Compositionally modulated zinc-manganese multilayered coatings

Patent metadata

Field	Value
Publication number	US-11066752-B2
Application number	US-201815971469-A
Country	US
Kind code	B2
Filing date	May 4, 2018
Priority date	Feb 28, 2018
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

The present disclosure provides electrolyte solutions for electrodeposition of zinc-manganese alloys, methods of forming electrolyte solutions, methods of electrodepositing zinc-manganese alloys, and multilayered zinc-manganese alloys. An electrolyte solution for electroplating can include a metal salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde. An electrolyte solution can be formed by dissolving a metal salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde in water or an aqueous solution. Electrodepositing zinc-manganese alloys on a substrate can include introducing a cathode and an anode into an electrolyte solution comprising a metal salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde. Electrodepositing can further include passing a current between the cathode and the anode through the electrolyte solution to deposit zinc and manganese onto the cathode.

First claim

What is claimed is:

1. A method for electrodepositing a zinc-manganese alloy on a substrate, the method comprising:
introducing a cathode and an anode with a solution selected from the group consisting of:
(a) a zinc salt, a manganese salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde;
(b) a zinc salt, a manganese salt, and an alkali metal citrate; and
(c) a zinc salt, a manganese salt, an alkali metal citrate, an alkali metal acetate, a citric acid, glycine, and a thiamine;

passing a first current between the cathode and the anode through the solution to deposit a first layer containing zinc and manganese onto the cathode; and
depositing a second layer comprising zinc and manganese onto the first layer by passing a second current between the cathode and the anode, the second current having a current density different than the current density of the first current.

2. The method of claim 1 , wherein the anode is a zinc material or a carbonaceous electrode material.

3. The method of claim 1 , wherein passing the first current comprises passing a current between the cathode and the anode at a current density of about 1 mA/cm 2 to about 200 mA/cm 2 .

4. The method of claim 3 , wherein the first current comprises a series of pulses and each pulse has a duration of about 20 milliseconds to about 800 milliseconds.

5. The method of claim 4 , wherein the temperature of the solution is maintained at a temperature of about 20° C. to about 35° C. while passing the first current.

6. The method of claim 1 , further comprising repeating passing currents between the cathode and the anode to form a coating having a plurality of alternating layers having a manganese content, wherein the currents have substantially the same duration and the layers have substantially the same thickness and substantially the same manganese content.

7. The method of claim 1 , further comprising repeating passing currents between the cathode and the anode to form a coating having a plurality of alternating layers, wherein the layers have substantially the same thickness and two or more of the layers have a different manganese content.

8. The method of claim 1 , further comprising repeating passing currents between the cathode and the anode to form a coating having a plurality of alternating layers, wherein two or more of the layers have a different thickness and two or more of the layers have a different manganese content.

9. The method of claim 1 , further comprising repeating passing currents between the cathode and the anode to form a coating having a plurality of alternating layers comprising:
a first layer having a first manganese content,
a second layer having a second manganese content different than the first manganese content,
a third layer having substantially the same manganese content as the first layer, and
a fourth layer having substantially the same manganese content as the second layer.

10. The method of claim 1 , further comprising repeating passing currents between the cathode and the anode to form a coating having a plurality of alternating layers, wherein each layer has substantially the same thickness and each layer has a different manganese content.

11. The method of claim 1 , further comprising repeating passing currents between the cathode and the anode to form a coating having a plurality of alternating layers, wherein each layer has a different thickness and each layer has a different manganese content.

12. A method for electrodepositing a zinc-manganese alloy on a substrate, the method comprising:
introducing a cathode and an anode with a solution selected from the group consisting of:
(a) a zinc salt, a manganese salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde;
(b) a zinc salt, a manganese salt, and an alkali metal citrate; and
(c) a zinc salt, a manganese salt, an alkali metal citrate, an alkali metal acetate, a citric acid, glycine, and a thiamine;
wherein the anode is a zinc material or a carbonaceous electrode material,

passing a first current between the cathode and the anode at a current density of about 1 mA/cm 2 to about 200 mA/cm 2 through the solution to deposit a first layer containing zinc and manganese onto the cathode; and
depositing a second layer comprising zinc and manganese onto the first layer by passing a second current between the cathode and the anode, the second current having a current density different than the current density of the first current.

13. A method for electrodepositing a zinc-manganese alloy on a substrate, the method comprising:
introducing a cathode and an anode with a solution selected from the group consisting of:
(a) a zinc salt, a manganese salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde;
(b) a zinc salt, a manganese salt, and an alkali metal citrate; and
(c) a zinc salt, a manganese salt, an alkali metal citrate, an alkali metal acetate, a citric acid, glycine, and a thiamine;

passing a first current between the cathode and the anode at a current density of about 1 mA/cm 2 to about 200 mA/cm 2 through the solution to deposit a first layer containing zinc and manganese onto the cathode, wherein the temperature of the solution is maintained at a temperature of about 20° C. to about 35° C. while passing the first current; and
depositing a second layer comprising zinc and manganese onto the first layer by passing a second current between the cathode and the anode, the second current having a current density different than the current density of the first current.

14. The method of claim 1 , wherein the solution comprises a zinc salt, a manganese salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde.

15. The method of claim 1 , wherein the solution comprises a zinc salt, a manganese salt, and an alkali metal citrate.

16. The method of claim 1 , wherein the solution comprises a zinc salt, a manganese salt, an alkali metal citrate, an alkali metal acetate, a citric acid, glycine, and a thiamine.

17. The method of claim 12 , wherein the solution comprises a zinc salt, a manganese salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde.

18. The method of claim 12 , wherein the solution comprises a zinc salt, a manganese salt, and an alkali metal citrate.

19. The method of claim 12 , wherein the solution comprises a zinc salt, a manganese salt, an alkali metal citrate, an alkali metal acetate, a citric acid, glycine, and a thiamine.

20. The method of claim 13 , wherein the solution comprises a zinc salt, a manganese salt, boric acid, an alkali metal chloride, polyethylene glycol, and a hydroxy benzaldehyde.

21. The method of claim 13 , wherein the solution comprises a zinc salt, a manganese salt, and an alkali metal citrate.

22. The method of claim 13 , wherein the solution comprises a zinc salt, a manganese salt, an alkali metal citrate, an alkali metal acetate, a citric acid, glycine, and a thiamine.

Assignees

• Boeing Co

Inventors

• Gaydos Stephen P
• Ijeri Vijaykumar S
• Prakash Om
• Tiwari Shashi Kant
• Singh Raghuvir
• Paswan Sharma
• Pathak Lokesh C

Classifications

• C25D3/565 Primary

  containing more than 50% by weight of zinc · CPC title

• B32B15/013 Primary

  one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium · CPC title

• C25D5/18

  Electroplating using modulated, pulsed or reversing current · CPC title

• C25D5/623

  Porosity of the layers · CPC title

• C25D5/10

  Electroplating with more than one layer of the same or of different metals (for bearings C25D7/10) · CPC title