Methods of forming a metal coated article

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 plating bath 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 , 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

increasing the first temperature to the second temperature.

4. The method of claim 2 , wherein the at least one functional metal halide electrolyte comprises a metal halide, the 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 , 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 metal halide 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 the 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 at least one functional metal halide 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 an 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 at least one functional metal halide electrolyte comprises from about 60 wt. % to about 80 wt. % of the molten salt plating bath, and wherein the at least two auxiliary metal halide electrolytes comprise 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 at least one functional metal halide 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 a titanium coating on the thermally conductive substrate.

14. The method of claim 13 , wherein plating the metal onto the thermally conductive substrate comprises plating two metals from the at least one metal halide functional electrolyte selected from the group consisting of titanium-zirconium, titanium-hafnium, titanium-lanthanum, titanium-palladium, zirconium-lanthanum, zirconium-hafnium, zirconium-palladium, hafnium-palladium, and palladium lanthanum.

15. The method of claim 14 , wherein introducing at least one of deuterium and tritium into the plated metal coating comprises introducing the deuterium or the tritium at a temperature of from about 400° C. to about 600° C.

16. The method of claim 12 , wherein the at least one metal halide functional electrolyte comprises from about 60 wt. % to about 80 wt. % of the molten salt plating bath, and wherein the ternary metal halide auxiliary electrolyte eutectic composition comprises from about 20 wt. % to about 40 wt. % of the molten salt plating bath.

17. The method of claim 15 , 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 deuterium or the tritium into the external coating.

18. The method of claim 12 , wherein the at least one metal halide functional electrolyte comprises from about 60 wt. % to about 80 wt. % of the molten salt plating bath, and wherein the ternary metal halide auxiliary electrolyte eutectic composition comprises from about 20 wt. bio 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 at least one metal halide functional electrolyte.

19. A method of forming a metal coated article comprising:

forming a metal oxide on a thermally conductive substrate;

reducing the metal oxide to a metal coating under conditions comprising a temperature from about 700° C. to about 900° C. in the presence of hydrogen gas;

applying a reducing potential to the thermally conductive substrate within a calcium chloride salt bath in a range from about 2.5 volts cathodic and about 3.1 volts cathodic relative to a counter electrode;

annealing the metal coating in an inert atmosphere at a temperature of between about 500° C. and about 600° C.; and

introducing at least one of deuterium and tritium into the metal coating.

20. The method of claim 19 , wherein reducing the metal oxide to a metal coating comprises reducing titanium dioxide to titanium.