CROSS-REFERENCE

[0001] This application claims the benefit of U.S. Provisional Application No. 62/805,729, filed February 14, 2019, and U.S. Provisional Application No. 62/873,640, filed July 12, 2019, which applications are incorporated herein by reference.

BACKGROUND

[0002] Steel can be an alloy of iron and other elements, including carbon. When carbon is the primary alloying element, its content in the steel may be from about 0.002% to 2.1% by weight. Without limitation, the following elements can be present in steel: carbon, manganese, phosphorus, sulfur, silicon, oxygen, nitrogen, and aluminum. Alloying elements added to modify the characteristics of steel can include without limitation: manganese, nickel, chromium, molybdenum, boron, titanium, vanadium and niobium.

[0003] Stainless steel can be a material that does not readily corrode, rust (or oxidize) or stain with water. There can be different grades and surface finishes of stainless steel to suit a given environment. Stainless steel can be used where both the properties of steel and resistance to corrosion are beneficial.

SUMMARY

[0004] The present disclosure provides systems and methods for depositing a metal layer adjacent to a substrate. The substrate may be a steel substrate. Examples of such metal layers include, but are not limited to, stainless steel, silicon steel, and noise vibration harshness damping steel. Such substrates can include, for example, one or more of iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium, and niobium, oxides thereof, nitrides thereof, sulfides thereof, or any combination thereof. Systems and substrates may generate desired resulting microstructures.

[0005] In an aspect, provided herein is a method for forming at least one metal layer adjacent to a substrate, comprising bringing said substrate in contact with a slurry comprising a metal oxide, a reducing metal agent and a metal transport activator, to provide a metal-containing layer adjacent to said substrate, and annealing said substrate and said at least one metal-containing layer such that said metal oxide and said metal transport activator undergo a metallothermic reduction reaction to yield said at least one metal layer and water, wherein said water is reduced by said reducing metal agent.

[0006] In some embodiments, the at least one metal layer has a grain size from about ASTM 000 to ASTM 30. [0007] In some embodiments, the substrate includes at least one of (i) carbon at less than or equal to about 0.1 wt %, (ii) about 0.1 wt% to 3 wt % manganese, (iii) silicon at less than or equal to about 1 wt %, (iv) vanadium at less than or equal to about 0.1 wt%, and (v) titanium at less than or equal to about 0.5 wt%. In some embodiments, the substrate includes at least two of (i) carbon at less than or equal to about 0.1 wt %, (ii) about 0.1 wt% to 3 wt % manganese, (iii) silicon at less than or equal to about 1 wt %, (iv) vanadium at less than or equal to about 0.1 wt%, and (v) titanium at less than or equal to about 0.5 wt%. In some embodiments, the substrate includes at least three of (i) carbon at less than or equal to about 0.1 wt %, (ii) about 0.1 wt% to 3 wt % manganese, (iii) silicon at less than or equal to about 1 wt %, (iv) vanadium at less than or equal to about 0.1 wt%, and (v) titanium at less than or equal to about 0.5 wt%. In some embodiments, the substrate includes at least four of (i) carbon at less than or equal to about 0.1 wt %, (ii) about 0.1 wt% to 3 wt % manganese, (iii) silicon at less than or equal to about 1 wt %, (iv) vanadium at less than or equal to about 0.1 wt%, and (v) titanium at less than or equal to about 0.5 wt%. In some embodiments, the substrate includes (i) carbon at less than or equal to about 0.1 wt %, (ii) about 0.1 wt% to 3 wt % manganese, (iii) silicon at less than or equal to about 1 wt %, (iv) vanadium at less than or equal to about 0.1 wt%, and (v) titanium at less than or equal to about 0.5 wt%.

[0008] In some embodiments, the metal layer is formed at an annealing temperature from about 0 °C to 1000 °C. In some embodiments, the metal layer is formed in an annealing atmosphere with a level of moisture below about 10 torr. In some embodiments, the annealing comprises heating said substrate at a rate of at least about 0.1 °C per second. In some

embodiments, the annealing is carried out at a temperature above about 500 °C. In some embodiments, the method further comprises cooling of said substrate after said annealing.

[0009] In some embodiments, the substrate transitions from ferrite to austenite during said annealing. In some embodiments, the temperature of said annealing is determined by a transition temperature at which ferrite transitions to austenite. In some embodiments, the addition of at least one austenite stabilizer lowers said transition temperature.

[0010] In some embodiments, the metal transport activator comprises a halide species, a metal halide species, a metal sulfide species, or a gaseous species. In some embodiments, the metal transport activator comprises hydrogen. In some embodiments, the metal transport activator comprises a species selected from the group consisting of magnesium chloride (MgCb), iron (II) chloride (FeCb), calcium chloride (CaCb), zirconium (IV) chloride (ZrCb), titanium (IV) chloride (TiCb), niobium (V) chloride (NbCb), titanium (III) chloride (TiCb), silicon tetrachloride (SiCb), vanadium (III) chloride (VCb), chromium (III) chloride (CrCb), trichlorosilance (SiHC13), manganese (II) chloride (MnCh), chromium (II) chloride (CrCb), cobalt (II) chloride (C0CI2), copper (II) chloride (CuCk), nickel (II) chloride (NiCh), vanadium (II) chloride (VCb), ammonium chloride (NH4CI), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), iron disulfide (FeS2), chromium sulfide (CrS), iron sulfide (FeS), copper sulfide (CuS), nickel sulfide (NiS) and a combination thereof.

[0011] In some embodiments, the method further comprises drying said substrate subsequent to said annealing.

[0012] In an aspect, provided herein is a steel composition comprising a constituent metal selected from the group consisting of: i) titanium at greater than about 0.2 wt%, and ii) manganese at greater than about 0.8 wt%, wherein said steel composition has a measured plastic strain ratio exceeding 1.8. In some embodiments, the steel composition has a measured plastic strain ratio exceeding 2.

[0013] In some embodiments, the steel composition has undergone an annealing at a temperature between about 750°C and about 1100°C. In some embodiments, the steel

composition transitions from ferrite to austenite during said annealing. In some embodiments, the steel composition comprises a grain size between about ASTM 000 and ASTM 30. In some embodiments, the steel composition comprises titanium at greater than about 0.2 wt%, and two or more constituent elements selected from: i) carbon at greater than about 0.01 wt%, ii) aluminum at greater than about 0.02 wt%, and iii) sulfur at no more than about 0.004 wt%, and iv) niobium at less than about 0.02 wt%. In some embodiments, the steel composition comprises manganese at greater than about 0.8 wt%, and two or more constituent elements selected from: i) carbon at less than about 0.01 wt%, ii) aluminum at less than about 0.02 wt%, and iii) sulfur at greater than about 0.004 wt%, and iv) niobium at greater than about 0.02 wt%.

[0014] In another aspect, provided herein is a composition for forming at least one metal layer adjacent to a substrate, comprising a slurry comprising a metal oxide, a reducing metal agent and a metal transport activator, wherein said slurry is configured to provide a metal- containing layer adjacent to said substrate, wherein said metal oxide and said metal transport activator are configured to undergo a metallothermic reduction reaction to yield said at least one metal layer and water.

[0015] In some embodiments, the metal oxide is selected from the group consisting of (¾0 ₃ , TiCk, FeCr204, SiCk, Ta2C , and MgC^Ck. [0016] In some embodiments, the reducing metal agent comprises an element selected from the group consisting of iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium, and niobium.

[0017] In some embodiments, the metal transport activator comprises a halide species, a metal halide species, a metal sulfide species, or a gaseous species. In some embodiments, the metal transport activator comprises hydrogen. In some embodiments, the metal transport activator comprises a species selected from the group consisting of magnesium chloride (MgCb), iron (II) chloride (FeCb), calcium chloride (CaCb), zirconium (IV) chloride (ZrCb), titanium (IV) chloride (TiCb), niobium (V) chloride (NbCb), titanium (III) chloride (TiCb), silicon tetrachloride (SiCb), vanadium (III) chloride (VCb), chromium (III) chloride (CrCb), trichlorosilance (SiHC13), manganese (II) chloride (MnCb), chromium (II) chloride (CrCb), cobalt (II) chloride (CoCb), copper (II) chloride (CuCb), nickel (II) chloride (NiCb), vanadium (II) chloride (VCb), ammonium chloride (NbbCl), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), iron disulfide (FeSi), chromium sulfide (CrS), iron sulfide (FeS), copper sulfide (CuS), nickel sulfide (NiS) and a combination thereof.

[0018] In some embodiments, the composition further comprises a solvent. In some embodiments, the solvent comprises water. In some embodiments, the solvent comprises an organic species.

[0019] Another aspect of the present disclosure provides a non-transitory computer readable medium comprising machine executable code that, upon execution by one or more computer processors, implements any of the methods above or elsewhere herein.

[0020] Another aspect of the present disclosure provides a system comprising one or more computer processors and computer memory coupled thereto. The computer memory comprises machine executable code that, upon execution by the one or more computer processors, implements any of the methods above or elsewhere herein.

[0021] Additional aspects and advantages of the present disclosure will become readily apparent to those skilled in this art from the following detailed description, wherein only illustrative embodiments of the present disclosure are shown and described. As will be realized, the present disclosure is capable of other and different embodiments, and its several details are capable of modifications in various obvious respects, all without departing from the disclosure. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive. INCORPORATION BY REFERENCE

[0022] All publications and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative

embodiments, in which the principles of the invention are utilized, and the accompanying drawings (also“figure” and“FIG.” herein), of which:

[0024] FIG. 1 schematically illustrates a method for forming a metal layer adjacent to a substrate;

[0025] FIG. 2 illustrates a steel substrate after coating with a metal layer;

[0026] FIG. 3 illustrates a steel substrate after coating with a metal layer; and

[0027] FIG. 4 schematically a computer control system that is programmed or otherwise configured to implement methods provided herein.

DETAILED DESCRIPTION

[0028] While various embodiments of the invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. Numerous variations, changes, and substitutions may occur to those skilled in the art without departing from the invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.

[0029] The term“slurry,” as used herein, generally refers to a solution comprising a liquid phase and a solid phase. The solid phase may be in the liquid phase. A slurry may have one or more liquid phases and one or more solid phases.

[0030] The term“adjacent” or“adjacent to,” as used herein, generally refers to‘next to’, ‘adjoining’,‘in contact with,’ and‘in proximity to.’ In some instances adjacent to may be ‘above’ or‘below.’ A first layer adjacent to a second layer may be in direct contact with the second layer, or there may be one or more intervening layers between the first layer and the second layer.

[0031] Whenever the term“at least,”“greater than,” or“greater than or equal to” precedes the first numerical value in a series of two or more numerical values, the term“at least,”“greater than” or“greater than or equal to” applies to each of the numerical values in that series of numerical values. For example, greater than or equal to 1, 2, or 3 is equivalent to greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3.

[0032] Whenever the term“no more than,”“less than,” or“less than or equal to” precedes the first numerical value in a series of two or more numerical values, the term“no more than,” “less than,” or“less than or equal to” applies to each of the numerical values in that series of numerical values. For example, less than or equal to 3, 2, or 1 is equivalent to less than or equal to 3, less than or equal to 2, or less than or equal to 1.

[0033] The present disclosure provides parts, articles, or objects (e.g., sheets, tubes or wires) coated with one or metal layers. A part may be at least a portion of an object or may be an entirety of the object. A metal layer may comprise one or more metals. In some cases, a substrate may be coated with a metal layer. The coating may comprise an alloying agent having at least one elemental metal. A slurry-coated substrate may be formed when a substrate is coated with a slurry comprising an alloying agent having at least one elemental metal. The substrate that has been coated with an alloying agent may be subjected to annealing conditions to yield a metal layer adjacent to the substrate. The metal layer may be coupled to a substrate with the aid of a diffusion layer between the metal layer and the substrate.

[0034] Substrates may generate an alloy layer of >50 microns while still retaining fine grains (>7 ASTM grain size) in the substrate. The grades developed and presented above are grades that may not be standard grades. The grades may be useful for high temperature annealing or high temperature applications not pertaining to metallizing processes.

Substrate and Slurry

[0035] The present disclosure provides substrates and methods that employ depositing metal layers adjacent to substrates. Such substrates can include, for example, one or more of the following elements: carbon, manganese, silicon, vanadium, titanium, nickel, chromium, molybdenum, boron, and niobium. Examples of substrates include but are not limited to stainless steel, silicon steel, and noise vibration harshness damping steel.

[0036] The substrate may be provided as a coil, coiled mesh, wire, pipe, tube, slab, mesh, dipped formed part, foil, plate, a wire rope, a rod, or a threaded rod where a screw pattern has been applied to any length or thickness of rod, a sheet, or a planar surface. For example, a sheet may have a thickness anywhere from 0.001 inches to 1 inch.

[0037] A substrate may comprise an elemental species that is a transition metal, a nonmetal element, a metal oxide, a reducing metal element, a metal halide, an activator, a metalloid, or a combination thereof (e.g., a plurality of elemental metals). A substrate may comprise a transition metal. A substrate may comprise a nonmetal element. A substrate may comprise a metalloid. A substrate may comprise an elemental species selected from, for example, chromium, nickel, aluminum, silicon, vanadium, titanium, boron, tungsten, molybdenum, cobalt, manganese, zirconium, niobium, carbon, nitrogen, sulfur, oxygen, phosphorus, copper, tin, calcium, arsenic, lead, antimony, tantalum, zinc, or any combination thereof. A substrate may comprise an elemental species that is configured to be a reducing metal agent. A reducing metal agent may comprise aluminum, titanium, zirconium, silicon, or magnesium. A substrate may comprise a carrier solvent, such as water, isopropanol, or methyl ethyl ketone.

[0038] A substrate may comprise metal such as iron, copper, aluminum, or any combination thereof. The substrate may comprise an alloy of metals and/or non-metals. The alloy may comprise impurities. The substrate may comprise steel. The substrate may be a steel substrate. The substrate may comprise ceramic. The substrate may be devoid of free carbon. The substrate can be made from melt phase. The substrate may be in a cold reduced state, in a full hard state (e.g., not subjected to an annealing step after cold reduction), or in a hot rolled pickled state.

[0039] A substrate may comprise a metal oxide. A metal oxide may comprise, but is not limited to, AI2O3, MgO, CaO, (¾03, TiC , FeC^Cri, S1O2, Ta20s, or MgC^Cri, or a combination thereof. A metal oxide may be incorporated directly in to the substrate. A metal oxide may be formed in the substrate by a metallothermic reduction reaction between an elemental metal and a thermodynamically less-stable metal oxide. Suitable pairs of elemental metals and

thermodynamically less-stable metal oxides may be chosen from pairs whose Gibbs free energy of formation is reduced by an oxidation of the elemental metal by the metal oxide. A

metallothermic reduction reaction may occur spontaneously. A metallothermic reduction reaction may occur in the presence of a metal transportactivator, such as a halide, metal halide, metal sulfide, or hydrogen. A metal oxide may comprise a powder.

[0040] A powder (e.g., comprising a metal, metal oxide, metal halide, or other substrate component) may comprise individual particles with a particle size (e.g., average particle size) from about 0.01 micrometer (pm) to 1 mm. The powder may have an average particle size of at least about 0.01 pm, 0.1 pm, 1 pm, 20 pm, 30 pm, 50 pm, 100 pm, 250 pm, 500 pm, or about 1 mm. The powder may an average particle size of no more than about 1mm, 500 pm, 250 pm,

100 pm, 50 pm, 30 pm, 20 pm, 10 pm, 1 pm, 0.1 pm, or about 0.01 pm. The powder may have an average particle size from about 0.01 pm to 0.1 pm, 0.01 pm to 1 pm, 0.01 pm to 20 pm,

0.01 pm to 30 pm, 0.01 pm to 50 pm, 0.01 pm to 100 pm, 0.01 pm to 250 pm, 0.01 pm to 500 pm, 0.01 pm to 1mm, 0.1 pm to 1 pm, 0.1 pm to 20 pm, 0.1 pm to 30 pm, 0.1 pm to 50 pm,

0.1 pm to 100 pm, 0.1 pm to 250 pm, 0.1 pm to 500 pm, 0.1 pm to 1mm, 1 pm to 20 pm, 1 pm to 30 pm, 1 pm to 50 pm, 1 pm to 100 pm, 1 pm to 250 pm, 1 pm to 500 pm, 1 pm to lmm, 10 mih to 100 mih, 10 mih to 250 mih, 10 mih to 500 mih, 10 mih to 1mm, 100 mih to 250 mih, 100 mih to 500 mih, 100 mih to lmm, 250 mih to 500 mih, 250 mih to lmm or 500 mih to lmm. The powder may have individual particles with an average particle size of at least about 0.01 pm, 0.1 pm, 1 pm, 20 pm, 30 pm, 50 pm, 100 pm, 250 pm, 500 pm, lmm or more. The powder may have individual particles with a particle size of at most about 1 millimeter (mm), 500 pm, 250 pm, 100 pm, 50 pm, 30 pm, 20 pm, 1 pm, 0.1 pm, or 0.01 pm or less. A powder may comprise particles that may pass through a sieve with a mesh size of at least 325 or smaller. A powder comprising a metal, metal oxide, metal halide, or other substrate component may comprise particles that may pass through a sieve with a mesh size of at least aboutl8, 20, 25, 30, 35, 40, 45, 50, 60, 65, 80, 100, 115, 150, 170, 200, 250, 270, or a mesh size of at least about 400 or more.

[0041] A slurry mixture may comprise a metal oxide amounting to about 30 weight percent (wt%), 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or about 95 wt% of the total weight of the slurry. A slurry mixture may comprise a metal oxide amounting to at least about 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or about 95 wt% or more of the total weight of the slurry. A slurry mixture may comprise a metal oxide amounting to no more than about 95 wt%, 90 wt%, 85 wt%, 80 wt%, 75 wt%, 70 wt%, 65 wt%, 60 wt%, 55 wt%, 50 wt%, 45 wt%, 40 wt%, 35 wt%, or no more than about 30 wt% or less of the total weight of the slurry. A slurry mixture may comprise a metal oxide in a range from about 30 to about 95 wt% of the total weight of the slurry. A metal oxide may comprise about 1 to about 95 wt%, about 1 to about 85 wt%, about 1 to about 75 wt%, about 1 to about 60 wt%, about 1 to about 50 wt%, about 1 to about 40 wt%, about 1 to about 30 wt%, about 1 to about 20 wt%, about 1 to about 10 wt%, about 5 to about 95 wt%, about 5 to about 85 wt%, about 5 to about 75 wt%, about 5 to about 60 wt%, about 5 to about 50 wt%, about 5 to about 40 wt%, about 5 to about 30 wt%, about 5 to about 20 wt%, about 5 to about 10 wt%, about 10 to 95 wt%, about 10 to about 85 wt%, about 10 to about 75 wt%, about 10 to about 60 wt%, about 10 to about 50 wt%, about 10 to about 40 wt%, about 10 to about 30 wt%, about 10 to about 20 wt%, about 20 to about 95 wt%, about 20 to about 85 wt%, about 20 to about 75 wt%, about 20 to about 60 wt%, about 20 to about 50 wt%, about 20 to about 40 wt%, about 20 to about 30 wt%, about 30 to about 85 wt%, about 30 to about 75 wt%, about 30 to about 60 wt%, about 30 to about 50 wt%, about 30 to about 40 wt%, about 1 to about 95 wt%, about 40 to about 85 wt%, about 40 to about 75 wt%, about 40 to about 60 wt%, about 40 to about 50 wt%, about 50 to about 95 wt%, about 50 to about 85 wt%, about 50 to about 75 wt%, or about 50 to about 60 wt% of the total weight of the slurry. A metal oxide or reducing metal may be selected for its relative purity. A metal oxide or reducing metal may comprise a purity of at least about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99%, 99.9%, or at least about 99.99% or more on a weight basis. A metal oxide or reducing metal may comprise a purity of no more than about 99.99%, 99%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, or no more than about 25% or less on a weight basis.

[0042] A reducing metal may comprise an about 0.6 to 2.0 atomic ratio to the oxide source.

A reducing metal may comprise an about 0.01 to 10.0 atomic ratio, an about 0.01 to 1.0 atomic ratio, an about 0.01 to 1.5 atomic ratio, an about 0.01 to 3.0 atomic ratio, an about 0.01 to 4.0 atomic ratio, an about 0.01 to 5.0 atomic ratio, an about 0.1 to 1.0 atomic ratio, an about 0.1 to 1.5 atomic ratio, an about 0.1 to 3.0 atomic ratio, an about 0.1 to 4.0 atomic ratio, an about 0.1 to 5.0 atomic ratio, an about 0.1 to 10.0 atomic ratio, an about 0.5 to 1.0 atomic ratio, an about 0.5 to 1.5 atomic ratio, an about 0.5 to 3.0 atomic ratio, an about 0.5 to 4.0 atomic ratio, an about 0.5 to 5.0 atomic ratio, an about 0.5 to 10.0 atomic ratio, an about 1.0 to 1.5 atomic ratio, an about 1.0 to 3.0 atomic ratio, an about 1.0 to 4.0 atomic ratio, an about 1.0 to 5.0 atomic ratio, an about 1.0 to 10.0 atomic ratio, an about 2.0 to 3.0 atomic ratio, an about 2.0 to 4.0 atomic ratio, an about 2.0 to 5.0 atomic ratio, an about 2.0 to 10.0 atomic ratio, an about 3.0 to 4.0 atomic ratio, an about 4.0 to 5.0 atomic ratio, an about 4.0 to 10.0 atomic ratio, or an about 5.0 to 10.0 atomic ratio to the oxide source.

[0043] A metal substrate may comprise a metal transport activator component. The metal transport activator may comprise about 0.001 wt%, 0.01 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or about 50 wt% of the total substrate. The metal transport activator may comprise at least about 0.001 wt%, 0.01 wt%, 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or at least about 50 wt% or more of the total substrate. The metal transport activator may comprise no more than about 50 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 5 wt%, 4 wt%, 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, 0.1 wt%, 0.01 wt%, or no more than about 0.001 wt% or less of the total substrate. The metal transport activator may comprise about 0.001 to 1 wt%, about 0.001 to 2 wt%, about 0.001 to 3 wt%, about 0.001 to 4 wt%, about 0.001 to 5 wt%, about 0.001 to 10 wt%, about 0.001 to 15 wt%, about 0.001 to 20 wt%, about 0.001 to 30 wt%, about 0.001 to 50 wt%, about 0.01 to 1 wt%, about 0.01 to 2 wt%, about 0.01 to 3 wt%, about 0.01 to 4 wt%, about 0.01 to 10 wt%, about 0.01 to 15 wt%, about 0.01 to 20 wt%, about 0.01 to 30 wt%, about 0.01 to 50 wt%, about 0.1 to 1 wt%, about 0.1 to 2 wt%, about 0.1 to 3 wt%, about 0.1 to 4 wt%, about 0.1 to 5 wt%, about 0.1 to 10 wt%, about 0.1 to 15 wt%, about 0.1 to 20 wt%, about 0.1 to 30 wt%, about 0.1 to 50 wt%, about 1.0 to 2 wt%, about 1.0 to 3 wt%, about 1.0 to 4 wt%, about 1.0 to 10 wt%, about 1.0 to 15 wt%, about 1.0 to 20 wt%, about 1.0 to 30 wt%, about 1.0 to 50 wt%, or about 10 to 50 wt% of the total substrate.

[0044] The present disclosure provides substrates coated with one or more metal layers. In some cases, a substrate may be coated with at least one metal layer. A substrate may be coated with about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more metal layers. Asubstrate may be coated with at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more metal layers. A substrate may be coated with no more than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 metal layers. The coating may comprise an alloying agent having at least one elemental metal. The metal layer may be coupled to a substrate with the aid of a diffusion layer between the metal layer and the substrate.

[0045] A metal layer may have a thickness of at least about 1 nanometer, 10 nanometers, 100 nanometers, 500 nanometers, 1 micron, 5 microns, 10 microns, 25 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, or at least 100 microns or more. A metal layer may have a thickness of no more than about 100 microns, 90 microns, 80 microns, 70 microns, 60 microns, 50 microns, 25 microns, 10 microns, 5 microns, 1 micron, 500 nanometers, 100 nanometers, 10 nanometers, or no greater than about 1 nanometer or less. The thickness of the metal layer may be greater than a monoatomic layer. The thickness may be a multilayer.

[0046] A substrate may comprise about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 or more elemental species. A substrate may comprise at least about 2, 3, 4, 5, 6,

7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or about 20 or more elemental species. A substrate may comprise no more than about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, or no more than about 2 or less elemental species. A substrate may comprise at least two of the following elements: carbon, manganese, silicon, vanadium, and titanium. A substrate may comprise at least three of the following elements: carbon, manganese, silicon, vanadium, and titanium. A substrate may comprise at least four of the following elements: carbon, manganese, silicon, vanadium, and titanium.

[0047] A substrate may comprise multiple elements. A substrate may comprise carbon (C) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise carbon at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0048] A substrate may comprise manganese (Mn) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise manganese at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0049] A substrate may comprise niobium (Nb) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise niobium at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less. Niobium may be added to a substrate, so that the substrate may comprise niobium in an amount of at least about 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.003 wt%, 0.004 wt%, 0.005 wt%, 0.006 wt%, 0.007 wt%, 0.008 wt%, 0.009 wt%, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, or more. Without wishing to be bound by theory, niobium in a substrate may prevent chromium depletion in a substrate.

[0050] A substrate may comprise vanadium (V) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise vanadium at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0051] A substrate may comprise titanium (Ti) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise titanium at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less. In some cases, a substrate may comprise at least about 0.015 wt% titanium.

[0052] A substrate may comprise nitrogen (N) at greater than 0.0001 wt%, 0.0005 wt%,

0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise nitrogen at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0053] A substrate may comprise phosphorus (P) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise phosphorus at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less. [0054] A substrate may comprise sulfur (S) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise sulfur at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0055] A substrate may comprise aluminum (Al) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise aluminum at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0056] A substrate may comprise copper (Cu) at greater than 0.0001 wt%, 0.0005 wt%,

0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise copper at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0057] A substrate may comprise nickel (Ni) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise nickel at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0058] A substrate may comprise chromium (Cr) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise chromium at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0059] A substrate may comprise molybdenum (Mo) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%,

0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise molybdenum at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0060] A substrate may comprise tin (Sn) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise tin at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0061] A substrate may comprise boron (B) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise boron at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0062] A substrate may comprise calcium (Ca) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise calcium at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0063] A substrate may comprise arsenic (As) at greater than 0.0001 wt%, 0.0005 wt%,

0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise arsenic at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0064] A substrate may comprise cobalt (Co) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise cobalt at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0065] A substrate may comprise lead (Pb) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise lead at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%,

5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0066] A substrate may comprise antimony (Sb) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise antimony at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0067] A substrate may comprise tantalum (Ta) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise tantalum at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0068] A substrate may comprise tungsten (W) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise tungsten at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0069] A substrate may comprise zinc (Zn) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise zinc at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%,

5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0070] A substrate may comprise zirconium (Zr) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise zirconium at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%,

1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less. [0071] A substrate may comprise silicon (Si) at greater than 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.002 wt%, 0.004 wt%, 0.005 wt%, 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 2.5 wt%, 3 wt%, 5 wt% 7 wt%, 10 wt%, 15 wt%, 20 wt%, 30 wt%, or greater than about 40 wt% or more. A substrate may comprise silicon at less than or equal to about 40 wt%, 30 wt%, 20 wt%, 15 wt%, 10 wt%, 7 wt%, 5 wt%, 3 wt%, 2.5 wt%, 2 wt%, 1.9 wt%, 1.8 wt%, 1.7 wt%, 1.6 wt%, 1.5 wt%, 1.4 wt%, 1.3 wt%, 1.2 wt%, 1.1 wt%, 1 wt%, 0.9 wt%, 0.8 wt%, 0.7 wt%, 0.6 wt%, 0.5 wt%, 0.4 wt%, 0.3 wt%, 0.2 wt%, 0.1 wt%, 0.05 wt%, 0.01 wt%, 0.005 wt%, 0.004 wt%, 0.002 wt%, 0.001 wt%, 0.0005 wt%, or less than about 0.0001 wt% or less.

[0072] Free interstitials, such as nitrogen, carbon, and sulfur, may exist during formation of a substrate. Niobium in a substrate may bind to these free interstitials (e.g. nitrogen, carbon, and sulfur) in the substrate. Addition of niobium may prevent grain boundary precipitates, e.g.

chromium grain boundary precipitates. A decrease in grain boundary precipitates may lead to an increase in corrosion performance, which may be a desired property of a substrate. FIG. 3 illustrates a steel substrate after coating with a metal layer, wherein no grain boundary chromium precipitates are observed.

[0073] The weight % of chromium on the surface of a substrate may be measured. The chromium weight % may be of a coated substrate or of an uncoated substrate. In some cases, the chromium weight % of a substrate may be at least about 5%, 10%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, or 26% or more. The chromium weight % of a substrate may be no more than about 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18 %, 17%, 16%, 15%, 10%, or no more than about 5% or less. The chromium weight % of a substrate may be about 16%, 17%, 18%, 19%, 20%, 21%, 22%, or 23%. The chromium weight % of a coated substrate may be greater than, about, or less than the chromium weight % of an uncoated substrate.

[0074] Substrates may be purchased from a vendor. Substrates may be coated with a metal- containing layer the same day the substrate was prepared. Substrates may be prepared greater than about 2 days, 3 days, 1 week, 1 month, or 1 year or more before coating with a metal- containing layer. Substrates may be prepared less than about 1 year, 1 month, 1 week, 3 days, or less than 2 days before coating with a metal-containing layer. A reducing metal may be added to the substrate within at least about 30 seconds, 1 minute, 5 minutes, 10 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6, hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours,

12 hours, or more of adding a metal layer to the substrate. A reducing metal may be added to the substrate within no more than about 12 hours, 11 hours, 10 hours, 9 hours, 8 hours, 7 hours, 6 hours, or less than about 5 hours, 4hours, 3 hours, 2 hours, 1 hour, 30 minutes, 10 minutes, 5 minutes, 1 minute, 30 seconds or less of adding a metal layer to the substrate. In some examples, the reducing metal is added to the substrate within about 10 seconds, 20 seconds, 30 seconds, 1 minute, 5 minutes, 10 minutes, 20 minutes, 30 minutes, 45 minutes, 60 minutes, 1 hours, 2 hours, 3 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 18 hours, 24 hours or within about 2 days of adding a metal layer to the substrate.

[0075] The present disclosure provides methods for forming a metal layer adjacent to a substrate. The metal layer can be formed by application of a slurry adjacent to a substrate.

Deposition of a slurry adjacent to a substrate may form a metal-containing layer adjacent to the substrate. In some cases, the slurry comprises an alloying agent, a metal transport activator and a solvent, and wherein the alloying agent comprises the metal.

[0076] In some cases, a metal-containing layer comprises carbon. In some cases, the metal- containing layer comprises one or more of iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium, niobium and combinations thereof. The alloying agent may be selected from the group consisting of ferrosilicon (FeSi), ferrochrome (FeCr), chromium and combinations thereof.

[0077] A slurry may comprise a metal oxide. A metal oxide may comprise, but is not limited to, AI2O3, MgO, CaO, (¾03, TiCh, FeC^Cri, S1O2, Ta20s, or MgQ^Cri, or a combination thereof. A metal oxide may be incorporated directly in to the slurry. A metal oxide may be formed in the slurry by a metallothermic reduction reaction between an elemental metal and a thermodynamically less-stable metal oxide. Suitable pairs of elemental metals and

thermodynamically less-stable metal oxides may be chosen from pairs whose Gibbs free energy of formation is reduced by an oxidation of the elemental metal by the metal oxide. A

metallothermic reduction reaction may occur spontaneously. A metallothermic reduction reaction may occur in the presence of a metal transportactivator, such as a halide, metal halide, metal sulfide, or a gaseous species. A metal oxide may comprise a powder.

[0078] A slurry may comprise a metal transport activator that is configured to carry a metal species from the slurry to the surface of a substrate. The metal transport activator may comprise a halide species, a metal halide species, a sulfide species, or hydrogen. A metal transport activator may be introduced during slurry preparation, for example by the addition of one or more powders. A metal transport activator may be be introduced after slurry formation from an exogenous source, such as diffusion of hydrogen gas into a slurry layer after application to the substrate. In some cases, the metal transport activator includes a monovalent metal, a divalent metal or a trivalent metal. In some cases, the metal transport activator is selected from the group consisting of magnesium chloride (MgCb), iron (II) chloride (FeCb), calcium chloride (CaCb), zirconium (IV) chloride (ZrCb), titanium (IV) chloride (TiCb), niobium (V) chloride (NbCb), titanium (III) chloride (TiCb), silicon tetrachloride (SiCb), vanadium (III) chloride (VCb), chromium (III) chloride (CrCb), trichlorosilance (SiHC13), manganese (II) chloride (MnCb), chromium (II) chloride (CrCb), cobalt (II) chloride (CoCb), copper (II) chloride (CuCb), nickel (II) chloride (NiCb), vanadium (II) chloride (VCb), ammonium chloride (NH ₄ CI), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), iron disulfide (FeSi), chromium sulfide (CrS), iron sulfide (FeS), copper sulfide (CuS), nickel sulfide (NiS) and combinations thereof. In some embodiments, the halide activator is hydrated. In some embodiments, the halide activator is selected from the group consisting of iron chloride tetrahydrate (FeCb · 4FbO), iron chloride hexahydrate (FeCb · 6FbO) and magnesium chloride hexahydrate (MgCb · 6H ₂ O). In some embodiments, the halide activator is hydrated. In some embodiments, the halide activator is selected from the group consisting of iron chloride tetrahydrate (FeCb · 4FbO), iron chloride hexahydrate (FeCb · 6FbO) and magnesium chloride hexahydrate (MgCb · 6H2O).

[0079] In some cases, a metal layer is formed adjacent to a substrate after a metal-containing layer is annealed to a substrate. In some cases, a metal layer comprises carbon. In some cases, the metal layer comprises one or more of iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium, niobium and combinations thereof. In some embodiments, the alloying agent is selected from the group consisting of ferrosilicon (FeSi), ferrochrome (FeCr), chromium and combinations thereof.

[0080] A slurry may comprise a solvent. A solvent may be aqueous or organic. Solvents may include water, methanol, ethanol, isopropanol, acetone, or methyl ethyl ketone The boiling point (or boiling temperature) of the solvent may be less than or equal to about 200 °C, 190 °C, 180 °C, 170 °C, 160 °C, 150 °C, 140 °C, 130 °C, 120 °C, 110 °C, or 100 °C or less. The boiling point of the solvent may be greater than or equal to about 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, or greater than about 200 °C or more.

[0081] In some cases, the slurry comprises an inert species. A slurry may be formed by mixing various components in a mixing chamber (or vessel). Various components may be mixed at the same time or sequentially. For example, a solvent is provided in the chamber and an elemental species is subsequently added to the chamber. To prevent clumping, dry ingredients may be added to the solvent in controlled amounts. Some elemental metals may be in dry powder form. [0082] The blade used to mix the metal-containing layer components may be in the shape of a whisk, a fork, or a paddle. More than one blade may be used to mix the slurry components. Each blade may have different shapes or the same shape. Dry ingredients may be added to the solvent in controlled amounts to prevent clumping. A high shear rate may be used to help control viscosity. In a slurry, chromium particles may be larger in size than other particles, and may be suspended without high polymer additions.

[0083] The properties of the slurry can be a function of one or more parameters used to form the slurry, maintain the slurry or deposit the slurry. Such properties can include viscosity, shear thinning index, and yield stress. Such properties can include Reynolds number, viscosity, pH, and slurry component concentration. Parameters that can influence properties of the slurry can include water content, elemental species identity and content, temperature, shear rate and time of mixing.

[0084] FIG. 1 illustrates a method of forming a metal layer adjacent to a substrate. In operation 110, a metal composition is provided. Next, in operation 120, the slurry can be applied from the mixing vessel to the substrate to form a metal layer. In operation 130, the solvent in the slurry is removed after application by heat or vacuum drying at about 90 °C - 175 °C for about 10 - 60 seconds. In operation 140, the web or substrate material is rolled or otherwise prepared for thermal treatment. In operation 150, a metal layer is annealed adjacent to the substrate.

[0085] FIG. 2 illustrates an image of a steel substrate after coating with a metal layer. The grain size and coefficient of variation may be calculated according to the American Society of the International Association for Testing and Materials (ASTM) standard.

[0086] The slurry may exhibit thixotropic behavior, wherein the slurry exhibits a decreased viscosity when subjected to sheer strain. The shear thinning index of the slurry can be from about 1 to about 8. In order to achieve the target viscosity, mixing may occur at a high shear rate. The shear rate can be from about 1 s ¹ to about 10,000 s ¹ (or Hz). The shear rate may be about 1 s ¹ , about 10 s ¹ , about 100 s ¹ , about 1,000 s ¹ , about 5,000 s ¹ , or about 10,000 s ¹ . The shear rate may be at least about 1 s ¹ , about 10 s ¹ , about 100 s ¹ , about 1,000 s ¹ , about 5,000 s ¹ , or at least about 10,000 s ¹ or more. The shear rate may be less than about 10,000 s ¹ , 5,000 s ¹ , 1,000 s ¹ ,

100 s ¹ , 10 s ¹ , or less than about 1 s ¹ or less.

[0087] The shear rate of a slurry may be measured on various instruments. The shear rate may be measured on a TA Instruments DHR-2 rheometer, for example. The shear rate of a slurry may differ depending on the instrument used to perform the measurement.

[0088] In order to achieve the target or predetermined viscosity, mixing may occur for a period of time from about 1 minute to 2 hours. The time of mixing may be less than about 30 minutes. The viscosity of the slurry may decrease the longer the slurry is mixed. The time of mixing may correspond to the length of time used in homogenizing the slurry.

[0089] A properly mixed state may be a state where the slurry does not have water on the surface. A properly mixed state may be a state where there are no solids on the bottom of the vessel. The slurry may appear to be uniform in color and texture.

[0090] The desired viscosity of the metal-containing layer can be a viscosity that is suitable for roll coating. The viscosity of the slurry can be about 1 centipoise (cP), 5 cP, 10 cP, 50 cP,

100 cP, 200 cP, 500 cP, 1,000 cP, 10,000 cP, 100,000 cP, 1,000,000 cP, or about 5,000,000 cP. The viscosity of the slurry can be at least about 1 cP, 5 cP, 10 cP, 50 cP, 100 cP, 200 cP, 500 cP, 1,000 cP, 10,000 cP, 100,000 cP, 1,000,000 cP, or about 5,000,000 cP. The viscosity of the slurry can be no more than about 5,000,000 cP, 1,000,000 cP, 100,000 cP, 10,000 cP, 5,000 cP, 1,000 cP, 500 cP, 200 cP, 100 cP, 50 cP, 10 cP, 5 cP, or no more than about 1 cP. The viscosity of the slurry can be from about lcP to 5,000,000 cP. The viscosity of the slurry may be about 1 cP, about 5 cP, about 10 cP, about 50 cP, about 100 cP, about 200 cP, about 500 cP, about 1,000 cP, about 10,000 cP, about 100,000 cP, about 1,000,000 cP, or about 5,000,000 cP. The viscosity of the slurry may be from about 1 cP to 1,000,000 cP, or 100 centipoise cP to 100,000 cP. The viscosity of the slurry may depend on shear rate. The viscosity of the slurry may be from about 200 cP to about 10,000 cP, or about 600 cP to about 800 cP. The slurry may be from about 100 cP to about 200 cP in the application shear window that has shear rates from about 1000 s ¹ to about 1000000 s ¹ . The capillary number of the slurry may be about 0.01, 0.05, 0.1, 0.5, 1, 2, 3,

4 ,5, 6, 7, 8, 9, or about 10. The capillary number of a slurry may be at least about 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4 ,5, 6, 7, 8, 9, or about 10 or more. The capillary number of a slurry may be no more than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or no more than about 0.01 or less. The yield stress of a slurry may be about 0.0001 Pascal (Pa), 0.001 Pa, 0.01 Pa, 0.1 Pa, 0.2 Pa, 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa, or about 1 Pa. The yield stress of a slurry may be at least about 0.0001 Pascal (Pa), 0.001 Pa, 0.01 Pa, 0.1 Pa, 0.2 Pa, 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa,

0.7 Pa, 0.8 Pa, 0.9 Pa, or at least about 1 Pa or more. The yield stress of a slurry may be no more than 1 Pa, 0.9 Pa, 0.8 Pa, 0.7 Pa, 0.6 Pa, 0.5 Pa, 0.4 Pa, 0.3 Pa, 0.2 Pa, 0.1 Pa, 0.01 Pa, 0.001 Pa, or no more than about 0.001 Pa or less.

[0091] The settling rate of the slurry may be stable to separation or sedimentation for greater than about one minute, greater than about 15 minutes, greater than about 1 hour, greater than about 1 day, greater than about 1 month, or greater than about 1 year. The settling rate of the slurry may refer to the amount of time the slurry is able to withstand, without mixing, before settling occurs, or before the viscosity increases to values that are not suitable for roll coating. Similarly, the shelf-life of the slurry may refer to the time that slurry can withstand, without mixing, before the slurry thickens to an extent unsuitable for roll coating. Even if the slurry settles and thickens, however, the slurry may be remixed to its initial viscosity. The thixotropic index of the slurry can be stable such that the slurry does not thicken to unsuitable levels at dead spots in the pan of a roll coating assembly.

[0092] The viscosity of the slurry can be controlled by controlling the extent of hydrogen bonding by adding acid to the slurry during mixing. In addition, acid or base may be added to the slurry during mixing in order to control the pH level of the slurry. The pH of a slurry may be about 3, 4, 5, 6, 7, 8, 9, 10, 11, or about 12. The pH level of a slurry may be at least about 3, 4, 5, 6, 7, 8, 9, 10, 11, or at least about 12 or more. The pH level of a slurry may be no more than about 12, 11, 10, 9, 8, 7, 6, 5, 4 or no more than about 3 or less. The pH level of the slurry can be from about 3 to about 12. The pH level of the slurry can be about 5 to about 8. The pH level of the slurry can be about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, or about 12. The pH level of the slurry may change as the slurry settles. Remixing the slurry after the slurry settles may return the pH level of the slurry to initial pH levels. Varying levels of binder, for example, metal acetate, may be added to a slurry to increase green strength in a slurry. A slurry may include no binders. A slurry may include a metal transport activator that is configured to act as a binder.

[0093] The fluidity of a slurry can be measured by a tilt test. A tilt test can be an indication of yield stress and viscosity. As an alternative, a rheometer may be used to measure the fluidity of the slurry.

[0094] The drying time of the slurry can be sufficiently long such that the slurry remains wet during the roll coating process and does not dry until after a coating of the slurry is applied to the substrate. The slurry may not dry at room temperature. The slurry may become dry to the touch after subjecting the drying zone of a roll coating line to heat for around ten seconds. The temperature of heat applied may be around 120 °C.

[0095] The specific gravity of the slurry can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 g/cm ³ . The specific gravity of the slurry can be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, or at least about 10 g/cm ³ or more. The specific gravity of the slurry can be no more than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or no more than about 1 g/cm ³ or less. The green strength of the slurry can be such that the slurry is able to withstand roll coating such that the slurry coated substrate is not damaged. For example, a dry film of slurry, dried after roll-coating in the drying oven adjacent to the paint booth, may have a green strength that allows the film to survive a force that flexes the film, twenty times, in alternating negative and positive directions, to an arc with a diameter of about 20 inches. The green strength of the dry film of slurry may further allow the film to pass a tape test with a small amount of powdering. The tape test may involve contacting a piece of tape with the surface of the coated material. The tape, once removed from the surface of the coated material, may be clear enough to allow one to see through any powder that had adhered to the tape.

[0096] A slurry may be applied to a substrate before forming a metal layer on the substrate. The slurry may be applied in a uniform thickness over the substrate. A slurry may be applied in a varying thickness over the substrate. The average thickness of an applied slurry coating may be about 0.0001”, 0.0005”, 0.001”, 0.002”, 0.003”, 0.004”, 0.005”, 0.006”, 0.007”, 0.008”, 0.009”, 0.01”, 0.02”, 0.03”, 0.04”, 0.05”, 0.06”, 0.07”, 0.08”, 0.09”, 0.1”, 0.125, 0.25, 0.5”. The average thickness of an applied slurry coating may be at least about 0.0001”, 0.0005”, 0.001”, 0.002”, 0.003”, 0.004”, 0.005”, 0.006”, 0.007”, 0.008”, 0.009”, 0.01”, 0.02”, 0.03”, 0.04”, 0.05”, 0.06”, 0.07”, 0.08”, 0.09”, 0.1”, 0.125, 0.25, 0.5 or more. The average thickness of an applied slurry coating may be no more than about 0.5”, 0.25”, 0.125”, 0.1”, 0.09”, 0.08”, 0.07”, 0.06”, 0.05”, 0.04”, 0.03”, 0.02”, 0.01”, 0.009”, 0.008”, 0.007”, 0.006”, 0.005”, 0.004”, 0.003”, 0.002”,

0.001”, 0.0005”, 0.0001” or less.

[0097] A slurry may be applied adjacent to one or more surfaces of a substrate with a particular thickness. The thickness of the applied slurry coating may be relatively uniform over a surface or may vary. The thickness of the applied slurry coating may vary from one surface of the substrate to another. The thickness of the applied slurry coating adjacent to the substrate may be measured at any time, including immediately after application, during drying, or after all solvent has been removed. An applied coating of a slurry may be considered substantially uniform if at least 90%, 95%, 99% or more of the substrate surface has a slurry coating that does not deviate by more than about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or about 20% from the average thickness of the applied slurry coating.

[0098] A slurry coating applied adjacent to one or more surfaces of a substrate may have an average applied thickness before or after drying of about 5 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 40 pm, 50 pm, 60 pm, 70 pm, 80 pm, 90 pm, 100 pm, 150 pm, 200 pm, 250 pm, 300 pm, 400 pm, 500 pm, 600 pm, 700 pm, 800 pm, 900 pm, 1 mm, 2 mm, 5 mm, or about 1 cm. A slurry coating applied adjacent to one or more surfaces of a substrate may have an average applied thickness before or after drying of at least about 5 pm, 10 pm, 15 pm, 20 pm, 25 pm, 30 pm, 40 pm, 50 pm, 60 pm, 70 pm, 80 pm, 90 pm, 100 pm, 150 pm, 200 pm, 250 pm, 300 pm, 400 pm, 500 pm, 600 pm, 700 pm, 800 pm, 900 pm, 1 mm, 2 mm, 5 mm, or about 1 cm. A slurry coating applied adjacent to one or more surfaces of a substrate may have an applied thickness before or after drying of no more than about 1 cm, 5 mm, 2 mm, 1 mm, 900 pm, 800 pm, 700 pm, 600 pm, 500 pm, 400 pm, 300 pm, 250 pm, 200 pm, 150 pm, 100 pm, 90 pm, 80 pm, 70 pm, 60 pm, 50 pm, 40 pm, 30 pm, 25 pm, 20 pm, 15 pm, 10 pm, or 5 pm or less.

[0099] An elemental species in the slurry can diffuse to or into the substrate according to a concentration gradient. For example, the concentration of the elemental species in the metal- containing layer can be highest on the surface of the substrate and can decrease according to a gradient along the depth of the substrate. The decrease in concentration can be linear, parabolic, Gaussian, or any combination thereof. The concentration of the elemental species in the metal- containing layer can be selected based on the desired thickness of the alloy layer to be formed on the substrate.

[00100] An elemental species in the slurry may impact the adhesion of the metal-containing layer to the substrate. In addition, an elemental species may impact the viscosity of the metal- containing-containing layer composition. Further, an elemental species may influence the green strength of the metal-containing layer coated substrate. Green strength generally refers to the ability of a metal-containing layer coated substrate to withstand handling or machining before the metal-containing layer is completely cured. Accordingly, an elemental species may be selected based on the desired degree of adhesion of the metal-containing layer to the substrate, the desired viscosity of the metal-containing layer, and the ability of an elemental species to increase the green strength of the metal-containing layer coated substrate. In addition, some metal-containing halides can be corrosive to components of a roll coating assembly which applies the metal-containing layer to the substrate. Such corrosion may be undesirable. An elemental species may prevent the formation of Kirkendall voids at the boundary interface of the metal-containing layer and the substrate. Upon heating, an elemental species may decompose to an oxide. In addition, after annealing, an elemental species may become inert. The

concentration of various elemental species can be variable.

[00101] The substrate may be pretreated before a slurry is applied to the substrate. The substrate may be pretreated by using chemicals to modify the surface of the substrate in order to improve adhesion of the metal-containing layer to the surface of the substrate. Examples of such chemicals include chromates and phosphates.

[00102] The surface of the substrate may be free of processing oxides. This may be achieved by conventional pickling. The surface of the substrate can be reasonably free of organic materials. The surface of the substrate may be reasonably free of organic materials after processing with commercially available cleaners. [00103] Grain pinning particles may be added, removed, or withheld from the substrate during preparation of the substrate in order to control the grain size of the substrate. For example, grain pinners may be added to the substrate in order to keep the grain size small and to form pinning points. As another example, grain pinners may be withheld from the substrate to allow the grains to grow large and to allow for motor laminations. Grain pinners may be insoluble at the annealing temperatures.

[00104] Examples of grain pinning particles include an intermetallic, a nitride, a carbide, a carbonitride of titanium, aluminum, niobium, vanadium, and any combination thereof. Non limiting examples of grain pinning particles include titanium nitride (TiN), titanium carbide (TiC), and aluminum nitride (AIN).

Formation of Metal Lavers Adjacent to Substrates

[00105] A slurry can be applied or deposited adjacent to the substrate and form a metal- containing layer adjacent to the surface. The metal-containing layer can be annealed to form a metal layer adjacent to the substrate. The slurry can be applied by roll coating, split coating, spin coating, slot coating, curtain coating, slide coating, extrusion coating, painting, spray painting, electrostatic mechanisms, printing (e.g., 2-D printing, 3-D printing, screen printing, pattern printing), vapor deposition (e.g., chemical vapor deposition), electrochemical deposition, slurry deposition, dipping, spraying, any combination thereof, or through any other suitable method.

[00106] A slurry can be applied via roll coating. The roll coating process may begin by providing a substrate, such as a steel substrate. Next, the coiled substrate may be unwound.

Next, the unwound steel substrate may be provided to roll coaters, which may be coated with a metal-containing layer. Next, the roll coaters may be activated such that the roll coaters coat the substrate with a metal-containing layer. The substrate may be fed through the roll coaters through multiple cycles such that the metal-containing layer is applied to the substrate multiple times. Depending on the properties of the metal-containing layer, it may be desirable to apply multiple coatings to the substrate. Multiple coatings of the metal-containing layer can be applied to the substrate in order to achieve the desired thickness of the slurry. Different formulations or a metal-containing layer may be used in each of the multiple coatings. The metal-containing layer may be applied in a manner such as to form a pattern on the substrate. The pattern may in the form of, for example, a grid, stripes, dots, welding marks, or any combination thereof. Multiple coatings on the same substrate may form a split coat on a substrate.

[00107] A slurry can be applied, deposited, or annealed adjacent to the substrate. A slurry can be deposited at a temperature of about 0 °C, 25 °C, 50 °C, 75 °C, 100 °C, 200 °C, 300 °C, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C, 900 °C, or 1000 °C. A slurry can be deposited at a temperature of at least about 0 °C, 25 °C, 50 °C, 75 °C, 100 °C, 200 °C, 300 °C, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C, 900 °C, or 1000 °C or more. A slurry can be deposited at a temperature of no more than about 1000°C, 900 °C, 800 °C, 700 °C, 600 °C, 500 °C, 400 °C, 300 °C, 200 °C, 100 °C, 75 °C, 50 °C, 25 °C, or no more than about 0 °C or less. A slurry can be deposited at a temperature from about 0 °C to 1000 °C. A slurry can be deposited at a temperature from about 10 °C to 100 °C. A slurry can be deposited at a temperature from about 100 °C to 500°C. A slurry can be deposited at a temperature from about 500 °C to 1000 °C.

[00108] Deposition of a slurry on a substrate may occur in an atmosphere with a relative humidity of about 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or about 99%. Deposition of a slurry on a substrate may occur in an atmosphere with a relative humidity of at least about 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or at least about 99% or more. Deposition of a slurry on a substrate may occur in an atmosphere with a relative humidty of no more than about 99%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%,

20%, 10%, or no more than about 5% or less. Deposition of a slurry on a substrate may occur in an atmosphere with absolute levels of moisture of at least about 0.5 torr, 1 torr, 2 torr, 5 torr, 10 torr, 20 torr, 50 torr, 100 torr, 250 torr, or at least about 500 torr or more. Deposition of a slurry on a substrate may occur in an atmosphere with absolute levels of moisture of no more than about 760 torr, 500 torr, 250 torr, 100 torr, 50 torr, 20 torr, 10 torr, 5 torr, 2 torr, 1 torr, or 0.5 torr or less. In some embodiments, the relative humidity is about 50% during deposition of a metal- containing layer.

[00109] Deposition of a slurry on a substrate may occur in an atmosphere with levels of oxygen greater than or equal to about 0.001 torr, 0.01 torr, 0.05 torr, 0.1 torr, 0.5 torr, 1 torr, 2 torr, 5 torr, 10 torr, or greater than about 20 torr or more. Deposition of a slurry on a substrate may occur in an atmosphere with levels of oxygen of no more than about 20 torr, 10 torr, 5 torr,

2 torr, 1 torr, 0.5 torr, 0.1 torr, 0.05 torr, 0.01 torr, 0.005 torr, or 0.001 torr or less. Drying a slurry on a substrate may occur in ambient air conditions.

[00110] Annealing of the slurry on the substrate may occur in an atmosphere with low levels of oxygen, such as no more than about 0.5 torr, 0.1 torr, 0.05 torr, 0.01 torr, 0.005 torr, or 0.001 torr or less. Annealing of the slurry on the substrate may occur in an atmosphere with levels of oxygen greater than about 0.001 torr, 0.005 torr, 0.01 torr, 0.05 torr, 0.1 torr, or greater than about 0.5 torr or more.

[00111] Drying of a metal-containing layer may occur in an atmosphere with levels of hydrogen greater than about 0.001 torr, 0.005 torr, 0.01 torr, 0.05 torr, or greater than or about 0.1 torr or more. Drying of a metal-containing layer on a substrate may occur in an atmosphere with levels of hydrogen less than or about 0.1 torr, 0.05 torr, 0.01 torr, 0.005 torr, or 0.001 torr or less. Annealing of a metal-containing layer on a substrate may occur in an atmosphere of pure hydrogen, pure argon, or a mixture of hydrogen and argon.

[00112] After the slurry is applied to the substrate, the solvent in the metal-containing layer may be removed by heating, vaporization, vacuuming, or any combination thereof. After the solvent is driven off, the substrate may be recoiled. The slurry coated substrate may be incubated or stored under vacuum or atmospheric conditions after deposition and prior to annealing. This occurs prior to annealing and may be useful in removing residual contaminants from the coating, for example, solvent or binder leftover from the coating process. The incubation period may be about 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes. The incubation period may be at least about 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes or more. The incubation period may be no more than about 5 minutes, 4 minutes, 3 minutes, 2 minutes, 1 minute, 50 seconds, 40 seconds, 30 seconds, 20 seconds, or no more than about 10 seconds or less. The incubation period may be the time between coating and annealing, and may be the length of time used to transport the coated article to the heat treatment facility or equipment. For example, the incubation period may last for about 10 seconds, about 30 seconds, about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, or about 5 minutes. The incubation temperature may be about 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, or about 300°C. The incubation temperature may be at least about 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, or at least about 300°C or more. The incubation temperature may be no more than about 300°C, 275°C, 250°C, 225°C, 200°C, 175°C, 150°C, 125°C, 100°C, 75°C, or no more than about 50°C or less. The incubation temperature may range from about 50 °C to about 300 °C. For example, the incubation temperature may be greater than about 50 °C, about 75 °C, about 100 °C, about 125 °C, about 150 °C, about 175 °C, about 200 °C, about 225 °C, about 250 °C, about 275 °C, or about 300 °C or more. After incubating, and prior to annealing, the dry film of slurry on the substrate can be maintained under vacuum conditions. The coating may be dry to the touch immediately following the drying step after the roll- coating process. Absorbed water or other contaminants may be present with the coating anytime between roll coating and annealing.

[00113] A spatially-segregated alloy may be deposited on the surface of a metal substrate using an alloying metal that has been generated in situ from its metal oxide utilizing a metallothermic reduction (or reducing) reaction. The metallothermic reduction reaction may occur when a thermodynamically less stable metal oxide is brought in the presence of a reducing metal agent that forms a thermodynamically more stable metal oxide. A reducing metal agent may comprise any elemental species, including iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium, niobium and combinations thereof.

[00114] In some embodiments, a metallothermic reduction reaction may be initiated or enhanced by a metal transportactivator. A reducing metal compound may be selected such that its Gibbs free energy of formation for its corresponding metal oxide is relatively large, e.g. aluminum to aluminum oxide. Such reducing metals may serve as effective oxygen and water scavengers, thereby eliminating oxidizing species that would hinder the forward reaction of the metal oxide with an activator compound. An example of an overall metallothermic reduction reaction may comprise the reaction of chromium oxide with aluminum metal, such as:

1) Cr ₂ 0 ₃ + 3H ₂ -> 2Cr° + 3H ₂ 0

2) 2A1° + 3H ₂ 0 -> A1 ₂ 0 ₃ + 3H ₂

wherein the above-described reaction may be a source for the deposition of chromium in a metal layer on the surface of a substrate. The utilization of metal oxides as a source material for deposition may eliminate the use of additional inert powders in the reaction that act as scaffolds for the metal layer and as separators for alloying metal powders during sintering processes. The defect rate of the resultant metal layer may be reduced, for example, by including a secondary elemental powder, or alloying the reducing element with a species that increases the melting point of the reducing element to a temperature higher than that used for deposition. The resultant metal oxide from reaction of the reducing metal agent may be more easily removed by a post- thermal treatment cleaning process. The spatially-segregated alloy may comprise an alloy metal layer on a net shape part such as the inner diameter of metal tubes, rods, wires or other formats.

[00115] A metal layer on the surface of a substrate may comprise a slurry applied to the surface of the substrate. The slurry may comprise a metal oxide powder, a reducing metal agent, a metal halide precursor, or a solvent. A slurry comprising a metal oxide powder may be optimized for its chemical and rheological properties. Increased rheological control may provide more uniform coating, including the reduction of unwanted rheological effects such as ribbing, cascading, or other defects, and increased surface coverage on the surface of a substrate, and may lead to increased utilization of the metal. A slurry composition may be adjusted based at least upon the relative concentrations of components, the particle size of components, the pH, the ionic strength, reduced sedimentation, the slurry yield strength, the slurry viscosity and any other properties that may affect the performance of the slurry as a source for depositing a metal layer on a substrate surface. [00116] Pairs of metal oxides and reducing metal agents may be selected based upon a large Gibbs free energy of formation for a metallothermic reduction reaction between the metal oxide and the reducing metal agent. In some cases, a metal oxide and a reducing metal agent may undergo a spontaneous metallothermic reduction reaction. A metallothermic reduction reaction may have a Gibbs free energy of formation of at least about -50 kJ, -100 kJ, -150 kJ, -200 kJ, - 250 kJ, -300 kJ, - 350 kJ, -400 kJ, -450 kJ, -500 kJ, -550 kJ, -600 kJ, -650 kJ, -700 kJ, - 750 kJ, - 800 kJ, -850 kJ, -900 kJ, -950 kJ, -1000 kJ, or more than about -1000 kJ. A metallothermic reduction reaction may have a Gibbs free energy of formation of no more than about -1000 kJ, - 950 kJ, -900 kJ, -850 kJ, -800 kJ, - 750 kJ, -700 kJ, -650 kJ, -600 kJ, -550 kJ, -500 kJ, -450 kJ, - 400 kJ, - 350 kJ, -300 kJ, -250 kJ, -200 kJ, -150 kJ, -100 kJ, - 50 kJ or less than about -50 kJ.

[00117] A slurry coated substrate may be recoiled prior to annealing. The slurry coated substrate may be placed in a retort and subjected to a controlled atmosphere during heat treatment. Water may be removed. The vacuum may be pulled to force hydrogen between wraps. The annealing process may be via tight coil or loose coil annealing. Annealing the slurry layer coated substrate can allow the elemental species in the slurry to diffuse into or through the substrate. Less than about 100 wt%, 90 wt%, 80 wt%, 70 wt%, 60 wt%, 50 wt%, 40 wt%, 30 wt%, 20 wt%, 10 wt%, or 5 wt% or less of the elemental species may diffuse to or into the substrate upon annealing. At least about 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, or at least about 90 wt% or more of the elemental species may diffuse to or into the substrate upon annealing. Certain process conditions may afford about 1-5% of the elemental species diffusing from the coating into the substrate. Diffusion of the elemental species to the substrate may be aided by a component in the slurry layer. The annealing process may be a continuous annealing process. The annealing process may be a non-continuous annealing process. A slurry-coated substrate may undergo more than one annealing process to increase the utilization of an elemental species or alter the concentration gradient of an elemental species in the metal layer adjacent to the substrate.

[00118] The substrate may be heated at a rate of greater than about 0.01 °C per second, 0.1 °C per second, 1 °C per second, 5 °C per second, 10 °C per second, 15 °C per second, 20 °C per second, 25 °C per second, or 30 °C per second or more. The substrate may be heated at a rate of greater than about 0.01 °C per minute, 0.1 °C per minute, 1 °C per minute, 5 °C per minute, 10 °C per minute, 15 °C per minute, 20 °C per minute, 25 °C per minute, or 30 °C per minute or more. The substrate may be heated at a rate of less than about 30°C per minute, 25°C per minute, 20°C per minute, 15°C per minute, 10°C per minute, 5°C per minute, 1°C per minute, 0.1°C per minute, or less than about 0.01°C per minute or less. The substrate may be heated at a rate of less than about 30°C per second, 25°C per second, 20°C per second, 15°C per second, 10°C per second, 5°C per second, 1°C per second, 0.1°C per second, or less than about 0.01°C per second or less. The substrate that has been coated with a slurry can be annealed at a temperature of at least about 0 °C, 25 °C, 50 °C, 75 °C, 100 °C, 200 °C, 300 °C, 400 °C, 500 °C, 600 °C, 700 °C, 800 °C, 900 °C, 1000 °C, 1100 °C, 1200 °C, or 1300 °C or more. The annealing temperature may be no more than about 1300°C, 1200°C, 1100°C, 1000°C, 900°C, 800°C, 700°C, 600°C, 500°C, 400°C, 300°C, 200°C, 100°C, 75°C, 50°C, 25°C, or no more than about 0°C or less. The annealing temperature may be about 800 °C, 900 °C, 1000 °C, 1100 °C, 1200 °C, or 1300 °C. The heating temperature during annealing can be from about 800 °C to about 1300 °C, such as from about 900 °C to about 1000 °C. The annealing temperature can be about 900 °C, 925 °C, 950 °C or 1000°C.

[00119] During heating, iron in a substrate or metal-containing layer may transition from ferrite to austenite. The temperature at which the transition occurs may be referred to as the ferrite-austenite transition temperature. The ferrite-austenite transition temperature of a substrate or metal-containing layer may be no more than about 1600°C, 1500°C, 1400°C, 1300°C, 1200°C, 1100°C, 1000°C, 900°C, 800°C, 700°C, 600°C, or no more than about 500°C or less. The ferrite- austenite transition temperature of a substrate or metal-containing layer may be greater than about 500 °C, 600 °C, 700 °C, 800 °C, 900 °C, 1000 °C, 1100 °C, 1200 °C, 1300 °C, 1400 °C, 1500 °C, or 1600 °C or more. The ferrite-austenite transition temperature of a substrate may be about 900 °C, 1000 °C, 1100 °C, 1200 °C, or 1300 °C. The ferrite-austenite transition temperature of a substrate can be from about 900 °C to about 1300 °C, about 1000 °C to about 1200 °C, or about 1100 °C to about 1200 °C.

[00120] The total annealing time may be about 5 hours, 10 hours, 20 hours, 40 hours, 60 hours, 80 hours, 100 hours, 120 hours, 140 hours, 160 hours, 180 hours, or about 200 hours. The total annealing time may be at least about 5 hours, 10 hours, 20 hours, 40 hours, 60 hours, 80 hours, 100 hours, 120 hours, 140 hours, 160 hours, 180 hours, or about 200 hours or more. The total annealing time may be less than about 200 hours, 180 hours, 160 hours, 140 hours, 120 hours, 100 hours, 80 hours, 60 hours, 40 hours, 20 hours, 10 hours, or less than about 5 hours or less. The total annealing time, including heating, can range from about 5 hours to about 200 hours. For example, the total annealing time can be more than about 5 hours, about 20 hours, about 40 hours, about 60 hours, about 80 hours, about 100 hours, about 120 hours, about 140 hours, about 160 hours, about 180 hours, or about 200 hours or more. The maximum

temperature during the annealing process may be reached in about 1 hour to 100 hours. For example, the maximum temperature during the annealing process may be reached in about 1 hour, 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours, or 100 hours. The maximum temperature during the annealing process may be reached in at least about 1 hour, 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours, or at least about 100 hours or more. The maximum temperature during the annealing process may be reached in no more than about 100 hours, 90 hours, 80 hours, 70 hours, 60 hours, 50 hours, 40 hours, 30 hours, 20 hours, 10 hours, or no more than about 1 hour or less. In some cases, a substrate may be annealed at about 950 °C for at least about 5 hours. In some cases, a substrate may be annealed at about 950 °C for at least about 20 hours. In some cases, a substrate may be annealed at about 950 °C for at least about 40 hours. In some cases, a substrate may be annealed at about 900 °C for at least about 20 hours. In some cases, a substrate may be annealed at about 900 °C for at least about 40 hours. In some cases, a substrate may be annealed at about 900 °C for at least about 60 hours. In some cases, a substrate may be annealed at about 900 °C for at least about 80 hours.

[00121] The annealing atmosphere may comprise a gaseous species such as an inert or reactive gas, for example, hydrogen, helium, methane, ethylene, nitrogen, or argon. The annealing atmosphere may comprise a mixture of gases. The annealing atmosphere can be a vacuum. To prevent loss of an elemental species during annealing, hydrochloric acid may be added to the annealing gas. Minimizing the partial pressure of a component in the metal- containing layer in the reactor at high temperatures may maintain a low deposition rate that is essential for minimizing or stopping the formation of Kirkendall pores. Adding too much of an acidic component in the metal-containing layer may also cause corrosion of the coating equipment or the substrate.

[00122] After annealing, the metal layer coated substrate may be dried. The drying of the metal layer coated substrate may occur in a vacuum or near-vacuum atmosphere. The drying of the metal layer coated substrate may occur in an atmosphere of an inert gas. Examples of inert gas include hydrogen, helium, argon, nitrogen, or any combination thereof.

[00123] The substrate may be cooled for a period of time after annealing. The cooling time can range from about 1 hour to about 100 hours. For example, the cooling time can be at least about 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours, or at least about 100 hours or more. The cooling time can be less than about 100 hours, 90 hours, 80 hours, 70 hours, 60 hours, 50 hours, 40 hours, 35 hours, 25 hours, 20 hours, 15 hours, 10 hours, 9 hours, 8 hours, 7 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, or less than about 1 hour or less. For example, the cooling time can be from about 1 hour to about 100 hours, from about 5 hours to about 50 hours, or from about 10 hours to about 20 hours.

[00124] Large articles may have hot spots or cold spots during thermal treatment, where an article may be coated evenly but heated unevenly. Hot spots or cold spots may be indicated to control the diffusion of alloying element into the article as uniformly as possible.

[00125] After annealing, a metal layer may be formed on the substrate. The metal layer may have at least one elemental species selected from carbon, manganese, silicon, vanadium, titanium, niobium, phosphorus, sulfur, aluminum, copper, nickel, chromium, molybdenum, tin, boron, calcium, arsenic, cobalt, lead, antimony, tantalum, tungsten, zinc, silicon, and zirconium, where the elemental species has a concentration that varies by less than about 20 wt. %, about 15 wt. %, about 10 wt. %, about 5 wt. %, about 4 wt. %, about 3 wt. %, about 2 wt. %, about 1 wt. %, or about 0.5 wt. % or less in the outer layer. The metal layer may have at least one elemental species selected from carbon, manganese, silicon, vanadium, titanium, niobium, phosphorus, sulfur, aluminum, copper, nickel, chromium, molybdenum, tin, boron, calcium, arsenic, cobalt, lead, antimony, tantalum, tungsten, zinc, silicon, and zirconium, where the elemental species has a concentration that varies by at least about 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, 15 wt%, or at least about 20 wt% in the outer layer. The substrate may comprise a bonding layer adjacent to the metal layer. The concentration of an elemental species may decrease by less than about 1.0 wt % in the bonding layer. A metal or alloy layer may be uniform in appearance. The metal or alloy layer may be level, unvarying, smooth, even, and homogenous in appearance, weight, and thickness over the surface of the at least a portion of the layer. A metal or alloy layer may have grain boundary precipitates that may be visible. Alternatively, a metal or alloy layer formed with a composition or via a method described herein may have little or few grain boundary precipitates that are visible at about lOx, 50x, lOOx, 250x, 500x, lOOOx, or more magnification.

[00126] A metal-containing layer may comprise a metal oxide. A metal oxide may comprise, but is not limited to, AI2O3, MgO, CaO, C^Ch, TiCL, FeQ^Cri, S1O2, Ta20s, or MgC^Cri, or a combination thereof. A metal oxide may be formed in the metal-containing layer by a metallothermic reduction reaction between an elemental metal and a thermodynamically less- stable metal oxide. Suitable pairs of elemental metals and thermodynamically less-stable metal oxides may be chosen from pairs whose Gibbs free energy of formation is reduced by an oxidation of the elemental metal by the metal oxide.

[00127] A residue may remain on the substrate after the annealing process. Certain components in the metal layer may be consumed or removed (e.g., deposited on the walls of the retort), or its concentration reduced due to its diffusion to or into the substrate. However, after annealing, other residue in the form of, e.g., a powder, may remain on the substrate. The residue may comprise the inert material from the metal-containing layer. This residue may be removed prior to further processing (e.g., temper rolling). The reaction can be purged with HC1 gas to halt the reaction. The purging with HC1 gas can allow for the formation of a flat profile.

[00128] After a metal layer is formed adjacent to a substrate, the substrate may have a measurable grain size. Grain size may be measured and recorded in accordance to the American Society of the International Association for Testing and Materials (ASTM) standard. The substrate may have a grain size of about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, or 30. The substrate may have a grain size greater than about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, or 30 or more. The substrate may have a grain size of no more than about 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13,

12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0, 00, or no more than about 000 or less. In some cases, a metal layer may have a grain size from about ASTM 000 to about ASTM 30, from about ASTM 5 to about ASTM 16, from about ASTM 6 to about ASTM 14, or from about ASTM 8 to about ASTM 12. A substrate may have a grain size from about ASTM 7 to ASTM 9. A substrate may have a grain size about ASTM 7.

[00129] An elemental species in the slurry may lower the transition temperature of austenite to ferrite. An elemental species in the substrate may lower the transition temperature of austenite to ferrite. An elemental species may not substantially change the transition temperature of austenite to ferrite. In some cases, an elemental species may raise the transition temperature of austenite to ferrite. An elemental species that may lower the transition temperature of austenite to ferrite can be manganese, nitrogen, copper or gold.

[00130] The grain size of austenite and the grain size of ferrite may be measured. A ratio of austenite grain size to ferrite grain size may be greater than about 0.1, 0.5, 1, 2, 5, or 10 or more. A ratio of austenite grain size to ferrite grain size may be less than about 10, 5, 2, 1 0.5, or 0.1 or less. A ratio of austenite grain size to ferrite grain size may be about 0.1, 0.5, 1, 2, 5, or 10. A ratio of austenite grain size to ferrite grain size may be about 1. The ratio of grain size of austenite to grain size of ferrite may be calculated according to the following equation:

wherein D, i s the grain size of austenite in pm, D _a is the grain size of ferrite in pm, a is the cooling rate in °C/s. [00131] The amount of titanium equivalents stabilization may be calculated according to the following equation:

Ti equivalents stabilization = wt%Ti - 3.42*wt%N - 1.49 wt%S - 4wt%C + 0.516wt%Nb.

[00132] Without wishing to be bound by theory, a certain amount of titanium (Ti) equivalents stabilization in a metal layer that may give rise to a layer that is more resistant to grain boundary precipitation. A metal layer may comprise at least about 0.001 Ti equivalents, 0.005 Ti equivalents, 0.01 Ti equivalents, 0.015 Ti equivalents, 0.017 Ti equivalents, 0.02 Ti equivalents, 0.03 Ti equivalents, 0.04 Ti equivalents, 0.05 Ti equivalents, 0.06 Ti equivalents, 0.07 Ti equivalents, 0.08 Ti equivalents, 0.09 Ti equivalents, or more. A metal layer may comprise less than about 0.09 Ti equivalents, 0.08 Ti equivalents, 0.07 Ti equivalents, 0.06 Ti equivalents, 0.05 Ti equivalents, 0.04 Ti equivalents, 0.03 Ti equivalents, 0.02 Ti equivalents, 0.017 Ti equivalents, 0.015 Ti equivalents, 0.01 Ti equivalents, 0.005 Ti equivalents, or less than about 0.001 Ti equivalents or less.

[00133] The amount of an elemental metal in a metal layer on a substrate may change with depth. The amount of an elemental metal in a metal layer may have a change with depth at a certain rate, such as at least about -0.0001% per micrometer, at least about -0.001% per micrometer, at least about -0.01% per micrometer, at least about -0.05% per micrometer, at least about -0.1% per micrometer, at least about -0.5% per micrometer, at least about -1.0% per micrometer, at least about -3.0% per micrometer, at least about -5.0% per micrometer, at least about -7.0% per micrometer, or at least about -9.0% per micrometer or more. The amount of metal in a metal layer may have a change with depth at a certain rate, such as less than about - 9.0% per micrometer, -7.0% per micrometer, -5.0% per micrometer, -3.0% per micrometer, - 1.0% per micrometer, -0.5% per micrometer, -0.1% per micrometer, -0.05% per micrometer, - 0.01% per micrometer, -0.001% per micrometer, or less than about -0.001% per micrometer or less. The amount of an elemental metal in a metal layer may have a change with depth from about -0.01% per micrometer to -5.0% per micrometer, or from about -0.01% per micrometer to -3.0% per micrometer.

[00134] The amount of an elemental metal in a metal layer may have a change with depth at a certain rate, such as at least about -0.0001% per micrometer, -0.001% per micrometer, -0.01% per micrometer, -0.05% per micrometer, -0.1% per micrometer, -0.5% per micrometer, -1.0% per micrometer, -3.0% per micrometer, -5.0% per micrometer, -7.0% per micrometer, or at least about -9.0% per micrometer or more. The amount of elemental metal in a metal layer may have a change with depth at a certain rate, such as no more than about -9.0% per micrometer, -7.0% per micrometer, -5.0% per micrometer, -3.0% per micrometer, -1.0% per micrometer, -0.5% per micrometer, -0.1% per micrometer, -0.05% per micrometer, -0.01% per micrometer, -0.001% per micrometer, or no more than about -0.0001% per micrometer or less.

[00135] An elemental metal may have a concentration of at least about 5 wt % at a depth of less than or equal to 100 micrometers, about 5 wt % at a depth of less than or equal to 50 micrometers, about 10 wt % at a depth of less than or equal to 50 micrometers, about 10 wt % at a depth of less than or equal to 40 micrometers, about 10 wt % at a depth of less than or equal to 30 micrometers, about 15 wt % at a depth of less than or equal to 50 micrometers, about 15 wt % at a depth of less than or equal to 40 micrometers, about 15 wt % at a depth of less than or equal to 30 micrometers, or about 15 wt % at a depth of less than or equal to 10 micrometers from the surface of the substrate. X-ray photoelectron spectroscopy may be used to measure such change in amount, concentration, or wt% with depth.

[00136] A metal layer that is coated adjacent to a substrate may have a thickness less than about 1 millimeter, about 900 micrometers, about 800 micrometers, about 700 micrometers, about 600 micrometers, about 500 micrometers, 400 micrometers, about 300 micrometers, about 200 micrometers, or about 100 micrometers or less.

[00137] A metal layer that is coated adjacent to a substrate may have a thickness of at least about 1 micrometer, 5 micrometers, 10 micrometers, 20 micrometers, 30 micrometers, 40 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers, 100 micrometers, 200 micrometers, 300 micrometers, 400 micrometers, 500 micrometers, 600 micrometers, 700 micrometers, 800 micrometers, 900 micrometers, or more.

[00138] Properties of a substrate, prior to coating with a metal layer or after coating with a metal layer, may be determined by various techniques and instruments. Techniques and instruments include, for example, grain size calculations, scanning electron microscope (SEM), scanning electron microscope/ energy dispersive spectroscopy (SEM/EDS), microprobe analysis, and potentiostat measurements.

[00139] Properties of a substrate after coating with a metal layer may be measured. Properties of a substrate include, for example, chemical composition, yield strength, ultimate tensile strength, and percent elongation.

[00140] The substrate can be substantially free of Kirkendall voids after annealing. The layer can impart characteristics on the substrate which the substrate did not previously contain. For example, the layer may make the substrate harder, more wear resistant, more aesthetically pleasing, more electrically resistive, less electrically resistive, more thermally conductive, less thermally conductive, or any combination thereof. In addition, the layer may cause the speed of sound in the substrate to be faster or slower.

[00141] The yield strength of a substrate may be greater than about 100 psi, 1 ksi (kilopound per square inch), 2 ksi, 5 ksi, 10 ksi, 15 ksi, 20 ksi, 21 ksi, 22 ksi, 23 ksi, 24 ksi, 25 ksi, 26 ksi,

27 ksi, 28 ksi, 29 ksi, 30 ksi, 31 ksi, 32 ksi, 33 ksi, 34 ksi, 35 ksi, 36 ksi, 37 ksi, 38 ksi, 39 ksi, or greater than about 40 ksi or more. The yield strength of a substrate may be less than or equal to about 40 ksi, 39 ksi, 38 kis, 37 ksi, 36 ksi, 35 ksi, 34 ksi, 33 ksi, 32 ksi, 31 ksi, 30 ksi, 29 ksi, 28 kis, 27 ksi, 26 ksi, 25 ksi, 24 ksi, 23 ksi, 22 ksi, 21 ksi, 20 ksi, 15 ksi, 10 kis, 5 ksi, 2 ksi, 1 ksi, or less than or equal to about 100 psi or less. The yield strength of a substrate may be about 20 ksi, 21 ksi, 22 ksi, 23 ksi, 24 ksi, 25 ksi, 26 ksi, 27 ksi, 28 ksi, 29 ksi, 30 ksi, 31 ksi, 32 ksi, 33 ksi, 34 ksi, 35 ksi, 36 ksi, 37 ksi, 38 ksi, 39 ksi, 40 ksi, 45 ksi, or about 50 ksi.

[00142] The ultimate tensile strength of a substrate may be greater than or equal to about 30 ksi, 35 ksi, 40 ksi, 45 ksi, 46 ksi, 47 ksi, 48 ksi, 49 ksi, 50 ksi, 51 ksi, 52 ksi, 53 ksi, 54 ksi, 55 ksi, 56 ksi, 57 ksi, 58 ksi, 59 ksi, 60 ksi, 61 ksi, 62 ksi, 63 ksi, 64 ksi, 65 ksi, 66 ksi, 67 ksi, 68 ksi, 69 ksi, 70 ksi, 80 ksi, 90 ksi, 100 ksi, or more. The ultimate tensile strength of a substrate may be less than or equal to about 100 ksi, 90 ksi, 80 ksi, 70 ksi, 60 ksi, 59 ksi, 58 ksi, 57 ksi, 56 ksi, 55 ksi, 54 ksi, 53 ksi, 52 ksi, 51 ksi, 50 ksi, 49 ksi, 48 ksi, 47 ksi, 46 ksi, 45 ksi, 44 ksi, 43 ksi, 42 ksi, 41 ksi, 40 ksi, 35 ksi, or less than or equal to about 30 ksi. The ultimate tensile strength of a substrate may be about 30 ksi, 35 ksi, 40 ksi, 45 ksi, 46 ksi, 47 ksi, 48 ksi, 49 ksi,

50 ksi, 51 ksi, 52 ksi, 53 ksi, 54 ksi, 55 ksi, 56 ksi, 57 ksi, 58 ksi, 59 ksi, 60 ksi, 61 ksi, 62 ksi, 63 ksi, 64 ksi, 65 ksi, 66 ksi, 67 ksi, 68 ksi, 69 ksi, 70 ksi, 80 ksi, 90 ksi, 100 ksi, or more.

[00143] A substrate may exhibit a percent elongation, a maximum elongation of the gage divided by the original gage length, or the difference in distance prior to fracture before and after coating with a steel substrate. The percent elongation may be about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%. In some cases, the percent elongation may be about 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40%. In some cases, the percent elongation may be greater than about 5%, 10%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 50%, 60%, 70%, 80%, 90%, or greater than about 100% or more. In some cases, the percent elongation may be less than about 100%, 90%, 80%, 70%,

60%, 50%, 40%, 39%, 38%, 37%, 36%, 35%, 34%, 33%, 32%, 31%, 30%, 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 10%, or less than about 5% or less.

[00144] A substrate may exhibit a Ti/Nb stability. In some cases, the Ti/Nb stability may be greater than or equal to about 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.010, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.020, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.030, 0.040 or more. In some cases, the Ti/Nb stability may be less than or equal to about 0.040, 0.030, 0.029, 0.028, 0.027, 0.026, 0.025, 0.024, 0.023, 0.022, 0.021, 0.020, 0.019, 0.018, 0.017, 0.016, 0.015, 0.014, 0.013, 0.012, 0.011, 0.010, 0.009, 0.008, 0.007, 0.006, 0.005, 0.004, 0.003, 0.002, 0.001, or less. In some cases, the Ti/Nb stability may be about 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.010, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.020, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.030, 0.040, or more.

[00145] Any suitable analytical techniques may be used to measure the composition of a substrate, slurry, slurry component, or metal layer. Measurements may include amounts, concentrations, or weight percentage, thicknesses or other dimensions, changes of composition and/or structures with depth, and grain size. Exemplary analytical techniques may include, without limitation, glow discharge mass spectrometry, microprobe analysis, potentiostat measurements, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, energy-dispersive x-ray spectroscopy, and electron energy loss spectroscopy may be used to measure such change in amount, concentration, or wt% with depth.

[00146] Other properties of substrates coated with metal layers may be as described in, for example, U.S. Patent Publication No. 2013/0171471; U.S. Patent Publication No. 2013/0309410; U.S. Patent Publication No. 2013/0252022; U.S. Patent Publication No. 2015/0167131; U.S. Patent Publication No. 2015/0345041, U.S. Patent Publication No. 2015/0345041, U.S. Patent Publication No. 2016/0230284, each of which is incorporated herein by reference in its entirety.

[00147] Steel chemistry may be altered to enhance the forming properties and performance of the material when drawn, stretched, or both. The formability of a steel may be measured by the plastic strain ratio, often called the Lankford coefficient, r-bar, r _m , or, herein referred to as the r- value. The r-value may be defined as the ratio of plastic strain in the plane of a sheet to the plastic strain of the gauge or thickness of the sheet. The r-value may be calculated as:

wherein Ro, R45 and R90 are the plastic strain ratio relative to the direction of the sheet.

[00148] The r-value of a steel may be altered by the manipulation of steel chemistry and composition to create a highly formable steel composition. A common, interstitial-free steel may have an r-value between about 1.4 and 1.8. An altered steel may have an r-value exceeding about 2. In some embodiments, a steel may have an r-value exceeding about 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, or exceeding about 4.0 or more. An altered steel may have an r-value of no more than about 4.0, 3.8, 3.6, 3.4, 3.2, 3.0, 2.8, 2.6, 2.4, or no more than about 2.2 or less. [00149] Several chemistries may be employed to enhance the r-values of a highly formable steel composition. The steel chemistry may be selected to increase the overall incorporation of grain-pinning particles before the steel is annealed. In some embodiments, the presence of grain- pinning particles inhibits the formation of increased grain sizes during the annealing process. A stoichiometric excess of titanium (Ti) may be used. Such excess of Ti may permit the formation of TiC at elevated temperatures. TiC may serve to grain pin at elevated temperatures. Interstitial- free steels may also utilize more manganese with smaller amounts of TiN, AIN, NbC, NbN, or other components, which may act both as grain pins and interstitial element binders at elevated temperatures. An interstitial-free steel may comprise a composition similar to those listed in example 7.

[00150] A method for creating a highly formable steel composition may comprise several intermediate processes. A steel may be composed according to an above-described chemistry. An interstitial-free steel may undergo fine-grain practices to generate small prior grains. A cold reduction may be utilized to obtain a smooth finish and control grain sizes. After a cold reduction, a subsequent processing step may comprise a high-temperature annealing method. The high-temperature annealing may comprise annealing at a temperature above about 900°C. The annealing temperature may exceed about 950°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, 1500°C, or greater. The annealing temperature may be no more than about 1500°C, 1450°C, 1400°C, 1350°C, 1300°C, 1250°C, 1200°C, 1150°C, 1100°C, 1050°C, 1000°C, or no more than about 950°C or less. The annealing temperature may permit a transition of the steel from a ferritic phase to an austenitic phase. The selected composition of the interstitial-free steel may prevent grain growth. The stabilized grades may prevent strain aging and may improve the formability of the steel for further processing.

[00151] A highly formable steel composition may have a measurable grain size. Grain size may be measured and recorded in accordance to the American Society of the International Association for Testing and Materials (ASTM) standard. The substrate may have a grain size greater than about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, or 30 or more. A highly formable steel composition may have a grain size greater than about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, or 30 or more. A highly formable steel composition may have a grain size of no more than about 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0, 00, or no more than about 000 or less. In some embodiments, a metal layer may have a grain size from about ASTM 000 to about ASTM 10, about ASTM 000 to about ASTM 15, about ASTM 000 to about ASTM 20, about ASTM 000 to about ASTM 25, about ASTM 000 to about ASTM 30, from about ASTM 5 to about ASTM 16, about ASTM 5 to about ASTM 18, ASTM 5 to about ASTM 20, about ASTM 5 to about ASTM 22, about ASTM 5 to about ASTM 24, about ASTM 5 to about ASTM 26, about ASTM 5 to about ASTM 28, about ASTM 5 to about ASTM 30, about ASTM 6 to about ASTM 16, about ASTM 6 to about ASTM 18, about ASTM 6 to about ASTM 20, about ASTM 6 to about ASTM 22, about ASTM 6 to about ASTM 24, about ASTM 6 to about ASTM 26, about ASTM 6 to about ASTM 28, about ASTM 6 to about ASTM 30, about ASTM 7 to about ASTM 16, about ASTM 7 to about ASTM 18, about ASTM 7 to about ASTM 20, about ASTM 7 to about ASTM 22, ASTM 7 to about ASTM 24, about ASTM 7 to about ASTM 26, about ASTM 7 to about ASTM 28, about ASTM 7 to about ASTM 30, about ASTM 8 to about ASTM 16, about ASTM 8 to about ASTM 18, about ASTM 8 to about ASTM 20, about ASTM

8 to about ASTM 22, about ASTM 8 to about ASTM 24, about ASTM 8 to about ASTM 26, about ASTM 8 to about ASTM 28, about ASTM 8 to about ASTM 30, about ASTM 9 to about ASTM 16, about ASTM 9 to about ASTM 18, about ASTM 9 to about ASTM 20, about ASTM

9 to about ASTM 22, about ASTM 9 to about ASTM 24, about ASTM 9 to about ASTM 26, about ASTM 9 to about ASTM 28, about ASTM 9 to about ASTM 30, about ASTM 10 to about ASTM 16, about ASTM 10 to about ASTM 18, about ASTM 10 to about ASTM 20, about ASTM 10 to about ASTM 22, about ASTM 10 to about ASTM 24, about ASTM 10 to about ASTM 26, about ASTM 10 to about ASTM 28, about ASTM 10 to about ASTM 30, about ASTM 15 to about ASTM 20, about ASTM 15 to about ASTM 25, about ASTM 15 to about ASTM 30, or ASTM 20 to about ASTM 30 . A highly formable steel composition may have a grain size from about ASTM 7 to ASTM 9, from about ASTM 6 to about ASTM 14, or from about ASTM 8 to about ASTM 12. A highly formable steel composition may have a grain size of about ASTM 7, about ASTM 8, about ASTM 9, about ASTM 10, about ASTM 11, about ASTM 12, about ASTM 13, about ASTM 14, about ASTM 15, about ASTM 16, about ASTM 17, about ASTM 18, about ASTM 19, about ASTM 20, about ASTM 21, about ASTM 22, about ASTM 23, about ASTM 24, about ASTM 25, about ASTM 26, about ASTM 27, about ASTM 28, about ASTM 29, or about ASTM 30.

[00152] The substrates, metal layers, and compositions comprising metal layers described herein may be utilized in any processing method or series of processing methods. Substrates, metal layers, and compositions may be utilized in additional processing methods before, during, and/or after the deposition of a metal-containing layer. Substrates, metal layers, and

compositions may be utilized in additional processing methods before, during, and/or after the annealing of a metal layer. A composition comprising a metal layer may offer enhanced properties (e.g., formability, workability, improved thermal conductivity) for subsequent processing steps. A composition with enhanced properties after formation of a metal layer may be advantageous for a variety of applications, such as electrical alloys, electronic alloys, high- temperature alloys, high-strength alloys, corrosion-resistant alloys, construction alloys, structural alloys, consumer goods alloys, appliance-grade alloys, industrial alloys, biomedical-grade alloys, military-grade alloys, maritime-grade alloys, aviation-grade alloys, transportion grade alloys, aesthetic alloysand automotive-grade alloys.

[00153] A substrate, metal layer, or composition comprising a metal layer may undergo any processing methods before, during and/or after the deposition of a metal layer. Illustrative processes may comprise, without limitation, forming, soft or hard tooling, fastening, and seam or cut edge protection. Illustrative forming, soft or hard tooling processes may comprise stretch or draw forming, re-striking, crash forming, spin forming, roll forming, hydro-forming, CNC forming, flanging, crimping, hemming, hot stamping, extrusion, and forging. Illustrative fastening processes may comprise toggle locking, toxlocking, spot welding, soldering, stick welding, electric arc welding, MIG welding, TIG welding, acetylene gas welding, electric resistance welding, ultra-sonic welding, friction welding, laser welding, plasma welding, lock seaming, riveting, hot forging, and chemical adhesion (e.g., glue or epoxy joining). Illustrative seam or cut-edge protection processes may comprise hot dip galvanizing, electro-galvanizing, aluminum or aluminizing, alumino-siliconizing, cold spraying (e.g., Al, stainless steel of all grades, zinc, galvanize, nickel), hot spraying or plasma spray coating (e.g., Al, stainless steel of all grades, zinc, galvanize, nickel, copper, bronze), cladding, and liquid applied coatings (e.g., paints, UV cured, polymer paints).

[00154] A substrate or composition comprising a metal layer may be formed into one or more parts, pieces, or components. A part, piece, or component comprising a metal layer may be used in any suitable application including, without limitation, automotive, aviation, transportation, martime, appliance, construction, industrial, electrical, biomedical, military, consumer, aesthetic, electronic, and structural applications. Automotive applications may comprise automotive fuel tanks, exposed body panels (e.g., doors, hoods, and fenders), exhaust components (e.g., mufflers, catalytic converter housings, exhaust tubing, heat shielding), and unexposed body panels (e.g., dash panels, door inners, wheel house inners). Appliance applications may comprise exposed panels (e.g., door outers, vent hoods, splash guards) and unexposed panels (e.g., dishwasher inner panels, water heater tanks). Construction and structural applications may comprise architectural paneling, flow tubing, piping, beams, hinges, plates, and fasteners. Electrical applications may comprise electrical motor laminations, electric generator laminations, and electrical transformer core laminations.

Computer Systems

[00155] The present disclosure provides computer systems that are programmed to implement methods of the disclosure. FIG. 4 shows a computer control system 401 that is programmed or otherwise configured to produce the slurry and/or apply a coating of the slurry to a substrate.

The computer control system 401 can regulate various aspects of the methods of the present disclosure, such as, for example, methods of producing the slurry and methods of applying a coating of the slurry to the substrate. The computer control system 401 can be implemented on an electronic device of a user or a computer system that is remotely located with respect to the electronic device. The electronic device can be a mobile electronic device.

[00156] The computer system 401 includes a central processing unit (CPU, also“processor” and“computer processor” herein) 405, which can be a single core or multi core processor, or a plurality of processors for parallel processing. The computer control system 401 also includes memory or memory location 410 (e.g., random-access memory, read-only memory, flash memory), electronic storage unit 415 (e.g., hard disk), communication interface 420 (e.g., network adapter) for communicating with one or more other systems, and peripheral devices 425, such as cache, other memory, data storage and/or electronic display adapters. The memory 410, storage unit 415, interface 420 and peripheral devices 425 are in communication with the CPU 405 through a communication bus (solid lines), such as a motherboard. The storage unit 415 can be a data storage unit (or data repository) for storing data. The computer control system 401 can be operatively coupled to a computer network (“network”) 430 with the aid of the communication interface 420. The network 430 can be the Internet, an internet and/or extranet, or an intranet and/or extranet that is in communication with the Internet. The network 430 in some cases is a telecommunication and/or data network. The network 430 can include one or more computer servers, which can enable distributed computing, such as cloud computing. The network 430, in some cases with the aid of the computer system 401, can implement a peer-to- peer network, which may enable devices coupled to the computer system 401 to behave as a client or a server.

[00157] The CPU 405 can execute a sequence of machine-readable instructions, which can be embodied in a program or software. The instructions may be stored in a memory location, such as the memory 410. The instructions can be directed to the CPU 405, which can subsequently program or otherwise configure the CPU 405 to implement methods of the present disclosure. Examples of operations performed by the CPU 405 can include fetch, decode, execute, and writeback.

[00158] The CPU 405 can be part of a circuit, such as an integrated circuit. One or more other components of the system 401 can be included in the circuit. In some cases, the circuit is an application specific integrated circuit (ASIC).

[00159] The storage unit 415 can store files, such as drivers, libraries and saved programs.

The storage unit 415 can store user data, e.g., user preferences and user programs. The computer system 401 in some cases can include one or more additional data storage units that are external to the computer system 401, such as located on a remote server that is in communication with the computer system 401 through an intranet or the Internet.

[00160] The computer system 401 can communicate with one or more remote computer systems through the network 430. For instance, the computer system 401 can communicate with a remote computer system of a user (e.g., a user controlling the manufacture of a slurry coated substrate). Examples of remote computer systems include personal computers (e.g., portable PC), slate or tablet PC’s (e.g., Apple® iPad, Samsung® Galaxy Tab), telephones, Smart phones (e.g., Apple® iPhone, Android-enabled device, Blackberry®), or personal digital assistants. The user can access the computer system 401 via the network 430.

[00161] Methods as described herein can be implemented by way of machine (e.g., computer processor) executable code stored on an electronic storage location of the computer system 401, such as, for example, on the memory 410 or electronic storage unit 415. The machine executable or machine readable code can be provided in the form of software. During use, the code can be executed by the processor 405. In some cases, the code can be retrieved from the storage unit 415 and stored on the memory 410 for ready access by the processor 405. In some situations, the electronic storage unit 415 can be precluded, and machine-executable instructions are stored on memory 410.

[00162] The code can be pre-compiled and configured for use with a machine having a processer adapted to execute the code, or can be compiled during runtime. The code can be supplied in a programming language that can be selected to enable the code to execute in a pre compiled or as-compiled fashion.

[00163] Aspects of the systems and methods provided herein, such as the computer system 401, can be embodied in programming. Various aspects of the technology may be thought of as “products” or“articles of manufacture” typically in the form of machine (or processor) executable code and/or associated data that is carried on or embodied in a type of machine readable medium. Machine-executable code can be stored on an electronic storage unit, such as memory (e.g., read-only memory, random-access memory, flash memory) or a hard disk.

“Storage” type media can include any or all of the tangible memory of the computers, processors or the like, or associated modules thereof, such as various semiconductor memories, tape drives, disk drives and the like, which may provide non-transitory storage at any time for the software programming. All or portions of the software may at times be communicated through the Internet or various other telecommunication networks. Such communications, for example, may enable loading of the software from one computer or processor into another, for example, from a management server or host computer into the computer platform of an application server. Thus, another type of media that may bear the software elements includes optical, electrical and electromagnetic waves, such as used across physical interfaces between local devices, through wired and optical landline networks and over various air-links. The physical elements that carry such waves, such as wired or wireless links, optical links or the like, also may be considered as media bearing the software. As used herein, unless restricted to non-transitory, tangible “storage” media, terms such as computer or machine“readable medium” refer to any medium that participates in providing instructions to a processor for execution.

[00164] Hence, a machine readable medium, such as computer-executable code, may take many forms, including but not limited to, a tangible storage medium, a carrier wave medium or physical transmission medium. Non-volatile storage media include, for example, optical or magnetic disks, such as any of the storage devices in any computer(s) or the like, such as may be used to implement the databases, etc. shown in the drawings. Volatile storage media include dynamic memory, such as main memory of such a computer platform. Tangible transmission media include coaxial cables; copper wire and fiber optics, including the wires that comprise a bus within a computer system. Carrier-wave transmission media may take the form of electric or electromagnetic signals, or acoustic or light waves such as those generated during radio frequency (RF) and infrared (IR) data communications. Common forms of computer-readable media therefore include for example: a floppy disk, a flexible disk, hard disk, magnetic tape, any other magnetic medium, a CD-ROM, DVD or DVD-ROM, any other optical medium, punch cards paper tape, any other physical storage medium with patterns of holes, a RAM, a ROM, a PROM and EPROM, a FLASH-EPROM, any other memory chip or cartridge, a carrier wave transporting data or instructions, cables or links transporting such a carrier wave, or any other medium from which a computer may read programming code and/or data. Many of these forms of computer readable media may be involved in carrying one or more sequences of one or more instructions to a processor for execution. [00165] The computer system 401 can include or be in communication with an electronic display 435 that comprises a user interface (UI) 440 for providing, for example, parameters for producing the slurry and/or applying the slurry to a substrate. Examples of UTs include, without limitation, a graphical user interface (GUI) and web-based user interface.

[00166] Methods and systems of the present disclosure can be implemented by way of one or more algorithms. An algorithm can be implemented by way of software upon execution by the central processing unit 405. The algorithm can, for example, regulate the mixing shear rate of the slurry, the amount of each ingredient added to the slurry mixture, and the order in which the ingredients are added to the slurry mixture. As another example, the algorithm can regulate the speed at which the slurry is applied to the substrate and the number of coatings of slurry applied to the substrate.

EXAMPLES

Example 1

[00167] In an example, a slurry is formed by addition to a mixing chamber while mixing a resulting solution. The amount of water added to the slurry is varied to form a number of slurries, and the resulting effect on properties of the slurries is recorded. Next, the slurry is applied to a substrate via a roll coating process. The slurry is then annealed at about 200 °C for about 2 hours. The slurry is then dried to completeness from about 2 hours to about 100 hours or longer. The atmosphere near the chromized article’s surface may be below about -20 °F dew point.

Example 2

[00168] In another example, a substrate is heated at a rate of about 10 °C/min to about 500 °C. The temperature is held constant for about 2 hours, during which time a metal-containing layer is deposited adjacent the substrate. The substrate is then heated at a rate of about 10 °C/min to about 950 °C. The temperature is held constant during the annealing process. After about 30 hours, the substrate is cooled at a rate of approximately about 5 °C/min to room temperature. A flow of argon is constant during the entire process.

Example 3

[00169] In another example, a substrate undergoes a thermal cycle protocol. A substrate is heated at a rate of about 10 °C/min to about 500 °C. The temperature is held constant for about 2 hours, during which time a metal-containing layer is deposited adjacent to the substrate. The substrate is then heated at a rate of about 10 °C/min to about 925 °C, and the temperature is held constant for about 30 minutes. The substrate is cooled at a rate of about 5 °C/min to about 500 °C, where the temperature is held constant for about 30 minutes. The substrate is heated again, at a rate of about 5 °C/min to about 925 °C, held at a constant temperature for about 30 minutes, then cooled at a rate of about 5 °C/min to about 500 °C and held constant for about 30 minutes. The substrate is heated and cooled one more time in another cycle. The substrate is heated to about 925 °C, then the substrate is cooled at a rate of approximately about 5 °C/min to room temperature. A flow of argon is constant during the entire process.

Example 4

[00170] In another example, substrates were provided, comprising carbon, silicon, manganese, titanium, vanadium, aluminum, and nitrogen. In an example, substrates have the following components, in wt %:

Example 5

[00171] In another example, substrates were provided, comprising carbon, silicon, manganese, titanium, vanadium, aluminum, and nitrogen. In an example, substrates have the following components, in wt %:

Substrate MC-25 had about 0.089 wt% niobium. The resulting alloy layer had little observed grain boundary precipitation, as illustrated in FIG. 3. Fewer formation of pores were observed with this alloy layer. This stainless steel alloy layer had improved corrosion resistance, a desired effect of the substrate.

Example 6

[00172] In another example, substrates were formed and exhibited the following properties:

Example 7

[00173] In another example, substrates were formed and exhibited the following properties:

C-25 C Mn P S Si Cu Ni Cr Mo

[00174] The niobium weight percent of the alloy was calculated as:

Nb wt% = (0.017- (Ti wt% - 3.42*N wt% - 1.49*S wt% - 4*C wt% ))/0.516

[00175] The substrate chemistry was selected such that it has a calculated stabilization of

0.017 or greater, wherein stabilization was calculated as:

Stabilization = Ti wt% - 3.42*N wt% - 1.49*S wt% - 4*C wt% + 0.516*Nb wt%.

Example 8

[00176] In another example, substrates were formed and exhibited the following compositions of constituent metals and other elements, as measured in wt %:

Example 9 [00177] In another example, the substrates listed in Example 8 were thermo-mechanically tested to determine their r-values. The test results are as follows:

Example 10

[00178] In another example, a slurry suspension is created by mixing MgCriCh powder and MgCh powder together in water. The MgCriCh powder and MgCh powder are both screened to have a particle size between about 0.1 and 10 pm. The dry weight percentages of MgCriCh powder and MgCh powder are about 95% and 5% respectively. Four hours after mixing the MgCr ₂ 0 ₄ powder and MgCh powder, aluminum powder is added to the suspension. The aluminum powder has been sieved such that it passes through a 325 mesh screen. The aluminum is mixed into the slurry powder such that it has an atomic ratio of about 1.0 to oxide powder. The slurry mixture containing the aluminum powder is immediately roll-coated on to the surface of a metal sheet. The substrate is then heated at a rate of about 10 °C/min to about 950 °C. The temperature is held constant during the annealing process. After about 30 hours, the substrate is cooled at a rate of approximately 5 °C/min to room temperature. A flow of argon is constant during the entire process. After annealing, the metal substrate undergoes a cleaning process to remove AI2O3 from the substrate surface.

Example 11 [00179] In another example, substrates were composed to exhibit a higher yield strength by as much as 80%, and a higher tensile strength by as much as 50%. In some cases, substrates were formed and exhibited the following compositions of constituent metals and other elements, as measured in wt %:

Example 12

[00180] In another example, the substrates listed in Example 11 were thermo-mechanically tested to determine their Ti/Nb stability, yield strength, ultimate tensile strength and elongation. The test results are as follows:

[00181] Materials, devices, systems and methods herein, including material compositions (e.g., material layers), can be combined with or modified by other materials, devices, systems and methods, including material compositions, such as, for example, those described in U.S. Patent Publication No. 2013/0171471; U.S. Patent Publication No. 2013/0309410; U.S. Patent Publication No. 2013/0252022; U.S. Patent Publication No. 2015/0167131; U.S. Patent

Publication No. 2015/0345041; and Patent Cooperation Treaty Application No.

PCT/US2016/017155, each of which is incorporated herein by reference in its entirety.

[00182] While preferred embodiments of the present invention have been shown and described herein, it will be obvious to those skilled in the art that such embodiments are provided by way of example only. It is not intended that the invention be limited by the specific examples provided within the specification. While the invention has been described with reference to the aforementioned specification, the descriptions and illustrations of the embodiments herein are not meant to be construed in a limiting sense. Numerous variations, changes, and substitutions will now occur to those skilled in the art without departing from the invention. Furthermore, it shall be understood that all aspects of the invention are not limited to the specific depictions, configurations or relative proportions set forth herein which depend upon a variety of conditions and variables. It should be understood that various alternatives to the embodiments of the invention described herein may be employed in practicing the invention. It is therefore contemplated that the invention shall also cover any such alternatives, modifications, variations or equivalents. It is intended that the following claims define the scope of the invention and that methods and structures within the scope of these claims and their equivalents be covered thereby.