Producing titanium alloy materials through reduction of titanium tetrachloride

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 (e.g., Ti 3+ ) to Ti 2+ , which may then undergo a disproportionation reaction to form the titanium aluminum alloy.

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 Ti 3+  to form a first reaction product, wherein the input mixture comprises aluminum, and, optionally AlCl 3  and/or optionally one or more alloying element halides;   after TiCl 4  addition is stopped, heating the first reaction product at drying conditions to complete reduction of Ti 4+  or to remove substantially all of any remaining TiCl 4  to form a first intermediate mixture, wherein the first intermediate mixture is an AlCl 3 -based salt solution that includes Ti 3+ ;   heating the first intermediate mixture to a second reaction temperature such that at least a portion of the Ti 3+  is reduced to a second intermediate mixture, wherein the second intermediate mixture is an AlCl 3 -based salt solution that includes Ti 2+ ; and   further heating the second intermediate 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 comprises 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 , 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 Ti 4+  in the TiCl 4  to Ti 3+ . 
     
     
         8 . The process of  claim 1 , wherein TiCl 4  is added as a liquid or vapor mixed with other alloy chlorides. 
     
     
         9 . The process of  claim 1 , wherein reducing the Ti 4+  in the TiCl 4  to form Ti 3+  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 760 torr to about 1500 torr. 
     
     
         11 . The process of  claim 1 , wherein the Ti 3+  in the first intermediate 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 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 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 Ti 3+  in the first intermediate mixture is reduced to Ti 2+ , and wherein at least a portion of the Ti 2+  is in the form of TiCl 2  complexed with metal chloride(s). 
     
     
         17 . The process of  claim 1 , wherein reducing Ti 3+  to Ti 2+  and reacting the Ti 2+  via a disproportionation reaction are performed in a single reactor. 
     
     
         18 . The process of  claim 1 , reducing Ti 3+  to Ti 2+  and reacting the Ti 2+  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 Ti 3+  to Ti 2+  and/or Ti 2+  to Ti alloy.   
     
     
         20 . The process of  claim 19 , wherein any TiCl 4  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 Ti 2+  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 Ti 3+  formed during the disproportionation reaction is internally recycled to be reduced to Ti 2+  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 Ti 2+ , 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 TiCl 4  with an amount of aluminum, AlCl 3  and at least one metal chloride at a temperature below 180° C. to form a first intermediate product comprising Ti 3+ ; 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 TiCl 3 (AlCl 3 ) x , with x being greater than  0 . 
     
     
         31 . The process of  claim 29 , wherein the second intermediate product comprising Ti 2+  is a complex of [TiC 1   2 (AlCl 3 )] x , with x being greater than  0 . 
     
     
         32 . A process for producing a titanium-containing material, comprising:
 mixing Al particles, AlCl 3  particles, and, optionally, particles of at least one other alloy element chloride to form an input mixture;   adding TiCl 4  to the input mixture;   reducing Ti 4+  in the TiCl 4  in the presence of the input mixture at a first reaction temperature to form a first intermediate mixture comprising Ti 3+ , wherein the first reaction temperature is lower than about 180° C.   
     
     
         33 . The process of  claim 32 , wherein the Ti 3+  of the first intermediate mixture is in the form of TiCl 3  complexed with metal chloride(s).