CN114715894A - Preparation method of nano tungsten carbide powder - Google Patents
Preparation method of nano tungsten carbide powder Download PDFInfo
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- CN114715894A CN114715894A CN202210224914.0A CN202210224914A CN114715894A CN 114715894 A CN114715894 A CN 114715894A CN 202210224914 A CN202210224914 A CN 202210224914A CN 114715894 A CN114715894 A CN 114715894A
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- carbide powder
- tungsten carbide
- nano tungsten
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- 239000000843 powder Substances 0.000 title claims abstract description 46
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000001035 drying Methods 0.000 claims abstract description 18
- 150000003657 tungsten Chemical class 0.000 claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 alkyl alkoxy acrylate Chemical compound 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 2
- SSLSOHVYTNAFRT-UHFFFAOYSA-H [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[W+6] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[W+6] SSLSOHVYTNAFRT-UHFFFAOYSA-H 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- OTNVGWMVOULBFZ-UHFFFAOYSA-N sodium;hydrochloride Chemical compound [Na].Cl OTNVGWMVOULBFZ-UHFFFAOYSA-N 0.000 claims description 2
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 230000001788 irregular Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910009043 WC-Co Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000713 high-energy ball milling Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000004846 water-soluble epoxy resin Substances 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a preparation method of nano tungsten carbide powder, which specifically comprises the following steps; (1) dissolving tungsten salt, organic monomer, cross-linking agent and carburant in deionized water in sequence to form transparent solution, and then adding initiator to prepare gel; (2) and drying the gel and calcining to obtain the nano tungsten carbide powder. The WC powder prepared by the method has high quality, nearly spherical shape and fine and uniform granularity reaching the nanometer level, and avoids the defects of uneven granularity, irregular shape and the like of the powder prepared by other methods.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, and particularly relates to a preparation method and a detection method of nano tungsten carbide powder.
Background
The nano tungsten carbide powder is an important raw material for manufacturing products such as cutting tools, metal forming tools, mining tools, wear-resistant surfaces and the like, and is widely applied to the fields of aerospace, automobiles, household appliances and the like.
At present, various methods for preparing nano tungsten carbide are reported, but all methods have some problems. For example, Ma XM, Ling Z, Gang J, Dong YD.preparation and structure of bulk nanostructured WC-Co alloy by high energy ball-milling.J Mater Sci Lett 1997; 968-970, Zhang FL, Wang CY, Zhu M.nanostructured WC/Co composite powder prepared by high energy ball milling. script Mater 2003; 1123, 1128, Fecht HJ.Synthesis and properties of nanocrystalline metals and alloys prepared by mechanical authentication, nanostruct Mater 1992; 125-130, while the powder can be milled to 10-20nm, the method has the problems of long time consumption, serious pollution, high energy consumption and the like, and is not beneficial to large-scale industrial application; another approach is Mcpcandlish LE, Kear BH, Bhatia SJ. spray conversion process for the production of nanophase composite powders. US patent 5352269; 1994. span GE.History of fine grained hardmetel.int J Refract Metal Hard Mater 1995; 13(5) 241, the Spray conversion process comprises three basic processes of solution preparation, Spray drying and high-temperature carbonization, and can prepare pure-phase WC or WC-Co nano-powder, but the powder prepared by the method has uneven particle size distribution and is doped with some micro-powder; yet another approach is Swihart MT. vapor-phase synthesis of nanoparticles. curr Opin Colloid Interf Sci 2003; 127-6-CH4-H2 system.J Less-Common Metal1978；59(1):85-95、Fitzsimmons M,Sarin VK.Comparison of WCl6-CH4-H2 and WF6-CH4-H2 systems for growth of WC coatings.Surf Coat Technol 1995；76(1–3):250-255、Kim JC,Kim BK.Synthesis of nanosized tungst(iii) en carbide powder by the chemical vapor condensation process. script Mater 2004; 50(7) 969-972 by reducing and carbonizing a tungsten salt at a high temperature in an atmosphere of a hydrocarbon gas such as methane or the like, thereby preparing a nano WC powder, but the powder prepared by the method has high purity and controllable particle size, but has high requirements on production equipment.
At present, the problem that those skilled in the art need to solve is to provide a method for preparing nano tungsten carbide powder with high powder quality, high efficiency and easy operation.
Disclosure of Invention
In view of the above, the invention provides a method for preparing nano tungsten carbide powder, the WC powder prepared by the method has high quality, nearly spherical shape, fine and uniform particle size reaching the nano level, and the defects of uneven particle size, irregular shape and the like of powder prepared by other methods are avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of nano tungsten carbide powder specifically comprises the following steps:
(1) dissolving tungsten salt, organic monomer, cross-linking agent and carburant in water in sequence to form transparent solution, and then adding initiator to prepare gel;
(2) and drying the gel and calcining to obtain the nano tungsten carbide powder.
The process of the invention utilizes a macromolecule network to wrap the tungsten salt solution, and forms nano-scale tungsten salt after drying, and then tungsten salt particles are decomposed and carbonized into tungsten carbide at high temperature in the high-temperature calcination process; the polymer in the process plays 4 roles: 1) in the polymerization process, the tungsten salt solution is divided into micron-sized small-sized solvent pools;
2) the drying process always prevents the salt from being combined in the precipitation process, and the micron-sized small size is continuously maintained; 3) in the high-temperature calcination process, the formed decomposition products such as oxides are prevented from gathering, and the size of the products is continuously kept; 4) part of organic carbonization products play a role in providing a carbon source for tungsten high-temperature carbonization; in addition, the carburant added in the method is used for ensuring the supply of carbon sources required by carbonization and playing a role in carbon regulation.
Preferably, the mass fraction of the tungsten salt in the transparent solution in the step (1) is 0.1-50%.
Preferably, the tungsten salt in the step (1) is any one of tungstic acid, ammonium paratungstate, ammonium metatungstate, tungsten chloride, tungsten fluoride and hexahydroxytungsten.
Preferably, the organic monomer and the crosslinking agent in step (1) are at least one of acrylamide, methacrylamide, methylol acrylamide, acrylic acid, methacrylic acid, methoxy-poly (vinyl glycol) methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, alkyl alkoxy acrylate, alkyl alkoxy methacrylate, methyl hydroxyethyl acrylate, methyl hydroxypropyl acrylate, methyl propenyl acrylate, N' -methylene bisacrylamide, poly (vinyl glycol) bismethacrylic acid.
Preferably, the total mass fraction of the monomer and the crosslinking agent in the transparent solution in step (1) is 0.1 to 30%; wherein the mass ratio of the monomer to the crosslinking agent is 100:0.1-0.1: 100.
Preferably, in the step (1), the carburant is any one of sucrose, cellulose, epoxy resin, phenolic resin and glucose, and the molar ratio of carburant carbon to the tungsten salt is 0.1:10-10: 0.1.
Preferably, the initiator in step (1) is 0.01 to 10% by mass of the total mass of the monomer and the crosslinking agent.
Preferably, the initiator in the step (1) is any one of ammonium sulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, benzoic acid peroxide, azobisisobutyronitrile, azobiscyanovaleric acid sodium, azo (2- (2-imidurine) propane) sodium hydrochloride (AZIP) and azo (2-amidinopropane) hydrochloride.
Preferably, the reaction conditions after the initiator is added in the step (1) are as follows: reacting for 0.1-10h at 20-90 ℃.
Preferably, the specific conditions of the drying in step (2) are: the temperature control range of drying is lower than 100 ℃ before the moisture content of the gel is higher than 20%; after the moisture content of the gel is lower than 20%, the drying temperature control range is not higher than 200 ℃, and the moisture of the final xerogel is lower than 10%.
Preferably, the calcination process in step (2) is: heating to 500-1200 ℃ at the speed of 1-20 ℃/min, preserving the heat for 0.1-10h, then cooling to 500-800 ℃ in protective atmosphere or reducing atmosphere, preserving the heat for 0.1-10h, and finally cooling to room temperature.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method, organic matters are skillfully utilized, so that the organic matters have 4 functions of partitioning solution, maintaining the size of salt, preventing the aggregation of salt decomposition products and providing a high-temperature carbonized carbon source, and the like;
(2) compared with the traditional method for preparing nano WC, the method has lower energy consumption;
(3) the method is simple to operate and high in production efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a process flow diagram of a method for preparing nano tungsten carbide powder according to the present invention;
FIG. 2 is a scanning electron microscope image of the nano-tungsten carbide powder prepared in example 1 of the present invention;
fig. 3 is an XRD diffractogram of the nano tungsten carbide powder prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, a process flow diagram of a method for preparing nano tungsten carbide powder of the present invention specifically includes the following steps:
(1) dissolving tungsten salt, organic monomer, cross-linking agent and carburant in water in sequence to form transparent solution, and then adding initiator to prepare gel;
(2) and drying the gel and calcining to obtain the nano tungsten carbide powder.
Example 1
A preparation method of nano tungsten carbide powder specifically comprises the following steps:
(1) weighing 200g of ammonium metatungstate, adding the ammonium metatungstate into 1000ml of deionized water, and preparing a tungsten salt solution; then adding 100g of organic monomer acrylamide, 1g of cross-linking agent methylene bisacrylamide and 100g of carburant water-soluble epoxy resin, and uniformly stirring until all the materials are dissolved to form a transparent solution; adding 10ml of ammonium persulfate solution with the concentration of 10%, uniformly stirring, and placing into a water bath with the temperature set to 60 ℃ for reaction for 1h to prepare gel;
(2) crushing the prepared gel into small blocks, drying the small blocks in a drying oven set to 60 ℃ for 120 hours, then heating to 80 ℃ and drying for 24 hours; finally, carrying out calcination treatment in a calcination furnace in hydrogen atmosphere, wherein the process comprises the following steps: raising the temperature to 1000 ℃ at the heating rate of 5 ℃/min, preserving the heat for 2h, then continuously adjusting the temperature to 700 ℃, and preserving the heat for 3h to obtain WC powder;
fig. 2 and 3 show a scanning electron micrograph and an XRD diffraction pattern of the WC powder obtained by the method, respectively, from which it can be seen that the powder has a shape similar to a sphere, a very uniform and fine particle size, and a size of about 100nm to 200 nm.
Example 2
A preparation method of nano tungsten carbide powder specifically comprises the following steps:
(1) weighing 150g of tungstic acid, adding the tungstic acid into 1000ml of deionized water, and preparing a tungsten salt solution; then adding 120g of organic monomer acrylamide, 1.2g of cross-linking agent methylene bisacrylamide and 300g of recarburizing agent sucrose, and uniformly stirring until all the materials are dissolved to form a transparent solution; adding 8ml of potassium persulfate solution with the concentration of 12%, uniformly stirring, and placing into a water bath with the temperature set to 80 ℃ for reaction for 2 hours to prepare gel;
(2) crushing the prepared gel into small blocks, drying the small blocks in a drying oven with the temperature set to 80 ℃ for 160 hours, then heating to 90 ℃ and drying for 24 hours; and finally, carrying out calcination treatment in a calcination furnace in CO atmosphere, wherein the process comprises the following steps: heating to 800 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 1h, then continuously heating to 900 ℃, keeping the temperature for 2h, and obtaining WC powder.
Example 3
A preparation method of nano tungsten carbide powder specifically comprises the following steps:
(1) weighing 180g of tungsten chloride, and adding the tungsten chloride into 1000ml of deionized water to prepare a tungsten salt solution; then adding 100g of organic monomer HEMA100g, 0.8g of cross-linking agent methylene bisacrylamide and 400g of recarburizing agent glucose, and uniformly stirring until all the components are dissolved to form a transparent solution; adding 12ml of 10% sodium persulfate solution, stirring uniformly, and placing in a water bath with the temperature set to 60 ℃ for reaction for 1h to prepare gel;
(2) crushing the prepared gel into small blocks, drying the small blocks in a drying oven with the temperature set to 80 ℃ for 100 hours, and then heating to 120 ℃ and drying for 12 hours; finally, calcining in a calcining furnace in methane atmosphere, wherein the process comprises the following steps: raising the temperature to 900 ℃ at the heating rate of 2 ℃/min, preserving the heat for 2h, then continuously adjusting the temperature to 600 ℃, and preserving the heat for 3h to obtain WC powder.
The various embodiments are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the various embodiments can be referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of nano tungsten carbide powder is characterized by comprising the following steps:
(1) sequentially dissolving tungsten salt, organic monomer, cross-linking agent and carburant in water to form transparent solution, and then adding initiator to prepare gel;
(2) and drying the gel and calcining to obtain the nano tungsten carbide powder.
2. The method for preparing nano tungsten carbide powder according to claim 1, wherein the mass fraction of the tungsten salt in the transparent solution in the step (1) is 0.1-50%.
3. The method for preparing nano tungsten carbide powder according to claim 1, wherein the tungsten salt in the step (1) is any one of tungstic acid, ammonium paratungstate, ammonium metatungstate, tungsten chloride, tungsten fluoride and hexahydroxytungsten.
4. The method according to claim 1, wherein the organic monomer and the crosslinking agent in step (1) are at least one selected from acrylamide, methacrylamide, methylol acrylamide, acrylic acid, methacrylic acid, methoxy-poly (vinyl glycol) methacrylic acid, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, alkyl alkoxy acrylate, alkyl alkoxy methacrylate, methyl hydroxyethyl acrylate, methyl hydroxypropyl acrylate, methyl propenyl acrylate, N' -methylene bisacrylamide, and poly (vinyl glycol) bismethacrylic acid.
5. The method for preparing nano tungsten carbide powder according to claim 1, wherein the total mass fraction of the monomer and the cross-linking agent in the transparent solution in the step (1) is 0.1-30%; wherein the mass ratio of the monomer to the crosslinking agent is 100:0.1-0.1: 100.
6. The method for preparing nano tungsten carbide powder according to claim 1, wherein the carburant in step (1) is any one of sucrose, cellulose, epoxy resin, phenolic resin and glucose, and the molar ratio of carburant carbon to the tungsten salt is 0.1:10-10: 0.1.
7. The method for preparing nano tungsten carbide powder according to claim 1, wherein the initiator in the step (1) is 0.01-10% of the total mass of the monomer and the cross-linking agent.
8. The method for preparing nanometer tungsten carbide powder according to claim 1, wherein the initiator in step (1) is any one of ammonium sulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, benzoic peroxide, azobisisobutyronitrile, azobiscyanovaleric acid sodium, azo (2- (2-imidurine) propane) sodium hydrochloride (AZIP) and azo (2-amidinopropane) hydrochloride.
9. The method for preparing nano tungsten carbide powder according to claim 1, wherein the reaction conditions after the initiator is added in the step (1) are as follows: reacting for 0.1-10h at 20-90 ℃.
10. The method for preparing nano tungsten carbide powder according to claim 1, wherein the calcining process in the step (2) is as follows: heating to 500-1200 ℃ at the speed of 1-20 ℃/min, preserving the heat for 0.1-10h, then cooling to 500-800 ℃ in protective atmosphere or reducing atmosphere, preserving the heat for 0.1-10h, and finally cooling to room temperature.
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| CN108705086A (en) * | 2018-05-24 | 2018-10-26 | 北京科技大学 | A kind of method that the printing of 3D gels prepares steel bonded carbide |
| CN114634182B (en) * | 2022-04-21 | 2024-02-23 | 湖北绿钨资源循环有限公司 | Preparation method of tungsten carbide |
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| MARZIE MARDALI ET AL.: "Particle Size Controlling of WC-Co Nano Powders Prepared by Polyacrylamide Hydrogel method", 《4TH INTERNATIONAL CONFERENCE ON ULTRAFINE GRAINED AND NANOSTRUCTURED MATERIALS》, pages 1 - 5 * |
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