CN116143124B - Ultra-coarse uniform tungsten carbide powder and preparation method thereof - Google Patents
Ultra-coarse uniform tungsten carbide powder and preparation method thereof Download PDFInfo
- Publication number
- CN116143124B CN116143124B CN202310448322.1A CN202310448322A CN116143124B CN 116143124 B CN116143124 B CN 116143124B CN 202310448322 A CN202310448322 A CN 202310448322A CN 116143124 B CN116143124 B CN 116143124B
- Authority
- CN
- China
- Prior art keywords
- coarse
- ultra
- tungsten carbide
- ball
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000000843 powder Substances 0.000 title claims abstract description 120
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 238000000227 grinding Methods 0.000 claims abstract description 86
- 238000000034 method Methods 0.000 claims abstract description 72
- 238000003763 carbonization Methods 0.000 claims abstract description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims description 167
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 143
- 238000000498 ball milling Methods 0.000 claims description 98
- 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 description 57
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 229910052799 carbon Inorganic materials 0.000 claims description 53
- 239000002994 raw material Substances 0.000 claims description 51
- 239000011362 coarse particle Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 28
- 238000007873 sieving Methods 0.000 claims description 27
- 239000006229 carbon black Substances 0.000 claims description 25
- 239000005539 carbonized material Substances 0.000 claims description 25
- 238000000713 high-energy ball milling Methods 0.000 claims description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims description 20
- 150000001340 alkali metals Chemical class 0.000 claims description 20
- 239000002245 particle Substances 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000001694 spray drying Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- AAWZNWVCESLFTD-UHFFFAOYSA-N tungsten;hydrate Chemical compound O.[W] AAWZNWVCESLFTD-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to the technical field of tungsten carbide preparation, and particularly relates to ultra-coarse uniform tungsten carbide powder and a preparation method thereof, wherein the ultra-coarse uniform tungsten carbide powder is prepared through the processes of hydrogen reduction, high-energy crushing, air flow classification, three-stage carbonization, secondary air flow classification and the like 2 And C phase is generated, so that the wear resistance of the tungsten carbide is effectively improved. The ultra-coarse tungsten carbide powder with better wear resistance and more uniform particle size distribution can be prepared by adopting the preparation method, and the grinding state particle size of the prepared tungsten carbide powder is more than or equal to 6.5 mu m, thereby being beneficial to large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of tungsten carbide preparation, and particularly relates to ultra-coarse uniform tungsten carbide powder and a preparation method thereof.
Background
Tungsten carbide is an important component of cemented carbide, the properties of which depend to a large extent on the properties of tungsten carbide. The high-quality ultra-coarse WC has a series of advantages of complete crystal structure, few structural defects, high microhardness, coarse grain size, small microscopic deformation and the like. The method is used for producing hard alloy, can obviously improve the fracture toughness of the hard alloy, prolongs the service life of the hard alloy, is widely applied to continuous exploitation of soft rock under extreme working conditions and continuous operation of modern highways and bridges, and can also be used for stamping dies, cold heading dies, rollers and the like with high requirements on toughness, thermal fatigue resistance and thermal shock resistance.
At present, the technology for producing ultra-coarse crystal WC powder at home and abroad mainly comprises the following steps: firstly, preparing ultra-coarse tungsten carbide powder by adopting a high-temperature reduction and high-temperature carbonization process, wherein the ultra-coarse tungsten carbide powder prepared by the process has the defects of plump grain development, good wear resistance, high energy consumption, large equipment loss and the like; secondly, the ultra-coarse tungsten carbide powder is prepared by adopting the alkali metal doped tungsten oxide as a raw material, and the ultra-coarse tungsten carbide powder prepared by the process has the defects of more pseudo particles, poor wear resistance and the like. And thirdly, preparing ultra-coarse tungsten carbide powder by adopting wet hydrogen high-temperature reduction-high-temperature carbonization, wherein the tungsten carbide powder prepared by the process has the defects of good primary particle development, good wear resistance, high equipment requirement and unstable wet hydrogen atmosphere control. In the traditional alkali metal doping process, the alkali metal is easy to be doped unevenly in the alkali metal doping process, so that uneven alkali metal distribution is caused, and abnormal coarse particles are generated; in addition, tungsten powder is easy to sinter and grow up in the high-temperature carbonization process, so that carbonization is incomplete and W is used 2 C (brittle phase) exists, eventually leading to a decrease in the wear resistance of the tungsten carbide powder. Therefore, the process for preparing ultra-coarse tungsten carbide powder by adopting the doping process needs to be improved.
Disclosure of Invention
In order to solve the problems in the prior art, the main purpose of the invention is to provide ultra-coarse uniform tungsten carbide powder and a preparation method thereof.
In order to solve the technical problems, according to one aspect of the present invention, the following technical solutions are provided:
the preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device to carry out alkali metal doping on a tungsten oxide raw material;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, and performing air flow classification to obtain classified ultra-coarse tungsten powder;
s4, taking the components with the weight percentage of 3-10wt% and the specific surface area of5.0~10.0m 2 Mixing/g tungsten powder with 90-97wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, and adding carbon in a ball grinding carbon adding mode to obtain a mixed material;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1-3 h at 1750-1950 ℃;
preserving heat for 1-3 h at 1950-2150 ℃;
preserving heat for 3-8 hours at 2150-2190 ℃;
s6, ball milling and crushing the carbonized material, and sieving to remove coarse particles;
s7, carrying out air current classification on the sieved material to obtain ultra-coarse uniform tungsten carbide powder.
As a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S1, the doping apparatus is a doping apparatus in the patent No. ZL 202021830264.7.
As a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S1, the alkali metal is Na, and the doping amount of the alkali metal is 150-190 ppm.
As a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S2, the reduction temperature is 1000-1100 ℃, and the reduction time is 10-20 h.
As a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S3, the mass ratio of the ball materials is 2-4:1, and the ball milling time is 0.5-2 h;
as a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S3, the classification frequency is 10-30 Hz, and fine powder generated by ball milling and crushing can be removed through classification, so that the uniformity of tungsten powder is improved.
As a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S4, the ball material mass ratio of ball grinding carbon is 2-4:1, and the ball milling time is 1-2 hours.
As a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S6, the mass ratio of ball materials crushed by ball milling is 2-4:1, the ball milling time is 10-40 min, and coarse particles are removed by sieving.
As a preferable scheme of the preparation method of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: in the step S7, the classification frequency is 20-40 Hz, and fine powder generated by crushing is removed.
In order to solve the above technical problems, according to another aspect of the present invention, the following technical solutions are provided:
the ultra-coarse uniform tungsten carbide powder is prepared by adopting the preparation method.
As a preferable scheme of the ultra-coarse uniform tungsten carbide powder, the invention comprises the following steps: the grinding state granularity of the tungsten carbide powder is more than or equal to 6.5 mu m.
The beneficial effects of the invention are as follows:
the invention provides ultra-coarse uniform tungsten carbide powder and a preparation method thereof, wherein the ultra-coarse uniform tungsten carbide powder is prepared by the processes of hydrogen reduction, high-energy crushing, air classification, three-stage carbonization, air classification again and the like 2 And C phase is generated, so that the wear resistance of the tungsten carbide is effectively improved. The ultra-coarse tungsten carbide powder with better wear resistance and more uniform particle size distribution can be prepared by adopting the preparation method, and the grinding state particle size of the prepared tungsten carbide powder is more than or equal to 6.5 mu m, thereby being beneficial to large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a high-magnification SEM image of tungsten carbide powder prepared according to example 1 of the present invention;
FIG. 2 is a low-magnification SEM image of tungsten carbide powder prepared according to example 1 of the present invention;
FIG. 3 is an SEM image of the tungsten carbide powder prepared according to comparative example 1 of the present invention;
FIG. 4 is an SEM image of the tungsten carbide powder of comparative example 2;
fig. 5 is an SEM image of the tungsten carbide powder prepared in comparative example 3 of the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description will be made clearly and fully with reference to the technical solutions in the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
According to one aspect of the invention, the invention provides the following technical scheme:
the preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device to carry out alkali metal doping on a tungsten oxide raw material;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, and performing air flow classification to obtain classified ultra-coarse tungsten powder;
s4, taking the materials with the weight percentage of 3-10wt% and the specific surface area of 5.0-10.0 m 2 Mixing/g tungsten powder with 90-97wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, and adding carbon in a ball grinding carbon adding mode to obtain a mixed material;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
Preserving heat for 1-3 h at 1750-1950 ℃;
preserving heat for 1-3 h at 1950-2150 ℃;
preserving heat for 3-8 hours at 2150-2190 ℃;
s6, ball milling and crushing the carbonized material, and sieving to remove coarse particles;
s7, carrying out air current classification on the sieved material to obtain ultra-coarse uniform tungsten carbide powder.
The three-stage carbonization process can effectively reduce the solid-phase sintering effect between large-particle tungsten powder in the initial carbonization stage, reduce the generation probability of coarse particles, improve the carbonization degree and reduce W 2 And C phase is generated, so that the wear resistance of the tungsten carbide is effectively improved. In the solid-phase sintering, the sintering activity of the tungsten powder is higher than that of tungsten carbide, and the tungsten powder is easy to sinter and grow at high temperature, so that the heat is preserved at 1750-1950 ℃, the micro carbonization of the surface of the tungsten powder is promoted, and meanwhile, the probability of rapid sintering and growing between tungsten powder particles due to the overhigh temperature is reduced; preserving heat at 1950-2150 ℃ to further improve the carbonization degree of the tungsten powder; and preserving heat at 2150-2190 ℃ to ensure that tungsten carbide is completely carbonized and is grown by solid phase sintering at high temperature, so that ultra-coarse uniform tungsten carbide powder is prepared.
Preferably, in the step S1, the doping apparatus is a doping apparatus in the patent No. ZL202021830264.7, and the doping apparatus relates to a powder doping system, and the powder doping system includes: the stirring device is internally provided with a stirring assembly, the stirring device is provided with a water inlet, a doping agent inlet, a tungsten oxide inlet and a doping liquid outlet, and a first discharge valve is arranged at the doping liquid outlet; the spray drying tower is provided with a doping liquid inlet, an air outlet and a doped tungsten oxide drying outlet, the doping liquid inlet is connected with the doping liquid outlet, a rotatable centrifugal atomizing disc is arranged at the outlet section of the doping liquid inlet, and a second discharge valve is arranged at the discharge port; the heating device is connected with the air inlet; and the screening device is connected with the doped dry tungsten oxide outlet. According to the powder doping system, tungsten oxide, water and doping agents are stirred and mixed in the stirring device by utilizing the stirring assembly, namely, a liquid-solid doping mode is adopted, so that the doping uniformity can be ensured, the doping amount can be accurately controlled, and the uniformity of tungsten powder particles is improved. Then sequentially starting a blower, an exhaust fan and heating equipment, supplying hot air into the spray drying tower through an air inlet to preheat the spray drying tower, when the spray drying tower is heated to a preset temperature, starting a centrifugal atomizing disk on the spray drying tower, setting the rotating speed of the centrifugal atomizing disk, then starting a first discharge valve, a second discharge valve and a screening device, controlling the feeding speed, at the moment, feeding doping liquid to the centrifugal atomizing disk at the top of the spray drying tower through a doping liquid outlet at the bottom of a stirring device, dispersing the doping liquid into tiny mist droplets, greatly increasing the surface area of the doping liquid after atomization, fully contacting the mist droplets with the hot air, finishing instant drying, enabling the obtained powdery doped tungsten oxide to fall to the bottom of the spray drying tower, feeding the doped dried tungsten oxide outlet to the screening device, screening, removing abnormal coarse particles, and discharging waste gas generated in the drying process through an exhaust port by using the exhaust fan. The material is discharged from the bottom of the stirring device and directly enters the spray drying tower for drying, so that doping and drying are integrally finished, the labor intensity is greatly reduced, and the production efficiency is improved.
Preferably, in the step S1, the alkali metal is Na, and the doping amount of the alkali metal is 150-190 ppm. The inventors have found that in the preparation method of the present invention, the selection of the alkali metal as Na in step S1 has a relatively better effect. Furthermore, different alkali metal doping amounts can also generate different promotion effects on tungsten powder, and the alkali metal doping amount is too low to play a good role in promotion; and the excessive doping amount of alkali metal can lead to higher impurity content, thereby adversely affecting the properties of ultra-coarse tungsten powder and being unfavorable for subsequent high-temperature carbonization reaction. In the preparation method of the invention, the doping amount of the alkali metal in the step S1 is selected to be in the range of 150-190 ppm, so that the preparation method has relatively better effect. In particular, the alkali metal doping amount may be, for example, but not limited to, a range between any one or any two of 150ppm, 155ppm, 160ppm, 165ppm, 170ppm, 175ppm, 180ppm, 185ppm, 190 ppm;
preferably, in the step S2, the reduction temperature is 1000-1100 ℃ and the reduction time is 10-20 hours. The reduction temperature and the reduction time can have important influence on the preparation of ultra-coarse tungsten powder, and the reduction effect is poor when the reduction temperature is too low, so that incomplete reduction is easy to occur; when the reduction temperature is too high, a large number of sintering necks are formed, and solid phase agglomeration is serious, so that the uniformity of powder is reduced; in addition, the excessively high reduction temperature has higher requirements on equipment and higher cost, and is unfavorable for subsequent large-scale industrialized production. The reduction time is too short, and a good full reduction effect cannot be realized; and the long reduction time wastes energy, so that the cost is increased, and the subsequent large-scale industrialized production is not facilitated. Specifically, the reduction temperature may be, for example, but not limited to, any one or a range between any two of 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃, 1090 ℃, 1100 ℃; the reduction time may be, for example, but not limited to, any one or a range between any two of 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20 h;
Preferably, in the step S3, the ball material mass ratio is 2-4:1, and the ball milling time is 0.5-2 hours; the ball-to-material ratio is the ratio of the grinding body and the material quantity in each bin of the grinding machine, and indicates the size of the material quantity stored in the grinding machine in the grinding process under a certain grinding body loading capacity. If the material quantity is excessive and the ball milling time is too short, solid phase aggregates formed in the high-temperature reduction process cannot be effectively opened, so that the subsequent uniform mixing with the superfine nano tungsten powder is not facilitated, and the subsequent carbonization reaction is affected; if the amount of the material is too small and the ball milling time is too long, although solid-phase aggregates formed in the high-temperature reduction process can be fully opened, the too long ball milling time can simultaneously lead to serious material refinement, the mechanical strength of the material is affected, and the too long ball milling time can waste energy sources, thereby reducing the production efficiency and increasing the production cost. Specifically, the ball mass ratio may be, for example, but not limited to, a range between any one or any two of 2:1, 2.5:1, 3:1, 3.5:1, 4:1; the ball milling time may be, for example, but not limited to, any one or a range between any two of 0.5h, 0.75h, 1.0h, 1.25h, 1.5h, 1.75h, 2.0 h;
preferably, in the step S3, the classification frequency is 10 to 30hz, and fine powder generated by ball milling and crushing can be removed by classification, so as to improve uniformity of tungsten powder. In particular, the classification frequency may be, for example, but not limited to, a range between any one or any two of 10Hz, 15Hz, 20Hz, 25Hz, 30 Hz;
Preferably, in the step S4, the ball mass ratio of the ball milled carbon is 2-4:1, and the ball milling time is 1-2 hours. If the material amount is excessive and the ball milling time is too short, the superfine nano tungsten powder, the ultra-coarse tungsten powder and the carbon black cannot be uniformly mixed, so that the subsequent carbonization reaction is affected; if the material amount is too small and the ball milling time is too long, although the effect of fully mixing can be achieved, the too long ball milling time can also cause serious material refinement, influence the granularity of tungsten carbide prepared subsequently, and the too long ball milling time can waste energy, so that the production efficiency is reduced and the production cost is increased.
Preferably, in the step S6, the mass ratio of ball materials crushed by ball milling is 2-4:1, the ball milling time is 10-40 min, and coarse particles are removed by sieving. If the material quantity is too large or the ball milling time is too short, the tungsten carbide blocks cannot be crushed well, and the required tungsten carbide powder is prepared; if the material quantity is too small or the ball milling time is too long, although the tungsten carbide blocks can be fully crushed, the too long ball milling time can also cause serious refinement of tungsten carbide powder, tungsten carbide with the required granularity range cannot be prepared, and the too long ball milling time can waste energy, so that the production efficiency is reduced and the production cost is increased.
Preferably, in the step S7, the classification frequency is 20 to 40hz, which has a relatively better effect of removing fine powder generated by crushing; in particular, the classification frequency may be, for example, but not limited to, a range between any one or any two of 20Hz, 25Hz, 30Hz, 35Hz, 40 Hz;
according to another aspect of the invention, the invention provides the following technical scheme:
the ultra-coarse uniform tungsten carbide powder is prepared by the preparation method, and the grinding state granularity of the tungsten carbide powder is more than or equal to 6.5 mu m.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
s4, taking the components with the weight percentage of 3 weight percent and the specific surface area of 5.0m 2 Mixing/g tungsten powder with 97wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1h at 1750 ℃; preserving heat for 1h at 2150 ℃; preserving heat for 4 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity of the ultra-coarse uniform tungsten carbide powder is 6.5 mu m as shown in figures 1 and 2.
Example 2
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 weight percent and the specific surface area of 5.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1h at 1750 ℃; preserving heat for 1h at 2150 ℃; preserving heat for 4 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 6.85 mu m.
Example 3
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 10 percent and the specific surface area of 5.0m 2 Mixing/g tungsten powder with 90wt% of classified ultra-coarse tungsten powder, adding carbon black according to the technological requirement, adding carbon in a ball grinding carbon adding mode, and obtaining the tungsten powder by ball grinding, wherein the ball material mass ratio is 3:1, and the ball grinding time is 1hThe mixed materials;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1h at 1750 ℃; preserving heat for 1h at 2150 ℃; preserving heat for 4 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 6.6 mu m.
Example 4
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1h at 1750 ℃; preserving heat for 1h at 2150 ℃; preserving heat for 4 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.1 mu m.
Example 5
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1h at 1750 ℃; preserving heat for 2h at 2150 ℃; preserving heat for 4 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.3 mu m.
Example 6
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 2h at 1750 ℃; preserving heat for 2h at 2150 ℃; preserving heat for 6 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.4 mu m.
Example 7
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 2h at 1750 ℃; preserving heat for 2h at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.5 mu m.
Example 8
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 150ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 2h at 1750 ℃; preserving heat for 2h at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.2 mu m.
Example 9
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 170ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1000 ℃ for 20 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 2:1, and the ball milling time is 2 hours; air classification is carried out, the classification frequency is 18Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 3:1 and the ball grinding time is 1 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 2h at 1750 ℃; preserving heat for 2h at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 20min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 25Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.3 mu m.
Example 10
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 4 weight percent and the specific surface area of 7.0m 2 Mixing/g tungsten powder with 96wt% of classified ultra-coarse tungsten powder, and then pressingCarbon black is matched in the technological requirement, carbon is matched in a ball grinding and carbon matching mode, the mass ratio of ball materials is 2:1, and the ball milling time is 2 hours, so that mixed materials are obtained;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat at 2150 ℃ for 1.5h; preserving heat for 5h at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 6.9 mu m.
Example 11
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 weight percent and the specific surface area of 7.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat at 2150 ℃ for 1.5h; preserving heat for 5h at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.1 mu m.
Example 12
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 10 percent and the specific surface area of 7.0m 2 Mixing/g tungsten powder with 90wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat at 2150 ℃ for 1.5h; preserving heat for 5h at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 40min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.0 mu m.
Example 13
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 weight percent and the specific surface area of 10.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat at 2150 ℃ for 1.5h; preserving heat for 5h at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.6 mu m.
Example 14
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 weight percent and the specific surface area of 10.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat at 2150 ℃ for 1.5h; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.7 mu m.
Example 15
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 150ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 weight percent and the specific surface area of 10.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat at 2150 ℃ for 1.5h; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.4 mu m.
Example 16
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 170ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 weight percent and the specific surface area of 10.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat at 2150 ℃ for 1.5h; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.6 mu m.
Example 17
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material for 18 hours at 1050 ℃ to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 3:1, and the ball milling time is 1.5 hours; air classification is carried out, the classification frequency is 14Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 weight percent and the specific surface area of 10.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat for 1.5h at 2000 ℃; preserving heat at 2150 ℃ for 8 hours;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 30Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.1 mu m.
Example 18
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1100 ℃ for 14 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 4:1, and the ball milling time is 1h; air classification is carried out, the classification frequency is 25Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 4 weight percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 96wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat for 3 hours at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 35Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 6.9 mu m.
Example 19
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1100 ℃ for 14 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 4:1, and the ball milling time is 1h; air classification is carried out, the classification frequency is 25Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat for 3 hours at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 35Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.5 mu m.
Example 20
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 150ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1100 ℃ for 14 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 4:1, and the ball milling time is 1h; air classification is carried out, the classification frequency is 25Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat for 3 hours at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 35Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.2 mu m.
Example 21
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 170ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1100 ℃ for 14 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 4:1, and the ball milling time is 1h; air classification is carried out, the classification frequency is 25Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 8 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 92wt% of classified ultra-coarse tungsten powder, adding carbon black according to technological requirements, and adopting ball grinding carbon adding modePerforming carbon mixing, wherein the mass ratio of the ball materials is 2:1, and the ball milling time is 2h, so as to obtain mixed materials;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat for 3 hours at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 35Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.4 mu m.
Example 22
The preparation method of the ultra-coarse uniform tungsten carbide powder comprises the following steps:
s1, adopting a doping device in the patent with the patent number ZL202021830264.7 to carry out Na doping on a tungsten oxide raw material, wherein the Na doping amount is 190ppm;
s2, reducing the doped tungsten oxide raw material with hydrogen at 1100 ℃ for 14 hours to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, wherein the ball material mass ratio is 4:1, and the ball milling time is 1h; air classification is carried out, the classification frequency is 25Hz, and classified ultra-coarse tungsten powder is obtained;
S4, taking the components with the weight percentage of 10 percent and the specific surface area of 9.0m 2 Mixing/g tungsten powder with 90wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, adding carbon in a ball grinding carbon adding mode, and obtaining mixed materials, wherein the ball material mass ratio is 2:1 and the ball grinding time is 2 h;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
preserving heat for 1.5h at 1750 ℃; preserving heat for 3 hours at 2150 ℃; preserving heat for 8 hours at 2190 ℃;
s6, ball milling and crushing the carbonized materials, wherein the mass ratio of the ball materials is 2:1, the ball milling time is 30min, and coarse particles are removed through sieving;
s7, carrying out air current classification on the sieved material, wherein the classification frequency is 35Hz; the ultra-coarse uniform tungsten carbide powder is obtained, and the grinding state granularity is 7.1 mu m.
Comparative example 1
The difference from example 2 is that,
s5, carbonizing the mixed materials at 2300 ℃ for 6 hours.
The tungsten carbide powder with a grinding state granularity of 5.34 mu m is obtained.
Comparative example 2
Unlike example 18,
s5, carbonizing the mixed materials at 2300 ℃ for 12 hours.
The tungsten carbide powder with a grinding state granularity of 5.56 μm is obtained.
Comparative example 3
Unlike example 16,
s5, carbonizing the mixed materials at 2300 ℃ for 11h.
The tungsten carbide powder with a grinding state granularity of 5.85 μm is obtained.
The measurement method of the grinding state granularity is measured by adopting the 'dispersion treatment rule of GB/T37561-2019 refractory metals and compound powders thereof before granularity measurement' and the 'determination method of Fisher granularity of GB/T3249-2009 metals and compound powders thereof', wherein the numerical value represents the granularity of the powder after grinding, the larger the numerical value is, the stronger the abrasion resistance is, and the smaller the numerical value is, the poorer the abrasion resistance is.
The ultra-coarse uniform tungsten carbide powder is prepared by the processes of hydrogen reduction, high-energy crushing, air flow classification, three-stage carbonization, secondary air flow classification and the like, and the three-stage carbonization process can effectively reduce the solid-phase sintering effect among large-particle tungsten powder in the initial carbonization stage, reduce the generation probability of coarse particles, improve the carbonization degree and reduce W 2 And C phase is generated, so that the wear resistance of the tungsten carbide is effectively improved. The ultra-coarse tungsten carbide powder with better wear resistance and more uniform particle size distribution is prepared by adopting the preparation method of the invention, and the grinding state particle size of the prepared tungsten carbide powder is more than or equal to 6.5 mu m, thereby being beneficial to large-scale industrial production. The abrasion resistance of the tungsten carbide powder prepared by the preparation method (comparative examples 1-3) without adopting the three-stage carbonization process is obviously lower than that of the invention Examples.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the content of the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (9)
1. The preparation method of the ultra-coarse uniform tungsten carbide powder is characterized in that the grinding state granularity of the tungsten carbide powder is more than or equal to 6.5 mu m, and the preparation method comprises the following steps:
s1, adopting a doping device to dope tungsten oxide raw materials with alkali metal, wherein the doping amount of the alkali metal is 150-190 ppm;
s2, carrying out hydrogen reduction on the doped tungsten oxide raw material to prepare ultra-coarse tungsten powder;
s3, performing high-energy ball milling and crushing on the ultra-coarse tungsten powder, and performing air flow classification to obtain classified ultra-coarse tungsten powder;
s4, taking the materials with the weight percentage of 3-10wt% and the specific surface area of 5.0-10.0 m 2 Mixing/g tungsten powder with 90-97wt% of classified ultra-coarse tungsten powder, adding carbon black according to the process requirement, and adding carbon in a ball grinding carbon adding mode to obtain a mixed material;
s5, carrying out three-stage carbonization on the mixed materials, wherein the carbonization process comprises the following steps:
Preserving heat for 1-3 h at 1750-1950 ℃;
preserving heat for 1-3 h at 1950-2150 ℃;
preserving heat for 3-8 hours at 2150-2190 ℃;
s6, ball milling and crushing the carbonized material, and sieving to remove coarse particles;
s7, carrying out air current classification on the sieved material to obtain ultra-coarse uniform tungsten carbide powder.
2. The method for preparing ultra-coarse uniform tungsten carbide powder according to claim 1, wherein in step S1, the alkali metal is Na.
3. The method for preparing ultra-coarse uniform tungsten carbide powder according to claim 1, wherein in the step S2, the reduction temperature is 1000-1100 ℃ and the reduction time is 10-20 h.
4. The method for preparing ultra-coarse uniform tungsten carbide powder according to claim 1, wherein in the step S3, the ball material mass ratio is 2-4:1, and the ball milling time is 0.5-2 h.
5. The method for preparing ultra-coarse uniform tungsten carbide powder according to claim 1, wherein in the step S3, the classification frequency is 10-30 hz.
6. The method for preparing ultra-coarse uniform tungsten carbide powder according to claim 1, wherein in the step S4, the ball material mass ratio of ball grinding carbon is 2-4:1, and the ball milling time is 1-2 hours.
7. The method for preparing ultra-coarse uniform tungsten carbide powder according to claim 1, wherein in the step S6, the ball material mass ratio of ball milling and crushing is 2-4:1, and the ball milling time is 10-40 min.
8. The method for preparing ultra-coarse uniform tungsten carbide powder according to claim 1, wherein in the step S7, the classification frequency is 20-40 hz.
9. An ultra-coarse uniform tungsten carbide powder prepared by the method of any one of claims 1-8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310448322.1A CN116143124B (en) | 2023-04-24 | 2023-04-24 | Ultra-coarse uniform tungsten carbide powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310448322.1A CN116143124B (en) | 2023-04-24 | 2023-04-24 | Ultra-coarse uniform tungsten carbide powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116143124A CN116143124A (en) | 2023-05-23 |
| CN116143124B true CN116143124B (en) | 2023-08-08 |
Family
ID=86352916
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310448322.1A Active CN116143124B (en) | 2023-04-24 | 2023-04-24 | Ultra-coarse uniform tungsten carbide powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116143124B (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1445043A (en) * | 1965-07-28 | 1966-07-08 | Atomic Energy Authority Uk | Sintering process |
| US4983354A (en) * | 1989-02-10 | 1991-01-08 | Gte Products Corporation | Uniform coarse tungsten carbide powder and cemented tungsten carbide article and process for producing same |
| JPH0412013A (en) * | 1990-04-26 | 1992-01-16 | Mitsubishi Materials Corp | Preparation of equiaxial tungsten carbide ultrafine powder |
| RU2207320C1 (en) * | 2002-01-25 | 2003-06-27 | Московский государственный институт стали и сплавов (технологический университет) | Method of producing fine tungsten carbide or tungsten and cobalt carbide mixture |
| RU2009101478A (en) * | 2009-01-19 | 2010-07-27 | Государственное образовательное учреждение высшего профессионального образования Томский государственный университет (ТГУ) (RU) | METHOD AND DEVICE FOR PRODUCING TUNGSTEN CARBIDE NANOPOWDER |
| CN102557028A (en) * | 2010-12-16 | 2012-07-11 | 江西耀升工贸发展有限公司 | Preparation method of high-stability high-purity extra-coarse tungsten carbide powder |
| CN107973299A (en) * | 2017-11-30 | 2018-05-01 | 株洲三鑫硬质合金生产有限公司 | A kind of production system and its production technology of high temperature base WC powder |
| CN108529628A (en) * | 2018-05-28 | 2018-09-14 | 株洲硬质合金集团有限公司 | A kind of preparation method of Coarse Tungsten Carbide Powder |
| JP2018165233A (en) * | 2017-03-28 | 2018-10-25 | 日本新金属株式会社 | Method for producing fine tungsten carbide powder |
| CN110240163A (en) * | 2019-07-30 | 2019-09-17 | 株洲硬质合金集团有限公司 | A kind of method that coarse tungsten powder prepares fine grain WC powder in use |
| CN111573677A (en) * | 2020-05-20 | 2020-08-25 | 蓬莱市超硬复合材料有限公司 | Ultra-coarse grain tungsten carbide powder and preparation method thereof |
| CN113718124A (en) * | 2021-08-27 | 2021-11-30 | 崇义章源钨业股份有限公司 | Preparation method of bicrystal gradient hard alloy |
| CN114436263A (en) * | 2022-02-14 | 2022-05-06 | 崇义章源钨业股份有限公司 | Preparation method of ultra-coarse uniform tungsten carbide powder |
| CN115321537A (en) * | 2022-09-23 | 2022-11-11 | 西安稀有金属材料研究院有限公司 | Preparation method of high-dispersion particle size controllable nano tungsten carbide powder |
-
2023
- 2023-04-24 CN CN202310448322.1A patent/CN116143124B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1445043A (en) * | 1965-07-28 | 1966-07-08 | Atomic Energy Authority Uk | Sintering process |
| US4983354A (en) * | 1989-02-10 | 1991-01-08 | Gte Products Corporation | Uniform coarse tungsten carbide powder and cemented tungsten carbide article and process for producing same |
| JPH0412013A (en) * | 1990-04-26 | 1992-01-16 | Mitsubishi Materials Corp | Preparation of equiaxial tungsten carbide ultrafine powder |
| RU2207320C1 (en) * | 2002-01-25 | 2003-06-27 | Московский государственный институт стали и сплавов (технологический университет) | Method of producing fine tungsten carbide or tungsten and cobalt carbide mixture |
| RU2009101478A (en) * | 2009-01-19 | 2010-07-27 | Государственное образовательное учреждение высшего профессионального образования Томский государственный университет (ТГУ) (RU) | METHOD AND DEVICE FOR PRODUCING TUNGSTEN CARBIDE NANOPOWDER |
| CN102557028A (en) * | 2010-12-16 | 2012-07-11 | 江西耀升工贸发展有限公司 | Preparation method of high-stability high-purity extra-coarse tungsten carbide powder |
| JP2018165233A (en) * | 2017-03-28 | 2018-10-25 | 日本新金属株式会社 | Method for producing fine tungsten carbide powder |
| CN107973299A (en) * | 2017-11-30 | 2018-05-01 | 株洲三鑫硬质合金生产有限公司 | A kind of production system and its production technology of high temperature base WC powder |
| CN108529628A (en) * | 2018-05-28 | 2018-09-14 | 株洲硬质合金集团有限公司 | A kind of preparation method of Coarse Tungsten Carbide Powder |
| CN110240163A (en) * | 2019-07-30 | 2019-09-17 | 株洲硬质合金集团有限公司 | A kind of method that coarse tungsten powder prepares fine grain WC powder in use |
| CN111573677A (en) * | 2020-05-20 | 2020-08-25 | 蓬莱市超硬复合材料有限公司 | Ultra-coarse grain tungsten carbide powder and preparation method thereof |
| CN113718124A (en) * | 2021-08-27 | 2021-11-30 | 崇义章源钨业股份有限公司 | Preparation method of bicrystal gradient hard alloy |
| CN114436263A (en) * | 2022-02-14 | 2022-05-06 | 崇义章源钨业股份有限公司 | Preparation method of ultra-coarse uniform tungsten carbide powder |
| CN115321537A (en) * | 2022-09-23 | 2022-11-11 | 西安稀有金属材料研究院有限公司 | Preparation method of high-dispersion particle size controllable nano tungsten carbide powder |
Non-Patent Citations (1)
| Title |
|---|
| 陈爱荣.金属切削原理与刀具.中国商业出版社,2007,第26页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116143124A (en) | 2023-05-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114436263B (en) | Preparation method of ultra-coarse uniform tungsten carbide powder | |
| CN107475548B (en) | A kind of preparation method of nanometer of toughening superfine WC-Co cemented carbide | |
| CN107585768B (en) | Method for preparing superfine tungsten carbide powder by oxidation-reduction method | |
| CN107470639B (en) | A kind of preparation method of narrow size distribution globular tungsten powder | |
| CN113998680B (en) | Method for preparing lithium iron phosphate anode material by taking high-iron Bayer process red mud as iron source | |
| CN108356274A (en) | A kind of TiB used for hot spraying2- Ni based ceramic metal composite construction feedings and preparation method thereof | |
| WO2022095270A1 (en) | Continuous low-temperature plasma powder treatment and ball milling production device and method therefor | |
| CN102826736A (en) | Method for preparing hollow glass bead by using glass powder process | |
| CN110890537A (en) | Production method of high-purity nanocrystalline silicon | |
| CN104611600A (en) | Preparation method and system of super-thick cemented carbide | |
| CN116143124B (en) | Ultra-coarse uniform tungsten carbide powder and preparation method thereof | |
| CN108998659B (en) | Process for processing pellet ore by using siderite powder and vanadium-titanium magnetite powder | |
| CN112941352B (en) | Hard alloy and preparation method thereof | |
| CN105798316A (en) | Processing technology of nanoscale tungsten powder | |
| CN107116227B (en) | A kind of preparation method of ultrafine WC-Ni composite powder | |
| CN110416513B (en) | Preparation method of carbon-silicon composite material, carbon-silicon composite electrode and battery comprising carbon-silicon composite electrode | |
| CN108275688A (en) | A kind of high oil absorption amount kleit preparation method | |
| CN115602807B (en) | Industrial preparation method of carbon-coated silicon oxide negative electrode material | |
| CN111154993A (en) | Preparation method of tungsten carbide-titanium carbide solid solution | |
| CN114105134B (en) | Matrix graphite powder for high-temperature gas cooled reactor fuel element and preparation method thereof | |
| CN1434169A (en) | Coaseries kaolin calcined coating and preparation method thereof | |
| CN115717227A (en) | Metal-coated WC hard alloy coating and preparation method thereof | |
| CN115196970A (en) | Preparation method of high-fluidity AlON spherical powder | |
| CN210595289U (en) | Preparation device of carbon-silicon composite material | |
| CN112537959A (en) | Preparation method of ceramic powder for plasma physical vapor deposition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20230523 Assignee: DEZHOU ZHANGYUAN SPRAYING TECHNOLOGY CO.,LTD. Assignor: CHONGYI ZHANGYUAN TUNGSTEN Co.,Ltd. Contract record no.: X2023980053807 Denomination of invention: A super coarse and uniform tungsten carbide powder and its preparation method Granted publication date: 20230808 License type: Common License Record date: 20231222 |