# US 10,309,016 B2 · Method for preparing a carbide ceramics multilayer coating on, and optionally in, a part made of a carbon-containing material using a reactive melt infiltration RMI technique

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- Number: US 10,309,016 B2
- Document ID: US10309016B2
- Status: Granted
- Kind: B2
- Application number: 14/773,648
- Filed: 2014-03-07
- Published: 2016-02-11
- Granted: 2019-06-04
- Earliest claimed: 2013-03-08
- Assignees: Commissariat A L'energie Atomique Et Aux Energies Alternatives; Centre National De La Recherche Scientifique
- Applicants: Commissariat A L'energie Atomique Et Aux Energies Alternatives; Centre National De La Recherche Scientifique
- Inventors: Alexandre Allemand; Edouard Guillermin; Yann Le Petitcorps
- Web page: https://patentgrep.com/patent/US10309016B2

## CPC

- C23C 24/10: with intermediate formation of a liquid phase in the layer
- C01B 32/963: Preparation from compounds containing silicon
- C04B 41/009: {characterised by the material treated}
- C04B 41/52: Multiple coating or impregnating {multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation}
- C04B 41/89: for obtaining at least two superposed coatings having different compositions
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE

## Abstract

A method preparing a metals carbides multilayer coating on at least one surface of a first carbon layer of a substrate, or under the surface inside the first carbon layer, by a reactive melt infiltration technique, includes: a) putting the surface into contact with a solid metal disilicide MSi2, M is selected from hafnium, titanium, and tantalum; b) heating the substrate and the metal disilicide to above the melting temperature of the metal disilicide; c) observing a plateau at the temperature for a sufficient duration so that the metal disilicide reacts with the carbon and forms a first multilayer coating including a dense and continuous layer of SiC, fully covered by a dense and continuous layer of MC; d) cooling the part with the first multilayer coating; and then, at the end of d), optionally e) depositing a second carbon layer at the surface of the first multilayer coating.

## Claims

### Claim 1

A method for preparing a metals carbides multilayer coating on at least one surface of a first carbon layer of a substrate, or on the surface and under the surface inside the first carbon layer, by a reactive melt infiltration technique, the method comprising:
the following successive a) to d) being carried out:
a) putting the at least one surface into contact with a solid metal disilicide MSi2, wherein M is selected from hafnium, titanium, and tantalum;
b) heating the substrate and the metal disilicide up to a temperature TP above the melting temperature of the metal disilicide;
c) observing a plateau at the temperature TP for a sufficient duration so that the metal disilicide reacts with carbon of the first carbon layer and forms a first multilayer coating comprising a dense and continuous layer of SiC, fully covered by a dense and continuous layer of MC;
d) cooling the part provided with the first multilayer coating;
and then, at the end of d), the following e) is further carried out, and then the following successive f) to i) are carried out, or the following successive f) to i) are carried out without e);
e) depositing a second carbon layer at the surface of the first multilayer coating;
f) putting the surface of the first multilayer coating still containing the carbon of the first carbon layer or the surface of the second carbon layer into contact with a solid metal disilicide MSi2, wherein M is selected among hafnium, titanium, and tantalum;
g) heating the surface of the first multilayer coating still containing said carbon of the first carbon layer and the metal disilicide, or the second carbon layer and the metal disilicide, to a temperature TP above the melting temperature of the metal disilicide;
h) observing a plateau at a temperature TP for a sufficient duration so that the metal disilicide reacts with the carbon of the first carbon layer or with carbon of the second carbon layer and forms a second multilayer coating comprising a dense and continuous layer of SiC, fully covered by a dense and continuous layer of MC;
i) cooling the part provided with the second multilayer coating;
and then at the end of i), optionally the following j) is further carried out;
j) depositing a third carbon layer at the surface of the second multilayer coating;
and at the end of i) or of j), the following k) is further carried out;
k) carrying out silicidation of the surface of the second multilayer coating still containing carbon or of the third carbon layer with liquid Si, whereby a SiC layer is obtained on the second multilayer coating.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the first carbon layer is a carbon layer deposited on said substrate, said substrate being made of a material different from carbon.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the material different from carbon is selected from carbide ceramics or SiC; composite materials of carbide ceramics or SiC/SiC composites; nitride ceramics; boride ceramics; oxide ceramics; metals; and mixtures thereof.

### Claim 4 (depends on 1)

The method according to claim 1, wherein the first carbon layer is a layer of a substrate fully made of carbon.

### Claim 5 (depends on 4)

The method according to claim 4, wherein the carbon which constitutes the substrate is entirely made of graphite.

### Claim 6 (depends on 4)

The method according to claim 4, wherein the carbon which constitutes the substrate fully made of carbon is in a form of carbon fibers, carbon wires, or in a form of a carbon/carbon composite material or a 2D or 3D composite material.

### Claim 7 (depends on 4)

The method according to claim 4, wherein the carbon substrate has an average open porosity from 1% to 99% by volume, determined by measuring buoyancy force.

### Claim 8 (depends on 7)

The method according to claim 7, wherein the surface is put into contact with a volume of solid metal disilicide MSi2, of less than 30% of the volume of the average open porosity of the carbon substrate, or between 20% and 30% of the volume of the average open porosity of the carbon substrate.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the contacting of the surface with the solid metal disilicide MSi2 is achieved by depositing the metal disilicide MSi2 on the surface, or by depositing a carbon substrate and MSi2 in a crucible.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the metal disilicide MSi2 is deposited on the surface in a form of a powder, either compacted or not, or in a form of a slurry of a powder of the metal disilicide MSi2 and of a liquid.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the temperature TP is from 900° C. to 2,500° C.

### Claim 12 (depends on 1)

The method according to claim 1, wherein, during b) a rapid rise in temperature is carried out up to the temperature TP.

### Claim 13 (depends on 1)

The method according to claim 1, wherein the plateau at temperature TP is observed for a duration from 5 minutes to 15 minutes.

### Claim 14 (depends on 1)

The method according to claim 1, wherein e) is repeated, and then f) to i) are repeated; and then j) and k) are carried out.

### Claim 15 (depends on 1)

The method according to claim 1, wherein the temperature TP is 1,800° C.

### Claim 16 (depends on 1)

The method according to claim 1, wherein, during b) a rapid rise in temperature at a rate of 1,000° C. to 3,000° C./minute up to the temperature TP is carried out.

### Claim 17 (depends on 1)

The method according to claim 1, wherein, during b) a rapid rise in temperature at a rate of 2,800° C./minute up to the temperature TP is carried out.