Method for obtaining a carbonitrided zirconia-based article

Patent metadata

Field	Value
Publication number	US-11142487-B2
Application number	US-201716323628-A
Country	US
Kind code	B2
Filing date	Jun 16, 2017
Priority date	Aug 26, 2016
Publication date	Oct 12, 2021
Grant date	Oct 12, 2021

Abstract

The present invention concerns a method for obtaining a finished or semi-finished zirconia-based article (1), the article having a metallic external appearance and non-zero surface electrical conductivity, characterized in that the method includes the steps consisting in:taking at least one zirconia article, pre-shaped in its finished or semi-finished form;placing said article inside a chamber (10) in which a gaseous mixture is arranged, this gaseous mixture including at least a first hydrogen and carbon based gas compound in a first concentration (C1) and a second hydrogen and nitrogen based gas compound in a second concentration (C2);heating the gaseous mixture until the molecules of the first and second compounds dissociate and keeping said article in the reactive atmosphere thereby created to obtain diffusion of the carbon and nitrogen atoms in the external surface (2) of said article and to form stoichiometric carbonitride (ZrCx—Ny) at the surface, andprior to the step of heating the process gases contained in the chamber, a reduction step consisting in placing said article inside a chamber into which dihydrogen is injected and in heating the dihydrogen allowing diffusion towards the surface and release of the oxygen contained in said zirconia article.

First claim

The invention claimed is:

1. A method for obtaining a finished or semi-finished zirconia-based article that has a metallic external appearance and a non-zero surface electrical conductivity, the method comprising:
placing at least one zirconia article, pre-shaped in its finished or semi-finished form, inside a first chamber comprising a gaseous mixture comprising a first gas compound in a first concentration (C1) and a second gas compound in a second concentration (C2),
wherein:
the at least one zirconia article comprises zirconium oxide; and
the first gas compound comprises hydrogen and carbon atoms and the second gas compound comprises hydrogen and nitrogen atoms:
heating the gaseous mixture until molecules of the first and the second gas compounds dissociate to obtain a reactive atmosphere comprising carbon and nitrogen atoms, and
keeping the at least one zirconia article in the reactive atmosphere to obtain diffusion of the carbon and nitrogen atoms in an external surface of the at least one zirconia article, thereby forming a transformed layer comprising stoichiometric carbonitride (ZrC x —N y ) at the external surface,
wherein prior to the heating of the gaseous mixture, the at least one zirconia article is placed inside a second chamber comprising dihydrogen, and the dihydrogen is heated to obtain diffusion of oxygen of the zirconium oxide comprised by the at least one zirconia article towards the external surface, and thereby release of the oxygen.

2. The method of claim 1 , wherein the heating of the gaseous mixture further comprises diffusion of oxygen of the zirconium oxide comprised by the at least one zirconia article towards the external surface, and thereby release of the oxygen.

3. The method of claim 1 , wherein a thickness of the transformed layer at the external surface of the at least one zirconia article is between 10 and 1,000 nm.

4. The method of claim 3 , wherein the thickness is between 20 and 200 nm.

5. The method of claim 1 , wherein C2 is greater than C1.

6. The method of claim 1 , wherein C1 is between 5 and 100 sccm.

7. The method of claim 1 , wherein C2 is between 250 and 5000 sccm.

8. The method of claim 1 , wherein the first gas compound consists of hydrogen and carbon atoms.

9. The method of claim 1 , wherein the second gas compound consists of hydrogen and nitrogen atoms.

10. The method of claim 1 , wherein the first gas compound is CH 4 .

11. The method of claim 1 , wherein the second gas compound is NH 3 .

12. The method of claim 1 , wherein the heating of the gaseous mixture is provided by a resistive element.

13. The method of claim 1 , wherein the heating of the gaseous mixture is performed via plasma generation.

14. The method of claim 13 , wherein the plasma generation is achieved by electrical discharges, radiofrequency waves, and/or microwaves.

Assignees

• Swatch Group Res & Dev Ltd

Inventors

• Faure Cedric
• Curchod Loic

Classifications

• C23C8/30

  Carbo-nitriding · CPC title

• G04B37/225

  Non-metallic cases · CPC title

• C04B41/5062 Primary

  Borides, Nitrides or Silicides · CPC title

• C04B41/009

  characterised by the material treated · CPC title

• G04B45/0076

  Decoration of the case and of parts thereof, e.g. as a method of manufacture thereof (specially shaped G04B45/0061, G04B45/0069; decoration with inscriptions and pictures G04B45/0084; construction of the hands G04B19/042; decoration by adding extra pieces to the clockwork G04B47/04; colouring by treatment of the surface, e.g. by oxidation C25D) · CPC title