Articles with decorative surface coatings

Abstract

Decorative articles having surface coatings are described. The surface of the decorative article can include the surface coating. The surface coating can include many different materials, including metals or metal alloys, such as molybdenum alloys. A decorative coating layer including chromium or other materials can be present on the alloy layer, for example, on the molybdenum alloy layer.

Description

[Technical Field]

[0001] Priority claim This application claims priority to and benefit of U.S. Provisional Patent Application No. 63 / 433,363, filed December 16, 2022, the entire disclosure of which is incorporated herein by reference for all purposes.

[0002] Certain compositions described herein relate to decorative coatings that can be used on jewelry, silverware, automotive parts, connector shells, and other devices or parts thereof. Summary of the Invention [Means for solving the problem]

[0003] Certain aspects, embodiments and configurations are described below in the context of articles that include decorative surface coatings.

[0004] In one embodiment, the decorative article includes a decorative substrate, and at least a portion of the exterior surface of the decorative substrate includes a coated surface. For example, the coated surface includes a surface coating, and the surface coating includes an alloy layer including (i) molybdenum or tungsten, and (ii) at least one element selected from the group consisting of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, and boron, or at least one compound including one or more of nickel, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron.

[0005] In certain embodiments, the alloy layer is present on the entire surface of the decorative article substrate, while in other embodiments, the alloy layer is present on the interior surface of the decorative article substrate.

[0006] In certain configurations, molybdenum or tungsten is present in the surface coating at 40 wt.% or less based on the weight of the surface coating, or 20 wt.% or less based on the weight of the surface coating, or 10 wt.% or less based on the weight of the surface coating, or 40 wt.% or less based on the weight of the alloy layer, or 20 wt.% or less based on the weight of the alloy layer, or 10 wt.% or less based on the weight of the alloy layer.

[0007] In other embodiments, the surface coating comprises a surface roughness Ra of less than 1 micron or less than 10 microns.

[0008] In some embodiments, the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum and phosphorous, or consists essentially of nickel and tungsten, or consists essentially of nickel, tungsten and phosphorous.

[0009] In another embodiment, the surface coating comprises a surface roughness Ra of less than 1 micron, the molybdenum or tungsten is present in the alloy layer at 20 wt % or less based on the weight of the surface coating, and the surface coating is free of precious metals.

[0010] In certain configurations, the alloy layer is an electrodeposited alloy layer. In other configurations, the surface coating does not include a precious metal.

[0011] In certain embodiments, the alloy layer is the exposed outer layer of the surface coating. In some embodiments, the exposed outer layer consists essentially of (i) molybdenum or tungsten and only one element or compound including nickel, cobalt, tin, phosphorus, iron, chromium, or boron, or (ii) molybdenum or tungsten and only two elements or compounds including nickel, cobalt, tin, phosphorus, iron, chromium, or boron, or (iii) molybdenum, nickel, and elements or compounds including tungsten, cobalt, tin, phosphorus, iron, chromium, or boron, or (iv) tungsten, nickel, and elements or compounds including molybdenum, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron.

[0012] In certain configurations, an intermediate layer can be between the alloy layer and the surface of the substrate. In certain embodiments, the alloy layer is present as the exposed outer layer of the surface coating, the exposed outer layer being an electrodeposited alloy layer, and the electrodeposited alloy layer does not include a precious metal.

[0013] In some instances, additional layers may be formed on the alloy layer.

[0014] In other embodiments, the alloy layer is present as an electrodeposited alloy layer, and the electrodeposited alloy layer does not include a precious metal.

[0015] In certain embodiments, the decorative article substrate comprises a textured surface. In other embodiments, the coated surface comprises a textured surface. In certain embodiments, the textured surface comprises a surface roughness Ra of greater than 1 micron and less than 30 microns, or a surface roughness Ra of greater than 0.5 microns and less than 15 microns.

[0016] In certain embodiments, the coated surface is free of precious metals.

[0017] In some configurations, the decorative article substrate comprises stainless steel, hardened steel, carbon steel, alloy steel, precious metal or other metal, and the surface coating comprises a chrome layer over the alloy layer.

[0018] In other embodiments, the decorative article substrate comprises stainless steel, hardened steel, carbon steel, alloy steel, precious metals or other metals, and the surface coating is lead-free.

[0019] In some embodiments, the decorative article substrate comprises stainless steel, hardened steel, carbon steel, alloy steel, precious metals or other metals, and the surface coating is mercury-free.

[0020] In one aspect, an ornament includes an ornament substrate, at least a portion of an exterior surface of the ornament substrate includes a coated surface, the coated surface includes a surface coating, the surface coating includes an alloy layer including (i) molybdenum or tungsten, and (ii) at least one element selected from the group consisting of nickel, cobalt, tin, phosphorus, iron, magnesium, and boron, or at least one compound including one or more of nickel, cobalt, tin, phosphorus, iron, magnesium, or boron, and the alloy layer is free of chromium, lead, and mercury.

[0021] Further aspects, embodiments, examples and configurations are described in more detail below.

[0022] A brief description of some of the figures in the drawing

[0023] Certain aspects, embodiments and configurations are described with reference to the drawings. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 1 is a diagram of a device including a surface coating on a substrate. [Figure 2] FIG. 1 is a diagram of a device comprising two layers in a coating on a substrate. [Figure 3] FIG. 10 is another view of a device comprising two layers in a coating on a substrate. [Figure 4A] FIG. 1 is a diagram of a device including a textured surface. [Figure 4B] FIG. 1 is a diagram of a device including a textured surface. [Figure 5A] FIG. 1 is a diagram of a device comprising two or more layers. [Figure 5B] FIG. 1 is a diagram of a device comprising two or more layers. [Figure 6] FIG. 2 is a diagram of a coating layer. [Figure 7] FIG. 2 is a diagram of a coating layer. [Figure 8] FIG. 2 is a diagram of a coating layer. [Figure 9] FIG. [Figure 10] FIG. [Figure 11] FIG. [Figure 12] FIG. 1 is a diagram of a device with multiple coating layers. [Figure 13A] 1 shows various decorative coatings on automotive parts. [Figure 13B] 1 shows various decorative coatings on automotive parts. [Figure 13C] 1 shows various decorative coatings on automotive parts. [Figure 13D] 1 shows various decorative coatings on automotive parts. [Figure 13E] 1 shows various decorative coatings on automotive parts. [Figure 13F] 1 shows various decorative coatings on automotive parts. [Figure 13G] 1 shows various decorative coatings on automotive parts. [Figure 14A] 1 shows various decorative coatings on silverware. [Figure 14B] 1 shows various decorative coatings on silverware. [Figure 14C] 1 shows various decorative coatings on silverware. [Figure 14D]1 shows various decorative coatings on silverware. [Figure 14E] 1 shows various decorative coatings on silverware. [Figure 14F] 1 shows various decorative coatings on silverware. [Figure 14G] 1 shows various decorative coatings on silverware. [Figure 14H] 1 shows various decorative coatings on silverware. [Figure 14I] 1 shows various decorative coatings on silverware. [Figure 14J] 1 shows various decorative coatings on silverware. [Figure 14K] 1 shows various decorative coatings on silverware. [Figure 14L] 1 shows various decorative coatings on silverware. [Figure 14M] 1 shows various decorative coatings on silverware. [Figure 15A] 1 shows various decorative coatings on jewelry. [Figure 15B] 1 shows various decorative coatings on jewelry. [Figure 15C] 1 shows various decorative coatings on jewelry. [Figure 15D] 1 shows various decorative coatings on jewelry. [Figure 15E] 1 shows the decorative coating on the connector shell. [Figure 15F] 1 shows the decorative coating on the connector shell. [Figure 16] 1 is a photograph showing a coating on a surface. [Figure 17] 1 is a photograph showing a coating on a surface. [Figure 18] 18A-18D are photographs showing cracks in the coating before and after heat treatment. [Figure 19A] 1 is a photograph showing cracks in the coating. [Figure 19B] 1 is a photograph showing cracks in the coating. [Figure 20] 1 is a table showing corrosion scales. [Figure 21] 1 is a photograph showing corrosion on the surface. [Figure 22] 22A to 22E are photographs showing corrosion on the surface. [Figure 23] 1 is a graph showing corrosion versus exposure time. [Figure 24] 1 is a table showing corrosion ratings of different coatings. [Figure 25] Figures 25A, 25D and 25C are photographs showing corrosion. [Figure 26] 1 is a photograph showing a coating applied to a notch bar. [Figure 27] 1 is a photograph showing a coating applied to an article. [Figure 28] 28A and 28B show the results of the wear test. [Figure 29] FIG. 1 is a diagram of the device used to test the coefficient of friction. [Figure 30] 1 is a table showing coefficients of friction. [Figure 31] 1 is a table showing wear rates. [Figure 32] 1 is a table showing wear rates. [Figure 33] 1 is a graph showing Taber abrasion index values. [Figure 34] Photograph showing the discontinuity of a surface-coated socket. [Figure 35] 1 is a graph showing corrosion rates after acid exposure. [Figure 36] 1 is a photograph showing the test coating after stretching. [Figure 37] 37 is a microscope image of the coating of FIG. 36. DETAILED DESCRIPTION OF THE INVENTION

[0025] Given the benefit of this specification, it will be recognized by those skilled in the art that the layers and features shown in the figures are not necessarily drawn to scale. The arrangement and dimensions of the various layers and features in the figures do not imply that any one arrangement or thickness is required.

[0026] Detailed Description

[0027] There is a need for decorative coating technologies. In certain embodiments, the surface coatings described herein can be present in a variety of different types of decorative articles. The decorative article generally includes a substrate formed from a metal, metal alloy, or other material having a coated surface on some portion of the substrate. The entire exterior surface of the decorative article need not include a surface coating, but may include a surface coating if desired. The exact composition and placement of the surface coating can be varied as described below. As described in more detail below, the decorative article can include an outer decorative coating on top of one or more of the surface coatings or layers described with reference to Figures 1-12.

[0028] The coatings described herein can have numerous attributes and properties depending on the specific composition. The coatings can have different appearances. The coatings can be matte or glossy. In certain embodiments, the coatings can have a mirror-like appearance. The coatings can have different colors. For example, they can be metallic, or black, textured or non-textured.

[0029] In certain embodiments, the coatings and coated articles described herein can be heat-treated to increase the hardness of the coating. Hardness can be evaluated according to ASTM E384-17 to determine hardness in the absence of heat treatment and after heat treatment. The exact hardness of the coating can vary depending on the composition and any post-deposition treatments. For example, hardness can vary from 520 to 780 Vickers hardness (HV) after deposition. If desired, hardness can be increased after heat treatment. In some embodiments, hardness can be increased by at least 2%, at least 5%, at least 8%, at least 10%, or more after heat treatment. For example, hardness can be increased to 650 to 940 HV after heat treatment or other treatments.

[0030] Typically, hard chromium coatings have a Vickers hardness under ASTM E384-17 of approximately 800-1000 HV before heat treatment, with the hardness decreasing to 700-750 HV after 23 hours of heat treatment. It's worth noting that most specifications, such as MIL-STD-1501F, require a bake-out requirement at 191±14°C (375±25°F) for 23 hours to prevent hydrogen embrittlement. Therefore, under these bake-out conditions, the hard chromium coating loses its hardness. Furthermore, many applications experience high heat during operation or the coating is exposed to heat, and chromium softens under these operating conditions. In contrast to hard chromium coatings, the coatings described herein can increase their hardness after heat treatment.

[0031] In certain configurations, coatings can be designed to contain, be free of, or be substantially free of microcracks on their surfaces. For example, in applications where the coating is used on an article containing hydraulic fluid, lubricant, or other fluid, the presence of microcracks can enhance retention of the hydraulic fluid, lubricant, or other fluid on the surface of the article. Increasing the density of microcracks can achieve improved properties and longer article life. In some embodiments where microcracks are desirable, the coating can have a microcrack density of 150 to 300 individual cracks per linear inch in the horizontal dimension (based on the total thickness of the coating layer). In certain examples, the coating can be heat treated without changing the overall microcrack density to any substantial extent. If microcracks are present, the microcracks desirably do not penetrate so deeply as to expose the underlying substrate. In examples where microcracks may result in substrate exposure, one or more underlayers can first be coated onto the substrate prior to deposition of the coating to protect the underlying substrate from corrosion. In contrast to hard chromium coatings, which generally have microcracks that form macrocracks after heat treatment, the heat treatment of the coatings described herein generally results in no or few macrocracks, which can increase the overall corrosion resistance of the coatings described herein.

[0032] In certain configurations, the coatings described herein can provide significant corrosion resistance. In some examples, corrosion resistance can be measured by the ASTM B117-19 salt spray test, and the rating can be determined according to the ASTM B537 rust rating test. In essence, the salt spray test provides a controlled, accelerated corrosion environment for evaluating the relative corrosion resistance of a coating, substrate, or portion thereof. The corrosion level can be rated according to a 0-10 scale based on the percentage of visible rust, with 10 representing no surface rust, and the scale decreasing as surface rust appears. A rust scale rating table is provided below in the examples provided below. In certain embodiments, a hard chromium coating has an initial corrosion resistance of 10 that decreases to 4 or less after continuous salt spray exposure. A corrosion rate of 4 indicates that 3-10% of the surface area is corroded after 1000 hours. In certain embodiments, the coatings described herein can have an initial corrosion resistance of 10 that decreases to 9, 8, or 7 after continuous salt spray exposure. In some embodiments, the coatings described herein have a corrosion rating of 6 or greater after 1000 hours of salt spray exposure. In further embodiments, the coatings described herein have a corrosion rating of 7 or greater after 1000 hours of salt spray exposure. In other embodiments, the coatings described herein have a corrosion rating of 8 or greater after 1000 hours of salt spray exposure. In some embodiments, the coatings described herein have a corrosion rating of 9 or greater after 1000 hours of salt spray exposure. In other embodiments, the coatings described herein have a corrosion rating of 10 or greater after 1000 hours of salt spray exposure. In other embodiments, the coatings described herein have a corrosion rating of 6 or greater after 48 hours of salt spray exposure. These corrosion ratings are based on the scale set forth in ASTM B537. In certain embodiments, the coatings described herein exhibit 5% corrosion on their surface (based on total surface area) after 1000 hours of salt spray testing. In other embodiments, the coatings described herein exhibit 5% corrosion on their surface (based on total surface area) after 5000 hours of salt spray testing.In other embodiments, corrosion resistance can be measured by exposing the coating to a strong acid, such as concentrated HCl, concentrated HNO, or concentrated HSO. When acid is used as a measure of corrosion resistance, the weight of the coating before and after acid exposure is used to determine wear resistance. Weight decreases if material is removed as a result of exposure to the acidic environment. Acid resistance testing can involve exposing the coating to 32% HCl for 24 hours by immersing the coating and substrate in the acidic liquid. For consistent comparisons between different types of coatings, results can be normalized to mil-inches per year. Hard chromium coatings can exceed 90,000 mil-inches because these coatings are generally not acid-resistant and dissolve quickly in HCl. Nickel coatings can have an acid resistance of approximately 80 mil-inches per year. Hastelloy® B2 alloy has an acid resistance of 15 mil-inches per year, and Inconel® alloy has an acid resistance of 39 mil-inches per year. In certain embodiments, the coatings described herein can have an acid resistance of less than 30 mil-inches per year, or less than 20 mil-inches per year, or even less than 15 mil-inches per year. For example, the acid resistance of the coatings described herein can vary from 1 mil-inch per year to 20 mil-inches per year, or from 1 mil-inch per year to 14 mil-inches per year, or from 1 mil-inch per year to 13 mil-inches per year, or from 1 mil-inch per year to 12 mil-inches per year, or from 1 mil-inch per year to 11 mil-inches per year, or from 1 mil-inch per year to 10 mil-inches per year.

[0033] The coatings described herein can be more ductile than many existing coatings. Ductility is a measure of a coating's ability to bend without cracking or blistering. Ductility can be measured using ASTM E8 / 8M-22, with higher values ​​representing more ductile coatings. Hard chromium coatings typically have a ductility of less than 0.1%. Electroless nickel coatings have a ductility of 1-1.5%. In comparison, the coatings described herein can have a ductility of 2% or more, or 3% or more. In some embodiments, the ductility can be 4% or more, or even 5% or more. For example, the ductility of the coating can be 2% to 10%, 2% to 9%, 2% to 8%, 2% to 7%, 2% to 6%, 2% to 5%, 2% to 4%, or 2% to 3%. In other embodiments, the ductility of the coating may be 3% to 10%, 3% to 9%, or 3% to 8%, or 3% to 7%, or 3% to 6%, or 3% to 5%, or 3% to 4%. In other embodiments, the ductility of the coating may be 4% to 10%, 4% to 9%, or 4% to 8%, or 4% to 7%, or 4% to 6%, or 4% to 5%. In further embodiments, the ductility of the coating may be 5% to 10%, 5% to 9%, or 5% to 8%, or 5% to 7%, or 5% to 6%. Depending on the materials used, ductility may be greater than 10% for certain coatings, including those described herein. Increased ductility allows the coating to be used on parts that can be formed into shapes after deposition on a substrate, while reducing the risk of defects in the coated surface from the forming process.

[0034] In certain embodiments, the coatings described herein do not pose hydrogen embrittlement issues. In some instances, hydrogen-induced cracking of the coating is not observed after exposure to a hydrogen environment. For example, hydrogen embrittlement can be tested according to ASTM F519-18. In certain embodiments, the coatings described herein do not cause hydrogen embrittlement and do not require special bake-off treatments to avoid such hydrogen embrittlement. In contrast, many hard chromium coatings are susceptible to hydrogen embrittlement and require a tempering process within 1 to 3 hours of plating to avoid hydrogen embrittlement. It is important to note that hydrogen embrittlement depends on the pretreatment process in addition to the plating process. Depending on the pretreatment process, hydrogen embrittlement can occur in coatings regardless of the plating process. Therefore, bake-off is always recommended as a safety precaution for all coatings.

[0035] The coatings described herein can provide longer part life due to the coating's increased wear resistance. Wear resistance is typically measured by cycling a part in an environment that simulates continuous use. For example, and by way of example only, a part can be cycled through its use conditions or exposed to a use environment to simulate wear on the part. The specific movement of one part relative to another depends on the intended use of the article including the coating. Compared to the coatings described herein, the wear resistance of hard chromium coatings generally decreases at high temperatures. For example, hard chromium coatings may exhibit more wear after heat treatment, while the coatings described herein generally have increased wear resistance after heat treatment. This result allows the coatings described herein to be used in high-temperature environments that may not be suitable for hard chromium coatings.

[0036] In certain embodiments, the coefficient of friction of the coatings described herein is comparable to or better than that of hard chrome coatings. One method for measuring the coefficient of friction or wear is the ASTM G99-17 test. The test generally uses a hard ball that applies a force on a surface while the surface is rotating. A lower coefficient of friction generally results in lower wear for the part that includes the coating. The coatings described herein can have a coefficient of friction of 0.10 or less as tested by ASTM G99-17.

[0037] In some embodiments, the ASTM G99-17 test can also be used to measure wear in the presence and absence of a lubricant, if desired. In one particular embodiment, the wear rate of a hard chrome coating (in the absence of any lubricant on the surface) is 600×10 under the ASTM G99 test. -5 mm 3 / m, but the coatings described herein have a viscosity of 100×10 -5 mm 3 / m or less than 75 x 10 under ASTM G99 test -5 mm 3 / m or less than 50 x 10 under ASTM G99 test -5 mm 3 / m or less than 25 x 10 under ASTM G99 test -5 mm 3 / m (in the absence of any lubricant on the surface). In some embodiments, the wear rate of the disk under ASTM G99 test is less than 10 x 10 -5 mm 3 / m, or even less than 5 x 10 under ASTM G99 testing -5 mm 3 For example, the wear rate of a disk can be less than 0-5×10 / m under the ASTM G99 test. -5 mm 3 / m, or 1 x 10 under ASTM G99 testing -5 mm 3 / m~5×10 -5 mm 3 / m.

[0038] In certain configurations, the coatings described herein can have higher adhesion to the underlying substrate or layer compared to hard chrome coatings. Higher adhesion can often result in improved abrasion resistance and better corrosion resistance. Adhesion can be measured according to ASTM B571-18. Generally, the coatings described herein can pass adhesion testing such that no material transfers from the surface to the test tape used in the ASTM B571-18 test.

[0039] In certain embodiments, the coatings described herein can be more environmentally friendly. In some embodiments, the coatings can be lead-free. In other embodiments, the coatings can be cadmium-free. In further embodiments, the coatings can be mercury-free. In some embodiments, the coatings can be hexavalent chromium-free. In other embodiments, the coatings described herein can be fluorochemicals, such as PFAS or PFOS. In other embodiments, the coatings can be lead, cadmium, mercury, hexavalent chromium, and fluorochemicals-free.

[0040] The coatings described herein need not include all of the performance characteristics described above, but can include one or more of these attributes depending on the composition and intended use of the part including the coating.

[0041] Certain layers or coatings are described with reference to weight percent. The weight percent may be based on the weight of the entire layer or coating. In some embodiments, one metal in a layer is present in the layer at 20% by weight or less, e.g., 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% by weight or less. For example, one or more of molybdenum, tungsten, or cobalt may be present in the layer or coating at 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% or less. In other configurations, one or more of the layers can include a metal present at 80% or more by weight, e.g., 81%, 82%, 83%, 84%, 85%, 85%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more by weight in the layer or coating. For example, nickel can be present in the layer or coating at 80%, 81%, 82%, 83%, 84%, 85%, 85%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 99% or more by weight in the layer or coating.

[0042] In certain embodiments, the substrate can include one or more layers, as described below in connection with Figures 1-12. Specific articles or devices including the substrate and / or other layers are also described. The exact material(s) in the surface coating can vary. In some configurations, the surface coating includes one or more metals. In some embodiments, the surface coating can include a metal alloy, such as an alloy containing two or more metals. In some embodiments, the surface coating includes a metal alloy containing only two metals, or a metal and another material. In certain embodiments, the surface coating includes a metal alloy containing only three metals, or a metal and two other materials. In other embodiments, the surface coating can include only a single layer formed on the substrate. For example, the single layer can be exposed to the environment to protect the underlying substrate from degradation. In some examples, the surface coating can include only a first layer formed on the substrate and a second layer formed on the first layer.

[0043] In some embodiments, the alloy layer may "consist essentially of" two or more materials. The phrase "consisting essentially of" or "essentially consisting of" is intended to refer only to the specified materials and trace amounts of impurities, and to those materials that do not substantially adversely affect the fundamental properties of the composition. The term "consisting of" refers only to those materials and any impurities that cannot be removed through conventional refining techniques.

[0044] 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.

[0045] 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.

[0046] 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, and Lu), hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and mercury.

[0047] In other embodiments, the alloy layers described herein can include one, two, or more Group VII metals, including non-radioactive actinides (Th, Pa, U).

[0048] In some examples, 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.

[0049] 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.

[0050] 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.

[0051] In some embodiments, the alloy layers described herein include only two metals: one metal from Group VI metals and another metal from Group V, Group VI, or Group VII metals.

[0052] In some embodiments, the alloy layers described herein include only two metals: one metal from Group V metals and another metal from Group VI or Group VII metals.

[0053] In other embodiments, the alloy layers described herein include only two metals: one metal from Group VI metals and another metal from Group VII metals.

[0054] In some examples, the alloy layers described herein include only two metals, where both metals are Group IV metals.

[0055] In some embodiments, the alloy layers described herein include only two metals, where both metals are Group V metals.

[0056] In some embodiments, the alloy layers described herein include only two metals, where both metals are Group VI metals.

[0057] In some embodiments, the alloy layers described herein include only two metals, where both metals are Group VII metals.

[0058] If desired, the alloy layers described herein can also include, in addition to or in place of other metals, Group II materials (Li, Be, B, and C), or Group III materials (Na, Mg, Al, Si, P, and S). These materials can be present in combination with one, two, three, or more metals.

[0059] In some embodiments, the alloy layers described herein comprise molybdenum 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 molybdenum and only one additional metal, 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 molybdenum and only two additional metals or materials, such as two or more 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 single layer formed on the substrate, where the single layer comprises molybdenum 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 single layer formed on a substrate, where the single layer comprises molybdenum and only one additional metal, for example, 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 single layer formed on a substrate, where the single layer comprises molybdenum and only two additional metals or materials, for example, 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.

[0060] In some embodiments, the alloy layers described herein comprise 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 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 two additional metals or materials, such as two or more 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 single layer formed on the substrate, where the single layer 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 single layer formed on a substrate, where the single layer comprises tungsten and only one additional metal, for example, 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 single layer formed on a substrate, where the single layer comprises tungsten and only two additional metals or materials, for example, 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.

[0061] In some embodiments, the alloy layers described herein comprise nickel 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 nickel and only one additional metal, 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 nickel and only two additional metals or materials, such as two or more 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 single layer formed on the substrate, where the single layer comprises nickel 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 single layer formed on a substrate, where the single layer comprises nickel and only one additional metal, for example, 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 single layer formed on a substrate, where the single layer comprises nickel and only two additional metals or materials, for example, 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.

[0062] In certain configurations, the alloy layer comprises (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 comprising one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In certain embodiments, the alloy does not comprise a precious metal.

[0063] 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 thereof, or combinations thereof.

[0064] In other embodiments, the alloy layers described herein comprise 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 thereof, or combinations thereof.

[0065] In certain embodiments, the alloy layers described herein include (i) molybdenum, molybdenum oxide, or other compounds of molybdenum, and (ii) a transition metal, transition metal oxide, or other compounds of a transition metal.

[0066] In certain embodiments, the alloy layers described herein include only two metals: (i) molybdenum, molybdenum oxide, or other compounds of molybdenum, and (ii) a transition metal, transition metal oxide, or other compound of a transition metal.

[0067] In certain embodiments, the metal alloys of the layers described herein include only two metals from the group consisting of (i) tungsten, tungsten oxide, or other compounds of tungsten, and (ii) transition metals, transition metal oxides, or other compounds of transition metals.

[0068] In certain embodiments, the alloy layers described herein include only two metals: (i) nickel, nickel oxide, or other compounds 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 have only a Ni-Mo alloy or a Ni-W alloy.

[0069] In certain embodiments, the metal alloy layer exhibits at least two times greater corrosion resistance compared to 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.

[0070] In embodiments where the 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.

[0071] In some instances, 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 comprise the same material 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.

[0072] In some embodiments, the alloy layer can include an alloy of molybdenum, such as an alloy of molybdenum combined 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. More than two components or metals can be present if desired. In other embodiments, the surface coating can include an alloy of molybdenum and another metal or material, such as an alloy of molybdenum and another metal or material combined with only one of 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 and two other metals, for example, an alloy of molybdenum and two other metals in combination with only two of nickel, chromium, carbon, cobalt, tin, tungsten, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper.

[0073] In some embodiments, the alloy layer can include an alloy of tungsten, such as an alloy of tungsten combined 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 with one other metal or material, such as an alloy of tungsten with only one of 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 with two other metals, such as an alloy of tungsten with only two of 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 an alloy of tungsten combined 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 the other components can be present at 65% by weight or more. If desired, more than two components or metals can be present. In other embodiments, the surface coating can include an alloy of tungsten with one or two other metals or materials, such as tungsten combined with only one of 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 and two other metals, for example, an alloy of tungsten and two other metals in combination with only two of nickel, molybdenum, chromium, carbon, cobalt, tin, aluminum, vanadium, titanium, niobium, iron, boron, phosphorus, magnesium, or copper.

[0074] In some embodiments, the surface coatings described herein can provide desired performance criteria, including, but not limited to, a specific surface roughness (Ra) as described in the ISO 4287 and ISO 4288 standards. Roughness can be measured, for example, using a profilometer. Coating thickness can also be measured using non-destructive techniques such as magnetic measurement tools, XRF, or sampling, and destructive techniques such as cross-sectional analysis. The exact surface roughness (Ra) can vary, for example, and can be less than 1 micron, between 0.1 micron and 1 micron. The device can have a desired coefficient of friction (CoF). This characteristic generally depends on both the surfaces that are abraded against each other and the fluid disposed between them. The roughness of each surface, the viscosity of the fluid, and the temperature of the test can affect the measurement of the coefficient of friction. CoF can be measured, for example, according to a block-on-a-ring test, such as those described in ASTM G99-17 or ASTM G77-17. The coating, or one or more layers of the coating, can provide a specific hardness as tested by ASTM E384-17. For example, the coating may have a hardness greater than 600 Vickers as measured in accordance with ASTM E384-17. If the coating includes multiple layers, any one or more of the layers may have a hardness greater than 600 Vickers as measured in accordance with ASTM E384-17. In some embodiments, the outer layer of the coating may have a hardness 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 less than 600 Vickers as measured in accordance with ASTM E384-17.

[0075] Although the various layers and substrates are described below with reference to FIGS. 1-12 as having flat surfaces, flat surfaces may not be required or desired in some instances. For example, the substrate (or either or both of the layers) may have a rough surface, may be intentionally roughened, or may be intentionally smooth as desired. As an example, a substrate may have such a surface that includes a transfer texture, where a partial or complete replica of the transfer texture is transferred to other objects that come into contact with the textured surface with the transfer texture. In one embodiment, such a surface may be part of an article or device that contacts another material during use or movement. For example, a steel work roll used in a cold rolling process, where the surface of the steel work roll has a particular transfer texture that can be transferred to a steel plate during the rolling process. Another example is the steel work roll described in the previous embodiment, where the transfer texture is achieved using electrical discharge texturing (EDT). Another embodiment is a work roll used in a hot rolling process. In another embodiment, the transfer texture may be part of a die designed to transfer the texture to another object. In one embodiment, the texture is transferred to a metal. In one embodiment, the texture is transferred to a polymer. In one embodiment, the texture is transferred to a molten metal that subsequently solidifies. In one embodiment, the texture is transferred to a liquid or fluid that subsequently solidifies.

[0076] 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 a substrate to a thermal sprayed coating. In another embodiment, the adhesive texture is used to enhance adhesion of a tungsten-containing coating to the surface. In another embodiment, the adhesive layer is used to enhance coating adhesion relative 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, and oxide composites.

[0077] In another embodiment, roughness is added to affect light reflection. In one embodiment, the surface roughness is altered to be less rough. In one embodiment, the surface roughness Ra may be altered to be less than 1 μm rough. In another embodiment, the surface roughness is altered to be less than 0.5 μm rough. In one embodiment, the surface with altered roughness is glossy. In another embodiment, the surface with altered roughness is exposed and requires human contact. In another embodiment, the surface reflects less light and is less glossy. In one embodiment, the contact angle of water on the surface with altered roughness is smaller than the original surface.

[0078] In certain embodiments, the roughness may have an irregular shape or pattern. 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 roughness Ra of the coated 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 μm. In other embodiments, Ra is less than 0.3 μm. In other embodiments, Ra is less than 0.2 μm. In other embodiments, Ra is less than 0.1 μm. In another embodiment, the patterning is performed using grinding, blasting, sandblasting, shot blasting, sandblasting, burnishing, grinding, honing, mass finishing, tumble finishing, vibratory finishing, polishing, buffing, lapping, electrochemical etching, chemical etching, laser etching, laser patterning, or other methods. Alternatively, the surface is evaluated using shot blasting (SB), laser beam texturing (LBT), and electrical discharge texturing (EDT) or electron beam texturing (EBT). Electrical discharge texturing (EDT) can be used on steel substrates to create the texture. Electrodeposition techniques can be used to form the texture. Thermal spray processing techniques can be used to form the texture. The cross section of the pattern can have a specific geometric shape, such as a rectangle, a triangle, a star, a circle, or a combination thereof. The pattern can be ridge-shaped, pillar-shaped, spiral-shaped, a combination thereof, or other shapes. The Ra can be greater than 100 μm. The pattern may be created using cutting, milling, molding and other tools.

[0079] Certain embodiments are described in more detail below with reference to coatings or layers. Coatings or layers can include a single material, a combination of materials, an alloy, a composite material, or other materials and compositions as described herein. In embodiments where a layer refers to a metal alloy, the metal alloy can include two or more materials, e.g., two or more metals. In some configurations, one metal can be present at 79% or more by weight of the layer, and the other material can be present at 21% or less by weight of the layer. For example, one of the layers described herein can include a molybdenum alloy, a tungsten alloy, or a nickel alloy. One of the materials can be present at 79% or more by weight of the layer, and the other material can be present at 21% or less by weight of the layer. When the metal alloy includes molybdenum, the molybdenum can be present at 21% or less by weight or at 79% or more by weight in the layer, and the other material can be present such that the total weight percentages add up to 100% by weight. Alternatively, the other material can be present at 79% or more by weight in the layer, and molybdenum can be present at 21% or less by weight in the layer. One or more layers may also contain another metal or metal alloy. Trace amounts of impurities that add negligible weight to the overall alloy layer or surface coating may also be present.

[0080] The exact amount of each material present can be selected to provide a layer or article with the desired performance specifications. Weight percentages can 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 wt% or less, for example, 34 wt%, 33 wt%, 32 wt%, 31 wt%, 30 wt%, 29 wt%, 28 wt%, 27 wt%, 26 wt%, 25 wt%, 24 wt%, 23 wt%, 22 wt%, 21 wt%, 20 wt%, 19 wt%, 18 wt%, 17 wt%, 16 wt%, 15 wt%, 14 wt%, 13 wt%, 12 wt%, 10 wt%, 9 wt%, 8 wt%, 7 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, or less 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, e.g., 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 other configurations, one or more of the layers can include metal in the layer present at 65% or more by weight, e.g., 65%, 70%, 75%, 80%, 81%, 82%, 83%, 84%, 85%, 85%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% 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%, 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%, 87%, 88%, 89%, 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% or more by weight of the alloy layer or surface coating.

[0081] In some embodiments, the alloy layer described herein may be free of any 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 entire surface coating) may be free of (completely free of) each of gold, silver, ruthenium, rhodium, palladium, osmium, iridium, and platinum. The exclusion of precious metals may reduce overall costs.

[0082] In certain embodiments, when nickel is present in a metal alloy layer, the nickel can be present without any tungsten or cobalt in the same layer. For example, if a layer includes a nickel alloy, the layer does not include tungsten or cobalt, e.g., 0 wt.% cobalt or tungsten is present. This layer can also include 0 wt.% precious metal.

[0083] In certain examples, the alloy layer can include non-metallic materials and additives as desired. For example, particles, nanoparticles, nanomaterials, or other materials including one or more of polytetrafluoroethylene (PTFE), SiC, SiO2, diamond, graphite, graphene, boron, borides, functionalized silicon particles, fluorosilicones, siloxanes, TiO2, nanotubes, and nanostructures can be present in the metal alloy layer. Additional materials are described in more detail below.

[0084] In some examples, one of the metals in the layers described herein is nickel. For example, 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 any noble metal, nickel alloys containing at least nickel and a refractory metal other than any noble metal, nickel alloys containing at least nickel and a refractory metal other than tungsten, nickel alloys containing at least nickel and a refractory metal other than tungsten and any noble metal, nickel alloys containing at least nickel and excluding cobalt and any noble metal, composite alloys containing nickel and particles, composite alloys containing nickel and nanoparticles, nickel and SiO 2、 Composite alloys containing 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 of the layers described herein.

[0085] In certain embodiments, one of the metals in the alloy layers described herein is molybdenum. For example, 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, alloys containing at least molybdenum and phosphorus, alloys containing only nickel and molybdenum, alloys containing only tin and molybdenum, alloys containing only cobalt and molybdenum, alloys containing only nickel, molybdenum, and phosphorus, molybdenum alloys containing at least two metals other than noble metals, molybdenum alloys containing at least molybdenum and a transition metal, alloys containing at least molybdenum and a transition metal, , molybdenum alloys excluding precious metals, molybdenum alloys comprising at least two metals excluding substances of very high concern under European legislation, composite alloys comprising molybdenum and particles, composite alloys comprising molybdenum and soft particles, composite alloys comprising 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.

[0086] In another embodiment, one of the metals of the alloy layer described herein is cobalt. For example, cobalt, cobalt alloy, cobalt compound, cobalt composite, cobalt-phosphorus alloy, cobalt-molybdenum alloy, cobalt-molybdenum-phosphorus alloy, cobalt-tungsten alloy, cobalt-tungsten-phosphorus alloy, cobalt alloy containing only cobalt and molybdenum, cobalt alloy containing at least cobalt and a transition metal, cobalt alloy containing at least two metals other than any noble metal, cobalt alloy containing at least cobalt and a refractory metal other than any noble metal, cobalt alloy containing at least cobalt and a refractory metal other than tungsten, cobalt alloy containing at least cobalt, a refractory metal other than tungsten and any noble metal, cobalt alloy containing at least cobalt and excluding nickel and a noble metal, composite alloy containing cobalt and particles, composite alloy containing cobalt and nanoparticles, cobalt and SiO 2、 Composite alloys containing SiC or other silicon compounds, composite alloys containing cobalt and borides, bromine nitride or other boron compounds, composite alloys containing cobalt and PTFE or other fluorine compounds, composite alloys containing cobalt, molybdenum and chromium, chromium carbide, chromium oxide or other chromium compounds.

[0087] In some embodiments, one of the metals in 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 containing at least tin and a transition metal, tin alloys containing at least two metals other than any noble metal, tin alloys containing at least tin and a refractory metal other than any noble metal, tin alloys containing at least tin and a refractory metal other than tungsten, tin alloys containing at least tin and a refractory metal other than tungsten and any noble metal, tin alloys containing at least tin and excluding nickel and a noble metal, composite alloys containing tin and particles, composite alloys containing tin and nanoparticles, tin and SiO2、 Composite alloys containing SiC or other silicon compounds, composite alloys containing tin and borides, bromine nitrides or other boron compounds, composite alloys containing tin and PTFE or other fluorine compounds, composite alloys containing tin, molybdenum and chromium, chromium carbides, chromium oxides or other chromium compounds.

[0088] In another embodiment, one of the metals in the alloy layer described herein is tungsten.For example, tungsten, tungsten alloy, tungsten compound, tungsten composite material, 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 excluding noble metals, tungsten alloy containing at least tungsten and refractory metal excluding noble metals, tungsten alloy containing at least tungsten but excluding nickel and noble metals, composite alloy containing tungsten and particles, composite alloy containing tungsten and nanoparticles, tungsten and SiO 2、 Composite alloys containing SiC or other silicon compounds, composite alloys containing tungsten and borides, bromine nitrides or other boron compounds, composite alloys containing tungsten and PTFE or other fluorine compounds, composite alloys containing tungsten, molybdenum and chromium, chromium carbide, chromium oxide or other chromium compounds.

[0089] 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 underlying layers. Although not required, a hard layer is typically 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.

[0090] In certain embodiments, a simplified diagram of a substrate and alloy layer of a surface coating is shown in Figure 1. Article or device 100 includes substrate 105 (shown in cross section in Figure 1) and a first layer 110 on a first surface 106 of substrate 105. Although not shown, layers or coatings may also be present on surfaces 107, 108, and 109 of substrate 105. Layer 110 is shown in Figure 1 as a solid layer having a uniform thickness present across surface 106 of substrate 105. Although this configuration is not required, different regions of layer 110 may include different thicknesses or even different materials. Furthermore, certain regions of surface 106 may not include any 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 alloy, aluminum, aluminum alloy, chromium, chromium alloy, nickel, nickel alloy, titanium, titanium alloy, nickel-chromium superalloy, nickel-molybdenum alloy, brass, Hastelloy, Inconel, nichrome, Monel, other substrates comprising at least one metal, or nitrided or carburized substrates. In some embodiments, the substrate may be porous or non-porous. Layer 110 typically includes one or more metals, or two or more metals, or three or more metals or materials. For example, layer 110 may be a metal alloy formed from two or more metals. In some embodiments, layer 110 is an alloy layer formed from only two metals or only two materials. In some examples, layer 110 is the only layer present in the surface coating. In certain instances, layer 110 is an outer or exposed layer so that the layer can contact the surrounding fluid or other materials and protect the underlying substrate 105 and any layers between layer 110 and substrate 105.

[0091] 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 a further embodiment, 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 a combination 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.

[0092] In some configurations, the exact thickness of layer 110 can vary from 1 micron to about 2 mm, depending on the device in which layer 110 is present. For example, layer 110 can have a thickness of from about 5 microns to about 1 mm, or from about 7 microns to about 900 microns. If multiple layers are present in the surface coating, each layer may have a thickness of from 1 micron to about 2 mm, or the total thickness of all layers can be from about 1 micron to about 2 mm.

[0093] In certain embodiments, layer 110 can 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, silicon dioxide, silicon carbide, and other silicon compounds. The particles can be hydrophobic or hydrophilic. Hydrophobic particles, such as PTFE particles, Teflon particles, fluoropolymers, silicon-based particles, and hard particles functionalized with hydrophobic groups, hydrophilic groups, or both. For example, silicon dioxide or silicon carbide functionalized with fluoro compounds, fluoro-containing molecules, silicon compounds, silicon-containing molecules, and other polymers. Other particles such as titanium dioxide and other catalysts can be functionalized or used as is.

[0094] In other configurations, layer 110 is made of a nickel-molybdenum alloy, a nickel-molybdenum alloy with a weight percent of molybdenum less than 35% by weight, a nickel-molybdenum phosphorus alloy with a weight percent of molybdenum less than 35% by weight, a ductile alloy of a refractory metal containing nickel, a ductile alloy of nickel and molybdenum, a brittle alloy of a refractory metal containing nickel, a ductile alloy of nickel and molybdenum, a brittle alloy of a transition metal containing molybdenum, a ductile alloy of a transition metal containing molybdenum, an alloy of nickel and molybdenum having a hardness less than 1100 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 sizes, 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 containing materials with less magnetic properties than nickel, alloys of molybdenum containing materials with less hardness than molybdenum, high Melting point metals and conformal alloys of nickel, 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 with materials that can withstand higher temperatures than nickel, refractory metals, precious metals, hard particles, soft particles, hydrophobic particles, hydrophilic particles, catalysts, materials more conductive than nickel, materials more conductive than molybdenum, materials softer than nickel, materials harder than nickel and less hard than molybdenum, or phosphorus, boron, Nickel-molybdenum alloys containing a third element including, but not limited to, other compounds such as boron nitride, silicon carbide, silicon oxide, aluminum oxide, molybdenum disulfide, hard particles having a hardness of HV greater than 750 Vickers and / or hard particles having a size less than 1 micron, refractory metals, noble metals, hard particles, materials more conductive than nickel, materials more conductive than molybdenum, materials softer than nickel or phosphorus, boron, boron nitride, silicon carbide, silicon oxide, aluminum oxide, molybdenum disulfide,The nickel-molybdenum alloy may include a third element containing hard particles having a hardness of greater than 750 Vickers HV and / or hard particles having a size of less than 1 micron.

[0095] In some examples, the layer 110 on the substrate 105 can include a nickel-tungsten alloy or nickel-tungsten alloy containing a third element, including, but not limited to, an element that is a refractory metal, a noble metal, a hard particle, or other compound such as phosphorus, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, hard particles with a hardness of HV>750, hard particles with a size less than 500 nm, highly conductive particles, carbon nanotubes and / or carbon nanoparticles. Combinations of these materials can also be present in the layer 110 on the substrate 105.

[0096] In some embodiments, a simplified diagram of another device is shown in Figure 2. In this figure, article or device 200 includes an intermediate layer 210 between layer 110 and the underlying substrate 105. In some examples, 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-phosphorus alloys, molybdenum, molybdenum alloys, molybdenum composites, and at least one other metal, excluding precious metals. Nickel alloys containing 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 (excluding precious metals) containing at least nickel and a refractory metal, molybdenum-tin alloys, tungsten alloys, tungsten composites, or other materials may be present as layer 210 between layer 110 and substrate 105 to improve adhesion between layer 110 and layer 210. Such layers may be less than 10 μm, 9 μm, 8 μm, 7 μm, 2 μm, 1 μm, 0.75 μm, 0.5 μm, or 0.25 μm thick. As discussed herein, in some examples, 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.

[0097] In certain configurations, layer 210 can function as a brightener to increase the overall glossy appearance of article or device 200. Bright or semi-bright layers generally reflect 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 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 but 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 high melting point metal but excluding precious metals, a tungsten alloy, a tungsten composite, or other material may be present as layer 210 between layer 110 and substrate 105 to enhance the overall coating appearance.

[0098] 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-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 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 but excluding precious metals, a tungsten alloy, a nickel alloy comprising at least nickel and a transition metal, a nickel alloy comprising at least nickel and a refractory metal but excluding precious metals, a nickel alloy comprising at least nickel and a refractory metal but excluding precious metals, a nickel alloy comprising at least nickel and a refractory metal but excluding tungsten, a nickel alloy comprising at least nickel and a refractory metal but excluding precious metals, a tungsten alloy, a tungsten composite, a tungsten alloy but excluding alloys containing both nickel and tungsten, chromium, a chromium compound, or other material may be present as layer 210 between layer 110 and substrate 105 to enhance corrosion resistance.

[0099] In some embodiments, the substrate 105 used with the intermediate layer 210 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 may be porous or non-porous. In certain embodiments, the layer 210 may 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.

[0100] In certain embodiments, layer 110 used with intermediate layer 210 typically includes one or more metals or two or more metals. For example, layer 110 used with intermediate layer 210 can include any of the materials and configurations described with reference to FIG. 1 . For example, layer 110 used with layer 210 can be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 used with intermediate layer 210 is nickel. In other embodiments, one of the metals in layer 110 used with intermediate layer 210 is molybdenum. In a further embodiment, one of the metals in layer 110 used with intermediate layer 210 is tungsten. In a further embodiment, one of the metals in layer 110 used with intermediate layer 210 is cobalt. In a further embodiment, one of the metals in layer 110 used with intermediate layer 210 is chromium. In some embodiments, layer 110 used with layer 210 can include only two metals or materials, or only three metals or materials. For example, layer 110 used with layer 210 can 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.

[0101] In other embodiments, layer 110 used with intermediate layer 210 can include a nickel alloy, a molybdenum alloy, a tungsten alloy, a cobalt alloy, a chromium alloy, or a combination thereof. In other examples, layer 110 used with intermediate layer 210 can be nickel, a nickel-molybdenum alloy, a nickel-cobalt alloy, a nickel-tungsten alloy, a nickel-phosphorus alloy, 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, layer 110 used with intermediate layer 210 can be comprised of a nickel-molybdenum alloy with no other materials present in layer 110. In other configurations, layer 110 used with intermediate layer 210 can be comprised of a nickel-molybdenum-phosphorus alloy with no other materials present in layer 110. In another configuration, layer 110 used with intermediate layer 210 can be made of a cobalt-molybdenum alloy with no other materials present in layer 110. In another configuration, layer 110 used with intermediate layer 210 can be made of a cobalt-molybdenum-phosphorus alloy with no other materials present in layer 110. In another configuration, layer 110 used with intermediate layer 210 can be made of a nickel alloy containing at least two metals excluding precious metals. In another configuration, layer 110 used with intermediate layer 210 can be made of a molybdenum alloy containing at least two metals excluding precious metals. In another configuration, layer 110 used with intermediate layer 210 can be made of a molybdenum alloy containing at least molybdenum and a transition metal. In another configuration, layer 110 used with intermediate layer 210 can be made of a molybdenum alloy containing 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 can be from about 10 microns to about 200 microns thick. Similarly, the thickness of intermediate layer 210 can vary from 0.1 micron to about 2 mm, such as from about 1 micron to about 20 microns.The thickness of layer 210 can be less than or greater than the thickness of layer 110 .

[0102] In another configuration, two or more layers may be present on an underlying substrate. Referring to FIG. 3 , an article or device 300 is shown including a first layer 110 and a second layer 320 on a substrate 105. The order of layers 110, 320 can be reversed, so that layer 320 is closer to the substrate 105, if desired. Layers 110, 320 can include the same or different materials, or similar materials deposited in different ways or under different conditions. For example, layers 110, 320 in FIG. 3 can independently be any of the materials described herein, such as any of the materials described with reference to the layers in FIG. 1 or FIG. 2. In some configurations, layers 110, 320 can each be an alloy layer. For example, layers 110, 320 can each include one or more of nickel, copper, molybdenum, cobalt, or tungsten. The layers can be formed in similar or different ways. For example, layer 110 may be electrodeposited under basic conditions, while layer 220 may be electrodeposited under acidic conditions. As another example, layers 110 and 320 may each independently comprise nickel, copper, molybdenum, cobalt, or tungsten; however, layer 110 may be electrodeposited under basic conditions, and layer 220 may be deposited using physical vapor deposition, chemical vapor deposition, atomic layer deposition, thermal spray processing, or other methods. Layers 110 and 320 may comprise metals other than copper, such as nickel, molybdenum, cobalt, tungsten, or tin, or nonmetals, or both. Different conditions can provide different overall structures in layers 110 and 320, even when similar materials are present. In certain configurations, layer 110 can improve the adhesion of layer 320. In other configurations, layer 110 can "brighten" the surface of device 300, thereby giving device 300 a glossier overall appearance.

[0103] In some embodiments, the substrate 105 used with layers 110, 320 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. Layers 110, 320 typically each include one or more metals or two or more metals. For example, layers 110, 320 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layers 110, 320 is nickel. In other embodiments, one of the metals in layers 110, 320 is molybdenum. In a further embodiment, one of the metals in layers 110, 320 is cobalt. In a further embodiment, one of the metals in layers 110, 320 is tungsten. Layers 110, 320 need not have the same metal; desirably, the metals in layers 110, 320 are different. In other embodiments, layers 110, 320 can independently comprise a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, 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 layers 110, 320 can be comprised of a nickel-molybdenum alloy with no other materials present in each layer. In other configurations, one of layers 110, 320 can be comprised of a nickel-molybdenum-phosphorus 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, while in other configurations, one or both 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 can be made of a nickel alloy containing at least nickel and a transition metal, excluding precious metals. In other configurations, one or both of layers 110, 320 can be made of a molybdenum alloy containing at least molybdenum and a transition metal. In other configurations, one or both of layers 110, 320 can be made of a molybdenum alloy containing at least molybdenum and a transition metal, excluding precious metals. The exact thickness of layers 110, 320 can 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 identical in thickness. Layer 110 can be thicker or thinner than layer 320.

[0104] 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 those materials described with reference to layer 210 herein. Alternatively, the intermediate layer may be present between the substrate 105 and layer 110 when the coating includes the first layer 110 and the second layer 120. 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, a 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.

[0105] In other embodiments, the surface of the substrate may be treated or may include a transferred surface, such as, for example, a surface that has been carburized, nitrided, carbonitrided, induction hardened, age hardened, precipitation hardened, gas nitriding, normalized, subzero treated, annealed, shot pinned, or coated or treated with one or more other layers, chemically, thermally, or physically modified, or a combination thereof. Referring 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 in FIGS. 1-3, 5A, 5B, and 12. If desired, and as shown in FIG. 4B, a layer 420 can be present between the treated surface 410 and layer 110 of the device 450. The thickness of the layer / treated surface 410 can vary, for example, from about 0.1 micron to about 50 millimeters. The treated surface 410 can be harder than the underlying substrate 105, if desired. For example, the treated surface 410 can have a case hardness of 50 to 70 HRC. If the treated surface / layer 410 is a transferred surface, the base material can be, but is not limited to, steel (low carbon steel, stainless steel, nitrided steel, steel alloy, low alloy steel, etc.) or other metallic materials. The exact results of the treatment can vary, and typically treatments are performed to increase adhesion, modify surface roughness, improve wear resistance, improve internal stress, reduce internal stress, alter hardness, alter lubricity, or for other reasons. The layer 110 can be used to protect the device 450 from corrosion, abrasion, heat, and other influences. In some examples, the treated surface 410 can 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 layer 110 can be used to improve performance as needed.

[0106] In some embodiments, the substrate 105 in FIGS. 4A and 4B 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 layer 110 in 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 in FIGS. 4A and 4B may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the layer 110 in FIGS. 4A and 4B is nickel. In another embodiment, one of the metals in layer 110 of FIGS. 4A and 4B is molybdenum. In a further embodiment, one of the metals in layer 110 of FIGS. 4A and 4B is cobalt. In a further embodiment, one of the metals in layer 110 of FIGS. 4A and 4B is tungsten. In a further embodiment, one of the metals in layer 110 of FIGS. 4A and 4B is tin. In a further embodiment, one of the metals in layer 110 of FIGS. 4A and 4B is chromium. In another embodiment, layer 110 of FIGS. 4A and 4B can include a nickel alloy, a molybdenum alloy, or a combination thereof. In another embodiment, layer 110 of FIGS. 4A and 4B can include a molybdenum alloy including at least two metals (optionally excluding a noble 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 noble metal. In other embodiments, layer 110 of FIGS. 4A and 4B can include a nickel alloy comprising at least two metals excluding noble 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 noble metals.4A and 4B can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, layer 110 of FIGS. 4A and 4B can 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 can include any of these materials and combinations of materials described with reference to FIGS. 1, 2, or 3.

[0107] In certain embodiments, the exact thickness of layer 110 in Figures 4A and 4B can vary from 1 micron to about 2 mm depending on the article or device in which layer 110 resides; for example, the thickness can vary from about 5 microns to about 200 microns.

[0108] 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 can be present as a thin layer, e.g., 1 micron or less thick, between layer 110 and layer / surface 410. Although not shown, two or more layers can be present between layer / surface 410 and layer 110.

[0109] In certain embodiments, one or more layers may be present on top of 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 on top of layer 110. Referring to FIG. 5A, an article or device 500 is shown in which layer 510 is present on top of layer 110. If desired, an additional layer 560 can be present between layer 510 and layer 110, as shown in FIG. 5B. The exact materials present in layers 510, 560 may vary depending on the end use application of device 500.

[0110] In certain embodiments, the substrate 105 in FIGS. 5A and 5B 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 layer 110 in 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 herein. For example, the layer 110 in FIGS. 5A and 5B may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in the layer 110 in FIGS. 5A and 5B is nickel. In another embodiment, one of the metals in layer 110 of FIGS. 5A and 5B is molybdenum. In a further embodiment, one of the metals in layer 110 of FIGS. 5A and 5B is tungsten. In a further embodiment, one of the metals in layer 110 of FIGS. 5A and 5B is cobalt. In a further embodiment, one of the metals in layer 110 of FIGS. 5A and 5B is chromium. In other embodiments, 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, layer 110 of FIGS. 5A and 5B can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, layer 110 of FIGS. 5A and 5B can be comprised of a nickel-molybdenum-phosphorus alloy without the nickel-molybdenum alloy or other materials present in layer 110. In another example, layer 110 of FIGS. 5A and 5B can include a nickel-molybdenum-phosphorus alloy.5A and 5B may be comprised of nickel, a nickel-molybdenum alloy, a nickel-cobalt alloy, a nickel-tungsten alloy, a nickel-phosphorus alloy, 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, chromium, a chromium alloy, a molybdenum-tin alloy, or a chromium compound in layer 110. In other configurations, layer 110 of Figures 5A and 5B may be comprised of a molybdenum alloy comprising at least two metals (optionally excluding a precious metal), a molybdenum alloy comprising at least molybdenum and a transition metal, a molybdenum alloy comprising at least molybdenum and a transition metal but excluding a precious metal, a molybdenum alloy comprising at least molybdenum, a transition metal, and phosphorus, a molybdenum alloy comprising at least molybdenum, a transition metal, and tin, or a molybdenum alloy composite comprising particles and nanoparticles. In other configurations, layer 110 of Figures 5A and 5B can be comprised of a nickel alloy containing at least two metals excluding noble metals, a nickel alloy containing at least nickel and a refractory metal, or a nickel alloy containing at least nickel and a refractory metal excluding noble metals. The exact thickness of layer 110 of Figures 5A and 5B can 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 can 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 one or more of 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 may protect layer 510 from delamination, chipping off, or abrasion, and in another embodiment, layer 110 may increase the adhesion of layer 510 to substrate 105. In another embodiment, layer 110 may improve brightness, for example, by reflecting more light.

[0111] In other configurations, the article or device may include an outer metal layer and at least one underlying alloy layer. Referring to FIG. 6, several layers are shown, including layers 110, 610, and 620. The substrate is intentionally omitted from FIGS. 6-8 to simplify the illustrations. The substrate is typically adjacent to layer 110, but may be adjacent to another layer if desired. Layer 110 in FIG. 6 typically includes one or more metals or two or more metals described with reference to FIGS. 1-5B and 12, or other materials described herein. For example, layer 110 in FIG. 6 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 in FIG. 6 is nickel. In other embodiments, one of the metals in layer 110 in FIG. 6 is molybdenum. In other embodiments, layer 110 in FIG. 6 may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 in 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 in layer 110. The exact thickness of layer 110 of Figure 6 may vary from 1 micron to about 2 mm, such as from about 5 microns to about 200 microns, depending on the device in which layer 110 is present.

[0112] In certain embodiments, layer 610 of FIG. 6 typically includes one or more metals or metal alloys, such as nickel, copper, molybdenum, nickel-molybdenum, nickel-molybdenum-phosphorus, or combinations thereof. The thickness of layer 610 can typically be greater or less than the thickness of layer 110. For example, the thickness of layer 610 can vary from about 0.1 micron to about 1 micron. In some embodiments, the metal of layer 610 can be present in the form of an alloy with another metal. Layer 620 also typically includes one or more metals or metal alloys, such as nickel, copper, molybdenum, nickel-molybdenum, nickel-molybdenum-phosphorus, or combinations thereof. The metal of layer 620 can be present in an alloyed or unalloyed form and can be present at a thickness greater or less than the thickness of layer 610. For example, layer 620 can be present at a thickness of about 0.1 micron to about 0.5 micron. In some embodiments, layer 620 can enhance wear resistance, enhance electrical conductivity, or provide a glossier surface. In some configurations, layers 610, 620 can include the same material, but the material can 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.

[0113] In certain embodiments, layer 110, as described herein with reference to FIGS. 1-6, can be present between two incompatible materials, which can be present in a coating or device. The term "incompatible" generally refers to materials that do not readily bond or adhere to each other, or that have incompatible physical properties that make them unsuitable for use together. Including a metal alloy in layer 110 can enable the inclusion of certain coatings in devices having a copper substrate. For example, a Ni-Mo or Ni-Mo-P alloy layer can be present between a copper substrate and another metal layer. In certain embodiments, including layer 110 between a metal layer (or metal alloy layer) and the substrate can similarly enhance the overall wear resistance of the outer metal layer.

[0114] In certain embodiments, one or more of the layers shown in FIGS. 1-6 may include tin (Sn). For example, tin can provide some corrosion resistance. Referring to FIG. 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 in FIG. 7 typically includes one or more metals or two or more metals described with reference to FIGS. 1-6 and 12, or other materials described herein. For example, layer 110 in FIG. 7 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 in FIG. 7 is nickel. In other embodiments, one of the metals in layer 110 in FIG. 7 is molybdenum. In other embodiments, layer 110 in FIG. 7 may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 in FIG. 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 in 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 is present.

[0115] In certain embodiments, layer 710 of FIG. 7 typically comprises one or more metals or metal alloys, or a combination thereof. The thickness of layer 710 can be greater than or less than the thickness of layer 110. For example, the thickness of layer 710 can vary from about 0.1 micron to about 1 micron. In some embodiments, the metal of layer 710 can be present in the form of an alloy with another material, such as another metal. Layer 720 can comprise, for example, tin or a tin alloy. The exact thickness of layer 720 can vary and can be greater or less than the thickness of layer 710. For example, layer 720 can be present at a thickness greater than 5 microns, such as 10 to 300 microns or 10 to 100 microns. In some embodiments, layer 720 can be present to help keep the surface clean, increase wear resistance, increase electrical conductivity, provide a glossier surface, or resist corrosion by the working fluid. In some configurations, layers 710, 720 can include the same material, but the material can 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.

[0116] 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. No layers exist between layer 110 and layer 720. A substrate (not shown) is typically attached to layer 110. Layer 110 in FIG. 8 typically includes one or more metals or two or more metals described with reference to FIG. 1 , FIG. 2 , or FIG. 3 , or other materials described herein. For example, layer 110 in FIG. 8 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in layer 110 in FIG. 8 is nickel. In other embodiments, one of the metals in layer 110 in FIG. 8 is molybdenum. In other embodiments, layer 110 in FIG. 8 may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, layer 110 in FIG. 8 may be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, layer 110 of FIG. 8 can be comprised of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy with no other materials present in layer 110. The exact thickness of layer 110 of FIG. 8 can vary from 1 micron to about 2 mm, such as 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 can include, for example, tin or a tin alloy. The exact thickness of layer 720 can vary and is typically thicker than layer 710. For example, layer 720 can be present at a thickness greater than 5 microns, such as 10 to 500 microns or 10 to 200 microns. In some embodiments, layer 720 can be present to help keep the surface clean, increase wear resistance, increase electrical conductivity, or provide a glossier surface.

[0117] 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 as a decorative layer to enhance 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.

[0118] 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 various peaks and valleys on the surface. The thickness of the layer 912 may be the same or may vary in different areas. In some embodiments, the substrate 905 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 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 in 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 can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, coating 912 can 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 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 912 is present. While the exact function of layer 912 can vary, as described further below, layer 912 and the roughened surface of substrate 905 can provide a texture that is less susceptible to light scattering and fingerprints.

[0119] In certain embodiments, one or more layers may be present between the substrate 905 and the layer 912. For example, one or more intermediate layers may be present between the substrate 905 and the layer 912. In some examples, 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, e.g., a thickness of 1 micron or less, between the coating 912 and the substrate 905. In certain configurations, the intermediate layer may function as a brightener to enhance 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 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 can be a metal alloy formed from two or more metals, as described with reference to layer 110 in 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 is nickel. In other embodiments, one of the metals in the coating 912 used with the intermediate layer is molybdenum. In other embodiments, the coating 912 used with the intermediate layer can include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 912 used with the intermediate layer can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, the coating 912 used with the intermediate layer can 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, such as from about 5 microns to about 200 microns, depending on the article or device in which the coating 912 resides.

[0120] In certain embodiments, it may be preferable to have a roughened surface layer. Referring to FIG. 10 , an article or device is shown including a substrate 105 and a roughened surface layer 1012. The roughened surface layer 1012 can include any of those materials described in connection with layer 110. In this illustration, the substrate 105 is generally smooth, and the layer 1012 can be subjected to a post-deposition process to roughen the surface layer 1012. The thickness of the layer 1012 can vary 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 can be porous or non-porous. The coating 1012 typically comprises one or more metals or two or more metals described with reference to the layers of FIGS. 1-8 and 12, or other materials described herein. For example, the coating 1012 can 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 can include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1012 can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, the coating 1012 can 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 coating 1012 can 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 on which coating 1012 is present.As described further below, the exact function of layer 1012 may vary, but layer 1012 may provide a surface with a texture that scatters light and is less susceptible to fingerprints.

[0121] 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 examples, 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., a thickness of 1 micron or less, between the coating 1012 and the substrate 105. In certain configurations, the intermediate layer may function as a brightener to enhance the overall glossy appearance of the article or device. In other configurations, the intermediate layer may act to enhance 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 typically includes one or more metals or two or more metals described with reference to the layers in FIGS. 1-8 and 12, or other materials described herein. For example, the coating 1012 used with the intermediate layer 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 is nickel. In other embodiments, one of the metals in the coating 1012 used with the intermediate layer is molybdenum. In other embodiments, the coating 1012 used with the intermediate layer can include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1012 used with the intermediate layer can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy.In certain configurations, the coating 1012 used with the intermediate layer 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, such as from about 10 microns to about 200 microns, depending on the article or device in which the coating 1012 is present.

[0122] In certain embodiments, a surface coating can be applied to a roughened surface to provide an overall smoother surface. An illustration is shown in FIG. 11 , in which a roughened substrate 905 includes 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 in FIGS. 1-8 and 12 or other materials described herein. In this illustration, the substrate 905 may undergo a roughening process, and the layer 1110 may undergo a post-deposition process, 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, substrate 905 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, substrate 905 may be porous or non-porous. Coating 1110 typically includes one or more metals or two or more metals described herein in connection with layer 110. For example, coating 1110 may be a metal alloy formed from two or more metals. In some embodiments, one of the metals in coating 1110 is nickel. In other embodiments, one of the metals of coating 1110 is molybdenum. In other embodiments, coating 1110 may include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1110 can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy. In certain configurations, the coating 1110 can 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, for example, 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. As described further below, the exact function of layer 1110 can vary, but layer 1110 can provide a smoother or glossier surface that is aesthetically more pleasing.

[0123] 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 instances, 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., a thickness of 1 micron or less, between the coating 1110 and the substrate 905. In certain configurations, the intermediate layer may function as a brightener to enhance 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 layer 110 in FIGS. 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 is nickel. In other embodiments, one of the metals in the coating 1110 used with the intermediate layer is molybdenum. In other embodiments, the coating 1110 used with the intermediate layer can include a nickel alloy, a molybdenum alloy, or a combination thereof. In other examples, the coating 1110 used with the intermediate layer can be a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy.In certain configurations, the coating 1110 used with the intermediate layer may be comprised of a nickel-molybdenum alloy or a nickel-molybdenum-phosphorus alloy with no other materials present in the coating 1112. The exact thickness of the coating 1110 used with the intermediate layer may vary from 0.1 micron 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.

[0124] In certain embodiments, a device or article described herein can include a coating having 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 is shown including a substrate 105, a first layer 110, a second layer 320, and a third layer 1230. Each of layers 110, 320, and 1230 can include any of the materials described in connection with layers 110 and 320 above. In some embodiments, layer 1230 can be a polymer coating, a metal, or a non-metallic coating. Layer 110 is typically a metal alloy layer including two or more metals, such as those described in connection with layer 110 of FIGS. 1-8, or other materials described herein.

[0125] In certain configurations, the articles and devices described herein can include a substrate having a coated surface, where the coated surface includes a surface coating. The surface coating can include two or more layers. For example, an alloy layer, such as that described in connection with layer 110, can be on the surface of substrate 105, and a second layer can be on alloy layer 110. In some examples, the alloy layer can include molybdenum as described herein, such as molybdenum combined with one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. The second layer on the alloy layer can include a ceramic, or an alloy, or some material that can be harder than the underlying layer including molybdenum. In other examples, the alloy layer including molybdenum can be harder than the second layer, depending on the intended use of the article or device. In some embodiments, the second layer can include one or more of tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, or combinations thereof. (The ceramic may include one or more of a metal nitride, nitride, metal carbide, carbide, boride, tungsten, tungsten carbide, tungsten alloy, tungsten compound, stainless steel, ceramic, chromium, chromium carbide, chromium oxide, chromium compound, aluminum oxide, zirconia, zirconium oxide titania, nickel, nickel carbide, nickel oxide, nickel alloy, cobalt compound, cobalt alloy, cobalt phosphorus alloy, molybdenum, molybdenum compound, nanocomposite, oxide composite, or combinations thereof. In some examples, the second layer may have a Vickers hardness of 600 Vickers or greater.

[0126] In other configurations, the articles or devices described herein may include a material that provides a lubricating alloy layer. For example, a substrate may include a coated surface having a smooth alloy layer. In some embodiments, the alloy layer may be formed on the substrate and may include molybdenum or other materials, such as those described in connection with layer 110 in the figures. The weight percent of molybdenum or other metal may be 35% or less by weight. The surface roughness Ra of the lubricating alloy layer may be less than 1 micron. In some examples, the alloy layer may also include one or more of nickel, tungsten, cobalt, chromium, tin, phosphorus, iron, magnesium, or boron. In some embodiments, the surface coating may include two or more layers. For example, a base layer may exist with the alloy layer formed or applied to the base layer. The base layer may be an intermediate layer between the substrate and the alloy layer, or may be a self-supporting, stand-alone layer that is not present on any substrate. In some examples, the base layer may include one or more of a nickel layer, a copper layer, a nickel-phosphorus layer, a nickel-molybdenum layer, or other material. 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 examples, the alloy layer may be an exposed outer layer or may not contain precious metals. If desired, particles may also be present in one or more of the layers. Exemplary particles are described herein.

[0127] 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 self-supporting and freestanding, 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 examples, 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 percent of molybdenum in the second alloy layer may be less than 30 wt %, and the overall surface coating roughness may be less than 1 μm, 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 examples, one of the alloy layers may be free of precious metals. In other examples, each of the alloy layers is free of precious metals. If desired, particles may also be present in one or more of the alloy layers. Exemplary particles are described herein.

[0128] In certain embodiments, an article can include a surface coating having an alloy layer described herein with a chromium layer on top of 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 another metal or material. In some examples, the chromium layer does not include a precious metal. In other examples, the alloy layer and the chromium layer each do not include a precious metal.

[0129] In other configurations, the surface coating can include a nickel-molybdenum-phosphorus (Ni-Mo-P) alloy layer. In some examples, one or more other materials can be present in the nickel-molybdenum-phosphorus alloy layer. For example, one or more of tungsten, cobalt, chromium, tin, iron, magnesium, or boron can be present. Particles can also be present, if desired. The Ni-Mo-P alloy layer can include up to 35 wt. % molybdenum in the alloy layer or in the surface coating.

[0130] 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 plating, high velocity oxygen fuel (HVOF) coating, thermal spray processing, or other suitable methods.

[0131] In certain examples, one or more of the coating layers can be deposited using vacuum deposition. In certain embodiments, vacuum deposition generally deposits layers of material on the surface of a substrate atom by atom or molecule by molecule. Vacuum deposition processes can be used to deposit one or more materials having thicknesses ranging from one or more atoms up to several millimeters.

[0132] In certain embodiments, physical vapor deposition (PVD), a type of vacuum deposition, can be used to deposit one or more of the coating layers described herein. PVD generally uses a vapor of a material to produce a thin coating on a substrate. The coatings described herein may be sputtered onto the surface of the substrate, for example, or applied to the surface of the substrate using evaporative 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 surface of the substrate to provide a desired coating layer on the substrate. In other configurations, plasma deposition (PD), such as plasma-enhanced 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 containing the material to be deposited and / or subjecting an already deposited material to ions of a 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, a substrate surface is exposed to repeated doses of precursors that can react with the surface of the material to build up a coating layer.

[0133] In other examples, one or more of the coating layers described herein can be deposited onto the surface of the substrate using brushing, spin coating, spray coating, dip coating, electrodeposition (e.g., electrolytic plating, cathodic electrodeposition, anodic electrodeposition, etc.), electroless plating, electrocoating, electrophoretic deposition, or other techniques. When a current is used to deposit a coating layer on the substrate, the current can be continuous, pulsed, a combination of continuous and pulsed, or pulsed. Specific electrodeposition techniques are described in more detail below.

[0134] In some configurations, one or more layers of the coating can be applied using electrodeposition. Generally, 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 the bath can be reduced using an applied voltage to deposit the ionic species in solid form onto 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 and electrodeposition conditions and techniques used, the resulting properties of the formed, electrodeposited coating can be selected or tailored to provide desired results.

[0135] 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 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, containing greater than 50% by volume of non-aqueous species, and may include hydrocarbons, alcohols, liquefied gases, amines, aromatics, and other non-aqueous materials.

[0136] Generally, an electrodeposition bath contains a species to be deposited as a coating on a substrate. For example, if nickel is to be deposited onto a substrate, the bath can contain ionic nickel or solvated nickel. If molybdenum is to be deposited into a substrate, the bath can contain ionic molybdenum or solvated molybdenum. If an alloy is to be deposited on the substrate, the bath can contain multiple species; for example, the bath may contain 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, species can 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 sodium monohydrogen phosphates, metal sodium dihydrogen phosphates, metal sodium trihydrogen phosphates, sodium salts of metals, potassium salts of metals, metal sulfamates, metal nitrites, and combinations thereof. In some instances, a single material containing both metal species to be deposited can be dissolved in the electrodeposition bath; for example, a metal alloy salt can be dissolved in a suitable solution prior to electrodeposition. The particular material used in the electrodeposition bath depends 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, tin (II) sulfate, sodium stannate, hypophosphite, sulfuric acid, nickel carbonate, nickel hydroxide, potassium carbonate, ammonium hydroxide, hydrochloric acid, or other materials.

[0137] In certain embodiments, the exact amount or concentration of species electrodeposited onto the substrate can vary. For example, the concentration of the species can vary from about 1 gram / liter to about 400 grams / liter. If desired, the ionic species can be depleted as a result of the formation of a coating on the substrate, and additional material can be added to the bath to increase the amount of species available for electrodeposition. In some examples, the concentration of the deposited species can be maintained at a substantially constant level during electrodeposition by continuously adding material to the bath.

[0138] 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 vary from 1 to about 13, although in certain instances the pH may be less than 1, or even less than 0, or greater than 13, or even greater than 14. When metal species are deposited onto the substrate as a metal alloy, the pH may range from 4 to about 12, in certain instances. However, it will be recognized 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 combinations thereof.

[0139] In certain embodiments, alloy plating can use a complexing agent. For example, the primary role of a complexing agent in the alloy deposition process is to complex different metal ions. Therefore, without a suitable complexing agent, nickel and molybdenum cannot be simultaneously deposited and alloyed. Examples of complexing agents include phosphates, phosphonates, polycarboxylates, zeolites, citrates, ammonium hydroxide, ammonium salts, citric acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic 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(carboxymethyl)-L-glutamic acid), and MGDA (methylglycinediacetic acid), hexamine cobalt(III) chloride, ethylene glycol-bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA). acid), ferrocene, cyclodextrin, cholic acid, polymers, and any combination thereof.

[0140] In some examples, suitable voltages can be applied to the cathode and anode of the electrodeposition bath to promote the formation of the layers described herein on the substrate. In some embodiments, direct current (DC) voltage 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 generally be carried out with an AC voltage waveform such as a sine wave, square wave, or triangular wave. High voltages and current densities can be used to promote electron tunneling through the oxide-based layer that can form on the substrate. Furthermore, the base layer conducts electricity toward the cathode, thereby promoting the deposition of the material and avoiding its reoxidation during the oxidant half-cycle.

[0141] In certain embodiments, exemplary current densities that can be used in electrodeposition include 1 mA / cm 2 DC~about 600mA / cm 2 DC, more specifically 1mA / cm 2 DC~approx.300mA / cm 2 In some examples, the current density is in the range of, but not limited to, 5 mA / cm 2 DC~approx.300mA / cm 2 DC, 20mA / cm 2 DC~approx. 100mA / cm 2 DC, 100mA / cm 2 DC ~ approx. 400mA / cm 2 The current may vary from DC, or any value within these exemplary ranges. The exact time the current is applied may vary from about 10 seconds to several days, more particularly from about 40 seconds to about 2 hours. If desired, pulsed current may be applied instead of DC current.

[0142] In some instances, electrodeposition may use pulsed or reversed current during the deposition of the alloy layer. In pulsed electrodeposition (PED), the potential or current is rapidly alternated 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 the 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 atomically control the composition and thickness of the deposited film. This favors grain nucleation, increasing the number of grains per unit area and resulting in a fine-grained deposit with better properties than conventional plating coatings.

[0143] In examples where the coating includes two or more layers, the first and second layers of the coating can be applied using the same or different electrodeposition baths. For example, the first layer can be applied using a first aqueous solution in an electrodeposition bath. After applying a voltage for a period sufficient to deposit the first layer, the voltage can be reduced to zero, the first solution can be removed from the bath, and a second aqueous solution containing a different material can be added to the bath. The voltage can then be reapplied to electrodeposit the second layer. In other examples, two separate baths can be used, such as a reel-to-reel process, in which a first bath is used to electrodeposit the first layer and a second, different bath is used to electrodeposit the second layer.

[0144] In some examples, individual articles can be connected so that they can be sequentially exposed to separate electrodeposition baths, for example, in a reel-to-reel process. For example, the articles can be connected to a common conductive substrate (e.g., a strip). In some embodiments, each of the electrodeposition baths can be associated with a separate anode, and the interconnected individual articles can be commonly connected to a cathode.

[0145] While the exact materials used in electrolytic plating processes 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 anionic form of these metals can vary from chloride, acetate, sulfate, nitrate, nitrite, chromate, dichromate, permanganate, platinate, cobalt nitrite, hexachloroplatinate, citrate, cyanide, oxide, phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and combinations thereof.

[0146] In another example, the electrodeposition process can be designed to apply an alloy layer comprising molybdenum and one or more 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.

[0147] 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 onto the substrate surface 105 without an intermediate layer therebetween. In other examples, an intermediate layer may be present 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, nickel-phosphorus alloys containing hard particles, or other compounds such as phosphorus, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, hard particles having an HV hardness greater than 1000, hard particles having a size less than 500 nm, 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 examples, the intermediate layer may be substantially thinner 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.

[0148] In some embodiments, one or more of the materials of the coating layer can be provided using a soluble anode. The soluble anode can be dissolved in the electrodeposition bath to provide the species to be deposited. In some embodiments, the soluble anode can be in 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.

[0149] In some embodiments, one or more of the coating layers described herein can be deposited using an anodization process. Anodization generally uses a 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 an article 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 anodized layer is grown on the surface of a substrate by applying a direct current to an electrolyte solution containing the material to be deposited. The deposited materials may include magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys thereof, 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.

[0150] In certain embodiments, the coatings described herein may be applied in the presence of other additives or agents. For example, wetting agents, leveling agents, brighteners, antifoaming agents, and / or emulsifiers may be present in the aqueous solution containing the material to be deposited onto the substrate surface. Exemplary additives and agents include 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), and the like.surfactant), 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, optional redox active surfactants, optional conductive ionic liquids, polyglycol ethers, polyglycol alcohols, sulfonated oleic acid derivatives, sulfated forms of primary alcohols, alkyl sulfonates, alkyl sulfates, aralkyl sulfonates, sulfates, perfluoroalkyl sulfonates, alkyl and aralkyl phosphate esters, alkyl polyglycol ethers, alkyl polyglycol phosphate esters or their salts, N-containing and 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-diaminetriacetic acid, 2-butyne-1,4-diol, 2-azobis(2-methylpropionitrile) perfluoroammonoid acid, dextrose, cetylmethylammonium bromide, 1-hexadecylpyridinium chloride, d-mannitol, glycine, Rochelle salt, NThese include, but are not limited to, N'-diphenylbenzidine, glycolic acid, tetra-methyl-ammonium hydroxide, reaction products of amines with epichlorohydrin, reaction products of amines, epichlorohydrin and polyalkylene oxides, reaction products of amines with polyepoxides, polyvinylpyridines, polyvinylimidazoles, polyvinylpyrrolidone or copolymers thereof, nigrosine, pentamethyl-para-rosaniline, one or more of fats, oils, long chain alcohols or glycols, polyethylene glycols, polyethylene oxides such as Triton, alkyl phosphates, metal soaps, certain silicone antifoam agents, commercially available perfluoroalkyl-modified hydrocarbon antifoam agents and perfluoroalkyl-substituted silicones, fully fluorinated alkyl phosphonates, perfluoroalkyl-substituted phosphate esters, cationic, amphoteric and nonionic agents, citrates, acetates, gluconates and ethylenediamine tetra-acetic acid (EDTA) or combinations thereof.

[0151] 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 / electrolytic plating, an external current is not applied to the substrate in electroless plating. While not wishing to be bound by any particular configuration or example, electroless plating can provide a more uniform layer of material on a substrate compared to electrolytic plating. Furthermore, electroless plating can be used to apply a coating onto a non-conductive substrate.

[0152] In certain embodiments in which electroless plating is used, the substrate itself may act as a catalyst, reducing an ionic metal and forming a metal coating 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 instances, the substrate itself may not function as a catalyst, but a catalytic material may be added to the substrate to promote 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.

[0153] 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 monosodium phosphates, metal disodium phosphates, metal trisodium phosphates, and combinations thereof.

[0154] In certain embodiments, the substrates described herein may be subjected to pre-coating treatment steps to prepare the substrate for coating. These treatment steps may include, for example, cleaning, electrocleaning (anodic or cathodic), polishing, electropolishing, pre-plating, heat treatment, polishing treatment, and chemical treatment. For example, the substrate may be cleaned with an acid, base, water, a salt solution, an organic solution, an organic solvent, or other liquid or gas. The substrate may be polished using water, an acid or base such as sulfuric acid or phosphoric acid, or other materials, optionally in the presence of an electric current. The substrate may be exposed to one or more gases before application of the coating layer to promote the 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 before 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 any liquid from the surface before application of the coating. Other processes for treating the substrate before application of the coating may also be used.

[0155] In some embodiments, the coating layers described herein can be subjected to sealing. While the exact conditions and materials used to seal the coatings can vary, sealing can reduce the porosity of the coatings and increase their hardness. In some embodiments, sealing can be performed by subjecting the coating 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°C or higher, 50°C or higher, 90°C or higher, at room temperature, or below room temperature, e.g., 20°C or lower. In some examples, the substrate and coating layer can be heated to remove any 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 to 2 hours after coating.

[0156] It will be appreciated by those skilled in the art that a combination of post-deposition treatment methods can be used, for example, a coating layer can be sealed and then polished to reduce surface roughness.

[0157] In certain configurations, the substrate to be coated can be washed. The substrate can then be rinsed. The substrate can then be subjected to an acid treatment. The acid-treated substrate is then rinsed. The rinsed substrate is then added to a plating bath. The plated substrate can optionally be rinsed. The substrate with the coated surface can then be subjected to a post-plating process. Each of these steps is described in more detail below. An optional strike step to provide a nickel layer (or a layer of another material) on the surface of the substrate can be performed between the acid treatment step and the plating step, if desired.

[0158] In certain embodiments, the cleaning step can be performed in the presence or absence of an electric current. Cleaning is typically performed in the presence of one or more salts and / or detergents or surfactants, and can be performed at an acidic or basic pH. Cleaning is generally performed to remove oils, hydrocarbons, or other materials from the surface of the substrate.

[0159] After the substrate is cleaned, it is rinsed to remove any cleaning agents. Rinsing is typically performed in distilled water, but may be performed using one or more buffers or at an acidic or basic pH. Rinsing may be performed once or multiple times. The substrate is typically kept wet between various steps to minimize oxide formation on the surface. A water break test can be performed to ensure the surface is clean and / or free of any oils.

[0160] After rinsing, the substrate can be immersed in an acid bath to activate the surface for electrodeposition, e.g., pickling the surface. The exact acid used is not critical. The pH of the acid treatment can be from 0 to 7, or even less than 0 if desired. The time the substrate remains in the acid bath can vary, e.g., from 10 seconds to about 10 minutes. The acid solution can be stirred or dispensed over the substrate surface if desired, or the substrate can be moved within the acid bath during the pickling process.

[0161] After the pickling process, the surface can be rinsed to remove any acid. Rinsing can be performed by immersing the pickled substrate in a rinse bath, or by flowing a rinse agent over the surface, or both. Rinsing can be performed multiple times or once, if desired.

[0162] After pickling, the substrate can optionally be subjected to a strike. While not wishing to be bound by 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.

[0163] The rinsed and pickled substrate, or the rinsed substrate with the 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 carried out using AC or DC voltages and various waveforms. The exact current density used can be varied to favor or disadvantage the amounts of particular elements in the final coating. For example, if the alloy layer contains two metals, the current density can be selected so that one metal is present in greater amounts than the other in the resulting alloy layer. The pH of the electrodeposition bath can also be varied depending on the specific species intended to be present in the surface coating. For example, acidic baths (pH = 3-5.5), neutral pH baths, or basic pH baths (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°C) up to about 85°C. Temperatures below 100°C are desirable so that the water in the electrodeposition bath does not evaporate to a significant extent. The electrodeposition bath may contain the material to be deposited along with any agents, including brighteners, levelers, particles, etc., as described herein.

[0164] In some embodiments, the electrodeposition bath can include a brightener. Various 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 are used at relatively high concentrations and can produce hazy or cloudy deposits on metal substrates. Decomposition of Class I brighteners during the electroplating process can introduce sulfur into the deposit, thereby reducing the tensile stress of the deposit. Class II, or secondary brighteners, are used in combination with Class I brighteners to produce completely bright and flat deposits. Class II brighteners are generally unsaturated organic compounds. Various 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 acetylenic or ethylene alcohols, ethoxylated acetylenic alcohols, coumarins, and pyridine-based compounds. Mixtures of these unsaturated compounds, including mixtures of Class I brighteners, can be combined to obtain maximum brightness or ductility for a given leveling level. 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 coverage at low current densities.

[0165] In certain embodiments, the resulting amounts of metals present in the alloy layer may vary. For example, in certain electrodeposition processes in which two metals are present in the surface coating, one of the metals, e.g., molybdenum, may be present in an amount up to about 35 weight percent based on the weight of the surface coating. In other embodiments, one of the metals, e.g., molybdenum, may be present in an amount up to about 20 weight percent based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present in an amount up to about 16 weight percent based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present in an amount up to about 10 weight percent based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present in an amount up to about 6 weight percent based on the weight of the surface coating.

[0166] In certain configurations, the substrate with the surface coating can then be rinsed or subjected to another deposition process to apply a second layer onto 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 plating, high velocity oxygen fuel (HVOF) coating, thermal spray processing, or other suitable method. In some examples, 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 including one, two, three or more metals or other materials. If desired, an additional layer can be formed on the second layer using electrodeposition or any of the other processes mentioned herein.

[0167] In other configurations, layers 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, for example, vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless plating, high velocity oxygen fuel (HVOF) coating, thermal spray machining, or other suitable methods. A second layer can be formed on the first layer using an electrodeposition process as described herein. If desired, the first formed layer can be activated by a pickling process prior to electrodeposition of the second layer on the first layer.

[0168] In instances where a monolayer is formed by electrodeposition, the substrate having the coated surface can then be subjected to one or more post-treatment steps, including, for example, rinsing, abrading, sanding, heating, annealing, compacting, etching, or other steps, to either clean the coated surface or to change the physical or chemical properties of the coated surface. If desired, portions of the coating can be removed using acidic or basic solutions, depending on the materials present in the coating.

[0169] In certain embodiments, a method for producing an alloy layer on a substrate includes electrodepositing an alloy layer on the surface of the substrate to form a coated surface on the substrate. 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 containing 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 electrodeposition of the alloy layer, rinsing the cleaned substrate, activating the 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 further embodiments, the post-deposition treatment process is selected from the group consisting of rinsing, polishing, sanding, heating, annealing, and compaction. In some examples, the method includes providing an additional layer on the electrodeposited alloy layer. In other examples, the further layer is provided using one of vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless plating, high velocity oxygen fuel (HVOF) coating, and thermal spray processing.

[0170] 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 plating, high velocity oxygen-fuel thermal spray coating, and thermal spray processing. In certain embodiments, the electrodeposition uses a soluble anode or an insoluble anode. In some examples, the soluble anode comprises nickel or another metal.

[0171] 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 plating, high velocity oxygen fuel (HVOF) coating, thermal spray processing, or other suitable methods.

[0172] In certain examples, one or more of the coating layers can be deposited using vacuum deposition. In certain embodiments, vacuum deposition generally deposits layers of material on the surface of a substrate atom by atom or molecule by molecule. Vacuum deposition processes can be used to deposit one or more materials having thicknesses ranging from one or more atoms up to several millimeters.

[0173] In certain embodiments, physical vapor deposition (PVD), a type of vacuum deposition, can be used to deposit one or more of the coating layers described herein. PVD generally uses a vapor of a material to produce a thin coating on a substrate. The coatings described herein may be sputtered onto the surface of the substrate, for example, or applied to the surface of the substrate using evaporative 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 surface of the substrate to provide a desired coating layer on the substrate. In other configurations, plasma deposition (PD), such as plasma-enhanced 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 containing the material to be deposited and / or subjecting an already deposited material to ions of a 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, a substrate surface is exposed to repeated doses of precursors that can react with the surface of the material to build up a coating layer.

[0174] In other examples, one or more of the coating layers described herein can be deposited onto the surface of the substrate using brushing, spin coating, spray coating, dip coating, electrodeposition (e.g., electrolytic plating, cathodic electrodeposition, anodic electrodeposition, etc.), electroless plating, electrocoating, electrophoretic deposition, or other techniques. When a current is used to deposit a coating layer on the substrate, the current can be continuous, pulsed, a combination of continuous and pulsed, or pulsed. Specific electrodeposition techniques are described in more detail below.

[0175] In some configurations, one or more layers of the coating can be applied using electrodeposition. Generally, 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 the bath can be reduced using an applied voltage to deposit the ionic species in solid form onto 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 and electrodeposition conditions and techniques used, the resulting properties of the formed, electrodeposited coating can be selected or tailored to provide desired results.

[0176] 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 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, containing greater than 50% by volume of non-aqueous species, and may include hydrocarbons, alcohols, liquefied gases, amines, aromatics, and other non-aqueous materials.

[0177] Generally, an electrodeposition bath contains a species to be deposited as a coating on a substrate. For example, if nickel is to be deposited onto a substrate, the bath can contain ionic nickel or solvated nickel. If molybdenum is to be deposited into a substrate, the bath can contain ionic molybdenum or solvated molybdenum. If an alloy is to be deposited on the substrate, the bath can contain multiple species; for example, the bath may contain 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, species can 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 sodium monohydrogen phosphates, metal sodium dihydrogen phosphates, metal sodium trihydrogen phosphates, sodium salts of metals, potassium salts of metals, metal sulfamates, metal nitrites, and combinations thereof. In some instances, a single material containing both metal species to be deposited can be dissolved in the electrodeposition bath; for example, a metal alloy salt can be dissolved in a suitable solution prior to electrodeposition. The particular material used in the electrodeposition bath depends 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, tin (II) sulfate, sodium stannate, hypophosphite, sulfuric acid, nickel carbonate, nickel hydroxide, potassium carbonate, ammonium hydroxide, hydrochloric acid, or other materials.

[0178] In certain embodiments, the exact amount or concentration of species electrodeposited onto the substrate can vary. For example, the concentration of the species can vary from about 1 gram / liter to about 400 grams / liter. If desired, the ionic species can be depleted as a result of the formation of a coating on the substrate, and additional material can be added to the bath to increase the amount of species available for electrodeposition. In some examples, the concentration of the deposited species can be maintained at a substantially constant level during electrodeposition by continuously adding material to the bath.

[0179] 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 vary from 1 to about 13, although in certain instances the pH may be less than 1, or even less than 0, or greater than 13, or even greater than 14. When metal species are deposited onto the substrate as a metal alloy, the pH may range from 4 to about 12, in certain instances. However, it will be recognized 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 combinations thereof.

[0180] In certain embodiments, alloy plating can use a complexing agent. For example, the primary role of a complexing agent in the alloy deposition process is to complex different metal ions. Therefore, without a suitable complexing agent, nickel and molybdenum cannot be simultaneously deposited and alloyed. Examples of complexing agents include phosphates, phosphonates, polycarboxylates, zeolites, citrates, ammonium hydroxide, ammonium salts, citric acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic 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(carboxymethyl)-L-glutamic acid), and MGDA (methylglycinediacetic acid), hexamine cobalt(III) chloride, ethylene glycol-bis(β-aminoethyl ether)-N,N,N',N'-tetraacetic acid (EGTA). acid), ferrocene, cyclodextrin, cholic acid, polymers, and any combination thereof.

[0181] In some examples, suitable voltages can be applied to the cathode and anode of the electrodeposition bath to promote the formation of the layers described herein on the substrate. In some embodiments, direct current (DC) voltage 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 generally be carried out with an AC voltage waveform such as a sine wave, square wave, or triangular wave. High voltages and current densities can be used to promote electron tunneling through the oxide-based layer that can form on the substrate. Furthermore, the base layer conducts electricity toward the cathode, thereby promoting the deposition of the material and avoiding its reoxidation during the oxidant half-cycle.

[0182] In certain embodiments, exemplary current densities that can be used in electrodeposition include 1 mA / cm 2 DC~about 600mA / cm 2 DC, more specifically 1mA / cm 2 DC~approx.300mA / cm 2 In some examples, the current density is in the range of, but not limited to, 5 mA / cm 2 DC~approx.300mA / cm 2 DC, 20mA / cm 2 DC~approx. 100mA / cm 2 DC, 100mA / cm 2 DC ~ approx. 400mA / cm 2 The current may vary from DC, or any value within these exemplary ranges. The exact time the current is applied may vary from about 10 seconds to several days, more particularly from about 40 seconds to about 2 hours. If desired, pulsed current may be applied instead of DC current.

[0183] In some instances, electrodeposition may use pulsed or reversed current during the deposition of the alloy layer. In pulsed electrodeposition (PED), the potential or current is rapidly alternated 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 the 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 atomically control the composition and thickness of the deposited film. This favors grain nucleation, increasing the number of grains per unit area and resulting in a fine-grained deposit with better properties than conventional plating coatings.

[0184] In examples where the coating includes two or more layers, the first and second layers of the coating can be applied using the same or different electrodeposition baths. For example, the first layer can be applied using a first aqueous solution in an electrodeposition bath. After applying a voltage for a period sufficient to deposit the first layer, the voltage can be reduced to zero, the first solution can be removed from the bath, and a second aqueous solution containing a different material can be added to the bath. The voltage can then be reapplied to electrodeposit the second layer. In other examples, two separate baths can be used, such as a reel-to-reel process, in which a first bath is used to electrodeposit the first layer and a second, different bath is used to electrodeposit the second layer.

[0185] In some examples, individual articles can be connected so that they can be sequentially exposed to separate electrodeposition baths, for example, in a reel-to-reel process. For example, the articles can be connected to a common conductive substrate (e.g., a strip). In some embodiments, each of the electrodeposition baths can be associated with a separate anode, and the interconnected individual articles can be commonly connected to a cathode.

[0186] While the exact materials used in electrolytic plating processes 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 anionic form of these metals can vary from chloride, acetate, sulfate, nitrate, nitrite, chromate, dichromate, permanganate, platinate, cobalt nitrite, hexachloroplatinate, citrate, cyanide, oxide, phosphate, monosodium phosphate, disodium phosphate, trisodium phosphate, and combinations thereof.

[0187] In another example, the electrodeposition process can be designed to apply an alloy layer comprising molybdenum and one or more 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.

[0188] 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 onto the substrate surface 105 without an intermediate layer therebetween. In other examples, an intermediate layer may be present 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, nickel-phosphorus alloys containing hard particles, or other compounds such as phosphorus, boron, boron nitride, silicon carbide, aluminum oxide, molybdenum disulfide, hard particles having an HV hardness greater than 1000, hard particles having a size less than 500 nm, 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 examples, the intermediate layer may be substantially thinner 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.

[0189] In some embodiments, one or more of the materials of the coating layer can be provided using a soluble anode. The soluble anode can be dissolved in the electrodeposition bath to provide the species to be deposited. In some embodiments, the soluble anode can be in 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.

[0190] In some embodiments, one or more of the coating layers described herein can be deposited using an anodization process. Anodization generally uses a 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 an article 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 anodized layer is grown on the surface of a substrate by applying a direct current to an electrolyte solution containing the material to be deposited. The deposited materials may include magnesium, niobium, tantalum, zinc, nickel, molybdenum, copper, aluminum, cobalt, tungsten, gold, platinum, palladium, silver, or alloys thereof, 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.

[0191] In certain embodiments, the coatings described herein may be applied in the presence of other additives or agents. For example, wetting agents, leveling agents, brighteners, antifoaming agents, and / or emulsifiers may be present in the aqueous solution containing the material to be deposited onto the substrate surface. Exemplary additives and agents include 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), and the like.surfactant), 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, optional redox active surfactants, optional conductive ionic liquids, polyglycol ethers, polyglycol alcohols, sulfonated oleic acid derivatives, sulfated forms of primary alcohols, alkyl sulfonates, alkyl sulfates, aralkyl sulfonates, sulfates, perfluoroalkyl sulfonates, alkyl and aralkyl phosphate esters, alkyl polyglycol ethers, alkyl polyglycol phosphate esters or their salts, N-containing and 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-diaminetriacetic acid, 2-butyne-1,4-diol, 2-azobis(2-methylpropionitrile) perfluoroammonoid acid, dextrose, cetylmethylammonium bromide, 1-hexadecylpyridinium chloride, d-mannitol, glycine, Rochelle salt, NThese include, but are not limited to, N'-diphenylbenzidine, glycolic acid, tetra-methyl-ammonium hydroxide, reaction products of amines with epichlorohydrin, reaction products of amines, epichlorohydrin and polyalkylene oxides, reaction products of amines with polyepoxides, polyvinylpyridines, polyvinylimidazoles, polyvinylpyrrolidone or copolymers thereof, nigrosine, pentamethyl-para-rosaniline, one or more of fats, oils, long chain alcohols or glycols, polyethylene glycols, polyethylene oxides such as Triton, alkyl phosphates, metal soaps, certain silicone antifoam agents, commercially available perfluoroalkyl-modified hydrocarbon antifoam agents and perfluoroalkyl-substituted silicones, fully fluorinated alkyl phosphonates, perfluoroalkyl-substituted phosphate esters, cationic, amphoteric and nonionic agents, citrates, acetates, gluconates and ethylenediamine tetra-acetic acid (EDTA) or combinations thereof.

[0192] 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 / electrolytic plating, an external current is not applied to the substrate in electroless plating. While not wishing to be bound by any particular configuration or example, electroless plating can provide a more uniform layer of material on a substrate compared to electrolytic plating. Furthermore, electroless plating can be used to apply a coating onto a non-conductive substrate.

[0193] In certain embodiments in which electroless plating is used, the substrate itself may act as a catalyst, reducing an ionic metal and forming a metal coating 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 instances, the substrate itself may not function as a catalyst, but a catalytic material may be added to the substrate to promote 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.

[0194] 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 monosodium phosphates, metal disodium phosphates, metal trisodium phosphates, and combinations thereof.

[0195] In certain embodiments, the substrates described herein may be subjected to pre-coating treatment steps to prepare the substrate for coating. These treatment steps may include, for example, cleaning, electrocleaning (anodic or cathodic), polishing, electropolishing, pre-plating, heat treatment, polishing treatment, and chemical treatment. For example, the substrate may be cleaned with an acid, base, water, a salt solution, an organic solution, an organic solvent, or other liquid or gas. The substrate may be polished using water, an acid or base such as sulfuric acid or phosphoric acid, or other materials, optionally in the presence of an electric current. The substrate may be exposed to one or more gases before application of the coating layer to promote the 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 before 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 any liquid from the surface before application of the coating. Other processes for treating the substrate before application of the coating may also be used. For example, the substrate can be heated to high temperatures, such as greater than 100° C., greater than 200° C., greater than 500° C., greater than 700° C., or greater than 1000° C. Likewise, the final article including the coating can operate at such high temperatures.

[0196] In some embodiments, the coating layers described herein can be subjected to sealing. While the exact conditions and materials used to seal the coatings can vary, sealing can reduce the porosity of the coatings and increase their hardness. In some embodiments, sealing can be performed by subjecting the coating 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°C or higher, 50°C or higher, 90°C or higher, at room temperature, or below room temperature, e.g., 20°C or lower. In some examples, the substrate and coating layer can be heated to remove any 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 to 2 hours after coating.

[0197] It will be appreciated by those skilled in the art that a combination of post-deposition treatment methods can be used, for example, a coating layer can be sealed and then polished to reduce surface roughness.

[0198] In certain configurations, the electrodeposition process can include cleaning the substrate to receive the coating. The substrate can then be rinsed. The substrate can then be subjected to an acid treatment. The acid-treated substrate is then rinsed. The rinsed substrate is then added to a plating bath. The plated substrate can optionally be rinsed. The substrate with the coated surface can then be subjected to a post-plating process. Each of these steps is described in more detail below. An optional strike step to provide a nickel layer (or a layer of another material) on the surface of the substrate can be performed if desired.

[0199] In certain embodiments, the cleaning step can be performed in the presence or absence of an electric current. Cleaning is typically performed in the presence of one or more salts and / or detergents or surfactants, and can be performed at an acidic or basic pH. Cleaning is generally performed to remove oils, hydrocarbons, or other materials from the surface of the substrate.

[0200] After the substrate is cleaned, it is rinsed to remove any cleaning agents. Rinsing is typically performed in distilled water, but may be performed using one or more buffers or at an acidic or basic pH. Rinsing may be performed once or multiple times. The substrate is typically kept wet between various steps to minimize oxide formation on the surface. A water break test can be performed to ensure the surface is clean and / or free of any oils.

[0201] After rinsing, the substrate can be immersed in an acid bath to activate the surface for electrodeposition, e.g., pickling the surface. The exact acid used is not critical. The pH of the acid treatment can be from 0 to 7, or even less than 0 if desired. The time the substrate remains in the acid bath can vary, e.g., from 10 seconds to about 10 minutes. The acid solution can be stirred or dispensed over the substrate surface if desired, or the substrate can be moved within the acid bath during the pickling process.

[0202] After the pickling process, the surface can be rinsed to remove any acid. Rinsing can be performed by immersing the pickled substrate in a rinse bath, or by flowing a rinse agent over the surface, or both. Rinsing can be performed multiple times or once, if desired.

[0203] After pickling, the substrate can optionally be subjected to a strike. While not wishing to be bound by 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.

[0204] The rinsed and pickled substrate, or the rinsed substrate with the 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 carried out using AC or DC voltages and various waveforms. The exact current density used can be varied to favor or disadvantage the amounts of particular elements in the final coating. For example, if the alloy layer contains two metals, the current density can be selected so that one metal is present in greater amounts than the other in the resulting alloy layer. The pH of the electrodeposition bath can also be varied depending on the specific species intended to be present in the surface coating. For example, acidic baths (pH = 3-5.5), neutral pH baths, or basic pH baths (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°C) up to about 85°C. Temperatures below 100°C are desirable so that the water in the electrodeposition bath does not evaporate to a significant extent. The electrodeposition bath may contain the material to be deposited along with any agents, including brighteners, levelers, particles, etc., as described herein.

[0205] In some embodiments, the electrodeposition bath can include a brightener. Various 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 are used at relatively high concentrations and can produce hazy or cloudy deposits on metal substrates. Decomposition of Class I brighteners during the electroplating process can introduce sulfur into the deposit, thereby reducing the tensile stress of the deposit. Class II, or secondary brighteners, are used in combination with Class I brighteners to produce completely bright and flat deposits. Class II brighteners are generally unsaturated organic compounds. Various 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 acetylenic or ethylene alcohols, ethoxylated acetylenic alcohols, coumarins, and pyridine-based compounds. Mixtures of these unsaturated compounds, including mixtures of Class I brighteners, can be combined to obtain maximum brightness or ductility for a given leveling level. 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 coverage at low current densities.

[0206] In certain embodiments, the resulting amounts of metals present in the alloy layer may vary. For example, in certain electrodeposition processes in which two metals are present in the surface coating, one of the metals, e.g., molybdenum, may be present in an amount up to about 35 weight percent based on the weight of the surface coating. In other embodiments, one of the metals, e.g., molybdenum, may be present in an amount up to about 20 weight percent based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present in an amount up to about 16 weight percent based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present in an amount up to about 10 weight percent based on the weight of the surface coating. In some examples, one of the metals, e.g., molybdenum, may be present in an amount up to about 6 weight percent based on the weight of the surface coating.

[0207] In certain configurations, the substrate with the surface coating can then be rinsed or subjected to another deposition process to apply a second layer onto 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 plating, high velocity oxygen fuel (HVOF) coating, thermal spray processing, or other suitable method. In some examples, 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 including one, two, three or more metals or other materials. If desired, an additional layer can be formed on the second layer using electrodeposition or any of the other processes mentioned herein.

[0208] In other configurations, layers 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, for example, vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless plating, high velocity oxygen fuel (HVOF) coating, thermal spray machining, or other suitable methods. A second layer can be formed on the first layer using an electrodeposition process as described herein. If desired, the first formed layer can be activated by a pickling process prior to electrodeposition of the second layer on the first layer.

[0209] In instances where a monolayer is formed by electrodeposition, the substrate having the coated surface can then be subjected to one or more post-treatment steps, including, for example, rinsing, abrading, sanding, heating, annealing, compacting, etching, or other steps, to either clean the coated surface or to change the physical or chemical properties of the coated surface. If desired, portions of the coating can be removed using acidic or basic solutions, depending on the materials present in the coating.

[0210] In certain embodiments, a method for producing an alloy layer on a substrate includes electrodepositing an alloy layer on the surface of the substrate to form a coated surface on the substrate. 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 containing 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 electrodeposition of the alloy layer, rinsing the cleaned substrate, activating the 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 further embodiments, the post-deposition treatment process is selected from the group consisting of rinsing, polishing, sanding, heating, annealing, and compaction. In some examples, the method includes providing an additional layer on the electrodeposited alloy layer. In other examples, the further layer is provided using one of vacuum deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD), plasma deposition, brushing, spin coating, spray coating, electrodeposition / electroplating, electroless plating, high velocity oxygen fuel (HVOF) coating, and thermal spray processing.

[0211] 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 plating, high velocity oxygen-fuel thermal spray coating, and thermal spray processing. In certain embodiments, the electrodeposition uses a soluble anode or an insoluble anode. In some examples, the soluble anode comprises nickel or another metal.

[0212] In certain embodiments, the articles described herein can be configured as decorative articles or can include a decorative coating. For example, a decorative article can include a substrate and a surface coating on the substrate. The coating can include a single layer or multiple layers, such as those described above in connection with FIGS. 1-12. In some embodiments, a decorative article or decorative article substrate can include a first layer and a second layer, where the first layer includes a molybdenum alloy (as described in connection with FIGS. 1-12) and the second layer includes chromium. For example, the first layer can be formed on the substrate and the second layer can be on the first layer. In certain embodiments, a decorative article can be configured as a hand ornament, a machine ornament, a garden ornament, or a power ornament.

[0213] In some examples, the decorative article can include a substrate and a coating on the substrate. The decorative article coating can include a first layer and a second layer, where the first layer includes a molybdenum alloy, a nickel alloy, or both. The second layer can include chromium. The exact form of the decorative article can vary. In certain embodiments, the first layer can be formed on the substrate, and the second layer can be on the first layer.

[0214] In certain examples, the decorative article can include any of these materials described in connection with the articles described herein and illustrated in Figures 1-12. For example, the decorative article can include a substrate, at least a first layer and an optional second layer, and one or more other layers, if desired. The first layer can include a molybdenum alloy, a nickel alloy, or both, and optionally other materials. The second layer can include chromium, a chromium compound, and optionally other materials. In some examples, the first layer of the decorative coating includes a nickel-molybdenum alloy. For example, molybdenum can be present in the first layer at 35% by weight or less. Alternatively, nickel can be present in the first layer at 65% by weight or more.

[0215] In certain embodiments, the articles described herein can be configured as vehicle components. For example, the vehicle component can include a substrate configured to be coupled to a vehicle and a coating on the substrate, where the coating includes a first layer and a second layer, where the first layer includes a molybdenum alloy or a nickel alloy (or both), and the second layer includes chromium. In some embodiments, the vehicle component can be configured as an exterior vehicle component, an interior vehicle component, a bumper 1302 (see FIG. 13A), a mirror 1304 (FIG. 13B), a vehicle exhaust 1306 (FIG. 13C), a vehicle rim 1308 (FIG. 13D), a vehicle engine component 1310 (FIG. 13E), a motorcycle component 1312 (FIG. 13F), a recreational vehicle component or a recreational vehicle 1314 (FIG. 13G), or other vehicle component. In certain embodiments, the first layer can be formed on the substrate, and the second layer can be on the first layer.

[0216] In certain examples, the vehicle component can include any of these materials described in connection with the articles described herein and can include layers described with reference to Figures 1-12. For example, the vehicle component can include a substrate, at least a first layer, and a second layer. The first layer can include a molybdenum alloy, a nickel alloy, or both, and optionally other materials. The second layer can include chromium, a chromium compound, and optionally other materials. In some examples, the first layer of the coating on the vehicle component includes a nickel-molybdenum alloy. For example, molybdenum can be present in the first layer at 20% by weight or less. Alternatively, nickel can be present in the first layer at 80% by weight or more.

[0217] In other configurations, the vehicle component can include one or more layers between the first and second layers, while in some configurations, the coating can include only the first and second layers. For example, an intermediate layer can be present between the first and second layers, such that the vehicle component includes three layers on the substrate as described above. The exact materials present in the intermediate layer can vary. For example, the intermediate layer can include one or more transition metals, particles, nanoparticles, refractory metals, metal alloys, etc. In some embodiments, the intermediate layer can be a "gloss" or "semi-gloss" layer as described herein.

[0218] In certain embodiments, the first and second layers of the vehicle component can be formed or otherwise deposited in a number of different ways as described herein. In some examples, the first layer of the vehicle component can include an electrodeposited molybdenum alloy coating, an electrolytically plated molybdenum alloy coating, an electrolessly deposited molybdenum alloy coating, an electrodeposited nickel alloy coating, an electrolytically plated nickel alloy coating, or an electrolessly deposited nickel alloy coating.

[0219] In certain embodiments, the first and second layers of a vehicle component may together provide some corrosion resistance or other desired property. For example, a coating including the first and second layers (and optionally an intermediate layer) may exhibit less than 7% corrosion on its surface after 500 hours of standard salt spray testing according to ASTM B117-19.

[0220] In some configurations, the coating or individual layers of the coating may be free of certain metals or metal alloys to enhance overall performance. For example, the first layer, the second layer, or both of the vehicle component may be free of iron or may be free of precious metals. In other examples, the first layer, the second layer, or both of the vehicle component may be free of tungsten. If desired, the first layer and / or the second layer of the vehicle component may be free of both iron and tungsten.

[0221] In certain embodiments in which the vehicle component includes a first layer and a second layer comprising chromium, one or more layers may be present between the first layer (e.g., a layer comprising a Mo alloy or a Ni alloy) and the substrate of the vehicle component. For example, one or more of an adhesion-promoting layer, a corrosion-promoting layer, a grain-refining layer, etc. may be present between the substrate of the vehicle component and the first layer.

[0222] In certain configurations where the substrate of the vehicle component includes a first layer (e.g., a layer including a Mo alloy or a Ni alloy) and a second layer, the substrate of the vehicle component may be any of those materials listed herein for substrates. For example, the substrate may include one or more of copper, copper alloy, nickel, nickel alloy, cobalt, cobalt alloy, plastic, steel, carbon steel, stainless steel, tool steel, galvanized steel, alloy steel, superalloy, nickel-chromium superalloy, nickel-chromium-iron-molybdenum alloy, zinc, zinc alloy, titanium, titanium alloy, aluminum, aluminum alloy, or other materials and combinations described herein.

[0223] In some embodiments, one or more surfaces of the substrate of the vehicle component can be treated (e.g., physically or chemically) prior to providing the first layer on the substrate. For example, one or more substrate surfaces of the vehicle component can be hardened, carburized, nitrided, anodized, or may be treated to provide a combination thereof.

[0224] In other configurations, the articles described herein can be configured as home interior items. For example, the home interior item can include a substrate and a coating on the substrate. The coating of the home interior item can include a first layer and a second layer, where the first layer includes a molybdenum alloy, a nickel alloy, or both. The second layer can include chromium. The exact form of the home interior item can vary, and exemplary forms include items where it is desirable to have a shiny surface. For example, the household interior item may be a knife 1402 (FIG. 14A), a fork 1404 (FIG. 14B), a spoon 1406 (FIG. 14C), a bowl 1408 (FIG. 14D), a plate 1410 (FIG. 14E), a spatula 1412 (FIG. 14F), a vase 1414 (FIG. 14G), a tea kettle 1416 (FIG. 14H), a serving tray 1418 (FIG. 14I), a saucepan 14 (FIG. 14), a mug 1422 (FIG. 14K), a decorative vase 1424 (FIG. 14L), a frying pan 1426 (FIG. 14M), and other household items including, but not limited to, bathroom fixtures, cabinetry, refrigerators, stoves, washers, sinks, bathtubs, shower stalls or shower cubicle walls, etc. In certain embodiments, a first layer can be formed on a substrate, and a second layer can be on the first layer.

[0225] In certain examples, the household interior article can include any of these materials or layers described in connection with the articles of Figures 1-12. For example, the household interior article can include a substrate, at least a first layer, and a second layer. The first layer can include a molybdenum alloy, a nickel alloy, or both, and optionally other materials. The second layer can include chromium, a chromium compound, and optionally other materials. In some examples, the first layer of the coating of the household interior article includes a nickel-molybdenum alloy. For example, molybdenum can be present in the first layer at 20% by weight or less. Alternatively, nickel can be present in the first layer at 80% by weight or more.

[0226] In other configurations, the household interior article can include one or more layers between the first and second layers, while in some configurations, the coating can include only the first and second layers. For example, an intermediate layer can be present between the first and second layers, such that the household interior article includes three layers on the substrate as described above. The exact materials present in the intermediate layer can vary. For example, the intermediate layer can include one or more transition metals, particles, nanoparticles, refractory metals, metal alloys, etc. In some embodiments, the intermediate layer can be a "gloss" or "semi-gloss" layer as described herein.

[0227] In certain embodiments, the first and second layers of the indoor household article can be formed or otherwise deposited in a number of different ways as described herein. In some examples, the first layer of the indoor household article can include an electrodeposited molybdenum alloy coating, an electrolytically plated molybdenum alloy coating, an electrolessly deposited molybdenum alloy coating, an electrodeposited nickel alloy coating, an electrolytically plated nickel alloy coating, or an electrolessly deposited nickel alloy coating.

[0228] In certain embodiments, the first and second layers of a home interior article may together provide some corrosion resistance or other desired property. For example, a coating including the first and second layers (and optionally an intermediate layer) may exhibit less than 7% corrosion on its surface after 500 hours of standard salt spray testing according to ASTM B117-19.

[0229] In some configurations, the coating or individual layers of the coating of the indoor household article may be free of certain metals or metal alloys to enhance overall performance. For example, the first layer, the second layer, or both of the indoor household article may be free of iron. In other examples, the first layer, the second layer, or both of the indoor household article may be free of tungsten. If desired, the first layer and / or the second layer of the indoor household article may be free of both iron and tungsten.

[0230] In certain embodiments in which a household interior article includes a first layer and a second layer containing chromium, one or more layers may be present between the first layer (e.g., a layer containing a Mo alloy or a Ni alloy) and the substrate of the household interior article. For example, one or more of an adhesion-promoting layer, a corrosion-promoting layer, a grain-refining layer, etc. may be present between the substrate and the first layer of the household interior article. In certain configurations in which the substrate of the household interior article includes a first layer (e.g., a layer containing a Mo alloy or a Ni alloy) and a second layer, the substrate of the household interior article may be any of the materials listed herein for the substrate. For example, the substrate may include one or more of copper, copper alloy, nickel, nickel alloy, cobalt, cobalt alloy, plastic, steel, carbon steel, stainless steel, tool steel, galvanized steel, alloy steel, superalloy, nickel-chromium superalloy, nickel-chromium-iron-molybdenum alloy, zinc, zinc alloy, titanium, titanium alloy, aluminum, aluminum alloy, or other materials and combinations described herein.

[0231] In some embodiments, one or more surfaces of the substrate of the interior household article can be treated (e.g., physically or chemically) prior to providing the first layer on the substrate. For example, one or more substrate surfaces of the interior household article can be hardened, carburized, nitrided, anodized, or may be treated to provide a combination thereof.

[0232] In certain embodiments, the coatings described herein can be used as jewelry. Jewelry may be manufactured using gold, silver, stainless steel, or other metals, and coatings can be included on these metals to reduce corrosion and / or extend the life of the jewelry. Exemplary jewelry includes, but is not limited to, ring 1502 (FIG. 15A), necklace 1504 (FIG. 15B), earrings 1506 (FIG. 15C), bracelet 15 (FIG. 15D), or other jewelry. Jewelry can include any of the materials or layers described in connection with FIGS. 1-12. For example, jewelry can include a substrate, at least a first layer, and a second layer. The first layer can include a molybdenum alloy, a nickel alloy, or both, and optionally other materials. The second layer can include chromium, a chromium compound, and optionally other materials. In some examples, the first layer of a coating on a jewelry item includes a nickel-molybdenum alloy. For example, molybdenum can be present in the first layer at 20% by weight or less, or nickel can be present in the first layer at 80% by weight or more.

[0233] In other configurations, the jewelry may include one or more layers between the first and second layers, while in some configurations, the coating may include only the first and second layers. For example, an intermediate layer may be present between the first and second layers, such that the jewelry item includes three layers on the substrate as described above. The exact materials present in the intermediate layer may vary. For example, the intermediate layer may include one or more transition metals, particles, nanoparticles, refractory metals, metal alloys, etc. In some embodiments, the intermediate layer may be a "glossy" or "semi-glossy" layer as described herein.

[0234] In certain embodiments, the first and second layers of the jewelry can be formed or otherwise deposited in a number of different ways as described herein. In some examples, the first layer of the jewelry can include an electrodeposited molybdenum alloy coating, an electrolytically plated molybdenum alloy coating, an electrolessly deposited molybdenum alloy coating, an electrodeposited nickel alloy coating, an electrolytically plated nickel alloy coating, or an electrolessly deposited nickel alloy coating.

[0235] In certain embodiments, the first and second layers of the jewelry may together provide some corrosion resistance or other desired property. For example, a coating including the first and second layers (and optionally an intermediate layer) may exhibit less than 7% corrosion on its surface after 500 hours of standard salt spray testing according to ASTM B117-19.

[0236] In some configurations, the jewelry coating or individual layers of the coating may be free of certain metals or metal alloys to enhance overall performance. For example, the first layer, the second layer, or both of the jewelry may be free of iron. In other examples, the first layer, the second layer, or both of the jewelry may be free of tungsten. If desired, the first and / or second layers of the jewelry may be free of both iron and tungsten.

[0237] In certain embodiments in which jewelry includes a first layer and a second layer comprising chromium, one or more layers may be present between the first layer (e.g., a layer comprising a Mo alloy or a Ni alloy) and the jewelry substrate. For example, one or more of an adhesion-promoting layer, a corrosion-promoting layer, a grain-refining layer, etc. may be present between the jewelry substrate and the first layer. In certain configurations in which the jewelry substrate includes a first layer (e.g., a layer comprising a Mo alloy or a Ni alloy) and a second layer, the jewelry substrate may be any of the materials listed herein for the substrate. For example, the substrate may include one or more of copper, copper alloy, nickel, nickel alloy, cobalt, cobalt alloy, plastic, steel, carbon steel, stainless steel, tool steel, galvanized steel, alloy steel, superalloy, nickel-chromium superalloy, nickel-chromium-iron-molybdenum alloy, zinc, zinc alloy, titanium, titanium alloy, aluminum, aluminum alloy, or other materials and combinations described herein.

[0238] In some embodiments, one or more surfaces of the jewelry substrate can be treated (e.g., physically or chemically) prior to providing the first layer on the substrate. For example, one or more surfaces of the jewelry substrate can be hardened, carburized, nitrided, anodized, or may be treated to provide combinations thereof.

[0239] In certain embodiments, the articles described herein can be configured as connector shells. In certain embodiments, the coatings described herein can be used on connector shells. Connector shells can be manufactured using steel, steel alloys, zinc alloys, aluminum, copper, brass, nickel, nickel alloys, or other metals, and coatings can be included on these metals to reduce corrosion and / or extend the life of the connector shell. The connector shell can be a circular shell, an RF connector housing, or any other type. Exemplary connector shell articles include, but are not limited to, those shown in FIGS. 15E and 15F or other connector shell articles. The connector shell can include any of the materials or layers described in connection with FIGS. 1-12. For example, the connector shell can include a substrate, at least a first layer, and a second layer. The first layer can include a molybdenum alloy, a nickel alloy, or both, and optionally other materials. The second layer can include chromium, a chromium compound, and optionally other materials. In some examples, the first layer of the connector shell coating includes a nickel-molybdenum alloy. For example, molybdenum can be present in the first layer at 20% by weight or less, or nickel can be present in the first layer at 80% by weight or more.

[0240] In some examples, the connector shell can include a substrate and a coating on the substrate. The connector shell coating can include a first layer and a second layer, where the first layer includes a molybdenum alloy, a nickel alloy, or both. The second layer can include chromium. The exact form of the connector shell can vary. In certain embodiments, the first layer can be formed on the substrate, and the second layer can be on the first layer.

[0241] In certain examples, the connector shell can include any of these materials described in connection with the articles described herein. For example, the connector shell can include a substrate, at least a first layer, and a second layer. The first layer can include a molybdenum alloy, a nickel alloy, or both, and optionally other materials. The second layer can include chromium, a chromium compound, and optionally other materials. In some examples, the first layer of the connector shell coating includes a nickel-molybdenum alloy. For example, molybdenum can be present in the first layer at 20% by weight or less. Alternatively, nickel can be present in the first layer at 80% by weight or more.

[0242] In other configurations, the connector shell can include one or more layers between the first and second layers, while in some configurations, the coating can include only the first and second layers. For example, an intermediate layer can be present between the first and second layers, such that the connector shell includes three layers on the substrate as described above. The exact materials present in the intermediate layer can vary. For example, the intermediate layer can include one or more transition metals, particles, nanoparticles, refractory metals, metal alloys, etc. In some embodiments, the intermediate layer can be a "gloss" or "semi-gloss" layer as described herein.

[0243] In certain embodiments, the first and second layers of the connector shell can be formed or otherwise deposited in a number of different ways as described herein. In some examples, the first layer of the connector shell can include an electrodeposited molybdenum alloy coating, an electrolytically plated molybdenum alloy coating, an electrolessly deposited molybdenum alloy coating, an electrodeposited nickel alloy coating, an electrolytically plated nickel alloy coating, or an electrolessly deposited nickel alloy coating.

[0244] In certain embodiments, the first and second layers of the connector shell may together provide some corrosion resistance or other desired property. For example, a coating including the first and second layers (and optionally an intermediate layer) may exhibit less than 7% corrosion on its surface after 500 hours of standard salt spray testing according to ASTM B117-19.

[0245] In some configurations, the connector shell coating or individual layers of the coating may be free of certain metals or metal alloys to enhance overall performance. For example, the first layer, the second layer, or both of the connector shell may be free of iron. In other examples, the first layer, the second layer, or both of the connector shell may be free of tungsten. If desired, the first and / or second layers of the connector shell may be free of both iron and tungsten.

[0246] In certain embodiments in which the connector shell includes a first layer and a second layer comprising chromium, one or more layers may be present between the first layer (e.g., a layer comprising a Mo alloy or a Ni alloy) and the substrate of the connector shell. For example, one or more of an adhesion-promoting layer, a corrosion-promoting layer, a grain-refining layer, etc. may be present between the substrate and the first layer of the connector shell. In certain configurations in which the substrate of the connector shell includes a first layer (e.g., a layer comprising a Mo alloy or a Ni alloy) and a second layer, the substrate of the connector shell may be any of the materials listed herein for substrates. For example, the substrate may include one or more of copper, copper alloy, nickel, nickel alloy, cobalt, cobalt alloy, plastic, steel, carbon steel, stainless steel, tool steel, galvanized steel, alloy steel, superalloy, nickel-chromium superalloy, nickel-chromium-iron-molybdenum alloy, zinc, zinc alloy, titanium, titanium alloy, aluminum, aluminum alloy, or other materials and combinations described herein.

[0247] In some embodiments, one or more surfaces of the connector shell substrate can be treated (e.g., physically or chemically) prior to providing the first layer on the substrate. For example, one or more substrate surfaces of the connector shell can be hardened, carburized, nitrided, anodized, or may be treated to provide combinations thereof.

[0248] In certain embodiments, a decorative article includes a decorative article substrate, at least a portion of an exterior surface of the decorative article substrate includes a coated surface, the coated surface includes a surface coating, and the surface coating includes an alloy layer including (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.

[0249] In certain embodiments, the decorative article substrate comprises stainless steel, hardened steel, carbon steel, alloy steel, precious metal or other metal, and the surface coating comprises a chrome layer over the alloy layer.

[0250] In some embodiments, molybdenum is present in the surface coating at 35 wt% or less based on the weight of the surface coating, or 25 wt% or less based on the weight of the surface coating, or 15 wt% or less based on the weight of the surface coating, or 35 wt% or less based on the weight of the alloy layer, or 25 wt% or less based on the weight of the alloy layer, or 15 wt% or less based on the weight of the alloy layer. In other embodiments, molybdenum is present in the surface coating at 65 wt% or more based on the weight of the surface coating, or 75 wt% or more based on the weight of the surface coating, or 85 wt% or more based on the weight of the surface coating, or 65 wt% or less based on the weight of the alloy layer, or 75 wt% or less based on the weight of the alloy layer, or 85 wt% or less based on the weight of the alloy layer.

[0251] In further embodiments, the coated surface comprises a surface roughness Ra of less than 1 micron. 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.

[0252] In some examples, the coated surface comprises a surface roughness Ra of less than 1 micron, the molybdenum is present in the alloy layer at 20 wt % or less based on the weight of the surface coating, and the surface coating is free of precious metals.

[0253] In other examples, the alloy layer is an electrodeposited alloy layer. In some embodiments, the alloy layer is the exposed outer layer of a surface coating. In other embodiments, the exposed outer layer consists essentially of molybdenum and only one of nickel, tungsten, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron. In some examples, the exposed outer layer consists essentially of molybdenum and only two of nickel, tungsten, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron. In other examples, the exposed outer layer consists essentially of both molybdenum and phosphorus and at least one of nickel, cobalt, tin, chromium, tungsten, iron, magnesium, or boron.

[0254] In one particular example, the alloy layer is an electrodeposited alloy layer and further includes an intermediate layer between the surface and the alloy layer, the intermediate layer including 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 an alloy of both of these with at least one of nickel, cobalt, chromium, tin, phosphorus, iron, or boron.

[0255] In other embodiments, an additional layer is formed on the alloy layer, the additional layer comprising one or more of nickel, a nickel alloy, a nickel-tungsten alloy, a cobalt alloy, a cobalt-phosphorus alloy, a nickel-phosphorus alloy, an alloy of molybdenum and at least one of nickel, cobalt, chromium, tin, phosphorus, iron, or boron, a ceramic comprising tungsten, chromium, aluminum, zirconium, titanium, nickel, cobalt, molybdenum, silicon, boron, a metal nitride, a nitride, a metal carbide, a carbide, boron, tungsten, tungsten carbide, chromium carbide, chromium oxide, aluminum oxide, zirconia, zirconium oxide, titania, nickel carbide, nickel oxide, a nanocomposite, a compound of an oxide composite, or a combination thereof.

[0256] In some examples, 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.

[0257] In another example, the alloy layer is present as an exposed outer layer of a surface coating, the exposed outer layer being an electrodeposited alloy layer, and the electrodeposited alloy layer does not include a precious metal.

[0258] To test specific coating formulations, several examples are set forth below. These versions are referred to as H-max and O-Max for reference purposes and are collectively referred to as Maxshield or Maxshield coatings. The H-Max family includes nickel-molybdenum coatings, which are proposed replacements for electroplated hard chrome (EHC) coatings. Their wear resistance is higher than that of chrome and they can be used in severely abrasive environments. The O-max family is a nickel-molybdenum coating that is more chemically resistant than H-Max and offers extreme chemical resistance. The properties of the coating can be modified, for example, by changing the ratio of nickel and molybdenum in the coating.

[0259] Example 1

[0260] All versions of the coating have a metallic appearance. Figure 16 is a photograph showing the appearance of H-Max applied to a hydraulic rod after some minor polishing. All versions of the coating can be machined, polished, or buffed to modify their appearance and roughness. Bright coatings with a mirror-like appearance immediately after the electrolytic plating process can also be produced. The bright reflective coating shown in Figure 17 is the coating immediately after the plating process without any polishing or buffing. O-Max and H-Max can also be matte-finished if desired.

[0261] Example 2

[0262] The most common thickness of the coating is between 0.4 mil and 3 mil (10 micrometers to 75 micrometers). However, the coating thickness can be varied by the deposition time and the number of coating layers. Thus, coatings less than 0.4 mil and greater than 3 mil thick can be produced.

[0263] Example 3

[0264] This test was conducted to examine cross sections of O-Max, measure their thickness, and evaluate the effect of heat treatment on the coating structure. All metallographic processing was performed using in-house equipment. EHC samples with a thickness of approximately 100 μm were provided to us by a chrome plating facility. Cross sections of the as-plated and heat-treated EHC and O-Max samples are shown in Figures 18A-18D. The as-plated EHC has microcracks throughout its cross section, while the as-plated O-Max is nearly crack-free. After heat treatment of the EHC, the cracks grew into large macrocracks. As shown in Figures 18A-18D, some of the cracks grew all the way from the substrate to the surface. The presence of this type of macrocrack in the coating structure can significantly reduce the corrosion protection properties of the coating. In contrast, the cross section of O-Max remained the same after heat exposure, and no signs of crack growth were observed for O-Max. The reduction in the mechanical properties of EHC at high temperatures may be related to this crack growth mechanism and the degradation that occurs in EHC during heat exposure.

[0265] Figures 19A and 19B show cross sections of O-Max (Figure 19A) and H-Max (Figure 19B) coatings. The figures also show that the O-Max is largely crack-free, while the H-Max coating has some microcracks. As discussed herein, the presence of microcracks can enhance lubricity in applications where the coating comes into contact with oil or lubricants.

[0266] Example 4

[0267] Salt spray corrosion testing was performed by Assured Testing Services, a NADCAP-accredited testing facility. The standard corrosion test is also known as the salt fog test. During this test, coated samples are exposed to a mist of 5% sodium chloride, which simulates corrosion caused by a marine environment. Testing was performed in a testing laboratory according to ASTM B117. Assured Testing Services also determined the corrosion rating of different samples according to the ASTM B537 rust rating scale. This standard implies a rating ranging from 0 to 10, with 10 corresponding to the best corrosion resistance and 0 corresponding to the worst conditions. A table showing the corrosion rating scale is provided in Figure 20.

[0268] In one example, the corrosion performance of an EHC coating is compared to an O-Max coating after up to 1000 hours of exposure to salt fog. We provide the following samples. All O-Max coatings contain a metallic underlayer (the composition can vary depending on the intended use) and have the following characteristics: O-Max-V1 has a thickness of 20-30 μm, and O-Max-V2 has a thickness of 70-90 μm. O-Max-V2 is manufactured using heat treatment to improve hardness and wear performance, while O-Max-V3 is similar to O-Max-V2 but is not heat treated.

[0269] The corrosion rating of the EHC, with a thickness of 20–30 microns, was 10 at 200 hours and dropped to 4 at 400 hours. Figure 21 shows a photograph of the EHC sample at 400 hours. According to ASTM B537, 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 O-Max coatings after 1000 hours of salt spray exposure are shown in Figures 22A–22E. Four of these samples (Figures 22A, 22C, 22D, and 22E) exhibited a corrosion rating of 9, while one of the O-Max-V1 samples after 1000 hours has a corrosion rating of 10. A corrosion rate of 9 indicates rust formation on less than 0.03% of the surface area, according to the ASTM B537 standard. The O-Max-V1 sample, which was rated 10, showed no rust at all during the first 1000 hours.

[0270] Figure 23 compares the salt spray test results of our coatings with those of the EHC coating. As this figure shows, after 400 hours of salt spray exposure, the corrosion rate of the EHC coating dropped sharply to 4, while the corrosion rating of the fabricated coating remained higher than 9 up to 1000 hours of exposure. For the scribed O-Max-V1 coating, a corrosion rate of 9 was obtained on the area far from the scribed area. Based on ASTM D1654, the scribed area on this sample received a creep measurement rating of 8. Previous testing on scribed surfaces indicates that if the fabricated coating is scratched and the underlying steel surface is exposed at the scratch location, a significantly increased risk of accelerated corrosion is not expected.

[0271] In another example, salt spray corrosion testing was performed on O-Max samples for up to 5,000 hours. The sample ratings at different times during the salt spray test, up to 5,000 hours, are shown in the table in Figure 24. As shown in the table, O-Max-V2 and O-Max-V3 maintain a rating of 9 up to 4,000 hours of salt spray exposure. Three O-Max-V1 samples exhibit corrosion ratings of 7, 9, and 8. O-Max-V1 has a lower thickness compared to O-Max-V2 and O-Max-V3. With thinner coatings, pinholes and other defects in the coating are more likely to allow corrosive media to reach the underlying steel substrate and cause corrosion. This explains why O-Max-V2 and O-Max-V3 perform better than O-Max-V1 during extended exposure to corrosive media.

[0272] In another example, the corrosion performance of the H-Max family was tested. In this test, a 25 μm thick H-Max coating with a metal underlayer was tested in a salt spray chamber according to ASTM B117 by the Assured testing lab. Samples were tested in salt spray for up to 1000 hours. After 1000 hours, all three samples received a rating of 10, meaning that no corrosion was observed in the test area of ​​the sample. Figures 25A-25C show images of the samples after 1000 hours of salt spray. It is worth noting that the rust color at the edge of the third sample (Figure 25C) is bleeding from the backside of the sample.

[0273] In another example, H-Max and O-Max coated parts were tested according to the ASTM B117 salt spray corrosion test with less than 5% corrosion on the surface after 1000 hours.

[0274] In another example, H-Max and O-Max coated parts were tested according to the ASTM B117 salt spray corrosion test with less than 5% corrosion on the surface after 5000 hours.

[0275] In another example, carbon steel parts coated with H-Max and O-Max were tested according to the ASTM B117 salt spray corrosion test with a corrosion rating of greater than 6 after 48 hours. In another example, a socket coated with H-Max with a nickel underlayer showed no corrosion after 48 hours.

[0276] Example 5

[0277] This testing was performed by Assured Testing Services (Ridgway, PA), a NADCAP-accredited testing facility. Testing was performed on three sets of standard notch bars coated with O-Max and another three sets coated with H-Max. Each set contained four notch bars covered with these coatings. Images of one of these notch bars before and after the coating was applied are shown in Figure 26. The bars were tested in accordance with ASTM F519 for 200 hours under a sustained load of 75% of their fracture strength in a testing laboratory. Based on the standard, a plating process is considered non-embrittling if none of the plated samples fracture within 200 hours of loading. All of the O-Max and H-Max coated bars passed this test without fracture. These results indicate that the O-Max and H-Max coatings do not cause hydrogen-induced cracking (hydrogen embrittlement). None of the samples sent for this testing were heat-treated to mitigate hydrogen embrittlement. It is worth mentioning that EHC is susceptible to hydrogen embrittlement and therefore requires a tempering process (Federal Specification, 1967). It is important to note that hydrogen embrittlement depends on the pretreatment process as well as the plating process. Depending on the pretreatment process, hydrogen embrittlement can occur in coatings regardless of the plating process. Therefore, bake-off is always recommended as a safety precaution for all coatings.

[0278] Example 6

[0279] Shock absorbers are used in nearly all land vehicles. Chrome-coated cylinders are a typical part of the shock absorber for wear protection. In this example, we replaced the chrome used in the shock absorber cylinder with MaxShield.

[0280] A test rig that mimics the back-and-forth motion of a shock absorber, such as those used to test wear. The test is failed if fluid leakage from the shock absorber is due to wear of the seals (made from nitro rubber) or coating. In this test, the Hmax-coated shock absorbers tested outperformed the EHC by functioning flawlessly for 100,000 cycles.

[0281] The second H-Max application focuses on hydraulic components used in vehicle clutch systems. During clutch system operation, for example, when a driver presses the clutch pedal in a manual transmission vehicle, multiple components undergo constant wear, some of which are coated with electroless nickel. The inventors replaced the electroless nickel coating with H-Max. Chromium and other wear-resistant coatings cannot be used on these specific brake components due to their lack of ability to adequately coat internal surfaces and restricted areas. Figure 27 shows a photograph of a part coated with H-Max. The part has both internal and external surfaces. A test rig simulating forward and backward motion was used to determine the part's oil leakage and failure. Both the H-Max-coated and electroless nickel-coated parts were tested for 100,000 cycles. As shown in Figures 28A and 28B, after 100,000 cycles, the electroless nickel coating wore off, causing brake fluid to drip (Figure 28A) and the entire platform to become wet. In contrast, H-Max remained intact and no oil leakage was observed (Figure 28B).

[0282] The third H-Max application focuses on hydraulic components for industrial applications, including cranes. Two H-Max coated cylinders and one EHC coated cylinder were tested simultaneously. A test rig was set up with a triple parallel connection to charge every single cylinder. The three cylinders were mounted in parallel and subjected to the same motion. The rod was spun with no load in stage 1 and a 50 kg load in stage 2. The forward and backward active strokes included stage 1: 7992 and stage 2: 8362. No H-Max cylinder failed the test.

[0283] Example 7

[0284] Pin-on-disk testing was performed at EP Laboratories, a Qmed-listed independent testing laboratory specializing in nano- and micro-mechanical testing. In this test, the coefficient of friction of as-plated and heat-treated O-Max coatings with a thickness of 50 μm was measured according to ASTM G99 specifications by EP Laboratories. As shown in Figure 29, the test involved applying a force of 20 N to the lubricated coating surface at 200 revolutions per minute using a hard ball made of 440C stainless steel. One of the key characteristics of EHC is its low coefficient of friction, or its ability to slide in a lubricated environment. In this test, the coefficient of friction of EHC was measured and compared to that of the O-Max coating.

[0285] The measured coefficients of friction for the EHC coating, the as-plated O-Max coating, and the heat-treated O-Max coating are shown in the table in Figure 30. As shown in the table, the coefficients of friction for both versions of O-Max are very similar to that of the EHC coating.

[0286] In a separate test, the wear characteristics of H-Max were compared with those of EHC. Four carbon steel samples coated with 50 μm-thick EHC, as-plated H-Max, and heat-treated H-Max were sent to EP Laboratories for testing under unlubricated conditions according to ASTM G-99. The wear characteristics of these samples are listed in the table in Figure 31. As shown in this table, the H-Max product exhibited wear resistance more than two orders of magnitude better than EHC. Therefore, the wear rate of H-Max was significantly lower than that of EHC.

[0287] Another example of wear rate and wear rate for H-Max coatings is shown in the table in FIG.

[0288] Example 8

[0289] Numerous hardness tests have been performed on MaxShield coatings according to ASTM E384-17 using an in-house hardness tester (Stage 2, Upper Saddle River, NJ) and an independent third party. In one example, a Vickers hardness of 520-550 was obtained for O-Max. In one example, a Vickers hardness of 740-780 was obtained for H-Max coatings. In another example, a hardness of 680 was observed for as-plated H-Max coatings. Heat treatment can increase the hardness of all versions of the coating. In one example, hardness can be increased to approximately 650 HV for O-Max with the appropriate heat treatment process. In one example, heat treatment of H-Max results in a hardness of 850-940 HV. In another example, heat treatment of H-Max results in a hardness of 800. For one, the Vickers hardness of H-Max as plated is better than that of electroless nickel coatings as plated (480-500 HV) and almost the same as that of heat-treated electroless nickel (700-800 HV). It is worth mentioning that electroless nickel, known as one of the alternatives to EHC coatings, is a wear-resistant coating. For another, the hardness of H-Max as plated is comparable to that of EHC as plated.

[0290] The hardness of EHC coatings decreases at high temperatures. Heat treatment at 190°C for 23 hours reduces the hardness of EHC to 700-750 HV. As previously illustrated by the cross-sectional images, heat compromises the integrity of the EHC coating by generating large macrocracks in its structure. Thus, EHC loses its integrity at high temperatures.

[0291] Example 9

[0292] Standard Taber abrasion tests were performed according to ASTM D4060. For this test, abrasion was performed on the coating surface using a Tabor Industries (North Tonawanda, New York) abrasive wheel with a 1 kg load applied to each abrasive wheel. The Taber wear index (TWI) is the milligram weight loss per 1000 cycles. Examples of TWI values ​​for MaxShield coatings and EHC in as-plated and heat-treated conditions are shown in Figure 33. This test was performed on at least three different samples for each coating, and the results for the EHC coatings are consistent with literature results. These results show average TWI values ​​of 7.1 and 5.6 for the as-plated O-Max and heat-treated O-Max, respectively. For H-Max, average TWI values ​​of 3.1 and 2.5 were obtained for the as-plated and heat-treated conditions, respectively. The plated and heat-treated EHC yielded TWI values ​​of 3.5 and 6, respectively. These results confirm that the wear properties of EHC deteriorate upon heat exposure, unlike MaxShield, whose wear resistance improves with heat treatment. Our H-Max family coatings exhibit better TWI compared to EHC in the as-plated and heat-treated conditions. The TWI of O-Max in the as-plated condition is comparable to that of the heat-treated EHC, while the TWI of the heat-treated O-Max is better than that of the heat-treated EHC.

[0293] Example 10

[0294] An adhesive bend test was performed on heat-treated O-Max samples according to ASTM B571-18. If a coating does not provide strong adhesion, it will not provide wear and corrosion protection. 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 10 μm of O-Max. The coated sample was then placed in an oven at 700°C in air for 1 hour. A piece of tape was attached to the coated surface. Air bubbles were removed from the area under the tape to ensure strong adhesion between the coating and the tape. The taped sample was then bent 180°, and the tape was removed from the coated surface. If the coating peeled from the surface and transferred to the tape, the test was failed. The tape was clear during this test, and no coating peeling was observed. Therefore, this coating passed the adhesive bend test.

[0295] In another example, three steel sockets coated with H-Max were adhesion tested according to ASTM B571, Grind-Sawing Test. The crack was sawed into the socket as shown in Figure 34. All three parts passed the adhesion test without any visible lifting or plating delamination at the cut site.

[0296] Example 11

[0297] In one example, a third party ground a MaxShield coating from 0.006 inches thick to 0.003-0.005 inches thick and polished it to a final surface finish of 4-8 microns. No problems were encountered with the machining process. Our data indicates that the MaxShield coating can be machined without any adhesion failure. On the other hand, machined EHC and thermal spray coatings are known to suffer from chipping and peeling issues. It is difficult to polish thermal spray coatings to a roughness of 0.2 μm, which is the roughness suggested for most seals in hydraulic components. Furthermore, as-plated MaxShield coatings are typically more uniform than EHC coatings, and therefore less grinding is expected for MaxShield compared to EHC. The difficulty of grinding EHC is one of the reasons third parties are seeking replacement of EHC.

[0298] Example 12

[0299] The testing was performed by TÜV SÜD, a globally recognized and respected testing laboratory for environmental analysis. Two versions of MaxShield (O-Max and H-Max) were tested at this laboratory and found to be free of substances of very high concern (SVHC) according to REACH and RoHS regulations. SVHC is a list of 224 substances, including chromium, cadmium, cyanide, lead, PFOS, and PFAS. Tested samples did not contain any levels above 0.01 as defined by REACH. Tested samples also did not contain any heavy metals (Pb, Cd, Hg, or Cr VI), polybrominated biphenyls, polybrominated diphenyl ethers, or phthalates. This result is consistent with Maxterial coatings providing a more environmentally friendly coating.

[0300] Example 13

[0301] O-Max offers multiple performance factors, including the ability to perform in extremely acidic environments or when greater ductility is required.

[0302] An internal test was conducted to measure acid resistance. In this test, a freestanding coating was immersed in concentrated hydrochloric acid (32% HCl stock solution) for 24 hours. After 24 hours of exposure to the concentrated HCl solution, the weight loss of the coating was used to calculate the corrosion rate. It is worth noting that 32% HCl is a very strong acid with a negative pH. An example result comparing the corrosion rate of the O-Max coating with existing nickel and EHC coatings is shown in Figure 35. This figure also provides the corrosion rates of Inconel and Hastelloy as corrosion-resistant bulk materials for reference. The reported rate for the O-Max coating in this figure is the average of corrosion tests obtained on three samples. As this figure shows, the corrosion rate of the O-Max coating (less than 13 milliinches per year, sometimes as low as 1.5 milliinches per year) is much lower than the corrosion rate of existing nickel coatings (80 milliinches per year) (Nickel Development Institute) and is not comparable to the corrosion rate of EHC in concentrated HCl. The EHC coating dissolved in concentrated HCl in less than 10 minutes, and its corrosion rate is not on the scale of this figure. The figure also shows the corrosion rates of the corrosion-resistant bulk materials Hastelloy® B2 and Inconel® to concentrated HCl solutions, based on values ​​published in the literature. Interestingly, in this example, the O-Max coating exhibits a lower corrosion rate compared to Hastelloy® (15 milli-inches per year) and Inconel® (39 milli-inches per year). Hastelloy® and Inconel® are superalloys known for their extreme corrosion resistance in HCl environments.

[0303] Example 14

[0304] In one example, ductility testing was performed by Anamet, Inc., an A2LA-accredited testing laboratory, on two versions of the O-Max coating, with thicknesses of 25 μm and 50 μm. In this test, coated T-bone specimens are uniaxially tensile tested according to ASTM E8 / 8M-22. Strain is continued until the coating delaminates and the underlying surface can be seen under a 50x microscope. Both O-Max coatings were able to elongate beyond 6% without delamination or failure. A ductility value greater than 6% is significantly higher than the ductility of the EHC coating, which is less than 0.1% according to National Bureau of Standards. It is also higher than the ductility of electroless nickel coatings, which are 1% to 1.5%. Based on these results, it can be concluded that the O-Max coating is significantly more formable than the EHC and electroless nickel coatings. Figure 36 shows an image of the tested O-Max coating after 6% elongation. A microscope image of the 25 μm coating is shown in Figure 37. The figure shows a ductility of at least 6% without any fractures or blisters.

Claims

1. 1. A decorative article comprising a decorative article substrate, wherein at least a portion of an exterior surface of the decorative article substrate comprises a coated surface, the coated surface comprising a surface coating, the surface coating comprising an alloy layer comprising: (i) molybdenum or tungsten, and (ii) 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.

2. The decorative article of claim 1 , wherein the alloy layer is present on all surfaces of the decorative article substrate.

3. The decorative article of claim 1 , wherein the alloy layer is on an interior surface of the decorative article substrate.

4. 4. The decorative article of claim 3, wherein the molybdenum or tungsten is present in the surface coating at 40% by weight or less based on the weight of the surface coating, or 20% by weight or less based on the weight of the surface coating, or 10% by weight or less based on the weight of the surface coating, or 40% by weight or less based on the weight of the alloy layer, or 20% by weight or less based on the weight of the alloy layer, or 10% by weight or less based on the weight of the alloy layer.

5. The decorative article of claim 3 , wherein the surface coating comprises a surface roughness Ra of less than 1 micron.

6. The decorative article according to claim 3, wherein the alloy layer consists essentially of nickel and molybdenum, or consists essentially of nickel, molybdenum and phosphorus, or consists essentially of nickel and tungsten, or consists essentially of nickel, tungsten and phosphorus.

7. 7. The decorative article of claim 6, wherein the surface coating has a surface roughness Ra of less than 1 micron, the molybdenum or the tungsten is present in the alloy layer at 20% by weight or less based on the weight of the surface coating, and the surface coating does not contain any precious metals.

8. 8. The decorative article according to claim 1 or claim 7, wherein the alloy layer is an electrodeposited alloy layer.

9. The decorative article of claim 3 , wherein said surface coating is free of any precious metals.

10. The decorative article of claim 1 , wherein the alloy layer is the exposed outer layer of the surface coating.

11. 11. The decorative article of claim 10, wherein the exposed outer layer consists essentially of (i) molybdenum or tungsten and only one element or compound including nickel, cobalt, tin, phosphorus, iron, chromium, or boron, or (ii) molybdenum or tungsten and only two elements or compounds including nickel, cobalt, tin, phosphorus, iron, chromium, or boron, or (iii) molybdenum, nickel, and elements or compounds including tungsten, cobalt, tin, phosphorus, iron, chromium, or boron, or (iv) tungsten, nickel, and elements or compounds including molybdenum, cobalt, tin, phosphorus, iron, chromium, magnesium, or boron.

12. The decorative article according to claim 1 or 3, further comprising an intermediate layer between the alloy layer and the surface of the substrate.

13. The decorative article of claim 12, wherein the alloy layer is present as an exposed outer layer of the surface coating, the exposed outer layer being an electrodeposited alloy layer, and the electrodeposited alloy layer is free of precious metals.

14. The decorative article according to claim 1 or claim 3, further comprising a further layer formed on the alloy layer.

15. 2. The decorative article of claim 1, wherein the alloy layer is present as an electrodeposited alloy layer, and the electrodeposited alloy layer does not contain precious metals.

16. The decorative article of claim 1 , wherein the decorative article substrate comprises a textured surface.

17. The decorative article of claim 1 , wherein the coated surface comprises a textured surface.

18. 18. The decorative article of claim 16 or claim 17, wherein the textured surface comprises a surface roughness Ra greater than 1 micron and less than 30 microns.

19. 18. The decorative article of claim 16 or claim 17, wherein the textured surface comprises a surface roughness Ra greater than 0.5 microns and less than 15 microns.

20. 18. The decorative article of claim 17, wherein said coated surface is free of precious metals.

21. The decorative article of claim 1 , wherein the decorative article substrate comprises stainless steel, hardened steel, carbon steel, alloy steel, precious metal or other metal, and the surface coating comprises a chrome layer on the alloy layer.

22. The decorative article of claim 1 , wherein the decorative article substrate comprises stainless steel, hardened steel, carbon steel, alloy steel, precious metals or other metals, and the surface coating is lead-free.

23. The decorative article of claim 1 , wherein the decorative article substrate comprises stainless steel, hardened steel, carbon steel, alloy steel, precious metals or other metals, and the surface coating is mercury-free.

24. 1. A decorative article comprising a decorative article substrate, wherein at least a portion of an exterior surface of the decorative article substrate comprises a coated surface, the coated surface comprising a surface coating, the surface coating comprising an alloy layer comprising (i) molybdenum or tungsten, and (ii) at least one element selected from the group consisting of nickel, cobalt, tin, phosphorus, iron, magnesium, and boron, or at least one compound comprising one or more of nickel, cobalt, tin, phosphorus, iron, magnesium, or boron, wherein the alloy layer is free of chromium, lead, and mercury.

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