WO2023141411A1

WO2023141411A1 - Cemented carbide compositions

Info

Publication number: WO2023141411A1
Application number: PCT/US2023/060717
Authority: WO
Inventors: Olivier Lavigne; Nuria CINCA I LUIS; Neil KRISHNAN; Elena Tarres i PUIT
Original assignee: Hyperion Materials & Technologies, Inc.; Diamond Innovations, Inc.
Priority date: 2022-01-21
Filing date: 2023-01-17
Publication date: 2023-07-27

Abstract

Provided is a cemented carbide composition that includes a carbide phase including reclaimed carbide material in an amount of greater than 70 wt.% of the cemented carbide composition. The cemented carbide composition further includes a binder phase. The reclaimed carbide material includes from about 45 wt.% to about 100 wt.% zinc-reclaimed carbide. The cemented carbide composition is devoid of any electrochemically processed recycled material. The cemented carbide composition exhibits equivalent or superior mechanical properties including e.g. hardness, fracture toughness, and transverse rupture strength when compared to a reference material including solely virgin raw materials. Further provided is a method of making a sintered cemented carbide article as well as a cutting tool or cutting tool blank using the provided cemented carbide composition.

Description

HYPERION REF: H20057WO

CEMENTED CARBIDE COMPOSITIONS

FIELD OF THE DISCLOSURE

[0001] The present disclosure relates to cemented carbide compositions including reclaimed carbide materials. The reclaimed carbide material may include one or more of zinc-reclaimed carbide and reclaimed non-sintered carbide.

BACKGROUND

[0002] Several processes are currently used to recycle WC and tungsten products. These processes may include, for example, zinc processes, cold-stream processes, alkali-leach processes, chlorination systems, electrolysis, and high-temperature smelting. With the exception of the zinc and cold-stream processes, the other chemical methods involve numerous conversions, extraction and precipitation steps that increase the cycle time and cost. Many of these chemical methods also undesirably involve the use and exposure to chemically harsh acids, bases, and various inorganic salts.

[0003] US Patent No. 10,940,538, which is incorporated herein by reference in its entirety, describes sintered cemented carbide articles having a carbide phase and a binder phase. The carbide phase is present in an amount of at least 70 weight percent of the article. Of note, the carbide phase includes electrochemically-processed sintered carbide scrap in an amount of 60-90 weight percent of the carbide phase, and a balance of zinc-processed carbide scrap and/or ammonium paratungstate processed sintered carbide scrap. According to US Patent No. 10,940,538, electrochemically processed sintered carbide scrap is utilized in high concentrations, because other reclaimed or recycled carbide materials allegedly yield inferior chemical and mechanical properties, which is said to limit the use or reclaimed or recycled carbide compositions in the fabrication of new tooling.

[0004] However, as described herein, unexpectedly, the present disclosure provides cemented carbide compositions having equivalent, or superior mechanical and chemical properties, including, e.g., hardness, fracture toughness and transverse rupture strength, to the articles set forth in US Patent No. 10,940,538, which requires the use of

1 HYPERION REF: H20057WO electrochemically-processed sintered carbide scrap, as well as to other carbide compositions that include 100% virgin carbide material as the carbide phase. As a result, an advantageous improvement is thereby obtained over the prior known solutions, in part, due to the realization of carbide compositions with superior chemical and mechanical properties that do not require a cumbersome electrochemical recycling process-step.

SUMMARY

[0005] Provided is a cemented carbide composition comprising or consisting of a carbide phase and a binder phase. The carbide phase may be present in an amount of at least 70 wt.% of the cemented carbide composition. The carbide phase may comprise or consist of about 45 wt.% to about 100 wt.% zinc-reclaimed carbide based on the total weight of the carbide phase. The resulting cemented carbide may have transverse rupture strength (TRS-B) of at least about £3000 MPa, as measured according to the ISO 3327-2009 standard. Alternatively, the resulting cemented carbide may demonstrate a transverse rupture strength in a range of from about 320 Ksi to about 570 Ksi when determined pursuant to the ASTM B 406 standard for a sample having 100 wt.% reclaimed non-sintered carbide. In some examples, the transverse rupture strength is in a range of from about 330 Ksi to about 540 Ksi when measured pursuant to the ASTM B 406 standard for a sample having 90 wt.% zinc-reclaimed carbide and 10 wt.% reclaimed non-sintered carbide. A transverse rupture strength range of from about 320 Ksi to about 570 Ksi when determined pursuant to the ASTM B 406 standard was also demonstrated for samples defined by at least 80 wt.% zinc-reclaimed carbide and 20 wt.% reclaimed non-sintered carbide, 70 wt.% zinc-reclaimed carbide and 30 wt.% reclaimed nonsintered carbide, 60 wt.% zinc-reclaimed carbide and 40 wt.% reclaimed non-sintered carbide, 50 wt.% zinc-reclaimed carbide and 50 wt.% reclaimed non-sintered carbide, and 45 wt.% zinc-reclaimed carbide and 55 wt.% reclaimed non-sintered carbide.

[0006] According to the ISO 3327-2009 standard, the transverse rupture strength (TRS-B) is caused by the highest stress the cemented carbide composition is subjected to prior to its moment of fracture in a transverse rupture strength test. The carbide phase of the cemented carbide composition may comprise or consist of tungsten carbide.

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Further, the cemented carbide composition may be devoid of electrochemically processed recycled material. As provided, the cemented carbide composition exhibits superior, or at least substantially equivalent hardness, fracture toughness and transverse rupture strength when compared to a reference material composed of 10 wt.% Co and 90 wt.% virgin WC or a carbide material comprising.

[0007] Also provided is a method of making a sintered cemented carbide article. The method may comprise or consist of providing a carbide composition comprising a carbide phase and a binder phase. The carbide phase may be present in an amount of at least 70 wt.% of the cemented carbide composition. The carbide phase may comprise or consist of about 45 wt.% to about 100 wt.% zinc-reclaimed carbide based on the total weight of the carbide phase. The binder phase may comprise or consist of a metallic binder. According to the methods provided, the carbide composition may be subjected to a milling operation to form a powder blend. The powder blend may be subjected to a forming operation to form a green body. The green body may be subjected to a sintering operation to form the sintered cemented carbide article. The resulting sintered cemented carbide article may have a transverse rupture strength (TRS-B) of at least about £3000 MPa as measured by the ISO 3327-2009 standard. Alternatively, the resulting cemented carbide may have a transverse rupture strength in a range of from about 320 Ksi to about 570 Ksi when determined according to the ASTM B 406 standard for a sample having 100 wt.% reclaimed non-sintered carbide. In some examples, the transverse rupture strength is in a range of from about 330 Ksi to about 540 Ksi when measured pursuant to the ASTM B 406 standard for a sample having 90 wt.% zinc-reclaimed carbide and 10 wt.% reclaimed non-sintered carbide. A transverse rupture strength range of from about 320 Ksi to about 570 Ksi when determined according to the ASTM B 406 standard was equally obtained for compositions identified by at least 80 wt.% zinc-reclaimed carbide and 20 wt.% reclaimed non-sintered carbide, 70 wt.% zinc-reclaimed carbide and 30 wt.% reclaimed non-sintered carbide, 60 wt.% zinc-reclaimed carbide and 40 wt.% reclaimed non-sintered carbide, 50 wt.% zinc-reclaimed carbide and 50 wt.% reclaimed nonsintered carbide, and 45 wt.% zinc-reclaimed carbide and 55 wt.% reclaimed non-sintered carbide.

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[0008] Further provided is, a cutting tool or a blank for a cutting tool. The cutting tool or blank for a cutting tool may comprise or consist of the carbide composition described herein above. The cutting tool or blank for a cutting tool may be manufactured as an article according to the method described herein above.

[0009] Other systems, methods, features and advantages will be, or will become, apparent to one with skill in the art upon examination of the following figures and detailed description. It is intended that all such additional systems, methods, features and advantages be included within this description, be within the scope of the present disclosure, and be protected by the following claims. Nothing in this section should be taken as a limitation on those claims. Further aspects and advantages are discussed below in conjunction with the embodiments of the disclosure. It is to be understood that both the foregoing general description and the following detailed description of the present disclosure are examples and explanatory and are intended to provide further explanation of the disclosure as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The accompanying drawings, which are included to provide a further understanding of the subject matter and are incorporated in and constitute a part of this specification, illustrate implementations of the subject matter and together with the description serve to explain the principles of the disclosure.

[0011] FIG. 1A is a graphical representation of the hardness HV30 and the fracture toughness Kic for a reference material composed of 10 wt.% Co and 90 wt.% virgin WC (upper round point denotes hardness HV30 and lower round point denotes fracture toughness Kt) and a material according to the present subject matter, i.e., including reclaimed non-sintered carbide material and the residual being zinc-reclaimed carbide used as a balance to reach a total of 100 wt.% (HV30, dotted graph and Kic, dashed graph).

[0012] FIG. 1B is a graphical representation of the transverse rupture strength TRS- B measured according to the ISO 3327-2009 standard for a reference material composed

4 HYPERION REF: H20057WO of 10 wt.% Co and 90 wt.% virgin WC (round point) and a material according to the present subject matter, i.e., including reclaimed non-sintered carbide material and the residual being zinc-reclaimed carbide used as a balance to reach a total of 100 wt.% (dashed graph).

DETAILED DESCRIPTION

[0013] Unless defined otherwise all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently described subject matter pertains.

[0014] Where a range of values is provided, for example, concentration ranges, percentage ranges, or ratio ranges, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the described subject matter. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also encompassed within the described subject matter, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the described subject matter.

[0015] The following definitions set forth the parameters of the described subject matter.

[0016] As used herein, “wt. %” refers to a given weight percent (i) of the total weight of a cemented carbide composition, (ii) of the total weight of a sintered article, (iii) of the total weight of a carbide phase, or (iv) of the total weight of a powder composition, unless specifically indicated otherwise. When “wt.%” is mentioned in the disclosure or in the claims, it will also explicitly be mentioned, whether it refers to a given weight percent of (i), (ii), (iii), or (iv) in each given scenario. The given wt.% refers to the weight percent of reclaimed non-sintered carbide, and zinc-reclaimed carbide, metallic binders, and/or

5 HYPERION REF: H20057WO grain growth inhibitors may be used as a balance to reach a total amount of 100 wt.% of (i), (ii), (iii), or (iv).

[0017] As used herein, the term "D50" refers to a particle size corresponding to 50% of the volume of the sampled particles being smaller than and 50% of the volume of the sampled particles being greater than the recited D50 value. Similarly, the term "D90" refers to a particle size corresponding to 90% of the volume of the sampled particles being smaller than and 10% of the volume of the sampled particles being greater than the recited D90 value. The term "D10" refers to a particle size corresponding to 10% of the volume of the sampled particles being smaller than and 90% of the volume of the sampled particles being greater than the recited D10 value. A width of the particle size distribution can be calculated by determining the span, which is defined by the equation (D90- D10)/D50. The span gives an indication of how far the 10 percent and the 90 percent points are apart normalized with the midpoint.

[0018] To determine mean particle sizes from a given particle size distribution, a skilled artisan would be readily familiar with the ISO 4499-2:2008 standard. The ISO 4499-2:2008 standard provides guidelines for the measurement of hardmetal grain size by metallographic techniques using optical or electron microscopy. It is intended for sintered WC/Co hardmetals containing primarily WC as the hard phase. It is also intended for measuring the grain size and distribution by a linear-intercept technique.

[0019] To further supplement the ISO 4499-2:2008 standard, a skilled artisan would equally know about the ASTM B390-92 (2006) standard. This standard is used for visual comparison and classification of the apparent grain size and distribution of cemented tungsten carbides that typically contain cobalt as a metallic binder in the binder phase.

[0020] Cemented carbide grades can be classified according to the carbide grain size. Different types of grades have been defined as nano, ultrafine, submicron, fine, medium, medium coarse, coarse and extra coarse. As used herein, the term (I) “nano grade” is defined as a material with a grain size of less than about 0.2 pm; (II) “ultrafine grade” is defined as a material with a grain size from about 0.2 pm to about 0.5 pm; (III)

6 HYPERION REF: H20057WO

“submicron grade” is defined as a material with a grain size from about 0.5 pm to about 0.9 pm; (IV) “fine grade” is defined as a material with a grain size from about 1.0 pm to about 1.3 pm; (V) “medium grade" is defined as a material with a grain size from about 1.4 pm to about 2.0 pm; (VI) “medium coarse grade” is defined as a material with a grain size from about 2.1 pm to about 3.4 pm; (VII) “coarse grade" is defined as a material with a grain size from about 3.5 pm to about 5.0 pm; and (VIII) “extra coarse grade” is defined as a material with a grain size greater than about 5.0 pm.

[0021] As used herein this disclosure, the term “about” is meant to mean plus or minus 5% of the numerical value of the number with which it is being used in the claims and herein this disclosure. Thus, “about” may be used to provide flexibility to a numerical range endpoint, in which, a given value may be “above” or “below” the given value. As such, for example a value of 50% may be intended to encompass a range, which may be defined by for example ranges like 47.5%-52.25%, 47.5%-52.5%, 47.75%-50%, 50%- 52.5%, 48%-48.5%, 48%-48.75%, 48%-49%, 48%-49.5%, 48%-49.75%, 48%-50%, 48%-50.25%, 48%-50.5%, 48%-50.75%, 48%-51%, 48%-51.5%, 48%-51.75%, 48%- 52%, 48%-52.25%, 48%-52.5%, 48.25%-48.5%, 48.25%-48.75%, 48.25%-49%, 48.25%- 49.5%, 48.25%-49.75%, 48.25%-50%, 48.25%-50.25%, 48.25%-50.5%, 48.25%- 50.75%, 48.25%-51%, 48.25%-51.25%, 48.25%-51.5%, 48.25%-51.75%, 48.25%-52%, 48.25%-52.25%, 48.25%-52.5%, 48.5%-48.75%, 48.5%-49%, 48.5%-49.5%, 48.5%- 49.75%, 48.5%-50%, 48.5%-50.25%, 48.5%-50.5%, 48.5%-50.75%, 48.5%-51%, 48.5%- 51.25%, 48.5%-51.5%, 48.5%-51.75%, 48.5%-52%, 48.5%-52.25%, 48.5%-52.5%, 49%- 49.25%, 49% -49.5%, 49%-49.75%, 49%-50%, 49%-50.25%, 49%-50.5%, 49%-50.75%, 49%-51%, 49%-51.25%, 49%-51.5%, 49%-51.75%, 49%-52%, 49%-52.25%, 49%- 52.5% 49.5%-49.75%, 49.5%-50%, 49.5%-50.25%, 49.5%-50.5%, 49.5%-50.75%, 49.5%-51%, 49.5%-51.5%, 49.5%-51.75%, 49.5%-52%, 49.5%-52.25%, 49.5%-52.5%, 49.75%-50%, 49.75%-50.25%, 49.75%-50.5%, 49.75%-50.75%, 49.75%-51%, 49.75%- 51.25%, 49.75%-51.5%, 49.75%-51.75%, 49.75%-52%, 49.75%-52.25%, 49.75%- 52.5%, 50%-50.25%, 50%-50.5%, 50%-50.75%, 50%-51%, 50%-51.25%, 50%-51.5%, 50%-52%, 50%-52.25%, 50%-52.5% etc.

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[0022] As used herein, the term “predominantly” is meant to encompass at least 95% of a given entity.

[0023] As used herein, the term “green body” refers to a pressed material in the form of compacted powder, or compacted plates before the material has been sintered.

[0024] As used herein, “reclaimed carbide material” means any carbide material that has been recycled or reclaimed according to any known method. Reclaimed carbide material includes zinc-reclaimed carbide and reclaimed non-sintered carbide, among others.

[0025] As used herein “zinc-reclaimed carbide” refers to carbide that is reclaimed after being subjected to a zinc-recycling or reclaiming method. For example, zinc- reclaiming of cemented carbide material includes a process using molten zinc. In this process, the cemented carbide material is mixed with zinc ingots in a tray and the mixture is subsequently heated in a furnace to liquefy the zinc. The liquefied zinc permeates the WC material reacting with the metallic binder in the carbide material. The zinc is then volatilized leaving behind a porous WC, which is ultimately crushed into a powder form.

[0026] As used herein, “reclaimed non-sintered carbide” refers to any non-sintered carbide material that is reclaimed or recovered. Reclaimed non-sintered carbide includes soft reused carbide material obtained from non-sintered previously used carbide powders, or from the remains of scrap from carbide pressing and green machining processes. Thus, a clear distinction between the zinc-reclaimed carbide and the reclaimed nonsintered carbide is that no chemical process is applied to obtain the soft reclaimed nonsintered carbide for reusage.

[0027] As used herein, the term “transverse rupture strength” is a material property defined as the stress in a material just before the material yields in a flexure test. The transverse bending test is most frequently employed, in which, a specimen having for example either a chamfered circular or a rectangular cross-section is bent until fracture or yielding using a three point flexural test technique. The transverse rupture strength

8 HYPERION REF: H20057WO represents the highest stress experienced within the material immediately prior to its moment of yield. It is measured in terms of stress.

[0028] As used herein, the term “virgin raw materials” generally refer to materials that have not been part of a previously sintered carbide composition, and nor have they been recycled, as opposed to the reclaimed carbide material.

[0029] As used herein, the term “Palmqvist fracture toughness” i.e. Kt, refers to the ability of a material with pre-cracks to resist further fracture propagation upon absorbing energy.

[0030] As used herein, the term “HV30 Vickers hardness” (i.e. applying a 30 kgf load) is a measure of the resistance to localized plastic deformation, which is obtained by indenting the sample with a Vickers tip at 30 kgf.

[0031] As used herein, the ISO 28079-2009 standard specifies a method for measuring the fracture toughness and the hardness of hardmetals, cermets and cemented carbides at room temperature by an indentation method. The ISO 28079-2009 standard applies to a measurement of the fracture toughness and hardness calculated by using the diagonal lengths of indentations and cracks emanating from the corners of a Vickers hardness indentation, and it is intended for use with metal-bonded carbides and carbonitrides (e g. hardmetals, cermets or cemented carbides). The test procedures proposed in the ISO 28079-2009 standard are intended for use at ambient temperatures but can be extended to higher or lower temperatures by agreement. The test procedures proposed in the ISO 28079-2009 standard are also intended for use in a normal laboratory-air environment. They are typically not intended for use in corrosive environments, such as strong acids or seawater. The ISO 28079-2009 standard is directly comparable to the standard ASTM B771 as disclosed for example in “Comprehensive Hard Materials book”, 2014, Elsevier Ltd. Page 312, which is incorporated herein by reference in its entirety. Thus, it can be assumed that the measured fracture toughness and the hardness using the ISO 28079-2009 standard will be the same as the measured values employing the ASTM B771 standard.

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[0032] As used herein, the ISO 3327-2009 standard specifies a method, known as a transverse rupture strength test, for the determination of the transverse rupture strength of hardmetals. The method is performed by placing a specimen of a specified length with a circular or a chamfered rectangular cross section on two supports and loaded centrally until fracture happens. Transverse rupture strength is taken as the mean of several observed values. Transverse rupture strength also known as “modulus of rupture”, “bend strength", or “flexural strength" is a material property defined as the stress in a material just before the material yields or fractures in a transverse rupture strength test. Thus, the transverse rupture strength represents the highest stress experienced within the material immediately prior to its moment of yield. This method is applicable to hardmetals of negligible ductility. If it is used for hardmetals showing significant plastic deformation before breaking, incorrect results may be obtained. In such cases, the method may be used for comparison purposes only. In general, type B test pieces result in strength values, which are approximately 10% to 20% higher than those obtained using type A test pieces, depending on the material tested and provided that they have the same surface conditions. The repeatability is similar for all types of test piece. Type C test pieces result in strength values, which are about 5% to 10% higher than type B specimens, whereas the increase of the strength-values are material-related.

[0033] As used herein, the ASTM B 406 standard specifies a method for determining the transverse rupture strength of cemented carbides, where the cemented carbide specimen is ground to the following specific dimensions: 0.200 +/- 0.010 inches (5.00 +/- 0.25 mm) of thickness, 0.250 +/- 0.010 inches (6.25 +/- 0.25 mm) of wideness, and 0.750 inches (19.0 mm) of length. The load is applied in a three-point fixture including: (i) two ground-cemented-carbide cylinders 0.250 +/- 0.001 inches (6.35 +/- 0.02 mm) in diameter, at least 0.500 inches (13 mm) in length with the long axes parallel, and center to center spacing of 0.563 +/- 0.005 inches (14.3 +/- 0.1 mm), and (ii) a movable member (i.e. free to move substantially only in a line perpendicular to the plane established by the axes of the two cylinders) having a cemented-tungsten-carbide ball with the dimensions 0.4 +/- 0.05 inches (10 +/- 1.3 mm), or a ground-cemented-carbide cylinder with the same dimensions as, and with an axis parallel to, those of the previously mentioned cylinders.

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[0034] As used herein, the term “Weibull modulus” refers to a dimensionless parameter of the Weibull distribution, which is used to describe the variability of the measured transverse rupture strength of cemented carbide materials.

[0035] As used herein, the term “superabrasive ultrahard material” or simply interchangeably used term “superabrasive material” refers to a material as found in, but not limited to, single crystal diamond, polycrystalline diamond (PCD), thermally stable polycrystalline diamond (PCD), chemical vapor deposition (CVD) diamond, metal matrix diamond composites, ceramic matrix diamond composites, nanodiamond, cubic boron nitride (cBN), polycrystalline cubic boron nitride (PCBN), or combinations of superabrasive or other superabrasive material used in superabrasive cutting elements.

[0036] As used herein, “physical vapor deposition (PVD)” describes a variety of vacuum deposition methods, which can be used to produce thin films and coatings. PVD is characterized by a process, in which, the material that is deposited goes from a condensed phase to a vapor phase and then back to a thin film condensed phase. The most common PVD processes are sputtering and evaporation.

[0037] As used herein, “chemical vapor deposition (CVD)” refers to a method, where the substrate (i.e. cemented carbide composition or cemented carbide article) is exposed to one or more volatile precursors, which react and/or decompose on the substrate surface to produce the desired deposit. Frequently, volatile by-products are also produced, which are removed by gas flow through a reaction chamber.

[0038] As used herein, the term “substantially” refers to the complete or nearly complete extent or degree of an action, characteristic, property, state, structure, item, or result.

[0039] Wherever used throughout the disclosure, the term “generally” has the meaning of “approximately”, “typically” or “closely” or “within the vicinity or range of.

[0040] As used herein, “spherical” refers to the grains having a substantially “round” shape.

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[0041] The current disclosure stems from the notion of demonstrating surprising and novel and inventive solutions over the prior art, in part, by producing cemented carbide compositions comprising (i) zinc-reclaimed carbide and (ii) reclaimed nonsintered carbide. The cemented carbide composition is devoid of any electrochemically- processed recycled material. This advantageously affords improved, or at the very least equivalent hardness, fracture toughness, and transverse rupture strength mechanical properties, when compared to cemented carbides used as a reference material including only virgin raw materials. Consequently, an advantageous improvement is thereby obtained over the prior known solutions due to the elimination of a cumbersome electrochemical recycling process-step.

[0042] In one aspect, provided is a cemented carbide composition including a carbide phase (or carbide material) that may generally include reclaimed carbide material in an amount of greater than 70 wt.% of the cemented carbide composition. The carbide phase may alternatively be present in an amount of greater than 75 wt.% of the cemented carbide composition, greater than 80 wt.% of the cemented carbide composition, greater than 85 wt.% of the cemented carbide composition, greater than 89 wt.% of the cemented carbide composition, greater than 90 wt.% of the cemented carbide composition, greater than 95 wt.% of the cemented carbide composition, from about 70 wt.% to about 95 wt.% of the cemented carbide composition, from about 70 wt.% to about 90 wt.% of the cemented carbide composition, from about 75 wt.% to about 95 wt.% of the cemented carbide composition, from about 70 wt.% to about 95 wt.% of the cemented carbide composition, from about 80 wt.% to about 95 wt.% of the cemented carbide composition, from about 80 wt.% to about 90 wt.% of the cemented carbide composition, from about 85 wt.% to about 95 wt.% of the cemented carbide composition, or from about 85 wt.% to about 90 wt.% of the cemented carbide composition.

[0043] The carbide phase may comprise or consist of zinc-reclaimed carbide, reclaimed non-sintered carbide, virgin carbide, ammonium paratungstate-processed sintered carbide scrap, among other carbide materials.

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[0044] Zinc-reclaimed carbide material may be present in the carbide phase in an amount of from about 45 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 100 wt.% based

13 HYPERION REF: H20057WO on the weight of the carbide phase, from about 70 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 80 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 80 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 80 wt.% to about 90 wt.% based on the weight of the carbide phase, or from about 80 wt.% to about 85 wt.% based on the weight of the carbide phase.

[0045] Reclaimed non-sintered carbide material may be present in the carbide phase in an amount of from about 0 wt.% to about 5 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 10 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 30 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 40 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 45 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 10 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 30 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 40wt.% based on the weight of the carbide phase, from about 5 wt.% to about 45 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 30 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 40 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 45 wt.% based

14 HYPERION REF: H20057WO on the weight of the carbide phase, 15 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 30 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 40 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 45 wt.% based on the weight of the carbide phase. Alternatively, the reclaimed non-sintered carbide may be present in any amount of the carbide phase up to 100%.

[0046] The cemented carbide compositions disclosed herein exhibits a transverse rupture strength (TRS-B) determined pursuant to the ISO 3327-2009 standard of at least about £3000 MPa. Further, the cemented carbide composition may not comprise electrochemically processed recycled material. Alternatively, the resulting cemented carbide may have a transverse rupture strength in a range of from about 320 Ksi to about 570 Ksi when determined pursuant to the ASTM B 406 standard for a sample having 100 wt.% reclaimed non-sintered carbide. In some examples, the transverse rupture strength is in a range of from about 330 Ksi to about 540 Ksi when measured pursuant to the ASTM B 406 standard for a sample having 90 wt.% zinc-reclaimed carbide and 10 wt.% reclaimed non-sintered carbide. A transverse rupture strength range of from about 320 Ksi to about 570 Ksi when determined pursuant to the ASTM B 406 standard was further demonstrated for compositions defined by 80 wt.% zinc-reclaimed carbide and 20 wt.% reclaimed non-sintered carbide, 70 wt.% zinc-reclaimed carbide and 30 wt.% reclaimed non-sintered carbide, 60 wt.% zinc-reclaimed carbide and 40 wt.% reclaimed nonsintered carbide, 50 wt.% zinc-reclaimed carbide and 50 wt.% reclaimed non-sintered carbide, and 45 wt.% zinc-reclaimed carbide and 55 wt.% reclaimed non-sintered carbide.

[0047] As provided, the cemented carbide compositions comprising reclaimed carbide materials as described herein exhibit superior mechanical properties, or to a bare minimum, properties that are substantially alike virgin carbide. Accordingly, significant flexibility exists to combine the reclaimed non-sintered carbide and the zinc-reclaimed carbide with fresh metallic binders, grain growth inhibitors, organic binder(s) and other components to provide new powder compositions for production of cemented carbide parts.

15 HYPERION REF: H20057WO

[0048] For example, the reclaimed non-sintered carbide and the zinc-reclaimed carbide may typically comprise or consist of tungsten carbide as the carbide material. Alternatively, the reclaimed non-sintered carbide and the zinc-reclaimed carbide may include tungsten carbide and at least one or more metal carbides, borides, nitrides or carbonitrides, whose metal is selected from the group consisting of Group IVB, Group VB, and Group VIB of the periodic table.

[0049] The reclaimed non-sintered carbide and the zinc-reclaimed carbide may exhibit any average particle size that is not inconsistent and incompatible with the objectives of the present disclosure. Generally, the reclaimed non-sintered carbide and the zinc-reclaimed carbide of the cemented carbide composition may typically have an average particle size ranging for example from 0.5 pm to 30 pm. In certain particular embodiments, the reclaimed non-sintered carbide and the zinc-reclaimed carbide of the cemented carbide composition may have an average particle size in the range of from 1 pm to 5 pm, from 1 pm to 10 pm, from 1 pm to 15 pm, from 1 pm to 20 pm, from 1 pm to 25 pm, from 1 pm to 30 pm, from 5 pm to 10 pm, from 10 pm to 15 pm, from 5 pm to 15 pm, from 15 pm to 20 pm, from 5 pm to 20 pm, from 20 pm to 25 pm, from 5 pm to 25 pm, from 25 pm to 30 pm, or from 5 pm to 30 pm.

[0050] For determining a particle size, one having ordinary skill in the art may typically employ either dynamic digital image analysis (DIA), static laser light scattering (SLS) also known as laser diffraction, or by visual measurement by electron microscopy, a technique known as image analysis and light obscuration. Each method covers a characteristic size range within which measurement is possible. These ranges partly overlap. However, the results for measuring the same sample may vary all depending on the particular method that is used. A skilled artisan who wants to determine particle sizes or particle size distributions would readily know how each mentioned method is commonly performed and practiced. Thus, the reader is directed to for example, (i) “Comparison of Methods. Dynamic Digital Image Analysis, Laser Diffraction, Sieve Analysis”, Retsch Technology and (ii) the scientific publication by Kelly et a/., “Graphical comparison of image analysis and laser diffraction particle size analysis data obtained from the measurements of nonspherical particle systems”, AAPS PharmSciTech. 2006 Aug 18; Vol.7(3):69, to

16 HYPERION REF: H20057WO further gain insight into each procedure and methodology, all of which documents, are incorporated herein by reference in their entirety.

[0051] A desired particle size of the cemented carbide and the cermet powders can be produced by subjecting the cemented carbide and cermet powders to a milling operation for several hours (e.g. 8, 16, 32, 64 hours) under ambient conditions (i.e. 25° C, 298.15 K and a pressure of 101.325 kPa in a ball mill or an attritor mill) with metallic binders) in the production of the powders. As would be apparent to a skilled artisan, the milling is made by first adding a milling liquid to the powder to form a milling powder slurry composition. The milling liquid may be water, an alcohol such as but not limited to ethanol, methanol, isopropanol, butanol, cyclohexanol, an organic solvent in the likes of for example acetone or toluene, an alcohol mixture, an alcohol and a solvent mixture or like constituents. The properties of the milling powder slurry composition are dependent on, among other things, the amount of the milling liquid that is added. Because the drying of the milling powder slurry composition requires energy, the amount of the used milling liquid should preferably be minimized to keep costs down. However, enough milling liquid needs to be added to achieve a pumpable milling powder slurry composition and to avoid clogging of the system. Moreover, other compounds commonly known in the art to a skilled artisan can be added to the slurry e.g. dispersion agents, pH-adjusters, etc. An organic binders), such as e.g. polyethylene glycol (PEG), paraffin, polyvinyl alcohol (PVA), long chain fatty acids, wax, or any combination thereof or like components may be added to the milling powder slurry composition prior to the milling typically from for example 15 vol. % to 25 vol. % of the total volume of the formed slurry to facilitate the formation of a cemented carbide phase and a metallic binder phase powder blend during the milling operation, and additionally to act as a pressing agent, and lasty to allow easy handling of the formed green article in the following pressing/forming steps described below in paragraph If [0056],

[0052] The main purpose of the milling operation is to facilitate a good metallic binder distribution and a good wettability between the hard cemented carbide constituent grains and the metallic binder powder to strengthen the physical integrity of the milled powder slurry composition, and in some cases, to deagglomerate tungsten carbide (WC) crystals.

17 HYPERION REF: H20057WO

[0053] An acceptable metallic binder distribution and a good quality of wettability are fundamental and essential parameters for obtaining cemented carbide materials of stellar physical quality. On the other hand, if the metallic binder distribution or wettability is of a rather poor nature, pores and cracks may undesirably be formed as a result of this in the final sintered cemented carbide body, which is detrimental to the produced cemented carbide.

[0054] The milled powder slurry composition can be conveniently spray-dried, freeze-dried or vacuum-dried and granulated to provide free-flowing powder aggregates of various shape including for example a spherical shape. Alternatively, the milled powder slurry composition can be vacuum-dried to provide powder suitable for isostatic compaction when forming green bodies. In some instances, the reclaimed carbide material can be crushed or otherwise comminuted prior to milling with the metallic binder(s).

[0055] In the case of spray drying, the milled powder slurry composition containing the powdered materials mixed with the organic liquid, and the organic binder(s) may be atomized through an appropriate nozzle in a drying tower, where the small drops are instantaneously dried by a stream of hot gas, for instance in a stream of nitrogen, to form spherical powder agglomerates displaying non-restricted flow properties.

[0056] The powder is formed or consolidated into a green article or body in the preparation for the sintering procedure. A green body is formed of the powder blend using conventional techniques such as cold tool pressing technology including multi axial pressing, extruding or metal injection molding, cold isostatic pressing, pill pressing, tape casting and other methods known in the powder metallurgy art. Any consolidation method can be utilized that is not inconsistent with the objectives of the present subject matter. Forming yields a green density and/or strength that permits easy handling and green machining of the powder agglomerates due to the processed material being in the form of a compacted powder. In one example of the present disclosure, the forming is done by a pressing operation. Here, the pressing may be conducted by a uniaxial pressing operation at a force commonly used from 5 ton to 40 ton.

18 HYPERION REF: H20057WO

[0057] The green bodies may be subjected to a pre-sintering temperature elevation procedure, to completely remove the organic binder(s). This may be done in the same apparatus when executing the sintering process further described hereinbelow in paragraph If [0058], Suitable temperatures for the removal of the organic binder(s) may be employed from 200°C to 450°C, from 200°C to 500°C, from 200°C to 600°C, from 250°C to 450°C, from 250°C to 500°C, from 250°C to 600°C, from 300°C to 450°C, from 300°C to 500°C, or from 300°C to 600°C under typically a reactive H2 atmosphere generally with a H2 flow rate from 1000 L/Hour to 10000 L/Hour by customarily increasing the temperature at a rate of for example approximately 0.70°C/min. In some examples, after the organic binder(s) removal, the temperature is increased at a rate of about 2°C/min. to about 10°C/min., or at a rate of about 2°C/min. to about 5°C/min. up to a desired pre-sintering temperature. The temperature may be maintained for 1 minute to 90 minutes until the entire change of bodies in the sintering furnace has reached the desired temperature, and the desired phase-transformation has been completed (i.e. removal of the organic binders). In general, the pre-sintering step may be conducted in vacuum, or in a reactive (H2), or a non-reactive atmosphere e.g. nitrogen (N2), argon (Ar).

[0058] The pre-sintered and debinded green bodies subsequently undergo a consolidation process to ultimately form the sintered end-material. This may usually be performed typically using a pressure from 50 kbar to 75 kbar, from 50 kbar to 80 kbar, from 50 kbar to 85 kbar, from 50 kbar to 90 kbar, from 60 kbar to 75 kbar, from 60 kbar to 80 kbar, from 60 kbar to 85 kbar, from 60 kbar to 90 kbar, from 70 kbar to 75 kbar, from 70 kbar to 80 kbar, from 70 kbar to 85 kbar, or from 70 kbar to 90 kbar. Depending however on the composition, this pressure-range might be lowered to a range from 35 kbar to 60 kbar at a temperature range from 1300°C to 1500°C, from 1300°C to 1600°C, from 1300°C to 1700°C, from 1300°C to 1800°C, from 1400°C to 1500°C, from 1400°C to 1600°C, from 1400°C to 1700°C, from 1400°C to 1800°C, from 1500°C to 1600°C, from 1500°C to 1700°C, or from 1500°C to 1800°C, with a dwell time employed at a maximum temperature, which is typically from 1 minute and 60 minutes.

[0059] The green bodies can either be subjected to vacuum sintering or sintering under an argon (Ar) or hydrogen atmosphere. During vacuum sintering, the green body

19 HYPERION REF: H20057WO is placed in a vacuum furnace and sintered at temperatures of generally about 1300°C to 1500°C, 1300°C to 1600°C, 1300°C to 1700°C, 1300°C to 1800°C, 1400°C to 1500°C, 1400°C to 1600°C, 1400°C to 1700°C, 1400°C to 1800°C, 1500°C to 1600°C, 1500°C to 1700°C, or 1500°C to 1800°C. In some examples, hot isostatic pressing (HIP) may be added to the vacuum sintering process. Hot isostatic pressing (HIP) can be administered as a post-sintering operation, or even during vacuum sintering thereby yielding a sinter- HIP process. The resulting sintered cemented carbide article can exhibit fracture hardness, fracture toughness and transverse rupture strength values as described herein this disclosure.

[0060] The reclaimed carbide material of the cemented carbide composition may, as described previously, consist of zinc-reclaimed carbide. For example, the zinc- reclaimed carbide may be the sole species of the recycled powder component. Alternatively, the reclaimed carbide material may include sintered zinc-reclaimed carbide and sintered cemented carbide processed by one or more different and additional recycling methods, such as but not limited to a cold-stream process, an alkali-leach process, chlorination systems, and high-temperature smelting. The sintered zinc- reclaimed carbide may be mixed with other recycled sintered cemented carbide materials in any amount that is not inconsistent and incompatible with the objectives of the present subject matter. The amount of sintered zinc-reclaimed carbide material in the recycled carbide powder component can be selected according to several considerations including the desired mechanical and chemical properties of articles formed from the powder.

[0061] The cemented carbide composition may alternatively in some cases also additionally include a virgin carbide component with the purpose of further improving its mechanical properties. The virgin carbide component may include carbides, borides, nitrides and/or carbonitrides of one or more metals selected from Groups IVB, VB and VIB of the periodic table. In being virgin, the metal carbides, borides, nitrides and/or carbonitrides have not previously been part of a sintered carbide composition, and nor have they been recycled. In some examples, the virgin carbide component may include at least one of tungsten carbide, tantalum carbide, niobium carbide, vanadium carbide, chromium carbide, zirconium carbide, hafnium carbide, or titanium carbide or any

20 HYPERION REF: H20057WO combinations thereof. The virgin carbide component can be present in the powder composition in any amount that is not inconsistent and incompatible with the objectives of the present subject matter. The amount of the virgin carbide component can be selected according to several considerations including, but not limited to, desired mechanical and chemical properties of sintered articles formed of the powder and specific compositional identity of the recycled carbide powder component. The virgin carbide component may typically be present in an amount of 0.05 wt.%-20 wt.% based on the weight of the carbide phase, such as for example 0.1 wt.%-5 wt.%, 0.1 wt.%-7 wt.%, 0.1 wt.%-10 wt.%, 0.1 wt.%-12 wt.%, 0.1 wt.%-15 wt.%, 0.1 wt.%-17 wt.%, or 0.1 wt.%-20 wt.% based on the weight of the carbide phase.

[0062] The cemented carbide composition may also include at least one or more metallic binders and grain growth inhibitors. Non-limiting examples of grain growth inhibitors include carbides like vanadium carbide (VC), chromium carbide (CrsCa). tantalum carbide (TaC), titanium carbide (TiC), zirconium carbide (ZrC) and niobium carbide (NbC). The metallic binder can include one or more transition metals of Group VI I IB of the periodic table. In certain particular embodiments, the metallic binder may be a cobalt, or a cobalt-based alloy. Powder cobalt-based alloy binder, in some particular embodiments, may include a cobalt-transition metal alloy. For example, transition metals of the binder alloy can appropriately be selected from the group consisting of molybdenum, ruthenium, rhenium, rhodium, platinum, palladium, manganese, copper, iron, nickel, or combinations thereof. In certain other embodiments, the powder cobaltbased metallic binder may equally well include a metalloid like silicon, and/or aluminum.

[0063] The metallic binder can be present in the cemented carbide composition in any amount that is not inconsistent and incompatible with the objectives of the present subject matter. The metallic binder may generally be present in an amount of 1 wt.% to 30 wt.% of the total weight of the cemented carbide powder composition. In some examples, the metallic binder may be present in an amount of 1 wt.% to 3 wt.% of the total weight of the cemented carbide powder composition. In other examples, the metallic binder can be present in an amount of 1 wt.% to 5 wt.% of the total weight of the cemented carbide powder composition. In yet other examples, the metallic binder may be present

21 HYPERION REF: H20057WO in an amount of 1 wt.% to 7 wt.% of the total weight of the cemented carbide powder composition. In still other examples, the metallic binder may be present in an amount of 1 wt.% to 10 wt.% of the total weight of the cemented carbide powder composition. In further examples, the metallic binder may be present in an amount of 1 wt.% to 15 wt.% of the total weight of the cemented carbide powder composition. In further other examples, the metallic binder may be present in an amount of 1 wt.% to 20 wt.% of the total weight of the cemented carbide powder composition. In other embodiments, the metallic binder may be present in an amount of 1 wt.% to 25 wt.% of the total weight of the cemented carbide powder composition. In still other embodiments, the metallic binder may be present in an amount of 1 wt.% to 27 wt.% of the total weight of the cemented carbide powder composition. In certain particular embodiments, the metallic binder and the grain growth inhibitor may be present in an amount of 1 wt.% to 2 wt.%, 2 wt.% to 5 wt.%, 5 wt.% to 7 wt.%, 3 wt.% to 7 wt.%, or 7 wt.% to 10 wt.%, 10.1 wt%.,10.2 wt.%, 10.3 wt.%, 10.4 wt.%, 10.5 wt.%, 10.6 wt.%, 10.7 wt.%, 10.8 wt.%, or 10.9 wt.% of the total weight of the cemented carbide powder composition. The metallic binder coats carbide components of the cemented carbide composition including individual particles of the reclaimed carbide components and virgin carbide component, if present.

[0064] In the case of a sintered cemented carbide article, such sintered cemented carbide article may be produced from a powder of a cemented carbide composition including a carbide phase (or carbide material) that may generally include reclaimed carbide material in an amount of greater than 70 wt.% of the sintered cemented carbide article. The carbide phase may alternatively be present in an amount of greater than 75 wt.% of the sintered cemented carbide article, greater than 80 wt.% of the sintered cemented carbide article, greater than 85 wt.% of the sintered cemented carbide article, greater than 89 wt.% of the sintered cemented carbide article, greater than 90 wt.% of the sintered cemented carbide article, greater than 95 wt.% of the sintered cemented carbide article, from about 70 wt.% to about 95 wt.% of the sintered cemented carbide article, from about 70 wt.% to about 90 wt.% of the sintered cemented carbide article, from about 75 wt.% to about 95 wt.% of the sintered cemented carbide article, from about 70 wt.% to about 95 wt.% of the sintered cemented carbide article, from about 80 wt.% to about 95 wt.% of the sintered cemented carbide article, from about 80 wt.% to about 90 wt.% of

22 HYPERION REF: H20057WO the sintered cemented carbide article, from about 85 wt.% to about 95 wt.% of the sintered cemented carbide article, or from about 85 wt.% to about 90 wt.% of the sintered cemented carbide article.

[0065] The carbide phase may comprise or consist of zinc-reclaimed carbide, reclaimed non-sintered carbide, virgin carbide, ammonium paratungstate-processed sintered carbide scrap, among other carbide materials.

[0066] Zinc-reclaimed carbide material may be present in the carbide phase in an amount of from about 45 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 45 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 50 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 55 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 100 wt.% based on the weight of the carbide

23 HYPERION REF: H20057WO phase, from about 60 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 70 wt.% based on the weight of the carbide phase, from about 60 wt.% to about 65 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 70 wt.% to about 75 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 90 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 85 wt.% based on the weight of the carbide phase, from about 75 wt.% to about 80 wt.% based on the weight of the carbide phase, from about 80 wt.% to about 100 wt.% based on the weight of the carbide phase, from about 80 wt.% to about 95 wt.% based on the weight of the carbide phase, from about 80 wt.% to about 90 wt.% based on the weight of the carbide phase, or from about 80 wt.% to about 85 wt.% based on the weight of the carbide phase.

[0067] Reclaimed non-sintered carbide material may be present in the carbide phase in an amount of from about 0 wt.% to about 5 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 10 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 30 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 0 wt.% to about 40wt.% based on the weight of the carbide phase, from about 0 wt.% to about 45 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 10 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 30 wt.% based on the weight of the

24 HYPERION REF: H20057WO carbide phase, from about 5 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 5 wt.% to about 40wt.% based on the weight of the carbide phase, from about 5 wt.% to about 45 wt.% based on the weight of the carbide phase, 10 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 30 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 10 wt.% to about 40wt.% based on the weight of the carbide phase, from about 10 wt.% to about 45 wt.% based on the weight of the carbide phase, 15 wt.% to about 20 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 30 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 35 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 40 wt.% based on the weight of the carbide phase, from about 15 wt.% to about 45 wt.% based on the weight of the carbide phase. Alternatively, the reclaimed non-sintered carbide may be present in any amount of the carbide phase up to 100%.

[0068] Additionally, the reclaimed non-sintered carbide and the zinc-reclaimed carbide of the cemented carbide article may exhibit any average particle size that is not inconsistent and incompatible with the objectives of the present disclosure. Generally, the reclaimed non-sintered carbide and the zinc-reclaimed carbide of the cemented carbide article may typically have an average particle size ranging for example from 0.5 pm to 30 pm. In certain particular embodiments, the reclaimed non-sintered carbide and the zinc-reclaimed carbide of the cemented carbide article may have an average particle size in the range from 1 pm to 5 pm, from 1 pm to 10 pm, from 1 pm to 15 pm, from 1 pm to 20 pm, from 1 pm to 25 pm, from 1 pm to 30 pm, from 5 pm to 10 pm, from 10 pm to 15 pm, from 5 pm to 15 pm, from 15 pm to 20 pm, from 5 pm to 20 pm, from 20 pm to 25 pm, from 5 pm to 25 pm, from 25 pm to 30 pm, or from 5 pm to 30 pm.

[0069] As previously described, for determining the particle size, one having ordinary skill in the art may typically employ methodologies like either dynamic digital image analysis (DIA), static laser light scattering (SLS), or by visual measurement by electron microscopy.

25 HYPERION REF: H20057WO

[0070] The sintered cemented carbide articles employing recycled carbide powders described herein exhibit superior mechanical properties, or to a bare minimum, are substantially comparable to sintered articles formed solely from virgin carbide powder compositions, particularly in which, the sintered cemented article has a transverse rupture strength (TRS-B) of at least about £3000 MPa measured according to the ISO 3327-2009 standard. Alternatively, the resulting cemented carbide may have a transverse rupture strength in a range of from about 320 Ksi to about 570 Ksi when determined pursuant to the ASTM B 406 standard for a sample having 100 wt.% reclaimed non-sintered carbide. In some examples, the transverse rupture strength is in a range of from about 330 Ksi to about 540 Ksi when measured pursuant to the ASTM B 406 standard for a sample having 90 wt.% zinc-reclaimed carbide and 10 wt.% reclaimed non-sintered carbide. A transverse rupture strength range of from about 320 Ksi to about 570 Ksi when determined pursuant to the ASTM B 406 standard was also achieved for compositions identified by at least 80 wt.% zinc-reclaimed carbide and 20 wt.% reclaimed non-sintered carbide, 70 wt.% zinc-reclaimed carbide and 30 wt.% reclaimed non-sintered carbide, 60 wt.% zinc-reclaimed carbide and 40 wt.% reclaimed non-sintered carbide, 50 wt.% zinc- reclaimed carbide and 50 wt.% reclaimed non-sintered carbide, and 45 wt.% zinc- reclaimed carbide and 55 wt.% reclaimed non-sintered carbide.

[0071] Moreover, the sintered cemented carbide articles may display a high-density material for example ranging from 11 g/cm³-15 g/cm³, 12 g/cm³-15 g/cm³, 13 g/cm³-15 g/cm³, or from 14 g/cm³-15 g/cm³. Moreover, sintered cemented carbide articles described herein can be free, or substantially free of lower carbide materials, including eta material [(CoW)C], W2C and/or W3C. In some embodiments, the sintered cemented carbide articles described herein may be free of at least one of A-type porosity and B- type porosity. Moreover, in particular embodiments, the sintered cemented carbide articles described herein may further be free of free graphite (C-type porosity).

[0072] The sintered cemented carbide articles and cemented carbide compositions described herein can advantageously be incorporated as cutting elements or otherwise as components of cutting elements for various applications. In some embodiments, the sintered cemented carbide articles and cemented carbide compositions may include

26 HYPERION REF: H20057WO cutting inserts for machining of metals and/or metal alloys. In other embodiments, the sintered cemented carbide articles and cemented carbide compositions may include interrupted cutting tooling such as drills, end mills and/or milling inserts.

[0073] Moreover, the sintered cemented carbide articles described herein can be combined with what is known in the art as superabrasive ultrahard materials including but not limited to single crystal diamond, polycrystalline diamond (PCD), thermally stable polycrystalline diamond (PCD), chemical vapor deposition (CVD) diamond, metal matrix diamond composites, ceramic matrix diamond composites, nanodiamond, cubic boron nitride (cBN), polycrystalline cubic boron nitride (PCBN). For example, the sintered cemented carbide articles described herein this disclosure can structurally serve as an anchoring substrate or a support body to achieve improved functionality, to which, the superabrasive material is sintered in a high temperature and high pressure (HTHP) process.

[0074] In such a scenario, the layer of the superabrasive ultrahard material can in turn provide enhanced wear resistance leading to increased lifetimes of cutting elements and/or wear parts employing the sintered cemented carbide compositions making up the cemented carbide articles described herein. In some particular embodiments, the sintered cemented carbide articles may be used for manufacturing of drilling, rotary or cutting tools, as a wear part e.g. wire drawing die, or in earth boring and mining apparatus incorporating earth boring bodies, drill bits and cutters.

[0075] The sintered cemented carbide articles or cemented carbide powder compositions having the unique mechanical properties described herein, may be coated with one or more refractory materials. As used herein, refractory materials refer to materials that are resistant to decomposition by heat, pressure or chemical attack. The coating may be done by physical vapor deposition (PVD), or by chemical vapor deposition (CVD) selected from aluminum and metallic elements of Groups IVB, VB and VIB of the periodic table and one or more elements selected from Groups I HA, IVA, VA and VIA of the periodic table. For example, the refractory coating can include one or more carbides, nitrides, carbonitrides, oxides or borides of one or more metallic elements selected from

27 HYPERION REF: H20057WO aluminum and Groups IVB, VB and VIB of the periodic table. Moreover, the coating can suitably be a single-layer coating or a multi-layer coating. When a refractory material is used, it may be present in a weight of up to 10 wt.%. In some examples, the refractory material is present from 1 wt.% to 2 wt.%, from 1 wt.% to 3 wt.%, from 1 wt.% to 4 wt.%, from 3 wt.% to 4 wt.%, from 3 wt.% to 5 wt.%, from 3 wt.% to 6 wt.%, from 5 wt.% to 6 wt.%, from 5 wt.% to? wt.%, from 5 wt.% to 8 wt.% or from 5 wt.% to 10wt.%.

EXAMPLE

[0076] The following example is put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how to make and use the described subject matter and is not intended to limit the scope of what the inventors regard as their disclosure nor is it intended to represent that the experiments below are all or the only experiments performed. Efforts have been made to ensure accuracy with respect to numbers used but some experimental errors and deviations should be accounted for. Unless indicated otherwise, parts are by weight, molecular weight is weight average molecular weight, temperature is in degrees Centigrade, and pressure is at or near atmospheric.

EXAMPLE 1

[0077] RECLAIMED CARBIDE MATERIAL COMPOSED OF A COMBINED ZINC- RECLAIMED CARBIDE AND/OR A RECLAIMED NON-SINTERED CARBIDE EXHIBITS SUPERIOR HARDNESS, FRACTURE TOUGHNESS AND TRANSVERSE RUPTURE STRENGTH MECHANICAL PROPERTIES WHEN COMPARED TO CEMENTED CARBIDES INCLUDING ONLY VIRGIN RAW MATERIALS

[0078] A cemented carbide composition was prepared according to the subject matter described herein. The cemented carbide composition includes at least 70 wt.% reclaimed carbide material, of which, from 45 wt.% to 100 wt.% is zinc-reclaimed carbide. A reference comparative composition constituted of 10 wt.% Co and 90 wt.% virgin WC was also prepared. As shown in FIGS. 1A and 1B, the cemented carbide composition according to the present subject matter surprisingly exhibits superior, or at the very least,

28 HYPERION REF: H20057WO substantially equivalent hardness and fracture toughness characteristics when compared to the reference cemented carbide (i.e. round points).

[0079] FIGS. 1A and 1B display the mechanical properties measured for (I) the reference material composed of 10 wt.% Co and 90 wt.% virgin WC and (II) the materials in accordance with the embodiments of the present subject matter, which are composed of at least 70 wt.% reclaimed carbide material composed of a combined zinc-reclaimed carbide and reclaimed non-sintered carbide.

[0080] A zinc-reclaimed carbide was mixed as a combination with a reclaimed non- sintered carbide in an amount ranging from 0 wt.% to 50 wt.% of the total weight of the cemented carbide composition. Hardness (i.e. HV30) and fracture toughness (i.e. Kic) (FIG. 1A) were measured according to the ISO 28079-2009 standard. Transverse rupture strength TRS-A (FIG. 1B) was measured according to the ISO 3327-2009 standard and subsequently converted to transverse rupture strength TRS-B values by applying a multiplication factor of 1.15 as described in paragraph If [0032] of this disclosure.

[0081] In FIGS. 1A and 1B, the X-axis depicts the wt.% combined composition of the zinc-reclaimed carbide and the reclaimed non-sintered carbide (i.e. depicts reclaimed non-sintered carbide and the residual being zinc-reclaimed carbide used as a balance to reach a total of 100 wt.%), while the Y-axis of FIG. 1A shows measured (I) hardness, HV30 (FIG. 1A dotted graph), (II) fracture toughness, Kic (FIG. 1A dashed graph), and (III) transverse rupture strength TRS-B (FIG. 1B dashed graph).

[0082] As can evidently be seen from FIGS. 1A and 1B, the material composed of at least 70 wt.% reclaimed carbide material, of which, from 45 wt.% to 100 wt. % is zinc- reclaimed carbide is superior to, or at least substantially similar mechanical properties (e.g., when taking the standard deviations into consideration) characterized by hardness, HV30 and fracture toughness, Kt, when compared to the reference material composed of 10 wt.% Co and 90 wt.% WC including merely virgin raw materials (i.e. upper round point denotes the hardness, HV30 and lower round point denotes the fracture toughness, Kic). Additionally, adding reclaimed non-sintered carbide to the mix of up to 50 wt.% notably provides the zinc-reclaimed carbide with robust and advantageous combinations

29 HYPERION REF: H20057WO of hardness, fracture toughness, and TRS-B values of at least about a; 3000 MPa measured according to the ISO 3327-2009 standard.

[0083] Further, the transverse rupture strength was also measured according to the ASTM B 406 standard and reported in Ksi as shown below in Table 1. Table 1 shows the minimum, the maximum, and the average values obtained for the transverse rupture strength measured according to the ASTM B 406 standard in Ksi for (i) the reference material composed of 10 wt.% Co and 90 wt.% virgin WC, and for (ii) the reclaimed carbide material either composed of a combined zinc-reclaimed carbide and/or reclaimed non-sintered carbide (i.e. composition A and composition B). Composition A only included 100 wt.% reclaimed non-sintered carbide, and the shown values obtained for composition A in Table 1 below, are an average from multiple compositions only including 100 wt.% reclaimed non-sintered carbide. Composition B included 90 wt.% zinc- reclaimed carbide and 10 wt.% reclaimed non-sintered carbide. As demonstrated in

Table 1 , the average obtained transverse rupture strength value determined according to the ASTM B 406 standard for the material defined by composition A including only 100 wt.% reclaimed non-sintered carbide was 462 Ksi. This was comparable to the obtained average value of 473 Ksi for the reference material composed of 10 wt.% Co and 90 wt.% virgin WC. The reclaimed cemented carbide material disclosed herein exhibited a transverse rupture strength determined according to the ASTM B 406 standard in a range of from about 328 Ksi to about 543 Ksi for composition B, and from about 320 Ksi to about 571 Ksi for composition A.

[0084] [Table 1]

Material Average (Ksi) Maximum (Ksi) Minimum (Ksi) Weibull modulus

Reference 473 615 330 6.4 material

Composition A 462 571 320 5.3 (100 wt.%

30 HYPERION REF: H20057WO reclaimed non- sintered carbide)

Composition B 454 543 328 7.3 (90 wt.% zinc- reclaimed carbide and 10 wt.% reclaimed non-sintered carbide)

[0085] Although the present disclosure has been described in connection with embodiments thereof, it will be appreciated by those skilled in the art that additions, deletions, modifications, and substitutions not specifically described may be made without departure from the spirit and scope of the disclosure as defined in the appended claims.

[0086] With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations are not expressly set forth herein for sake of clarity.

[0087] The herein described subject matter sometimes illustrates different components contained within, or connected with, different other components. It is to be understood that such depicted architectures are merely exemplary, and that in fact many other architectures may be implemented which achieve the same functionality. In a conceptual sense, any arrangement of components to achieve the same functionality is effectively “associated” such that the desired functionality is achieved. Hence, any two components herein combined to achieve a particular functionality can be seen as “associated with” each other such that the desired functionality is achieved, irrespective of architectures or intermedia! components. Likewise, any two components so associated can also be viewed as being “operably connected”, or “operably coupled,” to each other to achieve the desired functionality, and any two components capable of being so

31 HYPERION REF: H20057WO associated can also be viewed as being “operably couplable,” to each other to achieve the desired functionality. Specific examples of operably couplable include but are not limited to physically mateable and/or physically interacting components, and/or wirelessly interactable, and/or wirelessly interacting components, and/or logically interacting, and/or logically interactable components.

[0088] In some instances, one or more components may be referred to herein as “configured to,” “configured by,” “configurable to,” “operable/operative to,” “adapted/adaptable,” “able to,” “conformable/conformed to,” etc. Those skilled in the art will recognize that such terms (e.g., “configured to”) can generally encompass activestate components and/or inactive-state components and/or standby-state components, unless context requires otherwise.

[0089] While particular aspects of the present subject matter described herein have been shown and described, it will be apparent to those skilled in the art that, based upon the teachings herein, changes and modifications may be made without departing from the subject matter described herein and its broader aspects and, therefore, the appended claims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of the subject matter described herein. It will be understood by those within the art that, in general, terms used herein, and especially in the appended claims (e.g., bodies of the appended claims) are generally intended as “open” terms (e.g., the term “including” should be interpreted as “including but not limited to,” the term “having” should be interpreted as “having at least,” the term “includes” should be interpreted as “includes but is not limited to,” etc.). It will be further understood by those within the art that if a specific number of an introduced claim recitation is intended, such an intent will be explicitly recited in the claim, and in the absence of such recitation no such intent is present. For example, as an aid to understanding, the following appended claims may contain usage of the introductory phrases “at least one” and “one or more” to introduce claim recitations. However, the use of such phrases should not be construed to imply that the introduction of a claim recitation by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim recitation to claims containing only one such recitation, even when the same claim includes the introductory

32 HYPERION REF: H20057WO phrases “one or more” or “at least one” and indefinite articles such as “a” or “an” (e.g., “a” and/or “an” should typically be interpreted to mean “at least one” or “one or more”); the same holds true for the use of definite articles used to introduce claim recitations.

[0090] In addition, even if a specific number of an introduced claim recitation is explicitly recited, those skilled in the art will recognize that such recitation should typically be interpreted to mean at least the recited number (e.g., the bare recitation of “two recitations,” without other modifiers, typically means at least two recitations, or two or more recitations).

[0091] Furthermore, in those instances where a convention analogous to “at least one of A, B, and C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, and C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). In those instances where a convention analogous to “at least one of A, B, or C, etc.” is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., “a system having at least one of A, B, or C” would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.).

[0092] It will be further understood by those within the art that typically a disjunctive word and/or phrase presenting two or more alternative terms, whether in the description, claims, or drawings, should be understood to contemplate the possibilities of including one of the terms, either of the terms, or both terms unless context dictates otherwise. For example, the phrase “A or B” will be typically understood to include the possibilities of “A” or“B” or “A and B.”

[0093] With respect to the appended claims, those skilled in the art will appreciate that recited operations therein may generally be performed in any order. Also, although various operational flows are presented in a sequence(s), it should be understood that the various operations may be performed in other orders than those which are illustrated, or may be performed concurrently. Examples of such alternate orderings may include

33 HYPERION REF: H20057WO overlapping, interleaved, interrupted, reordered, incremental, preparatory, supplemental, simultaneous, reverse, or other variant orderings, unless context dictates otherwise. Furthermore, terms like “responsive to,” “related to,” or other past-tense adjectives are generally not intended to exclude such variants, unless context dictates otherwise.

[0094] Those skilled in the art will appreciate that the foregoing specific exemplary processes and/or devices and/or technologies are representative of more general processes and/or devices and/or technologies taught elsewhere herein, such as in the claims filed herewith and/or elsewhere in the present application.

[0095] While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.

[0096] The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented here.

[0097] Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range is encompassed within the disclosure. The upper and lower limits of these smaller ranges which can independently be included in the smaller ranges is also encompassed within the disclosure, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either both of those included limits are also included in the disclosure.

[0098] One skilled in the art will recognize that the herein described components (e.g., operations), devices, objects, and the discussion accompanying them are used as examples for the sake of conceptual clarity and that various configuration modifications are contemplated. Consequently, as used herein, the specific exemplars set forth and

34 HYPERION REF: H20057WO the accompanying discussion are intended to be representative of their more general classes. In general, use of any specific exemplar is intended to be representative of its class, and the non-inclusion of specific components (e.g., operations), devices, and objects should not be taken as limiting.

[0099] Additionally, for example any sequence(s) and/or temporal order of sequence of the system and method that are described herein this disclosure are illustrative and should not be interpreted as being restrictive in nature. Accordingly, it should be understood that the process steps may be shown and described as being in a sequence or temporal order, but they are not necessarily limited to being carried out in any particular sequence or order. For example, the steps in such processes or methods generally may be carried out in various different sequences and orders, while still falling within the scope of the present disclosure.

[00100] Finally, the discussed application publications and/or patents herein are provided solely for their disclosure prior to the filing date of the described disclosure. Nothing herein should be construed as an admission that the described disclosure is not entitled to antedate such publication by virtue of prior disclosure.

35

Claims

HYPERION REF: H20057WO What is claimed is:

1. A cemented carbide composition, comprising: a carbide phase comprising from about 45 wt.% to about 100 wt.% zinc-reclaimed carbide, the carbide phase being present in an amount of at least 70 wt.% of the cemented carbide composition; and a binder phase, wherein the cemented carbide composition has a transverse rupture strength in a range of from about 330 Ksi to about 540 Ksi as measured by the ASTM B 406 standard.

2. The cemented carbide composition of claim 1 , wherein the carbide phase further comprises reclaimed non-sintered carbide.

3. The cemented carbide composition of claim 1 , wherein the carbide phase is present in an amount of at least 80 wt.% of the cemented carbide composition.

4. The cemented carbide composition of claim 1 , wherein the carbide phase is present in an amount of from about 89 wt.% to about 99 wt.% of the cemented carbide composition.

5. The cemented carbide composition of claim 1 , wherein the cemented carbide composition does not comprise electrochemically processed carbide recycle material.

6. The cemented carbide composition of claim 1, wherein the zinc-reclaimed carbide comprises tungsten carbide.

7. The cemented carbide composition of claim 2, wherein the reclaimed non-sintered carbide comprises tungsten carbide.

8. The cemented carbide composition of claim 1 , wherein the binder phase comprises a metallic binder.

36 HYPERION REF: H20057WO

9. The cemented carbide composition of claim 8, wherein the metallic binder comprises Co.

10. The cemented carbide composition of claim 1 , wherein the binder phase is present in an amount of from about 1 wt.% to about 11 wt.% of the cemented carbide composition.

11. A method of manufacturing a sintered cemented carbide article, comprising: providing a cemented carbide composition, comprising a carbide phase comprising from about 45 wt.% to about 100 wt.% zinc- reclaimed carbide, the carbide phase being present in an amount of at least 70 wt.% of the carbide composition, and a binder phase comprising a metallic binder; subjecting the carbide composition to a milling operation to form a powder blend; subjecting the powder blend to a forming operation to form a green body; and subjecting the green body to a sintering operation to form the sintered cemented carbide article, wherein the sintered cemented carbide article has a transverse rupture strength in a range of from about 330 Ksi to about 540 Ksi as measured by the ASTM B 406 standard.

12. The method of claim 11 , wherein the carbide phase further comprises reclaimed non-sintered carbide.

13. The method of claim 11 , wherein the carbide phase is present in an amount of at least 80 wt. % of the cemented carbide composition.

14. The method of claim 11 , wherein the carbide phase is present in an amount of from about 89 wt.% to about 99 wt.% of the cemented carbide composition.

15. The method of claim 11 , wherein the cemented carbide composition does not comprise electrochemically processed carbide recycle material.

37 HYPERION REF: H20057WO

16. The method of claim 11 , wherein the zinc-reclaimed carbide comprises tungsten carbide.

17. The method of claim 12, wherein the reclaimed non-sintered carbide comprises tungsten carbide.

18. The method of claim 11 , wherein the binder phase comprises a metallic binder.

19. The method of claim 18, wherein the metallic binder comprises Co.

20. The method of claim 11 , wherein the binder phase is present in an amount of from about 1 wt.% to about 11 wt.% of the cemented carbide composition.

21. A cutting tool, comprising the cemented carbide composition of claim 1.

38