Fine-grained metallic coatings having the coeficient of thermal expansion matched to one of the substrate

• US 8,129,034 B2
• Filed: 02/11/2011
• Issued: 03/06/2012
• Est. Priority Date: 12/17/2004
• Status: Active Grant

• Current Assignee: Integran Technologies Incorporated (Analog Devices, Inc.)
• Original Assignee: Integran Technologies Incorporated (Analog Devices, Inc.)
• Inventors: Palumbo, Gino, McCrea, Jonathan, Tomantschger, Klaus, Brooks, Iain, Jeong, Daehyun, Limoges, Dave, Panagiotopoulos, Konstantinos, Erb, Uwe
• Primary Examiner(s): McNeil, Jennifer
• Assistant Examiner(s): SAVAGE, JASON L
• Application Number:
  US13/025,487
• Publication Number:
  US 20110143159A1
• Time in Patent Office: 389 Days
• Field of Search: None
• US Class Current: 428/548
• CPC Class Codes: A01K 87/00 Fishing rods
• CPC Class Codes: A45B 9/00 Details
• CPC Class Codes: A63B 2209/00 Characteristics of used materials
• CPC Class Codes: A63B 2209/02 with reinforcing fibres, e.g. carbon, polyamide fibres
• CPC Class Codes: A63B 2209/023 Long, oriented fibres, e.g. wound filaments, woven fabrics, mats
• CPC Class Codes: A63B 49/10 made of non-metallic materials, other than wood
• CPC Class Codes: A63B 49/12 made of metal
• CPC Class Codes: A63B 53/04 Heads
• CPC Class Codes: A63B 53/0416 Heads having an impact surface provided by a face insert
• CPC Class Codes: A63B 53/10 Non-metallic shafts
• CPC Class Codes: A63B 53/12 Metallic shafts
• CPC Class Codes: A63B 59/00 Bats, rackets, or the like, not covered by groups A63B49/00 - A63B57/00
• CPC Class Codes: A63B 59/50 Substantially rod-shaped bats for hitting a ball in the air, e.g. for baseball
• CPC Class Codes: A63B 59/70 with bent or angled lower parts for hitting a ball on the ground, on an ice-covered surface, or in the air, e.g. for hockey or hurling
• CPC Class Codes: A63B 60/54 with means for damping vibrations
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C23C 24/04 Impact or kinetic deposition of particles
• CPC Class Codes: C23C 28/021 including at least one metal alloy layer
• CPC Class Codes: C23C 28/027 including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
• CPC Class Codes: C25D 15/02 Combined electrolytic and electrophoretic processes with charged materials
• CPC Class Codes: C25D 5/605 : Surface topography of the layers, e.g. rough, dendritic or nodular layers
• CPC Class Codes: C25D 7/00 : Electroplating characterised by the article coated
• CPC Class Codes: C25D 7/0607 : Wires
• CPC Class Codes: F41H 5/0457 : Metal layers in combination with additional layers made of fibres, fabrics or plastics
• CPC Class Codes: F42B 12/80 : Coatings
• CPC Class Codes: F42B 5/30 : of plastics , i.e. the cartridge-case tube is of plastics
• CPC Class Codes: F42B 6/04 : Archery arrows F42B6/08, F41B5/06, F42B12/362 take precedence
• CPC Class Codes: Y10T 428/12028 : Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
• CPC Class Codes: Y10T 428/12063 : Nonparticulate metal component
• CPC Class Codes: Y10T 428/12146 : Nonmetal particles in a component
• CPC Class Codes: Y10T 428/12292 : Workpiece with longitudinal passageway or stopweld material [e.g., for tubular stock, etc.]
• CPC Class Codes: Y10T 428/12493 : Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
• CPC Class Codes: Y10T 428/12535 : with additional, spatially distinct nonmetal component
• CPC Class Codes: Y10T 428/12597 : Noncrystalline silica or noncrystalline plural-oxide component [e.g., glass, etc.]
• CPC Class Codes: Y10T 428/12674 : Ge- or Si-base component
• CPC Class Codes: Y10T 428/12701 : Pb-base component
• CPC Class Codes: Y10T 428/12708 : Sn-base component
• CPC Class Codes: Y10T 428/12736 : Al-base component
• CPC Class Codes: Y10T 428/12743 : Next to refractory [Group IVB, VB, or VIB] metal-base component
• CPC Class Codes: Y10T 428/1275 : Next to Group VIII or IB metal-base component
• CPC Class Codes: Y10T 428/12757 : Fe
• CPC Class Codes: Y10T 428/12764 : Next to Al-base component
• CPC Class Codes: Y10T 428/12778 : Alternative base metals from diverse categories
• CPC Class Codes: Y10T 428/12937 : Co- or Ni-base component next to Fe-base component
• CPC Class Codes: Y10T 428/12972 : Containing 0.01-1.7% carbon [i.e., steel]
• CPC Class Codes: Y10T 428/13 : Hollow or container type article [e.g., tube, vase, etc.]
• CPC Class Codes: Y10T 428/24942 : including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/256 : Heavy metal or aluminum or compound thereof
• CPC Class Codes: Y10T 428/26 : Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• CPC Class Codes: Y10T 428/2918 : including free carbon or carbide or therewith [not as steel]
• CPC Class Codes: Y10T 428/2956 : Glass or silicic fiber or filament with metal coating
• CPC Class Codes: Y10T 428/2958 : Metal or metal compound in coating
• CPC Class Codes: Y10T 428/2964 : Artificial fiber or filament
• CPC Class Codes: Y10T 428/30 : Self-sustaining carbon mass or layer with impregnant or other layer
• CPC Class Codes: Y10T 428/31678 : Of metal

Abstract

Fine-grained (average grain size 1 nm to 1,000 nm) metallic coatings optionally containing solid particulates dispersed therein are disclosed. The fine-grained metallic materials are significantly harder and stronger than conventional coatings of the same chemical composition due to Hall-Petch strengthening and have low linear coefficients of thermal expansion (CTEs). The invention provides means for matching the CTE of the fine-grained metallic coating to the one of the substrate by adjusting the composition of the alloy and/or by varying the chemistry and volume fraction of particulates embedded in the coating. The fine-grained metallic coatings are particularly suited for strong and lightweight articles, precision molds, sporting goods, automotive parts and components exposed to thermal cycling. The low CTEs and the ability to match the CTEs of the fine-grained metallic coatings with the CTEs of the substrate minimize dimensional changes during thermal cycling and prevent premature failure.

Claims

1. An article comprising

(a) a permanent substrate which at room temperature has a minimum coefficient of thermal expansion of 0×

10<sup>−

6</sup>K<sup>−

1</sup>;

(b) a fine grained metallic coating extending over at least part of an inner and/or outer surface on the permanent substrate, having an average grain size between 2 and 1,000 nm, and a minimum coefficient of thermal expansion of 0×

10<sup>−

6</sup>K<sup>−

1</sup>; and

(c) said article exhibiting no delamination and the displacement of the coating relative to the underlying substrate is less than 1% after said article has been exposed to one temperature cycle consisting of exposure to liquid nitrogen for one minute followed by exposure to 90°

C. hot water for one minute, or one temperature cycle according to ASTM B553-71 service condition 1, 2, 3 or 4;

wherein

said fine-grained metallic coating has a ductility ranging from 1 to 15%.

2. The article according to claim 1 wherein said fine grained metallic coating comprises multi layer laminates.

3. The article according to claim 2, wherein said fine-grained metallic coating comprises Ni.

4. The article according to claim 3, wherein said fine-grained metallic coating comprising Ni further comprises at least one more element selected from the group consisting of Cu, Co, Fe, Mo, W, Zn, P, B and C.

5. The article according to claim 3, wherein said fine-grained metallic coating comprises Ni and P.

6. The article according to claim 3, wherein said fine-grained metallic coating comprises Ni and W.

7. The article according to claim 3, wherein said fine-grained metallic coating comprises Ni and Co.

8. The article according to claim 3, wherein said fine-grained metallic coating comprises Ni and Zn.

9. The article according to claim 3, wherein said fine-grained metallic coating comprises Ni and Fe.

10. The article according to claim 2, wherein said permanent substrate is steel.

11. The article according to claim 10, wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of Al, Ni, Co, Cu, Fe, Mo, W, Zn, P, and C.

12. The article according to claim 11, wherein said article comprises at least one intermediate conductive layer between said fine-grained metallic coating and the steel substrate.

13. The article according to claim 1 or 2 wherein said fine grained metallic coating has an average grain size between 5 and 500 nm.

14. The article according to claim 1 or 2 wherein said fine-grained metallic coating has an average grain size between 10 and 100 nm.

15. The article according to claim 1 or 2, wherein said fine-grained metallic coating is selected from the group consisting of:

(i) a pure metal selected from the group consisting of Al, Cu, Co, Ni, Fe, Mo, Pt, Ti and Zr,

(ii) an alloy comprising at least two elements selected from the group consisting of Al, Cu, Co, Ni, Fe, Mo, Pt, Ti and Zr;

(iii) pure metals or an alloy comprising at least one element selected from the group consisting of Al, Cu, Co, Ni, Fe, Mo, Pt, Ti and Zr, further comprising at least one element selected from the group consisting of Ag, Au, B, C, Cr, Mo, Mn, P, S, Si, Pb, Pd, Rh, Ru, Sn, V, W, and Zn; and

(iv) any of (i), (ii) or (iii) wherein said fine-grained metallic coating also comprises particulate additions in the volume fraction of between 0 and 95% by volume.

16. The article according to claim 1 or 2, wherein said fine-grained metallic coating comprises Co.

17. The article according to claim 1 or 2, wherein said fine-grained metallic coating comprises Co and P.

18. The article according to claim 1 or 2, wherein said fine-grained metallic coating comprises Co and P and furthermore contains diamond particles.

19. The article according to claim 1 or 2, wherein said fine-grained metallic coating comprises Fe.

20. The article according to claim 1, wherein said fine-grained metallic coating comprises Ni.

21. The article according to claim 1 or 2, wherein said fine-grained metallic coating comprises particulate addition of one or more materials selected from the group consisting of:

(a) metals selected from the group consisting of Ag, Al, Cu, In, Mg, Si, Sn, Pt, Ti, V, W and Zn;

(b) metal oxides selected from the group consisting of Ag₂O, Al₂O₃, SiO₂, SnO₂, TiO₂ and ZnO;

(c) carbides selected from the group consisting of B, Cr, Bi, Si and W carbides; and

(d) carbon materials selected from the group consisting of carbon, carbon nanotubes, diamond, graphite, graphite fibers, ceramic and glass; and

(e) polymer materials selected from the group consisting of PTFE, PVC, PE, PP, ABS and epoxy resin.

22. The article according to claim 1 or 2, wherein said permanent substrate comprises one or more materials selected from the group consisting of metals, metal alloys, glass, ceramics, filled polymeric materials, composites, and carbon-based materials selected from the group consisting of graphite, graphite fibers and carbon nanotubes.

23. The article according to claim 1 or 2, wherein said fine-grained metallic coating has a thickness ranging from 25 microns to 50 mm.

24. The article according to claim 1 or 2, wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN.

25. The article according to claim 1 or 2, wherein said fine-grained metallic coating has a resilience ranging from 0.25 to 25 MPa.

26. The article according to claim 1 or 2, wherein said article comprises at least one intermediate conductive layer between said permanent substrate and said fine-grained metallic coating.

27. The article according to claim 1 or 2, wherein said article is a component or part of an automotive, aerospace, sporting equipment, manufacturing and/or industry application.

28. The article according to claim 1 or 2, wherein said permanent substrate comprises at least one material selected from the group consisting of steel, glass fibers, graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes.

29. The article according to claim 1 or 2, wherein

(a) said fine-grained metallic coating comprises at least one element selected from the group consisting of Al, Ni, Co, Cu and Fe;

and

(b) said permanent substrate comprises at least one metallic material selected from the group consisting of Al, Cu, Co, Ni, Fe, Mo, Pt, Ti and W, with optional alloying additions of Ag, Au, B, Cr, P, Pb, Pd, Rh, Ru, Sn, Zn, and C.

30. The article according to claim 1, wherein said permanent substrate is steel.

31. The article according to any one of claims 1 or 2 wherein said article is selected from the group consisting of a golf club shaft, a golf club face plate, a golf club head, an arrow shaft, a cartridge casing, a baseball bat, a softball bat, a fishing rod, a ski pole, a hiking pole, a mold, a mold component, a tooling part, an automotive part, an aerospace part and a bicycle part.

32. The article according to claim 1 or 2, wherein

(a) said fine-grained metallic coating comprises at least one element selected from the group consisting of Ni, Co, Fe and Zn;

and

(b) said permanent substrate comprises at least one material selected from the group consisting of Al, Fe, steel, carbon, graphite, glass and ceramics.

33. The article according to claim 1 or 2, wherein said article has a tubular structure.

34. The article according to claim 1 or 2, wherein said article is at least 5% lighter than an article of equivalent strength not containing said fine-grained metallic coating.

35. The article according to claim 1 or 2, wherein said fine-grained metallic coating represents more than 5% of the cross sectional area or the total weight of the article.

36. The article according to claim 1 or 2, wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of Al, Ni, Co, Cu, W, P, Fe, Sn, and Zn.

37. The article according to claim 1 or 2 or wherein said article comprises at least one intermediate conductive layer between said fine-grained metallic coating and said permanent substrate.

38. The article according to claim 1 or 2 wherein the ratio of coating thickness to grain size is greater than 25.

39. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Fe and Zn.

40. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Fe and Zn and said permanent substrate is steel.

41. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Fe and Zn and said permanent substrate is a filled polymeric material.

42. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Fe and Zn and said permanent substrate comprises a carbon based material.

43. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Zn.

44. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Zn and said permanent substrate is steel.

45. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Zn and said permanent substrate is a filled polymeric material.

46. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Zn and said permanent substrate comprises a carbon based material.

47. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Sn.

48. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Sn and said permanent substrate is steel.

49. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Sn and said permanent substrate is a filled polymeric material.

50. The article according to claim 1 or 2 wherein said fine-grained metallic coating comprises Cu and Sn and said permanent substrate comprises a carbon based material.