Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes

• US 10,808,322 B2
• Filed: 09/15/2015
• Issued: 10/20/2020
• Est. Priority Date: 03/15/2013
• Status: Active Grant

• Current Assignee: Modumetal Incorporated
• Original Assignee: Modumetal Incorporated
• Inventors: Whitaker, John D., Lomasney, Christina A., Caldwell, Richard J., Krupps, William, Unger, Jesse
• Primary Examiner(s): Moore, Margaret G
• Application Number:
  US14/855,192
• Publication Number:
  US 20160002790A1
• Time in Patent Office: 1,862 Days
• CPC Class Codes: B33Y 10/00 Processes of additive manufacturing
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: B82Y 40/00 Manufacture or treatment of nanostructures
• CPC Class Codes: C23C 18/1653 Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• CPC Class Codes: C23C 18/1689 After-treatment
• CPC Class Codes: C23F 17/00 Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25 coating for obtaining at least two superposed coatings either by methods not provided for in a single one of main groups C23C2/00 - C23C26/00, or by combinations of methods providedfor in subclasses C23C and C25D, C23C28/00
• CPC Class Codes: C25D 5/14 two or more layers being of nickel or chromium, e.g. duplex or triplex layers
• CPC Class Codes: C25D 5/18 Electroplating using modulated, pulsed or reversing current
• CPC Class Codes: C25D 5/605 Surface topography of the layers, e.g. rough, dendritic or nodular layers
• CPC Class Codes: C25D 5/617 Crystalline layers
• CPC Class Codes: C25D 5/627 Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
• CPC Class Codes: Y02P 10/25 Process efficiency

Abstract

Articles prepared by additive manufacturing of preforms that are coated by electrodeposition of nanolaminate materials, and methods of their production are described.

Claims

1. An article comprising:

a polymer preform; and

a material on the preform, the material comprising a plurality of layers comprising alternating first layers and second layers, the first layers being compositionally different from the second layers, each first layer comprising a first alloy of nickel and cobalt, the first alloy comprising nickel in a concentration of at least 1% and cobalt in a concentration of at least 1%, by weight, each second layer comprising a second alloy of nickel and cobalt, the second alloy comprising nickel in a concentration of at least 1% and cobalt in a concentration of at least 1%, by weight.

2. The article of claim 1, wherein the polymer comprises:

polyetherimide, polyetherketoneketone, nylon, polyvinyl alcohol (PVA), acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polylactic acid (PLA), PC/ABS, wood fiber, polyphenylsulfone (PPSU), or a combination thereof.

3. The article of claim 1, wherein the polymer preform comprises a conductive material.

4. The article of claim 1, wherein the material is a structurally modulated material.

5. The article of claim 4, wherein the material comprises at least one portion having a plurality of layers with wavelengths ranging from about 1 nm to about 250 nm.

6. The article of claim 1, wherein the article has a property selected from the group consisting of hardness, toughness, or both, that is greater than that of the polymer preform.

7. The article of claim 1, wherein the material has a microhardness ranging from about 400 to about 500 Vickers units measured according to American Society for Testing and Materials (ASTM) E384-11e1.

8. The article of claim 1, wherein the material comprises a plurality of layers and displays Hall-Petch hardening or strengthening relative to a homogeneous electrodeposited composition having the average composition and substantially the same thickness of the plurality of layers.

9. The article of claim 1, wherein a portion of the polymer preform includes a honeycomb network.

10. The article of claim 1, wherein the plurality of layers have discrete interfaces between adjacent layers.

11. The article of claim 1, wherein the plurality of layers have diffuse interfaces between adjacent layers.

12. The article of claim 1, wherein the concentration of cobalt in each second layer ranges from 1% to 35%, by weight.

13. The article of claim 1, further comprising a conductive layer between the polymer preform and the material.

20. The article of claim 1, wherein the concentration of nickel in at least one layer of the plurality of layers ranges from 1% to 35%, by weight.

21. The article of claim 1, wherein the concentration of nickel in each layer of the plurality of layers ranges from 1% to 35%, by weight.

22. The article of claim 1, wherein the plurality of layers further comprises a third layer between one of the first layers and one of the second layers.

26. The article of claim 1, wherein the plurality of layers further comprises a third layer between each of the first and the second layers.

28. The article of claim 1, wherein each of the first layers is compositionally the same and each of the second layers is compositionally the same.

14. A method comprising:

electrodepositing a material on a polymer preform prepared by additive manufacturing, the material comprising a plurality of layers comprising alternating first layers and second layers, the first layers being compositionally different from the second layers, each first layer comprising a first alloy of nickel and cobalt, the first alloy comprising nickel in a concentration of at least 1% and cobalt in a concentration of at least 1%, by weight, each second layer comprising a second alloy of nickel and cobalt, the second alloy comprising nickel in a concentration of at least 1% and cobalt in a concentration of at least 1%, by weight.

15. The method of claim 14, further comprising contacting at least a part of the polymer preform with an electroless plating solution to produce an electroless plated polymer preform prior to the electrodepositing.

16. The method of claim 14, further comprising preparing the polymer preform by additive manufacturing.

17. The method of claim 16, wherein the additive manufacturing comprises direct digital manufacturing.

18. The method of claim 14, wherein electrodepositing the material comprising the metal comprises:

providing a bath including at least one electrodepositable component that comprises the metal;

contacting at least part of the polymer preform with the bath; and

applying voltage or current to the polymer preform to deposit the material.

19. The method of claim 14, wherein the electrodepositing comprises applying a time varying current density wherein the time varying current density oscillates for a plurality of cycles to deposit the material on the polymer preform, and wherein the material is a structurally modulated material.

23. The method of claim 14, wherein the concentration of nickel in at least one layer of the plurality of layers ranges from 1% to 35%, by weight.

24. The method of claim 14, wherein the concentration of nickel in each layer of the plurality of layers ranges from 1% to 35%, by weight.

25. The method of claim 14, wherein the plurality of layers further comprises a third layer between one of the first layers and one of the second layers.

27. The method of claim 14, wherein the plurality of layers further comprises a third layer between each of the first and the second layers.

29. The method of claim 14, wherein each of the first layers is compositionally the same and each of the second layers is compositionally the same.