ELECTRODEPOSITED METALLIC-MATERIALS COMPRISING COBALT

• US 20100304182A1
• Filed: 08/27/2009
• Published: 12/02/2010
• Est. Priority Date: 06/02/2009
• Status: Active Grant

• Current Assignee: Integran Technologies Incorporated (Analog Devices, Inc.)
• Original Assignee: Integran Technologies Incorporated (Analog Devices, Inc.)
• Inventors: McCrea, Jonathan, Tomantschger, Klaus, Gonzalez, Francisco, Palumbo, Gino, Facchini, Diana, Uetz, Mike
• Granted Patent: US 8,367,217 B2
• Time in Patent Office: Days
• US Class Current: 428/652
• CPC Class Codes: B32B 15/01 all layers being exclusively metallic making layered metal workpieces by pressure cladding B23K20/22; making coatings with a metallic material characterised by its composition C23C30/00
• CPC Class Codes: B32B 15/013 one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
• CPC Class Codes: B32B 15/017 one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
• CPC Class Codes: C22C 19/07 based on cobalt
• CPC Class Codes: C23C 30/00 Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process C23C26/00, C23C28/00 take precedence
• CPC Class Codes: C25D 15/00 Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
• CPC Class Codes: C25D 3/12 of nickel or cobalt
• CPC Class Codes: C25D 3/562 containing more than 50% by weight of iron or nickel or cobalt
• CPC Class Codes: C25D 5/18 Electroplating using modulated, pulsed or reversing current
• CPC Class Codes: C25D 5/50 by heat-treatment
• CPC Class Codes: C25D 5/617 Crystalline layers
• CPC Class Codes: C25D 5/619 Amorphous 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: C25D 5/67 Electroplating to repair workpiece
• CPC Class Codes: C25D 7/00 Electroplating characterised by the article coated
• CPC Class Codes: C25D 7/04 Tubes; Rings; Hollow bodies
• CPC Class Codes: Y10T 428/12458 having composition, density, or hardness gradient
• CPC Class Codes: Y10T 428/12493 Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
• CPC Class Codes: Y10T 428/12625 Free carbon containing component
• CPC Class Codes: Y10T 428/12729 Group IIA metal-base component
• CPC Class Codes: Y10T 428/1275 : Next to Group VIII or IB metal-base component
• CPC Class Codes: Y10T 428/12778 : Alternative base metals from diverse categories
• CPC Class Codes: Y10T 428/12861 : Group VIII or IB metal-base component
• CPC Class Codes: Y10T 428/12882 : Cu-base component alternative to Ag-, Au-, or Ni-base component
• CPC Class Codes: Y10T 428/1291 : Next to Co-, Cu-, or Ni-base component
• CPC Class Codes: Y10T 428/12937 : Co- or Ni-base component next to Fe-base component
• CPC Class Codes: Y10T 428/12944 : Ni-base component
• CPC Class Codes: Y10T 428/12951 : Fe-base component
• CPC Class Codes: Y10T 428/12972 : Containing 0.01-1.7% carbon [i.e., steel]
• CPC Class Codes: Y10T 428/12979 : Containing more than 10% nonferrous elements [e.g., high alloy, stainless]
• 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 428/24967 : Absolute thicknesses specified
• 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 428/263 : Coating layer not in excess of 5 mils thick or equivalent
• CPC Class Codes: Y10T 428/264 : Up to 3 mils
• CPC Class Codes: Y10T 428/265 : 1 mil or less

Abstract

Free standing articles or articles at least partially coated with substantially porosity free, fine-grained and/or amorphous Co-bearing metallic materials optionally containing solid particulates dispersed therein, are disclosed. The electrodeposited metallic layers and/or patches comprising Co provide, enhance or restore strength, wear and/or lubricity of substrates without reducing the fatigue performance compared to either uncoated or equivalent thickness chromium coated substrate. The fine-grained and/or amorphous metallic coatings comprising Co are particularly suited for articles exposed to thermal cycling, fatigue and other stresses and/or in applications requiring anti-microbial properties.

Claims

1. An article comprising:

(i) a substrate material;

(ii) an electrodeposited substance forming a metallic layer and/or patch on said substrate material or on structure thereon, said metallic layer or patch comprising Co having a microstructure which is fine-grained with an average grain size between 2 and 5,000 nm and/or amorphous, said metallic layer or patch exhibiting a tensile or compressive internal stress in the range of between 2.5 and 30 ksi, and having a thickness between 5 micron and 2.5 mm and a porosity in the range of between 0 and 1.5%;

(iii) with or without at least one intermediate structure between said substrate material and the electrodeposited layer and/or patch comprising Co; and

(IV) said article exhibiting a fatigue life cycle number equivalent to or exceeding the one of either the uncoated substrate material or equivalent thickness chromium coated substrate material when tested at an applied stress of between ⅓ and

⅔

of the yield strength of said uncoated substrate material.

2. The article of claim 1 wherein said ratio between the number of fatigue life cycles of the article with the electrodeposited metallic layer and/or patch comprising Co and either uncoated or equivalent thickness chromium coated substrate is equal to or more than 1.00.

3. The article of claim 1 wherein at least one of said substrate material or said article is exposed to a heat treatment and/or cold deformation.

4. An article according to claim 1 wherein said electrodeposited metallic layer and/or patch comprising Co is selected from the group of:

(i) Co metal with unavoidable impurities;

(ii) alloys of Co with one or more metals selected from the group consisting of Ag, Al, Au, Cr, Cu, Fe, Ni, Mo, Pd, Pt, Rh, Ru, Sn, Ti, W, Zn and Zr,

(iii) Co metal or Co alloys as defined in (ii) further containing at least one element selected from the group consisting of B, C, H, O, P and S;

(iv) any of (i), (ii) or (iii) where said metallic layer and/or patch comprising Co also contains particulate additions in a volume fraction up to 95%.

5. An article according to claim 4, wherein the electrodeposited metallic layer and/or patch comprising Co 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 structure or material selected from the group consisting of carbon nanotubes, diamond, graphite, graphite fibers;

ceramic, glass; and

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

6. An article according to any one of claims 1 to 5, wherein the electrodeposited metallic layer and/or patch comprising Co has a hardness in the range of between 200 and 3,000 VHN.

7. An article according to claim 1 wherein the electrodeposited metallic layer and/or patch comprising Co represents between 1 and 95% of the total weight of the article.

8. An article according to claim 1 containing an intermediate structure between said electrodeposited metallic layer and/or patch comprising Co and said substrate, which is electricity conductive.

9. An article according to claim 8 where the intermediate conductive structure is a metallic layer comprising at least one metal selected from the group consisting of Ag, Co, Ni, Cu or a carbon based material.

10. An article according to claim 1 wherein said article exhibits no delamination after said article has been exposed to at least one temperature cycle according to ASTM B553-71 service condition 1, 2, 3 or 4.

11. An article according to any one of claims 1-5, wherein said article is a component or part of an automotive, aerospace, sporting equipment, manufacturing or industry application.

12. An article according to claim 1 selected from the group consisting of landing gear, actuators, bearings, gun components, hydraulics, journals, valves, connectors, engines, compressors, cutting tools, drills, augers, rollers, liquid conduits, fuel rails, spoilers, grill-guards, running boards, brake, transmission, clutch, steering and suspension parts, brackets and pedals, muffler components, wheels, vehicle frames, fluid pumps, housings and tank components such as oil, transmission or other fluid pans, gas tanks, electrical and engine covers and turbocharger components, molds, plane fuselage, wings, rotors, propellers, medical implants, surgical tools, molds and molding tools, golf club heads, hockey sticks, baseball/softball bats, tennis racquets, lacrosse sticks, ski poles, walking sticks, skate blades, snowboards, bicycle frames, cell phones, personal digital assistants (PDAs) devices, walkmen, discmen, MP3 players, digital cameras and recording devices.

13. An article according to claim 1, wherein said article has a tubular structure and said electrodeposited metallic layer and/or patch comprising Co extends over at least part of the inner or outer surface of said tubular structure.

14. An article according to claim 13 selected from the group of gun barrels, drive shafts, arrow shafts, golf shafts, tubes, pipes, rods, fishing rods, hydraulic rods and tubes, cartridge casing, baseball/softball bats, hockey sticks, wires, cables, fishing, skiing and hiking poles.

15. The article according to claim 1, wherein said electrodeposited metallic layer and/or patch comprising Co contains Co in the range of about 75 to 100% per weight, W in the range of 0 to 25% per weight, P in the range of about 0 to 25% per weight and boron in the range of between 0 and 5% per weight.

16. The article according to claim 1, wherein said electrodeposited metallic layer and/or patch comprising Co has a ductility in the range of 0.1 to 35%

17. An article according to claim 1, wherein said substrate material is constituted of a substance from the group consisting of Al, Mg, Co, Cr, Cu, brass, bronze, Fe, steel, Ni, Sn, Ti, W, Zn, carbon, graphite, and graphite composites.

18. The article according to claim 1, wherein said substrate material is constituted of a substance selected from the group consisting of ferrous alloys, nickel alloys, copper alloys, and aluminum alloys.

19. An electrodeposited free-standing layer or a coating comprising Co having a microstructure which is fine-grained with an average grain size between 2 and 5,000 nm and/or is amorphous, the Co-comprising layer or coating, having a thickness between 5 micron and 2.5 mm, a porosity between 0 and 1.5% and wherein said electrodeposited Co-comprising material after 24 hrs at 37°

C. displays a “

radius of no growth”

on the zone inhibition test for salmonella or listeria ranging from range of 0.5 mm to 50 mm.

20. The free-standing layer or a coating comprising Co according to claim 19 which, apart from unavoidable impurities, is free of Ni, Cr, Pb, Sb and As.

21. The free-standing layer or a coating comprising Co according to claim 19 which, apart from unavoidable impurities, is free of Ag, Cu, Sn, Zn and noble metals.

22. The free-standing layer or coating comprising Co, according to claim 21 which is

(i) Co metal with unavoidable impurities,

(ii) alloy of Co with one or more metals selected from the group consisting of Al, Fe, Mo, Ti, W and Zr;

(iii) Co metal or Co alloy as defined in (ii) also containing at least one element selected from the group consisting of B C, H, O, P and S;

(iv) any of (i), (ii) or (iii), where said layer or coating comprising Co also contains particulate additions in a volume fraction up to 95%.

23. The free-standing layer or coating comprising Co according to claim 21 which contains particulate additions of one or more metals selected from the group consisting of Al, In, Mg, Si, Ti, V and W, a metal oxide, a carbon structure or material, ceramic, glass, and/or polymer material.

24. A method for forming a metal-coated article comprising the steps of

(i) providing a substrate material,

(ii) optionally applying one or more electricity conductive intermediate structures or layers to a surface of the substrate material,

(iii) applying one or more fine-grained and or amorphous Co-containing coatings to part or all of said surface by DC or pulse electrodeposition.