CN113748228A

CN113748228A - Method and system for coating a steel substrate

Info

Publication number: CN113748228A
Application number: CN202080028565.4A
Authority: CN
Inventors: 扎卡里·M·戴特威勒; 亚当·G·托马斯; 特拉维斯·W·肖
Original assignee: Sherwell Public Co ltd
Current assignee: Sherwell Public Co ltd
Priority date: 2019-02-14
Filing date: 2020-02-14
Publication date: 2021-12-03
Also published as: TW202045746A; EP3924533A4; EP3924533A1; JP2022520117A; WO2020168163A1

Abstract

The present invention provides methods and systems for depositing a metal layer near or on a substrate. A substrate may be provided. The substrate can be contacted with a slurry comprising a metal oxide, a metal reducing agent, and a metal transport activator to provide a metal-containing layer adjacent to the substrate. The substrate and the at least one metal-containing layer can be annealed such that the metal oxide and the metal transport activator undergo a metallothermic reduction reaction to produce the at least one metal-containing layer and water. The water may be reduced by a metal reducing agent.

Description

Method and system for coating a steel substrate

Cross referencing

This application claims benefit from united states provisional application number 62/805729 filed on day 14, 2, 2019 and united states provisional application number 62/873640 filed on day 12, 7, 2019, which are incorporated herein by reference.

Background

The steel may be an alloy of iron and other elements, including carbon. When carbon is the main alloying element, it is present in the steel in an amount of about 0.002% to 2.1% by weight. The following elements may be present in the steel but are not limited to: carbon, manganese, phosphorus, sulfur, silicon, oxygen, nitrogen, and aluminum. Alloying elements added to alter the properties of the steel may include, but are not limited to: manganese, nickel, chromium, molybdenum, boron, titanium, vanadium and niobium.

Stainless steel may be a material that is not easily corroded, rusted (or oxidized), or contaminated by water. Stainless steel may be of various grades and surface finishes to suit a particular environment. Stainless steel may be used where both the properties and corrosion resistance of the steel are advantageous.

Disclosure of Invention

The present invention provides systems and methods for depositing a metal layer near 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 smoothness damping steel. Such substrates may 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. The system and substrate can produce a desired microstructure.

In one aspect, the present invention provides a method for forming at least one metal layer adjacent to a substrate, comprising contacting the substrate with a slurry comprising a metal oxide, a metal reducing agent, and a metal transport activator to provide a metal-containing layer adjacent to the substrate; and annealing the substrate and the at least one metal-containing layer such that the metal oxide and the metal transport activator undergo a metallothermic reduction reaction to produce the at least one metal layer and water, wherein the water is reduced by the metal reducing agent.

In some embodiments, the grain size of the at least one metal layer is about ASTM000 to ASTM 30.

In some embodiments, the substrate comprises at least one of the following (i) to (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium. In some embodiments, the substrate comprises at least two of the following (i) to (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium. In some embodiments, the substrate comprises at least three of the following (i) to (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium. In some embodiments, the substrate comprises at least four of the following (i) to (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium. In some embodiments, the substrate comprises: (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium.

In some embodiments, the metal layer is formed at an annealing temperature of about 0 ℃ to 1000 ℃. In some embodiments, the metal layer is formed in an annealing atmosphere having a humidity level below about 10 torr. In some embodiments, the annealing comprises heating the substrate at a rate of at least about 0.1 ℃/sec. In certain embodiments, the annealing is performed at a temperature greater than about 500 ℃. In some embodiments, the method further comprises cooling the substrate after the annealing.

In some embodiments, during the annealing, the substrate transforms from ferritic to austenitic. In some embodiments, the temperature of the annealing is determined by the transformation temperature of ferrite to austenite. In some embodiments, the addition of at least one austenite stabilizer may lower the transformation temperature.

In some embodiments, the metal transport activator comprises a halide species, a metal sulfide species, or a gas species. In some embodiments, the metal transport activator comprises hydrogen. In some embodiments, the metal transport activator comprises a material selected from the group consisting of: magnesium chloride (MgCl)₂) Iron (II) chloride (FeCl)₂) Calcium chloride (CaCl)₂) Zirconium (IV) chloride (ZrCl)₄) Titanium (IV) chloride (TiCl)₄) Niobium (V) chloride (NbCl)₅) Titanium (III) chloride (TiCl)₃) Silicon tetrachloride (SiCl)₄) Vanadium (III) chloride (VCl)₃) Chromium (III) chloride (CrCl)₃) Trichlorosilane (SiHCl)₃) Manganese (II) chloride (MnCl)₂) Chromium (II) chloride (CrCl)₂) Cobalt (II) chloride (CoCl)₂) Copper (II) chloride (CuCl)₂) Nickel (II) chloride (NiCl)₂) Vanadium (II) chloride (VCl)₂) Ammonium chloride (NH)₄Cl), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), bisIron sulfide (FeS)₂) Chromium sulfide (CrS), iron sulfide (FeS), copper sulfide (CuS), nickel sulfide (NiS), and combinations thereof.

In some embodiments, the method further comprises drying the substrate after the annealing.

In one aspect, the invention provides a steel composition comprising a constituent metal selected from the group consisting of i) and ii) below: i) greater than about 0.2 wt% titanium; and greater than about 0.8 wt% manganese, wherein the steel composition has a measured plastic strain ratio in excess of 1.8. In some embodiments, the steel composition has a measured plastic strain ratio in excess of 2.

In some embodiments, the steel composition has been annealed at a temperature of about 750 ℃ to about 1100 ℃. In some embodiments, the steel composition transforms from ferritic to austenitic during the annealing. In some embodiments, the steel composition has a grain size of about ASTM000 to ASTM 30. In some embodiments, the steel composition comprises greater than about 0.2 wt% titanium, and two or more constituent elements selected from the following i) through iii): i) greater than about 0.01 wt% carbon; ii) greater than about 0.02 wt% aluminum; and iii) not more than about 0.004 wt% sulfur, and iv) less than about 0.02 wt% niobium. In some embodiments, the steel composition comprises greater than about 0.8 wt% manganese, and two or more constituent elements selected from the following i) through iii): i) less than about 0.01 wt% carbon; ii) less than about 0.02 wt% aluminum; and iii) greater than about 0.004 wt% sulfur; and iv) greater than about 0.02 wt% niobium.

In another aspect, the present disclosure provides a composition for forming at least one metal layer adjacent to a substrate, the composition comprising a slurry comprising a metal oxide, a metal reducing agent, and a metal transport activator, wherein the slurry is configured to provide a metal-containing layer adjacent to the substrate, wherein the metal oxide and the metal transport activator are configured to undergo a metallothermic reduction reaction to produce the at least one metal layer and water.

In some embodiments, the metal oxide is selected from Cr₂O₃、TiO₂、FeCr₂O₄、SiO₂、Ta₂O₅And MgCr₂O₄The group consisting of.

In some embodiments, the metallic reducing 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.

In some embodiments, the metal transport activator comprises a halide species, a metal sulfide species, or a gas species. In some embodiments, the metal transport activator comprises hydrogen. In some embodiments, the metal transport activator comprises a material selected from the group consisting of: magnesium chloride (MgCl)₂) Iron (II) chloride (FeCl)₂) Calcium chloride (CaCl)₂) Zirconium (IV) chloride (ZrCl)₄) Titanium (IV) chloride (TiCl)₄) Niobium (V) chloride (NbCl)₅) Titanium (III) chloride (TiCl)₃) Silicon tetrachloride (SiCl)₄) Vanadium (III) chloride (VCl)₃) Chromium (III) chloride (CrCl)₃) Trichlorosilane (SiHCl)₃) Manganese (II) chloride (MnCl)₂) Chromium (II) chloride (CrCl)₂) Cobalt (II) chloride (CoCl)₂) Copper (II) chloride (CuCl)₂) Nickel (II) chloride (NiCl)₂) Vanadium (II) chloride (VCl)₂) Ammonium chloride (NH)₄Cl), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), and iron disulfide (FeS)₂) Chromium sulfide (CrS), iron sulfide (FeS), copper sulfide (CuS), nickel sulfide (NiS), and combinations thereof.

In some embodiments, the composition further comprises a solvent. In some embodiments, the solvent comprises water. In some embodiments, the solvent comprises an organic.

Another aspect of the invention provides a non-transitory computer readable medium containing machine executable code which, when executed by one or more computer processors, performs any of the methods described above or elsewhere herein.

Another aspect of the invention provides a system that includes one or more computer processors and computer memory coupled thereto. The computer memory includes machine executable code that, when executed by one or more computer processors, performs any of the methods described above or elsewhere herein.

Other aspects and advantages of the present invention will become apparent to those skilled in the art from the following detailed description, wherein only exemplary embodiments of the invention are shown and described. As will be realized, the invention is capable of other and different embodiments and its several details are capable of modifications in various obvious respects, all without departing from the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.

Is incorporated by reference

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.

Drawings

The novel features believed characteristic 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 of which:

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

FIG. 2 shows a steel substrate after application of a metal layer;

FIG. 3 shows a steel substrate after application of a metal layer; and

FIG. 4 schematically illustrates a computer control system programmed or otherwise configured to implement the methods provided by the present invention.

Detailed Description

While various 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. Numerous variations, changes, and substitutions will occur to those skilled in the art without departing from the invention herein. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.

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 form of a liquid phase. The sauce may have one or more liquid phases and one or more solid phases.

The term "adjacent" or "adjacent to … …" as used herein generally refers to "adjacent", "contiguous", "in contact with … …", and "proximate". In some cases, the adjacency may be "above" or "below". The first layer adjacent to the second layer may be in direct contact with the second layer, or there may be one or more intermediate layers between the first and second layers.

The terms "at least," "greater than," or "greater than or equal to" when preceded by the first of two or more numerical ranges, are applicable to each of the numerical ranges. 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.

The terms "not greater than," "less than," or "less than or equal to" when preceded by the first of two or more numerical values in a series, apply to each numerical value in the series. 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.

The present invention provides a component, article or object (e.g., a sheet, tube or wire) coated with one or more layers of metal. The member may be at least a part of the object or may be the entire object. The metal layer may comprise one or more metals. In some cases, the substrate may be coated with a metal layer. The coating may include an alloying agent with at least one elemental metal. When the substrate is coated with a slurry of an alloying agent comprising at least one elemental metal, a slurry coated substrate can be formed. The substrate coated with the alloying agent may be subjected to annealing conditions to produce a metal layer adjacent the substrate. The metal layer may be coupled to the substrate by means of a diffusion layer between the metal layer and the substrate.

The substrate can produce an alloy layer greater than 50 microns while still retaining fine grains (>7ASTM grain size) in the substrate. The ratings listed above may not be standard ratings. The grade may be used for high temperature annealing or high temperature applications unrelated to metallization processes.

Substrate and paste

The invention provides a substrate and a method employing deposition of a metal layer in the vicinity of the substrate. Such substrates may 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 smoothness damping steel.

The substrate may be provided as a coil, coiled wire, pipe, tube, slab, mesh, dip-formed part, foil, plate, wire rope, rod, or threaded rod, wherein the thread pattern has been applied to any length or thickness of rod, sheet, or plane. For example, the sheet may have a thickness of between 0.001 inches and 1 inch.

The substrate can include elemental species that are transition metals, non-metallic elements, metal oxides, reduced metallic elements, metal halides, activators, metalloids, or combinations thereof (e.g., multiple elemental metals). The substrate may include a transition metal. The substrate may comprise a non-metallic element. The substrate may comprise a metalloid. The substrate may include 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. The substrate may contain an elemental species configured as a metal reducing agent. The metal reducing agent may include aluminum, titanium, zirconium, silicon, or magnesium. The substrate may contain a carrier solvent, for example, water, isopropyl alcohol, or methyl ethyl ketone.

The substrate may comprise a metal such as iron, copper, aluminum, or any combination thereof. The substrate may comprise an alloy of a metal and/or a non-metal. The alloy may contain impurities. The substrate may comprise steel. The substrate may be a steel substrate. The substrate may comprise a ceramic. The substrate may be free of free carbon. The substrate may be made of a molten phase. The substrate may be in a cold reduced state, an all hard state (e.g., not subjected to an annealing step after cold reduction), or a hot rolled pickled state.

The substrate may comprise a metal oxide. The metal oxide may include, but is not limited to, Al₂O₃、MgO、CaO、Cr₂O₃、TiO₂、FeCr₂O₄、SiO₂、Ta₂O₅Or MgCr₂O₄Or a combination thereof. The metal oxide may be incorporated directly into the substrate. Metal oxides can be formed in the substrate by a metallothermic reduction reaction between the elemental metal and the less thermodynamically stable metal oxide. Suitable pairs of elemental metal and thermodynamically less stable metal oxide may be selected from pairs whose gibbs free energy of formation is reduced by oxidation of the elemental metal by the metal oxide. The metallothermic reduction reaction may occur spontaneously. The metallothermic reduction reaction may occur in the presence of a metal transport activator (e.g., halide, metal sulfide, or hydrogen). The metal oxide may comprise a powder.

The powder (e.g., comprising a metal, metal oxide, metal halide, or other substrate component) may comprise individual particles having a particle size (e.g., average particle size) of about 0.01 micrometers (μm) to 1 mm. The powder may have an average particle size of at least about 0.01 μm, 0.1 μm, 1 μm, 20 μm, 30 μm, 50 μm, 100 μm, 250 μm, 500 μm, or about 1 mm. The average particle size of the powder may be no more than about 1mm, 500 μm, 250 μm, 100 μm, 50 μm, 30 μm, 20 μm, 10 μm, 1 μm, 0.1 μm, or about 0.01 μm. The powder may have an average particle size of about 0.01 to 0.1 μm, 0.01 to 1 μm, 0.01 to 20 μm, 0.01 to 30 μm, 0.01 to 50 μm, 0.01 to 100 μm, 0.01 to 250 μm, 0.01 to 500 μm, 0.01 to 1mm, 0.1 to 1 μm, 0.1 to 20 μm, 0.1 to 30 μm, 0.1 to 50 μm, 0.1 to 100 μm, 0.1 to 250 μm, 0.1 to 500 μm, 0.1 to 1 μm, 1 to 20 μm, 1 to 30 μm, 1 to 50 μm, 1 to 100 μm, 1 to 250 μm, 1 to 1mm, 1 to 20 μm, 1 to 30 μm, 1 to 10 μm, 1 to 100 μm, 1 to 250 μm, 1 to 10 mm, 1 to 100 μm, or more, or less, or more, one or more, one or more, one or more, one or more, 250 μm to 500 μm, 250 μm to 1mm, 500 μm to 1 mm. The powder may have individual particles with an average particle size of at least about 0.01 μm, 0.1 μm, 1 μm, 20 μm, 30 μm, 50 μm, 100 μm, 250 μm, 500 μm, lmm, or greater. The powder can have individual particles up to about 1 millimeter (mm), 500 μm, 250 μm, 100 μm, 50 μm, 30 μm, 20 μm, 1 μm, 0.1 μm, or 0.01 μm or less in diameter. The powder may include particles that pass through a screen having a mesh size of at least 325 or less. A powder comprising a metal, metal oxide, metal halide, or other substrate component may comprise particles that pass through a screen having a mesh size of at least about 18, 20, 25, 30, 35, 40, 45, 50, 60, 65, 80, 100, 115, 150, 170, 200, 250, 270, or at least about 400 or more mesh size.

The slurry mixture can comprise a metal oxide that comprises about 30 wt% (weight percent), 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. The slurry mixture can comprise a metal oxide that comprises 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. The slurry mixture can include a metal oxide that does not exceed 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% of the total weight of the slurry, or that does not exceed about 30 wt% or less of the total weight of the slurry. The slurry mixture may comprise about 30 wt% to about 95 wt% of the metal oxide, based on the total weight of the slurry. The metal oxide may comprise from about 1 wt% to about 95 wt%, from about 1 wt% to about 85 wt%, from about 1 wt% to about 75 wt%, from about 1 wt% to about 60 wt%, from about 1 wt% to about 50 wt%, from about 1 wt% to about 40 wt%, from about 1 wt% to about 30 wt%, from about 1 wt% to about 20 wt%, from about 1 wt% to about 10 wt%, from about 5 wt% to about 95 wt%, from about 5 wt% to about 85 wt%, from about 5 wt% to about 75 wt%, from about 5 wt% to about 60 wt%, from about 5 wt% to about 50 wt%, from about 5 wt% to about 40 wt%, from about 5 wt% to about 30 wt%, from about 5 wt% to about 20 wt%, from about 5 wt% to about 10 wt%, from about 10 wt% to about 95 wt%, from about 10 wt% to about 85 wt%, from about 10 wt% to about 75 wt%, from about 10 wt% to about 60 wt%, from about 10 wt% to about 50 wt%, from about 10 wt% to about 40 wt%, from about 10 wt% to about 95 wt%, from about 10 wt% to about 50 wt%, or from about 10 wt% of the total weight of the slurry, About 10 wt% to about 30 wt%, about 10 wt% to about 20 wt%, about 20 wt% to about 95 wt%, about 20 wt% to about 85 wt%, about 20 wt% to about 75 wt%, about 20 wt% to about 60 wt%, about 20 wt% to about 50 wt%, about 20 wt% to about 40 wt%, about 20 wt% to about 30 wt%, about 30 wt% to about 85 wt%, about 30 wt% to about 75 wt%, about 30 wt% to about 60 wt%, about 30 wt% to about 50 wt%, about 30 wt% to about 40 wt%, about 1 wt% to about 95 wt%, about 40 wt% to about 85 wt%, about 40 wt% to about 75 wt%, about 40 wt% to about 60 wt%, about 40 wt% to about 50 wt%, about 50 wt% to about 95 wt%, about 50 wt% to about 85 wt%, about 50 wt% to about 75 wt%, or about 50 wt% to about 60 wt%. The relative purity of the metal oxide or reduced metal may be selected. The metal oxide or reduced metal can include 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. The metal oxide or reduced metal can include 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% by weight or less, on a weight basis.

The atomic ratio of the reducing metal to the oxide source can be about 0.6 to 2.0. The reduced metal to oxide source can comprise an atomic ratio of about 0.01 to 10.0, about 0.01 to 1.0, about 0.01 to 1.5, about 0.01 to 3.0, about 0.01 to 4.0, about 0.01 to 5.0, about 0.1 to 1.0, about 0.1 to 1.5, about 0.1 to 3.0, about 0.1 to 4.0, about 0.1 to 5.0, about 0.1 to 10.0, about 0.5 to 1.0, about 0.5 to 1.5, about 0.5 to 3.0, about 0.5 to 4.0, about 0.5 to 5.0 atomic ratio, about 0.5 to 10.0 atomic ratio, about 1.0 to 1.5 atomic ratio, about 1.0 to 3.0 atomic ratio, about 1.0 to 4.0 atomic ratio, about 1.0 to 5.0 atomic ratio, about 1.0 to 10.0 atomic ratio, about 2.0 to 3.0 atomic ratio, about 2.0 to 4.0 atomic ratio, about 2.0 to 5.0 atomic ratio, about 2.0 to 10.0 atomic ratio, about 3.0 to 4.0 atomic ratio, about 4.0 to 5.0 atomic ratio, about 4.0 to 10.0 atomic ratio, or about 5.0 to 10.0 atomic ratio.

The metal substrate may comprise a metal transport activator component. The metal transport activator can 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 can 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. The metal transport activator can 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 wt% to 1 wt%, about 0.001 wt% to 2 wt%, about 0.001 wt% to 3 wt%, about 0.001 wt% to 4 wt%, about 0.001 wt% to 5 wt%, about 0.001 wt% to 10 wt%, about 0.001 wt% to 15 wt%, about 0.001 wt% to 20 wt%, about 0.001 wt% to 30 wt%, about 0.001 wt% to 50 wt%, about 0.01 wt% to 1 wt%, about 0.01 wt% to 2 wt%, about 0.01 wt% to 3 wt%, about 0.01 wt% to 4 wt%, about 0.01 wt% to 10 wt%, about 0.01 wt% to 15 wt%, about 0.01 wt% to 20 wt%, about 0.01 wt% to 30 wt%, about 0.01 wt% to 50 wt%, about 0.1 wt% to 1 wt%, about 0.1 wt% to 2 wt%, about 0.1 wt% to 1 wt%, about 0.1 wt%, about 1 wt% to 1 wt%, about 1 wt% to 1 wt%, about 0.1 wt%, about 1 wt%, about 0.1 wt% to 1 wt%, about 1 wt% to 1 wt%, about 1 wt% to 1 wt%, about 1 wt% to 1 wt%, about 0.1 wt%, about 1 wt%, about 0.1 wt%, about 0., About 0.1 wt% to 50 wt%, about 1.0 wt% to 2 wt%, about 1.0 wt% to 3 wt%, about 1.0 wt% to 4 wt%, about 1.0 wt% to 10 wt%, about 1.0 wt% to 15 wt%, about 1.0 wt% to 20 wt%, about 1.0 wt% to 30 wt%, about 1.0 wt% to 50 wt%, or about 10 wt% to 50 wt%.

The present invention provides a substrate coated with one or more metal layers. In some cases, the substrate may be coated with at least one metal layer. The substrate may be coated with about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more metal layers. The substrate may be coated with at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more metal layers. The substrate may be coated with no more than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or 1 metal layer. The coating may include an alloying agent with at least one elemental metal. The metal layer may be coupled to the substrate by means of a diffusion layer between the metal layer and the substrate.

The metal layer can 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. The metal layer can 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 more than about 1 nanometer or less. The metal layer may have a thickness greater than a monoatomic layer. The thickness may be a multilayer film.

The substrate may contain 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. The substrate may include 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. The substrate can 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 fewer elemental species. The substrate may comprise at least two of the following elements: carbon, manganese, silicon, vanadium and titanium. The substrate may comprise at least three of the following elements: carbon, manganese, silicon, vanadium and titanium. The substrate may comprise at least four of the following elements: carbon, manganese, silicon, vanadium and titanium.

The substrate may comprise a plurality of elements. The substrate can comprise 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%, 1.5 wt%, 1.6 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 carbon (C). The substrate can comprise 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 carbon.

The substrate can include 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 manganese (Mn). The substrate can comprise 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% manganese, or less than about 0.0001 wt% manganese or less.

The substrate can comprise 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 w%, 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 niobium (Nb). The substrate can comprise 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. Niobium can be added to the substrate such that the substrate can comprise 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 niobium. Without wishing to be bound by theory, niobium in the substrate may prevent chromium depletion in the substrate.

The matrix may comprise 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 vanadium (V). The substrate can comprise 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 vanadium.

The substrate may comprise 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 titanium (Ti). The substrate can comprise 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 titanium. In some cases, the substrate may comprise at least about 0.015 wt% titanium.

The substrate can comprise 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% or more nitrogen (N). The substrate can comprise 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% nitrogen or less.

The substrate can comprise 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 phosphorus (P). The substrate can comprise 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 phosphorus.

The substrate can comprise 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 sulfur (S). The substrate can comprise 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 sulfur.

The substrate can comprise 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 aluminum (Al). The substrate can comprise 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 aluminum.

The substrate may comprise 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 40 wt% or more copper (Cu). The substrate can comprise 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 copper.

The substrate may comprise 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 nickel (Ni). The substrate can comprise 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 nickel.

The matrix may comprise 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 chromium (Cr). The substrate can comprise 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% chromium or less.

The substrate can comprise 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 molybdenum (Mo). The substrate can comprise 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% molybdenum.

The substrate can comprise 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 tin (Sn). The substrate can comprise 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 tin.

The substrate may comprise 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 boron (B). The substrate can comprise 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 boron.

The substrate may comprise 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 calcium (Ca). The substrate can comprise 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 calcium.

The substrate may comprise more 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 more than 40 wt% or more arsenic (As). The substrate can comprise 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% arsenic.

The substrate may comprise 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 cobalt (Co). The substrate can comprise 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% cobalt or less.

The substrate can comprise 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 lead (Pb). The substrate can comprise 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 lead.

The substrate can comprise 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 antimony (Sb). The substrate can comprise 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 antimony.

The substrate can comprise 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 tantalum (Ta). The substrate can comprise 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 tantalum.

The substrate can comprise 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 tungsten (W). The substrate can comprise 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 tungsten.

The substrate can comprise 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 zinc (Zn). The substrate can comprise 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 zinc.

The substrate can comprise 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 zirconium (Zr). The substrate can comprise 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 zirconium.

The substrate may comprise 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 silicon (Si). The substrate can comprise 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%, 0.3 wt%, 0.2 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 silicon.

During the formation of the substrate, free interstitial atoms such as nitrogen, carbon and sulfur may be present. Niobium in the substrate may combine with these free interstitial atoms (e.g., nitrogen, carbon, and sulfur) in the substrate. The addition of niobium may prevent grain boundary precipitates, for example, chromium grain boundary precipitates. The reduction of grain boundary precipitates may result in an increase in corrosion performance, which may be a desired property of the substrate. Fig. 3 shows the steel substrate after coating with a metal layer, wherein no grain boundary chromium precipitates are observed.

The weight percentage of chromium on the substrate surface can be measured. The chromium weight percent may be based on the coated substrate or the uncoated substrate. In some cases, the chromium weight percent of the 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 percent of the 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 percent of the substrate may be about 16%, 17%, 18%, 19%, 20%, 21%, 22%, or 23%. The chromium weight percent of the coated substrate may be greater than, about equal to, or less than the chromium weight percent of the uncoated substrate.

The substrate may be purchased from a supplier. The metal-containing layer may be applied to the substrate on the same day as the substrate is prepared. The preparation time of the substrate may exceed about 2 days, 3 days, 1 week, 1 month, or 1 year or more before the metal-containing layer is applied. The substrate may be prepared less than about 1 year, 1 month, 1 week, 3 days, or less than 2 days prior to applying the metal-containing layer. The 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 the metal layer being added to the substrate. The 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, 4 hours, 3 hours, 2 hours, 1 hour, 30 minutes, 10 minutes, 5 minutes, 1 minute, 30 seconds, or less of the metal layer being added to the substrate. In some examples, the reduced metal may be 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 hour, 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 the metal layer to the substrate.

The invention provides a method of forming a metal layer adjacent to a substrate. The metal layer may be formed by applying a paste near the substrate. The deposition of the slurry adjacent the substrate can form a metal-containing layer adjacent the substrate. In some cases, the slurry comprises an alloying agent, a metal transport activator, and a solvent, wherein the alloying agent comprises the metal.

In some cases, the metal-containing layer comprises carbon. In some cases, the metal-containing layer includes 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.

The slurry may comprise a metal oxide. The metal oxide may include, but is not limited to, Al₂O₃、MgO、CaO、Cr₂O₃、TiO₂、FeCr₂O₄、SiO₂、Ta₂O₅Or MgCr₂O₄Or a combination thereof. The metal oxide may be introduced directly into the slurry. The metal oxide may be formed in the slurry by a metallothermic reduction reaction between the elemental metal and the thermodynamically less stable metal oxide. Suitable counterparts of the elemental metal and the thermodynamically less stable metal oxide may be selected from those whose gibbs free energy of formation is reduced by oxidation of the elemental metal by the metal oxide. The metallothermic reduction reaction may occur spontaneously. The metallothermic reduction reaction may occur in the presence of a metal transport activator such as a halide, metal sulfide or a gaseous species. The metal oxide may comprise a powder.

The slurry may include a metal transport activator configured to transport the metal species from the slurry to the substrate surface. The metal transport activator may comprise halides, metal halides, sulfides or hydrogen. The metal transport activator may be introduced during slurry preparation, for example, by addition of one or more powders. Metal transport activity may be introduced from an external source after slurry formationThe oxidizing agent, for example, diffuses hydrogen into the slurry layer after application to the substrate. In some cases, the metal transport activator comprises 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 (MgCl)₂) Iron (II) chloride (FeCl)₂) Calcium chloride (CaCl)₂) Zirconium (IV) chloride (ZrCl)₄) Titanium (IV) chloride (TiCl)₄) Niobium (V) chloride (NbCl)₅) Titanium (III) chloride (TiCl)₃) Silicon tetrachloride (SiCl)₄) Vanadium (III) chloride (VCl)₃) Chromium (III) chloride (CrCl)₃) Trichlorosilane (SiHCl)₃) Manganese (II) chloride (MnCl)₂) Chromium (II) chloride (CrCl)₂) Cobalt (II) chloride (CoCl)₂) Copper (II) chloride (CuCl)₂) Nickel (II) chloride (NiCl)₂) Vanadium (II) chloride (VCl)₂) Ammonium chloride (NH)₄Cl), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), and iron disulfide (FeS)₂) 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 ferrous chloride tetrahydrate (FeCl)₂·4H₂O), ferrous chloride hexahydrate (Fe Cl)₂·6H₂O) and magnesium chloride hexahydrate (MgCl)₂·6H₂O). In some embodiments, the halide activator is hydrated. In some embodiments, the halide activator is selected from ferrous chloride tetrahydrate (FeCl)₂·6H₂O), ferrous chloride hexahydrate (FeCl)₂·6H₂O) and magnesium chloride hexahydrate (MgCl)₂·6H₂O)。

In some cases, the metal layer is formed adjacent to the substrate after the metal-containing layer is annealed to the substrate. In some cases, the metal layer includes carbon. In some cases, the metal layer includes 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 silicon iron (FeSi), ferrochrome (FeCr), chromium, and combinations thereof.

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

In some cases, the slurry comprises an inert material. The slurry may be formed by mixing the various ingredients in a mixing chamber (or vessel). The various ingredients may be mixed simultaneously or sequentially. For example, a solvent is provided in the chamber, and then the elemental species are added to the chamber. To prevent caking, a controlled amount of a dry ingredient may be added to the solvent. Some elemental metals may be in the form of a dry powder.

The blade for mixing the metal layer-containing components may be in the shape of a stirrer, fork or paddle. Multiple blades may be used to mix the slurry components. Each blade may have a different shape or the same shape. The dry ingredients may be added to the solvent in controlled amounts to prevent caking. High shear rates can be used to help control viscosity. In the slurry, the chromium particles may be larger in size than the other particles and may be suspended without adding high polymer addition.

The characteristics of the slurry may be a function of one or more parameters used to form the slurry, maintain the slurry, or deposit the slurry. These properties may include viscosity, shear thinning index, and yield stress. These properties include reynolds number, viscosity, pH, and slurry constituent concentration. Parameters that affect the properties of the slurry may include water content, elemental type and content, temperature, shear rate, and mixing time.

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 may 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 about 10 to 60 seconds by heating or vacuum drying at about 90 ℃ to 175 ℃. In operation 140, the web or substrate material is rolled or otherwise prepared for heat treatment. In operation 150, the metal layer is annealed near the substrate.

Fig. 2 shows an image of a steel substrate after coating with a metal layer. The particle size and coefficient of variation may be calculated according to the American International test and materials Standard (ASTM) standard.

The paste may exhibit thixotropic properties, wherein the paste exhibits a decrease in viscosity when subjected to shear strain. The shear thinning index of the slurry may be between about 1 and about 8. To achieve the target viscosity, mixing may be performed at high shear rates. The shear rate may be about 1s^-1To about 10000s^-1(or Hz). The shear rate may be about 1s^-1About 10s^-1About 100s^-1About 1000s^-1About 5000s^-1Or about 10000s^-1. The shear rate may be at least about 1s^-1About 10s^-1About 100s^-1About 1000s^-1About 5000s^-1Or at least about 10000s^-1Or more. The shear rate may be less than about 10000s^-1、5000s^-1、1000s^-1，100s^-1、10s^-1Or less than about 1s^-1Or smaller.

The shear rate of the slurry can be measured on various instruments. For example, the shear rate can be measured on a TA Instruments DHR-2 rheometer. The shear rate of the slurry may vary depending on the instrument used to make the measurement.

Mixing may be performed for about 1 minute to 2 hours in order to achieve a target or predetermined viscosity. The mixing time may be less than about 30 minutes. The viscosity of the slurry may decrease as the slurry mixing time increases. The mixing time may correspond to the length of time it takes to homogenize the slurry.

The state of suitable mixing may be a state where the surface of the slurry is free from water. A suitable mixing regime may be one in which there is no solids in the bottom of the vessel. The color and texture of the slurry can appear uniform.

The desired viscosity of the metal-containing layer may be a viscosity suitable for roll coating. Pulp and its production processThe viscosity of the material may be about 1 centipoise (cP), 5cP, 10cP, 50cP, 100cP, 200cP, 500cP, 1000cP, 10000cP, 100000cP, 1000000cP, or about 5000000 cP. The viscosity of the slurry may be at least about 1cP, 5cP, 10cP, 50cP, 100cP, 200cP, 500cP, 1000cP, 10000cP, 100000cP, 1000000cP, or about 5000000 cP. The viscosity of the slurry may be no more than about 5000000cP, 1000000cP, 100000cP, 10000cP, 5000cP, 1000cP, 500cP, 200cP, 100cP, 50cP, 10cP, 5cP, or no more than about 1 cP. The viscosity of the slurry may be about lcP to 5000000 cP. The viscosity of the slurry may be about 1cP, about 5cP, about 10cP, about 50cP, about 100cP, about 200cP, about 500cP, about 1000cP, about 10000cP, about 100000cP, about 1000000cP, or about 5000000 cP. The viscosity of the slurry may be between about 1cP to 1000000cP or 100cP to 100000 cP. The viscosity of the slurry may depend on the shear rate. The viscosity of the slurry may be from about 200cP to about 10000cP, or from about 600cP to about 800 cP. In the presence of about 1000s^-1To about 1000000s^-1Application of shear rate the slurry may be between about 100cP and about 200cP in the shear window. 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 the 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 the slurry can be no greater than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or no greater than about 0.01 or less. The yield stress of the slurry can be about 0.0001 pascal (Pa), 0.001Pa, 0.01Pa, 0.1Pa, 0.2Pa, 0.3Pa, 0.4Pa, 0.5Pa, 0.6Pa, 0.7Pa, 0.8Pa, 0.9Pa, or about 1 Pa. The yield stress of the slurry can be at least about 0.0001 pascals (Pa), 0.001Pa, 0.01Pa, 0.1Pa, 0.2Pa, 0.3Pa, 0.4Pa, 0.5Pa, 0.6Pa, 0.7Pa, 0.8Pa, 0.9Pa, or at least about 1Pa or higher. The yield stress of the slurry can be no more than 1Pa, 0.9Pa, 0.8Pa, 0.7Pa, 0.6Pa, 0.5Pa, 0.4Pa, 0.3Pa, 0.2Pa, 0.1Pa, 0.01Pa, 0.001Pa, or no more than about 0.001Pa or less.

The settling rate of the slurry can be stable to separation or settling over a period of greater than about 1 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 can withstand without mixing before settling occurs or before the viscosity increases to a value unsuitable for roll coating. Similarly, the shelf life of the slurry may refer to the time the slurry can withstand without mixing before thickening to a degree that is not suitable for roll coating. However, even if the slurry settles and thickens, the slurry may be remixed to its initial viscosity. The thixotropic index of the slurry may be stable so that the slurry does not thicken to an undesirable level at dead spots in the roll-coating assembly pan.

The degree of hydrogen bonding can be controlled by adding acid to the slurry during mixing to control the viscosity of the slurry. In addition, an acid or base may be added to the slurry during mixing to control the pH level of the slurry. The pH of the slurry may be about 3, 4, 5, 6, 7, 8, 9, 10, 11, or about 12. The pH of the slurry may be at least about 3, 4, 5, 6, 7, 8, 9, 10, 11 or at least about 12 or higher. The pH level of the slurry can be no greater than about 12, 11, 10, 9, 8, 7, 6, 5, 4, or no greater than about 3 or less. The pH of the slurry may be from about 3 to about 12. The pH level of the slurry may be from about 5 to about 8. The pH of the slurry may be about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, or about 12. The pH of the slurry may vary as the slurry settles. Remixing the slurry after the slurry has settled may restore the pH of the slurry to the original pH level. Various levels of binders, e.g., metal acetates, may be added to the slurry to increase green strength in the slurry. The slurry may be free of binder. The slurry may include a metal transport activator configured to act as a binder.

The fluidity of the slurry can be measured by the tilt test. The tilt test may indicate yield stress and viscosity. Alternatively, the fluidity of the slurry can be measured using a rheometer.

The drying time of the slurry may be long enough to keep the slurry wet during the roll coating process until the slurry coating is applied to the substrate before drying. The slurry may not dry at room temperature. After heating the drying zone of the roll coating line for about 10 seconds, the slurry may dry out. The applied heat temperature may be around 120 ℃.

The specific gravity of the slurry may be about 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10g/cm³. The specific gravity of the slurry may be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9 or at least about 10g/cm³Or higher. The specific gravity of the slurry may be no more than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or no more than about 1g/cm³Or smaller. The green strength of the slurry is such that the slurry can withstand roll coating without damaging the slurry coated substrate. For example, a dry film of slurry dried after rolling in a drying oven near a spray booth may have a green strength that allows the film to withstand forces that bend the film twenty times in alternating positive and negative directions forming an arc of about 20 inches in diameter. The green strength of the slurry dry film may further allow the film to pass a tape test with a small amount of powder. The tape test may include contacting the tape with a surface of the coating material. Once the tape is removed from the surface of the coating material, it is clear enough to allow one to see any powder that adheres to the tape.

The slurry may be applied to the substrate prior to forming the metal layer on the substrate. The slurry may be applied to a substrate in a uniform thickness. The slurry may be applied at different thicknesses on the substrate. The average thickness of the applied slurry coating may be about 0.0001 inch, 0.0005 inch, 0.001 inch, 0.002 inch, 0.003 inch, 0.004 inch, 0.005 inch, 0.006 inch, 0.007 inch, 0.008 inch, 0.009 inch, 0.01 inch, 0.02 inch, 0.03 inch, 0.04 inch, 0.05 inch, 0.06 inch, 0.07 inch, 0.08 inch, 0.09 inch, 0.1 inch, 0.125 inch, 0.25 inch, 0.5 inch. The average thickness of the applied slurry coating can be at least about 0.0001 inch, 0.0005 inch, 0.001 inch, 0.002 inch, 0.003 inch, 0.004 inch, 0.005 inch, 0.006 inch, 0.007 inch, 0.008 inch, 0.009 inch, 0.01 inch, 0.02 inch, 0.03 inch, 0.04 inch, 0.05 inch, 0.06 inch, 0.07 inch, 0.08 inch, 0.09 inch, 0.1 inch, 0.125 inch, 0.25 inch, 0.5 inch or more. The average thickness of the applied slurry coating can be no more than about 0.5 inch, 0.25 inch, 0.125 inch, 0.1 inch, 0.09 inch, 0.08 inch, 0.07 inch, 0.06 inch, 0.05 inch, 0.04 inch, 0.03 inch, 0.02 inch, 0.01 inch, 0.009 inch, 0.008 inch, 0.007 inch, 0.006 inch, 0.005 inch, 0.004 inch, 0.003 inch, 0.002 inch, 0.001 inch, 0.0005 inch, 0.0001 inch, or less.

The slurry may be applied near one or more surfaces of a substrate having a particular thickness. The thickness of the applied slurry coating may be relatively uniform across the surface, or may vary. The thickness of the applied slurry coating may vary from one surface of the substrate to the other. The thickness of the applied slurry coating near the substrate can be measured at any time, including immediately after application, during drying, or after removal of all solvents. An applied slurry coating can be considered substantially uniform if at least 90%, 95%, 99% or more of the substrate surface has a slurry coating that does not deviate 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.

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

Depending on the concentration gradient, the elemental species in the slurry may diffuse into or enter the substrate. For example, the concentration of elemental species in the metal-containing layer may be highest at the substrate surface and may decrease according to a gradient along the depth of the substrate. The decrease in concentration may be linear, parabolic, gaussian, or any combination thereof. The concentration of the elemental species in the metal-containing layer may be selected based on the desired thickness of the alloy layer to be formed on the substrate.

The elemental species in the slurry may affect the adhesion of the metal-containing layer to the substrate. In addition, the elemental species may affect the viscosity of the metal layer-containing composition. In addition, the elemental species can affect the green strength of the metal-containing coated substrate. Green strength generally refers to the ability of the metal-containing layer coated substrate to withstand handling or machining before the metal-containing layer is fully cured. Thus, the elemental species may be selected based on a desired degree of adhesion of the metal-containing layer to the substrate, a desired viscosity of the metal-containing layer, and the ability of the elemental species to increase the green strength of the metal-containing layer coated substrate. In addition, some metal-containing halides may corrode parts of the roll coating assembly that apply the metal-containing layer to the substrate. Such corrosion may be undesirable. The elemental species may prevent formation of Kirkendall voids (Kirkendall void) at the boundary interface of the metal-containing layer and the substrate. Upon heating, the elemental species may decompose into oxides. Further, after annealing, the element species may become inert. The concentration of the various element species may vary.

The substrate may be pretreated prior to applying the slurry to the substrate. The substrate surface may be pretreated by using chemicals to improve the adhesion of the metal-containing layer to the substrate surface. Examples of such chemicals include chromates and phosphates.

The substrate surface may be free of process oxide. This can be achieved by conventional pickling. The substrate surface may be reasonably free of organic materials. After treatment with a commercially available cleaner, the substrate surface may be free of organic materials.

During the preparation of the substrate, the grain pinning particles on the substrate may be added, removed, or retained to control the grain size of the substrate. For example, grain pinning can be added to the substrate to keep the grain size small and form pinning sites. As another example, the grain pins may be trapped from the substrate to allow grain growth and allow for lamination of the motor. The grain nails may be insoluble at the annealing temperature.

Examples of grain pinning particles include intermetallics of aluminum, niobium, vanadium, nitrides, carbides, and any combination thereof. Non-limiting examples of the grain pinning particles include titanium nitride (TiN), titanium carbide (TiC), and aluminum nitride (AIN).

Formation of a metal layer adjacent to a substrate

The slurry may be applied or deposited near the substrate and the metal-containing layer formed near the surface. The metal-containing layer may be annealed to form a metal layer adjacent to the substrate. The slurry may be applied by: roll coating, dispensing, spin coating, slot coating, curtain coating, slide coating, extrusion coating, painting coating, spray painting coating, electrostatic machine coating, printing (e.g., two-dimensional printing, three-dimensional printing, screen printing, pattern printing), vapor deposition (e.g., chemical vapor deposition), electrochemical deposition, slurry deposition, dipping, spray coating, any combination thereof, or by any other suitable method.

The slurry may be applied by roll coating. The roll coating process may begin by providing a substrate (e.g., a steel substrate). Next, the wound substrate may be unwound. Next, the unwound steel substrate may be provided to a roll coater, which may be coated with a metal-containing layer. Next, the roll coater may be activated such that the roll coater coats the substrate with the metal-containing layer. The substrate may be fed through the roll coater in a plurality of cycles such that the metal-containing layer is applied to the substrate a plurality of times. Depending on the nature of the metal-containing layer, it may be desirable to apply multiple coatings on the substrate. Multiple metal-containing layers may be coated on the substrate to achieve the desired slurry thickness. Each of the plurality of coatings may use a different formulation or metal-containing layer. The metal-containing layer may be applied, for example, in a pattern on the substrate. The pattern may be in the form of, for example, a grid, stripes, dots, weld marks, or any combination thereof. Multiple coatings on the same substrate may form separate coatings on the substrate.

The slurry may be applied, deposited, or annealed near the substrate. The slurry may be deposited at a temperature of about 0 ℃, 25 ℃, 50 ℃, 75 ℃, 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃ or 1000 ℃. The slurry can be deposited at a temperature of at least about 0 ℃, 25 ℃, 50 ℃, 75 ℃, 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, or 1000 ℃ or more. The slurry can be deposited at a temperature of no more than about 1000 ℃, 900 ℃, 800 ℃, 700 ℃, 600 ℃, 500 ℃, 400 ℃, 300 ℃, 200 ℃, 100 ℃, 75 ℃, 50 ℃, 25 ℃ or no more than about 0 ℃ or less. The slurry may be deposited at a temperature of about 0 ℃ to 1000 ℃. The slurry may be deposited at a temperature of about 10 ℃ to 100 ℃. The slurry may be deposited at a temperature of about 100 ℃ to 500 ℃. The slurry may be deposited at a temperature of about 500 ℃ to 1000 ℃.

Deposition of the slurry on the substrate may occur in an atmosphere having a relative humidity of about 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or about 99%. Deposition of the slurry on the substrate may occur in an atmosphere having 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 the slurry on the substrate may occur in an atmosphere having a relative humidity 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 the slurry on the substrate may occur in an atmosphere having an absolute humidity level 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 higher. Deposition of the slurry on the substrate can occur in an atmosphere having an absolute humidity level 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 the metal-containing layer.

Deposition of the slurry on the substrate can occur in an atmosphere having an oxygen content 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 the slurry on the substrate may occur in an atmosphere having an oxygen content 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. The slurry may be dried on the substrate under ambient air conditions.

The annealing of the paste on the substrate can be performed in an atmosphere containing low oxygen, e.g., 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. The annealing of the paste on the substrate may be performed in an atmosphere having an oxygen content 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 higher.

Drying of the metal-containing layer may occur in an atmosphere having a hydrogen content greater than about 0.001 torr, 0.005 torr, 0.01 torr, 0.05 torr, or greater than or about 0.1 torr or greater. Drying of the metal-containing layer on the substrate can occur in an atmosphere having a hydrogen level of less than or about 0.1 torr, 0.05 torr, 0.01 torr, 0.005 torr, or 0.001 torr or less. The annealing of the metal-containing layer on the substrate can be carried out in an atmosphere of pure hydrogen, pure argon or a mixture of hydrogen and argon.

After applying the slurry to the substrate, the solvent in the metal-containing layer may be removed by heating, evaporation, vacuum, or any combination thereof. After removal of the solvent, the substrate may be crimped. After deposition and before annealing, the slurry coated substrate may be incubated or stored under vacuum or atmospheric conditions. This occurs prior to annealing and may help remove residual contaminants in the coating, such as residual solvents or adhesives from the coating process. The incubation time may be 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes. The incubation time 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 time 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 time may be the time between coating and annealing, or the length of time the coated article is transported to a thermal treatment facility or apparatus. For example, the incubation time may last 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 ℃, 75 ℃, 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃ or about 300 ℃. The incubation temperature can be at least about 50 ℃, 75 ℃, 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃ or at least about 300 ℃ or higher. The incubation temperature may be no more than about 300 ℃, 275 ℃, 250 ℃, 225 ℃, 200 ℃, 175 ℃, 150 ℃, 125 ℃, 100 ℃, 75 ℃ or no more than about 50 ℃ or less. The incubation temperature may be in the range of about 50 ℃ to about 300 ℃. For example, the incubation temperature can be greater than about 50 ℃, about 75 ℃, about 100 ℃, about 125 ℃, about 150 ℃, about 175 ℃, about 200 ℃, about 225 ℃, about 250 ℃, about 275 ℃, or about 300 ℃ or higher. After incubation and before annealing, the dry film of slurry on the substrate may be maintained under vacuum conditions. A drying step may be performed immediately after the roll coating process to dry the coating to the touch. Any time between roll coating and annealing, the coating may have absorbed water or other contaminants.

Spatially separated alloys can be deposited on a metal substrate surface using an alloying metal generated in situ from its metal oxide using a metallothermic reduction reaction. Metallothermic reduction reactions can occur when a thermodynamically less stable metal oxide is produced in the presence of a metal reducing agent (which forms a thermodynamically more stable metal oxide). The metallic reducing agent may comprise any element species including iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium, niobium, and combinations thereof.

In some embodiments, the metallothermic reduction reaction may be initiated or enhanced by a metal transport activator. The reduced metal compound may be selected such that its corresponding metal oxide has a relatively large gibbs free energy of formation, e.g., aluminum versus aluminum oxide. The reduced metal acts as an effective oxygen and water scavenger, thereby eliminating oxide species that would otherwise impede forward reaction of the metal oxide with the activator compound. Examples of the bulk metallothermic reduction reaction may include the reaction of chromium oxide with aluminum metal, such as:

1)Cr₂O₃+3H₂-->2Cr⁰+H₂O

2)2A1⁰+H₂O-->A1₂O₃+3H₂

wherein the reaction may be a source of depositing chromium in a metal layer on the substrate surface. The use of metal oxides as deposition source materials may avoid the use of additional inert powders in the reaction that act as a support for the metal layer and a spacer for the alloying metal powder during sintering. For example, the defect rate of the resulting metal layer may be reduced by including a secondary element powder or alloying a reducing element with a substance that raises the melting point of the reducing element above the temperature used for deposition. The metal oxide formed by the reaction of the metal reducing agent can be more easily removed by a post heat treatment cleaning process. The space-insulating alloy may include a layer of alloy metal on the net-shape portion, such as a metal tube, rod, wire, or other form of inner diameter.

The metal layer on the surface of the substrate may comprise a paste applied to the surface of the substrate. The slurry may comprise a metal oxide powder, a metal reducing agent, a metal halide precursor, or a solvent. The slurry comprising the metal oxide powder can be optimized for its chemical and rheological properties. Increased rheology control can provide a more uniform coating, including reducing unwanted rheological effects such as ribbing, stacking, or other defects; as well as increasing the surface coverage of the substrate surface and can result in an increase in metal utilization. The slurry composition can be tailored for use as a source for depositing a metal layer on a substrate surface based on at least the following characteristics: relative concentrations of components, particle size of components, pH, ionic strength, reduced settling, slurry yield strength, slurry viscosity, and any other characteristic that may affect slurry performance.

The metal oxide and reducing metal agent pair may be selected based on the large gibbs free energy of formation of the metallothermic reduction reaction between the metal oxide and the metal reducing agent. In some cases, the metal oxide and the reduced metal agent may undergo a spontaneous metallothermic reduction reaction. The Gibbs free energy of formation of the metallothermic reduction reaction is at least about-50 kJ, -100kJ, -150kJ, -200kJ, -250kJ, -300kJ, -350kJ, -400kJ, -450kJ, -500kJ, -550kJ, -600kJ, -650kJ, -700kJ, -750kJ, -800kJ, -850kJ, -900kJ, -950kJ, -1000kJ, or greater than-1000 kJ. Gibbs formation free energy of metallothermic reduction reaction does not exceed about-1000 kJ, -950kJ, -900kJ, -850kJ, -800kJ, -750kJ, -700kJ, -650kJ, -600kJ, -550kJ, -500kJ, -450kJ, -400kJ, -350kJ, -300kJ, -250kJ, -200kJ, -150kJ, -100kJ, -50kJ or less than about-50 kJ.

The slurry coated substrate may be crimped prior to annealing. During the thermal treatment, the slurry coated substrate may be placed in a retort and placed in a controlled atmosphere. The water may be removed. A vacuum may be drawn to force hydrogen gas between the wraps. The annealing process may be performed by a coil-up or coil-down anneal. Annealing the slurry layer coated substrate may allow the elemental species in the slurry to diffuse into or through the substrate. After annealing, 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 into or enter the substrate. After 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 into or into the substrate. Certain process conditions can cause about 1-5% of the elemental species to diffuse from the coating into the substrate. The components in the slurry layer facilitate diffusion of the elemental species toward the substrate. The annealing process may be a continuous annealing process. The annealing process may be a discontinuous annealing process. The slurry coated substrate may be subjected to a plurality of annealing processes to increase the utilization of the elemental species or to alter the concentration gradient of the elemental species in the metal layer adjacent the substrate.

The substrate can be heated at a rate of greater than about 0.01 deg.C/s, 0.1 deg.C/s, 1 deg.C/s, 5 deg.C/s, 10 deg.C/s, 15 deg.C/s, 20 deg.C/s, 25 deg.C/s, or 30 deg.C/s or more. The substrate can be heated at a rate of greater than about 0.01 deg.C/min, 0.1 deg.C/min, 1 deg.C/min, 5 deg.C/min, 10 deg.C/min, 15 deg.C/min, 20 deg.C/min, 25 deg.C/min, or 30 deg.C/min or more. The substrate can be heated at a rate of less than about 30 deg.C/minute, 25 deg.C/minute, 20 deg.C/minute, 15 deg.C/minute, 10 deg.C/minute, 5 deg.C/minute, 1 deg.C/minute, 0.1 deg.C/minute, or less than about 0.01 deg.C/minute. The substrate may be heated at a rate of less than about 30 heat/second, 25 heat/second, 20 heat/second, 15 heat/second, 10 heat/second, 50/second, 10/second, 0.1 speed/second, or less than about 0.01 about/second or less. The substrate coated with the slurry can be annealed at a temperature of at least about 0 ℃, 25 ℃, 50 ℃, 75 ℃, 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, or 1300 ℃ or more. The annealing temperature may be no more than about 1300 ℃, 1200 ℃, 1100 ℃, 1000 ℃, 900 ℃, 800 ℃, 700 ℃, 600 ℃, 500 ℃, 400 ℃, 300 ℃, 200 ℃, 100 ℃, 75 ℃, 50 ℃, 25 ℃ or no more than about 0 ℃ or less. The annealing temperature may be about 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or 1300 ℃. The heating temperature during annealing may be about 800 ℃ to about 1300 ℃, for example, about 900 ℃ to about 1000 ℃. The annealing temperature may be about 900 ℃, 925 ℃, 950 ℃ or 1000 ℃.

During heating, the iron in the matrix or metal-containing layer may transform from ferrite to austenite. The temperature at which the transformation occurs may be referred to as the ferrite-austenite transformation temperature. The ferrite-austenite transition temperature of the substrate or metal-containing layer may be no more than about 1600 ℃, 1500 ℃, 1400 ℃, 1300 ℃, 1200 ℃, 1100 ℃, 1000 ℃, 900 ℃, 8000, 7000, 6000 or no more than about 500 ℃ or less. The ferrite-austenite transition temperature of the substrate or metal-containing layer can be greater than about 500 ℃, 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, or 1600 ℃ or higher. The ferrite-austenite transformation temperature of the matrix may be about 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃ or 1300 ℃. The ferrite-austenite transition temperature of the matrix may be from about 900 ℃ to about 1300 ℃, from about 1000 ℃ to about 1200 ℃, or from about 1100 ℃ to about 1200 ℃.

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, may be about 5 hours to 200 hours. For example, the total annealing time may exceed 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 annealing can be reached in about 1 hour to 100 hours. For example, the maximum temperature during annealing may be reached within 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 annealing can be reached for 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 annealing can 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, the substrate may be annealed at about 950 f for at least about 5 hours. In some cases, the substrate may be annealed at about 950 f for at least about 20 hours. In some cases, the substrate may be annealed at about 950 f for at least about 40 hours. In some cases, the substrate may be annealed at about 900 f for at least about 20 hours. In some cases, the substrate may be annealed at about 900 f for at least about 40 hours. In some cases, the substrate may be annealed at about 900 f for at least about 60 hours. In some cases, the substrate may be annealed at about 900 f for at least about 80 hours.

The annealing atmosphere may include gases such as inert or reactive gases, for example, hydrogen, helium, methane, ethylene, nitrogen, or argon. The annealing atmosphere may comprise a gas mixture. The annealing atmosphere may be vacuum. To prevent loss of elemental species during annealing, hydrochloric acid may be added to the annealing gas. Minimizing the partial pressure of the components in the metal-containing layer in the reactor at elevated temperatures can maintain a low deposition rate, which is critical to minimize or prevent the formation of kirkendall voids. The addition of too much acidic components in the metal-containing layer may also lead to corrosion of the coating equipment or the substrate.

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

After annealing, the substrate may be cooled for a period of time. The cooling time may be 1 hour to 100 hours. For example, the cooling time may 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 may 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 may 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.

During heat treatment, large articles may have hot or cold spots, wherein the coating of the article may be uniform but the heating is not uniform. Hot or cold spots may be displayed to control the diffusion of the alloying elements in the article as uniformly as possible.

After annealing, a metal layer may be formed on the substrate. The metal layer may have at least one element species selected from the group consisting of 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, wherein a concentration of the element species in the outer layer 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. The metal layer may have at least one element species selected from the group consisting of 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, wherein the concentration of the element species in the outer layer 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%. The substrate may include an adhesion layer adjacent to the metal layer. The concentration of the elemental species in the bonding layer may be reduced by at least about 1.0 wt%. The appearance of the metal or alloy layer may be uniform. The metal or alloy layer may be horizontal, constant, smooth and uniform in appearance, weight and thickness over the surface of at least a portion of the layer. The metal or alloy layer may have visible grain boundary precipitates. Alternatively, the metal or alloy layer formed with the composition or by the methods described herein can have small or few grain boundary precipitates that are visible at about 10 ×, 50 ×, 100 ×, 250 ×, 500 ×, 1000 ×, or more magnification.

The metal-containing layer may comprise a metal oxide. The metal oxide may include, but is not limited to, Al₂O₃、MgO、CaO、Cr₂O₂、TiO₂、FeCr₂O₄、S1O₂、Ta₂O5 or MgCr₂O₄Or a combination thereof. Metal oxides may be formed in metal-containing layers by metallothermic reduction reactions between elemental metals and metal oxides of less thermodynamic stability. Suitable counterparts of elemental metal and metal oxides of less thermodynamic stability may be selected from counterparts whose gibbs free energy of formation is reduced by oxidation of the elemental metal by the metal oxide.

After the annealing process, a residue may remain on the substrate. Some components of the metal layer may be consumed or removed (e.g., deposited on the walls of the distillation vessel), or its concentration may be reduced by diffusion into or into the substrate. However, other residues in the form of, for example, a powder or the like, may remain on the substrate after annealing. The residue may comprise an inert material from the metal-containing layer. These residues may be removed prior to further processing (e.g., temper rolling). The reaction can be stopped using HC1 gas purge. Purging with HC1 gas can form a flat profile.

After forming the metal layer proximate to the substrate, the substrate may have a measurable grain size. The grain size may be measured and recorded according to the American Society for Testing and Materials (ASTM) standard. The substrate may have a grain size of about ASTM000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 18, 19, 20, 22, 23, 24, 25, 26, 27, 28, 39, or 30. The grain size of the substrate may be greater than about ASTM000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, or 30 or more. The grain size of the substrate may be 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, the metal layer may have a particle size of about ASTM000 to about ASTM 30, about ASTM 5 to about ASTM 16, about ASTM 6 to about ASTM 14, or about ASTM8 to about ASTM 12. The substrate may have a particle size of between about ASTM 7 and ASTM 9. The particle size of the substrate may be about ASTM 7.

The elemental species in the slurry may lower the austenite to ferrite transformation temperature. The elemental species in the substrate may lower the austenite to ferrite transformation temperature. The elemental species may not significantly alter the austenite to ferrite transition temperature. In some cases, the elemental species may increase the austenite to ferrite transformation temperature. The group of elements that can lower the austenite to ferrite transformation temperature can be manganese, nitrogen, copper or gold.

The austenite grain size and ferrite grain size can be measured. The 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. The 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. The ratio of austenite grain size to ferrite grain size may be about 0.1, 0.5, 1, 2, 5, or 10. The ratio of austenite grain size to ferrite grain size may be about 1. The ratio of austenite grain size to ferrite grain size can be calculated according to the following equation:

D_γ/D_α＝1+(0.0026+0.053wt％C+0.006wt％Mn+0.009wt％Nb+4.23wt％V*N-0.081et％Ti)*(1.5+α^1/2)*D_γ

in the formula, D_γAustenite grain size, D, in μ_αFerrite grain size in μ and cooling rate in α/s.

The amount of titanium equivalent stabilization can be calculated according to the following equation:

ti equivalent stabilization amount-wt% Ti-3.42 wt% N-1.49 wt% S-4 wt% C +0.516 wt% Nb.

Without wishing to be bound by theory, a certain amount of titanium (Ti) -equivalent stabilization in the metal layer may form a layer that is more resistant to grain boundary precipitation. The metal layer may include at least about 0.001 Ti equivalent, 0.005 Ti equivalent, 0.01 Ti equivalent, 0.015 Ti equivalent, 0.017 Ti equivalent, 0.02 Ti equivalent, 0.03Ti equivalent, 0.04 Ti equivalent, 0.05 Ti equivalent, 0.06 Ti equivalent, 0.07 Ti equivalent, 0.08 Ti equivalent, 0.09 Ti equivalent, or more. The metal layer may include 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, 0.03Ti 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.

The content of elemental metal in the metal layer on the substrate may vary with depth. The amount of elemental metal in the metal layer can vary with depth at a rate, for example, of at least about-0.0001% per micron, at least about-0.001% per micron, at least about-0.01% per micron, at least about-0.05% per micron, at least about-0.1% per micron, at least about-0.5% per micron, at least about-1.0% per micron, at least about-3.0% per micron, at least about-5.0% per micron, at least about-7.0% per micron, or at least about-9.0% or more per micron. The amount of metal in the metal layer can vary with depth at a rate, for example, less than about-9.0% per micron, 7.0% per micron, 5.0% per micron, 3.0% per micron, 1.0% per micron, 0.5% per micron, 0.1% per micron, 0.05% per micron, 0.01% per micron, 0.001% per micron, or less than about-0.001% per micron or less. The amount of elemental metal in the metal layer may vary with depth from about-0.01% per micron to-5.0% per micron or from about-0.01% per micron to-3.0% per micron.

The amount of elemental metal in the metal layer can vary with depth at a rate, for example, of at least about-0.0001%, 0.001%, 0.01%, 0.05%, 0.1%, 0.5%, 1.0%, 3.0%, 5.0%, 7.0%, or at least about-9.0% or more per micron. The amount of elemental metal in the metal layer can vary with depth at a rate, for example, of no more than about-9.0% per micron, 7.0% per micron, 5.0% per micron, 3.0% per micron, 1.0% per micron, 0.5% per micron, 0.1% per micron, 0.05% per micron, 0.01% per micron, 0.001% per micron, or no more than about-0.0001% or less per micron.

The elemental metals may have the following concentrations: a concentration of at least about 5 wt% at a depth of less than or equal to 100 microns from the substrate surface, a concentration of at least about 5 wt% at a depth of less than or equal to 50 microns from the substrate surface, a concentration of at least about 10 wt% at a depth of less than or equal to 40 microns from the substrate surface, a concentration of at least about 10 wt% at a depth of less than or equal to 30 microns from the substrate surface, the concentration is at least about 15 wt% at a depth of less than or equal to 50 microns from the substrate surface, at least about 15 wt% at a depth of less than or equal to 40 microns from the substrate surface, at least about 15 wt% at a depth of less than or equal to 30 microns from the substrate surface, or at least about 15 wt% at a depth of less than or equal to 10 microns from the substrate surface. X-ray photoelectron spectroscopy can be used to measure such quantities, concentrations, or weight percent as a function of depth.

The metal layer applied proximate the substrate may have a thickness of less than about 1 millimeter, about 900 microns, about 800 microns, about 700 microns, about 600 microns, about 500 microns, 400 microns, about 300 microns, about 200 microns, or about 100 microns or less.

The metal layer applied proximate the substrate may have a thickness of at least about 1 micron, 5 microns, 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, 200 microns, 300 microns, 400 microns, 500 microns, 600 microns, 700 microns, 800 microns, 900 microns or more.

The properties of the substrate can be determined by various techniques and instruments before or after the application of the metal layer. For example, techniques and instruments include, for example, particle size calculation, Scanning Electron Microscope (SEM), scanning electron microscope/energy dispersive spectroscopy (SEM/EDS), microprobe analysis, and potentiostat measurements.

The properties of the substrate after coating with the metal layer can be measured. Properties of the substrate include, for example, chemical composition, yield strength, ultimate tensile strength, and percent elongation.

After annealing, the substrate is substantially free of kirkendall voids. The layer may impart properties on the substrate not previously included in the substrate. For example, the layer may make the substrate harder, more wear resistant, more aesthetically pleasing, more electrically resistive, less electrically resistive, better thermally conductive, less thermally conductive, or any combination thereof. Further, the layer may cause the speed of sound in the substrate to propagate faster or slower.

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

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

The substrate may exhibit a percent elongation, a measured maximum elongation divided by the original measured length, or the difference in distance before break before and after coating the steel substrate. The elongation may be about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 100%. In certain instances, 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 certain instances, 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 certain instances, 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.

The substrate may exhibit Ti/Nb stability. In some cases, the Ti/Nb stability can 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 can 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, 0.002, or less. In some cases, the Ti/Nb stability can 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, or higher.

The composition of the substrate, slurry components, or metal layer may be measured using any suitable analytical technique. Measurements may include amounts, concentrations or weight percentages, thickness or other dimensions, variations in composition and/or structure with depth, and grain size. Exemplary analytical techniques may include, but are not limited to, glow discharge mass spectrometry, microprobe analysis, potentiostatic 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 the change in such amounts, concentrations, or weight percentages with depth.

Other characteristics of the metal layer coated substrate are described in the following patent applications: U.S. patent publication numbers 2013/0171471; U.S. patent publication numbers 2013/0309410; U.S. patent publication numbers 2013/025222; U.S. patent publication numbers 2015/0167131; U.S. patent publication numbers 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.

When stretched, or both, the chemical properties of the steel can be altered to improve formability and material properties. The formability of a steel can be measured by the ratio of plastic strains, commonly referred to as the Lankford coefficients r-bar, r_mOr referred to herein as the r value. The r value may be defined as the ratio of the plastic strain in the plane of the sheet to the plastic strain of the gauge or sheet thickness. The r value can be calculated as:

wherein R is₀、R₄₅And R₉₀Is the ratio of plastic strain with respect to the direction of the sheet.

The r-value of the steel can be varied by controlling the chemistry and composition of the steel to produce a highly formable steel composition. The r-value of a conventional interstitial free steel may be between about 1.4 and 1.8. The r-value of the modified steel may exceed about 2. In some embodiments, the r-value of the steel may exceed about 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, or exceed about 4.0 or more. The r-value of the modified steel may be 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.

Various chemical methods may be employed to increase the r-value of the highly formable steel composition. The chemical quality of the steel may be selected to increase the total incorporation of grain pinning particles prior to annealing of the steel. In some embodiments, the presence of the grain pinning particles inhibits the formation of increased grain size during annealing. A stoichiometric excess of titanium (Ti) may be used. This excess Ti may allow TiC to form at high temperatures. TiC can be used for grain pinning at high temperatures. Interstitial free steels may also use more manganese and smaller amounts of TiN, AIN, NbC, NbN or other components that act both as grain pinning and interstitial element binders at high temperatures. The interstitial free steel may comprise a composition similar to the composition listed in embodiment 7.

The method of manufacturing the high-formability steel composition may comprise several intermediate processes. The steel may be according to the above chemical composition. The interstitial free steel may undergo a fine grain treatment to produce fine primary grains. Cold reduction may be used to obtain a smooth surface and control grain size. After cold reduction, subsequent processing steps may include high temperature annealing methods. The high temperature annealing may include annealing at a temperature greater than about 900 ℃. The annealing temperature may exceed about 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃, 1400 ℃, 1500 ℃ or more. The annealing temperature may be no more than about 1500 ℃, 1450 ℃, 1400 ℃, 1350 ℃, 1300 ℃, 1250 ℃, 1200 ℃, 1150 ℃, 1100 ℃, 1050 ℃, 1000 ℃ or no more than about 950 ℃ or less. The annealing temperature may allow the steel to transform from the ferrite phase to the austenite phase. The composition of the interstitial free steel is chosen to prevent grain growth. The stabilized grade may prevent strain aging and may improve the formability of the steel for further processing.

The high-profile steel composition may have a measurable grain size. The grain size may be measured and recorded according to the American Society for Testing and Materials (ASTM) standard. The grain size of the substrate may be greater than about ASTM000, 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 higher. The grain size of the high profile steel composition may be greater than ASTM000, 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 higher. The grain size of the highly formable steel composition may be 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, the metal layer may have the following grain size: about ASTM000 to about ASTM 10, about ASTM000 to about ASTM 15, about ASTM000 to about ASTM 20, about ASTM000 to about ASTM 25, about ASTM000 to about ASTM 30, about ASTM 5 to about ASTM 16, about ASTM 5 to about ASTM 18, about 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 ASTM 18, about ASTM 6 to ASTM 20, about ASTM 6 to ASTM 22, about ASTM 6 to ASTM 24, about ASTM 6 to ASTM 26, about ASTM 6 to ASTM 28, about ASTM 6 to ASTM 30, about ASTM 7 to ASTM 16, about ASTM 7 to ASTM 18, about ASTM 7 to ASTM 20, about ASTM 7 to ASTM 22, ASTM 7 to about ASTM 24, about ASTM 7 to ASTM 26, about ASTM 7 to about ASTM 6 to ASTM 26, About ASTM 7 to about ASTM 28, about ASTM 7 to about ASTM 30, about ASTM8 to about ASTM 16, about ASTM8 to about ASTM 18, about ASTM8 to about ASTM 20, about ASTM8 to about ASTM 22, about ASTM8 to about ASTM 24, about ASTM8 to about ASTM 26, about ASTM8 to about ASTM 28, about ASTM8 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 10 to about ASTM 15 to about ASTM 20, About ASTM 15 to ASTM 25, about ASTM 15 to ASTM 30, or ASTM 20 to ASTM 30. The grain size of the high-profile steel composition may be between ASTM 7 to ASTM 9, ASTM 6 to ASTM 14, or ASTM8 to ASTM 12. The grain size of the high-profile steel composition may be ASTM 7, ASTM8, ASTM 9, ASTM 10, ASTM 11, ASTM 12, ASTM 13, 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.

The substrates, metal layers, and compositions comprising metal layers described herein can be used in any treatment process or series of treatment processes. The substrate, metal layer, and composition can be used in additional processing methods before, during, and/or after deposition of the metal-containing layer. The substrate, metal layer, and composition may be used in additional processing methods before, during, and/or after annealing of the metal layer. Compositions comprising a metal layer may provide enhanced properties (e.g., formability, processability, improved thermal conductivity) for subsequent processing steps. The composition having enhanced properties after forming the metal layer can be beneficial for a variety of applications, for example, electrical alloys, electronic alloys, high temperature alloys, high strength alloys, corrosion resistant alloys, construction alloys, structural alloys, consumer alloys, electrical grade alloys, industrial alloys, biomedical grade alloys, military grade alloys, marine grade alloys, aerospace grade alloys, transportation grade alloys, aesthetic alloys, and automotive grade alloys.

The substrate, metal layer, or composition comprising the metal layer may be subjected to any processing method before, during, and/or after deposition of the metal layer. Exemplary processes may include, but are not limited to, forming, soft or hard tools, fastening, and seam or cut edge protection. Exemplary forming, soft or hard die processing may include stretching or drawing, re-stamping, impact forming, rotational forming, roll forming, hydroforming, CNC forming, flanging, crimping, hot stamping, extrusion, and forging. Exemplary fastening processes may include toggle locking, arcuate locking, spot welding, brazing, rod welding, arc welding, MIG welding, TIG welding, acetylene gas welding, resistance welding, ultrasonic welding, friction welding, laser welding, plasma welding, crimping, riveting, hot forging, and chemical bonding (e.g., glue or epoxy bonding). Exemplary seam or cut edge protection processes may include hot dip galvanization, electro-galvanization, aluminum or aluminizing, aluminum siliconization, cold spray (e.g., aluminum, all grades of stainless steel, zinc, galvanization, nickel), thermal or plasma spray (e.g., aluminum, all grades of stainless steel, zinc, galvanization, nickel, copper, bronze), cladding, and liquid coatings (e.g., paint, UV curing, polymer paint).

The substrate or composition comprising the metal layer may form one or more components, parts or assemblies. The part, or assembly comprising the metal layer may be used in any suitable application, including but not limited to automotive, aerospace, transportation, marine, military, electrical, construction, industrial, electrical, biomedical, military, consumer, aesthetic, electronic, and structural applications. Automotive applications may include automotive fuel tanks, exposed body panels (e.g., doors, hoods, and fenders), exhaust components (e.g., mufflers, catalytic converter housings, exhaust pipes, thermal shields), and unexposed body panels (e.g., instrument panels, door liners, wheel cover liners). Device applications may include exposed panels (e.g., outdoor doors, ventilation hoods, splash guards) and unexposed panels (e.g., dishwasher interior panels, water heater tanks). Building and structural applications may include building panels, flow tubes, pipes, beams, hinges, plates, and fasteners. Electrical applications may include motor laminations, generator laminations, and power transformer core laminations.

Computer system

The present invention provides a computer system programmed to perform the method of the present invention. Fig. 4 illustrates a computer control system 401 programmed or otherwise configured to generate a slurry and/or apply a coating of the slurry to a substrate. The computer control system 401 may regulate various aspects of the method of the present invention, such as the method of producing the slurry and the method of applying a coating of the slurry to a substrate. The computer control system 401 may be implemented on the user's electronic device or a computer system remotely located from the electronic device. The electronic device may be a mobile electronic device.

The computer system 401 includes a central processing unit (CPU, also referred to herein as a "processor" and a "computer processor") 405, which may be a single or multi-core processor or a plurality of processors for parallel processing. The computer control system 401 also includes a memory or memory unit 410 (e.g., random access memory, read only memory, flash memory), an electronic storage unit 415 (e.g., hard disk), a communication interface 420 (e.g., a network adapter) for communicating with one or more other systems, and peripheral devices 425 such as a cache, other memory, data storage, and/or an electronic display adapter. Memory 410, storage unit 415, interface 420, and peripherals 425 communicate with CPU 405 over a communication bus (solid lines), such as a motherboard. The storage unit 415 may be a data storage unit (or data repository) for storing data. Computer control system 401 may be operatively coupled to a computer network ("network") 430 by way of a communication interface 420. The network 430 may be the internet, the internet and/or an extranet, or an intranet and/or extranet in communication with the internet. In some cases, network 430 is a telecommunications and/or data network. Network 430 may include one or more computer servers, which may implement distributed computing such as cloud computing. In some cases, with the aid of computer system 401, network 430 may implement a peer-to-peer network that may cause devices coupled to computer system 401 to act as clients or servers.

The CPU 405 may execute a series of machine-readable instructions, which may be embodied in a program or software. These instructions may be stored in a storage unit, such as memory 410. These instructions may be directed to the CPU 405, and the CPU 405 may then program or otherwise configure the CPU 405 to implement the methods of the present disclosure. Examples of operations performed by the CPU 405 may include fetch, decode, execute, and write-back.

The CPU 405 may be part of a circuit such as an integrated circuit. One or more other components of system 401 may be included in the circuit. In some cases, the circuit is an Application Specific Integrated Circuit (ASIC).

The storage unit 415 may store files such as drives, libraries, and saved programs. The storage unit 415 may store user data, such as user preferences and user programs. In some cases, computer system 401 may include one or more additional data storage units external to computer system 401, for example, located on a remote server in communication with computer system 401 via an intranet or the Internet.

Computer system 401 may communicate with one or more remote computer systems over a network 430. For example, computer system 401 may communicate with a remote computer system of a user (e.g., to control the manufacture of slurry coated substratesA user). Examples of remote computer systems include personal computers (e.g., pocket PCs), tablet computers, or tablet computers (e.g., laptop PCs)

iPad、

Galaxy Tab), telephone, smartphone (e.g., smart phone)

iPhone, Android-enabled device,

) Or a personal digital assistant. A user may access computer system 401 via network 430.

The methods described herein may be implemented by machine (e.g., computer processor) executable code stored on an electronic storage unit of computer system 401, for example, on memory 410 or electronic storage unit 415. The machine executable code or machine readable code may be provided in the form of software. During use, the code may be executed by processor 405. In some cases, the code may be retrieved from storage unit 415 and stored on memory 410 for ready access by processor 405. In some cases, electronic storage unit 415 may be eliminated, and the machine executable instructions stored on memory 410.

The code may be pre-compiled and configured for use with a machine having a processor adapted to execute the code, or may be compiled at runtime. The code may be provided in a programming language, which may be selected to cause the code to be executed in a pre-compiled or compiled form.

Aspects of the systems and methods provided herein, such as computer system 401, may be embodied in programming. Various aspects of the technology may be considered an "article of manufacture" or an "article of manufacture" typically in the form of machine (or processor) executable code and/or associated data carried or embodied in a machine-readable medium. The machine executable code may be stored on an electronic storage unit, such as a memory (e.g., read only memory, random access memory, flash memory) or a hard disk. "storage" type media may include any or all tangible memory of a computer, processor, or the like; or its associated modules, such as various semiconductor memories, tape drives, disk drives, etc., which may provide non-transitory storage for software programming at any time. All or portions of the software may sometimes communicate over the internet or various other telecommunications networks. For example, such communication may enable loading of software from one computer or processor to another computer or processor, e.g., from a management server or host to the computer platform of an application server. Thus, another type of media that may carry software elements includes optical, electrical, and electromagnetic waves, for example, used across physical interfaces between local devices, through wired and fiber-optic landline networks and various air links. The physical elements carrying such waves, e.g. wired or wireless links, optical links, etc., may also be considered as media carrying software. As used herein, unless limited to a non-transitory, tangible "storage" medium, terms such as a computer or machine "readable medium" refer to any medium that participates in providing instructions to a processor for execution.

Thus, a machine-readable medium, such as computer executable code, may take many forms, including but not limited to tangible storage media, carrier wave media, or physical transmission media. Non-volatile storage media include, for example, optical or magnetic disks, any storage device in any computer, etc., such as may be used to implement the databases and the like shown in the figures. Volatile storage media includes dynamic memory, such as the 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 can take the form of electrical or electromagnetic signals, or acoustic or light waves, such as those generated during Radio Frequency (RF) and Infrared (IR) data communications. Thus, common forms of computer-readable media 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, a cable or link transporting such a carrier wave, or any other medium from which a computer can 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.

The computer system 401 may include, or be in communication with, an electronic display 435, the electronic display 435 including a User Interface (UI)440 for providing parameters, for example, for producing the slurry and/or applying the slurry to the substrate. Examples of UIs include, but are not limited to, Graphical User Interfaces (GUIs) and web-based user interfaces.

The method and system of the present invention may be implemented by one or more algorithms. The algorithm may be implemented by software when the central processing unit 405 executes. The algorithm may, for example, adjust 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 adjust the speed at which the slurry is applied to the substrate and the amount of coating that the slurry is applied to the substrate.

Examples

Example 1

In an embodiment, the slurry is formed by addition to a mixing chamber while mixing the resulting solution. The amount of water added to the slurry was varied to form a wide variety of slurries, and the effect on the slurry properties as a result was recorded. Next, the slurry is applied to the substrate by a roll coating process. The slurry was then annealed at about 200 ℃ for about 2 hours. The slurry is then dried to completion for a drying time of about 2 hours to about 100 hours or more. The atmosphere near the surface of the chrome-plated article may be below a dew point of about-20 ° f.

Example 2

In another embodiment, the substrate is heated to about 500 ℃ at a rate of about 10 ℃/min. The temperature is held constant for about 2 hours during which time a metal-containing layer is deposited adjacent the substrate. The substrate was then heated to about 950 c at a rate of about 10 c/min. The temperature remains constant during the annealing. After about 30 hours, the substrate was cooled to room temperature at a rate of about 5 deg.C/min. The argon flow was constant throughout the process.

Example 3

In another embodiment, the substrate is subjected to a thermal cycling protocol. The substrate is heated to about 500c at a rate of about 10 c/min. The temperature is held constant for about 2 hours during which time a metal-containing layer is deposited adjacent the substrate. The substrate was then heated to about 925 c at a rate of about 10 c/min and the temperature was held constant for about 30 minutes. The substrate was heated to about 500c at a rate of about 5 c/min, with the temperature held constant for about 30 minutes. The substrate was heated again, heated at a rate of about 5 deg.C/min to about 925 deg.C, held at a constant temperature for about 30 minutes, then cooled at a rate of about 5 deg.C/min to about 500 deg.C, and the temperature was held constant for about 30 minutes. The substrate is heated and cooled again in another cycle. The substrate was heated to about 925 c and then cooled to room temperature at a rate of about 5 c/min. The argon flow was constant throughout the process.

Example 4

In another embodiment, a substrate is provided that includes carbon, silicon, manganese, titanium, vanadium, aluminum, and nitrogen. In an embodiment, the substrate has the following composition (in wt%):

substrate	C	Si	Mn	TI	V	Al	N
								S-03	0.035	0.333	0.634	0.281	0.018	0.059	0.0051
S-04	0.032	0.031	0.592	0.245	0.015	0.03	0.0065
								C13	0.0072	0.016	1.6	0.019	0.11	0.0012	0.012
C19	0.007	0.02	1.23	0.016	0.09	0.008	0.01
								C20	0.007	0.02	1.25	0.015	0	0.006	0.008
C21	0.004	0.02	1.24	0.014	0.09	0.011	0.009

Example 5

substrate	C	Mn	Al	P	S	Cr	N	V	Nb	Ti
											C20_2	0.002	1.27	0.008	0.009	0.002	0.04	0.008	0.004	0.004	0.016
MC-25	0.002	1.26	0.004	0.005	0.008	0.04	0.082	0	0.089	0.015

Substrate MC-25 contains about 0.089 wt% niobium. The obtained alloy layer was observed to have almost no grain boundary precipitation as shown in fig. 3. Less pore formation was observed with this alloy layer. This stainless steel alloy layer improves the corrosion resistance of the substrate and the desired effect.

Example 6

In another embodiment, a substrate is formed and exhibits the following properties:

example 7

the niobium weight percent of the alloy is calculated as follows:

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

the substrate chemistry is selected such that its calculated stability is 0.017 or higher, where stability is calculated as follows:

stability of Ti wt% -3.42N wt% -1.49^*S wt％-4*C wt％+0.516*Nb wt％.。

Example 8

In another embodiment, a substrate is formed and exhibits the following composition (measured in wt%) of constituent metals and other elements:

substrate	C	Mn	Al	P	S	Cr	N	V	Nb	Ti
											S-3.1	0.035	0.634	0.059	0.009	0.002	0.039	0.005	0.018	0.005	0.281
S-4	0.32	0.7	0.034	0.012	0.001	0.057	0.007	0.01	0	0.21
											M	0.002	1.26	0.004	0.005	0.008	0.04	0.008	0	0.089	0.015
A	0.004	1.38	0.007	0.01	0.007	0.03	0.011	0	0.137	0.018

Example 9

In another embodiment, the substrates listed in example 8 were subjected to thermomechanical testing to determine their r-values. The test results were as follows:

example 10

In another embodiment, the composition is prepared by mixing MgCr₂O₄Powder and MgCl₂The powders are mixed together in water to form a slurry suspension. For MgCr₂O₄Powder and MgCl₂The powder is sieved to have a particle size of about 0.1 to 10 μm. MgCr₂O₄Powder and MgCl₂The dry weight percentages of the meal were about 95% and 5%, respectively. Mixing MgCr₂O₄Powder and MgCl₂After four hours of powder, aluminum powder was added to the suspension. The aluminum powder was sieved through a 325 mesh screen. Aluminum was mixed into the slurry powder to give an atomic ratio to the oxide powder of about 1.0. The slurry mixture containing aluminum powder was immediately roll-coated onto the surface of the metal plate. The substrate was then heated to about 950 c at a rate of about 10 c/min. The temperature remains constant during the annealing process. After about 30 hours, the substrate was cooled to room temperature at a rate of about 5 deg.C/min. The argon flow was constant throughout the process. After annealing, the metal substrate is subjected to a cleaning process to remove Al from the surface of the substrate₂O₃。

Example 11

In another embodiment, the composition of the substrate exhibits a yield strength of up to 80% and a tensile strength of up to 50%. In some cases, the substrate was formed and showed the following composition (measured in wt%) of the constituent metals and other elements:

substrate	C	Mn	Si	Al	N	Nb	Ti	P	B	S
											HS-1	0.0087	1.68	0.5	0.01	0.007	0.12	0.016	0.008	0.0002	0.0062
HS-2	0.0095	2.22	0.96	0.01	0.007	0.16	0.015	0.008	0.0002	0.0064
											HS-3	0.009	2.20	0.95	0.01	0.008	0.16	0.015	0.005	0.0005	0.0063

Example 12

In another example, the substrates listed in example 11 were subjected to thermomechanical testing to determine their Ti/Nb stability, yield strength, ultimate tensile strength, and elongation. The test results were as follows:

the materials, devices, systems, and methods, including material compositions (e.g., material layers), herein can be combined with or modified by other materials, devices, systems, and methods, including material compositions (e.g., material compositions described in U.S. patent publication No. 2013/0171471; U.S. patent publication No. 2013/0309410; U.S. patent publication No. 2013/025222; U.S. patent publication No. 2015/0167131; U.S. patent publication No. 2015/0345041; and patent Cooperation treaty application No. PCT/US 2016/017155), each of which is incorporated herein by reference in its entirety.

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. The invention is not limited by the specific examples provided in the specification. While the invention has been described with reference to the foregoing specification, the description and illustrations of the embodiments herein are not meant to be construed in a limiting sense. Numerous variations, changes, and substitutions will occur to those skilled in the art without departing from the invention herein. Further, it is to be understood that all aspects of the invention are not limited to the specific description, and that the configurations or relative proportions described herein depend on various 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 present 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.

Claims

1. A method for forming at least one metal layer adjacent to a substrate, comprising:

(a) contacting the substrate with a slurry comprising a metal oxide, a metal reducing agent, and a metal transport activator to provide a metal-containing layer adjacent to the substrate; and

(b) annealing the substrate and the at least one metal-containing layer such that the metal oxide and the metal transport activator undergo a metallothermic reduction reaction to produce the at least one metal layer and water, wherein the water is reduced by the metal reducing agent.

2. The method of claim 1, wherein the at least one metal layer has a grain size of about ASTM000 to ASTM 30.

3. The method of claim 1, wherein the substrate comprises at least one of the following (i) to (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium.

4. The method of claim 1, wherein the substrate comprises at least two of the following (i) through (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium.

5. The method of claim 1, wherein the substrate comprises at least three of the following (i) to (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium.

6. The method of claim 1, wherein the substrate comprises at least four of the following (i) through (v): (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium.

7. The method of claim 1, wherein the substrate comprises: (i) less than or equal to about 0.1 wt% carbon; (ii) about 0.1 wt% to 3 wt% manganese; (iii) less than or equal to about 1 wt% silicon; (iv) less than or equal to about 0.1 wt% vanadium; and (v) less than or equal to about 0.5 wt% titanium.

8. The method of claim 1, wherein the metal layer is formed at an annealing temperature of about 0 ℃ to 1000 ℃.

9. The method of claim 1, wherein the metal layer is formed in an annealing atmosphere having a humidity level below about 10 torr.

10. The method of claim 1, wherein the annealing comprises heating the substrate at a rate of at least about 0.1 ℃/sec.

11. The method of claim 1, wherein the annealing is performed at a temperature greater than about 500 ℃.

12. The method of claim 1, further comprising cooling the substrate after the annealing.

13. The method of claim 1, wherein the substrate transforms from ferritic to austenitic during the annealing.

14. The method of claim 1, wherein the temperature of the annealing is determined by a transformation temperature of ferrite to austenite.

15. The method of claim 14, wherein adding at least one austenite stabilizer lowers the transformation temperature.

16. The method of claim 1, wherein the metal transport activator comprises a halide species, a metal sulfide species, or a gas species.

17. The method of claim 16, wherein the metal transport activator comprises hydrogen.

18. The method of claim 16, wherein the metal transport activator comprises a metal selected from magnesium chloride (MgCl)₂) Iron (II) chloride (FeCl)₂) Calcium chloride (CaCl)₂) Zirconium (IV) chloride (ZrCl)₄) Titanium (IV) chloride (TiCl)₄) Niobium (V) chloride (NbCl)₅) Titanium (III) chloride (TiCl)₃) Silicon tetrachloride (SiCl)₄) Vanadium (III) chloride (VCl)₃) Chromium (III) chloride (CrCl)₃) Trichlorosilane (SiHCl)₃) Manganese (II) chloride (MnCl)₂) Chromium (II) chloride (CrCl)₂) Cobalt (II) chloride (CoCl)₂) Copper (II) chloride (CuCl)₂) Nickel (II) chloride (NiCl)₂) Vanadium (II) chloride (VCl)₂) Ammonium chloride (NH)₄Cl), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), and iron disulfide (FeS)₂) Chromium sulfide (CrS), iron sulfide (FeS), copper sulfide (CuS), nickel sulfide (NiS), and combinations thereof.

19. The method of claim 1, further comprising drying the substrate after the annealing.

20. A steel composition comprising a constituent metal selected from the group consisting of i) and ii) below: i) greater than about 0.2 wt% titanium; and ii) greater than about 0.8 wt% manganese, wherein the steel composition has a measured plastic strain ratio in excess of 1.8.

21. The steel composition of claim 20, wherein the steel composition has a measured plastic strain ratio in excess of 2.

22. The steel composition of claim 20, wherein the steel composition has been annealed at a temperature of about 750 ℃ to about 1100 ℃.

23. The steel composition of claim 22, wherein the steel composition transforms from ferritic to austenitic during the annealing.

24. The steel composition of claim 22, wherein the steel composition comprises a grain size of about ASTM000 to ASTM 30.

25. The steel composition of claim 20, wherein the steel composition comprises greater than about 0.2 wt% titanium, and two or more constituent elements selected from the following i) through iii): i) greater than about 0.01 wt% carbon; ii) greater than about 0.02 wt% aluminum; and iii) not greater than about 0.004 wt% sulfur, and iv) less than about 0.02 wt% niobium.

26. The steel composition of claim 20, wherein the steel composition comprises greater than about 0.8 wt% manganese, and two or more constituent elements selected from the following i) through iii): i) less than about 0.01 wt% carbon; ii) less than about 0.02 wt% aluminum; and iii) greater than about 0.004 wt% sulfur, and iv) greater than about 0.02 wt% niobium.

27. A composition for forming at least one metal layer adjacent to a substrate, comprising a slurry comprising a metal oxide, a metal reducing agent, and a metal transport activator, wherein the slurry is configured to provide a metal-containing layer adjacent to the substrate, wherein the metal oxide and the metal transport activator are configured to undergo a metallothermic reduction reaction to produce the at least one metal layer and water.

28. The composition of claim 27, wherein the water is reduced by the metal reducing agent.

29. The composition of claim 27, wherein the metal oxide is selected from Cr₂O₃、TiO₂、FeCr₂O₄、SiO₂、Ta₂O₅And MgCr₂O₄The group consisting of.

30. The composition of claim 27, wherein the metallic reducing 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.

31. The composition of claim 27, wherein the metal transport activator comprises a halide species, a metal sulfide species, or a gas species.

32. The composition of claim 30, wherein the metal transport activator comprises hydrogen.

33. The composition of claim 30, wherein the metal transport activator comprises a metal selected from magnesium chloride (MgCl)₂) Iron (II) chloride (FeCl)₂) Calcium chloride (CaCl)₂) Zirconium (IV) chloride (ZrCl)₄) Titanium (IV) chloride (TiCl)₄) Niobium (V) chloride (NbCl)₅) Titanium (III) chloride (TiCl)₃) Silicon tetrachloride (SiCl)₄) Vanadium (III) chloride (VCl)₃) Chromium (III) chloride (CrCl)₃) Trichlorosilane (SiHCl)₃) Manganese (II) chloride (MnCl)₂) Chromium (II) chloride (CrCl)₂) Cobalt (II) chloride (CoCl)₂) Copper (II) chloride (CuCl)₂) Nickel (II) chloride (NiCl)₂) Vanadium (II) chloride (VCl)₂) Ammonium chloride (NH)₄Cl), sodium chloride (NaCl), potassium chloride (KC1), molybdenum sulfide (MoS), manganese sulfide (MnS), and iron disulfide (FeS)₂) Chromium sulfide (CrS), iron sulfide (FeS), copper sulfide (CuS), nickel sulfide (NiS), and combinations thereof.

34. The composition of claim 27, further comprising a solvent.

35. The composition of claim 33, wherein the solvent comprises water.

36. The composition of claim 33, wherein the solvent comprises an organic.