Producing titanium alloy materials through reduction of titanium tetrachloride

Patent metadata

Field	Value
Publication number	US-11193185-B2
Application number	US-201716343445-A
Country	US
Kind code	B2
Filing date	Oct 20, 2017
Priority date	Oct 21, 2016
Publication date	Dec 7, 2021
Grant date	Dec 7, 2021

Abstract

Process for producing a titanium alloy material, such as a titanium aluminum alloy, are provided. The process includes reduction of TiCl 4 , which includes a titanium ion (Ti 4+ ), through intermediate ionic states of an AlCl 3 -based salt solution that includes Ti 3+ and an AlCl 3 -based salt solution that includes Ti 2+ , which may then undergo a disproportionation reaction to form the titanium aluminum alloy.

First claim

What is claimed:

1. A process for producing a titanium alloy material, comprising:
adding TiCl 4 to an input mixture at a first reaction temperature such that at least a portion of the Ti 4+ in the TiCl 4 is reduced to a first intermediate reaction mixture, wherein the input mixture comprises aluminum, optionally AlCl 3 , and, optionally, one or more alloying element chloride, and wherein the first intermediate reaction mixture comprises an AlCl 3 -based salt solution that includes Ti 3+ ;
thereafter, drying the first intermediate reaction mixture at a drying temperature of about 160° C. to about 175° C.;
thereafter, heating to a second reaction temperature such that at least a portion of the Ti 3+ of the first intermediate reaction mixture is reduced to a second intermediate reaction mixture, wherein the second intermediate reaction mixture is an AlCl 3 -based salt solution that includes Ti 2+ , wherein adding TiCl 4 to the input mixture at the first reaction temperature and heating to the second reaction temperature are performed sequentially in a reaction process; and
further heating the second intermediate reaction mixture to a third reaction temperature such that the Ti 2+ 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, AlCl 3 , 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 μm to about 25 μm.

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 is selected from the group consisting of VCl 3 , CrCl 2 , CrCl 3 , NbCl 5 , FeCl 2 , FeCl 3 , YCl 3 , BCl 3 , MnCl 2 , MoCl 3 , MoCl 5 , SnCl 2 , ZrCl 4 , NiCl 2 , CuCl, CuCl 2 , WCl 4 , WCl 6 , BeCl 2 , ZnCl 2 , LiCl, MgCl 2 , ScCl 3 , PbCl 2 , Ga 2 Cl 4 , GaCl 3 , ErCl 3 , CeCl 3 , and mixtures thereof.

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

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

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 present in the input mixture reduces the Ti 4+ in the TiCl 4 to Ti 3+ .

8. The process of claim 1 , wherein the TiCl 4 is added as a liquid or vapor mixed with the one or more alloying element chloride.

9. The process of claim 1 , wherein reducing the Ti 4+ in the TiCl 4 to form Ti 4+ is performed in a plow reactor, a ribbon blender, or another liquid/solid/vapor reactor.

10. The process of claim 1 , wherein adding the TiCl 4 to the input mixture is performed in an inert atmosphere having a pressure of about 700 torr to about 3800 torr.

11. The process of claim 1 , wherein the Ti 3+ in the first intermediate reaction mixture is in the form of TiCl 3 complexed with at least one metal chloride.

12. The process of claim 1 , wherein the Ti 3+ in the first intermediate reaction mixture is in the form of TiCl 3 (AlCl 3 ) x with x being greater than 0 to 10.

13. The process of claim 1 , wherein adding TiCl 4 to an input mixture at a first reaction temperature and heating to a second reaction temperature are performed in a single step reaction.

14. The process of claim 1 , wherein adding TiCl 4 to an input mixture at a first reaction temperature and heating to a second reaction temperature are performed in separate steps as a two-step reaction process.

15. The process of claim 1 , wherein heating the first intermediate reaction mixture to a second reaction temperature is performed in an inert atmosphere, and wherein the inert atmosphere has a pressure of about 700 torr to about 3800 torr.

16. The process of claim 1 , wherein at least a portion of the Ti 2+ in the second intermediate reaction mixture is in the form of TiCl 2 complexed with metal chloride(s).

17. The process of claim 1 , wherein substantially all of the Ti 2+ in the second intermediate reaction mixture is in the form of TiCl 2 complexed with the one or more alloying element chloride(s), and wherein substantially all of the TiCl 4 is reacted or distilled from the first intermediate reaction mixture prior to Ti 3+ reduction to Ti 2+ .

18. The process of claim 1 , reacting the to the Ti 2+ titanium alloy material via a disproportionation reaction is performed in a multi-zone reaction chamber.

19. The process of claim 1 , further comprising:
flowing an inert gas through a multi-zone reaction chamber, wherein the inert gas flow is counter to the progression of the first intermediate reaction mixture and the second intermediate reaction mixture, 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 Ti 3+ to Ti 2+ and/or Ti 2+ to Ti alloy.

20. The process of claim 1 , wherein reacting the Ti 2+ via a disproportionation reaction to form the titanium alloy material is performed at an inert atmosphere has a pressure of about 700 torr to about 3800 torr.

21. The process of claim 1 , wherein any Ti 3+ formed during the disproportionation reaction is internally recycled to be reduced to Ti 2+ and further reacted in a disproportionation reaction.

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

23. 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.

24. The process of claim 23 , wherein the high temperature processing also continues disproportionation reactions to produce Ti alloy from any residual Ti 2+ .

25. The process of claim 23 , wherein the processing temperature is about 800° C. or higher.

26. The process of claim 1 , further comprising:
adding alloying element halides into input mixture, during the reaction forming the first intermediate reaction mixture, during the reaction forming the second intermediate reaction mixture, during the disproportionation reaction, or during post processing.

27. A process for producing a titanium alloy material, comprising:
adding TiCl 4 to an input mixture at a first reaction temperature such that at least a portion of the Ti 4+ in the TiCl 4 is reduced to a first intermediate reaction mixture, wherein the input mixture comprises aluminum, optionally AlCl 3 , and, optionally, one or more alloying element chloride, and wherein the first intermediate reaction mixture comprises an AlCl 3 -based salt solution that includes Ti 3+ ;
heating to a second reaction temperature such that at least a portion of the Ti 3+ of the first intermediate reaction mixture is reduced to a second intermediate reaction mixture, wherein the second intermediate reaction mixture is an AlCl 3 -based salt solution that includes Ti 2+ , wherein adding TiCl 4 to the input mixture at the first reaction temperature and heating to the second reaction temperature are performed seq

Assignees

• Gen Electric

Inventors

• Copland Evan H
• Stella Albert Santo
• Ott Eric Allen
• Woodfield Andrew Philip
• Prentice Leon Hugh

Classifications

• C22C1/0458

  Alloys based on titanium, zirconium or hafnium · CPC title

• C22B34/12 Primary

  Obtaining titanium {or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08} · CPC title

• C22B34/1277

  using other metals, e.g. Al, Si, Mn · CPC title

• C22C14/00

  Alloys based on titanium · CPC title

• B22F9/20

  starting from solid metal compounds · CPC title