# US 11,111,591 B2 · Methods and compositions for electrochemical deposition of metal rich layers in aqueous solutions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,591 B2 - Document ID: US11111591B2 - Status: Granted - Kind: B2 - Application number: 15/995,220 - Filed: 2018-06-01 - Published: 2018-12-06 - Granted: 2021-09-07 - Earliest claimed: 2017-06-01 - Assignees: LumiShield Technologies Incorporated - Applicants: LumiShield Technologies Incorporated - Inventors: Hunaid B. Nulwala; John D. Watkins - Web page: https://patentgrep.com/patent/US11111591B2 ## CPC - C25D 3/44: Aluminium - C25D 3/54: of metals not provided for in groups C25D3/04 - C25D3/50 - C25D 3/56: of alloys - C25D 5/10: Electroplating with more than one layer of the same or of different metals (for bearings C25D7/10) - C25D 5/605: {Surface topography of the layers, e.g. rough, dendritic or nodular layers} - C25D 5/623: {Porosity of the layers} - C25D 5/625: {Discontinuous layers, e.g. microcracked layers} - C25D 9/08: by cathodic processes - C25D 9/10: on iron or steel - C25D 9/12: on light metals - C25D: PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR ## Abstract Methods and compositions for electrodepositing mixed metal reactive metal layers by combining reactive metal complexes with electron withdrawing agents are provided. Modifying the ratio of one reactive metal complex to the other and varying the current density can be used to vary the morphology the metal layer on the substrate. ## Claims ### Claim 1 A composition comprising a first metal complex comprising a first reactive metal and a first electron withdrawing ligand wherein the first electron withdrawing ligand is OSO2R1, wherein R1 is halo; substituted or unsubstituted C6-C18-aryl; substituted or unsubstituted C1-C6-alkyl; and substituted or unsubstituted C6-C18-aryl-C1-C6-alkyl, and a second metal complex comprising a second reactive metal and a second electron withdrawing ligand wherein the second withdrawing ligand is N(SO3R1), wherein R1 is halo; substituted or unsubstituted C6-C18-aryl; substituted or unsubstituted C1-C6-alkyl; and substituted or unsubstituted C6-C18-aryl-C1-C6-alkyl, wherein the first reactive metal has a more negative reduction potential than the second reactive metal, wherein the first electron withdrawing ligand decreases the reduction potential of a metal center in the first metal complex below an over-potential for an evolution of hydrogen gas due to a water splitting and the second electron withdrawing ligand decreases the reduction potential of a metal center in the second metal complex below the over-potential for the evolution of hydrogen gas due to the water splitting, wherein the composition further comprises a substantially aqueous medium, wherein the first reactive metal and the second reactive metal can be deposited onto a substrate via electrochemical reduction and wherein the pH of the composition is from about 2 to about 5. ### Claim 2 (depends on 1) The composition of claim 1, wherein the first reactive metal is selected from the group consisting of zirconium, aluminum, titanium, manganese, gallium, vanadium, and niobium. ### Claim 3 (depends on 1) The composition of claim 1, wherein the second reactive metal is selected from the group consisting of aluminum, zirconium, titanium, manganese, gallium, vanadium, and niobium. ### Claim 4 (depends on 1) The composition of claim 1, wherein the first electron withdrawing ligand and second electron withdrawing ligand are independently selected from the group consisting of: ### Claim 5 (depends on 1) The composition of claim 1, further comprising an electrolyte, wherein a concentration of the electrolyte is from about 0.01M to about 1M. ### Claim 6 (depends on 1) The composition of claim 1, further comprising a chelating agent. ### Claim 7 (depends on 6) The composition of claim 6, wherein the chelating agent is selected from the group consisting of sodium bicarbonate, methanesulfonic acid, and organic carboxylate. ### Claim 8 (depends on 7) The composition of claim 7, wherein the pH of the composition is adjusted to between about 2 and about 5. ### Claim 9 (depends on 6) The composition of claim 6, wherein the concentration of the chelating agent is from about 0.01M to about 1M. ### Claim 10 (depends on 1) The composition of claim 1, wherein a ratio of the first metal complex to the second metal complex is from about 0.1:1 to about 1:0.1. ### Claim 11 (depends on 10) The composition of claim 10, wherein the ratio of the first metal complex to the second metal complex is about 1:1. ### Claim 12 (depends on 11) The composition of claim 11, wherein the first metal complex comprises zirconium and the second metal complex comprises aluminum. ### Claim 13 (depends on 1) The composition of claim 1, wherein the concentration of the first metal complex is from about 0.01M to about 0.5M and the concentration of the second metal complex is from about 0.01M to about 0.5M. ### Claim 14 (depends on 13) The composition of claim 13, wherein the concentration of the first metal complex is 0.05M and the concentration of the second metal complex is 0.05M. ### Claim 15 (depends on 14) The composition of claim 14, wherein the first metal complex comprises zirconium and the second metal complex comprises aluminum. ### Claim 16 (depends on 1) The composition of claim 1, further comprising an electrolyte and a chelating agent. ### Claim 17 (depends on 16) The composition of claim 16, wherein the electrolyte and the chelating agent are the same.