A tungsten alloy material and its preparation method

Abstract

The present invention relates to the technical field of tungsten alloys, and discloses a tungsten alloy material and a preparation method thereof, comprising the following raw materials in parts by mass: 90-100 parts of modified tungsten powder, 8-10 parts of nickel powder, 5-7 parts of iron powder, 4-6 parts of cobalt powder, and 1-3 parts of modified carbon fiber. The molten nickel powder, iron powder, and cobalt powder penetrate into the tungsten powder through the pores uniformly distributed on the surface of the modified tungsten powder by the porous carbon, forming a uniform and dense alloy material, avoiding the uneven distribution of nickel powder, iron powder, and cobalt powder in the tungsten alloy material due to the large melting point difference between tungsten powder and nickel powder, iron powder, and cobalt powder, and reducing the mechanical strength of the alloy material; the pretreated silicon carbide whiskers adhere to the surface of the carbon fiber loaded with graphene oxide to form modified carbon fiber, which can absorb and disperse the interfacial stress, reduce stress concentration, prevent cracks and debonding phenomena at the interface, and enhance the mechanical properties of the tungsten alloy material.

Description

Technical Field

[0001] The present invention relates to the technical field of tungsten alloys, and particularly to a tungsten alloy material and a preparation method thereof. Background Art

[0002] Tungsten alloys are a class of alloys based on tungsten powder (with a tungsten content of 85-99%), and appropriately adding elements such as nickel, copper, iron, cobalt, molybdenum, chromium, etc. They are generally referred to as high specific gravity alloys, heavy alloys or high density tungsten alloys, and have excellent properties such as high density, high melting point, and low coefficient of thermal expansion. They are widely used in cemented carbide roll rings, rolling rolls, high-performance nano-cemented carbide tools, large-grain cemented carbide shield tools, cemented carbide deep-processing products and their supporting tools, etc.

[0003] However, in the existing production and manufacturing process of tungsten alloys, due to the large difference in melting points between tungsten powder and other metal elements, during the sintering process, poor interfacial bonding is likely to occur, forming pores or cracks, which affects the mechanical properties of the alloy. Moreover, the brittleness of tungsten powder is relatively high, and the fracture toughness of the prepared tungsten alloy is poor. In addition, the tungsten alloy material also has problems such as coarse grains and poor tissue uniformity, which limit the application fields of tungsten alloy materials. Summary of the Invention

[0004] The present invention provides a tungsten alloy material, which solves the problems of low mechanical strength and poor tissue uniformity existing in tungsten alloys.

[0005] The technical solution of the present invention:

[0006] A tungsten alloy material, comprising the following raw materials in parts by mass: 90-100 parts of modified tungsten powder, 8-10 parts of nickel powder, 5-7 parts of iron powder, 4-6 parts of cobalt powder, and 1-3 parts of modified carbon fiber;

[0007] The modified tungsten powder is obtained by mixing tungsten powder, citric acid and glucose for reaction, and then mixing and reacting with zirconium oxychloride octahydrate and ammonia water;

[0008] The modified carbon fiber is obtained by mixing graphene oxide, silane coupling agent and carbon fiber for reaction, and then mixing with pretreated silicon carbide whiskers;

[0009] A preparation method of a tungsten alloy material, comprising the following preparation steps:

[0010] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, and perform vacuum drying and ball milling to obtain a mixture;

[0011] S2. Place the mixture in a pressure mold to be pressed into a preform, and then place the preform in a sintering furnace for high-temperature sintering and cooling to room temperature to obtain a tungsten alloy material.

[0012] Further, in step S1, the vacuum drying process: the drying temperature is 90 - 110 °C, the vacuum degree is 4 - 6 Pa, and the drying time is 5 - 15 min.

[0013] Further, in step S1, ball milling is carried out using a ball mill. The ball material is tungsten carbide with a diameter of 10 mm. The ball-to-material ratio in the ball mill is (5 - 10):1, the rotation speed is 1500 - 1700 r / min, and the ball milling time is 8 - 10 h.

[0014] Further, in step S2, the pressing pressure is 300 - 400 MPa, and the pressing time is 40 - 50 s.

[0015] Further, in step S2, the high-temperature sintering temperature is 1650 - 1750 °C, the high-temperature sintering time is 2 - 4 h, and the high-temperature sintering vacuum pressure is 40 - 50 Pa.

[0016] Further, the modified tungsten powder is specifically prepared by the following steps:

[0017] A1. Add tungsten powder, glucose, and citric acid into ethanol, stir evenly, add hydrochloric acid, stir and react at 65 - 75 °C for 30 - 40 min, filter, wash, dry, place in a tubular furnace, add potassium hydroxide solution, introduce nitrogen, carbonize at 750 - 850 °C for 3 - 5 h, cool to room temperature, take out, wash, and dry to obtain tungsten powder loaded with porous carbon;

[0018] A2. Add zirconium oxychloride octahydrate and tungsten powder loaded with porous carbon into deionized water, stir evenly, add ammonia water, glycine, and potassium chloride, stir at 80 - 90 °C for 8 - 10 min, place in a reaction kettle, carry out hydrothermal reaction at 170 - 190 °C for 20 - 22 h, cool to room temperature, filter, wash, and dry to obtain modified tungsten powder.

[0019] Further, during the above A1 reaction process, the large number of hydroxyl groups contained in citric acid can bind to micron-sized tungsten powder through hydrogen bonds, and citric acid can also bind to glucose through chemical bonds, enabling glucose to adhere to the surface of micron-sized tungsten powder through citric acid. After high-temperature carbonization, glucose decomposes by heat to form a dense carbon layer. Potassium hydroxide solution, as an activator, can form pores on the surface of the dense carbon layer, realizing the synthesis of a porous carbon structure on the surface of tungsten powder to obtain tungsten powder loaded with porous carbon.

[0020] Furthermore, during the above A2 reaction process, the tungsten powder loaded with porous carbon has excellent adsorption performance, and can adsorb zirconium oxychloride octahydrate and ammonia water onto the surface of the tungsten powder loaded with porous carbon. Ammonia water serves as a precipitating agent, and glycine and potassium chloride serve as additives, which can react with zirconium oxychloride octahydrate to form zirconium hydroxide deposited on the surface of the oxidized glass fiber. Continuing the reaction, zirconium hydroxide decomposes upon heating, realizing the synthesis of nano-zirconia in the porous carbon on the surface of the tungsten powder loaded with porous carbon, and obtaining modified tungsten powder.

[0021] Furthermore, in step A1, the dosage ratio of the tungsten powder, glucose, citric acid, ethanol, hydrochloric acid, and potassium hydroxide solution is (8 - 12) g : (5 - 6) g : (1.2 - 1.4) g : (180 - 220) mL : (0.4 - 0.6) mL : (4 - 6) mL.

[0022] Furthermore, in step A2, the dosage ratio of zirconium oxychloride octahydrate, tungsten powder loaded with porous carbon, deionized water, ammonia water, glycine, and potassium chloride is (3 - 4) g : (8 - 12) g : (90 - 110) mL : (6 - 8) mL : (0.3 - 0.5) g : (0.7 - 0.9) g.

[0023] Furthermore, the modified carbon fiber is specifically prepared by the following steps:

[0024] B1. Add the carbon fiber into ethanol and deionized water, stir evenly, add the silane coupling agent, stir and react at 65 - 75 °C for 1 - 2 h, add graphene oxide, raise the temperature to 80 - 90 °C, and stir and react at 350 - 400 r / min for 4 - 5 h. After filtration, washing, and drying, obtain the carbon fiber loaded with graphene oxide.

[0025] B2. Add the silicon carbide whiskers into the Tris - HCl buffer solution, stir evenly, add dopamine, continue stirring, and after filtration, washing, and drying, obtain the pretreated silicon carbide whiskers.

[0026] B3. Add the carbon fiber loaded with graphene oxide into deionized water, stir evenly, add the pretreated silicon carbide whiskers, stir and mix at 900 - 1000 r / min for 1 - 2 h, and after filtration, washing, and drying, obtain the modified carbon fiber.

[0027] Furthermore, during the above B1 reaction process, the silanol groups generated by the hydrolysis of the silane coupling agent can be chemically bonded to the oxygen - containing functional groups on the surface of the carbon fiber, enabling the silane coupling agent to be grafted onto the surface of the carbon fiber. Moreover, the amino groups contained in the silane coupling agent can be chemically bonded to the carboxyl and hydroxyl groups in the graphene oxide, causing the graphene oxide to be deposited on the surface of the carbon fiber, and obtaining the carbon fiber loaded with graphene oxide.

[0028] Furthermore, in the above B2 reaction process, in Tris-HCl buffer solution, dopamine can self-polymerize on the surface of silicon carbide whiskers to form polydopamine, forming polydopamine-modified silicon carbide whiskers, which is beneficial for the silicon carbide whiskers to coat on the surface of carbon fibers loaded with graphene oxide, enhancing the mechanical strength of the tungsten alloy material.

[0029] Furthermore, in the above B3 reaction process, the pretreated silicon carbide whiskers and carbon fibers loaded with graphene oxide are mixed. The pretreated silicon carbide whiskers have excellent adhesion and a large number of phenolic hydroxyl groups, enabling the pretreated silicon carbide whiskers to adhere to the surface of carbon fibers loaded with graphene oxide, obtaining modified carbon fibers.

[0030] Furthermore, in step B1, the dosage ratio of the carbon fiber, ethanol, deionized water, silane coupling agent, and graphene oxide is (2 - 3) g : (80 - 100) mL : (20 - 40) mL : (0.6 - 1) g : (1 - 1.4) g.

[0031] Furthermore, in step B2, the dosage ratio of the silicon carbide whiskers, Tris-HCl buffer solution, and dopamine is (1 - 2) g : (90 - 110) mL : (0.5 - 0.9) g.

[0032] Furthermore, in step B3, the dosage ratio of the carbon fibers loaded with graphene oxide, deionized water, and pretreated silicon carbide whiskers is (1 - 2) g : (90 - 110) mL : (1.1 - 1.5) g.

[0033] Furthermore, the diameter of the carbon fiber is 1 - 2 µm, and the length is 15 - 20 µm.

[0034] Furthermore, the diameter of the silicon carbide whiskers is 0.5 - 0.8 µm, and the length is 10 - 15 µm.

[0035] Furthermore, the silane coupling agent is γ-aminopropyltriethoxysilane.

[0036] The present invention has the following beneficial effects:

[0037] (1) In the technical solution of the present invention, after mixing tungsten powder, citric acid, and glucose and reacting, tungsten powder loaded with porous carbon is obtained. On the one hand, a porous carbon structure is synthesized on the surface of the tungsten powder, improving the surface roughness of the tungsten powder and increasing the contact area between the tungsten powder and other metal elements, which is beneficial for synthesizing a denser tungsten alloy material. On the other hand, during the sintering process, the synthesized porous carbon can adsorb more molten metal elements, and the carbon element in the porous carbon can chemically react with the molten nickel powder, iron powder, and cobalt powder to form metal carbides, which are filled into the grain boundaries and defects of the tungsten alloy material, improving the density of the alloy, and thus enhancing the mechanical strength of the tungsten alloy material.

[0038] (2) In the technical solution of the present invention, nano-zirconia is synthesized in the porous carbon on the surface of tungsten powder loaded with porous carbon. On the one hand, the synthesized nano-zirconia serves as a support framework for the porous carbon in the tungsten powder loaded with porous carbon, improving the compressive strength of the pores and preventing the pores of the porous carbon from collapsing under external forces during the high-temperature sintering and pressing process, which affects the densification performance and mechanical strength of the tungsten alloy material. Moreover, the nano-zirconia is randomly distributed inside the porous carbon, which can effectively transfer stress and prevent cracks from occurring at the grain boundaries of the tungsten alloy material under external forces, thereby improving the strength of the alloy. On the other hand, the nano-zirconia can be dispersed in the tungsten alloy material, playing a role of dispersion strengthening, improving the core hardness of the tungsten alloy, and enhancing the mechanical strength of the tungsten alloy. In addition, the molten nickel powder, iron powder, and cobalt powder penetrate into the tungsten powder through the uniformly distributed pores of the porous carbon, enabling the nickel powder, iron powder, and cobalt powder to form a uniform and dense alloy material with the tungsten powder, preventing the uneven distribution of the nickel powder, iron powder, and cobalt powder in the tungsten alloy material due to the large difference in melting points, which reduces the mechanical strength of the alloy material.

[0039] (3) In the technical solution of the present invention, graphene oxide is deposited on the surface of carbon fiber through a silane coupling agent. On the one hand, the carbon fiber serves as a carrier for the graphene oxide. When added to the tungsten alloy material, it can prevent the agglomeration and stacking of the graphene oxide, improving the dispersion of the graphene oxide in the tungsten alloy material. Moreover, the sheet structure of the graphene oxide serves as a physical barrier for the dislocation movement of the alloy material, hindering the dislocation slip of the alloy material and improving the fracture toughness of the tungsten alloy. On the other hand, the carbon fiber forms a carbon fiber network that can absorb stress in the alloy, further enhancing the mechanical properties of the tungsten alloy. During the preparation of the tungsten alloy, the carbon fiber and graphene oxide can fill the pores and cracks of the tungsten alloy material, improving the densification of the tungsten alloy.

[0040] (4) In the technical solution of the present invention, in the Tris-HCl buffer solution, dopamine can self-polymerize on the surface of silicon carbide whiskers to form polydopamine, forming pretreated silicon carbide whiskers, which is beneficial for the pretreated silicon carbide whiskers to coat on the surface of carbon fiber loaded with graphene oxide, enhancing the mechanical strength of the tungsten alloy material; the pretreated silicon carbide whiskers adhere to the surface of the carbon fiber loaded with graphene oxide, enabling the graphene oxide to be coated between the pretreated silicon carbide whiskers and the carbon fiber, improving the fixation of the graphene oxide and preventing the migration of the graphene oxide under external forces in the alloy material. Moreover, the graphene oxide serves as a buffer layer for the alloy material in the modified carbon fiber, which can absorb and disperse the interfacial stress, reduce stress concentration, prevent cracks and debonding phenomena from occurring at the interface, and enhance the mechanical properties of the tungsten alloy material. Detailed implementation manners

[0041] Next, in combination with the embodiments of the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative efforts belong to the scope of protection of the present invention.

[0042] The raw materials used in the embodiments of the present invention are as follows, and all the reagents used are of analytical grade.

[0043] Among them, tungsten powder: Fisher particle size 3.1 µm, purchased from Ultra-fine Nano Co., Ltd.

[0044] Nickel powder: average particle size 2.5 µm, purchased from Shanghai Shuitian Technology Co., Ltd.

[0045] Iron powder: average particle size 2.5 µm, purchased from Ultra-fine Nano Co., Ltd.

[0046] Cobalt powder: average particle size 2.5 µm, Ultra-fine Nano Co., Ltd.

[0047] The carbon fiber has a diameter of 1.5 µm and a length of 18 µm.

[0048] The silicon carbide whiskers have a diameter of 0.7 µm and a length of 13 µm.

[0049] The graphene oxide has a particle size of 2 µm and a thickness of 8 nm.

[0050] The silane coupling agent is γ-aminopropyltriethoxysilane.

[0051] Example 1

[0052] A tungsten alloy material, comprising the following raw materials in parts by mass: 90 parts of modified tungsten powder, 8 parts of nickel powder, 5 parts of iron powder, 4 parts of cobalt powder, and 1 part of modified carbon fiber;

[0053] A method for preparing a tungsten alloy material, comprising the following preparation steps:

[0054] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder, and modified carbon fiber, and perform vacuum drying and ball milling to obtain a mixed material;

[0055] S2. Place the mixed material in a pressure mold to be pressed into a preform, and then place the preform in a sintering furnace for high-temperature sintering and cooling to room temperature to obtain the tungsten alloy material;

[0056] Among them, in step S1, the vacuum drying process: the drying temperature is 90 °C, the vacuum degree is 4 Pa, and the drying time is 5 min;

[0057] In step S1, ball milling is carried out using a ball mill. The ball material is tungsten carbide with a diameter of 10 mm. The ball-to-material ratio in the ball mill is 5:1, the rotation speed is 1500 r / min, and the ball milling time is 8 h;

[0058] In step S2, the pressing pressure is 300 MPa and the pressing time is 40 s;

[0059] In step S2, the high-temperature sintering temperature is 1650 °C, the high-temperature sintering time is 2 h, and the high-temperature sintering vacuum pressure is 40 Pa;

[0060] The modified tungsten powder is specifically prepared by the following steps:

[0061] A1. Add 8 g of tungsten powder, 5 g of glucose, and 1.2 g of citric acid to 180 mL of ethanol, stir evenly, add 0.4 mL of hydrochloric acid with a mass fraction of 36%, stir and react at 65 °C for 30 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add 4 mL of potassium hydroxide solution with a mass fraction of 30%, introduce nitrogen, carbonize at 750 °C for 3 h, cool to room temperature, take out, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain tungsten powder loaded with porous carbon;

[0062] A2. Add 3 g of zirconium oxychloride octahydrate and 8 g of tungsten powder loaded with porous carbon to 90 mL of deionized water, stir evenly, add 6 mL of ammonia water, 0.3 g of glycine, and 0.7 g of potassium chloride, stir at 80 °C for 8 min, place in a reaction kettle, carry out hydrothermal reaction at 170 °C for 20 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 3 h to obtain the modified tungsten powder.

[0063] The modified carbon fiber is specifically prepared by the following steps:

[0064] B1. Add 2 g of carbon fiber to 80 mL of ethanol and 20 mL of deionized water, stir evenly, add 0.6 g of γ-aminopropyltriethoxysilane, stir and react at 65 °C for 1 h, add 1 g of graphene oxide, raise the temperature to 80 °C, and stir and react at 350 r / min for 4 h, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 15 min to obtain carbon fiber loaded with graphene oxide;

[0065] B2. Add 1 g of silicon carbide whiskers to 90 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 25 °C and 2000 r / min for 20 min, add 0.5 g of dopamine, stir at 30 °C and 2000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain pretreated silicon carbide whiskers;

[0066] B3. Add 1 g of carbon fiber loaded with graphene oxide to 90 mL of deionized water, stir evenly, add 1.1 g of pretreated silicon carbide whiskers, stir and mix at 900 r / min for 1 h, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 15 min to obtain modified carbon fiber.

[0067] Example 2

[0068] A tungsten alloy material comprises the following raw materials in parts by mass: 95 parts of modified tungsten powder, 9 parts of nickel powder, 6 parts of iron powder, 5 parts of cobalt powder, and 2 parts of modified carbon fiber;

[0069] A preparation method of a tungsten alloy material comprises the following preparation steps:

[0070] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, and obtain a mixture through vacuum drying and ball milling;

[0071] S2. Place the mixture in a pressure mold to be pressed into a preform, and then place the preform in a sintering furnace for high-temperature sintering, and cool to room temperature to obtain the tungsten alloy material;

[0072] Among them, in step S1, the vacuum drying process: the drying temperature is 100 °C, the vacuum degree is 5 Pa, and the drying time is 10 min;

[0073] In step S1, ball milling is carried out using a ball mill, the ball material is tungsten carbide with a diameter of 10 mm, the ball-to-material ratio in the ball mill is 8:1, the rotation speed is 1600 r / min, and the ball milling time is 9 h;

[0074] In step S2, the pressing pressure is 350 MPa and the pressing time is 45 s;

[0075] In step S2, the high-temperature sintering temperature is 1700 °C, the high-temperature sintering time is 3 h, and the high-temperature sintering vacuum pressure is 45 Pa;

[0076] The modified tungsten powder is specifically prepared by the following steps:

[0077] A1. Add 10 g of tungsten powder, 5.5 g of glucose and 1.3 g of citric acid to 200 mL of ethanol, stir evenly, add 0.5 mL of hydrochloric acid with a mass fraction of 36%, stir and react at 70 °C for 35 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tube furnace, add 5 mL of potassium hydroxide solution with a mass fraction of 30%, introduce nitrogen, carbonize at 800 °C for 4 h, cool to room temperature, take out, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain tungsten powder loaded with porous carbon;

[0078] A2. Add 3.5 g of zirconium oxychloride octahydrate and 10 g of tungsten powder supported on porous carbon to 100 mL of deionized water, stir evenly, add 7 mL of ammonia water, 0.4 g of glycine and 0.8 g of potassium chloride, stir at 85 °C for 9 min, place it in a reaction kettle, carry out hydrothermal reaction at 180 °C for 21 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 3 h to obtain modified tungsten powder.

[0079] The modified carbon fiber is specifically prepared by the following steps:

[0080] B1. Add 2.5 g of carbon fiber to 90 mL of ethanol and 30 mL of deionized water, stir evenly, add 0.8 g of γ-aminopropyltriethoxysilane, stir and react at 70 °C for 1.5 h, add 1.2 g of graphene oxide, raise the temperature to 85 °C, and stir and react at 380 r / min for 4.5 h, filter, wash with deionized water 3 times, and dry in an oven at 60 °C for 15 min to obtain carbon fiber loaded with graphene oxide;

[0081] B2. Add 1.5 g of silicon carbide whiskers to 100 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 25 °C and 2000 r / min for 20 min, add 0.7 g of dopamine, stir at 30 °C and 2000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain pretreated silicon carbide whiskers;

[0082] B3. Add 1.5 g of carbon fiber loaded with graphene oxide to 100 mL of deionized water, stir evenly, add 1.3 g of pretreated silicon carbide whiskers, stir and mix at 950 r / min for 1.5 h, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 15 min to obtain modified carbon fiber.

[0083] Example 3

[0084] A tungsten alloy material, comprising the following raw materials in parts by mass: 100 parts of modified tungsten powder, 10 parts of nickel powder, 7 parts of iron powder, 6 parts of cobalt powder, and 3 parts of modified carbon fiber;

[0085] A preparation method of a tungsten alloy material, comprising the following preparation steps:

[0086] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, and obtain a mixture through vacuum drying and ball milling;

[0087] S2. Place the mixture in a pressure mold to be pressed into a preform, and then place the preform in a sintering furnace for high-temperature sintering, and cool to room temperature to obtain a tungsten alloy material;

[0088] Among them, in step S1, the vacuum drying process: the drying temperature is 110°C, the vacuum degree is 6 Pa, and the drying time is 15 min;

[0089] In step S1, ball milling is carried out using a ball mill. The ball material is tungsten carbide with a diameter of 10 mm. The ball-to-material ratio in the ball mill is 10:1, the rotation speed is 1700 r / min, and the ball milling time is 10 h;

[0090] In step S2, the pressing pressure is 400 MPa and the pressing time is 50 s;

[0091] In step S2, the high-temperature sintering temperature is 1750°C, the high-temperature sintering time is 4 h, and the high-temperature sintering vacuum pressure is 50 Pa;

[0092] The modified tungsten powder is specifically prepared by the following steps:

[0093] A1. Add 12 g of tungsten powder, 6 g of glucose, and 1.4 g of citric acid to 220 mL of ethanol, stir evenly, add 0.6 mL of hydrochloric acid with a mass fraction of 36%, stir and react at 75°C for 40 min, filter, wash with deionized water 3 times, dry in an oven at 70°C for 10 min, place in a tubular furnace, add 6 mL of potassium hydroxide solution with a mass fraction of 30%, introduce nitrogen, carbonize at 850°C for 5 h, cool to room temperature, take out, wash with deionized water 3 times, and dry in an oven at 70°C for 10 min to obtain tungsten powder loaded with porous carbon;

[0094] A2. Add 4 g of zirconium oxychloride octahydrate and 12 g of tungsten powder loaded with porous carbon to 110 mL of deionized water, stir evenly, add 8 mL of ammonia water, 0.5 g of glycine, and 0.9 g of potassium chloride, stir at 90°C for 10 min, place in a reaction kettle, carry out hydrothermal reaction at 190°C for 22 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80°C for 3 h to obtain the modified tungsten powder.

[0095] The modified carbon fiber is specifically prepared by the following steps:

[0096] B1. Add 3 g of carbon fiber to 100 mL of ethanol and 40 mL of deionized water, stir evenly, add 1 g of γ-aminopropyltriethoxysilane, stir and react at 75°C for 2 h, add 1.4 g of graphene oxide, raise the temperature to 90°C, stir and react at 400 r / min for 5 h, filter, wash with deionized water 3 times, and dry in an oven at 60°C for 15 min to obtain carbon fiber loaded with graphene oxide;

[0097] B2. Add 2 g of silicon carbide whiskers to 110 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 25 °C and 2000 r / min for 20 min, add 0.9 g of dopamine, stir at 30 °C and 2000 r / min for 2 h, filter, wash with deionized water three times, and dry in an oven at 70 °C for 10 min to obtain pretreated silicon carbide whiskers;

[0098] B3. Add 2 g of carbon fiber loaded with graphene oxide to 110 mL of deionized water, stir evenly, add 1.5 g of pretreated silicon carbide whiskers, stir and mix at 1000 r / min for 2 h, filter, wash with deionized water three times, and dry in an oven at 80 °C for 15 min to obtain modified carbon fiber.

[0099] Comparative Example 1

[0100] A tungsten alloy material comprises the following raw materials in parts by mass: 100 parts of modified tungsten powder, 10 parts of nickel powder, 7 parts of iron powder, 6 parts of cobalt powder, and 3 parts of modified carbon fiber;

[0101] A preparation method of a tungsten alloy material comprises the following preparation steps:

[0102] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, and obtain a mixture through vacuum drying and ball milling;

[0103] S2. Place the mixture in a pressure mold to be pressed into a preform, then place the preform in a sintering furnace for high-temperature sintering, and cool to room temperature to obtain the tungsten alloy material;

[0104] Among them, in step S1, the vacuum drying process: the drying temperature is 110 °C, the vacuum degree is 6 Pa, and the drying time is 15 min;

[0105] In step S1, ball milling is carried out using a ball mill, the ball material is tungsten carbide with a diameter of 10 mm, the ball-to-material ratio in the ball mill is 10:1, the rotation speed is 1700 r / min, and the ball milling time is 10 h;

[0106] In step S2, the pressing pressure is 400 MPa and the pressing time is 50 s;

[0107] In step S2, the high-temperature sintering temperature is 1750 °C, the high-temperature sintering time is 4 h, and the high-temperature sintering vacuum pressure is 50 Pa;

[0108] The modified tungsten powder is specifically prepared by the following steps:

[0109] 4 g of zirconium oxychloride octahydrate and 12 g of tungsten powder were added to 110 mL of deionized water, stirred evenly, 8 mL of ammonia water, 0.5 g of glycine and 0.9 g of potassium chloride were added, stirred at 90 °C for 10 min, placed in a reaction kettle, hydrothermally reacted at 190 °C for 22 h, cooled to room temperature, filtered, washed 3 times with deionized water, and dried in an oven at 80 °C for 3 h to obtain modified tungsten powder.

[0110] The modified carbon fiber was specifically prepared by the following steps:

[0111] B1. 3 g of carbon fiber was added to 100 mL of ethanol and 40 mL of deionized water, stirred evenly, 1 g of γ-aminopropyltriethoxysilane was added, stirred and reacted at 75 °C for 2 h, 1.4 g of graphene oxide was added, the temperature was raised to 90 °C, and stirred and reacted at 400 r / min for 5 h, filtered, washed 3 times with deionized water, and dried in an oven at 60 °C for 15 min to obtain carbon fiber loaded with graphene oxide;

[0112] B2. 2 g of silicon carbide whiskers were added to 110 mL of Tris-HCl buffer solution with a pH of 8.5, stirred at 25 °C and 2000 r / min for 20 min, 0.9 g of dopamine was added, stirred at 30 °C and 2000 r / min for 2 h, filtered, washed 3 times with deionized water, and dried in an oven at 70 °C for 10 min to obtain pretreated silicon carbide whiskers;

[0113] B3. 2 g of carbon fiber loaded with graphene oxide was added to 110 mL of deionized water, stirred evenly, 1.5 g of pretreated silicon carbide whiskers was added, stirred and mixed at 1000 r / min for 2 h, filtered, washed 3 times with deionized water, and dried in an oven at 80 °C for 15 min to obtain modified carbon fiber.

[0114] Comparative Example 2

[0115] A tungsten alloy material, comprising the following raw materials in parts by mass: 100 parts of modified tungsten powder, 10 parts of nickel powder, 7 parts of iron powder, 6 parts of cobalt powder, and 3 parts of modified carbon fiber;

[0116] A preparation method of a tungsten alloy material, comprising the following preparation steps:

[0117] S1. The modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber were mixed, vacuum dried and ball milled to obtain a mixture;

[0118] S2. The mixture was placed in a pressure mold to be pressed into a preform, and then the preform was placed in a sintering furnace for high-temperature sintering, cooled to room temperature to obtain a tungsten alloy material;

[0119] Among them, in step S1, the vacuum drying process: the drying temperature is 110°C, the vacuum degree is 6 Pa, and the drying time is 15 min;

[0120] In step S1, ball milling is carried out using a ball mill. The ball material is tungsten carbide with a diameter of 10 mm. The ball-to-material ratio in the ball mill is 10:1, the rotation speed is 1700 r / min, and the ball milling time is 10 h;

[0121] In step S2, the pressing pressure is 400 MPa and the pressing time is 50 s;

[0122] In step S2, the high-temperature sintering temperature is 1750°C, the high-temperature sintering time is 4 h, and the high-temperature sintering vacuum pressure is 50 Pa;

[0123] The modified tungsten powder is specifically prepared by the following steps:

[0124] Add 12 g of tungsten powder, 6 g of glucose, and 1.4 g of citric acid to 220 mL of ethanol, stir evenly, add 0.6 mL of hydrochloric acid with a mass fraction of 36%, stir and react at 75°C for 40 min, filter, wash with deionized water 3 times, dry in an oven at 70°C for 10 min, place in a tubular furnace, add 6 mL of potassium hydroxide solution with a mass fraction of 30%, introduce nitrogen, carbonize at 850°C for 5 h, cool to room temperature, take out, wash with deionized water 3 times, and dry in an oven at 70°C for 10 min to obtain the modified tungsten powder.

[0125] The modified carbon fiber is specifically prepared by the following steps:

[0126] B1. Add 3 g of carbon fiber to 100 mL of ethanol and 40 mL of deionized water, stir evenly, add 1 g of γ-aminopropyltriethoxysilane, stir and react at 75°C for 2 h, add 1.4 g of graphene oxide, raise the temperature to 90°C, stir and react at 400 r / min for 5 h, filter, wash with deionized water 3 times, and dry in an oven at 60°C for 15 min to obtain carbon fiber loaded with graphene oxide;

[0127] B2. Add 2 g of silicon carbide whiskers to 110 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 25°C and 2000 r / min for 20 min, add 0.9 g of dopamine, stir at 30°C and 2000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 70°C for 10 min to obtain pretreated silicon carbide whiskers;

[0128] B3. Add 2 g of carbon fiber loaded with graphene oxide to 110 mL of deionized water, stir evenly, add 1.5 g of pretreated silicon carbide whiskers, stir and mix at 1000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 15 min to obtain modified carbon fiber.

[0129] Comparative Example 3

[0130] A tungsten alloy material, comprising the following raw materials in parts by mass: 100 parts of modified tungsten powder, 10 parts of nickel powder, 7 parts of iron powder, 6 parts of cobalt powder, and 3 parts of modified carbon fiber;

[0131] A preparation method of a tungsten alloy material, comprising the following preparation steps:

[0132] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, and perform vacuum drying and ball milling to obtain a mixture;

[0133] S2. Place the mixture in a pressure mold to press into a preform, and then place the preform in a sintering furnace for high-temperature sintering, and cool to room temperature to obtain a tungsten alloy material;

[0134] Among them, in step S1, the vacuum drying process: the drying temperature is 110 °C, the vacuum degree is 6 Pa, and the drying time is 15 min;

[0135] In step S1, ball milling is carried out using a ball mill, the ball material is tungsten carbide with a diameter of 10 mm, the ball-to-material ratio in the ball mill is 10:1, the rotation speed is 1700 r / min, and the ball milling time is 10 h;

[0136] In step S2, the pressing pressure is 400 MPa and the pressing time is 50 s;

[0137] In step S2, the high-temperature sintering temperature is 1750 °C, the high-temperature sintering time is 4 h, and the high-temperature sintering vacuum pressure is 50 Pa;

[0138] The modified tungsten powder is specifically prepared by the following steps:

[0139] A1. Add 12 g of tungsten powder, 6 g of glucose and 1.4 g of citric acid to 220 mL of ethanol, stir evenly, add 0.6 mL of hydrochloric acid with a mass fraction of 36%, stir and react at 75 °C for 40 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add 6 mL of potassium hydroxide solution with a mass fraction of 30%, introduce nitrogen, carbonize at 850 °C for 5 h, cool to room temperature, take out, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain tungsten powder loaded with porous carbon;

[0140] A2. Add 4 g of zirconium oxychloride octahydrate and 12 g of tungsten powder supported on porous carbon to 110 mL of deionized water, stir evenly, add 8 mL of ammonia water, 0.5 g of glycine and 0.9 g of potassium chloride, stir at 90 °C for 10 min, place in a reaction kettle, carry out hydrothermal reaction at 190 °C for 22 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 3 h to obtain modified tungsten powder.

[0141] The modified carbon fiber is specifically prepared by the following steps:

[0142] B1. Add 2 g of silicon carbide whiskers to 110 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 25 °C and 2000 r / min for 20 min, add 0.9 g of dopamine, stir at 30 °C and 2000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain pretreated silicon carbide whiskers;

[0143] B2. Add 2 g of carbon fiber to 110 mL of deionized water, stir evenly, add 1.5 g of pretreated silicon carbide whiskers, stir and mix at 1000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 15 min to obtain modified carbon fiber.

[0144] Comparative Example 4

[0145] A tungsten alloy material, including the following raw materials in parts by mass: 100 parts of modified tungsten powder, 10 parts of nickel powder, 7 parts of iron powder, 6 parts of cobalt powder, and 3 parts of modified graphene oxide;

[0146] A preparation method of a tungsten alloy material, including the following preparation steps:

[0147] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder and modified graphene oxide, carry out vacuum drying and ball milling to obtain a mixture;

[0148] S2. Place the mixture in a pressure mold to be pressed into a preform, and then place the preform in a sintering furnace for high-temperature sintering, and cool to room temperature to obtain a tungsten alloy material;

[0149] Among them, in step S1, the vacuum drying process: the drying temperature is 110 °C, the vacuum degree is 6 Pa, and the drying time is 15 min;

[0150] In step S1, ball milling is carried out using a ball mill, the ball material is tungsten carbide with a diameter of 10 mm, the ball-to-material ratio in the ball mill is 10:1, the rotation speed is 1700 r / min, and the ball milling time is 10 h;

[0151] In step S2, the pressing pressure is 400 MPa and the pressing time is 50 s;

[0152] In step S2, the high-temperature sintering temperature is 1750 °C, the high-temperature sintering time is 4 h, and the high-temperature sintering vacuum pressure is 50 Pa;

[0153] The modified tungsten powder is specifically prepared by the following steps:

[0154] A1. Add 12 g of tungsten powder, 6 g of glucose, and 1.4 g of citric acid to 220 mL of ethanol, stir evenly, add 0.6 mL of hydrochloric acid with a mass fraction of 36%, stir and react at 75 °C for 40 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place in a tubular furnace, add 6 mL of potassium hydroxide solution with a mass fraction of 30%, introduce nitrogen, carbonize at 850 °C for 5 h, cool to room temperature, take out, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain tungsten powder loaded with porous carbon;

[0155] A2. Add 4 g of zirconium oxychloride octahydrate and 12 g of tungsten powder loaded with porous carbon to 110 mL of deionized water, stir evenly, add 8 mL of ammonia water, 0.5 g of glycine, and 0.9 g of potassium chloride, stir at 90 °C for 10 min, place in a reaction kettle, carry out hydrothermal reaction at 190 °C for 22 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 3 h to obtain the modified tungsten powder.

[0156] The modified graphene oxide is specifically prepared by the following steps:

[0157] B1. Add 2 g of silicon carbide whiskers to 110 mL of Tris-HCl buffer solution with a pH of 8.5, stir at 25 °C and 2000 r / min for 20 min, add 0.9 g of dopamine, stir at 30 °C and 2000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain pretreated silicon carbide whiskers;

[0158] B2. Add 2 g of graphene oxide to 110 mL of deionized water, stir evenly, add 1.5 g of pretreated silicon carbide whiskers, stir and mix at 1000 r / min for 2 h, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 15 min to obtain the modified graphene oxide.

[0159] Comparative Example 5

[0160] A tungsten alloy material includes the following raw materials in parts by mass: 100 parts of modified tungsten powder, 10 parts of nickel powder, 7 parts of iron powder, 6 parts of cobalt powder, and 3 parts of modified carbon fiber;

[0161] A preparation method of a tungsten alloy material includes the following preparation steps:

[0162] S1. Mix the modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, and obtain a mixture through vacuum drying and ball milling.

[0163] S2. Place the mixture in a pressure mold to press it into a preform, and then place the preform in a sintering furnace for high-temperature sintering and cool it to room temperature to obtain a tungsten alloy material.

[0164] Among them, in step S1, for the vacuum drying process: the drying temperature is 110 °C, the vacuum degree is 6 Pa, and the drying time is 15 min.

[0165] In step S1, ball milling is carried out using a ball mill. The ball material is tungsten carbide with a diameter of 10 mm. The ball-to-material ratio in the ball mill is 10:1, the rotation speed is 1700 r / min, and the ball milling time is 10 h.

[0166] In step S2, the pressing pressure is 400 MPa and the pressing time is 50 s.

[0167] In step S2, the high-temperature sintering temperature is 1750 °C, the high-temperature sintering time is 4 h, and the high-temperature sintering vacuum pressure is 50 Pa.

[0168] The modified tungsten powder is specifically prepared by the following steps:

[0169] A1. Add 12 g of tungsten powder, 6 g of glucose and 1.4 g of citric acid to 220 mL of ethanol, stir evenly, add 0.6 mL of hydrochloric acid with a mass fraction of 36%, stir and react at 75 °C for 40 min, filter, wash with deionized water 3 times, dry in an oven at 70 °C for 10 min, place it in a tube furnace, add 6 mL of potassium hydroxide solution with a mass fraction of 30%, introduce nitrogen, carbonize at 850 °C for 5 h, cool to room temperature, take out, wash with deionized water 3 times, and dry in an oven at 70 °C for 10 min to obtain tungsten powder loaded with porous carbon.

[0170] A2. Add 4 g of zirconium oxychloride octahydrate and 12 g of tungsten powder loaded with porous carbon to 110 mL of deionized water, stir evenly, add 8 mL of ammonia water, 0.5 g of glycine and 0.9 g of potassium chloride, stir at 90 °C for 10 min, place it in a reaction kettle, carry out hydrothermal reaction at 190 °C for 22 h, cool to room temperature, filter, wash with deionized water 3 times, and dry in an oven at 80 °C for 3 h to obtain the modified tungsten powder.

[0171] The modified carbon fiber is specifically prepared by the following steps:

[0172] B1. Add 3 g of carbon fiber into 100 mL of ethanol and 40 mL of deionized water, stir evenly, add 1 g of γ-aminopropyltriethoxysilane, stir and react at 75 °C for 2 h, add 1.4 g of graphene oxide, raise the temperature to 90 °C, stir and react at 400 r / min for 5 h, filter, wash with deionized water three times, and dry in an oven at 60 °C for 15 min to obtain carbon fiber loaded with graphene oxide;

[0173] B2. Add 2 g of carbon fiber loaded with graphene oxide into 110 mL of deionized water, stir evenly, add 1.5 g of silicon carbide whiskers, stir and mix at 1000 r / min for 2 h, filter, wash with deionized water three times, and dry in an oven at 80 °C for 15 min to obtain modified carbon fiber.

[0174] Now, perform performance tests on the tungsten alloy materials prepared in Examples 1-3 and Comparative Examples 1-5.

[0175] In accordance with the standards of GB / T228-2010 (Test Method for Tensile Properties of Metallic Materials at Room Temperature) and GB / T4340-2009, measure the elongation at break, yield strength, and tensile strength of the above-prepared tungsten alloy materials.

[0176] Microhardness test: Place the above-prepared tungsten-molybdenum-tantalum-niobium alloy powder material on a Vickers hardness tester of type HXD-1000T to measure the surface hardness of the sintered sample. Apply a load of 0.2 kg to make the rhombic indentation profile clearly visible. The indenter presses into the surface of the tested sample under the action of the applied load. After maintaining the pressure for a certain time, remove the load and read the value to record the microhardness.

[0177] As shown in Table 1 below.

[0178] Table 1 Performance tests of tungsten alloy materials prepared in Examples 1-3 and Comparative Examples 1-5

[0179]

[0180] It can be seen from the data in Table 1 that the tungsten alloy materials prepared in Examples 1-3 have high mechanical strength.

[0181] In Comparative Example 1, the modified tungsten powder prepared by replacing the tungsten powder loaded with porous carbon with tungsten powder was added to the tungsten alloy material, and its mechanical properties decreased. This proves that synthesizing a porous carbon structure on the surface of tungsten powder can improve the surface roughness of tungsten powder, increase the contact area between tungsten powder and other metal elements, and the carbon element in the porous carbon can chemically react with molten nickel powder, iron powder, and cobalt powder and fill into the grain boundaries and defects of the tungsten alloy material, thereby enhancing the mechanical strength of the tungsten alloy material. In addition, the molten nickel powder, iron powder, and cobalt powder penetrate into the tungsten powder through the uniformly distributed pores of the porous carbon to form a uniform and dense alloy material.

[0182] The modified tungsten powder prepared without adding zirconium oxychloride octahydrate and ammonia water in Comparative Example 2 was added to the tungsten alloy material, and its mechanical properties decreased. This proves that synthesizing nano-zirconia in the porous carbon on the surface of the tungsten powder loaded with porous carbon as the supporting framework of the porous carbon can improve the compressive strength of the pores, avoid the collapse of the pores caused by external forces, and affect the densification performance and mechanical strength of the tungsten alloy material. Moreover, the nano-zirconia is randomly distributed inside the porous carbon, which can effectively transfer stress, avoid the generation of cracks at the grain boundaries of the tungsten alloy material under external forces, and thus improve the strength of the alloy.

[0183] The modified carbon fiber prepared by replacing the carbon fiber loaded with graphene oxide with carbon fiber in Comparative Example 3 was added to the tungsten alloy material, and its mechanical properties decreased. This proves that graphene oxide is coated between the pretreated silicon carbide whiskers and the carbon fiber and serves as a buffer layer of the alloy material, which can absorb and disperse the interfacial stress, reduce stress concentration, prevent the generation of cracks and debonding phenomena at the interface, and the sheet structure of graphene oxide serves as a physical barrier for the dislocation movement of the alloy material, hindering the dislocation slip of the alloy material and improving the fracture toughness of the tungsten alloy.

[0184] The modified graphene oxide prepared by replacing the carbon fiber loaded with graphene oxide with graphene oxide in Comparative Example 4 was added to the tungsten alloy material, and its mechanical properties decreased. This proves that the carbon fiber forms a carbon fiber network capable of absorbing stress in the alloy, further enhancing the mechanical properties of the tungsten alloy, and the carbon fiber can fill the pores and cracks of the tungsten alloy material, improving the densification of the tungsten alloy.

[0185] The modified carbon fiber prepared by replacing the pretreated silicon carbide whiskers with silicon carbide whiskers in Comparative Example 5 was added to the tungsten alloy material, and its mechanical properties decreased. This proves that dopamine can self-polymerize on the surface of the silicon carbide whiskers to form polydopamine, which is beneficial to the coating of the pretreated silicon carbide whiskers on the surface of the carbon fiber loaded with graphene oxide, improving the fixation of graphene oxide, avoiding the migration of graphene oxide under external forces of the alloy material, being able to absorb and disperse the interfacial stress of the tungsten alloy material, reducing stress concentration, and enhancing the mechanical strength of the tungsten alloy material.

[0186] In the description of the specification, the description referring to terms such as "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0187] The above content is only an example and illustration of the present invention. Those skilled in the art to which the present technology pertains may make various modifications or supplements to the described specific embodiments, or use similar methods for substitution. As long as they do not deviate from the invention or exceed the scope defined by the claims of the present invention, they shall fall within the protection scope of the present invention.

Claims

1. A tungsten alloy material, characterized in that: The invention comprises the following raw materials by weight: 90-100 parts of modified tungsten powder, 8-10 parts of nickel powder, 5-7 parts of iron powder, 4-6 parts of cobalt powder and 1-3 parts of modified carbon fiber; The preparation method of the tungsten alloy material is specifically prepared by the following steps: S1, mixing modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, vacuum drying, and ball milling to obtain a mixture; S2, placing the mixed material in a pressure mold and pressing it into a preform, then placing the preform in a sintering furnace, sintering for 2-4 hours at 40-50Pa and 1650-1750°C, and cooling to room temperature to obtain a tungsten alloy material; The modified tungsten powder is prepared by mixing tungsten powder, citric acid and glucose, and then mixing with zirconium oxychloride octahydrate and ammonia water. The modified tungsten powder is specifically prepared by the following steps: A1. Add tungsten powder, glucose and citric acid to ethanol, stir evenly, add hydrochloric acid, stir and react at 65-75℃ for 30-40min, filter, wash, dry, place in a tube furnace, add potassium hydroxide solution, introduce nitrogen, carbonize at 750-850℃ for 3-5h, cool to room temperature, take out, wash, dry, and obtain tungsten powder loaded with porous carbon; A2. Add zirconium oxychloride octahydrate and tungsten powder loaded with porous carbon into deionized water, stir evenly, add ammonia water, glycine and potassium chloride, stir at 80-90°C for 8-10 minutes, place in a reactor, perform hydrothermal reaction at 170-190°C for 20-22 hours, cool to room temperature, filter, wash and dry to obtain modified tungsten powder; The modified carbon fiber is prepared by mixing graphene oxide, a silane coupling agent and carbon fiber, and then mixing with pretreated silicon carbide whiskers; The modified carbon fiber is specifically prepared by the following steps: B1. Add carbon fiber to ethanol and deionized water, stir evenly, add silane coupling agent, stir and react at 65-75°C for 1-2h, add graphene oxide, heat to 80-90°C, stir and react at 350-400r / min for 4-5h, filter, wash and dry to obtain carbon fiber loaded with graphene oxide; B2. Add the silicon carbide whiskers to Tris-HCl buffer, stir evenly, add dopamine, continue stirring, filter, wash, and dry to obtain pretreated silicon carbide whiskers; B3. Add the carbon fiber loaded with graphene oxide into deionized water, stir evenly, add the pretreated silicon carbide whisker, stir and mix at 900-1000 r / min for 1-2 hours, filter, wash and dry to obtain modified carbon fiber.

2. A tungsten alloy material according to claim 1, characterized in that: In step A1, the usage ratio of the tungsten powder, glucose, citric acid, ethanol, hydrochloric acid and potassium hydroxide solution is (8-12) g: (5-6) g: (1.2-1.4) g: (180-220) mL: (0.4-0.6) mL: (4-6) mL.

3. A tungsten alloy material according to claim 1, characterized in that: In step A2, the amount ratio of zirconium oxychloride octahydrate, tungsten powder loaded with porous carbon, deionized water, ammonia water, glycine and potassium chloride is (3-4) g: (8-12) g: (90-110) mL: (6-8) mL: (0.3-0.5) g: (0.7-0.9) g.

4. A tungsten alloy material according to claim 1, characterized in that: In step B1, the amount ratio of the carbon fiber, ethanol, deionized water, silane coupling agent and graphene oxide is (2-3) g: (80-100) mL: (20-40) mL: (0.6-1) g: (1-1.4) g.

5. A tungsten alloy material according to claim 1, characterized in that: In step B2, the ratio of the silicon carbide whisker, Tris-HCl buffer and dopamine is (1-2) g: (90-110) mL: (0.5-0.9) g.

6. A tungsten alloy material according to claim 1, characterized in that: In step B3, the amount ratio of the carbon fiber loaded with graphene oxide, deionized water and pretreated silicon carbide whiskers is (1-2) g: (90-110) mL: (1.1-1.5) g.

7. A method for preparing the tungsten alloy material according to any one of claims 1 to 6, characterized in that: The method comprises the following preparation steps: S1, mixing modified tungsten powder, nickel powder, iron powder, cobalt powder and modified carbon fiber, vacuum drying, and ball milling to obtain a mixture; S2. The mixed material is placed in a pressure mold and pressed into a preform, and then the preform is placed in a sintering furnace. The preform is sintered at 40-50Pa and 1650-1750°C for 2-4h, and cooled to room temperature to obtain a tungsten alloy material.

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