METHOD FOR FORMING A LAYER OF ALUMINA AT THE SURFACE OF A METALLIC SUBSTRATE

Abstract

A method for forming a layer of alumina on the surface of a metal alloy substrate including aluminium, includes depositing a first aluminium layer on a surface of the metallic substrate, depositing a second layer by vapour-phase deposition on the first layer, the second layer comprising aluminium, a halogen and oxygen, and heat treatment of the substrate coated with the first and second layers under oxidising atmosphere in order to form the layer of alumina at the surface of the metallic substrate.

Claims

1. A method for forming a layer of alumina on the surface of a metal alloy substrate comprising aluminium, the method comprising: depositing a first aluminium layer on a surface of the metal alloy substrate, depositing a second layer by vapour-phase deposition on the first aluminium layer, the second layer comprising aluminium, a halogen and oxygen, and heat treatment of the metal alloy substrate coated with the first and second layers under oxidising atmosphere in order to form the layer of alumina at the surface of the metal alloy substrate.

2. The method according to claim 1, wherein a thickness e.sub.1 of the first aluminium layer is comprised between 20 nm and 1000 nm.

3. The method according to claim 1 wherein the halogen is fluorine.

4. The method according to claim 1, wherein the second layer is deposited by a method chosen from among physical vapour deposition, chemical vapour deposition, plasma-enhanced chemical vapour deposition and case hardening.

5. The method according to claim 1, wherein a thickness of the second layer is greater than or equal to 10 μm.

6. The method according to claim 1, wherein the second layer is deposited from a gas phase comprising oxygen, a halogen gas and aluminium.

7. The method according to claim 6, wherein the second layer is deposited by sputtering of a target comprising aluminium in an atmosphere comprising oxygen and halogen gas.

8. The method according to claim 1, wherein the heat treatment is conducted at a temperature greater than or equal to 800° C.

9. The method according to claim 1, wherein the metal alloy substrate is a titanium aluminide based alloy.

10. The method according to claim 1, wherein the metal alloy substrate is a turbomachine part.

11. A coated metallic substrate comprising: a metal alloy substrate comprising aluminium, a first aluminium layer on a surface of the metal alloy substrate, and a second layer comprising aluminium, a halogen and oxygen, the second layer coating the first aluminium layer.

12. The coated metallic substrate according to claim 11, wherein the first aluminium layer has a thickness e.sub.1 comprised between 20 nm and 1000 nm.

13. The coated metallic substrate according to claim 11, wherein the second layer comprises a compound of formula AlO.sub.nF.sub.m wherein n and m are each strictly positive.

Description

DESCRIPTION OF THE FIGURES

[0034] FIG. 1 illustrates the substrate coated with the first aluminium layer after implementing a first step of an example of the method according to the invention.

[0035] FIG. 2 illustrates the substrate coated with the first and second layers after implementing a second step of an example of the method according to the invention.

[0036] FIG. 3 illustrates the substrate coated with an alumina layer of the surface obtained after heat treatment under oxidising atmosphere.

[0037] FIG. 4 schematically describes a device for vapour phase deposition of the layers onto a substrate that can be implemented in the context of the invention.

[0038] FIG. 5 shows a photograph obtained by scanning electron microscopy of the result obtained after implementing a method according to the invention.

[0039] FIG. 6 shows a photograph obtained by scanning electron microscopy of the result obtained after implementing a method not according to the invention in which the first aluminium layer is not deposited.

DESCRIPTION OF EMBODIMENTS

[0040] The present invention concerns the coating of a metal alloy substrate 11 of an alloy comprising aluminium. The treated substrate can be a titanium aluminide based alloy, such as a gamma-TiAl alloy.

[0041] The treated substrate can constitute a turbomachine part, for example an aeronautical turbomachine part. The substrate is intended to be used in oxidising atmosphere and at a temperature greater than or equal to 800° C. The substrate may, for example, be a turbine part. For example, it may be a turbine blade or a turbine ring sector.

[0042] First aluminium layer 12 is first of all deposited onto an external surface S of the substrate. First layer 12 can be deposited on contact of external layer S of the substrate. First layer 12 formed of elemental aluminium (AI) can be deposited by implementing a technique known in and of itself. In particular, it may be deposited by physical vapour deposition, for example by vacuum evaporation or by sputtering.

[0043] First aluminum layer 12 can be deposited by other deposition methods such as, for example, electrochemical deposition, chemical vapour deposition (CVD), plasma enhanced chemical vapour deposition (PECVD) or case hardening. The temperature imposed when depositing first layer 12 can be comprised between 20° C. and 600° C., for example between 20° C. and 400° C.

[0044] In one example of embodiment, first aluminium layer 12 can be deposited by radio-frequency magnetron sputtering, for example power equal to 200 W, under reduced pressure, for example 0.66 bar, by using an argon flow, for example 60 standard cubic centimeters per minute, and temperature of 400° C., for example.

[0045] First layer 12 can have a thickness e.sub.1 comprised between 20 nm and 1000 nm.

[0046] Metallic substrate 11 coated with first layer 12 is illustrated in FIG. 1.

[0047] Second layer 13 comprising aluminium, a halogen and oxygen is then formed on first layer 12. Second layer 13 can be deposited in contact with first layer 12. First layer 12 is interposed between substrate 11 and second layer 13. Second layer 13 is formed by vapour deposition.

[0048] As indicated above, second layer 13 comprises a compound of formula AlO.sub.nX.sub.m wherein n and m are each strictly positive and X represents halogen. Second layer 13 may comprise a mixture of aluminium halide and aluminium oxyhalide, optionally with alumina. The halogen can be fluorine or chlorine as indicated above.

[0049] Second layer 13 can comprise, in atomic percentages: [0050] 3% to 70% halogen, for example 55% to 65% halogen, [0051] 5% to 40% aluminium, for example 10% to 30% aluminium, and [0052] 1% to 20% oxygen, for example 3% to 15% oxygen.

[0053] Second layer 13 can have an atomic ratio between halogen and oxygen comprised between 2:1 and 8:1.

[0054] The inventors have observed that halogen is an activator of the alumina formation reaction by oxidation of the aluminium with oxygen.

[0055] Second layer 13 is made by vapour phase deposition, in particular by magnetron cathode sputtering. The temperature imposed when depositing second layer 13 can be comprised between 20° C. and 800° C., for example between 20° C. and 400° C.

[0056] FIG. 4 schematically shows a device to perform deposition by magnetron cathode sputtering.

[0057] Into a chamber 101, a gas is introduced by inlet 106 and a plasma is generated between target 105 and substrate 111 to be coated. Under the effect of an electrical field, obtained by imposing a voltage between target 105 and substrate 111, electrons are generated by the target and can ionise the atoms making up the plasma by collision. The presence of a magnetic field generated by a magnet 104 positioned near target 105 confines the generated electrons close to the target and increases the probability that a collision between an electron and an atom in the plasma will occur there. When such a collision has occurred, a high energy space is generated and this can bombard target 105 and tear particles from target 105 by elastic shock The particles of target 105 thus tom can then be deposited on substrate 111 to form the deposit.

[0058] Second layer 13 can be deposited under vacuum, for example at a pressure less than or equal to 10 Pa (75 mTorr), for example comprised between 0.67 Pa (5 mTorr) and 10 Pa (75 mTorr). During deposition, the following can be imposed: [0059] a flow rate of oxygen injected into the chamber 101 comprised between 1 standard cm.sup.3 per minute (sccm) and 100 standard cm.sup.3 per minute, and [0060] a flow rate of halogen gas in chamber 101 comprised between 2.5 standard cm.sup.3 per minute and 100 standard cm.sup.3 per minute, [0061] and, optionally, a flow rate of inert gas injected into chamber 101 comprised between 1 standard cm.sup.3 per minute and 100 standard cm.sup.3 per minute.

[0062] The inert gas can be argon, for example.

[0063] In the case where the halogen is fluorine, the halogen gas can be chosen from CF.sub.4, C.sub.2F.sub.6, SiF.sub.4, SF.sub.6 or a mixture of these compounds.

[0064] In the case where the halogen is chlorine, the halogen gas can be chosen from SiCl.sub.4, du Cl.sub.2 or a mixture of these compounds.

[0065] Second layer 13 can have a thickness e.sub.2 greater than or equal to 0.1 μm, for example 10 μm, for example comprised between 10 μm and 100 μm.

[0066] FIG. 2 represents a substrate 11 coated with a first aluminium layer 12 and a second layer 13 such as described above.

[0067] Then a heat treatment is performed under an oxidising atmosphere so as to form alumina layer 14 on surface S of the metallic substrate.

[0068] The heat treatment can then be done at a temperature greater than or equal to 800° C., for example comprised between 800° C. and 1000° C., for example comprised between 850° C. and 900° C.

[0069] The heat treatment can be conducted under air. The heat treatment can be annealing.

[0070] As described above, due to the presence of aluminium layer 12, the growth of alumina layer 14 during heat treatment takes place while limiting or even eliminating aluminium depletion near substrate surface S.

[0071] At the end of heat treatment, and as shown schematically in FIG. 3, an alumina layer 14 is formed at surface S of metallic substrate 11.

[0072] The heat treatment can also be conducted at the formation on alumina layer 14 of a layer 15 comprising titanium, aluminium and oxygen.

[0073] In one example of embodiment, alumina layer 14 has a thickness e.sub.3 comprised between 10 nm and 50,000 nm.

[0074] FIG. 5 is a photograph of a gamma-TiAl substrate 201 coated by implementing a method such as described above Substrate 201 is coated with alumina layer 203 and has a layer 204 at its surface comprising titanium, aluminium and oxygen.

[0075] For comparison purposes, FIG. 6 is a photograph of a gamma-TiAl substrate 301 coated with a layer of alumina 303 by a method not of the invention, not comprising the initial deposition of the aluminium layer. The substrate also has a layer 304 at its surface comprising titanium, aluminium and oxygen.

[0076] It can be observed that the implementation of the method described above significantly reduces the area depleted in aluminium (202 in FIGS. 5 and 302 in FIG. 6) present at the surface of the substrate during coating of a metal substrate.

[0077] In the examples presented in FIGS. 5 and 6, an effect is observed that the area depleted in aluminium near the coated surface substrate surface is 2 μm thick when the alumina layer is prepared by a method of the invention (area 202 FIG. 5), versus 4 μm when the alumina layer is prepared by a method not of the invention (area 302 FIG. 6).

[0078] In the present invention the expression “comprised between . . . and . . . ” should be understood to include the limits unless explicitly stated otherwise.