CN109019692B - Preparation method of tungsten carbide - Google Patents

Preparation method of tungsten carbide Download PDF

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CN109019692B
CN109019692B CN201811221978.5A CN201811221978A CN109019692B CN 109019692 B CN109019692 B CN 109019692B CN 201811221978 A CN201811221978 A CN 201811221978A CN 109019692 B CN109019692 B CN 109019692B
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HUNAN JINDIAO ENERGY TECHNOLOGY Co.,Ltd.
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Abstract

The invention provides a preparation method of tungsten carbide. The method takes nano tungsten trioxide powder as a raw material, ball-milling is carried out under the action of a crystal grain inhibitor, and then the nano tungsten powder is reduced to obtain the nano tungsten powder, then the nano tungsten powder is added into concentrated ammonia water, heating reaction is carried out under the condition of introducing methane, and vacuum carbonization treatment is carried out to obtain the nano tungsten carbide, the granularity of the nano tungsten carbide is small and uniform, the surface chemical activity of the prepared nano particles is low, and the occurrence of agglomeration is inhibited.

Description

Preparation method of tungsten carbide
Technical Field
The invention relates to the field of powder metallurgy, in particular to a preparation method of tungsten carbide.
Background
Tungsten carbide is an important raw material for preparing hard alloy, and is widely applied to the fields of metal and nonmetal cutting, transportation industry and building. Too high a cobalt content causes excessive wear and, in turn, a reduction in the service life of the material, so the cobalt content in the alloy must be moderate. In the case of a constant cobalt content, the method of increasing toughness and increasing wear resistance is to reduce the grain size of tungsten carbide.
The existing method for preparing the nano tungsten carbide powder comprises the steps of firstly preparing the nano tungsten oxide powder and then obtaining the nano tungsten carbide powder by reduction and carbonization. The preparation method of the nano tungsten oxide powder comprises sol-gel glue, a chemical precipitation method and the like, and a large amount of industrial wastewater is generated in the production process, so that the environment is polluted. In order to avoid environmental pollution, methods for producing nano tungsten carbide powder, such as a spraying method and a coating method, have been developed, but the particle size of the obtained powder is unstable and cannot easily reach 100nm or less.
Disclosure of Invention
The invention aims to provide a preparation method of tungsten carbide, which aims to solve the technical problem of obtaining nano-scale tungsten carbide.
In order to realize the purpose, the invention provides a preparation method of tungsten carbide, which comprises the following specific steps:
(1) uniformly mixing nano magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in a flowing nitrogen atmosphere to obtain the crystal grain inhibitor, wherein the flow rate of nitrogen is 30-40 cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1000-1100 ℃, and introducing methane at the same time, wherein the flow velocity of the methane is 300-320 cm3The reaction is carried out for 1 to 2 hours in a heat preservation way;
(5) carbonizing for 2-5 hours under a vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
Preferably, in the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.2-0.3: 0.5-0.6: 0.5-0.6: 0.3 to 0.4.
Preferably, in the step (1), the sintering process conditions are as follows: sintering at 1500-1700 ℃ for 1-2 hours.
Preferably, in the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the grain inhibitor and the absolute ethyl alcohol is 100 g: 0.2-0.3 g: 200-300 mL.
Preferably, in the step (2), the preparation method of the nano tungsten trioxide powder is as follows: and (3) loading the ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1000-1200 ℃ for 2-3 minutes, then cooling to 600-700 ℃ at a cooling rate of 20-30 ℃/minute, and preserving heat for 10-15 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
Preferably, in the step (2), the ball milling process conditions are as follows: the ball material ratio is 6-8: 1, ball milling time is 10-12 hours.
Preferably, in step (2), ethanol is removed by rotary evaporation.
Preferably, in the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 3-5 mm, and the hydrogen flow is 25-35 mL/(min cm)2) And carrying out heat preservation treatment at 600-650 ℃ for 30-40 minutes.
Preferably, in the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 5-8 mL of concentrated ammonia water, wherein the concentrated ammonia water is an aqueous solution containing 25-28% of ammonia.
Preferably, in the step (5), the temperature of the carbonization treatment is 1200-1400 ℃.
The invention has the following beneficial effects:
the method takes nano tungsten trioxide powder as a raw material, ball-milling is carried out under the action of a crystal grain inhibitor, and then the nano tungsten powder is reduced to obtain the nano tungsten powder, then the nano tungsten powder is added into concentrated ammonia water, heating reaction is carried out under the condition of introducing methane, and vacuum carbonization treatment is carried out to obtain the nano tungsten carbide, the granularity of the nano tungsten carbide is small and uniform, the surface chemical activity of the prepared nano particles is low, and the occurrence of agglomeration is inhibited.
The grain inhibitor is prepared by taking nano magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid as raw materials, sintering the raw materials in a flowing nitrogen atmosphere, and controlling a small nitrogen flow rate to enable metal ions such as magnesium, chromium and the like to be dissociated and dispersed into loose pores formed by the maltose and the citric acid to form a hard phase, so that the grain inhibitor can play a role in blocking in the grain growth process, and further inhibit the grain growth. The sintering temperature is a relatively critical factor, the formation of a hard phase is influenced by overhigh temperature, and the uniformity of a grain inhibitor is influenced by overlow temperature, so that the grain inhibition effect is influenced.
The nano tungsten powder is added into concentrated ammonia water, and is heated under the condition of introducing methane, so that the flow rate of the methane is controlled to promote the rapid volatilization of the ammonia water and the water, and the effect of refining particles is achieved.
When the nano tungsten trioxide powder is prepared, firstly, the ammonium paratungstate is quickly heated to a higher temperature, ammonia and water are dissociated under the condition, and then, the temperature is reduced at a higher cooling rate, so that the rapid dissociation of the ammonia and the water is facilitated, and the effect of refining particles is achieved.
The nano tungsten carbide of the invention is easy to disperse and has good fluidity, and depends on several key steps: the mechanical force of ball milling is helpful for forming a protective layer on the surface of the nano particles, a large amount of ammonia and water volatilize under the flowing condition of methane to form an isolation interface between the nano particles, the surface of the nano particles is passivated, and agglomeration is effectively avoided.
In addition to the objects, features and advantages described above, other objects, features and advantages of the present invention are also provided. The present invention will be described in further detail below.
Detailed Description
The following is a detailed description of embodiments of the invention, but the invention can be implemented in many different ways, as defined and covered by the claims.
Example 1:
a preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 30cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1000 ℃, and introducing methane at the same time, wherein the flow velocity of the methane is 300cm3S, keeping the temperature for reaction for 1 hour;
(5) carbonizing for 2 hours under the vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.2: 0.5: 0.5: 0.3.
in the step (1), the sintering process conditions are as follows: sintering at 1400 deg.C for 1 hr.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.2 g: 200 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1000 ℃ within 2 minutes, then cooling to 600 ℃ at a cooling rate of 20 ℃/minute, and preserving heat for 10 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 6: 1, ball milling time is 10 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 3mm, and the hydrogen flow is 25mL/(min cm)2) And keeping the temperature at 600 ℃ for 30 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 5mL of concentrated ammonia water is an aqueous solution containing 25% ammonia.
In the step (5), the temperature of the carbonization treatment is 1200 ℃.
Example 2:
a preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 40cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1100 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 320cm3S, keeping the temperature for reaction for 2 hours;
(5) carbonizing for 5 hours under vacuum condition, naturally cooling to room temperature (25 ℃), and obtaining the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.3: 0.6: 0.6: 0.4.
in the step (1), the sintering process conditions are as follows: sintering at 1800 deg.c for 2 hr.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.3 g: 300 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1200 ℃ within 3 minutes, then cooling to 700 ℃ at a cooling rate of 30 ℃/minute, and preserving heat for 15 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 8: 1, ball milling time 12 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 5mm, and the hydrogen flow is 35mL/(min cm)2) And keeping the temperature at 650 ℃ for 40 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 8mL, the concentrated ammonia water is an aqueous solution containing 28% ammonia.
In the step (5), the temperature of the carbonization treatment was 1400 ℃.
Example 3:
a preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesia, silicon carbide, chromium carbide, maltose and citric acid, flowing nitrogenSintering in atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 30cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1100 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 300cm3S, keeping the temperature for reaction for 2 hours;
(5) carbonizing for 2 hours under the vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.3: 0.5: 0.6: 0.3.
in the step (1), the sintering process conditions are as follows: sintering at 1700 ℃ for 1 hour.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.3 g: 200 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1000 ℃ within 3 minutes, then cooling to 600 ℃ at a cooling rate of 30 ℃/minute, and preserving heat for 15 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 6: 1, ball milling time 12 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 3mm, and the hydrogen flow is 35mL/(min cm)2) And keeping the temperature at 600 ℃ for 40 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 5mL of strong ammonia water is an aqueous solution containing 28% of ammonia.
In the step (5), the temperature of the carbonization treatment is 1200 ℃.
Example 4:
a preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 40cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1000 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 320cm3S, keeping the temperature for reaction for 1 hour;
(5) carbonizing for 5 hours under vacuum condition, naturally cooling to room temperature (25 ℃), and obtaining the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.2: 0.6: 0.5: 0.4.
in the step (1), the sintering process conditions are as follows: sintering at 1500 ℃ for 2 hours.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.2 g: 300 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1200 ℃ within 2 minutes, then cooling to 700 ℃ at a cooling rate of 20 ℃/minute, and preserving heat for 10 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 8: 1, ball milling time is 10 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 5mm, and the hydrogen flow is 25mL/(min cm)2) And keeping the temperature at 650 ℃ for 30 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 8mL, the concentrated ammonia water is an aqueous solution containing 25% ammonia.
In the step (5), the temperature of the carbonization treatment was 1400 ℃.
Example 5:
a preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 35cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1050 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 310cm3S, keeping the temperature for reaction for 1.5 hours;
(5) carbonizing for 4 hours under the vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.25: 0.55: 0.55: 0.35.
in the step (1), the sintering process conditions are as follows: sintering at 1600 deg.c for 1.5 hr.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.25 g: 250 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading the ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1100 ℃ within 3 minutes, then cooling to 650 ℃ at a cooling rate of 25 ℃/minute, and preserving heat for 12 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 7: 1, ball milling time 11 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 4mm, and the hydrogen flow is 30mL/(min cm)2) And keeping the temperature at 620 ℃ for 35 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 6mL of strong ammonia water is an aqueous solution containing 28% of ammonia.
In the step (5), the temperature of the carbonization treatment was 1300 ℃.
Comparative example 1
A preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 35cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1050 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 310cm3S, keeping the temperature for reaction for 1.5 hours;
(5) carbonizing for 4 hours under the vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
Wherein in the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the maltose to the citric acid is 1: 0.25: 0.55: 0.35.
in the step (1), the sintering process conditions are as follows: sintering at 1600 deg.c for 1.5 hr.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.25 g: 250 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading the ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1100 ℃ within 3 minutes, then cooling to 650 ℃ at a cooling rate of 25 ℃/minute, and preserving heat for 12 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 7: 1, ball milling time 11 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 4mm, and the hydrogen flow is 30mL/(min cm)2) And keeping the temperature at 620 ℃ for 35 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 6mL of strong ammonia water is an aqueous solution containing 28% of ammonia.
In the step (5), the temperature of the carbonization treatment was 1300 ℃.
Comparative example 2
A preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 35cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) heating the nano tungsten powder to 1050 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 310cm3S, keeping the temperature for reaction for 1.5 hours;
(5) carbonizing for 4 hours under the vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.25: 0.55: 0.55: 0.35.
in the step (1), the sintering process conditions are as follows: sintering at 1600 deg.c for 1.5 hr.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.25 g: 250 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading the ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1100 ℃ within 3 minutes, then cooling to 650 ℃ at a cooling rate of 25 ℃/minute, and preserving heat for 12 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 7: 1, ball milling time 11 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 4mm, and the hydrogen flow is 30mL/(min cm)2) And keeping the temperature at 620 ℃ for 35 minutes.
In the step (5), the temperature of the carbonization treatment was 1300 ℃.
Comparative example 3
A preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 35cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1050 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 290cm3S, keeping the temperature for reaction for 1.5 hours;
(5) carbonizing for 4 hours under the vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.25: 0.55: 0.55: 0.35.
in the step (1), the sintering process conditions are as follows: sintering at 1600 deg.c for 1.5 hr.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.25 g: 250 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading the ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1100 ℃ within 3 minutes, then cooling to 650 ℃ at a cooling rate of 25 ℃/minute, and preserving heat for 12 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 7: 1, ball milling time 11 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 4mm, and the hydrogen flow is 30mL/(min cm)2) And keeping the temperature at 620 ℃ for 35 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 6mL of strong ammonia water is an aqueous solution containing 28% of ammonia.
In the step (5), the temperature of the carbonization treatment was 1300 ℃.
Comparative example 4
A preparation method of tungsten carbide comprises the following specific steps:
(1) mixing nanometer magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in flowing nitrogen atmosphere to obtain crystal grain inhibitor, wherein the flow rate of nitrogen is 35cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1050 ℃, and introducing methane at the same time, wherein the flow rate of the methane is 310cm3S, keeping the temperature for reaction for 1.5 hours;
(5) carbonizing for 4 hours under the vacuum condition, and naturally cooling to room temperature (25 ℃) to obtain the tungsten carbide.
In the step (1), the mass ratio of the nano magnesium oxide to the silicon carbide to the chromium carbide to the maltose to the citric acid is 1: 0.25: 0.55: 0.55: 0.35.
in the step (1), the sintering process conditions are as follows: sintering at 1600 deg.c for 1.5 hr.
In the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.25 g: 250 mL.
In the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: and (3) loading the ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1100 ℃ within 3 minutes, then cooling to 650 ℃ at a cooling rate of 25 ℃/minute, and preserving heat for 12 minutes under the temperature condition to obtain the nano tungsten trioxide powder with the particle size of less than 10 nm.
In the step (2), the ball milling process conditions are as follows: ball material ratio 7: 1, ball milling time 11 hours.
In the step (2), ethanol is removed by rotary evaporation.
In the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 4mm, and the hydrogen flow is 30mL/(min cm)2) And keeping the temperature at 620 ℃ for 35 minutes.
In the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 6mL of strong ammonia water is an aqueous solution containing 28% of ammonia.
In the step (5), the temperature of the carbonization treatment was 1300 ℃.
Test examples
The tungsten carbide obtained in examples 1 to 5 and comparative examples 1 to 2 was subjected to angle of repose measurement using an angle of repose measuring instrument, and the average particle diameter and the particle diameter range were counted, and the results are shown in table 1.
TABLE 1 product comparison
Average particle diameter (nm) Particle size range (nm) Angle of repose (°)
Example 1 10 5～15 26
Example 2 9 5～10 28
Example 3 7 5～10 25
Example 4 7 5～10 25
Example 5 6 5～10 24
Comparative example 1 25 5～55 30
Comparative example 2 20 10～30 38
Comparative example 3 15 10～20 30
Comparative example 4 10 8～15 37
As is clear from Table 1, the tungsten carbide obtained in examples 1 to 5 has a small average particle diameter, a small particle diameter range, a small angle of repose, and good fluidity. The sintering temperature of the embodiment 1 is slightly low, the uniformity of the grain inhibitor is affected by too low temperature, the grain inhibition effect is further affected, and the product has large grain diameter and large grain diameter range; the sintering temperature in example 2 is slightly higher, which affects the formation of hard phase and the product flowability is slightly poor.
The method has the advantages that chromium carbide is omitted when the grain inhibitor is prepared in the comparative example 1, the average grain size of the product is large, the grain size range is large, concentrated ammonia water is not introduced in the step (4) in the comparative example 2, the flowability of the product is poor, the methane flow rate in the step (4) in the comparative example 3 is low, the grain size of the product is large, the ball milling treatment is not performed in the step (2) in the comparative example 4, and the flowability of the product is poor obviously compared with those in the examples 1-5.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (1)

1. The preparation method of the tungsten carbide is characterized by comprising the following specific steps:
(1) uniformly mixing nano magnesium oxide, silicon carbide, chromium carbide, maltose and citric acid, and sintering in a flowing nitrogen atmosphere to obtain the crystal grain inhibitor, wherein the flow rate of nitrogen is 30-40 cm3/s；
(2) Mixing nano tungsten trioxide powder with the particle size of less than 10nm with a crystal grain inhibitor, pouring the mixture into absolute ethyl alcohol, carrying out ball milling, taking out, and removing the ethyl alcohol;
(3) reducing to obtain nano tungsten powder;
(4) adding nano tungsten powder into concentrated ammonia water, heating to 1000-1100 ℃, and introducing methane at the same time, wherein the flow velocity of the methane is 300-320 cm3S, securityReacting for 1-2 hours at a warm temperature;
(5) carbonizing for 2-5 hours under a vacuum condition, and naturally cooling to room temperature to obtain tungsten carbide;
in the step (1), the mass ratio of the nano magnesium oxide, the silicon carbide, the chromium carbide, the maltose and the citric acid is 1: 0.2-0.3: 0.5-0.6: 0.5-0.6: 0.3 to 0.4;
in the step (1), the sintering process conditions are as follows: sintering at 1500-1700 ℃ for 1-2 hours;
in the step (2), the mass-to-volume ratio of the nano tungsten trioxide powder to the crystal grain inhibitor and the absolute ethyl alcohol is 100 g: 0.2-0.3 g: 200-300 mL;
in the step (2), the preparation method of the nano tungsten trioxide powder comprises the following steps: putting ammonium paratungstate powder into a vacuum medium-frequency induction heating furnace, heating to 1000-1200 ℃ for 2-3 minutes, then cooling to 600-700 ℃ at a cooling rate of 20-30 ℃/minute, and preserving heat for 10-15 minutes under the temperature condition to obtain nano tungsten trioxide powder with the particle size of less than 10 nm;
in the step (2), the ball milling process conditions are as follows: the ball material ratio is 6-8: 1, ball milling for 10-12 hours;
in the step (3), a tubular furnace is adopted for hydrogen reduction, the thickness of a material layer is 3-5 mm, and the hydrogen flow is 25-35 mL/(min cm)2) Carrying out heat preservation treatment at 600-650 ℃ for 30-40 minutes;
in the step (4), the mass-to-volume ratio of the nano tungsten powder to the concentrated ammonia water is 1 g: 5-8 mL of concentrated ammonia water which is an aqueous solution containing 25-28% of ammonia;
in the step (5), the temperature of the carbonization treatment is 1200-1400 ℃.
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