Method for enhancing the adhesion of a layer for the protection of silver against tarnishing on a substrate comprising a silver surface

Patent metadata

Field	Value
Publication number	US-11345993-B2
Application number	US-201916572203-A
Country	US
Kind code	B2
Filing date	Sep 16, 2019
Priority date	Sep 21, 2018
Publication date	May 31, 2022
Grant date	May 31, 2022

Abstract

A method is described for protecting a silver surface against tarnishing. This involves depositing a layer of a silver-copper alloy on a substrate, which may be a silver substrate. The alloy comprises between 0.1 wt % and 10 wt % of copper relative to the total weight of the alloy. At least one layer of a metal oxide or a nitride having a thickness in a range of 1 nm to 200 nm is deposited on the alloy to protect against tarnishing. The presence of copper in the silver-copper alloy enhances the alloy's adhesion without altering the silver color.

First claim

The invention claimed is:

1. A method for making a final silver surface that is protected against tarnishing, the method comprising:
depositing a layer comprising a silver-copper alloy on an initial silver surface, obtaining the final silver surface; and
depositing a first layer of a metal oxide or a nitride and optionally a second layer of a metal oxide or a nitride different than the first layer on at least one part of the final silver surface to protect the final silver surface against tarnishing,
wherein the initial silver surface is formed by depositing an intermediate layer of silver on a non-silver substrate,
wherein the intermediate layer of silver has a thickness in the range of 200 nm to 3,000 nm,
wherein the silver-copper alloy comprises between 0.1 wt % and 10 wt % copper relative to the total weight of the alloy,
wherein the first layer has a thickness in the range of 1 nm to 200 nm, and
wherein the second layer, if present, has a thickness in the range of 1 nm to 200 nm.

2. The method according to claim 1 , wherein the intermediate layer of silver has a thickness in the range of 200 nm to 600 nm.

3. The method according to claim 1 , wherein the intermediate layer of silver has a thickness in the range of 1,000 nm to 3,000 nm.

4. The method according to claim 3 , wherein the intermediate layer of silver has a thickness in the range of 2,500 nm to 3,000 nm.

5. The method according to claim 1 , wherein the silver-copper alloy layer has a thickness in the range 200 nm to 600 nm.

6. The method according to claim 1 , wherein the silver-copper alloy comprises between 0.5 wt % and 7 wt % of copper relative to the total weight of the alloy.

7. The method according to claim 1 , wherein the first layer is of a metal oxide, optionally the second layer is of a metal oxide, and the metal oxide of the first layer and optionally the metal oxide of the second layer are independently selected from the group consisting of Al 2 O 3 , Ta 2 O 5 , HfO 2 , ZnO, SiO 2 , and TiO 2 .

8. The method according to claim 1 , wherein the first layer and the second layer are deposited on at least one part of the final silver surface, and
wherein the metal oxide of the first layer is Al 2 O 3 and the metal oxide of the second layer is TiO 2 .

9. The method according to claim 8 , further comprising a plasma treating before and/or after the step of depositing the second TiO 2 layer.

10. The method according to claim 8 , wherein the first layer has a thickness in the range of 1 nm to 100 nm, and
wherein the second layer has a thickness in the range of 1 nm to 100 nm.

11. The method according to claim 10 , wherein the first layer has a thickness in the range of 30 nm to 50 nm,
and wherein the second layer in the range of 10 nm to 50 nm.

12. The method according to claim 1 , wherein the depositing of the first layer and optionally the second layer is carried out by a method chosen from the group consisting of ALD, PVD, CVD, and sol-gel.

13. The method according to claim 12 , wherein the depositing of the first layer and optionally the second layer is carried out by ALD.

14. The method according to claim 1 , further comprising heat treating the initial silver surface before depositing the layer comprising the silver-copper alloy and/or heat treating the final silver surface before the depositing of the first layer and optionally the second layer.

15. The method according to claim 1 , further comprising plasma treating the final silver surface before the depositing of the first layer and optionally the second layer.

16. The method according to claim 15 , wherein the plasma of the plasma treatment consists of an Ar plasma or an Ar/H 2 plasma.

17. The method according to claim 15 , wherein the plasma treatment and the depositing of the first layer and optionally the second layer are implemented in the same comprehensive treatment machine.

18. The method according to claim 15 , further comprising pre-treating by oxidation the final silver surface between the plasma treatment and the depositing of the first layer and optionally the second layer.

19. The method according to claim 18 , wherein the oxidation pre-treatment consists of pretreating with a plasma of an oxidising agent.

20. The method according to claim 18 , wherein the oxidation pretreatment consists of injecting water or hydrogen peroxide, in liquid form, into a pre-treatment chamber in a vacuum.

21. The method according to claim 18 , wherein the plasma treatment and the oxidation pre-treatment are implemented in the same comprehensive treatment machine.

22. The method according to claim 18 , wherein the oxidation pre-treatment and the depositing of the first layer and optionally the second layer are implemented in the same comprehensive treatment machine.

23. The method according to claim 22 , wherein the plasma treatment, the oxidation pre-treatment, and the depositing of the first layer and optionally the second layer are implemented in the same comprehensive treatment machine.

24. The method according to claim 1 , wherein the initial silver surface and/or the non-silver substrate is a horological element.

25. The method according to claim 24 , wherein a structuring is produced on the surface of the initial silver surface and/or the non-silver substrate.

26. The method according to claim 1 , wherein the non-silver substrate is metallic.

27. The method according to claim 23 , wherein the non-silver substrate is gold.

28. The method according to claim 1 , wherein the second layer is not deposited.

Assignees

• Swatch Group Res & Dev Ltd

Inventors

• Manasterski Christian
• Spassov Vladislav
• Faure Cedric

Classifications

• C23C8/80

  After-treatment · CPC title

• C23C16/0272

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

• C23C16/56

  After-treatment · CPC title

• C23C28/345

  with at least one oxide layer · CPC title

• C23C16/02

  Pretreatment of the material to be coated (C23C16/04 takes precedence) · CPC title