer can be provided using a soluble anode. The soluble anode can dissolve in the electrodeposition bath to provide the species to be deposited. In some embodiments, the soluble anode can take the form of a disk, rod, sphere, strip of material, or other form. The soluble anode can be present in a carrier or basket that is coupled to a power source.

[0132] In some embodiments, one or more of the coating layers described herein can be deposited using an anodization process. Anodization generally uses the substrate as the anode of an electrolytic cell. Anodization can change the microscopic texture of the surface and the resulting metallic coating near the surface. For example, thick coatings are often porous and can be sealed to increase corrosion resistance. Anodization can result in a harder, more corrosion resistant surface. In some examples, one of the coating layers of the articles described herein can be produced using an anodization process, and another coating layer can be produced using a non-anodization process. In other examples, each coating layer in the article can be produced using an anodization process. The exact materials and process conditions used for anodization can vary. Generally, an anodization layer is grown on the surface of the substrate by applying a direct current to an electrolyte solution containing the material to be deposited. The material to be deposited can include magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys or combinations thereof. Anodization is typically carried out under acidic conditions, which may include chromic acid, sulfuric acid, phosphoric acid, organic acids, or other acids.

[0133] In certain embodiments, the coatings described herein may be applied in the presence of other additives or agents. For example, wetting agents, leveling agents, gloss agents, defoaming agents, and / or emulsifying agents may be present in the aqueous solution containing the material to be deposited on the substrate surface. Exemplary additives and agents include, but are not limited to, thiourea, domiphen bromide, acetone, ethanol, cadmium ions, chloride ions, stearic acid, ethylenediamine dihydrochloride (EDA), saccharin, cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate, sodium lauryl sulfate (SLS), saccharin, naphthalenesulfonic acid, benzenesulfonic acid, coumarin, ethyl vanillin, ammonia, ethylenediamine, polyethylene glycol (PEG), bis(3-sulfopropyl) disulfide (SPS), Janus Green B (JGB), azobenzene-based surfactants (AZTAB), the polyoxyethylene family of surfactants, sodium citrate, perfluorinated alkyl sulfates, additive K, calcium chloride, ammonium chloride, potassium chloride, boric acid, myristic acid, choline chloride, citric acid, any redox active surfactant, any conductive ionic liquid, polyglycol ethers, polyglycol alcohols, sulfonated oleic acid derivatives, Sulfate forms of primary alcohols, alkylsulfonates, alkylsulfates, aralkylsulfonates, sulfates, perfluoroalkylsulfonates, acid alkyl and aralkyl phosphate esters, alkyl polyglycol ethers, alkyl polyglycol phosphate esters or their salts, N-containing and optionally substituted and / or quaternized polymers such as polyethyleneimine and its derivatives, polyglycine, poly(allylamine), polyaniline (sulfonated), polyvinylpyrrolidone, gelatin, polyvinylpyridine, polyvinylimidazole, polyurea, polyacrylamide, poly(melamine-co-formaldehyde), polyalkanolamines, polyaminoamides and their derivatives, polyalkanolamines and their derivatives, polyethyleneimine and its derivatives, quaternized polyethyleneimine, poly(allylamine), polyaniline, polyurea, polyacrylamide, poly(melamine-co-formaldehyde), hydroxy-ethyl-ethylene-diamine triacetic acid,2-butyne-14-diol, 22-azobis(2-methylpropionitrile), perfluoroammonium acid, dextrose, cetylmethylammonium bromide, 1-hexadecylpyridinium chloride, d-mannitol, glycine, Roselle salt, N-N'-diphenylbenzidine, glycolic acid, tetramethylammonium hydroxide, reaction products of amines with epichlorohydrin, reaction products of amines with epichlorohydrin and polyalkylene oxides, amines with polyepoxides, polyvinylpyridine, polyvinylimidazole, polyvinyl pyrrolidone or its reaction products with copolymers, nigrosine, pentamethyl-para-aniline, fats, oils, long chain alcohols, or glycols, polyethylene glycols, polyethylene oxides such as Triton, alkyl phosphates, metal soaps, specialty silicone defoamers, commercially available perfluoroalkyl modified hydrocarbon defoamers and perfluoroalkyl substituted silicones, fully fluorinated alkyl phosphonates, perfluoroalkyl substituted phosphate esters, cationic agents, amphoteric-based agents, and nonionic agents; chelating agents such as citrates, acetates, gluconates, and ethylenediaminetetraacetic acid (EDTA), or any combination thereof.

[0134] In embodiments where electroless plating is used, a metal coating can be produced on a substrate by the autocatalytic chemical reduction of metal cations in a bath. In contrast to electrodeposition / electroplating, in electroless plating, no external current is applied to the substrate. While not wishing to be bound to any particular configuration or example, electroless plating can provide a more uniform layer of material on a substrate compared to electroplating. Additionally, electroless plating can be used to add coatings to non-conductive substrates.

[0135] In certain embodiments where electroless plating is used, the substrate itself may act as a catalyst to reduce an ionic metal and form a coating of the metal on the surface of the substrate. If it is desired to produce a metal alloy coating, the substrate may act to reduce two or more different ionic metals using a complexing agent to form a metal alloy containing the two different metals. In some examples, the substrate itself may not function as a catalyst, but a catalytic material may be added to the substrate to facilitate the formation of a metal coating on the substrate. Exemplary catalytic materials that may be added to the substrate include, but are not limited to, palladium, gold, silver, titanium, copper, tin, niobium, and any combination thereof.

[0136] While the exact materials used in the electroless plating process can vary, exemplary materials include one or more of the following cations: magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys or combinations thereof. For example, any one or more of these cations can be added to the aqueous solution as a suitable salt. Exemplary suitable salts include, but are not limited to, metal halides, metal fluorides, metal chlorides, metal carbonates, metal hydroxides, metal acetates, metal sulfates, metal nitrates, metal nitrites, metal chromates, metal dichromates, metal permanganates, metal platinates, metal cobalt nitrites, metal hexachloroplatinates, metal citrates, metal cyanides, metal oxides, metal phosphates, metal monobasic sodium phosphates, metal dibasic sodium phosphates, metal tribasic sodium phosphates, and combinations thereof.

[0137] In certain embodiments, the substrates described herein may be subjected to pre-coating processing steps to prepare the substrate to receive the coating. These processing steps may include, for example, washing, electro-cleaning (anodic or cathodic), polishing, electropolishing, pre-plating treatment, heat treatment, polishing treatment, and chemical treatment. For example, the substrate may be washed with an acid, base, water, salt solution, organic solution, organic solvent, or other liquid or gas. The substrate may be optionally polished using water, an acid or base, such as sulfuric acid, phosphoric acid, etc., or other materials in the presence of an electric current. The substrate may be exposed to one or more gases prior to application of the coating layer to facilitate removal of oxygen or other gases from the surface of the substrate. The substrate may be washed with or exposed to an oil or hydrocarbon fluid prior to application of the coating to remove any aqueous solutions or materials from the surface. The substrate may be heated or dried in an oven to remove liquids from the surface prior to application of the coating. Other steps for treating the substrate prior to application of the coating may also be used. The substrate may be heated after deposition of the coating or after deposition of the coating. For example, the substrate may be heated to high temperatures, such as greater than 100 degrees, greater than 200° C., greater than 500° C., greater than 700° C., or greater than 1000° C. Similarly, the final article including the coating may operate at such high temperatures.

[0138] In some embodiments, the coating layers described herein can be subjected to sealing. The exact conditions and materials used to seal the coatings can vary, but sealing can reduce the porosity of the coatings and increase their hardness. In some embodiments, sealing can be performed by subjecting the coatings to steam, organic additives, metals, metal salts, metal alloys, metal alloy salts, or other materials. Sealing can be performed at temperatures above room temperature, e.g., 30 degrees Celsius, 50 degrees Celsius, 90 degrees Celsius or higher, at room temperature or below room temperature, e.g., 20 degrees Celsius or lower. In some examples, the substrate and coating layer can be heated to remove hydrogen or other gases in the coating layer. For example, the substrate and coating can be baked to remove hydrogen from the article within 1-2 hours after coating.

[0139] It will be appreciated by those skilled in the art that a combination of post-deposition processing methods may be used, for example, a coating layer may be sealed and then polished to reduce surface roughness.

[0140] In a particular configuration, a flow chart of the electrodeposition process is shown in FIG. 13. In step 1310, the substrate to be coated may be washed. The substrate may then be rinsed in step 1315. The substrate may then be subjected to an acid treatment in step 1320. The acid treated substrate is then rinsed in step 1330. The rinsed substrate is then added to a plating bath in step 1335. The plated substrate may optionally be rinsed. The substrate with the coated surface may then be subjected to a post-plating process in step 1340. Each of these steps is described in more detail below. An optional strike step 1322 to provide a nickel layer (or a layer of another material) on the surface of the substrate may be performed between steps 1320 and 1330 prior to plating, if desired.

[0141] In certain embodiments, the cleaning step can be carried out in the presence or absence of an electric current. Cleaning is typically carried out in the presence of one or more salts and / or detergents or surfactants and can be carried out at an acidic or basic pH. Cleaning is generally carried out to remove oils, hydrocarbons or other materials from the surface of the substrate.

[0142] After the substrate is cleaned, it is rinsed to remove the cleaning agent. Rinsing is typically done in distilled water, but may also be done using one or more buffers, or at an acidic or basic pH. Rinsing may be done once or multiple times. The substrate is typically kept wet between the various steps to minimize oxide formation on the surface. A water break test can be performed to ensure that the surface is clean and / or oil-free.

[0143] After rinsing, the substrate may be immersed in an acid bath to activate the surface for electrodeposition, e.g., to pickle the surface. The exact acid used is not critical. The pH of the acid treatment may be 0-7 or less than 0, as desired. The time the substrate remains in the acid bath may vary, for example, from 10 seconds to about 10 minutes. The acid solution may be stirred or pumped over the substrate surface as desired, or the substrate may be moved within the acid tank during the pickling process.

[0144] After the pickling process, the surface can be rinsed to remove the acid. Rinsing can be done by immersing the pickled substrate in a rinse bath, or by running a rinse agent over the surface, or both. Rinsing can be done multiple times or once, as needed.

[0145] After pickling, the substrate may optionally be subjected to a strike. Without wishing to be bound to any one configuration, a strike applies a thin layer of material to the substrate that is typically inert or less reactive with the material being deposited. Examples of inert substrates include, but are not limited to, stainless steel, titanium, certain metal alloys, and other materials. In the strike process, a thin layer of material, for example up to a few microns thick, is applied using electrodeposition.

[0146] The water-washed substrate, pickled substrate, or water-washed substrate with a strike layer can then be subjected to an electrodeposition process as described above to apply a layer of material to the substrate surface. As described herein, electrodeposition can be performed using AC or DC voltages and various waveforms. The exact current density used can be varied to favor or disadvantage certain amounts of elements that end up in the resulting coating. For example, if the alloy layer includes two metals, the current density can be selected so that there is more of one metal in the resulting alloy layer than the other. The pH of the electrodeposition bath can also be varied depending on the particular species that are intended to be present in the surface coating. For example, an acidic bath (pH=3-5.5), a neutral pH bath, or a basic pH bath (pH 9-12) can be used depending on the materials present in the electrodeposition bath and the anode. The exact temperature used during the electrodeposition process can vary from room temperature (about 25 degrees Celsius) to about 85 degrees Celsius. It is desirable for the temperature to be below 100 degrees Celsius so that the water in the electrodeposition bath does not evaporate to any significant extent. The electrodeposition bath may include the material to be deposited along with any agents, including brighteners, levelers, particles, and the like, as described herein.

[0147] In some embodiments, the electrodeposition bath may include a brightener. A variety of organic compounds are used as brighteners to provide bright, flat, and ductile nickel deposits. Brighteners can generally be divided into two classes. Class I or primary brighteners include compounds such as aromatic or unsaturated aliphatic sulfonic acids, sulfonamides, sulfonimides, and sulfimides. Class I brighteners can be used in relatively high concentrations and produce hazy or cloudy deposits on the metal substrate. Decomposition of Class I brighteners during the electroplating process can result in sulfur incorporation into the deposit, lowering the tensile stress of the deposit. Class II or secondary brighteners are used in combination with Class I brighteners to produce perfectly bright and flat deposits. Class II brighteners are generally unsaturated organic compounds. A variety of organic compounds containing unsaturated functional groups such as alcohol groups, diol groups, triol groups, aldehyde groups, olefin groups, acetylene groups, nitrile groups, and pyridine groups can be used as Class II brighteners. Typically, class II brighteners are derived from acetylene or ethylenic alcohols, ethoxylated acetylenic alcohols, coumarins, and pyridine-based compounds. Mixtures of such unsaturated compounds and mixtures of class I brighteners can be combined to obtain maximum brightness or ductility for a given leveling speed. Various amine compounds can also be used as brighteners or leveling agents. Acyclic amines can be used as class II brighteners. Acetylenic amines can be used in combination with acetylenic compounds to improve leveling and low current density coverage.

[0148] In certain embodiments, the resulting amount of metals present in the alloy layer may vary. For example, in a monoelectrodeposition process where two metals are present in the surface coating, one of the metals, e.g., molybdenum, may be present at up to about 35 wt. % based on the weight of the surface coating. In other embodiments, one of the metals, e.g., molybdenum, may be present at up to about 20 wt. % based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present at up to about 16 wt. % based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present at up to about 10 wt. % based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present at up to about 6 wt. % based on the weight of the surface coating.

[0149] In certain configurations, the substrate with the surface coating can then be rinsed or subjected to another deposition process to apply a second layer on the formed first layer. The second deposition process can be, for example, vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel (HVOF) coating, thermal spraying, or other suitable methods. In some cases, a second electrodeposition step can be used to apply a second layer on top of the formed first layer. For example, the second layer can be an electrodeposited layer that includes one, two, three or more metals or other materials. If desired, additional layers can be formed on the second layer using electrodeposition or any of the other processes described herein.

[0150] In other configurations, a layer of material can be deposited on a cleaned or pickled substrate before forming the layer using an electrodeposition process. For example, one or more layers can first be formed on the substrate using vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel (HVOF) coating, thermal spraying, or other suitable methods. A second layer can be formed on the first layer using the electrodeposition process described herein. If necessary, the first formed layer can be activated by a pickling process before electrodepositing the second layer on the first layer.

[0151] If a monolayer is formed on a substrate by electrodeposition, the substrate with the coated surface may then be subjected to one or more post-processing steps including, for example, rinsing, polishing, sanding, heating, annealing, compacting, etching, or other steps to clean the coated surface or to modify the physical or chemical properties of the coated surface. If desired, portions of the coating may be removed using acidic or basic solutions, depending on the materials present in the coating.

[0152] In certain embodiments, a method of producing an alloy layer on a substrate includes forming a coated surface on the substrate by electrodepositing an alloy layer on the substrate surface. The electrodeposited alloy layer includes (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound including one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some examples, the method includes cleaning the substrate prior to electrodepositing the alloy layer, rinsing the cleaned substrate, activating a surface of the cleaned substrate to provide an activated substrate, rinsing the activated substrate, and electrodepositing the alloy layer on the activated substrate. In some embodiments, the method includes subjecting the electrodeposited alloy layer to a post-deposition treatment process. In additional embodiments, the post-deposition treatment process is selected from the group consisting of rinsing, polishing, sanding, heating, annealing, and consolidating. In some examples, the method includes providing an additional layer on the electrodeposited alloy layer. In other examples, the additional layer is provided using one of vacuum deposition, physical vapor deposition, chemical vapor deposition, plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxy-fuel coating, or thermal spraying.

[0153] In some configurations, an intermediate layer of material can be provided between the substrate and the electrodeposited alloy layer prior to electrodepositing the alloy layer. In some examples, the intermediate layer is provided using one of vacuum deposition, physical vapor deposition, chemical vapor deposition, plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel coating, or thermal spraying. In certain embodiments, the electrodeposition uses a soluble anode or uses an insoluble anode. In some cases, the soluble anode includes nickel or another metal.

[0154] In certain examples, the coating layers described herein can be applied to a substrate using any suitable method, including, but not limited to, vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel (HVOF) coating, thermal spraying, or other suitable methods.

[0155] In certain examples, one or more coating layers may be deposited using vacuum deposition. In certain embodiments, vacuum deposition generally deposits a layer of material on the surface of a substrate, either atom by atom or molecule by molecule. The vacuum deposition process can be used to deposit one or more materials having a thickness ranging from one or more atoms to several millimeters.

[0156] In certain embodiments, one or more coating layers described herein can be deposited using physical vapor deposition (PVD), a type of vacuum deposition. PVD generally uses vapors of a material to produce a thin coating on a substrate. The coatings described herein can be, for example, sputtered onto the surface of the substrate or applied onto the surface of the substrate using vapor deposition PVD. In other embodiments, one or more coating layers can be produced on the substrate using chemical vapor deposition (CVD). CVD generally involves exposing the substrate to one or more materials that react and / or decompose on the substrate's surface to provide the desired coating layer on the substrate. In other configurations, plasma deposition (PD), such as plasma accelerated chemical vapor deposition or plasma assisted chemical vapor deposition, can be used to provide a coating layer on the substrate. PD generally involves generating a plasma discharge from a reactive gas that includes the material to be deposited and / or subjecting an already deposited material to ions in the plasma gas to modify the coating layer. In another example, atomic layer deposition (ALD) can be used to provide a coating layer on a surface. In ALD, the substrate surface is exposed to repeated doses of precursors that can react with the surface of the material to build up the coating layer.

[0157] In other examples, one or more coating layers described herein can be deposited on the surface of the substrate using brushing, spin coating, spray coating, dip coating, electrodeposition (e.g., electroplating, cathodic electrodeposition, anodic electrodeposition, etc.), electroless plating, electrocoating, electrophoretic deposition, or other techniques. When an electric current is used to deposit the coating layer on the substrate, the electric current can be continuous, pulsed, or a combination of continuous and pulsed current. Certain electrodeposition techniques are described in more detail below.

[0158] In some configurations, one or more layers of the coating can be applied using electrodeposition. In general, electrodeposition uses a voltage applied to a substrate placed in a bath to form a coating on a charged substrate. For example, ionic species present in a solution can be reduced using an applied voltage to deposit the ionic species in solid form on a surface (or all surfaces) of the substrate. As described in more detail below, the ionic species can be deposited to provide a metal coating, a metal alloy coating, or a combination thereof. Depending on the exact ionic species used and the electrodeposition conditions and techniques, the resulting properties of the formed electrodeposited coating can be selected or tailored to provide a desired result.

[0159] In certain embodiments in which electrodeposition is used, the ionic species may be dissolved or solvated in an aqueous solution or water. The aqueous solution may contain suitable dissolved salts, inorganic species, or organic species to facilitate the electrodeposition of the coating layer(s) on the substrate. In other embodiments in which electrodeposition is used, the liquid used in the electrodeposition bath may be generally non-aqueous, for example, may contain more than 50% by volume of non-aqueous species, and may include hydrocarbons, alcohols, liquefied gases, amines, aromatics, and other non-aqueous materials.

[0160] Generally, an electrodeposition bath includes a species that is deposited as a coating on a substrate. For example, if nickel is deposited on the substrate, the bath can include ionic nickel or solvated nickel. If molybdenum is deposited in the substrate, the bath can include ionic molybdenum or solvated molybdenum. If an alloy is deposited on the substrate, the bath can include multiple species, for example, the bath can include ionic nickel and ionic molybdenum that are co-electrodeposited to form a nickel-molybdenum alloy as a coating layer on the substrate. The exact form of the material added to the bath to provide the ionic or solvated species can vary. For example, the species may be added to the bath as metal halides, metal fluorides, metal chlorides, metal carbonates, metal hydroxides, metal acetates, metal sulfates, metal nitrates, metal nitrites, metal chromates, metal dichromates, metal permanganates, metal platinates, metal cobalt nitrites, metal hexachloroplatinates, metal citrates, ammonium salts of metals, metal cyanides, metal oxides, metal phosphates, metal monobasic sodium phosphates, metal dibasic sodium phosphates, metal tribasic sodium phosphates, sodium salts of metals, potassium salts of metals, metal sulfamates, metal nitrites, and combinations thereof. In some instances, a single material containing both of the metal species to be deposited may be dissolved in the electrodeposition bath, e.g., a metal alloy salt may be dissolved in a suitable solution prior to electrodeposition. The particular material used in the electrodeposition bath will depend on the particular alloy layer to be deposited. Exemplary materials include, but are not limited to, nickel sulfate, nickel sulfamate, nickel chloride, sodium tungstate, tungsten chloride, sodium molybdate, ammonium molybdate, cobalt sulfate, cobalt chloride, chromium sulfate, chromium chloride, chromic acid, stannous sulfate, sodium stannate, hypophosphorous acid, sulfuric acid, nickel carbonate, nickel hydroxide, potassium carbonate, ammonium hydroxide, hydrochloric acid, or other materials.

[0161] In certain embodiments, the exact amount or concentration of the species electrodeposited on the substrate may vary. For example, the concentration of the species may vary from about 1 gram / liter to about 400 grams / liter. If necessary, as the ionic species is depleted as a result of the formation of the coating on the substrate, additional material may be added to the bath to increase the amount of the species available for electrodeposition. In some cases, the concentration of the deposited species may be maintained at a substantially constant level during electrodeposition by continuously adding material to the bath.

[0162] In certain embodiments, the pH of the electrodeposition bath may vary depending on the particular ionic species present in the bath. For example, the pH may range from 1 to about 13, although in certain cases the pH may be less than 1, or less than 0, or greater than 13, or even greater than 14. When the metal species is deposited on the substrate as a metal alloy, the pH may range from 4 to about 12, in certain instances. However, it will be appreciated that the pH may vary depending on the particular voltage and electrodeposition conditions selected for use. Several pH adjusters and buffers may be added to the bath. Examples of pH adjusters include, but are not limited to, boric acid, hydrochloric acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide, glycine, sodium acetate, buffered saline, cacodylate buffer, citrate buffer, phosphate buffer, phosphate-citrate buffer, barbital buffer, TRIS buffer, glycine-NaOH buffer, and any combination thereof.

[0163] In certain embodiments, the alloy plating can use a complexing agent. For example, the main role of a complexing agent in the alloy deposition process is to complex different metal ions. Thus, without a suitable complexing agent, the simultaneous deposition and alloy formation of nickel and molybdenum will not occur. Examples of complexing agents include, but are not limited to, phosphates, phosphonates, polycarboxylates, zeolites, citrates, ammonium hydroxide, ammonium salts, citric acid, ethylenediaminetetraacetic acid, diethylene-triaminepentaacetic acid, aminopolycarboxylates, nitrilotriacetic acid, IDS (N-(1,2-dicarboxyethyl)-D,L-aspartic acid (iminodisuccinic acid), DS (polyaspartic acid), EDDS (N,N'-ethylenediaminedisuccinic acid), GLDA (N,N-bis(carboxylmethyl)-L-glutamic acid), and MGDA (methylglycine diacetate), hexamine cobalt(III) chloride, ethylene glycol-bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA), ferrocene, cyclodextrin, cholic acid, polymers, and any combination thereof.

[0164] In some examples, appropriate voltages can be applied to the cathode and anode of the electrodeposition bath to promote the formation of the layer(s) described herein on the substrate. In some embodiments, direct current (DC) voltages can be used. In other examples, alternating current (AC), optionally in combination with current pulses, can be used to electrodeposit the layer. For example, AC electrodeposition can be performed with AC voltage waveforms, typically sinusoidal, square, triangular, etc. High voltages and current densities can be used to promote tunneling of electrons through the oxide-based layer, which can form on the substrate. Additionally, the base layer can be conducted in the direction of the cathode, which promotes the deposition of material and avoids reoxidation during the oxidant half cycle.

[0165] In certain embodiments, an exemplary current density range that can be used for electrodeposition is 1 mA / cm 2 DC~about 600mA / cm 2 DC, more specifically, about 1mA / cm2 DC~approx.300mA / cm 2 In some examples, the current density is 5 mA / cm 2 DC~approx.300mA / cm 2 DC, 20mA / cm 2 DC~approx. 100mA / cm 2 DC, 100mA / cm 2 DC~about 400mA / cm 2 The current may vary from about 10 seconds to several days, more specifically from about 40 seconds to about 2 hours. If desired, a pulsed current may be applied instead of a direct current.

[0166] In some instances, electrodeposition can use pulsed current or pulsed reverse current during electrodeposition of the alloy layer. In pulsed electrodeposition (PED), the potential or current is rapidly alternating between two different values. This results in a series of pulses of equal amplitude, duration and polarity, separated by zero current. Each pulse consists of an on-time (TON) during which potential and / or current is applied, and an off-time (TOFF) during which zero current is applied. By adjusting the pulse amplitude and width, it is possible to control the composition and thickness of the deposited film in atomic order. They favor the initiation of grain nuclei, greatly increasing the number of grains per unit area, resulting in finer grained deposits with better properties than conventional plated coatings.

[0167] In examples where the coating includes two or more layers, the first and second layers of the coating may be applied using the same or different electrodeposition baths. For example, the first layer may be applied using a first aqueous solution in the electrodeposition bath. After applying a voltage for a period of time sufficient to deposit the first layer, the voltage may be reduced to zero, the first solution may be removed from the bath, and a second aqueous solution containing a different material may be added to the bath. The voltage may then be reapplied to electrodeposit the second layer. In other examples, two separate baths may be used, for example a reel-to-reel process may be used, where a first bath is used to electrodeposit the first layer and a second, different bath is used to deposit the second layer.

[0168] In some cases, the individual articles may be connected such that they can be sequentially exposed to separate electrodeposition baths, such as in a reel-to-reel process. For example, the articles may be connected to a common conductive substrate (e.g., a strip). In some embodiments, each of the electrodeposition baths may be associated with a separate anode, and the interconnected individual articles may be commonly connected to a cathode.

[0169] While the exact materials used in the electroplating process can vary, exemplary materials include cations of one or more of the following metals: nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or combinations thereof. The exact anion forms of these metals can vary from chloride, acetate, sulfate, nitrate, nitrite, chromate, dichromate, permanganate, platinate, cobalt nitrite, hexachloroplatinate, citrate, cyanide, oxide, phosphate, sodium phosphate monobasic, sodium phosphate dibasic, sodium phosphate tribasic, and combinations thereof.

[0170] In another example, the electrodeposition process can be designed to apply an alloy layer comprising molybdenum and at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some embodiments, the resulting alloy layer may be free of precious metals.

[0171] In some embodiments, there may be no intervening or intermediate layer between the coating layer 110 and the substrate 105. For example, the coating layer 110 may be deposited directly on the substrate surface 105 without an intervening layer therebetween. In other examples, there may be an intermediate layer between the coating layer 110 and the surface 106 of the substrate 105. The intermediate layer may be formed using the same method used to form the coating layer 110 or a different method used to form the coating layer 110. In some embodiments, the intermediate layer may include one or more of copper, copper alloys, nickel, nickel alloys, nickel-phosphorus alloys, hard particles or nickel-phosphorus alloys with other compounds such as phosphorus, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, hard particles with a hardness of HV>1000, hard particles less than 500 nm in size, highly conductive particles, carbon nanotubes, and / or carbon nanoparticles. In other examples, the intermediate layer may include an alloy of nickel that is less magnetic than nickel alone. In some cases, the intermediate layer may be substantially smaller than the coating layer 110 and may be used to enhance adhesion of the coating layer 110 to the substrate 105. For example, the intermediate layer may be 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, or 10% thinner than the thickness of the coating layer 110. In certain embodiments, the layer between the substrate and the alloy layer may be a "nickel strike" layer, as is commonly known in the electroplating art.

[0172] In some embodiments, one or more of the materials of the coating layer can be provided using a soluble anode. The soluble anode can dissolve in the electrodeposition bath to provide the species to be deposited. In some embodiments, the soluble anode can take the form of a disk, rod, sphere, strip of material, or other form. The soluble anode can be present in a carrier or basket that is coupled to a power source.

[0173] In some embodiments, one or more of the coating layers described herein can be deposited using an anodization process. Anodization generally uses the substrate as the anode of an electrolytic cell. Anodization can change the microscopic texture of the surface and the resulting metallic coating near the surface. For example, thick coatings are often porous and can be sealed to increase corrosion resistance. Anodization can result in a harder, more corrosion resistant surface. In some examples, one of the coating layers of the articles described herein can be produced using an anodization process, and another coating layer can be produced using a non-anodization process. In other examples, each coating layer in the article can be produced using an anodization process. The exact materials and process conditions used for anodization can vary. Generally, an anodization layer is grown on the surface of the substrate by applying a direct current to an electrolyte solution containing the material to be deposited. The material to be deposited can include magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys or combinations thereof. Anodization is typically carried out under acidic conditions, which may include chromic acid, sulfuric acid, phosphoric acid, organic acids, or other acids.

[0174] In certain embodiments, the coatings described herein may be applied in the presence of other additives or agents. For example, wetting agents, leveling agents, gloss agents, defoaming agents, and / or emulsifying agents may be present in the aqueous solution containing the material to be deposited on the substrate surface. Exemplary additives and agents include, but are not limited to, thiourea, domiphen bromide, acetone, ethanol, cadmium ions, chloride ions, stearic acid, ethylenediamine dihydrochloride (EDA), saccharin, cetyltrimethylammonium bromide (CTAB), sodium dodecyl sulfate, sodium lauryl sulfate (SLS), saccharin, naphthalenesulfonic acid, benzenesulfonic acid, coumarin, ethyl vanillin, ammonia, ethylenediamine, polyethylene glycol (PEG), bis(3-sulfopropyl) disulfide (SPS), Janus Green B (JGB), azobenzene-based surfactants (AZTAB), the polyoxyethylene family of surfactants, sodium citrate, perfluorinated alkyl sulfates, additive K, calcium chloride, ammonium chloride, potassium chloride, boric acid, myristic acid, choline chloride, citric acid, any redox active surfactant, any conductive ionic liquid, polyglycol ethers, polyglycol alcohols, sulfonated oleic acid derivatives, Sulfate forms of primary alcohols, alkylsulfonates, alkylsulfates, aralkylsulfonates, sulfates, perfluoroalkylsulfonates, acid alkyl and aralkyl phosphate esters, alkyl polyglycol ethers, alkyl polyglycol phosphate esters or their salts, N-containing and optionally substituted and / or quaternized polymers such as polyethyleneimine and its derivatives, polyglycine, poly(allylamine), polyaniline (sulfonated), polyvinylpyrrolidone, gelatin, polyvinylpyridine, polyvinylimidazole, polyurea, polyacrylamide, poly(melamine-co-formaldehyde), polyalkanolamines, polyaminoamides and their derivatives, polyalkanolamines and their derivatives, polyethyleneimine and its derivatives, quaternized polyethyleneimine, poly(allylamine), polyaniline, polyurea, polyacrylamide, poly(melamine-co-formaldehyde), hydroxy-ethyl-ethylene-diamine triacetic acid,2-butyne-14-diol, 22-azobis(2-methylpropionitrile), perfluoroammonium acid, dextrose, cetylmethylammonium bromide, 1-hexadecylpyridinium chloride, d-mannitol, glycine, Roselle salt, N-N'-diphenylbenzidine, glycolic acid, tetramethylammonium hydroxide, reaction products of amines with epichlorohydrin, reaction products of amines with epichlorohydrin and polyalkylene oxides, amines with polyepoxides, polyvinylpyridine, polyvinylimidazole, polyvinyl pyrrolidone or its reaction products with copolymers, nigrosine, pentamethyl-para-aniline, fats, oils, long chain alcohols, or glycols, polyethylene glycols, polyethylene oxides such as Triton, alkyl phosphates, metal soaps, specialty silicone defoamers, commercially available perfluoroalkyl modified hydrocarbon defoamers and perfluoroalkyl substituted silicones, fully fluorinated alkyl phosphonates, perfluoroalkyl substituted phosphate esters, cationic agents, amphoteric-based agents, and nonionic agents; chelating agents such as citrates, acetates, gluconates, and ethylenediaminetetraacetic acid (EDTA), or any combination thereof.

[0175] In embodiments where electroless plating is used, a metal coating can be produced on a substrate by the autocatalytic chemical reduction of metal cations in a bath. In contrast to electrodeposition / electroplating, in electroless plating, no external current is applied to the substrate. While not wishing to be bound to any particular configuration or example, electroless plating can provide a more uniform layer of material on a substrate compared to electroplating. Additionally, electroless plating can be used to add coatings to non-conductive substrates.

[0176] In certain embodiments where electroless plating is used, the substrate itself may act as a catalyst to reduce an ionic metal and form a coating of the metal on the surface of the substrate. If it is desired to produce a metal alloy coating, the substrate may act to reduce two or more different ionic metals using a complexing agent to form a metal alloy containing the two different metals. In some examples, the substrate itself may not function as a catalyst, but a catalytic material may be added to the substrate to facilitate the formation of a metal coating on the substrate. Exemplary catalytic materials that may be added to the substrate include, but are not limited to, palladium, gold, silver, titanium, copper, tin, niobium, and any combination thereof.

[0177] While the exact materials used in the electroless plating process can vary, exemplary materials include one or more of the following cations: magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys or combinations thereof. For example, any one or more of these cations can be added to the aqueous solution as a suitable salt. Exemplary suitable salts include, but are not limited to, metal halides, metal fluorides, metal chlorides, metal carbonates, metal hydroxides, metal acetates, metal sulfates, metal nitrates, metal nitrites, metal chromates, metal dichromates, metal permanganates, metal platinates, metal cobalt nitrites, metal hexachloroplatinates, metal citrates, metal cyanides, metal oxides, metal phosphates, metal monobasic sodium phosphates, metal dibasic sodium phosphates, metal tribasic sodium phosphates, and combinations thereof.

[0178] In certain embodiments, the substrates described herein may be subjected to pre-coating processing steps to prepare the substrate to receive the coating. These processing steps may include, for example, washing, electrocleaning (anodic or cathodic), polishing, electropolishing, pre-plating treatment, heat treatment, polishing treatment, and chemical treatment. For example, the substrate may be washed with an acid, base, water, salt solution, organic solution, organic solvent, or other liquid or gas. The substrate may be optionally polished using water, an acid or base, such as sulfuric acid, phosphoric acid, etc., or other materials, in the presence of an electric current. The substrate may be exposed to one or more gases prior to application of the coating layer to facilitate removal of oxygen or other gases from the surface of the substrate. The substrate may be washed with or exposed to an oil or hydrocarbon fluid prior to application of the coating to remove any aqueous solutions or materials from the surface. The substrate may be heated or dried in an oven to remove liquids from the surface prior to application of the coating. Other steps for treating the substrate prior to application of the coating may also be used.

[0179] In some embodiments, the coating layers described herein can be subjected to sealing. The exact conditions and materials used to seal the coatings can vary, but sealing can reduce the porosity of the coatings and increase their hardness. In some embodiments, sealing can be performed by subjecting the coatings to steam, organic additives, metals, metal salts, metal alloys, metal alloy salts, or other materials. Sealing can be performed at temperatures above room temperature, e.g., 30 degrees Celsius, 50 degrees Celsius, 90 degrees Celsius or higher, at room temperature or below room temperature, e.g., 20 degrees Celsius or lower. In some examples, the substrate and coating layer can be heated to remove hydrogen or other gases in the coating layer. For example, the substrate and coating can be baked to remove hydrogen from the article within 1-2 hours after coating.

[0180] It will be appreciated by those skilled in the art that a combination of post-deposition processing methods may be used, for example, a coating layer may be sealed and then polished to reduce surface roughness.

[0181] In a particular configuration, a flow chart of the electrodeposition process is shown in FIG. 13. In step 1310, the substrate to be coated may be washed. The substrate may then be rinsed in step 1315. The substrate may then be subjected to an acid treatment in step 1320. The acid treated substrate is then rinsed in step 1330. The rinsed substrate is then added to a plating bath in step 1335. The plated substrate may optionally be rinsed. The substrate with the coated surface may then be subjected to a post-plating process in step 1340. Each of these steps is described in more detail below. An optional strike step 1322 to provide a nickel layer (or a layer of another material) on the surface of the substrate may be performed between steps 1320 and 1330 prior to plating, if desired.

[0182] In certain embodiments, the cleaning step can be carried out in the presence or absence of an electric current. Cleaning is typically carried out in the presence of one or more salts and / or detergents or surfactants and can be carried out at an acidic or basic pH. Cleaning is generally carried out to remove oils, hydrocarbons or other materials from the surface of the substrate.

[0183] After the substrate is cleaned, it is rinsed to remove the cleaning agent. Rinsing is typically done in distilled water, but may also be done using one or more buffers, or at an acidic or basic pH. Rinsing may be done once or multiple times. The substrate is typically kept wet between the various steps to minimize oxide formation on the surface. A water break test can be performed to ensure that the surface is clean and / or oil-free.

[0184] After rinsing, the substrate may be immersed in an acid bath to activate the surface for electrodeposition, e.g., to pickle the surface. The exact acid used is not critical. The pH of the acid treatment may be 0-7 or less than 0, as desired. The time the substrate remains in the acid bath may vary, for example, from 10 seconds to about 10 minutes. The acid solution may be stirred or pumped over the substrate surface as desired, or the substrate may be moved within the acid tank during the pickling process.

[0185] After the pickling process, the surface can be rinsed to remove the acid. Rinsing can be done by immersing the pickled substrate in a rinse bath, or by running a rinse agent over the surface, or both. Rinsing can be done multiple times or once, as needed.

[0186] After pickling, the substrate may optionally be subjected to a strike. Without wishing to be bound to any one configuration, a strike applies a thin layer of material to the substrate that is typically inert or less reactive with the material being deposited. Examples of inert substrates include, but are not limited to, stainless steel, titanium, certain metal alloys, and other materials. In the strike process, a thin layer of material, for example up to a few microns thick, is applied using electrodeposition.

[0187] The water-washed substrate, pickled substrate, or water-washed substrate with a strike layer can then be subjected to an electrodeposition process as described above to apply a layer of material to the substrate surface. As described herein, electrodeposition can be performed using AC or DC voltages and various waveforms. The exact current density used can be varied to favor or disadvantage certain amounts of elements that end up in the resulting coating. For example, if the alloy layer includes two metals, the current density can be selected so that there is more of one metal in the resulting alloy layer than the other. The pH of the electrodeposition bath can also be varied depending on the particular species that are intended to be present in the surface coating. For example, an acidic bath (pH=3-5.5), a neutral pH bath, or a basic pH bath (pH 9-12) can be used depending on the materials present in the electrodeposition bath and the anode. The exact temperature used during the electrodeposition process can vary from room temperature (about 25 degrees Celsius) to about 85 degrees Celsius. It is desirable for the temperature to be below 100 degrees Celsius so that the water in the electrodeposition bath does not evaporate to any significant extent. The electrodeposition bath may include the material to be deposited along with any agents, including brighteners, levelers, particles, and the like, as described herein.

[0188] In some embodiments, the electrodeposition bath may include a brightener. A variety of organic compounds are used as brighteners to provide bright, flat, and ductile nickel deposits. Brighteners can generally be divided into two classes. Class I or primary brighteners include compounds such as aromatic or unsaturated aliphatic sulfonic acids, sulfonamides, sulfonimides, and sulfimides. Class I brighteners can be used in relatively high concentrations and produce hazy or cloudy deposits on the metal substrate. Decomposition of Class I brighteners during the electroplating process can result in sulfur incorporation into the deposit, lowering the tensile stress of the deposit. Class II or secondary brighteners are used in combination with Class I brighteners to produce perfectly bright and flat deposits. Class II brighteners are generally unsaturated organic compounds. A variety of organic compounds containing unsaturated functional groups such as alcohol groups, diol groups, triol groups, aldehyde groups, olefin groups, acetylene groups, nitrile groups, and pyridine groups can be used as Class II brighteners. Typically, class II brighteners are derived from acetylene or ethylenic alcohols, ethoxylated acetylenic alcohols, coumarins, and pyridine-based compounds. Mixtures of such unsaturated compounds and mixtures of class I brighteners can be combined to obtain maximum brightness or ductility for a given leveling speed. Various amine compounds can also be used as brighteners or leveling agents. Acyclic amines can be used as class II brighteners. Acetylenic amines can be used in combination with acetylenic compounds to improve leveling and low current density coverage.

[0189] In certain embodiments, the resulting amount of metals present in the alloy layer may vary. For example, in a monoelectrodeposition process where two metals are present in the surface coating, one of the metals, e.g., molybdenum, may be present at up to about 35 wt. % based on the weight of the surface coating. In other embodiments, one of the metals, e.g., molybdenum, may be present at up to about 20 wt. % based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present at up to about 16 wt. % based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present at up to about 10 wt. % based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present at up to about 6 wt. % based on the weight of the surface coating.

[0190] In certain configurations, the substrate with the surface coating can then be rinsed or subjected to another deposition process to apply a second layer on the formed first layer. The second deposition process can be, for example, vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel (HVOF) coating, thermal spraying, or other suitable methods. In some cases, a second electrodeposition step can be used to apply a second layer on top of the formed first layer. For example, the second layer can be an electrodeposited layer that includes one, two, three or more metals or other materials. If desired, additional layers can be formed on the second layer using electrodeposition or any of the other processes described herein.

[0191] In other configurations, a layer of material can be deposited on a cleaned or pickled substrate before forming the layer using an electrodeposition process. For example, one or more layers can first be formed on the substrate using vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel (HVOF) coating, thermal spraying, or other suitable methods. A second layer can be formed on the first layer using the electrodeposition process described herein. If necessary, the first formed layer can be activated by a pickling process before electrodepositing the second layer on the first layer.

[0192] If a monolayer is formed on a substrate by electrodeposition, the substrate with the coated surface may then be subjected to one or more post-processing steps including, for example, rinsing, polishing, sanding, heating, annealing, compacting, etching, or other steps to clean the coated surface or to modify the physical or chemical properties of the coated surface. If desired, portions of the coating may be removed using acidic or basic solutions, depending on the materials present in the coating.

[0193] In certain embodiments, a method of producing an alloy layer on a substrate includes forming a coated surface on the substrate by electrodepositing an alloy layer on the substrate surface. The electrodeposited alloy layer includes (i) molybdenum and (ii) at least one element selected from the group consisting of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound including one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some examples, the method includes cleaning the substrate prior to electrodepositing the alloy layer, rinsing the cleaned substrate, activating a surface of the cleaned substrate to provide an activated substrate, rinsing the activated substrate, and electrodepositing the alloy layer on the activated substrate. In some embodiments, the method includes subjecting the electrodeposited alloy layer to a post-deposition treatment process. In additional embodiments, the post-deposition treatment process is selected from the group consisting of rinsing, polishing, sanding, heating, annealing, and consolidating. In some examples, the method includes providing an additional layer on the electrodeposited alloy layer. In other examples, the additional layer is provided using one of vacuum deposition, physical vapor deposition, chemical vapor deposition, plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxy-fuel coating, or thermal spraying.

[0194] In some configurations, an intermediate layer of material can be provided between the substrate and the electrodeposited alloy layer prior to electrodepositing the alloy layer. In some examples, the intermediate layer is provided using one of vacuum deposition, physical vapor deposition, chemical vapor deposition, plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless deposition / plating, high velocity oxygen fuel coating, or thermal spraying. In certain embodiments, the electrodeposition uses a soluble anode or uses an insoluble anode. In some cases, the soluble anode includes nickel or another metal.

[0195] To facilitate a better understanding of the technology described herein, specific examples are set forth.

[0196] Example 1 Several tests were performed on a coating containing a molybdenum-nickel alloy (hereafter referred to as MaxShield) on the surface of a test substrate (steel substrate). Three different versions of the MaxShield coating were tested to better understand the effect of thickness and heat on the performance of MaxShield. MaxShield-V1 has a thickness between 20 and 30 μm. In addition, MaxShield-V1 was also tested as-plated, after bake-off at 190°C for 23 hours (V1-BR), and after heat treatment at 400°C for 2 hours (V1-HT). MaxShield-V2 has a thickness between 70 and 90 μm. The manufacture of MaxShield-V2 uses a heat treatment process to improve hardness and wear performance. MaxShield-V3 is similar to MaxShield-V2, but is not heat treated.

[0197] The key process factors of MaxShield were also compared to EHC (electroplated hard chrome). At a current density of 500 ASF, the EHC process is not efficient as the deposition rate is about 0.7 mil / hr. For MaxShield, the deposition rate is twice as fast at about 14 times less current, but the higher deposition rate makes the MaxShield process more efficient compared to the EHC process.

[0198] Example 2 The original appearance of the coating is close to that of a typical nickel coating. Figure 14 shows a hydraulic bar coated with MaxShield and compared to one coated with EHC. Both MaxShield and EHC were ground and polished after plating. Through some preliminary testing, a black version of the coating was possible. The coating can be further polished and machined to change the appearance. It is conformal and can be applied to rough surfaces.

[0199] Example 3 The most common thicknesses for MaxShield range from 1 micron to 75 microns. Coatings thicker than 0.5 mm can also be produced. Coating thicknesses can be less than 1 micrometer to over 1.5 mm if desired. Coating thickness is controlled primarily by deposition time.

[0200] Example 4 A testing laboratory (Assured Testing Services, a NADCAP certified testing facility) was used to measure corrosion. The test was a standard corrosion test, also known as a salt fog test. During this test, the coated samples are exposed to a 5% sodium chloride mist that simulates the corrosion of a marine environment. The test was performed at the testing laboratory according to ASTM B117-19. This test compares the corrosion performance of the EHC coating and the electroless nickel coating with the corrosion performance of our coating up to 5000 hours of exposure to salt fog. Assured Testing Services determined the corrosion rating of the different samples according to ASTM D610 Rust Grade. This standard means a rating range between 0 and 10, with 10 corresponding to the best corrosion resistance and 0 corresponding to worse corrosion resistance. The testing laboratory also performed a salt fog test on two samples of the MaxShield-V1 coating. Tests were also performed on two samples of the MaxShield-V2 and MaxShield-V3 coatings. The inventors also provided the EHC and electroless nickel coatings to the testing laboratory as control samples. Assured Testing Services scribed one MaxShield-V 1 coating and also tested it in a salt fog chamber.

[0201] Results for the first 1000 hours. Figures 15A and 15B show carbon steel samples coated with EHC and electroless nickel coatings with corrosion ratings of 4 and 0, respectively, after 1000 hours of exposure to salt fog. Both of these two samples were produced by an independent plating department. According to ASTM D610, a corrosion rate of 0 for electroless nickel after 1000 hours indicates rust formation on more than 50% of the surface area. Furthermore, a corrosion rate of 4 for the EHC coating indicates that 3-10% of the surface area is corroded after 1000 hours. Images of all five MaxShield coatings after 1000 hours of exposure to salt fog are shown in Figures 16A-E. Four of these samples show a rating of 9, while one of the Maxshield-V1 samples has a corrosion rating of 10 after 1000 hours. A corrosion rate of 9 indicates rust formation on less than 0.03% of the surface area according to the ASTM D610 standard. The Maxshield-V1 sample, rated 10, had no rust in the first 1000 hours.

[0202] Figure 17 compares the salt spray test results of our coating with those of the EHC coating. As the figure shows, the corrosion rating of the EHC coating drops sharply to 4 after 400 hours of exposure to salt spray, while the corrosion rate of our coating remains above 9 up to 1000 hours of exposure.

[0203] The scribed MaxShield-V1 coating resulted in a corrosion rate of 9 in the area far from the scribed area. A creep measurement rating of 8 was obtained for the scribed area on this specimen based on ASTM D1654. Preliminary testing of the scribed surface indicates that MaxShield is not expected to pose a significant risk of accelerated corrosion if scratched and the underlying steel surface is exposed in the scratched location.

[0204] Corrosion test results after 1000 hours: Salt spray corrosion testing was continued on the MaxShield samples after 1000 hours. The grades of the samples at different times of salt spray testing and the appearance of the samples after 5000 hours are shown in Figure 18A-18E. As shown in Table 1, the grades of Maxshield-V2 and MaxShield-V3 remain at 9 up to 4000 hours of salt spray.

[0205] [Table 1]

[0206] Three samples of MaxShield-V1 show corrosion ratings of 7, 9, and 8, respectively. MaxShield-V1 is thinner in thickness compared to Maxshield-V2 and MaxShield-V3. With thinner coatings, there is a higher chance that corrosive media can reach the base steel substrate through pinholes and defects on the coating, resulting in corrosion. This may be the reason why Maxshield-V2 and MaxShield-V3 perform better than MaxShield-V1 in this extended exposure to corrosive media. As shown in the images in Figures 26A-26E, MaxShield creates a greenish tarnish that can be easily distinguished from rust.

[0207] Example 5 Testing Laboratory: Assured Testing Services, a NADCAP accredited testing facility. Procedure: Three sets of specimens were tested. Each set included four notched bars covered with a version of the MaxShield coating. Images of one of these notched bars before and after the coating was applied are shown in Figure 19. The bars were tested by the testing laboratory in accordance with ASTM F519-18 at a sustained load of 75% of the breaking strength for 200 hours. Results: All four notched bars of both MaxShield-V 1 and MaxShield-V 2 passed the test and showed no spallation. These results demonstrate that the MaxShield-V1 and MaxShield-V2 coatings do not cause hydrogen-induced cracking and can withstand hydrogen embrittlement. It is worth mentioning that MaxShield-V3 is a thicker version of MaxShield-V1 that offers greater protection against hydrogen embrittlement. Therefore, since MaxShield-V1 passed the test, it is expected that MaxShield-V3 will also pass the test.

[0208] Example 6 Testing Laboratory: A2LA Certified Testing Laboratory at Anamet, Inc. Procedure: The ductility of MaxShield-V1 and MaxShield-V2 coatings was determined by the testing laboratory in accordance with ASTM E8-21 (Tensile Testing of Metallic Materials), in which coated T-bone specimens are uniaxially tensile tested until the coating falls off and the underlying surface becomes visible in a 50x microscope image.

[0209] Results: Testing showed that both MaxShield-V1 and MaxShield-V2 coatings can be stretched to more than 6% without spalling or fracturing. The ductility value of more than 6% is significantly higher than the ductility of the EHC coating, which is less than 0.1% (1). It is also higher than the ductility of the electroless nickel coating, which is 1% to 1.5% (2). Based on these results, it can be concluded that the MaxShield coating is much more formable compared to the EHC and electroless nickel coatings. Figures 20A and 20B show images of the MaxShield-V1 (Figure 20B) and MaxShield-V2 (Figure 20A) coatings after 6% stretching. A microscope image of the MaxShield-V1 coating is shown in Figure 21. As Figures 20A-21 show, the coatings exhibit a ductility of at least 6% without any fracturing or blistering.

[0210] Example 7 Testing Laboratory: EP Laboratories is listed on Qmed as an independent testing laboratory specializing in mechanical testing at the nano and micro levels. Procedure: The coefficient of friction of MaxShield-V2 and MaxShield-V3 coatings was measured by EP Laboratories according to ASTM G99-17 specifications. As shown in Figure 22, the test involved applying a force of 20N through a hard ball made of 440C stainless steel to a lubricated coated surface rotating at 200 revolutions per minute. One of the main characteristics of EHC is its low coefficient of friction or slipperiness in a lubricated environment. The test also measured the coefficient of friction of EHC and compared it to the MaxShield coating.

[0211] Results: The measured coefficients of friction for EHC, Maxshield-V2 and MaxShield-V3 coatings are shown in Table 2. As shown in the table, the coefficients of friction for both versions of MaxShield are slightly lower than the EHC coating. Based on these results, we expect roughly similar performance of the MaxShield coatings in lubricated wear conditions. It is worth mentioning that MaxShield-V1 may have lower performance in severe wear environments, which is why it was not tested here.

[0212] [Table 2]

[0213] Example 8 Testing Laboratory: EPI Materials Testing Group, an Iso certified independent laboratory. Procedure: Hydrogen sulfide cracking tests were performed on the coated surfaces in accordance with NACE TM-0284. The carbon steel coated surfaces were subjected to an acidic environment for 96 hours during which H2S gas and nitrogen purge gas were introduced. The coated surfaces were metallographically polished to highlight the cracks caused by H2S gas. The cracks are measured and reported as stated by the standard, as shown in Figure 23. Two samples of MaxShield-V1 were tested.

[0214] Results: As reported by a third-party testing center, visual and stereoscopic inspection as well as subsequent inverted microscopic examination revealed that our coatings were free of cracking. Figures 24A and 24B show images of two carbon steel bars coated with MaxShield-V1 after (Figure 24B) and before (Figure 24A) testing. As shown in the microscopic image in Figure 25, the surface covered with MaxShield-V1 coating was free of hydrogen-induced blistering or cracking. It is worth mentioning that MaxShield-V2 and MaxShield-V3 are less susceptible to hydrogen sulfide cracking compared to MaxShield-V1 due to their larger thickness. This is the reason why this test was only performed on MaxShield-V1.

[0215] Microhardness Testing Testing Laboratory: Previous microhardness testing was performed by Anamet, inc., an A2LA certified testing laboratory, with additional testing performed by Maxterial Inc. Procedure: Testing was performed according to ASTM E384-17 standard. Previous Results Obtained by Anamet: Testing was performed on four coated carbon steel specimens. A description of the specimens and their test results is as follows: Specimen 1 is coated with MaxShield-V3. A Vickers hardness of 660 was obtained for this specimen. Specimen 2 is coated with MaxShield-V3. A Vickers hardness of 605 was obtained for this specimen. Specimen 3 is coated with MaxShield-V2. An average Vickers hardness of 750 was obtained for this specimen. Specimen 4 is also coated with MaxShield-V2. An average Vickers hardness of 822 was obtained for this specimen.

[0216] These results show the effect of heat treatment on improving the hardness of the MaxShield-V2 coating. Many internal hardness tests were performed on the 50 μm MaxShield coating. These results confirm that the Vickers hardness of the plated MaxShield is in the range of 630 to 670. The microhardness values ​​obtained in this test are compared in Table 3 with those of several other hard coatings obtained from the literature. As Table 3 shows, all the microhardnesses of our coatings are better than those of the plated electroless nickel coating. Furthermore, the MaxShield-V2 coating shows a slightly better Vickers hardness than the heat-treated electroless nickel coating. It is worth mentioning that electroless nickel is a wear-resistant coating known as one of the alternatives to EHC coatings. The hardness of the MaxShield-V2 coating is also comparable to that of the EHC coating. Furthermore, the hardness of MaxShield is much higher than the hardness of Hastelloy-B2(3), which is 241.

[0217] High temperature performance and comparison with EHC: An important point, also highlighted in Table 3, is that the hardness of the EHC coating decreases at high temperatures (4). In a normal bake-off process at 190°C for 23 hours, the hardness of the EHC decreases from 800-1000 to values ​​between 700-750. Furthermore, as shown by the cross-sectional images discussed in Example 11, heat compromises the integrity of the EHC coating by generating large macrocracks in its structure. Thus, the coating is expected to lose its corrosion protection at higher temperatures. As a result, despite environmental regulations and mandates regarding the elimination of EHC coatings, this coating will not function at high operating temperatures.

[0218] In contrast, the hardness of the MaxShield-V2 coating is expected to increase at elevated temperatures. In real-world applications, the coating will be exposed to heat under some circumstances. As an example, unlike chrome, when specimens are ground or used in high friction or high temperature environments, MaxShield is expected to have increased hardness in these environments.

[0219] [Table 3]

[0220] Example 9 Taber abrasion test Testing Facility: Maxterial Inc. Procedure: Standard Taber abrasion test was performed by us according to ASTM D4060-19 standard. In this test, the surface of the coating is abraded by applying a load of 1 kg to each abrasive wheel using the abrasive machine shown in Figure 26.

[0221] Results: Taber Abrasion Index is the milligram weight loss per 1000 cycles. We have recently tested modified versions of MaxShield. Samples were prepared and tested as plated (MaxShield-V1) and after heat treatment at 400°C for 2 hours (MaxShield-V2). The TWI results for the MaxShield samples are shown in Figure 27. This figure also shows the TWI values ​​for plated, heat treated EHC and electroless nickel coatings. Tests were performed on at least three different samples for each coating, and the results for the electroless nickel and EHC coatings are consistent with those in the literature (2). These results show an average TWI of 6 and 5 for plated and heat treated MaxShield, respectively, which are very close to those obtained for EHC. The TWI of the heat treated MaxShield is even slightly better than the TWI of 6 for the heat treated EHC.

[0222] Considering the huge challenge for EHC coatings due to environmental regulations, it is worth mentioning that electroless nickel coatings have been accepted in the industry as one of the viable alternatives. As the figure shows, the plated version of the coating (MaxShield-V3) with an average TWI of 6 is expected to show better wear performance compared to the plated electroless nickel with an average TWI of 15. The heat-treated version of our coating (MaxShield-V2) with an average TWI of 5 also shows better wear performance compared to the heat-treated electroless nickel with an average TWI of 7. As explained before, the wear performance of EHC coatings degrades after exposure to heat. The average TWI of the heat-treated EHC is 6, which is greater than the average TWI of 5 for the MaxShield-V2 coating.

[0223] Example 10 Block on ring test Test Facility: Falex Corporation Procedure: Testing was performed per ASTM G-77-17 by Falex Corporation, one of the industry pioneers in performing this test. In this test, the test block was loaded with 30 pounds against the test ring rotating 500,000 times at 197 rpm. Block scar volume was calculated from the block scar width and ring scar volume was calculated from the ring weight loss. Additionally, CoF values ​​were measured continuously during the test. Testing was performed on ring specimens coated with MaxShield with a minimum thickness of 0.006 inches. The rings were made of 4620 steel. They were ground and polished to a coating thickness of 0.003 inches to 0.005 inches and a surface finish of 4 to 8 micro inches. In this test, the blocks were uncoated PH13-8Mo steel. Testing of chrome coated rings is in progress and results will be provided shortly.

[0224] Results: The test results are summarized in Table 4. As shown in the table, a CoF of 0.045 was obtained for MaxShield in this test. Compared to the CoF of 0.146 reported in the literature (5) for chromium in this test, the CoF of MaxShield is more than three times lower. Figure 28 shows a graph of CoF vs. cycles. As shown in this figure, the CoF remains almost constant during the test. This result means that the MaxShield coating does not cause any gouging issues.

[0225] [Table 4]

[0226] Example 11 Corrosion testing in aggressive acidic environments. Test Facility: Maxterial Inc. Procedure: In-house testing performed by our company. In this test, coated carbon steel specimens were immersed in an aqueous solution of concentrated hydrochloric acid (32% HCl) for 24 hours. The weight loss of the coating after 24 hours of exposure to the concentrated HCl solution was used to calculate the corrosion rate. It is worth mentioning that 32% HCl is a very strong acid with a negative pH.

[0227] Results: Figure 29 compares the corrosion rates of the modified MaxShield-V1 coating with existing nickel coatings, Monel, Inconel, and Hastelloy. The rates reported for these coatings in Figure 29 are averages of corrosion tests obtained on at least three different samples. As the figure shows, the corrosion rates of the MaxShield-V1 coating (less than 13 milliinches per year, and sometimes less than 1.5 milliinches per year) are much slower than the corrosion rates of existing nickel coatings (80 milliinches per year) (6). Figure 29 also shows the corrosion rates of the corrosion-resistant bulk materials Hastelloy® B2 and Inconel® against concentrated HCl solutions, based on values ​​published in the literature (7), (8). Interestingly, our coatings show a lower corrosion rate compared to Hastelloy® (15 milliinches per year) and Inconel® (39 milliinches per year). Hastelloy® and Inconel® are superalloys known for their extremely high corrosion resistance in HCl environments. The EHC coating dissolves in concentrated HCl in less than 10 minutes, and its corrosion rate is not on the scale of this figure.

[0228] Example 12 Form Test Facility: Maxterial Inc. Procedure: This test was performed at Maxterial to examine cross sections of MaxShield, measure thickness, and evaluate the effect of heat treatment on the coating structure. All metal processing was performed by Maxterial using their in-house equipment. EHC samples with a thickness of approximately 100 μm were provided to the inventors by the chrome plating department. Cross sections of plated and heat treated EHC and MaxShield-V1 samples are shown in Figures 30A and 30B, respectively. Heat treatment was performed at 400C for 2 hours. This cross section analysis was performed on the 2021 modified MaxShield-V1. As shown in this figure, the plated EHC has microcracks throughout the cross section, while the plated MaxShield is much smaller and has fewer cracks. After heat treatment, the EHC cracks occurred. Some of the cracks grew from the substrate all the way to the surface, as shown in Figures 30A and 30B. The presence of this type of macrocrack in the coating structure can significantly reduce the corrosion protection of the coating. On the other hand, the cross section of MaxShield remained the same after thermal exposure and no signs of crack initiation were observed in MaxShield. The decrease in mechanical properties of EHC at high temperatures can be related to this crack initiation and growth mechanism that occurs in EHC during thermal exposure. This decrease was shown earlier in this report by the results of Taber abrasion and Vickers hardness tests.

[0229] Example 13: Effects of Heating and Adhesion Bending Tests Testing Facility: Maxterial Inc. Procedure: Adhesion bending test was performed on heat treated MaxShield samples. It is worth mentioning that adhesion bending test according to ASTM B571-18 is always an important part of our evaluation because if the coating does not provide strong adhesion, it cannot provide wear and corrosion protection either.

[0230] In this test, a strip of 1008 carbon steel (CS) with an exposed area of ​​3 cm x 5 cm was coated on one side with MaxShield. The coated specimen was then placed in an oven at 700°C in air for 1 hour. An adhesion bend test was performed on the specimen according to ASTM B571-18. The test steps and results are shown in Figures 31A-31D. In this test, a piece of tape was attached to the coating surface. Strong adhesion between the coating and the tape was confirmed by the removal of air bubbles from the area under the tape. The taped specimen was then bent 180 degrees and the tape was removed from the coating surface. If the coating peels off from the surface and transfers to the tape, the test fails.

[0231] Results: The tape was transparent. No delamination of the coating was observed. The coating passed the adhesion bend test. The uncoated areas of the CS were covered with iron rust scale after heating. These uncoated areas were covered with tape before the bend test to avoid migration of loose rust particles to the coating surface.

[0232] Example 14 Moldability Procedure: A number of 180 degree bend tests were performed with MaxShield V1, always with promising results. A flat sheet of carbon steel was coated with a 6 μm thick layer of MaxShield. The coated sheet was subjected to forming processes to produce parts. During these processes the coating has to be bent and formed.

[0233] Results: The coating remained intact after forming, with no peeling or defects observed. It is worth mentioning that EHC and thermal spray coatings are more likely to peel off under these circumstances.

[0234] Example 15 Machining We perform various machining operations on the samples. For example, we may drill holes in the coated parts to prepare test specimens, polish the coating to a high shine, or grind to adjust thickness. We have not experienced any problems in these machining processes. Our data shows that MaxShield can be machined without adhesion failure. On the other hand, machining chrome is known to be problematic due to chipping and delamination issues. We believe this is because Maxshield has much better ductility than EHC. Additionally, MaxShield adheres well to most substrates.

[0235] Example 16 Process Factor Overview MaxShield is usually manufactured using a typical electroplating process. The process involves electrodeposition followed by proper cleaning and activation of the substrate. Some of the process factors of MaxShield are as follows: Power source: MaxShield uses a DC current power source; Deposition rate: The typical deposition rate of MaxShield (1.5 mil / hr) is twice as fast as that of EHC (0.7 mil / hr). The deposition rate of MaxShield can vary depending on multiple factors such as current density; Plating efficiency: The plating efficiency of MaxShield (80-90%) is much higher than that of EHC (10-35%). It is worth mentioning that in most cases, the plating efficiency of EHC is less than 20%. Electroplating process temperature: The plating temperature of MaxShield is in the industry normal range (140-170F).

[0236] Example 17: Safety and Environmental Compliance Testing Facility: TUV SUD, 2021 Testing performed for both REACH and RoHS.

[0237] The result: MaxShield passed both tests. The chemicals used in the manufacture of MaxShield, called MaxShield coating and LeanX, are free of substances of very high concern (SVHCs). Notably, both MaxShield and LeanX are free of chromium, cadmium, cyanide, lead, and fluorochemicals such as PFOS and PFAS.

[0238] References 1.Physical Properties of Electrodeposited Chromium.USDepartment of Commerce,National Bureau of Standards.sl:Journal of Research of the National Bureau of Standards,1948. 2.Tech Metals.THE ENGINEERING PROPERTIES OF ELECTROLESS NICKEL COATINGS.Dayton:Tech Metals,1983. 3.AZO Materials.Super Alloy HASTELLOY(r)B-2 Alloy(UNS N10665).[Online] https: / / www.azom.com / article.aspx?ArticleID=7680. 4.Prado, R.Electrodeposition of Nanocrystalline Cobalt Phosphorous Coatings as a Hard Chrome Alternative.Jacksonville.sl:NavAir,2014. 5.Prado,RA,et al.Electrodeposited Nanocrystalline Co-P Alloy Coatings as a Hard Chrome Alternative.sl:ESTCP Project WP-200936,2015. 6.Nickel Development Institute.Resistance of Nickel and High Nickel Alloys to Corrosion by Hydrochloric Acid,Hydrogen Chloride,and Chlorine. 7.Osborne,P.E.,Icenhour,A.S.and Cul,G.D.Del.Corrosion Test Results for Inconel 600 vs Inconel-Stainless UG Bellows.Oak Ridge,Tennessee:OAK RIDGE NATIONAL LABORATORY,2002. 8.Corrosion Materials.Hastelloy B2 Datasheet.[Online] https: / / www.corrosionmaterials.com / documents / dataSheet / alloyB2DataSheet.pdf. 9.Residual Stresses and Strength of Hard Chromium Coatings.Pfeiffer,W.,et al.s.l.:Materials Science Forum,2011,Vol.681. 10.Toll Bridge Program Oversight Committee,California Transportation Commision.Report on the A354 Grade BD High-Strength Steel Rods on the New East Span of the San Francisco-Oakland Bay Bridge With Findings and Decisions.2013. 11.Nickel Development Institute.Resistance of Nickel and High Nickel Alloys to Corrosion by Hydrochloric Acid,Hydrogen Chloride and Chlorine.[Online] https: / / www.nickelinstitute.org / ~ / media / Files / TechnicalLiterature / ResistanceofNickelandHigh_NickelAlloystoCorrosionbyHydrochloricAcid_HydrogenChlorideandChlorine_279_.ashx. 12.Corrosion Materials.Alloy B2 Data Sheet.[Online] http: / / www.corrosionmaterials.com / documents / dataSheet / alloyB2DataSheet.pdf.

Claims

**Claim 1** A coated surface provided with a surface coating, wherein the surface coating comprises an alloy layer containing molybdenum or tungsten and at least one element selected from the group consisting of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium and boron, or at least one compound containing one or more of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium or boron. The coated surface. **Claim 2** The coated surface according to claim 1, wherein the surface coating is an exposed outer layer and does not contain silver or gold, or does not contain all noble metals. **Claim 3** The coated surface according to claim 1 or claim 2, wherein the molybdenum or tungsten is present in the surface coating at 35% by weight or less, or 25% by weight or less, or 15% by weight or less based on the weight of the surface coating. **Claim 4** The coated surface according to claim 1 or claim 2, wherein the molybdenum or tungsten is present in the alloy layer at 35% by weight or less, or 25% by weight or less, or 15% by weight or less based on the weight of the alloy layer. **Claim 5** The coated surface according to claim 1 or claim 2, wherein the molybdenum or tungsten is present in the surface coating at 65% by weight or more, or 75% by weight or more, or 85% by weight or more based on the weight of the surface coating. **Claim 6** The coated surface according to claim 1 or claim 2, wherein the molybdenum or tungsten is present in the alloy layer at 65% by weight or less, or 75% by weight or less, or 85% by weight or less based on the weight of the alloy layer. **Claim 7** The coated surface according to claim 1 or claim 2, wherein the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum and one of tin, phosphorus, iron or boron, or nickel and tungsten, or nickel, tungsten, molybdenum and one of tin, phosphorus, iron or boron. Claim 8 The coated surface is present on a substrate, and the substrate is carburized steel, nitrided steel, carbonitrided steel, stainless steel, carbon steel, alloy steel, titanium, copper, or a copper alloy. The coated surface according to claim 1. Claim 9 The coated surface has a surface roughness Ra of less than 1 micron. The coated surface according to claim 7. Claim 10 The coated surface has a surface roughness Ra of 1 micron or more and less than 15 microns. The coated surface according to claim 7. Claim 11 The alloy layer is an electrodeposited exposed alloy layer, and the electrodeposited exposed alloy layer consists essentially of (i) molybdenum and only one of nickel, tungsten, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (ii) molybdenum and only two of nickel, tungsten, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (iii) both molybdenum and phosphorus and at least one of nickel, cobalt, tin, chromium, tungsten, iron, magnesium, or boron, or (iv) tungsten and only one of nickel, molybdenum, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (v) tungsten and only two of nickel, molybdenum, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron, or (vi) both tungsten and phosphorus and at least one of nickel, molybdenum, cobalt, tin, chromium, tungsten, iron, magnesium, or boron. The coated surface according to claim 2. Claim 12 The alloy layer is an electrodeposited alloy layer, and further includes an intermediate layer under the alloy layer. The intermediate layer includes one or more of nickel, nickel alloy, copper, copper alloy, nickel-tungsten alloy, cobalt alloy, nickel-phosphorus alloy, molybdenum or tungsten alloy, or both, and at least one of nickel, cobalt, chromium, tin, phosphorus, iron, or boron. The coated surface according to claim 1 or claim 2. Claim 13 Further comprising an additional layer formed on the alloy layer, wherein the additional layer comprises one or more of nickel, nickel alloy, nickel-tungsten alloy, cobalt alloy, cobalt-phosphorus alloy, nickel-phosphorus alloy, molybdenum alloy, and at least one of nickel, cobalt, chromium, tin, phosphorus, iron or boron, ceramics, and the ceramics comprise tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, metal nitride, nitride, metal carbide, carbide, boron, tungsten, tungsten carbide, chromium carbide, chromium oxide, aluminum oxide, zirconia, zirconium oxide, titania, nickel carbide, nickel oxide, nanocomposite, oxide composite, or a combination of these compounds, the coated surface according to claim 1 or claim 2.

14. The coated surface according to claim 1 or claim 2, further comprising an additional layer formed on the alloy layer containing ceramics.

15. The coated surface according to claim 14, wherein the coated surface has a surface roughness Ra of less than 1 micron, or 1 micron or more and less than 5 microns, or 5 microns or more and less than 15 microns.

16. The coated surface according to claim 1 or claim 2, wherein the alloy layer further comprises one or more particles selected from the group consisting of solid nanoparticles, polymer particles, hard particles, silicon dioxide particles, silicon carbide particles, titanium dioxide particles, polytetrafluoroethylene particles, hydrophobic particles, diamond particles, particles functionalized with hydrophobic groups, solid particles, and combinations thereof.

17. The coated surface according to claim 1, wherein the alloy layer exists as an exposed outer layer of the surface coating, the exposed outer layer is an electrodeposited alloy layer, and the electrodeposited alloy layer excludes silver or gold, or excludes all noble metals.

18. The coated surface according to claim 17, wherein the alloy layer further comprises particles.

19. The coated surface according to claim 1, wherein the surface coating comprises a first layer and a second layer, and the first layer or the second layer, or both, comprise the alloy layer.

20. The coated surface according to claim 19, wherein the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum and one of tin, phosphorus, iron, magnesium or boron, or consists essentially of nickel and tungsten, or consists essentially of nickel, tungsten and one of tin, phosphorus, iron, magnesium or boron.

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