Golf club and other structures, and novel methods for making such structures

• US 6,723,279 B1
• Filed: 03/15/1999
• Issued: 04/20/2004
• Est. Priority Date: 03/15/1999
• Status: Expired due to Fees

• Current Assignee: Materials and Electrochemical Research Corporation
• Original Assignee: Materials and Electrochemical Research Corporation
• Inventors: Newell, Kenneth J., Pickard, Sion M., Kelly, William B., Withers, James C., Loutfy, Raouf O.
• Primary Examiner(s): Jenkins, Daniel J.
• Application Number:
  US09/268,251
• Time in Patent Office: 1,863 Days
• Field of Search: 419/10, 419/12, 419/14, 419/27
• US Class Current: 419/27
• 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 53/04 Heads
• CPC Class Codes: A63B 53/0433 with special sole configurations
• CPC Class Codes: A63B 53/0466 wood-type
• CPC Class Codes: A63B 53/047 iron-type
• CPC Class Codes: A63B 53/10 Non-metallic shafts
• CPC Class Codes: A63B 53/12 Metallic shafts
• CPC Class Codes: B22F 1/052 characterised by a mixture of particles of different sizes or by the particle size distribution
• CPC Class Codes: B22F 2207/03 of the metallic binder phase in cermets
• CPC Class Codes: B22F 2999/00 Aspects linked to processes or compositions used in powder metallurgy
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C22C 1/1021 the preform being ceramic
• CPC Class Codes: C22C 1/1036 starting from a melt
• CPC Class Codes: C22C 1/1057 Reactive infiltration
• CPC Class Codes: C22C 1/1073 Infiltration or casting under mechanical pressure, e.g. squeeze casting
• CPC Class Codes: C22C 2026/001 Fullerenes
• CPC Class Codes: C22C 2204/00 End product comprising different layers, coatings or parts of cermet
• CPC Class Codes: C22C 47/04 by coating, e.g. with a protective or activated covering
• CPC Class Codes: C22C 47/06 by forming the fibres or filaments into a preformed structure, e.g. using a temporary binder to form a mat-like element
• CPC Class Codes: C22C 47/10 : Infiltration in the presence of a reactive atmosphere; Reactive infiltration
• CPC Class Codes: C22C 47/12 : Infiltration or casting under mechanical pressure

Abstract

Golf club structures, including club heads and shafts, composed of composites comprised of a matrix of metal, such as an aluminum alloy, or a plastic material and a fiber such as graphite or a ceramic, which may be whiskerized, and which may also be selectively weighted as in the toe and heel of a club head, with heavy particles such as tungsten metal. The club structure may also be surface hardened by applying a coating of fullerenes to a metal club structure and heat treating it to produce a hard coating of metal carbide, preferably by coating a titanium golf club structure with fullerenes and heat treating the coated structure to produce a titanium carbide surface.

Claims

1. The method of making a golf club structure that comprises preparing a preform array comprising a ceramic fiber, placing said preform in a mold configured to form a golf club structure, and squeeze casting said preform with molten superheated aluminum to cause full penetration of said molten aluminum into said preform and form a fiber reinforced metal composite golf club structure.

2. The method of claim 1 wherein the preform array includes PBO fiber in a mixture with said ceramic fiber.

3. The method of claim 1 wherein the ceramic fiber preform is impregnated with titanium powder particles prior to the squeeze casting step.

4. The method of claim 3 wherein the ceramic fiber comprises silicon carbide, whereby the resulting squeeze cast golf club structure is formed of a composite comprising a silicon carbide fiber reinforced titanium aluminide matrix.

5. The method of claim 3 wherein the preform is impregnated with titanium by vacuum impregnation of the fiber preform with a slurry of titanium powder in an alcohol solvent, followed by evaporation of the solvent.

9. The method of claim 1 wherein the ceramic fiber of the preform array is TiB₂ powder, wherein the TiB₂ powder is mixed with titanium metal powder, wherein the mixture of the TiB₂ powder is die pressed and pre heated to about 600°

C. in an inert non-oxidizing atmosphere prior to the step of squeeze casting the preform with molten superheated aluminum to cause the titanium powder to react with the molten aluminum to form a titanium aluminide matrix containing titanium boride powder, said matrix being molded to form the golf club structure.

10. The method of claims 1 wherein the ceramic fiber of the preform array is TiB₂ powder, wherein the TiB₂ powder is mixed with titanium metal powder comprised of metal particles in the 1-10 micron size range, wherein the squeeze casting step is carried out, without preheating, using molten superheated aluminum to form a titanium aluminide matrix golf club structure containing titanium diboride powder.

11. The method of claim 1 wherein the ceramic fiber of the preform is SiC powder comprised of particles of less than one micron in diameter suspended in deionized water and pressed in a die mold configured to form the golf club structure in order to force out the water from the resulting preform which is then subjected to the squeeze casting step using molten superheated aluminum.

12. The method of claim 1 wherein the ceramic fiber of the preform is SiC powder comprised of particles size graded from nanoparticle size to course grid particle size, wherein the golf club structure is a golf club head having a front surface defining the striking areas and a rear surface that does not strike the ball, wherein the ceramic particles are dispersed in the preform in a size graduated manner with a higher density of the smaller particles toward the front surface and lower density of smaller particles toward the rear surface and, conversely, with a higher density of the larger particles toward the rear surface and lower density of the larger particles toward the front surface, whereby the squeeze casting step results in an aluminum metal matrix golf club head structure having a higher density of smaller diameter SiC particles dispersed toward the front striking surface and a higher density of larger diameter SiC particles dispersed toward the rear non striking surface.

13. The method of claim 12 wherein powdered nickel particles are mixed with the size graded SiC powder particles forming the preform, whereby the molten aluminum squeeze casting step results in the production of a nickel aluminide matrix golf club head with the size graded SiC particles dispersed therein.

6. The method of making a golf club structure that comprises placing a relatively porous preform in a squeeze casting die configured to form the golf club structure, subjecting the mold to heat to bring it to a temperature above room temperature but no higher than the melting point temperature of a selected matrix metal to be introduced into the mold, subjecting a quantity of the selected matrix metal to sufficient heat to bring its temperature above its melting point to its superheat temperature point, and introducing the superheated matrix metal into the mold under sufficient pressure to cause it to fully penetrate the porous preform and to rapidly solidify.

7. The method of claim 6 wherein the preform is comprised essentially of one or more of metal, ceramic, carbon or plastic.

8. The method of claim 6 wherein the matrix metal is comprised of one or more of magnesium, aluminum, copper, nickel or iron metal or a complex alloy of one or more of these metals.

14. The method of making a golf club structure that comprises preparing a component preform of such structure by pressing a quantity of tungsten metal particles in a first die mold configured to form a preform of such component, placing said preform in a selected region of a second die mold configured to form the golf club structure together with a quantity of ceramic particles that are less dense than the tungsten particles to form a hybrid preform in said second die mold comprising the tungsten component preform and the ceramic particles and squeeze casting said hybrid preforms in the second die mold with a molten superheated metal matrix material to produce a composite molded golf club structure that is selectively weighted as determined by the placement of the tungsten component preform in the mold employed to form said golf club structure.

15. The method of claim 14 herein the second die mold is configured to form a golf club head structure, the component preform is configured by the first mold to conform to a selected region of the second die mold where it is desired to provide greater weight in the corresponding region of the molded golf club head.

16. The method of claim 14 wherein the ceramic particles are comprised essentially of SiC.

17. The method of claim 15 wherein the ceramic particles are comprised essentially of SiC.

18. The method of claim 15 wherein the tungsten metal component preform is configured to conform to the toe and head region of the molded golf club head and is placed in the corresponding region of the second mold.

19. The method of claim 17 wherein the tungsten metal component preform is configured to conform to the toe and head region of the molded golf club head and is placed in the corresponding region of the second mold.

20. The method of claim 19 wherein a second component preform corresponding to a second selected region of the second mold is prepared by pressing another quantity of tungsten metal particles in a mold configured to form such second component preform, and wherein the second component preform is placed in the second selected region of the second mold prior to the squeeze casting step.

33. A golf club structure produced by the method of claim 14.

34. A golf club structure as defined in claim 33 wherein the golf club structure comprises:

a composite formed of tungsten metal particles and a ceramic phase in a metal matrix comprised primarily of aluminum.

35. A golf club structure as defined in claim 34 wherein the ceramic phase is comprised essentially of SiC.

21. The method of making a golf club head structure that comprises:

selectively placing quantities of tungsten metal powder in each of the toe, sole and heel regions of a mold configured to form a golf club head, placing a powder mixture of ceramic SiC particles and diamond particles in the remaining space of said mold, pressing the contents of the mold to produce a combined loading of greater than 50% by volume, thereby producing a hybrid powder preform of the golf club head, squeeze casting the hybrid powder preform with molten superheated aluminum to produce a composite club head that is selectively weighted in the toe, sole and heel and having a hard club head face comprised of both SiC and diamond.

36. A golf club structure produced by the method of claim 21.

22. A method of making a golf club structure that comprises:

forming a relatively porous ceramic preform shaped to form the golf club structure, said ceramic preform being formed essentially of TiB₂ powder that is incorporated in a slurry and cast in a mold configured to form the golf club structure and dried to produce a green body structure that is subjected to heat under appropriate temperatures and atmosphere conditions to sinter the green body structure and produce a porous sintered TiB₂ body having the desired golf club structure shape, subjecting the porous sintered TiB₂ structure to infiltration with matrix metal by a squeeze casting process using molten superheated matrix metal to produce the final golf club structure formed of a composite comprising a continuous phase of TiB₂and a continuous phase of matrix metal.

23. The method of claim 22 wherein the ceramic preform is prepared by dispersing the TiB₂ powder in an organic solvent, mixing a binder with a plasticizer and adding this mixture to the TiB₂ dispersion to form the slurry that is cast in the mold to form the green body structure that is used to produce the porous sintered TiB₂ body.

24. The method of claim 22 wherein the matrix metal is a stainless steel alloy.

25. The method of claim 22 wherein the matrix metal is comprised primarily of aluminum.

26. The method of claim 22 wherein the golf club structure is a club head.

27. The method of claim 24 wherein the golf club structure is a club head.

28. The method of claim 25 wherein the golf club structure is a club head.

37. A golf club structure formed by the method of claim 22.

38. A golf club structure as defined in claim 37 wherein the golf club structure comprises:

a composite formed of a continuous phase of TiB₂ and a continuous phase of metal that is essentially stainless steel alloy.

29. The method of making a golf club structure comprising a club shaft that comprises:

assembling a bundle of hollow glass fiber, steel capillary tubes and graphite fibers, squeeze casting the bundle with molten superheated aluminum in a mold configured to form the golf club structure to produce a hybrid composite tube configured as a golf club shaft.

30. The method of making a golf club structure that comprises laying up a quantity of whiskerized graphite fibers to provide a preform in a mold configured to form the golf club structure, infiltrating the whiskerized graphite fibers with matrix metal by squeeze casting with molten superheated aluminum in the mold to cause full penetration of said molten aluminum into said preform and produce aluminum matrix composite golf club structure.

31. The method of claim 30 wherein the mold is configured to produce a golf shaft structure.

32. The method of making a golf club structure that comprises:

preparing a preform comprising a mixture of buckytubes containing single and multiwalled fullerenes with soot that also contains other fullerenes, placing the preform in a mold configured to form the golf club structure, and introducing molten superheated aluminum into the mold with the preform and squeeze casting the contents of the mold to produce a composite golf club structure.

39. The method of making a composite structure that comprises the steps of:

forming a fibrous preform of said structure from a naturally occurring starting product or a product derived therefrom that contains one or more of a cellulose, semi cellulose or lignin and which, upon pyrolization, forms a carbonaceous char, subjecting said fibrous preform to heat under non oxidizing pyrolyzing condition to form a porous char of said preform, and infiltrating said porous char with a matrix metal by a squeeze casting process using molten superheated matrix metal to cause full penetration of said molten matrix metal into said porous char.

40. The method of claim 39 wherein the starting product is wood.

41. The method of claim 40 wherein the starting product is laminated wood.

42. The method of claim 39 wherein the starting product is paper.

43. The method of claim 42 wherein the paper is disposed in layers alternately with layers of carbon fabric and subjected to heat and pressure in a die to form the preform prior to subjecting it to the pyrolysis step.

44. The method of claim 40 wherein the infiltration step comprises infiltration of the porous char by molten superheated aluminum.

45. The method of claim 44 wherein the infiltration is carried out in two steps, first by placing the porous char in a metal die and introducing molten superheated aluminum into the porous char under pressure, then by moving the aluminum impregnated char from the die and further infiltrating it with molten aluminum.

46. The method of claim 40 wherein the infiltration step comprises placing the porous char in a vacuum chamber containing a suspension of isopropyl alcohol and silicon carbide with diamond particles to selectively impregnate a portion of the porous char with said particles, evaporating the isopropyl alcohol and infiltrating the particle impregnated char with molten superheated aluminum by squeeze casting in a heated die mold.

47. The method of claim 46 wherein the composite structure is a golf club, and the portion of the structure impregnated with particles is the face and sole of the club structure.

48. The method of claim 40 wherein the infiltration step comprises infiltration of the porous char by squeeze casting with molten superheated bronze.

49. The med of claim 39 wherein the infiltration step comprises squeeze casting with molten superheated aluminum.

50. The method of claim 42 wherein the infiltration step comprises squeeze casting with molten superheated aluminum.

51. The method of claim 42 wherein the paper starting product is shredded and soaked with water and water-soluable glue and molded under heat and pressure to form a preform in the shape of an engine piston and wherein the pyrolyzed char preform is infiltrated with molten superheated magnesium by squeeze casting to produce a composite carbon fiber reinforced magnesium piston.

52. The method of claim 39 wherein the starting product is comprised of alternate layers of shredded paper and carbon fabric that is cured and die formed under heat and pressure prior to the pyrolysis step and wherein the preformed pyrolyzed char is infiltrated with molten superheated aluminum by squeeze casting.

53. The method of claim 39 wherein the starting product is comprised of softened paper and carbon fibers and wherein the infiltration step involves infiltration with molten superheated magnesium by squeeze casting.

54. The method of claim 39 wherein the starting product is comprised of cotton.

55. The method of claim 39 wherein the starting product is comprised of wool.

56. The method of claim 53 wherein the infiltration step involved infiltration with molten superheated aluminum by squeeze casting.

57. The method of claim 56 wherein the porous char is infiltrated with particles of silicon carbide and diamond prior to the step of infiltrating it with molten superheated aluminum.

58. The method of claim 56 wherein the porous char is converted to silicon carbide by chemical vapor reaction processing prior to the step of infiltrating it with molten superheated aluminum.