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

• US 7,320,832 B2
• Filed: 12/09/2005
• Issued: 01/22/2008
• 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: McCrea, Jonathan, Tomantschger, Klaus, Panagiotopoulos, Konstantinos, Limoges, Dave, Jeong, Daehyun, Erb, Uwe, Palumbo, Gino, Brooks, Iain
• Primary Examiner(s): McNeil; Jennifer C.
• Assistant Examiner(s): Savage; Jason L.
• Application Number:
  US11/297,805
• Publication Number:
  US 20070281176A1
• Time in Patent Office: 774 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 coefficient of thermal expansion in the range between −

5.0×

10<sup>−

6</sup>K<sup>−

1</sup> and 25×

10<sup>−

6</sup>K<sup>−

1</sup>;

(b) a fine grained metallic coating on the permanent substrate, having an average grain size between 2 and 1,000 nm, a thickness between 25 micron and 5 cm and a coefficient of thermal expansion in the range between −

5.0×

10<sup>−

6</sup>K<sup>−

1</sup> and 25×

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 2% 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.

2. An article according to claim 1 wherein said fine-grained metallic coating is selected from the group of:

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

(ii) an alloy containing at least two elements selected from Al, Cu, Co, Ni, Fe, Mo, Pt, Ti and Zr;

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

(iv) any of (i), (ii) or (iii) where said metallic coating also contains particulate additions in the volume fraction between 0 and 95% by volume.

3. An article according to claim 2, wherein the metallic coating contains particulate addition and said particulate addition is of one or more materials which is a metal selected from the group consisting of Ag, Al, Cu, In, Mg, Si, Sn, Pt, Ti, V, W, Zn;

a metal oxide selected from the group consisting of Ag₂O, Al₂O₃, SiO₂, SnO₂, TiO₂, ZnO;

a carbide of B, Cr, Bi, Si, W;

carbon including carbon nanotubes, diamond, graphite, graphite fibers;

ceramic, glass; and

polymer material including PTFE, PVC, PE, PP, ABS, epoxy resin.

4. An article according to any one of claims 1 to 3 containing a permanent substrate selected from the group of metals, metal alloys, glass, ceramics, filled polymeric materials and composites, carbon based materials selected from the group of graphite, graphite fibers and carbon nanotubes.

5. An article according to claim 1 wherein said fine-grained metallic layer is deposited by electrodeposition, physical vapor deposition (PVD), chemical vapor deposition (CVD) and cold spraying techniques including kinetic metallization.

6. An article according to claim 1 wherein said fine-grained metallic coating has a hardness between 200 and 2,000 VHN and a yield strength of at least 300 MPa.

7. An article according to claim 1 containing an intermediate conductive layer between said metallic material and said substrate.

8. An article according to claim 7 where the intermediate conductive layer comprises a metallic layer constituted of Ag, Ni or Cu or a combination of any two or all of these, and where the intermediate conductive layer is deposited by electroless deposition, sputtering, thermal spraying, chemical vapor deposition, physical vapor deposition or by any two or more of these.

9. An article according to claim 7 where the intermediate conductive layer comprises polymeric material with conductive particulates therein.

10. An article according to claim 9 where the intermediate conductive layer is a conductive paint or a conductive epoxy.

11. An article according to claim 9 where the conductive particulates are composed of or contain Ag, Ni or Cu or graphite or other conductive carbon or a combination of two or more thereof.

12. An article according to claim 1, wherein said article is a component or part of an automotive, aerospace, sporting equipment, manufacturing or industry application.

13. An article according to claim 12 selected from the group consisting of golf clubs, fishing rods, arrows, hockey sticks, baseball/soft ball bats, tennis racquets, lacrosse sticks, ski poles, walking sticks, skate blades, snowboards, bicycle frames and molds.

14. An article according to claim 1, wherein said article has a tubular structure and said fine-grained metallic material extends over at least part of the inner or outer surface of said tubular structure.

15. An article according to claim 14 selected from the group of golf club shaft, arrow shaft, cartridge casing, baseball/softball bat, fishing rod, ski and hiking poles and bicycle parts.

16. An article according to claim 14 wherein said article comprises a substrate made of a carbon-containing material selected from the group of glass fibers, graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes.

17. An article according to claim 14, having a fine-grained metallic coating with a hardness of greater than 500 VHN and a ratio of wall thickness to grain size of greater than 1,000.

18. An article according to claim 14, wherein said article is wire or cable and said fine-grained metal, metal alloy or metal matrix composite coating represents between 5 and 95% of the total weight of said article.

19. An article according to claim 1 having an fine-grained metallic material coating on a substrate containing graphite/carbon fibers embedded in epoxy, wherein the weight of the fine-grained metallic material is between 5 and 95% of the total weight of the article.

20. An article according to claim 1, wherein said fine-grained metallic material is a Ni, Co or Fe based alloy and the substrate contains graphite/carbon fibers embedded in epoxy.

21. An article according to claim 19 or 20, wherein said article is a golf club shaft, arrow shaft, cartridge casing, baseball/softball bat, fishing rod, ski and hiking poles;

a mold, mold component or tooling part;

or an automotive or bicycle part.