Methods of forming a metal coated article

Patent metadata

Field	Value
Publication number	US-2023047624-A1
Application number	US-202217813920-A
Country	US
Kind code	A1
Filing date	Jul 20, 2022
Priority date	Jul 21, 2021
Publication date	Feb 16, 2023
Grant date	—

Abstract

A method of forming a metal coated article, comprises forming a metal halide in a molten salt plating bath at a first temperature, wherein forming the metal halide in the molten salt further comprises forming at least one functional metal halide electrolyte; and forming at least two auxiliary metal halide electrolytes at eutectic conditions; increasing the first temperature to a second temperature; forming a plated metal coating from the at least one functional metal halide electrolyte, onto a thermally conductive substrate; and introducing at least one of deuterium and tritium into the plated metal coating.

First claim

1 . A method of forming a metal coated article, comprising:
forming a metal halide in a molten salt plating bath at a first temperature, wherein forming the metal halide in the molten salt further comprises:
forming at least one functional metal halide electrolyte; and
forming at least two auxiliary metal halide electrolytes at eutectic conditions;
increasing the first temperature to a second temperature; forming a plated metal coating from the at least one functional metal halide electrolyte, onto a thermally conductive substrate; and introducing at least one of deuterium and tritium into the plated metal coating.

2 . The method of claim 1 , wherein forming at least two auxiliary metal halide electrolytes at eutectic conditions comprises forming the at least two auxiliary metal halide electrolytes comprising a eutectic composition including metal halides, metals of the metal halide including lithium, potassium and cesium, and the halides comprising
fluorine, chlorine, bromine and iodine and at least two of fluorine, iodine and bromine.

3 . The method of claim 2 , wherein the at least one functional metal halide electrolyte comprises a metal halide selected from the group consisting of TiBr 4 , TiI 4 , TiF 4 , ZrBr 4 , ZrI 4 , ZrF 4 , HfBr 4 , HfI 4 , HfF 4 , VI 3 , VF 3 , NbBr 5 , NbI 5 , NbF 5 , LaBr 3 , LaI 3 , LaF 3 , YBr 3 , YI 3 , YF 3 , NdBr 3 , NdI 3 , NdF 3 , ThBr 4 , ThI 4 , ThF 4 , PdBr 2 , PdF 2 , and PdI 2 ; and
wherein forming a metal halide in a molten salt plating bath comprises: forming a binary metal halide auxiliary electrolyte composition at the first temperature; adding a metal halide auxiliary electrolyte to form a ternary metal halide auxiliary electrolyte composition; and increasing the first temperature to the second temperature.

4 . The method of claim 2 , wherein the at least one functional electrolyte comprises a metal halide, the metal selected from the group consisting of TiBr 4 , TiF 4 , ZrBr 4 , ZrI 4 , ZrF 4 , HfBr 4 , HfI 4 , HfF 4 , VBr 3 , VI 3 , VF 3 , NbBr 5 , NbI 5 , NbF 5 , LaBr 3 , LaI 3 , LaF 3 , YBr 3 , YI 3 , YF 3 , NdBr 3 , NdI 3 , NdF 3 , ThBr 4 , ThI 4 , ThF 4 , PdBr 2 , PdF 2 , and PdI 2 ; and
wherein forming a metal halide in a molten salt plating bath comprises: forming a binary metal halide auxiliary electrolyte composition at the first temperature; adding a metal halide auxiliary electrolyte to form a ternary metal halide auxiliary electrolyte composition; and incrementally replacing the at least one functional electrolyte during forming the plated metal coating from the at least one functional metal halide electrolyte.

5 . The method of claim 1 , wherein:
forming a plated metal coating onto a thermally conductive substrate comprises:
plating titanium onto the thermally conductive substrate; and
further comprising annealing the titanium under conditions to achieve a titanium plated metal coating on the thermally conductive substrate.

6 . The method of claim 1 , wherein:
forming a plated metal coating; onto a thermally conductive substrate comprises:
plating a metal alloy coating selected from the group consisting of:
titanium-lean solid-solution titanium-zirconium, stoichiometric titanium-zirconium, and titanium-rich solid-solution rich titanium-zirconium onto the thermally conductive substrate; and
titanium-lean solid solution titanium-lanthanum, stoichiometric titanium-lanthanum, and titanium-rich solid-solution titanium-lanthanum onto the thermally conductive substrate.

7 . The method of claim 1 , wherein introducing at least one of deuterium and tritium into the plated metal coating comprises introducing at least one of the deuterium and tritium at a temperature of from about 400° C. to about 600° C.

8 . The method of claim 1 , wherein forming the plated metal coating comprises one of:
forming the plated metal coating selected from the group consisting of Ti, Zr, Hf, La, V, Hf, Nb 5 , Y, Nd, Th, and Pd; or forming a metal alloy plated coating selected from the group consisting of a plated material of Ti x Zr y , a plated material of Ti x La y , and plated material of Zr x La y , wherein y=4, and x is in a range from 0.5 to 2.

9 . The method of claim 1 :
wherein forming at least one functional metal halide electrolyte comprises forming the functional electrolyte comprising from about 60 wt. % to about 80 wt. % of the molten salt plating bath, and wherein forming at least two auxiliary metal halide electrolytes comprises forming the auxiliary electrolyte comprising a ternary metal halide auxiliary electrolyte eutectic composition comprising from about 20 wt. % to about 40 wt. % of the molten salt plating bath, the method further comprising: forming a metal alloy plated coating selected from the group consisting of a titanium-lean solid solution plated material of Ti x Zr y , a titanium-rich solid solution plated material of Ti x Zr y , a titanium-lean solid solution plated material of Ti x La y , a titanium-rich solid solution plated material of Ti x La y , a zirconium-lean solid solution plated material of Zr x La y , and zirconium-rich solid solution plated material of Zr x La y , wherein y=4, and wherein x is in a range from 0.5 to 2.

10 . The method of claim 1 , wherein forming the plated metal coating further comprises:
forming a metallic interface coating on the thermally conductive substrate; annealing the metallic interface coating; forming an external coating on the metallic interface coating; annealing the external coating; and introducing the at least one of deuterium and tritium into the plated metal coating at the external coating.

11 . The method of claim 1 , wherein the functional electrolyte comprises from about 60 wt. % to about 80 wt. % of the molten salt plating bath, and wherein the auxiliary electrolyte comprises a ternary metal halide auxiliary electrolyte eutectic composition comprising from about 20 wt. % to about 40 wt. % of the molten salt plating bath, the method further comprising:
incrementally immersing a counter electrode into the molten salt plating bath during forming the plated metal coating, wherein the counter electrode comprises a metallic material consonant with the functional electrolyte.

12 . A method of forming a metal coated article comprising:
plating a metal onto a thermally conductive substrate to form a plated metal coating on the thermally conductive substrate, the thermally conductive substrate selected from the group consisting of oxygen free high conductivity (OFHC) copper, copper, silver, aluminum, and nickel;
wherein plating the metal further comprises plating from a molten salt plating bath further comprising:
a ternary metal halide auxiliary electrolyte eutectic composition including lithium, potassium and cesium salts; and
at least one metal halide functional electrolyte consisting of TiBr 4 , TiI 4 , TiF 4 , ZrBr 4 , ZrI 4 , ZrF 4 , HfBr 4 , HfI 4 , HfF 4 , VBr 3 , VI 3 , VF 3 , NbBr 5 , NbI 5 , NbF 5 , LaBr 3 , LaI 3 , LaF 3 , YBr 3 , YI 3 , YF 3 , NdBr 3 , NdI 3 , NdF 3 , ThBr 4 , ThI 4 , ThF 4 , PdBr 2 , PdF 2 , and PdI 2 ;

cleaning the plated metal coating to remove at least some halides; annealing the plated metal coating to achieve at least one of:
altering grain morphology of the plated metal coating; and
decreasing porosity of the plated metal coating; and
introducing at least one of deuterium and tritium into the plated metal coating.

13 . The method of claim 12 , wherein:
plating a metal onto a thermally conductive substrate comprises plating a titanium metal coating onto the thermally conductive substrate; and annealing the titanium metal coating to produce

Assignees

• Battelle Energy Alliance Llc

Inventors

• Tripathy Prabhat K

Classifications

• C25D5/34

  Pretreatment of metallic surfaces to be electroplated · CPC title

• C25D17/12

  Shape or form (C25D17/14 takes precedence) · CPC title

• C25D11/26

  of refractory metals or alloys based thereon · CPC title

• C25D3/66 Primary

  from melts · CPC title

• C25D5/48

  After-treatment of electroplated surfaces · CPC title