JPS62500599A - Method of applying a hard coating or similar coating to a metal object and the resulting product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Methods of applying hard coatings or similar coatings to metal bodies and the resulting products Goods Technical field The present invention is based on a metal body (hereinafter referred to as 1 substrate "or 1 substrate gold PA" or 1 metal substrate 1 The present invention relates to a method for applying a coating to a material (referred to as a "coating"). However, the present invention is particularly applicable to metals. Coating to form a hard surface entirely on the surface, or coating with good chemical resistance, etc. The present invention also relates to metal products coated in this way. do.

Hard metals are used to give relatively inexpensive metal bodies a high degree of utility, such as wear resistance and corrosion resistance. Techniques for applying coatings have been previously developed, and this technology has made great advances. considerably more Previously developed coating or surface treatment methods used diffusion to deposit carbon, nitrogen or In this method, silicon is attached to the surface of a metal substrate, that is, a hard substance is directly attached to the surface of the metal substrate. It consisted of directly generating the On the other hand, recently developed techniques This technology includes the application of a hard layered coating as a coating. Specific examples include chemical vapor deposition (CVD), physical vapor deposition (PVD), laser welding, Nupattaring, flame or plasma-nulllaying, and detonation There are techniques that can be used to remove cancer.These techniques, with the exception of the CVD method, have low operating costs. The thickness of the coating can only be adjusted within the visible range, especially at the corners of the metal being treated. , holes, and metals with complex shapes, the thickness of the coating layer changes gradually, i.e., the thickness of the coating layer changes gradually. It is ensured that a homogeneous coating results.

Purpose of invention The object of the present invention is to provide a metal substrate with the following formula: (where Ml is the metal component of the compound applied to the substrate, X is an element such as nitrogen, carbon, boron or silicon, and n represents the atomic ratio of X7M The object of the present invention is to provide a new method for applying a coating having a composition having

Another object of the invention is to apply a coating having the composition M1xn as described above on a substrate in a homogeneous and firm manner. It is an object of the present invention to provide a coated metal body formed by applying a coating.

The above objects and other objects of the present invention are achieved in the following description and claims. According to the present invention, which will become clearer from the above description, the following operations can be carried out. In other words, the postscript An alloy or physical alloy consisting of two metals M and M2 selected according to the criteria of Make a mixture. This alloy or metal mixture is then melted to create a homogeneous melt. , by immersing the metal substrate in this melt, the melt is coated on the metal substrate. It is. Alternatively, the metal mixture or alloy described above is ground and this powdered metal is produced. Make a slurry in a volatile solvent and spray or spray this slurry onto a metal substrate. Coating can also be done by brushing. The coating applied in this way is inert. heating in an atmosphere to volatilize the volatile bath agent and remove this coating (alloy or gold). (physical mixture of metals) is welded to the metal substrate surface (physical mixing of metals). When using a material, melt it and convert it into an alloy, or convert it into an alloy as described above. alloyed in situ as mentioned in the description of the slurry method, i.e. It can be melted into an alloy]. Consisting of alloys due to their high melting points This alloy is suitable for plastics where the metal substrate is adversely affected during melting of the coating. It can be coated onto a metal substrate by a Zumanuzolaying operation.

Gold AM and M2 can be selected according to the following criteria.

That is, M is an atmosphere containing X with a low degree of agglomeration, or an X-containing compound that can be dissociated. Or, when heated to high temperature in an atmosphere containing X-containing molecules, it combines with X and generates heat. Forms stable compounds (i.e. nitrides, carbides, borides or silicides) It is a metal that can be used. The above stable compound formed when Ml combines with X is expressed by the following formula (this The atomic ratio of n is X7M).

Metal M2 cannot combine with X to form a stable compound under the above conditions. A metal that remains completely or substantially completely in metallic form. Furthermore, M2 is compatible with the metal substrate, i.e. the metal substrate and the outer coating +! (M, Forms an intermediate layer between the compound M (formed by the reaction between It is possible. This intermediate layer (M2) firmly connects the M and Xn layers on the metal substrate. It is useful for Therefore, mutual diffusion between the M2 layer and the metal substrate (int@rdlffuslon) obviously helps the above binding effect. be.

As can be easily understood, M is a metal of 21! or more that meets the above-mentioned criteria for M. M2 may be a mixture or alloy of two or more of the above @M2 criteria 2. The coating layer formed as described above may be a mixture or alloy of the above metals. is preferably immediately followed by an annealing operation.

However, if the coated metal body is annealed during use, the above-mentioned The kneeling step can be omitted.

by dip coating or slurry coating operations or other suitable coating operations as described above. If a coating of appropriate thickness is applied to the alloy substrate (thus, slurry coating During operation, the solvent is evaporated and the M,/M2 metal alloy or metal mixture is (after welding onto a metal substrate), the surface is exposed to a given reactive atmosphere at a suitable high temperature. It is exposed to the surrounding air.

Nitrogen is used to form a nitride, carbide, boride or silicide layer on a metal substrate. element, carbon 1. Any suitable thermally decomposable compound or molecule containing boron or silicon can be used. Ru. A further example of a gaseous medium, that is, an example of a gaseous medium when X = nitrogen, etc. It is shown in the following part 1.

Table 1 Gaseous medium that can be used for the production of nitrides, carbides, borides and silicides N　N2. NH, or a mixture of the one.

C methane, acetylene. − B Boran, Ginoran? Donkey ride.

Sl Silane, trichlorosilane, tribromosilane, silicon tetrachloride.

If a very low partial pressure of a reactive substance (reactive species) is the It can be diluted with an inert gas such as Rougon. Due to the reaction of two breaker substances, If a certain active substance (reactive substance) is obtained, these two breaker lengths -vI By adjusting the J quality ratio, the rotation of the active substance can be adjusted.

The cover formed by this method! :jk, 4 wheels are shown in the attached drawing, Figure 1, for example. It has a structure similar to that shown below.

Figure 1 shows the cross section of the alloy substrate (10) covered with the laminated coating layer (//). The seven laminated coating layers (//) shown in the drawing include an intermediate metal layer (/2) and an outer layer (M, It consists of Xn) (/3). Figure 1 shows the thickness (comparison) between layer (/2) and layer (/3). vs. values) are shown as induced.

The thickness of the layer (10) which is the base body may be an appropriate value depending on its use.

Generally, the thickness + of the layer (/2) is about 2! The thickness of the layer (/3) is approximately rOi cm. The total thickness of layer (/2) and layer (/3) is approximately 23-0 microns. It is about 300-Kron. As can be easily understood, layer (/2) is It is preferable to have a thickness that can be firmly bonded to the substrate, and the layer (/3) preferably has a thickness suitable for the desired use.

FIG. 1 is the simplest diagram of the layers coated on a substrate. In contrast, a little more detail The drawing I drew is Figure 1A. FIG. 1A shows a substrate (10 ) and the outer 1i1 (M, Xn) (/j) are shown. But then? A diffusion band (D) is also depicted in FIG. 1A. Counting band (D) is /a1 or more It may be made of an alloy of the upper metal base and metal M2, or the base As a result of the diffusion of the metal M2 from the outside into the metal substrate and from the outside to the inner substrate It may also be a formed interdiffusion layer (ie, a layer produced by interdiffusion). difference Furthermore, there is an intermediate layer or intermediate band (1), which consists of M, Xn(!:M2 The cermet may be formed by bonding with the cermet.

Metals M and M2 can be selected depending on the desired use.

Table Ⅰ shows metals that can be used as metal M, and Table 1 shows metals that can be used as metal Metals that can be used as M2 are shown. In the 7 pairs of metals M, /M2, M2 is It is also necessary for Ml to be a noble. Seven more articles The issue is the desired use in each case. Examples of desired applications include hard surface formation, water resistance Formation of surfaces, formation of lubricating surfaces, etc. can be performed. Furthermore, the properties of the substrate are also taken into account. Should be. In No. ■ Clothes and No. 1 [1fi, some types of metals are is displayed. The metals M and (A) listed in Table ■ are the w Jt listed in Table ■. It can be used together with another metal M1(B) with a lower degree of s, but then M and (A) are used together with @M2 (a metal that is "more noble") #.

Chapter ■Table (M,) actinium neodymium aluminum niobium barium graseodymium Perilium Samaricum Calcium scandium Cerium silicon element chrome tantalum Dysglosium Terbium Erbium Thorium europium thulium is trinium titanium hafnium tungsten Holmium Bananoum Lantern Ytterbium Lithium Yztrium Magnesium norconium molybdenum Table 1 (M2) cobalt palladium copper white gold molybdenum silver nickel tin Osmium Zinc For the formation of a coating layer consisting of an alloy or metal mixture, two selected from Table ■ More than one metal, and two or more metals selected from Table 1 can also be used.

Suitable /set M, /M2 (containing two or more metals M and two or more metals M2) Specific examples of M1/M2 (including M1/M2) are shown in Part ①.

Table ■ As is easily understood, all of these golds, 110ffl, are suitable for all uses. It doesn't mean you have to do it. For example, if Ml is silicon, vL tends to be brittle. be. Some other metals are suitable for the formation of hard surfaces, and some other The metals of the group are suitable for the formation of oxidation- and corrosion-resistant surfaces.

Examples of eutectic alloys are shown in Section V. As is easily understood, all these alloys It is not suitable for all uses. Only approximate values can be obtained for the melting point. There are cases where it is not possible. The number before metal M2 represents the amount (weight i%) of metal M2 in the alloy. vinegar.

T1-2 and jNi data 4t2 Tl-j, 2F・10 TI-2fCo 102! TI-jOcu tayo! Ti-7.2Cu I do 'ri-4Ldo Pd 70♂0 Zr-/7Nf Ta L! ,0 Zr -, 27Nl 1010 Zr-/4F@23≠ Zr-27Co 101y/ Zr-J”ACu II! Zr-, 27Pd 1030 Zr-37Pt //16 Zr-, 2j'Rh 10IJ Hf　-7,2Nl　//30 Hf-j! rcu tough 0 Table V (continued) Tb-, 36Ni / 037 Th-/7F@! 7! Th-J’(1:’CO773’ Th-2,2,3Cu 110 Th　-73′　Al　Otsu32 Sc-IAj Al //30 Sc-77Cu 17! So-214Fe Ta 10 Se-, 22Pd 1000 Sc-/7 Ru/100 Y-ta 3A1 Otsu 1lLO Y-/LiAl/100 YljA1 5> Otsu O Y-2fCo 726 Y-If Cu 190 Y-6Cu ♂4L0 Y-! OCu　130 Y-27Cu 7 O Y-Jj Fs 5700 Y-J7Ni tayo0 Y-26NL Za02 Y-311-Pd ta 03 Y −, 21rPd 907 Y-/7Ru 10za0 Nb-7J, jNl /27O Nb-Hirootsu≠Ni / /7j S1-♂OtsujAl yo77 St-37J Co/2jY Sl-J’1ACu 102 S1-≠2F@　/200 Si-/2Mo/1It10 S1-Otsu, 2Ni Ta Otsu≠ 5t-7! LtPd 70 sl-77pt 97ri Section Vh is a table showing specific examples of ternary alloys suitable for the present invention.

Table VA If Tl-23,/3 Nb-2/, If Nl'A0.31 Tt- Hiro 3゜! 2 Zr-/Otsu, 10NS≠0.07 Ti-IA’A3! Zr -/yojlc.

, 2i37 Ti-gigri Zr-//, ri≠F・/73 Otsu T1 -31.0 /Zr-4t'Aot3 Cuot'Zot! Zr-/Otsu, 07Y-/4',,2 6Nl! Yori Otsu Zr-23,311LY-,20,70Ni≠3.0fZr -Hiro 0. ri fY -/IILc.

! Otsu, 7 Otsu Zr -32,'A3 Y -10,1/ Fs417, fri Zr -3'A3FY-/7.72PdtA,,! , ♂Zr-, 22.3riNb-, IQ, 77NilA9.33 Zr-32,1A3 Hf-lA3.244N 12'A, 20 Zr-4#, 3/Hf-, 27,2 Nl zirconium- Noble gold K(N2) alloys include yttrium, calcium or magnesium Particularly advantageous is the addition of F to form a ternary alloy. Because these ingredients are Rufea (zirconium oxide stabilized in cube form) Because it does. Specific examples of this ternary alloy are shown below.

and construction] A1 soil 7ta! /z Specific examples of metal (alloy) substrates that can be coated with each of the above metals are shown in Table (1).

Cast nickel-based (e.g. IN-73♂) Cast cobalt-based (e.g. MAR- Ml0ri] wrought nickel type (for example Reneta phantom) Wrought cobalt type (e.g. Highness Alloy, i/I wrought iron type (e.g. Jisca) Roy) Hastelloy-X R2H-/Doyo Incoloy-907 Coated soot/base alloy (corrosion resistant coated Co (or N1)-Cr- Aj-Y alloy (its composition is, for example, Cr/!-1yos, yio-irs, Super alloy tool steel coated with YO, YOCH, remainder CG or Nl) (%O made by forging, casting or powder metallurgy; *e.g. AISIM- , 2, Al5IW-/) Stainless steel Onutenite series -30≠ Ferrite type-’A30 Martensitic-≠70 Table ■ (continued) Carbon steel Al5I-#)/♂ Alloy steel Al5I-≠／≠0 Maraging-2jO cast iron Gray ductile malleable alloy UMSF-7000ri nonferrous metals Titanium metal and titanium alloys (e.g. ASTM-Grade/; T1-O) A) −≠■) Nickel metals and nickel alloys (e.g. Nickel-2001 Monel aOO ) cobalt Copper and its alloys (e.g. C-10100SC-77200, C-26000 , C-tayo 200) Refractory metals and their alloys Molybdenum alloy (e.g. TZM) Niobium alloy (for example, FS-♂ri) Tantalum alloy (e.g. T-///) Tungsten alloy (e.g. W-Mo alloy) Cemented carbide (c@mented ca rbld@s) Nf/Coi unified carbide (Nl and aobalt bo nded earbid*s) (e.g. WC-3 or L2JCo) steel bond - Carbide (e.g. TlC4LO-JU alloy with volume t%, balance being steel: Tic) 10-. The ratio of alloy 9M1 to M2, which is 20% and the balance is iron, is the selected M, or and the type of M2, the properties of the metal substrate, the type of reactive gaseous substance selected, and the conversion temperature. depending on the purpose of coating (e.g. forming a thermal barrier or hard surface) can be varied within a wide range.

Preferably, the coating is applied according to the dip coverage method. This method is easy to implement.

Oxides on the surface of the metal substrate are removed by the molten alloy (if oxides are present on the surface) (This may cause peeling of the coating layer.)

This method uses a molten M1/M2 alloy, and a metal (alloy) substrate is molten for the coating. Immerse into the alloy. The time period for which the substrate is immersed in the molten alloy and the duration of the molten alloy. Temperature is a factor that determines the thickness and smoothness of this coating. Surface materials for aircraft When making cutlery, a smoother surface is required than with metals used for other purposes. It is desirable to form a coating with a thickness of about 7 microns to several millimeters. When making a heat shield material, the thickness of the coating should be approximately 300-≠00 microns. It is preferable that there be. In the case of forming hard surfaces, it is not possible to increase the thickness of the coating. The thickness of the coating, which is not absolutely necessary, should be adjusted to suit the conditions of the field of application of the final product. This should be clear to those skilled in the art.

The advantage of dip coating or slurry melting is that the coating alloy or metal mixture The thickness of the coating on the substrate can be well controlled as the coating is diluted.

In addition, it can be coated on substrates with complex shapes, and it can be coated until the coating is completely thick. It is also possible to repeat this method many times. Generally, this slurry coating method The method is as follows: and organic cement [and J-i? “Nicroplas-!00” (Well Col. commercially available from Monoi Co.), or @MPA-O” (Baker Canuter Oy) Commercially available product 9] manufactured by Le Co., Ltd. The blending ratio of these raw materials in the slurry is Coating alloy l/LJ'wt%, mineral spirit 70wt%, organic cement It is 45% by weight. Place this mixture directly behind a porcelain rig containing alumina oxide balls. Grind in Lumir.

After separating the resulting slurry from the aluminum oxide spheres, it is applied to the substrate surface. If this coating is to be applied by, for example, a dip coating operation, the slurry may be It is preferred to keep it under agitation to ensure that the alloy particles remain homogeneously dispersed in the liquid medium. evaporate the solvent. This evaporation occurs, for example, in air at room temperature or slightly elevated temperature. Perform at eye temperature. Coating layer containing alloy and cement (r@5idu@ ) by heating it to an appropriate temperature in an inert gas atmosphere such as argon. fuse it to the body (this inert gas has previously passed over the getter, such as a piece of calcium). Let it pass through to remove oxygen.]

The cement will decompose and the decomposition products will volatilize.

The melting point of the alloy of M and M2 is p higher than the melting point of the substrate or very close to the melting point of the substrate. value, the alloy can be processed by sputtering or vapor deposition techniques or other suitable It can be coated onto the substrate using various techniques.

M, and M2 are in the form of an alloy with a composition of a eutectic mixture or an alloy with a composition close to it. It is advantageous to use it in

In this case, the following benefits are obtained: a coating of a certain known composition is homogeneous. It can be formed into In addition, eutectic mixtures and mixtures with similar compositions are non-eutectic. It has a lower melting point than the mixture. Therefore, unlike high melting point alloys, these and they sinter more easily than high melting point alloys.

Example EXAMPLES In order to more specifically illustrate the structure and effects of the present invention, Examples will be shown below.

example/ The metal substrate was tool steel in the form of a bar. The coating alloy is Tl77! r% and N It was a eutectic alloy containing +21 J%. The melting point of this fusion metal is 4t. The temperature was 2°C.

Gold xi of AiJ was immersed in the alloy of ilJ at 7000°C for 70 seconds. , take it out of the bath and keep it at 00℃; Ta. The metal ring was then exposed to oxygen-free nitrogen gas at 00°C for 75 hours. exposed for a while. This nitrogen gas is passed slowly over a metal rod at a pressure of /atmospheres. I set it. As a result, a continuous state of ``$, cover, 1-'' was produced, and the adhesion was also good. .

The titanium nitride TiNxL:D composition in this case depends on the temperature and nitrogen pressure. It will change.

example! Example/I performed roughly the same operation as the self-contribution operation, but this time I used mild steel as the metal base. did. Titanium nitride N on a metal substrate! i was formed.

The coatings described in Example/and Example 2 are useful.

This is because the treated surface, ie, the coated surface, is hard.

This is a particularly useful operation for mild steel, which is inexpensive but soft. i.e. The present invention also provides a useful means for forming hard surfaces on inexpensive metals. It is.

Example 3 I performed the operation in Example/ and the operation similar to P1. However, the operating temperature this time was 0°C. . The 2 micron thick coating formed in this example is greater than the coating obtained in Example/ It was a brighter color.

The relatively dark colored coating obtained at higher temperatures is due to the stoichiometric composition of TIN. '(It was found that it contains +-.

Similar coatings could be applied to nutless steel.

Example≠ A eutectic alloy (melting point = ?O/C) consisting of 13% Zr and 177% N was used as the coating material. I used it. A dip coating operation was carried out on a metal substrate (tool steel) at 7000°C, and 7 An annealing operation was carried out at 000° C. for 3 hours and then as in Example/and Example 3. Similarly, it was exposed to nitrogen gas at f00°C. Homogeneous with a diameter of 2-3 microns, A coating layer with good adhesion was formed.

An example. Melting point containing Zr Hirozachi and Cumu J♂Complete! ℃ eutectic alloy as coating material I used it. The tool steel was immersed in this alloy bath for 10 seconds at tiooo°C, and then removed from the bath. It was taken out and annealing was carried out at 7000° C. for a long time. Next, this The specimens were exposed to nitrogen gas at high pressure for 0 hours at 00°C. A homogeneous coating with good adhesion. A covering layer was formed.

The following benefits are obtained by using copper as metal M2: has good heat conductivity, so it is possible to conduct heat during cutting (main material made of tool steel). It is useful for 9 escaping towards the body.

Example B A eutectic alloy of 77% TI and 23% Cu (melting point &'76°C) was used. hot soak The soaking operation was carried out at 70-7°C for 70 seconds and the annealing operation was carried out at 700°C for 5 seconds. The sample was exposed to N2 at 7000° C. for 700 hours. Continuous good adhesion A state coating layer was formed. The metal substrate was high speed steel.

Example 7 Tool steel was coated with Ti-N1 alloy by a method similar to that of Example 3 and annealed. performed the operation. The reactive gas used was methane. Methane is argon or Can be used with an inert gas diluent such as helium, or can be used alone. Wear. The coated tool steel bar was exposed to methane at 7000°C for 20 hours. Ta.

A hard coating layer made of titanium carbide and having good adhesion was formed.

Example g The same operation as in Example 7 was carried out, but this time BH3 was used as the reaction gas and the temperature was 700°C. (e.g. >700°C to 7000°C) for 10-20 hours. Used for a while. A titanium boride coating layer was formed, but it was hard and had good adhesion. It was good.

example The same operation as in Example 7 was performed, but this time silane 5IF4 was used alone as the reaction gas. or with an inert gas diluent such as argon or helium. gas Base B%) The temperature and time of e-cropping are 〉7oO℃ to 7000℃ and respectively. 10-. It may be 20 hours. Titanium silicide coating is hard and has good adhesion. was formed.

Next, we will explain the main considerations regarding the site.

The metal M2 should be compatible with the metal substrate. For example, this is gold It must not combine with metal substrates to form brittle intermetallic compounds. Preferably, this does not significantly change the mechanical properties of the metal substrate; Furthermore, it exhibits solid solubility over a wide range of metal substrates. It is preferable that there be. Furthermore, M2 forms a low melting point eutectic alloy with Ml. is preferably a very stable carbide, nitride, boride or preferably does not form a silicide, e.g. converting M to a nitride. If it is necessary, M2 does not stably produce nitrides under the nitride production conditions of M. It should be a good thing.

When coating M,/M2 alloy by hot dipping method, spinning operation and / or the wiping operation prevents the formation of a coating layer with a non-planar surface. or the non-flatness of the coated surface can be reduced.

After coating the alloy or mixture of M and M2, an annealing operation is carried out to A strong surface bond should be ensured with the metal substrate.

In order to convert the coating obtained from the alloy into the final product (flnal product) The conversion operation is carried out by exposure to a reactive gas in the form of a slow fluid. is preferred, and this operation is therefore performed when the molecules or compounds of this reactive gas are M. should be carried out at a temperature and pressure such that M2 reacts sufficiently but does not react with M2. It is. However, in this case, the temperature slightly above the melting point of the coating alloy, e.g. It is advantageous to carry out the gas exposure operation at a temperature slightly above the eutectic alloy. liquid phase If present, this results in the movement of M to the clothing surface and in the outer layer Elimination of M2 will be facilitated.

The operating temperature is lower than the melting point of the coating alloy, and M, and the reactive gas If the compound grows quickly, M2 will be trapped in the growing compound. Therefore, the particles consisting of M and XU are bound together by M2. Dew. Therefore, in this case, cermet is produced, which is a useful material. For example, W or N cemented with cobalt or nickel. The carbide b is a useful material.

As is clear from the above description, the present invention provides a method for applying an M1Xn coating to a metal substrate. The present invention provides new and useful methods of, and new and useful products for.

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Claims (23)

[Claims] 1. (a) provide a metal substrate to be coated; (b) meet criteria (i)-(ii) below; ) An alloy of one or more metals M1 selected according to ) and another one or more metals M2 or prepare a mixture, (i) M1 is the element X under the given temperature and pressure of the following reactive gaseous substance (where X is nitrogen, carbon, boron or silicon) Accordingly, it is a metal that easily forms a stable compound of M1 and X, (ii) M2 does not form a stable compound with X under the above conditions and M2 is coated. is bonded to the substrate during heat treatment of the substance, (c) coating the surface of the substrate with the alloy or mixture; (d) A compound of M1 and X is generated, but the generation of a compound of M2 and X is avoided. M1 and the reactive gas at high temperature under conditions such that the selectively reacts with the solid substance A method for applying a protective coating to a metal substrate, characterized in that: 2. Claims characterized in that after step (c), the coating is subjected to an annealing operation. The method described in paragraph 1. 3. The method according to claim 1, wherein the metal substrate is an iron-based alloy. . 4. The method according to claim 1, characterized in that the metal substrate is a non-ferrous alloy. . 5. A method according to claim 1, characterized in that X is nitrogen. 6. A method according to claim 1, characterized in that X is carbon. 7. A method according to claim 1, characterized in that X is boron. 8. A method according to claim 1, characterized in that X is silicon. 9. Claims characterized in that M1 is selected from lanthanide metals The method described in box 1. 10. Claims characterized in that M1 is selected from actinide metals. The method described in Scope No. 1. 11. M2 is nickel, cobalt, aluminum, yttrium, chromium and Claim 1, characterized in that the metal is selected from the group consisting of iron. How to put it on. 12. Characterized by M1 being titanium and M2 being cobalt or nickel. The method according to claim 1. 13. M1 is a group consisting of metals from group IIIb, group IVb, and group Vb of the periodic table of elements. A method according to claim 1, characterized in that the method is selected from: 14. 13. A method according to claim 12, characterized in that X is nitrogen. 15. 13. A method according to claim 12, characterized in that X is carbon. 16. (a) a metal base; (b) a protective coating adhered to at least one surface of the metal substrate; , This coating consists of an outer layer and an inner layer, where the outer layer is M1Xn (Here, X is nitrogen, carbon, boron, or silicon, and n is the atomic ratio of X and M1. ) and the inner layer is composed of one or more metals M2 bonded to said substrate. wherein the metals M1 and M2 are selected according to the following criteria: It was used in (i) M1 is element X (where X is nitrogen, carbon, boron, or silicon as described above); ) at a given temperature and pressure of the reactive gaseous substance. It is a metal that can easily react under the conditions to produce a stable compound of M1 and X, (ii) M2 does not react with X to form a stable compound under the above conditions. and M2 has the function of bonding the coating to the substrate. A coated metal product characterized by: 17. Claim 16, wherein the metal base is an iron-based alloy. Coated metal products. 18. Claim 16, wherein the metal base is a non-ferrous alloy. Coated metal products. 19. Coated according to claim 16, characterized in that X is nitrogen metal products. 20. Coated according to claim 16, characterized in that X is carbon metal products. 21. Coated according to claim 16, characterized in that X is boron. metal products. 22. Coated according to claim 16, characterized in that X is silicon metal products. 23. M1 is a metal of group IIIb, table IVb, or group Vb of the periodic table of elements; The object according to claim 16, characterized in that the object is selected from the group consisting of: overturned metal products.