Metallic Structures with Variable Properties

Abstract

Variable property deposit, at least partially of fine-grained metallic material, optionally containing solid particulates dispersed therein, is disclosed. The electrodeposition conditions in a single plating cell are suitably adjusted to once or repeatedly vary at least one property in the deposit direction. In one embodiment denoted multidimension grading, property variation along the length and/or width of the deposit is also provided. Variable property metallic material deposits containing at least in part a fine-grained microstructure and variable property in the deposit direction and optionally multidimensionally, provide superior overall mechanical properties compared to monolithic fine-grained (average grain size: >20 micron) or entirely amorphous metallic material deposits.

1 . A method of preparing a variable property metallic deposit, comprising the steps of electrodepositing a metallic material from an aqueous electrolyte bath in a single electrolytic cell having at least one anode and at least one cathode with electrodepositing parameters being average current density ranging from 5 to 10,000 mA/cm 2 , forward pulse on time ranging from 0.1 to 500 ms, pulse off time ranging from 0 to 10,000 ms, reverse pulse on time ranging from 0 to 500 ms, peak forward current density ranging from 5 to 10,000 mA/cm 2 ; peak reverse current density ranging from 5 to 20,000 mA/cm 2 ; frequency ranging from 0 to 1,000 Hz; a duty cycle ranging from 5 to 100%; bath temperature ranging from 0 to 100° C.; working electrode rotation speed ranging from 0 to 1,000 rpm; when two or more soluble anodes of different compositions are used, average current fraction in each anode ranging from 5 to 95%; bath agitation rate ranging from 1 to 6,000 ml/(min/cm 2 ); bath flow direction at cathode ranging from incident {perpendicular) to tangential; shielding anode by covering between 0-95% of the geometrical anode surface area; and bath electrochemically inert particulate content ranging from 0 to 70% by volume; and modulating at least one of these parameters during the electrodepositing to cause variation in a deposit property by more than 10% to vary at least one property selected from the group consisting of grain size, hardness, yield strength, Young's modulus, resilience, elastic limit, ductility, internal or residual deposit stress, stiffness, chemical composition, coefficient of thermal expansion, coefficient of friction, electrical conductivity, magnetic coercive force, thickness; and in the case of electrodeposit of metal matrix composites, volume particulate fraction particulate particle size, particulate shape and/or particulate chemistry; and provide a deposit thickness ranging from 20 microns to 5 cm having a fine-grained microstructure with an average grain size ranging from 2 nm to 10,000 nm throughout 1.5 nm to 5 cm of said thickness. 
     
     
         2 . The method of  claim 1  where at least two of the electrodeposition parameters are varied to cause at least two of said properties to vary by more than ten percent. 
     
     
         3 . A method of  claim 1  wherein said deposit thickness furthermore contains coarse-grained and/or and amorphous sections. 
     
     
         4 . The method according to  claim 1  wherein the metallic material is a metal selected from the group consisting of Ag, Au, Cu, Co, Cr, Mo, Ni, Sn, Fe, Pd, Pb, Pt, Rh, Ru and Zn. 
     
     
         5 . The method according to  claim 1  wherein the metallic materials an alloy of one or more elements selected from the group consisting of Ag, Au, Cu, Co, Cr, Mo, Ni, Sn, Fe, Pd, Pt, Rh, Ru, and Zn and optionally one or more elements selected from the group consisting of B, P, C, Mo, S and W; wherein a binary alloy in which an element is Ni, Fe, or Co, the other element is not W, Mo or P; and wherein in a binary allow in which an element is Ni, the other element is not Fe; and wherein in a binary alloy in which one element is Co, the other element is not Zn; and wherein in a binary alloy in which one element is Cu, the other element is not Ag; and wherein in a binary alloy in which one element is Cr, the other element is not P; and wherein the ternary allows Ni—W-B and Co—Ni—P are excluded. 
     
     
         6 . A method according to  claim 1  wherein said metallic material contains:
 (i) one or more metals selected from the group consisting of Ag, Au, Cu, Co, Cr, Mo, Ni, Sn, Fe, Pd, Pb, Pt, Rh, Ru and Zn; 
 (ii) at least one element selected from the group consisting of C, O and S; and 
 (iii) optionally at least one or more elements selected from the group consisting of B, P, Mo, and W. 
 
     
     
         7 . A method according to  claim 1  wherein said bath composition is selectively and reversibly modulated by one or more steps comprising use of two anodes with individual current control; adding components using a metering pump, air agitation to selectively oxidize bath component, agitation to keep particles in suspension so they are deposited; addition, modification or removal of bath components via a fluid circulation loop, and mixing to affect local ion concentration(s) at the cathode surface. 
     
     
         8 . The method of  claim 1  carried out to produce a freestanding variable property metallic deposit. 
     
     
         9 . The method of  claim 1  carried out to produce a freestanding variable property layered structure. 
     
     
         10 . The method of  claim 1  where the electrodepositing is onto at least part of a surface of a substrate. 
     
     
         11 . The method of claim w where the electrodepositing is onto a porous substrate to infiltrate at least part of the substrate. 
     
     
         12 . The method of  claim 1  where electrodepositing is onto a substrate of an orthopedic prosthesis, firearm component, mold, sporting good, electronic appliance, sputter target or automotive component. 
     
     
         13 . (canceled) 
     
     
         14 . The method of  claim 1  where electrodepositing is not only to cause variation by more than 10% in property along the depth of the deposit but also along the length and/or width of the deposit. 
     
     
         15 . The method of  claim 14  where electrodepositing is onto a substrate of an orthopedic prosthesis, firearm component, sporting good, electronic appliance or automotive component. 
     
     
         16 . (canceled) 
     
     
         17 . (canceled) 
     
     
         18 . An article having a metallic layer, having
 a. a thickness between 30 μm and 5 cm and a weight between 5 and 100% of the total weight of the article;   b. at least one deposit property of said metallic layer selected from the group consisting of chemical composition, grain size, hardness, yield strength, Young's modulus, resilience, elastic limit, ductility, internal stress, residual stress, stiffness, coefficient of thermal expansion, coefficient of friction, electrical conductivity, magnetic coercive force, thickness; and in the case of metal matrix composites, volume particulate fraction particulate particle size, particulate shape and/or particulate chemistry, varied by more than 10% in the layer height direction; and   c. said metallic layer having a fine-grained microstructure with an average size ranging from 2 nm to 10,000 nm throughout between 1.5 nm to 5 cm of said thickness.   
     
     
         19 . An article according to  claim 18 , wherein said deposit property is varied by more than 10% in the layer height direction and also at least in one of the length or width directions. 
     
     
         20 . An article according to  claim 18 , wherein said metallic layer is a pure metal selected from the group Ag, Au, Cu, Co, Cr, Ni, Sn, Fe, Pt and Zn; and alloy of two or more of these metals, or an alloy of at least one of these metals and a component selected from the group consisting of Mo, W, C, P, S and Si. 
     
     
         21 . An article according to  claim 20 , wherein said metallic layer further comprises between 2.5% and 75% by volume of particulate material. 
     
     
         22 . An article according to  claim 21 , wherein said particulate material is selected from the group consisting of metal powders, metal alloy powders and metal oxide powders of Al, Co, Cu, In, Mg, Ni, Si, Sn, V and Zn; nitrides of Al, B and Si; graphite, diamond, nanotubes, and/or Buckminster Fullerenes; carbides of B, Cr, Si, W; self lubricating materials such as MoS 2  and substantially inert polymeric materials. 
     
     
         23 . An article according to  claim 18 , wherein said article is a component or part of an automotive, aerospace, sputter target, sporting good, electronic appliance, industrial, manufacturing or defense industry application. 
     
     
         24 . An article according to  claim 23 , wherein said article is a component or part of a sporting equipment selected from the group consisting of golf clubs, golf club heads and faceplates, arrows, fishing rods, hockey sticks, baseball bats, tennis racquets, skate blades, skis, snowboards, bicycle frames and firearms selected from the group consisting of handguns, rifles and shotguns. 
     
     
         25 . An article according to  claim 24 , wherein said article is a golf club shaft, arrow shaft or baseball bat and said metallic layer extends over at least part of the inner or outer surface of said shaft or bat. 
     
     
         26 . A golf club shaft, arrow shaft or baseball bat according to  claim 24  made of a graphite-containing material, wherein said metallic layer comprises at least one metal selected from the group of Ni, Co and Fe. 
     
     
         27 . An article according to  claim 23 , wherein said article is the faceplate of a golf club head. 
     
     
         28 . An article according to  claim 23 , wherein said article is an automotive part selected from the group consisting of liquid conduits such as fuel rails; spoilers, grill-guards and running boards; brake, transmission, clutch, steering and suspension parts; brackets and pedals, muffler components, wheels, vehicle frames; fluid pump, housing and tank components such as oil, transmission or other fluid pans including gas tanks; electrical and engine covers; seat and armature components; and turbocharger components or electronic component selected from the group of laptops, cell phones, personal digital assistant devices, walkmen, disemen, MP3 players and digital cameras or an industrial application selected from the group of drills, files, knives, saws, blades, sharpening devices, cutting tools, polishing tools, grinding tools, housing, frames hinges, antennas and electromagnetic interference shields. 
     
     
         29 . An article according to  claim 18 , wherein said article is a component or part of a sputter target. 
     
     
         30 . A sputter target according to  claim 29 , wherein said sputter target is recrystallized. 
     
     
         31 . A sputter.target according to  claim 29 , wherein said sputter target contains at least two distinct grain sizes, with the surface layer of the sputter target comprising a fine-grained layer of equiaxed grains with a texture intensity value of between 1 and 10 times random and a thickness of 50 micron to 2.5 cm.