CN115321537B - 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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- 239000000843 powder Substances 0.000 title claims abstract description 118
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002245 particle Substances 0.000 title claims abstract description 57
- 239000006185 dispersion Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 126
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 121
- 238000005336 cracking Methods 0.000 claims abstract description 111
- 239000000725 suspension Substances 0.000 claims abstract description 68
- 238000003756 stirring Methods 0.000 claims abstract description 58
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 33
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000007524 organic acids Chemical class 0.000 claims abstract description 16
- 238000001291 vacuum drying Methods 0.000 claims abstract description 16
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 27
- 230000000694 effects Effects 0.000 claims description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 21
- 239000010937 tungsten Substances 0.000 claims description 21
- 230000007547 defect Effects 0.000 claims description 18
- 239000011852 carbon nanoparticle Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000011258 core-shell material Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 239000007790 solid phase Substances 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000009832 plasma treatment Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 8
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000002114 nanocomposite Substances 0.000 abstract description 3
- 239000002667 nucleating agent Substances 0.000 abstract description 3
- 230000033228 biological regulation Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- 238000006722 reduction reaction Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000000956 alloy Substances 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 8
- 229910009043 WC-Co Inorganic materials 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003916 acid precipitation Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 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
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000009656 pre-carbonization Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method of high-dispersion particle size controllable nano tungsten carbide powder, which comprises the following steps: 1. adjusting 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 organic acid or inorganic acid; 5. carrying out vacuum drying treatment on the suspension; 6. heating the composite powder, and stirring at an ultra-high speed; 7. and carrying out primary heat treatment and secondary heat treatment on the product to obtain the nano tungsten carbide powder. According to the invention, amorphous cracking carbon particles are used as a nucleating agent, tungstic acid is deposited through an acid adding precipitation process, tungsten dioxide/amorphous cracking carbon nano composite powder is obtained through low-temperature hydrogen reduction, and then nano tungsten carbide powder is obtained through a two-step carbonization method, so that the problems of uneven particle size distribution, poor dispersibility and difficult regulation and control of the particle size of the nano tungsten carbide in the preparation process of the nano tungsten carbide are solved.
Description
Technical Field
The invention belongs to the technical field of nano powder material preparation, and particularly relates to a preparation method of nano tungsten carbide powder with controllable high dispersion granularity.
Background
The superfine/nanocrystalline tungsten carbide-cobalt (WC-Co) hard alloy has higher hardness, wear resistance, strength and toughness, is rapidly and widely focused after appearance and becomes a research hot spot, has become the development trend of the hard alloy in the future, 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 processing and the like. However, nano WC-Co cemented carbide production has been limited by the inability to obtain large quantities of high quality nano tungsten carbide (WC) powder.
At present, the nano WC powder is industrially produced mainly by reducing 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 the mixture, or directly preparing tungsten oxide and carbon powder into microspheres with certain particle size and carbonizing the microspheres at a continuous high temperature. Wherein the WC prepared by hydrogen reduction is not sufficiently fine in particle size. This is due to hydrogen reduction of WO 3 When a Chemical Vapor Transport (CVT) process is present, the resulting intermediate product (WO 2 (OH) 2 ) The W powder is promoted to gather and grow up, so that the WC powder granularity is increased in the carbonization process, the finally obtained WC-Co hard alloy has coarse grains, the performance is reduced, and the effect of fine grain strengthening cannot be achieved. Whereas WC particles produced by conventional continuous carbon reduction are not uniformly distributed due to WO 3 And carbon powder can not be uniformly distributed and tightly combined everywhere during mechanical mixing, so that the prepared WC powder has wide particle size distribution. The large-particle WC powder and the small-particle WC powder are aggregated and grown in the preparation process of the hard alloy, so that abnormal grown WC grains appear in the WC-Co hard alloy, thereby causing the comprehensive performance of the alloy to decline and increasing the accident risk.
In conclusion, some difficulties still exist in industrially producing nano WC powder with good dispersibility, uniform and controllable particle size dispersion.
Therefore, a method for efficiently preparing the nano WC powder with controllable high dispersion granularity is needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of nano tungsten carbide powder with controllable high dispersion granularity aiming at the defects of the prior art. According to the method, amorphous cracking carbon particles are used as a nucleating agent, tungstic acid is deposited on the amorphous cracking carbon particles precisely through an acid adding precipitation process, a core-shell structure of tungsten acid coated amorphous cracking carbon is formed, the dispersion and combination degree of amorphous cracking carbon nano particles and tungsten sources is effectively improved, tungsten dioxide/amorphous cracking carbon nano composite powder is obtained through low-temperature hydrogen reduction, the tungsten dioxide/amorphous cracking carbon nano composite powder inherits the distribution and combination modes of the tungstic acid and the amorphous cracking carbon, then nano tungsten carbide powder is obtained through a two-step carbonization method, chemical vapor transport growth in an intermediate reaction process is inhibited, and the problems of uneven distribution, poor dispersibility and difficult regulation of particle size of nano tungsten carbide in the preparation process of nano tungsten carbide are solved.
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the nano tungsten carbide powder with controllable high dispersion granularity is characterized by comprising the following steps of:
step one, adjusting the activity, the defect, the granularity and the dispersity of the amorphous cracking carbon to obtain amorphous cracking carbon particles;
step two, mixing the amorphous cracking carbon particles obtained in the step one, a dispersing agent and water to obtain an amorphous cracking carbon suspension with uniform dispersion;
step three, adding ammonium metatungstate into the amorphous cracking carbon suspension obtained in the step two while stirring to obtain a mixed suspension containing the ammonium metatungstate and the amorphous cracking 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 an amorphous cracked carbon suspension for depositing and coating tungstic acid;
step five, carrying out vacuum drying treatment on the amorphous cracking carbon suspension of the deposited coated tungstic acid obtained in the step four to obtain nano-scale mixed tungstic acid coated amorphous cracking carbon composite powder;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-scale mixed tungsten dioxide/amorphous cracking carbon composite powder, and then stirring at an ultra-high speed to obtain a nano-scale 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 cracking 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, the defect, the granularity and the dispersibility of the amorphous cracking carbon are regulated, so that the reactivity in the raw material reaction process is improved, the free energy of reaction Gibbs is reduced in thermodynamics, the reaction temperature is reduced, the abnormal growth of WC powder particle diameter at a higher temperature is avoided, and the nano WC powder is more easily obtained in a large scale;
according to the invention, the acid precipitation reaction is realized by reacting ammonium metatungstate with acid to generate tungstic acid, the generated tungstic acid is a 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 the carbon source in a nanoscale, so that the problems of nonuniform mixing and impurity introduction in the traditional ball milling mode are avoided, and nano WC with higher purity can be generated;
the invention carries out reduction by heating composite powder obtained by acid precipitation reaction in hydrogen-containing atmosphere, and 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 there is WO which is not completely reacted 3 When a subsequent heat treatment is carried out, i.e. during the first carbonization step, WO is experienced 2.72 →WO 2 Topology transformation Process of W, WO 2.72 The nano W powder is in a micron-sized rod-shaped structure, and one-stage carbonization is carried out on the rod-shaped structure, so that a large amount of aggregation phenomenon can occur on the finally generated nano W powder, the nano W powder is densely distributed along the rod-shaped structure, and the W powder is sintered and the WC powder is abnormally grown when the nano W powder is subjected to subsequent high-temperature secondary heat treatment, namely, two-stage carbonization; when the temperature is higher than 650 ℃, the abnormal growth of W powder exists due to the aggravation of the chemical vapor transmission process,also, during the subsequent carbonization process, WC powder with abnormal growth is produced, so that the hydrogen reduction temperature is controlled at 500-650 ℃ to obtain WO without other impurity phases 2 The generation of abnormally long W powder in the subsequent primary carbonization process is avoided, and the particle size of WC in the secondary 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 preparing the WO 2 Reduction to W and further formation of W on the W surface 2 C pre-carbonizing layer to block the aggregation growth of W powder in space and avoid subsequent high temperature carbonization to produce WC powder with abnormal growth, and the second stage carbonization is W, W 2 C is further carbonized to completely generate WC, and as the aggregation and growth of nano powder can be promoted by high temperature, the problem of overlarge WC particle size caused by direct high-temperature carbonization can be avoided by adopting a two-stage heating carbonization mode, and the W with uniform distribution can be formed by the first stage temperature of 850-930 DEG C 2 C pre-carbonization layer, too low temperature, can not form W effectively 2 A layer C; too high a temperature W 2 C is converted into WC, the subsequent carbonization can lead the particle size of the WC to reach the micron level, and the temperature of the second stage is 950 ℃ to 1300 ℃ to ensure W 2 The C and W powder are completely converted into WC, and the temperature is too low to be completely converted into pure-phase WC; the temperature is too high, the generated WC powder can generate aggregation growth, and abnormal grown WC is generated; the invention uses super-high speed stirring to break powder agglomeration and increase powder porosity.
The preparation method of the nano tungsten carbide powder with controllable high dispersion granularity is characterized in that the amorphous cracking carbon in the first step 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 /g; the manner of the adjustment of the activity, the defect, the granularity and the dispersivity is ultrasonic treatment, plasma treatment or friction treatment. The invention obtains amorphous cracking carbon particles with high defect, high reaction activity, fine granularity and high dispersibility by adopting amorphous cracking carbon generated by gas phase or solid phase carbon source cracking and adjusting the activity, defect, granularity and dispersibility, and the treated carbon has the advantages of nuclear formation, granularity and uniformity adjustment and controlThe method has the very remarkable advantage that the reaction temperature and the reaction time can be remarkably reduced.
The preparation method of the nano tungsten carbide powder with controllable granularity is characterized in that the dispersing agent in the second step is one or more than two 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 in the third step. According to the invention, the addition amount of the dispersing agent is controlled, so that the amorphous cracking carbon nano particles are uniformly dispersed, and when the content of the dispersing agent is too low, partial agglomeration of the amorphous cracking carbon particles can occur, so that the effect of uniform dispersion cannot be achieved; when the content is too high, the viscosity of the solution becomes high, the fluidity becomes poor, the effect of uniform dispersion cannot be achieved, and when the addition amount of the dispersing agent is controlled to be 0.5% -1% of the mass of the ammonium metatungstate, amorphous cracking carbon particles can be uniformly distributed in the solution and form stable suspension without layering for a long time.
The preparation method of the nano tungsten carbide powder with the controllable high dispersion granularity is characterized in that the mass purity of the ammonium metatungstate in the third step is more than 99.95%; the mass of the amorphous cracking carbon particles in the mixed suspension is 15% -18% of the mass of the ammonium metatungstate. The mass content of the amorphous cracking carbon is determined according to the effective mass of W atoms in tungsten source, namely ammonium metatungstate, firstly, tungsten acid is reduced by hydrogen to generate WO 2 The following chemical reactions all have amorphous cracking carbon to participate, and the following reactions are satisfied: WO (WO) 2 +3c=wc+2co, so that one part of W atom needs to consume three parts of carbon atoms, and according to theoretical calculation and actual experimental results, it is determined that the mass content of amorphous cracking carbon is 15% -18% of the addition amount of ammonium meta-tungstate, and when the amorphous cracking carbon content is too small, the reaction is incomplete, and WC cannot be completely generated; when the content is too high, excessive free carbon exists in the generated WC, so that the subsequent sintering of WC-Co hard alloy is seriously affected, and the WC-Co hard alloy is an impurity which needs to be removed.
The preparation method of the nano tungsten carbide powder with the controllable high dispersion granularity is characterized in that 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 adding amount of the organic acid is 5% -10% of the mass of the ammonium metatungstate in the mixed suspension in the third step. The inorganic acid is hydrochloric acid solution, sulfuric acid solution or nitric acid solution, and the adding amount of the inorganic acid is 2% -10% of the mass of the ammonium metatungstate in the mixed suspension in the third step. According to the invention, the reaction process is accelerated by heating and stirring, so that the tungstic acid can be rapidly deposited on the surface of amorphous cracking carbon particles, the production efficiency is improved, the acid precipitation reaction is ensured to be smoothly carried out by controlling the components and the addition amount of organic acid or inorganic acid, the addition amount of an acid solution is determined according to the theoretical calculation of an actual reaction equation and the actual experiment, the ammonium metatungstate cannot be completely reacted to generate the tungstic acid when the content is too small, the acid precipitation reaction is severe when the content is too high, the product morphology is not easy to control, and a new carbon source is introduced to influence the subsequent carbonization process.
The preparation method of the nano tungsten carbide powder with the controllable high dispersion granularity is characterized in that the temperature of the vacuum drying treatment in the fifth step is not lower than 60 ℃. The invention ensures that the product is not destroyed and simultaneously carries out drying by controlling the temperature of vacuum drying treatment.
The preparation method of the nano tungsten carbide powder with the controllable high dispersion granularity is characterized in that the volume content of hydrogen in the atmosphere containing hydrogen in the step six is not less than 10 percent, and the balance is inert gas; the heating treatment time is 0.5-4 hours, 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 atmosphere of the invention adopts the hydrogen mixed gas to avoid the CVT process in the process of accelerating the reduction of the hydrogen tungstate by pure hydrogen, prevent the excessive reaction, and effectively control WO 2 Particle size and morphology, by controlling the time and heating rate of the heating treatment, are used for the purpose of WO 2 The morphology and granularity of the tungsten are controlled within a certain range, the treatment time is too short, and the tungsten acid can not be completely converted into WO 2 The method comprises the steps of carrying out a first treatment on the surface of the The processing time is too long, the actual production efficiency is affected, and the resource waste is caused. The heating speed is too slow, and the production efficiency is affected; the temperature rising speed is too high, the reaction is severe, the spraying phenomenon is easy to cause, and the expected reaction can not be completed.
The preparation method of the nano tungsten carbide powder with the controllable high dispersion granularity is characterized in that the atmosphere of the primary heat treatment and the secondary heat treatment in the step seven is vacuum atmosphere or hydrogen atmosphere; the time of the primary heat treatment and the secondary heat treatment is 0.5-5 h, and the heating rate is not lower than 5 ℃/min; the bulk density of the nano tungsten carbide powder is less than 0.5g/cm 3 The porosity is more than 95%. The invention controls W, W by controlling the heating time and the heating rate 2 C and WC have the shape and granularity, the treatment time is too short, and a target product cannot be obtained; the processing time is too long, the actual production efficiency is affected, and the resource waste is caused. The heating speed is too slow, so that the preparation efficiency is affected; the temperature rising speed is too high, the reaction is severe, the material spraying phenomenon is easy to occur or the 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 pretreated amorphous cracking carbon particles with high activity and good dispersibility as a 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 growth of the WC powder, and the loose structure of the nano WC powder is beneficial to the penetration of a tungsten source on the surface of the nano WC powder, and increases the dispersion uniformity among raw materials to prepare the nano WC powder with uniform particle size distribution.
2. The invention takes pretreated amorphous cracking carbon particles with good dispersibility as WO in the reduction process 2 Is a nucleating agent which in situ hinders WO 2 Agglomeration of powder and CVT growth phenomenon in the hydrogen reduction process are avoided, so that subsequent aggregation growth of W powder and WC powder is prevented, and the particle size of nano WC powder is effectively controlled.
3. According to the invention, the tungsten acid is deposited on the amorphous cracking carbon particles in situ, so that the carbon source and the tungsten source are uniformly mixed in nano-scale, the problems of nonuniform mixing and impurity introduction in the traditional ball milling mode are avoided, the operation is convenient, the cost is low, and the engineering application is easy.
4. According to the invention, the nano tungsten carbide powder with the average particle diameter of 100-300 nm is prepared step by regulating and controlling the mixing uniformity of the reaction raw materials and the nucleation growth process of the product in the reduction and carbonization processes, so that the method has the advantages of low cost, low energy consumption, short reaction time and high industrial application prospect.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Drawings
Fig. 1 is an SEM image of a composite powder of tungsten carbide, tungsten and amorphous cracked carbon nano-particles of a high dispersion core-shell structure 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 pattern of 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, the defect, the granularity and the dispersity of the amorphous cracking carbon to obtain amorphous cracking carbon particles; the amorphous cracking carbon is generated by cracking a gas phase or solid phase organic carbon source and is of an amorphous structure, and the specific surface area is more than 150cm 2 /g; the mode of the activity, defect, granularity and dispersivity adjustment is ultrasonic treatment; the ultrasonic treatment process comprises the following steps: putting 4g of amorphous cracked carbon nano particles into 300ml of deionized water, performing ultrasonic treatment for 6 hours, and then performing suction filtration and drying;
step two, mixing 3g of the amorphous cracking carbon particles obtained in the step one, 0.2g of a dispersing agent and 300mL of water to obtain an amorphous cracking carbon suspension with uniform dispersion; the dispersing agent is polyvinylpyrrolidone, and the adding amount of the dispersing agent is 0.5% -1% of the mass of the ammonium metatungstate in the mixed suspension in the third step;
step three, adding 20g of ammonium metatungstate into the amorphous cracking carbon suspension obtained in the step two while stirring to obtain a mixed suspension containing the ammonium metatungstate and the amorphous cracking carbon; the mass purity of the ammonium metatungstate is more than 99.95%;
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 of deposited and coated tungstic acid; the temperature of the heating and stirring 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 cracking carbon suspension of the deposited coated tungstic acid obtained in the step four to obtain nano-scale mixed tungstic acid coated amorphous cracking 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-scale mixed tungsten dioxide/amorphous cracking carbon composite powder, and then stirring at an ultra-high speed to obtain a nano-scale mixed product; the temperature of the heating treatment is 550 ℃; the volume content of hydrogen in the atmosphere containing hydrogen is 90%, and the balance is argon; the heating treatment time is 2 hours, and the heating rate is 10 ℃/min; the stirring speed of the ultra-high 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 cracking 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 vacuum atmosphere; the time of the primary heat treatment and the secondary heat treatment is 2 hours, and the heating rate is 10 ℃/min.
According to detection, the bulk 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 highly dispersed core-shell structured tungsten carbide, tungsten and amorphous carbon nanoparticles, wherein the W particles and amorphous carbon nanoparticles are uniformly distributed in the W particles as can be seen from FIG. 1 2 C. Around WC, conditions are provided for preparing nano WC powder through further secondary carbonization.
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 shows XRD patterns of the nano tungsten carbide powder prepared in this example, and as can be seen from FIG. 3, the diffraction peaks in the patterns are those 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 defect, the granularity and the dispersity of the amorphous cracking carbon to obtain amorphous cracking carbon particles; the amorphous cracking carbon is generated by cracking a gas phase or solid phase organic carbon source and is of an amorphous structure, and the specific surface area is more than 150cm 2 /g; the mode of the activity, defect, granularity and dispersivity adjustment is plasma treatment;
step two, mixing 3.2g of the amorphous cracking carbon particles obtained in the step one, 0.16g of a dispersing agent and 300mL of water to obtain an amorphous cracking carbon suspension with uniform dispersion; the dispersing agent is polyethylene glycol;
step three, adding 20g of ammonium metatungstate into the amorphous cracking carbon suspension obtained in the step two while stirring to obtain a mixed suspension containing the ammonium metatungstate and the amorphous cracking carbon; the mass purity of the ammonium metatungstate is more than 99.95%;
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 for depositing and coating tungstic acid; the temperature of the heating and stirring 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 cracking carbon suspension of the deposited coated tungstic acid obtained in the step four to obtain nano-scale mixed tungstic acid coated amorphous cracking 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-scale mixed tungsten dioxide/amorphous cracking carbon composite powder, and then stirring at an ultra-high speed to obtain a nano-scale mixed product; the temperature of the heating treatment is 500 ℃; the volume content of hydrogen in the atmosphere containing hydrogen 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 cracking 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 vacuum atmosphere; the time of the primary heat treatment and the secondary heat treatment is 0.5h, and the heating rate is 8 ℃/min.
According to detection, the bulk 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 defect, the granularity and the dispersity of the amorphous cracking carbon to obtain amorphous cracking carbon particles; the amorphous cracking carbon is generated by cracking a gas phase or solid phase organic carbon source and is of an amorphous structure, and the specific surface area is more than 150cm 2 /g; the mode of the activity, defect, granularity and dispersivity adjustment is friction treatment;
step two, mixing 3.4g of the amorphous cracking carbon particles obtained in the step one, 0.14g of a dispersing agent and 300mL of water to obtain an amorphous cracking carbon suspension with uniform dispersion; the dispersing agent is polyvinyl alcohol;
step three, adding 20g of ammonium metatungstate into the amorphous cracking carbon suspension obtained in the step two while stirring to obtain a mixed suspension containing the ammonium metatungstate and the amorphous cracking carbon; the mass purity of the ammonium metatungstate is more than 99.95%;
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 for depositing and coating tungstic acid; the temperature of the heating and stirring 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 cracking carbon suspension of the deposited coated tungstic acid obtained in the step four to obtain nano-scale mixed tungstic acid coated amorphous cracking 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-scale mixed tungsten dioxide/amorphous cracking carbon composite powder, and then stirring at an ultra-high speed to obtain a nano-scale mixed product; the temperature of the heating treatment is 600 ℃; the volume content of hydrogen in the atmosphere containing hydrogen 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 cracking 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 vacuum atmosphere; the time of the primary heat treatment and the secondary heat treatment is 3 hours, and the heating rate is 5 ℃/min.
According to detection, the bulk 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 4
The embodiment comprises the following steps:
step one, adjusting the activity, the defect, the granularity and the dispersity of the amorphous cracking carbon to obtain amorphous cracking carbon particles; the amorphous cracking carbon is generated by cracking a gas phase or solid phase organic carbon source and is of an amorphous structure, and the specific surface area is more than 150cm 2 /g; the mode of the activity, defect, granularity and dispersivity adjustment is ultrasonic treatment;
step two, mixing 3.6g of the amorphous cracking carbon particles obtained in the step one, 0.1g of a dispersing agent and 300mL of water to obtain an amorphous cracking carbon suspension with uniform dispersion; the dispersing agent is polyethylene glycol and polyvinylpyrrolidone;
step three, adding 20g of ammonium metatungstate into the amorphous cracking carbon suspension obtained in the step two while stirring to obtain a mixed suspension containing the ammonium metatungstate and the amorphous cracking carbon; the mass purity of the ammonium metatungstate is more than 99.95%;
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 of deposited and coated tungstic acid; the temperature of the heating and stirring 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 cracking carbon suspension of the deposited coated tungstic acid obtained in the step four to obtain nano-scale mixed tungstic acid coated amorphous cracking 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-scale mixed tungsten dioxide/amorphous cracking carbon composite powder, and then stirring at an ultra-high speed to obtain a nano-scale mixed product; the temperature of the heating treatment is 650 ℃; the volume content of hydrogen in the atmosphere containing hydrogen 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 cracking 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 primary heat treatment and the secondary heat treatment are performed in vacuum and in hydrogen; the time of the primary heat treatment and the secondary heat treatment is 1h, and the heating rate is 8 ℃/min.
According to detection, the bulk 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, the defect, the granularity and the dispersity of the amorphous cracking carbon to obtain amorphous cracking carbon particles; the amorphous cracking carbon is generated by cracking a gas phase or solid phase organic carbon source and is of an amorphous structure, and the specific surface area is more than 150cm 2 /g; the mode of the activity, defect, granularity and dispersivity adjustment is friction treatment;
step two, mixing 3.4g of the amorphous cracking carbon particles obtained in the step one, 0.14g of a dispersing agent and 300mL of water to obtain an amorphous cracking carbon suspension with uniform dispersion; the dispersing agent is polyvinyl alcohol;
step three, adding 20g of ammonium metatungstate into the amorphous cracking carbon suspension obtained in the step two while stirring to obtain a mixed suspension containing the ammonium metatungstate and the amorphous cracking carbon; the mass purity of the ammonium metatungstate is more than 99.95%;
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 for depositing and coating tungstic acid; the temperature of the heating and stirring 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 cracking carbon suspension of the deposited coated tungstic acid obtained in the step four to obtain nano-scale mixed tungstic acid coated amorphous cracking 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-scale mixed tungsten dioxide/amorphous cracking carbon composite powder, and then stirring at an ultra-high speed to obtain a nano-scale mixed product; the temperature of the heating treatment is 600 ℃; the volume content of hydrogen in the atmosphere containing hydrogen is 50%, and the balance is argon; the heating treatment time 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 cracking 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 primary heat treatment and the secondary heat treatment are performed in vacuum and in hydrogen; the time of the primary heat treatment and the secondary heat treatment is 3 hours, and the heating rate is 5 ℃/min.
According to detection, the bulk 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 differs from embodiment 5 in that: heating and stirring the mixed suspension obtained in the step three, and adding 0.4g of inorganic acid into the mixed suspension to obtain an amorphous cracked carbon suspension for depositing and coating tungstic acid; the temperature of the heating and stirring is 70 ℃, and the stirring speed is 150rpm; the inorganic acid is sulfuric acid solution.
Example 7
This embodiment differs from embodiment 5 in that: heating and stirring the mixed suspension obtained in the step three, and adding 4g of inorganic acid into the mixed suspension to obtain an amorphous cracked carbon suspension for depositing and coating tungstic acid; the temperature of the heating and stirring is 70 ℃, and the stirring speed is 150rpm; the inorganic acid is nitric acid solution.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the present invention. Any simple modification, variation and equivalent variation of the above embodiments according to the technical substance of the invention still fall within the scope of the technical solution of the invention.
Claims (7)
1. The preparation method of the nano tungsten carbide powder with controllable high dispersion granularity is characterized by comprising the following steps of:
step one, adjusting the activity, the defect, the granularity and the dispersity of the amorphous cracking carbon to obtain amorphous cracking carbon particles; the amorphous cracking carbon is generated by cracking a gas phase or solid phase organic carbon source and is of an amorphous structure, and the specific surface area is more than 150cm 2 /g; the mode of the activity, defect, granularity and dispersivity adjustment is ultrasonic treatment, plasma treatment or friction treatment;
step two, mixing the amorphous cracking carbon particles obtained in the step one, a dispersing agent and water to obtain an amorphous cracking carbon suspension with uniform dispersion;
step three, adding ammonium metatungstate into the amorphous cracking carbon suspension obtained in the step two while stirring to obtain a mixed suspension containing the ammonium metatungstate and the amorphous cracking 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 an amorphous cracked carbon suspension for depositing and coating tungstic acid;
step five, carrying out vacuum drying treatment on the amorphous cracking carbon suspension of the deposited coated tungstic acid obtained in the step four to obtain nano-scale mixed tungstic acid coated amorphous cracking carbon composite powder;
step six, heating the composite powder obtained in the step five in an atmosphere containing hydrogen to obtain nano-scale mixed tungsten dioxide/amorphous cracking carbon composite powder, and then stirring at an ultra-high speed to obtain a nano-scale mixed product; the temperature of the heating treatment is 500-650 ℃; the volume content of hydrogen in the atmosphere containing hydrogen is not less than 10%, and the balance is inert gas;
step seven, carrying out primary heat treatment on the product obtained in the step six to obtain tungsten carbide, tungsten and amorphous cracking 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 preparation method of the nano tungsten carbide powder with controllable high dispersion granularity according to claim 1, wherein in the second step, the dispersing agent is one or more than two 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 in the third step.
3. The method for preparing the nano tungsten carbide powder with controllable high dispersion granularity 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 cracking carbon particles in the mixed suspension is 15% -18% of the mass of the ammonium metatungstate.
4. The method for preparing nano tungsten carbide powder with controllable high dispersion granularity 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 adding amount of the organic acid is 5% -10% of the mass of the ammonium metatungstate in the mixed suspension in the third step; the inorganic acid is hydrochloric acid solution, sulfuric acid solution or nitric acid solution, and the adding amount of the inorganic acid is 2% -10% of the mass of the ammonium metatungstate in the mixed suspension in the third step.
5. The method for preparing nano tungsten carbide powder with controllable high dispersion granularity according to claim 1, wherein the temperature of the vacuum drying treatment in the fifth step is not lower than 60 ℃.
6. The method for preparing the nano tungsten carbide powder with controllable high dispersion granularity according to claim 1, wherein the heating treatment time in the step six is 0.5-4 h, 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.
7. The method for preparing nano tungsten carbide powder with controllable high dispersion granularity as claimed in claim 1, which is characterized in thatThe method is characterized in that the atmosphere of the primary heat treatment and the secondary heat treatment in the step seven is vacuum atmosphere or hydrogen atmosphere; the time of the primary heat treatment and the secondary heat treatment is 0.5-5 h, 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 more than 95%.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400163A (en) * | 2001-07-30 | 2003-03-05 | 三菱麻铁里亚尔株式会社 | Fine tungsten carbide powder and its production process |
| CN1563461A (en) * | 2004-03-26 | 2005-01-12 | 武汉理工大学 | Method for preparing composite powder of nano tungsten carbide-coblt through direct reducition and carbonization |
| CN1789461A (en) * | 2004-12-14 | 2006-06-21 | 中国科学院金属研究所 | Method for preparing tungsten carbide-cobalt nano composite powder by low-temperature carbonization of solid carbon |
| CN102351179A (en) * | 2011-10-10 | 2012-02-15 | 北京科技大学 | Process for preparing nanometer WC (wolfram carbide) powder through vacuum aerogel carbonization process |
| CN103302309A (en) * | 2013-06-17 | 2013-09-18 | 南昌大学 | Preparation method of nano tungsten carbide |
| CN106654280A (en) * | 2017-01-11 | 2017-05-10 | 安徽工业大学 | W2C@onion-shaped carbon/amorphous carbon nanometer composite and preparing method and application thereof |
| JP2018165233A (en) * | 2017-03-28 | 2018-10-25 | 日本新金属株式会社 | Method for producing fine tungsten carbide powder |
| CN112030025A (en) * | 2020-08-26 | 2020-12-04 | 江西理工大学 | W/WC composite grain reinforced tungsten-copper composite material and preparation method thereof |
| CN112222421A (en) * | 2020-12-07 | 2021-01-15 | 西安稀有金属材料研究院有限公司 | Preparation method and application of nano tungsten trioxide and nano tungsten powder |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100769348B1 (en) * | 2006-03-17 | 2007-11-27 | 주식회사 나노테크 | Manufacturing method for ultra fine composite powder of tungsten carbide and cobalt |
-
2022
- 2022-09-23 CN CN202211166922.0A patent/CN115321537B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400163A (en) * | 2001-07-30 | 2003-03-05 | 三菱麻铁里亚尔株式会社 | Fine tungsten carbide powder and its production process |
| CN1563461A (en) * | 2004-03-26 | 2005-01-12 | 武汉理工大学 | Method for preparing composite powder of nano tungsten carbide-coblt through direct reducition and carbonization |
| CN1789461A (en) * | 2004-12-14 | 2006-06-21 | 中国科学院金属研究所 | Method for preparing tungsten carbide-cobalt nano composite powder by low-temperature carbonization of solid carbon |
| CN102351179A (en) * | 2011-10-10 | 2012-02-15 | 北京科技大学 | Process for preparing nanometer WC (wolfram carbide) powder through vacuum aerogel carbonization process |
| CN103302309A (en) * | 2013-06-17 | 2013-09-18 | 南昌大学 | Preparation method of nano tungsten carbide |
| CN106654280A (en) * | 2017-01-11 | 2017-05-10 | 安徽工业大学 | W2C@onion-shaped carbon/amorphous carbon nanometer composite and preparing method and application thereof |
| JP2018165233A (en) * | 2017-03-28 | 2018-10-25 | 日本新金属株式会社 | Method for producing fine tungsten carbide powder |
| CN112030025A (en) * | 2020-08-26 | 2020-12-04 | 江西理工大学 | W/WC composite grain reinforced tungsten-copper composite material and preparation method thereof |
| CN112222421A (en) * | 2020-12-07 | 2021-01-15 | 西安稀有金属材料研究院有限公司 | Preparation method and application of nano tungsten trioxide and nano tungsten powder |
Non-Patent Citations (3)
| Title |
|---|
| Tungsten Carbide Nanoparticles as Efficient Cocatalysts for Photocatalytic Overall Water Splitting;Garcia-Esparza, AT;CHEMSUSCHEM;第6卷(第1期);全文 * |
| 用钨酸钠制备纳米钨粒子的研究;曾效舒, 韩丽芬, 刘文;中国粉体技术(03);全文 * |
| 碳负载碳化钨复合材料的制备及其对甲醇催化氧化性能的研究;陈佐;《中国优秀硕士学位论文全文数据库》;全文 * |
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