Sporting goods article

Abstract

The fine-grained and/or amorphous metallic coatings are particularly suited for strong and lightweight sporting goods exposed to thermal cycling although the coefficient of linear thermal expansion (CLTE) of the metallic layer and the substrate are mismatched.

1 . A sporting goods article comprising:
 (i) a polymeric material which at room temperature has a coefficient of linear thermal expansion in the range between 30×10 −6  K −1  and 250×10 −6  K −1  in at least one direction; and   (ii) a metallic material having a microstructure which is fine-grained with an average grain size between 2 and 500 nm and/or an amorphous microstructure, the metallic material being in the form of a metallic layer having a thickness between 10 microns and 500 microns and a coefficient of linear thermal expansion at room temperature in all directions in the range between −5.0×10 −6  K −1  and 25×10 −6  K −1 ;   (iii) with at least one intermediate layer between the polymeric material and the metallic material;   (iv) an interface between the polymeric material and one intermediate layer and an interface between one intermediate layer and the metallic material;   (v) anchoring structures at said interfaces comprising recesses and/or protrusions to increase the interface area and provide enhanced physical bond between adjacent layers;   (vi) said sporting goods article exhibiting a pull-off strength between the polymeric material and the metallic material exceeding 200 psi as determined by ASTM D4541-02 Method A-E; and   (vii) said sporting goods article or portions thereof containing said metallic material having a yield strength and/or ultimate tensile strength of between 10 and 7,500 MPa and an elastic limit between 0.5 and 30%.   
     
     
         2 . The sports article according to  claim 1  exhibiting no delamination after said sporting goods article has been exposed to at least one temperature cycle according to ASTM B553-71 service condition 1, 2, 3 or 4. 
     
     
         3 . The sporting goods article according to  claim 1  wherein the surface roughness of the polymeric material and/or the metallic material at any of said interfaces is in the range of Ra=1 micron and Ra=500 microns. 
     
     
         4 . The sporting goods article according to  claim 1  wherein said metallic material comprises at least one metal selected from the group consisting of Al, Co, Cr, Cu, Fe, Ni, Mo, Sn, Ti, W, and Zn. 
     
     
         5 . The sporting goods article according to  claim 1 , wherein said polymeric material comprises at least one material selected from the group consisting of epoxy resins, phenolic resins, polyester resins, urea resins, melamine resins, and thermoplastic polymers. 
     
     
         6 . The sporting goods article according to  claim 1  wherein said metallic material represents between 5 and 95% of the total weight of the sporting goods article. 
     
     
         7 . The sporting goods article according to  claim 1 , wherein at least one intermediate layer comprises a polymeric material. 
     
     
         8 . The sporting goods article according to  claim 7 , wherein said at least one polymeric intermediate layer is an adhesive layer. 
     
     
         9 . The sporting goods article according to  claim 7 , wherein said at least one polymeric intermediate layer comprises an elastomer. 
     
     
         10 . The sporting goods article according to  claim 7 , wherein said at least one polymeric intermediate layer contains epoxy. 
     
     
         11 . The sporting goods article according to  claim 1  comprising at least one intermediate layer which is conductive between said metallic material and said polymeric material. 
     
     
         12 . The sporting goods article according to  claim 11 , wherein said at least one conductive intermediate layer comprises at least one metal selected from the group consisting of Ag, Ni, Co and Cu. 
     
     
         13 . The sporting goods article according to  claim 1 , wherein said sporting goods article is selected from the group consisting of golf shafts, heads and faceplates, lacrosse sticks, hockey sticks, arrows, fishing poles, skiing and hiking pole shafts, skis and snowboards as well as their components including bindings, racquets for tennis, squash, and badminton, baseball bats and bicycle parts. 
     
     
         14 . The sporting goods article according to  claim 1 , wherein said fine-grained and/or amorphous metallic material extends over at least part of the inner or outer surface of said polymeric material. 
     
     
         15 . The sporting goods article according to  claim 14  which is a hockey stick, and comprises a polymeric substrate containing glass fibers and/or a carbon-containing material selected from the group consisting of graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes. 
     
     
         16 . The hockey stick of  claim 15 , wherein said hockey stick contains at least one intermediate layer between the polymeric material and the metallic material which is electrically conductive and comprises at least one material selected from the group consisting of Cu, Ni, Co, Ag, and carbon and/or at least one adhesive layer. 
     
     
         17 . A hockey stick comprising:
 (i) a polymeric material which at room temperature has a coefficient of linear thermal expansion in the range between 30×10 −6  K −1  and 250×10 −6  K −1  in at least one direction and containing at least one material selected from the group consisting of glass fibers, graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes; and   (ii) a metallic material containing at least one metal selected from the group consisting of Cu, Co, Ni and Fe having a microstructure which is fine-grained with an average grain size between 2 and 500 nm and/or an amorphous microstructure, the metallic material being in the form of a metallic layer having a thickness between 10 microns and 500 microns and a coefficient of linear thermal expansion at room temperature in all directions in the range between −5.0×10 −6  K −1  and 25×10 −6  K −1 ;   (iii) with at least one intermediate layer comprising a polymer and/or at least one intermediate layer which is electrically conductive comprising at least one material selected from the group consisting of Cu, Ni, Co, Ag, and carbon between the polymeric material and the metallic material;   (iv) an interface between the polymeric material and an intermediate layer and an interface between an intermediate layer and the metallic material;   (v) anchoring structures at said interfaces comprising recesses and/or protrusions to increase the interface area and provide enhanced physical bond between adjacent layers; and   (vi) said hockey stick exhibiting a pull-off strength between the polymeric material and the metallic material exceeding 200 psi as determined by ASTM D4541-02 Method A-E.   
     
     
         18 . The hockey stick of  claim 17 , wherein the surface roughness of the polymeric material and/or the metallic material at any of said interfaces is in the range of Ra=1 micron and Ra=50 microns. 
     
     
         19 . The hockey stick according to  claim 17 , wherein said metallic material represents between 5 and 95% of the total weight of the hockey stick. 
     
     
         20 . The hockey stick according to  claim 17  exhibiting 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.