CN110199040B

CN110199040B - Titanium alloy material production by reduction of titanium tetrachloride

Info

Publication number: CN110199040B
Application number: CN201780078870.2A
Authority: CN
Inventors: E·H.·科普兰; A·S·斯特拉; E·A·奥特; A·P·伍德菲尔德; L·H·普伦蒂斯
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 2016-10-21
Filing date: 2017-10-20
Publication date: 2022-10-04
Anticipated expiration: 2037-10-20
Also published as: WO2018075887A1; CN110199040A; AU2017345609A1; AU2017345609B2; EP3512973A1; RU2734225C1; US20190314896A1

Abstract

Methods of making titanium alloy materials, such as titanium-aluminum alloys, are provided. The methodComprises titanium ion (Ti) ⁴⁺ ) Of TiCl ₄ Via an intermediate ionic state (e.g. Ti) ³⁺ ) Reduction to Ti ²⁺ A disproportionation reaction may then be performed to form a titanium-aluminum alloy.

Description

Titanium alloy material production by reduction of titanium tetrachloride

PRIORITY INFORMATION

This application claims priority from U.S. provisional patent application serial No. 62/411,205, filed 2016, month 10, day 21, which is incorporated herein by reference.

Technical Field

The invention relates generally to the treatment of AlCl ₃ Reduction of titanium tetrachloride (TiCl) in a reaction medium ₄ ) To a method for manufacturing a titanium alloy material. More specifically, the titanium alloy material is formed by the following method: mixing TiCl ₄ Ti of (1) ⁴⁺ Reduced to lower valent titanium (e.g. Ti) ³⁺ And Ti ²⁺ ) Followed by Ti ²⁺ Disproportionation reaction of (1). Alternatively, other alloying elements (alloying elements) may also be formed from the salt into an alloy in the reduction and/or disproportionation process.

Background

Titanium alloy materials containing aluminum, such as titanium-aluminum (Ti-Al) alloys and alloys based on titanium-aluminum (Ti-Al) intermetallic compounds, are very valuable materials. However, they are difficult and expensive to produce, especially in powder form, and certain alloys are difficult to obtain by conventional melting processes. This manufacturing expense limits the wide use of these materials even though they have highly desirable properties for use in aerospace, automotive and other industries.

Reactors and methods for forming titanium-aluminum based alloys and intermetallic compounds have been disclosed. For example, WO2007/109847 teaches a stepwise process for the manufacture of titanium-aluminum based alloys and intermetallic compounds by a two-stage reduction process based on the reduction of titanium tetrachloride with aluminum. WO2009/129570 discloses a reactor suitable for solving one of the above problems, which reactor is used in combination with the reactor and process disclosed in WO2007/109847, when it is used under conditions requiring the formation of a low-aluminium titanium-aluminium based alloy.

However, the discussion of the chemical processes that actually occur in the processes described in WO2007/109847 and WO2009/129570 does not represent a complete understanding of the actual reactions that occur in forming metal alloys from metal halide precursors.

In view of these teachings, there is a better understanding of TiCl reduction by titanium tetrachloride ₄ The need for chemical processes to produce titanium aluminum alloys and improved processing techniques for such reactions.

The above references to background art do not constitute an admission that such art forms part of the common general knowledge of a person of ordinary skill in the art.

Disclosure of Invention

Aspects and advantages of the invention will be set forth in part in the following description, or may be obvious from the description, or may be learned through practice of the invention.

A method of making a titanium alloy material, such as a titanium aluminum alloy, is generally provided. In one embodiment, the method comprises: reacting TiCl at a first reaction temperature ₄ Is added to the input mixture so that TiCl is formed ₄ Of Ti ⁴⁺ Is reduced to Ti ³⁺ Forming a first reaction product. The input mixture may comprise: aluminum, optionally AlCl ₃ And/or optionally one or more alloying element halides. On TiCl ₄ After the addition is stopped, the first reaction product may be heated under dry conditions to completely reduce the Ti ⁴⁺ Or removing substantially all of any remaining TiCl ₄ To form a first intermediate mixture, the first intermediate mixture being Ti-containing ³⁺ AlCl of ₃ -saline solution. The first intermediate mixture may then be heated to a second reaction temperature to cause Ti ³⁺ Is reduced to a second intermediate mixture, the second intermediate mixture being Ti-containing ²⁺ AlCl of ₃ Saline solution. Then, the second intermediate mixture is further heated to a third reaction temperature to cause Ti ²⁺ Forming the titanium alloy material through disproportionation reaction.

In an embodiment, a method of manufacturing a titanium alloy material may include: at a temperature of less than 180 ℃, using a certain amount of aluminum and AlCl ₃ And at least one metal chloride reducing an amount of TiCl ₄ Form a film containing Ti ³⁺ A first intermediate product of (a); and reducing the first intermediate product to a temperature of less than 900 ℃ to form a titanium aluminum alloy.

In an embodiment, a method of making a titanium-containing material can comprise: mixing Al particles and AlCl ₃ Particles and optionally particles of at least one other alloying element chloride, forming an input mixture; mixing TiCl ₄ Adding the input mixture; reducing TiCl in the presence of the input mixture at a first reaction temperature (e.g., less than about 180 ℃ C.) ₄ Of Ti ⁴⁺ Form a film containing Ti ³⁺ A first intermediate mixture of (a).

These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description and appended claims. The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the principles of the invention.

Drawings

A full and enabling disclosure of the present invention, including the best mode thereof to one of ordinary skill in the art, is set forth in the specification, which makes reference to the following figures, in which:

FIG. 1 illustrates a diagram of an exemplary method of an embodiment of the present disclosure;

FIG. 2 shows a schematic diagram of an exemplary embodiment of a stage 1 reaction of the exemplary process of FIG. 1;

FIG. 3 shows a schematic diagram of an exemplary embodiment of the stage 2 reaction of the exemplary process of FIG. 1 and post-treatment of the resulting titanium alloy material; and

FIG. 4 shows equilibrium stability plots (in mol Cl units) for overlapping Ti-Cl and Al-Cl systems ₂ Gibbs energy (Gibbs energy)/absolute value T) to show the reduction potential of metallic Al. Only pure elements (Ti, al and Cl) are considered ₂ ) And pure salt compound (TiCl) ₄ 、TiCl ₃ 、TiCl ₂ And AlCl ₃ ) This is because there is no solution phase for the salt (TiCl) ₄ (AlCl ₃ ) _x 、TiCl ₃ (AlCl ₃ ) _x 、TiCl ₂ (AlCl ₃ ) _x ) Evaluation thermodynamic data of (a).

Repeat use of reference characters in the present specification and drawings is intended to represent same or analogous features or elements of the invention.

Detailed Description

Reference will now be made in detail to embodiments of the invention, one or more examples of which are illustrated in the drawings. Examples are provided by way of illustration of the invention and not by way of limitation. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used with another embodiment to yield a still further embodiment. It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.

The terms "first," "second," and "third" as used herein are used interchangeably to distinguish one element from another and are not intended to denote the position or importance of the respective element.

Common chemical abbreviations for chemical elements (e.g., those commonly found in the periodic table of elements) are used in this disclosure to discuss chemical elements. For example, hydrogen is represented by its common chemical abbreviation H; helium is represented by its common chemical abbreviation He; and so on.

The term "titanium alloy material" or the like as used herein is to be understood to encompass titanium-based alloys or alloys based on titanium intermetallic compounds and optionally other additional alloying elements than Ti and Al. Similarly, the term "titanium-aluminum alloy" or the like is to be understood to encompass titanium-aluminum based alloys or alloys based on titanium-aluminum intermetallic compounds and optionally other additional alloying elements besides Ti and Al.

The term "aluminum chloride" as used herein is understood to mean aluminum chloride species or mixtures of such aluminum chloride species, including AlCl ₃ (solid, liquid or vapor) or any other Al-Cl compound or ionic species (e.g., alCl) ₂ 、(AlCl ₄ ) ^﹣ 、Al ₂ Cl ₆ And (Al) ₂ Cl ₇ ) ^﹣ )。AlCl _x The use of (b) refers to the term "aluminium chloride" and is understood to refer to such aluminium chloride species or mixtures of such aluminium chloride species, regardless of the stoichiometric ratio.

The term "titanium chloride" as used herein is understood to mean titanium trichloride (TiCl) ₃ ) And/or titanium dichloride (TiCl) ₂ ) Or other combinations of titanium and chlorine, rather than referring to TiCl, referred to herein as titanium tetrachloride ₄ . In some parts of the description, the more general term "TiCl" may be used _x ", which is understood to mean both titanium chlorides and titanium tetrachloride (TiCl) in solid, liquid or vapour form ₄ ) Titanium trichloride (TiCl) ₃ ) Titanium dichloride (TiCl) ₂ ) And/or other combinations of titanium and chlorine. Because various solution phases and titanium chloride complexes also exist, reference herein is made to Ti ions (e.g., ti) in the general phase (i.e., salt mixture) ²⁺ 、Ti ³⁺ And Ti ⁴⁺ ) Rather than any particular compound.

The term "halide of an alloying element" as used herein refers to a halide with (e.g., chloride, fluoride,Bromide, iodide, or astatide). The alloying element may be any element contained in the final titanium alloy material, such as metals and other elements. The "halide of an alloying element" may be represented by MX _x Where M is an alloying element ion and X is a halide (i.e., a halide ion), regardless of the stoichiometric ratio (represented by X). For example, the alloying element chloride may be prepared from MCl _x And (4) showing.

Generally provides titanium ion (Ti) by reduction ⁴⁺ ) Of TiCl ₄ To a method of manufacturing a titanium alloy material (e.g., a titanium aluminum alloy). More specifically, the titanium alloy material is formed by the following method: mixing TiCl ₄ Ti of (1) ⁴⁺ Reduced to lower valent titanium (e.g. Ti) ³⁺ And Ti ²⁺ ) Followed by Ti ²⁺ To form the titanium alloy material. It should be noted that the valence state of titanium (e.g., ti) ⁴⁺ 、Ti ³⁺ And/or Ti ²⁺ ) Can be present in the reaction and/or intermediate materials as complexes with other substances in the mixture (e.g., chlorine, other elements, and/or other substances such as chloroaluminates, metal haloaluminates, etc.), and may not necessarily be in the pure form of TiCl, respectively ₄ 、TiCl ₃ And TiCl ₂ Are present. For example, among these intermediates, the metal halide aluminate may pass through MX _x With AlCl ₃ The complex formation is, for example, as described below. Typically, alCl ₃ Providing a reaction medium, i.e. a reactive species (e.g. Ti), for all reactions ⁴⁺ 、Ti ³⁺ 、Ti ²⁺ 、Al、Al ⁺ 、Al ²⁺ 、Al ³⁺ And alloying element ions). Without wishing to be bound by any particular theory, it is believed that: the presence of the salt solution in the stage 1 and stage 2 reactions allows Ti to occur in condensed states (e.g., solid and liquid), such as at temperatures below about 700 ℃ (e.g., below about 300 ℃), for example ⁴⁺ Reduction to Ti ³⁺ And Ti ³⁺ Reduction to Ti ²⁺ 。

FIG. 1 shows the reaction of TiCl ₄ A general flow diagram of an exemplary method 100 for reduction to a titanium alloy material. The method 100 is generally performed in a cis-transThe sequence stage shows: a reaction precursor 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.

I. Reaction precursor

The reaction precursors for the stage 1 reaction at 104 in the method 100 shown in fig. 1 comprise at least: tiCl (titanium dioxide) ₄ And an input mixture comprising aluminum (Al) alone or in combination with an additional chloride component. In one embodiment, the reactive precursor comprises: as an input mixture of solid material at ambient conditions (e.g. about 25 ℃ and 1 atmosphere), and TiCl in liquid form ₄ . Additional materials (e.g., alCl) ₃ And/or other alloying element halides) may be included in the reaction precursors at the various stages of the process 100 (e.g., included in the input mixture, included in the TiCl ₄ Internal), and/or as a separate input into the stage 1 reaction and/or the stage 2 reaction. That is, more than one alloying element chloride may optionally be introduced into the stage 1 reaction material (e.g., into the input mixture (if solid), into the TiCl, etc ₄ (if liquid or soluble solid material), and/or directly separately into the stage 1 reactor), dissolved in other components of the input material, and/or optionally input into the stage 2 reaction material. In certain embodiments, the alloying element halide is specifically added to the liquid TiCl ₄ In (e.g. dissolved in liquid TiCl) ₄ In (1), liquid TiCl may be added ₄ Filtration is performed to remove any particles in the liquid stream. Such a filter (in certain embodiments) may refine the liquid stream by removing oxygen species from the liquid, due to the extremely low solubility of oxygen species and oxidizing species. Thus, tiCl ₄ The filtering of the liquid (with or without any alloying element halide dissolved therein) may customize the chemistry of the liquid and remove oxygen species from the liquid.

For example, the reactive precursor may contain some or all of the alloying elements (alloy elements) to achieve the desired chemistry in the titanium alloy materialAnd (4) properties. In one embodiment, the alloying element is a halide (MX) _x ) Can be chloride of alloy element (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.

As shown in fig. 1, at 102, the input mixture is formed from aluminum (Al), optionally aluminum chloride (e.g., alCl) ₃ ) And optionally one or more alloying element chlorides. Without wishing to be bound by any particular theory, it is presently believed that: alCl ₃ Can be used as a component in the input mixture, but if it is carried out under TiCl under the reaction conditions of stage 1 ₄ In which a soluble or miscible chloride of an alloying element is present to form AlCl in situ from the chloride of the alloying element and aluminum _x In all, alCl ₃ It is not necessary. In one embodiment, alCl ₃ Is included as a material in the input mixture. However, in another embodiment, the input mixture may be substantially free of AlCl ₃ . As used herein, the term "substantially free" means that no more than a negligible trace amount is present, and encompasses "completely free" (e.g., "substantially free" can be 0 atomic%, up to 0.2 atomic%). If AlCl is present ₃ If not present in the feed mixture, then Al and other metal chlorides are present and used to form AlCl ₃ So that the stage 1 reaction can proceed.

Chlorides of more than one alloying element (MCl) if solid at ambient conditions _x ) May optionally be included in the input mixture to form the input mixture. Particularly suitable with aluminium and optionally AlCl ₃ Alloying element chlorides contained together in the solid state 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. One or more of these alloying element chlorides may also be included in other stages of the process (including but not limited to titanium tetrachloride) and/or after stage 1.

In one embodiment, the input mixture is in the form of a plurality of particles (i.e., in powder form). For example, the mixture is fed by comminuting aluminum (Al), optionally aluminum chloride (e.g., alCl) ₃ ) And optionally one or more halides of the alloying element (e.g., chlorides of the alloying element). The materials of the input mixture may be combined into a solid material and comminuted together to form a plurality of particles having a mixed composition. In an embodiment, a mixture of aluminum particles, optional aluminum chloride particles, and optional particles of one or more alloying element chlorides are mixed together and sized (e.g., comminuted) to form a plurality of particles of the input mixture. For example, the aluminum particles may be aluminum particles having a pure aluminum core with an aluminum oxide layer formed on the surface of the particles. Alternatively, the aluminum particles may comprise a core of aluminum and at least one other alloying element or a master alloy of aluminum and an alloying element. The aluminum particles can have any suitable morphology, including platelet, substantially spherical, and the like.

Since aluminum particles typically form an aluminum oxide layer on the surface of the particles, the comminution process is conducted in a substantially oxygen-free atmosphere to inhibit the formation of any additional aluminum oxide in the input mixture. For example, the pulverization process may be performed under an inert atmosphere (such as an argon atmosphere) having a pressure of about 700 torr (torr) to about 3800 torr (torr). Without wishing to be bound by any particular theory, it is believed that AlCl is present during comminution of Al (solid state) (Al (s)) ₃ With surface Al ₂ O ₃ The reaction between the two makes AlCl ₃ Mixing Al ₂ O ₃ Conversion to AlOCl (e.g. by Al) ₂ O ₃ +AlCl ₃ →3A1OCl)。Al ₂ O ₃ The surface layer protects the lower Al(s) layer, then the powderDuring the crushing process, the Al is removed ₂ O ₃ The surface layer is converted to AlOCl, so that Al is dissolved and diffused in the salt as Al ²⁺ Al of (2) ⁺ . Without wishing to be bound by any particular theory, it is believed that less than stable Al is present ₂ O ₃ The required partial pressure of oxygen (i.e., under an inert atmosphere) allows these reactions to convert Al ₂ O ₃ (otherwise Al) ₂ O ₃ Very stable in oxygen). The particles obtained are then "activated" Al powder.

In addition, reducing the particle size increases the particle surface area to extend the availability of aluminum surface area for subsequent reduction reactions. The plurality of particles can have any suitable morphology, including platelet, substantially spherical, and the like. In a particular embodiment, the plurality of particles of the input mixture have a minimum average particle size of about 0.5 μm to about 25 μm (e.g., about 1 μm to about 20 μm), which is calculated by averaging the minimum sizes of the particles. For example, in one embodiment, a sheet can define planar particles having dimensions in the x-y plane, and a thickness in the z-dimension having a minimum average size of about 0.5 μm to about 25 μm (e.g., about 1 μm to about 20 μm), with the x-dimension and the y-dimension having larger average sizes. In one embodiment, the pulverization is carried out at a pulverization temperature of about 40 ℃ or less to suppress agglomeration of Al particles.

The pulverization can be accomplished using a high intensity process or a low intensity process to produce a plurality of particles of the input mixture, such as using ball milling, or other size reduction methods.

⁴⁺ ³⁺ Stage 1 reaction (Ti → reduction of Ti)

As mentioned above, the reactive precursor comprises at least: tiCl in liquid or vapour form ₄ 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). TiCl (titanium dioxide) ₄ Can be TiCl ₄ Pure liquid or liquid mixed with other alloy chlorides. In certain embodiments, tiCl can be heated ₄ And other alloy chlorides toThe resulting solution is kept unsaturated, which enables the components to precipitate out of solution. Examples of mixed liquid precursors include TiCl ₄ And VCl ₄ To form a titanium alloy containing vanadium. Various metal chlorides (i.e., alCl) ₃ 、VCl ₄ 、VCl ₃ 、MCl _x Etc.) can be dissolved in TiCl ₄ (liquid) (TiCl) ₄ (l) Of (TiCl), it may be prepared from (TiCl) ₄ ) _x (AlCl ₃ ) _y (MCl _x ) _z Where M is any suitable metal described herein and x, y, and z are mole fractions of specific components of the salt solution. Such salt solutions may be generally referred to as [ Ti ] for short ⁴⁺ : salt (salt)]Wherein, the bracket [ 2 ]]Is represented by having Ti ⁴⁺ The "salt" means all of the minor species or alloying elements.

These reaction precursors are added together in the stage 1 reaction at 104 for the addition of Ti ⁴⁺ Reduction to Ti ³⁺ . For the stage 1 reaction, the reaction precursors are heated to a first reaction temperature that is high enough to cause chemical reduction but low enough to suppress the liquid TiCl ₄ And (4) forming. For example, a stage 1 reaction can be performed in which the reaction precursors are heated to a first reaction temperature that is below about 180 ℃ (e.g., from about 100 ℃ to about 165 ℃, such as from about 140 ℃ to about 160 ℃). In one embodiment, tiCl is reacted with a nitrogen source ₄ The input mixture is heated to a first reaction temperature prior to addition of the input mixture. Alternatively or additionally, tiCl may be heated while the input mixture is heated to the first reaction temperature ₄ The input mixture is added.

Without wishing to be bound by any particular theory, it is believed that aluminum (e.g., as metallic aluminum or aluminum salts such as AlCl) is present in the input mixture ₃ And/or AlCl _x Form) of TiCl by means of aluminothermic process at a first reaction temperature ₄ Of Ti ⁴⁺ Reduction to Ti ³⁺ Wherein AlCl ₃ With AlCl ₃ The salt solution in form serves as the reaction medium. In addition, it is considered that Ti ⁴⁺ And Al dissolved in AlCl ₃ Neutralization is produced by reaction of the feed mixtureTiCl formed ₃ (AlCl ₃ ) _x In order to make Ti ⁴⁺ And Al can react. It is also considered that Al is present as Al ⁺ Or Al ²⁺ Dissolved in the salt and these Al species diffuse to Ti ⁴⁺ And reacted to form new TiCl ₃ (AlCl ₃ ) _x And (3) a reaction product. Finally, it is believed that Al(s) passes through AlCl on Al(s) ₃ Or the AlOCl surface layer is dissolved in a salt solution. For example, without wishing to be bound by any particular theory, it is believed that TiCl ₄ Of Ti ⁴⁺ Is reduced to TiCl in the form of a complex with a metal chloride ₃ In the form of (e.g. in TiCl) ₃ (AlCl ₃ ) _x (wherein x is greater than 0, such as greater than 0 to 10 (e.g., x is 1 to 5)) Ti ³⁺ The TiCl ₃ (AlCl ₃ ) _x Is on TiCl ₃ With AlCl ₃ Or the following two solutions: rich in TiCl ₃ Of TiCl (A) to (B) ₃ (AlCl ₃ ) _x And is rich in AlCl ₃ AlCl of ₃ (TiCl ₃ ) _x Wherein the two solutions have similar crystal structures. Therefore, it is considered that substantially all of Ti is formed ³⁺ The species is in the form of this metal chloride complex, not pure TiCl ₃ 。

The reaction product thus obtained is Ti-containing ³⁺ AlCl of the class of substances ₃ Saline solution. With [ Ti ] as described above ⁴ ⁺ : salt (I)]Similarly, various metal chlorides (i.e., alCl) ₃ 、VCl ₄ 、VCl ₃ 、MCl _x Etc.) are dissolved in TiCl ₃ (solid or liquid) from (TiCl) ₃ ) _x (AlCl ₃ ) _y (MCl _x ) _z Wherein M is any suitable metal and x, y and z represent the mole fraction of the salt solution. TiCl (titanium dioxide) ₃ (AlCl ₃ ) _x Is a subset (sub-set) of the larger solution phase, even if all the alloying element chlorides MCl _x Dissolved in the solution phase. In addition, ti ⁴⁺ Also dissolved in the solution phase, which can be described as the Cl-rich side of the phase field. When TiCl is mixed ₄ When the reaction mixture is added to the reaction mixture,there may be a certain time ratio of AlCl ₃ Poly TiCl ₄ /TiCl ₃ This makes the salt TiCl rich ₃ . Such salt solutions may be commonly referred to as [ Ti ] for short ³⁺ : salt (salt)]Wherein, the bracket [ 2 ]]Is represented by having Ti ³⁺ The "salt" means all of the minor species or alloying elements.

When TiCl is reacted in a controlled manner at the first reaction temperature ₄ The reaction can be carried out while the input mixture is added. For example, tiCl can be added continuously or in a semi-batch manner ₄ . In one embodiment, excess Al is included in the reaction to ensure substantially complete incorporation of Ti ⁴⁺ Reduction to Ti ³⁺ And used for subsequent reactions. Thus, tiCl may be added ₄ To obtain the desired Ti/Al ratio to produce the desired salt composition.

During the reaction, the input mixture may remain substantially solid at the first reaction conditions (e.g., the first reaction temperature and the first reaction pressure). In particular embodiments, the stage 1 reaction is carried out in a plow reactor (plow reactor), ribbon blender, or other liquid/solid/vapor reactor. For example, ti ⁴⁺ The reduction reaction can be carried out in an apparatus to reflux during the reaction phase and/or to distill any unreacted TiCl after the reaction phase ₄ Steam is used for continuing the reduction and/or to prevent TiCl loss during the reaction ₄ (g)。

The stage 1 reaction may be carried out under an inert atmosphere (e.g., including argon). Thus, the uptake (uptake) of oxygen (O) by aluminium and/or other compounds during the reduction reaction can be avoided ₂ ) Water vapor (H) ₂ O), nitrogen (N) ₂ ) Carbon oxides (e.g., CO) ₂ Etc.) and/or hydrocarbons (e.g., CH) ₄ Etc.). In certain embodiments, the inert atmosphere has a pressure of from 1 atmosphere (e.g., about 760 torr) to about 5 atmospheres (e.g., about 3800 torr), such as from about 760 torr to about 1500 torr. While a pressure of less than about 760 torr may be used in certain embodiments, it is not desirable in most embodiments because of the oxygen at such lower pressuresWater, carbon oxides and/or nitrogen may enter. For example, the pressure of the inert atmosphere is from 0.92 atmospheres (e.g., about 700 torr) to about 5 atmospheres (e.g., about 3800 torr), such as from about 700 torr to about 1500 torr.

In the presence of Ti ⁴⁺ Reduction to Ti ³⁺ After the stage 1 reaction, the first reaction product may be dried under drying conditions to remove substantially all of any residual unreacted TiCl ₄ (due to kinetic limitations) to form an intermediate mixture. For example, the first reaction product may be dried by heating and/or vacuum conditions. In one embodiment, the polymer is heated to a temperature higher than TiCl ₄ (e.g., about 136 ℃) but less than the boiling point of Ti ³⁺ Temperatures (e.g., above about 180 ℃) for the further reduction (e.g., drying temperatures of about 160 ℃ to about 180 ℃ (e.g., about 160 ℃ to about 170 ℃)), removing any entrained TiCl from the first reaction product ₄ 。

However, it should be noted that Al can react Ti at all temperatures (including less than 20 ℃ C.) to form Ti ⁴⁺ Reduction to Ti ³⁺ And mixing Ti ³⁺ Reduction to Ti ²⁺ . The above temperatures are due to kinetic limitations and/or solid state transitions in the reaction product. Furthermore, without wishing to be bound by any particular theory, it is believed that: the presence of Ti in the stage 1 reaction product ⁴⁺ When Ti is not generated ³⁺ →Ti ²⁺ Due to the Gibbs phase law and phase equilibrium of the Ti-Al-Cl-O system. That is, al oxidation can drive both reduction steps at the same temperature, but the order of these reactions is due to Ti ⁴⁺ And Ti ²⁺ Current beliefs that cannot exist simultaneously in the same location of the isolation system. Therefore, these reactions are carried out in order to form Ti in the system ²⁺ Previously, substantially all of Ti ⁴⁺ Reduction to Ti ³⁺ . Thus, the reduction process is carried out in a sequential manner by the method disclosed herein.

After drying the first reaction mixture and before heating the intermediate mixture to the second reaction temperature for the stage 2 reaction described below, [ Ti ] may be contained prior to further reaction ³⁺ : salt (I)]The intermediate mixture of (2) is stored, for example, under an inert atmosphere. In one embodiment, ti may be added ³⁺ The intermediate mixture of complexes is cooled to a temperature of less than about 100 deg.C (e.g., less than about 50 deg.C or less than about 25 deg.C) for storage.

Referring to fig. 2, a process schematic 200 of one exemplary embodiment of the reaction precursor at 101 (including the formation of the input mixture at 102) and the stage 1 reaction at 104 of the exemplary method 100 shown in fig. 1 is shown. In the illustrated embodiment, the first liquid reservoir 202 and the optional second liquid reservoir 204 are in liquid communication with a liquid mixing device 206 for supplying liquid reaction precursors thereto via supply line 208. Typically, the first liquid storage tank 202 contains TiCl ₄ In the form of TiCl ₄ In the form of pure liquids or liquids mixed with other alloying element chlorides. A valve 210 and pump 212 control the flow of liquid 201 from the liquid storage tank 202 into the liquid mixing device 206. Similarly, the second liquid reservoir 204 is in liquid communication with the liquid mixing device 206 for supplying liquid reaction precursor thereto via supply line 214. In one embodiment, the second liquid storage tank 204 contains a liquid 205 of at least one alloying element chloride. A valve 216 and pump 218 control the flow of liquid 205 from the liquid storage tank 204 into the liquid mixing device 206.

Further, as shown in fig. 2, from Al storage 222, optionally aluminum chloride (e.g., alCl) ₃ ) Storage 224 and optionally one or more storage 226 for alloying element chlorides, the solid reaction precursors are fed to ball milling apparatus 220. Although a ball milling apparatus 220 is illustrated, any suitable size reduction apparatus (e.g., a pulverizing apparatus) may be used in accordance with the present method. As shown, an aluminum chloride storage 224 and one or more alloying element chloride storage 226 are supplied to the comminution apparatus 220 by an optional mixing apparatus 228. From the comminution apparatus 220, an input mixture 221 is provided to the stage 1 reaction apparatus 230 through a feed hopper 232. In addition, the mixed liquor from the liquor mixer 206 is fed in a controlled manner to the stage 1 reaction apparatus 230 via supply line 234, wherein the flow of the mixed liquor is controlled by pump 236 and valve 238. Can be used forOptionally, the aluminum chloride storage 224 and the one or more alloying element chloride storage 226 may be fed directly to the feed hopper 232 through an optional mixing device 228.

In the stage 1 reaction apparatus 230, ti is introduced under the above-mentioned conditions ⁴⁺ Reduction to Ti ³⁺ Forming a first reaction product. The first reaction product can be dried at the end of the stage 1 reaction apparatus 230 (e.g., in a drying zone 229 having drying conditions (e.g., drying conditions as described above)) to remove substantially all any residual TiCl by a condenser 231 ₄ To form an intermediate mixture (containing Ti) ³⁺ E.g. TiCl in complex with metal chlorides ₃ Forms of e.g. TiCl ₃ (AlCl ₃ ) _x ) The intermediate mixture is supplied to a production line 244 for further reduction of the titanium. Any remaining TiCl may be reacted as shown ₄ Or the liquid mixture is vaporized and optionally recycled (e.g., by distillation, not shown) in the recycle loop 246. In an alternative embodiment, the size reduction device may be integrated within stage 1 reaction device 230. In one embodiment, the conditions of the stage 1 reaction unit 230 during the reaction maintain liquid in the reactor or condense vapor for return to the stage 1 reactor. Then, during drying, the condenser is heated to a temperature greater than the boiling point of the liquid mixture to allow drying.

The intermediate mixture (containing Ti) may be stored after drying but before further reduction process ³⁺ E.g. in the form of TiCl complexed with other materials ₃ In the form of (d). In one embodiment, the intermediate mixture is stored under an inert atmosphere to inhibit and prevent the formation of any alumina, other oxide complex, or oxychloride complex in the intermediate mixture.

³⁺ ²⁺ ²⁺ Stage 2 reaction (Ti → Ti and Ti → Ti alloy)

Stage 2 reaction at 106 in method 100, mixing the intermediate by heating to a second reaction temperature and with Al present as solid Al or as an Al species dissolved in the complexT of compound ³⁺ And any alloying element halide MX _x Reduction to Ti ²⁺ And M sub-halide, followed by subjecting Ti to endothermic disproportionation reaction at a third reaction temperature (which is higher than the second reaction temperature) ²⁺ And reducing the alloy into Ti alloy. Further, at a temperature within the range of the stage 2 process, the metal subhalide is reduced by Al reduction to form a base alloying metal (base alloying metal) M. In an embodiment, these reactions may be carried out in a single step reaction at different temperatures in sequential reactions or in separate steps (e.g., staged as the temperature increases) in a two or more step process.

Without wishing to be bound by any particular theory, it is believed that at the second reaction temperature, aluminum (e.g., as metallic aluminum or an aluminum salt such as AlCl) is present in the intermediate mixture ₃ And/or AlCl _x In the form of) TiCl to be complexed with the metal chloride ₃ Such as TiCl ₃ (AlCl ₃ ) _x Of Ti ³⁺ Reduction to Ti ²⁺ . For example, without wishing to be bound by any particular theory, it is believed that the reaction may form on TiCl complexed with the metal chloride ₂ Of Ti ²⁺ To form titanium-based aluminum chloride complexes (e.g., tiAlCl) with optional additional alloying elements or elemental halides or elemental chloro-aluminates ₅ 、Ti(AlCl ₄ ) ₂ ) Or mixtures thereof).

Without wishing to be bound by any particular theory, it is generally believed that there are three possible forms of TiCl ₂ : (1) Substantially pure TiCl ₂ It dissolves only small amounts of any substance; (2) TiAlCl ₅ (solid state) (TiAlCl ₅ (s)), which also does not dissolve large amounts of other substances and may only be stable to about 200 ℃; and (3) { Ti (AlCl) ₄ ) ₂ } _n It may be an inorganic polymeric material (long chain molecules) present as a liquid or gas, a glass material and a fine powder. That is, { Ti (AlCl) ₄ ) ₂ } _n Has a large composition range (e.g., n can be from 2 to about 500, such as from 2 to about 100, such as from 2 to about 50, such as from 2 to about 10), and dissolves all of the alloying elements chlorineAnd (4) melting the mixture. In a specific embodiment, the gas { Ti (AlCl) ₄ ) ₂ } _n Helping to remove unreacted salts from the Ti-alloy particles (e.g., at a later stage of the reaction, at a lower temperature). As a result, it contains Ti ²⁺ Based on a reaction product between TiCl ₂ And AlCl ₃ Complex between (e.g. Ti (AlCl) ₄ ) ₂ Etc.). Such complexes may be referred to as [ Ti ] for short ²⁺ : salt (salt)]A salt solution, wherein, the bracket [ 2 ]]Is shown to have AlCl ₃ As the main kind of solvent, ti ²⁺ And "salt" means all of the minor species or alloying elements.

Ti may be carried out at a second reaction temperature above about 180 deg.C (e.g., from about 180 deg.C to about 900 deg.C, such as from about 180 deg.C to about 500 deg.C, or from about 180 deg.C to about 300 deg.C) ³⁺ →Ti ²⁺ Reduction of (2). Without wishing to be bound by any particular theory, it is believed that Ti ²⁺ At least a part of TiCl being complexed with the metal chloride ₂ In the form of (1).

Without wishing to be bound by any particular theory, it is believed that AlCl is present in the process ₃ Chemically bonded to TiCl ₃ (AlCl ₃ ) _x 、TiAlCl ₅ And { Ti (AlCl) ₄ ) ₂ } _n In (1). Due to its significant chemical activity (e.g.,<1) Thus AlCl ₃ Can not resemble pure AlCl ₃ As expected, and no significant AlCl until the reaction temperature reaches or exceeds about 600 c ₃ And (4) evaporating. Thus, alCl ₃ A reaction medium is provided to allow the reaction to occur, and AlCl ₃ Providing stable Ti ²⁺ Ionic chemical environment and allows for the reaction of Ti at reaction temperatures of less than about 250 ℃ (e.g., about 180 ℃ to about 250 ℃) ³⁺ Conversion to Ti ²⁺ 。

After complexing TiCl with the metal chloride ₃ (e.g. in TiCl form ₃ -(AlCl ₃ ) _x And/or TiAlCl ₆ (gaseous) (TiAlCl) ₆ (g) Form) of Ti ³⁺ Reduction to Ti ²⁺ (e.g. in the form of TiCl complexed with a metal chloride ₂ Form(s) can be followed by disproportionationReacting Ti ²⁺ And converted into a Ti alloy. In one embodiment, tiAlCl may be present ₆ (g) To assist in the removal of Ti from the Ti-alloy formation ³⁺ By-products and/or recycling Ti in the reaction chamber ³⁺ . For example, ti can be reacted by disproportionation at a third reaction temperature above about 250 deg.C (e.g., about 250 deg.C to about 1000 deg.C, such as about 500 deg.C to about 1000 deg.C) ²⁺ And converted into a Ti alloy. Although the third reaction temperature may extend to about 1000 ℃ in some embodiments, the upper temperature limit of the third reaction temperature is about 900 ℃ in other embodiments. For example, ti can be reacted by disproportionation at a third reaction temperature of from about 300 deg.C to up to about 900 deg.C (e.g., from about 300 deg.C to about 900 deg.C, such as from about 500 deg.C to about 900 deg.C) ²⁺ Reducing the alloy into Ti alloy. Without wishing to be bound by any particular theory, it is believed that maintaining the third reaction temperature less than about 900 ℃ ensures that any oxygen contamination present within the reaction chamber remains as a stable volatile species that can be driven off to limit the oxygen in the resulting Ti alloy product. On the other hand, at reaction temperatures greater than 900 ℃, the oxygen contamination is no longer in the form of volatile species, which makes it more difficult to reduce residual oxygen. Any other volatile substances such as oxychlorides, chlorides and/or oxides (containing carbon) can be removed by thermal distillation.

Generally, this reaction of Ti alloy formation can be divided into: an alloy formation stage via disproportionation (e.g., at a disproportionation temperature of about 250 ℃ to about 650 ℃), and a distillation stage (e.g., at a distillation temperature of about 650 ℃ to about 1000 ℃).

For example, ti alloy formation can be divided into two processes: nucleation and particle growth (which may also be referred to as particle coarsening). During nucleation, at lower temperatures (e.g., about 250 ℃ to about 400 ℃) [ Ti ] ²⁺ : salt (salt)]A first Ti alloy is formed. The local composition of the salt (component activity), the surface energy and the disproportionation kinetics determine the resulting Ti alloy composition. Then, particle growth occurs, wherein the particles are grown in a condensed state at an elevated temperature (e.g., about 400 ℃ to about 700 ℃) and in a gas-solid reaction at a temperature greater than 700 ℃ (e.g., about 700 ℃ to about 1000 ℃)[Ti ²⁺ : salt (salt)]And continuously growing the Ti alloy. These higher temperature reactions (e.g., greater than about 700 ℃) may also be referred to as distillation processes, wherein Cl is removed from the Ti alloy product, which occurs while the Ti alloy particles grow. These methods are all based on disproportionation reactions, but are capable of producing Ti alloys of different compositions. Furthermore, it should be noted that for both Ti and Al during the reaction, there is a disproportionation reaction: ti (titanium) ²⁺ ＝1/3[Ti]+2/3Ti ³⁺ And Al ⁺ ＝2/3[Al]+1/3Al ³⁺ . The equipment design of the process can be configured to independently control residence time at each temperature (e.g., hot zone), which can help control the process.

In one embodiment, will have Ti ²⁺ Until substantially all of the Ti is present ²⁺ Is reacted to obtain the titanium alloy material. In the reaction, any Ti formed during disproportionation ³⁺ Can be recycled internally to be reduced to Ti by hot aluminum reduction ²⁺ And further reacting in a disproportionation reaction. Alternatively, ti may be formed by competing for disproportionation of Ti ⁴⁺ (e.g. in TiCl form ₄ Forms of (e)) which can be vented out of the reaction system as a gaseous by-product for continued reaction (e.g., reduction back to Ti ³⁺ Then reduced to Ti ²⁺ ) Or as a by-product (take-off by-product) to be discharged out of the reaction system (for example, by countercurrent flow of an inert gas).

The stage 2 reaction (e.g., ti) may be carried out under an inert atmosphere (e.g., comprising argon and/or substantially free of oxygen, nitrogen, moisture, hydrocarbons, and other impurities) ³⁺ →Ti ²⁺ And/or Ti ²⁺ → Ti alloy). In certain embodiments, the pressure of the inert atmosphere is between about 1 atmosphere (e.g., about 760 torr) and about 5 atmospheres (e.g., about 3800 torr), such as about 760 torr and about 1500 torr. As shown in FIG. 1, an inert gas may be introduced as a counter current to adjust the reaction atmospheric pressure and to react the gaseous titanium chloride complex and AlCl _x Strip titanium alloy material and return to T ³⁺ →Ti ²⁺ And/or Ti ²⁺ → in the reflux reaction zone of the Ti alloy.Additionally or alternatively, any TiCl produced during the reaction may be reacted ₄ Carried away from the reactor as a by-product of the disengagement. Therefore, the reaction can be carried out efficiently without a significant waste of the Ti material.

For example, as described above (Ti) ²⁺ ＝1/3[Ti]+2/3Ti ³⁺ ) From Ti in salt solutions (condensation and vapour) by disproportionation ²⁺ Formation of Ti in Ti-Al system alloy, and formation of Ti in salt solution (condensation and vapor) ³⁺ . For Al dissolved in salt solution and formed in Ti-Al series alloy ⁺ /Al/Al ³⁺ And other alloying elements, with similar corresponding disproportionation reactions occurring. Therefore, no pure Ti product is formed during these disproportionation reactions. Without wishing to be bound by any particular theory or particular reaction sequence, it is believed that Ti-Al alloy formation occurs through an endothermic reaction involving the input of heat to drive the reaction toward the Ti-Al alloy product.

The Ti-Al alloy formed by the above reaction may be in the form of a Ti-Al alloy mixed with other metallic materials. The alloying elements may also be contained in the titanium chloroaluminate consumed and formed in the disproportionation reaction described above. Controlling at least the Ti in the reaction entering stage 2 by means of a control system ²⁺ /Al/AlCl ₃ Temperature, heat flux, pressure, gas flow rate, al/AlCl of the mixture ₃ Ratio and particle size/aggregation state, fine and uniform alloyed particles can be produced from the desired composition.

Forming, as a reaction product of the stage 2 reaction, a titanium alloy material comprising: elements from the reaction precursors, and any additional alloying elements added during the stage 1 reaction and/or the stage 2 reaction. For example, ti-6Al-4V (in weight percent), ti-4822 intermetallic compounds (48 Al, 2Cr, and 2Nb in atomic percent) may be formed as the titanium alloy material. In one embodiment, 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.).

Referring to fig. 3, a process diagram 300 of an exemplary embodiment of the stage 2 reaction at 106 and the post-processing at 108 of the exemplary method shown in fig. 1 is shown.In the illustrated embodiment, the intermediate mixture is supplied to stage 2 reaction apparatus 302 via line 244 after passing through optional mixing apparatus 306. In stage 2 reaction apparatus 302, the Ti of the intermediate mixture is heated to a second reaction temperature as detailed above ³⁺ Reduction to Ti ²⁺ And then reacting Ti by disproportionation at a third reaction temperature which is higher than the second reaction temperature ²⁺ Reducing the alloy into Ti alloy. The illustrated exemplary stage 2 reaction apparatus 302 is a single stage reactor that includes a zone heating apparatus 304 surrounding a reaction chamber 306. The zone heating apparatus 304 may effect a temperature change, increase, etc. within the reaction chamber 306 as the intermediate mixture flows through the reaction chamber 306. For example, the zone heating apparatus 304 can have a first reaction temperature at an input of the reaction chamber 306 (e.g., the first zone 308) and a second reaction temperature at an output of the reaction chamber 306 (e.g., the second zone 310). The apparatus may also have a gradient of reaction temperature between more than 2 zones. The apparatus may also have a gradient of reaction temperature between more than 2 zones. The present method/process is designed to enable uniform mixing and continuous flow through the temperature gradient.

The vaporous reaction product (e.g., alCl) may be reacted using a counter current flow of inert gas ₃ 、Al ₂ Cl ₆ 、TiCl ₄ 、TiAlCl ₆ 、AlOCl、TiOCl(AlOCl) _x Etc.) are removed from the reaction chamber 306. For example, an inert gas may be supplied from an inert gas supply 313 to the second region 310 of the reaction chamber 306 through a supply pipe 312. The inert gas may then be counter flowed to the solid material advancing in the reaction chamber 306 to carry the gaseous titanium chloride complex away from the titanium alloy material formed in the second zone 310 and back to the Ti occurring in the first zone 308 ³⁺ →Ti ²⁺ In the lower temperature reaction. Additionally or alternatively, the gaseous titanium chloride complexes produced during the reaction may be transported back into the reaction chamber 306, where they condense at a lower temperature, thereby controlling the Ti stoichiometry of the reaction salts. Any residual AlCl formed during the disproportionation reaction is removed via output line 315 (which may be a heating line to prevent condensation and plugging) _x He renWhat TiCl is ₄ Removed from reaction chamber 306 and collected in condenser/sublimator 317 (e.g., a single stage condenser or a multi-stage condenser) for recapture. Therefore, the reaction can be carried out efficiently without significant waste of the Ti material.

It is preferred to use a low impurity inert gas (e.g., low impurity argon, such as high purity argon) process gas to minimize the formation of oxychloride phases such as TiOCl in the process _x And AlOCl _x And finally inhibit the formation of TiO, tiO ₂ 、Al ₂ O ₃ And/or TiO ₂ -Al ₂ O ₃ And (3) mixing. Other inert gases, such as helium or other noble gases, which are inert to the reaction process, may also be used.

In-process monitoring can be used to determine reaction completion by measuring equilibrium, temperature, pressure, process gas chemistry, output product chemistry, and by-product chemistry.

The titanium alloy material may be collected by 314 to be provided to an aftertreatment device 316, for example, as described below. The post-treatment step may be carried out in a separate apparatus or may be carried out in the same or a connected apparatus used for the stage 2 process.

Post-treatment of titanium alloys

After formation, the titanium alloy material may be machined (processed) at 108. For example, titanium alloy powders may be processed for coarsening, sintering, direct consolidation, additive manufacturing, bulk melting (bulk melting), or spheroidizing. For example, the titanium alloy material may be subjected to a high temperature treatment to purify the Ti alloy by removing residual chlorides and/or allowing diffusion to reduce compositional gradients, such as at treatment temperatures above about 800 ℃ (e.g., about 800 ℃ to about 1,000 ℃).

In one embodiment, the high temperature treatment also allows the disproportionation reaction to continue from any residual Ti ²⁺ To produce a Ti alloy.

Examples

As shown in FIG. 4, the overlay stability plots (relative to Cl per mole) for the Ti-Cl and Al-Cl systems were determined by examining ₂ Gibbs energy/absolute value T) the methods described herein can be explained in the most general and simplest terms.

Although no alloying or salt solutions are considered, it shows the maximum available chemical energy in the Ti-Al-Cl system. By oxidation of Al metal to Al at temperatures below 1000K (730 ℃ C.) ³⁺ (in the form of AlCl) ₃ (solid state) (AlCl ₃ (s))、Al ₂ Cl ₆ (gaseous) (Al) ₂ Cl ₆ (g) And/or AlCl ₃ (gaseous) (AlCl) ₃ (g) Form) of Ti may be added ⁴⁺ (with TiCl) ₄ (liquid, gaseous) (TiCl ₄ (l, g)) form) reduction to Ti ³⁺ (with TiCl) ₃ (solid state) (TiCl ₃ (s)) and subsequently reduced to Ti ²⁺ (with TiCl) ₂ (solid state) (TiCl ₂ (s)) form), but Ti cannot be oxidized by oxidizing metallic Al ²⁺ Reducing the Ti into metal Ti. In the process, in a salt solution [ Ti ] ²⁺ : salt (I)]In the middle by Ti ²⁺ Disproportionation reaction of (Ti) ²⁺ ＝1/3[Ti]+2/3Ti ³⁺ ) (preparation of [ Ti)]Particles and as salt solution [ Ti ³⁺ : salt (salt)]Or steam of Ti ³⁺ ) In the temperature range of 523K-923K (250-650 ℃), metallic titanium [ Ti ] alloyed with Al can be formed]. Ti driven by Al ⁴⁺ And Ti ³⁺ Is an exothermic process and is carried out in the low temperature part of the first stage (S1) reactor and the second stage (S2) reactor at a temperature below 523K (or 250 ℃), while Ti ²⁺ The disproportionation reaction is an endothermic process and is carried out at a moderate temperature range in the S2 reactor.

Ti ⁴⁺ 、Ti ³⁺ (and other alloying elements M) ^x+ ) The reduction, oxidation of Al and subsequent disproportionation mean that the process is essentially an electrochemical process. The methods described herein do not rely on electrodes or external circuitry and thus are expected to be charge neutral throughout the interaction region. This means that the alloy particles may consist of [ Ti ] ²⁺ : salt (I)]A homogeneous mass is formed provided that the local heat flux and composition support an endothermic disproportionation reaction. This is a significant advantage of the present method over electrochemical deposition and related methods.

In addition, in the case of the present invention,without wishing to be bound by any particular theory, it is believed that by the corresponding disproportionation reaction (i.e., for Al: al) ⁺ ＝2/3[Al]+1/3Al ³⁺ [9]For M: m ^x+ ＝1/(x+1)[M]+x/(x+1)M ^(x+1)+ ) Metallic Al and other alloying elements M and Ti ²⁺ While precipitating out of the salt and the supply of low oxidation state ions from the salt to the growth front of the alloy particles is not hindered. Furthermore, the low temperature nature of the present process means that the crystalline structure and phase boundaries typically observed with conventional processing routes (i.e., solidification and thermomechanical processing) do not necessarily form or are even expected.

The details of the method will be described with a general/high level of specificity of the method in mind. In a particular embodiment, it is possible to ensure that the starting reactants (TiCl) ₄ 、AlCl ₃ And the halide MX of the alloying element _x ) Virtually free of H ₂ O and O are followed by the following process because all metal halides will react with H ₂ O reacts strongly and is difficult to remove from some salts once oxygen is introduced. In addition, it is believed that oxygen contamination in the salt causes Ti ³⁺ Than Ti ²⁺ Stabilization, which hinders Ti ²⁺ And thus the composition of the alloy formed.

Example 1: )

Initially in TiCl form ₄ (l) Form (A) of Ti ⁴⁺ →Ti ³⁺ (with TiCl) ₃ (AlCl ₃ ) _x Form(s) was conducted in a stage 1 reactor and evaluated under an inert environment. The feed mixture contained 201.8g of Al flakes, 100.5g of AlCl ₃ 34.3g of NbCl ₅ And 20.1g of CrCl ₃ Loaded into a closed ball mill under a high purity argon atmosphere and ground at near room temperature for 16 hours (multiple ball mills providing feeds for each stage 1 run). The ground material was sieved at 150 μm sieve size and 594.1 grams (typically from two mills) were loaded into a plow mixer reactor under a high purity argon atmosphere. The reactor was maintained at a pressure of 1.2bar, wherein a low flow (less than 1 liter/min) of high purity argon was passed through the reactor. Injecting 11 at a rate of 6.5 + -2.0 g/min while continuously mixing64g of TiCl ₄ (l) Previously, the reactor and feed were preheated to 130 ℃ and stabilized. In the injection of TiCl ₄ (l) During which it evaporates initially, but TiCl is formed over time while maintaining the reactor wall at about 130 ℃ ₄ (l) Whereas the bulk free stream in the process feed { salt + Al } can reach temperatures as high as 145 ℃. Adding all TiCl ₄ (l) Thereafter, the reactor wall temperature is maintained at 130 ℃ usually with TiCl ₄ The injection takes place for the same period of time, during which the condensed TiCl absorbed in the input mixture and in the reaction product salt ₄ (l) The reaction was continued and reduced. Condensing TiCl in the major part ₄ (l) After being reduced (as indicated by a drop in bulk change temperature (bulk change temperature) and gas temperature above the mixed feed), the reactor wall temperature was raised to 160 ℃ and maintained. This ensured that all the condensed TiCl at the reactor wall ₄ (l) Can be reduced or can be removed. The intermediate material was cooled and removed from the reactor. XRD, ICP, cl titration and electron microscopy as well as EDS analysis were used to characterize representative samples taken from the product of the process to assess the form of metal chlorides, provided appropriate precautions were taken to stop the reaction with air. The results of this characterization confirm: the product contained residual unreacted Al particles of consistent shape and size observed in the ground product loaded into the plow reaction and also of consistent shape and size with the TiCl added ₄ By a consistent amount. The microstructure observed with SEM showed: the Al particles are surrounded by a graded layer of product salt, the salt in contact with the Al surface is enriched in AlCl ₃ And segregation of O is generally observed at this interface as an oxychloride layer "AlOCl". Further forming the surface of Al particles, tiCl ₃ (AlCl ₃ ) _x Phase is present and represents the bulk of the reaction product. The salt product has poor mechanical properties and easily separates the Al core particles and can exist separately from the Al particles. XRD analysis showed that: tiCl (titanium dioxide) ₃ (AlCl ₃ ) _x The salt phase generally exists as an alpha phase, hexagonal close-packed structure. The crystal structure and AlCl ₃ (TiCl ₃ ) _x In line with, and with continuous anchoringEvidence of bulk solution. The measured composition of the bulk sample composition corresponds to XRD and observed microstructure.

The equilibrated material was fed into a HED rotary kiln reactor with Ar counter-current gas, the rotary kiln reactor having 5 zones, wherein the zone temperatures were from about 250 ℃ to about 300 ℃, from about 300 ℃ to about 650 ℃, and from about 650 ℃ to about 1000 ℃. After reaction to a maximum temperature of 800 ℃ in a rotary kiln, sample material was collected and analyzed by XRD, ICP, cl titration and electron microscopy and EDS showing the formation of a gamma titanium aluminide metal alloy powder having a size <150 μm particle size 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 and a small residual chlorine content (0.6 wt%)).

Example 2:

the chemical reduction reaction was performed and evaluated under an inert environment. The feed mixture contained 250g of Al flakes, 62.5g of AlCl ₃ 42.75g of NbCl ₅ And 25.0g of CrCl ₃ And pulverized at room temperature for 16 hours. The crushed material was sieved at a sieve size of 150 μm and 714 grams (typically the product from two crushers) were charged to a plow mixer reactor. The reactor was preheated to 130 ℃ and TiCl was injected at a rate of 6.5g/min while mixing ₄ . After addition of 1541g of TiCl ₄ Thereafter, the reactor temperature was raised to 160 ℃ and maintained to dry/remove the excess TiCl ₄ . The intermediate material was cooled and removed from the reactor. The material from 3 similar first stage processes was fed into a HED rotary kiln reactor with Ar counter-current gas, having 5 zones, all zone temperatures set at 250 ℃. The { Al + TiCl ] from the first stage reaction ₃ (AlCl ₃ ) _x Product is fed into the rotary kiln at a constant rate of 1.0 + -0.2 kg/hour, passed through the heating zone at a range of speeds controlled by the rotational speed of the work tube (6 RPM residence time of about 13 min; 4RPM residence time of about 20 min; 2RPM residence time of about 40 min). In-process samples were collected throughout the run and characterized using XRD, ICP, cl titration and electron microscopy and EDS analysis. KnotAs shown, the starting material { Al + TiCl ₃ (AlCl ₃ ) _x The reaction is quenched in a rotary kiln. Al particles remain in the XRD spectrum and are also clearly visible in the microstructure, but in reduced amounts. This is combined with continued oxidation to convert Ti ³⁺ Reduction to Ti ²⁺ And (6) matching. alpha-TiCl ₃ (AlCl ₃ ) _x The characteristic XRD peaks disappear leaving only the peaks of the starting Al and alloy. Bulk composition of the sample, condensed AlCl collected ₃ The microstructure and amount of the vapor confirmed: the majority of the collected sample was salt and the salt did not have a defined crystalline structure (i.e., amorphous glass or polymeric material), which means that Al readily donates Ti at temperatures less than 250 ℃ ³⁺ (with TiCl) ₃ (AlCl ₃ ) _x Form (d) to Ti ²⁺ (with Ti (AlCl) ₄ ) ₂ Form (e) without a significant amount of AlCl ₃ And (4) evaporating. Ti (AlCl) ₄ ) ₂ Phases are known in the literature to be amorphous.

Except for Ti ³⁺ In addition to the low temperature reduction of (a), the results clearly show that the Ti alloy starts to form from the salt phase (by simultaneous disproportionation) at temperatures as low as 250 ℃. The reaction conditions described herein are not optimized and a wide variety of alloys are formed: alpha- [ Ti]、α2-Ti ₃ Al、γ-TiAl、TiAl ₂ 、TiAl ₃ (also contains Nb and Cr). The alloy particles coexist with salt and unreacted Al particles. Due to the various salt compositions/inhomogeneities, a wide variety of alloy phases is contemplated. This experimental production was carried out to demonstrate the ease of incorporation of Ti ³⁺ Reduction to Ti ²⁺ And that the Ti-alloy was formed by a simultaneous disproportionation process.

This written description uses examples to disclose the invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.

Claims

1. A method of making a titanium alloy material, comprising:

reacting TiCl at a first reaction temperature ₄ Is added to the input mixture so that TiCl ₄ Of Ti ⁴⁺ Is reduced to Ti ³⁺ Forming a first reaction product, wherein the input mixture comprises aluminum and optionally AlCl ₃ And/or optionally one or more alloying element halides;

on TiCl ₄ After the addition is stopped, the first reaction product is heated under dry conditions to completely reduce the Ti ⁴⁺ Or removing substantially all of the remaining TiCl ₄ Forming a first intermediate mixture, wherein the first intermediate mixture is Ti-containing ³⁺ AlCl of ₃ A salt solution of said Ti-containing ³⁺ AlCl of ₃ In a salt solution of Ti ³⁺ The specie is in the form of a metal chloride complex;

heating the first intermediate mixture to a second reaction temperature such that Ti ³⁺ Is reduced to a second intermediate mixture, wherein the second intermediate mixture is Ti-containing ²⁺ AlCl of ₃ A salt solution of said Ti-containing ²⁺ AlCl of ₃ The salt solution is based on titanium aluminum chloride complex; and the number of the first and second groups,

heating the second intermediate mixture to a third reaction temperature to obtain Ti ²⁺ Forming the titanium alloy material through disproportionation reaction.

2. The method of claim 1, wherein the input mixture comprises a plurality of particles comprising aluminum, alCl ₃ And optionally one or more alloying element chlorides, the plurality of particles of the input mixture having a minimum average particle size of from 0.5 μm to 25 μm.

3. The method of claim 2, wherein more than oneAlloying element chlorides are present in the input mixture, at least one of the alloying element chlorides comprising 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 method of claim 1, wherein the input mixture comprises a reaction mixture to form Ti-6Al-4V in weight%.

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

6. The process of claim 1, wherein the first reaction temperature is from 100 ℃ to 165 ℃.

7. The method of claim 1, wherein the aluminum present in the input mixture imparts TiCl ₄ Of Ti ⁴⁺ Reduction to Ti ³⁺ 。

8. The process of claim 1, wherein TiCl is used ₄ Added as a liquid or vapor mixed with other alloy chlorides.

9. The process of claim 1, wherein the TiCl is introduced in a plow reactor, ribbon blender or other liquid/solid/vapor reactor ₄ Of Ti ⁴⁺ Reduction to form Ti ³⁺ 。

10. The process of claim 1, wherein TiCl is reacted under an inert atmosphere at a pressure of 760 Torr to 1500 Torr ₄ Added to the input mixture.

11. The method of claim 1, wherein Ti in the first intermediate mixture ³⁺ In the form of TiCl ₃ (AlCl ₃ ) _x In which x is greater than 0 to 10.

12. The process of claim 1, wherein the second reaction temperature is from 180 ℃ to 500 ℃.

13. The method of claim 1, wherein the first intermediate mixture is heated to the second reaction temperature in at least one rotary kiln.

14. The process of claim 1, wherein the first intermediate mixture is heated to the second reaction temperature under an inert atmosphere having a pressure of from 760 torr to 3800 torr.

15. The method of claim 1, wherein the first intermediate mixture is maintained at the second reaction temperature until substantially all Ti in the first intermediate mixture ³⁺ Reduction to Ti ²⁺ To Ti ²⁺ At least a part of which is TiCl complexed with the metal chloride ₂ In the form of (1).

16. The process of claim 1, wherein Ti is reacted in a single reactor ³⁺ Reduction to Ti ²⁺ And reacting Ti by disproportionation ²⁺ And (4) reacting.

17. The method of claim 1, wherein Ti is introduced into the multi-zone reaction chamber ³⁺ Reduction to Ti ²⁺ And reacting Ti by disproportionation ²⁺ And (4) reacting.

18. The method of claim 1, wherein the method further comprises:

flowing an inert gas through the multi-zone reaction chamber, wherein the inert gas flow is counter current to the advancement of the reaction products, introducing the inert gas as a counter current to carry gaseous titanium chloride complex away from the formed titanium alloy material and back into the reaction zone for Ti ³⁺ →Ti ²⁺ And/or Ti ²⁺ Either or both of the reactions of the → Ti alloy.

19. The process of claim 18, wherein TiCl is generated during the reaction ₄ Reduced by aluminum chloride or carried away from the reactor as a by-product of the removal.

20. The method of claim 1, wherein Ti is caused to react by disproportionation reaction under an inert atmosphere having a pressure of 760 torr to 3800 torr ²⁺ And reacting to form the titanium alloy material.

21. The method of claim 1 wherein Ti formed during the disproportionation reaction is reduced ³⁺ Internal recycle to reduce to Ti ²⁺ And further reacted in a disproportionation reaction.

22. The process of claim 1, wherein the third reaction temperature is from 300 ℃ to 900 ℃.

23. The method of claim 1, wherein the titanium alloy material is a titanium alloy powder.

24. The method of claim 1, wherein the method further comprises:

the titanium alloy material is subjected to a high temperature treatment at a treatment temperature to purify the Ti alloy by removing residual chlorides and/or allowing diffusion to reduce the compositional gradient.

25. The method of claim 24 wherein the high temperature treatment further continues the disproportionation reaction to remove residual Ti ²⁺ The high temperature treatment also continues the distillation of unreacted metal hypohalides to produce a Ti alloy.

26. The method of claim 24, wherein the treatment temperature is 800 ℃ or higher.

27. The method of claim 1, wherein the method further comprises:

the alloying element halide is added to the input mixture during the reaction to form the first intermediate mixture or during the reaction to form the second intermediate mixture or during the disproportionation reaction or during post-processing.

28. A method of manufacturing a titanium alloy material, comprising:

at a temperature of less than 180 ℃, using a certain amount of aluminum and AlCl ₃ And at least one metal chloride reducing an amount of TiCl ₄ Form a film containing Ti ³⁺ Said first intermediate product comprising Ti ³⁺ Of the first intermediate product of (1), ti ³⁺ The specie is in the form of a metal chloride complex; and (c) a second step of,

the first intermediate product is reduced to a temperature of less than 900 ℃ to form a titanium aluminum alloy.

29. The process of claim 28 wherein the first intermediate product is a product comprising TiCl ₃ (AlCl ₃ ) _x Wherein x is greater than 0.

30. The method of claim 28, comprising Ti ²⁺ The second intermediate product of (2) is [ TiCl ₂ (AlCl ₃ )] _x Wherein x is greater than 0.

31. A method of making a titanium-containing material, comprising:

mixing Al particles and AlCl ₃ Particles and optionally at least one other alloying element chloridePellets forming an input mixture;

mixing TiCl ₄ Adding to the input mixture;

reducing TiCl in the presence of the input mixture at a first reaction temperature ₄ Of Ti ⁴⁺ Form a film containing Ti ³⁺ Wherein the first reaction temperature is less than 180 ℃;

said Ti-containing ³⁺ In the first intermediate mixture of (2), ti ³⁺ The specie is in the form of a metal chloride complex.

32. The method of claim 1, wherein the Ti ³⁺ The specie is in the form of an alpha phase, hexagonal close-packed structure metal chloride complex.