Heterogeneous grain-refined metallic materials

Abstract

Articles including anisotropic electrodeposited layers of fine-grained alloys of Co, Cu, Fe, Ni and/or Zn with minor additions of B, O, P and S that provide high strength, ductility and heat-resistance, are disclosed as well as a process for making the articles. Non-metallic additions of ≤2% are required to significantly increase the maximum temperature at which softening and grain-growth occurs. Electrodeposition conditions in a single plating cell are adjusted and/or modulated to vary at least one property in the deposit direction and/or along the length and/or width of the workpiece once, constantly or repeatedly, to form a graded and/or layered electrodeposit. Variable property metallic material deposits containing, at least in part, a fine-grained microstructure and variable property in the deposit direction and optionally multi-dimensionally, provide superior overall mechanical properties and temperature stability. Various methods and electroplating apparatuses and approaches to practice the invention are also provided.

1 . A heterogeneous electrodeposited metallic material comprising:
 (i) a microcrystalline grain structure with an average grain-size in the range of 2 to 1,000 nm;   (ii) at least one metallic element selected from the group consisting of Co, Cu, Fe, Ni and Zn;   (iii) at least 100 ppm P present in its elemental form having an oxidation state of zero;   (iv) at least one additional non-metallic element consisting of O comprising up to 300 ppm per weight of the metallic material;   (v) phosphorous [PO 3 ] 3−  and less than 90 ppm of P is present in the form of [PO 3 ] 3− ;   (vi) optionally at least one additional non-metallic element comprising between 50 ppm and 20,000 ppm per weight of said metallic material selected from the group consisting of B and S;   (vii) particulates in the range of 0 to 95% per volume of said metallic material;   (viii) wherein said metallic material being compositionally graded and/or layered in the deposition direction; and   (ix) wherein the concentration of at least one of the chemical elements and/or the average grain size varies by at least 5% in the deposition direction and/or along a length of said metallic material.   
     
     
         2 . The metallic material of  claim 1 , wherein said metallic material is layered in the deposition direction and comprises at least 25 sublayers. 
     
     
         3 . The metallic material of  claim 2 , wherein said sublayers have a thickness in the range of 25 nm to 250 nm. 
     
     
         4 . The metallic material of  claim 1 , wherein said metallic material contains S, and P and S comprising combined between 50 ppm and 20,000 ppm per weight of said metallic material. 
     
     
         5 . The metallic material of  claim 1 , wherein said metallic material contains at least 100 ppm per weight of S. 
     
     
         6 . The metallic material of  claim 1 , wherein said metallic material contains B. 
     
     
         7 . The metallic material of  claim 1 , wherein the hardness of said metallic material, after heat-treatment for 12 hours at a temperature of 350° C. in an inert atmosphere, retains at least 90% of the as-deposited hardness. 
     
     
         8 . The metallic material of  claim 1 , wherein said metallic material comprises Co or Ni. 
     
     
         9 . The metallic material of  claim 1 , wherein said metallic material comprises Co and Ni. 
     
     
         10 . The metallic material of  claim 1 , wherein said metallic material comprises Fe and at least one selected from the group of Ni and Co. 
     
     
         11 . The metallic material of  claim 1 , wherein said metallic material comprises Cu and at least one selected from the group of Ni and Co. 
     
     
         12 . The metallic material of  claim 1 , wherein said metal material comprises Zn and at least one selected from the group of Ni and Co. 
     
     
         13 . The metallic material of  claim 1 , wherein said metallic material comprises B and/or S which, if present, form alloying agents with said metallic material and are present in the oxidation state of zero. 
     
     
         14 . The metallic material of  claim 1 , wherein said metallic material, as deposited, contains oxygen having an oxidation state of −II and forming a metal oxide MeO x  or a metal oxi-hydroxide MeO x H y , with x and y<1, where Me is the grain-refined electrodeposited metallic element selected from the group consisting of Co, Cu, Fe, Ni and Zn. 
     
     
         15 . An article comprising:
 a heterogeneous electrodeposited metallic material consisting of:   (i) a microcrystalline grain structure with an average grain-size in the range of 2 to 1,000 nm;   (ii) Ni and at least one additional metallic element selected from the group consisting of Co, Cu, Fe and Zn, and each of said metallic elements comprising at least 5% per weight of the metallic alloy material;   (iii) two non-metallic elements comprising P and S, both present in their elementary form, and the combined P and S content is below 2% of the metallic material composition;   (iv) particulates in the range of 0 to 95% per volume;   (v) wherein said heterogeneous electrodeposited metallic material is compositionally graded and/or layered in the deposition direction; and   (vi) wherein the concentration of at least one of the chemical elements varies by at least 5% in the deposition direction.   
     
     
         16 . The article of  claim 15 , wherein said heterogeneous electrodeposited metallic material comprises Co. 
     
     
         17 . The article of  claim 15 , wherein said heterogeneous electrodeposited metallic material comprises Fe. 
     
     
         18 . The article of  claim 15 , wherein said heterogeneous electrodeposited metallic material comprises Cu. 
     
     
         19 . The article of  claim 15 , wherein said heterogeneous electrodeposited metallic material comprises Zn. 
     
     
         20 . The article of  claim 15 , wherein said heterogeneous electrodeposited metallic material is layered in the deposition direction and comprises at least 25 sublayers.