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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 d

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: 2 nm-5 micron), entirely coarse-grained (average grain size: 20 micron) or entirely amorphous metallic material deposits.

대표청구항 ▼

1. A method of preparing a variable property metallic deposit, comprising the steps: electrodepositing a metallic material from an aqueous electrolyte in a single electrolytic cell having at least one anode and at least one cathode using DC and/or pulse electrodeposition;modulating at least one elec

1. A method of preparing a variable property metallic deposit, comprising the steps: electrodepositing a metallic material from an aqueous electrolyte in a single electrolytic cell having at least one anode and at least one cathode using DC and/or pulse electrodeposition;modulating at least one electrodeposition parameter selected from the group consisting of average current density ranging from 5 to 10,000 mA/cm2, 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/cm2; peak reverse current density ranging from 5 to 20,000 mA/cm2; frequency ranging from 0 to 1,000 Hz; a duty cycle ranging from 5 to 100%;varying a grain size in a deposit direction by more than 10%;varying at least one additional deposit property selected from the group consisting of hardness, yield strength, Young's modulus, resilience, elastic limit, ductility, deposit stress, coefficient of thermal expansion, coefficient of friction, electrical conductivity, and magnetic coercive force, andwherein said metallic material deposit has 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 5,000 nm throughout 1.5 nm to 5 cm of said thickness and said metallic material deposit has a chemical composition that does not change throughout the thickness of the deposit, andwherein at least two of the electrodeposition parameters are modulated and varying at least two of said properties by more than ten percent. 2. A method of preparing a variable property metallic deposit, comprising the steps: electrodepositing a metallic material from an aqueous electrolyte in a single electrolytic cell having at least one anode and at least one cathode using DC and/or pulse electrodeposition;varying at least one deposit property in a deposit direction by more than 10% by modulating at least one electrodeposition parameter selected from the group consisting of average current density ranging from 5 to 10,000 mA/cm2, forward pulse on time ranging from 0.1 to 500 ms, reverse pulse on time ranging from 0 to 500 ms, peak forward current density ranging from 5 to 10,000 mA/cm2, 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, bath pH ranging from 0 to 12, bath flow direction at cathode ranging from incident (perpendicular) to tangential, shielding anode by covering between 0-95% of the geometrical anode surface area; andvarying the at least one deposit property by more than 10% along a length, width, or combinations thereof of the deposit by modulating at least one electrodeposition parameter selected from the group consisting of flow direction at cathode ranging from perpendicular to tangential, shielding anode by covering between 0 and 95% of the geometrical anode surface area, flow rate ranging from 0-10 gpm, reverse pulse peak current density ranging from 5 to 20,000 mA/cm2, and total average current density ranging from 5-20,000 mA/cm2,wherein the at least one deposit property is selected from the group consisting of grain size yield strength, resilience, chemical composition, coefficient of thermal expansion, and magnetic coercive force; andwherein said metallic deposit has a deposit thickness ranging from 20 microns to 5cm having a fine-grained microstructure with an average grain size ranging from 2 nm to 5,000 nm throughout 1.5 nm to 5 cm of said thickness. 3. The method of claim 2, where at least two of the electrodeposition parameters are modulated and varying at least two of said properties by more than ten percent. 4. The method according to claim 2, wherein the metallic material comprises a single chemical element. 5. A method of claim 1 or claim 2, wherein said deposit thickness furthermore contains coarse-grained and/or amorphous sections. 6. The method according to claim 1 or claim 2, wherein the metallic material is a pure metal comprising of a single element selected from the group consisting of Ag, Au, Cu, Co, Cr, Mo, Ni, Sn, Fe, Pd, Pb, Pt, Rh, Ru and Zn. 7. The method according to claim 1 or claim 2, wherein the metallic material is an alloy of one or more elements selected from the group consisting of Ag, Au, Cu, Co, Cr, Mo, Ni, Sn, Fe, Pd, Pb, Pt, Rh, Ru, and Zn. 8. A method according to claim 1 or claim 2, 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. 9. The method of claim 1 or claim 2, carried out to produce a freestanding variable property deposit. 10. The method of claim 1 or claim 2 carried out to produce a freestanding variable property layered deposit. 11. The method of claim 1 or claim 2 where the electrodepositing is onto at least part of a surface of a substrate. 12. The method of claim 1 or claim 2, where the electrodepositing is onto a porous substrate to infiltrate at least part of said porous substrate. 13. The method of claim 1 or claim 2 where electrodepositing is onto a substrate of an orthopedic prosthesis, gun barrel, mold, sporting good, cell phone or automotive component. 14. A method according to claim 1 or claim 2, wherein electrodepositing the metallic material occurs on the inside of a substrate of a gun barrel, and wherein the electrodeposit is a metal matrix composite containing diamond particles. 15. The method of claim 1 or claim 2, wherein the metallic material is a layered deposit and the sublayer thickness is in the range of 1.5 nm to 500 μm. 16. The method of claim 1 or claim 2, wherein the metallic material is a layered deposit and the maximum sublayer thickness is 500 μm. 17. The method of claim 1 or claim 2, wherein said metallic material comprises both layered and graded sections. 18. The method of claim 1 or claim 2, wherein said metallic material comprises both layered and graded sections whereby at least one uniform layer is located between two graded layers. 19. The method of claim 1 or 2, further comprising the step of periodically alternating layers of soft, low internal stress electrodeposited metallic material with harder, higher stressed layers of deposited metallic material with a same metal. 20. The method of claim 1 or 2, wherein said fine grained microstructure exhibits internal stress and/or brittleness without multidimension grading. 21. A method for preparing a pure iron multi-layer deposit having a variable grain size comprising the steps of: electrodepositing iron from an aqueous electrolyte in a single electrolytic cell;modulating the average current density from about 80 to about 200 mA/cm2, the frequency ranging from about 0 to about 100 Hz, and the duty cycle ranging from about 70to about 100%;varying the grain size of directly adjacent layers by more than 10%; andwherein said pure iron multi-layer deposit has a fine-grained microstructure wherein the individual pure iron layers of the pure iron multi-layer deposit have an average grain size ranging from about 30 to about 5,000 nanometers throughout said deposit thickness, and wherein each individual pure iron layer of the multi-layer pure iron deposit has an internal stress ranging from about 3 to about 30 ksi and said pure multi-layer deposit has a chemical composition that does not change throughout the deposit thickness. 22. A method for preparing a multi-layer nickel deposit having variable grain size comprising the steps: electrodepositing pure nickel from an aqueous electrolyte in a single electrolytic cell;modulating the average current density from about 50 to about 80 mA/cm2, the frequency ranging from about 10 to about 125 Hz, the duty cycle ranging from about 25 to about 90%;varying the grain size of a deposit direction by more than 10%; andwherein said multi-layer pure nickel deposit has a fine-grained microstructure wherein the individual layers of the multi-layer deposit have an average grain size ranging from about 30 to about 275 nanometers and wherein said multi-layer nickel deposit has a chemical composition that does not change throughout the deposit thickness.