TW202045746A - Methods and systems for coating a steel substrate - Google Patents

Abstract

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

Description

Method and system for coating steel substrate

The present invention provides methods and systems for adjoining a substrate or depositing a metal layer on the substrate.

Steel can be an alloy of iron and other elements (including carbon). When carbon is the main alloying element, its content in steel can be about 0.002 wt% to 2.1 wt%. Without limitation, the following elements may be present in steel: carbon, manganese, phosphorus, sulfur, silicon, oxygen, nitrogen, and aluminum. The alloying elements added to modify the characteristics of the steel may include but are not limited to: manganese, nickel, chromium, molybdenum, boron, titanium, vanadium and niobium.

Stainless steel can be a material that is not easily corroded, rusted (or oxidized) or contaminated by water. There are different grades and surface finishes of stainless steel to suit the given environment. Stainless steel can be used when the properties and corrosion resistance of steel are beneficial.

The present invention provides a system and method for depositing a metal layer adjacent to a substrate. The substrate can be a steel substrate. Examples of such metal layers include, but are not limited to, stainless steel, silicon steel, and noise vibration harshness damping steel. Such substrates may include, for example, iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium and niobium, their oxides, their nitrides, their sulfides or their Any combination of one or more. The system and substrate can produce the desired resulting microstructure.

In one aspect, provided herein is a method for forming at least one metal layer adjacent to a substrate, the method comprising contacting the substrate with a slurry comprising a metal oxide, a reducing metal agent, and a metal transfer activator to provide Adjacent to the metal-containing layer of the substrate, and annealing the substrate and the at least one metal-containing layer so that the metal oxide and the metal transfer activator undergo a metal thermal reduction reaction to generate the at least one metal layer and water, wherein The water system is reduced by the reducing metal agent.

In some embodiments, the at least one metal layer has a grain size of about ASTM 000 to ASTM 30.

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

In some embodiments, the metal layer is formed at an annealing temperature of about 0°C to 1000°C. In some embodiments, the metal layer is formed in an annealing atmosphere with a moisture content of less than about 10 Torr. In some embodiments, annealing includes heating the substrate at a rate of at least about 0.1°C/sec. In some embodiments, annealing is performed at a temperature higher than about 500°C. In some embodiments, the method further includes cooling the substrate after the annealing.

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

In some embodiments, the metal transfer activator includes a halide, metal halide, metal sulfide, or gaseous substance. In some embodiments, the metal transfer activator includes hydrogen gas. In some embodiments, the metal transfer activator includes a substance selected from the group consisting of magnesium chloride (MgCl ₂ ), iron (II) chloride (FeCl ₂ ), calcium chloride (CaCl ₂ ), zirconium chloride ( IV) (ZrCl ₄ ), titanium(IV) chloride (TiCl ₄ ), niobium(V) chloride (NbCl ₅ ), titanium(III) chloride (TiCl ₃ ), silicon tetrachloride (SiCl ₄ ), chlorine Vanadium (III) (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 ₄ Cl), sodium chloride (NaCl), potassium chloride (KCl), molybdenum sulfide (MoS), manganese sulfide (MnS), iron disulfide (FeS ₂ ), chromium sulfide (CrS), iron sulfide (FeS), Copper sulfide (CuS), nickel sulfide (NiS) and combinations thereof.

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

In one aspect, provided herein is a steel composition comprising a constituent metal selected from the group consisting of: i) greater than about 0.2% by weight of titanium, and ii) greater than about 0.8% by weight of manganese, wherein the steel composition The object has a measured value of plastic strain ratio exceeding 1.8. In some embodiments, the steel composition has a plastic strain ratio measurement value exceeding 2.

In some embodiments, the steel composition undergoes annealing at a temperature between about 750°C and about 1100°C. In some embodiments, during the annealing, the steel composition transforms from ferrite to austenite. In some embodiments, the steel composition includes a grain size between about ASTM 000 and ASTM 30. In some embodiments, the steel composition includes more than about 0.2% by weight of titanium, and two or more constituent elements selected from: i) more than about 0.01% by weight of carbon, ii) more than about 0.02% by weight And iii) not more than about 0.004% by weight of sulfur, and iv) less than about 0.02% by weight of niobium. In some embodiments, the steel composition includes more than about 0.8% by weight of manganese, and two or more constituent elements selected from: i) less than about 0.01% by weight of carbon, ii) less than about 0.02% by weight And iii) more than about 0.004% by weight of sulfur, and iv) more than about 0.02% by weight of niobium.

In another aspect, provided herein is a composition for forming at least one metal layer adjacent to a substrate, the composition comprising a slurry comprising a metal oxide, a reducing metal reagent and a metal transfer activator, wherein the The slurry is configured to provide a metal-containing layer adjacent to the substrate, wherein the metal oxide and the metal transfer activator are configured to undergo a metal thermal reduction reaction to generate the at least one metal layer and water.

In some embodiments, the metal oxide is selected from the group consisting of Cr ₂ O ₃ , TiO ₂ , FeCr ₂ O ₄ , SiO ₂ , Ta ₂ O ₅ and MgCr ₂ O ₄ .

In some embodiments, the reducing metal agent includes 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 transfer activator includes a halide, metal halide, metal sulfide, or gaseous substance. In some embodiments, the metal transfer activator includes hydrogen gas. In some embodiments, the metal transfer activator includes a substance selected from the group consisting of magnesium chloride (MgCl ₂ ), iron (II) chloride (FeCl ₂ ), calcium chloride (CaCl ₂ ), zirconium chloride ( IV) (ZrCl ₄ ), titanium(IV) chloride (TiCl ₄ ), niobium(V) chloride (NbCl ₅ ), titanium(III) chloride (TiCl ₃ ), silicon tetrachloride (SiCl ₄ ), chlorine Vanadium (III) (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 ₄ Cl), sodium chloride (NaCl), potassium chloride (KCl), molybdenum sulfide (MoS), manganese sulfide (MnS), 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 includes a solvent. In some embodiments, the solvent includes water. In some embodiments, the solvent contains organic substances.

Another aspect of the present invention provides a non-transitory computer-readable medium including machine-executable code that, when executed by one or more computer processors, implements any of the methods above or elsewhere.

Another aspect of the present invention provides a system including 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, implements any of the methods above or elsewhere in this document.

Those skilled in the art can easily understand other aspects and advantages of the present invention from the following detailed description, in which only illustrative embodiments of the present invention are shown and described. As will be clear, the present invention is capable of other and different embodiments, and some of its details can be modified in various obvious ways, all without departing from the present invention. Therefore, the drawings and description should be regarded as illustrative in nature and not restrictive. Incorporated by reference

All publications and patent applications mentioned in this specification are incorporated herein by reference, and the degree of incorporation is as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference.

Cross-reference This application claims the rights of U.S. Provisional Application No. 62/805,729 filed on February 14, 2019 and U.S. Provisional Application No. 62/873,640 filed on July 12, 2019. These applications are based on The way of reference is incorporated into this article.

Although various embodiments of the present invention have been shown and described herein, those skilled in the art will obviously understand that these embodiments are provided by way of example only. Those skilled in the art can make many changes, changes and substitutions without departing from the present invention. It should be understood that various alternatives to the embodiments of the invention described herein may be employed.

As used herein, the term "slurry" generally refers to a solution containing a liquid phase and a solid phase. The solid phase may be contained in the liquid phase. The slurry may have one or more liquid phases and one or more solid phases.

As used herein, the term "adjacent/adjacent to" generally refers to "close", "adjacent", "contact" and "close". In some cases, the adjacency can 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 intervening layers between the first layer and the second layer.

The term "at least", "greater than" or "greater than or equal to" applies whenever the term "at least", "greater than" or "greater than or equal to" precedes the first number in a series of two or more numbers For each value in the series of values. For example, greater than or equal to 1, 2, or 3 is equivalent to greater than or equal to 1, greater than or equal to 2, or greater than or equal to 3.

Whenever the term "not greater than", "less than" or "less than or equal to" precedes the first number in a series of two or more numbers, the term "not greater than", "less than" or "less than or equal to" "Apply to each 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 parts, articles or articles (for example, sheets, pipes or wires) coated with one or more metal layers. The component can be at least a part of the object or can be the whole of the object. The metal layer may include one or more metals. In some cases, the substrate may be coated with a metal layer. The coating may include an alloying agent having at least one elemental metal. When a substrate is coated with a slurry containing an alloying agent having at least one elemental metal, a slurry-coated substrate can be formed. The substrate that has been coated with the alloying agent can be subjected to annealing conditions to produce a metal layer adjacent to the substrate. The metal layer can be coupled to the substrate by means of a diffusion layer between the metal layer and the substrate.

The substrate can produce alloy layers >50 microns while still retaining fine grains (>7 ASTM grain size) in the substrate. The levels developed and proposed above may be non-standard levels. These grades can be used for high temperature annealing or high temperature applications that are not related to the metallization process. Substrate and slurry

The present invention provides a substrate and a method for depositing a metal layer adjacent to 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 and roughness damping steel.

The base material can be provided as coils, wound nets, wires, pipes, tubes, slabs, nets, dip-molded parts, foils, plates, wire ropes, rods or threaded rods (which have been The screw pattern is applied to any length or thickness of the rod, sheet or flat surface. For example, the sheet may have any thickness from 0.001 inch to 1 inch.

The substrate may include an element material, which is a transition metal, a non-metal element, a metal oxide, a reduced metal element, a metal halide, an activator, a metalloid, or a combination thereof (for example, a plurality of element metals). The substrate may include a transition metal. The substrate may contain non-metallic elements. The substrate may include a metalloid. The substrate may comprise 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 of element substances. The substrate may include an element substance configured as a reducing metal agent. The reducing metal agent may include aluminum, titanium, zirconium, silicon, or magnesium. The substrate may include a carrier solvent such as water, isopropanol, or methyl ethyl ketone.

The substrate may comprise metal, such as iron, copper, aluminum, or any combination thereof. The substrate may include metal and/or non-metal alloys. The alloy may contain impurities. The substrate may comprise steel. The substrate may be a steel substrate. The substrate may include ceramic. The substrate may not contain free carbon. The substrate can be made from the molten phase. The substrate may be in a cold reduced state, in a completely hard state (for example, without an annealing step after cold reduction), or in a hot rolled and pickled state.

The substrate may include a metal oxide. The metal oxide may include, but is not limited to, Al ₂ O ₃ , MgO, CaO, Cr ₂ O ₃ , TiO ₂ , FeCr ₂ O ₄ , SiO ₂ , Ta ₂ O _5, or MgCr ₂ O ₄ , or a combination thereof. The metal oxide can be directly incorporated into the substrate. The metal oxide can be formed in the substrate by the metal thermal reduction reaction between the elemental metal and the thermodynamically unstable metal oxide. Suitable elemental metals and thermodynamically unstable metal oxide pairs can be selected from the pairs whose Gibbs free formation can be reduced by the oxidation of elemental metals by metal oxides. The thermal reduction of metals can occur spontaneously. The metal thermal reduction reaction can occur in the presence of a metal transfer activator such as a halide, metal halide, metal sulfide, or hydrogen. The metal oxide may include powder.

The powder (e.g., containing metals, metal oxides, metal halides, or other substrate components) may include individual particles having a particle size (e.g., average particle size) of about 0.01 microns (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 powder may have an average particle size of no greater than about 1 mm, 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 can have about 0.01 µm to 0.1 µm, 0.01 µm to 1 µm, 0.01 µm to 20 µm, 0.01 µm to 30 µm, 0.01 µm to 50 µm, 0.01 µm to 100 µm, 0.01 µm to 250 µm, 0.01 µm to 500 µm, 0.01 µm to 1 mm, 0.1 µm to 1 µm, 0.1 µm to 20 µm, 0.1 µm to 30 µm, 0.1 µm to 50 µm, 0.1 µm to 100 µm, 0.1 µm to 250 µm, 0.1 µm to 500 µm, 0.1 µm to 1 mm, 1 µm to 20 µm, 1 µm to 30 µm, 1 µm to 50 µm, 1 µm to 100 µm, 1 µm to 250 µm, 1 µm to 500 µm, 1 µm to 1 mm, 10 µm To 100 µm, 10 µm to 250 µm, 10 µm to 500 µm, 10 µm to 1 mm, 100 µm to 250 µm, 100 µm to 500 µm, 100 µm to 1 mm, 250 µm to 500 µm, 250 µm to 1 mm or 500 µm to 1 mm average particle size. The powder may have individual particles having 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, 1 mm or greater. The powder may have individual particles with a particle size of at most 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. The powder may comprise particles that can pass through a sieve having a mesh size of at least 325 or less. Powders containing metals, metal oxides, metal halides, or other substrate components may contain at least about 18, 20, 25, 30, 35, 40, 45, 50, 60, 65, 80, 100, 115 , 150, 170, 200, 250, 270 mesh size or at least about 400 or larger mesh size sieve particles.

The slurry mixture may comprise about 30% by weight (weight%), 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight of the total weight of the slurry. % By weight, 80% by weight, 85% by weight, 90% by weight or about 95% by weight of metal oxide. The slurry mixture may comprise at least about 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, 85% by weight, 90% by weight, or about 95% by weight or more of metal oxide. The slurry mixture may comprise not more than about 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50% by weight of the total weight of the slurry. , 45% by weight, 40% by weight, 35% by weight or not more than about 30% by weight or less of metal oxide. The slurry mixture may include metal oxides in the range of about 30 to about 95% by weight of the total weight of the slurry. The metal oxide may account for about 1 to about 95% by weight, about 1 to about 85% by weight, about 1 to about 75% by weight, about 1 to about 60% by weight, about 1 to about 50% by weight, about 1% by weight of the total weight of the slurry. To about 40% by weight, about 1 to about 30% by weight, about 1 to about 20% by weight, about 1 to about 10% by weight, about 5 to about 95% by weight, about 5 to about 85% by weight, about 5 to about 75% by weight, about 5 to about 60% by weight, about 5 to about 50% by weight, about 5 to about 40% by weight, about 5 to about 30% by weight, about 5 to about 20% by weight, about 5 to about 10% by weight %, about 10 to 95% by weight, about 10 to about 85% by weight, about 10 to about 75% by weight, about 10 to about 60% by weight, about 10 to about 50% by weight, about 10 to about 40% by weight, about 10 to about 30% by weight, about 10 to about 20% by weight, about 20 to about 95% by weight, about 20 to about 85% by weight, about 20 to about 75% by weight, about 20 to about 60% by weight, about 20 to about About 50% by weight, about 20 to about 40% by weight, about 20 to about 30% by weight, about 30 to about 85% by weight, about 30 to about 75% by weight, about 30 to about 60% by weight, about 30 to about 50 Weight%, about 30 to about 40% by weight, about 1 to about 95% by weight, about 40 to about 85% by weight, about 40 to about 75% by weight, about 40 to about 60% by weight, about 40 to about 50% by weight , About 50 to about 95% by weight, about 50 to about 85% by weight, about 50 to about 75% by weight, or about 50 to about 60% by weight. The metal oxide or reduced metal can be selected for its relative purity. The metal oxide or reduced metal may comprise at least about 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% by weight. %, 90%, 95%, 99%, 99.9% or at least about 99.99% or greater purity. The metal oxide or reduced metal may contain no more than about 99.99%, 99%, 95%, 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30% or not more than about 25% or less purity.

The reducing metal may comprise an atomic ratio of about 0.6 to 2.0 to the oxide source. The reducing metal may comprise an atomic ratio of about 0.01 to 10.0 and an oxide source, about 0.01 to 1.0 atomic ratio, about 0.01 to 1.5 atomic ratio, about 0.01 to 3.0 atomic ratio, about 0.01 to 4.0 atomic ratio, about 0.01 to 5.0 atomic ratio , About 0.1 to 1.0 atomic ratio, about 0.1 to 1.5 atomic ratio, about 0.1 to 3.0 atomic ratio, about 0.1 to 4.0 atomic ratio, about 0.1 to 5.0 atomic ratio, about 0.1 to 10.0 atomic ratio, about 0.5 to 1.0 atomic ratio, About 0.5 to 1.5 atomic ratio, about 0.5 to 3.0 atomic ratio, about 0.5 to 4.0 atomic ratio, 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 include a metal transfer activator component. The metal transfer activator can account for about 0.001% by weight, 0.01% by weight, 0.1% by weight, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight, or about 50% by weight. The metal transfer activator may account for at least about 0.001%, 0.01%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 10% by weight of the total substrate , 15% by weight, 20% by weight, 30% by weight, or at least about 50% by weight or more. The metal transfer activator may account for no more than about 50%, 30%, 20%, 15%, 10%, 5%, 4%, 3%, 2%, 1% by weight of the total substrate %, 0.5% by weight, 0.1% by weight, 0.01% by weight, or not more than about 0.001% by weight or less. The metal transfer activator may account for about 0.001 to 1% by weight, about 0.001 to 2% by weight, about 0.001 to 3% by weight, about 0.001 to 4% by weight, about 0.001 to 5% by weight, about 0.001 to 10% by weight of the total substrate , About 0.001 to 15% by weight, about 0.001 to 20% by weight, about 0.001 to 30% by weight, about 0.001 to 50% by weight, about 0.01 to 1% by weight, about 0.01 to 2% by weight, about 0.01 to 3% by weight, About 0.01 to 4% by weight, about 0.01 to 10% by weight, about 0.01 to 15% by weight, about 0.01 to 20% by weight, about 0.01 to 30% by weight, about 0.01 to 50% by weight, about 0.1 to 1% by weight, about 0.1 to 2% by weight, about 0.1 to 3% by weight, about 0.1 to 4% by weight, about 0.1 to 5% by weight, about 0.1 to 10% by weight, about 0.1 to 15% by weight, about 0.1 to 20% by weight, about 0.1 To 30% by weight, about 0.1 to 50% by weight, about 1.0 to 2% by weight, about 1.0 to 3% by weight, about 1.0 to 4% by weight, about 1.0 to 10% by weight, about 1.0 to 15% by weight, about 1.0 to 20% by weight, about 1.0 to 30% by weight, about 1.0 to 50% by weight, or about 10 to 50% by weight.

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 layers. The coating may include an alloying agent having at least one elemental metal. The metal layer can be coupled to the substrate by means of a diffusion layer between the metal layer and the substrate.

The metal layer may have at least about 1 nanometer, 10 nanometers, 100 nanometers, 500 nanometers, 1 micrometer, 5 micrometers, 10 micrometers, 25 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers or at least Thickness of 100 microns or greater. The metal layer may have a thickness not greater than about 100 microns, 90 microns, 80 microns, 70 microns, 60 microns, 50 microns, 25 microns, 10 microns, 5 microns, 1 microns, 500 nanometers, 100 nanometers, 10 nanometers, or not Thickness greater than about 1 nanometer or less. The thickness of the metal layer can be greater than the single atomic layer. The thickness can be multiple layers.

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

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

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of manganese (Mn). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of manganese.

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

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of vanadium (V). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of vanadium.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of titanium (Ti). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of titanium. In some cases, the substrate may include at least about 0.015% by weight titanium.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more nitrogen (N). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less nitrogen.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of phosphorus (P). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less phosphorus.

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

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of aluminum (Al). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less aluminum.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of copper (Cu). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less copper.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of nickel (Ni). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less nickel.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of chromium (Cr). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of chromium.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more molybdenum (Mo). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of molybdenum.

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

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of boron (B). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less boron.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of calcium (Ca). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less calcium.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of arsenic (As). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of arsenic.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of cobalt (Co). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of cobalt.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of lead (Pb). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of lead.

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

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of tantalum (Ta). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of tantalum.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of tungsten (W). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less tungsten.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of zinc (Zn). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of zinc.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of zirconium (Zr). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of zirconium.

The substrate may contain more than 0.0001% by weight, 0.0005% by weight, 0.001% by weight, 0.002% by weight, 0.004% by weight, 0.005% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4 Weight%, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight, 1% by weight, 1.1% by weight, 1.2% by weight, 1.3% by weight, 1.4% by weight, 1.5% by weight, 1.6% by weight , 1.7% by weight, 1.8% by weight, 1.9% by weight, 2% by weight, 2.5% by weight, 3% by weight, 5% by weight, 7% by weight, 10% by weight, 15% by weight, 20% by weight, 30% by weight or more About 40% by weight or more of silicon (Si). The substrate may comprise less than or equal to about 40% by weight, 30% by weight, 20% by weight, 15% by weight, 10% by weight, 7% by weight, 5% by weight, 3% by weight, 2.5% by weight, 2% by weight, 1.9% by weight %, 1.8% by weight, 1.7% by weight, 1.6% by weight, 1.5% by weight, 1.4% by weight, 1.3% by weight, 1.2% by weight, 1.1% by weight, 1% by weight, 0.9% by weight, 0.8% by weight, 0.7% by weight, 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% by weight or less of silicon.

There may be free gaps during the formation of the substrate, such as nitrogen, carbon, and sulfur. The niobium in the substrate can bond to these free gaps in the substrate (for example, nitrogen, carbon, and sulfur). The addition of niobium can prevent grain boundary precipitation, such as chromium grain boundary precipitation. The reduction of grain boundary precipitation can lead to an increase in corrosion performance, which can be a required property of the substrate. Figure 3 illustrates the steel substrate after coating with a metal layer, in which no grain boundary chromium precipitation is observed.

It can measure the weight% of chromium on the surface of the substrate. The chromium weight% can be the chromium weight% of the coated substrate or the uncoated substrate. In some cases, the weight% of chromium 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% of the substrate can be no more than about 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 10%, Or not more than about 5% or less. The weight% of chromium of the substrate can be about 16%, 17%, 18%, 19%, 20%, 21%, 22% or 23%. The chromium weight% of the coated substrate can be greater than, about, or less than the chromium weight% of the uncoated substrate.

Substrates can be purchased from suppliers. The substrate can be coated with the metal-containing layer on the same day the substrate is prepared. The substrate can be prepared more than about 2 days, 3 days, 1 week, 1 month, or 1 year or more before coating the metal-containing layer. The substrate can be prepared less than about 1 year, 1 month, 1 week, 3 days, or less than 2 days before coating the metal-containing layer. The metal layer can be added to the substrate 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, Add reducing metal to the substrate for 9 hours, 10 hours, 11 hours, 12 hours or longer. Can add the metal layer to the substrate 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 Add reducing metal to the substrate in hours, 30 minutes, 10 minutes, 5 minutes, 1 minute, 30 seconds or less. In some examples, after adding the metal layer to the substrate 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, Add the reduced metal to the substrate within 3 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 18 hours, 24 hours, or within about 2 days.

The present invention provides a method for forming a metal layer adjacent to a substrate. The metal layer can be formed by applying a slurry adjacent to the substrate. Depositing the slurry adjacent to the substrate can form a metal-containing layer adjacent to the substrate. In some cases, the slurry includes an alloying agent, a metal transfer activator, and a solvent, and wherein the alloying agent includes a metal.

In some cases, the metal-containing layer contains 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 can be selected from the group consisting of FeSi, FeCr, chromium and combinations thereof.

The slurry may contain metal oxides. The metal oxide may include, but is not limited to, Al ₂ O ₃ , MgO, CaO, Cr ₂ O ₃ , TiO ₂ , FeCr ₂ O ₄ , SiO ₂ , Ta ₂ O _5, or MgCr ₂ O ₄ or a combination thereof. The metal oxide can be incorporated directly into the slurry. The metal oxide can be formed in the slurry by the metal thermal reduction reaction between the elemental metal and the thermodynamically unstable metal oxide. Suitable elemental metal and thermodynamically unstable metal oxide pairs can be selected from the pairs whose Gibbs free formation energy is reduced by the oxidation of elemental metals by metal oxides. The thermal reduction of metals can occur spontaneously. The metal thermal reduction reaction can occur in the presence of a metal transfer activator (such as a halide, a metal halide, a metal sulfide, or a gaseous substance). The metal oxide may include powder.

The slurry may include a metal transfer activator that is configured to carry the metal material from the slurry to the surface of the substrate. The metal transfer activator may include halide, metal halide, sulfide, or hydrogen. The metal transfer activator can be introduced during slurry preparation, for example, by adding one or more powders. The metal transfer activator may be introduced after the slurry is formed from an external source, such as to diffuse hydrogen gas into the slurry layer after the slurry layer is applied to the substrate. In some cases, the metal transfer activator includes a monovalent metal, a divalent metal, or a trivalent metal. In some cases, the metal transfer 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 chloride ( III) (VCl ₃ ), chromium(III) chloride (CrCl ₃ ), trichlorosilane (SiHCl ₃ ), manganese(II) chloride (MnCl ₂ ), chromium(II) chloride (CrCl ₂ ), chlorinated Cobalt(II) (CoCl ₂ ), copper(II) chloride (CuCl ₂ ), nickel(II) chloride (NiCl ₂ ), vanadium(II) chloride (VCl ₂ ), ammonium chloride (NH ₄ Cl) , Sodium chloride (NaCl), potassium chloride (KCl), molybdenum sulfide (MoS), manganese sulfide (MnS), 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 the group consisting of iron chloride tetrahydrate (FeCl ₂ ·4H ₂ O), iron chloride hexahydrate (FeCl ₂ ·6H ₂ O) and magnesium chloride hexahydrate (MgCl ₂ ·6H ₂ O) Group of composition. In some embodiments, the halide activator is hydrated. In some embodiments, the halide activator is selected from the group consisting of iron chloride tetrahydrate (FeCl ₂ ·4H ₂ O), iron chloride hexahydrate (FeCl ₂ ·6H ₂ O) and magnesium chloride hexahydrate (MgCl ₂ ·6H ₂ O) Group of composition.

In some cases, after annealing the metal-containing layer to the substrate, the metal layer is formed adjacent to the substrate. In some cases, the metal layer contains 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 ferrosilicon (FeSi), ferrochromium (FeCr), chromium, and combinations thereof.

The slurry may contain a solvent. The solvent can be water-based 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 lower than or equal to about 200℃, 190℃, 180℃, 170℃, 160℃, 150℃, 140℃, 130℃, 120℃, 110℃ or 100℃ or lower . The boiling point of the solvent may be higher than or equal to about 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, or higher than about 200°C or higher.

In some cases, the slurry contains inert materials. The slurry can be formed by mixing various components in a mixing chamber (or container). The various components can be mixed at the same time or sequentially. For example, a solvent is provided in the chamber and then elemental substances are added to the chamber. To prevent caking, dry ingredients can be added to the solvent in controlled amounts. Some elemental metals may be in dry powder form.

The blade used for mixing the components of the metal-containing layer may be in the shape of a stirring member, fork or paddle. More than one blade can be used to mix the slurry components. Each blade may have a different shape or the same shape. Dry ingredients can 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 size of chromium particles can be larger than other particles, and can be suspended without adding high polymer.

The properties of the slurry can be a function of one or more parameters used to form the slurry, maintain the slurry, or deposit the slurry. Such properties can include viscosity, shear thinness index, and yield stress. Such properties may include Reynolds number, viscosity, pH, and slurry component concentration. The parameters that can affect the properties of the slurry can include water content, element identity and content, temperature, shear rate, and mixing time.

Figure 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 to the substrate from the mixing container to form a metal layer. In operation 130 , after application, the solvent in the slurry is removed by heating or vacuum drying at about 90°C to 175°C for about 10 to 60 seconds. In operation 140 , the mesh or substrate material is rolled or otherwise prepared for heat treatment. In operation 150 , the metal layer is annealed adjacent to the substrate.

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

The slurry can exhibit thixotropic behavior, where the slurry exhibits a reduced viscosity when subjected to shear strain. The shear thinness index of the slurry can be from about 1 to about 8. To achieve the target viscosity, mixing can occur at a high shear rate. The shear rate may be about 1 s ^-1 to about 10,000 s ^-1 (or Hz). The shear rate may be about 1 s ^-1 , about 10 s ^-1 , about 100 s ^-1 , about 1,000 s ^-1 , about 5,000 s ^-1, or about 10,000 s ^-1 . The shear rate may be at least about 1 s ^-1 , about 10 s ^-1 , about 100 s ^-1 , about 1,000 s ^-1 , about 5,000 s ^-1, or at least about 10,000 s ^-1 or greater. The shear rate may be less than about 10,000 s ^-1 , 5,000 s ^-1 , 1,000 s ^-1 , 100 s ^-1 , 10 s ^-1 , or less than about 1 s ^-1 or less.

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

In order to achieve the target viscosity or predetermined viscosity, mixing can be carried out for a period of about 1 minute to 2 hours. The mixing time can be less than about 30 minutes. The longer the slurry is mixed, the viscosity of the slurry will decrease. The mixing time may correspond to the length of time used to homogenize the slurry.

The proper mixing state can be a state where the slurry does not have water on the surface. The proper mixing state can be the state without solids on the bottom of the container. The slurry appears to be uniform in color and texture.

The required viscosity of the metal-containing layer can be the viscosity suitable for roll coating. The viscosity of the slurry can be about 1 centipoise (cP), 5 cP, 10 cP, 50 cP, 100 cP, 200 cP, 500 cP, 1,000 cP, 10,000 cP, 100,000 cP, 1,000,000 cP, or about 5,000,000 cP. The viscosity of the slurry can be at least about 1 cP, 5 cP, 10 cP, 50 cP, 100 cP, 200 cP, 500 cP, 1,000 cP, 10,000 cP, 100,000 cP, 1,000,000 cP, or about 5,000,000 cP. The viscosity of the slurry can be no more than about 5,000,000 cP, 1,000,000 cP, 100,000 cP, 10,000 cP, 5,000 cP, 1,000 cP, 500 cP, 200 cP, 100 cP, 50 cP, 10 cP, 5 cP, or no more than about 1 cP. The viscosity of the slurry can be about 1 cP to 5,000,000 cP. The viscosity of the slurry can be about 1 cP, about 5 cP, about 10 cP, about 50 cP, about 100 cP, about 200 cP, about 500 cP, about 1,000 cP, about 10,000 cP, about 100,000 cP, about 1,000,000 cP, or about 5,000,000 cP. The viscosity of the slurry can be about 1 cP to 1,000,000 cP or 100 centipoise (cP) to 100,000 cP. The viscosity of the slurry can depend on the shear rate. The viscosity of the slurry may be about 200 cP to about 10,000 cP or about 600 cP to about 800 cP. In an application shear window having a shear rate of about 1000 s ^-1 to about 1,000,000 s ^-1 , the slurry may be about 100 cP to about 200 cP. The number of capillaries of the slurry can be about 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10. The number of capillaries of the slurry can 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 number of capillaries of the slurry can be no more than about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, or no more than about 0.01 or less. The yield stress of the slurry can be about 0.0001 Pascal (Pa), 0.001 Pa, 0.01 Pa, 0.1 Pa, 0.2 Pa, 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa, or about 1 Pa. The yield stress of the slurry may be at least about 0.0001 Pascal (Pa), 0.001 Pa, 0.01 Pa, 0.1 Pa, 0.2 Pa, 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, 0.8 Pa, 0.9 Pa or at least about 1. Pa or greater. The yield stress of the slurry can be no more than 1 Pa, 0.9 Pa, 0.8 Pa, 0.7 Pa, 0.6 Pa, 0.5 Pa, 0.4 Pa, 0.3 Pa, 0.2 Pa, 0.1 Pa, 0.01 Pa, 0.001 Pa or no more than 0.001 Pa or more small.

The sedimentation rate of the slurry can be stable for separation or sedimentation for greater than about one minute, greater than about 15 minutes, greater than about 1 hour, greater than about 1 day, greater than about 1 month, or greater than about 1 year. The sedimentation rate of the slurry can refer to the time that the slurry can withstand without mixing before the sedimentation occurs, or before the viscosity increases to a value that is not suitable for roll coating. Similarly, the shelf life of a slurry can refer to the time the slurry can withstand without mixing before the slurry thickens to an extent unsuitable for roll coating. However, even if the slurry settles and thickens, the slurry can be remixed to its original viscosity. The thixotropic index of the slurry can be stable, so that the slurry will not thicken to an unsuitable level at the dead spot in the pan of the roller coating component.

The viscosity of the slurry can be controlled by adding acid to the slurry during mixing to control the degree of hydrogen bonding. In addition, acid or alkali can be added to the slurry during mixing to control the pH level of the slurry. The pH of the slurry can be about 3, 4, 5, 6, 7, 8, 9, 10, 11, or about 12. The pH level of the slurry can 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 may be no greater than about 12, 11, 10, 9, 8, 7, 6, 5, 4, or no greater than about 3 or less. The pH level of the slurry can be from about 3 to about 12. The pH level of the slurry can be from about 5 to about 8. The pH level of the slurry can be about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, or about 12. The pH level of the slurry can change as the slurry settles. After the slurry settles, mixing the slurry can restore the pH level of the slurry to the initial pH level. Different amounts of binder (such as metal acetate) can be added to the slurry to increase the green strength in the slurry. The slurry may not contain a binder. The slurry may include a metal transfer activator configured to act as a binder.

The fluidity of the slurry can be measured by the tilt test. Tilt test can indicate yield stress and viscosity. As an alternative, a rheometer can be used to measure the fluidity of the slurry.

The drying time of the slurry can be long enough so that the slurry remains wet during the roll coating process and will not dry until the coating of the slurry is applied to the substrate. The slurry may not dry out at room temperature. After heating the drying zone of the roll coating line for about ten seconds, the slurry can become dry. The temperature of the applied heat may be about 120°C.

The specific gravity of the slurry can be about 1, 2, 3, 4, 5, 6, 7, 8, 9, or about 10 g/cm ³ . The specific gravity of the slurry may be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, or at least about 10 g/cm ³ or higher. The specific gravity of the slurry can be no more than about 10, 9, 8, 7, 6, 5, 4, 3, 2, or no more than about 1 g/cm ³ or less. The green strength of the slurry can be such that the slurry can withstand roll coating so that the substrate coated with the slurry is not damaged. For example, after roll coating, the dry film of the slurry dried in the drying oven adjacent to the coating room can have a green strength that allows the film to withstand a force that bends the film into an arc with a diameter of about 20 inches in alternating negative and positive directions Twenty times. The green strength of the dry film of the slurry can further allow the film to pass the tape test with a small amount of powder. The tape test may involve contacting a piece of tape with the surface of the coated material. Once removed from the surface of the coated material, the tape may be transparent enough to see through any powder that has adhered to the tape.

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

The slurry can be applied adjacent to one or more surfaces of the substrate in a specific thickness. The thickness of the applied slurry coating can be relatively uniform or variable over the surface. The thickness of the applied slurry coating can vary from one surface of the substrate to another surface. The thickness of the applied slurry coating adjacent to the substrate can be measured at any time, including immediately after application, during drying, or after all solvents have been removed. If at least 90%, 95%, 99% or more of the surface of the substrate has a deviation from the average thickness of the applied slurry coating not 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% of the slurry coating is applied The slurry coating can be regarded as substantially uniform.

The average coating thickness of the slurry coating applied on one or more surfaces adjacent to the substrate 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, 1 mm, 2 mm, 5 mm, or about 1 cm. The average application thickness of the slurry coating applied on one or more surfaces adjacent to the substrate before or after drying can be 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, 1 mm , 2 mm, 5 mm, or about 1 cm. The coating thickness of the slurry coating applied on one or more surfaces adjacent to the substrate before or after drying can be no more than about 1 cm, 5 mm, 2 mm, 1 mm, 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.

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

Elemental substances in the slurry can affect the adhesion of the metal-containing layer to the substrate. In addition, elemental substances can affect the viscosity of the metal-containing layer composition. In addition, elemental substances can affect the green strength of the substrate coated with the metal-containing layer. Generally speaking, green strength refers to the ability of a substrate coated with a metal-containing layer to withstand treatment or machining before the metal-containing layer is fully cured. Therefore, the element material can be selected based on the required degree of adhesion of the metal-containing layer to the substrate, the required viscosity of the metal-containing layer, and the ability of the element material to increase the green strength of the substrate coated with the metal-containing layer. In addition, some metal-containing halides can corrode the components of the roll-coated components that apply the metal-containing layer to the substrate. Such corrosion may be undesirable. The element substance can prevent the formation of Kirkendall pores at the boundary interface between the metal-containing layer and the substrate. When heated, elemental substances can be decomposed into oxides. In addition, after annealing, the element material can become inert. The concentration of various element substances can vary.

The substrate can be pre-treated before applying the slurry to the substrate. The surface of the substrate can be modified by pretreating the substrate with chemicals to improve the adhesion of the metal-containing layer to the surface of the substrate. Examples of such chemicals include chromate and phosphate.

The surface of the substrate may not contain processing oxides. This can be achieved by conventional pickling. The surface of the substrate can be reasonably free of organic materials. After treatment with commercially available cleaners, the surface of the substrate can be reasonably free of organic materials.

Die pinning particles can be added, removed or detained from the substrate during the preparation of the substrate to control the grain size of the substrate. For example, die pinning can be added to the substrate to keep the die size small and form pinning points. As another example, a die pinning agent can be withheld from the substrate to allow the die to grow large and allow motor lamination. The grain pinning agent is insoluble at the annealing temperature.

Examples of grain pinning particles include intermetallics, nitrides, carbides, carbonitrides of titanium, aluminum, niobium, vanadium, and any combination thereof. Non-limiting examples of grain pinning particles include titanium nitride (TiN), titanium carbide (TiC), and aluminum nitride (AlN). Formation of the metal layer adjacent to the substrate

The slurry can be applied or deposited adjacent to the substrate and form a metal-containing layer adjacent to the surface. The metal-containing layer can be annealed to form a metal layer adjacent to the substrate. The slurry can be applied by roller coating, split coating, spin coating, slit coating, curtain coating, sliding coating, extrusion coating, paint coating, spraying, electrostatic mechanism, printing (for example, 2-D printing, 3- D printing, screen printing, pattern printing), vapor deposition (for example, chemical vapor deposition), electrochemical deposition, slurry deposition, dip coating, spraying, any combination thereof, or application by any other suitable method.

The slurry can be applied by roller coating. The roll coating process can be started by providing a substrate (such as a steel substrate). Next, the wound substrate can be unwound. Next, the unwound steel substrate can be provided to a roll coater, which can be coated with a metal-containing layer. Next, the roll coater can be activated so that the roll coater coats the substrate with the metal-containing layer. The substrate can be fed through a roll coater through multiple cycles so that the metal-containing layer is applied to the substrate multiple times. Depending on the nature of the metal-containing layer, it may be desirable to apply multiple coatings to the substrate. Multiple coatings containing metal layers can be applied to the substrate to achieve the desired slurry thickness. Different formulations or metal-containing layers can be used in each of the multiple coatings. The metal-containing layer can be applied in a manner such as forming a pattern on the substrate. The pattern may be in the form of, for example, a grid, stripes, dots, welding marks, or any combination thereof. Multiple coatings on the same substrate can form separate coatings on the substrate.

The slurry can be applied, deposited or annealed adjacent to the substrate. The slurry can be deposited at a temperature of about 0℃, 25℃, 50℃, 75℃, 100℃, 200℃, 300℃, 400℃, 500℃, 600℃, 700℃, 800℃, 900℃ or 1000℃. Can be at least about 0℃, 25℃, 50℃, 75℃, 100℃, 200℃, 300℃, 400℃, 500℃, 600℃, 700℃, 800℃, 900℃ or 1000℃ or higher temperature The slurry is deposited under. Can be at no higher than about 1000℃, 900℃, 800℃, 700℃, 600℃, 500℃, 400℃, 300℃, 200℃, 100℃, 75℃, 50℃, 25℃ or not higher than about 0 Deposit the slurry at a temperature of ℃ or lower. The slurry can be deposited at a temperature of about 0°C to 1000°C. The slurry can be deposited at a temperature of about 10°C to 100°C. The slurry can be deposited at a temperature of about 100°C to 500°C. The slurry can be deposited at a temperature of about 500°C to 1000°C.

It can occur in an atmosphere with a relative humidity of about 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or about 99%. Deposition of sizing liquid on wood. Can be at least about 0%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or at least about 99% or higher relative humidity The deposition of slurry on the substrate occurs in the atmosphere. It can be used when the relative humidity is not more than about 99%, 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or not more than about 5% or less. The deposition of slurry on the substrate occurs in the atmosphere. The substrate sizing can occur in an atmosphere with an absolute moisture content of at least about 0.5 Torr, 1 Torr, 2 Torr, 5 Torr, 10 Torr, 20 Torr, 50 Torr, 100 Torr, 250 Torr, or at least about 500 Torr or more The deposition. The substrate can be produced in an atmosphere with an absolute moisture content of not 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 Deposition of sizing liquid. In some embodiments, during the deposition of the metal-containing layer, the relative humidity is about 50%.

The substrate sizing can occur in an atmosphere where the oxygen content is 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 The deposition. It can occur on the substrate in an atmosphere where the oxygen content is not 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 deposition of slurry. The drying of the slurry on the substrate can occur under ambient air conditions.

Annealing of the slurry on the substrate can occur in an atmosphere with a low oxygen content (such as not greater 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 sizing liquid on the substrate can occur in an atmosphere with 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 more.

The drying of the metal-containing layer can occur in an atmosphere where the hydrogen content is 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. The drying of the metal-containing layer on the substrate can occur in an atmosphere with a hydrogen content 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 occur 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 can be removed by heating, vaporizing, vacuuming, or any combination thereof. After the solvent is driven off, the substrate can be rewinded. After deposition and before annealing, the slurry-coated substrate can be cultured or stored under vacuum or atmospheric conditions. This occurs before annealing and can be used to remove residual contaminants from the coating, for example, to remove residual solvents or binders from the coating process. The incubation period can be about 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes. The incubation period can 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 longer. The incubation period can be no more than about 5 minutes, 4 minutes, 3 minutes, 2 minutes, 1 minute, 50 seconds, 40 seconds, 30 seconds, 20 seconds, or no more than about 10 seconds or less. The incubation period can be the time between coating and annealing, and can be the length of time used to transport the coated product to a heat treatment facility or equipment. For example, the incubation period may last for about 10 seconds, about 30 seconds, about 1 minute, about 2 minutes, about 3 minutes, about 4 minutes, or about 5 minutes. The culture temperature can be about 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, or about 300°C. The culture temperature may be at least about 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, or at least about 300°C or higher. The culture temperature can be no more than about 300°C, 275°C, 250°C, 225°C, 200°C, 175°C, 150°C, 125°C, 100°C, 75°C, or no more than about 50°C or lower. The culture temperature can be in the range of about 50°C to about 300°C. For example, the culture temperature may be greater than about 50°C, about 75°C, about 100°C, about 125°C, about 150°C, about 175°C, about 200°C, about 225°C, about 250°C, about 275°C, or about 300°C Or higher. After incubation and before annealing, the dry film of the slurry on the substrate can be maintained under vacuum. The coating can be dried immediately following the drying step after the roll coating process. At any time between roll coating and annealing, absorbed water or other contaminants can be present with the coating.

The spatially separated alloy can be deposited on the surface of the metal substrate using alloying metal, which has been generated in situ from its metal oxide by metal thermal reduction (or reduction) reaction. When a thermodynamically unstable metal oxide is introduced in the presence of a reducing metal agent, a metal thermal reduction reaction can occur, which forms a thermodynamically more stable metal oxide. The reducing metal agent may include any elemental substance, including iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium, niobium, and combinations thereof.

In some embodiments, the metal thermal reduction reaction can be initiated or enhanced by a metal transfer activator. The metal compound can be reduced so that the Gibbs free formation energy of its corresponding metal oxide is relatively large, for example, aluminum to aluminum oxide. Such reduced metals can be used as effective oxygen and water scavengers to eliminate oxidizing substances that would hinder the positive reaction of metal oxides and activator compounds. An example of the overall metal thermal reduction reaction may include the reaction of chromium oxide and aluminum metal, such as: 1) Cr ₂ O ₃ + 3H ₂ --> 2Cr + 3H ₂ O 2) 2Al + 3H ₂ O --> Al ₂ O ₃ + 3H ₂ wherein the above reaction can be used to deposit the source of chromium in the metal layer on the surface of the substrate. The use of metal oxides as the source material for deposition can eliminate the need for additional inert powders in the reaction, which serve as a support for the metal layer and as a separator for alloying the metal powder during the sintering process. For example, by including the powder of the second element, or alloying the reducing element with a substance that increases the melting point of the reducing element to a temperature higher than the temperature used for deposition, the defect rate of the resulting metal layer can be reduced. The post-heat treatment cleaning process can more easily remove the resulting metal oxide from the reaction of the reducing metal agent. The spatially separated alloy may include an alloy metal layer on a net shape part (such as a metal tube, rod, wire, or other form of inner diameter).

The metal layer on the surface of the substrate may include a slurry applied to the surface of the substrate. The slurry may contain metal oxide powder, reducing metal agent, metal halide precursor or solvent. The chemical and rheological properties of the slurry containing metal oxide powder can be optimized. Increased rheology control can provide more uniform coating, including reducing undesired rheological effects such as ribs, cascades or other defects, and increasing surface coverage on the substrate surface, and can lead to metal utilization度 Increase. It can be based at least on the relative concentration of the components, the particle size of the components, pH, ionic strength, reduced sedimentation, slurry yield strength, slurry viscosity, and can affect the performance of the slurry as a source for depositing a metal layer on the substrate surface Any other properties to adjust the slurry composition.

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

The slurry-coated substrate can be rewinded before annealing. During the heat treatment, the slurry-coated substrate can be placed in a retort and in a controlled atmosphere. Can remove water. A vacuum can be drawn to force hydrogen between the claddings. The annealing process can be either tight coil or loose coil annealing. Annealing the substrate coated with the slurry layer can allow elemental substances in the slurry to diffuse into or through the substrate. After annealing, less than about 100% by weight, 90% by weight, 80% by weight, 70% by weight, 60% by weight, 50% by weight, 40% by weight, 30% by weight, 20% by weight, 10% by weight or 5% by weight or Less elemental substances can diffuse into or into 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 elements The substance can diffuse into or into the substrate. Certain process conditions can provide about 1 to 5% of the element material diffused from the coating into the substrate. The diffusion of elemental substances to the substrate can be assisted by the components in the slurry layer. The annealing process may be a continuous annealing process. The annealing process may be a discontinuous annealing process. The slurry-coated substrate can undergo more than one annealing process to increase the utilization of elemental substances or change the concentration gradient of elemental substances in the metal layer adjacent to the substrate.

The substrate may be greater than about 0.01°C/sec, 0.1°C/sec, 1°C/sec, 5°C/sec, 10°C/sec, 15°C/sec, 20°C/sec, 25°C/sec or 30°C/sec or Heating at a greater rate. The substrate can be greater than about 0.01°C/minute, 0.1°C/minute, 1°C/minute, 5°C/minute, 10°C/minute, 15°C/minute, 20°C/minute, 25°C/minute or 30°C/minute or Heating at a greater rate. The substrate can be less than about 30°C/minute, 25°C/minute, 20°C/minute, 15°C/minute, 10°C/minute, 5°C/minute, 1°C/minute, 0.1°C/minute, or less than about 0.01°C/minute Heating at a rate of minutes or less. The substrate may be less than about 30°C/sec, 25°C/sec, 20°C/sec, 15°C/sec, 10°C/sec, 5°C/sec, 1°C/sec, 0.1°C/sec, or less than about 0.01°C /Sec or less for heating. The substrate coated with the slurry can be at least about 0℃, 25℃, 50℃, 75℃, 100℃, 200℃, 300℃, 400℃, 500℃, 600℃, 700℃, 800℃, 900℃ , 1000℃, 1100℃, 1200℃ or 1300℃ or higher temperature for annealing. The annealing temperature can be no more than about 1300℃, 1200℃, 1100℃, 1000℃, 900℃, 800℃, 700℃, 600℃, 500℃, 400℃, 300℃, 200℃, 100℃, 75℃, 50 °C, 25 °C or no more than about 0 °C or lower. The annealing temperature can be about 800°C, 900°C, 1000°C, 1100°C, 1200°C, or 1300°C. The heating temperature during annealing may be about 800°C to about 1300°C, such as about 900°C to about 1000°C. The annealing temperature may be about 900°C, 925°C, 950°C, or 1000°C.

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

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 can be less than about 200 hours, 180 hours, 160 hours, 140 hours, 120 hours, 100 hours, 80 hours, 60 hours, 40 hours, 20 hours, 10 hours, or less than about 5 hours or less . The total annealing time (including heating) can range from about 5 hours to about 200 hours. For example, the total annealing time can be more than about 5 hours, about 20 hours, about 40 hours, about 60 hours, about 80 hours, about 100 hours, about 120 hours, about 140 hours, about 160 hours, about 180 hours, or about 200 hours. Hours or more. The maximum temperature during the annealing process can be reached within about 1 hour to 100 hours. For example, the maximum temperature during the annealing process can 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 the annealing process can be reached in at least about 1 hour, 10 hours, 20 hours, 30 hours, 40 hours, 50 hours, 60 hours, 70 hours, 80 hours, 90 hours, or at least about 100 hours or longer . The maximum temperature during the annealing process can be 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 Reached within. In some cases, the substrate may be annealed at a temperature of about 950°C for at least about 5 hours. In some cases, the substrate may be annealed at a temperature of about 950°C for at least about 20 hours. In some cases, the substrate may be annealed at a temperature of about 950°C for at least about 40 hours. In some cases, the substrate may be annealed at a temperature of about 900°C for at least about 20 hours. In some cases, the substrate may be annealed at a temperature of about 900°C for at least about 40 hours. In some cases, the substrate may be annealed at a temperature of about 900°C for at least about 60 hours. In some cases, the substrate may be annealed at a temperature of about 900°C for at least about 80 hours.

The annealing atmosphere may contain gaseous substances, such as inert or reactive gases, such as hydrogen, helium, methane, ethylene, nitrogen, or argon. The annealing atmosphere may include a mixture of gases. The annealing atmosphere can be vacuum. To prevent the loss of elemental substances during annealing, hydrochloric acid can be added to the annealing gas. Minimizing the partial pressure of the components in the metal-containing layer in the reactor at high temperatures can maintain a low deposition rate, which is necessary to minimize or stop the formation of Kirkendall holes. Adding too much acidic components to the metal-containing layer can also cause corrosion of coating equipment or substrates.

After annealing, the substrate coated with the metal layer can be dried. The drying of the substrate coated with the metal layer can occur in a vacuum or an atmosphere close to vacuum. The drying of the substrate coated with the metal layer can be carried out in an atmosphere of inert gas. Examples of inert gases include hydrogen, helium, argon, nitrogen, or any combination thereof.

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

Large-scale products can have hot or cold spots during heat treatment, where the product can be uniformly coated but unevenly heated. Hot or cold spots can be indicated to control the diffusion of alloying elements into the product as uniformly as possible.

After annealing, a metal layer can be formed on the substrate. The metal layer can be selected from carbon, manganese, silicon, vanadium, titanium, niobium, phosphorus, sulfur, aluminum, copper, nickel, chromium, molybdenum, tin, boron, calcium, arsenic, cobalt, lead, antimony, tantalum, tungsten At least one element material of zinc, silicon and zirconium, wherein the element material in the outer layer has a change of less than about 20% by weight, about 15% by weight, about 10% by weight, about 5% by weight, about 4% by weight, about 3% by weight , About 2% by weight, about 1% by weight, or about 0.5% by weight or less. The metal layer can be selected from carbon, manganese, silicon, vanadium, titanium, niobium, phosphorus, sulfur, aluminum, copper, nickel, chromium, molybdenum, tin, boron, calcium, arsenic, cobalt, lead, antimony, tantalum, tungsten , Zinc, silicon and zirconium at least one element material, wherein the element material in the outer layer has a change of at least about 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, A concentration of 15% by weight or at least about 20% by weight. The substrate may include an adhesive layer adjacent to the metal layer. The concentration of elemental substances in the bonding layer can be reduced by less than about 1.0% by weight. The appearance of the metal or alloy layer can be uniform. The appearance, weight and thickness of the metal or alloy layer on at least a part of the surface of the layer can be flat, constant, smooth, even and uniform. The metal or alloy layer may have visible grain boundary precipitation. Alternatively, a metal or alloy layer formed with the composition described herein or by the method described herein may have little or no grain boundary precipitation, which is about 10x, 50x, 100x, 250x, 500x, 1000x or Visible at higher magnifications.

The metal-containing layer may include a metal oxide. The metal oxide may include, but is not limited to, Al ₂ O ₃ , MgO, CaO, Cr ₂ O ₃ , TiO ₂ , FeCr ₂ O ₄ , SiO ₂ , Ta ₂ O _5, or MgCr ₂ O ₄ or a combination thereof. The metal oxide can be formed in the metal-containing layer through the metal thermal reduction reaction between the elemental metal and the thermodynamically unstable metal oxide. Suitable elemental metal and thermodynamically unstable metal oxide pairs can be selected from the pairs whose Gibbs free formation energy is reduced by the oxidation of elemental metals by metal oxides.

After the annealing process, the residue may remain on the substrate. Certain components in the metal layer can be consumed or removed (for example, deposited on the wall of a retort furnace), or their concentration is reduced due to their diffusion into the substrate or into the substrate. However, after annealing, other residues in the form of, for example, powder may remain on the substrate. The residue may contain inert materials from the metal-containing layer. This residue can be removed before further processing (e.g. temper rolling). The reaction can be stopped by purging the reaction with HCl gas. Purge with HCl gas allows a flat profile to be formed.

After the metal layer is formed adjacent to the substrate, the substrate may have a measurable grain size. The grain size can be measured and recorded according to ASTM standards. The substrate may have about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39 or 30 grain size. The substrate may have greater than about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 21, 22, 23, 24, 25, 26, 27, 28, 39 or 30 or larger grain size. The substrate may have 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 a grain size not greater than about 000 or less. In some cases, the metal layer may have a grain size of about ASTM 000 to about ASTM 30, about ASTM 5 to about ASTM 16, about ASTM 6 to about ASTM 14, or about ASTM 8 to about ASTM 12. The substrate may have a grain size of about ASTM 7 to ASTM 9. The substrate may have a grain size of about ASTM 7.

The element substances in the slurry can lower the transition temperature from austenite to ferrite. The element material in the base material can lower the transition temperature from austenite to ferrite. The element substance may not substantially change the transformation temperature from austenite to ferrite. In some cases, elemental substances can increase the austenite to ferrite transition temperature. The element substance that can lower the transition temperature from austenite to ferrite can be manganese, nitrogen, copper or gold.

It can measure the grain size of austenite and the grain size of ferrite. 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 the austenite grain size to the ferrite grain size may be less than about 10, 5, 2, 1, 0.5, or 0.1 or less. The ratio of the austenite grain size to the ferrite grain size may be about 0.1, 0.5, 1, 2, 5, or 10. The ratio of the austenite grain size to the ferrite grain size may be about 1. The ratio of austenite grain size to ferrite grain size can be calculated according to the following formula: D _γ /D _α =1+(0.0026+0.053wt% C+0.006wt% Mn+0.009wt% Nb+4.23wt% V*N-0.081% by weight Ti)*(1.5+α ^1/2 )*D _γ where D _γ system austenite grain size, unit is μm, D _α system ferrite grain size, unit is μm, α is the cooling rate, the unit is °C/s.

The stabilized amount of titanium equivalent can be calculated according to the following formula: Ti equivalent stabilization = weight% Ti-3.42 * weight% N-1.49 weight% S-4 weight% C + 0.516 weight% Nb.

Without wishing to be bound by theory, the stabilization of a certain amount of titanium (Ti) equivalent in the metal layer can result in 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, 0.03 Ti 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 contain less than about 0.09 Ti equivalent, 0.08 Ti equivalent, 0.07 Ti equivalent, 0.06 Ti equivalent, 0.05 Ti equivalent, 0.04 Ti equivalent, 0.03 Ti equivalent, 0.02 Ti equivalent, 0.017 Ti equivalent, 0.015 Ti equivalent, 0.01 Ti equivalent, 0.005 Ti equivalent or less than about 0.001 Ti equivalent or less.

The amount of elemental metal in the metal layer on the substrate can vary with depth. The amount of elemental metal in the metal layer can vary with depth at a specific rate, such as at least about -0.0001%/micron, at least about -0.001%/micron, at least about -0.01%/micron, at least about -0.05%/micron, at least about- 0.1%/micron, at least about -0.5%/micron, at least about -1.0%/micron, at least about -3.0%/micron, at least about -5.0%/micron, at least about -7.0%/micron, or at least about -9.0% /Micron or larger. The amount of metal in the metal layer can vary with depth at a specific rate, such as less than about -9.0%/micron, -7.0%/micron, -5.0%/micron, -3.0%/micron, -1.0%/micron, -0.5%/ Micron, -0.1%/micron, -0.05%/micron, -0.01%/micron, -0.001%/micron, or less than about -0.001%/micron or less. The amount of elemental metal in the metal layer can vary with depth from about -0.01%/micron to -5.0%/micron, or from -0.01%/micron to -3.0%/micron.

The amount of elemental metal in the metal layer can vary with depth at a specific rate, such as at least about -0.0001%/micron, -0.001%/micron, -0.01%/micron, -0.05%/micron, -0.1%/micron, -0.5% /Micron, -1.0%/micron, -3.0%/micron, -5.0%/micron, -7.0%/micron, or at least about -9.0%/micron or more. The amount of elemental metal in the metal layer can vary with depth at a specific rate, such as not greater than about -9.0%/micron, -7.0%/micron, -5.0%/micron, -3.0%/micron, -1.0%/micron, -0.5 %/Micron, -0.1%/micron, -0.05%/micron, -0.01%/micron, -0.001%/micron, or not more than about -0.0001%/micron or less.

The element metal can have a concentration of at least about 5 wt% at a depth less than or equal to 100 microns from the surface of the substrate, and a concentration of about 5 wt% at a depth less than or equal to 50 microns from the surface of the substrate. The surface of the material can have a concentration of about 10% by weight at a depth less than or equal to 50 microns, and a concentration of about 10% by weight at a depth less than or equal to 40 microns from the surface of the substrate. A depth of 30 microns can have a concentration of about 10% by weight, a depth of less than or equal to 50 microns from the surface of the substrate can have a concentration of about 15% by weight, and a depth of less than or equal to 40 microns from the surface of the substrate can have a concentration of about 15% by weight. A concentration of about 15% by weight, a concentration of about 15% by weight at a depth less than or equal to 30 microns from the surface of the substrate, or a concentration of about 15% by weight at a depth less than or equal to 10 microns from the surface of the substrate concentration. X-ray photoelectron spectroscopy can be used to measure this change in amount, concentration or weight% with depth.

The metal layer coated adjacent to the substrate may have a size of less than about 1 mm, about 900 microns, about 800 microns, about 700 microns, about 600 microns, about 500 microns, about 400 microns, about 300 microns, about 200 microns, or about 100 microns. Or smaller thickness.

The metal layer coated adjacent to the substrate can have 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 greater thickness.

Before coating with the metal layer or after coating with the metal layer, the properties of the substrate can be measured by various techniques and instruments. Technologies and instruments include, for example, grain size calculation, scanning electron microscope (SEM), scanning electron microscope/energy dispersive spectroscopy (SEM/EDS), microprobe analysis, and potentiostat measurement.

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

After annealing, the substrate may be substantially free of Kirkendall porosity. This layer can impart characteristics on the substrate that the substrate did not previously contain. For example, the layer can make the substrate harder, more wear-resistant, more beautiful, more resistive, less resistive, more conductive, less conductive, or any combination thereof. In addition, this layer can cause the speed of sound in the substrate to be faster or slower.

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

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

The substrate can exhibit a percentage of elongation, the maximum elongation of the gauge divided by the original gauge length or the difference in distance before and after coating the steel substrate before breaking. The percent elongation can be about 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or 100%. In some cases, the percent elongation may be about 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39% or 40%. In some cases, the percent elongation may be greater than about 5%, 10%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30% , 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 50%, 60%, 70%, 80%, 90% or greater than about 100% Or bigger. In some cases, the percent elongation may be less than about 100%, 90%, 80%, 70%, 60%, 50%, 40%, 39%, 38%, 37%, 36%, 35%, 34% , 33%, 32%, 31%, 30%, 29%, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 10% or less than about 5% Or smaller.

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

Any suitable analytical technique can be used to measure the composition of the substrate, slurry, slurry component, or metal layer. Measurements can include amount, concentration or weight percentage, thickness or other dimensions, composition and/or structure changes with depth, and grain size. Exemplary analysis techniques can include, but are not limited to, glow discharge mass spectrometry, microprobe analysis, potentiostat measurement, scanning electron microscope, transmission electron microscope, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, and electron energy loss spectroscopy to measure the amount , Concentration or weight% changes with depth.

Other properties of the substrate coated with the metal layer can be, for example, U.S. Patent Publication No. 2013/0171471; U.S. Patent Publication No. 2013/0309410; U.S. Patent Publication No. 2013/0252022; U.S. Patent Publication No. 2015 /0167131; U.S. Patent Publication No. 2015/0345041, U.S. Patent Publication No. 2015/0345041, U.S. Patent Publication No. 2016/0230284, each of which is incorporated herein by reference in its entirety .

其中R₀ 、R₄₅ 及R₉₀ 係相對於片材之方向之塑性應變比。When pulling, stretching or both, the steel chemistry can be changed to enhance the forming properties and performance of the material. The formability of steel can be measured by the plastic strain ratio (commonly referred to as the Lankford coefficient, r-bar, r _m , or r value herein). The r value can 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:

Among them, R ₀ , R ₄₅ and R ₉₀ are the plastic strain ratios relative to the direction of the sheet.

The r value of steel can be changed by manipulating steel chemistry and composition to form highly formable steel composition. Common gapless steels can have an r value between about 1.4 and 1.8. The modified steel may have an r value in excess of about 2. In some embodiments, the steel may have an r value of more than about 2.2, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.6, 3.8, or more than about 4.0 or more. The modified steel may have an r value not greater than about 4.0, 3.8, 3.6, 3.4, 3.2, 3.0, 2.8, 2.6, 2.4, or not greater than about 2.2 or less.

Several chemistries can be used to increase the r value of highly formable steel compositions. The steel chemistry can be selected to increase the overall incorporation of grain pinning particles before annealing the steel. In some embodiments, the presence of grain pinning particles inhibits the formation of increased grain size during the annealing process. A stoichiometric excess of titanium (Ti) can be used. This excess of Ti may allow TiC to form at elevated temperatures. TiC can be used for grain pinning at high temperatures. Non-interstitial steel can also use more manganese and a smaller amount of TiN, AlN, NbC, NbN or other components, which can be used as grain pinning at high temperatures and as interstitial element binders. The gapless steel may include a composition similar to that listed in Example 7.

The method used to form the highly formable steel composition may include several intermediate processes. Steel can be constructed according to the above chemistry. Interstitial steel can undergo fine-grain practice to generate small prior grains. Cold reduction can be used to obtain smooth trim and control grain size. After cold reduction, subsequent processing steps may include high temperature annealing methods. High temperature annealing may include annealing at a temperature higher than about 900°C. The annealing temperature may exceed about 950°C, 1000°C, 1050°C, 1100°C, 1150°C, 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, 1500°C or higher. The annealing temperature can be no more than about 1500°C, 1450°C, 1400°C, 1350°C, 1300°C, 1250°C, 1200°C, 1150°C, 1100°C, 1050°C, 1000°C, or no more than about 950°C or lower. The annealing temperature may allow the steel to transform from the ferrite phase to the austenite phase. The composition of the selected gapless steel can prevent grain growth. The stabilization grade can prevent strain curing and can improve the formability of steel for further processing.

The highly formable steel composition can have a measurable grain size. The grain size can be measured and recorded according to ASTM standards. The substrate may have greater than about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 21, 22, 23, 24, 25, 26, 27, 28, 39 or 30 or larger grain size. The highly formable steel composition can have greater than about ASTM 000, 00, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 , 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39 or 30 or larger grain size. The height formable steel composition may have 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 a grain size not greater than about 000 or less. In some embodiments, the metal layer may have from about ASTM 000 to about ASTM 10, from about ASTM 000 to about ASTM 15, from about ASTM 000 to about ASTM 20, from about ASTM 000 to about ASTM 25, from about ASTM 000 to about ASTM 30, About ASTM 5 to about ASTM 16, about ASTM 5 to about ASTM 18, ASTM 5 to about ASTM 20, about ASTM 5 to about ASTM 22, about ASTM 5 to about ASTM 24, about ASTM 5 to about ASTM 26, about ASTM 5 To about ASTM 28, about ASTM 5 to about ASTM 30, about ASTM 6 to about ASTM 16, about ASTM 6 to about ASTM 18, about ASTM 6 to about ASTM 20, about ASTM 6 to about ASTM 22, about ASTM 6 to about ASTM 24, about ASTM 6 to about ASTM 26, about ASTM 6 to about ASTM 28, about ASTM 6 to about ASTM 30, about ASTM 7 to about ASTM 16, about ASTM 7 to about ASTM 18, about ASTM 7 to about ASTM 20 , About ASTM 7 to about ASTM 22, ASTM 7 to about ASTM 24, about ASTM 7 to about ASTM 26, about ASTM 7 to about ASTM 28, about ASTM 7 to about ASTM 30, about ASTM 8 to about ASTM 16, about ASTM 8 to about ASTM 18, about ASTM 8 to about ASTM 20, about ASTM 8 to about ASTM 22, about ASTM 8 to about ASTM 24, about ASTM 8 to about ASTM 26, about ASTM 8 to about ASTM 28, about ASTM 8 to About ASTM 30, about ASTM 9 to about ASTM 16, about ASTM 9 to about ASTM 18, about ASTM 9 to about ASTM 20, about ASTM 9 to about ASTM 22, about ASTM 9 to about ASTM 24, about ASTM 9 to about ASTM 26, about ASTM 9 to about ASTM 28, about ASTM 9 to about ASTM 30, about ASTM 10 to about ASTM 16, about ASTM 10 to about ASTM 18, about ASTM 10 to about ASTM 20, about ASTM 10 to about ASTM 22, About ASTM 10 to about ASTM 24, about ASTM 10 to about ASTM 26, about ASTM 10 to about ASTM 28, about ASTM 10 to about ASTM 30, about ASTM 15 to about ASTM 20, about ASTM 15 to about ASTM 25, about ASTM 15 to about ASTM 30 or ASTM 20 to about ASTM 3 0 grain size. The highly formable steel composition may have a grain size of about ASTM 7 to ASTM 9, about ASTM 6 to about ASTM 14, or about ASTM 8 to about ASTM 12. The highly formable steel composition may have about ASTM 7, about ASTM 8, about ASTM 9, about ASTM 10, about ASTM 11, about ASTM 12, about ASTM 13, about ASTM 14, about ASTM 15, about ASTM 16, about ASTM 17, about ASTM 18, about ASTM 19, about ASTM 20, about ASTM 21, about ASTM 22, about ASTM 23, about ASTM 24, about ASTM 25, about ASTM 26, about ASTM 27, about ASTM 28, about ASTM 29 or Approximately ASTM 30 grain size.

The substrate, metal layer, and composition containing the metal layer described herein can be used in any treatment method or series of treatment methods. Before, during, and/or after depositing the metal-containing layer, the substrate, metal layer, and composition can be used in additional processing methods. Before, during, and/or after annealing the metal layer, the substrate, metal layer, and composition can be used in additional processing methods. The composition comprising the metal layer can provide enhanced properties (eg, formability, processability, improved thermal conductivity) for subsequent processing steps. The composition with enhanced properties after forming the metal layer can be advantageously used in a variety of applications, such as electrical alloys, electronic alloys, high-temperature alloys, high-strength alloys, corrosion-resistant alloys, construction alloys, structural alloys, consumer goods alloys, appliance grades Alloys, industrial alloys, biomedical grade alloys, military grade alloys, maritime grade alloys, aviation grade alloys, transportation grade alloys, aesthetic alloys and automotive grade alloys.

The substrate, the metal layer, or the composition containing the metal layer may undergo any treatment method before, during, and/or after the deposition of the metal layer. Exemplary manufacturing processes may include, but are not limited to, forming, soft or hard tool handling, fastening, and seam or cut edge protection. Exemplary forming, soft or hard tool processing processes may include stretching or pulling forming, re-molding, impact forming, spinning forming, roll forming, hydroforming, CNC forming, flanging, crimping, hemming ), hot stamping, extrusion and forging. Exemplary fastening processes may include toggle locking, bow locking, spot welding, welding, rod welding, arc welding, MIG welding, TIG welding, acetylene welding, resistance welding, ultrasonic welding, friction welding, laser welding, plasma Welding, seaming, riveting, hot forging and chemical adhesion (for example, glue or epoxy bonding). Exemplary seam or cut edge protection processes may include hot-dip galvanizing, electro-galvanizing, aluminum or aluminum plating, aluminum silicidation, cold spraying (e.g., Al, all grades of stainless steel, zinc, galvanized, nickel), thermal spraying or Plasma spraying (e.g., Al, all grades of stainless steel, zinc, galvanized, nickel, copper, bronze), cladding, and liquid applied coatings (e.g., lacquer, UV cured, polymer paint).

The substrate or composition containing the metal layer can be formed into one or more parts, components, or assemblies. The parts, components or assemblies containing the metal layer can be used in any suitable applications, including but not limited to automotive, aviation, transportation, maritime, household appliances, components, industrial, electrical, biomedical, military, consumer, aesthetics, electronic and structural applications . Automotive applications can include automotive fuel tanks, exposed body panels (e.g., doors, hoods, and fenders), exhaust components (e.g., silencers, catalytic converter housings, exhaust pipes, heat shields), and unexposed Body panels (for example, instrument panels, door interiors, wheel house interiors). Electrical applications may include exposed panels (for example, door exteriors, fume hoods, splash guards) and unexposed panels (for example, dishwasher interior panels, water heater tanks). Construction and structural applications may include building panels, draft tubes, pipes, beams, hinges, plates, and fasteners. Electrical applications can include motor stacks, generator stacks, and generator core stacks. computer system

The invention provides a computer system programmed to implement the method of the invention. Fig. 4 shows a computer control system 401, which is programmed or otherwise configured to generate slurry and/or apply a coating of slurry to a substrate. The computer control system 401 can adjust various aspects of the method of the present invention, such as, for example, a method of preparing a slurry and a method of applying a coating of the slurry to a substrate. The computer control system 401 can be implemented on a user's electronic device or a computer system located far away from the electronic device. The electronic device can be a mobile electronic device.

The computer system 401 includes a central processing unit (CPU, also referred to herein as "processor" and "computer processor") 405, which can be a single-core or multi-core processor, or a plurality of processors for parallel processing. The computer control system 401 also includes a memory or memory location 410 (e.g., random access memory, read-only memory, flash memory) for communicating with one or more other systems, and an electronic storage unit 415 (e.g., , Hard disk), communication interface 420 (for example, network adapter), and peripheral devices 425 (such as cache, other memory, data storage and/or electronic display adapter). The memory 410, the storage unit 415, the interface 420, and the peripheral device 425 communicate with the CPU 405 through a communication bus (solid line) (such as a motherboard). The storage unit 415 may be a data storage unit (or data storage library) for storing data. The computer control system 401 can be operatively coupled to a computer network ("network") 430 via the communication interface 420. The network 430 may be an international network (Internet), an internal network (internet) and/or an extranet, or an intranet and/or an extranet communicating with the international network. In some cases, the network 430 is a telecommunications and/or data network. The network 430 may include one or more computer servers, which may enable distributed computing, such as cloud computing. In some cases, with the aid of the computer system 401, the network 430 can implement a peer-to-peer network, which enables devices coupled to the computer system 401 to act as a client or server .

The CPU 405 can execute a series of machine-readable instructions that can be implemented in a program or software. The instructions may be stored in a memory location (such as memory 410). Instructions can be directed to the CPU 405, which can then be programmed or otherwise configured to implement the method of the present invention. Examples of operations performed by the CPU 405 may include get, 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 the system 401 may be included in the circuit. In some cases, the circuit uses a specific integrated circuit (ASIC).

The storage unit 415 can store files, such as drives, libraries, and saved programs. The storage unit 415 can store user data, such as user preferences and user programs. In some cases, the computer system 401 may include one or more additional data storage units located outside the computer system 401 (such as on a remote server communicating with the computer system 401 via an intranet or an international network).

The computer system 401 can communicate with one or more remote computer systems via the network 430. For example, the computer system 401 can communicate with a remote computer system of a user (eg, a user who controls the manufacture of a slurry-coated substrate). Examples of remote computer systems include personal computers (e.g., portable PCs), tablet or desktop PCs (e.g., Apple® iPad, Samsung® Galaxy Tab), telephones, smart phones (e.g. Apple® iPhone, Android Start the device, Blackberry®) or personal digital assistant. The user can access the computer system 401 through the network 430.

The method as described herein can be implemented by machine (for example, a computer processor) executable code stored in an electronic storage location of the computer system 401 (such as, for example, stored on the memory 410 or the electronic storage unit 415) . The machine executable or machine readable code can be provided in the form of software. During use, the code can be executed by the processor 405. In some cases, the code may be retrieved from the storage unit 415 and stored on the memory 410 for immediate access by the processor 405. In some cases, the electronic storage unit 415 may not be included, and the machine executable instructions may be stored on the memory 410.

The code can be pre-compiled and configured for use with a machine with a processor suitable for executing the code, or it can be compiled during runtime. The code can be provided in an optional programming language so that the code can be executed in a pre-compiled or compile-time manner.

The aspect of the system and method (such as the computer system 401) provided herein can be implemented programmatically. Various aspects of technology can be regarded as "products" or "articles" usually in the form of machine (or processor) executable code and/or related data, which are carried on machine-readable media or Reflected in the type of machine-readable medium. The machine executable code may be stored on an electronic storage unit, such as a memory (for example, read-only memory, random access memory, flash memory) or hard disk. "Storage" type media can include any or all tangible memory of computers, processors or the like, or related modules, such as various semiconductor memories, tape drives, disk drives and the like, which can be provided at any time Non-temporary storage for software programming. All or part of the software can sometimes be communicated via an international network or various other telecommunication networks. For example, this type of communication may enable software to be loaded from one computer or processor to another computer or processor, for example, from a management server or a host computer to a computer platform of an application server. Therefore, another type of medium that can carry software components includes light waves, electric waves, and electromagnetic waves, such as through wired and optical landline networks, and across various air links across physical interfaces between local devices. The physical components that carry such waves (such as wired or wireless links, optical links, or the like) can also be regarded as media that carry software. As used herein, unless restricted to non-transitory tangible "storage" media, terms (such as computer or machine "readable media") refer to any medium that participates in providing instructions to a processor for execution.

Therefore, 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 transfer media. The non-volatile storage medium includes, for example, an optical disk or a magnetic disk that can be used to implement the database shown in the drawings, and any storage device in any computer or the like. Volatile storage media include dynamic memory, such as the main memory of this computer platform. The tangible transfer medium includes coaxial cable; copper wire and optical fiber, including the wires that make up the bus in a computer system. The carrier transfer medium may 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). Therefore, common forms of computer readable media include (for example): floppy disks, flexible disks, hard disks, magnetic tapes, any other magnetic media, CD-ROM, DVD or DVD-ROM, any other optical media, punched cardboard tape, Any other physical storage media with hole patterns, RAM, ROM, PROM and EPROM, FLASH-EPROM, any other memory wafer or cassette, carrier for transferring data or instructions, cable or link for transferring such carrier, or computer Any other medium from which programmed code and/or data can be read. Many of these forms of computer-readable media may involve carrying one or more sequences of one or more instructions to a processor for execution.

The computer system 401 may include or communicate with an electronic display 435 that includes a user interface (UI) 440 for providing parameters such as for generating the slurry and/or applying the slurry to the substrate. Examples of UI include, but are not limited to, graphical user interfaces (GUI) and website-based user interfaces.

The method and system of the present invention can be implemented by one or more algorithms. The algorithm can be implemented by the central processing unit 405 by software during execution. The algorithm can, for example, adjust the mixing shear rate of the slurry, the amount of each component added to the slurry mixture, and the order in which the components are added to the slurry mixture. As another example, the algorithm can adjust the speed of applying the slurry to the substrate and the number of coatings of the slurry applied to the substrate. Examples Example 1

In one example, the slurry is formed by adding to the mixing chamber while mixing the resulting solution. The amount of water added to the slurry was changed to form a variety of slurries, and the effect on the properties of the slurry was recorded. Next, the slurry is applied to the substrate through a roll coating process. The slurry is then annealed at about 200°C for about 2 hours. The slurry is then dried to complete for about 2 hours to about 100 hours or more. The atmosphere near the surface of the chromed product can be below about -20°F dew point. Example 2

In another example, the substrate is heated to about 500°C at a rate of about 10°C/min. The temperature is kept constant for about 2 hours, during which time the metal-containing layer is deposited adjacent to the substrate. The substrate is then heated to about 950°C at a rate of about 10°C/min. Keep this temperature constant during the annealing process. After about 30 hours, the substrate was cooled to room temperature at a rate of about 5°C/min. During the whole process, the flow rate of argon is constant. Example 3

In another example, the substrate undergoes a thermal cycling protocol. The substrate is heated to about 500°C at a rate of about 10°C/min. The temperature is kept constant for about 2 hours, during which time the metal-containing layer is deposited adjacent to the substrate. The substrate is then heated at a rate of about 10°C/min to about 925°C, and the temperature is kept constant for about 30 minutes. The substrate is cooled to about 500°C at a rate of about 5°C/min, where the temperature is kept constant for about 30 minutes. The substrate is heated again at a rate of about 5°C/min to about 925°C, kept at a constant temperature for about 30 minutes, and then cooled to about 500°C at a rate of about 5°C/min and kept constant for about 30 minutes. In another cycle, the substrate is heated and cooled again. Heat the substrate to about 925°C, and then cool the substrate to room temperature at a rate of about 5°C/min. During the whole process, the flow rate of argon is constant. Example 4

In another example, a substrate comprising carbon, silicon, manganese, titanium, vanadium, aluminum, and nitrogen is provided. In one example, the substrate has the following components, in% by weight: 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 0.321 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

In another example, a substrate comprising carbon, silicon, manganese, titanium, vanadium, aluminum, and nitrogen is provided. In one example, the substrate has the following components, in% by weight: Substrate C Mn Al P S Cr N V Nb Ti C20_2 0.002 1.27 0.008 0.009 0.005 0.04 0.008 0.004 0.004 0.016 MC-25 0.002 1.26 0.004 0.005 0.008 0.04 0.008 0 0.089 0.015 The base material MC-25 has about 0.089% by weight of niobium. As illustrated in Fig. 3, almost no grain boundary precipitation was observed in the obtained alloy layer. Less pore formation was observed in the alloy layer. The stainless steel alloy layer has improved corrosion resistance (required effect of the substrate). Example 6

In another example, the substrate is formed and exhibits the following properties: Substrate Average grain size (ASTM) Coefficient of variation (%) Yield strength (ksi) Ultimate tensile strength (ksi) Percent elongation S-03 7.33 3 22.8 54.5 33 S-04 7.4 9 23.3 55 36 C20 7.25 4 20.4 48 36 Example 7

In another example, the substrate is formed and exhibits the following properties: C-25 C Mn P S Si Cu N i C r Mo Min 1.25 aims ＜0.002 1.3 ＜0.008 ＜0.005 Max 0.004 1.35 0.012 0.012 0.034 0.1 0.1 0.1 0.03 C-25 V Ti Nb Al Sn N Min 0.014 See Eq 0.007 aims 0.015 0.008 Max 0.008 0.016 0.01 0.03 0.009

The weight percentage of niobium in the alloy is calculated as follows: Nb weight%=(0.017-(Ti weight%-3.42*N weight%-1.49*S weight%-4*C weight%))/0.516

The substrate chemistry is selected to have a stabilization calculation value of 0.017 or higher, where the stabilization calculation is as follows: Stabilization = Ti wt%-3.42*N wt%-1.49*S wt%-4*C wt%+0.516* Nb wt%. Example 8

In another example, the substrate is formed and exhibits the following composition of the constituent metals and other elements, measured in wt%: 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 example, thermomechanical testing was performed on the substrates listed in Example 8 to determine their r value. The test results are as follows: Substrate specification Tensile strength (ksi) Yield strength (ksi) With 2" elongation % (4W) n value r value r-δ S-4 0.025 52.41 20.43 35.47 0.24 2.28 0.58 M 0.020 47.40 18.28 35.03 0.24 1.52 -0.52 A 0.023 47.76 19.46 34.63 0.23 1.47 0.93 A 0.052 49.86 19.76 35.47 0.23 1.62 -0.53 S-3.1 0.024 53.27 20.80 34.87 0.24 2.62 -0.33 S-4 0.026 52.87 20.43 33.13 0.24 2.52 -0.28 S-4 0.026 50.03 19.73 31.17 0.23 2.43 -0.64 M 0.020 45.10 22.10 36.57 0.23 2.19 -0.85 A 0.023 56.57 35.43 25.10 0.15 1.99 -0.64 A 0.051 53.30 24.70 32.40 0.21 1.78 -0.42 Example 10

In another example, a slurry suspension is produced by mixing MgCr ₂ O ₄ powder and MgCl ₂ powder together in water. Both the MgCr ₂ O ₄ powder and the MgCl ₂ powder were sieved to have a particle size between about 0.1 μm and 10 μm. The dry weight percentages of MgCr ₂ O ₄ powder and MgCl ₂ powder are about 95% and 5%, respectively. After mixing MgCr ₂ O ₄ powder and MgCl ₂ powder for four hours, aluminum powder is added to the suspension. The aluminum powder is sieved so that it passes through a 325 mesh screen. The aluminum is mixed into the slurry powder so that its atomic ratio to the oxide powder is about 1.0. The slurry mixture containing aluminum powder was immediately roll-coated onto the surface of the metal sheet. The substrate is then heated to about 950°C at a rate of about 10°C/min. Keep the temperature constant during the annealing process. After about 30 hours, the substrate was cooled to room temperature at a rate of about 5°C/min. During the whole process, the flow rate of argon is constant. After annealing, the metal substrate undergoes a cleaning process to remove Al ₂ O ₃ from the surface of the substrate. Example 11

In another example, the substrate is constructed to exhibit a higher yield strength of up to 80% and a higher tensile strength of up to 50%. In some cases, the substrate is formed and exhibits the following composition of the constituent metals and other elements, measured in wt%: 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, thermomechanical testing was performed on the substrate listed in Example 11 to determine its Ti/Nb stability, yield strength, ultimate tensile strength, and elongation. The test results are as follows: Substrate Ti/Nb stability Yield strength (ksi) Ultimate tensile strength (ksi) Percent elongation HS-1 0.009942 26.4 57.4 21.1 HS-2 0.026084 35 66.6 27.8 HS-3 0.024813 37.5 68.3 27.7

The materials, devices, systems, and methods (including material compositions (such as material layers)) herein can be combined with or modified by other materials, devices, systems, and methods (including material compositions), such as, for example, they are described in U.S. Patent Publication No. 2013/0171471; U.S. Patent Publication No. 2013/0309410; U.S. Patent Publication No. 2013/0252022; U.S. Patent Publication No. 2015/0167131; U.S. Patent Publication No. 2015/0345041; And Patent Cooperation Treaty Application No. PCT/US2016/017155, each of which is incorporated herein by reference in its entirety.

Although the preferred embodiments of the present invention have been shown and described herein, those skilled in the art will understand that these embodiments are provided by way of example only. It is not intended to limit the present invention by the specific examples provided in this specification. Although the present invention has been described with reference to the foregoing specification, the description and description of the embodiments herein are not meant to be interpreted in a limiting sense. Those who are familiar with this technology will now make many changes, changes and substitutions without departing from the present invention. In addition, it should be understood that all aspects of the present invention are not limited to the specific depictions, configurations or relative proportions described herein, which depend on various conditions and variables. It should be understood that various alternatives to the embodiments of the invention described herein can be used to practice the invention. Therefore, it is expected that the present invention should also cover any such alternatives, modifications, changes or equivalents. It is hoped that the scope of the following patent applications will limit the scope of the present invention and thus cover the methods and structures within the scope of these patent applications and their equivalents.

110: Operation 120: Operation 130: Operation 140: Operation 401: computer control system/computer system 405: Central Processing Unit 410: Memory/Memory Location 415: electronic storage unit 420: Communication interface 425: Peripheral Devices 430: Network 435: electronic display 440: User Interface (UI)

The specific novel features of the present invention are stated in the scope of the attached patent application. The features and advantages of the present invention will be better understood by referring to the following detailed description and accompanying drawings (also referred to as "figure" and "FIG." in this article). The detailed description states that the present invention is utilized An exemplary embodiment of the principle, the drawing is:

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

Figure 2 illustrates the steel substrate after coating with a metal layer;

Figure 3 illustrates the steel substrate after coating with a metal layer; and

Figure 4 schematically illustrates a computer control system, which is programmed or otherwise configured to implement the methods provided herein.

Claims (36)

A method for forming at least one metal layer adjacent to a substrate, the method comprising: (a) contacting the substrate with a slurry containing a metal oxide, a reducing metal agent and a metal transfer activator to provide a metal-containing layer adjacent to the substrate; and (b) Annealing the substrate and the at least one metal-containing layer to subject the metal oxide and the metal transfer activator to a metal thermal reduction reaction to produce the at least one metal layer and water, wherein the water system is subjected to the reduced metal Agent reduction. The method of claim 1, wherein the at least one metal layer has a grain size of about ASTM 000 to ASTM 30. The method of claim 1, wherein the substrate comprises at least one of the following: (i) less than or equal to about 0.1% by weight of carbon, (ii) about 0.1% to 3% by weight of manganese, (iii) less than Or about 1% by weight of silicon, (iv) less than or equal to about 0.1% by weight of vanadium, and (v) less than or equal to about 0.5% by weight of titanium. The method of claim 1, wherein the substrate comprises at least two of the following: (i) less than or equal to about 0.1% by weight of carbon, (ii) about 0.1% to 3% by weight of manganese, (iii) less than Or about 1% by weight of silicon, (iv) less than or equal to about 0.1% by weight of vanadium, and (v) less than or equal to about 0.5% by weight of titanium. The method of claim 1, wherein the substrate comprises at least three of the following: (i) less than or equal to about 0.1% by weight of carbon, (ii) about 0.1% to 3% by weight of manganese, (iii) less than Or about 1% by weight of silicon, (iv) less than or equal to about 0.1% by weight of vanadium, and (v) less than or equal to about 0.5% by weight of titanium. The method of claim 1, wherein the substrate comprises at least four of the following: (i) less than or equal to about 0.1% by weight of carbon, (ii) about 0.1% to 3% by weight of manganese, and (iii) less than Or about 1% by weight of silicon, (iv) less than or equal to about 0.1% by weight of vanadium, and (v) less than or equal to about 0.5% by weight of titanium. The method of claim 1, wherein the substrate comprises (i) less than or equal to about 0.1% by weight of carbon, (ii) about 0.1% to 3% by weight of manganese, and (iii) less than or equal to about 1% by weight Silicon, (iv) less than or equal to about 0.1% by weight of vanadium, and (v) less than or equal to about 0.5% by weight of titanium. The method of claim 1, wherein the metal layer is formed at an annealing temperature of about 0°C to 1000°C. The method of claim 1, wherein the metal layer is formed in an annealing atmosphere with a moisture content of less than about 10 Torr. The method of claim 1, wherein the annealing comprises heating the substrate at a rate of at least about 0.1°C/sec. The method of claim 1, wherein the annealing is performed at a temperature higher than about 500°C. The method of claim 1, the method further comprising cooling the substrate after the annealing. The method of claim 1, wherein during the annealing, the substrate is transformed from ferrite to austenite. The method of claim 1, wherein the annealing temperature is determined by the transformation temperature of ferrite to austenite. The method of claim 14, wherein at least one austenite stabilizer is added to reduce the transformation temperature. The method of claim 1, wherein the metal transfer activator comprises a halide, a metal halide, a metal sulfide or a gaseous substance. The method of claim 16, wherein the metal transfer activator comprises hydrogen. The method of claim 16, wherein the metal transfer activator comprises a substance selected from the group consisting of magnesium chloride (MgCl ₂ ), iron (II) chloride (FeCl ₂ ), calcium chloride (CaCl ₂ ), chlorinated Zirconium (IV) (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 ₄ Cl), sodium chloride (NaCl), potassium chloride (KCl), molybdenum sulfide (MoS), manganese sulfide (MnS), iron disulfide (FeS ₂ ), chromium sulfide (CrS), iron sulfide (FeS) ), copper sulfide (CuS), nickel sulfide (NiS) and combinations thereof. The method of claim 1, the method further comprising drying the substrate after the annealing. A steel composition comprising a constituent metal selected from the group consisting of: i) greater than about 0.2% by weight of titanium, and ii) greater than about 0.8% by weight of manganese, wherein the steel composition has a plastic strain ratio of more than 1.8 Measurements. The steel composition of claim 20, wherein the steel composition has a plastic strain ratio measurement value exceeding 2. The steel composition of claim 20, wherein the steel composition has undergone annealing at a temperature between about 750°C and about 1100°C. The steel composition of claim 22, wherein during the annealing, the steel composition transforms from ferrite to austenite. The steel composition of claim 22, wherein the steel composition comprises a grain size between about ASTM 000 and ASTM 30. The steel composition of claim 20, wherein the steel composition comprises more than about 0.2% by weight of titanium and two or more constituent elements selected from the group consisting of: i) more than about 0.01% by weight of carbon, ii) more than About 0.02% by weight of aluminum, and iii) not more than about 0.004% by weight of sulfur, and iv) less than about 0.02% by weight of niobium. The steel composition of claim 20, wherein the steel composition contains more than about 0.8% by weight of manganese and two or more constituent elements selected from the group consisting of i) less than about 0.01% by weight of 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. A composition for forming at least one metal layer adjacent to a substrate, the composition comprising a slurry comprising a metal oxide, a reducing metal agent, and a metal transfer activator, wherein the slurry is configured to provide adjacent to the substrate The metal-containing layer of the material, wherein the metal oxide and the metal transfer activator are configured to undergo a metal thermal reduction reaction to generate the at least one metal layer and water. The composition of claim 27, wherein the water system is reduced by the reducing metal agent. Such as the composition of claim 27, wherein the metal oxide is selected from the group consisting of Cr ₂ O ₃ , TiO ₂ , FeCr ₂ O ₄ , SiO ₂ , Ta ₂ O ₅ and MgCr ₂ O ₄ . The composition of claim 27, wherein the reducing metal agent comprises an element selected from the group consisting of iron, chromium, nickel, silicon, vanadium, titanium, boron, tungsten, aluminum, molybdenum, cobalt, manganese, zirconium and niobium. The composition of claim 27, wherein the metal transfer activator comprises a halide, a metal halide, a metal sulfide or a gaseous substance. The composition of claim 30, wherein the metal transfer activator comprises hydrogen. The composition of claim 30, wherein the metal transfer activator comprises a substance selected from the group consisting of magnesium chloride (MgCl ₂ ), iron (II) chloride (FeCl ₂ ), calcium chloride (CaCl ₂ ), chlorine Zirconium (IV) (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 (SiHCl3), 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 ₄ Cl), sodium chloride (NaCl), potassium chloride (KCl), molybdenum sulfide (MoS), manganese sulfide (MnS), iron disulfide (FeS ₂ ), chromium sulfide (CrS), iron sulfide (FeS) ), copper sulfide (CuS), nickel sulfide (NiS) and combinations thereof. The composition of claim 27, which further comprises a solvent. The composition of claim 33, wherein the solvent includes water. The composition of claim 33, wherein the solvent includes an organic substance.

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