A cemented carbide material containing graphene oxide and a method for producing the same

Abstract

The application relates to the technical field of hard alloy, and particularly discloses a hard alloy material containing graphene oxide and a preparation method thereof, which comprises the following steps: S1, preparing graphene suspension aqueous solution, cobalt chloride aqueous solution and ammonium oxalate aqueous solution respectively; S2, mixing the graphene suspension aqueous solution and the cobalt chloride aqueous solution to obtain a GO / CoCl2.6H2O mixed aqueous solution, then adding the ammonium oxalate aqueous solution, uniformly mixing, heating and performing a hydrothermal reaction to obtain a GO / CoC2O4 precursor; S3, placing the GO / CoC2O4 precursor in a reducing atmosphere, heating and calcining to obtain a GO / Co composite powder; and S4, mixing and sintering the GO / Co composite powder and tungsten-carbon powder to obtain the hard alloy material. Through the hydrothermal reaction and the processing mode of high-heat reduction calcination, the graphene oxide is uniformly dispersed in cobalt powder and is made into a GO / Co composite powder, and then the GO / Co composite powder is compounded and sintered with the hard alloy powder, so that the problems of uneven dispersion and easy agglomeration of graphene in the hard alloy can be effectively solved.

Description

Technical Field

[0001] This invention relates to the field of cemented carbide technology, and more specifically, to a cemented carbide material containing graphene oxide and its preparation method. Background Technology

[0002] Graphene is a type of graphene produced by sp 2 Two-dimensional carbon nanomaterials, formed by the periodic hexagonal arrangement of hybrid carbon atoms, have a single-layer thickness of only 0.335 nm, making them the thinnest, strongest, and hardest materials discovered to date. Their elastic modulus reaches 1100 GPa, and their tensile strength is 125 GPa. In the field of cemented carbide, graphene, with its small size and excellent mechanical properties, has become a very promising reinforcing phase. It has been found that adding a small amount of graphene to cemented carbide can significantly improve its transverse fracture strength and fracture toughness while maintaining high hardness.

[0003] However, due to its large specific surface area, graphene powder is prone to agglomeration under van der Waals forces to maintain a stable low-energy state, resulting in poor dispersibility. This hinders graphene from fully exerting its toughening and reinforcing effects. To address the aforementioned problems of graphene agglomeration and poor dispersibility, existing treatment methods mainly fall into two categories: one is to add graphene dispersants, such as hexadecyltrimethylammonium bromide and N-methylpyrrolidone, to improve the dispersion effect of graphene; the other is to prepare modified graphene through chemical plating, thereby enhancing the dispersion and bonding effect between graphene and cemented carbide powder.

[0004] The existing methods mentioned above have the following problems: (1) Directly mixing graphene with cemented carbide powder can easily cause sedimentation, which exacerbates the problem of graphene dispersion difficulties; (2) The use of organic solvents in the process has a significant environmental pollution problem, and the process is complex and costly. Summary of the Invention

[0005] The purpose of this invention is to solve the problem of uneven graphene dispersion in cemented carbide.

[0006] This invention is achieved through the following technical solution:

[0007] This invention provides a method for preparing a hard alloy material containing graphene oxide, comprising the following steps:

[0008] S1 prepares graphene suspension aqueous solution and cobalt chloride aqueous solution respectively;

[0009] S2 mixes graphene suspension aqueous solution with cobalt chloride aqueous solution, heats and carries out hydrothermal reaction to obtain GO / CoC2O4 precursor;

[0010] S3 placed the GO / CoC2O4 precursor in a reducing atmosphere and heated it to calcine to obtain GO / Co composite powder;

[0011] S4 involves mixing and sintering GO / Co composite powder with tungsten carbide powder to obtain the cemented carbide material.

[0012] Preferably, in step S2, after the graphene suspension aqueous solution is mixed with the cobalt chloride aqueous solution, an ammonium oxalate aqueous solution is added, mixed well, and a hydrothermal reaction is carried out.

[0013] Preferably, in step S2, the hydrothermal reaction temperature is 70-90℃ and the hydrothermal reaction time is 10-15h.

[0014] Preferably, in step S2, after the hydrothermal reaction is completed, the product is first washed with deionized water and then dried at a constant temperature of 60-120℃ to obtain the GO / CoC2O4 precursor.

[0015] Preferably, in step S3, the calcination temperature is 490-810℃ and the calcination time is 100-150 min.

[0016] Preferably, the specific calcination process is as follows:

[0017] First, heat to 500±10℃ at 10℃ / min, and then keep warm at 500±10℃ for 30min;

[0018] Then heat to 650±10℃ at 5℃ / min, and keep warm at 650±10℃ for 60min;

[0019] Finally, heat to 800±10℃ at 5℃ / min and hold at 800±10℃ for 30min.

[0020] Preferably, in step S3, a reducing gas is continuously introduced during the calcination process, and the gas flow rate is 30-50 mL / min.

[0021] The hard alloy material containing graphene oxide prepared by the above preparation method includes, by mass, 65-93.5 wt% tungsten carbide powder, 6-30 wt% cobalt powder and 0.5-5 wt% graphene oxide.

[0022] Preferably, the FASS particle size of the tungsten carbide powder is 0.2-1.0 μm.

[0023] The technical solution of the present invention has the following beneficial effects:

[0024] This invention uses cobalt chloride hexahydrate as the cobalt source. Through hydrothermal reaction and high-temperature reduction calcination, graphene oxide is first uniformly dispersed in cobalt powder to form GO / Co composite powder. Then, the GO / Co composite powder is compounded and sintered with cemented carbide powder. Because graphene has a smaller density difference with cobalt, sedimentation problems caused by density differences can be reduced. Furthermore, the graphene first undergoes a hydrothermal reaction to form a composite GO / CoC2O4 precursor, which is then calcined to reduce the CoC2O4 to elemental cobalt powder. This method allows graphene to maintain a good lamellar morphology. The density difference between the GO / Co composite powder and the tungsten carbide powder is also small. Therefore, when the GO / Co composite powder is further compounded with the tungsten carbide powder, the density differences between the components of the cemented carbide can be effectively reduced, solving the problem of sedimentation and agglomeration. Ultimately, graphene maintains a high degree of dispersion in the cemented carbide powder and exhibits an excellent lamellar morphology. This effectively hinders the dissolution and exudation between tungsten carbide particles, preventing grain growth. Through crack bridging, graphene also prevents crack propagation, significantly improving the strength and toughness of the cemented carbide. Attached Figure Description

[0025] Figure 1 This is a scanning electron microscope image of the GO / CoC2O4 precursor in Example 1;

[0026] Figure 2 The XRD pattern of the GO / Co composite powder in Example 1;

[0027] Figure 3 This is a scanning electron microscope image of the GO / Co composite powder in Example 1;

[0028] Figure 4 Metallographic image of the cemented carbide material in Example 1;

[0029] Figure 5 The image shows the fracture morphology of the sintered cemented carbide material in Example 1, which is related to its bending strength.

[0030] Figure 6 This is a Vickers hardness indentation diagram of the sintered cemented carbide material in Example 1;

[0031] Figure 7 The image shows the fracture morphology of the sintered cemented carbide material in Comparative Example 1, which is a fracture surface morphology diagram for its bending strength. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, they are performed according to conventional conditions or conditions recommended by the manufacturer; where the manufacturers of the instruments, equipment, reagents, or raw materials used are not specified, they are all conventional products that can be purchased commercially.

[0033] This invention provides a hard alloy material containing graphene oxide, the preparation method of which includes the following steps:

[0034] (1) Take graphene oxide, cobalt chloride hexahydrate, ammonium oxalate and tungsten carbide powder as raw materials. First, mix graphene oxide and cobalt chloride hexahydrate separately, place them in deionized water, and disperse them by ultrasonication to obtain a uniformly dispersed graphene suspension aqueous solution and cobalt chloride aqueous solution. Then, mix the two solutions at room temperature to obtain a GO / CoCl2·6H2O mixed aqueous solution.

[0035] The tungsten carbide powder (FASS) particle size is controlled between 0.2 and 1.0 μm; the total raw materials contain 65-93.5 wt% tungsten carbide powder, 6-30 wt% cobalt, and 0.5-5 wt% graphene oxide. In this invention, those skilled in the art can adjust the amount of the above-mentioned raw material components according to the performance requirements of the product to obtain the desired product.

[0036] (2) Add a certain amount of ammonium oxalate to the GO / CoCl2·6H2O mixed aqueous solution prepared above, stir with magnetic ultrasonic force for 30-60 min to disperse it evenly, and then add it to a high pressure vessel containing tetrafluoroethylene, heat to 70-90℃, and perform hydrothermal reaction for 10-15 h; take the product after hydrothermal reaction, wash it several times with deionized water, and then place it in a constant temperature drying oven to dry at 60-120℃ to obtain the GO / CoC2O4 precursor.

[0037] (3) Place the GO / CoC2O4 precursor in a N2 / H2 reducing atmosphere and heat it to 490-810℃ for high-temperature reduction calcination. The heating rate is 5-10℃ / min and the calcination time is 100-150min. The gas flow rate is controlled at 30-50mL / min for continuous ventilation. After calcination, cool it to obtain GO / Co composite powder.

[0038] Preferably, the specific processing steps for temperature and time during the heating and calcination process are as follows:

[0039] First, heat to 500±10℃ at a rate of about 10℃ / min, and then keep warm at 500±10℃ for 30 minutes;

[0040] Then heat to 650±10℃ at about 5℃ / min, and keep warm at 650±10℃ for 60min;

[0041] Finally, the temperature was increased to 800±10℃ at a rate of approximately 5℃ / min, and held at 800±10℃ for 30 min. Through strict temperature control, the reduction effect of CoC2O4 was improved, resulting in a GO / Co composite powder with good morphology and more uniform dispersion.

[0042] (4) The above GO / Co composite powder is mixed with tungsten carbide powder, and then wet-milled, dried and granulated, pressed and sintered in sequence to obtain a high-strength and high-toughness hard alloy material containing graphene oxide.

[0043] In this invention, graphene and cobalt composite powder is first prepared by hydrothermal and high-temperature reduction calcination. Since the density difference between graphene and cobalt is smaller, the sedimentation problem caused by density difference can be reduced. Furthermore, the graphene is first reacted with hydrothermally to form a composite GO / CoC2O4 precursor, and then the CoC2O4 is reduced to elemental cobalt powder by calcination. This method can maintain the good sheet-like morphology of graphene. The density difference between GO / Co composite powder and tungsten carbide powder is also small. Therefore, when GO / Co composite powder is compounded with tungsten carbide powder, the density difference between the components of cemented carbide can also be effectively reduced, thus solving the sedimentation problem. Ultimately, the graphene maintains a high degree of dispersion in the cemented carbide powder and exhibits an excellent sheet-like morphology, which significantly improves the strength and toughness of the cemented carbide.

[0044] Example 1

[0045] Prepare tungsten carbide powder, cobalt chloride hexahydrate, and graphene oxide according to the formula WC-6Co-0.5wt%GO, with the tungsten carbide powder having a FASS particle size of approximately 0.8 μm. First, take cobalt chloride hexahydrate with a purity ≥99.5%, place it in deionized water, and ultrasonically disperse it to prepare a 1 mol / L cobalt chloride hexahydrate aqueous solution. Then, take graphene oxide with a purity ≥99.9%, place it in deionized water, and ultrasonically disperse it to prepare a 10 mg / mL graphene suspension aqueous solution.

[0046] The cobalt chloride hexahydrate aqueous solution and graphene suspension aqueous solution prepared above were mixed at room temperature to obtain a GO / CoCl2·6H2O mixed aqueous solution. Then, ammonium oxalate aqueous solution was added to the GO / CoCl2·6H2O mixed aqueous solution at a molar ratio of ammonium oxalate to cobalt ions of 1:1. The mixture was stirred magnetically and ultrasonically for 50 min, and then transferred to a tetrafluoroethylene autoclave. The mixture was heated to 80°C for hydrothermal reaction. After reacting for 12 h, the reaction material was placed in a centrifuge and washed three times with deionized water at 1000 rpm for 5 min each time. The washed material was then placed in a constant temperature drying oven at 60°C for thorough drying to obtain the GO / CoC2O4 precursor.

[0047] The GO / CoC2O4 precursor was placed in a tube furnace with an equal volume of mixed N2 / H2 atmosphere. The temperature was first increased to 500℃ at 10℃ / min and held for 30 min; then increased to 650℃ at 5℃ / min and held for 60 min; finally, increased to 800℃ at 5℃ / min and held for 30 min. During calcination, the mixed gas was continuously introduced at a flow rate of 30 mL / min. After calcination, the furnace was cooled to obtain GO / Co composite powder.

[0048] GO / Co composite powder was mixed with tungsten carbide powder, and ethane was used as the wet grinding medium and paraffin as the forming agent. The mixture was wet-milled at a ball-to-powder ratio of 4:1 for 24 hours. After wet milling, the mixture was unloaded, dried and granulated, and then pressed into blocks. The blocks were placed in a low-pressure sintering furnace and heated to 1410±10℃ at a heating rate of 2℃ / min. Argon gas at 5MPa was introduced for sintering, and the holding time was 60 minutes. The blocks were then cooled to room temperature with the furnace, and the sintered product was removed, which is the cemented carbide material.

[0049] Example 2

[0050] Prepare tungsten carbide powder, cobalt chloride hexahydrate, and graphene oxide according to the formula WC-6Co-1.0wt%GO, with the tungsten carbide powder having a FASS particle size of approximately 1 μm. First, take 66.1 g of cobalt chloride hexahydrate with a purity ≥99.5%, place it in deionized water, and ultrasonically disperse it to prepare a 1 mol / L cobalt chloride hexahydrate aqueous solution. Then, take 5 g of graphene oxide with a purity ≥99.9%, place it in deionized water, and ultrasonically disperse it to prepare a 10 mg / mL graphene suspension aqueous solution.

[0051] The cobalt chloride hexahydrate aqueous solution and graphene suspension aqueous solution prepared above were mixed at room temperature to obtain a GO / CoCl2·6H2O mixed aqueous solution. 70g of ammonium oxalate was fully dissolved in deionized water to obtain an ammonium oxalate aqueous solution, which was then added to the GO / CoCl2·6H2O mixed aqueous solution. The mixture was stirred magnetically and ultrasonically for 60 min, and then transferred to a tetrafluoroethylene autoclave. The mixture was heated to 80℃ for hydrothermal reaction. After reacting for 12 h, the reaction material was placed in a centrifuge and washed three times with deionized water at 1000 rpm for 5 min each time. The washed material was then placed in a constant temperature drying oven at 80℃ to dry thoroughly to obtain the GO / CoC2O4 precursor.

[0052] The GO / CoC2O4 precursor was placed in a tube furnace with an equal volume of mixed N2 / H2 atmosphere. The temperature was first increased to 500℃ at 10℃ / min and held for 30 min; then increased to 650℃ at 5℃ / min and held for 60 min; finally, increased to 800℃ at 5℃ / min and held for 30 min. During calcination, the mixed gas was continuously introduced at a flow rate of 30 mL / min. After calcination, the furnace was cooled to obtain GO / Co composite powder.

[0053] GO / Co composite powder was mixed with 465g of tungsten carbide powder. Ethane was used as the wet grinding medium and paraffin as the forming agent. The mixture was wet-milled at a ball-to-powder ratio of 4:1 for 24 hours. After wet milling, the mixture was unloaded, dried and granulated, and then pressed into blocks. The blocks were placed in a low-pressure sintering furnace and heated to 1410±10℃ at a heating rate of 2℃ / min. Argon gas at 5MPa was introduced for sintering, and the holding time was 60min. The blocks were then cooled to room temperature with the furnace. The sintered product was then removed, which is the cemented carbide material.

[0054] Example 3

[0055] Prepare tungsten carbide powder, cobalt chloride hexahydrate, and graphene oxide according to the formula WC-10Co-0.5wt%GO, with the tungsten carbide powder having a FASS particle size of approximately 1 μm. First, take 110.2 g of cobalt chloride hexahydrate with a purity ≥99.5%, place it in deionized water, and ultrasonically disperse it to prepare a 1 mol / L cobalt chloride hexahydrate aqueous solution. Then, take 2.5 g of graphene oxide with a purity ≥99.9%, place it in deionized water, and ultrasonically disperse it to prepare a 10 mg / mL graphene suspension aqueous solution.

[0056] The cobalt chloride hexahydrate aqueous solution and graphene suspension aqueous solution prepared above were mixed at room temperature to obtain a GO / CoCl2·6H2O mixed aqueous solution. 120g of ammonium oxalate was fully dissolved in deionized water to obtain an ammonium oxalate aqueous solution, which was then added to the GO / CoCl2·6H2O mixed aqueous solution. The mixture was stirred magnetically and ultrasonically for 60 min, and then transferred to a tetrafluoroethylene autoclave. The autoclave was heated to 90℃ for hydrothermal reaction. After reacting for 10 h, the reaction material was placed in a centrifuge and washed three times with deionized water at 1000 rpm for 5 min each time. The washed material was then placed in a constant temperature drying oven at 80℃ to dry thoroughly to obtain the GO / CoC2O4 precursor.

[0057] The GO / CoC2O4 precursor was placed in a tube furnace with an equal volume of mixed N2 / H2 atmosphere. The temperature was first increased to 500℃ at 10℃ / min and held for 30 min; then increased to 650℃ at 5℃ / min and held for 60 min; finally, increased to 800℃ at 5℃ / min and held for 30 min. During calcination, the mixed gas was continuously introduced at a flow rate of 30 mL / min. After calcination, the furnace was cooled to obtain GO / Co composite powder.

[0058] GO / Co composite powder was mixed with 447.5g of tungsten carbide powder. Ethane was used as the wet grinding medium and paraffin as the forming agent. The mixture was wet-milled at a ball-to-powder ratio of 4:1 for 24 hours. After wet milling, the mixture was unloaded, dried and granulated, and then pressed into blocks. The blocks were placed in a low-pressure sintering furnace and heated to 1410±10℃ at a heating rate of 2℃ / min. Argon gas at 5MPa was introduced for sintering, and the holding time was 60 minutes. The blocks were then cooled to room temperature with the furnace. The sintered product was then removed, which is the cemented carbide material.

[0059] Comparative Example 1

[0060] Tungsten carbide powder, cobalt powder, and graphene oxide were prepared according to WC-10Co-0.5wt%GO, with the FASS particle size of the tungsten carbide powder and cobalt powder being approximately 1μm. 447.5g of tungsten carbide powder, 50g of cobalt powder, and 2.5g of graphene oxide were taken. The tungsten carbide powder and graphene oxide powder were first mixed, and hexane was used as the wet grinding medium. Wet grinding was carried out at a ball-to-material ratio of 4:1 for 12 hours. Then, cobalt powder (binder) and paraffin wax (forming agent) were added, and wet grinding continued for another 12 hours. The mixture was then unloaded, dried, granulated, and pressed into blocks. In a low-pressure sintering furnace, the temperature was raised to 1410℃±10℃ at a heating rate of 2℃ / min, and 5MPa Ar gas was introduced for pressure sintering. The holding time was 60 minutes, and the mixture was then cooled to room temperature in the furnace. The sample was then removed to obtain the cemented carbide material.

[0061] In this comparative example, graphene oxide was first mixed with tungsten carbide powder, which had a significant density difference. Traditional wet milling processes failed to disperse the graphene uniformly, and the large density difference exacerbated graphene agglomeration. Ultimately, in the sintered alloy, the originally layered elemental graphene agglomerated to form a graphite phase, deteriorating the alloy's mechanical properties. The fracture morphology of the alloy in this comparative example exhibits the following bending strength characteristics: Figure 7 As shown, the unevenly dispersed agglomerated graphene structure can be clearly seen.

[0062] Comparative Example 2

[0063] Tungsten carbide powder, cobalt powder, and graphene oxide were prepared according to the formula WC-10Co-0.5wt%GO, with the FASS particle size of the tungsten carbide powder and cobalt powder being approximately 1μm. 447.5g of tungsten carbide powder, 50g of cobalt powder, and 2.5g of graphene oxide were mixed simultaneously. Ethane was used as the wet grinding medium, and paraffin wax was used as the forming agent. Wet grinding was performed at a ball-to-material ratio of 4:1 for 24 hours. After wet grinding, the material was unloaded, dried, granulated, and pressed into blocks. These blocks were then placed in a low-pressure sintering furnace and heated to 1410±10℃ at a heating rate of 2℃ / min. Argon gas at 5MPa was introduced for sintering, and the holding time was 60min. The furnace was then cooled to room temperature, and the sintered product was removed, which is the cemented carbide material.

[0064] Comparative Example 3

[0065] Tungsten carbide powder and cobalt powder were prepared according to WC-10Co, with a FASS particle size of approximately 1 μm. 450 g of tungsten carbide powder and 50 g of cobalt powder were mixed and wet-milled using ethane as the grinding medium and paraffin wax as the forming agent at a ball-to-powder ratio of 4:1 for 24 hours. The mixture was then unloaded, dried, granulated, and pressed into blocks. These blocks were placed in a low-pressure sintering furnace and heated to 1410 ± 10 °C at a heating rate of 2 °C / min. Argon gas at 5 MPa was introduced for sintering, and the holding time was 60 minutes. The furnace was then cooled to room temperature, and the sintered product was removed, yielding the cemented carbide material.

[0066] Test case

[0067] Samples: Examples 1-3, Comparative Examples 1-3

[0068] (1) As Figures 1 to 3 The images shown are, respectively, a scanning electron microscope (SEM) image of the GO / CoC2O4 precursor, an XRD pattern of the GO / Co composite powder, and a SEM image of the GO / Co composite powder in Example 1; Figures 4 to 6 The figures shown are, respectively, the metallographic image of the cemented carbide material in Example 1, the fracture morphology image of the sintered cemented carbide material in terms of bending strength, and the Vickers hardness indentation image of the sintered cemented carbide material; as shown... Figure 7 The image shown is a fracture morphology diagram of the sintered cemented carbide material in Comparative Example 1, illustrating its bending strength.

[0069] Depend on Figures 1 to 7 The comparison shows that in Comparative Example 1, graphene oxide was first mixed with tungsten-carbon powder with large density differences, and then the graphene oxide was incorporated into the cemented carbide powder using a traditional mechanical mixing method. As a result, the graphene was not evenly dispersed, and the originally sheet-like graphene aggregated into clumps, forming a graphite phase in the sintered alloy, which deteriorated the material properties of the cemented carbide. In contrast, the cemented carbide material in Example 1 had uniformly dispersed graphene in a sheet-like morphology, which effectively and fully utilized the reinforcing and toughening effect of graphene.

[0070] (2) Random samples were taken from the cemented carbide materials prepared in Examples 1-3 and Comparative Examples 1-3, respectively, as test samples. The strength, toughness, and other material properties of the samples were measured, and the results are summarized in Table 1 below:

[0071] Table 1. Material property test results of different samples

[0072] Sample Hardness (HRA) TRS(MPa) <![CDATA[Fracture toughness K IC (MPa·m 1 / 2 )]]> Impact toughness (J) Example 1 93.2 3286 11.2 4.3 Example 2 93.6 3482 13.3 4.8 Example 3 92.5 3940 15.2 6.2 Comparative Example 1 89.1 1420 8.9 1.9 Comparative Example 2 89.3 1500 9.3 2.1 Comparative Example 3 91.2 2900 9.1 2.9

[0073] As shown in Table 1 above, the hardness and toughness of the cemented carbide materials prepared using the methods described in Examples 1 to 3 are significantly higher than those prepared using comparative examples 1 to 3. This demonstrates that the cemented carbide materials and their preparation methods proposed in this invention can effectively solve the problem of limited reinforcement and toughening effects of cemented carbide due to uneven dispersion after the introduction of graphene oxide.

[0074] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for producing an oxygen-containing graphene-containing cemented carbide material, characterized in that, The method comprises the following steps: S1: preparing a graphene suspension aqueous solution and a cobalt chloride aqueous solution respectively, wherein the preparation process of the graphene suspension aqueous solution is as follows: graphene oxide is placed in deionized water and ultrasonically dispersed to obtain the graphene suspension aqueous solution; S2: mixing the graphene suspension aqueous solution and the cobalt chloride aqueous solution, then adding an ammonium oxalate aqueous solution according to a molar ratio of 1:1 of ammonium oxalate to cobalt ions, heating, and performing a hydrothermal reaction to obtain a GO / CoC2O4 precursor; S3: placing the GO / CoC2O4 precursor in a reducing atmosphere, heating and calcining to obtain a GO / Co composite powder; The specific treatment process of calcining is as follows: firstly, heating at 10 ℃ / min to 500±10 ℃, and keeping the temperature at 500±10 ℃ for 30 min; secondly, heating at 5 ℃ / min to 650±10 ℃, and keeping the temperature at 650±10 ℃ for 60 min; finally, heating at 5 ℃ / min to 800±10 ℃, and keeping the temperature at 800±10 ℃ for 30 min; S4: mixing and sintering the GO / Co composite powder and tungsten-carbon powder to obtain the hard alloy material.

2. The method for preparing the hard alloy material containing graphene oxide according to claim 1, characterized in that, In step S2, the hydrothermal reaction temperature is 70-90 ℃, and the hydrothermal reaction time is 10-15 h.

3. The method for preparing the hard alloy material containing graphene oxide according to claim 1, characterized in that, In step S2, after the hydrothermal reaction, the GO / CoC2O4 precursor is obtained by first washing with deionized water and then being placed in a constant-temperature drying oven at 60-120 ℃.

4. The method for preparing the hard alloy material containing graphene oxide according to claim 1, characterized in that, In step S3, a reducing gas is continuously introduced during the calcining process, and the gas flow rate is 30-50 mL / min.

5. A cemented carbide material comprising graphene oxide, characterized in that, The hard alloy material is prepared by the preparation method in any one of claims 1-4.

6. The graphene oxide-containing cemented carbide material according to claim 5, c h a r a c t e r i z e d i n that The hard alloy material comprises, by mass, 65-93.5 wt% tungsten-carbon powder, 6-30 wt% cobalt powder, and 0.5-5 wt% graphene oxide.

7. The graphene oxide-containing cemented carbide material according to claim 6, c h a r a c t e r i z e d i n that The FASS particle size of the tungsten-carbon powder is 0.2-1.0 μm.

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