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

Abstract

Fine-grained (average grain size 1 nm to 1,000 nm) metallic coatings optionally containing solid particulates dispersed therein. 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 CTE of the fine-grained metallic coating is matched 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.

1 . An article comprising
 (a) a permanent substrate which at room temperature has a minimum coefficient of thermal expansion of 0×10 −6 K −1 ;   (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 1 and 1,000 nm, and a minimum coefficient of thermal expansion of 0×10 −6 K −1 ; and   (c) said article exhibiting no delamination, blistering or cracking and the displacement of the coating relative to the underlying substrate is less than 2% after said article has been exposed to at least 5 temperature cycles according to ASTM B553-71 service condition 1, 2, 3 or 4; wherein   said fine-grained metallic coating has a ductility in the range of 1 to 20%.   
     
     
         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 multi-layer laminates comprise alternating layers of fine-grained metallic coatings. 
     
     
         4 . The article according to  claim 1 , wherein said fine-grained metallic coating has an average grain size between 5 and 500 nm. 
     
     
         5 . The article according to  claim 1 , wherein said fine-grained metallic coating has an average grain size between 2 and 100 nm and a modulus of resilience of at least 0.25 MPa. 
     
     
         6 . The article according to  claim 1 , wherein said article comprises at least one intermediate layer between said permanent substrate and said fine-grained metallic coating. 
     
     
         7 . The article according to  claim 1 , wherein the ratio of coating thickness to grain size is greater than 25. 
     
     
         8 . The article according to  claim 1 , wherein said article has a tubular structure. 
     
     
         9 . The article according to  claim 1 , wherein said article is at least 5% lighter than an article of equivalent strength not containing said fine-grained metallic coating. 
     
     
         10 . The article according to  claim 1 , wherein said fine-grained metallic coating represents more than 5% of the cross sectional area or the total weight of the article. 
     
     
         11 . The article according to  claim 1 , 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.   
     
     
         12 . The article according to  claim 1 , 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 Ag 2 O, Al 2 O 3 , SiO 2 , SnO 2 , TiO 2  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.   
     
     
         13 . The article according to  claim 1 , 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.   
     
     
         14 . The article according to  claim 1 , 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. 
     
     
         15 . The article according to  claim 1 , wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         16 . The article according to  claim 1 , wherein said fine-grained metallic coating comprises P and at least one element selected from the group consisting of Ni, Co and Fe. 
     
     
         17 . The article according to  claim 1 , wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe and furthermore contains diamond particles. 
     
     
         18 . The article according to  claim 1 , wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe and furthermore comprises between 1 and 50% per volume of at least one carbide selected from the group consisting of B, Cr, Bi, Si and W. 
     
     
         19 . The article according to  claim 1 , wherein said fine-grained metallic coating comprises Ni and/or Co and further comprises at least one more element selected from the group consisting of Cu, Fe, Mo, W, Zn, P, B and C. 
     
     
         20 . The article according to  claim 1 , wherein said fine-grained metallic coating comprising Ni and W. 
     
     
         21 . The article according to  claim 1 , 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. 
     
     
         22 . The article according to  claim 1 , 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. 
     
     
         23 . The article according to  claim 1 , wherein said permanent substrate comprises Al. 
     
     
         24 . The article according to  claim 23 , which is selected from the group consisting of golf club shaft, golf club head and golf club face plate. 
     
     
         25 . The article according to  claim 23 , which is a baseball bat. 
     
     
         26 . The article according to  claim 23 , which is a skiing or hiking pole. 
     
     
         27 . The article according to  claim 23 , which is a bicycle part. 
     
     
         28 . The article according to  claim 23 , which is an aerospace part. 
     
     
         29 . The article according to  claim 23 , which has a tubular structure. 
     
     
         30 . The article according to  claim 23 , wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         31 . The article according to  claim 23 , wherein said article comprises at least one layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         32 . The article according to  claim 23 , wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN and/or a resilience ranging from 0.25 to 25 MPa. 
     
     
         33 . The article according to  claim 24 , wherein said fine-grained coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         34 . The article according to  claim 24 , wherein said article comprises at least one layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         35 . The article according to  claim 24 , wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN and/or a resilience ranging from 0.25 to 25 MPa. 
     
     
         36 . The article according to  claim 25 , wherein said fine-grained coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         37 . The article according to  claim 25 , wherein said article comprises at least one layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         38 . The article according to  claim 25 , wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN and/or a resilience ranging from 0.25 to 25 MPa. 
     
     
         39 . The article according to  claim 26 , wherein said fine-grained coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         40 . The article according to  claim 26 , wherein said article comprises at least one layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         41 . The article according to  claim 26 , wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN and/or a resilience ranging from 0.25 to 25 MPa. 
     
     
         42 . The article according to  claim 27 , wherein said fine-grained coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         43 . The article according to  claim 27 , wherein said article comprises at least one layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         44 . The article according to  claim 27 , wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN and/or a resilience ranging from 0.25 to 25 MPa. 
     
     
         45 . The article according to  claim 28 , wherein said fine-grained coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         46 . The article according to  claim 28 , wherein said article comprises at least one layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         47 . The article according to  claim 28 , wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN and/or a resilience ranging from 0.25 to 25 MPa. 
     
     
         48 . The article according to  claim 29 , wherein said fine-grained coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         49 . The article according to  claim 29 , wherein said article comprises at least one layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         50 . The article according to  claim 29 , wherein said fine-grained metallic coating has a hardness ranging from 200 to 2,000 VHN and/or a resilience ranging from 0.25 to 25 MPa. 
     
     
         51 . The article according to  claim 1 , wherein said permanent substrate is steel. 
     
     
         52 . The article according to  claim 51 , 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. 
     
     
         53 . The article according to  claim 51 , wherein the fine-grained metallic coating comprises Ni and W. 
     
     
         54 . The article according to  claim 51 , wherein said article comprises at least one intermediate layer between said fine-grained metallic coating and the steel substrate. 
     
     
         55 . The article according to  claim 51  wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe and furthermore contains diamond particles. 
     
     
         56 . The article according to  claim 51 , wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe and furthermore comprises between 1 and 50% per volume of at least one carbide selected from the group consisting of B, Cr, Bi, Si and W. 
     
     
         57 . The article according to  claim 51 , wherein said fine-grained metallic coating comprises Ni and/or Co and optionally furthermore comprises at least one more element selected from the group consisting of Cu, Fe, Mo, W, Zn, P, B and C. 
     
     
         58 . The article according to  claim 2 , wherein said permanent substrate is steel. 
     
     
         59 . The article according to  claim 58 , wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe and furthermore contains diamond particles. 
     
     
         60 . The article according to  claim 1 , wherein said permanent substrate comprises at least one material selected from the group consisting of glass fibers, graphite, graphite fibers, carbon, carbon fibers and carbon nanotubes. 
     
     
         61 . The article according to  claim 60  wherein said article comprises at least one intermediate layer between said fine-grained metallic coating and said permanent substrate. 
     
     
         62 . The article according to  claim 60 , wherein said article is a bicycle part. 
     
     
         63 . The article according to  claim 60  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. 
     
     
         64 . The article according to  claim 60  wherein said fine-grained metallic coating comprises at least one element selected from the group consisting of P, Ni, Co, Cu and Fe. 
     
     
         65 . The article according to  claim 63 , wherein said fine-grained metallic coating comprises an element selected from the group consisting of P, Ni, Co, Cu and Fe.