CN115321537A - Preparation method of high-dispersion particle size controllable nano tungsten carbide powder - Google Patents
Preparation method of high-dispersion particle size controllable nano tungsten carbide powder Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 77
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000006185 dispersion Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 123
- 238000010438 heat treatment Methods 0.000 claims abstract description 123
- 239000000725 suspension Substances 0.000 claims abstract description 67
- 238000003756 stirring Methods 0.000 claims abstract description 59
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 35
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- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
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- 239000012071 phase Substances 0.000 claims description 10
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- 238000009775 high-speed stirring Methods 0.000 claims description 7
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
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- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
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- 239000013078 crystal Substances 0.000 description 1
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- 229910021641 deionized water Inorganic materials 0.000 description 1
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
The invention discloses a preparation method of high-dispersion particle size controllable nano tungsten carbide powder, which comprises the following steps: 1. adjusting the amorphous cracked carbon; 2. mixing amorphous cracked carbon particles, a dispersant and water; 3. adding ammonium metatungstate into the suspension; 4. heating and stirring the suspension, and adding an organic acid or an inorganic acid; 5. carrying out vacuum drying treatment on the suspension; 6. heating the composite powder, and then stirring at a super high speed; 7. and carrying out primary heat treatment and secondary heat treatment on the product to obtain the nano tungsten carbide powder. The invention takes amorphous cracked carbon particles as a nucleating agent, deposits tungstic acid through an acid-adding precipitation process, obtains tungsten dioxide/amorphous cracked carbon nano composite powder through low-temperature hydrogen reduction, and then obtains nano tungsten carbide powder through a two-step carbonization method, thereby solving the problems of uneven particle size distribution, poor dispersibility and difficult particle size control of nano tungsten carbide in the preparation process of nano tungsten carbide.
Description
Technical Field
The invention belongs to the technical field of preparation of nano powder materials, and particularly relates to a preparation method of high-dispersion particle size controllable nano tungsten carbide powder.
Background
The superfine/nanocrystalline tungsten carbide-cobalt (WC-Co) hard alloy has higher hardness, wear resistance, strength and toughness, rapidly receives wide attention since the appearance and becomes a research hotspot, becomes a future development trend of hard alloys, and has great application potential in the fields of high-temperature alloy die preparation, high-hardness steel die preparation, composite material/printed circuit board cutting and processing and the like. But the production of the nano WC-Co hard alloy is always limited because large-batch high-quality nano tungsten carbide (WC) powder cannot be obtained.
Currently, the industrial production of nano WC powder is mainly to reduce tungsten oxide by low-temperature cis-hydrogen (WO) 3 ) Firstly preparing nano tungsten (W) powder, then ball-milling and mixing the W powder and carbon powder and carbonizing to prepare the nano tungsten (W) powder, or directly preparing the tungsten oxide and the carbon powder into microspheres with a certain particle size and continuously carbonizing the microspheres at high temperature to prepare the nano tungsten (W) powder. Wherein the WC particle size produced by hydrogen reduction is not sufficiently fine. This is due to the reduction of WO with hydrogen 3 There is a Chemical Vapor Transport (CVT) process, with intermediate products being formed (WO) 2 (OH) 2 ) The W powder is promoted to aggregate and grow, so that the WC particle size is increased in the carbonization process, finally obtained WC-Co hard alloy has large grains and reduced performance, and the effect of fine grain strengthening cannot be achieved. The WC produced by the conventional continuous carbon reduction had a nonuniform particle size distribution due to WO 3 When the WC powder is mechanically mixed with carbon powder, the uniform distribution and tight combination of all parts can not be ensured, so that the prepared WC powder has wide particle size distribution. During the preparation process of the hard alloy, large-particle WC powder and small-particle WC powder can be subjected to aggregation growth, so that abnormally-long WC grains appear in the WC-Co hard alloy, the comprehensive performance of the alloy is reduced, and the accident risk is increased.
In conclusion, the industrial production of nano WC powder with good dispersibility, uniform and controllable particle size dispersion still has certain difficulties.
Therefore, a method suitable for industrially and efficiently preparing the nano WC powder with controllable high dispersion particle size is needed.
Disclosure of Invention
The technical problem to be solved by the present invention is to provide a method for preparing high dispersion particle size controllable nano tungsten carbide powder, aiming at the defects of the prior art. The method takes amorphous cracked carbon particles as a nucleating agent, precisely deposits tungstic acid on the amorphous cracked carbon particles through an acid-adding precipitation process to form a tungstic acid coated amorphous cracked carbon core-shell structure, effectively improves the dispersion and combination degree of the amorphous cracked carbon nanoparticles and a tungsten source, obtains tungsten dioxide/amorphous cracked carbon nano composite powder through low-temperature hydrogen reduction, ensures that the tungsten dioxide/amorphous cracked carbon nano composite powder inherits the distribution and combination mode of the tungstic acid and the amorphous cracked carbon, then obtains nano tungsten carbide powder through a two-step carbonization method, inhibits chemical vapor transmission growth in an intermediate reaction process, and solves the problems of uneven particle size distribution, poor dispersion and difficult particle size regulation of nano tungsten carbide in the preparation process of the nano tungsten carbide.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of high-dispersion particle size controllable nano tungsten carbide powder is characterized by comprising the following steps:
step one, adjusting the activity, the defects, the granularity and the dispersity of the amorphous cracked carbon to obtain amorphous cracked carbon particles;
step two, mixing the amorphous cracked carbon particles obtained in the step one, a dispersing agent and water to obtain uniformly dispersed amorphous cracked carbon suspension;
step three, adding ammonium metatungstate into the amorphous cracked carbon suspension obtained in the step two while stirring to obtain mixed suspension containing ammonium metatungstate and amorphous cracked carbon;
step four, heating and stirring the mixed suspension obtained in the step three, and adding organic acid or inorganic acid into the mixed suspension to obtain amorphous cracked carbon suspension deposited and coated with tungstic acid;
step five, carrying out vacuum drying treatment on the amorphous cracked carbon suspension deposited and coated with the tungstic acid obtained in the step four to obtain nano-mixed tungstic acid-coated amorphous cracked carbon composite powder;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-grade mixed tungsten dioxide/amorphous cracked carbon composite powder, and then stirring at an ultrahigh speed to obtain a nano-grade mixed product; the temperature of the heating treatment is 500-650 ℃;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracked carbon nano-particle composite powder with a high-dispersion core-shell structure, and then carrying out secondary heat treatment to obtain nano tungsten carbide powder; the temperature of the primary heat treatment is 850-930 ℃, and the temperature of the secondary heat treatment is 950-1300 ℃.
According to the invention, the activity, defects, granularity and dispersity of the amorphous cracked carbon are adjusted, so that the reaction activity of the raw materials in the reaction process is improved, the Gibbs free energy of the reaction is reduced thermodynamically, the reaction temperature is reduced, the abnormal growth of the WC powder particle diameter at a higher temperature is avoided, and the nano WC powder can be obtained in a large scale more easily;
the invention realizes acid precipitation reaction by the reaction of ammonium metatungstate and acid to generate tungstic acid, the generated tungstic acid is precipitate and can be coated on the surface of amorphous cracking carbon, the tungstic acid is used as a tungsten source for subsequent reduction reaction and can be uniformly mixed with a carbon source in a nanometer grade, the problems of nonuniform mixing and impurity introduction in the traditional ball milling mode are avoided, and nanometer WC with higher purity can be generated;
the invention reduces the composite powder obtained by acid precipitation reaction by heating treatment in the atmosphere containing hydrogen, wherein the reduction refers to the reaction of tungstic acid and hydrogen to generate WO 2 When the temperature is lower than 500 ℃, the reaction is incomplete and incompletely reacted WO exists 3 WO is experienced during the subsequent heat treatment, i.e. the first stage of carbonization 2.72 →WO 2 Topology transformation procedure of → W, WO 2.72 Is a rod-shaped structure of micron scale, and a section of carbon is arranged on the rod-shaped structureThe final generated nano W powder is subjected to a large amount of aggregation phenomenon and is densely distributed along the rod-shaped structure, and the W powder is sintered and the WC powder grows abnormally due to two-stage carbonization during subsequent high-temperature secondary heat treatment; when the temperature is higher than 650 ℃, due to the aggravation of the chemical vapor transmission process, abnormally long W powder exists, and also abnormally long WC powder is generated in the subsequent carbonization process, so that the hydrogen reduction temperature is controlled to be 500-650 ℃ to obtain WO which is basically free of other impurity phases 2 The abnormal long W powder generated in the subsequent first-stage carbonization process is avoided, and the particle size of WC in the second-stage carbonization process can be ensured to be nano-scale;
the invention sequentially carries out primary heat treatment and secondary heat treatment on the product, namely sequentially carries out first-stage carbonization and second-stage carbonization, wherein the first-stage carbonization is used for carbonizing WO 2 Reducing the W into W and further forming W on the surface of the W 2 A C pre-carbonization layer for blocking the aggregation growth of W powder in space and avoiding the generation of abnormal-growth WC powder by subsequent high-temperature carbonization, wherein the two-stage carbonization is to carry out W and W carbonization 2 C is further carbonized to completely generate WC, and the aggregation and growth of the nano powder can be promoted due to high temperature, so that the problem of overlarge WC particle size caused by direct high-temperature carbonization can be solved by adopting a two-stage heating carbonization mode, the temperature of the first stage is 850-930 ℃, and the formation of W with uniform distribution can be ensured 2 C pre-carbide layer, too low temperature to form W effectively 2 A layer C; excessive temperature, W 2 C is converted into WC, the subsequent carbonization can lead the particle size of WC to reach micron level, and the second-stage temperature is 950-1300 ℃ so as to ensure W 2 C and W powder is completely converted into WC, and the temperature is too low to be completely converted into pure-phase WC; when the temperature is too high, the generated WC powder can generate aggregation growth to generate WC with abnormal growth; the invention breaks the powder agglomeration and improves the powder porosity by ultra-high speed stirring.
The preparation method of the high-dispersion particle size-controllable nano tungsten carbide powder is characterized in that in the step one, the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase organic carbon source and has an amorphous structure, and the specific surface area of the amorphous cracked carbon is larger than 150cm 2 (ii)/g; the regulation mode of the activity, the defect, the granularity and the dispersity is ultrasonic treatment and plasma treatmentOr a rubbing treatment. The amorphous cracked carbon generated by cracking the gas-phase or solid-phase carbon source is adopted, and the activity, the defect, the granularity and the dispersity are adjusted to obtain the amorphous cracked carbon particles with high defect, high reaction activity, fine granularity and high dispersity, the treated carbon has very remarkable advantages in nucleation, granularity and uniformity regulation, and the reaction temperature and the reaction time can be remarkably reduced.
The preparation method of the particle size-controllable nano tungsten carbide powder is characterized in that in the second step, the dispersing agent is one or more of polyethylene glycol, polyvinylpyrrolidone and polyvinyl alcohol, and the adding amount of the dispersing agent is 0.5-1% of the mass of ammonium metatungstate in the mixed suspension liquid in the third step. According to the invention, the addition amount of the dispersing agent is controlled, so that the amorphous cracked carbon nano-particles are uniformly dispersed, and when the content of the dispersing agent is too low, the amorphous cracked carbon nano-particles can partially agglomerate and cannot achieve the effect of uniform dispersion; when the content is too high, the viscosity of the solution is high, the fluidity is poor, the effect of uniform dispersion can not be achieved, and when the adding amount of the dispersing agent is controlled to be 0.5-1% of the mass of the ammonium metatungstate, the amorphous cracking carbon particles can be uniformly distributed in the solution to form stable turbid liquid, so that the amorphous cracking carbon particles are not layered for a long time.
The preparation method of the high-dispersion particle size controllable nano tungsten carbide powder is characterized in that the mass purity of the ammonium metatungstate in the step three is more than 99.95%; the mass of the amorphous cracked carbon particles in the mixed suspension is 15-18% of the mass of the ammonium metatungstate. The mass content of the amorphous cracked carbon is determined according to the effective mass of W atoms in a tungsten source, namely ammonium metatungstate, and the tungstic acid is reduced by hydrogen to generate WO 2 And the following chemical reactions all involve amorphous cracked carbon, and the following reactions are satisfied: WO 2 +3C = WC +2CO, so that three parts of carbon atoms need to be consumed by one part of W atoms, and according to theoretical calculation and actual experiment results, the mass content of amorphous cracking carbon is determined to be 15% -18% of the addition amount of ammonium metatungstate, and when the content of amorphous cracking carbon is too low, the reaction is incomplete, and WC cannot be completely generated; when the content is too high, too much free carbon exists in the produced WC, and the subsequent WC-Co hard property is seriously influencedSintering of the alloy is an impurity that must be removed.
The preparation method of the high-dispersion particle size controllable nano tungsten carbide powder is characterized in that the heating and stirring temperature in the fourth step is not lower than 50 ℃, and the stirring speed is not lower than 100rpm; the organic acid is oxalic acid solution or succinic acid solution, and the adding amount of the organic acid is 5-10% of the mass of the ammonium metatungstate in the mixed suspension in the step three. The inorganic acid is hydrochloric acid solution, sulfuric acid solution or nitric acid solution, and the addition amount of the inorganic acid is 2-10% of the mass of the ammonium metatungstate in the mixed suspension in the step three. The invention accelerates the reaction process by heating and stirring, ensures that tungstic acid can be rapidly deposited on the surface of amorphous cracking carbon particles, improves the production efficiency, ensures that the acid precipitation reaction is smoothly carried out by controlling the components and the adding amount of organic acid or inorganic acid, ensures that the adding amount of acid solution is calculated according to the theory of an actual reaction equation and determined by an actual experiment, cannot enable ammonium metatungstate to be completely reacted to generate tungstic acid when the content is too low, has violent acid precipitation reaction when the content is too high, is difficult to control the appearance of a product, has excessive acid, introduces a new carbon source and influences the subsequent carbonization process.
The preparation method of the high-dispersion particle size controllable nano tungsten carbide powder is characterized in that the temperature of the vacuum drying treatment in the fifth step is not lower than 60 ℃. The invention can control the temperature of vacuum drying treatment to dry while ensuring that the product is not damaged.
The preparation method of the high-dispersion particle size controllable nano tungsten carbide powder is characterized in that the volume content of hydrogen in the atmosphere containing hydrogen in the sixth step is not less than 10%, and the balance is inert gas; the time of the heating treatment is 0.5h to 4h, and the heating rate is not lower than 5 ℃/min; the stirring speed of the ultra-high speed stirring is not lower than 5000rpm, and the stirring time is not lower than 15s. The hydrogen gas mixture is adopted in the atmosphere of the invention, so that the CVT process in the process of accelerating the hydrogen tungstate reduction by pure hydrogen is avoided, the excessive reaction is prevented, and the WO is effectively controlled 2 The particle size and the morphology are controlled by controlling the time of the heating treatment and the temperature rising speed so as to ensure that the WO is mixed with the crystal 2 Morphology and particle size ofThe tungstic acid is controlled within a certain range, the treatment time is too short, and the tungstic acid cannot be completely converted into WO 2 (ii) a The processing time is too long, the actual production efficiency is influenced, and the resource waste is caused. The heating speed is too slow, which affects the production efficiency; the temperature rise speed is too high, the reaction is violent, the material spraying phenomenon is easy to cause, and the expected reaction can not be finished.
The preparation method of the high-dispersion particle size controllable nano tungsten carbide powder is characterized in that the atmosphere of the primary heat treatment and the atmosphere of the secondary heat treatment in the seventh step are vacuum atmosphere or hydrogen atmosphere; the time of the primary heat treatment and the time of the secondary heat treatment are both 0.5h to 5h, and the heating rate is not lower than 5 ℃/min; the apparent density of the nano tungsten carbide powder is less than 0.5g/cm 3 The porosity is greater than 95%. The invention controls the time and temperature rise rate of heating treatment to control W and W 2 The morphology and granularity of C and WC are too short, and a target product cannot be obtained; the processing time is too long, the actual production efficiency is influenced, and the resource waste is caused. The temperature rising speed is too slow, so that the preparation efficiency is influenced; the temperature rise speed is too fast, the reaction is violent, the material spraying phenomenon is easy to cause or excessive reaction occurs, and the required product cannot be obtained.
Compared with the prior art, the invention has the following advantages:
1. the invention adopts the pretreated amorphous cracked carbon particles with high activity and good dispersibility as the carbon source for preparing WC and WO 3 The reducing agent in the reduction process can effectively reduce the preparation temperature of the nano WC powder, inhibit the WC powder from growing and has a loose structure, so that the tungsten source can permeate on the surface of the nano WC powder, the dispersion uniformity among raw materials is improved, and the nano WC powder with uniform particle size distribution is prepared.
2. The invention takes the pretreated amorphous cracked carbon particles with good dispersibility as WO in the reduction process 2 Nucleating agents of, in situ inhibition of WO 2 The powder is agglomerated, and the CVT growth phenomenon in the hydrogen reduction process is avoided, so that the subsequent agglomeration growth of the W powder and the WC powder is prevented, and the particle size of the nanometer WC powder is effectively controlled.
3. The method deposits the tungstic acid on the amorphous cracked carbon particles in situ, so that the carbon source and the tungsten source are uniformly mixed at a nanometer level, the problems of nonuniform mixing and impurity introduction in the traditional ball milling mode are solved, and the method is convenient to operate, low in cost and easy for engineering application.
4. The invention prepares the nano tungsten carbide powder with the average grain diameter of 100nm to 300nm step by regulating the mixing uniformity of reaction raw materials and the nucleation growth process of products in the reduction and carbonization processes, and has the advantages of low cost, low energy consumption, short reaction time and higher industrial application prospect.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is an SEM image of the highly dispersed core-shell structured composite powder of tungsten carbide, tungsten and amorphous cracked carbon nanoparticles prepared in example 1 of the present invention.
FIG. 2 is an SEM image of the nano tungsten carbide powder prepared in example 1 of the present invention.
Fig. 3 is an XRD spectrum of the nano tungsten carbide powder prepared in example 1 of the present invention.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, adjusting the activity, defects, granularity and dispersity of amorphous cracked carbon to obtain amorphous cracked carbon particles; the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase organic carbon source, has an amorphous structure and a specific surface area of more than 150cm 2 (ii)/g; the mode of adjusting the activity, the defects, the granularity and the dispersity is ultrasonic treatment; the ultrasonic treatment process comprises the following steps: putting 4g of amorphous cracked carbon nano-particles into 300ml of deionized water, carrying out ultrasonic treatment for 6 hours, and then carrying out suction filtration and drying;
step two, mixing 3g of the amorphous cracked carbon particles obtained in the step one, 0.2g of a dispersing agent and 300mL of water to obtain uniformly dispersed amorphous cracked carbon suspension; the dispersant is polyvinylpyrrolidone, and the addition amount of the dispersant is 0.5-1% of the mass of the ammonium metatungstate in the mixed suspension in the step III;
step three, adding 20g of ammonium metatungstate into the amorphous cracked carbon suspension obtained in the step two while stirring to obtain mixed suspension containing ammonium metatungstate and amorphous cracked carbon; the mass purity of the ammonium metatungstate is more than 99.95 percent;
step four, heating and stirring the mixed suspension obtained in the step three, and adding 2g of organic acid into the mixed suspension to obtain an amorphous cracked carbon suspension deposited and coated with tungstic acid; the heating and stirring temperature is 70 ℃, and the stirring speed is 600rpm; the organic acid is oxalic acid solution;
step five, carrying out vacuum drying treatment on the amorphous cracked carbon suspension deposited and coated with the tungstic acid obtained in the step four to obtain nano-mixed tungstic acid-coated amorphous cracked carbon composite powder; the temperature of the vacuum drying treatment is 80 ℃;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-grade mixed tungsten dioxide/amorphous cracked carbon composite powder, and then stirring at an ultrahigh speed to obtain a nano-grade mixed product; the temperature of the heating treatment is 550 ℃; the volume content of hydrogen in the hydrogen-containing atmosphere is 90%, and the balance is argon; the time of the heating treatment is 2h, and the heating rate is 10 ℃/min; the stirring speed of the ultrahigh-speed stirring is 10000rpm, and the stirring time is 60s;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracked carbon nano-particle composite powder with a high-dispersion core-shell structure, and then carrying out secondary heat treatment to obtain nano tungsten carbide powder; the temperature of the primary heat treatment is 900 ℃, and the temperature of the secondary heat treatment is 1100 ℃; the atmosphere of the primary heat treatment and the secondary heat treatment is a vacuum atmosphere; the time of the primary heat treatment and the time of the secondary heat treatment are both 2h, and the heating rate is both 10 ℃/min.
Through detection, the apparent density of the nano tungsten carbide powder prepared in the embodiment is 0.4g/cm 3 The porosity was 96%, and the average particle diameter was 150nm.
FIG. 1 is an SEM image of a composite powder of tungsten carbide, tungsten and amorphous cracked carbon nanoparticles with a highly dispersed core-shell structure prepared in this example, and as can be seen from FIG. 1, W particles and amorphous cracked carbon nanoparticles in the composite powderThe type cracking carbon nano particles are uniformly distributed in W 2 C. And providing conditions for preparing nano WC powder by further secondary carbonization around WC.
Fig. 2 is an SEM image of the nano tungsten carbide powder prepared in this example, and it can be seen from fig. 2 that the nano tungsten carbide powder has a small particle size, an average particle size of about 150nm, and a certain porosity.
FIG. 3 is the XRD pattern of the nano-tungsten carbide powder prepared in this example, and it can be seen from FIG. 3 that the diffraction peaks in the XRD pattern are diffraction peaks of WC, the powder is tungsten carbide powder, and there is no W which is not completely reacted 2 C。
Example 2
The embodiment comprises the following steps:
step one, adjusting the activity, the defects, the granularity and the dispersity of the amorphous cracked carbon to obtain amorphous cracked carbon particles; the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase organic carbon source, is of an amorphous structure, and has a specific surface area of more than 150cm 2 (ii)/g; the mode of adjusting the activity, the defects, the granularity and the dispersity is plasma treatment;
step two, mixing 3.2g of the amorphous cracked carbon particles obtained in the step one, 0.16g of a dispersing agent and 300mL of water to obtain an amorphous cracked carbon suspension which is uniformly dispersed; the dispersing agent is polyethylene glycol;
step three, adding 20g of ammonium metatungstate into the amorphous cracked carbon suspension obtained in the step two while stirring to obtain mixed suspension containing ammonium metatungstate and amorphous cracked carbon; the mass purity of the ammonium metatungstate is more than 99.95 percent;
step four, heating and stirring the mixed suspension obtained in the step three, and adding 1.8g of organic acid into the mixed suspension to obtain an amorphous cracked carbon suspension deposited and coated with tungstic acid; the heating and stirring temperature is 90 ℃, and the stirring speed is 500rpm; the organic acid is oxalic acid solution;
step five, carrying out vacuum drying treatment on the amorphous cracked carbon suspension deposited and coated with the tungstic acid obtained in the step four to obtain nano-mixed tungstic acid-coated amorphous cracked carbon composite powder; the temperature of the vacuum drying treatment is 70 ℃;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-grade mixed tungsten dioxide/amorphous cracked carbon composite powder, and then stirring at an ultrahigh speed to obtain a nano-grade mixed product; the temperature of the heating treatment is 500 ℃; the volume content of hydrogen in the hydrogen-containing atmosphere is 70%, and the balance is argon; the heating treatment time is 1h, and the heating rate is 5 ℃/min; the stirring speed of the ultra-high speed stirring is 15000rpm, and the stirring time is 30s;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracked carbon nano-particle composite powder with a high-dispersion core-shell structure, and then carrying out secondary heat treatment to obtain nano tungsten carbide powder; the temperature of the primary heat treatment is 870 ℃, and the temperature of the secondary heat treatment is 1150 ℃; the atmosphere of the primary heat treatment and the secondary heat treatment is a vacuum atmosphere; the time of the primary heat treatment and the time of the secondary heat treatment are both 0.5h, and the heating rate is both 8 ℃/min.
Through detection, the apparent density of the nano tungsten carbide powder prepared in the embodiment is 0.4g/cm 3 The porosity was 97%, and the average particle diameter was 100nm.
Example 3
The embodiment comprises the following steps:
step one, adjusting the activity, the defects, the granularity and the dispersity of the amorphous cracked carbon to obtain amorphous cracked carbon particles; the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase organic carbon source, is of an amorphous structure, and has a specific surface area of more than 150cm 2 (iv) g; the mode of regulating the activity, the defects, the granularity and the dispersity is rubbing treatment;
step two, mixing 3.4g of the amorphous cracked carbon particles obtained in the step one, 0.14g of a dispersing agent and 300mL of water to obtain an amorphous cracked carbon suspension which is uniformly dispersed; the dispersing agent is polyvinyl alcohol;
step three, adding 20g of ammonium metatungstate into the amorphous cracked carbon suspension obtained in the step two while stirring to obtain mixed suspension containing ammonium metatungstate and amorphous cracked carbon; the mass purity of the ammonium metatungstate is more than 99.95 percent;
step four, heating and stirring the mixed suspension obtained in the step three, and adding 1.4g of organic acid into the mixed suspension to obtain an amorphous cracked carbon suspension deposited and coated with tungstic acid; the heating and stirring temperature is 80 ℃, and the stirring speed is 100rpm; the organic acid is succinic acid solution;
step five, carrying out vacuum drying treatment on the amorphous cracked carbon suspension deposited and coated with the tungstic acid obtained in the step four to obtain nano-mixed tungstic acid-coated amorphous cracked carbon composite powder; the temperature of the vacuum drying treatment is 60 ℃;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-grade mixed tungsten dioxide/amorphous cracked carbon composite powder, and then stirring at an ultrahigh speed to obtain a nano-grade mixed product; the temperature of the heating treatment is 600 ℃; the volume content of hydrogen in the hydrogen-containing atmosphere is 50%, and the balance is argon; the heating treatment time is 0.5h, and the heating rate is 7 ℃/min; the stirring speed of the ultra-high speed stirring is 5000rpm, and the stirring time is 180s;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracked carbon nano-particle composite powder with a high-dispersion core-shell structure, and then carrying out secondary heat treatment to obtain nano tungsten carbide powder; the temperature of the primary heat treatment is 930 ℃, and the temperature of the secondary heat treatment is 1100 ℃; the atmosphere of the primary heat treatment and the secondary heat treatment is a vacuum atmosphere; the time of the primary heat treatment and the time of the secondary heat treatment are both 3h, and the heating rate is both 5 ℃/min.
Through detection, the apparent density of the nano tungsten carbide powder prepared by the embodiment is 0.4g/cm 3 The porosity was 96%, and the average particle diameter was 300nm.
Example 4
The embodiment comprises the following steps:
step one, adjusting the activity, the defects, the granularity and the dispersity of the amorphous cracked carbon to obtain amorphous cracked carbon particles; said amorphous crackingThe carbon is generated by cracking a gas-phase or solid-phase organic carbon source, has an amorphous structure and a specific surface area of more than 150cm 2 (ii)/g; the mode of adjusting the activity, the defects, the granularity and the dispersity is ultrasonic treatment;
step two, mixing 3.6g of the amorphous cracked carbon particles obtained in the step one, 0.1g of a dispersing agent and 300mL of water to obtain uniformly dispersed amorphous cracked carbon suspension; the dispersing agent is polyethylene glycol and polyvinylpyrrolidone;
step three, adding 20g of ammonium metatungstate into the amorphous cracked carbon suspension obtained in the step two while stirring to obtain mixed suspension containing ammonium metatungstate and amorphous cracked carbon; the mass purity of the ammonium metatungstate is more than 99.95 percent;
step four, heating and stirring the mixed suspension obtained in the step three, and adding 1g of organic acid into the mixed suspension to obtain an amorphous cracked carbon suspension deposited and coated with tungstic acid; the heating and stirring temperature is 50 ℃, and the stirring speed is 550rpm; the organic acid is succinic acid solution;
step five, carrying out vacuum drying treatment on the amorphous cracked carbon suspension deposited and coated with the tungstic acid obtained in the step four to obtain nano-mixed tungstic acid coated amorphous cracked carbon composite powder; the temperature of the vacuum drying treatment is 80 ℃;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-grade mixed tungsten dioxide/amorphous cracked carbon composite powder, and then stirring at a super high speed to obtain a nano-grade mixed product; the temperature of the heating treatment is 650 ℃; the volume content of hydrogen in the hydrogen-containing atmosphere is 10%, and the balance is argon; the heating treatment time is 1.5h, and the heating rate is 8 ℃/min; the stirring speed of the ultra-high speed stirring is 20000rpm, and the stirring time is 15s;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracked carbon nano-particle composite powder with a high-dispersion core-shell structure, and then carrying out secondary heat treatment to obtain nano tungsten carbide powder; the temperature of the primary heat treatment is 850 ℃, and the temperature of the secondary heat treatment is 950 ℃; the atmosphere of the primary heat treatment and the atmosphere of the secondary heat treatment are a vacuum atmosphere and a hydrogen atmosphere; the time of the primary heat treatment and the time of the secondary heat treatment are both 1h, and the heating rate is both 8 ℃/min.
Through detection, the apparent density of the nano tungsten carbide powder prepared in the embodiment is 0.4g/cm 3 The porosity was 96%, and the average particle diameter was 200nm.
Example 5
The embodiment comprises the following steps:
step one, adjusting the activity, defects, granularity and dispersity of amorphous cracked carbon to obtain amorphous cracked carbon particles; the amorphous cracked carbon is generated by cracking a gas-phase or solid-phase organic carbon source, has an amorphous structure and a specific surface area of more than 150cm 2 (ii)/g; the activity, defect, granularity and dispersity are adjusted by friction treatment;
step two, mixing 3.4g of the amorphous cracked carbon particles obtained in the step one, 0.14g of a dispersing agent and 300mL of water to obtain uniformly dispersed amorphous cracked carbon suspension; the dispersing agent is polyvinyl alcohol;
step three, adding 20g of ammonium metatungstate into the amorphous cracked carbon suspension obtained in the step two while stirring to obtain mixed suspension containing ammonium metatungstate and amorphous cracked carbon; the mass purity of the ammonium metatungstate is more than 99.95 percent;
step four, heating and stirring the mixed suspension obtained in the step three, and adding 0.6g of inorganic acid into the mixed suspension to obtain an amorphous cracked carbon suspension deposited and coated with tungstic acid; the heating and stirring temperature is 70 ℃, and the stirring speed is 150rpm; the inorganic acid is hydrochloric acid solution;
step five, carrying out vacuum drying treatment on the amorphous cracked carbon suspension deposited and coated with the tungstic acid obtained in the step four to obtain nano-mixed tungstic acid-coated amorphous cracked carbon composite powder; the temperature of the vacuum drying treatment is 60 ℃;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-grade mixed tungsten dioxide/amorphous cracked carbon composite powder, and then stirring at an ultrahigh speed to obtain a nano-grade mixed product; the temperature of the heating treatment is 600 ℃; the volume content of hydrogen in the hydrogen-containing atmosphere is 50%, and the balance is argon; the time of the heating treatment is 0.5h, and the heating rate is 5 ℃/min; the stirring speed of the ultra-high speed stirring is 5000rpm, and the stirring time is 180s;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracked carbon nano-particle composite powder with a high-dispersion core-shell structure, and then carrying out secondary heat treatment to obtain nano tungsten carbide powder; the temperature of the primary heat treatment is 930 ℃, and the temperature of the secondary heat treatment is 1100 ℃; the atmosphere of the primary heat treatment and the atmosphere of the secondary heat treatment are a vacuum atmosphere and a hydrogen atmosphere; the time of the primary heat treatment and the time of the secondary heat treatment are both 3h, and the heating rate is both 5 ℃/min.
Through detection, the apparent density of the nano tungsten carbide powder prepared in the embodiment is 0.4g/cm 3 The porosity was 96%, and the average particle diameter was 300nm.
Example 6
This embodiment is different from embodiment 5 in that: heating and stirring the mixed suspension obtained in the third step, and adding 0.4g of inorganic acid into the mixed suspension to obtain an amorphous cracked carbon suspension deposited and coated with tungstic acid; the heating and stirring temperature is 70 ℃, and the stirring speed is 150rpm; the inorganic acid is sulfuric acid solution.
Example 7
This embodiment is different from embodiment 5 in that: heating and stirring the mixed suspension obtained in the third step, and adding 4g of inorganic acid into the mixed suspension to obtain an amorphous cracked carbon suspension deposited and coated with tungstic acid; the heating and stirring temperature is 70 ℃, and the stirring speed is 150rpm; the inorganic acid is a nitric acid solution.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modifications, alterations and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (9)
1. A preparation method of high-dispersion particle size controllable nano tungsten carbide powder is characterized by comprising the following steps:
step one, adjusting the activity, the defects, the granularity and the dispersity of the amorphous cracked carbon to obtain amorphous cracked carbon particles;
step two, mixing the amorphous cracked carbon particles obtained in the step one, a dispersing agent and water to obtain an amorphous cracked carbon suspension which is uniformly dispersed;
step three, adding ammonium metatungstate into the amorphous cracked carbon suspension obtained in the step two while stirring to obtain mixed suspension containing ammonium metatungstate and amorphous cracked carbon;
step four, heating and stirring the mixed suspension obtained in the step three, and adding organic acid or inorganic acid into the mixed suspension to obtain amorphous cracked carbon suspension deposited and coated with tungstic acid;
step five, carrying out vacuum drying treatment on the amorphous cracked carbon suspension deposited and coated with the tungstic acid obtained in the step four to obtain nano-mixed tungstic acid-coated amorphous cracked carbon composite powder;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-grade mixed tungsten dioxide/amorphous cracked carbon composite powder, and then stirring at a super high speed to obtain a nano-grade mixed product; the temperature of the heating treatment is 500-650 ℃;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracked carbon nano-particle composite powder with a high-dispersion core-shell structure, and then carrying out secondary heat treatment to obtain nano tungsten carbide powder; the temperature of the primary heat treatment is 850-930 ℃, and the temperature of the secondary heat treatment is 950-1300 ℃.
2. The method for preparing nano tungsten carbide powder with controllable high dispersion particle size as claimed in claim 1, wherein the amorphous cracked carbon is generated by cracking a gas phase or solid phase organic carbon source and has an amorphous structure in step oneSpecific surface area of more than 150cm 2 (ii)/g; the mode of adjusting the activity, the defects, the granularity and the dispersity is ultrasonic treatment, plasma treatment or friction treatment.
3. The method for preparing high-dispersion particle size controllable nano tungsten carbide powder according to claim 1, wherein the dispersant in the second step is one or more of polyethylene glycol, polyvinylpyrrolidone and polyvinyl alcohol, and the addition amount of the dispersant is 0.5-1% of the mass of ammonium metatungstate in the mixed suspension in the third step.
4. The method for preparing the nano tungsten carbide powder with the controllable high dispersion particle size according to claim 1, wherein the mass purity of the ammonium metatungstate in the third step is more than 99.95%; the mass of the amorphous cracked carbon particles in the mixed suspension is 15-18% of the mass of the ammonium metatungstate.
5. The method for preparing nano tungsten carbide powder with controllable high dispersion particle size according to claim 1, wherein the temperature of heating and stirring in the fourth step is not lower than 50 ℃, and the stirring speed is not lower than 100rpm; the organic acid is oxalic acid solution or succinic acid solution, and the addition amount of the organic acid is 5-10% of the mass of the ammonium metatungstate in the mixed suspension in the step three.
6. The inorganic acid is hydrochloric acid solution, sulfuric acid solution or nitric acid solution, and the addition amount of the inorganic acid is 2-10% of the mass of the ammonium metatungstate in the mixed suspension in the step three.
7. The method for preparing nano tungsten carbide powder with controllable high dispersion particle size according to claim 1, wherein the temperature of the vacuum drying treatment in the fifth step is not lower than 60 ℃.
8. The method for preparing nano tungsten carbide powder with controllable high dispersion particle size according to claim 1, wherein the volume content of hydrogen in the atmosphere containing hydrogen in the sixth step is not less than 10%, and the balance is inert gas; the heating treatment time is 0.5h to 4h, and the heating rate is not lower than 5 ℃/min; the stirring speed of the ultra-high speed stirring is not lower than 5000rpm, and the stirring time is not lower than 15s.
9. The method for preparing high dispersion particle size controllable nano tungsten carbide powder according to claim 1, wherein the atmosphere of the primary heat treatment and the secondary heat treatment in the seventh step is vacuum atmosphere or hydrogen atmosphere; the time of the primary heat treatment and the time of the secondary heat treatment are both 0.5h to 5h, and the heating rate is not lower than 5 ℃/min; the loose packed density of the nano tungsten carbide powder is less than 0.5g/cm 3 The porosity is greater than 95%.
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