WO2023220220A1 - Poudre d'alliage lourd de tungstène à faible empreinte carbone pour fabrication additive sur lit de poudre - Google Patents

Poudre d'alliage lourd de tungstène à faible empreinte carbone pour fabrication additive sur lit de poudre Download PDF

Info

Publication number
WO2023220220A1
WO2023220220A1 PCT/US2023/021794 US2023021794W WO2023220220A1 WO 2023220220 A1 WO2023220220 A1 WO 2023220220A1 US 2023021794 W US2023021794 W US 2023021794W WO 2023220220 A1 WO2023220220 A1 WO 2023220220A1
Authority
WO
WIPO (PCT)
Prior art keywords
heavy alloy
powder
tungsten heavy
alloy powder
composite tungsten
Prior art date
Application number
PCT/US2023/021794
Other languages
English (en)
Inventor
Salvator Nigarura
Leo JANKA
Teemu KARHUMAA
Juan R.L. Trasorras
Original Assignee
Global Tungsten & Powders Llc
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 Global Tungsten & Powders Llc filed Critical Global Tungsten & Powders Llc
Publication of WO2023220220A1 publication Critical patent/WO2023220220A1/fr

Links

Classifications

    • 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
    • C22C1/045—Alloys based on 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with metal
    • 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
    • B22F10/10—Formation of a green body
    • B22F10/14—Formation of a green body by jetting of binder onto a bed of metal powder
    • 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
    • B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • 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
    • 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
    • B22F2009/001—Making metallic powder or suspensions thereof from scrap particles
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing

Definitions

  • tungsten heavy alloys Due to their high density (17-18.5g/cm 3 ), high mechanical properties, and good machinability, tungsten heavy alloys (WHA) have many applications ranging from radiation shields to kinetic energy penetrators. These alloys are produced from powder blends containing W elemental powder (in the range 90-98 wt%) and additions of two or more of the elements consisting of Ni, Fe, Co, Cu. Typically a W powder with a size of approximately 4-5 pm is used.
  • W powder is produced industrially by reduction of WOs under a H2 atmosphere.
  • the morphology of the W powder that results is highly irregular.
  • Ni, Fe, Co and Cu powders are produced by melt atomization or other chemical processes. Since the W particles are small and of highly irregular shape, the WHA powder blends have very poor flow characteristics (“non-flowable powders”).
  • AM additive manufacturing
  • Additive manufacturing refers to several technologies that produce parts in an additive way.
  • the starting point is a digital 3D model of a part which is then sliced in thin layers by computer software.
  • An additive manufacturing machine builds the part from this series of layers - each one applied directly on top of the previous one.
  • the ones that are best suited for the production of WHA components are the ones based on powder bed systems.
  • a uniform layer of powder typically 20-50 microns thick, is deposited on the building platform and consolidated.
  • the powder platform descends by the layer thickness and a subsequent layer of powder is delivered and consolidated. The process is repeated until the complete part is formed.
  • each layer of powder is sintered/melted by a focused laser or electron beam, immediately after each powder layer is deposited (FIG. 2).
  • a printing head scans the surface of the powder depositing a binder on the area defined by a layer of the model (FIG. 3).
  • the part produced is in the green state (powder particles embedded in a binder matrix) and surrounded by lose powder. The lose powder is removed (de-powdering) to expose the part.
  • BJ3DP is applied to metals, the green part is subsequently consolidated by removing the binder thermally or chemically, and by sintering under a proper atmosphere.
  • Powder bed systems require powders with excellent flowability in order to deposit power layers with uniform density that, in turn, result in consistent shrinkage during the densification step.
  • Typical powder size requirements are shown in Table 1.
  • the predominantly non-spherical composite tungsten heavy alloy powders can comprise tungsten particles bonded to or partially coated with a matrix binder comprising at least two elements selected from nickel, iron, cobalt, copper, and molybdenum.
  • the composite tungsten heavy alloy powder comprises 90% by weight or more of tungsten and 10% by weight or less of the matrix binder.
  • the composite tungsten heavy alloy powder has the following characteristics: a median particle size (D50) ranging from 10-100 pm; and a D ⁇ >o of less than 100 pm.
  • the composite tungsten heavy alloy powder is produced from a tungsten heavy alloy scrap feedstock having an average sintered tungsten grain size of 35 pm or less.
  • the composite tungsten heavy alloy powders can be used in a variety of applications, including a powder bed-based additive manufacturing (AM) process using the composite tungsten heavy alloy powder.
  • AM additive manufacturing
  • the method of making a tungsten heavy alloy body can generally comprise providing a composite tungsten heavy alloy powder comprising tungsten particles bonded or partially coated with a matrix binder comprising at least two elements selected from nickel, iron, cobalt, copper, and molybdenum; wherein the composite tungsten heavy alloy powder comprises 90% by weight or more of tungsten and 10% by weight or less of the matrix binder; and wherein the composite tungsten heavy alloy powder has the following characteristics: a median particle size (D50) ranging from 10-100 pm; and a D90 of less than 100 pm.
  • a green body can be 3D printed from the provided composite tungsten heavy alloy powder, and the green body can be sintered to form the composite tungsten heavy alloy body.
  • FIG. 1 is an image showing the microstructure of sintered WHA.
  • the sintered microstructure consists of relatively round body centered cubic (BCC) tungsten grains dispersed in a solidified face centered cubic (FCC) matrix phase.
  • BCC body centered cubic
  • FCC solidified face centered cubic
  • FIG. 2 is a schematic of a typical SLM machine.
  • FIG. 3 is a schematic of a Binder Jetting 3D Printing (BJ3DP) machine.
  • FIG. 4A is an SEM micrograph showing spherical plasma densified WHA powder.
  • FIG. 4B is an SEM micrograph showing spherical plasma densified WHA powder.
  • FIG. 5A is an SEM micrograph showing the new, non-spherical, irregularly shaped Zn reclaimed WHA powder (NP).
  • FIG. 5B is an SEM micrograph showing the new, non-spherical, irregularly shaped Zn reclaimed WHA powder (NP).
  • FIG. 6A is an SEM micrograph showing the standard, non-spherical, irregularly shaped Zn reclaimed WHA powder.
  • FIG. 6B is an SEM micrograph showing the standard, non-spherical, irregularly shaped Zn reclaimed WHA powder.
  • FIG. 7 is an optical micrograph that shows the reaction of WHA with Zn.
  • the heavy metal part is exposed to liquid Zn at 600°C for 3 h.
  • Ni-Fe-containing y-phase is formed [1] in contact with metallic binder [2], It grows into the binder area and shifts the W grains grain by grain towards the melt [3], Further access becomes possible.
  • the reaction is governed by diffusion of Zn into the Fe-Ni-W binder.
  • FIG. 8 is a high level flow chart of the Zn reclaim process to produce WHA powder.
  • FIG. 9A is an SEM micrograph showing the morphology of the standard WHA powder.
  • FIG. 9B is an SEM micrograph showing the morphology of the standard WHA powder.
  • FIG. 10 is a plot showing the proportion of the total volume of the particles in each sphericity range for the Plasma Densified Powder (PD) and for the New Powder (NP).
  • FIG. 11 is a plot showing the proportion of the total volume of the particles in each aspect ratio range for the Plasma Densified Powder (PD) and for the New Powder (NP).
  • FIG. 12A is an SEM micrograph showing backscattered electron (BEI) image in the spherical plasma densified WHA powder.
  • BEI backscattered electron
  • FIG. 12B is an SEM micrograph showing the Fe distribution in the spherical plasma densified WHA powder.
  • FIG. 12C is an SEM micrograph showing the Ni distribution in the spherical plasma densified WHA powder.
  • FIG. 12D is an SEM micrograph showing the W distribution in the spherical plasma densified WHA powder.
  • FIG. 13A is an SEM micrograph showing BEI image in the new WHA powder.
  • FIG. 13B is an SEM micrograph showing the Fe distribution in the new WHA powder.
  • FIG. 13C is an SEM micrograph showing the Ni distribution in the new WHA powder.
  • FIG. 13D is an SEM micrograph showing the W distribution in the new WHA powder.
  • FIG. 14A is a photograph showing a few of the sintered and printed rods.
  • FIG. 14B is a schematic showing the dimensions of the tensile sample.
  • FIG. 15 is a plot showing the variation in green strength of printed samples at different saturation levels for the Plasma Densified Powder (PD) and for the New Powder (NP).
  • FIG. 16A is an image showing the pore-free microstructure of sintered BJ3DP samples for the new Zn reclaimed Powder.
  • FIG. 16B is an image showing the pore-free microstructure of sintered BJ3DP samples for the new Zn reclaimed powder.
  • FIG. 16C is an image showing the pore-free microstructure of sintered BJ3DP samples for the Plasma Densified Powder.
  • FIG. 16D is an image showing the pore-free microstructure of sintered BJ3DP samples for the Plasma Densified Powder.
  • FIG. 16E is an image showing the low density, pore containing microstructure of sintered BJ3DP samples for the standard Zn reclaimed powder.
  • FIG. 16F is an image showing the low density, pore containing microstructure of sintered BJ3DP samples for the standard Zn reclaimed powder.
  • FIG. 17A is a photograph showing a WHA casting mold insert (chills) produced by BJ3DP (dimensions 1.5 x 4 in)
  • FIG. 17B is a photograph showing a WHA casting mold insert (chills) produced by BJ3DP (dimensions 1.5 x 4 in)
  • FIG. 18A is a photograph showing examples of BJ3DP WHA parts with helical gear with integral dog clutch.
  • FIG. 18B is a photograph showing examples of BJ3DP WHA parts with spiral bevel gear.
  • FIG. 19 is a high level flow chart of the AM WHA powder manufacturing processes.
  • FIG. 20 is a flow chart showing the dissolution, purification and conversion of W ore concentrate to pure ammonium paratungstate (APT).
  • the liquid ion exchange (LIX) process is common in Western countries, the solid ion exchange process (SIX) is widely used in China.
  • FIG. 21 is a plot showing Calculated CO2 emissions for the WHA powder manufacturing processes. (Calculations per ISO 14064, Scope 1, Scope 2, Scope 3.)
  • D50 refers to the particle diameter of the powder where 50 weight % of the particles in the total distribution of the reference sample have the noted particle diameter or smaller.
  • D90 refers to the particle diameter where 90 weight % of the particles in the total distribution of the reference sample have the noted particle diameter or smaller.
  • Particle sizes can be measured by any suitable method including laser diffraction. In this case, powder size distribution was measured using a Malvern, Mastersizer 2000 per the ASTM B822 standard.
  • an “an average sintered tungsten grain size” refers to the average size of tungsten grains in a sintered microstructure, as measured according to TEM image analysis software known in the art or as determined using the mean linear intercept grain size of the tungsten grains to express the mean tungsten grain size.
  • the mean linear intercept is the intercept length averaged over all directions.
  • binder and “particles” are meant to include particulate having a variety of shapes and sizes, including generally spherical or irregular shapes, flakes, needle-like particles, chips, fibers, equiaxed particles, etc.
  • the composite tungsten heavy alloy powders are generally used for additive manufacturing of parts, among other applications, due to characteristics of the composite powders (homogeneity and uniform bonding of W particles with alloying elements) that are required in such applications.
  • the predominantly non-spherical composite tungsten heavy alloy powder comprises tungsten particles bonded or partially coated with a matrix binder comprising at least two elements selected from nickel, iron, cobalt, copper, and molybdenum.
  • the composite tungsten heavy alloy powder comprises 90% by weight or more of tungsten and 10% by weight or less of the matrix binder.
  • the composite tungsten heavy alloy powder has the following characteristics: (a) a median particle size (D50) ranging from 10-100 pm; (b) a D90 of less than 100 pm.
  • the composite tungsten heavy alloy powder has a high apparent density that is suitable for a variety of additive manufacturing techniques, by enabling a highly packed powder bed which is critical for improved sintering densification.
  • the powder in some aspects also has suitable dispersability and flow characteristics that aid in such manufacturing techniques.
  • the composite tungsten heavy allow powder has an apparent density of at least 6 g/cm 3 .
  • the tungsten heavy alloy powder has an apparent density of at least 7 g/cm 3 .
  • the tungsten heavy alloy powder has an apparent density ranging from 7-10 g/cm 3 .
  • the particle size of the composite tungsten heavy alloy powder can also provide for improved ability to use the powder in additive manufacturing techniques.
  • the composite tungsten heavy alloy powder has a D50 ranging from 15-30 pm.
  • the composite tungsten heavy alloy powder has a D90 of less than 50 pm.
  • the composite tungsten heavy alloy powder has an average particle size of 35 pm or less.
  • the composite tungsten heavy alloy powder has an average particle size of 25 pm or less.
  • the disclosed composite tungsten heavy alloy powders also exhibit good flowability.
  • the composite tungsten heavy alloy powder exhibits a flowability ranging from 8 seconds per 50 grams to 15 seconds per 50 grams, as measured by a Hall flowmeter.
  • the composite tungsten heavy' alloy powder exhibits a flowability of about 10 seconds per 50 grams, as measured by a Hall flowmeter.
  • the disclosed particle shape of the composite tungsten heavy alloy powder is also desirable for a variety of applications.
  • the predominantly irregular shape can make the as printed part strong and easy to handle by increasing the interlocking of the particles within the powder.
  • less than 20% by volume of the powder has a sphericity in the range of 0.95-1.
  • less than 17% by volume of the powder has a sphericity in the range of 0.95-1.
  • less than 25% by volume of the powder has an aspect ratio of 0.85 or greater.
  • less than 15% by volume of the powder has an aspect ratio of 0.9 or greater.
  • less than 5% by volume of the powder has an aspect ratio of 0.95 or greater.
  • the composite powder comprises tungsten particles bonded or partially coated with a matrix binder comprising at least two elements selected from nickel, iron, cobalt, copper, and molybdenum.
  • the bonding and coating morphology of the powder can be readily determined my microscopy techniques, such as SEM.
  • the composite tungsten heavy alloy powder comprises tungsten; and two or more of nickel, iron, cobalt, and copper in the matrix binder.
  • the composite tungsten heavy alloy powder comprises tungsten; and nickel and iron in the matrix binder.
  • the weight percentages of tungsten and other metals in the matrix binder can vary.
  • the composite tungsten heavy alloy powder comprises tungsten in an amount ranging from 90-97% by weight of composite tungsten heavy alloy powder.
  • the composite tungsten heavy alloy powder comprises nickel in the matrix binder in an amount ranging from 4-7% by weight of composite tungsten heavy alloy powder.
  • the composite tungsten heavy alloy powder comprises iron in the matrix binder in an amount ranging from 1-3% by weight of composite tungsten heavy alloy powder.
  • the composite tungsten heavy alloy powder comprises tungsten in an amount ranging from 90-97% by weight of composite tungsten heavy alloy powder, nickel in the matrix binder in an amount ranging from 4-7% by weight of composite tungsten heavy alloy powder, and iron in the matrix binder in an amount ranging from 1-3% by weight of composite tungsten heavy alloy powder.
  • the composite tungsten heavy allow powders can be made using a zinc reclaim process with tungsten heavy allow solid scrap as a feedstock.
  • the process is shown in the flow chart of FIG. 8.
  • cleaned and sorted tungsten heavy alloy scrap can be contacted with molten Zn at 600- l()5() C under an inert atmosphere (e.g., N2 atmosphere) for a suitable time, typically several hours.
  • the tungsten heavy alloy scrap has an average particle size of 35 microns or less, e.g., 25 microns or less.
  • the second step involves the distillation ofZn under vacuum (0.06-0.13 mbar) at 1000-1050°C for a suitable time, typically several hours.
  • the cooled down material can then be crushed, ball milled, and screened.
  • the top screen material that did not react fully with Zn
  • the crushing and milling involve fracture, primarily of the binder matrix phase and not the tungsten phase.
  • the disclosure also relates to a powder bed-based additive manufacturing (AM) process using any of the described composite tungsten heavy alloy powders.
  • AM additive manufacturing
  • the method comprises providing a composite tungsten heavy alloy powder comprising tungsten particles bonded to or partially coated with a matrix binder comprising at least two elements selected from nickel, iron, cobalt, copper, and molybdenum (including any of the specific composite tungsten heavy' alloy powders described above).
  • the composite tungsten heavy alloy powder comprises 90% by weight or more of tungsten and 10% by weight or less of the matrix binder.
  • the composite tungsten heavy alloy powder has the following characteristics: (a) a median particle size (D50) ranging from 10-100 pm; and (b) a Ds>o of less than 100 pm.
  • the method further comprises 3D printing a green body from the composite tungsten heavy' alloy powder and a printing binder, followed by sintering the green body to form the composite tungsten heavy alloy body.
  • the method further comprises sinter-HIPing the green body or the tungsten heavy alloy body.
  • the step of 3D printing the tungsten heavy alloy body from the powder consolidating the powder using energy from a laser or an electron beam to thereby form the tungsten heavy alloy body.
  • the method further comprises the step of sinter-HIPing the tungsten heavy body after the 3D printing step.
  • the 3D printing step comprises selective laser melting (SLM), electron beam melting (EBM), or direct energy deposition (DED).
  • SLM selective laser melting
  • EBM electron beam melting
  • DED direct energy deposition
  • the tungsten heavy alloy body is a balancing weight for a rotorcraft application, a balancing weight for an internal combustion engine crankshaft, a radiation shielding component, a chill for a die-casting mold, or a penetrator or an array thereof for a kinetic energy device.
  • a predominantly non-spherical composite tungsten heavy alloy powder comprising tungsten particles bonded or partially coated with a matrix binder comprising at least two elements selected from nickel, iron, cobalt, copper, and molybdenum; wherein the composite tungsten heavy alloy powder comprises 90% by weight or more of tungsten and 10% by weight or less of the matrix binder; wherein the composite tungsten heavy alloy powder has the following characteristics: a median particle size (D50) ranging from 10-100 pm; a D90 of less than 100 pm; and wherein the composite tungsten heavy alloy powder is produced from a tungsten heavy alloy scrap feedstock having an average sintered tungsten grain size of 35 pm or less.
  • D50 median particle size
  • any preceding composite, wherein the zinc reclaim process comprises contacting the tungsten heavy alloy scrap feedstock with molten zinc followed by vacuum distilling at least a portion of the zinc.
  • Any preceding composite having an apparent density of at least 6 g/cm 3 .
  • Any preceding composite having an apparent density of at least 7 g/cm 3 .
  • Any preceding composite which exhibits a flowability ranging from 8 seconds per 50 grams to 15 seconds per 50 grams, as measured by a Hall flowmeter.
  • any preceding composite wherein less than 20% by volume of the powder has a sphericity in the range of 0.95-1.
  • any preceding composite, wherein less than 25% by volume of the powder has an aspect ratio of 0.85 or greater.
  • any preceding composite, wherein less than 15% by volume of the powder has an aspect ratio of 0.9 or greater.
  • any preceding composite, wherein less than 5% by volume of the powder has an aspect ratio of 0.95 or greater.
  • any preceding composite comprising tungsten and two or more of nickel, iron, cobalt, and copper in the matrix binder.
  • any preceding composite comprising tungsten; and nickel and iron in the matrix binder.
  • Any preceding composite comprising tungsten in an amount ranging from 90-97% by weight of composite tungsten heavy alloy powder.
  • any preceding composite comprising iron in the matrix binder in an amount ranging from 1-3% by weight of composite tungsten heavy alloy powder.
  • any preceding composite comprising tungsten in an amount ranging from 90-97% by weight of composite tungsten heavy alloy powder, nickel in the matrix binder in an amount ranging from 4-7% by weight of composite tungsten heavy alloy powder, and iron in the matrix binder in an amount ranging from 1-3% by weight of composite tungsten heavy alloy powder.
  • a method of making a tungsten heavy alloy body comprising: a) providing a composite tungsten heavy alloy powder comprising tungsten particles bonded or partially coated with a matrix binder comprising at least two elements selected from nickel, iron, cobalt, copper, and molybdenum; wherein the composite tungsten heavy alloy powder comprises 90% by weight or more of tungsten and 10% by weight or less of the matrix binder; and wherein the composite tungsten heavy alloy powder has the following characteristics: i) a median particle size (D50) ranging from 10-100 pm; and ii) a D90 of less than 100 pm; b) 3D printing a green body from the composite tungsten heavy alloy powder and a printing binder; and c) sintering the green body to form the composite tungsten heavy alloy body.
  • a median particle size D50
  • the composite tungsten heavy alloy powder is produced from a tungsten heavy alloy scrap feedstock having an average sintered tungsten grain size of 35 pm or less.
  • any preceding method wherein the composite tungsten heavy alloy powder is produced from a tungsten heavy alloy scrap feedstock having an average sintered tungsten gram size of 25 pm or less.
  • Any preceding method further comprising sinter-HIPing the green body or the tungsten heavy alloy body.
  • a method of making a tungsten heavy alloy body comprising 3D printing the tungsten heavy alloy body from the powder of any preceding embodiment by consolidating the powder using energy from a laser or an electron beam to thereby form the tungsten heavy alloy body.
  • any one of the preceding two methods, wherein the 3D pnnting step comprises selective laser melting (SLM), electron beam melting (EBM), or direct energy deposition (DED).
  • SLM selective laser melting
  • EBM electron beam melting
  • DED direct energy deposition
  • tungsten heavy alloy body is a balancing weight for a rotorcraft application, a balancing weight for an internal combustion engine crankshaft, a radiation shielding component, a chill for a die-casting mold, or a penetrator or an array thereof for a kinetic energy device.
  • a WHA scrap is treated by molten Zn to produce a WHA powder with only a very gentle post zincing grinding step.
  • An intensive grinding would deform, break or otherwise change the morphology and the physical characteristics of recycled WHA powder.
  • the feed WHA scrap is preferably produced using standard manufacturing processes for WHA components.
  • the as produced component microstructure preferably has an average W grain size of 35 microns or smaller and in some embodiments, 25 microns or smaller. It will be understandable that such a small W grain in the component sintered microstructure can be achieved by a controlled sintering cycle where temperature and time at temperature are optimized.
  • a WHA scrap meeting the above characteristics for W grain size is treated in molten Zn, which reacts with the low temperature melting binder matrix and separates it from W particles.
  • the optical micrograph in FIG 7 shows the reaction mechanisms and the separation of the different phases of WHA metal exposed to liquid Zn at 600°C for 3h.
  • the reaction is governed by diffusion of Zn into the Fe, Ni and/or Co-rich binder.
  • the separation of the different phases is governed by the reaction of liquid Zn with the (Ni, Fe, Co) rich binder matrix and the formation of Zn-rich intermetallic phases (yl, 5, y).
  • the formation of these intermetallic phases at the reaction front is followed by crack formation along the reaction interface and by further penetration of the Zn-melt in the reacting body. These reactions lead to a volume expansion of the matrix alloy and bloat the scrap.
  • After vacuum distillation of the Zn the material is friable and can be readily disintegrated.
  • the condensed Zn can be re-used.
  • the reclaimed WHA sponge contains ⁇ 50 ppm Zn.
  • FIG. 8 shows a high-level flow chart for the process.
  • the cleaned and sorted WHA scrap is contacted with molten Zn at 600-1050°C under aN2 atmosphere for several hours.
  • the second stage is the distillation of Zn under vacuum (0.06- 0.13 mbar) at 1000-1050°C, which can take several hours.
  • the cooled down material is crushed, ball milled and screened.
  • the top screen material that did not react fully with Zn
  • the crushing and milling involve fracture, primarily of the matrix phase and not the W phase. A detailed characterization of the WHA powder is provided in the following discussion.
  • the powder size distribution was measured using a Malvern, Mastersizer 2000 per the ASTM B822 standard.
  • the particle shape characterization was carried out using a Camsizer XT per ISO 13322-2 with direct comparison between the plasma densified powder and the new powder.
  • FIG 9A and FIG 9B The morphology of the standard WHA powder is shown in FIG 9A and FIG 9B.
  • the W particles (4-6 pm) are bonded together forming large agglomerates.
  • Such agglomerated powder results in compacts with non-uniform particle packing.
  • the external compaction force helps particle rearrangement and promotes homogeneous distribution inside the molding tool.
  • a pre-processing of the fine W particles and the alloying elements into spherical granules is the best method to improve powder flow and powder packing to achieve a uniform distribution within the green component.
  • Plasma densification is one known methods for creating homogeneous, spherical granules containing W and the alloying elements.
  • the particles of the plasma densified powder are shown in FIG 4A and FIG 4B.
  • the plasma densified powder has spherical particles with smooth surface.
  • the Zn reclaimed powder micrographs in FIG 5 and FIG 6 show a more irregular shape and rough surface.
  • the powder in FIG 5 has a smaller particle size than the powder in FIG 6.
  • the production of the powder in FIG. 5 uses a feed material with an average W grain size below 35 microns and in some embodiments 25 microns.
  • the plasma densified powder has more particles in the sphericity range > 0.95 and more particles with aspect ratio > 0.85.
  • Powder Flow
  • a homogeneous distribution of alloying elements in the powder mix is critical for controlling sintering dimensions as well as sintered microstructures and sintered properties.
  • BEI images in FIG. 12A-FIG. 12D and FIG. 13A-FIG. 13D compare the distribution of the alloying elements between plasma densified powder and the new Zn reclaimed powder. Both powders show a very homogeneous distribution of Ni, Fe and W in the powder. However, the Zn reclaimed powder shows a presence of uniformly distributed binder rich particles with less W content.
  • Cylindrical rods (figure 14) were used for the assessment of sintered properties for all the four powders (standard premix powder, Zn reclaimed powders and plasma densified powder). These rods were machined into tensile specimens after sintering. Rods from the standard powder mix were pressed isostatically at 241 MPa in a 25.4 mm diameter dry bag mold. After pressing, rods had approximately 16 mm diameter. Dry bag pressed rods from standard powder did not contain lubricant.
  • NP and SZR new Zn reclaimed powders
  • PD plasma densified powder
  • a water based solvent binder was used for printing the samples. These samples were printed at 40%/65%/75% binder saturation and a powder layer thickness of 60 pm was used for printing. 18.54 mm diameter x 117.35 mm long specimens were printed at binder set time of 7sec and speed of 100 mm/sec. BJ3DP samples were cured for 6 hours by heating to 180°C before normal de-binding and sintering processes.
  • Binder Jet printed rods (Zn reclaimed and plasma densified powders) were debound at 750°C under a protective atmosphere prior to sintering. After de-binding, all the materials were sintered in a box furnace under flowing hydrogen to a maximum temperature of 1540°C, with a hold of Ih at max temperature. At this temperature, the plasma densified powder did not sinter to full density. A second sintering at 1550°C did not achieve full density either. After two trials, the temperature was increased to 1560°C to achieve full density. After sintering, all the rods were measured for density per the ASTM E8 standard. As sintered samples were mounted and polished for optical microscopy.
  • the sintered microstructures are shown in FIG. 16A-FIG. 16F.
  • the WHAs produced via BJ3DP using the new Zn reclaimed powder and the plasma densified powder are free of porosity and have microstructures that are very similar to those of WHA produced by conventional powder metallurgy (PM).
  • the sintered microstructure of WHA component produced via BJ3DP using the standard Zn reclaimed powder shows porosity.
  • Binder jetting printed rods were sintered and tested for mechanical properties. Table 4 gives the density measured for each rod after sintering and the tensile properties from machined samples. Table 4. Sintered Density and Tensile properties of Binder Jet Printed Parts
  • the standard Zn reclaimed powder does not sinter to full density due to large W particle size (FIG6A-FIG 6B). It is known that WHA sintering densification especially in the solid state sintering stage is partially controlled by W gram size. With large grams, the contribution of the grain boundary diffusion is reduced. [00132] Based on the sintered density and sintered microstructure, one could predict that mechanical properties of the standard Zn reclaimed powder will be lower. As shown in the Table 4, parts made with this powder do not meet minimum properties per the SAE AMS 7725F specification for the Class 2 WHA.
  • the plasma densified powder required higher temperature sintering to achieve equivalent properties in part because of the slightly higher W content but mostly due to slower sintering.
  • FIG. 17A-FIG 17B and FIG. 18A-FIG 18B provide examples of WHA parts produced with the new Zn reclaimed WHA powder using the BJ3DP process. WHA parts of great complexity can be produced to net or near-net shape using this technology.
  • FIG. 19 provides a high-level flow chart of WHA powder manufacturing processes
  • FIG. 20 provides more details of the chemical purification and conversion to ammonium paratungstate (APT).
  • the chemical recycling process eliminates the need for the mining and ore beneficiations steps while adding an oxidation step. Overall, this results in an important reduction in CO2 emissions.
  • the Zn reclaim goes even further by eliminating the need for chemical purification and conversion to APT, and the downstream steps to produce W oxide and W powder (FIG. 19).
  • the Zn reclaim process adds the zincing step.
  • the greatly simplified Zn reclaim process also results in a reduction in the manufacturing cost of the WHA powder of approximately 50-66%, as compared to plasma densified WHA powder.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne des poudres d'alliage lourd de tungstène composite appropriées pour être utilisées dans diverses applications, notamment des procédés de fabrication additive sur lit de poudre.
PCT/US2023/021794 2022-05-13 2023-05-11 Poudre d'alliage lourd de tungstène à faible empreinte carbone pour fabrication additive sur lit de poudre WO2023220220A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263341476P 2022-05-13 2022-05-13
US63/341,476 2022-05-13

Publications (1)

Publication Number Publication Date
WO2023220220A1 true WO2023220220A1 (fr) 2023-11-16

Family

ID=88730952

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2023/021794 WO2023220220A1 (fr) 2022-05-13 2023-05-11 Poudre d'alliage lourd de tungstène à faible empreinte carbone pour fabrication additive sur lit de poudre

Country Status (1)

Country Link
WO (1) WO2023220220A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021081143A1 (fr) * 2019-10-22 2021-04-29 Milwaukee Electric Tool Corporation Outil plaqué et procédé de fabrication d'un outil plaqué

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021081143A1 (fr) * 2019-10-22 2021-04-29 Milwaukee Electric Tool Corporation Outil plaqué et procédé de fabrication d'un outil plaqué

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KOERBLER ET AL.: "Layer Growth in Co(W)-Zn Systems at Hard Metal Recycling", JOM, vol. 72, no. 2, 4 December 2019 (2019-12-04), pages 847 - 853, XP036995743, DOI: 10.1007/s11837-019-03929-3 *
LI JUNFENG, WEI ZHENGYING, ZHOU BOKANG, WU YUNXIAO, CHEN SHENG-GUI, SUN ZHENZHONG: "Densification, Microstructure and Properties of 90W-7Ni-3Fe Fabricated by Selective Laser Melting", METALS, M D P I AG, CH, vol. 9, no. 8, CH , pages 884, XP093112775, ISSN: 2075-4701, DOI: 10.3390/met9080884 *
SKOCZYLAS PAWEŁ, GOROCH OLGIERD, GULBINOWICZ ZBIGNIEW, PENKUL ANDRZEJ: "The Effect of Cold Swaging of Tungsten Heavy Alloy with the Composition W91-6Ni-3Co on the Mechanical Properties", MATERIALS, M D P I AG, CH, vol. 14, no. 23, CH , pages 7300, XP093112774, ISSN: 1996-1944, DOI: 10.3390/ma14237300 *

Similar Documents

Publication Publication Date Title
Upadhyaya Powder metallurgy technology
Dilip et al. A novel method to fabricate TiAl intermetallic alloy 3D parts using additive manufacturing
Bose Advances in particulate materials
EP2393949A2 (fr) Procede de conversion pour des alliages d aluminium l12 pouvant subir un traitement thermique
CA2488990A1 (fr) Procede de preparation d'articles en alliage metallique sans fusion
Moon et al. Full densification of loosely packed W–Cu composite powders
WO2017063923A1 (fr) Poudres à base de fer pour moulage par injection de poudre
Rominiyi et al. Synthesis, microstructural and phase evolution in Ti–2Ni and Ti–10Ni binary alloys consolidated by spark plasma sintering technique
CN108277412A (zh) 一种纳米钨合金材料及其制备方法
US7297310B1 (en) Manufacturing method for aluminum matrix nanocomposite
Li et al. Effects of processing parameters on rapid manufacturing 90W–7Ni–3Fe parts via selective laser melting
KR20220099107A (ko) 3차원 물체를 제조하기 위한 구형 분말
WO2023220220A1 (fr) Poudre d'alliage lourd de tungstène à faible empreinte carbone pour fabrication additive sur lit de poudre
CN112626404A (zh) 一种3D打印高性能WMoTaTi高熵合金及其低成本粉末制备方法
EP3730231B1 (fr) Matériau en poudre, utilisation d'un matériau en poudre pour la fabrication additive et procédé destiné à la production d'un matériau en poudre
Takekawa et al. Effect of the processing conditions on density, strength and microstructure of Ti-12Mo alloy fabricated by PIM process
WO2019123537A1 (fr) Poudre d'alliage de magnésium et élément fritté faisant appel à celle-ci
Dias et al. Analysis of the densification of a composite obtained by sintering process of aluminum bronze powders with different carbides
KR20180021536A (ko) 소결용 조성물
JP2001294905A (ja) 微小モジュール歯車の製造方法
CN112792333A (zh) 环氧树脂包覆不锈钢粉末的制备方法及其应用
KR100509938B1 (ko) 금속사출성형법을 이용한 티타늄 알루미나이드금속간화합물 물품의 제조 방법
US20240261854A1 (en) Methods of making gold-titanium alloys from sintered powders
RU2447177C1 (ru) Способ получения модификатора для никелевых сплавов
CN114653958B (zh) 超细碳化物增强的高速工具钢粉末原料及烧结方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23804233

Country of ref document: EP

Kind code of ref document: A1