WO1986002290A1

WO1986002290A1 - Process for applying coatings to metals and resulting product

Info

Publication number: WO1986002290A1
Application number: PCT/US1985/002035
Authority: WO
Inventors: Robert W. Bartlett; Paul J. Jorgensen; Ibrahim Mohamed Allam; David J. Rowcliffe
Original assignee: Sri International
Priority date: 1984-10-17
Filing date: 1985-10-16
Publication date: 1986-04-24
Also published as: GB8613491D0; DK282286D0; JPS62500574A; SE8602596L; SE8602596D0; EP0198078A1; DK282286A; EP0198078A4; DE3590538T1; GB2178449B; NO862389L; GB2178449A; NO862389D0

Abstract

Protective coatings are applied to substrate metals by coating the metal surface, e.g. by dipping the substrate metal (10) in a molten alloy of the coating metals, and then exposing the coating at an elevated temperature to an atmosphere containing a reactive gaseous species which forms an oxide, a nitride, a carbide, a boride or a silicide (13). The coating material is a mixture of the metals M1? and M2? of which M1? forms a stable oxide, nitride, carbide, boride or silicide (13) under the prevailing conditions and of which M2? (12) does not form a stable oxide, nitride, carbide, a boride or silicide. M2? (12) serves to bond the oxide, etc. of M1? (13) to the substrate metal (10). Mixtures of M1? and/or M2? metals may be employed. This method is much easier to carry out than prior methods.

Description

-1 -

^■PROCESS FOR APPLYING COATINGS TO METALS AND RESULTING PRODUCT"

This application is a continuation-in-part of our copending application Serial No. 325,504, filed November 27, 1981, entitled "PROCESS FOR APPLYING THERMAL BARRIER COATINGS TO METALS AND RESULTING PRODUCT".

This invention relates to the coating of metals (hereinafter referred to as "substrates" or "substrate metals") with coatings that serve to provide hard surfaces, thermal barriers, oxidation barriers, chemically resistant coatings, etc.

By way of example, certain alloys known as "superalloys" are used as gas turbine components where high temperature oxidation resistance and high mechanical strength are required. In order to extend the useful temperature range, the alloys must be provided with a coating which acts as a thermal barrier to insulate and protect the underlying alloy or substrate from high temperatures and oxidizing conditions to which they are exposed. Zirconium oxide is employed for this purpose because it has a thermal expansion coefficient approximating that of the superalloys and because it functions as an efficient thermal barrier. It has been applied heretofore to alloy substrates by plasma spraying, in which an inner layer or bond coat, for example NiCrAlY alloy, protects the superalloy substrate from oxidation and bonds to the superalloy and to the zirconium oxide. The zirconium oxide forms an outer layer or thermal barrier and the -zirconia is partially stabilized with a second oxide such as calcia, yttria or magnesia. The plasma spray technique usually results in a nonuniform coating; and it is not applicable or it is difficultly applicable to re-entrant surfaces. The plasma sprayed coatings often have microcracks and pinholes that lead to catastrophic failure.

Thermal barrier coatings can also be applied using electron beam vaporization. This method of application is expensive and limited to line of sight application. Variations in coating compositions often occur because of differences in vapor pressures of the coating constituent elements.

It is an object of the present invention to provide an improved method of applying to substrate metals coatings of M,X where M, is the metal whose compound is to be applied to the substrate, X is an element such as oxygen, nitrogen, carbon, boron or silicon, and n is a number indicating the atomic proportions of X to M.

It is a further object of the invention to provide coated substrate metals in which the coatings, M, as described above, are uniform and adherent to the substrate.

The above and other objects of the invention will be apparent from the ensuing description and the appended claims. In accordance with the present invention, an alloy or a physical mixture of metals is provided comprising two metals M, and - which are selected in accordance with the criteria described below. This alloy or metal mixture is then melted to provide a uniform melt which is then applied to a metal substrate by dipping the substrate into the melt. Alternatively, the metal mixture or alloy is reduced to a finely divided state, and the finely divided metal is incorporated in a volatile solvent to form a slurry which is applied to the metal substrate by spraying or brushing. The resulting coating is heated in an inert atmosphere to accomplish evaporation of the volatile solvent and the . fusing of the alloy or metal mixture onto the surface of the substrate. (Where physical mixtures of metals are used, they are converted to an alloy by melting or they are alloyed or fused together in situ as in the slurry method of application described above.) In certain instances, as where the alloy melts at a high temperature such that the substrate metal might be adversely affected by melting a coating of alloy, the alloy may be applied by plasma spraying.

The metals M, and M~ are selected according to the following criteria: M, forms a thermally stable compound with X (i.e., an oxide, a nitride, a carbide, a boride or a silicide) when exposed at a high temperature to an atmosphere containing a small concentration of X or of a dissociable molecule or compound of X. The stable compound that M, forms with X may be represented as M,X_ where n represents the atomic ratio of X to M,. The metal M-, under such conditions, does not form a stable compound with X and remains entirely or substantially entirely in metallic form. Further, M, is compatible with the substrate metal in the sense that it results in an intermediate layer between the Mi.X.n. outer layer (resulting from reaction with X) and the substrate, such intermediate layer serving to bond the M,X_ layer to the substrate. Interdiffusion of ₂ and the substrate metal aids in this bonding effect.

It will be understood that M, may be a mixture or alloy of two or more metals meeting the requirements of M, and that M. may also be a mixture or alloy of two or more metals meeting the requirements of M~.

The coating thus formed and applied is then preferably subjected to an annealing step. The annealing step may be omitted when annealing occurs under conditions of use.

When a coating of suitable thickness has been applied to the substrate alloy by the dip coating process or by the slurry process described above (and in the latter case after the solvent has been evaporated and the , metal alloy or mixture is fused onto the surface of the substrate) or by any other suitable process the surface is then exposed to a selectively reactive atmosphere at an appropriate elevated temperature. Where an oxide coating is desired (i.e. X » 0) a mixture of carbon dioxide and carbon monoxide (hereinafter referred to as CO./CO) may be used. A typical C0₂/C0 mixture contains 90 percent of C0₂ and 10 percent of CO. When such a mixture is heated to a high temperature, an equilibrium mixture results in accordance with the following equation:

CO + 1/2 0₂ ^==s C0₂ The concentration of oxygen in this equilibrium mixture is very small, e.g. , at 800°C the equilibrium oxygen partial

-17 pressure is approximately 2 x 10 atmosphere, but is sufficient at such temperature to bring about selective oxidation of M_ . Other oxidizing atmospheres may be used, e.g., mixtures of oxygen and inert .gases such as argon or mixtures of hydrogen and water vapor which provide oxygen partial pressures lower than the dissociation pressures of the oxides of the metals M,, and higher than the dissociation pressure of the oxide of M,.

Where it is desired to form a nitride, carbide, boride or silicide layer on the substrate metal, an appropriate, thermally dissociable compound or molecule of nitrogen, carbon, boron or silicon may be used. Examples of suitable gaseous media are set forth in Table I below including media where X * oxygen, nitrogen, etc.

Table I. Gaseous Media for Forming

Oxides, Nitrides, Carbides, ^• Borides and Suicides

X Gaseous Media

O H₂/H₂0, CO/C0₂, 0₂/inert gas.

N N«, NH- or mixtures of the two.

C Methane, acetylene.

B Borane, diborane, borohalides.

Si Silane, trichloro silane, tribromosilane, silicon tetrachloride. Where a very low partial pressure of the reactive species is needed, that species may be diluted by an inert gas, e.g. argon or its concentration may be adjusted as in the case of a CO/C0₂ mixture or an H₂ H₂0 mixture where the partial pressure of oxygen is adjusted by adjusting the ratio of CO and CO- or H₂ and H₂°~

There results from this process a structure such as shown in Figure 1 of the drawings.

Referring now to Figure 1, this figure represents a cross-section through a substrate alloy indicated at 10 coated with a laminar coating indicated at 11. The laminar coating 11 consists of an intermediate metallic layer 12 and an outer Mi,Xn layer 13. The relative thicknesses of the layers 12 and 13 are exaggerated.. The substrate layer 10 is as thick as required for the intended service.

The layers 12 and 13 together typically will be about 300 to 400 microns thick, the layer 12 will be about 250 microns thick, and the layer 13 will be about 150 microns thick. It will be understood that the layer 12 will have a thickness adequate to form a firm bond with the substrate and that the layer 13 will have a thickness suiting it to its intended use. If, for example, an oxide layer is provided which will act as a thermal barrier, a thicker layer may be desired than in the case where the purpose is to provide a hard surface. Figure 1 is a simplified representation of the coating and substrate. A more accurate representation is shown in Figure 1A in which the substrate 10 and outer layer M,X are as described in Figure 1. However there is a diffusion zone D which may be an alloy of one or more substrate metals and the metal M₂ or it may be an inter- diffusion layer resulting from diffusion of substrate metal outwardly away from the substrate and of M₂ inwardly into the substrate. There is also an intermediate zone I which may be a cermet formed as a composite of M,X and M₂.

The metals M^ and M₂ will be selected according to the intended use. Table II below lists metals which may be used as M^ and Table III lists metals that may be used as M.». Not every metal in Table II may be used with every metal in Table III; it is required that M₂ be more noble than M₁ in any M,/M₂ pair. Another factor is the intended use, e.g. whether a hard surface, a thermal' barrier, a surface which is resistant to aqueous environments is desired, a surface which acts as a lubricant, etc. Also the nature of the substrate should be considered. It will be seen that some metals appear in both tables; that is a metal M, appearing in Table II may be used as M₂ (the more noble metal) with a less noble metal M^ from Table III.

Tab e II (M_χ)

Actinium Neodymium

Aluminum Niobium

Barium Praseodymium

Beryllium Samarium

Calcium Scandium

Cerium Silicon

Chromium Tantalum

Dysprosium Terbium

Erbium Thorium

Europium Thulium

Gadolinium Titanium

Hafnium Tungsten

Holmium Vanadium

Lanthanum Ytterbium

Lithium Yttrium

Magnesium Zirconium

Molybdenum

Table III (M₂)

Cobalt Palladium

Copper Platinum

Gold Rhenium

Iridium Rhodium

Iron Rubidium

Manganese Ruthenium

Molybenum Silver

Nickel Tin

Osmium Zinc It will be understood that two or more metals chosen from Table II and two or more metals chosen from Table III may be employed to form the coating alloy or mixture. Examples of suitable M,/M₂ metal pairs including mixtures of two or more metals M 1, and two or more metals ₂ are set forth in Table IV.

Table IV

Ti Ni Th Ni

Ti Fe Th Fe

Ti Co Th Co

Ti Cu Th Mg

^• Ti Pd

Ti + Nb Ni „

Ti + Zr Co Th Cu

Ti + Zr Fe Th Al

Ti + Zr Cu Sc Al

Zr Fe

Zr Co Sc Cu

Zr Cu Sc Fe

Zr Pd

Zr Pt Sc Pd

Zr Rh Sc Ru

Zr + Y Ni Y Al

Zr + Y Co Y Co

Zr + Y Fe

Zr + Y Pd Y Cu Y Fe Table IV (Cont ' d . )

It will be understood that not every metal pair will be suitable for all purposes. For example, where M, is silicon the coating tends to be brittle; some pairs are better suited for hardness, others for service as thermal barriers, others for oxidation and corrosion resistance, etc.

Examples of eutectic alloys are listed in Table V. It will be understood that not all of these alloys are useful on all substrates. In some cases the melting points are approximate. Numbers indicate the approximate percentage by weight of M₂» Table V

Eutectic Alloy Melting Point (^βC)

Ti - 28.5 Ni 942

Ti - 32 Fe 1085

Ti - 28 Co 1025

Ti - 50 Cu 955

Ti - 72 Cu 885

Ti - 48 Pd 1080

Zr - 17 Ni 960

Zr - 27 Ni 1010

Zr - 16 Fe 934

Zr - 27 Co 1061

Zr - 54 Cu 885

Zr - 27 Pd 1030

Zr - 37 Pt 1185

Zr - 25 Rh 1065

Hf - 72 Ni 1130

Hf - 38 Cu 970

Th - 36 Ni 1037

Th - 17 Fe 875

Th - 30 Co 975

Th - 22.5 Cu 880

Th - 75 Al 632

Sc - 45 Al 1150

Sc - 77 Cu 875

Sc - 24 Fe 910

Sc - 22 Pd 1000

Sc - 17 Ru 1100

Y - 93 Al 640

Y - 19 Al 1100 Table V (Cont ' d. )

Eutectic Alloy Melting Point (°C)

Y - 9.5 Al 960

Y - 28 Co 725

Y - 88 Cu 890

Y - 66 Cu 840

Y - 50 Cu 830

Y - 27 Cu 760

Y - 25 Fe 900

Y - 47 Ni 950

Y - 25 Ni 802

Y - 34 Pd 903

Y - 28 Pd 907

Y - 17 Ru 1080

Nb - 76.5 Ni 1270

Nb - 48.4 Ni 1175

Si - 88.3 Al 577

Si - 37.8 Co .1259

Si - 84 Cu 802

Si - 42 Fe 1200

Si - 12 Mo 1410

Si - 62 Ni 964

Si - 74 Pd 870

Si - 77 Pt 979

Table VA lists certain tertiary alloys that are useful in the practice of the present invention. Table VA

55.18 Ti - 23.13 Nb - 21.69 Ni

40.38 Ti - 43.52 Zr - 16.10 Ni

40.07 Ti - 44.35 Zr - 15.58 Co 25.37 Ti - 65.69 Zr - 11.94 Fe 17.36 Ti - 38.01 Zr - 44.63 Cu 69.65 Zr - 16.07 Y - 14.26 Ni 55.96 Zr - 23.34 Y - 20.70 Ni

43.08 Zr - 40.98 Y - 15.94 Co 56.76 Zr - 32.43 Y - 10.81 Fe 47.89 Zr - 34.39 Y - 17.72 Pd 56.68 Zr - 22.35 Nb - 20.97 Ni 49.33 Zr - 32.43 Hf - 43.94 Ni 24.20 Zr - 48.51 Hf - 27.29 Ni

Yttrium, calcium and magnesium are especially beneficial in zirconium-noble metal (M₂) alloys because they stabilize zirconia in the cubic form. Examples of such ternary alloys are as follows.

Zj_ Y Ca M£ Ni

76 8 16

77 7 16 79 5 16

Table VI provides examples of metal substrates to which the metal pairs may be applied.

Table VI

Superalloys

Cast nickel base such as IN 738

Cast cobalt base such as MAR-M509

Wrought nickel base such as Rene 95

Wrought cobalt base such as Haynes alloy No. 188

Wrought iron base such as Discaloy

Hastalloy X

RSR 185

Incoloy 901

Coated superalloys (coated for corrosion resistance) Superalloys coated with Co(or Ni)-Cr-Al-Y alloy, e.g. 15-25% Cr, 10-15% Al, 0.5% Y, balance is ^" Co or Ni

Steels

Tool Steels (wrought, cast or powder metallurgy) such as AISIM2; AISIW1

Stainless Steels

Austenitic 304 Ferritic 430 Martensitic 410

Carbon Steels AISI 1018 Alloy Steels

AISI 4140 Maraging 250

Cast irons

Gray, ductile, malleable, alloy UNSF 10009

Non-ferrous Metals

Titanium and titanium alloys, e.g. ASTM Grade 1;

Ti-6A1-4V Nickel and nickel alloys, e.g. nickel 200, Monel 400 Cobalt Copper and its alloys, e.g. C 10100; C 17200;

C 26000; C 95200

Refractory metals and alloys

Molybdenum alloys, e.g'. TZM Niobium alloys, e.g. FS-85 Tantalum alloys, e.g. T-lll Tungsten alloys, e.g. W-Mo alloys

Cemented Carbides

Ni and cobalt bonded carbides, e.g. WC-3 to 25 Co Steel bonded carbides, e.g. 40-55 vol.% TiC, balance steel; 10-20% TiC-balance steel

The proportions of M, to M₂ may vary widely depending upon such factors as the choice of M. and M₂, the nature of the substrate metal, the choice of the reactive gaseous species, the conversion temperature, the purpose of the coating (e.g. whether it is to serve as a thermal barrier or as a hardened surface), etc.

The dip coating method is preferred. It is easy to carry out and the molten alloy removes surface oxides (which tend to cause spallation). In this method a molten M,/M₂ alloy is provided and the substrate alloy is dipped into a body of the coating alloy. The temperature of the alloy and the time during which the substrate is held in the molten alloy will control the thickness and smoothness of the coating. If an aerodynamic surface or a cutting edge is being prepared a smoother surface will be desired than for some other purposes. The thickness of the applied coating can range between a fraction of one micron to a few millimeters. Preferably, a coating of about 300 microns to 400 microns is applied if the purpose is to provide a thermal barrier. A hardened surface need not be as thick. It will be understood that the thickness of the coating will be provided in accordance with the requirements of a particular end use.

The slurry fusion method has the advantage that it dilutes the coating alloy or metal mixture and therefore makes it possible to effect better control over the thickness of coating applied to the substrate. Also complex shapes can be coated and the process can be repeated to build up a coating of desired thickness. Typically, the slurry coating technique may be applied as follows: A powdered alloy of M₁ and M₂ is mixed with a mineral spirit and an organic cement such as Nicrobraz 500 (Well Colmonoy Corp. ) and MPA-60 (Baker Caster Oil Co.). Typical proportions used in the slurry are coating alloy 45 weight percent, mineral spirit 10 weight percent, and organic cement, 45 weight percent. This mixture is then ground, for example, in a ceramic ball mill using aluminum oxide balls. After separation of the resulting slurry from the alumina balls, it is applied (keeping it stirred to insure uniform dispersion of the particles of alloy in the liquid medium) to the substrate surface and the solvent is evaporated, for example, in air at ambient temperature or at a somewhat elevated temperature. The residue of alloy and cement is then fused onto the surface by heating it to a suitable temperature in an inert atmosphere such as argon that has

» been passed over hot calcium chips to getter oxygen. The cement will be decomposed and the products of decomposition are volatilized.

If the alloy of M, and M₂ has a melting point which is sufficiently high that it exceeds or closely approaches the melting point of the substrate, it may be applied by sputtering, by vapor deposition or some other technique.

It is advantageous to employ M, and M₂ in the form of an alloy which is a eutectic or near eutectic mixture. This has the advantage that a coating of definite, predictable composition is uniformly applied. Also eutectic and near eutectic mixtures have lower melting points than non-eutectic mixtures. Therefore they are less likely than high melting alloys to harm the substrate metal and they sinter more readily than high melting alloys. The following specific examples will serve further to illustrate the practice and advantages of the invention.

Example 1. The substrate was a nickel base superalloy known as IN 738, which has a composition as follows:

61% Ni 1.75% Mo

8.5% Co 2.6% W

16% Cr 1.75% Ta

3.4% Al 0.9% Nb

- 4% Ti

The coating alloy was in one case an alloy containing 90 percent cerium and 10 percent cobalt, and in another case an alloy containing 90 percent cerium and 10 percent nickel. The substrate was coated by dipping a bar of the substrate alloy into the molten coating alloy. The temperature of the coating alloy was 600°C, which is above the liquidus temperatures of the coating alloys. By experiment it was determined that a dipping time of about one minute provided a coating of satisfactory thickness.

The bar was then extracted from the melt and was exposed to a C0₂/CO mixture containing 90.33 percentage C0₂ and 9.67 percent CO. The exposure periods ranged from 30 minutes to two hours and the temperature of exposure was 800°C. The equilibrium oxygen partial pressure of the

CO,/CO mixture at 800^βC is about 2.25 x 10 atmosphere,

-15 and at 900°C it is about 7.19 x 10 atmosphere. The dissociation pressures of CoO were calculated at 800° and 900° to be about 2.75 x 10 ⁶ atmosphere and about 3.59 x 10 -14 atmosphere, respectively, and the dissociation pressures of NiO were calculated to be about 9.97 x 10 atmosphere and about 8.98 x 10 -13 atmosphere, respectively.

Under these circumstances neither cobalt nor nickel was oxidized.

Each coated specimen was then annealed in the absence of oxygen in a horizontal tube furnace at 900° or 1000°C for periods up to two hours. This resulted in recrystallization of oxide grains in the intermediate layer.

Examination of the treated specimens, treated in this manner with the cerium-cobalt alloy, revealed a structure in cross-section as shown in Figure 2. In Figure 2, as in Figure 1, the thickness of the various layers is not to scale, thickness of the layers of the coating being exaggerated.

Referring to Figure 2, the substrate is shown at 10, an interaction zone at 12A, a subscale zone at 12B and a dense oxide zone at 13. The dense oxide zone consists substantially entirely of Ce0₂; the subscale zone 12B contains both e0₂ and metallic cobalt and the interaction zone 12A contains cobalt and one or more metals extracted from the substrate.

Similar results are obtained using a cerium- nickel alloy containing 90% cerium and 10% nickel. Exa ple 2

The coating alloy composition was 70%Zr-25%Ni-5%Y by weight. Yttrium was added to the Zr-Ni coating alloy to provide a dopant to stabilize r0₂ in the cubic structure during the selective oxidation stage, and also because there is some evidence that yttrium improves the adherence of plasma-sprayed ZrO_ coatings. The weight ratio of Zr to Ni in this alloy was 2.7, which is similar to that of the NiZr₂-NiZr eutectic composition. The 5%Y did not significantly alter the melting temperature of the Zr-Ni eutectic. The substrates were dipped into the molten coating alloy at 1027^βC.

Two substrate alloys were coated, namely MAR-M509 and Co-10%Cr-3%Y. The results obtained indicated that the Zr0₂-based coatings applied by this technique to Co-Cr-Y alloy are highly adherent, uniform and have very low porosity. Little or no diffusion zone was observed between the coating and the substrate alloy. The coating layer was established totally above the substrate surface, and its composition was not significantly altered by the substrate constituents.

EDAX-concentration profiles were determined of different elements within the Zr-rich layer after hot dipping the substrate alloy (Co-10Cr-3Y) in the coating alloy, followed by an annealing treatment. The coating layer was about 150-160^ thick with a relatively thin (= 20 tt ) diffusion zone at the interface with the under¬ lying substrate. Cr was virtually nonexistent within the coating layer and a small amount of Co diffused from the substrate right through the coating to the external surface. Selective oxidation was conducted at 1027°C in a gas mixture of hydrogen/water vapor/argon at appropriate proportions to provide an oxygen partial pressure of about

-17 10 atm. At this pressure, both nickel and cobalt are thermodynamically stable in the metallic form. The scale produced by this process consists of an outer oxide layer about 40 thick and an inner subscale composite layer of about 120 /U. thick. The outer layer contained only Zr0₂ and Y₂° _* The subscale also consisted of a Zr0₂/Y₂0. matrix, but contained a large number of finely dispersed metallic particles, essentially nickel and cobalt.

Although nickel and cobalt were present uniformly within the outer region of the metallic coating after hot dipping and annealing and before the conversion of Zr and Y into oxides, they were virtually absent from this same region after the selective oxidation treatment. X-ray diffraction analysis of the surface of the sample indicated that this outer oxide layer was formed exclusively of a mixture of monoclinic zirconia and yttria.

It is believed that the final distribution of elements across the duplex coating layer and the subsequent oxide morphology are determined largely by the conditions of the final selective oxidation treatment. We believe that oxidation proceeds as follows: The melt composition at the sample surface before the selective oxidation treatment consists largely of Zr and Ni, smaller con¬ centrations of Y and Co, and virtually no Cr. Once oxygen

is admitted at P_n * 10 -17 atm, Zr and Y atoms diffuse ^υ2 rapidly in the melt toward the outer oxygen/metal interface to form a solid Zr0₂/Y₂0₃ mixture. The more noble elements (Ni and Co) are then excluded from the melt and accumulate in the metal side of the interface. The depletion of Zr from this melt increases the nickel content of the alloy and renders it more refractory. Once the coating alloy solidifies, atoms of all elements in the remaining metallic part of the coating become less mobile than in the molten state, and further oxidation proceeds as a solid state reaction. The continued growth of the Zr0₂ Y₂0. continues to promote a countercurrent solid state diffusion process in the metal side of the interface in which Zr and Y diffuse toward the interface, while nickel and cobalt diffuse away from the interface.

The profile indicated that, under the external Zr0₂ Y₂0. layer, nickel and cobalt exist as small particles embedded in the subscale composite layer.' The reason for their existence in such a distribution within a matrix of the Zr0₂/Y₂0_ subscale is not well understood. It should be emphasized that the weight fraction of nickel present in the coating layer, before oxidation, amounts to about 25%, which corresponds to about 20% in volume fraction. This amount will increase in the subscale after the exclusion of nickel from the outer Zr0₂/Y₂0, external scale during selective oxidation. This substantial amount of nickel, added to cobalt diffusing from the substrate, is expected to remain trapped in the subscale layer of the coating during the completion of selective oxidation of Zr and Y. The configuration and distribution of nickel and cobalt within this zone is likely to be determined by the mechanisms of oxidation of Zr and Y within the subscale zone. At least two possibilities exist:

(1) The concentration of nickel and cobalt in the metal ahead of the interface becomes very high as a result of their exclusion from the Zr0₂/Y₂0₃ scale initially formed from the melt. Some back-diffusion of both elements in the solid state is likely to continue during further exposure, but the remaining portion of both elements may be overrun by the advancing oxide/metal interface. This is believed to be more probable than possibility (2).

(2) A transition from internal to external oxidation occurs. After the initial formation of a Zr0₂/Y₂0₃ layer at the surface, Zr0₂ internal oxide particles may form ahead of the interface when the concentration of dissolved oxygen and zirconium exceeds the solubility product necessary for their nucleation. Then, these particles may partially block further Zr-0 reaction because the diffusion of oxygen atoms to the reaction front (of internal oxidation) can occur only in the channels between the particles that were previously precipitated. Further reaction at the reaction front may occur either by sideways growth of the existing particles, which requires a very small supersaturation, or by nucleation of a new particle. The sideways growth of the particles can thus lead to a compact oxide layer, which can entrap metallic constituents existing within the same region. In general, regardless of the mechanism involved, in determining the morphology and distribution of the metallic particles within the subscale zone, the formation of such a ceramic/metallic composite layer between the outer ceramic layer and the inner metallic substrate is highly advantageous. This is due to its ability to reduce the stresses generated from the mismatch in coefficients of thermal expansion of the outer ceramic coating and the inner metallic substrate.

Coating adhesion was evaluated by exposure of several test specimens to 10 thermal cycles between 1000°C and ambient temperature in air. The Zr0₂/Y-0₃ coating on the alloy Co-10Cr-3Y remained completely adherent and showed no sign of spallation or cracking. Careful metallurgical examination along the whole length of the specimen did not reveal any sign of cracking. The coating, appears completely pore free.. Furthermore, microprobe analyses across this section showed that the distributions of Zr, Y, Ni, Co, and Cr were essentially the same as those samples that had not been cycled. The coatings are not equally effective on all substrates. For example, a similar Zr0₂ Y₂0₃ coating on the alloy MAR.-M509 spalled after the second cycle.

It is believed that the presence of yttrium in both the Co-Cr-Y substrate and in the coating alloy promotes adhesion of the oxide layer.

Another significant observation is as follows: Zirconia-yttria mixtures have been prepared before but as far as we know no one has heretofore subjected an alloy of zirconium, yttrium and a more noble metal to selective oxidation. Heating the resulting Zr0₂-Y₂0₃-M₂ product at 1100°C resulted in the in situ formation of the cubic or the stabilized form of Zr0₂. Ex ample 3.

The substrate metal was tool steel in the form of a rod. The coating alloy was a eutectic alloy containing 71.5% Ti and 28.5% Ni. This eutectic has a melting point of 942°C. The rod was dipped into this alloy at 1000°C for 10 seconds and was removed and annealed for 5 hours at 800°C. It was then exposed to oxygen free nitrogen for 15 hours at 800°C. The nitrogen was passed slowly over the rod at atmospheric pressure. The resulting coating was continuous and adherent. The composition of the titanium nitride, TiN , depends upon the temperature and the nitrogen pressure.

Example 4.

Example 3 was repeated using mild steel as the substrate. A titanium nitride layer was applied.^*

The coatings of Examples 3 and 4 are useful because the treated surface is hard. This is especially helpful with mild steel which is inexpensive but soft. This provides a way of providing an inexpensive metal with a hard surface.

Example 5.

The same procedure was carried out as in Example 3 but at 650^βC. The coating, 2 microns thick, was lighter in color than the coating of Example 3.

Darker colors obtained at higher temperatures indicated a stoichiometric composition, TiN.

-

Similar coatings were applied to stainless steel. Example 6.

A eutectic alloy of 83% Zr and 17% Ni (melting point ■ 961°C) is employed. The substrate metal (tool steel) is dip coated at 1000°C, annealed 3 hours at 1000°C and exposed to nitrogen as in Examples 3 and 5 at 800°C. A uniform adherent coating 2 to 3 microns thick resulted.

Example 7.

A 48% Zr - 52% Cu eutectic alloy, melting point 885°C was used. Tool steel was dipped into the alloy for 10 seconds at 1000°C and was withdrawn and annealed 5 hours at 1000°C. It was then exposed to nitrogen at one atmosphere for 50 hours at 800°C. A uniform adherent coating resulted.

An advantage of copper as the metal M₂ is that it is a good heat conductor which is helpful in carrying away heat (into the body of the tool) in cutting.

Example 8.

A 77% Ti - 23% Cu alloy, a eutectic alloy, melting at 875°C was used. Hot dipping was at 1027°C for 10 seconds; annealing at 900°C for 5 hours; exposure to N₂ at 900°C for 100 hours. An adherent continuous coating resulted. The substrate metal was high speed steel.

Example 9.

Tool steel was coated with a Ti-Ni alloy and annealed as in Example 3. The reactive gas species is methane which may be used with or without an inert gas diluent such as argon or helium. The coated steel rod is exposed to methane at 1000°C for 20 hours. A hard, adherent coating of titanium carbide results. Example 10.

The procedure of Example 9 may be repeated using BH₃ as the reactive gas species at a temperature above 700^βC, e.g. >700^βC to 1000^βC, for ten to twenty hours. A titanium boride coating is formed which is hard and adherent.

Example 11.

The procedure of Example 9 is repeated using silane, Si H., as the reactive gas species, with or without a diluting inert gas such as argon or helium. The temperature and time of exposure may be >700°C to 1000°C for ten to twenty hours. A titanium silicide coating is formed which is hard and adherent.

Ti0₂-M₂ coatings may be applied to a substrate metal similarly using an oxygen atmosphere as in Examples 1 and 2. An advantage of Ti0₂-M₂ coatings is that Ti0₂ is resistant to attack by aqueous environments and it also inhibits diffusion of hydrogen into the substrate metal.

Among other considerations are the following:

The metal M₂ should be compatible with the substrate. For example, it should not form brittle inter- metallic compound with metals of the substrate. Preferably it does not alter seriously the mechanical properties of the substrate and has a large range of solid solubility in the substrate. Also it preferably forms a low melting eutectic with M,. Also it should not form a highly stable oxide, carbide, nitride, boride or silicide. For example, if M. is to be converted to an oxide, M₂ should not form a stable oxide under the conditions employed to form the M, oxide. In the hot dipping method of application of an M,/M₂ alloy, uneven surface application may be avoided or diminished by spinning and/or wiping.

The annealing step after application of the alloy or mixture of M, and M₂ should be carried out to secure a good bond between the alloy and the substrate.

Conversion of the alloy coating to the final product is preferably carried out by exposure to a slowly flowing stream of the reactive gas at a temperature and pressure sufficient to react the reactive gaseous molecule or compound with M, but not such as to react with M_2> It is also advantageous to employ a temperature slightly above the melting point of the coating alloy, e.g. slightly above its eutectic melting point. The presence of a liquid phase promotes migration of M, to the surface and displacement of M₂ in- the outer layer.

If the temperature is below the melting point of the coating alloy and if the compound formed by M. and the reactive gaseous species grows fast, M₂ will be entrapped in the growing compound, thus bonding the particles of

M,Xn. In this case a cermet will be formed which may be advantageous, e.g. a W or Nb carbide cemented by cobalt or nickel.

It will therefore be apparent that a new and useful method of applying M.X coating to a metal substrate, and new and useful products are provided.

Claims

WE CLAIM:

1. A method of coating a metal substrate with a protective coating which comprises:

(a) providing a substrate metal to be coated,

(b) providing an alloy or mixture of at least one metal M,, and at least one other metal M₂ selected according to the following criteria:

(1) M. is susceptible to reaction with a reactive gaseous species of an element X

(X being oxygen, nitrogen, carbon, boron or silicon) to form a stable compound of M. and X at a selected temperature and pressure of such reactive species,

(2) M₂ does not form a stable compound with X under such conditions and it bonds to the substrate on heat treatment of the coated material;

(c) applying such alloy or mixture to a surface of the substrate to provide a coating and

(d) effecting selective reaction of M, with such gaseous species at an elevated temperature under conditions to produce a compound of M, and X and to avoid or minimize formation of a compound of M₂ with X.

2. The method of Claim 1 wherein after step (c) the coating is annealed.

3. The method of Claim 1 wherein the substrate metal is a ferrous alloy.

4. The method of Claim 1 wherein the substrate metal is a non-ferrous alloy.

5. The method of Claim 1 wherein the substrate metal is a super alloy.

6. The method of Claim 3 wherein the substrate is tool steel.

7. The method of Claim 3 wherein the substrate is stainless steel.

8. The method of Claim 1 wherein M, is selected from the lanthanide metals.

9. The method of Claim 1 wherein M, is selected from the actinide metals.

10. The method of Claim 1 wherein M, is cerium.

11. The method of Claim 1 wherein M₂ is selected from the group nickel, cobalt, aluminum, yttrium, chromium and iron.

12. The method of Claim 1 wherein M, is cerium, M₂ is cobalt or nickel and the substrate metal is a superalloy.

13. The method of Claim 1 wherein M, is selected from groups III b, IV b and V b of the Periodic Table.

14. A coated metal article comprising:

(a) a metal substrate and

(b) a protective coating on and adherent to at least one surface of the metal substrate, such coating comprising an outer layer of a compound M,X wherein X is oxygen, nitrogen, carbon, boron or silicon and n represents the atomic proportion of X to M, and an inner layer of at least one metal M₂ bonded to the substrate, said metals M, and M₂ being selected according to the following criteria:

(1) M, is susceptible to reaction with a reactive gaseous species of an element X

(X being oxygen, nitrogen, carbon, boron or silicon) to form a stable compound of M^ and X at a selected temperature and pressure of such reactive species,

(2) M₂ does not form a stable compound with X under such conditions and it bonds the coating to the substrate.

15. The coated metal article of Claim 14 wherein the metal substrate is a ferrous alloy.

16. The coated metal article of Claim 14 wherein the metal substrate is a non-ferrous alloy.

17. The coated metal article of Claim 14 wherein the metal substrate is stainless steel.

18. The coated metal article of Claim 14 wherein the metal substrate is a superalloy.

19. The coated metal article of Claim 14 wherein M, is a lanthanide metal.

20. The coated metal article of Claim 14 wherein M. is a actinide metal.

21. The coated metal of Claim 14 wherein M, is selected from groups III b, IV b and V b of the Periodic Table. -x