Method for obtaining a zirconia-based article having a metallic appearance

Patent metadata

Field	Value
Publication number	US-11549170-B2
Application number	US-201715666886-A
Country	US
Kind code	B2
Filing date	Aug 2, 2017
Priority date	Aug 26, 2016
Publication date	Jan 10, 2023
Grant date	Jan 10, 2023

Abstract

The present invention concerns a method for obtaining a finished or semi-finished zirconia-based article, the surface of the article having a metallic external appearance and non-zero surface electrical conductivity, wherein the method includes the steps of:taking at least one zirconia article, pre-shaped in its finished or semi-finished form;placing said article in a chamber in which a hydrogen and carbon/nitrogen gas mixture is heated;heating said article and the gas mixture using at least one resistive element traversed by an electric current to obtain dissociation of the hydrogen and carbon/nitrogen based gas molecules and an increase in the temperature of said article;keeping said article in the reactive atmosphere thus created to obtain diffusion of the carbon/nitrogen atoms in the external surface of said article.

First claim

What is claimed is:

1. A method for obtaining a finished or semi-finished zirconia-based article, the finished or semi-finished zirconia-based article having a metallic external appearance and non-zero surface electrical conductivity, wherein the method comprises:
placing a zirconia article, pre-shaped in a finished or semi-finished form, in a primary chamber in which a gas mixture of process gases made of hydrogen and carbon-based gas molecules is heated by a resistive element, wherein the resistive element is made of a conductive material and is traversed by an electrical current, to reach a temperature of more than 1500° C.; and
heating the gas mixture in the primary chamber to obtain dissociation of the hydrogen and carbon-based gas molecules, which heats the zirconia article and obtains a diffusion of carbon atoms in an external surface of the zirconia article towards a core of the zirconia article to form a transformed layer on the external surface, to produce the finished or semi-finished zirconia-based article,
wherein prior to the heating of the gas mixture in the primary chamber, the method comprises a reduction step consisting of placing the zirconia article inside a secondary chamber into which dihydrogen is injected and heating the dihydrogen allowing diffusion of oxygen towards the surface and release of part of the oxygen contained in the zirconia article.

2. The method according to claim 1 , wherein the method further comprises, during the heating of the gas mixture contained in the primary chamber, a further diffusion of oxygen towards the surface and further release of oxygen contained in the zirconia article.

3. The method according to claim 1 , wherein a thickness of the transformed layer on the external surface of the finished or semi-finished zirconia-based article is between 10 and 1,000 nm.

4. The method according to claim 3 , wherein the thickness of the transformed layer on the external surface of the finished or semi-finished zirconia-based article is between 20 and 200 nm.

5. The method according to claim 1 , wherein said resistive element is made of a refractory metal selected from the group consisting of niobium, molybdenum, tantalum, tungsten and rhenium.

6. The method according to claim 1 , wherein the resistive element is a filament.

7. The method according to claim 1 , wherein the primary chamber comprises only one of the resistive element which is arranged inside the primary chamber for heating the gas mixture and the zirconia article to be treated so as to carbide the zirconia article in a homogeneous manner.

8. The method according to claim 1 , wherein the primary chamber comprises a plurality of the resistive elements distributed inside the primary chamber for heating the gas mixture and the zirconia article to be treated so as to carbide the zirconia article in a homogeneous manner.

9. The method according to claim 1 , wherein at least one of the process gases of the hydrogen and carbon-based gas molecules of the gas mixture is injected via the resistive element heated by the electric current passing therethrough.

10. The method according to claim 1 , wherein the method further comprises, during the heating of the gas mixture contained in the primary chamber, a further diffusion of oxygen towards the surface and further release of oxygen contained in the zirconia article,
wherein
a thickness of the transformed layer on the external surface of the finished or semi-finished zirconia-based article is between 20 and 200 nm,
said resistive element is made of a refractory metal selected from the group consisting of niobium, molybdenum, tantalum, tungsten and rhenium, and
the chamber comprises only one of the resistive element which is arranged inside the primary chamber for heating the gas mixture and the at least one zirconia article to be treated so as to carbide the at least one zirconia article in a homogeneous manner.

11. A method for obtaining a finished or semi-finished zirconia-based article, the finished or semi-finished zirconia-based article having a metallic external appearance and non-zero surface electrical conductivity, wherein the method consists essentially of:
placing a zirconia article, pre-shaped in a finished or semi-finished form, in a primary chamber in which a gas mixture of process gases made of hydrogen and carbon-based gas molecules is heated by a resistive element, wherein the resistive element is made of a conductive material and is traversed by an electrical current; and
heating the gas mixture in the primary chamber to obtain dissociation of the hydrogen and carbon-based gas molecules, which heats the zirconia article and obtains a diffusion of carbon atoms in an external surface of the zirconia article towards a core of the zirconia article to form a transformed layer on the external surface and a further diffusion of oxygen towards the surface and further release of oxygen contained in the zirconia article, to produce the finished or semi-finished zirconia-based article,
wherein prior to the heating of the gas mixture in the primary chamber, the method comprises a reduction step consisting of placing the zirconia article inside a secondary chamber into which dihydrogen is injected and heating the dihydrogen allowing diffusion of oxygen towards the surface and release of part of the oxygen contained in the zirconia article.

12. A method for obtaining a finished or semi-finished zirconia-based article, the finished or semi-finished zirconia-based article having a metallic external appearance and non-zero surface electrical conductivity, wherein the method consists of:
placing a zirconia article, pre-shaped in a finished or semi-finished form, in a primary chamber in which a gas mixture of process gases made of hydrogen and carbon-based gas molecules is heated by a resistive element, wherein the resistive element is made of a conductive material and is traversed by an electrical current, to reach a temperature of more than 1500° C.; and
heating the gas mixture in the primary chamber to obtain dissociation of the hydrogen and carbon-based gas molecules, which heats the zirconia article and obtains a diffusion of carbon atoms in an external surface of the zirconia article towards a core of the zirconia article to form a transformed layer on the external surface and a further diffusion of oxygen towards the surface and further release of oxygen contained in the zirconia article, to produce the finished or semi-finished zirconia-based article,

wherein prior to the heating of the gas mixture in the primary chamber, the method comprises a reduction step consisting of placing the zirconia article inside a secondary chamber into which dihydrogen is injected and heating the dihydrogen allowing diffusion of oxygen towards the surface and release of part of the oxygen contained in the zirconia article.

Assignees

• Swatch Group Res & Dev Ltd

Inventors

• Faure Cedric
• Curchod Loic

Classifications

• G04B37/225

  Non-metallic cases · CPC title

• C23C8/06 Primary

  using gases (C23C8/36 takes precedence) · CPC title

• C04B41/5057

  Carbides · 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

• C04B41/87

  Ceramics · CPC title