Low temperature process for depositing inorganic particles onto a metal substrate and articles produced thereby - Patents.com

Abstract

A method for depositing inorganic particles comprising titanium carbonitride on a metal substrate by chemical vapor deposition (CVD). In some embodiments, the CVD process may be supplied with two or more source gases that react to form the inorganic particles. At least one of the source gases may comprise a titanium source gas. The carbon and nitrogen sources may also be: (a) a single source gas comprising a carbon and nitrogen source gas, the single source gas having a thermal energy of formation of less than 65.9 kilojoules / mole; and / or (b) two source gases comprising a carbon source gas and a nitrogen source gas, the carbon source gas comprising gas molecules having a carbon-nitrogen single bond. In some embodiments, the CVD process may be supplied with an organometallic compound for forming the inorganic particles. In some embodiments, the CVD process may be supplied with an aluminum-containing organometallic reducing agent.

Description

Priority

[0001] This application claims the benefit of priority under 35 U.S.C. §119 to U.S. Provisional Patent Application No. 62 / 738,622, filed September 28, 2018, the contents of which are incorporated herein by reference in their entirety. [Technical field]

[0002] The present disclosure relates to a low temperature method for depositing inorganic particles onto a metal substrate, and in particular to a method for depositing inorganic particles onto a metal substrate below the austenite transformation temperature of the metal substrate. [Background technology]

[0003] The manufacture of a particular tool, such as a honeycomb extrusion die, may involve material selection and manufacturing processes that affect the final properties and performance of the tool. In general, it may be desirable to select materials and processes to achieve one or more properties depending on the particular type of tool or intended end use. These properties may include parameters such as dimensional accuracy, strength, toughness, service life, etc. For example, some honeycomb extrusion dies may be made from steel with a wear-resistant coating to improve performance or life. Summary of the Invention [Problem to be solved by the invention]

[0004] During the manufacture of tools, there is a continuing demand for new materials and manufacturing processes that can be selected to achieve different combinations of properties for the tools. [Means for solving the problem]

[0005] The present disclosure is directed to a method for depositing an abrasion-resistant coating, such as inorganic particles, on a surface of a metal substrate at a temperature not exceeding the austenite transformation temperature of the metal material of the metal substrate. In particular, the disclosed system and method are applicable to various materials, such as steel, and extrusion dies, such as honeycomb extrusion dies, made from these materials. For some tools, an abrasion-resistant coating may be applied, for example, to maintain dimensional stability of the tool features to extend the tool's life. For example, an abrasion-resistant coating may be utilized in a honeycomb extrusion die to help maintain and control the die dimensions (e.g., width of the slots that define the shape of the honeycomb extrusion body) over the life of the die.

[0006] Such abrasion resistant coatings (sometimes called wear resistant coatings) can be formed of inorganic material particles and can serve to extend the life of the tool. The abrasion resistant coatings may be applied to die substrate materials such as martensitic or precipitation hardened stainless steels. However, the process of applying the abrasion resistant coating may create thermal stresses in the steel due to the processing temperatures required to apply the coating.

[0007] For example, a steel, such as a martensitic steel, will begin to transform to the austenitic crystalline phase at a certain temperature during heating, which is called the austenitic transformation (Ac1) temperature. The steel can complete the transformation to the austenitic crystalline phase at a temperature higher than the Ac1 temperature, which is called the Ac3 temperature. These temperatures may be related to factors such as the material composition (e.g., the particular type of steel selected) and / or the processing technique utilized (e.g., the heating rate applied to the steel).

[0008] In some embodiments, deposition process parameters can be controlled to effectively deposit inorganic particles below the austenite transformation temperature of the metallic material. In some embodiments, alloy compositions of the metallic material may be developed to increase the austenite transformation temperature above which deposition of inorganic particles occurs. Stresses resulting from the change in crystalline phase may exceed the yield strength of steel, thus permanently deforming parts of the tool (e.g., pins of a honeycomb extrusion die) and generating undesirable dimensional changes in the tool (e.g., slot width variability between adjacent pins of a honeycomb extrusion die).

[0009] The change in crystalline phase also changes the coefficient of thermal expansion (CTE) of the steel. This change in CTE can also create thermal stresses at the surface of the steel at the interface with the wear-resistant coating, which may have a different CTE than the steel before and / or after it transforms to austenite. As the steel transforms to austenite during heating, the interface stresses created by the transformation to austenite can cause deformation of the pin (or other parts) in the extrusion die. Interface stresses can also occur if the steel transforms from austenite to a different crystalline structure (e.g., martensite) as it cools. Avoiding thermal stresses due to crystalline phase changes can reduce the amount of stresses created during the deposition process and the adverse effects created by these stresses.

[0010] In this regard, the present disclosure provides a method for determining whether a ΔCTE (as defined herein) between a metal material of a metal substrate is within a target, desired, or preset value, such as 10×10 -6 The present invention is directed to a method for depositing inorganic particles such that the temperature at which the inorganic particles are deposited does not exceed a target temperature (e.g., 10×10 -6A ΔCTE of 0.18 to 0.55 °C or less can be achieved by depositing inorganic particles at a temperature such that the metallic material does not exceed the austenite transformation temperature of the metallic material during the deposition process. In some embodiments, the deposition temperature does not exceed the austenite transformation temperature of the metallic material. In some embodiments, the composition of the multilayer coating formed with inorganic particles is within a target (e.g., 10×10 -6 The material can be developed to have a ΔCTE of 0.1° C. or less.

[0011] Some embodiments are directed to a method for depositing inorganic material on a metal substrate, the method comprising: depositing inorganic particles comprising titanium carbonitride on a surface of the metal substrate by a chemical vapor deposition process at a deposition temperature of 900° C. or less, the chemical vapor deposition process being provided with two or more feedstock gases that react to form the inorganic particles, at least one of the feedstock gases comprising a titanium feedstock gas, and a carbon and nitrogen source providing at least another of the feedstock gases, selected from the following: (a) a single feedstock gas, the single feedstock gas comprising a carbon and nitrogen feedstock gas having a thermal energy of formation less than 65.9 kilojoules / mole; (b) two feedstock gases, the two feedstock gases comprising a carbon feedstock gas and a nitrogen feedstock gas comprising gas molecules having a carbon-nitrogen single bond; and (c) a combination of (a) and (b).

[0012] In some embodiments, the method according to the embodiment in the immediately preceding paragraph may be a method in which the source of carbon and nitrogen (a) comprises the single feed gas. In some embodiments, the method according to the embodiment in the previous paragraph may be a method in which the source of carbon and nitrogen (b) comprises the two feed gases.

[0013] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include (a) the single feed gas, which may include a nitrile. In some embodiments, the nitrile may be a nitrile selected from the group: trichloroacetonitrile, propionitrile, acrylonitrile, isobutyronitrile, benzonitrile, butyronitrile, trans-2-butyronitrile, 3-butenenitrile, succinonitrile, cyclobutanecarbonitrile, cyclohexanecarbonitrile, 1-cyclohexenecarbonitrile, cyclopentanecarbonitrile, 1-cyclopentenecarbonitrile, cyclopropanecarbonitrile, octanenitrile, 2,2-dimethylpropanenitrile, heptanenitrile, adiponitrile, malononitrile, methacrylonitrile, 2-methylpropanenitrile, and trans-3-pentenenitrile.

[0014] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include (a) the single feed gas, which may include gas molecules having carbon chains of four or more carbon atoms.

[0015] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include (b) the two feed gases, where the gas molecule having a carbon-nitrogen single bond is an amine. In some embodiments, the amine may include a dialkyl or trialkylamine. In some embodiments, the amine may be selected from the group consisting of trimethylamine, dimethylamine, dimethylamine hydrochloride, and triethylamine. In some embodiments, the amine may include trimethylamine borane.

[0016] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include (b) the two source gases, wherein the nitrogen source gas is not a source of carbon for the chemical vapor deposition process.

[0017] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include (b) the two feed gases, wherein the nitrogen feed gas is ammonia. In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include a titanium source gas that is titanium tetrachloride.

[0018] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include a titanium source gas that is an organometallic compound. In some embodiments, the organometallic compound is tetrakis(dimethylamido)titanium.

[0019] In some embodiments, the method according to any of the embodiments in the preceding paragraphs may include a deposition temperature between 400°C and 750°C.

[0020] In some embodiments, the method according to any of the embodiments in the preceding paragraphs may include a deposition temperature between 600°C and 750°C.

[0021] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include maintaining the metal substrate at a temperature less than 900° C. during the chemical vapor deposition process.

[0022] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include a deposition temperature of 600° C. to 750° C., and the metal substrate may be maintained at a temperature of less than 900° C. during the chemical vapor deposition process.

[0023] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include a deposition temperature not exceeding the austenitic transformation temperature of a metallic material of the metallic substrate. In some embodiments, the metallic material may be steel. In some embodiments, the metallic material may be stainless steel. In some embodiments, the metallic material may be martensitic stainless steel.

[0024] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include a chemical vapor deposition process further provided with a boron-containing source gas, which may include a gas selected from the group of borane, diborane, boron trichloride, and trimethylamine borane.

[0025] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include inorganic particles formed on the surface of the substrate comprising boron-doped titanium carbonitride.

[0026] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include a metal substrate including an extruder part. In some embodiments, the extruder part may include an extrusion die. In some embodiments, the extrusion die may include a plurality of pins, an exterior surface of one or more of the plurality of pins defining the surface of the metal substrate on which the inorganic particles are deposited.

[0027] In some embodiments, the method according to any of the embodiments of the preceding paragraphs may include forming a titanium carbonitride coating on the metal substrate by depositing inorganic particles, the coating having a thickness of 1 micrometer to 100 micrometers.

[0028] Some embodiments are directed to a metal substrate coated with inorganic particles comprising titanium carbonitride by a method according to any of the embodiments of the preceding paragraphs, the metal substrate comprising an extrusion die.

[0029] Some embodiments are directed to a method for depositing inorganic material on a metal substrate, the method comprising: depositing inorganic particles comprising titanium carbonitride on a surface of the metal substrate by a chemical vapor deposition process at a deposition temperature of 900° C. or less, the chemical vapor deposition process being supplied with a source gas comprising an organometallic compound to form the inorganic particles, the inorganic particles forming a coating having a thickness of 1 micrometer to 100 micrometers.

[0030] In some embodiments, the method according to the embodiment in the immediately preceding paragraph may include an organometallic compound that includes tetrakis(dimethylamido)titanium.

[0031] In some embodiments, the method according to any of the embodiments of the two immediately preceding paragraphs may include an organometallic compound that includes tetrakis(ethylmethylamino)titanium.

[0032] In some embodiments, the method according to any of the embodiments of the three immediately preceding paragraphs may include a deposition temperature between 400°C and 750°C.

[0033] In some embodiments, the method according to any of the embodiments of the four immediately preceding paragraphs may include a deposition temperature between 600°C and 750°C.

[0034] In some embodiments, the method according to any of the embodiments of the five immediately preceding paragraphs may include a deposition temperature that does not exceed the austenitic transformation temperature of the metallic material of the metallic substrate. In some embodiments, the metallic material may be stainless steel. In some embodiments, the metallic material may be martensitic stainless steel.

[0035] Some embodiments are directed to a method of depositing inorganic material on a metal substrate, the method comprising depositing inorganic particles comprising titanium carbonitride on a surface of the metal substrate by a chemical vapor deposition process at a deposition temperature of 900° C. or less, the chemical vapor deposition process being provided with two or more source gases that react to form the inorganic particles and an aluminum-containing organometallic reducing agent.

[0036] In some embodiments, the method according to the embodiment in the immediately preceding paragraph may include an aluminum-containing organometallic reducing agent that includes a trialkylaluminum organometallic compound.

[0037] In some embodiments, the method according to any of the embodiments of the two immediately preceding paragraphs may include an aluminum-containing organometallic reducing agent selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and alane aluminum hydride.

[0038] In some embodiments, the method according to any of the embodiments of the three immediately preceding paragraphs may include an aluminum-containing organometallic reducing agent comprising an alane aluminum hydride, which in some embodiments is selected from the group consisting of dimethyl aluminum hydride, dimethyl aluminum hydride, and dimethylethylamine alane.

[0039] In some embodiments, the method according to any of the embodiments of the four immediately preceding paragraphs may deposit inorganic particles having less than 30 mol % aluminum.

[0040] In some embodiments, the method according to any of the embodiments of the five immediately preceding paragraphs may include a deposition temperature between 400°C and 600°C.

[0041] The accompanying drawings incorporated herein form a part of the specification and illustrate embodiments of the present disclosure. These drawings, together with the description, further serve to explain the principles of the embodiments of the present disclosure and to enable one skilled in the art of one or more related arts to make and use the embodiments of the present disclosure. These drawings are intended to be illustrative and not limiting. While the present disclosure has been generally described in the context of these embodiments, it should be understood that it is not intended to limit the scope of the present disclosure to these particular embodiments. In the drawings, like reference numbers refer to identical or functionally similar elements. [Brief description of the drawings]

[0042] [Figure 1] FIG. 1 is a perspective view of a portion of an extrusion die, according to some embodiments. [Diagram 2] Graph of the thermal expansion coefficient of exemplary steels over a range of temperatures during heating and cooling. [Diagram 3] Graph of thermal expansion coefficient over a range of temperatures for an exemplary steel during a high temperature coating process. [Figure 4] Graph of thermal expansion coefficient over a range of temperatures for an exemplary steel during a low temperature coating process, according to some embodiments. [Diagram 5] 1 is a graph of standard deviation of overall slot width distribution for honeycomb extrusion dies coated with inorganic particles by a deposition process according to some embodiments and by a conventional high temperature deposition process; [Figure 6] 1 is a bar graph showing the distribution of slot widths in honeycomb extrusion dies coated with inorganic particles by a conventional high temperature deposition process and by a low temperature deposition process according to some embodiments. [Figure 7] 1 is a graph of the variance of slot widths in a honeycomb extrusion die as a function of the number of hot coating processes used to deposit inorganic particles on the honeycomb extrusion die; [Figure 8] Deposition process according to some embodiments [Figure 9]Coated Articles According to Some Embodiments [Figure 10] Graph of thermal expansion coefficient over a range of temperatures for conventional 422 martensitic stainless steel during an exemplary coating process. [Figure 11] Graph of thermal expansion coefficient over a range of temperatures for martensitic stainless steel according to some embodiments during an exemplary coating process. [Figure 12] A graph showing the effect of various alloying elements on the austenite transformation temperature of steels. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0043] The following examples are illustrative rather than limiting of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the art and obvious to those skilled in the art are within the spirit and scope of the present disclosure.

[0044] By depositing inorganic particles, the wear resistance of a tool (e.g., an extrusion die) can be improved. By depositing the particles, a wear-resistant coating can be formed on the surface of the tool. As used herein, the "particles" deposited during the deposition process can be formed loosely in the deposition chamber, directly on a surface in the deposition chamber (e.g., directly on a target substrate), or a combination thereof. Particles deposited loosely are formed in the deposition chamber by reactions between vapor molecules, and after formation, these particles are deposited on the surface. Particles formed directly on a surface are formed by reactions of vapor molecules on the surface in the deposition chamber. By depositing particles on a surface, a continuous or discontinuous film of material can be formed on the surface.

[0045] Some deposition processes for depositing inorganic particles (e.g., chemical vapor deposition (CVD) processes) require deposition temperatures in excess of 800°C, which is higher than the austenite transformation temperature of many conventional steels, such as stainless steels. When steel is held at a temperature higher than its austenite transformation temperature, the steel's crystal structure changes to austenite. This change to austenite, induced by such high deposition temperatures, changes the coefficient of thermal expansion (CTE) of the steel. For example, for 422 martensitic stainless steel, the CTE of the steel is approximately 12×10 -6 / ℃ to about 18×10 -6 / ° C. Such an increase in CTE creates a significant difference between the CTE of the steel and the CTE of the deposited inorganic particles (referred to herein as "ΔCTE").

[0046] For the purposes of this application, the following temperatures have the following meanings and can be measured in the following ways: Deposition or surface preparation temperature is the temperature of the atmosphere in the deposition chamber during steady-state deposition of inorganic particles or of the gas flow used for surface preparation. For example, the deposition or surface preparation temperature can be measured using a temperature probe located in the deposition chamber or measurement chamber wall. Austenite transformation temperature is the temperature above which a metallic material transforms from a non-austenitic crystalline phase to an austenitic crystalline phase. For example, the austenite transformation temperature can be measured by dilatometry, ASTM E228 method. For the purpose of measuring the CTE of a material at a particular temperature, the temperature of the material can be measured by dilatometry, ASTM E228 method.

[0047] Some inorganic wear resistant coatings have a wear resistance greater than the CTE of the steel that is to be coated with the particles (e.g., approximately 12×10 for a particular steel). -6 / °C). Furthermore, the CTE of steels generally decreases with the formation of austenite in the steel (e.g., 18×10 -6 / °C). As a result, the ΔCTE between the wear resistant coating and the steel is greater due to the formation of austenite than if austenite were not formed in the steel. For extrusion dies, this increased ΔCTE is sufficient to cause deformation or bending of the pins, which leads to asymmetries in manufacturing, such as differences in hole-slot alignment or coating thickness, for example on the order of 1-2 micrometers (μm). These thermal stresses can increase the slot width variability (e.g., by a factor of 2, 3, 4, etc.) and exceed the yield strength of the steel, thus permanently deforming the pins even after removal of the coating, and the increased slot width variability can persist even after cooling, significantly reducing the web uniformity of the extrudates produced by such dies.

[0048] According to embodiments disclosed herein, undesirably high ΔCTE can be avoided by reducing the extent of austenite transformation of the steel caused by the deposition process or by preventing austenite transformation altogether. As described herein, the reduction or elimination of austenite transformation can be achieved by one or both of: (i) a low-temperature coating process performed at a temperature that remains below the austenite transformation temperature of the steel; and (ii) the development of an alloy composition with a target transformation temperature. Furthermore, undesirably high ΔCTE can be avoided by developing a coating layer with an apparent CTE of a target value or range.

[0049] Conventional CVD processes for deposition of inorganic particles require temperatures to produce an austenite transformation in steels such as martensitic and precipitation hardened steels. The low temperature CVD process described herein deposits inorganic particles (e.g., TiCN, boron doped TiCN, and / or multi-layer coatings including one or more layers of TiCN and / or boron doped TiCN) at temperatures below the austenite transformation temperature of the steel. By holding below this transformation temperature, the CTE of the steel remains stable and does not increase the ΔCTE between the steel and the deposited material. For example, the ΔCTE of conventional 422 stainless steel, with a yield strength of approximately 80 ksi, can be reduced by 10×10 to maintain low slot width variability by reducing or minimizing the amount of deformation of the corresponding die pins made of steel. -6 It has been found beneficial to keep the ΔCTE between the deposited material and the steel below 100 / °C. It is also preferable to minimize the ΔCTE between the deposited material and the steel to a small value, since any ΔCTE can cause some pin deformation and therefore increased slot width variability.

[0050] The low temperature deposition process described herein includes multiple parameters that achieve stable steel CTE, suitable particle adhesion, and suitable surface finish properties. These parameters include process temperature, gas flow rate, and specific process for laying down TiN (titanium nitride). In some embodiments, deposition of inorganic particles (e.g., TiCN (titanium carbonitride), boron doped TiCN, and / or multi-layer coatings including one or more layers of TiCN and / or boron doped TiCN) according to embodiments described herein can be achieved at a maximum deposition temperature of 400°C to 900°C. The low temperature deposition process described herein can result in suitable deposition of inorganic particles on steel substrates, which forms high quality wear resistant coatings without inducing austenitic transformation in the steel.

[0051] In addition to the low-temperature process, inorganic particle layer formation techniques can be used to increase the apparent CTE of the wear-resistant coating to a ΔCTE of, for example, 10 × 10 -6 / °C. For example, in one embodiment, the coating process may be controlled to minimize deformation of the pin by controlling the transformation to austenite to, for example, 10×10 -6 The method includes depositing a multi-layer wear resistant coating having an apparent CTE close enough to the CTE of the metallic material so as not to develop a ΔCTE that exceeds a target value of 1000 / ° C. The low temperature processes described herein can aid in the formation of wear resistant coatings with relatively low internal stresses and improved thickness uniformity, both of which can translate into reduced slot width variability in extrusion dies.

[0052] In some embodiments, the austenite transformation temperature of the steel may be manipulated (e.g., increased) to reduce or prevent austenite transformation during the coating deposition process and / or in use. In embodiments described herein, a step of modifying the composition of the steel alloy may be used to increase the austenite transformation temperature, for example, by as much as 100° C. By increasing the austenite transformation temperature, a relatively high temperature coating deposition process may be utilized without causing significant or no transformation to the austenite crystalline phase in the steel. By avoiding a significant amount of such transformation, or avoiding such transformation altogether, the ΔCTE between the steel and the deposited inorganic particles may be reduced to a target value, for example, less than 10×10 -6 / ° C. In this manner, maintaining a small ΔCTE can be used to improve the dimensional stability (i.e., reduce the amount of bending, warping, distortion, or other deformation caused by thermal stresses induced by the high temperatures required by the deposition process) of extrusion die components (e.g., pins in a honeycomb extrusion die) that are exposed to high temperature coating processes.

[0053] According to embodiments described herein, suitable alloy modifications for developing steels with increased Ac1 temperatures are derived based on empirical and computational thermodynamic calculations. These calculations demonstrate that significant increases in Ac1 temperatures can be achieved by decreasing the carbon (C), manganese (Mn), and / or nickel (Ni) content and / or increasing the chromium (Cr), molybdenum (Mo), vanadium (V), tungsten (W), copper (Cu), niobium (Nb), and / or silicon (Si) content in steels (e.g., conventional 422 stainless steel).

[0054] The compositional changes required to achieve the desired increase in Ac1 temperature may be small. In the case of conventional 422 stainless steel, such changes may be small enough that the steel can still be classified as a martensitic stainless steel (but technically deviate from the typical specifications for 422), and the 422 steel still retains the desired mechanical properties, including the ability to be hardened to a hardness of 40-50 on the Rockwell C scale, and to be strengthened to a hardness of 20-30 on the Rockwell C scale for machinability. The increased Ac1 temperature described herein is achieved by modifying the alloy content of the steel composition, not by heat treating or processing the steel alloy to manipulate the Ac1 temperature of the steel. However, the modified steels described herein may be heat treated or processed to produce the desired mechanical properties.

[0055] The alloying techniques described herein are applicable to a variety of steels, including high strength steels such as stainless steels, martensitic steels, martensitic stainless steels, and precipitation hardened steels, each of which is a suitable material for various high strength tools, such as extrusion dies, cutting tools, or grinding tools.

[0056] The effect of increasing the Ac1 temperature of steel has numerous benefits during high temperature processing such as inorganic particle deposition. These include at least the following three benefits, among others that will be appreciated by those skilled in the art:

[0057] First, increasing the Ac1 temperature can reduce or eliminate the volume change of the steel during the phase change to austenite at the Ac1 temperature and the subsequent transformation to martensite, if present, during cooling between the martensite start (Ms) and martensite finish (Mf) temperatures. These phase transformations can increase the internal stresses of any hard coating or plating (e.g., wear-resistant coating) applied to the tool (e.g., extrusion die), which can lead to geometric deformations. The internal stresses of the applied hard coating or plating can vary within the coating or plating due to the variation in the thickness of the coating or plating. In such cases, the variation in internal stresses can contribute significantly to the slot width variation of the extrusion die.

[0058] Second, increasing the Ac1 temperature can reduce the CTE of steel during hot processing by about 40%. For example, the CTE of martensitic stainless steel below the Ac1 temperature is about 11.5×10 -6 / °C, but from the Ac1 temperature to the Ms temperature upon cooling, the CTE is 18×10 -6 / °C or more. Such a reduction in CTE can reduce dimensional changes during high temperature processing and also reduce stresses in the steel and / or in the wear resistant coating after application of the wear resistant coating.

[0059] Third, increasing the Ac1 temperature can enable inorganic particle deposition via conventional coating deposition processes without having to modify the process parameters of such coating deposition processes.

[0060] Coating at or above the Ac1 temperature in conventional coating deposition processes results in significant austenite transformation of the steel and retransformation to martensite upon cooling. With respect to extrusion dies in particular, the transformation to austenite and retransformation to martensite upon cooling has been found to cause deformation and bending of pins in the extrusion die when depositing inorganic particles with relatively low CTE. This transformation and retransformation can occur multiple times during the deposition of different inorganic particle types for a multi-layer wear resistant coating. This transformation and retransformation can also occur multiple times over the life of the extrusion die when reapplying one or more wear resistant coatings. The deformation caused by this transformation and retransformation increases the slot width variability of the extrusion die and ultimately increases the variability of the web thickness of the extruded material.

[0061] Although various embodiments are described herein with respect to extrusion dies, and particularly honeycomb extrusion dies, the CTE control, low temperature deposition processes, and alloy manipulation of the austenite transformation temperature of metals can be applied to a variety of articles where dimensional stability and / or reduced ΔCTE are desired. Exemplary articles include metallic articles, such as cutting or grinding tools, coated with inorganic wear resistant particles.

[0062] 1 illustrates an exemplary extrusion die 100. The extrusion die 100 includes a die body 102 with a plurality of feed holes 104 and an array of pins 106. The outer surfaces of the pins 106 are defined by an intersecting array of discharge slots 108. And a discharge face 110 of the extrusion die 100 is formed by upper surfaces 112 of the pins 106 and the upper openings of the discharge slots 108. The extrusion die 100 may be a honeycomb extrusion die.

[0063] As discussed above, embodiments disclosed herein can be used to improve the dimensional accuracy or stability of extrusion die components (e.g., pins 106 and slots 108) during manufacture and use of the die. For example, in the present embodiments, because the spacing between pins 106 is used to set the width of slots 108, improving the dimensional stability of the pins corresponds to reducing the variability in the width of the slots ("slot width variability"). Reducing slot width variability can improve the shape, dimensions, and other parameters of the extrudates produced by the extrusion die. It should be understood that such improved dimensional accuracy, and corresponding reduced dimensional variability, is not limited to pins, slots, or slots formed by pins, but can be applied to any other features, shapes, profiles, or components of a tool, such as an extrusion die, to improve the performance, life, consistency, etc. of the parts produced.

[0064] In some embodiments, the materials used to construct the extrusion die 100 may be conventional and are coated according to the methods disclosed herein. Examples of conventional materials suitable for fabricating the main die elements include tool steels, so-called high-speed steels, martensitic steels, precipitation hardened steels, and stainless steels, such as martensitic stainless steels. In some embodiments, the materials used to construct the extrusion die 100 may be modified steel alloys as described herein and are coated according to conventional deposition methods or by the methods disclosed herein.

[0065] As used herein, "martensitic steel" or "martensitic stainless steel" refers to a steel or stainless steel that can be processed to contain about 90% or more by weight of a martensite crystal structure at room temperature (23° C.). In some embodiments, the martensitic steel or stainless steel contains about 90% or more by weight of a martensite crystal structure at room temperature, about 95% or more by weight of a martensite crystal structure at room temperature, about 96% or more by weight of a martensite crystal structure at room temperature, about 97% or more by weight of a martensite crystal structure at room temperature, or about 98% or more by weight of a martensite crystal structure at room temperature. Exemplary martensitic stainless steels include, but are not limited to, 400 series stainless steels, such as 422 stainless steel and 450 stainless steel, and precipitation hardened stainless steels, such as 17-4PH stainless steel.

[0066] The method of manufacturing the extrusion die 100 may depend at least in part on the designs selected for the assembly of the discharge slots 108, pins 106, and die body 102. For example, the construction of the extrusion die may be accomplished by hybrid electrical discharge section fabrication using a combination of electrical discharge machining (EDM) for the shaped feedhole extensions and wire EDM slot forming to form the slot and pin shapes. One skilled in the art will recognize other manufacturing techniques and combinations of manufacturing techniques that may be used to form the shapes, features, and / or components of the extrusion die.

[0067] Low delta coefficient of thermal expansion (CTE) deposition According to embodiments described herein, one or more methods may be utilized to control the ΔCTE between the metallic material or substrate of an article (e.g., extrusion die 100) and the inorganic particles deposited on the surface of the article or substrate. These methods include: (i) developing a deposition process capable of forming and depositing inorganic particles at or below the austenite transformation temperature of the metallic material; and developing a multi-layer coating formed by the deposited inorganic particles that has an apparent CTE within a target range. In this way, the ΔCTE can be controlled to, for example, 10×10 -6 / °C. In some embodiments, ΔCTE can be maintained at a target value of 10×10 -7 / ℃~10×10 -6 / °C.

[0068] In some embodiments, the thermal expansion coefficient of the metallic material and the deposited inorganic particles may be measured at a temperature at least 1° C. higher than the temperature at which the metallic material begins to transform to martensite during cooling after deposition of the wear-resistant coating (or would begin to transform to martensite if austenite transformation did not occur during deposition of the particles). Because the CTE changes when the material is cooled (e.g., decreases rapidly as the material transforms from austenite back to martensite), measuring the thermal expansion coefficient at such temperatures more accurately takes into account the effect that the austenite crystalline phase in the metallic material has on the CTE before the austenite transforms back to martensite. In some embodiments, the thermal expansion coefficient of the metallic material and the deposited inorganic particles may be measured at room temperature (e.g., 23° C.), after which the metallic material and the wear-resistant coating are quenched, thereby preventing the austenite from transforming back to martensite. That is, if the material is cooled quickly enough, the austenite crystalline phase does not have enough time to transform back to martensite during cooling.

[0069] In fact, by utilizing the methods described herein, slot width variability can be reduced by as much as 65% compared to conventional processes. Conventional coating processes have an additive effect of approximately linearly increasing slot width variability after each inorganic particle deposition process. Some coating processes according to embodiments described herein may not have an additive effect on slot width variability for each coating. If a coating process according to some embodiments has an additive effect on slot width variability, this additive effect is reduced. This is particularly advantageous because, in some cases, multiple coating cycles (e.g., six or more) may be used to deposit a suitable wear-resistant coating on the extrusion die. In some embodiments, a significant reduction in slot width variability compared to conventional coating processes can be achieved by the coating processes described herein.

[0070] In some embodiments, a method of applying an inorganic material to a metallic substrate (e.g., extrusion die 100) includes depositing the inorganic particles onto a surface of the metallic substrate at a deposition temperature that does not exceed the austenite transformation temperature of a metallic material of the metallic substrate and / or does not cause the metallic material to exceed the austenite transformation temperature of the metallic material. In some embodiments, a maximum deposition temperature for depositing inorganic particles may be less than the austenite transformation temperature of the metallic material of the metallic substrate. The austenite transformation temperature of a metallic material may be determined using a phase transformation diagram for the metallic material and / or by evaluating the change in CTE of the metallic material over a temperature range.

[0071] The CTE curves shown in graph 300 of FIG. 2 show the expansion / contraction strain curves of several conventional extrusion die steels. "422PM" is conventional 422 martensitic stainless steel. "450M SA" is conventional 450 martensitic stainless steel. "S240 SA" and "13-8ST SA" are conventional martensitic precipitation hardened stainless steels. "SA" stands for "solution annealed."

[0072] As shown in graph 300, these steels all have austenite transformation temperatures of about 805° C. or less, which can be below conventional inorganic particle deposition temperatures of 805° C. or more. The austenite transformation temperatures of the steels in graph 300 are illustrated by the significant change in curvature of the CTE curve for each steel at a particular temperature during heating. Also shown in graph 300, the CTE curve for each steel changes significantly upon cooling after the steel reaches a temperature where the austenite begins to transform back to martensite. For 422PM steel, this occurs at about 400° C. during cooling. For the other three steels shown, this increase in slope occurs at about 100° C. during cooling.

[0073] As shown in Figures 3 and 4, by maintaining the maximum deposition temperature below the austenite transformation temperature of the steel (e.g., 805°C transformation temperature for 422PM), the CTE of the steel remains stable at a relatively low value. Thus, the ΔCTE between the steel and the deposited inorganic particles does not increase dramatically as the steel begins to transform to austenite. Figure 3 shows a graph 400 of thermal expansion versus temperature (ΔL / L, ppm) for a deposition process having a maximum deposition temperature above the austenite transformation temperature of 422PM steel. As shown in graph 400, the steel thermally expands at an approximately linear rate up to about 805°C, a temperature at which the onset of austenite formation in the steel causes a significant change in the thermal expansion of the steel. This significant change is reversed as the steel cools due to the steel transforming from austenite to martensite upon cooling. In contrast, as shown in graph 500, if the maximum deposition temperature of the deposition process remains below 850° C. (eg, about 775° C. in graph 500), the steel is not subjected to significant changes in thermal expansion.

[0074] According to the embodiments disclosed herein, a CVD process with multiple process parameters was developed to obtain suitable inorganic particle formation and deposition at temperatures below the austenite transformation temperature of steel. Table 1 below shows a comparison of process parameters for a conventional CVD coating method for depositing TiN and boron doped TiCN (B-TiCN) particles and a low-temperature coating method for depositing TiN and B-TiCN particles according to some embodiments. To deposit TiCN particles, similar process parameters are used as those used for the deposition of boron doped TiCN, except that no boron source is included. The deposition chamber pressure for both the conventional CVD coating method and the low-temperature coating method may be between 140 mbar (millibar) and 180 mbar for TiN deposition. The deposition chamber pressure for both the conventional CVD coating method and the low-temperature coating method may be between 80 mbar and 120 mbar for B-TiCN deposition.

[0075] In the low temperature examples shown in Table 1, deposition of B-TiCN particles was achieved by ensuring complete coverage of approximately 1 micrometer thick TiN on the surface of the substrate before the start of deposition of B-TiCN particles, and by reducing the carrier gas flow (H2) by approximately 30% compared to conventional CVD deposition processes. In some embodiments, the flow rate of the H2 carrier gas can be 20 to 40 liters per minute (LPM), including subranges. For example, in some embodiments, the flow rate of the H2 carrier gas can be 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, or 40 LPM, or any range having any two of these values ​​as endpoints.

[0076] [Table 1]

[0077] By developing a coating process that allows one or more types of inorganic particles to be deposited below the austenite transformation temperature of the metallic material of the extrusion die, the variation in slot width of the extrusion die can be significantly reduced. FIG. 5 shows a graph 600 of the standard deviation of the total slot width for an extrusion die coated with the low temperature deposition process shown in Table 1 (labeled as "A die") and a die coated with the conventional deposition process shown in Table 1 (labeled as "B die"). The standard deviation of the total slot width is a measure of the variation in the width distance of the slots between adjacent pins of the extrusion die (e.g., slots 108 and pins 106 of extrusion die 100). In some embodiments, a smaller variation will produce an extruded honeycomb product with a consistent wall thickness, which is particularly desirable in high precision or dimensionally sensitive applications. In some embodiments, the variation is zero or as close to zero as possible.

[0078] The results reported in graph 600 are based on measurements of the total slot width variation for eight dies (four A dies and four B dies) that underwent the same number of coating cycles. By using a low temperature deposition process, the standard deviation of the total slot width can be reduced by more than 50%. Graph 600 shows a reduction of about 57%, from a deviation of about 3.5 to a deviation of about 1.5. As shown in graph 700 of FIG. 6, this results in a reduction of about 65% in the in-slot width variance of the extrusion die. Bar graph 700 shows the average in-slot width variance for the A and B dies tested.

[0079] For honeycomb extrusion dies, where the precision of the extruded part is dependent on the width of the die slots that define the walls of the extruded honeycomb, reducing the overall slot width variation can improve the useful life of the extrusion die. (i.e., the period during which the die consistently produces parts of a target quality and / or dimensional accuracy). As shown in graph 800 of FIG. 7, the slot width variance in an extrusion die increases significantly with subsequent high temperature coating cycles. In some cases, as shown in graph 800, this increase in slot width variance can be linear with each coating cycle. In some embodiments, the low temperature deposition process of the present application reduces the slope of this linear trend, thereby extending the life of the extrusion die, even if it undergoes multiple wear resistant coating and recoating processes during its life.

[0080] 5-7 are based on the low temperature deposition process shown in Table 1, similar results may be achieved using additional or alternative methods according to the present application. Any of the methods described herein for reducing or eliminating austenite transformation and / or controlling ΔCTE during the deposition process will reduce slot width variation in the extrusion die in a similar manner.

[0081] FIG. 8 illustrates a deposition process for depositing inorganic particles 920 on a surface 912 of a metal substrate 910 in a deposition chamber 900. The process illustrated in FIG. 8 may be a deposition process, such as a chemical vapor deposition (CVD) process. One or more gases 930 (e.g., gas 930a, gas 930b, and gas 930c) are introduced into the chamber 900 to form inorganic particles in the chamber 900, which are deposited on the surface 912. The one or more gases 930 may be source gases for one or more elements of the inorganic particles. The one or more gases 930 may be carrier gases. The inorganic particles 920 may be formed on the surface 912 of the substrate 910 by introducing any suitable type of source gas or carrier gas, including those described herein, into the chamber at an appropriate flow rate.

[0082] In some embodiments, the metal substrate 910 may be an extruder part. In some embodiments, the extruder part may include an extrusion die (e.g., extrusion die 100) or a part of an extrusion die (e.g., die body 102). In some embodiments, the substrate 910 may include an extrusion die 100 or a portion of an extrusion die 100 having a plurality of pins 106, an outer surface of one or more of the plurality of pins 106 defining a surface 912 of the metal substrate 910 on which the inorganic particles are deposited during a deposition process.

[0083] The inorganic particles 920 can be any type of inorganic particles described herein. The deposition process shown in Figure 8 can be used to deposit any number of inorganic particle layers or wear resistant coating layers described herein. The deposition process shown in Figure 8 can also be used to deposit inorganic particles according to any deposition process described herein. For example, the deposition process shown in Figure 8 can be used to deposit TiCN and / or boron doped TiCN particles according to the low temperature deposition process in Table 1.

[0084] In some embodiments, prior to deposition of the TiCN and / or boron doped TiCN particles 920, a layer of TiN particles 920 may be deposited on the surface 912 of the metal substrate 910 at a temperature above the austenite transformation temperature of the metallic material of the metal substrate 910. TiN adheres well to the metallic surface 912 and serves to adhere the B-TiCN particles and / or TiCN particles to the surface 912.

[0085] The deposition of TiN particles may be performed at a temperature between 820° C. and 860° C., inclusive. For example, the deposition of TiN particles may be performed at 820° C., 830° C., 840° C., 850° C., or 860° C., or any range having any two of these values ​​as endpoints. In some embodiments, the TiN deposition may be performed for 1 hour to 6 hours, inclusive. For example, the TiN deposition may be performed for 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, or any range having any two of these values ​​as endpoints. In some embodiments, the deposition of TiN particles may form a layer of TiN on surface 912 that is between 1 micrometer and 5 micrometers thick, inclusive. For example, deposition of TiN particles can form a layer of TiN on surface 912 having a thickness of 1 micrometer, 2 micrometers, 3 micrometers, 4 micrometers, or 5 micrometers, or any range having any two of these values ​​as endpoints.

[0086] In some embodiments, after deposition of the TiN particles 920, the layer of TiN particles 920 and the metal substrate 910 may be cooled to a temperature below the martensite transformation temperature of the metallic material of the substrate 910, thereby transforming any austenite formed in the metallic material during deposition of TiN to martensite. In some embodiments, the layer of TiN particles 920 and the metal substrate 910 may be cooled to a temperature between 100° C. and 400° C., including subranges. For example, the layer of TiN particles 920 and the metal substrate 910 may be cooled to 100° C., 150° C., 200° C., 250° C., 300° C., 350° C., or 400° C., or any range having as endpoints any two of these values. The layer of TiN particles 920 and the metal substrate 910 may be held at the low temperature, as discussed above, or within any of the low temperature ranges, as discussed above, for an amount of time sufficient to transform any austenite to martensite.

[0087] In some embodiments, prior to deposition of TiN particles 920, surface 912 may be prepared at an elevated temperature to clean surface 912. In some embodiments, the surface preparation may include removing organic particles from surface 912 by reacting the organic particles with hydrochloric acid (HCl) formed by flowing titanium tetrachloride (TiCl4) gas and hydrogen (H2) gas over surface 912. In some embodiments, the surface preparation may be performed at a temperature between 820° C. and 860° C., inclusive. For example, surface preparation may be performed at 820° C., 830° C., 840° C., 850° C., or 860° C., or any range having any two of these values ​​as endpoints. In some embodiments, surface preparation may be performed for 5 minutes to 30 minutes, inclusive. For example, surface preparation may be carried out for 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes, or over any range having any two of these values ​​as endpoints.

[0088] Although the surface preparation and TiN deposition processes may be performed above the austenite transformation temperature of the substrate 910, performing these high temperature steps on the surface 912 prior to deposition of additional coating layers (e.g., B-TiCN and / or TiCN) limits the amount of austenite transformation on the surface 912 and / or in the substrate 910. In some embodiments, some austenite transformation is permitted while still maintaining acceptable results, for example because the limited amount of austenite transformation in these steps tends not to result in significant slot width variations. Additionally, in some embodiments, after TiN deposition and / or surface preparation, the substrate 910 may be cooled below the martensite transformation temperature to transform any austenite formed during any of these steps back to martensite, thereby lowering the CTE of the substrate 910 for deposition of additional particles, such as boron doped TiCN particles and / or TiCN particles.

[0089] As shown in Table 1, deposition of B-TiCN particles 920 according to embodiments of the present application may be performed at a maximum deposition temperature of 770° C., which is below the austenite transformation temperature of some steels, such as conventional 422 martensitic stainless steel. In some embodiments, deposition of B-TiCN particles 920 may be performed at a maximum deposition temperature of 600° C. to 860° C. (including subranges). For example, deposition of B-TiCN particles 920 may be performed at a maximum deposition temperature of 600° C., 620° C., 640° C., 660° C., 680° C., 700° C., 720° C., 740° C., 760° C., 800° C., 820° C., 840° C., or 860° C., or any range having any two of these values ​​as endpoints.

[0090] In some embodiments, the deposition of B-TiCN particles at the maximum deposition temperature may be performed for 10 hours to 20 hours, including subranges. For example, the B-TiCN deposition may be performed for 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, or 20 hours, or any range having any two of these values ​​as endpoints. Multiple layers of B-TiCN particles may be deposited by multiple deposition processes, where each deposition process is performed for the same length of time or for different lengths of time. For example, the low temperature deposition process in Table 1 includes three depositions of B-TiCN at 770° C., each for 17 hours (51 hours total). Multiple layers of B-TiCN particles may be layered with TiCN particles as described herein.

[0091] TiCN particles may be deposited at any of the maximum deposition temperatures, temperature ranges, times, and time ranges described herein for B-TiCN. Other inorganic particles that may be deposited at these maximum deposition temperatures, temperature ranges, times, and time ranges include, but are not limited to, boron (B) particles, aluminum titanium nitride (Al-Ti-N) particles, titanium aluminum nitride (Ti-Al-N) particles, and chromium nitride (CrN) particles. In some embodiments, any combination of inorganic particles described herein may be deposited on the surface 912 of the substrate 910. The deposition of any of the inorganic particles described herein may form one or more layers of inorganic material on the surface 912 of the substrate 910. The inorganic particles deposited according to the embodiments described herein may form a wear-resistant coating (e.g., coating 1020) on the surface 912 of the substrate 910.

[0092] All or a portion of the metallic substrate 910 may be formed of a metallic material having an austenite transformation temperature. In some embodiments, at least a surface 912 of the substrate 910 may be formed of a metallic material having an austenite transformation temperature.

[0093] The composition of the metallic material forming the metallic substrate 910 will determine whether the maximum deposition temperature is below the austenite transformation temperature of said material. For example, TiN can be deposited above 820° C., so TiN particles will be deposited at temperatures below the austenite transformation temperature of the metallic material only if the austenite transformation temperature of the metallic material is higher than 820° C.

[0094] In some embodiments, the metallic material of the metallic substrate 910 may be steel. In some embodiments, the metallic material of the metallic substrate 910 may be martensitic steel. In some embodiments, the metallic material of the metallic substrate 910 may be martensitic stainless steel. In some embodiments, the metallic material of the metallic substrate 910 may be precipitation hardened martensitic steel. In some embodiments, the metallic material of the metallic substrate 910 may not be precipitation hardened martensitic stainless steel. In some embodiments, the metallic material of the metallic substrate 910 may be a conventional steel material. In some embodiments, the metallic substrate 910 may include an alloy metallic material with an elevated Ac1 temperature as described herein.

[0095] In some embodiments, the inorganic particles may be deposited onto a wear resistant coating already deposited on a surface of the substrate, such as surface 912, using a low temperature deposition process according to embodiments described herein. In such embodiments, the inorganic particles may be deposited onto the already deposited wear resistant coating at a temperature at or below the austenite transformation temperature of the metallic material of the substrate.

[0096] In some embodiments, the exterior surface of the previously deposited wear-resistant coating may be prepared before inorganic particles are deposited on the previously deposited wear-resistant coating. In such embodiments, the surface preparation may include removing oxides from the exterior surface by flowing boron trichloride (BCl3) over the exterior surface. In some embodiments, the surface preparation may include removing organic particles from the exterior surface by reacting them with hydrochloric acid (HCl) formed by flowing titanium tetrachloride (TiCl4) gas and hydrogen (H2) gas over the exterior surface. In some embodiments, the surface preparation may include removing organic particles from the exterior surface by flowing boron trichloride (BCl3) and reacting them with hydrochloric acid (HCl) formed by flowing titanium tetrachloride (TiCl4) gas and hydrogen (H2) gas over the exterior surface. Surface preparation of the exterior surface may aid in the adhesion of newly deposited inorganic particles to the exterior surface without the need to deposit a TiN layer for adhesion.

[0097] Although some embodiments described herein refer specifically to chemical vapor deposition for depositing the inorganic particles, any suitable vapor deposition process may be used to deposit the inorganic particles at or below the austenite transformation temperature of the substrate. For example, a physical vapor deposition (PVD) process may be used to deposit the inorganic particles on the substrate.

[0098] In some embodiments, the ΔCTE between the abrasion-resistant coating and the metallic material of the substrate can be controlled by developing the coating to have a target value (or range) of apparent CTE. In such embodiments, the ΔCTE between the abrasion-resistant coating and the metallic material of the substrate can be controlled by developing the coating to have a target value for the apparent CTE of the coating, such as 10×10 -6 A ΔCTE of 0.1 μm / ° C. or less can be achieved. The apparent CTE of the coating can be tuned by depositing a multi-layer coating with layers composed of inorganic particles with different CTE values ​​to control the apparent (cumulative) CTE of the entire coating.

[0099] This ΔCTE control approach utilizes the rules of mixing to develop a layered coating structure and composition that produces a desired apparent CTE for the coating. This approach can also optimize the surface finish properties of the coating by utilizing B-TiCN particles while minimizing the effect of the B-TiCN layer on the apparent CTE of the coating.

[0100] B-TiCN particles can form a coating layer with a surface roughness of less than 0.1 micrometers. It may therefore be desirable to include one or more B-TiCN coating layers to provide a smooth wear-resistant coating. In particular, it may be beneficial to deposit a B-TiCN coating layer as the outermost coating layer to provide a smooth wear-resistant coating.

[0101] However, as shown in Table 2 below, B-TiCN has a relatively low CTE compared to some other wear-resistant coating materials. Because B-TiCN has a lower CTE than the other coating materials, it has the highest ΔCTE with the metallic materials described herein. Using the rules of blending described herein, a coating layer can be designed that meets both the CTE and surface finish requirements.

[0102] [Table 2]

[0103] 9 shows a coated article 1000 according to some embodiments. The coated article 1000 includes a substrate 1010 and an abrasion-resistant coating 1020 disposed on a surface 1012 of the substrate. The substrate 1010 may be the same as or similar to the substrate 910. The abrasion-resistant coating 1020 is formed by depositing inorganic particles on the surface 1012 of the substrate 1010.

[0104] The abrasion-resistant coating 1020 may include one or more coating layers formed by deposition of inorganic particles, such as a first coating layer 1030, a second coating layer 1040, a third coating layer 1050, a fourth coating layer 1060, and a fifth coating layer 1070. Although the coated article 1000 is illustrated as having five coating layers, the abrasion-resistant coating 1020 may include any number of coating layers. For example, the abrasion-resistant coating 1020 may include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or even more coating layers. In embodiments including two or more coating layers, the abrasion-resistant coating 1020 may be referred to as a multi-layer abrasion-resistant coating.

[0105] Each coating layer of coating 1020 may be formed of deposited inorganic particles. In some embodiments, one or more coating layers may be composed of different types of inorganic particles. In some embodiments, one or more coating layers may be composed of the same type of inorganic particles. In some embodiments, one or more coating layers may be deposited using a conventional deposition process. In some embodiments, one or more coating layers may be deposited using a low temperature deposition process according to embodiments described herein.

[0106] In some embodiments, a first coating layer 1030 of inorganic particles may be deposited on the surface 1012 of the substrate 1010 in a first deposition process, and one or more additional coating layers (e.g., layers 1040, 1050, 1060, and / or 1070) may be deposited in additional deposition processes. For example, a second coating layer 1040 may be deposited in a second deposition process that deposits additional inorganic particles on the inorganic particles deposited in the first deposition process (i.e., on coating layer 1030). The additional coating layers may be deposited at or below the austenitic temperature (e.g., a temperature not exceeding the austenitic transformation temperature) of the metallic material of the substrate 1010.

[0107] The wear-resistant coating 1020 may have a total thickness 1022 between 1 micrometer and 100 micrometers (including subranges). For example, the thickness 1022 may be between 1 micrometer, 2 micrometers, 5 micrometers, 10 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 55 micrometers, 60 micrometers, 65 micrometers, 70 micrometers, 75 micrometers, 80 micrometers, 85 micrometers, 90 micrometers, 95 micrometers, or 100 micrometers, or a range having any two of these values ​​as endpoints. In some embodiments, the thickness 1022 may be between 2 micrometers and 65 micrometers.

[0108] Each individual coating layer (e.g., layers 1030, 1040, 1050, 1060, and / or 1070) of the multi-layer coating has a thickness 1032 that is a portion of the total thickness 1022. In some embodiments, the thickness 1032 of one or more individual coating layers may be the same. In some embodiments, the thickness 1032 of one or more individual coating layers may be different. By adjusting the thickness 1032 of the individual coating layers, a desired apparent CTE can be provided for the wear-resistant coating 1020. The thickness 1032 of each individual layer may be between 0.5 micrometers and 100 micrometers, inclusive. For example, the thickness 1032 of an individual layer can be 0.5 micrometers, 1 micrometer, 2 micrometers, 5 micrometers, 10 micrometers, 15 micrometers, 20 micrometers, 25 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 45 micrometers, 50 micrometers, 55 micrometers, 60 micrometers, 65 micrometers, 70 micrometers, 75 micrometers, 80 micrometers, 85 micrometers, 90 micrometers, 95 micrometers, 99 micrometers, or 100 micrometers, or a range having any two of these values ​​as endpoints.

[0109] In some embodiments, the individual thicknesses between particles deposited in successive deposition steps are not individually distinguishable, for example, multiple particle deposition runs (e.g., a first particle is deposited in a first run followed by a second particle in a second run) and / or multiple different materials (e.g., both B-TiCN and TiCN) may be combined or dispersed in or as a single layer having a single thickness.

[0110] The coating layers of the wear-resistant coating 1020 (e.g., layers 1030, 1040, 1050, 1060, and / or 1070) may be formed of any of the inorganic particles described herein. In some embodiments, one or more of the coating layers of the wear-resistant coating 1020 may include boron-doped titanium carbonitride particles forming a boron-doped titanium carbonitride layer. In some embodiments, one or more of the coating layers of the wear-resistant coating 1020 may include titanium carbonitride particles forming a titanium carbonitride layer. In some embodiments, one or more of the coating layers of the wear-resistant coating 1020 may include titanium nitride particles forming a titanium nitride layer. In some embodiments, the first coating layer 1030 may be a TiN particle layer to aid in the adhesion of additional layers to the surface 1012.

[0111] In some embodiments, the wear resistant coating 1020 may be a multi-layer coating including a boron doped titanium carbonitride layer and a titanium carbonitride layer. In some embodiments, the wear resistant coating 1020 may be a multi-layer coating including multiple boron doped titanium carbonitride layers and multiple titanium carbonitride layers. In some embodiments, the wear resistant coating 1020 may be a multi-layer coating including a boron doped titanium carbonitride layer, a titanium carbonitride layer, and a titanium nitride layer. In some embodiments, the wear resistant coating 1020 may be a multi-layer coating including multiple boron doped titanium carbonitride layers, multiple titanium carbonitride layers, and multiple titanium nitride layers.

[0112] In some embodiments, the outermost layer of the wear-resistant coating 1020 (e.g., the fifth coating layer 1070 shown in FIG. 9) may be a boron-doped titanium carbonitride layer formed with boron-doped titanium carbonitride particles. By forming the outermost layer of the wear-resistant coating 1020 using boron-doped titanium carbonitride particles, the wear-resistant coating 1020 can be provided with a desired top surface roughness, for example, a top surface roughness (R aAs shown in Table 2, other types of inorganic particles can provide a higher surface roughness (R a ) to form a layer having the following structure.

[0113] In some embodiments, the outermost layer of boron doped TiCN may have a thickness of at least 5 micrometers. In some embodiments, an outermost layer of boron doped TiCN having a thickness of at least 5 micrometers has been found to be sufficient to maintain the surface roughness of the multi-layer coating at an acceptable level, for example, especially for low extrusion pressures. In practice, acceptable surface finishes will depend on the extrusion batch composition and target performance parameters, but may range from a surface roughness (R) of 0.05 micrometers to 0.2 micrometers, especially for batches with high wall drag. a ) has been found to give acceptable results.

[0114] The apparent CTE of a multi-layer abrasion-resistant coating (e.g., abrasion-resistant coating 1020) can be controlled by adjusting the number, thickness, and inorganic materials of the individual coating layers of the multi-layer coating. For purposes of this application, the apparent CTE (A) of a multi-layer coating is defined by the following formula: A=(f1)(CTE1)+(f2)(CTE2)+(f3)(CTE3)…+(f n )(CTE n ) (Formula 1) where f = fractional thickness of the layer and CTE = coefficient of thermal expansion of the layer. The fractional thickness is calculated by dividing the thickness of the layer (Tl) by the total thickness of the multilayer coating (Tt).

[0115] Therefore, the fractional coefficient of thermal expansion of each layer is given by the following formula: fCTE=(Tl / Tt)*CTEl (Equation 2) where: fCTE = partial coefficient of thermal expansion of each layer, Tl = thickness of each layer, Tt = total thickness of the multilayer coating, and CTEl = thermal coefficient of expansion of each layer.

[0116] As an example, the apparent CTE of a multilayer coating having a 2-micrometer-thick TiN coating, a 36.6-micrometer-thick TiCN coating, and a 6.4-micrometer-thick B-TiCN coating is 8×10 -6 / °C. In this example, the steel transformed into austenite and the corresponding 18×10 -6 / °C, the ΔCTE between the steel and this multilayer coating is 10×10 -6 / °C.

[0117] In some embodiments, the apparent CTE of the multi-layer coating is 8×10 -6 / ℃~9×10 -6 / °C (including subranges). For example, the apparent CTE of the multilayer coating may be 8×10 -6 / ℃, 8.1×10 -6 / ℃, 8.2×10 -6 / ℃, 8.3×10 -6 / ℃, 8.4×10 -6 / ℃, 8.5×10 -6 / ℃, 8.6×10 -6 / ℃, 8.7×10 -6 / ℃, 8.8×10 -6 / ℃, 8.9×10 -6 / ℃ or 9×10 -6 / °C, or any range having any two of these values ​​as endpoints.

[0118] As shown in Table 2, the CTE of boron-doped TiCN itself is 5 × 10 -6 / °C. Therefore, when steel transforms into austenite, its CTE increases to 18×10 -6 / ℃, this is the boron-doped TiCN layer and 13 × 10 -6 / °C. As discussed above, this can cause dimensional changes in steel tools, such as permanent deformation of pins in an extrusion die. By controlling the CTE of the multi-layer coatings described herein, boron doped TiCN can be used in the multi-layer coatings, particularly as the outermost layer of the multi-layer coating, to control the surface roughness of the coating. In some embodiments, a smoother coating surface can be advantageously utilized to reduce the extrusion pressure required to extrude the extrusion batch composition and / or to increase throughput.

[0119] A variety of coated metal substrates may be produced by the low temperature deposition processes and methods of controlling apparent CTE described herein. Exemplary coated substrates include, but are not limited to, coated extrusion dies, coated honeycomb extrusion dies, and coated cutting tools, such as grinding tools, blades, or drill bits.

[0120] In some embodiments, the coated metal substrate may include a steel body (e.g., die body 102) and a multi-layer wear resistant coating (e.g., coating 1020) having multiple titanium carbonitride layers and multiple boron doped titanium carbonitride layers deposited on a surface of the steel body (e.g., an outer surface of one or more pins 106). The surface of the steel body may include steel having a coefficient of thermal expansion that is X / °C when measured at a temperature T°C, and the multi-layer wear resistant coating may have an apparent coefficient of thermal expansion that is Y / °C when measured at a temperature T, where the difference between X and Y is 10×10 -6 / °C or less. In such embodiments, the thermal expansion coefficients of the steel and the multi-layer wear resistant coating can be measured by heating the steel and the multi-layer wear resistant coating to a temperature equal to or greater than the austenite transformation temperature of the steel and cooling the steel and the multi-layer wear resistant coating to a temperature T, where T is equal to 1°C above the temperature at which the steel transforms to martensite (Ms) during cooling. After the steel transforms to austenite, measuring the ΔCTE at a temperature equal to 1°C above the temperature at which the steel transforms to martensite captures the maximum ΔCTE between the steel transformed to austenite and the multi-layer wear resistant coating according to embodiments described herein.

[0121] In some embodiments, a deposition method for producing a coated metal substrate may include depositing a multi-layer wear resistant coating having multiple titanium carbonitride layers and multiple boron doped titanium carbonitride layers on a surface of a steel substrate in multiple deposition processes, each depositing one layer of the multi-layer wear resistant coating at a deposition temperature above the austenite transformation temperature of the steel material of the metal substrate. In such embodiments, the apparent CTE of the multi-layer wear resistant coating may be greater than or equal to a ΔCTE of 10×10, where ΔCTE is measured at a temperature equal to 1° C. above the temperature at which the steel transforms to martensite during cooling. -6 / ℃ or less.

[0122] Alloy formation to control austenite transformation temperature In some embodiments, alloy compositions of steels are developed that have elevated austenite transformation (Ac1) temperatures relative to conventional steels with similar mechanical properties. For example, alloy compositions for conventional steels (e.g., 422 stainless steel) with Ac1 temperatures of about 805°C may be set to produce modified steels with Ac1 temperatures above 805°C (e.g., 850°C). Correspondingly, reduced austenite transformation can be achieved due to the effect that the compositions of the present disclosure have on the Ac1 temperature of the steel. As another example, the steel alloys described herein can be developed relative to a base composition, such as a conventional 17-4 precipitation hardened steel.

[0123] By modifying the Ac1 temperature of conventional steels, the ΔCTE during deposition of inorganic particles can be minimized by avoiding significant amounts of austenite formation in the steel, or by avoiding austenite formation altogether. As described herein, minimizing the ΔCTE can minimize pin deformations in extrusion dies, and thus slot width variability. This leads to improved consistency of extruded products, such as more consistent wall thickness for extruded honeycomb products.

[0124] As used herein, the term "conventional steel" refers to steel having an alloy defined and specified by industry recognized standards organizations such as the American Society for Testing and Materials (ASTM), the American Iron and Steel Institute (AISI), and the Society of Automotive Engineers (SAE). In some embodiments, the conventional steel may be a stainless steel. In some embodiments, the conventional steel may be a martensitic steel. In some embodiments, the conventional steel may be a martensitic stainless steel. In some embodiments, the conventional steel may be a precipitation hardened steel. In some embodiments, the conventional steel may be a magnetic steel. As used herein, "magnetic steel" is a steel that magnetically holds a magnet when a surface of a part made of the magnetic steel and a magnet placed on the surface are positioned perpendicular to the ground. Exemplary conventional steels include, but are not limited to, 422 stainless steel, 450 stainless steel, and 630 or 17-4PH (precipitation hardened) stainless steel.

[0125] Developing alloy compositions for steels according to embodiments described herein includes selecting the weight percentages of alloying elements present in the amounts and ranges disclosed herein. Alloy compositions developed according to embodiments described herein can have mechanical properties, such as hardness, hardenability, magnetic properties, or yield strength, that are generally comparable to or similar to conventional steels.

[0126] By increasing the austenite transformation temperature of the steel, inorganic particle deposition (and other manufacturing operations) can be carried out at temperatures above the austenite transformation temperature of conventional steel while maintaining a stable and nearly constant CTE. For extrusion dies in particular, this reduces the ΔCTE between the wear resistant coating (e.g., coating 1020) and the steel. This allows for the application of a variety of wear resistant coatings without significantly deforming the pins of the extrusion die. Some examples of these coatings used on extrusion dies include, but are not limited to, TiCN, boron doped TiCN, Al-Ti-N (aluminum titanium nitride), Ti-Al-N (titanium aluminum nitride), CrN, and TiN.

[0127] Table 3 below provides examples of alloy compositions of conventional 422 stainless steel compared to certain alloys developed in accordance with the disclosures herein. As shown in Table 3, the weight percent (wt%) of certain alloying elements may be higher or lower compared to conventional 422 stainless steel compositions, resulting in an Ac1 temperature of greater than 850° C. versus 805° C. for 422 stainless steel.

[0128] [Table 3]

[0129] In some embodiments, the Ac1 temperature of a stainless steel alloy developed as disclosed herein can be increased by at least 10° C. to 200° C. (including subranges) relative to a conventional alloy having similar mechanical properties. For example, the Ac1 temperature can be increased by 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., 160° C., 170° C., 180° C., 190° C., or 200° C., or any range having any two of these values ​​as endpoints.

[0130] In some embodiments, steels according to embodiments described herein may have an Ac1 temperature of 850° C. or greater. In some embodiments, steels according to embodiments described herein may have an Ac1 temperature of 850° C. to 1000° C. (including subranges). For example, the steels may have an Ac1 temperature of 850° C., 860° C., 870° C., 880° C., 890° C., 900° C., 910° C., 920° C., 930° C., 940° C., 950° C., 960° C., 970° C., 980° C., 990° C., or 1000° C., or any range having any two of these values ​​as endpoints.

[0131] The elevated Ac1 temperature of the modified 422 stainless steel of Table 3 is shown in Figures 10 and 11. Graphs 1100 and 1200 of Figures 10 and 11 show the thermal expansion (ΔL / L, ppm) versus temperature for an exemplary deposition process. For a conventional 422 stainless steel composition, the steel expands at an approximately linear rate up to about 805°C, a temperature at which the onset of austenite transformation in the steel causes a significant change in the thermal expansion of the steel. This significant change is reversed as the steel cools, due to the transformation of the steel from austenite to martensite upon cooling. In contrast, as shown in graph 1200, the modified 422 stainless steel composition is not subject to a change in thermal expansion at temperatures below 850°C. Thus, the Ac1 temperature of the modified 422 stainless steel composition is greater than 850°C.

[0132] Table 4 below shows high and low weight percentages for modified martensitic 422 stainless steel materials according to some embodiments having Ac1 temperatures above 850°C. The predicted Ac1 temperatures shown in Table 4 are based on empirical calculations using Ac1 temperature data for various steel materials available through the University of Cambridge's Materials Algorithms Project. Using the above data, empirical mathematical models were generated to predict the Ac1 temperature of steels based on their alloy content. To ensure that these models generate accurate predictions, the models were used to predict the Ac1 temperature of conventional 422 martensitic stainless steel. This prediction was then compared to the actual Ac1 temperature from the CTE curve of conventional 422 stainless steel. As shown in Table 4, the above model predicted an Ac1 temperature of 805°C, which is consistent with FIG. 10.

[0133] [Table 4]

[0134] As shown in Table 4, by modifying the alloy content, the Ac1 temperature of the steel can be increased significantly. This allows high temperature wear resistant coatings to be deposited on steel substrates with stable CTE values. The high and low weight percentages shown in Table 4 result in alloy steels that retain machinability and hardenability comparable to conventional 422 stainless steel.

[0135] In some embodiments, the modified steels according to embodiments described herein may have a yield strength of 85 kilopounds per square inch (ksi) to 200 kilopounds per square inch, including subranges. For example, the modified steels may have a yield strength of 85 ksi, 90 ksi, 100 ksi, 110 ksi, 120 ksi, 130 ksi, 140 ksi, 150 ksi, 160 ksi, 170 ksi, 180 ksi, 190 ksi, 200 ksi, or any range having any two of these values ​​as endpoints.

[0136] In some embodiments, modified steels according to embodiments described herein may have a Rockwell C hardness of 18 to 60. For example, modified steels may have a Rockwell C hardness of 18, 20, 25, 30, 35, 40, 45, 50, 55, or 60, or any range having any two of these values ​​as endpoints.

[0137] While Tables 3 and 4 show exemplary compositions that are mechanically similar to 422 stainless steel, other metallic materials having an austenite transformation temperature may also be modified to have an elevated Ac1 temperature as described herein, further examples of which are presented in comparison to the conventional 17-4 precipitation hardened (PH) alloy as shown in Table 5 below.

[0138] [Table 5]

[0139] The modified 17-4PH steel shown in Table 5 generally retains the mechanical and machining properties of conventional 17-4 steel, but has an elevated Ac1 temperature, like the modified 422 steel in Tables 3 and 4. Although the modified 17-4PH does not exhibit as high an elevated Ac1 temperature as the modified 422 stainless steel, by increasing the Ac1 temperature of conventional 17-4PH steel, a relatively low temperature coating of Al-Ti-N can be deposited with little or no austenite transformation occurring. This can also reduce the amount of austenite transformation for a given deposition process by increasing the austenite transformation temperature.

[0140] In some embodiments, the Ac1 temperature of the modified 17-4PH steel may be between 725° C. and 875° C. (including subranges). For example, the modified 17-4PH steel may have an Ac1 temperature of 725° C., 750° C., 775° C., 800° C., 825° C., 850° C., or 875° C., or any range having any two of these values ​​as endpoints.

[0141] FIG. 12 shows a graph 1300 of the effect of various alloying elements on the austenite transformation temperature of steel. As shown in the graph 1300, molybdenum (Mo) and manganese (Mn) have a tendency to contribute to the formation of austenite at relatively low temperatures. However, titanium (Ti), molybdenum (Mo), tungsten (W), silicon (Si), and chromium (Cr) have a tendency to reduce or prevent the formation of austenite at relatively low temperatures. The steeper the slope (positive or negative slope) of the curve in the graph 1300, the stronger the effect of that element on the austenite transformation temperature.

[0142] The following are exemplary metal compositions according to embodiments of the present application. In some embodiments, the metal may be steel, including iron, molybdenum, and tungsten, and at least one of manganese, nickel, chromium, and vanadium. In such embodiments, the manganese, nickel, chromium, and vanadium may be present in the following ranges: manganese: less than 0.1% by weight, nickel: less than 0.7% by weight, chromium: greater than 12.5% ​​by weight, and vanadium: greater than 0.3% by weight.

[0143] In some embodiments, the metal may include molybdenum in an amount of 1.0 wt.% to 1.5 wt.% (including subranges). For example, molybdenum may be present in an amount of 1.0 wt.%, 1.1 wt.%, 1.2 wt.%, 1.3 wt.%, 1.4 wt.%, or 1.5 wt.%, or any range having any two of these values ​​as endpoints. In some embodiments, the precipitation hardened steel may include molybdenum present in a range of 0.75 wt.% to 1.25 wt.% (including subranges). For example, molybdenum may be present in an amount of 0.75 wt.%, 0.8 wt.%, 0.9 wt.%, 1 wt.%, 1.1 wt.%, 1.2 wt.%, or 1.25 wt.%, or any range having any two of these values ​​as endpoints.

[0144] In some embodiments, the metal may include tungsten in an amount between 0.9% and 1.3% by weight (including subranges). For example, tungsten may be present in an amount of 0.9%, 1.0%, 1.1%, 1.2%, or 1.3% by weight, or any range having any two of these values ​​as endpoints.

[0145] In some embodiments, the metal may include manganese in an amount less than 0.1 wt.%. For example, the metal may include 0.09 wt.%, 0.08 wt.%, 0.07 wt.%, 0.06 wt.%, 0.05 wt.%, 0.04 wt.%, 0.03 wt.%, 0.02 wt.%, 0.01 wt.%, or 0 wt.%, or any range having any two of these values ​​as endpoints. In some embodiments, the metal may include manganese present at less than 0.05 wt.%. In some embodiments, the precipitation hardened steel may include manganese present in the range of 0.1 wt.% to 0.9 wt.% (including subranges). For example, manganese may be present at 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, or 0.9 wt%, or any range having any two of these values ​​as endpoints.

[0146] In some embodiments, the metal may include nickel present at less than 0.7 wt.%. For example, the metal may include 0.65 wt.%, 0.6 wt.%, 0.55 wt.%, 0.5 wt.%, 0.45 wt.%, 0.4 wt.%, 0.35 wt.%, 0.3 wt.%, 0.25 wt.%, 0.2 wt.%, 0.15 wt.%, 0.1 wt.%, 0.05 wt.%, or 0 wt.% nickel, or any range having any two of these values ​​as endpoints. In some embodiments, the precipitation hardened steel may include nickel present at a range of 3 wt.% to 4 wt.% (including subranges). For example, nickel may be present at 3 wt.%, 3.2 wt.%, 3.4 wt.%, 3.5 wt.%, 3.6 wt.%, 3.8 wt.%, or 4 wt.%, or any range having any two of these values ​​as endpoints.

[0147] In some embodiments, the metal may include chromium present at 12.5% ​​or more by weight. For example, the metal may include chromium present at 13%, 14%, 15%, 16%, 17%, or 18% by weight, or any range having any two of these values ​​as endpoints. In some embodiments, the precipitation hardened steel may include chromium present in the range of 16% to 19% by weight (including subranges). For example, chromium may be present at 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, or 19% by weight, or any range having any two of these values ​​as endpoints.

[0148] Vanadium, like titanium, molybdenum, tungsten, silicon, and chromium, has a tendency to reduce or prevent the formation of austenite at relatively low temperatures. In some embodiments, the metal may include vanadium present at more than 0.3 wt.%. For example, the metal may include vanadium present at 0.35 wt.%, 0.4 wt.%, 0.45 wt.%, 0.5 wt.%, 0.55 wt.%, 0.6 wt.%, 0.65 wt.%, 0.7 wt.%, 0.75 wt.%, 0.8 wt.%, 0.85 wt.%, 0.9 wt.%, 0.95 wt.%, or 1 wt.%, or any range having any two of these values ​​as endpoints.

[0149] Copper, like titanium, molybdenum, tungsten, silicon, and chromium, has a tendency to reduce or prevent the formation of austenite at relatively low temperatures. In some embodiments, the metal may include copper present in the range of 0 wt.% to 0.05 wt.%, inclusive of subranges. For example, copper may be present in the range of 0 wt.%, 0.01 wt.%, 0.02 wt.%, 0.03 wt.%, 0.04 wt.%, or 0.05 wt.%, or any range having any two of these values ​​as endpoints. In some embodiments, the metal may be copper-free. In some embodiments, the precipitation hardened steel may include copper present in the range of 1.5 wt.% to 3 wt.%, inclusive of subranges. For example, copper may be present in the range of 1.5 wt.%, 1.75 wt.%, 2 wt.%, 2.25 wt.%, 2.5 wt.%, 2.75 wt.%, or 3 wt.%, or any range having any two of these values ​​as endpoints.

[0150] Cobalt, like titanium, molybdenum, tungsten, silicon, and chromium, has a tendency to reduce or prevent the formation of austenite at relatively low temperatures. In some embodiments, the metal may include cobalt present in the range of 0 wt.% to 0.1 wt.%, including subranges. For example, cobalt may be present in the range of 0 wt.%, 0.01 wt.%, 0.02 wt.%, 0.03 wt.%, 0.04 wt.%, 0.05 wt.%, 0.06 wt.%, 0.07 wt.%, 0.08 wt.%, 0.09 wt.%, or 0.1 wt.%, or any range having any two of these values ​​as endpoints. In some embodiments, the metal may be free of cobalt.

[0151] Silicon, like titanium, molybdenum, tungsten, silicon, and chromium, has a tendency to reduce or prevent the formation of austenite at relatively low temperatures. In some embodiments, the metal may include silicon present in the range of 0% to 1.1% by weight, inclusive. For example, silicon may be present in the range of 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, or 1.1% by weight, or any range having any two of these values ​​as endpoints. In some embodiments, the precipitation hardened steel may include silicon present in the range of 0.75% to 1.25% by weight, inclusive. For example, silicon may be present at 0.75 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, or 1.25 wt%, or any range having any two of these values ​​as endpoints.

[0152] Niobium, like titanium, molybdenum, tungsten, silicon, and chromium, has a tendency to reduce or prevent the formation of austenite at relatively low temperatures. In some embodiments, the metal may include niobium present in the range of 0.75 wt.% to 1.25 wt.%, including subranges. For example, niobium may be present in the range of 0.75 wt.%, 0.8 wt.%, 0.85 wt.%, 0.9 wt.%, 0.95 wt.%, 1 wt.%, 1.05 wt.%, 1.1 wt.%, 1.15 wt.%, 1.2 wt.%, or 1.25 wt.%, or any range having any two of these values ​​as endpoints.

[0153] Carbon, like molybdenum and manganese, tends to contribute to the formation of austenite at relatively low temperatures. In some embodiments, the metals may include carbon present in the range of 0.15 wt.% to 0.25 wt.%, inclusive of subranges. For example, carbon may be present in the range of 0.15 wt.%, 0.16 wt.%, 0.17 wt.%, 0.18 wt.%, 0.19 wt.%, 0.2 wt.%, 0.21 wt.%, 0.22 wt.%, 0.23 wt.%, 0.24 wt.%, or 0.25 wt.%, or any range having any two of these values ​​as endpoints. In some embodiments, carbon may be present in the range of 0.15 wt.% to 0.2 wt.%. In some embodiments, the precipitation hardened steel may include carbon present in the range of 0.025 wt.% to 0.075 wt.%, inclusive of subranges. For example, carbon may be present at 0.025%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, or 0.075% by weight, or any range having any two of these values ​​as endpoints.

[0154] In some embodiments, the metal may be steel, including iron, molybdenum, and tungsten, and including manganese, nickel, chromium, and vanadium in the following ranges: manganese: 0% to 0.05% by weight, nickel: 0.35% to 0.65% by weight, chromium: 13% to 14% by weight, and vanadium: 0.35% to 0.65% by weight.

[0155] In some embodiments, the metal may be steel, including iron, molybdenum, and tungsten, and also including manganese, copper, nickel, chromium, molybdenum, and vanadium in the following ranges: manganese: 0% to 0.05% by weight, copper: 0% to 0.05% by weight, nickel: 0.35% to 0.65% by weight, chromium: 13% to 14% by weight, molybdenum: 1.0% to 1.5% by weight, and vanadium: 0.35% to 0.65% by weight.

[0156] In some embodiments, the metal may be steel, including iron, molybdenum, and tungsten, and including the following ranges of manganese, copper, nickel, chromium, molybdenum, vanadium, tungsten, and cobalt: manganese: 0% to 0.05% by weight, copper: 0% to 0.05% by weight, nickel: 0.35% to 0.65% by weight, chromium: 13% to 14% by weight, molybdenum: 1.0% to 1.5% by weight, vanadium: 0.35% to 0.65% by weight, tungsten: 0.9% to 1.3% by weight, and cobalt: 0% to 0.1% by weight.

[0157] In some embodiments, the metal may be steel, including iron, molybdenum, and tungsten, and including the following ranges of manganese, copper, nickel, chromium, molybdenum, vanadium, tungsten, cobalt, and carbon: manganese: 0% to 0.05% by weight, copper: 0% to 0.05% by weight, nickel: 0.35% to 0.65% by weight, chromium: 13% to 14% by weight, molybdenum: 1.0% to 1.5% by weight, vanadium: 0.35% to 0.65% by weight, tungsten: 0.9% to 1.3% by weight, cobalt: 0% to 0.1% by weight, and carbon: 0.15% to 0.25% by weight.

[0158] In some embodiments, the metal may be a martensitic stainless steel comprising iron and at least five of carbon, silicon, manganese, copper, nickel, chromium, molybdenum, vanadium, tungsten, and cobalt in the following ranges: carbon: 0.15% to 0.25% by weight, silicon: 0% to 1.1% by weight, manganese: 0% to 0.05% by weight, copper: 0% to 0.05% by weight, nickel: 0.35% to 0.65% by weight, chromium: 13% to 14% by weight, molybdenum: 1.0% to 1.5% by weight, vanadium: 0.35% to 0.65% by weight, tungsten: 0.9% to 1.3% by weight, and cobalt: 0% to 0.1% by weight. In some embodiments, the metal may be a martensitic stainless steel that includes iron and at least six of the above-mentioned ranges of carbon, silicon, manganese, copper, nickel, chromium, molybdenum, vanadium, tungsten, and cobalt, hi some embodiments, the metal may be a martensitic stainless steel that includes iron and at least seven of the above-mentioned ranges of carbon, silicon, manganese, copper, nickel, chromium, molybdenum, vanadium, tungsten, and cobalt.

[0159] In some embodiments, iron may be present in the range of 70% to 85% by weight (including subranges). For example, iron may be present in 70%, 72.5%, 75%, 77.5%, 80%, 82.5%, or 85% by weight, or any range having any two of these values ​​as endpoints.

[0160] Any of the above steels may be formed into a metallic body for a metallic article, and the metallic article may be coated with the inorganic particles described herein. For example, any of the above steels may be formed into an extrusion die or a portion thereof (e.g., extrusion die 100 or a portion thereof), a cutting tool, or a grinding tool, and the like, may be coated with the inorganic particles described herein. The inorganic particles may be disposed on the surface of the metallic body to form a wear-resistant coating on the surface of the metallic body.

[0161] In some embodiments, the modified steel according to embodiments described herein may have a coefficient of thermal expansion measured at 849° C. and the wear resistant coating may have a coefficient of thermal expansion measured at 849° C., and the ΔCTE between the modified steel and the wear resistant coating may be greater than or equal to 10×10. -6 / ℃ or less.

[0162] In some embodiments, the modified steel according to embodiments described herein may be formed into a metallic body by powder metallurgy and related processing. In such embodiments, the metallic material of the modified steel comprises consolidated metal powder. In some embodiments, the powder metallurgical forming and processing may be the same as or similar to the forming and processing described in U.S. Pat. No. 6,302,679.

[0163] For example, in some embodiments, forming the metallic body may include mixing and consolidating iron, molybdenum, and tungsten powders and at least one of manganese, nickel, chromium, and vanadium powders. Also, in some embodiments, the manganese, nickel, chromium, and vanadium powders may be within the following ranges: manganese: less than 0.1 wt.%, nickel: less than 0.7 wt.%, chromium: greater than 12.5 wt.%, and vanadium: greater than 0.3 wt.%. Other alloy compositions may be formed into the metallic body in the same manner.

[0164] Low temperature deposition of TiCN and / or boron-doped TiCN particles In some embodiments, the source gas for the TiCN and / or boron doped TiCN (B-TiCN) inorganic particle deposition process may be adjusted so that the inorganic particles are deposited at a temperature below the Ac1 temperature of the metal substrate. For example, the source gas 930 introduced into the deposition chamber 900 for the formation of the TiCN and / or boron doped TiCN inorganic particles 920 may be adjusted to reduce the temperature required for the formation of the inorganic particles 920 to below the Ac1 temperature of the metal material of the metal substrate 910. In some embodiments, the metal material may be a conventional metal alloy. In some embodiments, the metal material may be a modified metal alloy according to embodiments described herein.

[0165] The reduction in deposition temperature required for deposition of TiCN and / or B-TiCN particles may be achieved using at least one of the following methods. In some embodiments, a combination of one or more of the following methods may be utilized: 1) A deposition method including a single source gas for carbon and nitrogen having a thermal energy of formation less than 65.9 kilojoules / mole. 2) A deposition method including two source gases, one source gas for carbon including gas molecules having a carbon-nitrogen single bond and one source gas for nitrogen. 3) A deposition method including a source gas including an organometallic compound for forming inorganic particles. 4) A deposition method including two or more source gases that react to form inorganic particles and an aluminum-containing organometallic reducing agent.

[0166] In a first method, a single source gas for carbon and nitrogen having a thermal energy of formation less than 65.9 kilojoules / mole is utilized to reduce the temperature required for the formation of TiCN and / or B-TiCN particles in the deposition chamber 900. In conventional TiCN and / or B-TiCN deposition processes, acetonitrile (CH3CN) has been used as a source gas for both carbon and nitrogen. Acetonitrile has a thermal energy of formation of 65.9 kilojoules / mole. By utilizing suitable carbon and nitrogen source gases having a lower thermal energy of formation, TiCN and / or B-TiCN can be formed at lower temperatures. In some embodiments, the single source gas for carbon and nitrogen may include gas molecules having carbon chains of 4 or more carbon atoms. In this first method, the single source gas for carbon and nitrogen may be the only source of these elements in the deposited TiCN and / or B-TiCN particles. No additional sources of carbon and nitrogen may be present.

[0167] In this first method, a titanium source gas is required for the formation of TiCN or B-TiCN particles. In some embodiments, the titanium source gas can be titanium tetrachloride (TiCl4). In some embodiments, the titanium source gas can be an organometallic compound. Suitable organometallic compounds include those described herein, such as tetrakis(dimethylamido)titanium (TDMAT).

[0168] Carbon and nitrogen source gases having a thermal energy produced of less than 65.9 kilojoules / mole include nitriles, such as, but not limited to, trichloroacetonitrile (CCl3CN), propionitrile (CH3CH2CN), acrylonitrile, isobutyronitrile, benzonitrile, butyronitrile, trans2-butyronitrile, 3-butenenitrile, succinonitrile, cyclobutanecarbonitrile, cyclohexanecarbonitrile, 1-cyclohexenecarbonitrile, cyclopentanecarbonitrile, 1-cyclopentenecarbonitrile, cyclopropanecarbonitrile, octanenitrile, 2,2-dimethylpropanenitrile, heptanenitrile, adiponitrile, malononitrile, methacrylonitrile, 2-methylpropanenitrile, and trans-3-pentenenitrile. Suitable nitriles may include the basic formula A-CN, where A is an alkyl, alkenyl, cycloalkanyl, or cycloalkenyl, any of which may be optionally substituted with one or more chloro groups.

[0169] In embodiments of this first method including deposition of B-TiCN particles, one or more boron-containing source gases are introduced into the chamber 900. The one or more boron-containing source gases may be borane, diborane, boron trichloride, trimethylamine borane ((CH3)3NBH3) (TMAB), or combinations thereof.

[0170] The second method utilizes separate source gases for carbon and nitrogen to stimulate the temperature required for the formation of TiCN and / or B-TiCN particles in the deposition chamber 900. This second method embodiment utilizes at least two source gases, one source gas that is a source for at least carbon and one source gas that is a source for at least nitrogen. In some embodiments, the source for nitrogen may also be a source for carbon. In some embodiments, the source for nitrogen may not be a source for carbon. In some embodiments, the source for nitrogen may be ammonia (HN3).

[0171] In a method according to this second method embodiment, the source for carbon includes gas molecules having a carbon-nitrogen single bond. By utilizing suitable gas molecules having a carbon-nitrogen single bond, TiCN and / or B-TiCN can be formed at lower temperatures than conventional deposition processes.

[0172] Suitable carbon sources for this second method include amines, such as, but not limited to, dialkyl and trialkyl amines. Suitable dialkyl and trialkyl amines include, but are not limited to, trimethylamine ((CH3)3N), dimethylamine, dimethylamine hydrochloride, and trimethylamine. In some embodiments, the amine can be trimethylamine borane ((CH3)3NBH3) (TMAB), which can also be used as a source for boron when depositing B-TiCN particles.

[0173] In this second method, a titanium source gas is required for the formation of TiCN and / or B-TiCN particles. In some embodiments, the titanium source gas can be titanium tetrachloride (TiCl4). In some embodiments, the titanium source gas can be an organometallic compound. Suitable organometallic compounds include those described herein, such as tetrakis(dimethylamido)titanium (TDMAT).

[0174] In this second method embodiment involving deposition of B-TiCN particles, one or more boron-containing source gases are introduced into the chamber 900. The one or more boron-containing source gases may be borane, diborane, boron trichloride, trimethylamine borane ((CH3)3NBH3) (TMAB), or combinations thereof.

[0175] A third method uses a source gas that includes an organometallic compound that is a source for carbon, nitrogen, and titanium in the deposited TiCN and / or B-TiCN particles. Suitable organometallic compounds include, but are not limited to, tetrakis(dimethylamido)titanium, tetrakis(ethylmethylamino)titanium, tetrakis(diethylamido)titanium (TDEAT), tetrakis(methylethylamido)titanium (TMEAT), and metal organic compounds having Ti-N bonds.

[0176] In this third method embodiment involving deposition of B-TiCN particles, one or more boron-containing source gases are introduced into the chamber 900. The one or more boron-containing source gases may be borane, diborane, boron trichloride, trimethylamine borane ((CH3)3NBH3) (TMAB), or combinations thereof.

[0177] In a fourth method, two or more source gases that react to form TiCN and / or B-TiCN particles are introduced into the deposition chamber 900 along with an aluminum-containing organometallic reducing agent. The aluminum-containing organometallic reducing agent is utilized to reduce the temperature required to form TiCN and / or B-TiCN in the deposition chamber 900. The aluminum-containing organometallic reducing agent reduces the temperature required to form TiCN and / or B-TiCN by reducing Cl in the TiCl4 gas. The two or more source gases that react to form TiCN and / or B-TiCN particles in embodiments according to this fourth method include, in addition to TiCl4, any of the carbon and / or nitrogen source gases described herein, as well as conventional source gases such as acetonitrile.

[0178] In some embodiments, the aluminum-containing organometallic reducing agent may include a trialkylaluminum organometallic compound. In some embodiments, the aluminum-containing organometallic reducing agent may include trimethylaluminum, triethylaluminum, triisobutylaluminum, and / or alane aluminum hydride. Suitable alane aluminum hydrides include, but are not limited to, dimethylaluminum hydride, dimethylaluminum hydride, and dimethylethylamine alane.

[0179] In the method according to the fourth method embodiment, the amount of aluminum-containing organometallic reducing agent may be limited such that the composition of the deposited TiCN and / or B-TiCN particles includes a limited amount of aluminum. For example, the amount of aluminum-containing organometallic reducing agent may be limited such that the deposited TiCN and / or B-TiCN particles include no more than 30 mol% aluminum. In some embodiments, the deposited TiCN and / or B-TiCN particles may include 1 mol% to 30 mol% aluminum (including subranges). For example, the deposited TiCN and / or B-TiCN particles may include 1 mol% aluminum, 5 mol% aluminum, 10 mol% aluminum, 15 mol% aluminum, 20 mol% aluminum, 25 mol% aluminum, or 30 mol% aluminum, or a range having any two of these values ​​as endpoints.

[0180] Any of the four methods described above, or a combination of one or more of these methods, can deposit TiCN and / or B-TiCN particles at a deposition temperature of 900° C. or less. In some embodiments, one or more of the above methods can deposit TiCN and / or B-TiCN particles at a deposition temperature in the range of 400° C. to 900° C. (including subranges). For example, the deposition temperature can be 400° C., 450° C., 500° C., 550° C., 600° C., 650° C., 700° C., 750° C., 800° C., 850° C., or 900° C., or any range having any two of these values ​​as endpoints. In some embodiments, the deposition temperature can be in the range of 400° C. to 750° C. In some embodiments, the deposition temperature can be in the range of 600° C. to 750° C. In some embodiments, the deposition temperature can be in the range of 400° C. to 600° C.

[0181] In some embodiments, the metal substrate 910 may be maintained at a temperature less than 900° C. during the deposition process of the TiCN and / or B-TiCN particles according to any of these methods or combinations thereof. For example, in some embodiments, the deposition temperature for the deposition of the TiCN and / or B-TiCN particles may be in the range of 600° C. to 750° C., and the metal substrate may be maintained at a temperature less than 900° C. during the deposition process. In some embodiments, the metal substrate 910 may be maintained at a temperature in the range of 600° C. to 900° C. (including subranges) during the deposition process. For example, the metal substrate 910 may be maintained at a temperature of 600° C., 650° C., 700° C., 750° C., 800° C., 850° C., or 900° C., or any range having any two of these values ​​as endpoints.

[0182] Additionally, any of the four methods described above, or a combination of one or more of these methods, can form a wear-resistant coating (e.g., coating 1020) having any number of individual layers of TiCN or B-TiCN, as described herein. The thickness of the wear-resistant coating formed by any of these methods, or a combination thereof, can be the same as any thickness or thickness range described herein for thickness 1022. Also, the thickness of the individual layers of TiCN or B-TiCN can be the same as any thickness or thickness range described herein for thickness 1032.

[0183] Although various embodiments have been described herein, they are presented by way of example, not by way of limitation. It will be apparent that changes and modifications are intended to be within the meaning and range of equivalents of the embodiments of the present disclosure based on the teachings and guidance presented herein. Thus, it will be apparent to those skilled in the art that various changes in form and detail can be made to the embodiments disclosed herein without departing from the spirit and scope of the present disclosure. The elements of the embodiments presented herein are not necessarily mutually exclusive and can be interchanged to meet various situations, as will be understood by those skilled in the art.

[0184] The embodiments of the present disclosure are now described in detail with reference to the embodiments of the present disclosure as illustrated in the accompanying drawings, in which like reference numerals are used to refer to identical or functionally similar elements. References to "one embodiment," "an embodiment," "some embodiments," "certain embodiment," and the like indicate that a described embodiment may include a particular feature, structure, or characteristic, but not all embodiments may necessarily include the particular feature, structure, or characteristic. Moreover, such phrases are not necessarily referring to the same embodiment. Furthermore, when a particular feature, structure, or characteristic is described in connection with an embodiment, it is intended that it is within the knowledge of one of ordinary skill in the art to implement the particular feature, structure, or characteristic in connection with other embodiments, whether or not expressly described.

[0185] The foregoing examples are illustrative rather than limiting of the present disclosure. Other suitable modifications and adaptations of the variety of conditions and parameters normally encountered in the art and obvious to those skilled in the art are within the spirit and scope of the present disclosure.

[0186] As used herein, the term "or" is inclusive; more specifically, the phrase "A or B" means "A, B, or both A and B."

[0187] The indefinite articles "a" and "an" used to describe an element or component mean that there is one or at least one of that element or component. Although these articles are conventionally employed to indicate that the modified noun is a singular noun, as used herein, the articles "a" and "an" also include the plural, unless otherwise stated in the specific example. Similarly, the definite article "the", as used herein, also indicates that the modified noun may be either singular or plural, unless otherwise stated in the specific example.

[0188] When a range of numerical values, including upper and lower limits, is recited herein, unless otherwise specified under specific circumstances, the range is intended to include its endpoints, as well as all integers and fractions within the range. When a range is defined, it is not intended to limit the scope of the claims to the specific values ​​recited. Furthermore, when an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges, or a list of a preferred upper limit and a preferred lower limit, this should be understood as specifically disclosing all ranges formed from any pair of any range upper limit or preferred value with any range lower limit or preferred value, whether or not such pairs are individually disclosed. Finally, when the term "about" is used in describing a value or an endpoint of a range, it should be understood that the disclosure includes the specific value or endpoint mentioned. Regardless of whether a numerical value or an endpoint of a range is described as "about," the numerical value or endpoint of the range is intended to include two embodiments: those modified with "about" and those not modified with "about."

[0189] As used herein, the term "about" means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not, and need not be, exact, but may be approximate and / or more or less, as necessary, to reflect tolerances, conversion factors, rounding, measurement errors, and the like, as well as other factors known to those of ordinary skill in the art.

[0190] As used herein, the terms "substantial," "substantially," and variations thereof are intended to indicate that a described characteristic is equal or approximately equal to a value or description. For example, a "substantially planar" surface is intended to refer to a surface that is planar or approximately planar. Additionally, "substantially" is intended to indicate that two values ​​are equal or approximately equal.

[0191] One or more embodiments have been described above using functional building blocks that illustrate implementations of specified functions and relationships of the functions. The boundaries of these functional building blocks have been arbitrarily defined herein for convenience of description. Alternative boundaries may be defined as long as the specified functions and their relationships are appropriately expressed.

[0192] It is to be understood that the phraseology or terminology used herein is for the purpose of description and not of limitation. The scope of the present disclosure should not be limited by any of the above-described exemplary embodiments, but should be defined according to the following claims and their equivalents.

[0193] Preferred embodiments of the present invention will be described below in detail.

[0194] EMBODIMENT 1 1. A method for depositing an inorganic material onto a metal substrate, comprising: The above method: depositing inorganic particles comprising titanium carbonitride over the surface of the metal substrate by a chemical vapor deposition process at a deposition temperature of 900° C. or less; Including, The chemical vapor deposition process includes providing two or more source gases that react to form the inorganic particles; At least one of the source gases includes a titanium source gas; The carbon and nitrogen sources provide at least one other of the above feed gases, and include the following: (a) a single feed gas, the single feed gas comprising a carbon and nitrogen feed gas, the single feed gas having a thermal energy formed of less than 65.9 kilojoules / mole; (b) two feed gases, the two feed gases including a carbon feed gas that includes gas molecules having a carbon-nitrogen single bond, and a nitrogen feed gas; and (c) A combination of (a) and (b) A method selected from the group consisting of

[0195] EMBODIMENT 2 2. The method of embodiment 1, wherein the source of carbon and nitrogen comprises the single feed gas.

[0196] EMBODIMENT 3 3. The method of embodiment 2, wherein the single feed gas comprises a nitrile.

[0197] EMBODIMENT 4 The method of embodiment 3, wherein the nitrile is selected from the group consisting of: trichloroacetonitrile, propionitrile, acrylonitrile, isobutyronitrile, benzonitrile, butyronitrile, trans-2-butyronitrile, 3-butenenitrile, succinonitrile, cyclobutanecarbonitrile, cyclohexanecarbonitrile, 1-cyclohexenecarbonitrile, cyclopentanecarbonitrile, 1-cyclopentenecarbonitrile, cyclopropanecarbonitrile, octanenitrile, 2,2-dimethylpropanenitrile, heptanenitrile, adiponitrile, malononitrile, methacrylonitrile, 2-methylpropanenitrile, and trans-3-pentenenitrile.

[0198] EMBODIMENT 5 3. The method of embodiment 2, wherein the single feed gas comprises gas molecules having carbon chains of four or more carbon atoms.

[0199] EMBODIMENT 6 2. The method of embodiment 1, wherein the source of carbon and nitrogen comprises the two feed gases.

[0200] EMBODIMENT 7 7. The method of embodiment 6, wherein the gas molecule having a carbon-nitrogen single bond is an amine.

[0201] EMBODIMENT 8 8. The method of embodiment 7, wherein the amine comprises a dialkyl or trialkyl amine.

[0202] EMBODIMENT 9 8. The method of embodiment 7, wherein the amine is selected from the group consisting of trimethylamine, dimethylamine, dimethylamine hydrochloride, and triethylamine.

[0203] EMBODIMENT 10 8. The method of embodiment 7, wherein the amine comprises trimethylamine borane.

[0204] EMBODIMENT 11 7. The method of embodiment 6, wherein the nitrogen source gas is not a source of carbon for the chemical vapor deposition process.

[0205] EMBODIMENT 12 7. The method of embodiment 6, wherein the nitrogen source gas is ammonia.

[0206] EMBODIMENT 13 2. The method of embodiment 1, wherein the titanium source gas is titanium tetrachloride.

[0207] EMBODIMENT 14 2. The method of embodiment 1, wherein the titanium source gas is an organometallic compound.

[0208] EMBODIMENT 15 15. The method of embodiment 14, wherein the organometallic compound comprises tetrakis(dimethylamido)titanium.

[0209] EMBODIMENT 16 2. The method of embodiment 1, wherein the deposition temperature is in the range of 400° C. to 750° C.

[0210] EMBODIMENT 17 2. The method of embodiment 1, wherein the deposition temperature is in the range of 600° C. to 750° C.

[0211] EMBODIMENT 18 2. The method of embodiment 1, wherein the metal substrate is maintained at a temperature less than 900° C. during the chemical vapor deposition process.

[0212] EMBODIMENT 19 The deposition temperature is 600°C to 750°C. 2. The method of embodiment 1, wherein the metal substrate is maintained at a temperature less than 900° C. during the chemical vapor deposition process.

[0213] EMBODIMENT 20 2. The method of claim 1, wherein the deposition temperature does not exceed the austenite transformation temperature of a metallic material of the metallic substrate.

[0214] EMBODIMENT 21 21. The method of embodiment 20, wherein the metallic material is steel.

[0215] EMBODIMENT 22 21. The method of embodiment 20, wherein the metallic material is stainless steel.

[0216] EMBODIMENT 23 21. The method of embodiment 20, wherein the metallic material is a martensitic stainless steel.

[0217] EMBODIMENT 24 2. The method of embodiment 1, wherein the chemical vapor deposition process further comprises providing a boron-containing source gas.

[0218] EMBODIMENT 25 25. The method of embodiment 24, wherein the boron-containing source gas is selected from the group consisting of borane, diborane, boron trichloride, and trimethylamine borane.

[0219] EMBODIMENT 26 25. The method of embodiment 24, wherein inorganic particles formed on the surface of the substrate comprise boron-doped titanium carbonitride.

[0220] EMBODIMENT 27 2. The method of embodiment 1, wherein the metal substrate comprises an extruder part.

[0221] EMBODIMENT 28 28. The method of embodiment 27, wherein the extruder parts include an extrusion die.

[0222] EMBODIMENT 29 the extrusion die includes a plurality of pins; 29. The method of embodiment 28, wherein an exterior surface of one or more of the plurality of pins defines the surface of the metal substrate on which the inorganic particles are deposited.

[0223] EMBODIMENT 30 2. The method of embodiment 1, wherein the inorganic particles form a titanium carbonitride coating on the metal substrate, and the coating has a thickness of 1 micrometer to 100 micrometers.

[0224] EMBODIMENT 31 A metal substrate coated with inorganic particles comprising titanium carbonitride deposited by the method of embodiment 1, The metal substrate includes an extrusion die.

[0225] EMBODIMENT 32 1. A method for depositing an inorganic material onto a metal substrate, comprising: The above method: depositing inorganic particles comprising titanium carbonitride on the surface of the metal substrate by a chemical vapor deposition process at a deposition temperature of 900° C. or less; Including, The chemical vapor deposition process includes providing a source gas including an organometallic compound to form the inorganic particles; The inorganic particles form a coating having a thickness of from 1 micrometer to 100 micrometers.

[0226] EMBODIMENT 33 33. The method of embodiment 32, wherein the organometallic compound comprises tetrakis(dimethylamido)titanium.

[0227] EMBODIMENT 34 33. The method of embodiment 32, wherein the organometallic compound comprises tetrakis(ethylmethylamino)titanium.

[0228] EMBODIMENT 35 33. The method of embodiment 32, wherein the deposition temperature is in the range of 400° C. to 750° C.

[0229] EMBODIMENT 36 33. The method of embodiment 32, wherein the deposition temperature is in the range of 600° C. to 750° C.

[0230] EMBODIMENT 37 33. The method of embodiment 32, wherein the deposition temperature does not exceed the austenite transformation temperature of the metallic material of the metallic substrate.

[0231] EMBODIMENT 38 38. The method of embodiment 37, wherein the metallic material is stainless steel.

[0232] EMBODIMENT 39 38. The method of embodiment 37, wherein the metallic material is a martensitic stainless steel.

[0233] EMBODIMENT 40 1. A method for depositing an inorganic material on a metal substrate, comprising the steps of: The above method: depositing inorganic particles comprising titanium carbonitride on the surface of the metal substrate by a chemical vapor deposition process at a deposition temperature of 900° C. or less; Including, The method, wherein the chemical vapor deposition process is provided with two or more source gases that react to form the inorganic particles, and an aluminum-containing organometallic reducing agent.

[0234] EMBODIMENT 41 41. The method of embodiment 40, wherein the aluminum-containing organometallic reducing agent comprises a trialkylaluminum organometallic compound.

[0235] EMBODIMENT 42 41. The method of embodiment 40, wherein the aluminum-containing organometallic reducing agent is selected from the group consisting of trimethylaluminum, triethylaluminum, triisobutylaluminum, and alane aluminum hydride.

[0236] EMBODIMENT 43 41. The method of embodiment 40, wherein the aluminum-containing organometallic reducing agent comprises alane aluminum hydride.

[0237] EMBODIMENT 44 44. The method of embodiment 43, wherein the alane aluminum hydride is selected from the group consisting of dimethyl aluminum hydride, dimethyl aluminum hydride, and dimethylethylamine alane.

[0238] EMBODIMENT 45 41. The method of embodiment 40, wherein the inorganic particles comprise less than 30 mol % aluminum.

[0239] EMBODIMENT 46 41. The method of embodiment 40, wherein the deposition temperature is in the range of 400° C. to 600° C. [Explanation of symbols]

[0240] 100 Extrusion Die 102 Die body 104 Supply hole 106 pins 108 Ejection Slot 110 Ejection surface 112 Top of pin 106 900 Deposition Chamber 910 Metal Substrate 912 Surface 920 Inorganic particles 930, 930a, 930b, 930c Gas, raw gas 1000 Coated Articles 1010 Board 1012 Surface 1020 Wear-resistant coating 1022 Total thickness of wear-resistant coating 1020, thickness 1030 First coating layer 1032 Coating layer thickness 1040 Second coating layer 1050 3rd coating layer 1060 4th coating layer 1070 5th coating layer

Claims

1. 1. A method for depositing an inorganic material onto a metal substrate, comprising: The method comprises: depositing inorganic particles comprising titanium carbonitride by a chemical vapor deposition process over a surface of the metal substrate at a deposition temperature in the range of 400°C to 750°C, the deposition temperature not exceeding the austenite transformation temperature of the metal material of the metal substrate; Including, The chemical vapor deposition process includes providing two or more source gases that react to form the inorganic particles; At least one of the source gases includes a titanium source gas; The carbon and nitrogen sources provide at least one other of the feed gases, and include: (a) a single feed gas, the single feed gas comprising a carbon and nitrogen feed gas, the single feed gas having a thermal energy formed of less than 65.9 kilojoules / mole; (b) two feed gases, the two feed gases including a carbon feed gas that includes gas molecules having a carbon-nitrogen single bond, and a nitrogen feed gas; and (c) A combination of (a) and (b) A method selected from the group consisting of

2. The method of claim 1, wherein the metal substrate is a honeycomb extrusion die.

3. The method of claim 2 , wherein the metallic material is a martensitic stainless steel.

4. 1. A method for depositing an inorganic material onto a metal substrate, comprising: The method comprises: depositing inorganic particles comprising titanium carbonitride on a surface of the metal substrate by a chemical vapor deposition process at a deposition temperature in the range of 400°C to 750°C, the deposition temperature not exceeding the austenite transformation temperature of the metallic material of the metal substrate; Including, the chemical vapor deposition process includes providing a source gas including an organometallic compound to form the inorganic particles; The method wherein the inorganic particles form a coating having a thickness of from 1 micrometer to 100 micrometers.

5. The method of claim 4, wherein the metal substrate is a honeycomb extrusion die.

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