WO2023114632A1

WO2023114632A1 - Cemented carbide and cermet compositions having a high-entropy-alloy binder

Info

Publication number: WO2023114632A1
Application number: PCT/US2022/080483
Authority: WO
Inventors: Luis Fernando Garcia; Olivier Lavigne
Original assignee: Hyperion Materials & Technologies, Inc.
Priority date: 2021-12-13
Filing date: 2022-11-28
Publication date: 2023-06-22
Also published as: TW202323547A

Abstract

Provided are (I) cemented carbide compositions including a ceramic hard phase having metal carbides of niobium carbide, tungsten carbide, and tantalum carbide and (II) cermet compositions including a ceramic hard phase having metal carbides or carbonitrides of titanium carbonitride, niobium carbide, and tungsten carbide. The cemented carbide and the cermet compositions further include a high-entropy-alloy (HEA) binder phase having metals selected from one or more of nickel, molybdenum, cobalt, tungsten, iron and chromium. Associated methods of manufacturing cemented carbides and cermets and cutting tools incorporating the same are further contemplated.

Description

CEMENTED CARBIDE AND CERMET COMPOSITIONS HAVING A HIGH-ENTROPY-

ALLOY BINDER

FIELD OF THE DISCLOSURE

[0001] The present disclosure relates to cemented carbide and cermet compositions having a high-entropy-alloy (HEA) binder phase, associated methods of manufacturing cemented carbides and cermets having a high-entropy-alloy (HEA) binder phase, and cutting tools incorporating the cemented carbide and the cermet compositions.

BACKGROUND

[0002] Cemented carbide and cermet (e.g. ceramic plus metal) powders composed of a ceramic hard phase that is mixed with a metallic binder phase have been used for producing physically durable hard sintered bodies for e.g. cutting tools for metal machining, wear parts and in mining applications.

[0003] There is a myriad of standard methodological steps that can be employed to produce a cemented carbide and a cermet body. Cemented carbide and cermet materials are typically made by first forming a slurry of the cemented carbide and the cermet powders with a milling liquid (e.g. water, solvent(s), alcohol(s), or any mixtures thereof). This is then following by milling the constituents together with binder metal powders, organic binder(s) (e.g. polyethylene glycol, polyvinylglycol, wax or a combination thereof) in for instance either typically a ball mill or an attritor mill for generally several hours.

[0004] The milled slurry is usually subjected to a spray-drying operation to form granulated cemented carbide and cermet powders, which can be used to press green parts that are ultimately sintered.

[0005] The main purpose of the milling operation is to facilitate a good metallic binder phase distribution and a good wettability between the hard cemented carbide and cermet constituent grains and the metallic binder phase powder. Subjecting the cemented carbide and the cermet powders to the milling operation is elementary to strengthening the physical integrity of the milled cemented carbide and cermet compositions, and in some cases, to deagglomerate tungsten carbide (WC) crystals.

[0006] An acceptable metallic binder phase distribution and a good quality of wettability are fundamental and essential parameters for obtaining cemented carbide and cermet materials of stellar physical quality. On the other hand, if the metallic binder phase distribution and wettability are of a rather bad characteristic, pores and cracks may undesirably be formed as a result of this in the final sintered body, which is detrimental to the produced cemented carbide and cermet material.

[0007] Conventionally manufactured WC powders employing commonly used metallic binders, such as for example cobalt used for manufacturing of cemented carbide and cermet bodies may, at times, exhibit varying grain shapes and ranges. In this aspect, a non-uniformity of the WC powder may in part result from the heterogeneity of the W powder produced by reduction. This heterogeneity may even become more mixed and noticeable during the subsequent carburization stage. Moreover, during sintering any WC agglomerates may form larger sintered carbide grains and can further contain an increased frequency of sigma two boundaries, i.e. carbide grains adhering together without for example forming a coherent uniform metallic cobalt binder layer.

[0008] High-entropy-alloys (HEA) are known to be a metallic alloy including at least three or more metallic binder elements, where the atomic weight of each metallic binder element is generally composed of from 5% to 35% (i.e. not at.% of each metallic binder element in the final cemented carbide or cermet composition but % composition of each metallic binder element in the final HEA binder phase), and additionally, where no metallic binder element is substantially dominating the composition nor its properties.

[0009] HEAs have attracted a compelling interest over the years and most HEAs have been developed via ingot metallurgy. However more recently, powder metallurgy has appeared as an instrumental alternative for further developing this family of alloys to possibly widen the field of nanostructures in HEAs and improve capabilities of these alloys. Cemented carbides and cermets composed of an HEA binder phase have been successfully produced, albeit most commonly for WC-type cemented carbides and cermets. Thus, cemented carbides and cermets incorporating an HEA binder phase have been viewed as competitive solutions relative to other conventionally utilized hard metals.

[0010] With the above in mind, this disclosure now provides novel solutions over the mentioned shortcomings and limitations by specifically employing a ceramic hard phase in the cemented carbide and the cermet being rich in niobium carbide content. In addition to the ceramic hard phase, the cemented carbide and the cermet compositions are further composed of an HEA binder phase.

[0011] Consequently, cemented carbide and cermet compositions with superior wear resistance are advantageously provided.

SUMMARY

[0012] According to a first aspect, provided is a cemented carbide composition, including a ceramic hard phase present in an amount of from 70 wt.% to 93 wt.% based on the total weight of the cemented carbide composition. The cemented carbide composition further includes a high-entropy-alloy (HEA) binder phase present in an amount of from 7 wt.% to 30 wt.% based on the total weight of the cemented carbide composition including one or more of nickel, molybdenum, cobalt, iron and chromium.

[0013] In some examples, the cemented carbide composition has a HV30 Vickers hardness of up to 1650 HV30 and a Palmqvist fracture toughness, Kic, of up to 7.5 MPa√m.

[0014] In some examples, the ceramic hard phase includes tungsten carbide and niobium carbide, where the tungsten carbide may be present in an amount of from 1 wt.% to 45 wt.% and the niobium carbide may be present in an amount of from 45 wt.% to 90 wt.% based on the total weight of the cemented carbide composition.

[0015] In some examples, the niobium carbide is present in an amount of 88 wt.% and the tungsten carbide is present in an amount of 2 wt.% based on the total weight of the cemented carbide composition. [0016] In other examples, the niobium carbide is present in an amount of 69 wt.% and the tungsten carbide is present in an amount of 21 wt.% based on the total weight of the cemented carbide composition.

[0017] In yet other examples, the niobium carbide is present in an amount of 46 wt.% and the tungsten carbide is present in an amount of 44 wt.% based on the total weight of the cemented carbide composition.

[0018] In some examples, the nickel may be present in an amount of from 3 wt.% to 8 wt.%, the molybdenum may be present in an amount of from 2.75 wt.% to 5 wt.%, the cobalt may be present in an amount of from 2.5 wt.% to 8 wt.%, the iron may be present in an amount of from 0.75 wt.% to 4 wt.% and the chromium may be present in an amount of from 0.25 wt.% to 4 wt.% based on the total weight of the cemented carbide composition.

[0019] In some particular examples, the nickel is present in an amount of 3.15 wt.%, the molybdenum is present in an amount of 2.9 wt.%, the cobalt is present in an amount of 2.7 wt.%, the iron is present in an amount of 0.85 wt.% and the chromium is present in an amount of 0.4 wt.% based on the total weight of the cemented carbide composition.

[0020] According to a second aspect, provided is a cermet composition, including a ceramic hard phase present in an amount of from 60 wt.% to 82 wt.% based on the total weight of the cermet composition. The cermet composition further includes a high- entropy-alloy (HEA) binder phase present in an amount of from 18 wt.% to 40 wt.% based on the total weight of the cermet composition including one or more of cobalt, nickel and molybdenum.

[0021] In some examples, the ceramic hard phase includes titanium carbonitride, niobium carbide and tungsten carbide, where the titanium carbonitride may be present in an amount of from 50 wt.% to 70 wt.%, the niobium carbide may be present in an amount of from 1 wt.% to 20 wt.% and the tungsten carbide may be present in an amount of from 1 wt.% to 10 wt.% based on the total weight of the cermet composition. [0022] In some examples, the titanium carbonitride is present in an amount of 50 wt.%, the niobium carbide is present in an amount of 20 wt.% and the tungsten carbide is present in an amount of 8 wt.% based on the total weight of the cermet composition.

[0023] In some examples, the cobalt may be present in an amount of from 7 wt.% to 13 wt.%, the nickel may be present in an amount of from 7 wt.% to 13 wt.% and the molybdenum may be present in an amount of from 7 wt.% to 13 wt.% based on the total weight of the cermet composition.

[0024] In some particular examples, the cobalt is present in an amount of 7.3 wt.%, the nickel is present in an amount of 7.3 wt.% and the molybdenum is present in an amount of 7.3 wt.% based on the total weight of the cermet composition.

[0025] According to a third aspect, provided is a cemented carbide composition, including a ceramic hard phase present in an amount of from 60 wt.% to 85 wt.% based on the total weight of the cemented carbide composition. The cemented carbide composition further includes a high-entropy-alloy (HEA) binder phase present in an amount of from 15 wt.% to 40 wt.% based on the total weight of the cemented carbide composition including one or more of cobalt, nickel, molybdenum and tungsten.

[0026] In some examples, the ceramic hard phase includes niobium carbide and tantalum carbide, where the niobium carbide may be present in an amount of from 1 wt.% to 80 wt.% and the tantalum carbide may be present in an amount of from 1 wt.% to 20 wt.% based on the total weight of the cemented carbide composition.

[0027] In some examples, the niobium carbide is present in amount of 78 wt.% and the tantalum carbide is present in an amount of 3 wt.% based on the total weight of the cemented carbide composition.

[0028] In some examples, the cobalt may be present in an amount from 4.5 wt.% to 10 wt.%, the nickel may be present in an amount from 4.5 wt.% to 10 wt.%, the molybdenum may be present in an amount from 4.5 wt.% to 10 wt.% and the tungsten may be present in an amount from 4.5 wt.% to 10 wt.% based on the total weight of the cemented carbide composition. [0029] In some particular examples, the cobalt is present in an amount of 4.75 wt.%, the nickel is present in an amount of 4.75 wt.%, the molybdenum is present in an amount of 4.75 wt.% and the tungsten is present in an amount of 4.75 wt.% based on the total weight of the cemented carbide composition.

[0030] According to a fourth aspect, a method of making a sintered cemented carbide is provided. The method includes (a) providing a powder mixture including powders forming hard constituents of a ceramic hard phase present in an amount of from 70 wt.% to 93 wt.% based on the total weight of the powder mixture and a high-entropy- alloy (HEA) binder phase present in an amount of from 7 wt.% to 30 wt.% based on the total weight of the powder mixture, the HEA binder phase including one or more of nickel, molybdenum, cobalt, iron and chromium; (b) subjecting the powder mixture to a milling operation to form a powder blend; (c) subjecting the powder blend to a forming operation to form a green body; and (d) subjecting the green body to a sintering operation to form the sintered cemented carbide.

[0031] In some examples, the cemented carbide has a HV30 Vickers hardness of up to 1650 HV30 and a Palmqvist fracture toughness, Kic, of up to 7.5 MPa√m.

[0032] In some examples, the ceramic hard phase includes tungsten carbide and niobium carbide, where the tungsten carbide may be present in an amount of from 1 wt.% to 45 wt.% and the niobium carbide may be present in an amount of from 45 wt.% to 90 wt.% based on the total weight of the powder mixture.

[0033] In some examples, the niobium carbide is present in an amount of 88 wt.% and the tungsten carbide is present in an amount of 2 wt.% based on the total weight of the powder mixture.

[0034] In other examples, the niobium carbide is present in an amount of 69 wt.% and the tungsten carbide is present in an amount of 21 wt.% based on the total weight of the powder mixture. [0035] In yet other examples, the niobium carbide is present in an amount of 46 wt.% and the tungsten carbide is present in an amount of 44 wt.% based on the total weight of the powder mixture.

[0036] In some examples, the nickel may be present in an amount of from 3 wt.% to 8 wt.%, the molybdenum may be present in an amount of from 2.75 wt.% to 5 wt.%, the cobalt may be present in an amount of from 2.5 wt.% to 8 wt.%, the iron may be present in an amount of from 0.75 wt.% to 4 wt.% and the chromium may be present in an amount of from 0.25 wt.% to 4 wt.% based on the total weight of the powder mixture.

[0037] In some particular examples, the nickel is present in an amount of 3.15 wt.%, the molybdenum is present in an amount of 2.9 wt.%, the cobalt is present in an amount of 2.7 wt.%, the iron is present in an amount of 0.85 wt.% and the chromium is present in an amount of 0.4 wt.% based on the total weight of the powder mixture.

[0038] According to a fifth aspect, a method of making a sintered cermet is provided. The method includes (a) providing a powder mixture including powders forming hard constituents of a ceramic hard phase present in an amount of from 60 wt.% to 82 wt.% based on the total weight of the powder mixture and a high-entropy-alloy (HEA) binder phase present in an amount of from 18 wt.% to 40 wt.% based on the total weight of the powder mixture, the HEA binder phase comprising one or more of cobalt, nickel and molybdenum; (b) subjecting the powder mixture to a milling operation to form a powder blend; (c) subjecting the powder blend to a forming operation to form a green body; and (d) subjecting the green body to a sintering operation to form the sintered cermet.

[0039] In some examples, the ceramic hard phase includes titanium carbonitride, niobium carbide and tungsten carbide, where the titanium carbonitride may be present in an amount of from 50 wt.% to 70 wt.%, the niobium carbide may be present in an amount of from 1 wt.% to 20 wt.% and the tungsten carbide may be present in an amount of 1 wt.% to 10 wt.% based on the total weight of the powder mixture. [0040] In some examples, the titanium carbonitride is present in an amount of 50 wt.%, the niobium carbide is present in an amount of 20 wt.% and the tungsten carbide is present in an amount of 8 wt.% based on the total weight of the powder mixture.

[0041] In some examples, the cobalt may be present in an amount of from 7 wt.% to 13 wt.%, the nickel may be present in an amount of from 7 wt.% to 13 wt.% and the molybdenum may be present in an amount of from 7 wt.% to 13 wt.% based on the total weight of the powder mixture.

[0042] In some particular examples, the cobalt is present in an amount of 7.3 wt.%, the nickel is present in an amount of 7.3 wt.% and the molybdenum is present in an amount of 7.3 wt.% based on the total weight of the powder mixture.

[0043] According to a sixth aspect, cutting tools or drill bits incorporating the cemented carbide compositions and the cermet compositions are further contemplated.

[0044] 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

[0045] 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. [0046] FIG. 1 is a flow diagram showing the individual process steps of producing a cemented carbide in accordance with an exemplary embodiment of the subject matter.

[0047] FIG. 2 is a flow diagram showing the individual process steps of producing a cermet in accordance with an exemplary embodiment of the subject matter.

DETAILED DESCRIPTION

[0048] 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.

[0049] 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.

[0050] The following definitions set forth the parameters of the described subject matter.

[0051] As used herein this disclosure, “wt.%” refers to a given weight percent (I) based on the total weight of the cemented carbide composition, or (II) based on the total weight of the cermet composition, unless specifically indicated otherwise.

[0052] As used herein this disclosure, 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.

[0053] 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.

[0054] 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.

[0055] Cemented carbide grades can be classified according to the grain size. Different types of grades have been defined as nano, ultrafine, submicron, fine, medium, medium coarse, coarse and extra coarse. As used herein this disclosure, the term (I) “nano grade” is defined as a material with a grain size of less than 0.2 μm; (II) “ultrafine grade” is defined as a material with a grain size from 0.2 μm to 0.5 μm; (III) “submicron grade” is defined as a material with a grain size from 0.5 μm to 0.9 μm; (IV) “fine grade" is defined as a material with a grain size from 1.0 μm to 1.3 μm; (V) “medium grade” is defined as a material with a grain size from 1 .4 μm to 2.0 μm; (VI) “medium coarse grade" is defined as a material with a grain size from 2.1 μm and to 3.4 μm; (VII) “coarse grade" is defined as a material with a grain size from 3.5 μm to 5.0 μm; and (VIII) “extra coarse grade” is defined as a material with a grain size greater than 5.0 μm. [0056] As used herein this disclosure, high-entropy-alloy (HEA) binder refers to an alloy including at least three or more metallic binders, where the atomic weight of each metallic binder element is typically constituted of from approximately 5 % to 35 % (i.e. not at.% of each metallic binder element in the final cemented carbide or cermet composition, but instead % composition of each metallic binder element in the final HEA binder phase), and furthermore, where no metallic binder is substantially dominating the composition and properties.

[0057] As used herein this disclosure, the term “cermet” typically refers to a composite material composed of a ceramic (cer) embedded in a metal (met) binder matrix (i.e. metallic binder phase). A cermet is ideally designed to provide the physical optimal properties of both a ceramic, such as high temperature resistance, hardness and fracture toughness, and those of a metal, such as the capability to undergo plastic deformation. The ceramic hard phase of the cermets is typically composed of carbides, borides, nitrides, or carbonitrides of metals from groups 4, 5 and 6 of the periodic table, such as, but not limited to predominantly titanium, niobium, tungsten, and secondarily tantalum, chromium, vanadium, zirconium, molybdenum, hafnium, or any combination thereof. The ceramic hard phase can be present in the cermet powder in any possible combination encompassing the mentioned metals, and in a weight that is not inconsistent and incompatible with the objectives of the present subject matter. To qualify as a cermet herein this disclosure, a cermet typically has at least 50 wt.% of carbides, borides, nitrides or carbonitrides of titanium in the ceramic hard phase and typically from 25 wt.% to 40 wt.% of additional remaining metal carbides, borides, nitrides or carbonitrides based on the total weight of the cermet composition.

[0058] Generally, the binder metal powders can be a powder of an HEA chiefly creating a single- or a multi-phase of at least three or more metals. Binder metals in the formed cermet bodies may generally be selected from the following but not limited to cobalt, nickel, molybdenum, tungsten, chromium, iron, niobium, tantalum, aluminum, copper, manganese, vanadium, zirconium, magnesium, silicium, or titanium, thereby forming the HEA binder phase. Binder metals may be present in the cermet powder in any possible combination, and in a weight that is not inconsistent and incompatible with the objectives of the present subject matter.

[0059] As used herein this disclosure, the term “cemented carbide” generally refers to a composite material composed of a ceramic embedded in a metal binder element (i.e. metallic binder phase). A cemented carbide is ideally designed to provide the physical optimal properties of both a ceramic, such as high temperature resistance, hardness and fracture toughness, and those of a metal, such as the capability to undergo plastic deformation. The ceramic hard phase of the cemented carbides is typically composed of carbides, borides, nitrides, or carbonitrides of metals from groups 4, 5 and 6 of the periodic table, such as, but not limited to predominantly niobium, tungsten, and secondarily tantalum, chromium, vanadium, zirconium, molybdenum, hafnium, or any combination thereof. The ceramic hard phase can be present in the cermet powder in any possible combination encompassing the mentioned metals, and in a weight that is not inconsistent and incompatible with the objectives of the present subject matter. To qualify as a cemented carbide herein this disclosure, a cemented carbide generally has a ceramic hard phase constituted of at least 70 wt.% based on the total weight of the cemented carbide composition.

[0060] As used herein this disclosure, the term “superabrasive ultrahard material”, or simply “superabrasive material” refers to a material as found in the following but not limited to crystal diamond, polycrystalline diamond (PCD), thermally stable polycrystalline diamond, chemical vapor deposition (CVD) diamond, metal matrix diamond composites, ceramic matrix diamond composites, nanodiamond, cubic boron nitride (cBN), polycrystalline cubic boron nitride (PcBN), or any combinations thereof.

[0061] As used herein this disclosure, “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. [0062] As used herein this disclosure, “chemical vapor deposition (CVD)” refers to a method, where the substrate (i.e. cemented carbide or cermet powder) 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.

[0063] As used herein this disclosure, the terms “about” and “approximately” are used interchangeably. It is meant to mean plus or minus 1 % of the numerical value of the number with which it is being used. Thus, “about” and “approximately” are used to provide flexibility to a numerical range endpoint by providing that a given value may be “above” or “below” the given value. As such, for example a value of 50% is intended to encompass a range defined by 49.5%-50.5%.

[0064] As used herein this disclosure, the term “predominantly” is meant to encompass at least 95% of a given entity.

[0065] As used herein this disclosure, the term “green body" refers to the material in the form of bonded powder or plates before the material has physically been sintered.

[0066] Wherever used throughout the disclosure, the term “generally” has the meaning of “approximately”, “typically” or “closely” or “within the vicinity or range of’.

[0067] 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.

[0068] As used herein this disclosure, the term “Palmqvist fracture toughness” i.e. Kic, refers to the ability of a material with pre-cracks to resist further fracture propagation upon absorbing energy.

[0069] As used herein this disclosure, 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. [0070] As used herein this disclosure, the ISO 28079-2009 standard specifies a method for measuring the fracture toughness and the hardness of hardmetals, cemented carbides and cermets 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 treatment, 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.

[0071] The current disclosure stems from the premise of producing a ceramic hard phase in compositions of cemented carbides and cermets being rich in niobium carbide (NBC) content. In addition to the ceramic hard phase, the compositions of the cemented carbides and the cermets are further composed of an HEA binder phase.

[0072] The ceramic hard phase of the cermets herein this disclosure is typically composed of carbides, borides, nitrides or carbonitrides of metals selected from groups 4, 5 and 6 of the periodic table, such as, but not limited to predominantly titanium, niobium, tungsten, and secondarily tantalum, chromium, vanadium, zirconium or hafnium. In order to qualify as a cermet herein this disclosure, a cermet is typically composed of at least 50 wt.% of carbides, borides, nitrides, or carbonitrides of titanium in the ceramic hard phase and generally from 25 wt.% to 40 wt.% of additional metal carbides, borides, nitrides, or carbonitrides based on the total weight of the cermet composition. [0073] On the other hand, the ceramic hard phase of the cemented carbides disclosed herein this disclosure may be composed of carbides, borides, nitrides or carbonitrides of similar metals as aforementioned under paragraph [0072] for the

cermets except for the inclusion of titanium, which is excluded from the cemented carbides. The cemented carbides are composed of a ceramic hard phase of at least 70 wt.% based on the total weight of the cemented carbide composition.

[0074] The ceramic hard phase may be present in the cemented carbide and the cermet powders in any possible combination incorporating the aforementioned metals, and in any amount, that is not inconsistent and incompatible with the objectives of the present subject matter.

[0075] The ceramic hard phase may typically be present from 60 wt.% to 95 wt.% based on the total weight of the cemented carbide and the cermet composition. In some examples, the ceramic hard phase is present from 65 wt.% to 95 wt.% based on the total weight of the cemented carbide and the cermet composition. In other examples, the ceramic hard phase is present from 70 wt.% to 90 wt.% based on the total weight of the cemented carbide and the cermet composition. In yet other examples, the ceramic hard phase is present from 75 wt.% to 90 wt.% based on the total weight of the cemented carbide and the cermet composition. In still other examples, the ceramic hard phase is present from 80 wt.% to 90 wt.% based on the total weight of the cemented carbide and the cermet composition.

[0076] In certain particular embodiments, the ceramic hard phase is present from 60 wt.% to 78 wt.%, from 60 wt.% to 82 wt.%, from 60 wt.% to 85 wt.%, from 70 wt.% to 75 wt.%, from 70 wt.% to 80 wt.%, from 70 wt.% to 85 wt.%, from 70 wt.% to 93 wt.%, from 75 wt.% to 80 wt.%, from 75 wt.% to 85 wt.%, from 80 wt.% to 85 wt.%, or from 85 wt.% to 90 wt.% based on the total weight of the cemented carbide and the cermet composition.

[0077] Generally, the powder metallic HEA binder phase may be constituted of a powder of an alloy, thereby creating a single- or a multi-phase of at least three or more metals. Conventional binder metals of the HEA binder phase in the fabricated cemented carbide and the cermet bodies may generally be selected from one or more of cobalt, nickel, molybdenum, tungsten, chromium, iron, niobium, tantalum, aluminum, copper, manganese, vanadium, zirconium, magnesium, silicium, and titanium, thereby making up the anchoring HEA binder phase.

[0078] Binder metals and grain growth inhibitors typically characterized by carbides like vanadium carbide (VC), chromium carbide (Cr₃C₂), tantalum carbide (TaC), titanium carbide (TiC), zirconium carbide (ZrC) and niobium carbide (NbC) may be present in the cemented carbide and the cermet powders in any possible combination, and in a weight, that is not incompatible with the objectives of the present subject matter. The powder metallic HEA binder phase may generally be present in a weight from 1 wt.% to 40 wt.% based on the total weight of the cemented carbide and the cermet composition. In some examples, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 3 wt.% based on the total weight of the cemented carbide and the cermet composition. In other examples, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 5 wt.% based on the total weight of the cemented carbide and the cermet composition. In yet other examples, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 7 wt.% based on the total weight of the cemented carbide and the cermet composition. In still other examples, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 10 wt.% of based on the total weight of the cemented carbide and the cermet composition. In further other examples, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 15 wt.% based on the total weight of the cemented carbide and the cermet composition. In further other embodiments, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 20 wt.% based on the total weight of the cemented carbide and the cermet composition. In still other embodiments, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 25 wt.% based on the total weight of the cemented carbide and the cermet composition. In yet other embodiments, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 30 wt.% based on the total weight of the cemented carbide and the cermet composition. In certain embodiments, the powder metallic HEA binder phase is present in a weight from 1 wt.% to 35 wt.% based on the total weight of the cemented carbide and the cermet composition. [0079] In certain particular embodiments, the powder metallic HEA binder phase and the grain growth inhibitors are present in a weight from 1 wt.% to 2 wt.%, from 2 wt.% to 5 wt.%, from 5 wt.% to 7 wt.%, from 3 wt.% to 7 wt.%, from 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. %, 10.9 wt. %, from 7 wt.% to 20 wt.%, from 7 wt.% to 30 wt.%, from 10 wt.% to 15 wt.%, from 10 wt.% to 20 wt.%, from 15 wt.% to 20 wt.%, from 10 wt.% to 30 wt.%, from 20 wt.% to 30 wt.%, from 20 wt.% to 35 wt.%, from 15 wt.% to 40 wt.%, from 18 wt.% to 40 wt.%, from 20 wt.% to 40 wt.%, or from 22 wt.% to 40 wt.% based on the total weight of the cemented carbide and the cermet composition.

[0080] The cemented carbides and the cermets formed herein this disclosure may exhibit any average particle size that is not inconsistent and incompatible with the objectives of the present disclosure. The cemented carbide and the cermet body may generally have an average particle size ranging for example from 0.5 μm to 30 μm. In some examples, the cemented carbide and the cermet body have an average particle size in the range from 1 μm to 5 μm. In other examples, the cemented carbide and the cermet body have an average particle size in the range from 1 μm to 10 μm. In still other examples, the cemented carbide and the cermet body have an average particle size in the range from 1 μm to 15 μm. In yet other examples, the cemented carbide and the cermet body have an average particle size in the range from 1 μm to 20 μm. In further examples, the cemented carbide and the cermet body have an average particle size in the range from 1 μm to 25 μm. In further other examples, the cemented carbide and the cermet body have an average particle size in the range from 1 μm to 30 μm. In certain particular embodiments, the cemented carbide and the cermet body have an average particle size in the range from 5 μm to 10 μm, from 10 μm to 15 μm, from 5 μm to 15 μm, from 15 μm to 20 μm, from 5 μm to 20 μm, from 20 μm to 25 μm, from 5 μm to 25 μm, from 25 μm to 30 μm, or from 5 μm to 30 μm.

[0081 ] 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 al., “Graphical comparison of image analysis and laser diffraction particle size analysis data obtained from the measurements of nonspherical particle systems”, AAPS Pharm SciTech. 2006 Aug 18; VoL7(3):69, to further gain insight into each procedure and methodology, all of which documents, are incorporated herein by reference in their entirety.

[0082] A desired particle size of the cemented carbide and the cermet powders can be produced by subjecting the cemented carbide and the 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 binder(s) in the production of the powders. In some embodiments, besides using a ball or an attritor mill as the physical component, ultrasonic mixing may be the choice of mixing method. 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 fer 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 binder(s), 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 % (i.e. total volume % made up by each mentioned component) of the total volume of the formed slurry, to facilitate the formation of agglomerates, and additionally to act as a pressing agent in the subsequent following pressing steps.

[0083] The milled powder slurry composition may be 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 cemented carbide and the cermet powders can be crushed or otherwise comminuted prior to milling with the metallic binder(s).

[0084] In the case of spray-drying, the slurry containing the powdered materials mixed with the organic liquid, and possibly, the organic binder(s) may be atomized through an appropriate nozzle in the 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 with good and acceptable flow properties.

[0085] The powders are 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 (MAP), extruding or metal injection molding (MIM), cold isostatic pressing (CIP), pill pressing, tape casting and other methods known in the powder metallurgy art. Any consolidation method can be utilized that is not inconsistent and incompatible with the objectives of the present subject matter. Forming yields a green density and/or strength that permits easy handling and green machining. 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. [0086] The green body can take the form of a blank, or can otherwise assume, a near-net shape forth of the desired cutting element, including cutting insert, drill or endmill. In some examples, the green body is mechanically worked to provide the desired shape.

[0087] The green bodies may be subjected to a pre-sintering temperature elevation procedure, to successfully remove the organic binder(s). This may be done in the same apparatus when executing the sintering process further described hereinbelow. 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 550°C, from 200°C to 600°C, from 250°C to 450°C, from 250°C to 500°C, from 250°C to 550°C from 250°C to 600°C, from 300°C to 450°C, from 300°C to 500°C, 300°C to 550°C, or from 300°C to 600°C under typically a reactive H2 atmosphere generally with a H2 flow rate applied from 1000 liters/hour to 10000 liters/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 approximately 60 minutes to approximately 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. In general, the pre-sintering step may be conducted in vacuum, in a reactive (H2) atmosphere, in a non- reactive inert atmosphere e.g. nitrogen (N2) or argon (Ar), or in a carbon-containing gas atmosphere.

[0088] The pre-sintered and debinded green bodies subsequently undergo a sintering consolidation process to ultimately form the sintered end-material. This may usually be performed typically using a pressure from 50 bar to 75 bar, from 50 bar to 80 bar, from 50 bar to 85 bar, from 50 bar to 90 bar, from 60 bar to 75 bar, from 60 bar to 80 bar, from 60 bar to 85 bar, from 60 bar to 90 bar, from 70 bar to 75 bar, from 70 bar to 80 bar, from 70 bar to 85 bar, or from 70 bar to 90 bar. Depending however on the composition, this pressure range might be lowered to a range from 35 bar to 60 bar 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 to 60 minutes.

[0089] The green bodies can suitably be either subjected to vacuum sintering or sintering in a non-reactive an inert atmosphere e.g. nitrogen (N2) or argon (Ar), or in a reactive hydrogen/methane atmosphere. During vacuum sintering, the green body is placed in a vacuum furnace and sintered at temperatures of generally 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. In some examples, hot isostatic pressing (HIP) may be added to the vacuum sintering process. HIP can be administered as a post-sintering operation or during vacuum sintering thereby yielding a sinter-HIP process. The resulting sintered cemented carbide and cermet bodies exhibit hardness and fracture toughness as described herein this disclosure.

[0090] A skilled artisan would in practice readily know how a sintering procedure is commonly performed and practiced. Thus, the reader is directed to for example US Patent No. 6,814,775B2, US Patent No. 8,327,958B2, US Patent No. 8,342,268B2, US Patent No. 10,232,49362, US Patent No. 10,252,94762, US Patent No. 10,337,25662, US Patent No. 10,753,15862, US Patent No. 11 ,065,86362, and US Application Publication 2018/0009716A1 to further gain insight into sintering procedures and methodologies, all of which documents, are incorporated herein by reference in their entirety.

[0091] Turning now to FIG. 1, this figure shows a flow diagram depicting the individual process steps of producing a sintered cemented carbide in accordance with an embodiment of the subject matter. FIG. 1 demonstrates that in step 100, the process is initiated by providing a powder mixture including powders forming hard constituents of a ceramic hard phase present in an amount of from 70 wt.% to 93 wt.% based on the total weight of the powder mixture and a high-entropy-alloy (HEA) binder phase present in an amount of from 7 wt.% to 30 wt.% based on the total weight of the powder mixture, the HEA binder phase including one or more of nickel, molybdenum, cobalt, iron and chromium. In step 105, the powder mixture is subjected to a milling operation to form a powder blend. In step 110, the powder blend is subjected to a forming operation to produce a green body. In step 112, a pre-sintering temperature elevation procedure is executed to remove any potentially remaining organic binders that may still be present in the produced green body. Finally, in step 115, the produced green body is subjected to a sintering operation to ultimately form the sintered cemented carbide.

[0092] Similarly, FIG. 2 shows a flow diagram showing the individual process steps of producing a sintered cermet in accordance with an embodiment of the subject matter. FIG. 2 depicts that in step 200, the process is commenced by providing a powder mixture including powders forming hard constituents of a ceramic hard phase present in an amount of from 60 wt.% to 82 wt.% based on the total weight of the powder mixture and a high-entropy-alloy (HEA) binder phase present in an amount of from 18 wt.% to 40 wt.% based on the total weight of the powder mixture, the HEA binder phase including one or more of cobalt, nickel and molybdenum. In step 205, the powder mixture is subjected to a milling operation to form a powder blend. In step 210, the powder blend is subjected to a forming operation to obtain a green body. In step 212, a pre-sintering temperature elevation procedure is undertaken to remove any possibly residual organic binders that may still be present in the obtained green body. Lastly, in step 215, the obtained green body is subjected to a sintering consolidation procedure to finally form the sintered cermet.

[0093] The cemented carbide and the cermet compositions described herein can advantageously be incorporated as cutting elements or components of cutting elements for various applications.

[0094] In some embodiments, the cemented carbide and the cermet compositions may be used to form cutting inserts for machining metals and/or metal alloys. In other embodiments, the cemented carbide and the cermet compositions may be used to produce interrupted cutting tooling such as drills, end mills and/or milling inserts. [0095] Additionally, the cemented carbide and the cermet compositions described herein can be physically combined with what is generally known in the art as superabrasive ultrahard materials in the likes of the following but not limited to crystal diamond, polycrystalline diamond (PCD), thermally stable polycrystalline diamond, 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 cemented carbide and the cermet compositions described herein can serve as an anchoring and embedding substrate or support functionality, to which, the ultrahard material is sintered in a high temperature, high pressure (HTHP) process.

[0096] In such a scenario, the layer of the superabrasive ultrahard material can in turn provide an enhanced wear resistance leading to increased lifetimes of cutting elements and/or wear parts employing the cemented carbide and the cermet compositions described herein this disclosure. In some particular embodiments, the cemented carbide and the cermet compositions disclosed herein 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.

[0097] The sintered cemented carbides and the cermets are formed by a method that may optionally include an additive or a processing step that reduces the number and the extent of the ceramic hard phase and the high-entropy-alloy (HEA) binder phase bonding that occurs in the sintering consolidation process. In one example, an inert material can be included in the ceramic hard phase and the high-entropy-alloy (HEA) binder phase powders, prior to the sintering consolidation process to reduce the extent of reaction bonding occurring in the sintering consolidation process by displacing reactive material with the inert material. In another example, an inert material can be partially coated on the powders prior to the sintering consolidation process to inhibit or prevent the extent of reaction bonding that would otherwise occur in the sintering consolidation process. [0098] Examples of inert materials that can be employed, alone or in combination, in the disclosed method may include oxides, carbides, nitrides, aluminates, silicates, nitrates, carbonates, silica (quartz) sand and cubic boron nitride (cBN). In a particular embodiment, specific examples of inert material include AI₂O₃, SiO₂, and SiC. When an inert material is used, the inert material has a D50 in a range of approximately 1 to 50 microns and is present in a weight of up to 10 wt.% based on the total weight of the cemented carbide and the cermet composition. In some examples, the inert 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 7 wt.%, from 5 wt.% to 8 wt.% from 5 wt.% to 9 wt.%, or from 5 wt.% to 10 wt.% based on the total weight of the cemented carbide and the cermet composition.

[0099] The cemented carbide compositions described herein this disclosure, may also 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 for example physical vapor deposition (PVD) or by chemical vapor deposition (CVD) selected from aluminum and one or more metallic elements of Groups IVB, VB and VIB of the periodic table and one or more non-metallic elements selected from Groups IIIA, IVA, VA and VIA of the periodic table. In a particular embodiment, the refractory coating includes one or more carbides, nitrides, carbonitrides, oxides and/or borides of one or more metallic elements selected from aluminum and

Groups IVB, VB and VIB of the periodic table. Moreover, the coating can be a one-layer coating or a multi-layer coating. When a refractory material is used, it is present in a weight of up to 10 wt.% based on the total weight of the cemented carbide and the cermet composition. 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 7 wt.%, from 5 wt.% to 8 wt.%, from 5 wt.% to 9 wt.%, or from 5 wt.% to 10wt.% based on the total weight of the cemented carbide and the cermet composition. EXAMPLE

[00100] 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 are not intended to limit the scope of what the inventors regard as their disclosure nor are they 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.

EXAMPLE 1

[00101] CEMENTED NIOBIUM CARBIDE (NBC) AND TUNGSTEN CARBIDE (WC) COMPOSITIONS WITH A HIGH-ENTROPY-ALLOY (HEA) BINDER PHASE EXHIBIT A SUPERIOR HARDNESS COMPARED TO REFERENCE MATERIAL

[00102] [TABLE 1]

[00103] TTAABBLLEE 1 depicts compositions for the mmaatteerriiaallss hea_nbc_001 , hea_nbc_002 and hea_nbc_003 composed of (I) a high entropy alloy (HEA) composition having a 10 wt.% binder phase based on the total weight of the cemented carbide composition (i.e. nickel is in a weight of 3.15 wt.%, molybdenum is in a weight of 2.9 wt.%, cobalt is in a weight of 2.7 wt.%, iron is in a weight of 0.85 wt.% and chromium is in a weight of 0.4 wt.%) and (II) a 90 wt.% ceramic hard phase based on the total weight of the cemented carbide composition composed of varying weights of tungsten carbide and niobium carbide. Reference materials ref_nbc_001 , ref_nbc_002, ref_nbc_003, hea_nbc_004, hea_nbc_005 and hea_nbc_006 used for comparison are composed of a (I) 10 wt.% nickel binder phase based on the total weight of the cemented carbide composition or (II) 9.6 wt.% cobalt plus 0.4 wt.% chromium binder phase based on the total weight of the cemented carbide composition with the exact same ceramic hard phase weight (i.e. 90 wt.%) as the hea_nbc_001 , hea_nbc_002 and hea_nbc_003 materials, however with varying tungsten carbide and niobium carbide wt.%.

[00104] HV30 Vickers hardness and fracture toughness Kic measurements were determined in accordance with ISO 28079:2009 for cemented carbides as described under paragraph [0070]. Three indentations per material were performed at 30 kgf

using a Vickers Limited equipment. The indent diagonals and the crack lengths emerging from the indentation corners were measured with a light optical microscope at a magnification of 500X.

[00105] As demonstrated in TABLE 1 , the obtained HV30 Vickers hardness values were higher for the materials with an HEA binder phase (hea_nbc_001 , hea_nbc_002 and hea_nbc_003) in comparison to the reference materials (ref_nbc_001 , ref_nbc_002, ref_nbc_003, ref_nbc_004, ref_nbc_005 and ref_nbc_006). The results of the obtained HV30 Vickers hardness values amounted to an average increase of 26.3 % for the grades with the HEA binder phase in comparison to the reference material (i.e. average HV30 of 1530 for the grades with the HEA binder phase versus average HV30 of 1211 for the reference material grades).

[00106] Further, the obtained fracture toughness Kic values for the grades having an HEA binder phase (i.e. hea_nbc_001 , hea_nbc_002 and hea_nbc_003 had an average of 7.37 MPa√m) displayed at least comparable or increased levels of 7.1 % when compared to Kic values obtained for the reference material grades (i.e. ref_nbc_001 , ref_nbc_002, ref_nbc_003, ref_nbc_004, ref_nbc_005 and ref_nbc_006 had an average of 6.88 MPa^m).

[00107] Thus, from the presented results in TABLE 1 , it is clear that cemented niobium carbide and tungsten carbide compositions composed of an HEA binder phase, as opposed to merely a single or dual metallic binder element, demonstrate superior hardness.

[00108] 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.

[00109] 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.

[00110] 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 intermedial 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 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.

[00111] 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.

[00112] 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.).

[00113] 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 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.

[00114] 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).

[00115] 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.). 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.”

[00116] 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 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.

[00117] 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.

[00118] 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.

[00119] 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. [00120] 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.

[00121] 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 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.

[00122] 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.

[00123] 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.

Claims

What is claimed is:

1. A cemented carbide composition, comprising: a ceramic hard phase present in an amount of from 70 wt.% to 93 wt.% based on the total weight of the cemented carbide composition; and a high-entropy-alloy (HEA) binder phase present in an amount of from 7 wt.% to 30 wt.% based on the total weight of the cemented carbide composition, the HEA binder phase comprising one or more of nickel, molybdenum, cobalt, iron and chromium.

2. The cemented carbide composition of claim 1 , having an HV30 Vickers hardness of up to 1650 HV30 and a Palmqvist fracture toughness, Kic, of up to 7.5 MPa√m.

3. The cemented carbide composition of claim 1 , wherein the ceramic hard phase comprises tungsten carbide and niobium carbide.

4. The cemented carbide composition of claim 3, wherein the tungsten carbide is present in an amount of from 1 wt.% to 45 wt.% and the niobium carbide is present in an amount of from 45 wt.% to 90 wt.% based on the total weight of the cemented carbide composition.

5. The cemented carbide composition of claim 4, wherein the niobium carbide is present in an amount of 88 wt.% and the tungsten carbide is present in an amount of 2 wt.% based on the total weight of the cemented carbide composition.

6. The cemented carbide composition of claim 4, wherein the niobium carbide is present in an amount of 69 wt.% and the tungsten carbide is present in an amount of 21 wt.% based on the total weight of the cemented carbide composition.

7. The cemented carbide composition of claim 4, wherein the niobium carbide is present in an amount of 46 wt.% and the tungsten carbide is present in an amount of 44 wt.% based on the total weight of the cemented carbide composition.

8. The cemented carbide composition of claim 1 , wherein the nickel is present in an amount of from 3 wt.% to 8 wt.%, the molybdenum is present in an amount of from 2.75 wt.% to 5 wt.%, the cobalt is present in an amount of from 2.5 wt.% to 8 wt.%, the iron is present in an amount of from 0.75 wt.% to 4 wt.% and the chromium is present in an amount of from 0.25 wt.% to 4 wt.% based on the total weight of the cemented carbide composition.

9. The cemented carbide composition of claim 8, wherein the nickel is present in an amount of 3.15 wt.%, the molybdenum is present in an amount of 2.9 wt.%, the cobalt is present in an amount of 2.7 wt.%, the iron is present in an amount of 0.85 wt.% and the chromium is present in an amount of 0.4 wt.% based on the total weight of the cemented carbide composition.

10. A cermet composition, comprising: a ceramic hard phase present in an amount of from 60 wt.% to 82 wt.% based on the total weight of the cermet composition; and a high-entropy-alloy (HEA) binder phase present in an amount of from 18 wt.% to 40 wt.% based on the total weight of the cermet composition, the HEA binder phase comprising one or more of cobalt, nickel and molybdenum.

11. The cermet composition of claim 10, wherein the ceramic hard phase comprises titanium carbonitride, niobium carbide and tungsten carbide.

12. The cermet composition of claim 11 , wherein the titanium carbonitride is present in an amount of from 50 wt.% to 70 wt.%, the niobium carbide is present in an amount of from 1 wt.% to 20 wt.% and the tungsten carbide is present in an amount of from 1 wt.% to 10 wt.% based on the total weight of the cermet composition.

13. The cermet composition of claim 12, wherein the titanium carbonitride is present in an amount of 50 wt.%, the niobium carbide is present in an amount of 20 wt.% and the tungsten carbide is present in an amount of 8 wt.% based on the total weight of the cermet composition.

14. The cermet composition of claim 10, wherein the cobalt is present in an amount of from 7 wt.% to 13 wt.%, the nickel is present in an amount of from 7 wt.% to 13 wt.% and the molybdenum is present in an amount of from 7 wt.% to 13 wt.% based on the total weight of the cermet composition.

15. The cermet composition of claim 14, wherein the cobalt is present in an amount of 7.3 wt.%, the nickel is present in an amount of 7.3 wt.% and the molybdenum is present in an amount of 7.3 wt.% based on the total weight of the cermet composition.

16. A cemented carbide composition, comprising: a ceramic hard phase present in an amount of from 60 wt.% to 85 wt.% based on the total weight of the cemented carbide composition; and a high-entropy-alloy (HEA) binder phase present in an amount of from 15 wt.% to 40 wt.% based on the total weight of the cemented carbide composition, the HEA binder phase comprising one or more of cobalt, nickel, molybdenum and tungsten.

17. The cemented carbide composition of claim 16, wherein the ceramic hard phase comprises niobium carbide and tantalum carbide.

18. The cemented carbide composition of claim 17, wherein the niobium carbide is present in an amount of from 1 wt.% to 80 wt.% and the tantalum carbide is present in an amount of from 1 wt.% to 20 wt.% based on the total weight of the cemented carbide composition.

19. The cemented carbide composition of claim 18, wherein the niobium carbide is present in an amount of 78 wt.% and the tantalum carbide is present in an amount of 3 wt.% based on the total weight of the cemented carbide composition.

20. The cemented carbide composition of claim 16, wherein the cobalt is present in an amount of from 4.5 wt.% to 10 wt.%, the nickel is present in an amount of from 4.5 wt.% to 10 wt.%, the molybdenum is present in an amount of from 4.5 wt.% to 10 wt.% and the tungsten is present in an amount of from 4.5 wt.% to 10 wt.% based on the total weight of the cemented carbide composition.

21. The cemented carbide composition of claim 20, wherein the cobalt is present in an amount of 4.75 wt.%, the nickel is present in an amount of 4.75 wt.%, the molybdenum is present in an amount of 4.75 wt.% and the tungsten is present in an amount of 4.75 wt.% based on the total weight of the cemented carbide composition.

22. A method of making a sintered cemented carbide, comprising:

(a) providing a powder mixture comprising powders forming hard constituents of a ceramic hard phase present in an amount of from 70 wt.% to 93 wt.% based on the total weight of the powder mixture and a high-entropy-alloy (HEA) binder phase present in an amount of from 7 wt.% to 30 wt.% based on the total weight of the powder mixture, the HEA binder phase comprising one or more of nickel, molybdenum, cobalt, iron and chromium;

(b) subjecting the powder mixture to a milling operation to form a powder blend;

(c) subjecting the powder blend to a forming operation to form a green body; and

(d) subjecting the green body to a sintering operation to form the sintered cemented carbide.

23. The method of making a sintered cemented carbide of claim 22, having an HV30 Vickers hardness of up to 1650 HV30 and a Palmqvist fracture toughness, Kic, of up to 7.5 MPa√m.

24. The method of making a sintered cemented carbide of claim 22, wherein the ceramic hard phase comprises tungsten carbide and niobium carbide.

25. The method of making a sintered cemented carbide of claim 24, wherein the tungsten carbide is present in an amount of from 1 wt.% to 45 wt.% and the niobium carbide is present in an amount of from 45 wt.% to 90 wt.% based on the total weight of the powder mixture.

26. The method of making a sintered cemented carbide of claim 25, wherein the niobium carbide is present in an amount of 88 wt.% and the tungsten carbide is present in an amount of 2 wt.% based on the total weight of the powder mixture.

27. The method of making a sintered cemented carbide of claim 25, wherein the niobium carbide is present in an amount of 69 wt.% and the tungsten carbide is present in an amount of 21 wt.% based on the total weight of the powder mixture.

28. The method of making a sintered cemented carbide of claim 25, wherein the niobium carbide is present in an amount of 46 wt.% and the tungsten carbide is present in an amount of 44 wt.% based on the total weight of the powder mixture.

29. The method of making a sintered cemented carbide of claim 22, wherein the nickel is present in an amount of from 3 wt.% to 8 wt.%, the molybdenum is present in an amount of from 2.75 wt.% to 5 wt.%, the cobalt is present in an amount of from 2.5 wt.% to 8 wt.%, the iron is present in an amount of from 0.75 wt.% to 4 wt.% and the chromium is present in an amount of from 0.25 wt.% to 4 wt.% based on the total weight of the powder mixture.

30. The method of making a sintered cemented carbide of claim 29, wherein the nickel is present in an amount of 3.15 wt.%, the molybdenum is present in an amount of 2.9 wt.%, the cobalt is present in an amount of 2.7 wt.%, the iron is present in an amount of 0.85 wt.% and the chromium is present in an amount of 0.4 wt.% based on the total weight of the powder mixture.

31. A method of making a sintered cermet, comprising: (a) providing a powder mixture comprising powders forming hard constituents of a ceramic hard phase present in an amount of from 60 wt.% to 82 wt.% based on the total weight of the powder mixture and a high-entropy-alloy (HEA) binder phase present in an amount of from 18 wt.% to 40 wt.% based on the total weight of the powder mixture, the HEA binder phase comprising one or more of cobalt, nickel and molybdenum;

(d) subjecting the green body to a sintering operation to form the sintered cermet.

32. The method of making a sintered cermet of claim 31 , wherein the ceramic hard phase comprises titanium carbonitride, niobium carbide and tungsten carbide.

33. The method of making a sintered cermet of claim 32, wherein the titanium carbonitride is present in an amount of from 50 wt.% to 70 wt.%, the niobium carbide is present in an amount of from 1 wt.% to 20 wt.% and the tungsten carbide is present in an amount of 1 wt.% to 10 wt.% based on the total weight of the powder mixture.

34. The method of making a sintered cermet of claim 33, wherein the titanium carbonitride is present in an amount of 50 wt.%, the niobium carbide is present in an amount of 20 wt.% and the tungsten carbide is present in an amount of 8 wt.% based on the total weight of the powder mixture.

35. The method of making a sintered cermet of claim 31 , wherein the cobalt is present in an amount of from 7 wt.% to 13 wt.%, the nickel is present in an amount of from 7 wt.% to 13 wt.% and the molybdenum is present in an amount of from 7 wt.% to 13 wt.% based on the total weight of the powder mixture.

36. The method of making a sintered cermet of claim 35, wherein the cobalt is present in an amount of 7.3 wt.%, the nickel is present in an amount of 7.3 wt.% and the molybdenum is present in an amount of 7.3 wt.% based on the total weight of the powder mixture.

37. A cutting tool or a drill bit, comprising the cemented carbide composition of claim

1.

38. A cutting tool ora drill bit, comprising the cermet composition of claim 10.

39. A cutting tool or a drill bit, comprising the cemented carbide composition of claim

16.