Compositionally modulated zinc-manganese multilayered coatings
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.
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.