CN110983142A - Preparation method of tungsten carbide-nickel hard alloy - Google Patents
Preparation method of tungsten carbide-nickel hard alloy Download PDFInfo
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- CN110983142A CN110983142A CN201911165318.4A CN201911165318A CN110983142A CN 110983142 A CN110983142 A CN 110983142A CN 201911165318 A CN201911165318 A CN 201911165318A CN 110983142 A CN110983142 A CN 110983142A
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- 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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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a preparation method of tungsten carbide-nickel hard alloy, which comprises the following steps: (1) preparing NiCl with same volume and different concentrations2Solution and (NH)4)2C2O4Heating the solution in water bath; (2) mixing tungsten carbide powder with NiCl2The solution is mixed evenly to obtain WC-NiCl2Mixing the solution to obtain (NH)4)2C2O4Adding WC-NiCl into the solution2Heating the mixed solution in a water bath, and stirring, aging, filtering by suction, and drying to obtain mixture precursor powder; (3) calcining the mixture precursor powder in a protective atmosphere to obtain tungsten carbide-nickel composite powder; (4) and carrying out glue doping, granulation, compression molding and calcination on the tungsten carbide-nickel composite powder to obtain the tungsten carbide-nickel hard alloy. The method preparesThe tungsten carbide-nickel hard alloy has high purity, less impurities, high density, uniform nickel coating, and excellent hardness, density, bending strength and impact toughness.
Description
Technical Field
The invention relates to a preparation method of hard alloy, in particular to a preparation method of tungsten carbide-nickel hard alloy.
Background
The hard alloy is formed by hard phases: the powder metallurgy product is formed by sintering high-hardness and refractory metal carbide powder and binder phases such as Co, Fe, Ni and the like. The sintered and formed hard alloy product has the high hardness, high wear resistance, excellent red hardness, heat stability and corrosion resistance of ceramic, and the strength and toughness of metal. At present, the mixing of the hard phase and the binder phase is usually performed by mechanical mixing, such as hand-mixing wet milling process. The mechanical mixing process has low cost and easy operation, but has low efficiency, uneven mixing, more impurities in the product, non-compact sintered product and poor performance.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a preparation method of tungsten carbide-nickel hard alloy with high purity, less impurities, high density, good bending strength and good impact toughness.
The technical scheme is as follows: the invention relates to a preparation method of tungsten carbide-nickel hard alloy, which comprises the following steps:
(1) preparation of NiCl2Solution and (NH)4)2C2O4Heating the solution in water bath;
(2) mixing tungsten carbide powder with NiCl2The solution is mixed evenly to obtain WC-NiCl2Mixing the solution to obtain (NH)4)2C2O4Adding WC-NiCl into the solution2Heating the mixed solution in a water bath, and stirring, aging, filtering by suction, and drying to obtain mixture precursor powder;
(3) calcining the mixture precursor powder in a protective atmosphere to obtain tungsten carbide-nickel composite powder;
(4) and carrying out glue doping, granulation, compression molding and calcination on the tungsten carbide-nickel composite powder to obtain the tungsten carbide-nickel hard alloy.
Wherein, the water bath in the step (1) is heated to 35-65 ℃, and the reaction can be ensured to be in the same temperature condition in the whole process.
Wherein, in the step (2), the tungsten carbide powder is firstly added into the coarsening liquid for coarsening, and then the WC-NiCl is added2And in the mixed solution, the roughening solution is hydrofluoric acid-nitric acid roughening solution.
Wherein, NiCl prepared in the step (2)2The concentration of the solution is 0.2-0.8 mol/L, (NH)4)2C2O4The concentration of the solution is 0.1-0.4 mol/L.
Wherein, in the step (3), the WC-NiCl is mixed with acid solution2Adjusting the pH value of the mixed solution to 2.9-6.2, and then adding (NH)4)2C2O4The acid solution is hydrochloric acid solution, the concentration is 0.1-0.2 mol/L, and other impurities cannot be introduced into the hydrochloric acid.
Wherein, in the step (3), (NH)4)2C2O4The adding speed of the solution is 0.85 ml/s-0.017 ml/s, the powder coating effect can be guaranteed, the water bath heating temperature is 35-65 ℃, the stirring time is 80-90 min, and the aging time is 10-15 min.
Wherein the step (5) of preparing the tungsten carbide-nickel hard alloy comprises the following steps:
(a) mixing the alloy powder with a forming agent, drying, and then continuously adding the forming agent;
(b) granulating by adopting a screen;
(c) putting the graphite mould into a graphite mould for compaction, and placing a pressure head to complete mould assembly;
(d) and putting the die into a sintering cavity, vacuumizing, heating, sintering and cooling to obtain the tungsten carbide-nickel hard alloy. Wherein the forming agent is paraffin wax forming agent and SD-E forming agent.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: 1. the density reaches 99.63 percent, the hardness reaches 86.5HRA, and the bending strength reaches 1860N/mm2The impact toughness is as high as 53.91KJ/m2(ii) a 2. The nickel is uniformly coated, the purity is high, and impurities are few; 3. the method is simple to operate, high in repeatability, safe and reliable.
Drawings
FIG. 1 is a scanning electron microscope image of a mixture precursor powder prepared by the present invention;
FIG. 2 is a scanning electron micrograph, an EDS chart and an element distribution chart of the mixture precursor powder particles prepared by the invention;
FIG. 3 is an X-ray diffraction pattern of a raw powder of tungsten carbide, a precursor powder of a mixture prepared by the present invention, and a tungsten carbide-nickel composite powder prepared by the present invention;
FIG. 4 is a gold phase diagram of a tungsten carbide-nickel cemented carbide produced in the present invention;
fig. 5 is a gold phase diagram of a tungsten carbide-nickel cemented carbide prepared by a comparative example.
Detailed Description
Example 1
50g of tungsten carbide powder with the average particle size of 5.0 mu m and the purity of 99.9 percent is taken and put into 500ml of hydrofluoric acid-nitric acid mixed water solution to be coarsened under the condition of mechanical stirring, the concentration of the hydrofluoric acid is 30ml/L, the concentration of the nitric acid is 30ml/L, the stirring time is 30min, and after the stirring, the tungsten carbide powder is soaked for 20min and then is filtered and dried. At the same time, 19.06g of NiCl solid particle medicament is taken2·6H2Adding O into deionized water to prepare the solution with the concentration of 0.4 mol/LNiCl2200ml of the solution, 5.68g of solid granular medicament (NH) is taken4)2C2O4·H2Adding O into deionized water to prepare a concentration of 0.2mol/L (NH)4)2C2O4200ml of the solution and both solutions were heated to 50 ℃ in a simultaneous water bath. Then 21.2g of coarsened tungsten carbide powder is poured into the heated NiCl2In the solution, mechanically stirring for 20min and then adding NiCl2And adding a proper amount of hydrochloric acid solution into the tungsten carbide mixed solution to adjust the pH value of the mixed solution to 6.2. Then the prepared 0.2mol/L (NH)4)2C2O4The solution was added to NiCl as a precipitant at a rate of 0.17ml/s2Adding a precipitator into the tungsten carbide mixed solution, simultaneously carrying out water bath heating and mechanical stirring, wherein the water bath heating temperature is 50 ℃, the mechanical stirring time is 90min, and aging the mixed solution for 10min after the stirring is finished; finally, carrying out suction filtration on the mixed solution after precipitation, and drying in a vacuum drying oven to obtain the mixed solutionA compound precursor powder.
Weighing 100g of tungsten carbide-nickel composite powder prepared by the process flow, adding an SD-E forming agent into the tungsten carbide-nickel composite powder, then putting the tungsten carbide-nickel composite powder into a graphite mold for compaction, and placing a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; and in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode, and the tungsten carbide-10% nickel hard alloy is obtained.
Comparative example
Preparing tungsten carbide-nickel hard alloy by using a hand mixing wet milling process:
45g of pure tungsten carbide powder with the Fisher particle size of 5.0 mu m and 5g of pure metal nickel powder with the Fisher particle size of 1 mu m are taken, the two powders are placed into an agate mortar, absolute ethyl alcohol is added simultaneously as a wet grinding medium, wet grinding is carried out by a grinding pestle for 8 hours, and then the tungsten carbide-nickel composite powder is obtained after drying for 2 hours in a vacuum drying oven.
And adding the obtained tungsten carbide-nickel composite powder into an SD-E forming agent, then putting the mixture into a graphite mold for compaction, and putting a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode to obtain the tungsten carbide-10 percent nickel hard alloy
As can be seen from FIG. 1, the precursor powder of the mixture in example 1 was dispersed relatively uniformly (FIG. 1(a)), and tungsten carbideThe surface of the powder is coated with a layer of compact and uniform NiC2O4·2H2O particles (fig. 1 (b)); FIG. 2(a) is a scanning electron micrograph of the particles, FIG. 2(b) is an EDS map of the particles, and FIGS. 2(C), (d) and (e) are graphs showing the distribution of O, C and W elements of the particles, respectively, and it can be seen that the WC surface is coated with NiC2O4·2H2O, it can be seen from FIG. 3 that the precursor powder of the mixture obtained in example 1 contains no other impurity elements, the substance inside the particles is tungsten carbide, and the substance coated outside is NiC2O4·2H2O; it can be seen from FIGS. 4 and 5 that the tungsten carbide-nickel cemented carbide prepared by the comparative example had a large amount of A (d)<10μm)、B (10μm<d<25 μm) and super large pores, and also has the defects of nickel pool, tungsten carbide single phase aggregation and the like, while the tungsten carbide-nickel hard alloy prepared in the example 1 has less defects of pores, nickel pool and the like and is more compact.
TABLE 1 engineering Performance test results for tungsten carbide-10% nickel cemented carbide prepared in comparative example and example 1
| Hardness of | Compactness degree | Bending strength | Toughness of impact resistance | |
| Example 1 | 86.5HRA | 99.63％ | 1860N/mm2 | 53.91KJ/m2 |
| Comparative example | 85.4HRA | 99.19％ | 1491N/mm2 | 50.00KJ/m2 |
From the comparison of the engineering performance test results of the alloy bodies with the same nickel content prepared by the two processes, it can be seen that when the nickel content is also 10%, the tungsten carbide-10% nickel hard alloy obtained in example 1 is more excellent in the aspects of hardness, compactness, bending strength, impact toughness and other engineering performances than the alloy bodies prepared by the comparative example.
Example 2
50g of tungsten carbide powder with the average particle size of 5.0 mu m and the purity of 99.9 percent is taken and put into 500ml of hydrofluoric acid-nitric acid mixed water solution to be coarsened under the condition of mechanical stirring, the concentration of the hydrofluoric acid is 30ml/L, the concentration of the nitric acid is 30ml/L, the stirring time is 30min, and after the stirring, the tungsten carbide powder is soaked for 20min and then is filtered and dried. At the same time, 19.06g of NiCl solid particle medicament is taken2·6H2Adding O into deionized water to prepare the solution with the concentration of 0.4 mol/LNiCl2200ml of the solution, 5.68g of solid granular medicament (NH) is taken4)2C2O4·H2Adding O into deionized water to prepare a concentration of 0.2mol/L (NH)4)2C2O4The solution was 200ml and both solutions were heated to 65 ℃ in a water bath. Then 21.2g of coarsened tungsten carbide powder is poured into the heated NiCl2In the solution, mechanically stirring for 20min and then adding NiCl2And adding a proper amount of hydrochloric acid solution into the tungsten carbide mixed solution to adjust the pH value of the mixed solution to 6.2. Then the prepared 0.2mol/L (NH)4)2C2O4The solution was added to NiCl as a precipitant at a rate of 0.17ml/s2Adding precipitant into the mixed solution of tungsten carbide, and heating in water bath and mechanically stirringStirring, heating in water bath at 65 deg.C, mechanically stirring for 90min, and aging the mixed solution for 10 min; and finally, carrying out suction filtration on the precipitated mixed solution, and drying in a vacuum drying oven to obtain mixture precursor powder. Calcining the obtained mixture precursor powder for 1h at the high temperature of 500 ℃ in the hydrogen protective atmosphere to obtain the tungsten carbide-nickel composite powder.
Weighing 100g of tungsten carbide-nickel composite powder prepared by the process flow, adding an SD-E forming agent into the tungsten carbide-nickel composite powder, then putting the tungsten carbide-nickel composite powder into a graphite mold for compaction, and placing a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; and in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode, and the tungsten carbide-10% nickel hard alloy is obtained.
Example 3
50g of tungsten carbide powder with the average particle size of 5.0 mu m and the purity of 99.9 percent is taken and put into 500ml of hydrofluoric acid-nitric acid mixed water solution to be coarsened under the condition of mechanical stirring, the concentration of the hydrofluoric acid is 30ml/L, the concentration of the nitric acid is 30ml/L, the stirring time is 30min, and after the stirring, the tungsten carbide powder is soaked for 20min and then is filtered and dried. At the same time, 19.06g of NiCl solid particle medicament is taken2·6H2Adding O into deionized water to prepare the solution with the concentration of 0.4 mol/LNiCl2200ml of the solution, 5.68g of solid granular medicament (NH) is taken4)2C2O4·H2Adding O into deionized water to prepare a concentration of 0.2mol/L (NH)4)2C2O4200ml of the solution and both solutions were heated to 35 ℃ in a simultaneous water bath. Then 21.2g of coarsened tungsten carbide powder is poured into the heated NiCl2In the solution, mechanically stirring for 20min and then adding NiCl2Adding a proper amount of hydrochloric acid solution into the tungsten carbide mixed solution to adjust the pH value of the mixed solutionAdjusted to 6.2. Then the prepared 0.2mol/L (NH)4)2C2O4The solution was added to NiCl as a precipitant at a rate of 0.17ml/s2Adding a precipitator into the tungsten carbide mixed solution, simultaneously carrying out water bath heating and mechanical stirring, wherein the water bath heating temperature is 50 ℃, the mechanical stirring time is 90min, and aging the mixed solution for 10min after the stirring is finished; and finally, carrying out suction filtration on the precipitated mixed solution, and drying in a vacuum drying oven to obtain mixture precursor powder. Calcining the obtained mixture precursor powder for 1h at the high temperature of 500 ℃ in the hydrogen protective atmosphere to obtain the tungsten carbide-nickel composite powder.
Weighing 100g of tungsten carbide-nickel composite powder prepared by the process flow, adding an SD-E forming agent into the tungsten carbide-nickel composite powder, then putting the tungsten carbide-nickel composite powder into a graphite mold for compaction, and placing a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; and in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode, and the tungsten carbide-10% nickel hard alloy is obtained.
Example 4
50g of tungsten carbide powder with the average particle size of 5.0 mu m and the purity of 99.9 percent is taken and put into 500ml of hydrofluoric acid-nitric acid mixed water solution to be coarsened under the condition of mechanical stirring, the concentration of the hydrofluoric acid is 30ml/L, the concentration of the nitric acid is 30ml/L, the stirring time is 30min, and after the stirring, the tungsten carbide powder is soaked for 20min and then is filtered and dried. 38.04g of NiCl solid particle medicament are taken at the same time2·6H2O is added into deionized water to be prepared into the solution with the concentration of 0.8mol/LNiCl2200ml of the solution, 11.37g of solid granular medicament (NH) is taken4)2C2O4·H2Adding O into deionized water to prepare a concentration of 0.4mol/L (NH)4)2C2O4200ml of the solution, and mixing the two solutionsThe solution was heated to 50 ℃ in a water bath. Then 42.2g of coarsened tungsten carbide powder is poured into the heated NiCl2In the solution, mechanically stirring for 20min and then adding NiCl2And adding a proper amount of hydrochloric acid solution into the tungsten carbide mixed solution to adjust the pH value of the mixed solution to 6.2. Then the prepared 0.6mol/L (NH)4)2C2O4The solution was added to NiCl as a precipitant at a rate of 0.17ml/s2Adding a precipitator into the tungsten carbide mixed solution, simultaneously carrying out water bath heating and mechanical stirring, wherein the water bath heating temperature is 50 ℃, the mechanical stirring time is 90min, and aging the mixed solution for 10min after the stirring is finished; and finally, carrying out suction filtration on the precipitated mixed solution, and drying in a vacuum drying oven to obtain mixture precursor powder. Calcining the obtained mixture precursor powder for 1h at the high temperature of 500 ℃ in the hydrogen protective atmosphere to obtain the tungsten carbide-nickel composite powder.
Weighing 100g of tungsten carbide-nickel composite powder prepared by the process flow, adding an SD-E forming agent into the tungsten carbide-nickel composite powder, then putting the tungsten carbide-nickel composite powder into a graphite mold for compaction, and placing a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; and in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode, and the tungsten carbide-10% nickel hard alloy is obtained.
Example 5
50g of tungsten carbide powder with the average particle size of 5.0 mu m and the purity of 99.9 percent is taken and put into 500ml of hydrofluoric acid-nitric acid mixed water solution to be coarsened under the condition of mechanical stirring, the concentration of the hydrofluoric acid is 30ml/L, the concentration of the nitric acid is 30ml/L, the stirring time is 30min, and after the stirring, the tungsten carbide powder is soaked for 20min and then is filtered and dried. Simultaneously, 9.52g of solid particle medicament NiCl is taken2·6H2Adding O into deionized water to prepare the solution with the concentration of 0.2mol/LNiCl2200ml of the solution, 2.86g of solid granular medicament (NH) is taken4)2C2O4·H2Adding O into deionized water to prepare the solution with the concentration of 0.1mol/L (NH)4)2C2O4200ml of the solution and both solutions were heated to 50 ℃ in a simultaneous water bath. Then 10.5g of coarsened tungsten carbide powder is poured into the heated NiCl2In the solution, mechanically stirring for 20min and then adding NiCl2And adding a proper amount of hydrochloric acid solution into the tungsten carbide mixed solution to adjust the pH value of the mixed solution to 6.2. Then the prepared 0.6mol/L (NH)4)2C2O4The solution was added to NiCl as a precipitant at a rate of 0.17ml/s2Adding a precipitator into the tungsten carbide mixed solution, simultaneously carrying out water bath heating and mechanical stirring, wherein the water bath heating temperature is 50 ℃, the mechanical stirring time is 90min, and aging the mixed solution for 10min after the stirring is finished; and finally, carrying out suction filtration on the precipitated mixed solution, and drying in a vacuum drying oven to obtain mixture precursor powder. Calcining the obtained mixture precursor powder for 1h at the high temperature of 500 ℃ in the hydrogen protective atmosphere to obtain the tungsten carbide-nickel composite powder.
Weighing 100g of tungsten carbide-nickel composite powder prepared by the process flow, adding an SD-E forming agent into the tungsten carbide-nickel composite powder, then putting the tungsten carbide-nickel composite powder into a graphite mold for compaction, and placing a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; and in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode, and the tungsten carbide-10% nickel hard alloy is obtained.
Example 6
Taking 50g of tungsten carbide powder with the average particle size of 5.0 mu m and the purity of 99.9 percent, placing the tungsten carbide powder into 500ml of hydrofluoric acid-nitric acid mixed aqueous solution, and carrying out coarsening treatment under the condition of mechanical stirringThe acid concentration is 30ml/L, the nitric acid concentration is 30ml/L, the stirring time is 30min, and after the stirring, the powder is soaked for 20min and then filtered and dried. At the same time, 19.06g of NiCl solid particle medicament is taken2·6H2Adding O into deionized water to prepare the solution with the concentration of 0.4 mol/LNiCl2200ml of the solution, 5.68g of solid granular medicament (NH) is taken4)2C2O4·H2Adding O into deionized water to prepare a concentration of 0.2mol/L (NH)4)2C2O4200ml of the solution and both solutions were heated to 50 ℃ in a simultaneous water bath. Then 21.2g of coarsened tungsten carbide powder is poured into the heated NiCl2In the solution, mechanically stirring for 20min and then adding NiCl2And adding a proper amount of hydrochloric acid solution into the tungsten carbide mixed solution to adjust the pH value of the mixed solution to 2.9. Then the prepared 0.2mol/L (NH)4)2C2O4The solution was added to NiCl as a precipitant at a rate of 0.17ml/s2Adding a precipitator into the tungsten carbide mixed solution, simultaneously carrying out water bath heating and mechanical stirring, wherein the water bath heating temperature is 50 ℃, the mechanical stirring time is 90min, and aging the mixed solution for 10min after the stirring is finished; and finally, carrying out suction filtration on the precipitated mixed solution, and drying in a vacuum drying oven to obtain mixture precursor powder.
Weighing 100g of tungsten carbide-nickel composite powder prepared by the process flow, adding an SD-E forming agent into the tungsten carbide-nickel composite powder, then putting the tungsten carbide-nickel composite powder into a graphite mold for compaction, and placing a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; and in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode, and the tungsten carbide-10% nickel hard alloy is obtained.
Example 7
Taking the average particle size of 5.0 μm and the purity of 99.9%50g of tungsten carbide powder is placed in 500ml of hydrofluoric acid-nitric acid mixed aqueous solution to be coarsened under the condition of mechanical stirring, the concentration of hydrofluoric acid is 30ml/L, the concentration of nitric acid is 30ml/L, the stirring time is 30min, and after the stirring, the tungsten carbide powder is soaked for 20min and then is filtered and dried. At the same time, 19.06g of NiCl solid particle medicament is taken2·6H2Adding O into deionized water to prepare the solution with the concentration of 0.4 mol/LNiCl2200ml of the solution, 5.68g of solid granular medicament (NH) is taken4)2C2O4·H2Adding O into deionized water to prepare a concentration of 0.2mol/L (NH)4)2C2O4200ml of the solution and both solutions were heated to 50 ℃ in a simultaneous water bath. Then 21.2g of coarsened tungsten carbide powder is poured into the heated NiCl2In the solution, mechanically stirring for 20min and then adding NiCl2And adding a proper amount of hydrochloric acid solution into the tungsten carbide mixed solution to adjust the pH value of the mixed solution to 4.2. Then the prepared 0.2mol/L (NH)4)2C2O4The solution was added to NiCl as a precipitant at a rate of 0.17ml/s2Adding a precipitator into the tungsten carbide mixed solution, simultaneously carrying out water bath heating and mechanical stirring, wherein the water bath heating temperature is 50 ℃, the mechanical stirring time is 90min, and aging the mixed solution for 10min after the stirring is finished; and finally, carrying out suction filtration on the precipitated mixed solution, and drying in a vacuum drying oven to obtain mixture precursor powder.
Weighing 100g of tungsten carbide-nickel composite powder prepared by the process flow, adding an SD-E forming agent into the tungsten carbide-nickel composite powder, then putting the tungsten carbide-nickel composite powder into a graphite mold for compaction, and placing a pressure head to complete mold assembly. And then placing the die into a sintering cavity of the spark plasma sintering equipment, vacuumizing the cavity, and then starting heating and sintering. In the sintering process, the furnace temperature is increased to 200 ℃ from the room temperature at the speed of 3 ℃/min, the temperature is kept for 0.5h, then is increased to 470 ℃ at the speed of 2 ℃/min, the temperature is kept for 1.5h, then is increased to 900 ℃ at the speed of 6 ℃/min, the temperature is kept for 30min, then is increased to 1250 ℃ at the speed of 7 ℃/min, the temperature is kept for 30min, and finally is increased to 1450 ℃ at the speed of 2.5 ℃/min, and the temperature is kept for 1 h; and in the cooling stage, the temperature in the furnace is reduced to room temperature by adopting a furnace cooling mode, and the tungsten carbide-10% nickel hard alloy is obtained.
Claims (10)
1. The preparation method of the tungsten carbide-nickel hard alloy is characterized by comprising the following steps of:
(1) preparation of NiCl2Solution and (NH)4)2C2O4Heating the solution in water bath;
(2) mixing tungsten carbide powder with NiCl2The solution is mixed evenly to obtain WC-NiCl2Mixing the solution to obtain (NH)4)2C2O4Adding WC-NiCl into the solution2Heating the mixed solution in a water bath, and stirring, aging, filtering by suction, and drying to obtain mixture precursor powder;
(3) calcining the mixture precursor powder in a protective atmosphere to obtain tungsten carbide-nickel composite powder;
(4) and carrying out glue doping, granulation, compression molding and calcination on the tungsten carbide-nickel composite powder to obtain the tungsten carbide-nickel hard alloy.
2. The method for preparing tungsten carbide-nickel hard alloy according to claim 1, wherein the water bath in the step (1) is heated to 35 to 65 ℃.
3. The method for preparing the tungsten carbide-nickel hard alloy according to claim 1, wherein the tungsten carbide powder is added into the coarsening liquid for coarsening in the step (2), and then the WC-NiCl is added2Mixing the solution.
4. The method according to claim 3, wherein the roughening solution in the step (2) is a hydrofluoric acid-nitric acid roughening solution.
5. The method of claim 1, wherein the NiCl prepared in step (1) is added to the cemented tungsten carbide-nickel carbide alloy2The concentration of the solution is 0.2-0.8 mol/L, (NH)4)2C2O4The concentration of the solution is 0.1-0.4 mol/L.
6. The method for preparing WC-Ni cemented carbide as claimed in claim 1, wherein in the step (2), WC-NiCl is mixed with an acid solution2Adjusting the pH value of the mixed solution to 2.9-6.2, and then adding (NH)4)2C2O4And (3) solution.
7. The method for preparing the tungsten carbide-nickel hard alloy according to claim 6, wherein the acidic solution is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 0.1 to 0.2 mol/L.
8. The method of claim 1, wherein the step (2) is performed by (NH)4)2C2O4The adding speed of the solution is 0.85 ml/s-0.017 ml/s, the water bath heating temperature is 35-65 ℃, the stirring time is 80-90 min, and the aging time is 10-15 min.
9. The method for producing a tungsten carbide-nickel cemented carbide according to claim 1, wherein the step of producing a tungsten carbide-nickel cemented carbide in the step (4) is:
(a) mixing the alloy powder with a forming agent, drying, and then continuously adding the forming agent;
(b) granulating by adopting a screen;
(c) putting the graphite mould into a graphite mould for compaction, and placing a pressure head to complete mould assembly;
(d) and putting the die into a sintering cavity, vacuumizing, heating, sintering and cooling to obtain the tungsten carbide-nickel hard alloy.
10. The method of preparing a tungsten carbide-nickel cemented carbide according to claim 9, wherein the forming agent is a paraffin wax forming agent, rubber PEG, and SD-E forming agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636024A (en) * | 2020-05-26 | 2020-09-08 | 河海大学 | WC-Ni-Cr/Ta composite material hard alloy and preparation method and application thereof |
| CN111850369A (en) * | 2020-07-09 | 2020-10-30 | 南昌航空大学 | Method for preparing WC-6 Ni-graphite self-lubricating hard cutter material by mechanical alloying |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3558343A (en) * | 1966-08-18 | 1971-01-26 | Texas Instruments Inc | Dispersion strengthened titanium carbide and method for making same |
| JPS61217591A (en) * | 1985-03-22 | 1986-09-27 | Tokuyama Soda Co Ltd | Production of cathode |
| US5322711A (en) * | 1989-07-21 | 1994-06-21 | Minnesota Mining And Manufacturing Company | Continuous method of covering inorganic fibrous material with particulates |
| CN1640593A (en) * | 2004-12-31 | 2005-07-20 | 自贡科瑞德新材料有限责任公司 | Method for producing WC-Co hot spray powder using hard alkloy waste |
| CN101077476A (en) * | 2006-05-24 | 2007-11-28 | 比亚迪股份有限公司 | Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel |
| CN101824540A (en) * | 2009-12-10 | 2010-09-08 | 佛山市邦普镍钴技术有限公司 | Method for separating and reclaiming metal nickel and tin from waste materials containing nickel and tin |
| CN102649161A (en) * | 2011-02-23 | 2012-08-29 | 荆门市格林美新材料有限公司 | Nickel powder with large furnace safety supervision system (FSSS) particle size and preparation method thereof |
| CN105268983A (en) * | 2015-10-21 | 2016-01-27 | 陕西理工学院 | Preparation method of W-Ni-Cu prealloyed powder |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| CN107190165A (en) * | 2017-05-22 | 2017-09-22 | 重庆强锐科技有限公司 | A kind of method for preparing high intensity WC Ni hard alloy |
| CN109837446A (en) * | 2017-11-29 | 2019-06-04 | 祁阳华瑞特种材料有限公司 | A kind of WC-Ni hard alloy powder metallurgical method |
| CN110039070A (en) * | 2019-05-31 | 2019-07-23 | 湖南工业大学 | A kind of cracking prepares the hard alloy method of uniform composite powder |
-
2019
- 2019-11-25 CN CN201911165318.4A patent/CN110983142B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3558343A (en) * | 1966-08-18 | 1971-01-26 | Texas Instruments Inc | Dispersion strengthened titanium carbide and method for making same |
| JPS61217591A (en) * | 1985-03-22 | 1986-09-27 | Tokuyama Soda Co Ltd | Production of cathode |
| US5322711A (en) * | 1989-07-21 | 1994-06-21 | Minnesota Mining And Manufacturing Company | Continuous method of covering inorganic fibrous material with particulates |
| CN1640593A (en) * | 2004-12-31 | 2005-07-20 | 自贡科瑞德新材料有限责任公司 | Method for producing WC-Co hot spray powder using hard alkloy waste |
| CN101077476A (en) * | 2006-05-24 | 2007-11-28 | 比亚迪股份有限公司 | Method for preparing globular shape powdered nickel precursor body and globular shape powdered nickel |
| CN101824540A (en) * | 2009-12-10 | 2010-09-08 | 佛山市邦普镍钴技术有限公司 | Method for separating and reclaiming metal nickel and tin from waste materials containing nickel and tin |
| CN102649161A (en) * | 2011-02-23 | 2012-08-29 | 荆门市格林美新材料有限公司 | Nickel powder with large furnace safety supervision system (FSSS) particle size and preparation method thereof |
| CN105695837A (en) * | 2014-11-26 | 2016-06-22 | 自贡硬质合金有限责任公司 | Preparation method of WC-Ni fine grain cemented carbide |
| CN105268983A (en) * | 2015-10-21 | 2016-01-27 | 陕西理工学院 | Preparation method of W-Ni-Cu prealloyed powder |
| CN107190165A (en) * | 2017-05-22 | 2017-09-22 | 重庆强锐科技有限公司 | A kind of method for preparing high intensity WC Ni hard alloy |
| CN109837446A (en) * | 2017-11-29 | 2019-06-04 | 祁阳华瑞特种材料有限公司 | A kind of WC-Ni hard alloy powder metallurgical method |
| CN110039070A (en) * | 2019-05-31 | 2019-07-23 | 湖南工业大学 | A kind of cracking prepares the hard alloy method of uniform composite powder |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111636024A (en) * | 2020-05-26 | 2020-09-08 | 河海大学 | WC-Ni-Cr/Ta composite material hard alloy and preparation method and application thereof |
| CN111636024B (en) * | 2020-05-26 | 2021-10-29 | 河海大学 | WC-Ni-Cr/Ta composite material hard alloy and preparation method and application thereof |
| CN111850369A (en) * | 2020-07-09 | 2020-10-30 | 南昌航空大学 | Method for preparing WC-6 Ni-graphite self-lubricating hard cutter material by mechanical alloying |
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