CN111020337B - Inhibitor applied to preparation of superfine tungsten carbide and preparation method thereof - Google Patents
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- CN111020337B CN111020337B CN202010001403.3A CN202010001403A CN111020337B CN 111020337 B CN111020337 B CN 111020337B CN 202010001403 A CN202010001403 A CN 202010001403A CN 111020337 B CN111020337 B CN 111020337B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
Abstract
The invention discloses an inhibitor applied to preparation of superfine tungsten carbide and a preparation method thereof, wherein the inhibitor applied to preparation of the superfine tungsten carbide is cobalt-based composite powder containing Ta and V, and the mass ratio of Ta, V and Co in the cobalt-based composite powder containing Ta and V is 2: 1: (20-40). The doped composite powder of TaC-VC is obtained by a liquid-phase precipitation method and carbonization, the nano cobalt powder is prepared by a liquid-phase reduction method, then a composite phase formed by the TaC-VC is uniformly distributed in a Co-based bonding phase, a TaC-VC-Co composite system is used as an inhibitor, the TaC-VC-Co composite system is mixed with WC powder and calcined, the growth of WC grains is obviously inhibited, and the high temperature resistance and corrosion resistance of the hard alloy are improved.
Description
Technical Field
The invention relates to the field of hard alloy production, in particular to an inhibitor applied to preparation of superfine tungsten carbide and a preparation method thereof.
Background
The hard alloy is a composite metal material mainly prepared from a hard compound of refractory metal and bonding metal by a powder metallurgy technology, has the advantages of high hardness, high mechanical strength and higher wear resistance, and is generally used as a wear-resistant material, a die material, a cutter material and the like; however, as the production requirements of people gradually increase, the traditional hard alloy cannot meet the requirements of people on high quality in both toughness and hardness.
The research of the ultrafine hard alloy is the current focus research direction because the ultrafine hard alloy has very excellent performance and can have higher toughness and hardness at the same time. Bonding due to the common cobalt action in cemented carbideHowever, cobalt has poor corrosion resistance and oxidation resistance, and tungsten carbide has high solubility in cobalt, so that WC grains are easy to grow in the liquid phase sintering process, thereby hindering the preparation of ultrafine cemented carbide. In order to inhibit the grain growth, it is described in the literature that an inhibitor, such as Cr, is added to the alloy material3C2And the inhibitor is added into the alloy material, although the growth of the crystal grains can be effectively inhibited, the comprehensive performance of the hard alloy is reduced, and the inhibitor is difficult to be uniformly distributed in a refined alloy system, so that the abnormal growth of WC crystal grains is caused. Therefore, the effect of high temperature resistance and grain refinement is difficult to achieve in the prior art for preparing the ultrafine hard alloy, so a new scheme needs to be provided for solving the above problems.
Disclosure of Invention
The invention aims to provide an inhibitor applied to preparation of ultrafine tungsten carbide and a preparation method thereof, and aims to solve the problem that the effects of high temperature resistance and grain refinement are difficult to achieve in the prior art when ultrafine hard alloy is prepared.
In order to solve the above technical problem, a first solution provided by the present invention is: the inhibitor is cobalt-based composite powder containing Ta and V, and the mass ratio of Ta, V and Co in the cobalt-based composite powder containing Ta and V is 2: 1: (20-40).
Wherein the particle size of the cobalt-based composite powder containing Ta and V is 15-35 nm.
Wherein the mass fraction of carbon in the cobalt-based composite powder containing Ta and V is 10-15%.
In order to solve the above technical problem, a second solution provided by the present invention is: a preparation method of an inhibitor applied to preparation of superfine tungsten carbide comprises the following steps: preparing doped composite powder, preparing nano cobalt powder and preparing an inhibitor; the preparation method of the inhibitor applied to the preparation of the ultrafine tungsten carbide is used for preparing the inhibitor applied to the preparation of the ultrafine tungsten carbide in the previous claims; the step of preparing the inhibitor specifically comprises: mixing the doped composite powder and the nano cobalt powder in a mass ratio of 1: (4-8) uniformly mixing, and calcining for 2-3 hours in a hydrogen environment at the calcining temperature of 900-1050 ℃ to obtain the inhibitor applied to the preparation of the superfine tungsten carbide.
The preparation method of the doped composite powder comprises the following steps: dissolving soluble tantalum salt and soluble vanadate in water, uniformly mixing, adding oxalic acid, fully precipitating, filtering, and calcining filter residues to obtain mixed powder; mixing the mixed powder with carbon according to the following ratio of (3-4): 1, ball-milling and uniformly mixing, and carbonizing and calcining in a hydrogen environment to obtain the doped composite powder.
Wherein the soluble tantalum salt is tantalum pentachloride, and the soluble vanadate is ammonium metavanadate.
Wherein in the step of calcining the filter residue, the calcining temperature is 450-500 ℃, and the calcining time is 1-2 hours; in the step of carbonizing and calcining in a hydrogen environment, the calcining temperature is 1100-1500 ℃, and the sintering time is 1-2 h.
The preparation method of the nano cobalt powder comprises the following steps: firstly, mixing cobalt chloride and polyethylene glycol in a mass ratio of 100: (5-6) dissolving in deionized water, and adding ammonia water to adjust the pH value to 11-12 to obtain a dispersion liquid; and continuously dropwise adding the dispersion liquid and hydrazine hydrate into a reaction kettle, stirring and reacting for 0.5-1 h at 75-80 ℃, washing and drying to obtain the nano cobalt powder.
Wherein, in the step of continuously dropwise adding the dispersion liquid and hydrazine hydrate into the reaction kettle, the mass ratio of cobalt chloride to hydrazine hydrate in the dispersion liquid is 1: (2-4).
The inhibitor applied to the preparation of the superfine tungsten carbide is used for being added into WC powder to be calcined to prepare the superfine tungsten carbide, and the mixing mass ratio of the inhibitor applied to the preparation of the superfine tungsten carbide to the WC powder is 1:9, the calcining temperature is 950-1050 ℃.
The invention has the beneficial effects that: the invention is different from the condition of the prior art, and provides an inhibitor applied to preparation of ultrafine tungsten carbide and a preparation method thereof.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the method for preparing the inhibitor applied to the preparation of ultrafine tungsten carbide in the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
For the first solution provided by the invention, the inhibitor applied to the preparation of the ultrafine tungsten carbide is provided, the inhibitor is cobalt-based composite powder containing Ta and V, and the mass ratio of Ta, V and Co in the cobalt-based composite powder containing Ta and V is 2: 1: (20-40) is a TaC-VC-Co composite system. In the embodiment, the granularity of the cobalt-based composite powder containing Ta and V is 50-80 nm, and the mass fraction of carbon in the cobalt-based composite powder containing Ta and V is 10-15%.
Referring to fig. 1, fig. 1 is a process flow diagram of an embodiment of a method for preparing an inhibitor for ultra-fine tungsten carbide according to the present invention. The preparation method of the inhibitor applied to the preparation of the ultrafine tungsten carbide in the invention is used for preparing the inhibitor applied to the preparation of the ultrafine tungsten carbide in the first solution, and comprises the following steps:
s1: and preparing doped composite powder. Dissolving soluble tantalum salt and soluble vanadate in water, uniformly mixing, adding oxalic acid, fully precipitating, filtering, calcining filter residue to obtain mixed powder, wherein the soluble tantalum salt is tantalum pentachloride, the soluble vanadate is ammonium metavanadate, the calcining temperature of the filter residue is preferably 450-500 ℃, and the calcining time is 1-2 hours; mixing the mixed powder with carbon powder (3)4): 1, performing ball milling and mixing uniformly, and performing carbonization and calcination in a hydrogen environment, wherein the preferable calcination temperature is 1100-1500 ℃, and the sintering time is 1-2 h, so as to obtain the doped composite powder. The step is to obtain Ta by a liquid phase precipitation method2O5-V2O5And carrying out carbonization and reduction on the components to obtain TaC-VC doped composite powder.
S2: and preparing the nano cobalt powder. In the step, cobalt chloride and polyethylene glycol are mixed according to the mass ratio of 100: (5-6) dissolving in deionized water, and adding ammonia water to adjust the pH value to 11-12 to obtain a dispersion liquid; continuously dropwise adding the dispersion liquid and hydrazine hydrate into a reaction kettle, wherein the mass ratio of cobalt chloride to hydrazine hydrate in the dispersion liquid is 1: (2-4), stirring and reacting for 0.5-1 h at 75-80 ℃, washing and drying to obtain the nano cobalt powder. In the step, cobalt ions are reduced into nano cobalt by utilizing the strong reducibility of hydrazine hydrate, but the reduction reaction for actually preparing hydrazine hydrate is violent, and the particle size of the formed cobalt powder is uneven if the reaction intensity cannot be reasonably controlled; on one hand, the intensity of the reduction reaction is controlled by controlling the dropping rate of the dispersion liquid and the hydrazine hydrate, preferably, the flow rate of the dispersion liquid is 1-2 mL/s, and the flow rate of the hydrazine hydrate is 0.5-1.8 mL/s; on the other hand, before the cobalt chloride and the hydrazine hydrate are mixed, polyethylene glycol is introduced as a dispersing agent to be mixed with the cobalt chloride, so that the intensity of the subsequent reduction reaction can be relieved by improving the dispersing performance, the surface modification can be carried out on the cobalt powder produced in the subsequent reduction reaction, the surface hydroxyl acting force of the cobalt powder is reduced, the cobalt powder is prevented from agglomerating and growing, and the uniformity of cobalt powder particles is ensured.
S3: and (4) preparing an inhibitor. In the step, the doped composite powder and the nano cobalt powder are mixed according to the mass ratio of 1: (4-8), uniformly mixing, calcining for 2-3 hours in a hydrogen environment at 900-1050 ℃, and uniformly distributing a composite phase consisting of TaC-VC in a Co-based bonding phase to form a TaC-VC-Co composite system, thereby obtaining the inhibitor applied to the preparation of the superfine tungsten carbide.
In addition, when the prepared inhibitor is applied, the mixing mass ratio of the inhibitor applied to the preparation of the ultrafine tungsten carbide to the WC powder is 1:9, calcining at 950-1050 ℃ to obtain the superfine tungsten carbide powder.
Specifically, the mechanism and advantages of the inhibitor applied to the preparation of the ultrafine tungsten carbide and the preparation method thereof are elaborated in detail: 1) the component Ta prepared by a liquid phase precipitation method2O5-V2O5The mixed powder is carbonized to obtain TaC-VC doped composite powder, a liquid phase reduction method is adopted to prepare nano cobalt powder, finally, a composite phase formed by the TaC-VC is uniformly distributed in a bonding phase to prepare an inhibitor, cobalt is used as the bonding phase, and when the inhibitor is mixed with tungsten carbide powder, because the TaC-VC composite phase can effectively block the diffusion of W, C atoms, the dissolution and precipitation of W, C atoms can be further inhibited, the precipitation growth rate of WC in a Co-based bonding phase is remarkably reduced, and the uniform refinement of tungsten carbide grains is realized; 2) the strength, high temperature resistance and corrosion resistance of the Co-based bonding phase can be effectively improved by the addition of TaC, so that the comprehensive performance of the tungsten carbide material can be enhanced when the inhibitor is mixed with the tungsten carbide powder, and the defects of the pure Co-based bonding phase are overcome.
The effect of the inhibitor and the preparation method applied to the preparation of ultrafine tungsten carbide will be further detailed below with reference to specific examples and comparative examples.
Example 1
S1: dissolving 0.32mol of tantalum chloride and 0.5mol of ammonium metavanadate in water, adding oxalic acid with the same volume of 0.4mol/L, fully precipitating, filtering, and calcining filter residue at 450 ℃ for 2 hours to obtain mixed powder; and mixing the mixed powder with carbon according to the weight ratio of 3: 1, performing ball milling and mixing uniformly, and performing carbonization and calcination in a hydrogen environment, wherein the preferable calcination temperature is 1150 ℃ and the sintering time is 1h, so as to obtain the doped composite powder.
S2: firstly, 9mol of cobalt chloride and polyethylene glycol are mixed according to a mass ratio of 20: 1, dissolving in deionized water, and then adding ammonia water to adjust the pH value to 11.2 to obtain a dispersion liquid; and continuously dropwise adding the dispersion liquid and 48mol of hydrazine hydrate into the reaction kettle together, stirring and reacting at 75-80 ℃ for 0.5h, washing and drying to obtain the nano cobalt powder, wherein the flow rate of the dispersion liquid is 1mL/s and the flow rate of the hydrazine hydrate is 0.5 mL/s.
S3: the doped composite powder and the nano cobalt powder are uniformly mixed, and are calcined for 2 hours in a hydrogen environment at the calcining temperature of 950 ℃ to prepare the inhibitor applied to the preparation of the superfine tungsten carbide, namely the inhibitor of example 1, and the average particle size is measured to be 65 nm.
Example 2
S1: dissolving 0.32mol of tantalum chloride and 0.5mol of ammonium metavanadate in water, adding oxalic acid with the same volume of 0.4mol/L, fully precipitating, filtering, and calcining filter residue at 450 ℃ for 2 hours to obtain mixed powder; and mixing the mixed powder with carbon according to the weight ratio of 3: 1, performing ball milling and mixing uniformly, and performing carbonization and calcination in a hydrogen environment, wherein the preferable calcination temperature is 1300 ℃ and the sintering time is 1h, so as to obtain the doped composite powder.
S2: firstly, mixing 12mol of cobalt chloride and polyethylene glycol in a mass ratio of 20: 1, dissolving in deionized water, and then adding ammonia water to adjust the pH value to 11.5 to obtain a dispersion liquid; and continuously dropwise adding the dispersion liquid and 31mol of hydrazine hydrate into the reaction kettle together, stirring and reacting at 75-80 ℃ for 0.5h, washing and drying to obtain the nano cobalt powder, wherein the flow rate of the dispersion liquid is 1.2mL/s and the flow rate of the hydrazine hydrate is 1 mL/s.
S3: the doped composite powder and the nano cobalt powder are uniformly mixed, and are calcined for 2 hours in a hydrogen environment at the calcining temperature of 1000 ℃, so that the inhibitor applied to the preparation of the superfine tungsten carbide, namely the example sample 2, is prepared, and the measured average particle size is 60 nm.
Example 3
S1: dissolving 0.32mol of tantalum chloride and 0.5mol of ammonium metavanadate in water, adding oxalic acid with the same volume of 0.4mol/L, fully precipitating, filtering, and calcining filter residue at 450 ℃ for 2 hours to obtain mixed powder; and mixing the mixed powder with carbon according to the weight ratio of 3: 1, performing ball milling and mixing uniformly, and performing carbonization and calcination in a hydrogen environment, wherein the preferable calcination temperature is 1300 ℃ and the sintering time is 1h, so as to obtain the doped composite powder.
S2: firstly, 15mol of cobalt chloride and polyethylene glycol are mixed according to a mass ratio of 20: 1, dissolving in deionized water, and then adding ammonia water to adjust the pH value to 11.5 to obtain a dispersion liquid; and continuously dropwise adding the dispersion liquid and 39mol of hydrazine hydrate into the reaction kettle together, stirring and reacting at 75-80 ℃ for 0.5h, washing and drying to obtain the nano cobalt powder, wherein the flow rate of the dispersion liquid is 1.5mL/s and the flow rate of the hydrazine hydrate is 1.2 mL/s.
S3: the doped composite powder and the nano cobalt powder are uniformly mixed, and are calcined for 2 hours in a hydrogen environment at 1050 ℃ to prepare the inhibitor applied to the preparation of the superfine tungsten carbide, namely the inhibitor of example 3, and the average particle size is 76 nm.
Comparative example 1
And mixing and ball-milling 100nm cobalt powder and 100nm VC powder for 24 hours in a mass ratio of 25:1 to obtain a comparative example sample 1.
Further, four groups of equal 300nm WC powders were selected, mixed and ball milled with the above examples 1 to 3 and comparative example 1, respectively, and the mass ratio of the four groups of added samples to the WC powder was 1:9, ball milled in an ethanol solution for 2 hours and then sintered in a hydrogen atmosphere at 1000 ℃ for 2.5 hours, to obtain examples 1 to 3 and comparative example 1, and the results were measured for the four groups of samples, respectively, and are shown in table 1. As can be seen from Table 1, the average particle sizes of the samples 1-3 in the examples are all kept at about 300nm, and no obvious grain growth condition exists, while the average particle size of the sample 1 in the comparative example is 550nm, and obvious grain growth exists, so that the scheme of the invention can obviously inhibit the grain growth of WC powder, and the strength is also improved.
TABLE 1
| Rockwell hardness | Flexural Strength/MPa | Average grain size/nm | |
| Example sample 1 | 93.7 | 3800 | 320 |
| Example sample 2 | 94.2 | 4000 | 312 |
| Example sample 3 | 93.9 | 3700 | 318 |
| Comparative example sample 1 | 93.0 | 3100 | 552 |
The invention is different from the condition of the prior art, and provides an inhibitor applied to preparation of ultrafine tungsten carbide and a preparation method thereof.
It should be noted that the above embodiments belong to the same inventive concept, and the description of each embodiment has a different emphasis, and reference may be made to the description in other embodiments where the description in individual embodiments is not detailed.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The inhibitor applied to preparation of ultrafine tungsten carbide is characterized in that the inhibitor applied to preparation of ultrafine tungsten carbide is cobalt-based composite powder containing Ta and V, and the mass ratio of Ta, V and Co in the cobalt-based composite powder containing Ta and V is 2: 1: (20-40);
the inhibitor applied to the preparation of the superfine tungsten carbide is a TaC-VC-Co composite system and is prepared by mixing and calcining doped composite powder and nano cobalt powder, wherein the doped composite powder is the TaC-VC system and is prepared by a liquid phase precipitation method and carbonization, and the nano cobalt powder is prepared by a liquid phase reduction method;
the liquid phase precipitation method comprises the following steps: dissolving soluble tantalum salt and soluble vanadate in water, uniformly mixing, adding oxalic acid, fully precipitating, filtering, calcining filter residue to obtain mixed powder, wherein the soluble tantalum salt is tantalum pentachloride, the soluble vanadate is ammonium metavanadate, the calcining temperature of the filter residue is 450-500 ℃, and the calcining time is 1-2 hours;
the carbonization steps are specifically as follows: mixing the mixed powder with carbon according to the following ratio of (3-4): 1, performing ball milling and mixing uniformly, and performing carbonization and calcination in a hydrogen environment at the calcination temperature of 1100-1500 ℃ for 1-2 h to obtain the doped composite powder;
the liquid phase reduction method comprises the following steps: firstly, mixing cobalt chloride and polyethylene glycol in a mass ratio of 100: (5-6) dissolving in deionized water, and adding ammonia water to adjust the pH value to 11-12 to obtain a dispersion liquid; and continuously dropwise adding the dispersion liquid and hydrazine hydrate into a reaction kettle, wherein the mass ratio of cobalt chloride to hydrazine hydrate in the dispersion liquid is 1: (2-4), stirring and reacting for 0.5-1 h at 75-80 ℃, washing and drying to obtain the nano cobalt powder;
the preparation of the inhibitor applied to the preparation of the superfine tungsten carbide by mixing and calcining the doped composite powder and the nano cobalt powder comprises the following specific steps: mixing the doped composite powder and the nano cobalt powder according to a mass ratio of 1: (4-8) uniformly mixing, and calcining for 2-3 hours in a hydrogen environment at the calcining temperature of 900-1050 ℃ to obtain the inhibitor applied to the preparation of the superfine tungsten carbide.
2. The inhibitor for the preparation of ultrafine tungsten carbide according to claim 1, wherein the particle size of the cobalt-based composite powder containing Ta and V is 50 to 80 nm.
3. The inhibitor for preparing ultrafine tungsten carbide according to claim 1, wherein the mass fraction of carbon in the cobalt-based composite powder containing Ta and V is 10-15%.
4. A preparation method of an inhibitor applied to preparation of superfine tungsten carbide is characterized by comprising the following steps: preparing doped composite powder, preparing nano cobalt powder and preparing an inhibitor;
the preparation method of the inhibitor applied to the preparation of the ultrafine tungsten carbide is used for preparing the inhibitor applied to the preparation of the ultrafine tungsten carbide according to any one of claims 1 to 3, the inhibitor applied to the preparation of the ultrafine tungsten carbide is a TaC-VC-Co composite system and is prepared by calcining a doped composite powder and nano cobalt powder, the doped composite powder is a TaC-VC system and is prepared by a liquid phase precipitation method and carbonization, and the nano cobalt powder is prepared by a liquid phase reduction method;
the step of preparing the inhibitor specifically comprises: mixing the doped composite powder and the nano cobalt powder according to a mass ratio of 1: (4-8) uniformly mixing, and calcining for 2-3 hours in a hydrogen environment at the calcining temperature of 900-1050 ℃ to obtain the inhibitor applied to the preparation of the superfine tungsten carbide.
5. The method for preparing the inhibitor applied to the preparation of the ultrafine tungsten carbide according to claim 4, wherein the step of preparing the doped composite powder specifically comprises the following steps:
dissolving soluble tantalum salt and soluble vanadate in water, uniformly mixing, adding oxalic acid, fully precipitating, filtering, and calcining filter residues to obtain mixed powder;
mixing the mixed powder with carbon according to the following ratio of (3-4): 1, performing ball milling and mixing uniformly, and performing carbonization and calcination in a hydrogen environment to obtain the doped composite powder.
6. The method for preparing the inhibitor applied to the preparation of the ultrafine tungsten carbide according to claim 5, wherein the soluble tantalum salt is tantalum pentachloride, and the soluble vanadate is ammonium metavanadate.
7. The method for preparing the inhibitor applied to the preparation of the ultrafine tungsten carbide according to claim 5, wherein in the step of calcining the filter residue, the calcining temperature is 450-500 ℃, and the calcining time is 1-2 hours;
in the step of carbonizing and calcining in a hydrogen environment, the calcining temperature is 1100-1500 ℃, and the sintering time is 1-2 h.
8. The method for preparing the inhibitor applied to the preparation of the ultrafine tungsten carbide according to claim 4, wherein the step of preparing the nano cobalt powder comprises the following steps:
firstly, mixing cobalt chloride and polyethylene glycol in a mass ratio of 100: (5-6) dissolving in deionized water, and adding ammonia water to adjust the pH value to 11-12 to obtain a dispersion liquid;
and continuously dropwise adding the dispersion liquid and hydrazine hydrate into a reaction kettle, stirring and reacting for 0.5-1 h at 75-80 ℃, washing and drying to obtain the nano cobalt powder.
9. The method for preparing the inhibitor applied to the preparation of ultrafine tungsten carbide according to claim 8, wherein in the step of continuously dropwise adding the dispersion liquid and hydrazine hydrate into the reaction kettle, the mass ratio of cobalt chloride to hydrazine hydrate in the dispersion liquid is 1: (2-4).
10. The method for preparing the inhibitor for ultrafine tungsten carbide according to claim 4, wherein the inhibitor for ultrafine tungsten carbide is added into WC powder and calcined to prepare ultrafine tungsten carbide, and the mixing mass ratio of the inhibitor for ultrafine tungsten carbide to the WC powder is 1:9, the calcining temperature is 950-1050 ℃.
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