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WO2018089062A2 - Procédés de production de poudres métalliques et de mélanges maîtres métalliques - Google Patents

Procédés de production de poudres métalliques et de mélanges maîtres métalliques Download PDF

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Publication number
WO2018089062A2
WO2018089062A2 PCT/US2017/045656 US2017045656W WO2018089062A2 WO 2018089062 A2 WO2018089062 A2 WO 2018089062A2 US 2017045656 W US2017045656 W US 2017045656W WO 2018089062 A2 WO2018089062 A2 WO 2018089062A2
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WIPO (PCT)
Prior art keywords
metal
halide
molten reducing
salt
molten
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Ceased
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PCT/US2017/045656
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WO2018089062A3 (fr
Inventor
Donald FINNERTY
David Henderson
John KOENITZER
Andrew Matheson
Richard Van Lieshout
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Nanoscale Powders LLC
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Nanoscale Powders LLC
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Publication of WO2018089062A3 publication Critical patent/WO2018089062A3/fr
Anticipated expiration legal-status Critical
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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
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • 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
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous 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
    • 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
    • C22B34/14—Obtaining zirconium or hafnium
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
    • 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
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • 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
    • B22F2301/20—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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer

Definitions

  • the present invention relates to methods for producing metal powders, salt-coated metal powders, and metal masterbatches.
  • Metal powders can be used for advanced metallurgical processes, such as near net shape powder pressing, and additive manufactoing, including laser metal deposition (LMD), direct metal laser sintering (DMLS), selective laser sintering (SLS), and selective laser melting (SLM).
  • LMD laser metal deposition
  • DMLS direct metal laser sintering
  • SLS selective laser sintering
  • SLM selective laser melting
  • the end products find applications in a wide variety of industries, including aerospace, medical, and electronics. Other applications include the production of wire bar stock for rolling into medical alloys (e.g., superconducting wires for MRI machines), sputtering targets in electronics manufacturing for thin film metal deposition in displays, use in semiconductors and data storage devices, superalloy production, intermetallic powders for the manufacture of jet engine components, and photovoltaic cells.
  • Metal powders can also be pressed into dense objects using conventional pressing techniques. Salt-coated metal powders can be used for particle strengthening of metals.
  • metal powders are highly pure and have consistent flow properties.
  • processes for achieving metal powders having such characteristics require further development. Accordingly, there is a need in the art for methods of making pure metal powders that have adequate flow properties such that the powders can be used for advanced manufacturing applications.
  • a feature of the present invention is to provide a process for producing high purity, low oxygen content metal powders with good flow properties.
  • a further feature of the present invention is to provide a method for producing a metal masterbatch that comprises unreacted aluminum reducing metal and at least one other metal formed from a reaction of the aluminum metal and a metal halide.
  • a further feature of the present invention is to provide a method for producing a metal masterbatch that comprises unreacted magnesium reducing metal and at least one other metal formed from a reaction of the magnesium metal and a metal halide.
  • a further feature of the present invention is to provide a method for producing a metal masterbatch that comprises unreacted titanium reducing metal and at least one other metal formed from a reaction of the titanium metal and a metal halide.
  • the present invention relates to a method for producing a metal powder.
  • the method includes: a) combining at least one metal halide and at least one molten reducing metal in a space that is substantially free of oxygen and water to obtain a reaction product that includes at least one metal salt and metal; b) substantially removing the molten reducing metal in the reaction product; c) recovering at least the metal, and optionally the at least one metal salt.
  • the molten reducing metal is present in a stoichiometric excess to the metal halide.
  • the molten reducing metal can be primarily 1) sodium and/or potassium or 2) aluminum, or magnesium, or titanium.
  • the at least one metal halide is a solid or liquid, with the proviso that the molten reducing metal is different from the metal of the at least one metal halide.
  • the metal of the metal salt is the molten reducing metal
  • the 'metal' recovered from the reaction product is from the metal of the metal halide.
  • the present invention further relates to a method for producing a metal masterbatch.
  • the method includes: a) combining at least one metal halide and at least one molten reducing metal in a space that is substantially free of oxygen and water to obtain a reaction product that comprises at least one metal salt and metal; b) substantially removing the at least one metal salt to obtain the metal masterbatch comprising at least a portion of the molten reducing metal, and at least one other metal.
  • Step b) can occur as the reaction product forms and/or after the reaction product forms.
  • the molten reducing metal is present in a stoichiometric excess to the metal halide.
  • the molten reducing metal can be or primarily be aluminum or an alloy thereof, magnesium or an alloy thereof, or titanium or an alloy thereof.
  • the at least one metal halide is a solid or liquid, with the proviso that the molten reducing metal is different from the metal of the at least one metal halide.
  • the metal of the metal salt is the molten reducing metal, and the Other metal' recovered from the reaction product is from the metal of the metal halide.
  • FIG. 1 is a process flow chart describing a method according to an example of the present application.
  • FIG. 2 is a process flow diagram describing a method according to an example of the present application.
  • FIG. 3 is a process flow diagram describing a method according to an example of the present application.
  • FIG. 4 is a process flow diagram describing a method according to an example of the present application.
  • FIG. 5 is a process flow diagram describing a method according to an example of the present application.
  • FIG. 6 is a schematic illustration of a suitable bake out vessel for a process according to an example of the present application.
  • the present invention relates to methods of producing metal powders and/or metal masterbatches that incorporate metal halide reduction reactions. These processes can yield high purity and/or low oxygen content products. These methods can be practiced in continuous, semi- continuous, or batch arrangements. As an option, methods can be practiced as a continuous process with recycling of excess reactant.
  • metal powders can refer to metallic primary particles, aggregates, agglomerates, other discrete metal particles, or any combination thereof.
  • masterbatch can refer to a physical mixture comprised predominantly of two or more different kinds of metals (e.g. in elemental form), wherein the mixed metals retain their own respective chemical properties and have not chemically reacted with each other.
  • the masterbatch optionally can be or include a metal alloy, an intermetallic compound, metal carbide, metal nitride, metal boride, metal silicide, metal aluminide, or any combination thereof, or other metal compounds (e.g., one or more ceramics) in the alternative or in addition to the indicated physical mixture of different elemental metals.
  • a metal alloy an intermetallic compound, metal carbide, metal nitride, metal boride, metal silicide, metal aluminide, or any combination thereof, or other metal compounds (e.g., one or more ceramics) in the alternative or in addition to the indicated physical mixture of different elemental metals.
  • Metal powders can be formed in a method of the present invention by reducing a solid or liquid metal halide with a molten reducing metal in a sealed reaction vessel that is substantially free of oxygen and water (e.g., below 100 ppm oxygen and below 100 ppm water), wherein the molten reducing metal is present in a stoichiometric excess to the metal halide.
  • Metal powders and a metal salt can be produced, which are separated from the unreacted molten reducing metal.
  • the metal powder can be separated from the metal salt (e.g., from 95 wt% to 100 wt% of the total metal powder present can be separated from the metal salt).
  • the molten reducing metal means that the reducing metal is present as a liquid and not a vapor or a solid.
  • minor amounts such as below 5 wt%, below 2.5 wt%, below 1 wt%, below 0.5 wt%, below 0.25 wt%, below 0.1 wt%, below 0.05 wt%, below 0.01 wt% or below 0.001 wt% or zero wt% (based on the total weight of the reducing metal present) can be optionally present in a state other than a liquid or molten state.
  • the molten reducing metal can comprise, consists essentially of, or consists of, or include either 1) potassium metal or sodium metal or a combination of potassium metal and sodium metal (e.g., an alloy of sodium and potassium), or 2) aluminum metal or alloy thereof, or magnesium metal or alloy thereof, or titanium metal or alloy thereof.
  • the molten reducing metal can comprise at least 90 wt% sodium metal, at least 90 wt% potassium metal, or at least 90 wt% of a combination or mixture or alloy of potassium metal and sodium metal.
  • This percent of at least 90 wt% in each instance can be at least 95 wt%, at least 99 wt%, at least 99.5 wt%, at least 99.9 wt%, or 100 wt% such as from 90 wt% to 100 wt%, or from 95 wt% to 100 wt% (all based on the total weight of the molten reducing metal).
  • the amount of molten reducing metal for potassium and/or sodium is less than 100 wt% but at least 90 wt%, the remaining amount can be, or include for instance other metals in a molten state, such as calcium and/or magnesium and/or one or more other metals, and/or can be one or more oxides.
  • the molten reducing metal can comprise at least 90 wt% aluminum metal, or magnesium metal or titanium metal, such as at least 95 wt%, at least 99 wt%, at least 99.5 wt%, at least 99.9 wt%, or 100 wt% such as from 90 wt% to 100 wt%, or from 95 wt% to 100 wt% (all based on the total weight of the molten reducing metal).
  • the 'aluminum metal' can be or include one or more aluminum alloys. These aluminum alloys typically have about 90 wt% or more of aluminum in the alloy based on the total weight of the alloy.
  • the 'magnesium metal' can be or include one or more magnesium alloys. These magnesium alloys typically have about 90 wt% or more of magnesium in the alloy based on the total weight of the alloy.
  • the 'titanium metal' can be or include one or more titanium alloys. These titanium alloys typically have about 90 wt% or more of titanium in the alloy based on the total weight of the alloy.
  • these percentages for potassium, sodium, aluminum, magnesium, and titanium are based total weight of the components or materials only in the molten state and not in any other state.
  • An alloy is a mixture of metals or a mixture of a metal and another element. Alloys are defined by a metallic bonding character. An alloy may be a solid solution of metal elements (a single phase) or a mixture of metallic phases (two or more solutions).
  • the predominate element is aluminum.
  • magnesium alloy the predominate element is magnesium.
  • the predominate element is titanium. Preferred percentages are provided above.
  • the at least one metal halide can be, include, consists, of or comprises Ti halide, V halide, Cr halide, Mn halide, Fe halide, Co halide, Ni halide, Cu halide, Zn halide, Ga halide, Ge halide, As halide, Se halide, Zr halide, Nb halide, Mo halide, Ru halide, Rh halide, Pd halide, Ag halide, Cd halide, In halide, Sn halide, Sb halide, C halide, Si halide, Te halide, Hf halide, Ta halide, W halide, Hg halide, Tl halide, Pb halide, or Bi halide or any combination thereof.
  • the halide can be chloride, bromide or iodide. Any of the halides in this list can be or exclusively be a chloride.
  • the metal of the formed metal salt is (from) the molten reducing metal (e.g., Na, K, or Al, Mg, Ti), and the 'metal' recovered from the reaction product is from the metal of the metal halide (e.g, Ti, V, Ta, Nb, Sn, Si, Zr, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, C, Si, Ga, Ge, As, Se, Mo, Ru, Rh, Pd, Ag, Cd, In, Sb, Te, Hf, W, Hg, Tl, Pb, Bi, and the like), or a ceramic thereof, or a nitride thereof, or a boride thereof, or a carbide thereof.
  • the metal of the metal halide e.g, Ti, V, Ta, Nb, Sn, Si, Zr, Al, Cr, Mn, Fe, Co, Ni, Cu, Zn, C, Si, Ga, Ge, As, Se, Mo, Ru, Rh, Pd, Ag
  • Two or more halides can be used. When two or more metal halides are used, one metal halide is reactive and the second metal halide can be reactive or non-reactive with the molten reducing metal. When two or more metal halides are used (e.g, two metal halides, three metal halides or more), each of the metals of the metal halide, if reactive, can result in obtaining a metal alloy of these metals or an intermetallic compound of these metals. If a non-reactive metal halide is present, the metal of the metal halide will not be part of the resulting metal.
  • a non-reactive metal halide if present, for instance, can be used as an additive, forming a complex halide salt, to lower the melting point of the reactive metal halide, or to reduce the vapor pressure of the reactive metal halide, or to form liquid mixtures or solutions with other metal halides.
  • NaCl non-reactive metal halide
  • A1C1 3 reactive metal halide
  • the mol% of the non-reactive metal halide to reactive halide can be from 1 :99 to 99: 1 , and preferably is 20:80 to 80:20, or 40:60 to 60:40, or from 50 mol% to 65 mol% of the non-reactive metal halide to 60 mol% to 35 mol% of the reactive metal halide.
  • a phase diagram of the two metal halides can provide preferred mol% ratios to achieve the desired lower melting point. When two or more halides are used, they can be added as a mixture or separately or at different times. When a non-reactive metal halide is used with a reactive metal halide, the two should be added as a mixture and can be added as a liquid or solid. When two or more metal halides are used, at least one is a solid or liquid, but the other metal halide can be a vapor, liquid, or solid.
  • the metal salt formed in any of the processes of the present invention can form a partial or complete coating around the metal that is formed in the reaction product.
  • the metal that is formed can be present as a metal powder and be present as primary particles, agglomerates, aggregates, briquettes and the like.
  • the metal salt coating can be any thickness around the metal formed (e.g, around the metal powder), for instance, from about 1 nm to about 100 nm or more, such as from about 100 nm to about 5 ⁇ or from about 500 nm to about 10 um or thicknesses above or below any of these ranges.
  • the salt coating can be removed by any salt removing technique such as an aqueous washing or sublimation and the like.
  • the term "substantially free of oxygen and water” as used herein means that any content of oxygen or water present during the combining of the reducing metal and metal halide is insufficient to prevent the metal powder product from having the purity described herein.
  • the purity (e.g., by wt%) of the finished metal powder can be 95% metal or greater, or 99% metal or greater such as from about 99.5% metal or greater and more preferably 99.95% metal or greater and even more preferably 99.99%) metal or greater, or 99.995% metal or greater or 99.999%) metal or greater, wherein the metal refers to the metal of the metal halide reactant and not the reducing metal or other source of metal.
  • the metal powders produced by the methods described herein can be highly pure.
  • the metal powders can have a minimal amount of oxygen bonded to the metal. Reducing the quantity of oxygen bonded to the metal powder has been technically challenging in the art, and thus improvements in metal powder purity represent a substantial technical improvement.
  • the reaction vessel that is substantially free of oxygen and water can be filled or purged with an inert gas, preferably argon, prior to or while maintaining the molten reducing metal in the sealed reaction vessel.
  • At least one metal halide can be reacted with a stoichiometric excess of a reducing metal.
  • stoichiometric excess means the molar amount of the molten reducing metal present in the reaction zone is in excess based upon the amount of metal halide present and available to react therewith.
  • the molten reducing metal can be in at least a 5:1 stoichiometric excess to the metal halide, though in some cases it can be less than a 5:1 stoichiometric excess. In other cases, it can be more than a 5.T stoichiometric excess, such as at least a 10:1 stoichiometric excess, or other values.
  • the reducing metal is heated to a temperature above its melting point and below its boiling point to provide a molten material which can be split into a stream that is passed through a cooler to provide a cooled stream that has a temperature that is still above the melting point of the reducing metal and below a reaction temperature of the reducing metal with respect to metal halide, and another stream that is passed through a heater to provide a (further) heated stream of the reducing metal.
  • the split can be from 10:90 to 90:10 by volume (cooled stream:heated stream), or from 20:80 to 80:20, or from 40:60 to 60:40 and the like.
  • the cooled stream of reducing metal is combined with solid metal halide, such as metal halide in powder form, to disperse the metal halide therein to form a mixture (e.g., a slurry).
  • the heated stream of reducing metal can be heated to a temperature such that when its mass is combined with the mass of the mixture of solid metal halide and cooled reducing metal, the resulting combination has a temperature at or above a reaction temperature of the reducing metal with respect to metal halide.
  • additional heating can be provided before the combination reaches the reaction zone or, at the reaction zone, or both locations, to provide a reaction temperature.
  • the heated stream of reducing metal and the mixture of cooled reducing metal and solid metal halide can be combined, such as in an eductor, and passed through a reaction zone with the molten reducing metal present in stoichiometric excess to the metal halide to produce a metal reaction product.
  • additional heating of the reducing metal and metal halide materials can be provided before and/or in the reaction zone to raise the temperature of the mixture to a reaction temperature, or maintain the materials at a reaction temperature, or both.
  • the space where the metal halide and molten reducing metal are contacting at a reaction temperature, such as the reaction zone, and/or may be in the eductor, preferably are maintained to be substantially free of oxygen and water.
  • the metal reaction product and remaining molten reducing metal can be collected from the reaction zone in a settling and bake out vessel.
  • the remaining (unreacted) molten reducing metal in the reaction product can be substantially removed, such as by pouring or siphoning or other separation method.
  • Metal salt and the metal reaction products that remain in the vessel can be recovered, and the metal reaction product can be separated from the metal salt.
  • the reducing metal can be passed through a heater to provide a heated liquid stream, such as described hereinabove, that can provide a reaction temperature with respect to metal halide when the heated reducing metal and metal halide are combined, and without the reducing metal being split into different streams for separate cooling and heating.
  • Liquid metal halide is introduced into the heated stream of reducing metal, such as by injection, and the resulting mixture of heated reducing metal and liquid metal halide are passed through a reaction zone with the molten reducing metal present in stoichiometric excess to the metal halide to produce a metal reaction product.
  • the space such as the reaction zone, or which may be the flow passageway connecting the location of liquid metal halide introduction and the reaction zone, where the metal halide and molten reducing metal are contacting at a reaction temperature, can be maintained to be substantially free of oxygen and water as previously described.
  • the metal reaction product and remaining molten reducing metal can be collected from the reaction zone in a settling and bake out vessel, and the remaining molten reducing metal in the reaction product can be substantially removed, and the metal salt and the metal reaction products that remain can be recovered, and the metal reaction product can be separated from the metal salt, as previously described.
  • the molten reducing metal is sodium and/or potassium
  • at least a portion of the excess or unreacted molten reducing metal e.g., from 10 wt% to 100 wt%, or from 25 wt% to 99.5 wt%, or from 50 wt% to 99 wt%, or from 75 wt% to 99 wt%, or from 85 wt% to 99 wt%, or from 95 wt% to 99.5 wt% by weight of the excess or unreacted molten reducing metal
  • the reaction product e.g., the metal formed and the metal salt
  • the excess or unreacted molten metal will phase separate (liquid phase separation) and generally is on top with the other phase of metal and metal salt at the bottom.
  • This permits easy separation of the two phases by various techniques, such as decanting, siphoning, and the like.
  • the molten reducing metal is aluminum (or alloy thereof)
  • magnesium (or alloy thereof) or titanium (or alloy thereof) phase separation is not used and generally it is preferred to keep the excess or unused aluminum (or magnesium or titanium) present and to instead remove the metal salt of the reaction product by heating the reaction product and excess or unused aluminum (or magnesium or titanium) to a temperature that causes vaporization of the metal salt. This vaporization and removal can occur as the reaction product forms and/or after formation of the reaction product.
  • any amount of the metal salt can be removed this way, such as from about 10 wt% to 100 wt%, or from 25 wt% to 99.5 wt%, or from 50 wt% to 99 wt%, or from 75 wt% to 99 wt%, or from 85 wt% to 99 wt%, or from 95 wt% to 99.5 wt% by weight of the metal salt present.
  • the metal powders produced by the methods described herein can have a small particle size, and/or narrow particle size distribution, and/or improved flow characteristics, or any combinations of these, which can be determined using a Hall flow meter according to standardized testing procedures, such as ASTM B213.
  • the methods described herein can produce primary particles having a size ranging from about 5 to about 250 nanometers, or from about 25 to about 200 nanometers, or from about 50 to about 175 micrometers, or from about 75 to about 150 micrometers, or other sizes.
  • the primary particles can form aggregates having an aggregate size of from about 1 to about 250 microns in diameter, from about 25 to about 200 nanometers, or from about 50 to about 175 micrometers, or from about 75 to about 150 micrometers, or other sizes.
  • Particle size can be determined by scanning electron microscopy (SEM) imaging. The particle sizes indicated in this respect can refer to average size, D50 size, or D90 size.
  • Electron microscopy works by bombarding a sample with a stream of electrons and monitoring either the resulting scattering (SEM) effects. These electrons are detected and converted into magnified images of particles in the sample dispersion. Image analysis software uses this information to generate particle size data for individual particles, number based size distributions for the entire dispersion and various shape and morphological parameters.
  • reaction conditions that favor the production of smaller particles include a lower temperature and a low concentration of metal halide relative to the concentration of the reducing metal.
  • the process of particle and aggregate formation parallels standard particle flame synthesis processes.
  • a primary particle or cluster encounters another cluster, they stick together to form an aggregate that tends to have an open structure, provided the conditions (temperature and particle density) permit continued aggregation.
  • the concentration of the metal halide is lower because the metal powder particles that form are more dispersed in the reducing metal, and therefore the metal powder particles are less likely to physically interact and form aggregates.
  • the particles are large and cool enough that the aggregates freeze.
  • a method for producing a metal masterbatch uses a metal halide reduction reaction as part of the process.
  • reaction product metal and a salt can be produced in the reaction zone and collected with excess reducing metal in a separate vessel or tank, wherein the salt, and not the excess reducing metal, is separated out, so as to obtain a metal masterbatch comprising at least a portion of the reducing metal and reaction product metal.
  • the reaction product metal can be, depending on the number of different starting metal halides used and types, a metal, a metal alloy, an intermetallic (intermetallic compound), or a ceramic (boride or carbide).
  • the resulting metal can be an aluminum carbide.
  • the metal halides used are T1CI 4 and S1CI 4 , the resulting metal can be a Ti-Si alloy or intermetallic, and so on.
  • Aluminum trichloride for instance, sublimates at about 180°C at one atmosphere pressure, so it can be selectively volatized and removed from excess aluminum and the metal formed from the metal halide reduction reaction which have a higher boiling points.
  • Other aluminum halides with comparable sublimation or vaporization temperatures with respect to aluminum and reaction product metal can be selectively removed in a similar manner.
  • Another advantage of the methods described herein is that they can reduce the amount of corrosion that occurs. For example, previous gas phase reactions typically offer a lower reaction throughput, and they can also yield substantial corrosion because of the increase in the reaction rate for chloride corrosion processes at elevated temperatures. The methods of the present invention can avoid or have reduced risk of these drawbacks and disadvantages.
  • reacting a metal halide with a molten reducing metal using split flow of heated and cooled streams of molten reducing metal for solid metal halide processing, or injection of liquid metal halide can yield particles that are highly pure and provide improved flow properties.
  • the reactions occur under conditions that remain constant or bounded by a limited range of temperatures and stoichiometry.
  • the methods described herein typically involve steps that are shown in FIG. 1.
  • the overall process, indicated as 100 in FIG. 1, has several alternatives, including with respect to whether a solid or liquid metal halide is used, whether a metal powder product or a masterbatch product is desired, and other alternatives and options indicated herein.
  • molten reducing metal such as 1) sodium, potassium or both, or 2) aluminum or magnesium or titanium, is provided 101. These metals are used for illustration, and other reducing metals may be used.
  • Sodium has a melting point of about 98°C
  • aluminum has a melting temperature of about 660°C.
  • Alternative A in the process shown in FIG. 1 is for solid metal halide processing, and alternative B is for liquid metal halide processing.
  • the molten reducing metal is split into two streams (102), wherein a portion of the reducing metal is cooled below a reaction temperature of the metal halide (103 A) and the remaining portion is heated to a reaction temperature with metal halide (103B).
  • the cooled stream of reducing metal is fed to an area (e.g., funnel) where solid metal halide is added, such as gravity fed as a dry flowable powder, to the flow of reducing metal through the funnel (104).
  • the metal halide powder combines with the cooled reducing metal, and can form a slurry.
  • the slurry from step 104 and the heated reducing metal are combined in a mixing/dispersing device (105), such as in an eductor.
  • the resulting mixture or dispersion is fed to a reaction zone (106), such as a pipe, mixing tank with an agitator forming a vortex, or other reaction zone arrangement.
  • the metal halide can be reduced by the reducing metal to produce metal particles.
  • the molten reducing metal is heated (122) with no split stream for cooling.
  • Liquid metal halide is injected or otherwise introduced into the heated molten reducing metal (123), and the resulting combination is fed to the reaction zone (106).
  • the remaining, unreacted reducing metal can be removed from the metal particles in a settling bake out tank (107). The removed excess reducing metal can be recycled by filtering and cooling it for reuse (108).
  • another method of the present invention is the formation of a masterbatch, such as using aluminum reducing metal (or magnesium or titanium), wherein the reaction products and excess (unreacted) reducing aluminum metal (or magnesium metal or titanium metal) from the reaction zone (106) are fed to a volatization/masterbatch formation tank where aluminum salt reaction (or magnesium salt reaction or titanium salt reaction) by-product of the reduction reaction is removed, such as by heat-volatization (124) alone or in combination with other salt removal techniques, to leave unreacted aluminum (or magnesium or titanium) and reaction product metal in the tank as a masterbatch material.
  • a masterbatch such as using aluminum reducing metal (or magnesium or titanium), wherein the reaction products and excess (unreacted) reducing aluminum metal (or magnesium metal or titanium metal) from the reaction zone (106) are fed to a volatization/masterbatch formation tank where aluminum salt reaction (or magnesium salt reaction or titanium salt reaction) by-product of the reduction reaction is removed, such as by heat-volatization (124) alone or in combination with other salt removal techniques, to leave
  • FIGS. 2, 3, 4, and 5 Examples of process and equipment arrangements that can be used to perform these process flow options are shown in FIGS. 2, 3, 4, and 5.
  • a method for making a metal powder of the present invention is shown which includes use of a solid metal halide 207 and a storage tank 201 of molten reducing metal (e.g., 1) Na and/or K, or 2) Al, Mg, or Ti).
  • the reducing metal is introduced in stoichiometric excess with respect to the metal halide in this method, such as in a range described herein.
  • the sodium and/or potassium reducing metal or aluminum reducing metal (or magnesium reducing metal or titanium reducing metal) is pumped through a continuous loop 214 using pump 202, such as an electromagnetic pump (EM pump).
  • An electromagnetic pump is a pump that moves ionizable liquid metal using electromagnetism.
  • An electromagnetic pump can have no moving mechanical parts which can be corroded by heated reducing metal.
  • a cold trap 203 installed on the loop 214 is used to remove contaminants prior to starting up production. Once the contaminants are removed, the cold trap can be valved off until needed again.
  • the electromagnetic pump 202 pumps the molten sodium and/or potassium or molten aluminum (or molten magnesium or molten titanium) to a flow split 204.
  • more than a predominant (> 50%) amount, or from 51% to 95%, or from 60% to 90%, or from 65% to 85%, or other amounts of the mass flow of the molten reducing metal arriving at split 204 is directed into the stream feeding the heater 208, and a minority amount ( ⁇ 50%), or from 49% to 5%, or from 40% to 10%, or from 35% to 15%, or other amounts is directed to the cooler 205.
  • the flow to the cooler 205 can be from about 1 to about 7 gallons/min (GPM), or from about 2 to about 6 GPM, or about 3 GPM, or other values, and the flow to the heater 208 can be from about 11 to about 19 GPM, or from about 13 to about 18 GPM, or about 17 GPM, or other values.
  • the split flows can be controlled using valves and Coriolis flow meters (not shown).
  • The. cold sodium and/or potassium stream can be directed to flow around a funnel 206.
  • Metal halide powder as a solid form of metal halide, can be added to this funnel.
  • the sodium and/or potassium, or the aluminum (or magnesium or titanium) flows around the funnel 206 and can collect the metal halide powder and the resulting mixture or slurry can be drawn through an eductor 209.
  • the eductor 209 can use the hot sodium and/or potassium, or the hot aluminum (or magnesium or titanium) flow as the motive fluid sucking the metal halide slurry into it.
  • the additional heat provided by the hot sodium and/or potassium stream (or the aluminum or magnesium or titanium stream) can initiate the reduction reaction.
  • the reaction can occur in a reaction zone 210.
  • the reaction zone 210 can be a closed pipe, a draft-tube reactor, a stirred tank reactor, or other reactor. As an option, the reaction can occur down a length of spiraling pipe (as the reaction zone 210) to a vessel 211.
  • the reaction zone can be designed to provide turbulence to increase mixing of the reducing metal and metal halide during the reaction, such as by using spiraled piping or a stirred reactor, or other designs.
  • This vessel 210 can collect the product by utilizing the high density of reaction product metal and allowing it to settle to the bottom.
  • the excess sodium and/or potassium or the excess aluminum or magnesium or titanium 215 can flow out of the vessel 211 through an outlet, such as pour spout or decanter or siphon, and then through a filter 212 and a cooler 213 before making it back to the storage tank 201 for reuse.
  • the settling tank 211 can be used as a bake out vessel.
  • the vessel 211 can be heated to high temperatures until it is void of all excess sodium and/or potassium, or the excess aluminum (or magnesium or titanium), leaving behind a metal/salt mixture. This mixture can be used for post processing.
  • the feeding of the metal halide powder preferably should occur in an inert atmosphere due to its reactivity in air.
  • the powder transfer to the feed system and all working parts of the feeder itself preferably are maintained in an inert atmosphere, such as an argon atmosphere. If an inert atmosphere is not kept, there can be a risk of heavy chloride corrosion as well as contamination of the product.
  • a glove box set up around the feeding system can be used.
  • metal halide powders such as HfCLj powder
  • HfCLj powder is not wetted by liquid sodium, and does not easily disperse, and can form a crust of metal that surrounds and shields unreacted powder from the sodium and/or potassium.
  • the funnel/eductor design is used to disperse the powder into cold sodium and/or potassium or into cold aluminum (or cold magnesium or cold titanium) before sucking it down into the hot sodium and/or potassium, or the hot aluminum (or hot magnesium or hot titanium) and initiating the reaction.
  • This method can provide enough agitation to get the metal halide, such as HfCLj, mixed and promote reaction with sodium and/or potassium, or the aluminum (or magnesium or titanium) once mixed into the hot sodium and/or potassium or the hot aluminum (or hot magnesium or hot titanium).
  • Eductors work based on set flows and pressures on the inlets and the outlet. If the suction is too great for the slurry feed, argon gas can be sucked into the system and can cause problems.
  • a control system can be used to control each flow rate as well as the level in the funnel above the eductor.
  • heat tracing preferably is used throughout the system where reducing metal is stored and passes to monitor the temperatures and for control thereof. If a cold spot in the system should develop, it may cause the sodium or other reducing metal used to freeze and possibly plug up the system.
  • the settling/bake-out vessel can be a dual purpose piece of equipment that can collect and purify the product. If not transferred or recycled to tank 201 during the reaction and process as indicated, in post production, the vessel can be full of excess molten reducing metal that needs to be removed. This excess molten reducing metal can be removed by raising the temperature to extremely high levels and evaporating the molten reducing metal out. This high temperature may limit the applicable materials of construction and designs. Following this molten reducing metal removal, the vessel itself can be removed from the system for product recovery.
  • FIG. 3 a method of making a masterbatch of the present invention, indicated as 300, is shown.
  • a solid metal halide 307 is used and a tank 301 of aluminum (or magnesium or titanium) is used as a source of reducing metal.
  • Features and steps 302, 314, 303, 304, 305, 306, 307, 308, 309, and 310 can be similar to or the same as features and steps 202, 214, 203, 204, 205, 206, 207, 208, 209, and 210, respectively, as described with respect to method 200 in FIG. 2, and reference is made thereto.
  • the reducing metal is introduced in stoichiometric excess with respect to the metal halide in this method, such as in a range described herein.
  • the method 300 of FIG. 3 differs from the method 200 shown in FIG. 2 with regards to the materials that are removed and retained in the collection tank that receives materials from the reaction zone.
  • the volatization/masterbatch tank 311 is used to collect reaction product metal and a salt produced in the reaction zone 310, and also excess aluminum reducing metal (or excess magnesium metal or excess titanium metal).
  • the salt, and not the excess aluminum (or magnesium or titanium) reducing metal is separated out to obtain a metal masterbatch comprising at least a portion of the aluminum (or magnesium or titanium) reducing metal and reaction product metal.
  • the aluminum (or magnesium or titanium) and reaction product metal can be intermixed as a uniform or substantially uniform physical mixture thereof, which forms or can be formed into a unitary solid mass of material.
  • a method of making a metal powder of the present invention indicated as 400, is shown.
  • a liquid metal halide 405 is used instead of a solid metal halide as used in the methods of FIGS. 2 and 3.
  • a tank 401 of sodium and/or potassium, or a tank 401 of aluminum (or magnesium or titanium) is used as a source of reducing metal.
  • the reducing metal is introduced in stoichiometric excess with respect to the metal halide in this method, such as in a range described herein.
  • the liquid metal halide 405 can be introduced into the heated molten reducing metal using an injection or pumping device, such as using pressurized inert gas to force metal flow.
  • FIG. 5 a method of making a masterbatch of the present invention, indicated as 500, is shown.
  • a liquid metal halide 505 is used instead of a solid metal halide as used in the methods of FIGS. 2 and 3, and a masterbatch is formed in a volatization/masterbatch tank 507 used similarly to the tank 311 as used in the method 300 shown in FIG. 3.
  • tank 501 of aluminum (or magnesium or titanium) is used as a source of reducing metal.
  • Features and steps 502, 514, 503, 504, 506, 507, and 508 can be similar to or the same as features and steps 302, 314, 303, 308, 310, 311, and 312, respectively, as described with respect to method 300 in FIG.
  • the liquid metal halide 505 can be introduced into the heated molten aluminum (or magnesium or titanium) reducing metal using an injection or pumping device similar to or the same as that described for use in the method 400 of FIG. 4. As in the examples of the methods shown in FIGS. 2-4, the reducing metal is introduced in stoichiometric excess with respect to the metal halide in this method as well, such as in a range described herein. [0049] Additional information on the metal halide reaction and product processing which are related to methods described herein are provided in the following sections.
  • the metal halide reduction step when using the indicated liquid or solid forms thereof, the metal halide is reduced to a metal and a metal salt (e.g., from the reducing metal reacting with the halide from the metal halide) is produced as a byproduct.
  • a metal salt e.g., from the reducing metal reacting with the halide from the metal halide
  • the metal halides can be reacted with a stoichiometric excess of the reducing metal in methods of the present invention.
  • Metal halides that can be reacted include, for example, one or more halides of tantalum, nickel, aluminum, zirconium, vanadium, tin, titanium, silicon, niobium, or hafnium, or any combination thereof. Other examples are mentioned earlier.
  • the metal halide can be a metal chloride.
  • the metal halide can be a metal bromide or metal iodide.
  • the reducing metal is different from the metal of the metal halide, when one metal halide is used.
  • the reducing metal (in molten state) can be or include a Group I metal(s) or aluminum.
  • reductions include: TaCl 5 reduced by sodium; TaCl 5 reduced by a mixture of sodium and potassium; HfC reduced by sodium, HfCl 4 reduced by a mixture of sodium and potassium; HfCl 4 reduced by aluminum; a mixture of TaCl 5 and NiCl 2 reduced by a mixture of sodium and potassium; A1C1 3 reduced by sodium; ZrC reduced by sodium; ZrC reduced by aluminum; VCI 4 reduced by sodium; SnCl 4 reduced by sodium; T1CI4 reduced by sodium; and SiC reduced by sodium.
  • Subhalides e.g., halides of lower oxidation states of the metal elements that contain less halide (e.g., TiCl 2 or TiCl 3 ) than its common halide (e.g., TiCL ), including subchlorides, can also be reduced in the same manner, for example, titanium, zirconium, or tin subchlorides. Examples of reduction reactions can proceed according to Equations (2A), (2B), (2C), (2D), (2E), (2F), or (2G): TaCl 5 (s or 1) + 5Na (1) --> Ta (s) + 5NaCl (s) (2A),
  • the reducing metal is heated to a temperature above its melting point and below its boiling point before it is combined with metal halide and passed into a sealed reaction vessel that is substantially free of oxygen and water. Higher temperatures can lead to the generation of reducing metal vapors that must be controlled.
  • Sodium for instance, has a melting point temperature of about 98°C and a boiling point temperature of about 883°C (at about 1 atmosphere pressure).
  • Aluminum has a melting point temperature of about 660°C and a boiling point temperature of about 2470°C (at about 1 atmosphere pressure). It can be advantageous to stay at least 50°C, or at least 100°C, or at least 200°C, or at least 300°C above the melting point.
  • the heated reducing metal can be initially heated sufficiently to provide a pumpable molten material, and the mixture resulting from its combination with metal halide can have a temperature sufficient to support the metal halide reduction reaction by the initial heating, additional heating before combination with metal halide, or additional heating after combination with metal halide, or any combination thereof.
  • the molten reducing metal depending on the metal, can be heated and maintained at a temperature of from about 150°C to about 850°C, or from about 150°C to about 350°C, or from about 200°C to about 250°C.
  • the reducing metal is sodium
  • more typical reaction temperatures are from 150°C to 350°C, though temperatures up to about 850°C or other temperatures are possible.
  • the molten reducing metal is sodium
  • the sodium is heated and maintained at a temperature of from about 600°C to about 700°C until combined with the metal halide.
  • the reaction zone can be a closed pipe (e.g., a spiraled pipe), a draft-tube reactor, a stirred tank reactor, or other reactor.
  • the reaction zone preferably creates turbulence which encourages mixing of the reducing agent and metal halide in the reaction zone.
  • a stirred reactor that can be used, such as described in U.S. Patent Application No. 15/051,267, which is incorporated in its entirety by reference herein.
  • the reaction zone can be a sealed, reaction chamber, which can be an airtight glovebox.
  • An airtight glovebox can be constructed largely of glass plates attached to a metal frame.
  • a glovebox permits an operator to manipulate objects within the glovebox while maintaining an inert reaction environment.
  • the reaction chamber can be a bench-top glovebox, or it can be a larger glovebox suitable for pilot scale operations, in which case it may have work stations where several operators can access the interior of the glovebox.
  • the reaction chamber can also be large enough to house industrial- or commercial-scale reaction vessels. For commercial scale production, an airtight vessel having automated loading and unloading can be used.
  • a carbide forming, or nitride forming, or boride forming component i.e., ceramic forming components
  • the carbide forming component can comprise carbon containing gas, carbon tetrachloride, or solid carbon.
  • the boride forming component can comprise boron trichloride or one or more boron hydrides.
  • the nitride forming component can be titanium nitride (TiN).
  • the amount of metal carbide, metal nitride, and/or metal boride, or any combination thereof, in the reaction products in lieu of the metal formed can be from about 10 wt% to about 100 wt% of the total weight reaction product (e.g, from about 40 wt% to 100 wt%, or from 60 wt% from 100 wt% or from 90 wt% to 100 wt%, or from 98 wt% to 100 wt%).
  • From 40 wt% to 100 wt%, or from 60 wt% from 100 wt% or from 90 wt% to 100 wt%, or from 98 wt% to 100 wt% of the metal formed can be converted to the metal carbide, metal nitride, or metal boride in the reaction.
  • the other reactants, such as the carbide or boride or nitride forming component can be added at any stage of the process, such as at or before the reaction zone, or can be present with the reducing metal or with the metal halide introduction point, or be separately introduced using an additional inlet to the flow of the reducing metal or metal halide, or both.
  • the excess unreacted molten reducing metal can be separated so that it can preferably be reused in another reduction reaction.
  • the excess reducing metal can be as much as 50% by weight, or more in some cases, of the starting amount of molten reducing metal.
  • the excess molten sodium and/or potassium, or the excess molten aluminum (or magnesium or titanium) reducing metal 660, along with the metal powder and the sodium salt and/or potassium salt, or the aluminum salt (or magnesium salt or titanium salt) formed during the metal halide reduction reaction step can be decanted into a bake out vessel 610.
  • the bake out vessel 610 can have a lip 615 that can facilitate the placement of a lid 620 on top of the bake out vessel 610.
  • the bake out vessel 610 can have one or more ports 630 that can be used to remove excess reducing metal material from the bake out vessel 610.
  • the port 630 can be adjustable so that they can extend to differing depths within the bake out vessel 610.
  • the port 630 can be formed of a non-conducting ceramic in order to reduce long-range electron mediated reduction.
  • the bake out vessel can be heated to just above the melting point of the metal salt formed as a reaction byproduct.
  • the metal halide is hafnium chloride and the reducing metal is sodium
  • the salt produced is sodium chloride, which has a melting point of approximately 801°C.
  • the bake out vessel 610 can be heated to just above 801°C, which is just above the melting point of sodium chloride. At this temperature, the sodium chloride salt begins to melt and separate from the excess (unreacted) sodium reducing metal, thereby creating a salt bath 640 and a molten reducing metal phase 660.
  • the salt bath phase 640 includes sodium salt 641 and the metal powder 645 created by reducing the metal halide.
  • a first outlet or port 630 can use used to pour off (decant) or siphon out the bulk of the excess sodium molten reducing metal 660 by gravity (drain) or by applying a negative relative pressure (siphon) in a capture tank.
  • This molten sodium reducing metal 660 that has been poured off or siphoned off can be captured in a capture tank and reused, such as shown in FIGS. 2 and 4.
  • the bake out temperature can be adjusted by adding other salts and creating an eutectic system.
  • a 52:48 (by wt) mix of calcium chloride and sodium chloride melts at approximately 500°C.
  • the bake out can occur in a lower temperature range (e.g., where stainless steel can be used instead of more expensive metals).
  • the surface area of the resulting metal powder can also be increased since a higher temperature leads to increased sintering.
  • the amount of excess reducing metal (e.g., 1) Na and/or K, or 2) Al and/or Mg and/or Ti) after draining or siphoning can be 5,000 ppm or less in the metal and salt products, such as less than 3,000 ppm, or less than 2,000 ppm, or less than 1,000 ppm, or less than 500 ppm, or less than 250 ppm, or from 0 ppm to 5,000 ppm, or from 10 ppm to 2,000 ppm, or from 100 ppm to 1 ,500 ppm.
  • residual reducing metal can be reacted with an alcohol, such as methanol.
  • the remaining reducing metal can be reacted with an anhydrous chloride, such as anhydrous hydrogen chloride (HC1) or chlorine gas (Cl 2 ).
  • anhydrous chloride such as anhydrous hydrogen chloride (HC1) or chlorine gas (Cl 2 ).
  • HC1 anhydrous hydrogen chloride
  • Cl 2 chlorine gas
  • the hydrochloric acid can attack the metal particles that have been formed.
  • a salt can be added to the bake out vessel 610 either prior to or after pouring the molten reducing metal, salt, and metal powder into the bake out vessel 610.
  • the salt added is the same salt formed during the reduction of the metal halide by the reducing metal.
  • the salt produced in the neutralization reaction typically fills the voids in the metal, and chlorides can therefore attack the metal.
  • the chloride tends to neutralize the free sodium, which has valence electrons having a long mean free path in the molten salt.
  • the resulting product can be a metal powder at least partially or fully encapsulated in salt.
  • the salt can have a glass-like appearance because it was melted and cooled.
  • the salt can be removed.
  • Metal powder having a higher surface area is generally less dense and contains more salt in narrower voids.
  • the metal particles encapsulated in salt are washed with water.
  • the metal particles encapsulated in salt are transferred to a new vessel prior to the water wash in order to prevent oxidation of the bake out vessel.
  • the metal particles are washed in serial batches in a metal beaker or other metal container so that the concentration of salt is less than 1 ppm.
  • An example reaction for removing excess salt is Equation (3), after which the liquids and dissolved solids are removed:
  • the salt can be evaporated.
  • One method of evaporating the salt is by sweeping an inert gas, such as argon, through the chamber at a temperature close to or above the melting point of the salt, such that the salt has an adequate vapor pressure to permit it to be removed in a reasonable time.
  • the salt vaporizes, leaving behind the metal particles.
  • the procedure can be conducted within a rotary furnace, which can limit the formation of a sponge from the metal particles.
  • the inert gas can be recycled.
  • ultrafiltration can be used to remove excess salts.
  • One such system is provided by Koch Membranes.
  • the metal particles are recovered and can be subsequently dried if desired.
  • the particles can be dried in a vacuum oven. After drying the metal particles can be collected and recovered as a free flowing powder.
  • the metal powder When the metal powder is exposed to air, it can be highly flammable, and its dust can be explosive. Thus, it must be handled with care, and preferably in an inert atmosphere, until the powder has been consolidated into a desired final form or else until the powder surface has been passivated by controlled exposure to oxygen.
  • AICI3 aluminum trichloride
  • aluminum chloride is the salt formed in the reaction with metal halide
  • the aluminum trichloride can be selectively separated and removed to leave the reaction product metal and excess aluminum as a masterbatch.
  • the sublimation pressure of the aluminum trichloride reaches one atmosphere at about 179°C to 183°C at approximately 1 atmosphere pressure, and the melting-point of aluminum trichloride at 2.5 atmospheres pressure is about 190°C to 194°C.
  • Similar processes and reactions can be used when the reducing metal is magnesium or titanium and the a magnesium chloride or titanium chloride, for instance is the salt formed.
  • a storage tank containing 200 gallons of molten sodium is pumped through a continuous loop using an electromagnetic pump.
  • the electromagnetic pump pumps the molten sodium to a flow split.
  • the flow to the cooler can be roughly 3 GPM and the flow to the heater can be roughly 17 GPM.
  • the flows can be controlled using valves and Coriolis flow meters.
  • the cold sodium stream flows around a funnel.
  • the HfC powder is added to this funnel.
  • the sodium flows around the funnel and collects the powder and it is drawn through an eductor.
  • the eductor uses the hot sodium flow as the motive fluid sucking the HfCl 4 slurry into it.
  • the additional heat provided by the hot sodium stream initiates the reduction reaction.
  • Feeding of the HfCl 4 powder occurs in an inert atmosphere due to its reactivity in air. As such the powder transfer to the feed system and all working parts of the feeder itself is maintained in an inert atmosphere.
  • a small glove box is set up around the feeding system.
  • the reaction occurs down a length of spiraling pipe (reaction zone) to a vessel. This vessel collects the product by utilizing the high density of Hf metal and allowing it to settle to the bottom.
  • the excess sodium flows out of the top of the vessel through a filter and a cooler before making it back to the storage tank.
  • the settling tank is used as a bake out vessel.
  • the vessel is heated to high temperatures until it is void of all excess sodium, leaving behind a metal/salt mixture.
  • a powder trickier was used for all halide powder trials to feed the reactant powders to a beaker containing alkali metal(s).
  • This powder feeder consists of an adjustable hopper, discharge tube, stand, and 2-speed control pad. All reactant powders flowed readily through the tube given the vibration frequency at hand, except the TaCl 5 and NiCl 2 50/50 powder blend. This powder blend packed tightly inside both the tube and the hopper base. As a result, remaining powder was fed to the reaction beaker using a "hand-add" approach with a spatula for the TaCl 5 and NiCl 2 50/50 blend.
  • All tests utilized an IKA 70 Watt mixer with the capability of producing speeds from 60 to 2000 rpm.
  • a stainless steel, 1.20 inch diameter, turbine impeller blade was utilized for the first two tests performed, TaCl 5 in excess sodium. All subsequent tests were performed using a stainless steel, 1.65 inch diameter, Cowles blade impeller to improve the incorporation of the reactant powder in the alkali metal. Even though the mixer maximum capacity was specified as 2000 rpm maximum, the mixer was utilized at speeds as high as 2135 rpm in the powder feed tests.
  • a stainless steel 2000 n L beaker was implemented as the reaction vessel for all tests.
  • a lid was constructed for trial 3 with 3 ports for the mixer impeller, powder feed tube, and alkali metal temperature thermocouple (TE-0111A).
  • the lid eliminated a large amount of dusting within the glovebox while allowing for the reactant powder to be fed down into the alkali metal via a vertical feed tube.
  • the 4th and 5th trials used a similar lid with a reduced diameter port to further minimize dusting to the glovebox.
  • a test setup used for this example is shown and described with reference to FIG. 3 as described in U.S. Patent Application No. 15/051,267, which is incorporated in its entirety by reference herein.
  • the stainless steel beaker, V-0100 contained the alkali reducing metal.
  • the reaction beaker was maintained at 200 - 250°C using a heater band (controlled via TC-0111) and a hot plate (controlled via TC-0110).
  • the variation in alkali metal temperature was based upon the reactivity of the halide powder during each trial via physical observation.
  • Halide powders were pre- weighed using scale WI-0120 and fed from the powder feeder, F-0125, to V-0100 in 5-10 gram increments.
  • Argon was fed from an argon supply Dewar to the glovebox at a flow rate of 110 standard cubic feet per hour (scfh). Argon pressure was regulated down to 20 - 30 psig.
  • the glovebox oxygen and moisture content was recorded prior to the start of each trial.
  • the blower was de-energized and the purifier was isolated in an effort to preserve the integrity of the purifier. With the purifier isolated from the system, oxygen content was not accurately displayed on the glovebox control panel because the oxygen sensor was also sensitive to chlorides, and therefore provided an inaccurate reading due to the presence of chloride vapors in the glovebox.
  • a vacuum filtration system was incorporated for the trials using NaK.
  • This system consists of a filtration separation vessel, V-0134, that contains a 10 micron screen inserted within a stainless steel cup to retain the solids.
  • a catch vessel (flask), V-0135, was used to prevent any filtered NaK carry-over and to protect the vacuum pump, PU-0130.
  • This vacuum filtration set-up was also used to perform the methanol wash steps within product recovery when NaK was utilized.
  • an inert atmosphere having as little oxygen and moisture as possible was established in the glovebox.
  • the hot plate and heater bands were energized and set to 200°C.
  • a pinch test was performed by adding a small amount of reactant powder to the alkali metal. The pinch test must be performed with the lid removed from the vessel to observe for signs of reaction (such as a change in color or the generation of smoke). If no sign of reaction was observed at 200°C, then the temperature was increased in increments of 50°C and the pinch test was repeated until a reaction was observed. All reactions were performed at 250 °C or less.
  • halide powders were manually weighed in 5-10 gram increments before being added to the hopper. Powder was fed from the hopper to the vessel, with pauses in feeding when smoking was observed. When the reaction step was completed, the mixer, heater band, and hot plate were de-energized to allow for the system to cool before the start of product recovery.
  • the hafnium tetrachloride powder used in Test 4 was denser and chunkier than the tantalum pentachloride previously used. Larger HfC chunks appeared to sink in the NaK with no visible signs of reaction, whereas the loose, fine powder generated smoke and changed in color from white to black upon contact with NaK. The HfCLj powder was filtered to remove these larger chunks prior to feeding the hopper and starting the reaction.
  • a salt concentration test was performed to assess the quantity of metal halides that can be added while maintaining a vortex. A total of 797.17 grams of sodium were used, and a total of 477.69 g NaCl were added over the course of the trial. The first five salt charges were added in increments of 10 g, and all subsequent charges were fed in 25 g increments.
  • a dispersion of sodium and sodium chloride can have approximately 33 to 37 wt% salt before changes in fluid density and viscosity were observed and surface mixing no longer occurred.
  • Liquid halide transfer Vanadium (IV) Chloride, Tin (TV) Chloride, Titanium (IV) Chloride, and Silicon Tetrachloride were transferred into the reaction cups using 1 mL syringes. For each liquid halide, a volume of 0.1 mL was transferred into a syringe. The syringes were then placed in the glovebox. The syringes were then used to inject drops of each liquid halide into a reaction cup containing molten sodium metal.
  • Reaction vessel Stainless steel 2.5 oz. cups were implemented as the reaction vessels for all tests. When not in use, stainless steel foil was placed on top of each reaction cup.
  • a test setup used for this example is shown and described with reference to FIG. 4 as described in U.S. Patent Application No. 15/051,267, which is incorporated in its entirety by reference herein.
  • Each stainless steel cup, V-0100 through V-0600 contained sodium metal.
  • the reaction cups were maintained at 240 - 260°C using a hot plate (manually controlled via TC-0110).
  • Halide powders were pre-weighed using scale WI-0120 and poured into V-0100 and V-0200.
  • the scale used to weigh the powder halides only displays increments of 0.1 grams; therefore, the amount of halide powders added to each reaction cup was known to be less than 0.1 grams.
  • Halide liquids were injected into the reactions cups using 1 mL syringes.
  • the liquid halides were transferred from storage bottles into syringes under the fume hood. The syringes were then placed in the glovebox. For each halide liquid, 0.1 mL or less was injected into the reaction cups V-0300 through V-0600. The setup for the liquid halides was the same with the exception that four reaction cups were used instead of two.
  • Argon was fed from an argon supply Dewar to the glovebox at a flow rate of 65-70 scfh. Argon pressure was regulated down to 20 - 30 psig.
  • Each test began with equipment set-up in the glovebox, and establishing an inert atmosphere.
  • the hot plate was energized and set to 250°C. In order to reach and maintain a sodium temperature of 250°C, the hot plate was set between 350°C and 400°C.
  • the halides were added to the reactions cups one at a time.
  • the tests were performed with the lid (foil) removed from the cup to observe signs of reaction (such as a change in color or the generation of smoke). If no sign of reaction was observed at 250°C, then the temperature was increased in increments of 50°C and the test was repeated until a reaction was observed. All reactions were performed at 250 °C in order to establish a safe minimum temperature.
  • TiC changed from clear to yellow while in the syringe.
  • A1C1 3 , ZrCLj, VC , SnCl 4 , TiC , and SiC all react with sodium at approximately 250°C. There is potentially some evaporation when the liquid halides are introduced to sodium at 250°C.
  • Particle flow can be measured according to a standardized protocol, such as by using a Hall flow meter according ASTM International Standard B213.
  • Molecular content of the metal powders produced by the methods described herein can be determined using LECO testers. For example, nitrogen and oxygen content can be tested with LECO Model TC436DR. Carbon and sulfur content can be tested with LECO Model CS444LS. Nitrogen, oxygen, and hydrogen content can be tested with LECO Model TCH600.
  • the reactor vessel was sealed, transferred to a furnace, and heated to 825 °C for four hours to reduce the surface area of the titanium metal produced in the reaction.
  • the recovered titanium powder was dried overnight in a vacuum oven at 100°C.
  • the titanium powder thus produced was analysed by inductively coupled plasma mass spectrometry (ICP-MS) and LECO instruments, and was found to contain below 150 ppm iron, below 300 ppm total transition metals, and below 3000 ppm oxygen. The results demonstrate that the titanium powder falls within the purity limits as described in U S No. R50550.
  • the reactor vessel was sealed, transferred to a furnace, and heated to 825°C for four hours to reduce the surface area of the hafnium metal produced in the reaction. During this process step, unreacted sodium was removed from the hafnium metal to leave a hafnium-sodium chloride composite.
  • hafnium and sodium chloride mixture was then transferred to a vacuum furnace and heated under vacuum to 2300°C, held at that temperature for one hour, and then cooled. This removed the sodium chloride and produced a button of solid hafnium.
  • the hafnium button was analysed via glow discharge mass spectrometry (GDMS) and found to have 26 ppm oxygen content, 1690 ppm zirconium, and less than 150 ppm total transition metals.
  • GDMS glow discharge mass spectrometry
  • the Inconel reactor was then sealed, transferred to a furnace, and heated to 900°C for 1 hour. After this step, the unreacted sodium was removed and the metal powder washed to remove its salt coating. Washing continued until the wash water conductivity fell below 2 microsiemens. Finally, the powder was dried in a vacuum over for 24 hours.
  • the titanium-aluminum metal thus produced was found by ICPMS analysis to contain below 100 ppm iron and below 150 ppm total transition metals.
  • a titanium-aluminum-vanadium chloride mixture was prepared, by mixing liquid titanium chloride (from Sigma Aldrich), aluminum chloride powder (from Strem Chemical) and liquid vanadium chloride (from Acros Organics). The mixture was stirred constantly to dissolve the aluminum trichloride into the titanium chloride and vanadium chloride liquid.
  • tilmium-aluminum-niobium-chromium chloride mixture was prepared, by mixing liquid titanium chloride (from Sigma Aldrich), sodium aluminum chloride powder (NaAlCU) (from Sigma-Aldrich), niobium chloride (from Sigma Aldrich), and sodium chromium chloride powder (Na 3 CrCl 5 ) (produced from NaCl and CrCl 2 both from Sigma Aldrich).
  • liquid titanium chloride from Sigma Aldrich
  • NaAlCU sodium aluminum chloride powder
  • niobium chloride from Sigma Aldrich
  • sodium chromium chloride powder Na 3 CrCl 5
  • the reactor vessel was then sealed and transferred to a furnace, brought to 825°C and held at that temperature for approximately one hour before being allowed to cool.
  • the present invention includes the following aspects/embodiments/features in any order and/or in any combination:
  • a method for producing a metal powder comprising:
  • molten reducing metal comprises i) at least 90 wt% sodium or potassium or a mixture of potassium and sodium or ii) at least 90 wt% aluminum, magnesium, or titanium based on total weight of said molten reducing metal, and the at least one metal halide is a solid or liquid, with the proviso that the molten reducing metal is different from the metal of the at least one metal halide;
  • step c) the at least one metal salt is recovered with said metal.
  • step c) the at least one metal salt is recovered with said metal.
  • a method for producing a metal masterbatch comprising:
  • said at least one metal halide comprises Ti halide, V halide, Cr halide, Mn halide, Fe halide, Co halide, Ni halide, Cu halide, Zn halide, Ga halide, Ge halide, As halide, Se halide, Zr halide, Nb halide, Mo halide, u halide, Rh halide, Pd halide, Ag halide, Cd halide, In halide, Sn halide, Sb halide, C halide, Si halide, Te halide, Hf halide, Ta halide, W halide, Hg halide, Tl halide, Pb halide, or Bi halide or any combination thereof.
  • metal masterbatch comprises aluminum, hafnium, and zirconium.
  • carbide forming component comprises carbon containing gas, carbon tetrachloride or solid carbon.
  • boride forming component comprises boron trichloride or a boron hydride.
  • said molten reducing metal comprises said at least 90 wt% sodium or potassium or a mixture of potassium and sodium
  • combined at least one metal halide and at least one molten reducing metal passes through a reaction zone that empties into a settling tank that includes at least one outlet that is located at a height in the settling tank that permits said molten reducing metal from step b) to at least partly be removed by said outlet but not said molten salt or said metal
  • said combined at least one metal halide, at least one molten reducing metal, and at least one metal salt together are at a temperature that results in phase separation of the molten reducing metal from said metal salt and said metal.
  • molten reducing metal comprises at least 90 wt% sodium or potassium or a mixture of potassium and sodium, and wherein at least one metal halide, at least one molten reducing metal and at least one metal salt together are at a temperature that causes phase separation of the molten reducing metal from said metal salt and said metal.
  • the at least one metal halide comprises at least a first metal halide and a second metal halide, with the first metal halide reactive with the metal salt and the second metal halide non-reactive with the metal salt, wherein the metal of the second metal halide is the same or different from the molten reducing metal.
  • said at least one metal halide comprises a halide of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Hf, Ta, W, Hg, Tl, Pb, or Bi or any combination thereof
  • the present invention can include any combination of these various features or embodiments above and/or below as set forth in sentences and/or paragraphs. Any combination of disclosed features herein is considered part of the present invention and no limitation is intended with respect to combinable features.
  • Applicant specifically incorporates the entire contents of all cited references in this disclosure. Further, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.

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Abstract

L'invention concerne un procédé de production d'une poudre métallique qui combine un métal réducteur fondu et un halogénure métallisé dans un espace sensiblement dépourvu d'oxygène et d'eau, le métal réducteur fondu étant du sodium et/ou du potassium, ou de l'aluminium (ou du magnésium ou du titane) et étant présent dans un excès stœchiométrique par rapport à l'halogénure métallisé, qui est un solide ou un liquide, ce qui permet de produire des particules et un sel métalliques, d'éliminer le métal réducteur n'ayant pas réagi, d'éliminer éventuellement le sel, et de récupérer la poudre métallique. L'invention concerne également un procédé de production d'un mélange maître métallique, dans lequel le métal réducteur fondu est de l'aluminium, du magnésium et/ou du titane et, après la combinaison d'aluminium (ou de magnésium ou de titane) fondu et d'halogénure métallisé dans l'espace de réaction, le sel métallique produit est sensiblement éliminé en vue d'obtenir le mélange maître métallique qui comprend au moins une partie de l'aluminium (ou du magnésium ou du titane) fondu et au moins un métal.
PCT/US2017/045656 2016-08-12 2017-08-07 Procédés de production de poudres métalliques et de mélanges maîtres métalliques Ceased WO2018089062A2 (fr)

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