CN113149657A - Preparation method of titanium carbide/titanium diboride composite ceramic particle preform - Google Patents
Preparation method of titanium carbide/titanium diboride composite ceramic particle preform Download PDFInfo
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- CN113149657A CN113149657A CN202110456111.3A CN202110456111A CN113149657A CN 113149657 A CN113149657 A CN 113149657A CN 202110456111 A CN202110456111 A CN 202110456111A CN 113149657 A CN113149657 A CN 113149657A
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- 229910033181 TiB2 Inorganic materials 0.000 title claims abstract description 106
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 title claims abstract description 101
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000002245 particle Substances 0.000 title claims abstract description 96
- 239000000919 ceramic Substances 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 185
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 52
- 238000005469 granulation Methods 0.000 claims abstract description 46
- 230000003179 granulation Effects 0.000 claims abstract description 46
- 238000005245 sintering Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 15
- 239000000661 sodium alginate Substances 0.000 claims abstract description 15
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 8
- 238000001723 curing Methods 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 238000007780 powder milling Methods 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005496 eutectics Effects 0.000 abstract description 3
- 238000001272 pressureless sintering Methods 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 7
- 239000000956 alloy Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 244000035744 Hura crepitans Species 0.000 description 1
- 241000251131 Sphyrna Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011156 metal matrix composite Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
- C04B35/58064—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides
- C04B35/58071—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides based on refractory borides based on titanium borides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
- C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
The invention relates to a preparation method of a titanium carbide/titanium diboride composite ceramic particle preform, which comprises the following steps of firstly preparing titanium carbide/titanium diboride composite ceramic particles; and preparing the titanium carbide/titanium diboride composite ceramic particle preform. The titanium carbide/titanium diboride composite ceramic particles may be prepared by pressure granulation or sol gel granulation. The pressure granulation method is to utilize titanium carbide and titanium diboride to form eutectic phase with lower sintering temperature, then a small amount of metal sintering aid is added, and pressureless sintering can be carried out at the lower sintering temperature to form the titanium carbide/titanium diboride composite ceramic particles. The sol-gel granulation is prepared by adding water and water reducing agent and sodium alginate solution into mixed powder formed by titanium carbide powder, titanium diboride powder and metal powder, performing ball milling, curing and sintering at high temperature. The obtained composite ceramic particles have high hardness and high toughness, and compared with zirconia toughened alumina ceramic particles, the performance of the metal-based ceramic particle composite material can be further improved.
Description
Technical Field
The invention relates to preparation of a metal-based wear-resistant material, in particular to a preparation method of a titanium carbide/titanium diboride composite ceramic particle preform.
Background
In the industries of metallurgy, mine, electricity, building materials and the like, wear-resistant parts such as vertical grinding rollers, grinding discs, plate hammers, hammer heads and the like for crushing or grinding materials are developed from single wear-resistant metal materials to metal-based composite materials with high wear resistance. Because the nature of the reinforcing phase is greatly different from that of the metal matrix, a reinforcing phase prefabricated body is generally prepared firstly and then is compounded through different casting processes, the preparation of the ceramic prefabricated body has great influence on the production of the final metal matrix composite material, and the corresponding ceramic prefabricated body also has great influence on the final product by using different ceramic particles.
Titanium diboride (TiB)2) The wear-resistant alloy has the advantages of high hardness, high melting point, low specific gravity and the like, and has wide application prospect in the fields of wear-resistant parts (wire drawing forming dies, mechanical sealing parts, aerospace parts and the like), cutters and the like. However, TiB2It has anisotropy due to its hexagonal close packed (hcp) structure, which makes it difficult to sinter dense without microcracks. Titanium carbide (TiC) has a cubic structure similar to that of NaCl, considered as one of the most important metal carbides for the manufacture of a new generation of cermets, and has a low density (4.93 g/cm)3) Low coefficient of friction, thermal stability, high solubility with other carbides, high melting point (3067 ℃), high elastic modulus (410 ℃) 450 GPa, high thermal conductivity and higher thermodynamic stability and hardness than WC (33% higher than WC). TiC is difficult to sinter, usually requires the addition of other ceramic or metal components to facilitate sintering and improve toughness, produces TiC-based cermet, and is often added to WC-based cemented carbide to improve properties.
Compared with the traditional metal ceramic based on WC and TiC, the metal ceramic based on TiC-TiB2Cermets of composite materials exhibit higher hardness and chemical stability at high temperatures and are considered as good substitutes for wear resistant applications.
Patent (CN 109161720A) discloses a method for preparing a new composite alloy material, which is to add titanium carbide and titanium diboride into a chromium alloy to improve the wear resistance, strength, hardness and the like of the alloy, but the material still belongs to an alloy material and has limited wear resistance. Patent (CN 109355521A) discloses a method for preparing titanium diboride-based metal composite material, which comprises adding titanium-based alloy powder (10-20%) into titanium diboride (80-90%), sintering at 1000 ℃ in inert atmosphere to obtain titanium diboride-based metal composite material, thereby improving toughness of the composite material, but the titanium diboride with lower sintering temperature is difficult to form combination. The patent (CN 108823445A) discloses a method for preparing metal ceramic, which is to mix titanium dioxide, carbon powder, boron and ethyl orthosilicate, add other raw materials to react and burnTo form composite metal ceramic, and sintering at 950 deg.c. The patent (CN 108439990B) discloses a preparation method of a titanium diboride-based ceramic composite material, which comprises the steps of mixing a carbon source and TiB2The powder and the absolute ethyl alcohol are uniformly mixed, and then the titanium diboride-based ceramic composite material with high density is obtained through other steps of vacuum infiltration. The patent (CN 101941843B) discloses a TiB2Preparation method of-TiC-WC superhard material, namely TiB2TiC, WC and Ni powder as raw materials, and hot pressing and sintering the superhard material at 1500-1650 ℃.
Disclosure of Invention
The invention aims to provide a preparation method of a titanium carbide/titanium diboride composite ceramic particle preform, which comprises the steps of adding a proper amount of metal sintering aid into titanium carbide and titanium diboride, forming titanium carbide/titanium diboride composite ceramic particles by a pressure granulation method or a sol-gel granulation method, and adding an inorganic adhesive into the obtained composite ceramic particles to prepare the titanium carbide/titanium diboride composite ceramic particle preform, wherein the obtained preform has better hardness and toughness and can replace the original metal-based ceramic preform.
The technical problem to be solved is realized by adopting the following technical scheme, and the preparation method of the titanium carbide/titanium diboride composite ceramic particle preform provided by the invention comprises the following steps of (1) preparing titanium carbide/titanium diboride composite ceramic particles; (2) preparing a titanium carbide/titanium diboride composite ceramic particle preform; the key point of the invention is that the titanium carbide/titanium diboride composite ceramic particles can be prepared by a pressure granulation method or a sol-gel granulation method;
the pressure granulation method mainly comprises the following steps: mixing powder consisting of titanium carbide powder, titanium diboride powder and metal powder with the zinc stearate fine powder, adding absolute ethyl alcohol, mixing for 2-3 h, and then performing pressure granulation in a pressure granulator to obtain a material with the particle size of 1-6 mm; placing the materials at room temperature for more than 24 h, then placing the materials in an argon protection furnace, preserving heat for 1 h at 500 ℃, and then heating the argon protection furnace to 1500-1800 ℃ to sinter for 1-2 h to prepare titanium carbide/titanium diboride composite ceramic particles;
the sol-gel granulation method mainly comprises the following steps: adding deionized water and a basf water reducing agent FS20 into powder consisting of titanium carbide powder, titanium diboride powder and metal powder, and ball-milling the obtained mixed material in a ceramic ball-milling tank for 30-120 min; then adding a sodium alginate solution, and continuing to perform ball milling for 30-120min to obtain slurry; dripping or spraying the obtained slurry into sufficient calcium chloride solution or iridium nitrate solution, and curing for 1-5 h; filtering out particles, drying the particles in a drying oven at 80 ℃ for 6-12h, and drying the particles to obtain green body particles with the particle size of 1-6 mm; placing the obtained green body particles in an argon protection furnace, sintering for 1-5 h at 1500-1800 ℃, and obtaining titanium carbide/titanium diboride composite ceramic particles after sintering;
in the pressure granulation method and the sol-gel granulation method, the titanium carbide powder, the titanium diboride powder and the metal powder account for 30-70 percent, 30-70 percent and 2-5 percent of the total weight of the powder in sequence, and the sum of the weight percentages of the titanium carbide powder, the titanium diboride powder and the metal powder accounts for 100 percent of the total weight of the powder; the total weight of the powder is the sum of the weight of the titanium carbide powder, the titanium diboride powder and the metal powder.
Further, the metal powder is a mixed powder of two or more of nickel powder, molybdenum powder, vanadium powder, niobium powder and chromium powder.
Further, in the pressure granulation method, the addition weight of the zinc stearate fine powder accounts for 0.5-1% of the total weight of the powder.
Furthermore, in the pressure granulation method, the adding weight of the absolute ethyl alcohol accounts for 10-15% of the total weight of the powder.
Further, in the pressure granulation method, the pressure of granulation by the pressure granulator is 100-300 MPa.
Furthermore, in the sol-gel granulation method, the adding weight of the deionized water accounts for 20-40% of the total weight of the powder.
Further, in the sol-gel granulation method, the added weight of the basf water reducing agent FS20 was 0.5% of the total weight of the powder.
Further, in the sol-gel granulation method, the mass fraction of the used sodium alginate solution is 5-10%; the addition amount of the sodium alginate solution is that 5-15mL of the sodium alginate solution is added to every 100g of the powder.
Further, in the sol-gel granulation method, the mass fractions of the calcium chloride solution and the iridium nitrate solution are both 2 to 3%.
Further, the particle size of the titanium carbide/titanium diboride composite ceramic particles finally obtained by the pressure granulation method is 0.5-3.5 mm; the particle size of the titanium carbide/titanium diboride composite ceramic particles obtained finally by the sol-gel granulation method is 0.5-4 mm.
Compared with the prior art, the invention has the following advantages: both titanium carbide and titanium diboride have high hardness, and single titanium carbide and titanium diboride are difficult to sinter due to high melting point and can be sintered only by pressurization, and the toughness of single-phase ceramics is poor. The titanium carbide and the titanium diboride can form eutectic phase, the corresponding sintering temperature of the eutectic is lower, and then a small amount of metal sintering aid is added, and pressureless sintering can be carried out at the lower sintering temperature to form the titanium carbide/titanium diboride composite ceramic particles. In addition, the hardness and toughness of the ceramic particles can be adjusted by changing the content of the metal sintering aid and the sintering temperature, such as: the content of the sintering aid is reduced, the sintering temperature is increased, the hardness is increased, and the toughness is reduced; on the contrary, the hardness is reduced, and the toughness is improved, so the invention can be properly adjusted according to the use working condition.
Detailed Description
In order to further illustrate the technical means and technical effects adopted by the present invention, the present invention is described in detail below with reference to specific embodiments.
The preparation method of the titanium carbide/titanium diboride composite ceramic particle preform mainly comprises the following 2 steps:
(1) preparation of titanium carbide/titanium diboride composite ceramic particles
The titanium carbide/titanium diboride composite ceramic particles can be prepared by two methods, namely a pressure granulation method and a sol-gel granulation method:
(a) the pressure granulation method comprises mixing powder composed of 30-70wt% titanium carbide powder, 30-70wt% titanium diboride powder and 2-5wt% metal powder with zinc stearate fine powder, adding anhydrous ethanol, and mixing in polyethylene bottle for 2-3 hr; and after mixing, adding 100-300 Mpa pressure in a pressure granulator for granulation to obtain a material with the particle size of 1-6 mm, placing the material at room temperature for more than 24 h, then placing the material in an argon protection furnace, preserving heat for 1 h at 500 ℃, subsequently heating the argon protection furnace to 1500-1800 ℃ for sintering for 1-2 h, and finally obtaining the titanium carbide/titanium diboride composite ceramic particles with the particle size of 0.5-3.5 mm.
Wherein the adding weight of the zinc stearate fine powder accounts for 0.5-1% of the total weight of the powder. The weight of the absolute ethyl alcohol accounts for 10-15% of the total weight of the powder. The total weight of the powder is the sum of the weight of the titanium carbide powder, the titanium diboride powder and the metal powder, and the sum of the weight percentages of the titanium carbide powder, the titanium diboride powder and the metal powder in the total weight of the powder is 100 percent.
The metal powder is a mixed powder of two or more of nickel powder, molybdenum powder, vanadium powder, niobium powder, chromium powder and the like.
(b) The sol-gel granulation method is characterized in that deionized water accounting for 20-40wt% of the total weight of powder and a basf ceramic water reducing agent FS20 accounting for 0.5wt% of the total weight of the powder are added into the powder consisting of 30-70wt% of titanium carbide powder, 30-70wt% of titanium diboride powder and 2-5wt% of metal powder, the obtained mixed material is subjected to ball milling in a ceramic ball milling tank for 30-120min, then a sodium alginate solution accounting for 5-10% of the mass fraction is added, ball milling is continued for 30-120min, and slurry is obtained, and the viscosity of the slurry can be adjusted through the amount of the sodium alginate solution. Dropping or spraying the obtained slurry into sufficient calcium chloride solution or iridium nitrate solution (the volume of the calcium chloride solution or iridium nitrate solution is enough, the slurry is dropped or sprayed into the slurry and then solidified to form solid particles), solidifying for 1-5 h, filtering out particles, drying the particles in a drying oven at 80 ℃ for 6-12h to prepare green body particles with the particle size of 1-6 mm, placing the obtained green body particles in an argon protection furnace, sintering at 1500-1800 ℃ for 1-5 h, and obtaining the titanium carbide/titanium diboride composite ceramic particles with the particle size of 0.5-4 mm after sintering.
In the sol-gel method, the total weight of the powder refers to the sum of the weight of the titanium carbide powder, the titanium diboride powder and the metal powder, and the sum of the weight percentages of the titanium carbide powder, the titanium diboride powder and the metal powder in the total weight of the powder is 100%. The adding volume of the sodium alginate solution is 5-15mL based on the total weight of the powder as 100 g. The mass fractions of the calcium chloride solution and the iridium nitrate solution are both 2-3%, and the iridium nitrate solution is preferred.
(2) Preparation of titanium carbide/titanium diboride composite ceramic particle preform
And (2) adding 3% of inorganic adhesive into the titanium carbide/titanium diboride composite ceramic particles prepared in the step (1), uniformly mixing, filling into a resin mold, pressing, then placing into a microwave drying oven for drying, and curing the mixture by microwave heating, wherein the microwave power is 3 kilowatts, and the curing time is 3 min. And demolding the cured prefabricated part, and heating in a resistance furnace at 200-300 deg.c for 0.5-2 hr to obtain the composite ceramic particle prefabricated body of titanium carbide/titanium diboride. And then cast into a metal matrix ceramic composite according to the prior art.
The inorganic binder consists of 60-80% of sodium silicate, 10-30% of silica sol and 10-20% of oxide powder by weight, wherein the oxide powder is one or a mixture of aluminum oxide, magnesium oxide and nickel oxide, and the oxide powder is micron-sized or nano-sized. The added weight of the inorganic binder accounts for 3 percent of the weight of the titanium carbide/titanium diboride composite ceramic particles.
Example 1:
(1) preparing titanium carbide/titanium diboride composite ceramic particles by a pressure method: the powder consists of titanium carbide powder, titanium diboride powder and metal powder, wherein the titanium carbide powder and the titanium diboride powder are micron powder, the titanium carbide powder and the titanium diboride powder account for 95wt% of the total weight of the powder, and the metal powder accounts for 5wt% of the total weight of the powder. The weight ratio of the titanium carbide powder to the titanium diboride powder is 1:1 (namely, the weight of the titanium carbide powder and the titanium diboride powder accounts for 47.5wt% of the total weight of the powder), and the metal powder is nano mixed powder consisting of nickel powder, molybdenum powder and vanadium powder, wherein the weight percentages of the nickel powder, the molybdenum powder and the vanadium powder in the total weight of the powder are respectively 2.5wt%, 1.25wt% and 1.25 wt%. The adding weight of the zinc stearate fine powder accounts for 1wt% of the total weight of the powder, and the adding weight of the absolute ethyl alcohol accounts for 10wt% of the total weight of the powder.
Adding powder consisting of titanium carbide powder, titanium diboride powder and metal powder, zinc stearate fine powder and absolute ethyl alcohol into a polyethylene bottle, mixing for 2h, then adding 150 Mpa pressure granulation in a pressure granulator to obtain a material with the particle size of 2-5 mm, placing the material at room temperature for 24 h, then placing the material in an argon protection furnace, introducing argon atmosphere, keeping the temperature for 1 h at 500 ℃, then heating the argon protection furnace to 1550 ℃ for sintering for 1 h, and cooling to obtain the titanium carbide/titanium diboride composite ceramic particles with the particle size of 0.5-3.5 mm.
The test shows that the hardness HV of the obtained titanium carbide/titanium diboride composite ceramic particles is about 17GPa, and the fracture toughness KICA value of 8.5 MNm-3/2。
(2) Preparing a titanium carbide/titanium diboride composite ceramic particle preform: and uniformly mixing the prepared titanium carbide/titanium diboride composite ceramic particles with an inorganic adhesive accounting for 3 percent of the weight of the composite ceramic particles, filling the mixture into a resin mold, pressing the mixture, putting the mixture into a microwave drying oven for drying, and curing the mixture by microwave heating, wherein the microwave power is 3 kilowatts, and the curing time is 3 min. And demolding the cured prefabricated part, and heating in a resistance furnace at 200-300 deg.c for 0.5 hr to obtain the composite ceramic particle prefabricated body of titanium carbide/titanium diboride. And placing the obtained composite ceramic particle prefabricated body in a casting sand box according to a designed product, and casting metal liquid to obtain the metal-based ceramic composite material. The inorganic binder consists of 60-80% of sodium silicate, 10-30% of silica sol and 10-20% of oxide powder by weight, wherein the oxide powder is one or a mixture of aluminum oxide, magnesium oxide and nickel oxide, and the oxide powder is micron-sized or nano-sized.
Example 2:
(1) preparing titanium carbide/titanium diboride composite ceramic particles by adopting a sol-gel method: the powder consists of titanium carbide powder, titanium diboride powder and metal powder, wherein the titanium carbide powder and the titanium diboride powder are micron powder, the titanium carbide powder and the titanium diboride powder account for 96wt% of the total weight of the powder, and the metal powder accounts for 4wt% of the total weight of the powder. The weight ratio of the titanium carbide powder to the titanium diboride powder is 1:1 (namely the weight of the titanium carbide powder to the titanium diboride powder accounts for 48wt% of the total weight of the powder), and the metal powder is nano mixed powder consisting of nickel powder, molybdenum powder and vanadium powder, wherein the weight percentages of the nickel powder, the molybdenum powder and the vanadium powder in the total weight of the powder are respectively 2.5wt%, 0.75wt% and 0.75 wt%. The addition amount of the deionized water accounts for 25wt% of the total weight of the powder, and the addition amount of the Basff ceramic water reducing agent FS20 accounts for 0.5wt% of the total weight of the powder.
Putting powder consisting of titanium carbide powder, titanium diboride powder and metal powder, deionized water and a basf ceramic water reducing agent FS20 into a ceramic ball milling tank (taking zirconia ceramic balls as a ball milling medium), mixing and ball milling for 30min, wherein the rotating speed of the ball milling tank is 300 r/min, then adding a sodium alginate solution with the mass fraction of 5%, continuing ball milling for 30min to obtain slurry, dripping the obtained slurry into a sufficient iridium nitrate solution with the mass fraction of 2%, solidifying for 1 h, filtering out particles, drying the particles in a drying box at 80 ℃ for 6h to prepare green body particles with the particle size of 1.5-4.5 mm, putting the obtained green body particles into an argon atmosphere protective furnace, sintering for 1 h at 1650 ℃, and sintering to obtain titanium carbide/titanium diboride composite ceramic particles with the particle size of 0.5-4 mm. The adding volume of the sodium alginate solution is added according to the proportion of adding 10mL of the sodium alginate solution in every 100g of the powder.
The test shows that the hardness HV of the obtained titanium carbide/titanium diboride composite ceramic particles is about 19GPa, and the fracture toughness KICA value of 7.5 MNm-3/2。
(2) Preparing a titanium carbide/titanium diboride composite ceramic particle preform: the procedure for this step was the same as in example 1.
Example 3:
the powder consists of titanium carbide powder, titanium diboride powder and metal powder, wherein the titanium carbide powder and the titanium diboride powder are micron powder, the titanium carbide powder and the titanium diboride powder account for 95wt% of the total weight of the powder, the weight ratio of the titanium carbide powder to the titanium diboride powder is 1:1, and the metal powder accounts for 5wt% of the total weight of the powder. The metal powder is a nano mixed powder composed of nickel powder, molybdenum powder and niobium powder, and the nickel powder, the molybdenum powder and the niobium powder respectively account for 2.5wt%, 1.25wt% and 1.25wt% of the total weight of the powder. The sintering temperature of the obtained green body particles in an argon atmosphere protective furnace is 1600 ℃. Other preparation processes are the same as example 2, and after testing,the hardness HV of the obtained titanium carbide/titanium diboride composite ceramic particles is about 17GPa, and the fracture toughness KICA value of 8.6 MNm-3/2。
The process for preparing the titanium carbide/titanium diboride composite ceramic particle preform was the same as in example 2.
Example 4:
the powder consists of titanium carbide powder, titanium diboride powder and metal powder, wherein the titanium carbide powder and the titanium diboride powder are micron powder, the titanium carbide powder and the titanium diboride powder account for 97wt% of the total weight of the powder, the weight ratio of the titanium carbide powder to the titanium diboride powder is 1:1, and the metal powder accounts for 3wt% of the total weight of the powder. The metal powder is a nano mixed powder composed of nickel powder, molybdenum powder and niobium powder, and the nickel powder, the molybdenum powder and the niobium powder respectively account for 2wt%, 0.5wt% and 0.5wt% of the total weight of the powder. The sintering temperature of the obtained green body particles in an argon atmosphere protective furnace is 1700 ℃. The other preparation processes are the same as the example 2, and tests show that the hardness HV of the obtained titanium carbide/titanium diboride composite ceramic particles is about 21GPa, and the fracture toughness KICA value of 7.7 MNm-3/2。
The process for preparing the titanium carbide/titanium diboride composite ceramic particle preform was the same as in example 2.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and is not listed again. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (10)
1. A preparation method of a titanium carbide/titanium diboride composite ceramic particle preform comprises the following steps of (1) preparing titanium carbide/titanium diboride composite ceramic particles; (2) preparing a titanium carbide/titanium diboride composite ceramic particle preform; the method is characterized in that titanium carbide/titanium diboride composite ceramic particles are prepared by a pressure granulation method or a sol-gel granulation method;
the pressure granulation method mainly comprises the following steps:
mixing powder consisting of titanium carbide powder, titanium diboride powder and metal powder with the zinc stearate fine powder, adding absolute ethyl alcohol, mixing for 2-3 h, and then performing pressure granulation in a pressure granulator to obtain a material with the particle size of 1-6 mm; placing the materials at room temperature for more than 24 h, then placing the materials in an argon protection furnace, preserving heat for 1 h at 500 ℃, and then heating the argon protection furnace to 1500-1800 ℃ to sinter for 1-2 h to prepare titanium carbide/titanium diboride composite ceramic particles;
the sol-gel granulation method mainly comprises the following steps:
adding deionized water and a basf water reducing agent FS20 into powder consisting of titanium carbide powder, titanium diboride powder and metal powder, and ball-milling the obtained mixed material in a ceramic ball-milling tank for 30-120 min; then adding a sodium alginate solution, and continuing to perform ball milling for 30-120min to obtain slurry; dripping or spraying the obtained slurry into sufficient calcium chloride solution or iridium nitrate solution, and curing for 1-5 h; filtering out particles, drying the particles in a drying oven at 80 ℃ for 6-12h, and drying the particles to obtain green body particles with the particle size of 1-6 mm; placing the obtained green body particles in an argon protection furnace, sintering for 1-5 h at 1500-1800 ℃, and obtaining titanium carbide/titanium diboride composite ceramic particles after sintering;
in the pressure granulation method and the sol-gel granulation method, the titanium carbide powder, the titanium diboride powder and the metal powder account for 30-70 percent, 30-70 percent and 2-5 percent of the total weight of the powder in sequence, and the sum of the weight percentages of the titanium carbide powder, the titanium diboride powder and the metal powder accounts for 100 percent of the total weight of the powder; the total weight of the powder is the sum of the weight of the titanium carbide powder, the titanium diboride powder and the metal powder.
2. The method according to claim 1, wherein the metal powder is a mixed powder of two or more of nickel powder, molybdenum powder, vanadium powder, niobium powder, and chromium powder.
3. The method according to claim 1, wherein the fine zinc stearate powder is added in an amount of 0.5 to 1% by weight based on the total weight of the powder in the pressure granulation method.
4. The method according to claim 1, wherein the absolute ethyl alcohol is added in an amount of 10 to 15% by weight based on the total weight of the powder in the pressure granulation method.
5. The method according to claim 1, wherein in the pressure granulation method, the pressure of the granulation by the pressure granulator is 100-300 Mpa.
6. The method of claim 1, wherein the deionized water is added in an amount of 20 to 40% by weight based on the total weight of the powder in the sol-gel granulation process.
7. The method according to claim 1, wherein the weight of the added basf water reducer FS20 is 0.5% of the total weight of the powder in the sol-gel granulation process.
8. The preparation method as claimed in claim 1, wherein in the sol-gel granulation method, the mass fraction of the sodium alginate solution used is 5-10%; the addition amount of the sodium alginate solution is that 5-15mL of the sodium alginate solution is added to every 100g of the powder.
9. The method according to claim 1, wherein the calcium chloride solution and the iridium nitrate solution are each present in a mass fraction of 2 to 3% in the sol-gel granulation method.
10. The method according to claim 1, wherein the titanium carbide/titanium diboride composite ceramic particles obtained at the end of the pressure granulation process have a particle size of 0.5 to 3.5 mm; the particle size of the titanium carbide/titanium diboride composite ceramic particles obtained finally by the sol-gel granulation method is 0.5-4 mm.
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