A high wear resistance tungsten carbide alloy and a method for preparing the same

Abstract

The application discloses a high wear resistance tungsten carbide alloy and a preparation method thereof, and belongs to the technical field of tungsten carbide alloys. The high wear resistance tungsten carbide alloy is characterized in that hard particles in a spherical shape are uniformly distributed in a matrix, the mass percentage of the hard particles is 80wt.%-90wt.%, and the mass percentage of the matrix is 10wt.%-20wt.%; the hard particles comprise composite tungsten carbide particles with a mass percentage of 75wt.%-80wt.%, cobalt powder with a mass percentage of 5wt.%-10wt.%, titanium powder with a mass percentage of 2wt.%-3wt.%, zirconium powder with a mass percentage of 2wt.%-3wt.%, rare earth oxide with a mass percentage of 0.5wt.%-1wt.% and nano carbon black with a mass percentage of 5wt.%-10wt.%. The wear resistance tungsten carbide alloy and the preparation method thereof can solve the problem that the hardness and toughness of the existing tungsten carbide alloy cannot be synergistically enhanced, thereby affecting the wear resistance of the tungsten carbide alloy.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of tungsten carbide alloy, and particularly relates to a high wear-resistant tungsten carbide alloy and a preparation method thereof. BACKGROUND

[0002] As a typical hard alloy material, tungsten carbide alloy is widely used in cutting tools, mining machinery, oil exploitation, aerospace, etc. due to its high hardness, high wear resistance and good high-temperature stability. In actual working conditions, tungsten carbide alloy needs to have excellent strength, toughness and wear resistance to withstand complex mechanical stress, impact load and friction loss. The existing tungsten carbide alloy generally uses tungsten carbide as a hard phase and cobalt as a binder phase. Pure tungsten carbide as a hard phase can effectively improve the hardness of the tungsten carbide alloy. However, cobalt as a binder phase is prone to softening under high-temperature conditions, which affects the strength, hardness and wear resistance of the matrix.

[0003] Increasing the content of tungsten carbide particles and refining the grain size of the tungsten carbide particles can significantly enhance the hardness and strength of the alloy, thereby improving the wear resistance. However, this will cause the thickness of the binder phase between the tungsten carbide particles to be reduced, which reduces the ability of the alloy to resist crack propagation and causes the toughness to decrease significantly. Once a small crack occurs in the alloy during service, the crack will rapidly expand due to the lack of sufficient toughness buffer, which causes the material to fail, thereby weakening the wear resistance. On the contrary, increasing the content of the binder phase or improving the plasticity of the binder phase can effectively improve the toughness of the alloy. However, the binder phase itself has a relatively low hardness, and excessive binder phase will reduce the overall hardness of the alloy, making the material more prone to plastic deformation and adhesive wear during friction, which leads to a decrease in wear resistance.

[0004] The existing patent CN202111074553.8 discloses a WC-Co-based alloy with high wear resistance and a preparation method thereof. The preparation method comprises the following steps: S1, ball-milling and wet-mixing coarse-grained tungsten carbide, ultra-fine tungsten powder, ultra-fine cobalt powder, tantalum carbide, paraffin and stearic acid to obtain a slurry; S2, filtering and drying the slurry obtained in step S1 to obtain dry materials, and then granulating and pressing the dry materials to obtain a green body; and S3, sintering the green body obtained in step S2, which comprises four stages in sequence, namely, dewaxing, vacuum sintering, low-pressure sintering and cooling, to finally obtain a WC-Co-based alloy. By compounding the raw material formula of the alloy and combining a specific sintering process, nano-particle decarburized phases are precipitated in the Co phase of the alloy, thereby significantly enhancing the wear resistance of the alloy without significantly reducing the bending strength, and the service life of the tools / parts prepared is obviously improved. However, the nano-particle decarburized phases in the above-mentioned patent can effectively improve the wear resistance of the alloy, and cobalt as a binder phase is prone to softening under high-temperature conditions during cutting, which affects the wear resistance of the alloy. SUMMARY

[0005] The application aims to provide a high wear resistance tungsten carbide alloy and a preparation method thereof, and solve the problem that the hardness and toughness of the existing tungsten carbide alloy cannot be synergistically enhanced, thereby affecting the wear resistance of the tungsten carbide alloy.

[0006] To achieve the above-mentioned object, the application provides a high wear resistance tungsten carbide alloy, which comprises a base body and hard particles, the spherical hard particles are uniformly distributed in the base body, the mass percentage of the hard particles is 80wt.%-90wt.%, and the mass percentage of the base body is 10wt.%-20wt.%; the hard particles comprise 75wt.%-80wt.% of composite tungsten carbide particles, 5wt.%-10wt.% of cobalt powder, 2wt.%-3wt.% of titanium powder, 2wt.%-3wt.% of zirconium powder, 0.5wt.%-1wt.% of rare earth oxide and 5wt.%-10wt.% of nano carbon black.

[0007] Preferably, the composite tungsten carbide particles comprise the following components in the following mass percentages: 10wt.%-15wt.% of tungsten carbide particles with a particle size of 150nm-200nm, 50wt.%-70wt.% of tungsten carbide particles with a particle size of 0.8μm-1.0μm, and 20wt.%-30wt.% of tungsten carbide particles with a particle size of 2μm-3μm.

[0008] Preferably, the particle size of the cobalt powder is 3μm-5μm, the particle size of the titanium powder is 1μm-2μm, and the particle size of the zirconium powder is 1μm-2μm.

[0009] Preferably, the particle size of the rare earth oxide is 0.5μm-1.0μm, and the rare earth oxide is one of cerium oxide and yttrium oxide.

[0010] Preferably, the base body comprises the following components in the following mass percentages: 70wt.%-80wt.% of tungsten carbide, 4wt.%-6wt.% of molybdenum carbide, 3wt.%-5wt.% of aluminum oxide, 0.1wt.%-0.5wt.% of rare earth oxide, 0.5wt.%-1wt.% of copper, and 15wt.%-20wt.% of cobalt.

[0011] Preferably, the particle size of the tungsten carbide in the base body is 3μm-5μm, the particle size of the molybdenum carbide is 0.8μm-1μm, the particle size of the aluminum oxide is 0.2μm-0.4μm, the particle size of the copper is 0.3μm-0.5μm, the particle size of the cobalt is 1μm-2μm, the particle size of the rare earth oxide is 0.2μm-0.4μm, and the rare earth oxide is yttrium oxide.

[0012] The preparation method of the high wear resistance tungsten carbide alloy comprises the following steps:

[0013] S1, preparing hard particles;

[0014] S2, the tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, cobalt powder and copper powder are mixed in ethanol medium according to the mass ratio to obtain a matrix raw material;

[0015] S3, the hard particles are added to the matrix raw material for ball milling mixing, and after uniform mixing, a raw material powder is obtained; the raw material powder is dried and then pressed into a raw material blank;

[0016] S4, the raw material blank is placed in a plasma sintering furnace for sintering, and after natural cooling to room temperature, a tungsten carbide alloy is obtained.

[0017] Preferably, the S1 comprises the following steps:

[0018] S11, the tungsten carbide particles with a particle size of 150nm-200nm, the tungsten carbide particles with a particle size of 0.8-1.0μm and the tungsten carbide particles with a particle size of 2-3μm are weighed according to the mass ratio, and the tungsten carbide particles are ultrasonically dispersed in ethanol medium for 1-3h to obtain composite tungsten carbide particles;

[0019] S12, the composite tungsten carbide particles are dried; the nano carbon black is dried at 120℃ for 2-3h to remove the water in the nano carbon black;

[0020] S13, the composite tungsten carbide particles, nano carbon black, cobalt powder, titanium powder, zirconium powder and rare earth oxide are mixed according to the mass ratio, and ball milling mixing is carried out in ethanol medium to obtain a mixed powder;

[0021] S14, the mixed powder is dried, and the mixed powder is pressed at a pressure of 50MPa-100MPa for 5min-10min to obtain a blank;

[0022] S15, the blank is placed in a heating furnace for sintering, inert gas is used for protection during the sintering process, and after natural cooling to room temperature, a sintered material is obtained;

[0023] S16, the sintered material is crushed, ball milled and sieved to obtain hard particles with a particle size of 20-30μm.

[0024] Preferably, in the S15, the sintering temperature is 1400-1500℃, the sintering pressure is 10-30MPa, and the holding time is 0.5-1h.

[0025] Preferably, in the S4, the sintering temperature is 1300-1400℃, the sintering pressure is 30-50MPa, and the sintering time is 20-30min.

[0026] The high wear-resistant tungsten carbide alloy and the preparation method thereof have the advantages and positive effects that:

[0027] 1、The hard particles in the application use composite tungsten carbide particles, which improve the packing density of tungsten carbide and the compactness of the hard particle structure. The synergistic effect of the three levels of particles is conducive to significantly improving the toughness, strength and wear resistance of the material.

[0028] 2、The titanium powder and zirconium powder in the hard particles generate titanium carbide and zirconium carbide hard particles under the action of heating, and the hardness of titanium carbide and zirconium carbide is higher than that of tungsten carbide, which is uniformly distributed in the WC matrix in submicron size, and inhibits the growth of WC grains, thereby improving the hardness and toughness of the hard particles. TiC / ZrC particles act as "rigid anchor points" to fix the cobalt phase, prevent excessive flow of cobalt, and improve the high-temperature performance of the hard particles.

[0029] 3、Nano carbon black is filled between the ceramic particles and the cobalt binder phase to form a "nano bridging" structure, which enhances the interfacial bonding force through mechanical interlocking effect, and at the same time acts as a stress buffer layer to inhibit crack propagation along the interface, which is conducive to improving the toughness of the hard particles.

[0030] 4、The tungsten carbide and molybdenum carbide particles in the matrix fill the pores between the hard particles to form a "coarse particle skeleton-fine particle filling" structure, which is conducive to improving the overall hardness and strength of the tungsten carbide alloy.

[0031] 5、The particle size ratio of aluminum oxide to tungsten carbide in the matrix is 1:10. When dislocations move to the location of aluminum oxide, they need to bypass the particles in an arching mechanism, greatly increasing the energy consumption of dislocation movement and improving the strength and toughness of the matrix.

[0032] 6、Copper and cobalt are used as binders, and copper and cobalt form a continuous metal network at the interface. The continuous metal network bridges the two sides of the crack through plastic deformation, inhibits crack penetration, improves the bonding strength between the hard particles and the matrix, and reduces the shedding of the hard particles. Copper acts as a "rigid node" in the metal network, which can limit the plastic flow and softening deformation of cobalt at high temperatures, and alleviate the strength decrease caused by the softening of cobalt at high temperatures.

[0033] The technical solutions of the application will be further described in detail through examples. DETAILED DESCRIPTION

[0034] In the present application, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. If there is any inconsistency, the meaning described in the specification or derived from the content described in the specification shall prevail. In addition, the terms used herein are only for the purpose of describing the embodiments of the present application and are not intended to limit the present application.

[0035] The embodiments of the present application will be described in detail below.

[0036] A high wear-resistant tungsten carbide alloy, comprising a base body and hard particles, the spherical hard particles are uniformly distributed in the base body, the mass percentage of the hard particles is 80wt.%-90wt.%, and the mass percentage of the base body is 10wt.%-20wt.%. The hard particles comprise 75wt.%-80wt.% of composite tungsten carbide particles, 5wt.%-10wt.% of cobalt powder, 2wt.%-3wt.% of titanium powder, 2wt.%-3wt.% of zirconium powder, 0.5wt.%-1wt.% of rare earth oxide, and 5wt.%-10wt.% of nano carbon black.

[0037] The composite tungsten carbide particles comprise the following components in mass percentage: 10wt.%-15wt.% of tungsten carbide particles with a particle size of 150nm-200nm, 50wt.%-70wt.% of tungsten carbide particles with a particle size of 0.8μm-1.0μm, and 20wt.%-30wt.% of tungsten carbide particles with a particle size of 2μm-3μm.

[0038] In the hard particles, the tungsten carbide particles are composed of nano, sub-micron and micron tungsten carbide particles to form composite tungsten carbide particles. The nano tungsten carbide particles with a particle size of 150nm-200nm are filled into the pores between the sub-micron tungsten carbide particles with a particle size of 0.8μm-1.0μm and the micron tungsten carbide particles with a particle size of 2μm-3μm, so that the structure of the hard particles is more compact, the existence of defects is reduced, and the hardness and wear resistance of the hard particles are improved. When the material is subjected to external force to produce cracks, the micron tungsten carbide particles mainly bear the load and play a supporting role; the sub-micron particles can change the crack propagation path and make the crack propagation direction deflect; the nano particles can pin the crack and prevent its further propagation; through the synergistic effect of the three levels of particles, the toughness of the material is significantly improved. In the friction process, the particles of different particle sizes can uniformly distribute the stress on the particles of each level, avoiding local rapid wear caused by stress concentration, thereby improving the overall wear resistance of the material.

[0039] The particle size of the cobalt powder is 3μm-5μm, the particle size of the titanium powder is 1μm-2μm, and the particle size of the zirconium powder is 1μm-2μm. The particle size of the rare earth oxide is 0.5μm-1.0μm, and the rare earth oxide is one of cerium oxide and yttrium oxide.

[0040] The particle size of the titanium powder and the zirconium powder is similar to the particle size of the composite tungsten carbide particles, which is beneficial to improve the uniformity of the mixture of the titanium powder, the zirconium powder and the tungsten carbide particles and the uniformity of the hard particles. The metallic titanium powder and the cobalt powder react with the graphite under the action of heating to generate titanium carbide and zirconium carbide hard particles, and the hardness of the titanium carbide and the zirconium carbide is higher than that of the tungsten carbide, which is uniformly distributed in the WC matrix in the size of submicron. When the material is subjected to external force, the dislocation movement is hindered by the hard points, is forced to expand or deflect along the TiC / ZrC-WC interface, and needs to consume more energy, thereby being beneficial to improve the hardness and the toughness of the hard particles. The difference in the thermal expansion coefficients of TiC and WC causes the WC matrix around the TiC / ZrC particles to generate a circumferential residual compressive stress in the cooling process. The compressive stress can offset part of the applied tensile stress and improve the dislocation slip resistance, thereby improving the toughness of the hard particles. The TiC / ZrC particles inhibit the growth of the WC grains at high temperature sintering through the grain boundary pinning effect and improve the hardness and the toughness of the hard particles through the fine-grain strengthening mechanism.

[0041] The particle size of the nano-carbon black is below 50 nm, the particle size is extremely small, and the specific surface area is large. The nano-carbon black provides a high-activity carbon source, shortens the diffusion path, and makes the surface adsorption of cobalt, titanium and zirconium atoms of the nano-carbon black increase, forms an "atomic-level mixed interface", accelerates the reaction, promotes the rapid reaction of Ti and Zr atoms with C, and promotes the generation of titanium carbide and zirconium carbide. In addition, the nano-carbon black is filled between the ceramic particles and the cobalt binder phase to form a "nano-bridging" structure, enhances the interface bonding force through the mechanical interlocking effect, and at the same time, as a stress buffer layer, inhibits the crack propagation along the interface.

[0042] Rare earth oxides are added to the hard particles, the rare earth oxides are decomposed into Ce / Y cations and O anions at high temperature, diffuse to the grain boundaries, the rare earth cations fill the grain boundary defects, replace the impurity atoms at the grain boundaries, reduce the precipitation of grain boundary brittle phases, and reduce the interface energy. The rare earth oxides inhibit the growth of WC grains through the "pinning effect", the grain refinement leads to an increase in the number of grain boundaries and the dislocation slip resistance, which is beneficial to improve the hardness and the toughness of the hard particles. And the rare earth oxides reduce the surface tension of the molten cobalt phase, promote the infiltration of cobalt to the ceramic particles, and improve the interface bonding strength.

[0043] The cobalt powder acts as a binder, is melted to form a metallic binder phase in the sintering process, and fully penetrates between the tungsten carbide, titanium carbide and zirconium carbide under the action of pressure to form a metallic binder network, firmly binds the tungsten carbide hard particles through metallic bonds, forms a "ceramic skeleton-metal ligament" composite structure, and the cobalt absorbs impact energy through plastic deformation under the action of external force, while the TiC / ZrC particles fix the cobalt phase as "rigid anchor points" to prevent the strength from being reduced due to excessive flow, thereby improving the strength of the hard particles while ensuring the toughness of the hard particles.

[0044] The base body comprises the following components in mass percentage: 70wt.%-80wt.% tungsten carbide, 4wt.%-6wt.% molybdenum carbide, 3wt.%-5wt.% aluminum oxide, 0.1wt.%-0.5wt.% rare earth oxide, 0.5wt.%-1wt.% copper, and 15wt.%-20wt.% cobalt.

[0045] The particle size of tungsten carbide in the base body is 3μm-5μm, the particle size of molybdenum carbide is 0.8μm-1μm, the particle size of aluminum oxide is 0.2μm-0.4μm, the particle size of copper is 0.3μm-0.5μm, and the particle size of cobalt is 1μm-2μm; the particle size of rare earth oxide is 0.2μm-0.4μm, and the rare earth oxide is yttrium oxide.

[0046] Molybdenum carbide has very high hardness, and molybdenum carbide is uniformly distributed in the tungsten carbide and the binder phase of the base body as a hard second phase, hinders the movement of dislocations through the dispersion strengthening mechanism, and improves the toughness and hardness of the base body. Molybdenum carbide and tungsten carbide form a double-hard-phase system in the base body, which alternately bears cutting and reduces the wear damage of a single phase, which is beneficial to improve the wear resistance of the tungsten carbide alloy. Molybdenum carbide has a certain solid solubility in tungsten carbide, forming a substitutional solid solution, which causes lattice distortion of tungsten carbide, increases the dislocation slip resistance, and effectively improves the toughness and strength of the base body.

[0047] The particle size of tungsten carbide in the base body is 3μm-5μm, the particle size of molybdenum carbide is 0.3μm-0.5μm, the particle size of hard particles is 20μm-30μm, and the tungsten carbide and molybdenum carbide particles in the base body fill the pores between the hard particles to form a "coarse particle skeleton-fine particle filling" structure, which reduces defects and improves the bulk density, and is beneficial to improve the overall hardness and strength of the tungsten carbide alloy. Hard particles act as "main bearing phase" to bear the main load, and the fine particles in the base body act as "secondary strengthening phase" to share the load through interface stress transmission, avoiding the decrease in hardness caused by local stress concentration, which is beneficial to improve the hardness and strength of the tungsten carbide alloy. Because the particle size of tungsten carbide and molybdenum carbide in the base body is relatively small, when the crack propagates in the base body, due to the high hardness of tungsten carbide and molybdenum carbide, the propagation direction needs to be changed frequently, which increases the energy consumption of crack propagation, and is beneficial to improve the hardness, strength and toughness of the tungsten carbide alloy.

[0048] Aluminum oxide, as a high-hardness ceramic particle, is uniformly dispersed in the base body, hinders the movement of dislocations through dispersion strengthening, and is beneficial to improve the strength, hardness and toughness of the base body. The particle size ratio of aluminum oxide to tungsten carbide in the base body is 1:10, and when the dislocation moves to the position of aluminum oxide, it needs to bypass the particle in the arching mechanism, greatly increasing the energy consumption of dislocation movement and improving the strength and toughness of the base body.

[0049] The rare earth oxide can purify the grain boundary and inhibit the growth of tungsten carbide grains, thereby improving the strength and toughness of the substrate through fine-grain strengthening mechanism. Moreover, the rare earth oxide can reduce the surface tension of molten copper and enhance the wetting ability of copper to ceramic particles, thereby forming a uniform interface.

[0050] The melting point of copper is relatively low, and copper is molten during plasma sintering. Copper atoms are fully diffused on the surface of tungsten carbide, molybdenum carbide and aluminum oxide ceramic particles, thereby reducing the porosity in the substrate. The free electrons of copper form a metal bond with the unsaturated bond on the surface of the ceramic particles. Since the particle size of the copper powder is very small, the specific surface area of the copper powder is large, thereby increasing the contact sites of copper and ceramic particles and significantly improving the interface bonding strength. The copper in the substrate and cobalt form a continuous metal network at the interface. When the crack propagates at the interface between the hard particles and the substrate, the continuous metal network bridges the two sides of the crack through plastic deformation, thereby inhibiting the crack penetration and improving the bonding strength between the hard particles and the substrate. The energy absorption effect of cobalt and the bridging effect of copper cooperate with each other to form a multi-level crack inhibition mechanism, thereby significantly improving the fracture resistance of the alloy. Moreover, copper acts as a "rigid node" in the metal network, which can limit the plastic flow and softening deformation of cobalt at high temperature, thereby alleviating the strength decrease caused by the softening of cobalt at high temperature.

[0051] The preparation method of the high wear-resistant tungsten carbide alloy comprises the following steps:

[0052] S1, preparing hard particles.

[0053] comprises the following steps:

[0054] S11, according to the mass ratio, tungsten carbide particles with a particle size of 150-200 nm, tungsten carbide particles with a particle size of 0.8-1.0 μm and tungsten carbide particles with a particle size of 2-3 μm are weighed, and the tungsten carbide particles are ultrasonically dispersed in ethanol medium for 1-3 h to obtain composite tungsten carbide particles. Through ultrasonic dispersion, the uniformity of the dispersion of tungsten carbide particles with different particle sizes is improved.

[0055] S12, drying the composite tungsten carbide particles; drying the nano carbon black at 120°C for 2-3 hours to remove the water in the nano carbon black.

[0056] S13, mixing the composite tungsten carbide particles, nano carbon black, cobalt powder, titanium powder, zirconium powder and rare earth oxide according to the mass ratio, and ball milling in ethanol medium to obtain a mixed powder. Hard alloy balls are used for ball milling, the ball-to-material ratio is 6:1, the ball milling speed is 300-400 r / min, and the ball milling time is 12-24 h.

[0057] S14, drying the mixed powder in a vacuum drying oven at 60℃ for 12h-24h, and pressing the mixed powder at a pressure of 50MPa-100MPa for 5min-10min to obtain a green body.

[0058] S15, sintering the green body in a heating furnace, and using argon for protection during the sintering process. After natural cooling to room temperature, a sintered body is obtained. The sintering temperature is 1400℃-1500℃, the sintering pressure is 10MPa-30MPa, and the holding time is 0.5h-1h.

[0059] S16, crushing and ball milling the sintered body, and sieving to obtain hard particles with a particle size of 20μm-30μm.

[0060] S2, ball milling the tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, copper powder and cobalt powder in ethanol medium according to the mass ratio to obtain a base material. Hard alloy balls are used for ball milling, the ball-to-material ratio is 6:1, the ball milling speed is 300r / min-400r / min, and the ball milling time is 12h-24h.

[0061] S3, adding the hard particles to the base material for ball milling, and after uniform mixing, a raw material powder is obtained. Hard alloy balls are used for ball milling, the ball-to-material ratio is 6:1, the ball milling speed is 300r / min-400r / min, and the ball milling time is 12h-24h. The raw material powder is dried in a vacuum drying oven at 60℃ for 12h-24h, and then pressed into a raw material green body.

[0062] S4, sintering the raw material green body in a plasma sintering furnace, and after natural cooling to room temperature, a tungsten carbide alloy is obtained.

[0063] The sintering temperature is 1250℃-1350℃, the sintering pressure is 30MPa-50MPa, and the sintering time is 20min-30min.

[0064] The sintering is performed using a spark plasma sintering furnace, which has the advantages of fast heating speed, short sintering time and low sintering temperature. The sintering can be performed at a lower temperature and in a shorter time to obtain a dense tungsten carbide alloy, effectively inhibits the growth of tungsten carbide alloy grains, and obtains fine and uniform tungsten carbide grains, thereby improving the comprehensive performance of the tungsten carbide alloy.

[0065] Example 1

[0066] A high wear resistance tungsten carbide alloy, comprising a base body and hard particles, the spherical hard particles are uniformly distributed in the base body, the mass percentage of the hard particles is 81wt.%, and the mass percentage of the base body is 19wt.%. The hard particles comprise 78.5wt.% of composite tungsten carbide particles, 10wt.% of cobalt powder, 3wt.% of titanium powder, 2wt.% of zirconium powder, 0.5wt.% of rare earth oxides, and 6wt.% of nano carbon black.

[0067] The composite tungsten carbide particles comprise the following components in the following mass percentages: 15wt.% of tungsten carbide particles with a particle size of 150nm-200nm, 65wt.% of tungsten carbide particles with a particle size of 0.8μm-1.0μm, and 20wt.% of tungsten carbide particles with a particle size of 2μm-3μm.

[0068] The base body comprises the following components in the following mass percentages: 75.2wt.% of tungsten carbide, 4wt.% of molybdenum carbide, 4wt.% of aluminum oxide, 0.3wt.% of rare earth oxides, 0.5wt.% of copper, and 16wt.% of cobalt.

[0069] The particle size of the tungsten carbide in the base body is 3μm-5μm, the particle size of the molybdenum carbide is 0.8μm-1μm, the particle size of the aluminum oxide is 0.2μm-0.4μm, the particle size of the copper is 0.3μm-0.5μm, the particle size of the cobalt is 1μm-2μm, the particle size of the rare earth oxides is 0.2μm-0.4μm, and the rare earth oxides are yttrium oxides.

[0070] A preparation method of the high wear resistance tungsten carbide alloy, comprising the following steps:

[0071] S1, preparing hard particles.

[0072] comprising the following steps:

[0073] S11, weighing tungsten carbide particles with a particle size of 150nm-200nm, tungsten carbide particles with a particle size of 0.8μm-1.0μm, and tungsten carbide particles with a particle size of 2μm-3μm according to the mass ratio, and performing ultrasonic dispersion of the tungsten carbide particles in an ethanol medium for 1h to obtain composite tungsten carbide particles.

[0074] S12, drying the composite tungsten carbide particles; drying the nano carbon black at 120℃ for 2h to remove the water in the nano carbon black.

[0075] S13, mixing the composite tungsten carbide particles, the nano carbon black, cobalt powder, titanium powder, zirconium powder, and rare earth oxides according to the mass ratio, and ball milling the mixture in an ethanol medium to obtain a mixed powder. Hard alloy balls are used for ball milling, the ball-to-material ratio is 6:1, the ball milling speed is 300r / min, and the ball milling time is 20h.

[0076] S14, drying the mixed powder in a vacuum drying oven at 60℃ for 12-24h, and pressing the mixed powder at a pressure of 50MPa for 10min to obtain a green body.

[0077] S15, sintering the green body in a heating furnace, and using argon to protect during the sintering process. After naturally cooling to room temperature, a sintered body is obtained. The sintering temperature is 1400℃, the sintering pressure is 15MPa, and the holding time is 1h.

[0078] S16, crushing and ball-milling the sintered body, and sieving to obtain hard particles with a particle size of 20-30μm.

[0079] S2, ball-milling tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, copper powder, and cobalt powder in an ethanol medium according to the mass ratio to obtain a base material. Hard alloy balls are used for ball-milling, the ball-to-material ratio is 6:1, the ball-milling speed is 300r / min, and the ball-milling time is 20h.

[0080] S3, adding the hard particles to the base material and ball-milling to obtain a raw material powder. Hard alloy balls are used for ball-milling, the ball-to-material ratio is 6:1, the ball-milling speed is 300r / min, and the ball-milling time is 20h. The raw material powder is dried in a vacuum drying oven at 60℃ for 12h, and then pressed into a raw material green body.

[0081] S4, sintering the raw material green body in a plasma sintering furnace, and obtaining a tungsten carbide alloy after naturally cooling to room temperature.

[0082] The sintering temperature is 1300℃, the sintering pressure is 30MPa, and the sintering time is 30min.

[0083] Example 2

[0084] A high wear-resistant tungsten carbide alloy includes a base material and hard particles, the spherical hard particles are uniformly distributed in the base material, the mass percentage of the hard particles is 85wt.%, and the mass percentage of the base material is 15wt.%. The hard particles include 79.2wt.% of composite tungsten carbide particles, 6wt.% of cobalt powder, 2wt.% of titanium powder, 2wt.% of zirconium powder, 0.8wt.% of rare earth oxides, and 10wt.% of nano carbon black.

[0085] The composite tungsten carbide particles include the following components with the following mass percentages: 12wt.% of tungsten carbide particles with a particle size of 150-200nm, 64wt.% of tungsten carbide particles with a particle size of 0.8-1.0μm, and 24wt.% of tungsten carbide particles with a particle size of 2-3μm.

[0086] The base body comprises the following components in mass percentage: 75.8wt.% tungsten carbide, 4wt.% molybdenum carbide, 3wt.% aluminum oxide, 0.4wt.% rare earth oxide, 0.8wt.% copper, and 16wt.% cobalt.

[0087] The particle size of tungsten carbide in the base body is 3-5μm, the particle size of molybdenum carbide is 0.8-1μm, the particle size of aluminum oxide is 0.2-0.4μm, the particle size of copper is 0.3-0.5μm, the particle size of cobalt is 1-2μm, and the particle size of rare earth oxide is 0.2-0.4μm.

[0088] The preparation method of the high-wear-resistance tungsten carbide alloy comprises the following steps:

[0089] S1, preparing hard particles.

[0090] comprises the following steps:

[0091] S11, weighing tungsten carbide particles with a particle size of 150-200nm, tungsten carbide particles with a particle size of 0.8-1.0μm, and tungsten carbide particles with a particle size of 2-3μm according to the mass ratio, and performing ultrasonic dispersion on the tungsten carbide particles in an ethanol medium for 1-3h to obtain composite tungsten carbide particles.

[0092] S12, drying the composite tungsten carbide particles; drying the nano-carbon black at 120℃ for 2h to remove the water in the nano-carbon black.

[0093] S13, mixing the composite tungsten carbide particles, the nano-carbon black, cobalt powder, titanium powder, zirconium powder, and rare earth oxide according to the mass ratio, and ball-milling the mixture in an ethanol medium to obtain a mixed powder. Hard alloy balls are used for ball-milling, the ball-to-material ratio is 6:1, the ball-milling speed is 300r / min, and the ball-milling time is 20h.

[0094] S14, drying the mixed powder in a vacuum drying box at 60℃ for 12-24h, and pressing the mixed powder at a pressure of 70MPa for 6min to obtain a green body.

[0095] S15, placing the green body into a heating furnace for sintering, and using argon for protection during the sintering process. After natural cooling to room temperature, a sintered product is obtained. The sintering temperature is 1500℃, the sintering pressure is 10MPa, and the holding time is 1h.

[0096] S16, crushing the sintered product, ball-milling, and sieving to obtain hard particles with a particle size of 20-30μm.

[0097] S2, the tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, copper powder and cobalt powder are mixed in ethanol medium according to the mass ratio to obtain the matrix raw material. The ball milling adopts hard alloy ball, the ball-to-material ratio is 6:1, the ball milling speed is 300 r / min, and the ball milling time is 20 h.

[0098] S3, the hard particles are added to the matrix raw material for ball milling and mixing, and after uniform mixing, the raw material powder is obtained. The ball milling adopts hard alloy ball, the ball-to-material ratio is 6:1, the ball milling speed is 300 r / min, and the ball milling time is 20 h. After drying in a vacuum drying oven at 60℃ for 12 h, the raw material blank is pressed.

[0099] S4, the raw material blank is put into a plasma sintering furnace for sintering, and after natural cooling to room temperature, the tungsten carbide alloy is obtained.

[0100] The sintering temperature is 1250℃, the sintering pressure is 40 MPa, and the sintering time is 20 min.

[0101] Example 3

[0102] A high wear-resistant tungsten carbide alloy includes a matrix and hard particles, the spherical hard particles are uniformly distributed in the matrix, the mass percentage of the hard particles is 85wt.%, and the mass percentage of the matrix is 15wt.%. The hard particles include 77.2wt.% of composite tungsten carbide particles, 8wt.% of cobalt powder, 3wt.% of titanium powder, 3wt.% of zirconium powder, 0.8wt.% of rare earth oxide, and 8wt.% of nano carbon black.

[0103] The composite tungsten carbide particles include the following mass percentages of components: 15wt.% of tungsten carbide particles with a particle size of 150nm-200nm, 60wt.% of tungsten carbide particles with a particle size of 0.8μm-1.0μm, and 25wt.% of tungsten carbide particles with a particle size of 2μm-3μm.

[0104] The matrix includes the following mass percentages of components: 74wt.% of tungsten carbide, 5wt.% of molybdenum carbide, 4wt.% of aluminum oxide, 0.5wt.% of rare earth oxide, 0.5wt.% of copper, and 16wt.% of cobalt.

[0105] The particle size of the tungsten carbide in the matrix is 3μm-5μm, the particle size of the molybdenum carbide is 0.8μm-1μm, the particle size of the aluminum oxide is 0.2μm-0.4μm, the particle size of the copper is 0.3μm-0.5μm, and the particle size of the cobalt is 1μm-2μm; the particle size of the rare earth oxide is 0.2μm-0.4μm, and the rare earth oxide is yttrium oxide.

[0106] A method for preparing a high wear-resistant tungsten carbide alloy includes the following steps:

[0107] S1, preparing hard particles.

[0108] comprising the following steps:

[0109] S11, according to the mass ratio, the particle size of 150nm-200nm tungsten carbide particles, particle size 0.8-1.0um tungsten carbide particles and particle size 2-3um tungsten carbide particles are weighed, and the tungsten carbide particles are dispersed in ethanol medium for 2h, to obtain composite tungsten carbide particles.

[0110] S12, the composite tungsten carbide particles are dried; the nano carbon black is dried at 120℃ for 3h, and the water in the nano carbon black is removed.

[0111] S13, the composite tungsten carbide particles, nano carbon black, cobalt powder, titanium powder, zirconium powder and rare earth oxide are mixed according to the mass ratio, and ball milling is carried out in ethanol medium to obtain mixed powder. Hard alloy ball is used for ball milling, the ball to material ratio is 6:1, the ball milling speed is 400r / min, and the ball milling time is 20h.

[0112] S14, the mixed powder is dried in a vacuum drying oven at 60℃ for 12h, and the mixed powder is pressed at 80MPa for 10min to obtain a green body.

[0113] S15, the green body is put into a heating furnace for sintering, and argon is used for protection during sintering. After natural cooling to room temperature, the sintered material is obtained. The sintering temperature is 1500℃, the sintering pressure is 20MPa, and the holding time is 0.5h.

[0114] S16, the sintered material is crushed, ball milled and sieved to obtain hard particles with particle size of 20-30um.

[0115] S2, the tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, copper powder and cobalt powder are ball milled in ethanol medium according to the mass ratio to obtain the matrix raw material. Hard alloy ball is used for ball milling, the ball to material ratio is 6:1, the ball milling speed is 400r / min, and the ball milling time is 20h.

[0116] S3, the hard particles are added to the matrix raw material for ball milling, and after uniform mixing, the raw material powder is obtained. Hard alloy ball is used for ball milling, the ball to material ratio is 6:1, the ball milling speed is 400r / min, and the ball milling time is 20h. After drying the raw material powder in a vacuum drying oven at 60℃ for 12h, the raw material blank is pressed.

[0117] S4, the raw material blank is put into a plasma sintering furnace for sintering, and the tungsten carbide alloy is obtained after natural cooling to room temperature.

[0118] The sintering temperature is 1350℃, the sintering pressure is 50MPa, and the sintering time is 20min.

[0119] Embodiment 4

[0120] A high wear resistance tungsten carbide alloy comprises a base and hard particles, the spherical hard particles are uniformly distributed in the base, the mass percentage of the hard particles is 85wt.%, and the mass percentage of the base is 15wt.%. The hard particles comprise 75wt.% of composite tungsten carbide particles, 10wt.% of cobalt powder, 2wt.% of titanium powder, 2wt.% of zirconium powder, 1wt.% of rare earth oxide, and 10wt.% of nano carbon black.

[0121] The composite tungsten carbide particles comprise the following components in the following mass percentages: 15wt.% of tungsten carbide particles with a particle size of 150nm-200nm, 60wt.% of tungsten carbide particles with a particle size of 0.8μm-1.0μm, and 25wt.% of tungsten carbide particles with a particle size of 2μm-3μm.

[0122] The base comprises the following components in the following mass percentages: 74wt.% of tungsten carbide, 5wt.% of molybdenum carbide, 4wt.% of aluminum oxide, 0.5wt.% of rare earth oxide, 0.5wt.% of copper, and 16wt.% of cobalt.

[0123] The particle size of the tungsten carbide in the base is 3μm-5μm, the particle size of the molybdenum carbide is 0.8μm-1μm, the particle size of the aluminum oxide is 0.2μm-0.4μm, the particle size of the copper is 0.3μm-0.5μm, the particle size of the cobalt is 1μm-2μm, the particle size of the rare earth oxide is 0.2μm-0.4μm, and the rare earth oxide is yttrium oxide.

[0124] A method for preparing a high wear resistance tungsten carbide alloy, comprising the following steps:

[0125] S1, preparing hard particles.

[0126] comprising the following steps:

[0127] S11, weighing tungsten carbide particles with a particle size of 150nm-200nm, tungsten carbide particles with a particle size of 0.8μm-1.0μm, and tungsten carbide particles with a particle size of 2μm-3μm according to the mass ratio, and performing ultrasonic dispersion of the tungsten carbide particles in an ethanol medium for 2h to obtain composite tungsten carbide particles.

[0128] S12, drying the composite tungsten carbide particles; drying the nano carbon black at 120℃ for 3h to remove the water in the nano carbon black.

[0129] S13, the composite tungsten carbide particles, nano carbon black, cobalt powder, titanium powder, zirconium powder and rare earth oxide are mixed according to the mass ratio, and ball milling is carried out in an ethanol medium to obtain a mixed powder. Hard alloy balls are used for ball milling, the ball-to-material ratio is 6:1, the ball milling speed is 400 r / min, and the ball milling time is 20 h.

[0130] S14, the mixed powder is dried in a vacuum drying oven at 60℃ for 12 h, and the mixed powder is pressed at a pressure of 80 MPa for 10 min to obtain a green body.

[0131] S15, the green body is placed in a heating furnace for sintering, and argon is used for protection during the sintering process. After natural cooling to room temperature, a sintered body is obtained. The sintering temperature is 1500℃, the sintering pressure is 20 MPa, and the holding time is 0.5 h.

[0132] S16, the sintered body is crushed, ball milled and sieved to obtain hard particles with a particle size of 20-30 μm.

[0133] S2, the tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, copper powder and cobalt powder are ball milled in an ethanol medium according to the mass ratio to obtain a base material. Hard alloy balls are used for ball milling, the ball-to-material ratio is 6:1, the ball milling speed is 400 r / min, and the ball milling time is 20 h.

[0134] S3, the hard particles are added to the base material for ball milling, and after uniform mixing, a raw material powder is obtained. Hard alloy balls are used for ball milling, the ball-to-material ratio is 6:1, the ball milling speed is 400 r / min, and the ball milling time is 20 h. The raw material powder is dried in a vacuum drying oven at 60℃ for 12 h, and then pressed into a raw material green body.

[0135] S4, the raw material green body is placed in a plasma sintering furnace for sintering, and a tungsten carbide alloy is obtained after natural cooling to room temperature.

[0136] The sintering temperature is 1350℃, the sintering pressure is 50 MPa, and the sintering time is 20 min.

[0137] Example 5

[0138] A high wear-resistant tungsten carbide alloy includes a base and hard particles, the spherical hard particles are uniformly distributed in the base, the mass percentage of the hard particles is 85 wt.%, and the mass percentage of the base is 15 wt.%. The hard particles include 77.2 wt.% of composite tungsten carbide particles, 8 wt.% of cobalt powder, 3 wt.% of titanium powder, 3 wt.% of zirconium powder, 0.8 wt.% of rare earth oxide, and 8 wt.% of nano carbon black.

[0139] The composite tungsten carbide particles include the following components by mass percentage: 15 wt.% of tungsten carbide particles with a particle size of 150 nm-200 nm, 60 wt.% of tungsten carbide particles with a particle size of 0.8 μm-1.0 μm, and 25 wt.% of tungsten carbide particles with a particle size of 2 μm-3 μm.

[0140] The matrix includes the following components by mass percentage: 70 wt.% of tungsten carbide, 6 wt.% of molybdenum carbide, 5 wt.% of aluminum oxide, 0.5 wt.% of rare earth oxide, 0.5 wt.% of copper, and 18 wt.% of cobalt.

[0141] The particle size of the tungsten carbide in the matrix is 3 μm-5 μm, the particle size of the molybdenum carbide is 0.8 μm-1 μm, the particle size of the aluminum oxide is 0.2 μm-0.4 μm, the particle size of the copper is 0.3 μm-0.5 μm, and the particle size of the cobalt is 1 μm-2 μm; the particle size of the rare earth oxide is 0.2 μm-0.4 μm, and the rare earth oxide is yttrium oxide.

[0142] The method for preparing the high-wear-resistance tungsten carbide alloy includes the following steps:

[0143] S1, preparing hard particles.

[0144] The method includes the following steps:

[0145] S11, weighing tungsten carbide particles with a particle size of 150 nm-200 nm, tungsten carbide particles with a particle size of 0.8 μm-1.0 μm, and tungsten carbide particles with a particle size of 2 μm-3 μm according to the mass ratio, and performing ultrasonic dispersion of the tungsten carbide particles in an ethanol medium for 2 h to obtain composite tungsten carbide particles.

[0146] S12, drying the composite tungsten carbide particles; drying the nano carbon black at 120 ℃ for 3 h to remove the water in the nano carbon black.

[0147] S13, mixing the composite tungsten carbide particles, the nano carbon black, cobalt powder, titanium powder, zirconium powder, and rare earth oxide according to the mass ratio, and performing ball milling of the mixture in an ethanol medium to obtain a mixed powder. The ball milling uses hard alloy balls, the ball-to-material ratio is 6:1, the ball milling speed is 400 r / min, and the ball milling time is 20 h.

[0148] S14, drying the mixed powder in a vacuum drying box at 60 ℃ for 12 h, and pressing the mixed powder at a pressure of 80 MPa for 10 min to obtain a green body.

[0149] S15, placing the green body into a heating furnace for sintering, and using argon for protection during the sintering process. After natural cooling to room temperature, a sintered product is obtained. The sintering temperature is 1500 ℃, the sintering pressure is 20 MPa, and the holding time is 0.5 h.

[0150] S16, the sintered product is crushed, ball milled and sieved to obtain hard particles with a particle size of 20-30 μm.

[0151] S2, the tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, copper powder and cobalt powder are ball milled in ethanol medium according to the mass ratio to obtain a base material. The ball milling uses hard alloy balls, the ball-to-material ratio is 6:1, the ball milling speed is 400 r / min, and the ball milling time is 20 h.

[0152] S3, the hard particles are added to the base material and ball milled to obtain a raw material powder. The ball milling uses hard alloy balls, the ball-to-material ratio is 6:1, the ball milling speed is 400 r / min, and the ball milling time is 20 h. The raw material powder is dried in a vacuum drying oven at 60°C for 12 h, and then pressed into a raw material blank.

[0153] S4, the raw material blank is placed in a plasma sintering furnace for sintering, and then naturally cooled to room temperature to obtain a tungsten carbide alloy.

[0154] The sintering temperature is 1350°C, the sintering pressure is 50 MPa, and the sintering time is 20 min.

[0155] Comparative Example 1

[0156] The difference between this comparative example and Example 3 is that the hard particles in this comparative example only contain tungsten carbide particles with a particle size of 150-200 nm in the composite tungsten carbide particles.

[0157] Comparative Example 2

[0158] The difference between this comparative example and Example 3 is that the hard particles in this comparative example only contain tungsten carbide particles with a particle size of 2-3 μm in the composite tungsten carbide particles.

[0159] Comparative Example 3

[0160] The difference between this comparative example and Example 3 is that the hard particles in this comparative example do not contain zirconium powder and titanium powder, and the content of the composite tungsten carbide particles is 83.2 wt.%.

[0161] Comparative Example 4

[0162] The difference between this comparative example and Example 3 is that the base material in this comparative example does not contain aluminum oxide, and the content of molybdenum carbide is 9 wt.%.

[0163] Comparative Example 5

[0164] The difference between this comparative example and Example 3 is that the base material in this comparative example does not contain copper, and the content of cobalt is 16.5 wt.%.

[0165] The Rockwell hardness, fracture toughness, bending strength and wear loss of the tungsten carbide alloys prepared in Examples 1-5 and Comparative Examples 1-5 were detected, the fracture toughness was detected according to the standard ISO28079-2009, the hardness was detected according to GBT3849.1-2015, the bending strength was detected according to GBT3851-2015, and the wear loss was detected according to Q / 62071126-8F0524-2014. The properties of the tungsten carbide alloys prepared in Examples 1-5 and Comparative Examples 1-5 are shown in Table 1.

[0166] Table 1 Properties of tungsten carbide alloys prepared in Examples 1-5 and Comparative Examples 1-5

[0167]

[0168] As shown in Table 1, the use of composite tungsten carbide particles in the hard particles, the addition of zirconium powder and titanium powder can effectively improve the fracture toughness, hardness, wear resistance and wear resistance of the tungsten carbide alloy. The addition of copper in the matrix can improve the fracture toughness and bending strength of the tungsten carbide alloy, and the alumina in the matrix can effectively improve the wear resistance, hardness, fracture toughness and bending strength of the tungsten carbide alloy.

[0169] Therefore, the wear-resistant tungsten carbide alloy and the preparation method thereof can solve the problem that the hardness and toughness of the existing tungsten carbide alloy cannot be synergistically enhanced, which affects the wear resistance of the tungsten carbide alloy.

[0170] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application but not to limit it, although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can still be modified or replaced by equivalents, and these modifications or equivalent replacements cannot make the modified technical solutions deviate from the spirit and scope of the technical solutions of the present application.

Claims

1. A high wear resistant tungsten carbide alloy characterized by: The hard particles are evenly distributed in the matrix, and the mass percentage of the hard particles is 80wt.%-90wt.%, and the mass percentage of the matrix is 10wt.%-20wt.%. The composite tungsten carbide particles include the following components with the following mass percentages: 10wt.%-15wt.% of tungsten carbide particles with a particle size of 150nm-200nm, 50wt.%-70wt.% of tungsten carbide particles with a particle size of 0.8μm-1.0μm, and 20wt.%-30wt.% of tungsten carbide particles with a particle size of 2μm-3μm. The matrix includes the following components with the following mass percentages: 70wt.%-80wt.% of tungsten carbide, 4wt.%-6wt.% of molybdenum carbide, 3wt.%-5wt.% of aluminum oxide, 0.1wt.%-0.5wt.% of rare earth oxide, 0.5wt.%-1wt.% of copper, and 15wt.%-20wt.% of cobalt.

2. A high wear resistant tungsten carbide alloy as claimed in claim 1, wherein: The particle size of the cobalt powder is 3μm-5μm, the particle size of the titanium powder is 1μm-2μm, and the particle size of the zirconium powder is 1μm-2μm.

3. A high wear resistant tungsten carbide alloy as claimed in claim 2, wherein: The particle size of the rare earth oxide in the hard particles is 0.5μm-1.0μm, and the rare earth oxide is one of cerium oxide and yttrium oxide.

4. A high wear resistant tungsten carbide alloy as claimed in claim 1, wherein: The particle size of the tungsten carbide in the matrix is 3μm-5μm, the particle size of the molybdenum carbide is 0.8μm-1μm, the particle size of the aluminum oxide is 0.2μm-0.4μm, the particle size of the copper is 0.3μm-0.5μm, the particle size of the cobalt is 1μm-2μm, and the particle size of the rare earth oxide is 0.2μm-0.4μm, and the rare earth oxide is yttrium oxide.

5. The method of claim 1, wherein the tungsten carbide alloy has a hardness of at least 90 GPa. The method comprises the following steps: S1, preparing hard particles; S2, mixing tungsten carbide powder, molybdenum carbide powder, aluminum oxide powder, rare earth oxide powder, cobalt powder, and copper powder in ethanol medium according to the mass ratio to obtain matrix raw materials; S3, adding the hard particles to the matrix raw materials for ball milling and mixing, and then drying the raw material powder to obtain a raw material blank; S4, sintering the raw material blank in a plasma sintering furnace, and then naturally cooling to room temperature to obtain a tungsten carbide alloy; The S1 comprises the following steps: S11, weighing tungsten carbide particles with a particle size of 150nm-200nm, tungsten carbide particles with a particle size of 0.8μm-1.0μm, and tungsten carbide particles with a particle size of 2μm-3μm according to the mass ratio, and performing ultrasonic dispersion on the tungsten carbide particles in ethanol medium for 1h-3h to obtain composite tungsten carbide particles; S12, drying the composite tungsten carbide particles; and drying the nano carbon black at 120℃ for 2-3 hours to remove water in the nano carbon black. S13, the composite tungsten carbide particles, nano carbon black, cobalt powder, titanium powder, zirconium powder and rare earth oxide are mixed according to the mass ratio, and ball milling is carried out in the ethanol medium to obtain a mixed powder; S14, the mixed powder is dried, and the mixed powder is pressure-maintained at 50MPa-100MPa for 5min-10min to obtain a green body; S15, the green body is placed into a heating furnace for sintering, inert gas is used for protection during the sintering process, and the sintered product is obtained after natural cooling to room temperature; S16, the sintered product is crushed, ball milled and sieved to obtain hard particles with a particle size of 20μm-30μm.

6. A method of producing a high wear resistant tungsten carbide alloy as claimed in claim 5, wherein: In the S15, the sintering temperature is 1400℃-1500℃, the sintering pressure is 10MPa-30MPa, and the holding time is 0.5h-1h.

7. The method of claim 5, wherein the tungsten carbide alloy has a hardness of at least 90 GPa. In the S4, the sintering temperature is 1300℃-1400℃, the sintering pressure is 30MPa-50MPa, and the sintering time is 20min-30min.

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