Property modulated materials and methods of making the same

• US 9,938,629 B2
• Filed: 01/08/2016
• Issued: 04/10/2018
• Est. Priority Date: 07/07/2008
• Status: Active Grant

• Current Assignee: Modumetal Incorporated
• Original Assignee: Modumetal Incorporated
• Inventors: Whitaker, John D., Bao, Zhi Liang
• Primary Examiner(s): Ripa, Bryan D.
• Application Number:
  US14/991,719
• Publication Number:
  US 20160265130A1
• Time in Patent Office: 823 Days
• CPC Class Codes: C25D 1/04 Wires; Strips; Foils
• CPC Class Codes: C25D 17/10 Electrodes , e.g. composition, counter electrode
• CPC Class Codes: C25D 21/12 Process control or regulation controlling or regulating in general G05
• CPC Class Codes: C25D 3/20 of iron
• CPC Class Codes: C25D 3/665 from ionic liquids
• CPC Class Codes: C25D 5/18 Electroplating using modulated, pulsed or reversing current
• CPC Class Codes: C25D 5/615 Microstructure of the layers, e.g. mixed structure
• CPC Class Codes: C25D 5/617 Crystalline layers

Abstract

A method of making property modulated composite materials includes depositing a first layer of material having a first microstructure/nanostructure on a substrate followed by depositing a second layer of material having a second microstructure/nanostructure that differs from the first layer. Multiple first and second layers can be deposited to form a composite material that includes a plurality of adjacent first and second layers. By controlling the microstructure/nanostructure of the layers, the material properties of the composite material formed by this method can be tailored for a specific use. The microstructures/nanostructures of the composite materials may be defined by one or more of grain size, grain boundary geometry, crystal orientation, and a defect density.

Claims

1. A method for producing a property modulated composite, the method comprising:

providing a bath including at least one electrodepositable species;

immersing at least a portion of a substrate in the bath;

passing a current through the substrate at a first setting having a first determined value of beta for a first predetermined duration, beta being defined as a ratio of a value of peak cathodic current density to an absolute value of peak anodic current density, the current having a current density that is controlled as a function of time that is a sine wave, the first setting producing a first material having a first composition and a first nanostructure defined by one or more of a first average grain size, a first grain boundary geometry, a first crystal orientation, and a first defect density; and

passing the current through the substrate at a second setting having a second determined value of beta for a second predetermined duration, the first setting and the second setting further differing by a second plating parameter, the second setting producing a second material having a second composition and a second nanostructure defined by one or more of a second average grain size, a second grain boundary geometry, a second crystal orientation, and a second defect density, the first material and the second material comprising the at least one electrodepositable species, where

one or more of the first average grain size differs from the second average grain size, the first grain boundary geometry differs from the second grain boundary geometry, the first crystal orientation differs from the second crystal orientation, or the first defect density differs from the second defect density, thereby producing a property modulated composite on the substrate.

2. The method of claim 1, wherein the second plating parameter is duty cycle or mass transfer rate.

3. The method of claim 1, wherein the second plating parameter is temperature.

4. The method of claim 1, wherein beta is changed from the first determined value to the second determined value as a continuous function of time.

5. The method of claim 1, wherein the property modulated composite is a layered property modulated composite.

6. The method of claim 5, wherein a first layer of the layered property modulated composite exhibits a first mechanical property and a second layer of the layered property modulated composite, which is adjacent to the first layer, exhibits a second mechanical property, which differs from the first mechanical property.

7. The method of claim 6, wherein the first mechanical property and the second mechanical property are selected from the group consisting of hardness, elongation, tensile strength, elastic modulus, stiffness, impact toughness, abrasion resistance, and combinations thereof.

8. The method of claim 5, wherein a first layer of the layered property modulated composite exhibits a first thermal property and a second layer of the layered property modulated composite, which is adjacent to the first layer, exhibits a second thermal property, which differs from the first thermal property.

9. The method of claim 8, wherein the first thermal property and the second thermal property are selected from the group consisting of coefficient of thermal expansion, melting point, thermal conductivity, and specific heat.

10. The method of claim 5, wherein the layered property modulated composite includes a plurality of layers, each layer of the plurality of layers having a thickness ranging from about 1 nanometer to about 10,000 nanometers.

11. The method of claim 1, wherein the property modulated composite is a graded property modulated composite.

12. The method of claim 11, wherein a first section of the graded property modulated composite exhibits a first mechanical property and a second section of the graded property modulated composite, which is adjacent to the first section, exhibits a second mechanical property, which differs from the first mechanical property.

13. The method of claim 12, wherein the first mechanical property and the second mechanical property are selected from the group consisting of hardness, elongation, tensile strength, elastic modulus, stiffness, impact toughness, abrasion resistance, and combinations thereof.

14. The method of claim 11, wherein a first section of the graded property modulated composite exhibits a first thermal property and a second section of the graded property modulated composite, which is adjacent to the first section, exhibits a second thermal property, which differs from the first thermal property.

15. The method of claim 14, wherein the first thermal property and the second thermal property are selected from the group consisting of coefficient of thermal expansion, melting point, thermal conductivity, and specific heat.

16. The method of claim 1, wherein the first determined value of beta is less than 1.3 and the second determined value of beta is greater than 1.5.

17. The method of claim 1, wherein the first setting and the second setting further differ by a third plating parameter.

18. The method of claim 1, wherein the first setting has a first value of the second plating parameter, the second setting has a second value of the second plating parameter, and the second plating parameter is changed from the first value to the second value as a continuous function of time.

19. The method of claim 1, wherein the at least one electrodepositable species comprises one or more metals.

20. The method of claim 19, wherein the one or more metals comprise nickel, iron, cobalt, copper, zinc, manganese, platinum, palladium, hafnium, zirconium, chromium, tin, tungsten, molybdenum, phosphorous, barium, yttrium, lanthanum, rhodium, iridium, gold, or silver.

21. The method of claim 1, wherein the second plating parameter is peak-to-peak current density.

22. The method of claim 1, wherein the current has substantially a same peak-to-peak current density while the current is passed through the substrate.

23. The method of claim 1, wherein the second plating parameter is average current density.

24. The method of claim 1, wherein a temperature of the bath is maintained while the current is passed through the substrate.

25. The method of claim 1, further comprising removing the property modulated composite from the substrate.

26. The method of claim 1, wherein the property modulated composite comprises alternating first and second layers produced by the passing the current through the substrate at the first and second settings.

27. The method of claim 1, wherein the second plating parameter is DC offset, where the first setting has a first value of the DC offset and the second setting has a second value of the DC offset.

28. The method of claim 1, wherein the current density has a DC offset.

29. The method of claim 28, wherein the current density has substantially a same DC offset while the current is passed through the substrate.

30. The method of claim 1, wherein the current maintains substantially a same peak cathodic current density and substantially a same peak anodic current density while the current is passed through the substrate.

31. The method of claim 1, wherein the second plating parameter is frequency.

32. The method of claim 1, wherein the current has substantially a same frequency while the current is passed through the substrate.