Process of manufacture a nuclear component with metal substrate by DLI-MOCVD and method against oxidation/hydriding of nuclear component

Patent metadata

Field	Value
Publication number	US-11634810-B2
Application number	US-201716337623-A
Country	US
Kind code	B2
Filing date	Sep 28, 2017
Priority date	Sep 28, 2016
Publication date	Apr 25, 2023
Grant date	Apr 25, 2023

Abstract

Process for manufacturing a nuclear component comprising i) a support containing a substrate based on a metal (1), the substrate (1) being coated or not coated with an interposed layer (3) positioned between the substrate (1) and at least one protective layer (2) and ii) the protective layer (2) composed of a protective material comprising chromium; the process comprising a step a) of vaporizing a mother solution followed by a step b) of depositing the protective layer (2) onto the support via a process of chemical vapor deposition of an organometallic compound by direct liquid injection (DLI-MOCVD).

First claim

The invention claimed is:

1. A process for manufacturing a nuclear component via a method of chemical vapor deposition of an organometallic compound by direct liquid injection (DLI-MOCVD), the nuclear component chosen from a nuclear fuel cladding, a spacer grid, a guide tube, a plate fuel or an absorber rod, comprising:
i) a support containing a substrate based on a metal chosen from zirconium, titanium, vanadium, molybdenum or base alloys thereof, the substrate being coated or not with an interposed layer placed between the substrate and at least one protective layer;
ii) said at least one protective layer coating said support and composed of a protective material comprising chromium chosen from a carbide of a chromium alloy, a chromium nitride, a chromium carbonitride, a mixed chromium silicon carbide, a mixed chromium silicon nitride, a mixed chromium silicon carbonitride, or mixtures thereof; and
the process comprising the following successive steps:
a) vaporizing a mother solution containing a hydrocarbon-based solvent free of oxygen atoms, a bis(arene) precursor comprising chromium; and containing, where appropriate, an additional precursor, a carbon incorporation inhibitor or a mixture thereof; the precursors having a decomposition temperature comprised between 300° C. and 600° C.; and
b) in a chemical vapor deposition reactor in which is located said support to be covered and the atmosphere of which is at a deposition temperature comprised between 300° C. and 600° C. and at a deposition pressure comprised between 13 Pa and 7000 Pa; introducing the mother solution vaporized in step a), which brings about the deposition of said at least one protective layer on said support.

2. The process for manufacturing a nuclear component according to claim 1 , wherein the nuclear component further comprises a liner placed on the inner surface of said support, which is the surface of said support opposite to the medium that is external to the nuclear component; the liner being deposited, at a deposition temperature comprised between 200° C. and 400° C., onto the inner surface of said support by chemical vapor deposition of an organometallic compound (MOCVD) or DLI-MOCVD with, as precursor(s), a titanium amide and further a precursor comprising silicon, a precursor comprising aluminum and/or a liquid additive comprising nitrogen if the material of which the liner is composed comprises, respectively, silicon, aluminum and/or nitrogen.

3. The process for manufacturing a nuclear component according to claim 1 , wherein the process further comprises, after step b):
c) performing on said at least one protective layer at least one step chosen from a subsequent treatment step of ionic or gaseous nitridation, ionic or gaseous silicidation, ionic or gaseous carbosilicidation, or ionic or gaseous nitridation followed by ionic or gaseous silicidation or carbosilicidation.

4. The process for manufacturing a nuclear component according to claim 1 , wherein the mother solution contains the bis(arene) precursor comprising chromium, a precursor comprising silicon as additional precursor; such that, at a deposition temperature comprised between 450° C. and 500° C., the protective material comprising a mixed chromium silicon carbide is obtained.

5. The process for manufacturing a nuclear component according to claim 1 , wherein the mother solution contains the bis(arene) precursor comprising chromium, a precursor comprising silicon as additional precursor, a liquid precursor comprising nitrogen as additional precursor being present in the mother solution or a gaseous precursor comprising nitrogen being present in the chemical vapor deposition reactor; such that, at a deposition temperature comprised between 450° C. and 550° C., the protective material comprising a mixed chromium silicon nitride is obtained in the presence of the inhibitor or such that the protective material comprising a mixed chromium silicon carbonitride is obtained in the absence of the inhibitor.

6. The process for manufacturing a nuclear component according to claim 1 , wherein the bis(arene) precursor comprising chromium, a bis(arene) precursor comprising vanadium, a bis(arene) precursor comprising niobium or a bis(arene) precursor comprising the addition element comprise an element M, respectively, chosen from chromium, vanadium, niobium or the addition element; the element M being in oxidation state zero (M 0 ) so as to have a bis(arene) precursor comprising the element M 0 .

7. The process for manufacturing a nuclear component according to claim 1 , wherein the additional precursor is chosen from a bis(arene) precursor comprising vanadium, a bis(arene) precursor comprising niobium, a precursor comprising aluminum, a mixture of these additional precursors and a precursor comprising silicon and/or nitrogen.

8. In a method for combating oxidation and/or hydriding in a nuclear component in a humid atmosphere comprising water, or for combating hydriding in a nuclear component in an hydrogenated atmosphere comprising hydrogen, the improvement wherein the nuclear component is chosen from a nuclear fuel cladding, a spacer grid, a guide tube, a plate fuel or an absorber rod, and comprises:
i) a support containing a substrate based on a metal chosen from zirconium, titanium, vanadium, molybdenum or base alloys thereof, the substrate being coated or not with an interposed layer placed between the substrate and at least one protective layer;
ii) said at least one protective layer coating said support and composed of a protective material comprising chromium chosen from a chromium alloy unless the substrate is zirconium-based, a carbide of a chromium alloy, a chromium nitride, a chromium carbonitride, a mixed chromium silicon carbide, a mixed chromium silicon nitride, a mixed chromium silicon carbonitride, or mixtures thereof.

Assignees

• Commissariat Energie Atomique

Inventors

• Schuster Frédéric
• Lomello Fernando
• Maury Francis
• Michau Alexandre
• Boichot Raphaël
• Pons Michel

Classifications

• C23C16/4486

  by producing an aerosol and subsequent evaporation of the droplets or particles · CPC title

• C23C16/0272 Primary

  Deposition of sub-layers, e.g. to promote the adhesion of the main coating · CPC title

• C23C16/10

  Deposition of chromium only · CPC title

• C23C16/045

  Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates · CPC title

• C23C16/36

  Carbonitrides · CPC title