Hard alloy containing multi-component high-entropy carbide and / or multi-component high-entropy alloy

Abstract

A sintered cemented carbide includes a high-entropy carbide or a rotary knot decomposition product thereof; and a metal binder comprising at least one of Co, Co-Ru, Ni, Co-Ni, Co-Cr, Co-Ni-Cr, Co-Re, Co-Ni-Re, Co-Ni-Ru, or a high-entropy alloy wherein the high-entropy carbide is a single-phase solid solution carbide comprising four to ten metal elements, and the spin decomposition product thereof comprises two chemically different phases having the same crystal structure. The sintered cemented carbide further includes a carbide including at least one of WC, TiC, ZrC, HfC, NbC, TaC, or Cr3C2, and a metal binder; the metal binder comprises a high-entropy alloy. The high-entropy alloy is an alloy of four to ten alloy elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Application No. 17 / 974,101, filed on October 26, 2022, which is incorporated herein by reference in its entirety. Background Art

[0003] Cemented carbide is a hard material composed of fine particles of tungsten carbide, titanium carbide or tantalum carbide, which are bonded into a composite material by a binder metal such as cobalt. Although cemented carbide has been widely used in cutting tools, material properties (such as fracture strength, fracture toughness, wear resistance and corrosion resistance) can limit the use and performance of cemented carbide in various industrial applications. For example, cemented carbide fracture strength and wear resistance determine the durability of the cutting structure of the cone, and therefore may limit the design and performance of the drill bit. Therefore, there is a need for cemented carbide with improved material properties. Summary of the invention

[0004] In one aspect, the sintered cemented carbide comprises a high entropy carbide or a spinodal decomposition product thereof; and a metal binder comprising at least one of Co, Co-Ru, Ni, Co-Ni, Co-Cr, Co-Ni-Cr, Co-Re, Co-Ni-Re, Co-Ni-Ru or a high entropy alloy, wherein the high entropy carbide is a single-phase solid solution carbide comprising four to ten metal elements, and its spinodal decomposition product comprises two chemically different phases having the same crystal structure; and the high entropy alloy is an alloy comprising four to ten alloying elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si.

[0005] On the other hand, the sintered cemented carbide comprises: a carbide comprising at least one of WC, TiC, ZrC, HfC, NbC, TaC or Cr3C2; and a metal binder comprising a high entropy alloy, wherein the high entropy alloy is an alloy comprising four to ten alloying elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Zr, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si.

[0006] The earth-boring tool has a body and at least a cutting element fixed to the body, wherein the cutting element contains the above-mentioned cemented carbide.

[0007] The tool has a substrate and a polycrystalline diamond cutting element fixed to the substrate, wherein the substrate comprises the above-mentioned sintered cemented carbide. DETAILED DESCRIPTION

[0008] The inventors have discovered a new type of sintered cemented carbide which has improved material properties compared to cemented carbides based on tungsten carbide bonded by cobalt metal, such as increased fracture strength and / or increased wear resistance. This discovery allows the manufacture of high-performance tools with increased service life. Due to the improved material properties, the high-performance tools can also have a more flexible tool design.

[0009] On the one hand, sintered hard alloy comprises high entropy carbide and metal binder, and this metal binder comprises at least one in Co, Co-Ru, Ni, Co-Ni, Co-Cr, Co-Ni-Cr, Co-Re, Co-Ni-Re, Co-Ni-Ru or high entropy alloy.High entropy carbide can exist with the amount of about 60 volume % to about 98 volume %, about 70 volume % to about 95 volume % or about 75 volume % to about 95 volume %, each based on the total volume of sintered hard alloy.Metal binder can exist with the amount of about 40 volume % to about 2 volume %, about 30 volume % to about 5 volume % or about 25 volume % to about 5 volume %, each based on the total volume of sintered hard alloy.Preferably, sintered hard alloy does not contain any component except high entropy carbide or metal binder.In other words, sintered hard alloy is made up of high entropy carbide and metal binder.

[0010] As used herein, high entropy carbide can refer to a single-phase solid solution carbide comprising at least four metallic elements, such as four to ten metallic elements, four to eight metallic elements or four to six metallic elements. In high entropy carbide, each metallic element is present in an amount of about 5 mol % to about 30 mol %, preferably about 10 mol % to about 30 mol % or about 15 mol % to about 30 mol %, each based on the total number of moles of metallic elements. As used herein, high entropy carbide also includes a carbide that is high entropy carbide at high temperature but experiences spinodal decomposition at a lower temperature, thereby forming two chemically different phases of the same crystal structure. The two phases of decomposition are usually not considered to be high entropy. Spinodal decomposition is a mechanism by which a single phase spontaneously separates into two phases. Decomposition can occur during the synthesis of carbide powder, the synthesis of cemented carbide or during subsequent heat treatment.

[0011] In an embodiment, the high entropy carbide comprises carbon and at least four or at least five metal elements, for example, four to eight metal elements, four to six metal elements, four to five metal elements or five to six metal elements selected from W, Zr, V, Ti, Ta, Nb, Mo or Hf. Compared with the total molar content of the metal elements in the high entropy carbide, the molar content of carbon in the high entropy carbide can be stoichiometric or substoichiometric. For example, the ratio of the molar content of carbon in the high entropy carbide to the total molar content of the metal elements can be 0.9:1 to 1:1 or 0.95:1 to 1:1.

[0012] High entropy carbides can have the formula XC y , wherein X comprises at least four or at least five metal elements selected from W, Zr, V, Ti, Ta, Nb, Mo or Hf, C is elemental carbon, and y is 0.9 to 1. For example, the high entropy carbide may have the formula (Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 Zr 0.2 )C、(Hf 0.2 Nb 0.2 Ta 0.2 Ti 0.2 V 0.2 )C、(Hf 0.2 Mo 0.2 V 0.2 W 0.2 Zr 0.2 )C、(Hf 0.2 Mo 0.2 Ti 0.2 W 0.2 Zr 0.2 )C、(Nb 0.2 Ta 0.2 Ti 0.2 V 0.2 W 0.2 )C、(Hf 0.2 Ta 0.2 Ti 0.2 Zr 0.2 V 0.2 )C、(Hf 0.2 Mo 0.2 Ti 0.2 V 0.2 Zr 0.2 )C or (Hf 0.2 Ti 0.2 V 0.2 W 0.2 Zr 0.2 ) C. The high entropy carbide may have a crystal structure such as a BCC (body-centered cubic), FCC (face-centered cubic), or HCP (hexagonal close-packed) crystal structure.

[0013] High entropy carbide can be prepared by powder metallurgy process using each binary carbide as raw material. For example, at least four or at least five binary carbides can be mixed by mechanical mixing such as planetary ball milling and high energy ball milling, and then the mixture can be sintered via spark plasma sintering or spark plasma sintering to form high entropy carbide.

[0014] High entropy alloys can also be produced by a two-step synthesis process consisting of carbothermal reduction of metal oxides by carbon (such as carbon black) and subsequent solid solution formation. This process is described by Feng, Lun et al. in Scripta Materialia 162 (2019): 90-93.

[0015] Methods for preparing high entropy carbides are also described by Castle, Elinor et al. in Scientific reports 8.1 (2018): 1-12 and by Sarker, Pranab et al. in Nature communications 9.1 (2018): 1-10.

[0016] High entropy carbides can also be prepared by dissolving five or more metal salts such as chlorides or oxychloride salts in a solvent such as methanol, ethanol and / or water to form a solution, mixing the solution with a carbon source such as sucrose, fructose, glucose, decanol resin and phenol resin to allow a sol-gel reaction to occur, and then drying the reaction mixture and heat treating at about 1500°C to about 2500°C (as described, for example, in CN110104648) to form a high entropy carbide.

[0017] The metal binder may include at least one of Co, Co-Ru, Ni, Co-Ni, Co-Cr, Co-Ni-Cr, Co-Re, Co-Ni-Re, Co-Ni-Ru, or a high entropy alloy. As used herein, metal 1-metal 2 refers to an alloy of metal 1 and metal 2. For example, Co-Ru means an alloy of Co and Ru, and Co-Ni-Cr means an alloy of Co, Ni, and Cr.

[0018] As used herein, high entropy alloy refers to an alloy comprising four to ten, four to eight or four to six alloying elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Zr, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si, preferably selected from Co, Cr, Cu, W, Fe, Ni, Mo, Ru, Re or Mn. Each alloying element in the alloying element can be independently present in an amount of about 1 atomic percent (atomic %) to about 55 atomic %, preferably 10 atomic % to about 30 atomic %. The amount of each element can be the same, or it can be different. If present, the amount of C is less than 20 atomic %. Specific examples of high entropy alloys with six alloying elements include Cu x Fe y Ni z Ti a V b Zr c 、Cox Cr y Fe z Mn a Ni b V c , Cu x Co y Hf z Ni a Ti b Zr c , Cu x Hf y Nb z Ni a Ti b Zr c or Co x Ni y Fe z Mn a Al b C c , wherein x+y+z+a+b+c=1, and each of x, y, z, a, b, and c is between about 0.05 and about 0.25, preferably about 0.1 and about 0.2, or about 0.14 and about 0.18. Examples of high entropy alloys having five alloying elements include Co x Cr y Fe z Mn a Ni b 、Co x Ni y Fe z Mn a Cu b 、Co x Ni y Fe z Mn a Ru b , CoxNiyFezMnaReb, wherein x+y+z+a+b=1, and each of x, y, z, a and b is between about 0.1 to about 0.3, preferably about 0.15 to about 0.25, or about 0.18 to about 0.22.

[0019] The alloying elements may form a primary FCC or BCC solid solution phase. The high entropy alloy may also include a secondary strengthening phase. Based on the sum of the volumes of the primary solid solution phase and the secondary strengthening phase, the volume fraction of the secondary strengthening phase may be about 5% to about 50%, about 5% to about 40%, or about 5% to about 30%.

[0020] Examples of the secondary strengthening phase include at least one of an ordered L12 structural phase or an E21 structural phase. The secondary strengthening phase may be an intermetallic phase that exists as a precipitate dispersed in a solid solution matrix or as a constituent phase in a coupled eutectic.

[0021] The L12 phase may be of the form A3B, where A is one or more of Ni, Co, Fe, Mn, and B is one or more of Al, Ti, Sn, Si, Ge, Ru, Re, or W. Examples of high entropy alloys with an L12 phase are described by Yang, T et al., Science 362.6417 (2018): 933-937 and by Liang, Yao-Jian et al., Nature communications 9.1 (2018): 1-8.

[0022] E21 phase can adopt A3BC x , wherein C is elemental carbon and x can vary between 0.25 and 1, A is one or more of Co, Ni, Fe, Mn, Ti, Zr, Hf and B is one or more of Al, Ti, Sn, Si, Ge, Ru, Re or W. Examples of high entropy alloys with an E21 phase are described by Fan, JT et al., Materials Science and Engineering: A 728 (2018): 30-39.

[0023] High entropy alloys can be prepared by several methods. One method involves mechanically mixing element powders during powder processing of cemented carbide, and sintering the cemented carbide to produce high entropy alloys. Another method includes mechanical high-energy ball milling of the element powders, and adding the ground powder to the grinding process of the cemented carbide. High entropy alloys can also be prepared by atomizing alloying gases into powder form. The atomized powder can then be added to the grinding process of the cemented carbide.

[0024] On the other hand, the sintered cemented carbide comprises carbides and a metal binder, the carbides comprising at least one of WC, TiC, ZrC, HfC, NbC, TaC or Cr3C2; the metal binder comprises a high entropy alloy as described herein. The carbides may be present in an amount of about 60% by volume to about 98% by volume, about 70% by volume to about 95% by volume, or about 75% by volume to about 95% by volume, each based on the total volume of the sintered cemented carbide. The metal binder may be present in an amount of about 40% by volume to about 2% by volume, about 30% by volume to about 5% by volume, or about 25% by volume to about 5% by volume, each based on the total volume of the sintered cemented carbide. Preferably, the sintered cemented carbide does not include any component other than carbides or metal binders. In other words, the sintered cemented carbide is composed of carbides and metal binders.

[0025] The sintered cemented carbide as described herein may be prepared by mixing a carbide (such as a high entropy carbide or a carbide comprising at least one of WC, TiC, ZrC, HfC, NbC, TaC or Cr3C2) with a metal binder to form a mixture, and then grinding and sintering the mixture to form a sintered cemented carbide.

[0026] The method of grinding is not particularly limited. Wet grinding can be performed by mixing carbide powder, metal binder powder, and optionally an organic wax binder (such as paraffin or polyethylene glycol) for green strength with a solvent (such as alcohol, acetone, hexane, heptane, water, or a combination thereof), and grinding the mixture for up to about 72 hours using, for example, a ball mill, a rod mill, or an attritor, typically about 12 to about 48 hours for a ball mill. Dry grinding can be performed using, for example, a ball mill without any solvent.

[0027] After grinding, the slurry can be removed from the grinding vessel, and the solid particles in the slurry can then be separated from the liquid solvent. For example, the liquid solvent of the slurry can be evaporated, or the solid particles can be filtered from the slurry to form a powder mixture. The powder mixture can also be produced from the slurry using a spray drying process such as described in US 7,528,086. The dried powder can be pressed into a green state before sintering.

[0028] The sintering method may include vacuum sintering, hot isostatic pressing (HIP), spark plasma sintering, gas pressure sintering (GPS), etc. The sintering temperature is a temperature higher than the melting point of the metal binder, for example, about 10°C to about 100°C, or about 10°C to about 50°C higher than the melting point of the metal binder.

[0029] Sintered cemented carbide can be used in various tools. In one aspect, sintered cemented carbide can also be used as a substrate in the synthesis of polycrystalline diamond (PDC) cutting elements. The synthesis of PDC involves the use of a high pressure and high temperature (HPHT) device, such as a six-sided top press or a belt press, whereby the substrate and diamond powder are encapsulated in a refractory metal can and subjected to a synthesis cycle at a pressure greater than 5 GPa and a temperature greater than 1300° C. These conditions can cause the carbide binder phase to melt, flow into the diamond powder bed, and catalytically sinter the diamond powder particles together. Therefore, the present disclosure also provides a tool, such as a cutting element comprising a polycrystalline diamond composite material, wherein the polycrystalline diamond composite material comprises polycrystalline diamond and a substrate comprising a sintered cemented carbide as described herein.

[0030] In one aspect, the cutting element comprises sintered cemented carbide, with or without polycrystalline diamond. As used herein, the term "cutting element" means and includes any element of an earth-boring tool that is used to shear, crush, grind or otherwise remove formation material when using the earth-boring tool to form or enlarge a hole in the formation. The cutting element may have a generally cylindrical or disc-like shape.

[0031] The earth-boring tool may include a body; and at least one cutting element fixed to the body, wherein the cutting element includes a sintered cemented carbide as described herein. The cutting element may be first manufactured and then fixed to the drill bit body. The preparation of the cutting element is performed by sintering by the method described above. The attachment of the cutting element to the drill bit body may involve mechanical attachment (such as pressing the cutter / compact into a hole of an appropriately sized cone) or heat-assisted attachment (such as brazing the cutter / compact into a recess on the drill bit body).

[0032] As used herein, the term "earth-boring tool" refers to and includes any tool used to remove underground formation material and form a hole (e.g., a wellbore) through the formation by the removal of a portion of the formation material. Cutting elements can be fixed to and used on earth-boring tools, which include, for example, roller cone drill bits, percussion drill bits, coring drill bits, eccentric drill bits, bi-center drill bits, reamers, expandable reamers, milling cutters, hybrid drill bits, and other drill bits and tools known in the art. As an example, a rotary drill bit may include a drill bit body, and cutting elements fixed to the drill bit body.

[0033] Some embodiments of the foregoing disclosure are shown below.

[0034] Aspect 1. A sintered cemented carbide comprising: a high entropy carbide or a spinodal decomposition product thereof; and a metal binder, wherein the metal binder comprises at least one of Co, Co-Ru, Ni, Co-Ni, Co-Cr, Co-Ni-Cr, Co-Re, Co-Ni-Re, Co-Ni-Ru or a high entropy alloy, wherein the high entropy carbide is a single-phase solid solution carbide comprising four to ten metal elements, and its spinodal decomposition product comprises two chemically different phases having the same crystal structure; and the high entropy alloy is an alloy comprising four to ten alloying elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si.

[0035] Aspect 2. The sintered cemented carbide according to any of the previous aspects, wherein in the high entropy carbide or the spinodal decomposition product thereof, each metal element is present in an amount of about 5 mol% to about 30 mol% based on the total number of moles of the metal element.

[0036] Aspect 3. A sintered cemented carbide according to any of the previous aspects, wherein the high entropy carbide or the spinodal decomposition product thereof comprises carbon and at least four metal elements selected from W, Zr, V, Ti, Ta, Nb, Mo or Hf.

[0037] Aspect 4. A sintered cemented carbide according to any of the previous aspects, wherein the molar content of the carbon in the high entropy carbide or the spinodal decomposition products thereof is stoichiometric relative to the total molar content of the metal element in the high entropy carbide or the spinodal decomposition products thereof.

[0038] Aspect 5. A sintered cemented carbide according to any of the previous aspects, wherein the molar content of the carbon in the high entropy carbide is substoichiometric relative to the total molar content of the metal elements in the high entropy carbide or the spinodal decomposition product thereof.

[0039] Aspect 6. The sintered cemented carbide according to any of the previous aspects, wherein in the high entropy alloy, the alloying elements form a primary face-centered cubic or body-centered cubic solid solution phase.

[0040] Aspect 7. The sintered cemented carbide according to any previous aspect, wherein the high entropy alloy further comprises a secondary strengthening phase.

[0041] Aspect 8. The sintered cemented carbide according to any previous aspect, wherein the secondary strengthening phase comprises at least one of an ordered L12 structural phase or an E21 structural phase.

[0042] Aspect 9. A sintered cemented carbide according to any previous aspect, wherein the cemented carbide comprises about 60 volume % to about 98 volume % of the high entropy carbide and about 40 volume % to 2 volume % of the metallic binder, each based on the total volume of the sintered cemented carbide.

[0043] Aspect 10. The sintered cemented carbide according to any of the previous aspects, consisting of the high entropy carbide and the metal binder.

[0044] Aspect 11. A sintered cemented carbide comprising: a carbide comprising at least one of WC, TiC, ZrC, HfC, NbC, TaC or Cr3C2; and a metal binder comprising a high entropy alloy, wherein the high entropy alloy is an alloy comprising four to ten alloying elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si.

[0045] Aspect 12. The sintered cemented carbide according to any previous aspect, wherein the cemented carbide comprises about 60 volume % to about 98 volume % of the carbide and about 40 volume % to about 2 volume % of the metallic binder, each based on the total volume of the sintered cemented carbide.

[0046] Aspect 13. The sintered cemented carbide according to any of the previous aspects, consisting of the carbide and the metal binder.

[0047] Aspect 14. The sintered cemented carbide according to any of the previous aspects, wherein in the high entropy alloy, the alloying elements form a primary face-centered cubic or body-centered cubic solid solution phase.

[0048] Aspect 15. The sintered cemented carbide according to any previous aspect, wherein the high entropy alloy further comprises a secondary strengthening phase.

[0049] Aspect 16. The sintered cemented carbide according to any previous aspect, wherein the secondary strengthening phase comprises at least one of an ordered L12 structural phase or an E21 structural phase.

[0050] Aspect 17. A sintered cemented carbide according to any previous aspect, wherein the secondary strengthening phase comprises the L12 phase, and the L12 phase has the form A3B, wherein A is one or more of Ni, Co, Fe or Mn, and B is one or more of Al, Ti, Sn, Si, Ge, Ru, Re or W.

[0051] Aspect 18. The sintered cemented carbide according to any of the previous aspects, wherein the secondary strengthening phase comprises the E21 phase, and the E21 phase has the form A3BC x , C is elemental carbon, and x varies between 0.25 and 1; A is one or more of Co, Ni, Fe, Mn, Ti, Zr or Hf; and B is one or more of Al, Ti, Sn, Si, Ge, Ru, Re or W.

[0052] Aspect 19. An earth-boring tool comprising a body and at least a cutting element secured to the body, wherein the cutting element comprises a cemented carbide according to any preceding aspect.

[0053] Aspect 20. A tool comprising a polycrystalline diamond composite material, wherein the polycrystalline diamond composite material comprises polycrystalline diamond and a substrate comprising a sintered cemented carbide according to any preceding aspect.

[0054] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. As used herein, "combination" includes blends, mixtures, alloys, reaction products, etc. All references are incorporated herein by reference in their entirety.

[0055] In the context of describing the present invention (especially in the context of the appended claims), the use of the terms "a", "an", and "the", and similar references should be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms "about", "substantially", and "approximately" are intended to include the degree of error associated with the measurement of a particular quantity based on the equipment available at the time the application is filed. For example, "about" and / or "substantially" and / or "approximately" may include a range of ±8% or 5%, or 2% of a given value.

Claims

1. A sintered hard alloy, characterized in that: The sintered hard alloy comprises: High entropy carbides or their spinodal decomposition products; as well as A metal binder, wherein the metal binder comprises at least one of Co, Co-Ru, Ni, Co-Ni, Co-Cr, Co-Ni-Cr, Co-Re, Co-Ni-Re, Co-Ni-Ru or a high entropy alloy, wherein the high entropy carbide is a single-phase solid solution carbide comprising four to ten metal elements, and the spinodal decomposition product thereof comprises two chemically different phases having the same crystal structure; and The high entropy alloy is an alloy containing four to ten alloying elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si.

2. The sintered cemented carbide according to claim 1, wherein in the high entropy carbide or the spinodal decomposition product thereof, each metal element is present in an amount of about 5 mol% to about 30 mol% based on the total number of moles of the metal elements.

3. The sintered cemented carbide according to claim 1, wherein the high entropy carbide or the spinodal decomposition product thereof comprises carbon and at least four metal elements selected from W, Zr, V, Ti, Ta, Nb, Mo or Hf.

4. The sintered cemented carbide according to claim 3, wherein the molar content of the carbon in the high entropy carbide or the spinodal decomposition product thereof is stoichiometric or substoichiometric relative to the total molar content of the metal element in the high entropy carbide or the spinodal decomposition product thereof. 5 . The sintered hard alloy according to claim 1 , wherein in the high entropy alloy, the alloying elements form a primary face-centered cubic or body-centered cubic solid solution phase. 6 . The sintered cemented carbide according to claim 5 , wherein the high entropy alloy further comprises a secondary strengthening phase, wherein the secondary strengthening phase comprises at least one of an ordered L12 structural phase or an E21 structural phase.

7. The sintered cemented carbide according to claim 1, wherein the cemented carbide comprises about 60 volume % to about 98 volume % of the high entropy carbide and about 40 volume % to 2 volume % of the metallic binder, each based on the total volume of the sintered cemented carbide.

8. A sintered hard alloy, characterized in that: The sintered hard alloy comprises: A carbide comprising at least one of WC, TiC, ZrC, HfC, NbC, TaC or Cr3C2; and A metallic binder comprising a high entropy alloy, The high entropy alloy is an alloy containing four to ten alloying elements selected from Al, Be, Fe, Co, Cr, Ni, Cu, W, V, Zr, Ti, Mn, Hf, Nb, Mo, Ru, Re, Ge, Sn, C, B or Si.

9. The sintered cemented carbide according to claim 8, wherein the cemented carbide comprises about 60 volume % to about 98 volume % of the carbide and about 40 volume % to about 2 volume % of the metallic binder, each based on the total volume of the sintered cemented carbide. 10 . The sintered hard alloy according to claim 8 , wherein in the high entropy alloy, the alloying elements form a primary face-centered cubic or body-centered cubic solid solution phase. 11 . The sintered cemented carbide according to claim 10 , wherein the high entropy alloy further comprises a secondary strengthening phase, and the secondary strengthening phase comprises at least one of an ordered L12 structural phase or an E21 structural phase.

12. The sintered cemented carbide according to claim 11, wherein the secondary strengthening phase comprises the L12 phase, and the L12 phase has a form A3B, wherein A is one or more of Ni, Co, Fe or Mn, and B is one or more of Al, Ti, Sn, Si, Ge, Ru, Re or W.

13. The sintered cemented carbide according to claim 11, wherein the secondary strengthening phase comprises the E21 phase, and the E21 phase has the form A3BC x , C is elemental carbon, and x varies between 0.25 and 1; A is one or more of Co, Ni, Fe, Mn, Ti, Zr or Hf; and B is one or more of Al, Ti, Sn, Si, Ge, Ru, Re or W.

14. An earth-boring tool comprising a body and at least a cutting element fixed to the body, wherein the cutting element comprises a cemented carbide according to any one of claims 1 to 13.

15. A tool comprising a polycrystalline diamond composite material, wherein the polycrystalline diamond composite material comprises polycrystalline diamond and a substrate comprising a sintered cemented carbide according to any one of claims 1 to 13.