PRODUCING TITANIUM ALLOY MATERIALS THROUGH REDUCTION OF TITANIUM TETRACHLORIDE

• US 20190314896A1
• Filed: 10/20/2017
• Published: 10/17/2019
• Est. Priority Date: 10/21/2016
• Status: Active Application

• Current Assignee: General Electric Company
• Original Assignee: General Electric Company
• Inventors: Copland, Evan H., Stella, Albert Santo, Ott, Eric Allen, Woodfield, Andrew Philip, Prentice, Leon Hugh
• Application Number:
  US16/343,435
• Publication Number:
  US 20190314896A1
• Time in Patent Office: Days
• CPC Class Codes: B22F 1/142 Thermal or thermo-mechanical treatment
• CPC Class Codes: B22F 1/145 Chemical treatment, e.g. passivation or decarburisation
• CPC Class Codes: B22F 2301/052 Aluminium
• CPC Class Codes: B22F 2301/205 Titanium, zirconium or hafnium
• CPC Class Codes: B22F 2302/45 Others, including non-metals
• CPC Class Codes: B22F 2998/10 Processes characterised by the sequence of their steps
• CPC Class Codes: B22F 2999/00 Aspects linked to processes or compositions used in powder metallurgy
• CPC Class Codes: B22F 9/18 with reduction of metal compounds
• CPC Class Codes: C22B 34/1272 reduction of titanium halides, e.g. Kroll process
• CPC Class Codes: C22B 34/1277 using other metals, e.g. Al, Si, Mn
• CPC Class Codes: C22C 14/00 Alloys based on titanium

Abstract

Process for producing a titanium alloy material, such as a titanium aluminum alloy, are provided. The process includes reduction of TiCl₄), which includes a titanium ion (Ti⁴⁺), through intermediate ionic states (e.g., Ti³⁺) to Ti²⁺, which may then undergo a disproportionation reaction to form the titanium aluminum alloy.

Claims

1. A process for producing a titanium alloy material, comprising:

adding TiCl₄ to an input mixture at a first reaction temperature such that at least a portion of the Ti⁴⁺ in the TiCl₄ is reduced to Ti³⁺ to form a first reaction product, wherein the input mixture comprises aluminum, and, optionally AlCl₃ and/or optionally one or more alloying element halides;

after TiCl₄ addition is stopped, heating the first reaction product at drying conditions to complete reduction of Ti⁴⁺ or to remove substantially all of any remaining TiCl₄ to form a first intermediate mixture, wherein the first intermediate mixture is an AlCl₃-based salt solution that includes Ti³⁺;

heating the first intermediate mixture to a second reaction temperature such that at least a portion of the Ti³⁺ is reduced to a second intermediate mixture, wherein the second intermediate mixture is an AlCl₃-based salt solution that includes Ti²⁺; and

further heating the second intermediate mixture to a third reaction temperature such that the Ti²⁺ forms the titanium alloy material via a disproportionation reaction.

2. The process of claim 1, wherein the input mixture comprises a plurality of particles, and wherein the plurality of particles comprise aluminum, AlCl₃ and, optionally, one or more alloying element chloride, and further wherein the plurality of particles of the input mixture have a minimum particle dimension on average of about 0.5 μ

m to about 25 μ

m.

3. The process of claim 2, wherein the one or more alloying element chloride is present in the input mixture, and wherein the at least one alloy chloride comprises VCl₃, CrCl₂, CrCl₃, NbCl₅, FeCl₂, FeCl₃, YCl₃, BCl₃, MnCl₂, MoCl₃, MoCl₅, SnCl₂, ZrCl₄, NiCl₂, CuCl, CuCl₂, WCl₄, WCl₆, BeCl₂, ZnCl₂, LiCl, MgCl₂, ScCl₃, PbCl₂, Ga₂Cl₄, GaCl₃, ErCl₃, CeCl₃, or mixtures thereof.

4. The process of claim 1, wherein the input mixture comprises reaction mixture to form Ti-6Al-4V (weight %).

5. The process of claim 1, wherein the input mixture comprises reaction mixture to form Ti-48Al-2Cr-2Nb (atomic %).

6. The process of claim 1, wherein the first reaction temperature is about 100°

C. to about 165°

C.

7. The process of claim 1, wherein the aluminum is present the input mixture reduces the Ti⁴⁺ in the TiCl₄ to Ti³⁺.

8. The process of claim 1, wherein TiCl₄ is added as a liquid or vapor mixed with other alloy chlorides.

9. The process of claim 1, wherein reducing the Ti⁴⁺ in the TiCl₄ to form Ti³⁺ is performed in a plow reactor, a ribbon blender, or another liquid/solid/vapor reactor.

10. The process of claim 1, wherein adding the TiCl₄ to the input mixture is performed in an inert atmosphere having a pressure of about 760 torr to about 1500 torr.

11. The process of claim 1, wherein the Ti³⁺ in the first intermediate mixture is in the form of TiCl₃ complexed with at least one metal chloride.

12. The process of claim 1, wherein the Ti³⁺ in the first intermediate mixture is in the form of TiCl₃(AlCl₃)_x with x being greater than 0 to 10.

13. The process of claim 1, wherein the second reaction temperature is about 180°

C. to about 500°

C.

14. The process of claim 1, wherein heating the first intermediate mixture to a second reaction temperature is performed in at least one rotary kiln.

15. The process of claim 1, wherein heating the first intermediate mixture to the second reaction temperature is performed in an inert atmosphere having a pressure of about 760 torr to about 3800 torr.

16. The process of claim 1, wherein the first intermediate mixture is maintained at the second reaction temperature until substantially all of the Ti³⁺ in the first intermediate mixture is reduced to Ti²⁺, and wherein at least a portion of the Ti²⁺ is in the form of TiCl₂ complexed with metal chloride(s).

17. The process of claim 1, wherein reducing Ti³⁺ to Ti²⁺ and reacting the Ti²⁺ via a disproportionation reaction are performed in a single reactor.

18. The process of claim 1, reducing Ti³⁺ to Ti²⁺ and reacting the Ti²⁺ via a disproportionation reaction are performed in a multi-zone reaction chamber.

19. The process of claim 1, further comprising:

flowing an inert gas through the multi-zone reaction chamber, wherein the inert gas flow is counter to the progression of the reaction products, and wherein the inert gas is introduced as a counter flow to carry gaseous titanium chloride complexes away from the titanium alloy material formed and back into the reaction zone for either or both reactions of Ti³⁺ to Ti²⁺ and/or Ti²⁺ to Ti alloy.

20. The process of claim 19, wherein any TiCl₄ produced during the reaction is reduced by an aluminum chloride or carried out of the reactor as a take-off by-product.

21. The process of claim 1, wherein reacting the Ti²⁺ via a disproportionation reaction to form the titanium alloy material is performed at an inert atmosphere having a pressure of about 760 torr to about 3800 torr.

22. The process of claim 1, wherein any Ti³⁺ formed during the disproportionation reaction is internally recycled to be reduced to Ti²⁺ and further reacted in a disproportionation reaction.

23. The process of claim 1, wherein the third reaction temperature is about 300°

C. to about 900°

C.

24. The process of claim 1, wherein the titanium alloy material is a titanium alloy powder.

25. The process of claim 1, further comprising:

high temperature processing the titanium alloy material at a processing temperature to purify the Ti alloy by removing residual chlorides and/or allowing diffusion to reduce composition gradients.

26. The process of claim 25, wherein the high temperature processing also continues disproportionation reactions to produce Ti alloy from any residual Ti²⁺, and wherein the high temperature processing also continues distillation of any un-reacted metal sub-halides.

27. The process of claim 25, wherein the processing temperature is about 800°

C. or higher.

28. The process of claim 1, further comprising:

adding alloying element halides into input mixture, during the reaction forming the first intermediate mixture, during the reaction forming the second intermediate mixture, during the disproportionation reaction, or during post processing.

29. A process for producing a titanium alloy material, comprising;

reducing an amount of TiCl₄ with an amount of aluminum, AlCl₃ and at least one metal chloride at a temperature below 180°

C. to form a first intermediate product comprising Ti³⁺; and

reducing the first intermediate product to a temperature below 900°

C. to form a titanium aluminum alloy.

30. The process of claim 29, wherein the first intermediate product is a solid salt solution comprising a complex of TiCl₃(AlCl₃)_x, with x being greater than 0.

31. The process of claim 29, wherein the second intermediate product comprising Ti²⁺ is a complex of [TiC1₂(AlCl₃)]_x, with x being greater than 0.

32. A process for producing a titanium-containing material, comprising:

mixing Al particles, AlCl₃ particles, and, optionally, particles of at least one other alloy element chloride to form an input mixture;

adding TiCl₄ to the input mixture;

reducing Ti⁴⁺ in the TiCl₄ in the presence of the input mixture at a first reaction temperature to form a first intermediate mixture comprising Ti³⁺, wherein the first reaction temperature is lower than about 180°

C.

33. The process of claim 32, wherein the Ti³⁺ of the first intermediate mixture is in the form of TiCl₃ complexed with metal chloride(s).