CN115557501A - Method for preparing nano WC powder at low temperature and low cost - Google Patents
Method for preparing nano WC powder at low temperature and low cost Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000002245 particle Substances 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000006229 carbon black Substances 0.000 claims abstract description 21
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000005054 agglomeration Methods 0.000 claims abstract description 5
- 238000003763 carbonization Methods 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 39
- 230000009467 reduction Effects 0.000 claims description 29
- 238000000498 ball milling Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052721 tungsten Inorganic materials 0.000 claims description 12
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000008187 granular material Substances 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
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- 238000012545 processing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
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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
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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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- 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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- 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
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- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The invention provides a method for preparing nano WC powder at low temperature and low cost. The method adopts deagglomerated tungsten oxide powder as a raw material, mechanically mixes the tungsten oxide powder with a certain amount of carbon black, granulates the obtained product, reduces and carbonizes the product at low temperature, adjusts carbon and crushes the product to obtain WC powder with the particle size of less than 100nm. The WC powder prepared by the method has the advantages of fine granularity, narrow granularity distribution, less agglomeration, easily obtained raw materials, simple equipment, lower energy consumption and cost, capability of realizing industrial large-scale production and outstanding practical application advantages.
Description
Technical Field
The invention belongs to the technical field of metal powder preparation, and particularly relates to a method for preparing nano WC powder at low temperature and low cost.
Background
The ultrafine crystal hard alloy has high strength, high hardness and good toughness, effectively solves the contradiction that the hardness, the strength and the toughness of the traditional hard alloy are difficult to be considered, and is widely applied to manufacturing integrated circuit board micro drill bits, dot matrix printer printing needle heads, precision tools and dies, difficult-to-machine material cutters, woodworking cutters, medical dental drills and the like.
With the rapid development of high-end and fine processing and manufacturing industries, the grain size of ultra-fine grain cemented carbide is smaller and smaller, and the ultra-fine grain cemented carbide is developed towards the direction of nano-crystal. For preparing the alloy, WC powder with the particle size of less than 100nm is needed as a raw material for preparation.
At present, the research and production of nano WC powder are carried out in the scientific research field and the industrial production. In scientific research, a mechanical ball milling method, a spray conversion method, a plasma method, a direct carbonization method and a chemical method are mainly used, and most methods generally have the problems of higher cost, equipment limitation, less yield and the like, so that large-scale production is difficult to realize. The preparation temperature of the tungsten carbide powder is generally over 1000 ℃, the industrial production needs about 1200 ℃, and the traditional industrial preparation at present is that tungsten powder is obtained by reducing tungsten oxide hydrogen firstly, then the tungsten powder is mixed with carbon black for carbon preparation, and finally the WC powder is obtained by high-temperature carbonization. The method can generate a large amount of water vapor in the reduction process, and the water vapor reacts with the tungsten oxide to generate WO 2 (OH) 2 ，WO 2 (OH) 2 The tungsten powder is deposited on the surface of nucleated metal tungsten crystal grains through chemical vapor migration to grow, so that the WC powder below 100 nanometers is difficult to prepare after subsequent carbon preparation and carbonization, the over-fine W powder is easy to generate spontaneous combustion, the process control is complex, and the cost is high.
Therefore, the research of a new method for preparing the nano WC powder has important theoretical and practical significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a method for preparing nano WC powder at low temperature and low cost. The tungsten carbide powder with the granularity of below 100 nanometers is obtained through pretreatment of raw materials and low-temperature reduction carbonization, and carbon is used as a reducing agent in the method, so that the natural problems of chemical vapor phase migration and growth processes and excessive fineness of the obtained tungsten powder in the traditional industrial production reduction process are solved.
The invention provides a method for preparing nano WC powder at low temperature and low cost, which comprises the following steps:
s1, performing deagglomeration treatment on oxide powder of fine tungsten particles to obtain raw material powder;
s2, mechanically mixing the raw material powder obtained in the step S1 with carbon black, and granulating after mixing to obtain material particles;
s3, carrying out low-temperature reduction carbonization on the material particles obtained in the step S2 to obtain a primary product;
s4, mixing the primary product obtained in the step S3 with carbon black, and then carrying out secondary carbonization to obtain a secondary product;
and S5, crushing the secondary product obtained in the step S4 to obtain the nano WC powder.
As a specific embodiment of the present invention, in the step S1, the fine tungsten oxide particles are yellow tungsten (WO) 3 ) Blue tungsten (WO) 2.9 ) Purple tungsten (WO) 2.72 ) Tungsten dioxide (WO) 2 ) Of tungsten oxide fine particles, the Fisher size (Fsss) of the fine tungsten oxide is 5 μm or less, and specifically, the smaller the particle size, the more advantageous.
As a specific embodiment of the present invention, in the step S1, the deagglomeration treatment is one or more of airflow crushing, ball milling and classification methods; the Fisher size (Fsss) of the raw material powder obtained after the de-agglomeration treatment is less than or equal to 0.7 mu m.
In a specific embodiment of the present invention, in the step S2, the molar ratio of the raw material powder to the carbon black is 1 (2-4).
As a specific embodiment of the present invention, in the step S2, the granulation method includes rolling granulation or extrusion granulation, and the granulation process further includes adding a forming agent; the forming agent contains three elements of C, H and O, including one of PEG and PAA; the addition amount of the forming agent is less than 10% of the mass of the material.
As a specific embodiment of the present invention, the shape of the obtained pellets includes a spherical shape or a rod shape; the particle size of the spherical material particles is 1-3mm; the diameter of the rod-shaped granules is 1-3mm, and the length of the rod-shaped granules is 1-5mm.
In the step S3, the temperature of the low-temperature reduction carbonization is 800 to 950 ℃, and the time of the low-temperature reduction carbonization is 2 to 10 hours; the protective atmosphere is a non-reducing atmosphere and comprises nitrogen, argon and helium, and preferably nitrogen; the obtained primary reduction products are W and W 2 C. One or more of WC.
As a specific embodiment of the present invention, in the step S4, the molar ratio of the carbon black to the primary product is not more than 1.
In the step S4, the temperature of the secondary carbonization is 900-1000 ℃, and the protective atmosphere is H 2 The time of the secondary carbonization is 2-10h.
In a specific embodiment of the present invention, in the step S5, the crushing manner includes ball milling, and airflow crushing.
In a specific embodiment of the present invention, in the step S5, the particle size of the nano WC powder is less than 100nm.
The above raw materials in the present invention may be prepared by themselves or may be obtained commercially, and the present invention is not particularly limited thereto.
Compared with the prior art, the invention has the beneficial effects that:
1. the method for preparing the nano WC powder at low temperature and low cost adopts a de-agglomeration method, eliminates agglomeration and large particles in raw material powder, and avoids the problem that tungsten carbide powder below 100 nanometers is difficult to prepare due to genetic effect.
2. The method for preparing the nano WC powder at low temperature and low cost adopts the granulation technology, so that the tungsten oxide and the carbon are combined more tightly, the diffusion path of carbon elements in the reduction carbonization process is reduced, and the reaction temperature can be effectively reduced.
3. The method for preparing the nano WC powder at low temperature and low cost adopts carbon as a reducing agent, thereby avoiding the problem that the nano WC powder is not prepared at low temperatureIn the reduction process H 2 The chemical vapor phase migration caused by the generation of O grows, the growth of powder is inhibited, and the preparation of finer nanometer WC powder is facilitated.
4. The method for preparing the nano WC powder at low temperature and low cost adopts low-temperature reduction carbonization, avoids the powder granularity growth caused by high temperature in the whole production process, and is beneficial to obtaining finer nano WC powder.
5. The method for preparing the nano WC powder at low temperature and low cost has the advantages that the adopted temperature is below 1000 ℃, and compared with the temperature of more than 1000 ℃ and even 1200 ℃ in the prior art, the temperature of the preparation method is low, the power cost can be reduced, the energy consumption is saved, meanwhile, the method avoids the generation of the nano W powder in the intermediate process of the traditional method, the nano W powder is extremely easy to self-ignite, the subsequent protection cost is increased, the treatment cost of self-ignited waste materials is reduced, the production equipment is simple, the cost is low, the efficiency is high, and the industrialized mass production can be realized.
Drawings
FIG. 1 is an SEM image of a WC powder prepared in example 1 of the invention;
fig. 2 is an XRD pattern of the primary product after reduction-carbonization prepared in comparative example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way.
Example 1
The embodiment provides a method for preparing nano WC powder at low temperature and low cost, which comprises the following specific details:
s1: 1kg of WO having a Fisher-Tropsch particle size (Fsss) of 4.8 μm 2 Ball-milling and crushing the powder to obtain raw material powder with the Fisher particle size (Fsss) of 0.67 mu m;
s2: mixing the raw material powder obtained in the step S1 with 140g of carbon black for ball milling, wherein the ball milling time is 2 hours, the ball milling rotation speed is 60r/min, the ball material ratio is 1;
s3: drying the spherical material particles obtained in the step S2, and then placing the dried spherical material particles in a reducing furnace for reduction and carbonization at 950 ℃, wherein the protective atmosphere is nitrogen, and the reduction and carbonization time is 8 hours, so as to obtain a primary reduction product;
s4: mixing the primary product obtained in the step S3 with 30.7g of carbon black, and carrying out secondary carbonization on the mixed material in a molybdenum wire furnace, wherein the carbonization temperature is 1000 ℃, the carbonization time is 8 hours, and the protective atmosphere is hydrogen to obtain a secondary product;
s5: and (5) ball-milling and crushing the secondary product obtained in the step (S4), wherein the crushing parameters are as follows: the ball material ratio is 1.5:1, crushing for 4h to obtain the nanometer WC powder.
The average particle size of the nano WC powder obtained in example 1 was 91nm.
Example 2
The embodiment provides a method for preparing nano WC powder at low temperature and low cost, which comprises the following specific details:
s1: 1kg of WO having a Fisher-Tropsch particle size (Fsss) of 4.5 μm 2.9 Ball-milling and crushing the powder to obtain raw material powder with a Fisher size (Fsss) of 0.63 mu m;
s2: mixing the raw material powder obtained in the step S1 with 160g of carbon black for ball milling, wherein the ball milling time is 2 hours, the ball milling rotation speed is 60r/min, the ball-material ratio is 1;
s3: drying the spherical material particles obtained in the step S2, and then placing the dried spherical material particles in a reducing furnace for reduction carbonization at 900 ℃, wherein the protective atmosphere is nitrogen, and the reduction carbonization time is 5 hours, so as to obtain a primary product;
s4: mixing the primary product obtained in the step S3 with 32.3g of carbon black, and performing secondary carbonization on the mixed material in a molybdenum wire furnace, wherein the carbonization temperature is 950 ℃, the carbonization time is 5 hours, and the protective atmosphere is hydrogen to obtain a secondary product;
s5: and (5) ball-milling and crushing the secondary product obtained in the step (S4), wherein the crushing parameters are as follows: the ball material ratio is 1.5:1, crushing for 4h to obtain the nanometer WC powder.
The average particle size of the nano WC powder obtained in example 2 was 95nm.
Example 3
The embodiment provides a method for preparing nano WC powder at low temperature and low cost, which comprises the following specific details:
s1: 1kg of WO having a Fisher-Tropsch particle size (Fsss) of 3.3 μm 3 Performing airflow crushing on the powder until the powder is crushed into raw material powder with a Fisher particle size (Fsss) of 0.51 mu m;
s2: mixing the raw material powder obtained in the step S1 with 180g of carbon black for ball milling, wherein the ball milling time is 2 hours, the ball milling rotation speed is 60r/min, the ball material ratio is 1;
s3: drying the rod-shaped material particles obtained in the step S2, and then placing the rod-shaped material particles in a reducing furnace for reduction carbonization at 800 ℃, wherein the protective atmosphere is nitrogen, and the reduction carbonization time is 3 hours, so as to obtain a primary product;
s4: mixing the primary product obtained in the step S3 with 28.7g of carbon black, and carrying out secondary carbonization on the mixed material in a molybdenum wire furnace, wherein the carbonization temperature is 900 ℃, the reduction carbonization time is 3 hours, and the protective atmosphere is hydrogen to obtain a secondary product;
s5: and (5) performing ball milling and crushing on the secondary product obtained in the step (S4), wherein the crushing parameters are as follows: the ball material ratio is 1.5:1, crushing for 4h to obtain the nano WC powder.
The average particle size of the nano WC powder obtained in example 3 was 97nm.
Comparative example 1
The comparative example provides a method for preparing nano WC powder, which comprises the following specific details:
s1: 1kg of WO having a Fisher-Tropsch particle size (Fsss) of 4.8 μm 2 Mixing the powder with 140g of carbon black for ball milling, wherein the ball milling time is 2 hours, the ball milling rotation speed is 60r/min, the ball-to-material ratio is 1, the ball is a hard alloy ball, mixing the mixed powder after ball milling with water and PAA, adding the mixture into a roller granulator for granulation, and preparing spherical granules with the diameter of 1.5 mm;
s2: drying the spherical material particles obtained in the step S1, and then putting the dried spherical material particles into a reduction furnace to be reduced and carbonized at 950 ℃, wherein the protective atmosphere is nitrogen, and the reduction and carbonization time is 8 hours, so as to obtain a primary product;
the presence of tungsten oxide in the primary product obtained in comparative example 1 was detected, indicating that the reduction of the product of step S2 was not completed.
Comparative example 2
The comparative example provides a method for preparing nano WC powder, which comprises the following specific details:
s1: 1kg of WO having a Fisher-Tropsch particle size (Fsss) of 4.5 μm 2.9 Performing airflow crushing on the powder until the powder is crushed into raw material powder with the Fisher particle size (Fsss) of 0.63 mu m;
s2: mixing the raw material powder obtained in the step S1 with 160g of carbon black for ball milling, wherein the ball milling time is 2 hours, the ball milling rotation speed is 60r/min, the ball-to-material ratio is 1;
s3: the mixed material obtained in the step S2 is placed in a reducing furnace for reduction and carbonization at 900 ℃, the protective atmosphere is nitrogen, and the reduction and carbonization time is 5 hours, so that a primary product is obtained;
the presence of tungsten oxide in the primary product obtained in comparative example 2 was detected, indicating that the primary product of step S3 was not completely reduced.
Comparative example 3
The comparative example provides a method for preparing nano WC powder, which comprises the following specific details:
s1: 1kg of WO having a Fisher-Tropsch particle size (Fsss) of 3.3 μm 3 Performing airflow crushing on the powder until the powder is crushed into raw material powder with a Fisher particle size (Fsss) of 0.51 mu m;
s2: mixing the raw material powder obtained in the step S1 with 180g of carbon black, and carrying out ball milling for 2 hours at a ball milling rotation speed of 60r/min in a ball-to-material ratio of 1;
s3: mixing the mixed material obtained in the step S2 with water and PEG, adding the mixture into an extrusion granulator for granulation, and preparing rod-shaped granules with the diameter of 2mm and the length of 3mm;
s4: drying the rod-shaped material particles obtained in the step S3, and then placing the dried rod-shaped material particles in a reduction furnace for reduction carbonization at 1000 ℃, wherein the protective atmosphere is nitrogen, and the reduction carbonization time is 3 hours, so as to obtain a primary product;
s5: mixing the primary reduction product obtained in the step S4 with 28.7g of carbon black, and performing secondary carbonization on the mixed material in a molybdenum wire furnace at the reduction carbonization temperature of 1050 ℃, the carbonization time of 3 hours and the protective atmosphere of hydrogen to obtain a secondary product;
s6: and (5) crushing the secondary product obtained in the step (S5), wherein the crushing parameters are as follows: the ball material ratio is 1.5:1, crushing for 4h to obtain the nanometer WC powder.
The average particle size of the powder obtained in comparative example 3 was 107nm.
In conclusion, the preparation method of the invention adopts the deagglomerated tungsten oxide powder as the raw material, then mechanically mixes the tungsten oxide powder with a certain amount of carbon black, and the mixed product is granulated, reduced and carbonized at low temperature, and then subjected to carbon regulation and crushing to prepare the WC powder with the particle size of less than 100nm.
Any numerical value mentioned in this specification, if there is only a two unit interval between any lowest value and any highest value, includes all values from the lowest value to the highest value incremented by one unit at a time. For example, if it is stated that the amount of one component, or the value of a process variable such as temperature, pressure, time, etc., is 50 to 90, it is meant in this specification that values of 51 to 89, 52 to 88, 8230 \8230; \ 8230; and 69 to 71, and 70 to 71, etc., are specifically enumerated. For non-integer values, units of 0.1, 0.01, 0.001, or 0.0001 may be considered as appropriate. These are only some specifically named examples. In a similar manner, all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be disclosed in this application.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A method for preparing nano WC powder at low temperature and low cost is characterized by comprising the following steps:
s1, performing deagglomeration treatment on the tungsten oxide powder with fine particles to obtain raw material powder;
s2, mechanically mixing the raw material powder obtained in the step S1 with carbon black, and granulating to obtain material particles;
s3, carrying out low-temperature reduction carbonization on the material particles obtained in the step S2 under a protective atmosphere to obtain a primary product;
s4, mixing the primary reduction product obtained in the step S3 with carbon black in a protective atmosphere, and then carrying out secondary carbonization to obtain a secondary product;
and S5, crushing the secondary product obtained in the step S4 to obtain the nano WC powder.
2. The method according to claim 1, wherein in the step S1, the fine particle tungsten oxide is yellow tungsten (WO) 3 ) Blue tungsten (WO) 2.9 ) Purple tungsten (WO) 2.72 ) Tungsten dioxide (WO) 2 ) The Fisher-size (Fsss) of the fine tungsten oxide particles is less than or equal to 5 mu m.
3. The method according to claim 1 or 2, wherein in the step S1, the deagglomeration treatment is one or more of airflow crushing, ball milling, and classification; the Fisher size (Fsss) of the raw material powder obtained after the de-agglomeration treatment is less than or equal to 0.7 mu m.
4. The method according to any one of claims 1 to 3, wherein in the step S2, the molar ratio of the raw material powder to the carbon black is 1 (2-4).
5. The method according to any one of claims 1 to 4, wherein in step S2, the granulation method comprises tumbling granulation or extrusion granulation; and/or, adding a forming agent in the granulation process; preferably, the forming agent contains three elements of C, H and O, and more preferably comprises one of PEG and PAA; and/or the addition amount of the forming agent is less than 10% of the mass of the material, and/or the shape of the obtained material particles comprises a spherical shape or a rod shape, preferably, the particle diameter of the spherical material particles is 1-3mm, the diameter of the rod-shaped material particles is 1-3mm, and the length of the rod-shaped material particles is 1-5mm.
6. The method according to any one of claims 1 to 5, wherein in the step S3, the temperature of the low-temperature carbonization reduction is 800-950 ℃, and the time of the low-temperature reduction carbonization is 2-10h; the protective atmosphere is a non-reducing atmosphere and comprises nitrogen, argon and helium, and preferably nitrogen; the primary products are W and W 2 C. One or more of WC.
7. The method according to any one of claims 1 to 6, wherein in step S4, the molar ratio of the carbon black to the primary product is less than or equal to 1.
8. The method according to any one of claims 1 to 7, wherein in the step S4, the temperature of the secondary carbonization is 900 to 1000 ℃, and the protective atmosphere is H 2 The time of the secondary carbonization is 2-10h.
9. The method according to any one of claims 1 to 8, wherein in the step S5, the crushing manner comprises ball milling and airflow crushing.
10. The method according to any one of claims 1 to 9, wherein in step S5, the nano WC powder has a particle size < 100nm.
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| CN202211237547.4A CN115557501A (en) | 2022-09-30 | 2022-09-30 | Method for preparing nano WC powder at low temperature and low cost |
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Citations (4)
| 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 |
| CN108941598A (en) * | 2018-08-09 | 2018-12-07 | 蓬莱市超硬复合材料有限公司 | A kind of soilless sticking body, uniformly, crystallize complete ultra-fine and nano-tungsten powder preparation method |
| CN112079359A (en) * | 2020-07-31 | 2020-12-15 | 株洲硬质合金集团有限公司 | Preparation method of high-uniformity nano WC powder |
| CN114853021A (en) * | 2022-05-23 | 2022-08-05 | 赣州海盛钨业股份有限公司 | Nano tungsten carbide powder and preparation method thereof |
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Patent Citations (4)
| 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 |
| CN108941598A (en) * | 2018-08-09 | 2018-12-07 | 蓬莱市超硬复合材料有限公司 | A kind of soilless sticking body, uniformly, crystallize complete ultra-fine and nano-tungsten powder preparation method |
| CN112079359A (en) * | 2020-07-31 | 2020-12-15 | 株洲硬质合金集团有限公司 | Preparation method of high-uniformity nano WC powder |
| CN114853021A (en) * | 2022-05-23 | 2022-08-05 | 赣州海盛钨业股份有限公司 | Nano tungsten carbide powder and preparation method thereof |
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