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WO2019084045A1 - Procédés basés sur l'électrolyse pour le recyclage de particules de titane - Google Patents

Procédés basés sur l'électrolyse pour le recyclage de particules de titane

Info

Publication number
WO2019084045A1
WO2019084045A1 PCT/US2018/057159 US2018057159W WO2019084045A1 WO 2019084045 A1 WO2019084045 A1 WO 2019084045A1 US 2018057159 W US2018057159 W US 2018057159W WO 2019084045 A1 WO2019084045 A1 WO 2019084045A1
Authority
WO
WIPO (PCT)
Prior art keywords
received
titanium particles
titanium
oxygen
oxide layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2018/057159
Other languages
English (en)
Inventor
Jen C. Lin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Howmet Aerospace Inc
Original Assignee
Arconic Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Arconic Inc filed Critical Arconic Inc
Publication of WO2019084045A1 publication Critical patent/WO2019084045A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/70—Recycling
    • B22F10/73—Recycling of powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/12—Pickling; Descaling in melts
    • C25F1/16—Refractory metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present disclosure is directed towards electrolytic-based methods for recycling titanium particles.
  • Titanium particles are required to meet strict specifications for oxygen content for use in powder metallurgy processes. These requirements are laid out in ASTM B988-13.
  • the present disclosure relates to methods for recycling titanium metal-based particles, including, for example and without limitation, titanium alloy powders, as may be used in powder metallurgy or additive manufacturing (AM) processes.
  • titanium metal Due to titanium metal's affinity for oxygen, titanium particles tend to accumulate oxygen during their use and/or storage.
  • the accumulated oxygen may, for instance, be in the form of titanium oxides, such as titanium dioxide (T1O2), building-up as a surface oxide layer upon a titanium-based core body.
  • T1O2 titanium dioxide
  • oxygen content of the titanium particles may accumulate to such an extent that the titanium particles may no longer be used in those processes due to their oxygen content becoming excessive and, thus, outside of allowed oxygen limits.
  • a method may include receiving a feedstock comprising titanium particles (e.g., titanium metal particles; titanium alloy particles).
  • the as- received titanium particles may comprise oxygen and have a surface oxide layer thereon.
  • the method may include exposing the feedstock to reducing conditions in an electrolytic cell.
  • the method may include reducing the surface oxide layer of the titanium particles, thereby decreasing the oxygen of the as-received titanium particles by at least 10%.
  • the method may include recovering a purified feedstock from the electrolytic cell.
  • the as- recovered titanium particles generally have at least 10% less oxygen as compared to the as- received titanium particles.
  • additive manufacturing means "a process of joining materials to make objects from 3D model data, usually layer upon layer, as opposed to subtractive manufacturing methodologies," as defined in ASTM F2792-12A entitled “Standard Terminology for Additive Manufacturing Technologies.” Such materials may be manufactured via any appropriate additive manufacturing technique described in ASTM F2792-12A, such as binder jetting, directed energy deposition, material extrusion, material jetting, powder bed fusion, or sheet lamination, among others.
  • a "particle” means a distinct fragment of matter.
  • a particle may be produced, for example, via gas atomization.
  • a particle may be jagged or spherical.
  • a jagged particle may be spherodized by any suitable known process.
  • a particle may be of any suitable size, including of a size suitable for use in an additive manufacturing environment, as well as very small (e.g., fines) or very large (e.g., chips) fragments of matter.
  • titanium particles means particles based on titanium.
  • the titanium particles may be titanium metal particles, titanium alloy particles, and/or titanium aluminide particles, as defined below.
  • titanium metal particles means commercially pure (CP) titanium particles, as defined in ASTM B988-13 (2013).
  • titanium alloy particles means particles of a titanium alloy, where titanium is the predominant alloying element, or particles of a titanium aluminide.
  • titanium aluminide particles means particles having titanium and aluminum as the predominant alloying elements.
  • the term “or” is an inclusive “or” operator, and is equivalent to the term “and/or,” unless the context clearly dictates otherwise.
  • the term “based on” is not exclusive and allows for being based on additional factors not described, unless the context clearly dictates otherwise.
  • the meaning of “a,” “an,” and “the” include plural references, unless the context clearly dictates otherwise.
  • the meaning of “in” includes “in” and “on”, unless the context clearly dictates otherwise.
  • FIG. 1 is a schematic diagram of one embodiment of an electrolysis-based process for recycling titanium particles for use in one or more additive manufacturing processes.
  • FIG. 2a is a flow chart illustrating one embodiment of the receiving, preparing, exposing, and recovering steps of FIG. 1.
  • FIG 2b is a schematic diagram illustrating various optional embodiments of the receiving step of FIG 1.
  • FIG. 2c is a schematic diagram illustrating various optional embodiments of the preparing step of FIG 1.
  • FIG. 2d is a schematic diagram illustrating various optional embodiments of the exposing step of FIG 1.
  • FIG. 2e is a schematic diagram illustrating an optional embodiment of the recovering step of FIG 1.
  • FIG. 3a is a schematic cross-sectional diagram of one embodiment of an as-received titanium particle of the as-received feedstock of FIG. 1.
  • FIG. 3b is a schematic cross-sectional diagram of one embodiment of an as-recovered titanium particle of the purified feedstock of FIG. 1.
  • FIG. 4 is a flow chart illustrating embodiments of the exposing and recovering steps of FIG. 1.
  • FIG. 5 is a flow chart illustrating one embodiment of the process of FIG. 1.
  • a method (100) may be implemented, at least in part, through an electrolysis-based process (101).
  • the method (100) may include receiving (102) a feedstock at an electrolytic cell (104).
  • the feedstock may include titanium particles.
  • titanium particles in the as-received feedstock may include titanium alloy particles (e.g., Ti 6 Al4 particles), titanium aluminide particles, and titanium metal particles (e.g., commercially pure (CP) titanium particles, as defined in ASTM B988-13 (2013), which is incorporated herein by reference in its entirety).
  • the as-received feedstock may include any mixture of two or more of the types of titanium particles described above.
  • the feedstock of titanium particles may be received (102) from one or more AM processes (106).
  • the AM processes (106) may utilize the titanium particles only one time.
  • the titanium particles e.g., the same batch of powder material provided to a powder bed of an AM apparatus, not shown
  • the AM processes (106) may utilize the same batch of titanium particles two or more times. In these embodiments, a single batch of titanium particles may be reused in one or more subsequent runs of the AM process(es) (106).
  • the AM apparatus may not include sufficient capability to maintain a controlled atmosphere chamber under which the titanium particles are positioned for the AM process (106). Accordingly, the titanium particles may be oxidized and accumulate oxygen at a faster rate as compared to cases in which the controlled atmosphere may limit the rate of oxidation of the titanium particles.
  • the AM apparatus may include a capability to maintain a controlled atmosphere (e.g., inert gas(es) or vacuum) chamber under which the titanium particles are positioned for the AM process (106).
  • the titanium particles may be oxidized and accumulate oxygen at a slower rate, and the same batch of titanium particles may be reused for a greater number of runs of the AM process (106) relative to cases where the AM apparatus being used has a lesser developed atmosphere control capability to limit the oxidation rate of the titanium particles.
  • the permitted level of oxygen content of the titanium particles may be stringently controlled for quality control and/or specification compliance purposes.
  • a method (200) may include receiving (102) the titanium particles (301) (shown in FIG. 3a) which may include oxygen and may have a surface oxide layer (302a) thereon.
  • the oxygen content of the as-received titanium particles (301) may be determined as an average oxygen content value of the as-received feedstock.
  • the oxygen content of the as-received titanium particles (301) may be determined using the ASTM E1409-13 (2013) test method, which is incorporated by reference herein in its entirety.
  • the as-received titanium particles may include from 100 ppm (0.01 weight (wt.) %) to 5000 ppm (0.5 wt. %) oxygen.
  • the as-received titanium particles (301) may include at least 100 ppm oxygen. In another embodiment, the as-received titanium particles (301) may include at least 200 ppm oxygen. In yet another embodiment, the as-received titanium particles (301) may include at least 300 ppm oxygen. In still another embodiment, the as-received titanium particles (301) may include at least 500 ppm oxygen. In another embodiment, the as-received titanium particles (301) may include at least 1,000 ppm oxygen. In yet another embodiment, the as-received titanium particles (301) may include at least 2,000 ppm oxygen. In still another embodiment, the as-received titanium particles (301) may include at least 2,500 ppm oxygen.
  • the as-received titanium particles (301) may include at least 5,000 ppm oxygen. In one embodiment, the as-received titanium particles (301) may include less than or equal to 5,000 ppm oxygen. In one embodiment, an amount of the oxygen of the as-received titanium particles (301) is greater than a predetermined oxygen content specification (206b) (e.g., greater than the oxygen content allowed by ASTM B988-13).
  • the oxygen in the surface oxide layers (302a) of the as-received titanium particles (301) may be present as one or more oxides of the titanium metal and/or the other alloying elements of the as-received titanium particles (301).
  • the oxygen may include one or more oxides of titanium (e.g., T1O2) (202b).
  • the surface oxide layers (302a) of the as-received titanium particles (301) may contain one or more of hydrogen (water, hydrated oxides), nitrogen (e.g., nitrides, oxynitrides), carbon (e.g., carbides, organic residues), and sulfur (e.g., sulfides).
  • the hydrogen, nitrogen, carbon, and/or sulfur may be present in the surface oxide layers (302a) either instead of or in addition to oxygen.
  • a surface oxide layer (302a) of at least one of the as-received titanium particles (301) may consist essentially of oxygen and hydrogen (212b).
  • the reducing conditions of the electrolytic cell (104) during the exposing step (110) may facilitate decreasing the content of hydrogen, nitrogen, carbon, and/or sulfur in the surface oxide layers (302a).
  • One or more of the mechanisms described in International Patent Application No. PCT/GB99/01781 (“Removal of Oxygen from Metal Oxides and Solid Solutions by Electrolysis in a Fused Salt," International Publication No.
  • WO 99/64638 which is incorporated herein by reference in its entirety
  • the oxygen may be present in the surface oxide layers (302a) and/or the cores (308) of the as-received titanium particles (301) as interstitial (e.g., dissolved) oxygen.
  • the hydrogen, nitrogen, carbon, and/or sulfur may be present in the surface oxide layers (302a) and/or the cores (308) of the as-received titanium particles (301) as interstitial (e.g., dissolved) species.
  • the reducing conditions of the electrolytic cell (104) during the exposing step (110) may facilitate decreasing the content of interstitial oxygen and, where present, the content of interstitial species of hydrogen, nitrogen, carbon, and/or sulfur, in the surface oxide layers (302a) and/or the cores (308).
  • One or more of the mechanisms described in PCT/GB99/01781 may be involved during the exposing (110) step to reduce the content of interstitial oxygen and, where present, the content of interstitial species of hydrogen, nitrogen, carbon, and/or sulfur in the surface oxide layers (302a) and/or the cores (308) of the as-received titanium particles (301).
  • the oxygen of the as-received titanium particles (301) may be contained predominantly (204b) in the surface oxide layer (302a).
  • the surface oxide layer (302a) may contain from 50% to 100% of the oxygen of the as-received titanium particles (301). In one embodiment, at least 50% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302a). In another embodiment, at least 75% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302a). In yet another embodiment, at least 90% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302a).
  • At least 95% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302aY In another embodiment, at least 97% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302a). In yet another embodiment, at least 99% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302a). In still another embodiment, at least 99.5% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302a). In another embodiment, 100% of the oxygen of the as-received titanium particles (301) may be contained in the surface oxide layer (302a).
  • the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 10 ⁇ to 150 ⁇ (208b).
  • the as-received titanium particles (301) have an as- received particle size distribution (PSD) which may be expressed as a range of diameters along with the D50 value (304a).
  • PSD as- received particle size distribution
  • the surface oxide layer (302a) of the as-received titanium particles (301) may have an as-received thickness (306a).
  • the average value of the as-received thickness (306a) of the surface oxide layer (302a) may be determined under the assumption that the oxygen is predominantly (204b) contained in the surface oxide layer (302a).
  • the as- received thickness (306a) of the surface oxide layer may be from 0.50 to 12.50 nm (210b).
  • the as-received titanium particles (301) may have an as-received mean diameter (D50) (304a) of from 10 ⁇ to 150 ⁇ (208b).
  • the as- received titanium particles (301) have a mean diameter (D50) (304a) of at least 10 ⁇ .
  • the as-received titanium particles (301) have a mean diameter (D50) (304a) of at least 15 ⁇ .
  • the as-received titanium particles (301) have a mean diameter (D50) (304a) of at least 20 ⁇ .
  • the as-received titanium particles (301) have a mean diameter (D50) (304a) of at least 25 ⁇ .
  • the as-received titanium particles (301) have a mean diameter (D50) (304a) of at least 30 ⁇ . In one embodiment, the as-received titanium particles (301) have a mean diameter (D50) (304a) of not greater than 125 ⁇ . In another embodiment, the as-received titanium particles (301) have a mean diameter (D50) (304a) of not greater than 100 ⁇ . In yet another embodiment, the as-received titanium particles (301) have a mean diameter (D50) (304a) of not greater than 85 ⁇ . In yet another embodiment, the as-received titanium particles (301) have a mean diameter (D50) (304a) of not greater than 60 ⁇ . In yet another embodiment, the as-received titanium particles (301) have a mean diameter (D50) (304a) of not greater than 50 ⁇ . Other particle size distributions may be used.
  • the as-received titanium particles (301) may have an as-received mean diameter (D50) (304a) of from 15 ⁇ to 125 ⁇ (208b). In another embodiment, the as-received titanium particles (301) may have an as-received mean diameter (D50) (304a) of from 20 ⁇ to 100 ⁇ (208b). In yet another embodiment, the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 20 ⁇ to 85 ⁇ (208b).
  • the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 20 ⁇ to 60 ⁇ (208b). In yet another embodiment, the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 25 ⁇ to 60 ⁇ (208b). In another embodiment, the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 25 ⁇ to 50 ⁇ (208b).
  • the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 30 ⁇ to 50 ⁇ (208b). In another embodiment, the as- received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 50 ⁇ to 100 ⁇ (208b). In yet another embodiment, the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 75 ⁇ to 100 ⁇ (208b). In another embodiment, the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 25 ⁇ to 125 ⁇ (208b). In yet another embodiment, the as-received titanium particles (301) may have an as-received mean diameter (D 50 ) (304a) of from 75 ⁇ to 150 ⁇ (208b).
  • the as-received thickness (306a) of the surface oxide layer may be from 0.5 to 12.50 nm (210b). In one embodiment, the as-received thickness (306a) of the surface oxide layer is at least 0.5 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is at least 1.0 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is at least 1.25 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is at least 1.5 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is at least 1.67 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is at least 2.0 nm (210b). In one embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 12.5 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 11.75 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 11.0 nm (210b).
  • the as- received thickness (306a) of the surface oxide layer is not greater than 10.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 10.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 9.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 9.0 nm (210b). In another embodiment, the as-received thickness i306a " ) of the surface oxide layer is not greater than 8.5 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is not greater than 8.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 7.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 7.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 6.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 6.0 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is not greater than 5.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 5.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 4.5 nm (210b). In yet another embodiment, the as- received thickness (306a) of the surface oxide layer is not greater than 4.25 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 4.0 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is not greater than 3.75 nm (210b). In another embodiment, the as- received thickness (306a) of the surface oxide layer is not greater than 3.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 3.25 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 3.0 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is not greater than 2.8 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer may be from 0.5 to 12.50 nm (210b). In one embodiment, the as-received thickness (306a) of the surface oxide layer is from 0.5 to 11.75 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 0.5 to 11.0 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is from 0.5 to 10.5 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 0.5 to 10.0 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is from 0.5 to 9.5 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 0.5 to 9.0 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is from 0.5 to 8.5 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.0 to 8.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.0 to 8.0 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is from 1.25 to 7.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.25 to 7.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.25 to 6.5 nm (210b). In yet another embodiment, the as- received thickness (306a) of the surface oxide layer is from 1.25 to 6.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.25 to 5.5 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is from 1.25 to 5.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.5 to 5.0 nm (210b). In yet another embodiment, the as- received thickness (306a) of the surface oxide layer is from 1.5 to 4.5 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.5 to 4.25 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.5 to 4.0 nm (210b).
  • the as-received thickness (306a) of the surface oxide layer is from 1.67 to 4.0 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.67 to 3.75 nm (210b). In yet another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.67 to 3.5 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.67 to 3.25 nm (210b). In yet another embodiment, the as- received thickness (306a) of the surface oxide layer is from 1.67 to 3.0 nm (210b). In another embodiment, the as-received thickness (306a) of the surface oxide layer is from 1.67 to 2.8 nm (210b).
  • the as-received titanium particles (301) may comprise a titanium-based core (308).
  • the titanium -based core (308) may contain the majority of the mass of the titanium particle (301) and may contain all of the material of the titanium particle (301) other than the surface oxide layer (302a).
  • the titanium of the titanium particle (301) may be contained predominantly in the titanium-based core (308).
  • the surface oxide layer (302a) of the as- received titanium particles (301) may include the surface oxide layer (302a) deposited on the surface of the titanium -based core (308).
  • the oxygen-containing surface oxide layer (302a) may at least partially encapsulate the titanium-based core (308).
  • feedstocks may be received (102) from other titanium particle producing systems, methods and apparatuses, such as, for instance, powder metallurgy processes, mining processes, and other industrial processes where titanium-based particles are produced.
  • the method (100) may include a preparing step (108).
  • the preparing step (108) may include dispensing C201c) the as-received feedstock of titanium particles (301) into the electrolytic cell (104).
  • the as-received titanium particles (301) may be dispensed (201c) into one electrolytic cell (104), which may be suitably sized to accommodate all or a portion of the quantity of the titanium particles (301) received (102).
  • the as-received titanium particles (301) may be dispensed (201c) into a plurality of electrolytic cells (104).
  • the structure and configuration of the electrolytic cell(s) (104) may be those described PCT/GB99/01781.
  • the as-received feedstock of titanium particles (301) may be subjected to one of more preparatory steps prior to and/or during the preparing (108) step.
  • the preparing step (108) may include a blending (202c) step.
  • the blending (202c) step at least a portion of the as- received feedstock of titanium particles (301) may be blended using a blending machine (not shown in FIG. 2c).
  • the blending (202c) step may provide a consistent mixture of the as- received titanium particles (301) to be dispensed (201c) into the one or more electrolytic cells (104).
  • the blending (202c) step may be beneficial in cases where, for example, the as- received feedstock of titanium particles (301) is being supplied from more than one source.
  • the blending (202c) step may also be beneficial where the as-received titanium particles (301) may have an incompletely characterized composition, PSD, oxygen content, surface oxide layer (302a) thickness (306a), and/or D50 (304a).
  • the preparing step (108) may include a deagglomerating (204c) step.
  • a deagglomerating (204c) step at least a portion of the as-received feedstock of titanium particles (301) may be deagglomerated (204c) using a deagglomerating machine (not shown in FIG. 2c).
  • the apparatus employed for the deagglomerating (204c) step may be the same machine used for the blending step (202c).
  • separate machines may be utilized for the deagglomerating (204) and blending (202c) steps.
  • the deagglomerating (204c) step may provide a deagglomerated mixture of the as-received titanium particles (301) which may be dispensed (201c) into the electrolytic cell(s) (104).
  • the deagglomerating (204c) step may be beneficial in cases where, for example, at least a portion of the as-received feedstock of titanium particles (301) may be agglomerated and where such a state of agglomeration may be undesirable during subsequent steps of process (101) and/or may negatively impact the quality of a final product of process (101).
  • the preparing step (108) may include a treating (206c) step.
  • a treating (206c) step at least a portion of the as-received feedstock of titanium particles (301) may be subjected to one or more chemical treatments prior to and/or after the deagglomerating (204c) and blending C202c) steps.
  • the treating (206c) step may be accomplished using a treatment apparatus (not shown in FIG. 2c).
  • the apparatus employed for the treating (206c) step may be the same machine used for the blending (202c) and/or deagglomerating (204c) steps.
  • separate machines are utilized for the deagglomerating (204c), blending (202c), and treating (206c) steps.
  • the treating (206c) step may include a plurality of steps.
  • the treating (206c) step may include a cleaning (208c) step.
  • the cleaning (208c) step at least a portion of the as-received feedstock of titanium particles (301) may be cleaned with a suitable solvent and/or other method to remove, or at least decrease, a level of contamination present in the as-received feedstock of titanium particles (301).
  • the cleaning (208c) step may include contacting the as-received titanium particles (301) with a cleaning solvent to dissolve organic residues that may be present.
  • the cleaning (208c) step may include more extensive purification of the as-received feedstock of titanium particles (301).
  • the cleaning (208c) step may include wet and/or dry separation steps to remove undesired particulate matter (e.g., dirt and/or non-metallic particles) from the as-received feedstock of titanium particles (301).
  • solvents and other cleaning agents may be rinsed from the titanium particles (301) in preparation for subsequent steps of process (101).
  • the cleaning (208c) step may provide an at least partially purified mixture of the as-received titanium particles (301) to be dispensed (201c) into the electrolytic cell(s) (104).
  • the cleaning (208c) step may be beneficial in cases where, for example, at least a portion of the as-received feedstock of titanium particles (301) is known to contain undesirable levels of extraneous matter and/or residues which may diminish the efficiency and/or effectiveness of subsequent unit operations of process (101), and/or may negatively impact the quality of the final product of process (101).
  • the treating (206c) step may include a deoxidizing (210c) step.
  • the deoxidizing (210c) step at least a portion of the as-received feedstock of titanium particles (301) may be deoxidized with a suitable chemical agent and/or may be subjected to any other suitably deoxidizing condition(s).
  • the deoxidizing (210c) may include contacting the as-received titanium particles (301) with a suitably diluted acidic solution to dissolve, perforate, and/or soften the surface oxide layer (302a) of the as-received titanium particles (301).
  • the deoxidizing (210) step may include initially deoxidizing the as- received titanium particles (301) to a predetermined extent.
  • deoxidizing agents may be rinsed from the titanium particles (301) in preparation for subsequent steps of process (101).
  • the deoxidizing (210c) step may provide an at least partially deoxidized mixture of the as-received titanium particles (301) to be dispensed (201c) into the electrolytic cell(s) (104).
  • the deoxidizing (210c) step may be beneficial in cases where, for example, at least a portion of the as-received feedstock of titanium particles (301) is known to contain undesirable high levels of oxygen contained in the surface oxide layer (302a) which may diminish the effectiveness of subsequent unit operations of process (101).
  • the electrolytic cell (104) may include an electrolyte (402).
  • the electrolyte may comprise at least one of a liquid, gel, sponge or porous solid material (405)
  • the preparing (108) step may include suspending (412) the as-received titanium particles (301) in the electrolyte (402).
  • the electrolyte (402) may be those described in PCT/GB99/01781.
  • the suspending (412) step may be accomplished as described in PCT/GB99/01781.
  • the method (100) may include an exposing (110) step.
  • the feedstock of titanium particles (301) prepared (108) for the electrolytic cell (104) may be exposed (110) to reducing conditions in the electrolytic cell (104).
  • the reducing conditions in the electrolytic cell (104) may include one or more physical, chemical, and electrical conditions.
  • the reducing conditions in the electrolytic cell (104) may include the configuration(s) of the electrodes (403).
  • the reducing conditions may include the position(s) of the electrodes (403).
  • the reducing conditions may include the material(s) of the electrodes (403).
  • the reducing conditions may include the temperatures at which the electrolyte (402) is maintained. In another embodiment, the reducing conditions may include the duration of the exposing (110) step. In yet another embodiment, the reducing conditions may include the composition of the electrolyte (402). In still another embodiment, the reducing conditions may include the magnitude(s), waveform(s) and/or rate(s) of change of voltage(s) and/or current(s) induced across the electrodes (403) and flowing through the electrolyte (402), respectively, during the exposing (110) step. In another embodiment, the reducing conditions of the electrolytic cell (104) during the exposing (110) step may include one or more of those conditions described in PCT/GB99/01781.
  • the exposing (110) step may include reducing the surface oxide layer (302a) of the as-received titanium particles (301).
  • the exposing (110) step may include decreasing the amount of oxygen (212d) contained in the as-received titanium particles (301).
  • the oxygen contained in the as-received titanium particles (301) may be decreased by at least 10% during the exposing (110) step.
  • the oxygen contained in the as-received titanium particles (301) may be decreased by at least 25% during the exposing (110) step.
  • the oxygen contained in the as-received titanium particles (301) may be decreased by at least 50% during the exposing (110) step.
  • the oxygen contained in the as-received titanium particles (301) may be decreased by at least 75% during the exposing (110) step. In still another embodiment, the oxygen contained in the as-received titanium particles (301) may be decreased by at least 90% during the exposing (110) step. In another embodiment, the oxygen contained in the as-received titanium particles (301) may be decreased to less than 2000 ppm during the exposing (110) step.
  • the exposing (110) step may include decreasing (210d) the as-received thickness (306a) of the as-received surface oxide layer (302a).
  • the exposing (110) step may include controlling (404) one or more of the reducing conditions of the electrolytic cell (104).
  • the controlling (404) step may include establishing and controlling the reducing conditions of the electrolytic cell (104) to maintain the titanium -based core (308) while reducing or eliminating the oxygen-containing surface oxide layer (302a) of the as-received titanium particles (301) during the exposing (110) step.
  • the controlling (404) step may include establishing and controlling the reducing conditions of the electrolytic cell (104) to maintain the size of the titanium-based core (308) during the exposing (110) step.
  • the controlling (404) step may include establishing and controlling the reducing conditions of the electrolytic cell (104) to maintain the composition of the titanium- based core (308) during the exposing (110) step.
  • the controlling (404) step may include establishing and controlling the reducing conditions of the electrolytic cell (104) to maintain the morphology of the titanium -based core (308) during the exposing (110) step.
  • the controlling (404) step may include establishing and controlling the reducing conditions of the electrolytic cell (104) to maintain the surface topology of the titanium -based core (308) during the exposing (110) step.
  • the controlling (404) step may include establishing and controlling the reducing conditions of the electrolytic cell (104) to maintain the size and/or diameter of the titanium- based core (308) during the exposing (110) step.
  • the controlling (404) step may be employed to accomplish the desired extent of decreasing the oxygen content and as-received surface oxide layer (302a) thickness (306a) of the as-received titanium particles (301).
  • the parameters and variables of the process (101) upon which the controlling (404) step may be implemented may be specific to the particular nature of the as-received feedstock of titanium particles (301). If used in the process (101), the nature and extent the treating C206c), deagglomerating (204c), and/or blending (202c) step(s) may also influence how, when, and to what extent the controlling (404) step may be implemented during the exposing (110) step.
  • the parameters and variables of process (101) which may be targeted by the controlling (404) step may be predetermined prior to the receiving (102) and/or exposing (110) step(s). In another embodiment, the parameters and variables of process (101) which may be targeted by the controlling (404) step may be determined prior to the receiving (102) and/or exposing (110) step(s) based on one or more analytical characterizations of the as-received feedstock of titanium particles (301).
  • the parameters and variables of process (101) which may be targeted by the controlling (404) step may be determined continuously and/or in an in-process manner during the exposing (110) step as, for example, by monitoring (406) one or more of the reducing conditions of the electrolytic cell (104) and/or one or more characteristics of the titanium particles as the exposing (110) step progresses.
  • the parameters and variables of process (101) may be targeted by the controlling (404) step using a combination of two or more of the targeting schemes described above.
  • the parameters and variables of process (101) may be targeted by the controlling (404) step using one or more of the schemes described in PCT/GB99/01781.
  • the titanium-based core (308) may have a first size (e.g., characterized by a volume, a diameter, a major radius, and/or a minor radius) prior to reducing or eliminating the oxygen- containing surface oxide layer (302a) during the exposing (110) step.
  • the titanium-based core (308) may have a second size.
  • the second size of the titanium-based core (308) may be from 75% to 100%) of the first size of the titanium-based core (308).
  • the second size of the titanium-based core (308) may be within 75% of the first size of the titanium-based core (308) after the exposing (110) step. In another embodiment, the second size of the titanium-based core (308) may be within 80%> of the first size of the titanium-based core (308) after the exposing (110) step. In yet another embodiment, the second size of the titanium-based core (308) may be within 85%> of the first size of the titanium-based core (308) after the exposing (110) step. In still another embodiment, the second size of the titanium-based core (308) may be within 90% of the first size of the titanium-based core (308) after the exposing (110) step.
  • the second size of the titanium-based core (308) may be within 95% of the first size of the titanium-based core (308) after the exposing (110) step. In yet another embodiment, the second size of the titanium-based core (308) may be within 97% of the first size of the titanium-based core (308) after the exposing (110) step. In still another embodiment, the second size of the titanium-based core (308) may be within 99% of the first size of the titanium-based core (308) after the exposing (110) step. In another embodiment, the second size of the titanium-based core (308) may be within 99.5% of the first size of the titanium-based core (308) after the exposing (110) step.
  • the second size of the titanium-based core (308) may be equal to the first size of the titanium-based core (308) after the exposing (110) step.
  • the exposing (110) step may be performed in the absence of changing the PSD (208d) (FIG. 2d) of the as- received titanium particles (301).
  • the exposing (110) step may also include a maintaining step, which may be accomplished by way of the controlling (404) step.
  • the maintaining step may include maintaining a predetermined portion (214d) (FIG. 2d) of the as-received surface oxide layer (302a).
  • the maintaining step may include maintaining a predetermined fraction of the as-received thickness (306a) of the as-received surface oxide layer (302a).
  • the maintaining step may include maintaining the as-received surface oxide layer (302a) at a thickness value that may be approximately equal to a native oxide layer thickness.
  • the final thickness (306b) of the as-exposed surface oxide layer (302b) may be from 0.5 nm to 3.0 nm. In one embodiment, the final thickness (306b) of the as-exposed surface oxide layer (302b) may be at least 0.5 nm after the exposing (110) step. In another embodiment, the final thickness (306b) of the as-exposed surface oxide layer (302b) may be at least 1.0 nm after the exposing (110) step. In yet another embodiment, the final thickness (306b) of the as-exposed surface oxide layer (302b) may be at least 1.5 nm after the exposing (110) step.
  • the final thickness (306b) of the as-exposed surface oxide layer (302b) may be at least 2.0 nm after the exposing (110) step. In another embodiment, the final thickness (306b) of the as-exposed surface oxide layer (302b) may be at least 2.5 nm after the exposing (110) step. In yet another embodiment, the final thickness (306b) of the as-exposed surface oxide layer (302b) may be not greater than 3.0 nm after the exposing (110) step.
  • the exposing (110) step may be performed in the absence of changing the morphology (202d) of the as-received titanium particles (301).
  • both the as-received (301) and the as-recovered (310) titanium particles may have a spheroid morphology.
  • both the as-received (301) and the as-recovered (310) titanium particles may have an ellipsoid morphology.
  • both the as-received (301) and the as-recovered (310) titanium particles may have an equiaxed morphology.
  • the morphology of the as-received titanium particles (301) may be substantially the same as the morphology of the as-recovered (310) titanium particles.
  • the exposing (110) step may be performed in the absence of changing the surface topology (204d) of the as-received titanium particles (301).
  • both the as- received (301) and the as-recovered (310) titanium particles may have a rough surface topology.
  • both the as-received (301) and the as-recovered (310) titanium particles may have a smooth surface topology.
  • both the as-received (301) and the as-recovered (310) titanium particles may have a surface topology having an intermediate level of roughness.
  • the surface topology of the as-received titanium particles (301) may be substantially the same as the surface topology of the as-recovered (310) titanium particles.
  • the exposing (110) step may be performed in the absence of sintering (206d) the as-received titanium particles (301).
  • the exposing (110) step may be performed in the absence of deposition (420) of titanium (e.g., as titanium metal) of the as-received titanium particles (301) on one or more electrodes (403) of the electrolytic cell (104).
  • the reducing conditions of the electrolytic cell (104) during the exposing step (110) may facilitate decreasing the oxygen content of the as-received titanium particles (301) and decreasing the as-received thickness (306a) of the as-received surface oxide layer (302a).
  • One or more of the mechanisms described in PCT/GB99/01781 may be involved during the exposing (110) step.
  • PCT/GB99/01781 mainly discloses reduction of material composed primarily of Ti02 to titanium metal, where it is beneficial to achieve as full a deoxidization of the starting feedstock as possible to obtain the desired metallic end product.
  • the methods described herein begin with the as-received feedstock of oxidized as-received titanium particles (301) having a titanium-based core (308) and a surface oxide layer (302a).
  • the present disclosure is directed to decreasing the oxygen content and as-received surface oxide layer (302a) thickness (306a) of a primarily metallic, titanium-containing particulate starting material.
  • the method (100) may proceed from the exposing (110) step to a recovering (112) step.
  • a purified feedstock of as-recovered titanium particles (310) may be recovered from the electrolytic cell (104). Due to the exposing (110) step, the as-recovered titanium particles (310) may include at least 10% less oxygen as compared (202e) to the as-received titanium particles (301).
  • the amount of the oxygen of the as-recovered titanium particles (310) may be decreased to less than or equal to the predetermined oxygen content specification (e.g., less than the oxygen content allowed by ASTM B998-13) during the exposing (110) step.
  • the predetermined oxygen content specification e.g., less than the oxygen content allowed by ASTM B998-13
  • an as-exposed surface oxide layer (302b) of the as-recovered titanium particles (310) may have a final thickness (306b).
  • the final thickness (306b) of the surface oxide layer (302b) may be less than the initial thickness (306a) of the as-received titanium particles (301).
  • the as-recovered titanium particles (310) may have an as-recovered mean diameter (D50) (304b) of from 10 ⁇ to 150 ⁇ , such as any of the D50 ranges described above relative to the as-received titanium particles (304a).
  • the as-recovered titanium particles (310) may have an as-recovered PSD which may be expressed as a range of diameters along with the as-recovered D50 value (304b).
  • the average value of the as- exposed thickness (306b) of the surface oxide layer (302b) may be determined under the assumption that the oxygen is predominantly contained in the surface oxide layer (302b).
  • the recovering (112) step may include a separating (414) step.
  • the separating (414) step may include removing the titanium particles from the electrolytic cell (104) to yield the as-recovered titanium particles (310).
  • the separating (414) step may include removing the titanium particles from the electrolyte (402) to yield the as-recovered titanium particles (310).
  • the separating (414) step may include removing the electrolyte (402) from the titanium particles to yield the as-recovered titanium particles (310).
  • the recovering (112) step may include a rinsing (416) step.
  • a rinsing (416) step may be included in the electrolytic cell (104) during the exposing
  • the rinsing (416) step mav utilize one or more suitable rinsing solvents to accomplish sufficient removal of residual electrolyte (402) from the as-recovered titanium particles (310).
  • the rinsing (416) step is performed one time.
  • the rinsing (416) is performed two or more times, including using either the same or different rinsing solvents for each repetition of the rinsing (416) step during the recovering (112) step.
  • one or more repetitions of the rinsing (416) step are performed until such time when an amount and/or level of the residual electrolyte (402) associated with the as-recovered titanium particles (310) is decreased to at or below a predetermined threshold value.
  • the recovering (112) step may include a drying (418) step.
  • the drying (418) step may utilize one or more drying methods under one or more drying conditions (e.g., time, temperature, atmosphere, pressure, etc.). In one embodiment, one or more repetitions of the drying (418) step may be performed until such time when an amount and/or level of residual rinsing solvent(s) associated with the as-recovered titanium particles (310) is decreased to at or below a predetermined threshold value.
  • the recovering (112) step may not include the rinsing (416) step, and any residual electrolyte (402) associated with the as-recovered titanium particles (310) may be decreased to at or below the predetermined threshold value through the drying (418) step alone.
  • the method (500) may include a recycling (114) step.
  • the as-received titanium particles (301) may be scrap titanium particles (501) from at least a first additive manufacturing (AM) process (106a), and method (500) may include recycling the purified feedstock from the recovering (112) step for use in a second
  • method (500) may include recycling the purified feedstock from the recovering (112) step for use in powder metallurgy processes. In another embodiment, method (500) may include recycling the purified feedstock from the recovering
  • method (500) may include recycling the purified feedstock from the recovering
  • method (500) may include recycling the purified feedstock from the recovering (112) step for use in producing cosmetics.
  • method (500) may include recycling the purified feedstock from the recovering (112) step for use in other end-use applications that utilize titanium-based particles.
  • the scrap titanium oarticles (501) may include titanium particles rejected for use in one or more AM processes (106) (e.g., for having too much oxygen, but still having a composition that is within a predetermined specification for all other elements beside oxygen).
  • AM processes (106) e.g., for having too much oxygen, but still having a composition that is within a predetermined specification for all other elements beside oxygen.
  • at least a portion of the purified as- recovered feedstock of titanium particles (310) may be recycled to one or more AM process(es) (106).
  • the recovering (1 12) and/or recycling (1 14) steps may include a characterizing step.
  • properties of the as-recovered titanium particles (310) may be identified and/or determined in order to assess their suitability for use as a recycled feedstock to the one or more AM processes (106). If the identified and/or determined properties of the as-recovered titanium particles (310) indicate they are suitable as a recycled feedstock for use in the first AM process (106a), but not in the second manufacturing process (106b), the as-recovered titanium particles (310) may be delivered directly to the first AM process (106).
  • the first (106a) and second (106b) AM processes may be located in the same facility.
  • the first (106a) AM process may be the same as the second (106b) AM processes (510).
  • the facility may include two or more of the same type of AM apparatus which may use the same purified and recycled feedstock of as-recovered titanium particles (310).
  • the first (106a) AM process may not be the same as the second (106b) AM process, although the first (106a) and second (106b) AM processes may be co-located (508).
  • a single AM facility may include two or more different AM machines which may use different purified and recycled feedstocks of as- recovered titanium particles (310) having different properties and characteristics.
  • the first (106a) and second (106b) AM processes may be located in and may be performed in different locations that may not share the same facility (512). In one embodiment, although they may not be co-located, the first (106a) AM process may be the same as the second (106b) AM processes.
  • a first facility in a first location may include one or more of the type of AM apparatus for the same AM process performed by one of more of the same type of AM apparatus for the same AM process performed in a second facility in a second location.
  • the AM machines for the first (106a) and second (106b) AM processes occurring in the first and second facilities, respectively, may use the same purified and recycled feedstock of as-recovered titanium particles (310).
  • the first AM process (106a) performed in the first location may not be the same as the second AM process (106b) performed in the second location.
  • the first facility may include one or more AM machines which may use different purified and recycled feedstocks of as-recovered titanium particles (310) having different properties and characteristics than the as-recovered titanium particles (310) used bv one or more AM machines in the second facility.
  • the electrolytic cell (104) may be either co-located with or located in a different location relative to where the AM process(es) (106) are performed.
  • the recycling (114) step may include a maintaining (502) step.
  • the maintaining (502) step may include storing the as-recovered titanium particles (310) under controlled conditions such that they retain their desirable properties and characteristics (e.g., decreased oxygen content) attained through the exposing (110) step.
  • the recycling (114) step may include a refining (504) step. After the recovering (112) step, it may be determined (e.g., by the aforementioned characterizing step) that the as-recovered titanium particles (310) do not meet all requirements for use as a recycled feedstock in one or more AM processes (106).
  • the refining (504) step may be beneficial in such cases to ensure that the as-recovered titanium particles (310) may be used as a recycled feedstock in the one or more AM processes (106).
  • the refining (504) step may include a chemical treatment, such as a chemical deoxidizing, which may be similar to those described above with reference to the treating (206c) step.
  • the refining (504) step may include a mechanical treatment, which may be similar to those described above with reference to the blending (202c) and/or deagglomerating (204c) steps.
  • the refining (504) step may include at least one additional iteration of the methods (e.g. methods 100/200), as described above.
  • the refining (504) step may be performed by apparatuses and/or systems that may be either co-located with or located in a different location relative to where either the exposing (110) step or the AM process(es) (106) are performed.
  • the recycling (114) step may include a delivering (506) step.
  • the delivering (506) step may be performed, at least in part, concurrently with the maintaining
  • the delivering (506) step may include transporting the as-recovered feedstock of titanium particles (310) from the location of the electrolytic cell(s) (104) used for the exposing (110) step to one more other locations which may either be in close proximity to the electrolytic cell(s) (104) in the same facility or may be some distance from where the exposing (110) step was performed, including in one or more different facilities for AM process(es) (106).
  • the delivering (506) step may include transporting the as-recovered feedstock of titanium particles (310) directly from the location where the exposing (110) step was performed to the location where the as-recovered titanium particles
  • (310) may be used as a recycled feedstock for the AM process(es) (106).
  • the delivering (506) step may include one or more intervening step(s).
  • the one or more intervening step(s) of the delivering (506) step may include the refining (504) step.
  • the one or more intervening step(s) of the delivering (506) step may include receiving additional feedstock(s) of as-recovered titanium particles (310) from additional locations where the exposing (110) step was performed.
  • the delivering (506) step may include additional steps similar to the blending (202c) and/or deagglomerating (204c) step(s) to provide a consistent recycled feedstock for use in one or more AM process(es) (106) meeting the predetermined requirements and specifications.
  • the new titanium alloy particles produced by the methods described herein may be utilized to produce a variety of titanium alloy products.
  • the titanium alloy products may be suitable in aerospace and/or automotive applications.
  • aerospace applications may include heat exchangers and turbines.
  • a titanium alloy product is in the form of a compressor component (e.g., turbocharger impeller wheels).
  • automotive applications may include interior or exterior trim/appliques, pistons, valves, and/or turbochargers.
  • Other examples include any components close to a hot area of the vehicle, such as engine components and/or exhaust components, such as the manifold.
  • Titanium alloy products may be in the form of an engine component for an aerospace or automotive vehicle, wherein the method comprises incorporating the engine component into the aerospace or automotive vehicle.
  • a method may include operating such an aerospace or automotive vehicle.
  • the final titanium alloy particles may be used in a compressor wheel for a turbocharger.
  • the final titanium alloy product may be one of a heat exchanger and a piston.
  • the titanium alloy products may also be utilized in a variety of consumer products, such as any consumer electronic products, including laptops, cell phones, cameras, mobile music players, handheld devices, computers, televisions, microwave, cookware, washer/dryer, refrigerator, sporting goods, or any other consumer electronic product requiring durability and selective visual appearance.
  • the visual appearance of the consumer electronic product meets consumer acceptance standards.
  • the titanium alloy products may be utilized in a variety of products including non-consumer products including the likes of medical devices, transportation systems and security systems, to name a few.
  • the titanium alloy products may be incorporated in goods including the likes of car panels, media players, bottles and cans, office supplies, packages and containers, among others.
  • feedstocks comprising titanium particles (e.g., titanium-based powders)
  • those described embodiments are given only as examples.
  • Other tvoes of feedstocks may be used, and in addition to or in lieu of titanium particles.
  • suitable titanium feedstocks include chips and wires, among others.
  • electrolytic-based methods may be applicable for reducing the thicknesses of surface oxide layers (e.g., reducing the oxygen content) of other metal-based particles (e.g., metal-based powders other than titanium-based powders).
  • electrolytic-based recycling methods may be applicable to metal-based particles other than the described titanium particles for purposes of recycling them for re-use in AM processes and other environments where accumulated oxygen in surface oxide layers may be undesirable for similar reasons as described above.
  • Such other feedstocks for the herein-described electrolytic-based methods may include metal-based particles, as well as semi-metal-based particles, based in one or more (including, e.g., alloys) of the following elements: Al, Ni, Co, Cu, Mg, U, Nd, Sm, Ge, Si, refractory metals, including, without limitation, Ta, W, Nb, Mo, HE, Zr, Cr, and other rare earths.

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  • Electrolytic Production Of Metals (AREA)

Abstract

L'invention concerne un procédé de recyclage de particules de titane, notamment des poudres d'alliage de titane utilisées dans des procédés de fabrication additive. Le procédé comprend la réception d'une charge d'alimentation comprenant des particules de titane. Les particules de titane ainsi reçues comprennent de l'oxygène et ont une couche d'oxyde de surface sur elles. Le procédé comprend également l'exposition de la charge d'alimentation à des conditions de réduction dans une cellule électrolytique. L'exposition comprend la réduction de la couche d'oxyde de surface des particules de titane. L'exposition comprend également la réduction de l'oxygène des particules de titane ainsi reçues d'au moins 10 %. Le procédé comprend en outre la récupération d'une charge d'alimentation purifiée de la cellule électrolytique. Les particules de titane ainsi récupérées comprennent au moins 10 % d'oxygène de moins que les particules de titane reçues.
PCT/US2018/057159 2017-10-23 2018-10-23 Procédés basés sur l'électrolyse pour le recyclage de particules de titane Ceased WO2019084045A1 (fr)

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US201762576015P 2017-10-23 2017-10-23
US62/576,015 2017-10-23

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Publication number Priority date Publication date Assignee Title
US11608551B2 (en) 2017-10-31 2023-03-21 Howmet Aerospace Inc. Aluminum alloys, and methods for producing the same
US12123078B2 (en) 2019-02-20 2024-10-22 Howmet Aerospace Inc. Aluminum-magnesium-zinc aluminum alloys
US12194529B2 (en) 2018-11-07 2025-01-14 Arconic Technologies Llc 2XXX aluminum lithium alloys

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US20050121333A1 (en) * 2001-04-10 2005-06-09 Lazar Strezov Electrolytic reduction of metal oxides
JP2008143762A (ja) * 2006-12-13 2008-06-26 Toshibumi Kageyama 触媒の廃棄物から酸化チタンを回収する方法
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Publication number Priority date Publication date Assignee Title
US20050121333A1 (en) * 2001-04-10 2005-06-09 Lazar Strezov Electrolytic reduction of metal oxides
JP2008143762A (ja) * 2006-12-13 2008-06-26 Toshibumi Kageyama 触媒の廃棄物から酸化チタンを回収する方法
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11608551B2 (en) 2017-10-31 2023-03-21 Howmet Aerospace Inc. Aluminum alloys, and methods for producing the same
US12194529B2 (en) 2018-11-07 2025-01-14 Arconic Technologies Llc 2XXX aluminum lithium alloys
US12123078B2 (en) 2019-02-20 2024-10-22 Howmet Aerospace Inc. Aluminum-magnesium-zinc aluminum alloys

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