US20160263653A1 - Amorphous alloy containing feedstock for powder injection molding - Google Patents

Amorphous alloy containing feedstock for powder injection molding Download PDF

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US20160263653A1
US20160263653A1 US15/032,049 US201415032049A US2016263653A1 US 20160263653 A1 US20160263653 A1 US 20160263653A1 US 201415032049 A US201415032049 A US 201415032049A US 2016263653 A1 US2016263653 A1 US 2016263653A1
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component
feedstock
particulates
article
composition
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Choongnyun Paul Kim
John Kang
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GOLDEN INTELLECTUAL PROPERTY LLC
Liquidmetal Coatings LLC
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Liquidmetal Coatings LLC
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Assigned to GOLDEN INTELLECTUAL PROPERTY, LLC reassignment GOLDEN INTELLECTUAL PROPERTY, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KANG, JOHN, KIM, CHOONGNYUN PAUL
Assigned to LIQUIDMETAL COATINGS, LLC reassignment LIQUIDMETAL COATINGS, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GOLDEN INTELLECTUAL PROPERTY, LLC
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    • B22F1/0059
    • B22F1/0014
    • B22F1/0048
    • B22F1/0085
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • B22F1/052Metallic 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06Metallic powder characterised by the shape of the particles
    • B22F1/065Spherical particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/08Metallic powder characterised by particles having an amorphous microstructure
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14Treatment of metallic powder
    • B22F1/142Thermal or thermo-mechanical treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/004Filling molds with powder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10Sintering only
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/0433Nickel- or cobalt-based alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/11Making amorphous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/003Making ferrous alloys making amorphous alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C33/00Making ferrous alloys
    • C22C33/02Making ferrous alloys by powder metallurgy
    • C22C33/0257Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/008Amorphous alloys with Fe, Co or Ni as the major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/02Amorphous alloys with iron as the major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/04Amorphous alloys with nickel or cobalt as the major constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/10Amorphous alloys with molybdenum, tungsten, niobium, tantalum, titanium, or zirconium or Hf as the major constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05Metallic powder characterised by the size or surface area of the particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/04Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/045Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by other means than ball or jet milling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00Physical aspects of the powder
    • B22F2304/10Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10Processes characterised by the sequence of their steps

Definitions

  • Powder injection molding of metallic components may offer many advantages that have led to widespread use in a variety of applications. Among the advantages provided by powder injection molding is the ability to produce metal parts with complex shapes with reduced waste. Despite the many advantages provided by conventional powder injection molding processes, these processes do not offer the density and hardness of the finished product desired for many applications.
  • the Inventors have recognized and appreciated the advantages of feedstock materials for powder injection molding that provide finished products with improved properties, such as hardness and density, and methods of making and/or using same.
  • composition comprising a binder, and particulates.
  • the particulates may comprise an amorphous alloy, and the composition may be a feedstock for an injection molding process.
  • One embodiment provides a method comprising injecting a feedstock into a mold to produce a workpiece.
  • the feedstock may comprise a binder and particulates, and the particulates may comprise an amorphous alloy.
  • Another embodiment provides an article produced by sintering a workpiece produced by the method above.
  • FIG. 1 depicts a microstructure of a material produced according to one embodiment.
  • FIG. 2 depicts a microstructure of a material produced according to one embodiment.
  • FIG. 3 depicts a flow chart detailing a process according to one embodiment.
  • FIG. 4 depicts an X-ray Diffraction (“XRD”) pattern for a feedstock material that consists of a fully amorphous powder according to one embodiment, and an XRD pattern for a material with a similar composition that contains both amorphous and crystalline constituents according to another embodiment.
  • XRD X-ray Diffraction
  • FIG. 5 depicts a Differential Scanning calorimetry (“DSC”) plot for an amorphous alloy containing feedstock material, according to one embodiment.
  • DSC Differential Scanning calorimetry
  • One embodiment is related to a composition comprising a binder and particulates, wherein the particulates comprise an amorphous alloy, and the composition is a feedstock for an injection molding process.
  • Another embodiment is related to a method comprising injecting a feedstock into a mold to produce a workpiece, wherein the feedstock comprises a binder and particulates comprising an amorphous alloy.
  • Another embodiment is related to an article produced by sintering a workpiece produced by the preceding method.
  • An alloy may refer to a mixture, including a solid solution, of two or more metal elements—e.g., at least 2, 3, 4, 5, or more elements.
  • element herein may refer to a chemical represented by a symbol that may be found in a
  • a metal may refer to any of alkali metals, alkaline earth metals, transition metals, post-transition metals, lanthanides, and actinides.
  • An amorphous alloy may refer to an alloy having an amorphous, non-crystalline atomic structure or microstructure.
  • the amorphous structure may refer to a glassy structure with no observable long range order; in some instances, an amorphous structure may exhibit some short range order.
  • an amorphous alloy may sometimes be referred to as a “metallic glass.”
  • An amorphous alloy may refer to an alloy of which at least about 50% is an amorphous phase—e.g., at least about 60%, about 70%, about 80%, about 90%, about 95%, about 99%, or more.
  • the percentage herein may refer to volume percent or weight percent, depending on the context.
  • phase herein may refer to a physically distinctive form of a substance, such as microstructure. For example, a solid and a liquid are different phases. Similarly, an amorphous phase is different from a crystalline phase.
  • Amorphous alloys may contain a variety of metal elements.
  • the amorphous alloys may comprise iron, chromium, silicon, boron, manganese, nickel, molybdenum, niobium, copper, cobalt, carbon, zirconium, titanium, beryllium, aluminum, gold, platinum, palladium, phosphorous, tungsten, yttrium, tantalum, or combinations thereof.
  • the amorphous alloys may be zirconium-based, titanium-based, iron-based, copper-based, nickel-based, gold-based, platinum-based, palladium-based, or aluminum-based.
  • M-based when referring to an alloy may refer to an alloy comprising at least about 30% of the “M” element—e.g., about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or more.
  • the percentage herein may refer to volume percent or weight percent, depending on the context.
  • An amorphous alloy may be a bulk solidifying amorphous alloy.
  • a bulk solidifying amorphous alloy, bulk metallic glass (“BMG”), or bulk amorphous alloy may refer to an amorphous alloy that may be adapted to have at least one dimension in the millimeter range. In one embodiment, this dimension may refer to the smallest dimension. Depending on the geometry, the dimension may refer to thickness, height, length, width, radius, and the like. In some embodiments, this smallest dimension may be at least about 0.5 mm—e.g., about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 8 mm, about 10 mm, about 12 mm, or more. The magnitude of the largest dimension is not limited and may be in the millimeter range, centimeter range, or even meter range.
  • An amorphous alloy, including a bulk amorphous alloy, described herein may have a critical cooling rate of about 500 K/sec or less.
  • the term “critical cooling rate” herein may refer to the cooling rate below which an amorphous structure is not energetically favorable and thus is not likely to form during a fabrication process.
  • the critical cooling rate of the amorphous alloy may be, for example, about 400 K/sec or less—e.g., about 300 K/sec or less, about 250 K/sec or less, about 200 K/sec or less.
  • the amorphous alloy may be a ferrous-metal based alloy, such as (Fe, Ni, Co) based compositions.
  • ferrous-metal based alloy such as (Fe, Ni, Co) based compositions. Examples of such compositions are disclosed in U.S. Pat. No. 6,325,868 and in publications (A. Inoue et. al., Appl. Phys. Lett., Volume 71, p 464 (1997)), (Shen et. al., Mater. Trans., JIM, Volume 42, p 2136 (2001)), and Japanese patent application 2000126277 (Publ. # 2001303218 A).
  • the alloy may be Fe 72 A 15 Ga 2 P 11 C 6 B 4 , or Fe 72 A 17 Zr 10 Mo 5 W 2 B 15 .
  • the amorphous alloy may be at least one of Fe—Cr—B—Mo—C alloy, Ni—Cr—Si—B—Mo—Cu—Co alloy, Fe—Cr—B—Mn—Si alloy, Fe—Cr—B—Si alloy, Fe—Cr—B—Mn—Si—Cu—Ni—Mo alloy, Fe—Cr—B—Mn—Si—Ni alloy, Fe—Cr—Si—B—Mn—Ni—WC—TiC alloy, Fe—Cr—Si—Mn—C—Nd—Ti alloy, Fe—Cr—P—C alloy, Fe—Cr—Mo—P—C alloy, Fe—Cr—Mo—P—C—Ni alloy, Fe—P—C—B—Al alloy, Fe—Cr—Mo—B—C—Si—Ni—P alloy, Fe—Cr—Mo—B—C—Si—W—Ni alloy , Ni—Cr—M
  • Amorphous alloys including bulk solidifying amorphous alloys, may have higher strength and higher hardness than their crystalline counterparts.
  • the strength may refer to tensile or compressive strength, depending on the context.
  • Zr and Ti-based amorphous alloys may have tensile yield strengths of about 250 ksi or higher, hardness values of about 450 HV or higher, or both.
  • the tensile yield strength may be about 300 ksi or higher—e.g., at least about 400 ksi, about 500 ksi, about 600 ksi, about 800 ksi, or higher.
  • the hardness value may be at least about 500 HV—e.g., at least about 550 HV, about 600 HV, about 700 HV, about 800 HV, about 900 HV, about 1000 HV, or higher.
  • ferrous metal based amorphous alloys can have tensile yield strengths of about 500 ksi or higher and hardness values of about 1000 HV or higher.
  • the tensile yield strength may be about 550 ksi or higher—e.g., at least about 600 ksi, about 700 ksi, about 800 ksi, about 900 ksi, or higher.
  • the hardness value may be at least about 1000 HV—e.g., at least about 1100 HV, about 1200 HV, about 1400 HV, about 1500 HV, about 1600 HV, or higher.
  • any of the aforedescribed amorphous alloys may have a desirable strength-to-weight ratio.
  • amorphous alloys, particularly the Zr- or Ti-based alloys may exhibit desirable corrosion resistance and environmental durability.
  • the corrosion herein may refer to chemical corrosion, stress corrosion, or a combination thereof.
  • the amorphous alloys, including bulk amorphous alloys, described herein may have a high elastic strain limit of at least about 0.5%, including at least about 1%, about 1.2%, about 1.5%, about 1.6%, about 1.8%, about 2%, or more—this value is much higher than any other metal alloy known to date.
  • the amorphous alloys may additionally include some crystalline materials, such as crystalline alloys.
  • the crystalline material may have the same or different chemistry from the amorphous alloy. For example, in the case wherein the crystalline alloy and the amorphous alloy have the same chemical composition, they may differ from each other only with respect to their microstructures.
  • crystalline precipitates in amorphous alloys may have an undesirable effect on the properties of amorphous alloys, especially on the toughness and strength of these alloys, and as such it is generally preferred to minimize the volume fraction of these precipitates.
  • ductile crystalline phases precipitate in-situ during the processing of amorphous alloys, which may be beneficial to the properties of amorphous alloys, especially to the toughness and ductility of the alloys.
  • One exemplary case is disclosed in C. C. Hays et. al, Physical Review Letters, Vol. 84, p 2901, 2000.
  • the crystalline precipitates may comprise a metal or an alloy, wherein the alloy may have a composition that is the same as the composition of the amorphous alloy or a composition that is different from the composition of the amorphous alloy.
  • the alloy may have a composition that is the same as the composition of the amorphous alloy or a composition that is different from the composition of the amorphous alloy.
  • Such amorphous alloys comprising these beneficial crystalline precipitates may be employed in at least one embodiment described herein.
  • Powder injection molding is a process for producing complex components utilizing a feedstock that incorporates a powder material and a binder in an injection molding process.
  • Metal injection molding is a type of powder injection molding in which the powder may be a metal or alloy.
  • An MIM process may typically include injecting a feedstock into a mold, removing the binder from the molded workpiece, and sintering the workpiece from which the binder has been removed.
  • the feedstock utilized in the MIM process may be formed as part of the process or purchased in ready to use form.
  • the feedstock may be produced by mixing particulates with a binder.
  • the mixing may be performed in a sigma blade mixer or a twin-screw or shear roll extruder at an elevated temperature for a predetermined period of time.
  • the elevated temperature may be of any temperature higher than the room temperature, depending on the application.
  • the mixing may be performed at a temperature of about 150° C.
  • the mixing may be performed at a temperature of about 100° C. to about 200° C.—e.g., about 110° C. to about 190° C., about 120° C.
  • the predetermined period of time may be of any length of time, depending on the application.
  • the mixing may be performed for a time period of about 0.25 to about 3.75 hours—e.g., about 0.5 to about 3.5, about 0.75 to about 3.25, about 1 to about 3, about 1.25 to about 2.75, about 1.5 to about 2.5, about 1.75 to about 2.25 hours.
  • the mixing may be performed at a temperature in the range of from about 130° C. to about 160° C. for a period of about 2 hours.
  • the feedstock may be directly supplied to the injector apparatus after mixing or formed into granules for storage and later use.
  • the feedstock may be formed into pellets or granules with a size in the millimeter size range.
  • pellets or granules of feedstock may be purchased for use in the injection molding process.
  • the injection of the feedstock into a mold may occur at an elevated temperature.
  • the elevated temperature may be of any temperature higher than the room temperature, depending on the application.
  • the feedstock is at a temperature of about 100° C. to about 150° C.
  • the temperature at which the feedstock is injected may be referred to as the “nozzle temperature.”
  • the melting temperature of the binder included in the feedstock may affect the nozzle temperature utilized during injection.
  • the mold may be heated to improve the filling of the mold cavity by the feedstock during injection.
  • the mold may be at a temperature of about 50° C. during the injection process.
  • the workpiece that is removed from the mold may be referred to as a “green workpiece.”
  • the green workpiece may contain both the particulates and the binder, and maintain the shape imparted by the mold.
  • the binder may be removed from the green workpiece in a debinding process.
  • the binder may be removed by a thermal, catalytic, solvent or supercritical debinding process.
  • the binder may be removed by a thermal treatment process in which the green workpiece is heated in an electric furnace under a high purity hydrogen atmosphere.
  • a thermal debinding process may be employed in which the green workpiece is heated up to a temperature of about 300° C. at a heating rate of about 2° C./minute and maintained for about one hour, increasing the temperature up to about 500° C. at a rate of about 3° C./minute and maintained for about one hour, and increasing the temperature up to about 750° C. at a rate of about 3° C./minute and maintaining for about one hour.
  • the temperature ranges utilized in a thermal debinding process may depend on the binder selected.
  • the workpiece after binder removal may be referred to as a “brown workpiece.”
  • the brown workpiece may be sintered to produce a metal part.
  • the sintering process may result in shrinkage of the brown workpiece as any remaining binder is removed and sintering necks are formed between the metal particulates.
  • the part produced may be substantially free of the binder. In one embodiment, the part may be entirely free of the binder.
  • the temperature and time for the sintering may be dependent on the properties of the metal particulates.
  • the sintered metal part may be subjected to post-sintering treatment, such as machining or polishing.
  • post-sintering treatment such as machining or polishing.
  • additional heat treatments may be employed to remove residual porosity.
  • the feedstock for use in an MIM process may include particulates that include an amorphous alloy.
  • the amorphous alloy may be any of the amorphous alloys described herein.
  • the amorphous alloy may be a bulk amorphous alloy. In another embodiment, the amorphous alloy may not be a bulk amorphous alloy.
  • the feedstock material may further comprise a crystalline material.
  • the crystalline material may be a crystalline alloy having the same or different chemical composition from the amorphous alloy.
  • the crystalline material comprises crystal (or “grain”) sizes in the nanometer range, micron range, millimeter range, centimeter range, or any combinations thereof.
  • the first material may comprise a nano-crystalline material.
  • the crystalline material may comprise an alloy of the same composition as the amorphous alloy in the coating material, an alloy different from the amorphous alloy in the coating material, a metal, a non-metal, or any combinations thereof.
  • the feedstock material may additionally include a partially amorphous material, a ceramic material, a refractory particulate material, a soft particulate material, a crystalline metal particulate material, a crystalline alloy particulate material, or combinations thereof.
  • the ceramic material may include a carbide or an oxide—e.g., silica, alumina, zirconia, or magnesia.
  • the refractory particulate material may include niobium, molybdenum, tantalum, tungsten, carbides, or borides. In one embodiment, the refractory particulate material may be tungsten carbide, chromium carbide, silicon carbide, or combinations thereof.
  • the refractory particulate material may be chromium boride, silicon boride, or combinations thereof.
  • the soft particulate material may be copper, copper alloy, iron, or any particulate material with a hardness of less than the hardness of the amorphous containing particulate.
  • the crystalline metal particulate material may comprise iron or copper.
  • the crystalline alloy particulate material may comprise Fe, Cu, Co, Ni,
  • the crystalline alloy particulate material may comprise a stainless steel or Inconel.
  • the crystalline alloy powder may comprise Stainless Steel 316L, 630, or 17-4.
  • the feedstock material may additionally include a powder traditionally utilized in MIM processes. The powder traditionally utilized in MIM processes may be selected from low alloy steels, soft magnetic alloys, controlled expansion alloys, and combinations thereof.
  • the particulates may have any suitable geometry, depending on the application.
  • the particulates may have a spherical or rounded geometry.
  • a spherical particle at least substantially resembles a sphere.
  • a rounded particle lacks sharp angular edges, such as in the case of circular platelets.
  • spherical particulates are produced by a gas atomization process.
  • Spherical particulates may produce a higher density product after sintering as a result of increased packing efficiency.
  • rounded particulates may be produced by a water atomization process.
  • the particulates may have any suitable size, depending on the application. Depending on the geometry, the term “size” herein may refer to the diameter, radius, length, width, height, etc. of the particulates. In one embodiment, the particulates may have a size in the range of about 1 to about 150 microns—e.g., about 5 to about 120 microns, about 10 to about 100 microns, about 15 to about 90 microns, about 20 to about 85 microns, about 25 to about 80 microns, about 30 to about 75 microns.
  • a size in the range of about 1 to about 150 microns—e.g., about 5 to about 120 microns, about 10 to about 100 microns, about 15 to about 90 microns, about 20 to about 85 microns, about 25 to about 80 microns, about 30 to about 75 microns.
  • the particulates may have a size of less than about 100 microns—e.g., less than about 95 microns, about 90 microns, about 85 microns, about 80 microns, about 75 microns, about 70 microns, or less. In one embodiment, the particulates may have a size of greater than about 1 micron—e.g., greater than about 5 microns, about 10 microns, about 15 microns, about 20 microns, about 25 microns, about 30 microns, or more. In another embodiment, the particulates may have a size in the range of about 5 to about 30 microns.
  • the binder may be any binder suitable for use in MIM processes.
  • the binder may be a thermoplastic material.
  • the binder may be a mixture of ethylene vinyl acetate and paraffin.
  • the binder may be a mixture of about 20 wt. % ethyl vinyl acetate and about 80 wt. % paraffin.
  • the binder may include a bonding agent, a surfactant, a plasticizer, a lubricant, or combinations thereof.
  • the particulates may be contained in the feedstock material in an amount of about 30 to about 90 vol.%—e.g., about 35 to about 85 vol. %, about 40 to about 80 vol. %, about 45 to about 75 vol. %, or about 50 to about 70 vol. %. In another embodiment, the particulates are contained in the feedstock material in a larger concentration by volume than that of the binder.
  • the amorphous containing particulates in the feedstock material may allow the sintering temperature and time to be reduced, in comparison to traditional MIM feedstocks.
  • the sintering temperature may be less than 1300° C.—e.g., less than about 1200° C., about 1100° C., about 1000° C., or less.
  • the sintering was carried out at a temperature of about 1100° C. to about 1165° C. for about 30 minutes.
  • two traditional MIM crystalline feedstock materials Stainless Steel 316L and 630, are generally sintered at a temperature of 1350° C. for about 2 hours.
  • the reduced temperature and time of the sintering that results from the amorphous containing particulates provide substantial energy, cost and time savings in comparison to traditional MIM feedstock materials.
  • the sintering temperature and time may affect the hardness and density of the final product.
  • the sintering may be conducted under vacuum or a controlled gas atmosphere.
  • the sintered product produced utilizing the amorphous containing feedstock described herein may include an amorphous alloy.
  • the sintered product may be substantially free of an amorphous alloy.
  • the sintered product may be substantially free of a crystalline alloy material.
  • the sintered product produced utilizing the amorphous containing feedstock described herein may have a Vickers hardness of about 500 HV to about 1500 HV—e.g., about 550 HV to about 1450 HV, about 600 HV to about 1400 HV, about 650 HV to about 1350 HV, about 700 HV to about 1300 HV, about 750 HV to about 1250 HV, about 800 HV to about 1200 HV, about 850 HV to about 1150 HV, about 900 HV to about 1100 HV, or about 950 HV to about 1050 HV.
  • a Vickers hardness of about 500 HV to about 1500 HV—e.g., about 550 HV to about 1450 HV, about 600 HV to about 1400 HV, about 650 HV to about 1350 HV, about 700 HV to about 1300 HV, about 750 HV to about 1250 HV, about 800 HV to about 1200 HV, about 850 HV to about 1150 HV,
  • the coating material exhibits a Vickers hardness of at least about 500 HV—e.g., at least about 500 HV, about 525 HV, about 550 HV, about 575 HV, about 600 HV, about 625 HV, about 650 HV, about 675 HV, about 700 HV, about 725 HV, about 750 HV, about 775 HV, about 800 HV, about 825 HV, about 850 HV, about 875 HV, about 900 HV, about 925 HV, about 950 HV, about 975 HV, about 1000 HV, about 1025 HV, about 1050 HV, about 1075
  • the coating material may have a Vickers hardness of about 900 HV to about 1200 HV.
  • an Fe-based amorphous particulate containing feedstock produced a part with hardness of about 900 to about 1200 HV, depending on the sintering process chosen.
  • two traditional MIM crystalline feedstock materials Stainless Steel 316L and 630 produce parts with hardnesses of 97 HV and about 360 HV, respectively.
  • the amorphous containing feedstock provided herein allows for the production of parts utilizing MIM processes with surprisingly high hardness.
  • the sintered products produced utilizing the amorphous containing feedstock did not require additional heat treatment steps to achieve increased hardness levels.
  • the sintered product produced utilizing the amorphous containing feedstock described herein may have a density greater than about 99%—e.g., greater than about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about 99.5%, about 99.6%, about 99.7%, about 99.8%, or about 99.9%.
  • the sintered product produced may have a density of about 99.99%.
  • parts produced utilizing traditional MIM crystalline feedstock material Stainless Steel 316L exhibited a density of only about 96% after sintering.
  • the amorphous containing feedstock provided herein allows for the production of parts utilizing MIM processes with surprisingly high density.
  • the sintered product produced utilizing the amorphous containing feedstock described herein may have a tensile stiffness that is controlled based on the selection of the product design, feedstock composition, and sintering treatment.
  • the sintered product produced utilizing the amorphous containing feedstock described herein may be resistant to wear and/or corrosion.
  • the corrosion may refer to chemical corrosion, stress corrosion, or both.
  • the wear resistance may be directly related to the hardness of the material, with wear resistance increasing as hardness increases. In at least one embodiment, the wear resistance is at least about twice as high—e.g., at least about three times as high, about four times as high, or about five times as high, as the wear resistance of a sintered product produced from a feedstock that does not include an amorphous alloy.
  • the sintered product produced utilizing the amorphous containing feedstock described herein may exhibit improved properties when compared to sintered products produced from a feedstock that does not include an amorphous alloy.
  • the sintered product may exhibit improved hardness and wear resistance.
  • the sintered product may exhibit an improved fatigue resistance.
  • the sintered product may exhibit improved temperature resistance—i.e., improved hardness at high temperatures.
  • the sintered product may exhibit decreased volumetric shrinkage during the sintering process.
  • a property is considered to be improved when in comparison to another material the property is more desirable for any given application.
  • improvement may refer to an increase in magnitude.
  • the sintered product produced utilizing the amorphous containing feedstock described herein may be a medical component, orthodontic component, automotive component, electronic device component, telecommunication device component, aerospace component, firearm component, eyewear component, dental component, sporting good component, pump component, gear component, hinge component, knife or knife edge, cutting edge of a cutting instrument, casing component, and/or marine component.
  • the sintered product may be a component or device for use in the oil or gas industry.
  • the sintered product may be a military article or a component utilized in the defense industry.
  • the sintered product may be a jewelry or watch component.
  • the sintered product may be a micro component or tool component.
  • the sintered product may be a cutting device resistant to dulling—e.g., knives, scissors, or other cutting devices.
  • the sintered product may be a bearing or other anti-friction device or wear surface.
  • the sintered product may be a component of fishing gear or other off-shore item.
  • the amorphous alloy containing feedstock described herein may be employed in standard MIM processes as described above.
  • the sintering process may be conducted at a lower temperature and shorter time period when utilizing an amorphous alloy containing feedstock than in traditional MIM processes.
  • the lower temperature and shorter time period provide substantial energy, cost and time savings.
  • FIG. 3 depicts a flowchart describing an MIM process ( 100 ) for utilizing an amorphous alloy containing feedstock according to one embodiment.
  • the process includes optionally mixing ( 110 ) an amorphous alloy containing particulate with a binder to form a feedstock material.
  • the feedstock material may be injected ( 120 ) into a mold, and a green workpiece may be removed from the mold ( 130 ).
  • the binder may be removed from the green workpiece ( 140 ) forming a brown workpiece.
  • the brown workpiece may be sintered ( 150 ) to form a final product.
  • Exemplary products A and B were produced from the same feedstock containing an amorphous alloy and sintered under different conditions.
  • the amorphous alloy was an iron containing amorphous alloy.
  • the hardness of the sintered samples was tested at five different locations and an average hardness for each sample was determined.
  • Example A was sintered at 1120° C. for a period of 1 hour
  • Example B was sintered at a temperature of 1145° C. for a period of 1 hour.
  • Table 1 the sintering procedure of Example A produced a product with an average hardness of 910.1 HV
  • the sintering procedure of Example B produced a product with an average hardness of 1170.0 HV.
  • FIGS. 1 and 2 depict the microstructure produced by the differing sintering procedures of Examples A and B, respectively.
  • the sintering procedure of Example A produced a product with a smaller grain size than the sintering procedure of Example B.
  • FIG. 4 depicts an X-ray Diffraction (“XRD”) pattern for a feedstock material that consists of a fully amorphous powder according to one embodiment, and an XRD pattern for a material with a similar composition that contains both amorphous and crystalline constituents according to another embodiment.
  • XRD X-ray Diffraction
  • FIG. 5 depicts a Differential Scanning calorimetry (“DSC”) plot for an amorphous alloy containing feedstock material, according to one embodiment.
  • DSC Differential Scanning calorimetry
  • inventive embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed.
  • inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and/or method described herein.
  • the technology described herein may be embodied as a method, of which at least one example has been provided.
  • the acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.
  • substantially and “about” used throughout this Specification are used to describe and account for small fluctuations. For example, they can refer to less than or equal to ⁇ 5%, such as less than or equal to ⁇ 2%, such as less than or equal to ⁇ 1%, such as less than or equal to ⁇ 0.5%, such as less than or equal to ⁇ 0.2%, such as less than or equal to ⁇ 0.1%, such as less than or equal to ⁇ 0.05%.
  • a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
  • the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
  • This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified.
  • “at least one of A and B” can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

Abstract

Provided in one embodiment is a method for producing a composition, the method comprising injecting a feedstock into a mold to produce a workpiece; wherein the feedstock comprises a binder and particulates comprising an amorphous alloy. The feedstock composition is also described.

Description

    BACKGROUND
  • Powder injection molding of metallic components may offer many advantages that have led to widespread use in a variety of applications. Among the advantages provided by powder injection molding is the ability to produce metal parts with complex shapes with reduced waste. Despite the many advantages provided by conventional powder injection molding processes, these processes do not offer the density and hardness of the finished product desired for many applications.
  • SUMMARY
  • In view of the foregoing, the Inventors have recognized and appreciated the advantages of feedstock materials for powder injection molding that provide finished products with improved properties, such as hardness and density, and methods of making and/or using same.
  • Accordingly, provided in some embodiments herein is a composition comprising a binder, and particulates. The particulates may comprise an amorphous alloy, and the composition may be a feedstock for an injection molding process.
  • One embodiment provides a method comprising injecting a feedstock into a mold to produce a workpiece. The feedstock may comprise a binder and particulates, and the particulates may comprise an amorphous alloy.
  • Another embodiment provides an article produced by sintering a workpiece produced by the method above.
  • It should be appreciated that all combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are contemplated as being part of the inventive subject matter disclosed herein. In particular, all combinations of claimed subject matter appearing at the end of this disclosure are contemplated as being part of the inventive subject matter disclosed herein. It should also be appreciated that terminology explicitly employed herein that also may appear in any disclosure incorporated by reference should be accorded a meaning most consistent with the particular concepts disclosed herein.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The skilled artisan will understand that the drawings are primarily for illustrative purposes and are not intended to limit the scope of the inventive subject matter described herein. The drawings are not necessarily to scale; in some instances, various aspects of the inventive subject matter disclosed herein may be shown exaggerated or enlarged in the drawings to facilitate an understanding of different features. In the drawings, like reference characters generally refer to like features (e.g., functionally similar and/or structurally similar elements).
  • FIG. 1 depicts a microstructure of a material produced according to one embodiment.
  • FIG. 2 depicts a microstructure of a material produced according to one embodiment.
  • FIG. 3 depicts a flow chart detailing a process according to one embodiment.
  • FIG. 4 depicts an X-ray Diffraction (“XRD”) pattern for a feedstock material that consists of a fully amorphous powder according to one embodiment, and an XRD pattern for a material with a similar composition that contains both amorphous and crystalline constituents according to another embodiment.
  • FIG. 5 depicts a Differential Scanning calorimetry (“DSC”) plot for an amorphous alloy containing feedstock material, according to one embodiment.
  • DETAILED DESCRIPTION
  • Following below are more detailed descriptions of various concepts related to, and embodiments of, feedstock materials for powder injection molding that provide finished products with improved properties and methods of making and/or using same. It should be appreciated that various concepts introduced above and discussed in greater detail below may be implemented in any of numerous ways, as the disclosed concepts are not limited to any particular manner of implementation. Examples of specific implementations and applications are provided primarily for illustrative purposes.
  • One embodiment is related to a composition comprising a binder and particulates, wherein the particulates comprise an amorphous alloy, and the composition is a feedstock for an injection molding process. Another embodiment is related to a method comprising injecting a feedstock into a mold to produce a workpiece, wherein the feedstock comprises a binder and particulates comprising an amorphous alloy. Another embodiment is related to an article produced by sintering a workpiece produced by the preceding method.
  • Amorphous Alloys
  • An alloy may refer to a mixture, including a solid solution, of two or more metal elements—e.g., at least 2, 3, 4, 5, or more elements. The term “element” herein may refer to a chemical represented by a symbol that may be found in a
  • Periodic Table. A metal may refer to any of alkali metals, alkaline earth metals, transition metals, post-transition metals, lanthanides, and actinides.
  • An amorphous alloy may refer to an alloy having an amorphous, non-crystalline atomic structure or microstructure. The amorphous structure may refer to a glassy structure with no observable long range order; in some instances, an amorphous structure may exhibit some short range order. Thus, an amorphous alloy may sometimes be referred to as a “metallic glass.” An amorphous alloy may refer to an alloy of which at least about 50% is an amorphous phase—e.g., at least about 60%, about 70%, about 80%, about 90%, about 95%, about 99%, or more. The percentage herein may refer to volume percent or weight percent, depending on the context. The term “phase” herein may refer to a physically distinctive form of a substance, such as microstructure. For example, a solid and a liquid are different phases. Similarly, an amorphous phase is different from a crystalline phase.
  • Amorphous alloys may contain a variety of metal elements. In some embodiments, the amorphous alloys may comprise iron, chromium, silicon, boron, manganese, nickel, molybdenum, niobium, copper, cobalt, carbon, zirconium, titanium, beryllium, aluminum, gold, platinum, palladium, phosphorous, tungsten, yttrium, tantalum, or combinations thereof. In some embodiments, the amorphous alloys may be zirconium-based, titanium-based, iron-based, copper-based, nickel-based, gold-based, platinum-based, palladium-based, or aluminum-based. The term “M-based” when referring to an alloy may refer to an alloy comprising at least about 30% of the “M” element—e.g., about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, about 95%, or more. The percentage herein may refer to volume percent or weight percent, depending on the context.
  • An amorphous alloy may be a bulk solidifying amorphous alloy. A bulk solidifying amorphous alloy, bulk metallic glass (“BMG”), or bulk amorphous alloy may refer to an amorphous alloy that may be adapted to have at least one dimension in the millimeter range. In one embodiment, this dimension may refer to the smallest dimension. Depending on the geometry, the dimension may refer to thickness, height, length, width, radius, and the like. In some embodiments, this smallest dimension may be at least about 0.5 mm—e.g., about 1 mm, about 2 mm, about 3 mm, about 4 mm, about 5 mm, about 6 mm, about 8 mm, about 10 mm, about 12 mm, or more. The magnitude of the largest dimension is not limited and may be in the millimeter range, centimeter range, or even meter range.
  • An amorphous alloy, including a bulk amorphous alloy, described herein may have a critical cooling rate of about 500 K/sec or less. The term “critical cooling rate” herein may refer to the cooling rate below which an amorphous structure is not energetically favorable and thus is not likely to form during a fabrication process. In some embodiments, the critical cooling rate of the amorphous alloy may be, for example, about 400 K/sec or less—e.g., about 300 K/sec or less, about 250 K/sec or less, about 200 K/sec or less.
  • In some embodiments, the amorphous alloy may be a ferrous-metal based alloy, such as (Fe, Ni, Co) based compositions. Examples of such compositions are disclosed in U.S. Pat. No. 6,325,868 and in publications (A. Inoue et. al., Appl. Phys. Lett., Volume 71, p 464 (1997)), (Shen et. al., Mater. Trans., JIM, Volume 42, p 2136 (2001)), and Japanese patent application 2000126277 (Publ. # 2001303218 A). For example, the alloy may be Fe72A15Ga2P11C6B4, or Fe72A17Zr10Mo5W2B15.
  • In some embodiments, the amorphous alloy may be at least one of Fe—Cr—B—Mo—C alloy, Ni—Cr—Si—B—Mo—Cu—Co alloy, Fe—Cr—B—Mn—Si alloy, Fe—Cr—B—Si alloy, Fe—Cr—B—Mn—Si—Cu—Ni—Mo alloy, Fe—Cr—B—Mn—Si—Ni alloy, Fe—Cr—Si—B—Mn—Ni—WC—TiC alloy, Fe—Cr—Si—Mn—C—Nd—Ti alloy, Fe—Cr—P—C alloy, Fe—Cr—Mo—P—C alloy, Fe—Cr—Mo—P—C—Ni alloy, Fe—P—C—B—Al alloy, Fe—Cr—Mo—B—C—Si—Ni—P alloy, Fe—Cr—Mo—B—C—Si—W—Ni alloy , Ni—Cr—Mo—B alloy, Fe—B—Si—Cr—Nb—W alloy, Fe—Cr—Mo—B—C—Y alloy, Fe—Cr—Mo—B—C—Y—Co alloy, Fe—Cr—Mo—W—Nb alloy, Fe—Cr—Mo—B—C—Si—W—Mn alloy, and Fe—Cr—Si—W—Nb alloy. In at least one embodiment, the amorphous alloy may be an Fe-based alloy or an Ni/Cr-based alloy.
  • Amorphous alloys, including bulk solidifying amorphous alloys, may have higher strength and higher hardness than their crystalline counterparts.
  • The strength may refer to tensile or compressive strength, depending on the context. For example, Zr and Ti-based amorphous alloys may have tensile yield strengths of about 250 ksi or higher, hardness values of about 450 HV or higher, or both. In some embodiments, the tensile yield strength may be about 300 ksi or higher—e.g., at least about 400 ksi, about 500 ksi, about 600 ksi, about 800 ksi, or higher. In some embodiments, the hardness value may be at least about 500 HV—e.g., at least about 550 HV, about 600 HV, about 700 HV, about 800 HV, about 900 HV, about 1000 HV, or higher.
  • In one embodiment, ferrous metal based amorphous alloys, including the ferrous metal based bulk solidifying amorphous alloys, can have tensile yield strengths of about 500 ksi or higher and hardness values of about 1000 HV or higher. In some embodiments, the tensile yield strength may be about 550 ksi or higher—e.g., at least about 600 ksi, about 700 ksi, about 800 ksi, about 900 ksi, or higher. In some embodiments, the hardness value may be at least about 1000 HV—e.g., at least about 1100 HV, about 1200 HV, about 1400 HV, about 1500 HV, about 1600 HV, or higher.
  • As such, any of the aforedescribed amorphous alloys may have a desirable strength-to-weight ratio. Furthermore, amorphous alloys, particularly the Zr- or Ti-based alloys, may exhibit desirable corrosion resistance and environmental durability. The corrosion herein may refer to chemical corrosion, stress corrosion, or a combination thereof.
  • The amorphous alloys, including bulk amorphous alloys, described herein may have a high elastic strain limit of at least about 0.5%, including at least about 1%, about 1.2%, about 1.5%, about 1.6%, about 1.8%, about 2%, or more—this value is much higher than any other metal alloy known to date.
  • In some embodiments, the amorphous alloys, including bulk amorphous alloys, may additionally include some crystalline materials, such as crystalline alloys. The crystalline material may have the same or different chemistry from the amorphous alloy. For example, in the case wherein the crystalline alloy and the amorphous alloy have the same chemical composition, they may differ from each other only with respect to their microstructures.
  • In some embodiments, crystalline precipitates in amorphous alloys may have an undesirable effect on the properties of amorphous alloys, especially on the toughness and strength of these alloys, and as such it is generally preferred to minimize the volume fraction of these precipitates. However, there may be cases in which ductile crystalline phases precipitate in-situ during the processing of amorphous alloys, which may be beneficial to the properties of amorphous alloys, especially to the toughness and ductility of the alloys. One exemplary case is disclosed in C. C. Hays et. al, Physical Review Letters, Vol. 84, p 2901, 2000. In at least one embodiment herein, the crystalline precipitates may comprise a metal or an alloy, wherein the alloy may have a composition that is the same as the composition of the amorphous alloy or a composition that is different from the composition of the amorphous alloy. Such amorphous alloys comprising these beneficial crystalline precipitates may be employed in at least one embodiment described herein.
  • Powder Injection Molding
  • Powder injection molding (“PIM”) is a process for producing complex components utilizing a feedstock that incorporates a powder material and a binder in an injection molding process. Metal injection molding (“MIM”) is a type of powder injection molding in which the powder may be a metal or alloy. An MIM process may typically include injecting a feedstock into a mold, removing the binder from the molded workpiece, and sintering the workpiece from which the binder has been removed.
  • The feedstock utilized in the MIM process may be formed as part of the process or purchased in ready to use form. In one embodiment, the feedstock may be produced by mixing particulates with a binder. In another embodiment, the mixing may be performed in a sigma blade mixer or a twin-screw or shear roll extruder at an elevated temperature for a predetermined period of time. The elevated temperature may be of any temperature higher than the room temperature, depending on the application. For example, in one embodiment, the mixing may be performed at a temperature of about 150° C. In another embodiment, the mixing may be performed at a temperature of about 100° C. to about 200° C.—e.g., about 110° C. to about 190° C., about 120° C. to about 180° C., about 130° C. to about 170° C., or about 140° C. to about 160° C. The predetermined period of time may be of any length of time, depending on the application. In one embodiment the mixing may be performed for a time period of about 0.25 to about 3.75 hours—e.g., about 0.5 to about 3.5, about 0.75 to about 3.25, about 1 to about 3, about 1.25 to about 2.75, about 1.5 to about 2.5, about 1.75 to about 2.25 hours. In another embodiment, the mixing may be performed at a temperature in the range of from about 130° C. to about 160° C. for a period of about 2 hours.
  • The feedstock may be directly supplied to the injector apparatus after mixing or formed into granules for storage and later use. In one embodiment, the feedstock may be formed into pellets or granules with a size in the millimeter size range. In another embodiment, pellets or granules of feedstock may be purchased for use in the injection molding process.
  • The injection of the feedstock into a mold may occur at an elevated temperature. The elevated temperature may be of any temperature higher than the room temperature, depending on the application. For example, in one embodiment, the feedstock is at a temperature of about 100° C. to about 150° C.
  • The temperature at which the feedstock is injected may be referred to as the “nozzle temperature.” The melting temperature of the binder included in the feedstock may affect the nozzle temperature utilized during injection. In one embodiment, the mold may be heated to improve the filling of the mold cavity by the feedstock during injection. In another embodiment, the mold may be at a temperature of about 50° C. during the injection process.
  • The workpiece that is removed from the mold may be referred to as a “green workpiece.” The green workpiece may contain both the particulates and the binder, and maintain the shape imparted by the mold.
  • The binder may be removed from the green workpiece in a debinding process. The binder may be removed by a thermal, catalytic, solvent or supercritical debinding process. In one embodiment, the binder may be removed by a thermal treatment process in which the green workpiece is heated in an electric furnace under a high purity hydrogen atmosphere. In another embodiment, a thermal debinding process may be employed in which the green workpiece is heated up to a temperature of about 300° C. at a heating rate of about 2° C./minute and maintained for about one hour, increasing the temperature up to about 500° C. at a rate of about 3° C./minute and maintained for about one hour, and increasing the temperature up to about 750° C. at a rate of about 3° C./minute and maintaining for about one hour. The temperature ranges utilized in a thermal debinding process may depend on the binder selected. The workpiece after binder removal may be referred to as a “brown workpiece.”
  • The brown workpiece may be sintered to produce a metal part. The sintering process may result in shrinkage of the brown workpiece as any remaining binder is removed and sintering necks are formed between the metal particulates. After sintering, the part produced may be substantially free of the binder. In one embodiment, the part may be entirely free of the binder. The temperature and time for the sintering may be dependent on the properties of the metal particulates.
  • In some cases, the sintered metal part may be subjected to post-sintering treatment, such as machining or polishing. For some metal particulates and some applications, additional heat treatments may be employed to remove residual porosity.
  • Amorphous Alloy Containing Feedstock
  • In some embodiments disclosed herein, the feedstock for use in an MIM process may include particulates that include an amorphous alloy. The amorphous alloy may be any of the amorphous alloys described herein. In at least one embodiment, the amorphous alloy may be a bulk amorphous alloy. In another embodiment, the amorphous alloy may not be a bulk amorphous alloy.
  • The feedstock material may further comprise a crystalline material. The crystalline material may be a crystalline alloy having the same or different chemical composition from the amorphous alloy. In at least one embodiment, the crystalline material comprises crystal (or “grain”) sizes in the nanometer range, micron range, millimeter range, centimeter range, or any combinations thereof. For example, the first material may comprise a nano-crystalline material. The crystalline material may comprise an alloy of the same composition as the amorphous alloy in the coating material, an alloy different from the amorphous alloy in the coating material, a metal, a non-metal, or any combinations thereof.
  • In one embodiment, the feedstock material may additionally include a partially amorphous material, a ceramic material, a refractory particulate material, a soft particulate material, a crystalline metal particulate material, a crystalline alloy particulate material, or combinations thereof. The ceramic material may include a carbide or an oxide—e.g., silica, alumina, zirconia, or magnesia. The refractory particulate material may include niobium, molybdenum, tantalum, tungsten, carbides, or borides. In one embodiment, the refractory particulate material may be tungsten carbide, chromium carbide, silicon carbide, or combinations thereof. In another embodiment, the refractory particulate material may be chromium boride, silicon boride, or combinations thereof. The soft particulate material may be copper, copper alloy, iron, or any particulate material with a hardness of less than the hardness of the amorphous containing particulate. The crystalline metal particulate material may comprise iron or copper. The crystalline alloy particulate material may comprise Fe, Cu, Co, Ni,
  • Cr, Mo, B, C, Si, W, Mn, Y, Co, Al, Nb, P, or Ti alloy. In one embodiment, the crystalline alloy particulate material may comprise a stainless steel or Inconel. In another embodiment, the crystalline alloy powder may comprise Stainless Steel 316L, 630, or 17-4. In one embodiment, the feedstock material may additionally include a powder traditionally utilized in MIM processes. The powder traditionally utilized in MIM processes may be selected from low alloy steels, soft magnetic alloys, controlled expansion alloys, and combinations thereof.
  • The particulates may have any suitable geometry, depending on the application. For example, the particulates may have a spherical or rounded geometry. A spherical particle at least substantially resembles a sphere. A rounded particle lacks sharp angular edges, such as in the case of circular platelets. In one embodiment, spherical particulates are produced by a gas atomization process. Spherical particulates may produce a higher density product after sintering as a result of increased packing efficiency. In another embodiment, rounded particulates may be produced by a water atomization process.
  • The particulates may have any suitable size, depending on the application. Depending on the geometry, the term “size” herein may refer to the diameter, radius, length, width, height, etc. of the particulates. In one embodiment, the particulates may have a size in the range of about 1 to about 150 microns—e.g., about 5 to about 120 microns, about 10 to about 100 microns, about 15 to about 90 microns, about 20 to about 85 microns, about 25 to about 80 microns, about 30 to about 75 microns. In another embodiment, the particulates may have a size of less than about 100 microns—e.g., less than about 95 microns, about 90 microns, about 85 microns, about 80 microns, about 75 microns, about 70 microns, or less. In one embodiment, the particulates may have a size of greater than about 1 micron—e.g., greater than about 5 microns, about 10 microns, about 15 microns, about 20 microns, about 25 microns, about 30 microns, or more. In another embodiment, the particulates may have a size in the range of about 5 to about 30 microns.
  • The binder may be any binder suitable for use in MIM processes. In one embodiment, the binder may be a thermoplastic material. In another embodiment, the binder may be a mixture of ethylene vinyl acetate and paraffin. In one embodiment, the binder may be a mixture of about 20 wt. % ethyl vinyl acetate and about 80 wt. % paraffin. In another embodiment, the binder may include a bonding agent, a surfactant, a plasticizer, a lubricant, or combinations thereof.
  • The particulates may be contained in the feedstock material in an amount of about 30 to about 90 vol.%—e.g., about 35 to about 85 vol. %, about 40 to about 80 vol. %, about 45 to about 75 vol. %, or about 50 to about 70 vol. %. In another embodiment, the particulates are contained in the feedstock material in a larger concentration by volume than that of the binder.
  • The amorphous containing particulates in the feedstock material may allow the sintering temperature and time to be reduced, in comparison to traditional MIM feedstocks. In one embodiment, the sintering temperature may be less than 1300° C.—e.g., less than about 1200° C., about 1100° C., about 1000° C., or less. For example, in one embodiment utilizing an Fe-based amorphous particulate the sintering was carried out at a temperature of about 1100° C. to about 1165° C. for about 30 minutes. By contrast, two traditional MIM crystalline feedstock materials, Stainless Steel 316L and 630, are generally sintered at a temperature of 1350° C. for about 2 hours. The reduced temperature and time of the sintering that results from the amorphous containing particulates provide substantial energy, cost and time savings in comparison to traditional MIM feedstock materials. In some cases the sintering temperature and time may affect the hardness and density of the final product. The sintering may be conducted under vacuum or a controlled gas atmosphere.
  • The sintered product produced utilizing the amorphous containing feedstock described herein may include an amorphous alloy. In another embodiment, the sintered product may be substantially free of an amorphous alloy. In yet another embodiment, the sintered product may be substantially free of a crystalline alloy material.
  • The sintered product produced utilizing the amorphous containing feedstock described herein may have a Vickers hardness of about 500 HV to about 1500 HV—e.g., about 550 HV to about 1450 HV, about 600 HV to about 1400 HV, about 650 HV to about 1350 HV, about 700 HV to about 1300 HV, about 750 HV to about 1250 HV, about 800 HV to about 1200 HV, about 850 HV to about 1150 HV, about 900 HV to about 1100 HV, or about 950 HV to about 1050 HV. In one embodiment, the coating material exhibits a Vickers hardness of at least about 500 HV—e.g., at least about 500 HV, about 525 HV, about 550 HV, about 575 HV, about 600 HV, about 625 HV, about 650 HV, about 675 HV, about 700 HV, about 725 HV, about 750 HV, about 775 HV, about 800 HV, about 825 HV, about 850 HV, about 875 HV, about 900 HV, about 925 HV, about 950 HV, about 975 HV, about 1000 HV, about 1025 HV, about 1050 HV, about 1075
  • HV, about 1100 HV, about 1125 HV, about 1150 HV, about 1175 HV, about 1200 HV, about 1225 HV, about 1250 HV, about 1275 HV, about 1300 HV, about 1325 HV, about 1350 HV, about 1375 HV, or more. In another embodiment, the coating material may have a Vickers hardness of about 900 HV to about 1200 HV.
  • In one embodiment, an Fe-based amorphous particulate containing feedstock produced a part with hardness of about 900 to about 1200 HV, depending on the sintering process chosen. By contrast, two traditional MIM crystalline feedstock materials Stainless Steel 316L and 630 produce parts with hardnesses of 97 HV and about 360 HV, respectively. Thus, the amorphous containing feedstock provided herein allows for the production of parts utilizing MIM processes with surprisingly high hardness. In one embodiment, the sintered products produced utilizing the amorphous containing feedstock did not require additional heat treatment steps to achieve increased hardness levels.
  • The sintered product produced utilizing the amorphous containing feedstock described herein may have a density greater than about 99%—e.g., greater than about 99.1%, about 99.2%, about 99.3%, about 99.4%, about 99.5%, about 99.5%, about 99.6%, about 99.7%, about 99.8%, or about 99.9%. In one embodiment, the sintered product produced may have a density of about 99.99%. By contrast, parts produced utilizing traditional MIM crystalline feedstock material Stainless Steel 316L exhibited a density of only about 96% after sintering. Thus, the amorphous containing feedstock provided herein allows for the production of parts utilizing MIM processes with surprisingly high density.
  • The sintered product produced utilizing the amorphous containing feedstock described herein may have a tensile stiffness that is controlled based on the selection of the product design, feedstock composition, and sintering treatment.
  • The sintered product produced utilizing the amorphous containing feedstock described herein may be resistant to wear and/or corrosion. In one embodiment, the corrosion may refer to chemical corrosion, stress corrosion, or both. The wear resistance may be directly related to the hardness of the material, with wear resistance increasing as hardness increases. In at least one embodiment, the wear resistance is at least about twice as high—e.g., at least about three times as high, about four times as high, or about five times as high, as the wear resistance of a sintered product produced from a feedstock that does not include an amorphous alloy.
  • The sintered product produced utilizing the amorphous containing feedstock described herein may exhibit improved properties when compared to sintered products produced from a feedstock that does not include an amorphous alloy. In one embodiment, the sintered product may exhibit improved hardness and wear resistance. In another embodiment, the sintered product may exhibit an improved fatigue resistance. In one embodiment, the sintered product may exhibit improved temperature resistance—i.e., improved hardness at high temperatures. In one embodiment, the sintered product may exhibit decreased volumetric shrinkage during the sintering process.
  • A property is considered to be improved when in comparison to another material the property is more desirable for any given application. For example, in the case of tensile strength, improvement may refer to an increase in magnitude.
  • The sintered product produced utilizing the amorphous containing feedstock described herein may be a medical component, orthodontic component, automotive component, electronic device component, telecommunication device component, aerospace component, firearm component, eyewear component, dental component, sporting good component, pump component, gear component, hinge component, knife or knife edge, cutting edge of a cutting instrument, casing component, and/or marine component. In one embodiment, the sintered product may be a component or device for use in the oil or gas industry. In another embodiment, the sintered product may be a military article or a component utilized in the defense industry. In one embodiment, the sintered product may be a jewelry or watch component. In another embodiment, the sintered product may be a micro component or tool component. In one embodiment, the sintered product may be a cutting device resistant to dulling—e.g., knives, scissors, or other cutting devices. In another embodiment, the sintered product may be a bearing or other anti-friction device or wear surface. In one embodiment, the sintered product may be a component of fishing gear or other off-shore item.
  • Method of Using Amorphous Alloy Containing Feedstock
  • The amorphous alloy containing feedstock described herein may be employed in standard MIM processes as described above. The sintering process may be conducted at a lower temperature and shorter time period when utilizing an amorphous alloy containing feedstock than in traditional MIM processes. The lower temperature and shorter time period provide substantial energy, cost and time savings.
  • FIG. 3 depicts a flowchart describing an MIM process (100) for utilizing an amorphous alloy containing feedstock according to one embodiment. The process includes optionally mixing (110) an amorphous alloy containing particulate with a binder to form a feedstock material. The feedstock material may be injected (120) into a mold, and a green workpiece may be removed from the mold (130). The binder may be removed from the green workpiece (140) forming a brown workpiece. The brown workpiece may be sintered (150) to form a final product.
  • Non-Limiting Working Examples
  • The following non-limiting examples were produced and analyzed.
  • Examples A and B
  • Exemplary products A and B were produced from the same feedstock containing an amorphous alloy and sintered under different conditions. The amorphous alloy was an iron containing amorphous alloy. The hardness of the sintered samples was tested at five different locations and an average hardness for each sample was determined. Example A was sintered at 1120° C. for a period of 1 hour, and Example B was sintered at a temperature of 1145° C. for a period of 1 hour. As shown in Table 1, the sintering procedure of Example A produced a product with an average hardness of 910.1 HV, and the sintering procedure of Example B produced a product with an average hardness of 1170.0 HV.
  • TABLE 1
    Load 0.3 kgf Sintering A Sintering B
    1 911.8 1197.9
    2 926.8 1133.8
    3 890.5 1149.2
    4 915.3 1185.3
    5 906.1 1183.8
    Avg. (HV) 910.1 1170.0
  • FIGS. 1 and 2 depict the microstructure produced by the differing sintering procedures of Examples A and B, respectively. As can be readily observed in FIGS. 1 and 2, the sintering procedure of Example A produced a product with a smaller grain size than the sintering procedure of Example B.
  • FIG. 4 depicts an X-ray Diffraction (“XRD”) pattern for a feedstock material that consists of a fully amorphous powder according to one embodiment, and an XRD pattern for a material with a similar composition that contains both amorphous and crystalline constituents according to another embodiment.
  • FIG. 5 depicts a Differential Scanning calorimetry (“DSC”) plot for an amorphous alloy containing feedstock material, according to one embodiment.
  • Additional Notes
  • All literature and similar material cited in this application, including, but not limited to, patents, patent applications, articles, books, treatises, and web pages, regardless of the format of such literature and similar materials, are expressly incorporated by reference in their entirety. In the event that one or more of the incorporated literature and similar materials differs from or contradicts this application, including but not limited to defined terms, term usage, described techniques, or the like, this application controls.
  • While the present teachings have been described in conjunction with various embodiments and examples, it is not intended that the present teachings be limited to such embodiments or examples. On the contrary, the present teachings encompass various alternatives, modifications, and equivalents, as will be appreciated by those of skill in the art.
  • While various inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the inventive teachings is/are used. Those skilled in the art will recognize many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.
  • Also, the technology described herein may be embodied as a method, of which at least one example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.
  • All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.
  • The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.” Any ranges cited herein are inclusive.
  • The terms “substantially” and “about” used throughout this Specification are used to describe and account for small fluctuations. For example, they can refer to less than or equal to ±5%, such as less than or equal to ±2%, such as less than or equal to ±1%, such as less than or equal to ±0.5%, such as less than or equal to ±0.2%, such as less than or equal to ±0.1%, such as less than or equal to ±0.05%.
  • The phrase “and/or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and/or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and/or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
  • As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and/or” as defined above. For example, when separating items in a list, “or” or “and/or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.
  • As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and/or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
  • In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.
  • The claims should not be read as limited to the described order or elements unless stated to that effect. It should be understood that various changes in form and detail may be made by one of ordinary skill in the art without departing from the spirit and scope of the appended claims. All embodiments that come within the spirit and scope of the following claims and equivalents thereto are claimed.

Claims (22)

What is claimed:
1. A composition comprising:
a binder, and
particulates,
wherein the particulates comprise an amorphous alloy, and the composition is a feedstock for an injection molding process.
2. The composition of claim 1, further comprising a partially amorphous particulate material, a refractory particulate material, a soft particulate material, a crystalline metal particulate material, a crystalline alloy particulate material, or combinations thereof.
3. The composition of claim 1, further comprising an alloy particulate material comprising Fe, Cu, Co, Ni, Cr, Mo, B, C, Si, W, Mn, Y, Co, Al, Nb, P, Ti, or combinations thereof.
4. The composition of claim 1, wherein the binder comprises a thermoplastic material.
5. The composition of claim 1, wherein the particulates have a spherical or rounded geometry.
6. The composition of claim 1, wherein the particulates have a size of about 1 micron to about 75 microns.
7. The composition of claim 1, wherein the particulates are present in an amount of about 45 vol. % to about 75 vol. % of the composition.
8. The composition of claim 1, wherein the composition is in the form of granules.
9. A method comprising:
injecting a feedstock in to a mold to produce a workpiece,
wherein the feedstock comprises a binder and particulates comprising an amorphous alloy.
10. The method of claim 9, further comprising removing the binder from the workpiece.
11. The method of claim 9, further comprising sintering the workpiece at a temperature of less than or equal to about 1300° C.
12. The method of claim 9, further comprising producing the feedstock by mixing the binder with the particulates.
13. The method of claim 9, further comprising producing the feedstock in a method comprising:
forming particulates comprising an amorphous alloy, and
mixing the particulates with a binder,
wherein the forming comprises a gas atomization process, and the particulates are spherical.
14. The method of claim 9, further comprising heating the feedstock material prior to injecting the heated feedstock material into the mold.
15. The method of claim 9, wherein the feedstock material is at a temperature of about 100° C. to about 150° C. during the injecting.
16. An article produced by sintering a workpiece produced by the method of claim 9.
17. The article of claim 16, wherein the article is substantially free of binder after the sintering.
18. The article of claim 16, wherein the article is substantially free of the amorphous alloy.
19. The article of claim 16, wherein the article comprises the amorphous alloy.
20. The article of claim 16, wherein the article has a density of at least about 99%.
21. The article of claim 16, wherein the article has a hardness of at least about 500 HV.
22. The article of claim 16, wherein the article is at least one of a medical component, orthodontic component, automotive component, electronic device component, telecommunication device component, aerospace component, firearm component, eyewear component, dental component, sporting good component, pump component, gear component, hinge component, knife or knife edge, cutting edge of a cutting instrument, casing component, and marine component.
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