US20190314896A1 - Producing titanium alloy materials through reduction of titanium tetrachloride - Google Patents

Producing titanium alloy materials through reduction of titanium tetrachloride Download PDF

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US20190314896A1
US20190314896A1 US16/343,435 US201716343435A US2019314896A1 US 20190314896 A1 US20190314896 A1 US 20190314896A1 US 201716343435 A US201716343435 A US 201716343435A US 2019314896 A1 US2019314896 A1 US 2019314896A1
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reaction
ticl
mixture
alcl
titanium
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Evan H. Copland
Albert Santo Stella
Eric Allen Ott
Andrew Philip Woodfield
Leon Hugh Prentice
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General Electric Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—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
    • C22B34/1263—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 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1277—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 obtaining metallic titanium from titanium compounds, e.g. by reduction using other metals, e.g. Al, Si, Mn
    • B22F1/0085—
    • B22F1/0088—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/142—Thermal or thermo-mechanical treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—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
    • C22B34/1263—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 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • C22B34/1268—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 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams
    • C22B34/1272—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 obtaining metallic titanium from titanium compounds, e.g. by reduction using alkali or alkaline-earth metals or amalgams reduction of titanium halides, e.g. Kroll process
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/05—Light metals
    • B22F2301/052—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/20—Refractory metals
    • B22F2301/205—Titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/45—Others, including non-metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates generally to methods for producing titanium alloy materials through reduction of titanium tetrachloride (TiCl 4 ) in an AlCl 3 -based reaction media. More particularly, the titanium alloy materials are formed through reducing the Ti 4+ in the TiCl 4 to a lower valence form of titanium (e.g., Ti 3+ and Ti 2+ ), followed by a disproportionation reaction of Ti 2+ .
  • other alloying elements may also be formed from a salt to the alloy in a reduction and/or disproportionation process.
  • Titanium alloy materials that include aluminum, such as titanium-aluminum (Ti—Al) based alloys and alloys based on titanium-aluminum (Ti—Al) inter-metallic compounds, are very valuable materials. However, they can be difficult and expensive to prepare, particularly in a powder form, and there are certain alloys inaccessible by traditional melt processes. This expense of preparation limits wide use of these materials, even though they have highly desirable properties for use in aerospace, automotive and other industries.
  • Ti—Al titanium-aluminum
  • Ti—Al titanium-aluminum inter-metallic compounds
  • WO 2007/109847 teaches a stepwise method for the production of titanium-aluminum based alloys and inter-metallic compounds via a two stage reduction process, based on the reduction of titanium tetrachloride with aluminum.
  • WO 2009/129570 discloses a reactor adapted to address one of the problems associated with the reactors and methods disclosed in WO 2007/109847, when such are used under the conditions that would be required to form low-aluminum titanium-aluminum based alloys.
  • a process is generally provided for producing a titanium alloy material, such as a titanium aluminum alloy.
  • the process includes 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.
  • the input mixture may include aluminum, and, optionally AlCl 3 and/or optionally one or more alloying element halides.
  • the first reaction product may be heated 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 that is an AlCl 3 -based salt solution that includes Ti 3+ .
  • the first intermediate mixture may then be heated to a second reaction temperature such that at least a portion of the Ti 3+ is reduced to a second intermediate mixture that is an AlCl 3 -based salt solution that includes Ti 2+ .
  • the second intermediate mixture is then further heated to a third reaction temperature such that the Ti 2+ forms the titanium alloy material via a di sproportionation reaction.
  • the process for producing a titanium alloy material may include: 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.
  • the process for producing a titanium-containing material may include: 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 (e.g., lower than about 180° C.) to form a first intermediate mixture comprising Ti 3+ .
  • a first reaction temperature e.g., lower than about 180° C.
  • FIG. 1 shows a diagram of an exemplary process according to one embodiment of the present disclosure
  • FIG. 2 shows a schematic of one exemplary embodiment of the stage 1 reaction of the exemplary process of FIG. 1 ;
  • FIG. 3 shows a schematic of one exemplary embodiment of the stage 2 reactions and post-processing of the resulting titanium alloy material of the exemplary process of FIG. 1 ;
  • FIG. 4 shows an equilibrium stability diagram (Gibbs energy per mole of Cl 2 vs. absolute T) for Ti-Cl and Al-Cl systems overlaid to show reducing potential of metallic Al. Only pure elements (Ti, Al and Cl 2 ) and pure salt compounds (TiCl 4 , TiCl 3 , TiCl 2 and AlCl 3 ) are considered because there is no assessed thermodynamic data for salt solution phases (TiCl 4 (AlCl 3 ) x , TiCl 3 (AlCl 3 ) x , TiCl 2 (AlCl 3 ) x ).
  • first”, “second”, and “third” may be used interchangeably to distinguish one component from another and are not intended to signify location or importance of the individual components.
  • titanium alloy material is to be understood to encompass an alloy based on titanium or an alloy based on a titanium intermetallic compound and optionally other additional alloying elements in addition to Ti and Al.
  • titanium-aluminum alloy is to be understood to encompass an alloy based on titanium-aluminum or an alloy based on titanium-aluminum intermetallic compounds and optionally other additional alloying elements in addition to Ti and Al.
  • aluminum chlorides is to be understood to refer to aluminum chloride species or a mixture of such aluminum chloride species, including AlCl 3 (solid, liquid, or vapor) or any other Al—Cl compounds or ion species (e.g., AlCl, AlCl 2 , (AlCl 4 ) ⁇ , Al 2 Cl 6 and (Al 2 Cl 7 ) ⁇ ).
  • AlCl x refers to the term “aluminum chlorides” and is to be understood to refer to such aluminum chloride species or a mixture of such aluminum chloride species, no matter the stoichiometric ratio.
  • titanium chloride is to be understood to refer to titanium trichloride (TiCl 3 ) and/or titanium dichloride (TiCl 2 ), or other, combinations of titanium and chlorine, but not to TiCl 4 , which is referred to herein as titanium tetrachloride.
  • TiCl x may be used, which is to be understood to refer to titanium chloride species and forms of titanium tetrachloride (TiCl 4 ), titanium trichloride (TiCl 3 ), titanium dichloride (TiCl 2 ) and/or other combinations of titanium and chlorine in solid, liquid or vapor forms.
  • Ti ion e.g., Ti 2+ , Ti 3+ , and Ti 4+
  • a general phase i.e., salt mixture
  • the term “alloying element halides” refers to an alloying element ion coupled with a halide (e.g., a chloride, a fluoride, a bromide, an iodide, or an astatide).
  • the alloying element can be any element that would be included within the final titanium alloy material, such as metals and other elements.
  • the “alloying element halide” can be represented by MX x , where M is the alloying element ion and X is a halide (i.e., a halogen ion), no matter the stoichiometric ratio (represented by x).
  • an alloying element chloride can be represented by MCl x .
  • Processes are generally provided for producing titanium alloy materials (e.g., titanium aluminum alloys) through reduction of TiCl 4 , which includes a titanium ion (Ti 4+ ). More particularly, the titanium alloy materials are formed through reducing the Ti 4+ in the TiCl 4 to a lower valence form of titanium (e.g., Ti 3+ and Ti 2+ ), followed by a disproportionation reaction of Ti 2+ to form the titanium alloy material.
  • titanium alloy materials e.g., titanium aluminum alloys
  • Ti 4+ titanium ion
  • the valence form of titanium may be present in the reaction and/or intermediate materials as a complex with other species in the mixture (e.g., chlorine, other elements, and/or other species such as chloro-aluminates, metal halo aluminates, etc.), and may not necessarily be present in pure form of TiCl 4 , TiCl 3 , and TiCl 2 , respectively.
  • metal halide aluminates can be formed by MX x complexed with AlCl 3 in these intermediates, such as described below.
  • AlCl 3 provides the reaction media that the reactive species (e.g., Ti 4+ , Ti 3+ , Ti 2+ , Al, Al + , Al 2+ , Al 3+ , also alloying element ions) for all reactions.
  • the reactive species e.g., Ti 4+ , Ti 3+ , Ti 2+ , Al, Al + , Al 2+ , Al 3+ , also alloying element ions
  • the existence of salt solutions in the stage 1 and stage 2 reactions allows for the Ti 4+ reduction to Ti 3+ and for the Ti 3+ reduction to Ti 2+ to occur in the condensed state (e.g., solid and liquid), such as at temperatures of about 700° C. or less (e.g., about 300° C. or less).
  • FIG. 1 shows a general flow diagram of one exemplary process 100 that reduces TiCl 4 to a titanium alloy material.
  • the process 100 is generally shown in sequential stages: reaction precursors at 101 (including forming an input mixture at 102 ), a stage 1 reaction at 104 , a stage 2 reaction at 106 , and post processing at 108 .
  • the reaction precursors for the stage 1 reaction 104 in the process 100 of FIG. 1 include, at a minimum, TiCl 4 and an input mixture that includes aluminum (Al), either alone or with additional chloride components.
  • the reaction precursors include an input mixture as a solid material at ambient conditions (e.g., about 25° C. and 1 atm), and TiCl 4 in liquid form. Additional materials (e.g., AlCl 3 and/or other alloying element halides) may be included in the reaction precursors at various stages of process 100 , such as included within the input mixture, within the TiCl 4 , and/or as a separate input into the stage 1 and/or stage 2 reactions.
  • one or more alloying element chlorides can optionally be inputted into the stage 1 reaction materials (e.g., into the input mixture if a solid, into the TiCl 4 if a liquid or a soluble solid material, and/or directly into the stage 1 reaction vessel independently), dissolved into another component of the input materials, and/or may optionally be inputted into the Stage 2 reaction materials.
  • the liquid TiCl 4 may be filtering so as to remove any particulate within the liquid stream.
  • Such a filter may, in particular embodiments, refine the liquid stream by removing oxygen species from the liquid, since the solubility of oxygen and oxygenated species is extremely low.
  • filtering of the TiCl 4 liquid may tailor the chemistry of the liquid and remove oxygen species therefrom.
  • the reaction precursors can include some or all alloy elements to achieve a desired chemistry in the titanium alloy material.
  • the alloying element halide (MX x ) may an alloying element chloride (MCl x ).
  • Particularly suitable alloying elements (M) include, but are not limited to, vanadium, chromium, niobium, iron, yttrium, boron, manganese, molybdenum, tin, zirconium, silicon, carbon, nickel, copper, tungsten, beryllium, zinc, germanium, lithium, magnesium, scandium, lead, gallium, erbium, cerium, tantalum, osmium, rhenium, antimony, uranium, iridium, and combinations thereof.
  • the input mixture is formed from aluminum (Al), optionally an aluminum chloride (e.g., AlCl 3 ), and optionally one or more alloying element chloride.
  • AlCl 3 is useful as a component in the input mixture, but is not necessarily required if there is an alloying element chloride that is soluble or miscible in the TiCl 4 at the stage 1 reaction conditions to form AlCl in situ from the alloying element chloride and aluminum.
  • AlCl 3 is included as a material in the input mixture.
  • the input mixture may be substantially free from AlCl 3 .
  • the term “substantially free” means no more than an insignificant trace amount present and encompasses “completely free” (e.g., “substantially free” may be 0 atomic % up to 0.2 atomic %). If AlCl 3 is not present in the input mixture, then Al and other metal chlorides are present and utilized to form AlCl 3 such that the stage 1 reaction can proceed.
  • one or more alloying element chlorides can optionally be included into the input mixture to form the input mixture.
  • Particularly suitable alloying element chlorides in a solid state to be included with the aluminum and optional AlCl 3 include, but are not limited to, 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.
  • the input mixture is in the form of a plurality of particles (i.e., in powder form).
  • the input mixture is formed by milling a mixture of the aluminum (Al), optionally an aluminum chloride (e.g., AlCl 3 ), and optionally one or more alloying element halides (e.g., alloying element chlorides).
  • the material of the input mixture can be combined as solid materials and milled together to form the plurality of particles having a mixed composition.
  • a mixture of aluminum particles, optionally aluminum chloride particles, and optionally particles of one or more alloying element chlorides is mixed and resized (e.g., milled) together to form the plurality of particles of the input mixture.
  • the aluminum particles can be aluminum particles that have a pure aluminum core with an aluminum oxide layer formed on the surface of the particles.
  • the aluminum particles can include a core of aluminum and at least one other alloying element or a master alloy of aluminum and an alloying element.
  • the aluminum particles may have any suitable morphology, including a flake like shape, substantially spherical shape, etc.
  • the milling process is performed in an atmosphere that is substantially free of oxygen to inhibit the formation of any additional aluminum oxides within the input mixture.
  • the milling process can be performed in an inert atmosphere, such as an argon atmosphere, having a pressure of about 700 torr to about 3800 torr.
  • an inert atmosphere such as an argon atmosphere, having a pressure of about 700 torr to about 3800 torr.
  • the Al 2 O 3 surface layer protects the underlying Al(s), and then converting this Al 2 O 3 surface layer to AlOCl during milling allows Al to dissolve and diffuse into the salt, as Al + of Al 2+ .
  • a partial pressure of oxygen below that required to stabilize Al 2 O 3 (i.e., in an inert atmosphere) allows for these reactions to convert Al 2 O 3 , which is otherwise very stable in oxygen. As such, the resulting particles are an “activated” Al powder.
  • the plurality of particles may have any suitable morphology, including a flake like shape, substantially spherical shape, etc.
  • the plurality of particles of the input mixture have a minimum particle dimension on average of about 0.5 ⁇ m to about 25 ⁇ m (e.g., about 1 ⁇ m to about 20 ⁇ m), which is calculated by averaging the minimum dimension of the particles.
  • the flake may define a planar particle having dimensions in an x-y plane, and a thickness in a z-dimension with the minimum dimension on average of about 0.5 ⁇ m to about 25 ⁇ m (e.g., about 1 ⁇ m to about 20 ⁇ m), while the x- and y-dimensions having larger average sizes.
  • milling is performed at a milling temperature of about 40° C. or less to inhibit Al particle agglomeration.
  • Milling can be achieved using a high intensity process or a low intensity process to produce the plurality of particles of the input mixture, such as using a ball milling processes, grinding processes, or other size reduction methods.
  • the reaction precursors include, at a minimum, TiCl 4 in liquid or vapor form and an input mixture in powder form that includes aluminum (Al), and may include additional materials (e.g., AlCl 3 and/or other alloying element chlorides).
  • the TiCl 4 may be a pure liquid of TiCl 4 or liquid mixed with other alloy chlorides. Mixtures of TiCl 4 and another alloy chloride(s) may be heated, in certain embodiments, to ensure that the resulting solution is not saturated, which could result in components precipitating out of the solution.
  • An example of mixed liquid precursors includes a mixture of TiCl 4 and VCl 4 to form a vanadium containing titanium alloy.
  • TiCl 4 ( 1 ) may be dissolved into TiCl 4 ( 1 ), which can be represented by (TiCl 4 ) x (AlCl 3 ) y (MCl x ) z where M is any suitable metal, as discussed herein, and x, y, and z are the mole fraction of the particular components of the salt solution.
  • a salt solution can be generally defined in short hand as [Ti 4+ :salt], with the brackets [ ] represent the material as a solution phase having Ti 4+ as the major species of solvent and “salt” represents all of the minor species or alloying elements.
  • reaction precursors are added together for reduction of the Ti 4+ to Ti 3+ at the stage 1 reaction 104 .
  • the reaction precursors are heated to a first reaction temperature that is high enough to cause the chemical reduction but low enough to inhibit liquid TiCl 4 from forming.
  • the stage one reaction may be performed with the reaction precursors heated to a first reaction temperature that is about 180° C. or less (e.g., about 100° C. to about 165° C., such as about 140° C. to about 160° C.).
  • the input mixture is heated to the first reaction temperature prior to adding the TiCl 4 to the input mixture.
  • the TiCl 4 can be added to the input mixture simultaneously with heating the input mixture to the first reaction temperature.
  • the aluminum e.g., in a form of metallic aluminum or a salt of aluminum such as AlCl 3 and/or AlCl x
  • present the input mixture reduces the Ti 4+ in the TiCl 4 to Ti 3+ by an alumino-thermic process at the first reaction temperature, where AlCl 3 serves as the reaction media in the form of a AlCl 3 salt solution.
  • Ti 4+ and Al dissolve in AlCl 3 and in TiCl 3 (AlCl 3 ) x formed from the input mixture reaction products, such that the Ti 4+ and Al can react.
  • Al dissolves in the salt as Al + or Al 2+ , and that these Al species diffuse to the Ti 4+ and react to form new TiCl 3 (AlCl 3 ) x reaction product.
  • Al(s) dissolves into the salt solution through an AlCl 3 or AlOCl surface layer on the Al(s).
  • Ti 4+ in the TiCl 4 is reduced to Ti 3+ in the form of TiCl 3 complexed with metal chloride(s), such as TiCl 3 (AlCl 3 ) x with x being greater than 0, such as greater than 0 to 10 (e.g., x being 1 to 5), which is either a continuous solid solution between TiCl 3 and AlCl 3 or two solutions TiCl 3 -rich TiCl 3 (AlCl 3 ) x and AlCl 3 -rich AlCl 3 (TiCl 3 ) x where both solutions have similar crystal structures.
  • metal chloride(s) such as TiCl 3 (AlCl 3 ) x with x being greater than 0, such as greater than 0 to 10 (e.g., x being 1 to 5), which is either a continuous solid solution between TiCl 3 and AlCl 3 or two solutions TiCl 3 -rich TiCl 3 (AlCl 3 ) x and AlCl 3 -rich AlCl
  • the resulting reaction product is an AlCl 3 -based salt solution that includes the Ti 3+ species.
  • various metal chlorides i.e., AlCl 3 , VCl 4 , VCl 3 , MCl x , etc.
  • TiCl 3 solid or liquid
  • TiCl 3 solid or liquid
  • TiCl 3 (AlCl 3 ) x is a sub-set of the larger solution phase, even though all of the alloying element chlorides, MCl x , dissolve into this solution phase. Additionally, Ti 4+ also dissolves into this solution phases, which can be described as the Cl-rich side of the phase field. As TiCl 4 is added into the reaction mixture, at some point there may be more TiCl 4 /TiCl 3 than AlCl 3 , making the salt TiCl 3 -rich.
  • Such a salt solution can be generally defined in short hand as [Ti 3+ :salt], with the brackets [ ] represent the material as a solution phase having Ti 3+ as the major species of solvent and “salt” represents all of the minor species or alloying elements.
  • This reaction can be performed as TiCl 4 is added in a controlled manner to the input mixture at the first reaction temperature.
  • the TiCl 4 can be added continuously or in a semi batch manner.
  • excess Al is included in the reaction to ensure substantially complete reduction of Ti 4+ to Ti 3+ and for subsequent reductions.
  • TiCl 4 may be added to obtain a desired Ti/Al ratio to produce a desired salt composition.
  • the input mixture can substantially remain a solid at the first reaction conditions (e.g., the first reaction temperature and the first reaction pressure).
  • the stage 1 reaction is performed in a plow reactor, a ribbon blender, or another liquid/solid/vapor reactor.
  • the Ti 4+ reduction reaction can be performed in an apparatus to reflux during the reaction phase and/or to distill after the reaction phase any unreacted TiCl 4 vapor for continued reduction and/or to prevent loss of TiCl 4 (g) during the reaction.
  • the stage 1 reaction can be performed in an inert atmosphere (e.g., comprising argon).
  • an inert atmosphere e.g., comprising argon
  • the uptake of oxygen ( 0 2 ), water vapor (H 2 O), nitrogen (N 2 ), carbon oxides (e.g., CO, CO 2 , etc.) and/or hydrocarbons (e.g., CH 4 , etc.) by aluminum and/or other compounds can be avoided during the reduction reaction.
  • the inert atmosphere has a pressure of 1 atmosphere (e.g., about 760 torr) and about 5 atmospheres (e.g., about 3800 torr), such as about 760 torr to about 1500 torr.
  • the inert atmosphere has a pressure of 0.92 atmosphere (e.g., about 700 torr) and about 5 atmospheres (e.g., about 3800 torr), such as about 700 torr to about 1500 torr.
  • the first reaction product can be dried at drying conditions to remove substantially all of any remaining unreacted TiCl 4 (due to kinetic limitations) to form an intermediate mixture.
  • the first reaction product can be dried by heating and/or vacuum conditions.
  • any entrained TiCl 4 is removed from the first reaction product by heating to a temperature that is above the boiling point of TiCl 4 (e.g., about 136° C.) but below the temperature where Ti 3+ is further reduced (e.g., over about 180° C.), such as a drying temperature of about 160° C. to about 180° C. (e.g., about 160° C. to about 170° C.).
  • Al is capable of reducing Ti 4+ to Ti 3+ and Ti 3+ to Ti 2+ at all temperatures, including below 20° C.
  • the temperatures identified above are due to kinetic limitations and/or solid state transport in the reaction products.
  • the Ti 3+ to Ti 2+ reduction cannot occur while Ti 4+ exists in the stage 1 reaction products due to the Gibbs phase rule and phase equilibria of the Ti—Al—Cl—O system. That is, Al oxidation can drive both reduction steps at the same temperature, but the sequential aspect of these reactions is due to the present belief that Ti 4+ and Ti 2+ cannot exist at the same time in the same location of an isolated system.
  • the reactions are sequentially performed such that substantially all of the Ti 4+ is reduced to Ti 3+ prior to the formation of Ti 2+ in the system.
  • the reduction process is performed by the presently disclosed methods in a sequential nature.
  • the intermediate mixture containing the [Ti 3+ :salt] can be stored, such as in an inert atmosphere prior to further reaction.
  • the intermediate mixture containing the Ti 3+ complexes can be cooled to a temperature below about 100° C., such below about 50° C., or below about 25° C., for storage.
  • a first liquid storage tank 202 and an optional second liquid storage tank 204 are in liquid communication with a liquid mixing apparatus 206 so as to supply liquid reaction precursors thereto via supply line 208 .
  • the first liquid storage tank 202 includes liquid 201 of TiCl 4 , as a pure liquid of TiCl 4 or liquid mixed with other alloying element chlorides.
  • Valve 210 and pump 212 control flow of liquid 201 from the liquid storage tank 202 into the liquid mixing apparatus 206 .
  • the second liquid storage tank 204 is in liquid communication with the liquid mixing apparatus 206 so as to supply liquid reaction precursors thereto via supply line 214 .
  • the second liquid storage tank 204 includes, in one embodiment, a liquid 205 of at least one alloying element chloride.
  • Valve 216 and pump 218 control flow of liquid 205 from the liquid storage tank 204 into the liquid mixing apparatus 206 .
  • solid reaction precursors are supplied to the ball milling apparatus 220 from an Al storage apparatus 222 , an optional aluminum chloride (e.g., AlCl 3 ) storage apparatus 224 , and optionally one or more alloying element chloride storage apparatus 226 .
  • an optional size reduction apparatus e.g., a milling apparatus
  • the aluminum chloride storage apparatus 224 and the one or more alloying element chloride storage apparatus 226 are supplied via an optional mixing apparatus 228 to the milling apparatus 220 .
  • an input mixture 221 is provided to the stage 1 reaction apparatus 230 via a hopper 232 .
  • the mixed liquid from the liquid mixer 206 is added to the stage 1 reaction apparatus 230 in a controlled manner via supply tube 234 with the flow of the mixed liquid controlled by the pump 236 and valve 238 .
  • the aluminum chloride storage apparatus 224 and the one or more alloying element chloride storage apparatus 226 can be supplied via an optional mixing apparatus 228 directly to the hopper 232 .
  • any remaining TiCl 4 or liquid mixture can be evaporated and optionally recycled (e.g., via a distillation process, not shown) in recycle loop line 246 .
  • the size reduction apparatus can be integrated within the stage 1 reaction apparatus 230 .
  • the conditions of the stage 1 reaction apparatus 230 during reaction keep liquid in reactor or condense vapor to return to stage 1 reactor. Then, during drying the condenser is heated to a temperature above the boiling point of the liquid mixture to allow for drying.
  • the intermediate mixture (including Ti 3+ , such as in the form of TiCl 3 complexed with other materials) can be stored after drying but before further reduction processes.
  • the intermediate mixture is stored in an inert atmosphere to inhibit and prevent the formation of any aluminum oxides, other oxide complexes, or oxy-chloride complexes within the intermediate mixture.
  • the T 3+ and any alloying elements halides MX x of the intermediate mixture are reduced to Ti 2+ and M sub-halides by heating to a second reaction temperature and reacting with Al present as solid Al or as an Al species dissolved in a complex, and then the Ti 2+ is reduced to Ti alloy via an endothermic disproportionation reaction at a third reaction temperature that is greater than the second reaction temperature.
  • the metal sub-halides are also reduced via Al reduction to form base alloying metal M at temperatures within the range of the stage 2 process.
  • these reactions can be performed in sequential reactions at different temperatures in a single step reaction or as separate steps as a two-step process or more (e.g., in stages as the temperature is increased).
  • the aluminum e.g., in a form of metallic aluminum or a salt of aluminum such as AlCl 3 and/or AlCl x
  • present the intermediate mixture reduces the Ti 3+ in the TiCl 3 complexed with metal chloride(s), such as TiCl 3 (AlCl 3 ) x , to Ti 2+ at the second reaction temperature.
  • reaction may form Ti 2+ in a TiCl 2 complexed with metal chloride(s), to form salt solutions based on titanium aluminum chloride complexes, such as TiAlCl 5 , Ti(AlCl 4 ) 2 ), or a mixture thereof, with optionally additionally alloying elements or element halides, or element chloro-aluminates.
  • TiCl 2 there are three forms of TiCl 2 possible: (1) substantially pure TiCl 2 that only dissolves a small amount of anything, (2) TiAlCl 5 (s) that also does not dissolve much of anything else and is probably only stable up to about 200° C., and (3) ⁇ Ti(AlCl 4 ) 2 ⁇ n that is likely an inorganic polymeric material existing as a liquid or gas, glassy material and fine powder (long chain molecules).
  • ⁇ Ti(AlCl 4 ) 2 ⁇ n has a large composition range (e.g., n can be 2 to about 500, such as 2 to about 100, such as 2 to about 50, such as 2 to about 10) and dissolves all the alloy element chlorides.
  • the gaseous ⁇ Ti(AlCl 4 ) 2 ⁇ n helps remove unreacted salt from the Ti-alloy particles (e.g., at a low temperature in a later stage of the reaction).
  • the reaction product comprising Ti 2+ is a phase based on the complex between TiCl 2 and AlCl 3 (e.g., Ti(AlCl 4 ) 2 , etc.).
  • Such a complex can be a salt solution defined in short hand as [Ti 2+ :salt], with the brackets [ ] represent the material as a solution phase having AlCl 3 as the major species of solvent, Ti 2+ and “salt” represents all of the minor species or alloying elements.
  • the reduction of Ti 3+ to Ti 2+ can be performed at second reaction temperature of about 180° C. or higher (e.g., about 180° C. to about 900° C., such as about 180° C. to about 500° C., or about 180° C. to about 300° C.).
  • second reaction temperature of about 180° C. or higher (e.g., about 180° C. to about 900° C., such as about 180° C. to about 500° C., or about 180° C. to about 300° C.).
  • AlCl 3 is chemically bound in TiCl 3 (AlCl 3 ) x , TiAlCl 5 , and ⁇ Ti(AlCl 4 ) 2 ⁇ n in this process. Due to its significant chemical activity (e.g., ⁇ 1), AlCl 3 does not evaporate as would be expected for pure AlCl 3 , and there is no significant AlCl 3 evaporation until reaction temperatures reach or exceed about 600° C. Thus, AlCl 3 provides the reactor medium to allow the reaction to take place, and AlCl 3 provides the chemical environment that stabilizes the Ti 2+ ion and allows conversion of Ti 3+ to Ti 2+ at reaction temperatures less than about 250° C. (e.g., about 180° C. to about 250° C.).
  • Ti 3+ of the TiCl 3 complexed with metal chloride(s) e.g., in the form of TiCl 3 —(AlCl 3 ) x and/or TiAlCl 6 (g)
  • Ti 2+ can be converted to Ti alloy via a disproportionation reaction.
  • TiAlCl 6 (g) may be present to help remove Ti 3+ by-products from the Ti-alloy formation and/or recycling Ti 3+ within the reaction chamber.
  • the Ti 2+ can be converted to Ti alloy via a disproportionation reaction at a third reaction temperature of about 250° C.
  • the third reaction temperature may extend to about 1000° C. in certain embodiments, the third reaction temperature has an upper temperature limit of about 900° C. in other embodiments.
  • the Ti 2+ can be reduced to Ti alloy via a disproportionation reaction at a third reaction temperature of about 300° C. up to about 900° C. (e.g., about 300° C. to about 900° C., such as about 500° C. to about 900° C.).
  • any oxygen contaminants present in the reaction chamber remain stable volatile species that can be driven off so as to limit oxygen in the resulting Ti alloy product.
  • reaction temperatures above 900° C. the oxygen contaminants are no longer in the form of volatile species making it more difficult to reduce residual oxygen.
  • Any other volatile species, such as oxychlorides, chlorides, and/or oxides containing carbon, can be removed by thermal distillation.
  • this reaction of Ti alloy formation can be separated into an alloy formation stage via disproportionation reaction (e.g., at a disproportionation reaction temperature about 250° C. to about 650° C.) and a distillation stage (e.g., at a distillation temperature of about 650° C. to about 1000° C.).
  • disproportionation reaction e.g., at a disproportionation reaction temperature about 250° C. to about 650° C.
  • a distillation stage e.g., at a distillation temperature of about 650° C. to about 1000° C.
  • the Ti alloy formation can be divided into two processes: nucleation and particle growth (which may also be referred to as particle coarsening).
  • nucleation the first Ti alloy forms from the [Ti 2+ :SALT] at lower temperatures (e.g., about 250° C. to about 400° C.).
  • the local composition of the salt (component activities), surface energy, and kinetics of disproportionation determine the resulting Ti alloy composition.
  • particle growth occurs where the Ti alloy continues to grow from the [Ti 2+ :SALT] at higher temperatures (e.g., about 400° C. to about 700° C.) in the condensed state and at temperatures of greater than 700° C. (e.g., about 700° C.
  • the intermediate mixture having the Ti 2+ is maintained at the third reaction temperature until substantially all of the Ti 2+ is reacted to the titanium alloy material.
  • any Ti 3+ formed during the disproportionation reaction can be internally recycled to be reduced to Ti 2+ by thermos alumic reduction and further reacted in a disproportionation reaction.
  • Ti 4+ e.g., in the form of TiCl 4
  • TiCl 4 may be formed by a competing Ti disproportionation reaction, which can be evacuated out of the reaction system as a gas by-product for continued reaction (e.g., reducing back to Ti 3+ then to Ti 2+ ) or as a take-off by-product (e.g. carried out via an inert gas counter flow).
  • the stage 2 reactions can be performed in an inert atmosphere, such as comprising argon and/or substantially free of oxygen, nitrogen, moisture, hydrocarbons, and other impurities.
  • the inert atmosphere has a pressure between about 1 atmosphere (e.g., about 760 torr) and about 5 atmospheres (e.g., about 3800 torr), such as about 760 torr to about 1500 torr. As shown in FIG.
  • an inert gas can be introduced as a counter flow to regulate the reaction atmosphere, and to carry gaseous titanium chloride complexes and AlCl x away from the titanium alloy material and back into the reflux reaction zone of T 3+ to Ti 2+ and/or Ti 2+ to Ti alloy. Additionally or alternatively, any TiCl 4 produced during the reaction may be carried out of the reactor as a take-off by-product. Thus, the reaction can be performed efficiently without any significant waste of Ti materials.
  • the Ti-Al alloy formed by the reactions above can be in the form of an Ti-Al alloy mixed with other metal materials. Alloying elements may also be included in the titanium chloro-aluminates consumed and formed in the disproportionation reactions above.
  • fine, uniformly alloyed particulates can be produced of the desired composition through control of at least temperature, heat flux, pressure, gas flowrate, Al/AlCl 3 ratio, and particle size/state of aggregation of the Ti 2+ /Al/AlCl 3 mixture entering the stage 2 reaction.
  • a titanium alloy material is formed that includes elements from the reaction precursors and any additional alloying elements added during the stage 1 reaction and/or the stage 2 reactions.
  • Ti-6Al-4V in weight percent
  • Ti-4822 intermetallic 48A1, 2Cr, and 2Nb in atomic percent
  • the titanium alloy material is in the form of a titanium alloy powder, such as a titanium aluminide alloy powder (e.g., Ti-6Al-4V, Ti-4822, etc.).
  • a process schematic 300 of one exemplary embodiment of the stage 2 reaction at 106 and post processing at 108 of the exemplary process of FIG. 1 the intermediate mixture is supplied via line 244 into a stage 2 reaction apparatus 302 after passing through an optional mixing apparatus 306 .
  • the Ti 3+ of the intermediate mixture is reduced to Ti 2+ by heating to a second reaction temperature, and then the Ti 2+ is reduced to Ti alloy via a disproportionation reaction at a third reaction temperature that is greater than the second reaction temperature, as described in greater detail above.
  • the exemplary stage 2 reaction apparatus 302 shown is a single stage reactor that includes a zone heating apparatus 304 surrounding a reaction chamber 306 .
  • the zone heating apparatus 304 allows for a variable, increasing temperature within the reaction chamber 306 as the intermediate mixture flows through reaction chamber 306 .
  • the zone heating apparatus 304 can have a first reaction temperature towards the input end of the reaction chamber 306 (e.g., a first zone 308 ) and a second reaction temperature at the output end of the reaction chamber 306 (e.g., a second zone 310 ).
  • the apparatus may also have a gradation in reaction temperature between 2 or more zones.
  • the apparatus may also have a gradation in reaction temperature between 2 or more zones. This process is designed to allow for uniform mixing and continuous flow through the temperature gradient
  • Vapor reaction products such as AlCl 3 , Al 2 Cl 6 , TiCl 4 , TiAlCl 6 , AlOCl, TiOCl(AlOCl) x , etc.
  • a counterflow gas stream of inert gas can be supplied to the second zone 310 of the reaction chamber 306 via a supply tube 312 from an inert gas supply 313 .
  • the inert gas can then flow counter to the solid materials progressing through the reaction chamber 306 to carry gaseous titanium chloride complexes away from the titanium alloy material forming in the second zone 310 and back into the lower temperature reaction of Ti 3+ to Ti 2+ occurring in the first zone 308 .
  • gaseous titanium chloride complexes produced during the reaction may be carried back in the reaction chamber 306 where they condense at lower temperature, and thus control the Ti stoichiometry of the reacting salts.
  • Any remaining AlCl x and any TiCl 4 formed during disproportionation are removed from the reactor 306 by vent line 315 , which may be a heated line to prevent condensation and blockage, and collected in condenser/sublimator 317 (e.g., a single-stage condenser or a multi-stage condenser) for recapture.
  • condenser/sublimator 317 e.g., a single-stage condenser or a multi-stage condenser
  • a low impurity inert gas e.g., low impurity argon gas, such as a high purity argon gas
  • process gas is preferred to minimize the formation of oxychloride phases such as TiOCl x and AlOCl x in the process, and to ultimately inhibit the formation of TiO, TiO 2 , Al 2 O 3 , and/or TiO 2 -Al 2 O 3 mixtures.
  • inert gases can also be used, such as helium or other noble gases, which would be inert to the reaction process.
  • In-process monitoring can be used to determine reaction completion by measuring the balance, temperature, pressure, process gas chemistry, output product chemistry, and by-product chemistry.
  • the titanium alloy material can be collected via 314 to be provided into a post processing apparatus 316 , such as described below.
  • the post processing step may be performed in a separate apparatus or may be performed in the same or connected apparatus that is used for the Stage 2 process.
  • the titanium alloy material may be processed at 108 .
  • the titanium alloy powder can be processed for coarsening, sintering, direct consolidation, additive manufacturing, bulk melting, or spheroidization.
  • the titanium alloy material may be high temperature processed to purify the Ti alloy by removing residual chlorides and/or allowing diffusion to reduce composition gradients, such as at a processing temperature of about 800° C. or higher (e.g., about 800° C. to about 1,000° C.).
  • the high temperature processing also continues disproportionation reactions to produce Ti alloy from any residual Ti 2+ .
  • Ti 4+ can be reduced to Ti 3+ , as TiCl 3 (s), and subsequently to Ti 2+ , as TiCl 2 (s), by the oxidation of Al metal to Al 3+ (in the form of AlCl 3 (s), Al 2 Cl 6 (g) and/or AlCl 3 (g)), but Ti 2+ cannot be reduced to metallic Ti by oxidation of metallic Al.
  • Al-driven reduction of Ti 4+ and Ti 3+ is an exothermic process and is carried out in the stage one, S 1 , reactor and low temperature part of stage two, S 2 , reactor at temperatures below 523K or 250° C.), while Ti 2+ disproportionation is an endothermic process and is carried out at an intermediate temperature range in the S 2 reactor.
  • the following processes may be performed after ensuring that the starting reactants (TiCl 4 , AlCl 3 , and alloy element halides, MX x ) are effectively free of H 2 O and O, since all metal halides react strongly with H 2 O and once oxygen is introduced it can be difficult to remove form some salts. Additionally, it is believed that oxygen contamination in salt stabilizes Ti 3+ over Ti 2+ , which hiders Ti 2+ formation and thus influences the composition of alloy that forms.
  • the starting reactants TiCl 4 , AlCl 3 , and alloy element halides, MX x
  • a chemical reduction reaction of Ti 4+ was performed in the stage 1 reactor and evaluated in an inert environments.
  • the input mixture included 201.8 g Al flake, 100.5 g AlCl 3 , 34.3 g NbCl 5 and 20.1 g of CrCl 3 that was loaded under a high purity argon atmosphere into a sealed ball milled and milled for 16 hours at close to room temperature (multiple ball mills provide feed for each stage 1 run.
  • the milled material was sieved at 150 ⁇ m sieve size and 594.1 grams, nominally from two mills, were loaded into a plow mixer reactor, under a high purity argon atmosphere.
  • the reactor was maintained at a pressure of 1.2 barg with a low flow (less than 1 l/min) of high purity argon flowing through the reactor.
  • the reactor and charge was preheated to 130° C. and stabilized before 1164 g of TiCl 4 (l) was injected at a rate of 6.5 ⁇ 2.0 g/min while continuously mixing.
  • TiCl 4 (l) During the time TiCl 4 (l) is injected it initially evaporates, but overtime TiCl 4 (l) forms as the reactor wall is maintained at about 130° C., while the bulk free flowing in process charge, ⁇ salt+Al ⁇ , can reach temperatures up to 145° C. Following addition of all TiCl 4 (l) reactor wall temperature is maintained 130° C. for nominally the same time taken for TiCl 4 injection, during which the condensed TiCl 4 (l), was absorbed in the input mixture and reaction product salt, continues to reaction and is reduced. After the majority of condensed TiCl 4 (l) is reduced (indicated by a reduction in bulk change temperature and gas temperature above the mixed charge) the reactor wall temperature was increased to 160° C. and held.
  • the microstructure observed with SEM show the Al particles were surrounded by a graded layer of product salt, the salt in contact the Al surface is AlCl 3 -rich and it is common to observe segregation of 0 at this interface as an oxy-chloride layer “AlOCl”. Further form the surface of the Al particle, the TiCl 3 (AlCl 3 ) x phase existed and represented the bulk of the product of this reaction. This salt product had poor mechanical properties and easily separated the core Al particle and can exist isolated from Al particles. XRD analysis showed the TiCl 3 (AlCl 3 ) x salt phase exists as the ⁇ phase, hexagonal close packed structure. This crystal structure was consistent with AlCl 3 (TiCl 3 ) x , and there was evidence of a continuous solid solution. The measured composition of the bulk sample composition was consistent with XRD and the observed microstructure.
  • Balance of the material was fed into a HED rotary kiln reactor with Ar counter flow gas with 5 zones with zone temperatures of about 250° C. to about 300° C., about 300° C. to about 650° C., and about 650° C. to about 1000° C.
  • the sample material was collect and analyzed by XRD, ICP, Cl titration and electron microscopy and EDS and showed formation of gamma titanium aluminide metal alloy powder with a size of ⁇ 150 ⁇ m particle size and with a composition of 32.0 ⁇ 1.0 wt % Al, 61.4 ⁇ 1.7 wt % Ti, 2.6 ⁇ 0.1 wt % Cr, 4.5 ⁇ 0.1 wt % Nb as well as a small amount of residual chlorine content (0.6 wt %).
  • a chemical reduction reaction was performed and evaluated in an inert environment.
  • the input mixture includes 250 g Al flake, 62.5 g AlCl 3 , 42.75 g NbCl 5 and 25.0 g of CrCl 3 and milled at room temperature for 16 hours.
  • the milled material was sieved at 150 ⁇ m sieve size and 714 grams (nominally product from two mills) were loaded into a plow mixer reactor.
  • the reactor was preheated to 130° C. and TiCl 4 was injected at a rate of 6.5 g/min while mixing. Following addition of 1541 g of TiCl 4 , reactor temperature was increased to 160° C. and held to dry/remove excess TiCl 4 . Intermediate material was cooled and removed from the reactor.
  • the material from 3 similar stage one processes was fed into a HED rotary kiln reactor with Ar counter flow gas with 5 zones with all zone temperatures set to 250° C.
  • the ⁇ Al+TiCl 3 (AlCl 3 ) x ⁇ product from the above stage one reaction was feed into the rotary kiln at a constant rate of 1.0 ⁇ 0.2 kg/hr passed through the heated zone at a range of velocities controlled by the rotation speed of the work tube (6 RPM residence time of about 13 min; 4 RPM residence time of about 20 min; 2 RPM residence time of about 40 min).
  • In-process samples were collected throughout the run and were characterized using XRD, ICP, Cl titration and electron microscopy and EDS analysis.
  • Results showed that the starting ⁇ Al+TiCl 3 (AlCl 3 ) x ⁇ material quickly reacted in the rotary kiln.
  • the Al particles remained in the XRD spectrum and also clearly visible in the microstructure, but the amount was reduced. This was consistent with continued oxidation to reduce Ti 3+ to Ti 2+ .
  • the characteristic XRD peaks for ⁇ -TiCl 3 (AlCl 3 ) x disappeared leaving only the peaks for starting Al and alloy.
  • the bulk composition of the sample, microstructure and amount of condensed AlCl 3 vapour collected confirms the bulk of the collected sample is salt and this salt does not have a defined crystal structure (i.e., an amorphous, glass or polymeric material), which shows that Al easily reduces Ti 3+ as TiCl 3 (AlCl 3 ) x to Ti 2+ as Ti(AlCl 4 ) 2 at temperatures below 250° C. without a significant amount of AlCl 3 evaporation.
  • the Ti(AlCl 4 ) 2 phase is known in the literature to be non-crystalline.

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