Reclaimed niobium carbide (NBC-ni) compositions

Abstract

Provided is a cemented carbide composition including a ceramic hard phase having at least about 50 weight percent (wt.%) of reclaimed niobium carbide (NbC) material based on the total weight of the cemented carbide composition, and a binder phase including nickel (Ni) in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. The cemented carbide may be devoid of cobalt (Co) in the binder phase. Further provided are associated methods of reclaiming the NbC material from cemented carbide scrap, and tools prepared by incorporating the reclaimed NbC material, which may include at least zinc reclaimed NbC.

Description

RECLAIMED NIOBIUM CARBIDE (NBC-NI) COMPOSITIONSFIELD OF THE DISCLOSURE

[0001] The present disclosure relates to reclaimed niobium carbide (NbC) material including a nickel metallic binder, which may be free of any cobalt in the binder phase; to associated methods of reclaiming NbC material from cemented carbide scrap; and to tools produced by incorporating the reclaimed NbC material. The reclaimed NbC material may include at least zinc reclaimed NbC material.BACKGROUND

[0002] Cemented carbides, also known as hardmetals are commonly used powder metallurgy products that have wide industrial application. For instance, cemented carbides have been used in industries where hardness, wear-resistance and corrosion-resistance, and fracture toughness are typically needed, such as, in for instance in the manufacture of tools, wire drawing dies, drill bits and veined end mills for drilling metals, and rocks in the mining industry, machining of resilient individual metals, complex metallic alloys and superalloys, nozzles, and knives just to name a few routine uses. Cemented carbides generally include a soft binder that is made of a relatively ductile material, such as cobalt (Co), iron (Fe), nickel (Ni), and a relatively hard ceramic phase typically consisting of a carbide material, such as, tungsten carbide (WC), titanium carbide (TiC), tantalum carbide (TaC), niobium carbide (NbC). When the relatively soft and ductile binder material, and the relatively hard carbide material are combined and further processed (e.g., by pressing and sintering), the relatively hard carbide material becomes cemented in the relatively soft ductile binder, thus forming what is known as a cemented carbide. Cemented carbides can achieve a wide variety of properties, e.g., hardness, wear-resistance, fracture toughness, transverse rupture strength (TRS), compressive strength, modulus of elasticity, and thermal expansion coefficient.

[0003] Several processes are currently used to recycle and reclaim cemented carbide products. These processes may include, for example, zinc processes, coldstream 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 conversion-steps, extraction-steps, andprecipitation-steps that increase the cycle time and the cost. Many of these chemical methods also undesirably involve the use and exposure to chemically harsh acids, bases, and various inorganic salts.

[0004] When a product is no longer physically and mechanically fit for its main intended purpose, it becomes what is known as scrap in the art. In this regard, at least two categories of scrap exist, which are namely, (I) scrap which is generated once the tool has either failed in service, or ultimately reached the end of its functioning tool life cycle, and (II) scrap which is generated during the entire manufacturing stages of the tools. In the second category, it is possible for large numbers of tools simply to be rejected during the production stage of the tool in question, for example, due to the formation of incorrect dimensional tolerances, and / or formed cracks in the manufactured tools. Since this class of scrap materials will usually not generate any income to offset the production-costs, simply because they have flaws in them, tool manufacturing companies may mitigate such situations by recovering some of these costs by recycling the scrapped materials, and then incorporating them back into the production-cycle.

[0005] Recovery of metals from scrapped products has a long tradition in the application of metals, long before this activity gained popularity defined by the names of recycling, and sustainable economy. Recycling basically entails a process, whereby individual tool constituents are extracted from typically cemented carbide scrap for reuse in the production of first-use products, which need such extracted components as raw materials for their manufacture. With that in mind, to date the main impetus has been the monetary value of metals, which makes their recovery and reuse an important undertaking. In the case of for example tungsten-based cemented carbide materials, recovery from used products that eventually becomes scrap has routinely been performed.

[0006] Tungsten carbide (WC) is a commonly used ceramic hard phase component in cemented carbide compositions, especially in tungsten carbide-cobalt (i.e., WC-Co) systems. However, WC supplies have lately started to become increasingly exhausted due to the gained popularity of WC cemented carbides, and the global growth of the tungsten-processing industries. As a result of the limited supply, and progressively increased demand, the cost of WC has risen, and maycontinue to rise in the future. The industry is therefore desirous of available alternatives to WC that still maintain their robust mechanical and physical properties, but at the same time avoid, or even reduce the full reliance on tungsten supplies to sustain the industrial demand in the manufacturing of cemented carbide tools. What is more, there has further been a significant pressure to reduce cobalt usage due to rarity, health concerns (e.g. possibly carcinogenic to humans), and the inherent environmental risks associated with mining, and disposal of used cobalt.

[0007] As a result of intensified research efforts for the past few years with a focus much directed towards preparing tools made of improved cemented carbides, these studies have turned their attention to the use of NbC as a viable substitute source for WC. As it currently stands, to the best of the inventor’s knowledge no zinc- applied process has been utilized for specifically reclaiming NbC and having a nickel (Ni) binder from cemented carbide scrap, where the cemented carbide composition may be devoid of cobalt (Co) in the binder phase. Consequently, this affords cemented carbide manufacturers with much needed flexibility, such that excellent cemented carbide compositions can still be produced in the event of a potential WC- shortage and depletion, or even price fluctuations in the future. In view of the foregoing, there is therefore a need for alternatives to WC-recycling, which is directed towards solving the aforementioned issues.SUMMARY

[0008] Provided is a cemented carbide composition, which includes a ceramic hard phase having at least about 50 weight percent (wt.%) of reclaimed niobium carbide (NbC) material based on a total weight of the cemented carbide composition. The cemented carbide composition further has a binder phase including nickel (Ni) in a weight of from about 8 wt.% to about 25 wt.% based on a total weight of the cemented carbide composition. The cemented carbide may be devoid of cobalt (Co) in the binder phase.

[0009] Optionally, the ceramic hard phase of the cemented carbide composition further has tungsten carbide (WC) in a range of from about 0 wt.% to about 2 wt.% based on the total weight of the cemented carbide composition.

[0010] Optionally, the ceramic hard phase of the cemented carbide composition further has tantalum carbide (TaC) in a range of from about 0 wt.% to about 3 wt.% based on the total weight of the cemented carbide composition.

[0011] The binder phase of the cemented carbide composition may further optionally include molybdenum (Mo).

[0012] Optionally, the reclaimed NbC material is zinc reclaimed NbC material from cemented carbide scrap.

[0013] Also provided is a method of preparing a sintered NbC article, which includes providing a cemented carbide composition having a ceramic hard phase including at least about 50 weight percent (wt.%) of reclaimed NbC material based on a total weight of the cemented carbide composition, and a binder phase including Ni in a weight of from about 8 wt.% to about 25 wt.% based on a total weight of the cemented carbide composition. The cemented carbide may be devoid of cobalt (Co) in the binder phase. The cemented carbide composition is milled to form a powder blend, which is next followed by granulating the milled powder blend by spray-drying, freeze-drying, air-drying, or vacuum-drying to form a ready-to-press (RTP) powder, and thereafter compacting the ready-to-press (RTP) powder to obtain a green body. Finally, the green body is sintered to form the sintered NbC article.

[0014] Further provided is a method of reclaiming NbC from cemented carbide scrap, which includes heating the cemented carbide scrap with zinc ingots to a temperature up to about 1000°C in an argon or a nitrogen oxidation resistant and protective atmosphere. The cemented carbide scrap includes a reclaimable cemented carbide composition including a ceramic hard phase including at least about 50 weight percent (wt.%) of NbC based on a total weight of the cemented carbide composition, and a binder phase including Ni in a weight of from about 8 wt.% to about 25 wt.% based on a total weight of the cemented carbide composition. The cemented carbide may be devoid of cobalt (Co) in the binder phase. The zinc ingots are reacted with the Ni in the binder phase of the cemented carbide composition by infiltrating and permeating the cemented carbide composition in the cemented carbide scrap by forming a molten Zn-Ni alloy. This is next followed by vaporizing zinc from the formed molten Zn-Ni alloy, and distilling off the vaporized zinc under vacuum conditions. A sponge of the cemented carbide scrap is thereafter formed by cooling the temperaturedown to room temperature. Finally, the sponge is crushed to form a powder of the reclaimed NbC material.

[0015] Optionally, the method further includes milling the formed powder of the reclaimed NbC material in a ball mill, an attritor mill, or a planetary mill.

[0016] Optionally, the method further includes sieving the milled powder of the reclaimed NbC material through either a 625-mesh screen, a 1250-mesh screen, or a 2500-mesh screen.

[0017] Optionally, the sponge includes a maximum amount of from about 50 parts per million (ppm) to about 150 ppm of remaining non-vaporized zinc.

[0018] Optionally, the cemented carbide scrap is heated with the zinc ingots in a nitrogen or an argon protective atmosphere at a temperature range of from about 600°C to about 1000°C for about 3 hours, for about 4 hours, or for about 5 hours.

[0019] Further provided is a tool or a blank for a tool. The tool or blank for the tool may include or consist of the cemented carbide composition including reclaimed NbC material as described hereinabove. The tool or blank may be produced as an article according to the method described hereinabove.

[0020] 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

[0021] The accompanying drawings, which are included to provide a further understanding of the subject matter and are incorporated in and constitute a part ofthis specification, illustrate implementations of the subject matter and together with the description serve to explain the principles of the disclosure.

[0022] FIG. 1 shows a flow diagram of the individual process steps of reclaiming niobium carbide (NbC) material from cemented carbide scrap by a zinc-based process in accordance with the current present subject matter.

[0023] FIG. 2A shows a 250X magnification of a scanning electron microscope (SEM) image of a niobium carbide (NbC) microstructure before any zinc treatment in accordance with the current present subject matter.

[0024] FIG. 2B shows a 250X magnification of a scanning electron microscope (SEM) image of a niobium carbide (NbC) microstructure after a zinc infiltration of the heated cemented carbide scrap in accordance with the current present subject matter.

[0025] FIG. 2C shows a 250X magnification of a niobium element mapping of the niobium carbide (NbC) microstructure of the Zn-treated, and heated cemented carbide scrap shown in FIG. 2B in accordance with the current present subject matter.

[0026] FIG. 2D shows a 250X magnification of a nickel element mapping of the niobium carbide (NbC) microstructure of the Zn-treated, and heated cemented carbide scrap shown in FIG. 2B in accordance with the current present subject matter.

[0027] FIG. 2E shows a 250X magnification of a zinc element mapping of the niobium carbide (NbC) microstructure of the Zn-treated, and heated cemented carbide scrap shown in FIG. 2B in accordance with the current present subject matter.

[0028] FIG. 3 shows a flow diagram of the individual process steps applied to form a sintered reclaimed NbC-Ni article.

[0029] FIG. 4 shows a 500X magnification of a scanning electron microscope (SEM) image of a zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap in accordance with the current present subject matter.

[0030] FIG. 5 shows an energy-dispersive X-ray spectroscopy (EDS) spectrum of the zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap in FIG. 4 in accordance with the current present subject matter.

[0031] FIG. 6 shows an energy-dispersive X-ray spectroscopy (EDS) spectrum of the zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap collected from the region marked with “Spectrum 1 ” in FIG. 4 in accordance with the current present subject matter.

[0032] FIG. 7 shows an energy-dispersive X-ray spectroscopy (EDS) spectrum of the zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap collected from the region marked with “Spectrum 2” in FIG. 4 in accordance with the current present subject matter.

[0033] FIG. 8 shows an energy-dispersive X-ray spectroscopy (EDS) spectrum of the zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap collected from the region marked with “Spectrum 3” in FIG. 4 in accordance with the current present subject matter.

[0034] FIG. 9 shows an energy-dispersive X-ray spectroscopy (EDS) spectrum of the zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap collected from the region marked with “Spectrum 4” in FIG. 4 in accordance with the current present subject matter.DETAILED DESCRIPTION

[0035] 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.

[0036] 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.

[0037] The following definitions set forth the parameters of the described subject matter.

[0038] As used herein, “wt.%” refers to a given weight percent (i) of the total weight of a cemented carbide composition, or (ii) of the total weight of a sintered article, 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 wt.% of (i), or (ii) in each given scenario. In the context of the present subject matter, NbC material, metallic binders, and / or grain growth inhibitors may all individually be used as balance to reach a total weight of 100 wt.% of (i), or (ii).

[0039] 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 grains 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 grains 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.

[0040] 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) “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.

[0041] 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.

[0042] 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.

[0043] As used herein this disclosure, the term “sintering” refers to a process, where heating under a controlled pressure is conducted to minimize the surface of a particulate system, which is associated with generation of bonds between neighboring small particles or granules, and subsequent shrinkage of the aggregated particles orgranules. Compacting and forming a dense solid bulk mass is performed by heating the particles under a controlled pressure. As used herein, “ambient conditions” refer to a temperature of 25° C, 298.15 K and a pressure of 101 .325 kPa.

[0044] As used herein, “reclaimed NbC material” means NbC material that has been recycled, or reclaimed in any hape or form from cemented carbide scrap according to any known method. In the precise context of the present subject matter, reclaimed NbC material may generally include at least zinc reclaimed NbC material from the cemented carbide scrap.

[0045] As used herein “zinc reclaimed NbC” refers to NbC material that is reclaimed from cemented carbide scrap after being subjected to a zinc recycling, or a zinc reclaiming methodology. For example, zinc reclaiming of NbC material includes a process of using molten zinc. In this process, the cemented carbide scrap is mixed with zinc ingots (i.e. , pieces of relatively pure zinc that are cast into a specific desired shape suitable for further processing) in a tray, and the mixture is subsequently heated in a vacuum furnace in a nitrogen, or an argon oxidation resistant protective atmosphere to liquefy, and thus melt the zinc. The liquefied molten zinc permeates the NbC material in the cemented carbide scrap, and subsequently reacts with the Ni metallic binder, and thereby opens up the Ni metallic binder in the NbC material. The zinc is then volatilized by evaporation during continued heating in the vacuum furnace for typically several hours (e.g., 3 hours, 4 hours, 5 hours) in the nitrogen, or the argon oxidation resistant protective atmosphere, and then distilled off under vacuum conditions. This leaves behind a reclaimed, but a highly porous NbC material, which is ultimately crushed into a powder form for further processing, and reuse in the production of new tools.

[0046] As used herein, the term “transverse rupture strength (TRS)” is a material property defined as the stress in a material just before the material yields and breaks 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 represents the highest stress experienced within the material immediately prior to its moment of yield or breakage. It is measured in terms of stress.

[0047] As used herein, 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. Fracture toughness (Kic) is calculated according to: where A is a constant of 0.0028, HV is the hardness (N / mm2), P isthe applied load (N), and ZL is the sum of crack lengths (mm) of imprints.

[0048] 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.

[0049] 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 comers 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. 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.

[0050] 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 (TRS) 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 alsoknown 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, breaks, 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. As used herein this disclosure, the term “ductility” is defined by the degree, whereby a given material can sustain plastic deformation under tensile stress eventually up to a point, before ultimately undergoing failure and breakage. 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.

[0051] 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.

[0052] 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.

[0053] 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, boron carbide (B4C)-diamond composites, silicon carbide (SiC)- titanium nitride (TiN)-titanium carbonitride (TiCN)-diamond composites, 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 such foregoing superabrasive materials used in superabrasive elements.

[0054] As used herein, the term “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.

[0055] As used herein, the term “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.

[0056] As used herein, the term “vacuum” refers to a free space, which is devoid of matter. As used herein, the term “vacuum” is a region with a gaseous pressure, which is much less than atmospheric pressure under ambient conditions, i.e. at a temperature of 25° C, 298.15 K, and a pressure of 101.325 kPa.

[0057] 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.

[0058] Wherever used throughout the disclosure, the term “generally” has the meaning of “approximately”, “typically” or “closely” or “within the vicinity or range of”.

[0059] As used herein, “spherical” refers to the grains having a substantially “round” shape.Zinc reclaimed niobium (NbC) material

[0060] The current disclosure stems from the premise of reclaiming niobium carbide (NbC) material from cemented carbide scrap for new use in the manufacturing of tools for machining of isolated individual metals, difficult to cut complex metallic alloys, composites, and ultra-resilient metallic superalloys to name just a few applications. To the best of the inventor’s knowledge, no zinc-utilized process has been applied for reclaiming NbC material to obtain NbC systems and NbC-nickel systems, which may be devoid of Co in the binder.

[0061] Thus, according to the present subject matter, provided is a cemented carbide composition, which includes a ceramic hard phase having at least about 50 weight percent (wt.%) of reclaimed NbC material based on the total weight of the cemented carbide composition. The cemented carbide composition further includes a binder phase having Ni in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. According to the present subject matter, the cemented carbide composition may be devoid of any Co in the binder phase.

[0062] As seen above, the cemented carbide composition may include a ceramic hard phase typically having at least about 50 wt.% of reclaimed NbC material based on the total weight of the cemented carbide composition. The cemented carbide composition includes a ceramic hard phase of at least about 55 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In other examples, the cemented carbide composition includes a ceramic hard phase of at least about 60 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In still other examples, the cemented carbide composition includes a ceramic hard phase of at least about 65 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In yet other examples, the cemented carbide composition includes a ceramic hard phase of at least about 70 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In even other examples, the cemented carbidecomposition includes a ceramic hard phase of at least about 75 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In further other examples, the cemented carbide composition includes a ceramic hard phase of at least about 80 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In even further other examples, the cemented carbide composition includes a ceramic hard phase of at least about 85 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In still other examples, the cemented carbide composition includes a ceramic hard phase of at least about 90 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In even other examples, the cemented carbide composition includes a ceramic hard phase of at least about 95 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition.

[0063] The cemented carbide composition may also include a ceramic hard phase having reclaimed NbC material in a range of from about 50 wt.% to about 55 wt.%, from about 55 wt.% to about 60 wt.%, from about 60 wt.% to about 65 wt.%, from about 50 wt.% to about 60 wt.%, from about 50 wt.% to about 65 wt.%, from about 50 wt.% to about 70 wt.%, from about 50 wt.% to about 75 wt.%, from about 65 wt.% to about 70 wt.%, from about 70 wt.% to about 75 wt.%, from about 75 wt.% to about 80 wt.%, from about 65 wt.% to about 75 wt.%, from about 65 wt.% to about 80 wt.%, from about 65 wt.% to about 85 wt.%, from about 70 wt.% to about 80 wt.%, from about 80 wt.% to about 85 wt.%, from about 85 wt.% to about 90 wt.%, from about 90 wt.% to about 95 wt.%, from about 80 wt.% to about 90 wt.%, from about 80 wt.% to about 95 wt.%, from about 90 wt.% to about 95 wt.%, or from about 80 wt.% to about 100 wt.%, of the reclaimed NbC material based on the total weight of the cemented carbide composition.

[0064] Ni may be present in the binder phase of the reclaimed NbC material typically in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In some examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 11 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In other examples, the Ni is present in the binder phase of the reclaimed NbC material in aweight of from about 14 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In still other examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 17 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 20 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In even other examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 22 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition.

[0065] The Ni may also be present in the binder phase of the reclaimed NbC material in a range of from about 11 wt.% to about 14 wt.%, from about 14 wt.% to about 17 wt.%, from about 11 wt.% to about 17 wt.%, from about 17 wt.% to about 20 wt.%, from about 20 wt.% to about 22 wt.%, from about 14 wt.% to about 22 wt.%, from about 17 wt.% to about 22 wt.%, or from about 17 wt.% to about 25 wt.%, based on the total weight of the cemented carbide composition.

[0066] Optionally, the binder phase of the reclaimed NbC material may further include molybdenum (Mo).

[0067] The ceramic hard phase of the reclaimed NbC material may further include WC up to generally about 2.00 wt.% based on the total weight of the cemented carbide composition. In some examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1.75 wt.% based on the total weight of the cemented carbide composition. In other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1.50 wt.% based on the total weight of the cemented carbide composition. In still other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1.25 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1 .00 wt.% based on the total weight of the cemented carbide composition. In further other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 0.75 wt.% based on the total weight of the cemented carbide composition. In even further other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 0.50 wt.% based on the total weight of the cementedcarbide composition. In even other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 0.25 wt.% based on the total weight of the cemented carbide composition.

[0068] The ceramic hard phase of the reclaimed NbC material may also include the WC in a range of from about 1 .75 wt.% to about 2.00 wt.%, from about 1 .50 wt.% to about 1 .75 wt.%, from about 1 .25 wt.% to about 1 .50 wt.%, from about 1 .25 wt.% to about 1.75 wt.%, from about 1.25 wt.% to about 2.00 wt.%, from about 1.00 wt.% to about 1.25 wt.%, from about 0.75 wt.% to about 1.00 wt.%, from about 0.50 wt.% to about 0.75 wt.%, from about 0.25 wt.% to about 0.50 wt.%, from about 0.25 wt.% to about 0.75 wt.%, from about 0.25 wt.% to about 1.00 wt.%, from about 0.25 wt.% to about 1.25 wt.%, from about 0.25 wt.% to about 1.50 wt.%, from about 0.25 wt.% to about 1.75 wt.%, from about 0.25 wt.% to about 2.00 wt.%, from about 0.50 wt.% to about 1.00 wt.%, from about 0.50 wt.% to about 1.25 wt.%, from about 0.50 wt.% to about 1.50 wt.%, from about 0.50 wt.% to about 1.75 wt.%, from about 0.50 wt.% to about 2.00 wt.%, from about 0.75 wt.% to about 1.00 wt.%, from about 0.75 wt.% to about 1.25 wt.%, from about 0.75 wt.% to about 1.50 wt.%, from about 0.75 wt.% to about 1.75 wt.%, from about 0.75 wt.% to about 2.00 wt.%, from about 1.00 wt.% to about 2.00 wt.%, or from about 1 .50 wt.% to about 2.00 wt.% based on the total weight of the cemented carbide composition.

[0069] Additionally, the ceramic hard phase of the reclaimed NbC material may also typically include tantalum carbide (TaC) up to about 3.00 wt.% based on the total weight of the cemented carbide composition. In some examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.75 wt.% based on the total weight of the cemented carbide composition. In other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.50 wt.% based on the total weight of the cemented carbide composition. In still other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.25 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.00 wt.% based on the total weight of the cemented carbide composition. In even other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1.75 wt.% based on the total weight of thecemented carbide composition. In even further other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1 .50 wt.% based on the total weight of the cemented carbide composition. In other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1 .25 wt.% based on the total weight of the cemented carbide composition. In even other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1 .00 wt.% based on the total weight of the cemented carbide composition. In still other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 0.75 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 0.50 wt.% based on the total weight of the cemented carbide composition.

[0070] The ceramic hard phase of the reclaimed NbC material may also include the TaC in a range of from about 0.25 wt.% to about 2.00 wt.%, from about 0.50 wt.% to about 2.00 wt.%, from about 0.75 wt.% to about 2.00 wt.%, from about 1 .00 wt.% to about 2.00 wt.%, from about 1.25 wt.% to about 2.00 wt.%, from about 1 .50 wt.% to about 2.00 wt.%, from about 1.75 wt.% to about 2.00 wt.%, from about 0.25 wt.% to about 3.00 wt.%, from about 0.50 wt.% to about 3.00 wt.%, from about 0.75 wt.% to about 3.00 wt.%, from about 1.00 wt.% to about 3.00 wt.%, from about 1 .25 wt.% to about 3.00 wt.%, from about 1.50 wt.% to about 3.00 wt.%, from about 1 .75 wt.% to about 3.00 wt.%, from about 2.25 wt.% to about 3.00 wt.%, from about 2.50 wt.% to about 3.00 wt.%, from about 2.75 wt.% to about 3.00 wt.%, from about 2.50 wt.% to about 2.75 wt.%, from about 2.25 wt.% to about 2.50 wt.%, from about 2.25 wt.% to about 2.75 wt.%, from about 2.00 wt.% to about 2.25 wt.%, from about 2.00 wt.% to about 2.50 wt.%, from about 2.00 wt.% to about 2.75 wt.%, from about 2.25 wt.% to about 2.50 wt.%, from about 2.25 wt.% to about 2.75 wt.%, from about 1 .50 wt.% to about 1.75 wt.%, from about 1.50 wt.% to about 2.25 wt.%, from about 1 .75 wt.% to about 2.25 wt.%, from about 1.25 wt.% to about 1.50 wt.%, from about 1 .00 wt.% to about 1.25 wt.%, from about 0.75 wt.% to about 1.00 wt.%, from about 0.75 wt.% to about 1.25 wt.%, from about 0.75 wt.% to about 1.50 wt.%, from about 0.75 wt.% to about 1.75 wt.%, from about 0.50 wt.% to about 0.75 wt.%, from about 0.50 wt.% to about 1.00 wt.%, from about 0.50 wt.% to about 1.25 wt.%, from about 0.50 wt.% to about 1.50 wt.%, from about 0.50 wt.% to about 1.75 wt.%, from about 0.25 wt.% toabout 0.50 wt.%, or from about 0.25 wt.% to about 0.75 wt.%, based on the total weight of the cemented carbide composition.

[0071] The reclaimed NbC material may also include at least one or more grain growth inhibitors. Non-limiting examples of such grain growth inhibitors may include carbides like vanadium carbide (VC), chromium carbide (Cr3C2), titanium carbide (TiC), and zirconium carbide (ZrC) in a weight of from about 1 wt.% to about 2 wt.%, from about 2 wt.% to about 5 wt.%, from about 5 wt.% to about 7 wt.%, from about 3 wt.% to about 7 wt.%, from about 7 wt.% to about 10 wt.%, from about 10.1 wt.% to about 10.3 wt.%, from about 10.4 wt.% to about 10.6 wt.%, from about 10.1 wt.% to about 10.6 wt.%, or from about 10.7 wt.% to about 10.9 wt.% based on the total weight of the cemented carbide composition.

[0072] The reclaimed NbC material may exhibit any average grain size that is not inconsistent and incompatible with the objectives of the present disclosure. Generally, the reclaimed NbC material may typically demonstrate an average grain size (D50) ranging for example from about 0.5 pm to about 30 pm. In certain particular examples, the reclaimed NbC material may exhibit an average grain size in the range of from about 1 pm to about 5 pm, from about 1 pm to about 7 pm, from about 1 pm to about 10 pm, from about 1 pm to about 12 pm from about 1 pm to about 15 pm, from about 1 pm to about 17 pm, from about 1 pm to about 20 pm, from about 1 pm to about 22 pm, from about 1 pm to about 25 pm, from about 1 pm to about 27 pm, from about 1 pm to about 30 pm, from about 5 pm to about 7 pm, from about 5 pm to about 10 pm, from about 7 pm to about 10 pm, from about 5 pm to about 12 pm, from about 7 pm to about 12 pm, from about 10 pm to about 12 pm, from about 5 pm to about 15 pm, from about 7 pm to about 15 pm, from about 10 pm to about 15 pm, from about 12 pm to about 15 pm, from about 5 pm to about 20 pm, from about 7 pm to about 20 pm, from about 10 pm to about 20 pm, from about 12 pm to about 20 pm, from about 15 pm to about 20 pm, from about 17 pm to about 20 pm, from about 5 pm to about 25 pm, from about 7 pm to about 25 pm, from about 10 pm to about 25 pm, from about 12 pm to about 25 pm, from about 15 pm to about 25 pm, from about 17 pm to about 25 pm, from about 20 pm to about 25 pm, from about 22 pm to about 25 pm, from about 25 pm to about 30 pm, or from about 27 pm to about 30 pm.

[0073] The grain size defined by the reclaimed NbC material may be determined by a linear-intercept technique using a line drawn across a calibrated scanning electron microscope (SEM) image of the reclaimed NbC material. A length of the line may be measured by using a calibrated rule, where the line intercepts a grain of the reclaimed NbC material, and the linear-intercept technique is repeated for at least 100 NbC grains to obtain an average grain size of the reclaimed NbC material. For determining a specific grain 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 grain sizes, or grain 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 spherical particle systems”, AAPS PharmSciTech. 2006 Aug 18; Vol.7(3):69, to further gain insight into each procedure and methodology, all of which documents, are incorporated herein by reference in their entirety.Methods of reclaiming niobium carbide (NbC) material from cemented carbide scrap

[0074] Now the attention of the reader is specifically directed to FIGS. 1 , and 2A-2E where it will be described in greater detail the individual method steps applied for reclaiming niobium carbide (NbC) material from cemented carbide scrap, and the obtained microstructures before and after, respectively, zinc-treatment in the reclaiming process.

[0075] First, zinc ingots 10a, a cemented carbide scrap 10b, and a graphite crucible 10c are provided, which cemented carbide scrap 10b is first cleaned and then sorted. The graphite crucible 10c is next filled with the cemented carbide scrap 10b,and the zinc ingots 10a, and the filled graphite crucible 10c is thereafter placed in a vacuum furnace 12. The cemented carbide scrap 10b is heated mixed with the zinc ingots 10a in the graphite crucible 10c up to a temperature of typically about 1000°C generally for about a few hours, such as, for example 3 hours, 4 hours, or 5 hours in a nitrogen, or an argon oxidation resistant protective atmosphere. Alternatively, the cemented carbide scrap 10b may be heated mixed with the zinc ingots 10a in the graphite crucible 10c in the nitrogen, or the argon atmosphere to avoid oxidation at a temperature range of from about 600°C to about 1000°C, from about 700°C to about 1000°C, from about 800°C to about 1000°C, or from about 900°C to about 1000°C typically for about 3 hours, for about 4 hours, or for about 5 hours. During the heattreatment, the zinc ingots 10a permeate and diffuse into, and react with the Ni binder in the binder phase of the cemented carbide scrap 10b, and thus forming a molten Zn- Ni alloy 14 within the ceramic NbC hard particles of the cemented carbide scrap 10b. Liquid zinc reacts with the Ni binder to form intermetallic phases, which leads to a volume expansion of the Ni binder, and bloats up the carbide scrap parts. The heattreatment is still continued in the vacuum furnace, which then eventually causes a vaporization of the zinc from the formed molten Zn-Ni alloy 14, and the vaporized zinc is next distilled off under vacuum conditions, thereby leaving behind a weakened molten Ni binder phase within the NbC particles. Evaporation of zinc typically starts at atmospheric pressure at temperatures above the boiling point of zinc (i.e. , furnace temperatures of about 1000°C), and the pressure is gradually reduced to a final pressure of approximately 10-2mbar, which typically takes another few hours, i.e. generally about 3 hours, about 4 hours, or about 5 hours. The NbC reclaiming process is concluded by forming a sponge 15 of the zinc-infiltrated cemented carbide scrap 10b by cooling the temperature down to room temperature under ambient conditions (i.e., 25° C, 298.15 K and a pressure of 101.325 kPa), which sponge 15, is further crushed with typically a sponge crusher to form a crushed sponge 16, and ultimately a powder of the zinc reclaimed NbC as shown in FIG. 1. As used herein, the term “sponge” generally refers to a highly porous cemented carbide material with a complex, and an interconnected porosity signature. The crushed sponge 16 most typically contains a maximum amount of from about 50 parts per million (ppm) to about 150 ppm of remaining non-vaporized zinc in the reclaimed NbC material obtained from the cemented carbide scrap 10b.

[0076] FIG. 2A shows a 250X magnification of a scanning electron microscope (SEM) image of a niobium carbide (NbC) microstructure before any zinc treatment has taken place in accordance with the current subject matter. FIG. 2B shows a 250X magnification of a scanning electron microscope (SEM) image of a niobium carbide (NbC) microstructure after a zinc infiltration of the heated cemented carbide scrap has taken place in accordance with the current subject matter. FIG. 2C shows a 250X magnification of a niobium element mapping of the niobium carbide (NbC) microstructure of the Zn- treated, and heated cemented carbide scrap shown in FIG. 2B in accordance with the current subject matter. FIG. 2D shows a 250X magnification of a nickel element mapping of the niobium carbide (NbC) microstructure of the Zn- treated, and heated cemented carbide scrap shown in FIG. 2B in accordance with yet another example of the current subject matter. FIG. 2E shows a 250X magnification of a zinc element mapping of the niobium carbide (NbC) microstructure of the Zn- treated, and heated cemented carbide scrap shown in FIG. 2B in accordance with still another example of the current subject matter.

[0077] The method may further include milling the formed powder of the reclaimed NbC material in for example a ball mill, an attritor mill, or a planetary mill under ambient conditions (i.e. , 25° C, 298.15 K and a pressure of 101 .325 kPa), and followed by screening to >625-mesh. The reclaimed NbC material typically may exhibit an average particle size (D50) of about 30 pm. Any formed reclaimed NbC powder displaying an average particle size (D50) >625-mesh may be reused in the described zinc reclaiming process, as it is not retained in the 625-mesh screen, because the lower cut-off average particle size (D50) of a 625-mesh screen is about 20 microns. On the other hand, the reclaimed NbC material displaying an average particle size (D50) of about 30 pm will be retained by a >625-mesh screen.

[0078] As described above, for sieving, a 625-mesh screen may appropriately be used, which passes through a powder characterized by exhibiting an average particle size (D50) measuring less than about 20 microns, while retaining thus holding back a powder characterized by displaying an average particle size (D50) measuring greater than about 20 microns (i.e., reclaimed NbC powder with about an average D50 particle size of 30 pm in the present case). A person having ordinary skill in the art would know that the mesh-number correlates inversely with the average powder particle size (D50), which is passed through the mesh screen. That is the higher mesh-number of a used screen or a sieve, the smaller the average particle size (D50) thus passing through the used screen or the sieve. Alternatively in other examples, for sieving, a 1250-mesh screen, or a 2500-mesh screen may also be used, which respectively, pass through a powder characterized by exhibiting an average particle size (D50) of less than about 10 microns, or an average particle size (D50) less than about 5 microns, which may be reused in the zinc reclaiming process as previously mentioned. Moreover, one of ordinary skill in the would readily know different sieving methodologies, and non-limiting examples of such sieving techniques may for example include the following, but without limitation vibrational sieving, wet sieving, horizontal sieving, tap sieving, and air jet sieving.Methods of preparing sintered niobium carbide (Nbc-Ni) articles

[0079] A specifically targeted particle size of the niobium carbide (NbC) ceramic hard phase powder, and the Ni metal binder phase powder can be produced by subjecting the cemented carbide powders to a wet 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, a planetary mill, or an attritor mill. As would be apparent to a skilled artisan, the wet milling is made by first adding a milling liquid to the mixed powders to form a milling powder slurry composition. The milling liquid may be water, an alcohol, such as e.g. ethanol, methanol, isopropanol, butanol, cyclohexanol, another organic solvent in the likes of for example acetone, toluene, hexane, heptane, an alcohol mixture, an alcohol and another solvent mixture, or such like constituents. The properties of the milling powder slurry composition are dependent on, among other things, the weight of the milling liquid that is added. Because the drying of the milling powder slurry composition requires energy, the volume 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 wet milling slurry composition e.g., lubricants, anti-flocculating agents, dispersion agents, pH-adjusters. 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 about 10 vol. % to about 25 vol. %, from about 12 vol. % toabout 25 vol. %, from about 15 vol. % to about 25 vol. %, from about 17 vol. % to about 25 vol. %, from about 20 vol. % to about 25 vol. %, or from about 22 vol. % to about 25 vol. % of the total volume of the formed milling slurry composition. This is done to facilitate the formation of a proper ceramic hard phase powder, 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 obtained green body formed in the following pressing / forming steps described hereinbelow.

[0080] The main purpose of the wet milling process is to facilitate a uniform, and an even Ni binder distribution, and a good wettability between the ceramic hard phase constituent grains, and the Ni binder powder. This is done to strengthen the physical integrity of the milled powder slurry composition, and further to deagglomerate any potentially formed crystals during the wet milling process.

[0081] An acceptably uniform, and even Ni binder distribution, and a good quality of wettability are key to obtaining NbC materials of stellar physical quality. On the downside, if the metallic binder distribution, and the wettability between the constituents are of bad quality, pores and cracks may undesirably be formed as a result of this in the final sintered NbC body, which is detrimental to the produced NbC- Ni article.

[0082] The milled powder slurry composition can be granulated to form a ready- to-press (RTP) powder by spray-drying, freeze-drying, air-drying, or vacuum-drying, to essentially provide free-flowing cemented carbide powder aggregates with most typically a spherical shape, or a substantially spherical-like shape. In the case of spray drying, the milled powder slurry composition containing the powdered NbC ceramic hard phase, and the Ni binder materials mixed with the organic liquid, and the organic binder(s) may be atomized through a plurality of appropriate nozzles in a drying tower by forming sprays. The small discrete droplets are instantaneously dried by a stream of hot gas, for instance in a stream of nitrogen or argon, to generally form spherical ,or substantially spherical-like powder agglomerates displaying non-restricted free- flowing properties. As used herein, the term “free-flowing” refers to loosely packed agglomerated cemented carbide powders exhibiting a pore space between each free- flowing particle of the agglomerated cemented carbide powder with no physical restrictions, or barriers whatsoever, suppressing the free-flowing capability of theagglomerated particles of the cemented carbide powder. Further, as used herein, “atomization” refers to a process, where a bulk liquid feed is converted into discrete droplets by forming sprays, thereby significantly increasing the surface area of the feed liquid, and thus increasing significantly the achievable rates of evaporation of a solvent (i.e., the milling liquid). The atomization stage is designed to create optimum conditions for evaporation of the solvent from the milled slurry composition, and to lead to an optimally dried cemented carbide powder having desired free-flowing properties. Nozzles and rotary atomizers are used to form sprays. Drying towers may be equipped with just one nozzle, or a plurality of such nozzles to form the sphericalshaped, or substantially spherical-like shaped cemented carbide powder agglomerates with free-flowing properties.

[0083] The ready-to-press (RTP) agglomerated granules of the dried cemented carbide powder are next formed / pressed or consolidated into a green body in the preparation for the sintering procedure. A green body is formed of the ready-to-press (RTP) powder using conventional techniques, such as, cold tool pressing technology including multi axial pressing, extruding or metal injection molding, cold isostatic pressing (i.e., pressure is applied in 3 directions or axis), pill pressing, tape casting, additive manufacturing (AM), additive layer manufacturing (ALM), and other methodologies generally 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 / pressing yields a green density, and / or strength that permits easy handling, and green machining of the formed and pressed cemented carbide powder agglomerates, due to the processed green body essentially 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. Additionally, machining in the green state may be required to achieve a desired green body shape.

[0084] The green body may be subjected to a pre-sintering temperature elevation procedure, to completely remove the organic binder(s), which is also referred as “depegging”. This may be done in the same heating furnace when performing the sintering process. Suitable temperature ranges for the removal of the organic binder(s) may be employed from 150°C and ending at 450°C, starting from 150°C andending at 500°C, starting from 150°C and ending at 550°C, starting from 150°C and ending at 600°C, starting from 250°C and ending at 450°C, starting from 250°C and ending at 500°C, starting from 250°C and ending at 550°C, starting from 250°C and ending at 600°C, starting from 300°C and ending at 450°C, starting from 300°C and ending at 500°C, starting from 300°C and ending at 550°C, or starting from 300°C and ending at 600°C. This may typically be performed in a reactive H2 atmosphere with a hydrogen (H2) flow rate applied at about 1000 liters / hour to about 10000 liters / hour, applied at about 3000 liters / hour to about 10000 liters / hour, applied at about 6000 liters / hour to about 10000 liters / hour, or applied at about 9000 liters / hour to about 10000 liters / hour. The temperature may typically be increased constantly at a rate of for example about 0.70°C / min. In some examples, after the complete organic binder(s) removal, the temperature may be increased in tandem sequentially at a rate of about 2°C / min. shifted to about 10°C / min., when a certain temperature in an operated temperature range has been reached after the complete removal of the organic binder(s), or for example at a rate of about 2°C / min. changed to about 5°C / min., or changed to about 7°C / min., again when a particular temperature in an operated temperature range has been reached. The aforementioned temperature ranges for the depegging or dewaxing (i.e., debinding of the organic binder) may generally be reached after heating for about 60 minutes to about 90 minutes, or for about 60 minutes to about 7 hours in the sintering furnace. Thus, in general, the particular type of heating-pattern chosen is determined and performed, and for the particular amount of time, in a manner, that confers and thereby provides a desired complete dewaxed phase-transformation of the cemented carbide powder. In general, the pre-sintering cycle for complete dewaxing of the organic binder(s) may be conducted in a reactive (H2) atmosphere, under vacuum conditions, or in a non- reactive inert atmosphere e.g., nitrogen (N2) or argon (Ar).

[0085] The pre-sintered and debinded green body subsequently undergoes a consolidation process to ultimately form the sintered NbC-Ni articles. The cemented carbide powder thereafter undergoes a consolidation process to ultimately form the high density cemented carbide for neutron shielding. As used herein this disclosure, the term “consolidation process” is meant to either include (A) any process that in combination (i) compacts (i.e., presses), and (ii) consolidates (i.e., densifies, thus sinters the material by a high temperature heating operation) the cemented carbidepowder simultaneously, or (B) densifies only by a high temperature heating operation as applied solely during vacuum sintering, which does not have any compaction / pressure happening during the vacuum sintering / consolidation operation. 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 1200°C and ending at 1500°C, starting from 1200°C and ending at 1600°C, starting from 1200°C and ending at 1700°C, starting from 1200°C and ending at 1800°C, starting from 1400°C and ending at 1500°C, starting from 1400°C and ending at 1600°C, starting from 1400°C and ending at 1700°C, starting from 1400°C and ending at 1800°C, starting from 1500°C and ending at 1600°C, starting from 1500°C and ending at 1700°C, or starting from 1500°C and ending at 1800°C. The temperature may typically be increased constantly at a rate of for example about 0.70°C / min, or the temperature may be increased in tandem sequentially at a rate of about 2°C / min. shifted to about 10°C / min., when a certain temperature in an operated temperature range has been reached, or for example at a rate of about 2°C / min. changed to about 5°C / min., or changed to about 7°C / min., again when a particular temperature in an operated temperature range has been reached. A dwell time may be introduced at the maximum temperature in an adopted temperature range and a specific pressure range, which may typically be from 1 minute to 60 minutes, 20 minutes to 60 minutes, from 25 minutes to 60 minutes, from 30 minutes to 60 minutes, from 35 minutes to 60 minutes, from 40 minutes to 60 minutes, from 45 minutes to 60 minutes, from 50 minutes to 60 minutes, or from 55 minutes to 60 minutes. The particular sintering temperature range is chosen, in a manner, that will result in a sufficient melting of the metallic Ni binder phase. During this process, the Ni based metallic binder phase will eventually enter the liquid stage, while the reclaimed NbC grains having a considerably higher melting point will remain in a solid stage. At the sintering temperature, the Ni based metallic binder, and the reclaimed NbC grains will form a eutectic liquid phase, where the NbC grains are positioned, and subsequently coated with the Ni metallic binder. As a result of this process, the metallic Ni binder is anchoring, and therebycementing the reclaimed NbC grains, thus forming the metallic Ni binder matrix composite with its distinct material properties.

[0086] The pre-sintered and completely debinded (i.e., depegged) green body may alternatively be subjected to vacuum-sintering in a non-reactive inert atmosphere supplied with e.g., argon (Ar), or nitrogen (N2) at a minuscule pressure typically ranging from 10’2millibar (mbar) to 10’4millibar (mbar). During vacuum-sintering, the presintered green body is placed in a vacuum-furnace, and sintered at a temperature starting from 1200°C and ending at 1500°C, starting from 1200°C and ending at 1600°C, starting from 1200°C and ending at 1700°C, starting from 1200°C and ending at 1800°C, starting from 1400°C and ending at 1500°C, starting from 1400°C and ending at 1600°C, or starting from 1400°C and ending at 1700°C. A dwell-time may be introduced employed at a maximum temperature in an operated temperature range, which may typically be from about 1 minute to about 60 minutes. Alternatively, the dwell time may be introduced at the maximum temperature in the applied temperature range and at the specific pressure range, which may typically be from 20 minutes to 60 minutes, from 25 minutes to 60 minutes, from 30 minutes to 60 minutes, from 35 minutes to 60 minutes, from 40 minutes to 60 minutes, from 45 minutes to 60 minutes, from 50 minutes to 60 minutes, or from 55 minutes to 60 minutes.

[0087] In some examples, hot isostatic pressing (HIP) may also be added as a sequential post vacuum sintering operation typically for about 30 minutes to an hour, thus yielding a high-pressure sinter-HIP process. Thus, in the case, HIP may be performed on the cemented carbide powder, or alternatively, as an extra post vacuum sintering step performed sequentially on an already vacuum sintered cemented carbide. In this case, the ready-to-press (RTP) agglomerated granules of the dried cemented carbide powder will be pressed to form a green body and will typically be vacuum sintered in generally a non-reactive inert atmosphere e.g., argon (Ar), or nitrogen (N2) at a minuscule pressure typically ranging from 10’2mbar to 10’4mbar. Next, the vacuum sintered cemented carbide may undergo an additional sequential HIP-treatment step. This additional HIP-treatment step fulfils the significant purpose of eliminating the presence of any potential porosity that may be present in the vacuum sintered cemented carbide. HIP is a relatively slow process, and compacting is isostatic, i.e., pressure is applied in 3 directions or axis. Heating is performed at thesame time by elements that are integrated in the press. Thus, HIP subjects the cemented carbide powder to both an elevated temperature and isostatic gas pressure in, for example, a high pressure containment vessel. The pressurizing gas that is used may, for example, be argon. An inert gas such as argon is most typically used, so that the material undergoing HIP, does not chemically react. The chamber is heated, causing the pressure inside the vessel to increase. The applied temperature during the sinter-HIP process may, for example, range starting from 1300°C and ending at 1500°C, starting from 1300°C and ending at 1600°C, starting from 1300°C and ending at 1700°C, starting from 1300°C and ending at 1800°C, starting from 1300°C and ending at 1900°C, starting from 1300°C and ending at 2000°C, starting from 1400°C and ending at 1500°C, starting from 1400°C and ending at 1600°C, starting from 1400°C and ending at 1700°C, starting from 1400°C and ending at 1800°C, starting from 1400°C and ending at 1900°C, starting from 1400°C and ending at 2000°C, starting from 1500°C and ending at 1600°C, starting from 1500°C and ending at 1700°C, starting from 1500°C and ending at 1800°C, starting from 1500°C and ending at 1900°C, or starting from 1500°C and ending at 2000°C, with an applied pressure typically ranging from about 7,350 psi (about 50.7 MPa) to about 45,000 psi (about 310 MPa), with about 14,500 psi (about 100 MPa) generally being the most typical applied pressure, or alternatively from about from about 800 bar (80 MPa) to about 900 bar (90 MPa), from about 800 bar (80 MPa) to about 1000 bar (100 MPa), from about 800 bar (80 MPa) to about 1100 bar (110 MPa), 800 bar (80 MPa) to about 1200 bar (120 MPa), from about 900 bar (90 MPa) to about 1000 bar (100 MPa), from about 900 bar (90 MPa) to about 1100 bar (110 MPa), from about 900 bar (90 MPa) to about 1200 bar (120 MPa), from about 1000 bar (100 MPa) to about 1100 bar (110 MPa), from about 1000 bar (100 MPa) to about 1200 bar (120 MPa), or from about 1100 bar (110 MPa) to about 1200 bar (120 MPa).

[0088] FIG. 3 shows the foregoing steps summarized in a flow chart in accordance with the present subject matter. First in step 18, a cemented carbide composition is provided having a ceramic hard phase including at least about 50 weight percent (wt.%) of reclaimed NbC based on a total weight of the cemented carbide composition, and a binder phase including Ni in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. The cemented carbide may be devoid of cobalt (Co) in the binder phase. In step 20, amilling operation is performed on the cemented carbide composition to form a powder blend constituted of the reclaimed NbC and the Ni, which is next followed by granulating the milled reclaimed NbC and the Ni powder blend by spray-drying, freeze- drying, air-drying, or vacuum-drying in step 21 to form a ready-to-press (RTP) powder, and thereafter compacting the ready-to-press (RTP) powder to form a green body in step 22. Finally, in step 24, the green body is sintered to form the sintered NbC-Ni article.

[0089] It should however be understood and stressed that the overall concept of sintering generally falls under the standard umbrella of processes defined by depegging, solid state sintering, or liquid phase sintering, and ultimately cooling the sintered material down to ambient conditions after the sintering operation is fully complete. A person having ordinary skill in the art would know that the aforementioned steps in the consolidation processes described before can be performed all at once in the same consolidation equipment. Alternatively, a person having ordinary skill in the art would also know that they may equally be performed one straight after the other in different sintering equipments.

[0090] In the case of a sintered NbC article, such sintered NbC article may include a ceramic hard phase in the cemented carbide composition typically having at least about 50 wt.% of reclaimed NbC material based on the total weight of the cemented carbide composition. The cemented carbide composition includes a ceramic hard phase of at least about 55 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In other examples, the cemented carbide composition includes a ceramic hard phase of at least about 60 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In still other examples, the cemented carbide composition includes a ceramic hard phase of at least about 65 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In yet other examples, the cemented carbide composition includes a ceramic hard phase of at least about 70 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In even other examples, the cemented carbide composition includes a ceramic hard phase of at least about 75 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In further other examples, thecemented carbide composition includes a ceramic hard phase of at least about 80 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In even further other examples, the cemented carbide composition includes a ceramic hard phase of at least about 85 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In still other examples, the cemented carbide composition includes a ceramic hard phase of at least about 90 wt.% of the reclaimed NbC material based on the total weight of the cemented carbide composition. In even other examples, the cemented carbide composition includes a ceramic hard phase of at least about 95 wt.% of the reclaimed NbC based on the cemented carbide composition.

[0091] The sintered NbC article may also include a ceramic hard phase in the cemented carbide composition having the reclaimed NbC material in a range of from about 50 wt.% to about 55 wt.%, from about 55 wt.% to about 60 wt.%, from about 60 wt.% to about 65 wt.%, from about 50 wt.% to about 60 wt.%, from about 50 wt.% to about 65 wt.%, from about 65 wt.% to about 70 wt.%, from about 70 wt.% to about 75 wt.%, from about 75 wt.% to about 80 wt.%, from about 65 wt.% to about 80 wt.% from about 70 wt.% to about 80 wt.%, from about 80 wt.% to about 85 wt.%, from about 85 wt.% to about 90 wt.%, from about 90 wt.% to about 95 wt.%, from about 80 wt.% to about 90 wt.%, from about 80 wt.% to about 95 wt.%, from about 90 wt.% to about 95 wt.%, or from about 80 wt.% to about 100 wt.%, based on the total weight of the cemented carbide composition.

[0092] The sintered NbC article may further include Ni in the binder phase of the reclaimed NbC material generally in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In some examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 11 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In other examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 14 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In still other examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 17 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the Ni is present in the binder phase of the reclaimed NbC materialin a weight of from about 20 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition. In even other examples, the Ni is present in the binder phase of the reclaimed NbC material in a weight of from about 22 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition.

[0093] The sintered NbC article may also include Ni in the binder phase of the reclaimed NbC material in a range of from about 11 wt.% to about 14 wt.%, from about 14 wt.% to about 17 wt.%, from about 11 wt.% to about 17 wt.%, from about 17 wt.% to about 20 wt.%, from about 20 wt.% to about 22 wt.%, from about 17 wt.% to about 22 wt.%, or from about 17 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition.

[0094] Optionally, the binder phase of the reclaimed NbC material may further include molybdenum (Mo).

[0095] The sintered NbC article may additionally include WC up to generally about 2.00 wt.% in the ceramic hard phase of the reclaimed NbC material based on the total weight of the cemented carbide composition. In some examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1.75 wt.% based on the total weight of the cemented carbide composition. In other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1 .50 wt.% based on the total weight of the cemented carbide composition. In still other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1 .25 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 1.00 wt.% based on the total weight of the cemented carbide composition. In further other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 0.75 wt.% based on the total weight of the cemented carbide composition. In even further other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 0.50 wt.% based on the total weight of the cemented carbide composition. In even other examples, the ceramic hard phase of the reclaimed NbC material includes the WC up to about 0.25 wt.% based on the total weight of the cemented carbide composition.

[0096] The ceramic hard phase of the sintered NbC article may also include the WC in a range of from about 1 .75 wt.% to about 2.00 wt.%, from about 1 .50 wt.% to about 1.75 wt.%, from about 1.25 wt.% to about 1.50 wt.%, from about 1.25 wt.% to about 1.75 wt.%, from about 1.25 wt.% to about 2.00 wt.%, from about 1.00 wt.% to about 1.25 wt.%, from about 0.75 wt.% to about 1.00 wt.%, from about 0.50 wt.% to about 0.75 wt.%, from about 0.25 wt.% to about 0.50 wt.%, from about 0.25 wt.% to about 0.75 wt.%, from about 0.25 wt.% to about 1.00 wt.%, from about 0.25 wt.% to about 1.25 wt.%, from about 0.25 wt.% to about 1.50 wt.%, from about 0.25 wt.% to about 1.75 wt.%, from about 0.25 wt.% to about 2.00 wt.%, from about 0.50 wt.% to about 1.00 wt.%, from about 0.50 wt.% to about 1.25 wt.%, from about 0.50 wt.% to about 1.50 wt.%, from about 0.50 wt.% to about 1.75 wt.%, from about 0.50 wt.% to about 2.00 wt.%, from about 0.75 wt.% to about 1.25 wt.%, from about 0.75 wt.% to about 1.50 wt.%, from about 0.75 wt.% to about 1.75 wt.%, from about 0.75 wt.% to about 2.00 wt.%, from about 1 .00 wt.% to about 2.00 wt.%, for rom about 1 .50 wt.% to about 2.00 wt.% in the cemented carbide composition, based on the total weight of the cemented carbide composition.

[0097] The ceramic hard phase of the sintered NbC article may further include tantalum carbide (TaC) up to about 3.00 wt.% in the reclaimed NbC material based on the total weight of the cemented carbide composition. In some examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.75 wt.% based on the total weight of the cemented carbide composition. In other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.50 wt.% based on the total weight of the cemented carbide composition. In still other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.25 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 2.00 wt.% based on the total weight of the cemented carbide composition. In even other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1.75 wt.% based on the total weight of the cemented carbide composition. In even further other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1 .50 wt.% based on the total weight of the cemented carbide composition. In other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1 .25wt.% based on the total weight of the cemented carbide composition. In even other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 1 .00 wt.% based on the total weight of the cemented carbide composition. In still other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 0.75 wt.% based on the total weight of the cemented carbide composition. In yet other examples, the ceramic hard phase of the reclaimed NbC material includes the TaC up to about 0.50 wt.% based on the total weight of the cemented carbide composition.

[0098] The ceramic hard phase of the sintered NbC article may also include TaC in a range of from in a range of from about 0.25 wt.% to about 2.00 wt.%, from about 0.50 wt.% to about 2.00 wt.%, from about 0.75 wt.% to about 2.00 wt.%, from about1.00 wt.% to about 2.00 wt.%, from about 1.25 wt.% to about 2.00 wt.%, from about1.50 wt.% to about 2.00 wt.%, from about 1.75 wt.% to about 2.00 wt.%, from about0.25 wt.% to about 3.00 wt.%, from about 0.50 wt.% to about 3.00 wt.%, from about0.75 wt.% to about 3.00 wt.%, from about 1.00 wt.% to about 3.00 wt.%, from about1.25 wt.% to about 3.00 wt.%, from about 1.50 wt.% to about 3.00 wt.%, from about1.75 wt.% to about 3.00 wt.%, from about 2.25 wt.% to about 3.00 wt.%, from about2.75 wt.% to about 3.00 wt.%, from about 2.50 wt.% to about 2.75 wt.%, from about2.25 wt.% to about 2.50 wt.%, from about 2.25 wt.% to about 2.75 wt.%, from about2.00 wt.% to about 2.25 wt.%, from about 2.00 wt.% to about 2.50 wt.%, from about2.00 wt.% to about 2.75 wt.%, from about 2.25 wt.% to about 2.50 wt.%, from about2.25 wt.% to about 2.75 wt.%, from about 1.50 wt.% to about 1.75 wt.%, from about1.50 wt.% to about 2.25 wt.%, from about 1.75 wt.% to about 2.25 wt.%, from about1.25 wt.% to about 1.50 wt.%, from about 1.00 wt.% to about 1.25 wt.%, from about0.75 wt.% to about 1.00 wt.%, from about 0.75 wt.% to about 1.25 wt.%, from about0.75 wt.% to about 1.50 wt.%, from about 0.75 wt.% to about 1.75 wt.%, from about0.50 wt.% to about 0.75 wt.%, from about 0.50 wt.% to about 1.00 wt.%, from about0.50 wt.% to about 1.25 wt.%, from about 0.50 wt.% to about 1.50 wt.%, from about0.50 wt.% to about 1 .75 wt.%, from about 0.25 wt.% to about 0.50 wt.%, or from about 0.25 wt.% to about 0.75 wt.% in the cemented carbide composition, based on the total weight of the cemented carbide composition.

[0099] The reclaimed NbC materials described herein, may advantageously be used in the manufacturing of tools for various applications. In some examples, the reclaimed NbC materials may be used for manufacturing of tools for machining of isolated individual metals, difficult to cut complex metallic alloys, composites, and ultra-resilient metallic superalloys.

[0100] In other examples, the reclaimed NbC materials may also be used for manufacturing interrupted tools, such as, e.g. drill bits, veined end mills, and / or milling inserts.

[0101] Moreover, the sintered reclaimed NbC materials described herein can also be combined with what is known in the state of the art as superabrasive ultrahard materials (i.e., or simply superabrasive materials), including but not limited to single crystal diamond, monocrystalline diamond, polycrystalline diamond (PCD), boron carbide (B4C)-diamond composites, silicon carbide (SiC)-titanium nitride (TiN)- titanium carbonitride (TiCN)-diamond composites, thermally stable polycrystalline diamond (PCD), chemical vapor deposition (CVD) diamond, metal matrix diamond composites, ceramic matrix diamond composites, nanodiamond, cubic boron nitride (cBN), or polycrystalline cubic boron nitride (PCBN). For example, the reclaimed sintered NbC-Ni articles described herein this disclosure can structurally serve as an anchoring substrate material providing a physical support body to achieve improved functionality, to which, the superabrasive material may be sintered in a high temperature and high pressure (HTHP) consolidation process.

[0102] In such a given scenario, the layer of the superabrasive ultrahard material can in turn, provide an enhanced wear-resistance to the reclaimed sintered NbC-Ni articles, thus leading to increased lifetimes for such aforementioned tools. In some particular examples, the reclaimed NbC materials may be used for manufacturing insert blanks with a wide range of geometries, which insert blanks, may be used for drilling, reaming, milling, mining, threading, parting, grooving, grinding, and general machining purposes. In some other particular examples, the reclaimed NbC materials may also be used for manufacturing carbide rods with, or without coolant channels, or carbide rolls for hot rolling of for example long steel products, such as e.g. wires, bars, and tubes, as well as clamping systems, and for manufacturing of low weight cemented carbide punches exclusively used for beverage can tooling purposes.

[0103] The sintered NbC articles, or the reclaimed NbC materials having the unique mechanical properties described herein, may be coated with one or more refractory materials. As used herein this disclosure, “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 IIIA, 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 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.% based on the total weight of the sintered NbC article. In some examples, the refractory material is present from about 1 wt.% to about 2 wt.%, from about 1 wt.% to about 3 wt.%, from about 1 wt.% to about 4 wt.%, from about 2 wt.% to about 4 wt.%, from about 3 wt.% to about 4 wt.%, from about 3 wt.% to about 5 wt.%, from about 3 wt.% to about 6 wt.%, from about 4 wt.% to about 6 wt.%, from about 5 wt.% to about 6 wt.%, from about 6 wt.% to about 7 wt.%, from about 1 wt.% to about 7 wt.%, from about 2 wt.% to about 7 wt.%, from about 3 wt.% to about 7 wt.%, from about 4 wt.% to about 7 wt.%, from about 5 wt.% to about 7 wt.%, from about 6 wt.% to about 7 wt.%, from about 5 wt.% to about 8 wt.%, from about 6 wt.% to about 8 wt.%, from about 7 wt.% to about 8 wt.%, from about 5 wt.% to about 9 wt.%, from about 6 wt.% to about 9 wt.%, from about 7 wt.% to about 9 wt.%, from about 8 wt.% to about 9 wt.%, from about 5 wt.% to about 10 wt.%, from about 6 wt.% to about 10 wt.%, from about 7 wt.% to about 10 wt.%, from about 8 wt.% to about 10 wt.%, or from about 9 wt.% to about 10 wt.%, based on the total weight of the sintered NbC article.EXAMPLE

[0104] 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 accuracywith 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

[0105] PREPARATION OF ZINC RECLAIMED NIOBIUM CARBIDE (NBC) MATERIAL FROM CEMENTED CARBIDE SCRAP

[0106] Niobium carbide (NbC) was reclaimed from cemented carbide scrap by using a standard zinc reclaiming methodology according to known manufacturing methods.

[0107] FIG. 4 shows a 500X magnification of a scanning electron microscope (SEM) image of a zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap in accordance with the present subject matter. FIG. 5 shows an energy- dispersive X-ray spectroscopy (EDS) spectrum of the zinc reclaimed niobium carbide (NbC) material from cemented carbide scrap in FIG. 4 in accordance with the present subject matter. FIGS. 6-9 show EDS X-ray spectroscopy spectra of the zinc reclaimed NbC sample from the cemented carbide scrap in FIG. 4 collected, respectively, from the regions marked with “Spectrum 1”, “Spectrum 2”, “Spectrum 3”, and “Spectrum 4” in FIG. 4 in accordance with different examples of the subject matter. Importantly, the presence of the reclaimed NbC is verified by the apparent identification of the large Nb peaks seen between 2 keV and 2.5 keV on the x-axis demonstrated in FIGS. 5, and 7-8. Further, the presence of the Ni binder metal is also verified by the identification of the smaller shoulder peaks seen at 0.8 keV on the x-axis of the Zn peaks identified at 1.0 keV shown in FIGS. 5-6 and 9. Table 1 shows the amount of each atom detected in the EDS X-ray spectroscopy spectra seen in FIGS. 5-9 of the zinc reclaimed NbC sample from the cemented carbide scrap. As seen in FIGS. 5-9 and Table 1 , importantly there is no detection of Co in the zinc reclaimed NbC sample from the cemented carbide scrap.

[0108] [TABLE 1 ]

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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 active-state components and / or inactive-state components and / or standby-state components, unless context requires otherwise.

[0113] 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 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.

[0114] 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).

[0115] 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.).

[0116] 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.”

[0117] 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.

[0118] Those skilled in the art will appreciate that the foregoing specific exemplary processes and / or devices and / or technologies are representative of moregeneral processes and / or devices and / or technologies taught elsewhere herein, such as in the claims filed herewith and / or elsewhere in the present application.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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.

[0123] 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, itshould 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.

[0124] 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 comprising at least about 50 weight percent (wt.%) of reclaimed niobium carbide (NbC) material based on a total weight of the cemented carbide composition; and a binder phase comprising nickel (Ni), wherein the cemented carbide composition is devoid of cobalt (Co) in the binder phase.

2. The cemented carbide composition of claim 1 , wherein the ceramic hard phase of the cemented carbide composition further comprises tungsten carbide (WC) in a range of from about 0 wt.% to about 2 wt.% based on the total weight of the cemented carbide composition.

3. The cemented carbide composition of claim 1 , wherein the ceramic hard phase of the cemented carbide composition further comprises tantalum carbide (TaC) in a range of from about 0 wt.% to about 3 wt.%. based on the total weight of the cemented carbide composition.

4. The cemented carbide composition of claim 1 , wherein the binder phase of the cemented carbide composition further optionally comprises molybdenum (Mo).

5. The cemented carbide composition of claim 1 , wherein the binder phase of the cemented carbide composition comprises the Ni in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition.

6. The cemented carbide composition of claim 1 , wherein the reclaimed NbC material is zinc reclaimed NbC material from cemented carbide scrap.

7. A cemented carbide composition, comprising: a ceramic hard phase comprising reclaimed niobium carbide (NbC) material; anda binder phase comprising nickel (Ni) in a weight of from about 8 weight percent (wt.%) to about 25 wt.% based on a total weight of the cemented carbide composition, wherein the cemented carbide composition is devoid of cobalt (Co) in the binder phase.

8. The cemented carbide composition of claim 7, wherein the ceramic hard phase of the cemented carbide composition further comprises tungsten carbide (WC) in a range of from about 0 wt.% to about 2 wt.% based on the total weight of the cemented carbide composition.

9. The cemented carbide composition of claim 7, wherein the ceramic hard phase of the cemented carbide composition further comprises tantalum carbide (TaC) in a range of from about 0 wt.% to about 3 wt.%. based on the total weight of the cemented carbide composition.

10. The cemented carbide composition of claim 7, wherein the binder phase of the cemented carbide composition further optionally comprises molybdenum (Mo).11 . The cemented carbide composition of claim 7, wherein the ceramic hard phase of the cemented carbide composition comprises the reclaimed NbC material in a weight of least about 50 wt.% based on the total weight of the cemented carbide composition.

12. The cemented carbide composition of claim 7, wherein the reclaimed NbC material is zinc reclaimed NbC material from cemented carbide scrap.

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

14. A tool, comprising the cemented carbide composition of claim 7.

15. A method of preparing a sintered niobium carbide (NbC) article, comprising: providing a cemented carbide composition, comprisinga ceramic hard phase comprising at least about 50 weight percent (wt.%) of reclaimed NbC material based on a total weight of the cemented carbide composition, and a binder phase comprising nickel (Ni); milling the cemented carbide composition to form a powder blend; granulating the milled powder blend to form a ready-to-press (RTP) powder; compacting the ready-to-press (RTP) powder to form a green body; and sintering the green body to form the sintered NbC article, wherein the cemented carbide composition is devoid of cobalt (Co) in the binder phase.

16. The method of preparing a sintered niobium carbide NbC article of claim 15, wherein the milling is performed with one or more solvents comprising ethanol, methanol, isopropanol, butanol, cyclohexanol, acetone, hexane, heptane, toluene, water, or any combination thereof as a milling slurry of the powder blend.

17. The method of preparing a sintered niobium carbide NbC article of claim 15, wherein the ceramic hard phase of the cemented carbide composition further comprises tungsten carbide (WC) in a range of from about 0 wt.% to about 2 wt.% based on the total weight of the cemented carbide composition.

18. The method of preparing a sintered niobium carbide NbC article of claim 15, wherein the ceramic hard phase of the cemented carbide composition further comprises tantalum carbide (TaC) in a range of from about 0 wt.% to about 3 wt.%. based on the total weight of the cemented carbide composition.

19. The method of preparing a sintered niobium carbide NbC article of claim 15, wherein the binder phase of the cemented carbide composition further optionally comprises molybdenum (Mo).

20. The method of preparing a sintered niobium carbide NbC article of claim 15, wherein the binder phase of the cemented carbide composition comprises the Ni in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition.

21. The method of preparing a sintered niobium carbide NbC article of claim 15, wherein the reclaimed NbC material is zinc reclaimed NbC material from cemented carbide scrap.

22. A method of reclaiming niobium carbide (NbC) material from cemented carbide scrap, comprising: heating the cemented carbide scrap with zinc ingots to a temperature up to about 1000°C, the cemented carbide scrap comprising a reclaimable cemented carbide composition comprising a ceramic hard phase comprising at least about 50 weight percent (wt.%) of NbC based on a total weight of the cemented carbide composition, and a binder phase comprising nickel (Ni); reacting the zinc ingots with the Ni in the binder phase of the cemented carbide composition to form a molten Zn-Ni alloy; vaporizing zinc from the formed molten Zn-Ni alloy under vacuum conditions; forming a sponge of the cemented carbide scrap by cooling the temperature down to room temperature; and crushing the sponge of the cemented carbide scrap to form a powder of reclaimed NbC material, wherein the cemented carbide composition is devoid of cobalt (Co) in the binder phase.

23. The method of reclaiming NbC from cemented carbide scrap of claim 22, further comprising milling the formed powder of the reclaimed NbC material.

24. The method of reclaiming NbC from cemented carbide scrap of claim 23, further comprising sieving the milled powder of the reclaimed NbC material through a 625- mesh screen, a 1250-mesh screen, or a 2500-mesh screen.

25. The method of reclaiming NbC from cemented carbide scrap of claim 22, wherein the sponge comprises a maximum amount of from about 50 parts per million (ppm) to about 150 ppm of remaining non-vaporized zinc.

26. The method of reclaiming NbC from cemented carbide scrap of claim 23, wherein the milling is done in a ball mill, an attritor mill, or a planetary mill.

27. The method of reclaiming NbC from cemented carbide scrap of claim 22, wherein the heating the cemented carbide scrap with the zinc ingots is done in a nitrogen or an argon oxidation resistant atmosphere at a temperature range of from about 600°C to about 1000°C for about 5 hours.

28. The method of reclaiming NbC from cemented carbide scrap of claim 27, wherein the heating the cemented carbide scrap with the zinc ingots is done in a nitrogen or an argon oxidation resistant atmosphere at a temperature range of from about 600°C to about 1000°C for about 4 hours.

29. The method of reclaiming NbC from cemented carbide scrap of claim 28, wherein the heating the cemented carbide scrap with the zinc ingots is done in a nitrogen or an argon oxidation resistant atmosphere at a temperature range of from about 600°C to about 1000°C for about 3 hours.

30. The method of reclaiming NbC from cemented carbide scrap of claim 23, wherein the binder phase of the cemented carbide composition comprises Ni in a weight of from about 8 wt.% to about 25 wt.% based on the total weight of the cemented carbide composition.

31. The method of reclaiming NbC from cemented carbide scrap of claim 23, wherein the binder phase of the cemented carbide composition further optionally comprises molybdenum (Mo).

32. A method of preparing a sintered niobium carbide (NbC) article, comprising: providing a cemented carbide composition, comprising a ceramic hard phase comprising reclaimed NbC material, and a binder phase comprising nickel (Ni) in a weight of from about 8 weight percent (wt.%) to about 25 wt.% based on a total weight of the cemented carbide composition; milling the cemented carbide composition to form a powder blend;granulating the milled powder blend to form a ready-to-press (RTP) powder; compacting the ready-to-press (RTP) powder to form a green body; and sintering the green body to form the sintered NbC article, wherein the cemented carbide composition is devoid of cobalt (Co) in the binder phase.

33. The method of preparing a sintered niobium carbide NbC article of claim 32, wherein the milling is performed with one or more solvents comprising ethanol, methanol, isopropanol, butanol, cyclohexanol, acetone, hexane, heptane, toluene, water, or any combination thereof as a milling slurry of the powder blend.

34. The method of preparing a sintered niobium carbide NbC article of claim 32, wherein the ceramic hard phase of the cemented carbide composition further comprises tungsten carbide (WC) in a range of from about 0 wt.% to about 2 wt.% based on the total weight of the cemented carbide composition.

35. The method of preparing a sintered niobium carbide NbC article of claim 32, wherein the ceramic hard phase of the cemented carbide composition further comprises tantalum carbide (TaC) in a range of from about 0 wt.% to about 3 wt.%. based on the total weight of the cemented carbide composition.

36. The method of preparing a sintered niobium carbide NbC article of claim 32, wherein the binder phase of the cemented carbide composition further optionally comprises molybdenum (Mo).

37. The method of preparing a sintered niobium carbide NbC article of claim 32, wherein the ceramic hard phase of the cemented carbide composition comprises the reclaimed NbC material in a weight of least about 50 wt.% based on the total weight of the cemented carbide composition.

38. The method of preparing a sintered niobium carbide NbC article of claim 32, wherein the reclaimed NbC material is zinc reclaimed NbC material from cemented carbide scrap.

39. The method of preparing a sintered niobium carbide NbC article of claim 32, wherein granulating the milled powder blend to form the ready-to-press (RTP) powder is done by spray-drying, freeze-drying, air-drying, or vacuum-drying.

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