Material and process for electrochemical deposition of nanolaminated brass alloys

1. A method for preparing a nanolaminate brass article comprising a conductive plastic or polymeric substrate and a nanolaminated brass coating, the method comprising:

(a) providing a conductive plastic or polymeric substrate;

(b) contacting at least a portion of the conductive plastic or polymeric substrate with an electrolyte containing metal ions of zinc and copper, and optionally containing additional metal ions, wherein said electrolyte is in contact with an anode; and

(c) applying an electric current across the conductive plastic or polymeric substrate and the anode and varying in time one or more of: the amplitude of the electric current, the frequency of the electric current, the average electric current, the offset of an alternating current, the ratio of positive current and negative current, electrolyte temperature, electrolyte additive concentration, electrolyte agitation, or combinations thereof, in order to produce on at least a portion of the conductive plastic or polymeric substrate a nanolaminated brass coating having a desired thickness and comprising periodic layers of electrodeposited species and/or periodic layers of electrodeposited species microstructures;

wherein at least two of said periodic layers each have thicknesses from about 2 nm to about 200 nm; and

wherein said article has an ultimate tensile strength, flexural modulus, modulus of elasticity, and/or stiffness ratio that is greater than the ultimate tensile strength, flexural modulus, modulus of elasticity, and/or stiffness ratio of an identical conductive plastic or polymeric substrate upon which has been electrodeposited a homogenous brass coating having a thickness substantially equivalent to the desired thickness and wherein the homogenous brass coating has a composition substantially equivalent to the composition of said nanolaminated brass coating.

2. The method of claim 1 , further comprising after step (c):

(d) selectively etching said nanolaminated coating, until a second desired thickness and finish of the nanolaminated coating is achieved.

3. The method of claim 1 , wherein said conductive plastic or polymeric substrate comprises one or more of: ABS, ABS/polyamide blend, ABS/polycarbonate blend, a polyamide, a polyethylene imine, a poly ether ketone, a poly ether ether ketone, a poly aryl ether ketone, an epoxy, an epoxy blend, a polyethylene, or a polycarbonate.

4. The method of claim 3 , wherein said conductive plastic or polymeric substrate comprises glass or mineral fillers.

5. The method of claim 3 , wherein said conductive plastic or polymeric substrate is reinforced by carbon fiber and/or glass fiber.

6. The method of claim 1 , wherein the article comprising a conductive plastic or polymeric substrate and a nanolaminated brass coating comprises an outermost layer, said outermost layer comprising a metal or alloy either of which is more noble than any of said periodic layers.

7. The method of claim 1 , wherein the article having a nanolaminated brass coating exhibits an ultimate tensile strength that is at least 20% greater than the same article formed with a homogeneous brass coating that has a composition substantially equivalent to the composition of said nanolaminate brass coating.

8. The method of claim 1 , wherein said article exhibits about a threefold increase in flexural modulus relative to said plastic or polymeric substrate without said coating, when the nanolaminated brass coating has a cross-sectional area of 5%; or wherein said article exhibits about a fourfold increase in flexural modulus relative to said plastic or polymeric substrate without said coating, when the nanolaminated brass coating has a cross-sectional area of 10%.

9. The method of claim 1 , wherein the article has a modulus of elasticity greater than 140 GPa.

10. The method of claim 1 , wherein the article has a modulus of elasticity from about 60 to about 100, from about 100 to about 140, from about 140 to about 200, or from about 200 to about 300 GPa.

11. The method of claim 1 , wherein, relative to said plastic or polymeric substrate without said coating, the article comprising the conductive plastic or polymeric substrate and the nanolaminated brass coating exhibits more than about a 2.8 fold increase in stiffness when the nanolaminated brass coating has a cross-sectional area of about 10%, or more than a 4 fold increase in stiffness when said coating has a cross-sectional area of about 15%, or more than a 7 fold increase in stiffness when said coating has a cross-sectional area of about 20%.

12. The method of claim 1 , wherein the nanolaminated brass coating comprises greater than 30 periodic layers each have thicknesses from about 5 nm to about 75 nm.

13. The method of claim 1 , wherein the nanolaminated brass coating comprises greater than 30 periodic layers each have thicknesses from about 50 nm to about 100 nm.

14. The method of claim 1 , wherein the nanolaminated brass coating comprises greater than 30 periodic layers each have thicknesses from about 75 nm to about 200 nm.

15. The method of claim 13 , wherein the article has a modulus of elasticity from about 60 to about 100, from about 100 to about 140, from about 140 to about 200, or from about 200 to about 300 GPa.

16. The method of claim 13 , wherein the article exhibits an ultimate tensile strength that is at least 20% greater than the same article formed with a homogeneous brass coating that has a composition substantially equivalent to the composition of said nanolaminated brass coating.

17. The method of claim 1 , wherein the conductive plastic or polymeric substrate comprises a non-conductive plastic or polymer rendered conductive by the incorporation of conductive materials or by electroless deposition of a metal.