CN108675773B - A method for preparing alumina-based nano-eutectic composite fine powder by burning synthetic aerosol method - Google Patents
A method for preparing alumina-based nano-eutectic composite fine powder by burning synthetic aerosol method Download PDFInfo
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- CN108675773B CN108675773B CN201810753376.8A CN201810753376A CN108675773B CN 108675773 B CN108675773 B CN 108675773B CN 201810753376 A CN201810753376 A CN 201810753376A CN 108675773 B CN108675773 B CN 108675773B
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- 239000000843 powder Substances 0.000 title claims abstract description 138
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000001856 aerosol method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 149
- 238000005049 combustion synthesis Methods 0.000 claims abstract description 76
- 239000002994 raw material Substances 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000000155 melt Substances 0.000 claims abstract description 26
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 186
- 239000003085 diluting agent Substances 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 41
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 37
- 230000009471 action Effects 0.000 claims description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 15
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 6
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 3
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 3
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 3
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 3
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 3
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims description 3
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 3
- 229940075630 samarium oxide Drugs 0.000 claims description 3
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 3
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 3
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 3
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 3
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 3
- 229940075624 ytterbium oxide Drugs 0.000 claims description 3
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229940075616 europium oxide Drugs 0.000 claims 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims 1
- 229940043774 zirconium oxide Drugs 0.000 claims 1
- 230000005496 eutectics Effects 0.000 abstract description 105
- 239000000919 ceramic Substances 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 229910010293 ceramic material Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 description 93
- 229910001845 yogo sapphire Inorganic materials 0.000 description 93
- 238000001035 drying Methods 0.000 description 81
- 238000001816 cooling Methods 0.000 description 73
- 238000000498 ball milling Methods 0.000 description 71
- 239000012071 phase Substances 0.000 description 60
- 239000011812 mixed powder Substances 0.000 description 43
- 238000007873 sieving Methods 0.000 description 40
- 238000002156 mixing Methods 0.000 description 36
- 239000000463 material Substances 0.000 description 30
- 239000007800 oxidant agent Substances 0.000 description 21
- 238000001291 vacuum drying Methods 0.000 description 21
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 17
- 238000003825 pressing Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 230000036316 preload Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000005507 spraying Methods 0.000 description 7
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000002826 coolant Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 230000008520 organization Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000013001 point bending Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 241000968352 Scandia <hydrozoan> Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004857 zone melting Methods 0.000 description 1
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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
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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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
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
一种燃烧合成气雾法制备氧化铝基纳米共晶复合微粉的方法，涉及一种Al2O3基纳米共晶微粉的制备方法。是要解决现有制备Al2O3基共晶陶瓷强度和韧性差，制备周期长，难以实现工业化的问题。方法：将原料分别进行干燥，然后混合均匀，装入高压反应器中，在反应气氛下，引燃原料，进行高温燃烧合成反应，反应完全后得到高温熔体，保温，开启高压反应器喷嘴，熔体高流速喷出，经过气相快速冷却，获得Al2O3基纳米共晶复合微粉。本方法对原材料的粒度要求不高，因此采用的是微米级粉末，极大的降低了成本。工艺效率极高，每次可喷粉1‑30公斤，可以进行大批量生产。本发明用于复合陶瓷材料领域。
A method for preparing alumina-based nano-eutectic composite fine powder by combustion synthesis aerosol method relates to a preparation method of Al 2 O 3 -based nano-eutectic fine powder. The purpose is to solve the problems of poor strength and toughness of the existing preparation of Al 2 O 3 -based eutectic ceramics, long preparation period, and difficulty in realizing industrialization. Method: Dry the raw materials separately, then mix them evenly, and put them into a high-pressure reactor. Under the reaction atmosphere, the raw materials are ignited, and the high-temperature combustion synthesis reaction is carried out. After the reaction is complete, a high-temperature melt is obtained. The melt is sprayed out at a high flow rate and rapidly cooled in the gas phase to obtain Al 2 O 3 -based nano-eutectic composite fine powder. This method does not have high requirements on the particle size of the raw materials, so micron-sized powder is used, which greatly reduces the cost. The process efficiency is extremely high, and the powder can be sprayed 1-30 kg each time, which can be mass-produced. The invention is used in the field of composite ceramic materials.
Description
Technical Field
The invention relates to Al2O3A preparation method of a base nanometer eutectic micro powder.
Background
The oxide ceramic has excellent oxidation resistance and corrosion resistance, and can work for a long time in a high-temperature oxidation atmosphere. The polycrystalline oxide ceramic prepared by the traditional method has the defects of amorphous phase, air holes, inclusion and the like at crystal boundaries, the crystal boundaries are easy to diffuse and slide under a high-temperature environment, so that the mechanical properties such as strength, creep resistance and the like are rapidly deteriorated, and the polycrystalline oxide ceramic is not suitable for being used as a high-temperature structural material at the use temperature of 1000-1200 ℃.
The study shows that Al2O3/ZrO2The eutectic ceramic has the characteristics of high melting point, high strength, excellent oxidation resistance, creep resistance and the like, has high hardness, high strength, excellent high-temperature strength and high-temperature stability, can realize the condition of long-term service at 1600 ℃, and is considered to be one of the most promising structural materials for long-term work in a high-temperature oxidation atmosphere. The mechanical properties of eutectic ceramics depend on the microstructure of the material, generally speaking, the finer the microstructure, the better the properties. The higher cooling speed can effectively inhibit the growth of crystal grains and reduce the growth rate, thereby achieving the purpose of refining the tissue structure.
Early eutectic ceramic preparation methods were mainly directed solidification techniques including micro-pulling, bridgman, arc zone melting, laser heating melting, and the like.
The directional solidification technique can realize Al2O3The preparation of the basal eutectic ceramics, but the contradiction between large size and fine organization structure limits the industrial application of the basal eutectic ceramics. For example, a large-size sample can be prepared by the Bridgman method, but the eutectic spacing is increased due to the low growth speed, so that the strength and toughness of the material are poor, the preparation period is long, mass production cannot be realized, and industrialization cannot be realized.
Disclosure of Invention
The invention aims to solve the problem of the existing preparation of Al2O3The problems that the basal eutectic ceramics have poor strength and toughness, long preparation period and difficult industrialization realization are solved, and the Al prepared by the combustion synthesis aerosol method is provided2O3A method for preparing a nano eutectic composite micro powder.
The invention relates to a method for preparing alumina-based nano eutectic composite micro powder by a combustion synthesis aerosol method, which comprises the following steps:
respectively drying the raw materials, uniformly mixing, loading into a high-pressure reactor, igniting the raw materials in a reaction atmosphere, performing high-temperature combustion synthesis reaction, obtaining a high-temperature melt after complete reaction, keeping the temperature for 1-60 s, opening a nozzle of the high-pressure reactor, spraying the melt at a high flow rate under the action of high-pressure gas in the high-pressure reactor, and rapidly cooling in a gas phase to obtain Al2O3Base nanometer eutectic composite micro powder; wherein the raw materials comprise, by mass, x parts of aluminum powder, y parts of nitrate and z parts of diluent, wherein 10 parts of the diluent<x<35，0<y<40，25<z<90。
The gas-phase cooling is mainly carried out at normal temperature, and the gas-phase cooling medium can be stable gas flow, low-pressure gas flow and high-pressure gas flow (air and nitrogen inert gas).
Further, the nitrate is one or a mixture of more of aluminum nitrate, zirconium nitrate, magnesium nitrate, cerium nitrate, yttrium nitrate, terbium nitrate, holmium nitrate, erbium nitrate, dysprosium nitrate, thulium nitrate, ytterbium nitrate, samarium nitrate, gadolinium nitrate, samarium nitrate and europium nitrate according to any ratio.
Further, the diluent is a mixture composed of one or more of aluminum oxide, zirconium oxide, magnesium oxide, zinc oxide, yttrium oxide, cerium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, yttrium oxide, samarium oxide, europium oxide and erbium oxide according to any ratio.
Further, when the combustion synthesis reaction product contains zirconia, yttria is 0 to 20 mol% of the molar content of zirconia in the product, ceria is 0 to 30 mol% of the molar content of zirconia in the product, magnesia is 0 to 28 mol% of the molar content of zirconia in the product, calcia is 0 to 33.45 mol% of the molar content of zirconia in the product, titania is 0 to 44.41 mol% of the molar content of zirconia in the product, and scandia is 0 to 20 mol% of the molar content of zirconia in the product.
Control of t-ZrO by addition of phase change stabilizers (yttrium oxide, cerium oxide, magnesium oxide, calcium oxide, titanium oxide)2Content ofThe phase zirconia is stabilized to room temperature, and phase change toughening is facilitated.
Furthermore, the raw materials are preheated before being ignited, and the preheating temperature is 25-600 ℃. The raw materials are preheated, and the required reaction heat can be reduced at the same set temperature. Thereby reducing the reactant content to some extent.
Further, the reaction atmosphere is vacuum, air, inert gas and O2、N2One or more mixed gases composed according to any ratio. Said O is2The pressure of (A) is 0-30MPa, the said N2The pressure of (2) is 0-20MPa, the pressure of the air is 0.1-20MPa, and the pressure of the inert gas is 0-5 MPa.
The invention has the beneficial effects that:
the method takes active metal aluminum powder as a reducing agent and metal nitrate as an oxidizing agent, generates an exothermic reaction to provide a heat source, adds inert additives of aluminum oxide and zirconium oxide to control the reaction temperature and components, and introduces gas to adjust the reaction pressure to obtain Al of different systems2O3Based on nano eutectic composite ceramic powder.
Firstly, uniformly mixing raw materials, then placing the mixture into a reaction container, igniting the mixture by using a resistance wire to produce a rapid and stable combustion synthesis reaction with high heat release so as to make the temperature reach above the melting point of the system, keeping the temperature for a certain time to uniformly mix the components in a liquid phase state, opening a nozzle, and utilizing reaction high pressure to spray the molten product into a gas phase cooling medium for rapid cooling to form Al2O3Based nano eutectic composite ceramic powder.
With product Al2O3/ZrO2For example, if the nitrate is added as zirconium nitrate, the combustion synthesis reaction formula is:
20Al+3Zr(NO3)4→6N2+10Al2O3+3ZrO2
8Al+3N2+6ZrO2→4Al2O3+6ZrN
in the invention, O can be introduced on the basis of adding nitrate2、N2Or inert gasesControlling the reaction rate and regulating the reaction pressure. Ensuring the safety of the experiment and adjusting the spraying speed. When only N is introduced2In the time, the combustion synthesis reaction formula is as follows:
20Al+3Zr(NO3)4→6N2+10Al2O3+3ZrO2
8Al+3N2+6ZrO2→4Al2O3+6ZrN
when introducing O2/N2When the gas mixture is mixed, the combustion synthesis equation is (taking the final product as Al)2O3/ZrO2For example):
4Al+3O2→2Al2O3
20Al+3Zr(NO3)4→6N2+10Al2O3+3ZrO2
8Al+3N2+6ZrO2→4Al2O3+6ZrN
when N is introduced2Preparing Al by using Al powder and aluminum nitrate as raw materials2O3/ZrO2The combustion synthesis reaction formula is as follows:
16Al+2Al(NO3)3→3N2+9Al2O3
8Al+3N2+6ZrO2→4Al2O3+6ZrN
the invention can adjust the theoretical adiabatic temperature and reaction pressure of the combustion synthesis reaction by designing the proportion of the reactants.
The pressure is controlled mainly by three ways: 1) adjusting the gas pressure in the reaction vessel by changing the raw material ratio and the atmosphere pressure; 2) the pressure is regulated by the temperature generated by the reaction; 3) after the reaction, the system was reduced to the set pressure by reducing the pressure. Finally, the pressure range in the system is controlled to be 0.5-50 MPa.
The invention adopts a combustion synthesis aerosol method, and the method does not need an external heat source and relies on the heat emitted by the raw materials during the reaction to synthesize the inorganic refractory materials. Generally, solidification in an equilibrium state is achieved only by formation of a system corresponding to the eutectic pointThe other phase appears in other composition points due to the complete eutectic structure. When the system is rapidly cooled from the liquid phase to the pseudo eutectic region surrounded by the extensions of the two liquidus lines when solidification is away from the equilibrium state, 100% eutectic structure may occur in the system even if the two-phase components in the eutectic system do not satisfy the composition corresponding to the eutectic point. The combustion synthesis gas-spray method has extremely high cooling rate, which not only refines eutectic organization structure, but also greatly expands pseudo eutectic area. In the method, the system is subjected to exothermic reaction to generate a high-temperature and high-pressure environment, so that the raw materials reach a melting point or above to form a melt. The melt is sprayed out from a nozzle in a high-pressure environment and quenched by a gas-phase cooling medium to form the nano eutectic ceramic powder. Al prepared by the invention2O3/ZrO2Nano eutectic powder, for example, Al2O3/ZrO2ZrO in eutectic powder2The content can reach 20 wt% -80 wt%. The pseudo eutectic area is greatly widened.
The adiabatic temperature in the combustion synthesis reaction process is extremely high and can reach 2100-4000 ℃. The inert additive is added as a diluent, so that not only can the stability of combustion synthesis be improved, but also the proportion of a final product can be favorably regulated and controlled, and eutectic powder under different proportions can be obtained. In addition, a certain amount of excessive aluminum powder is added, nitrogen generated by reaction can be neutralized, reaction pressure can be conveniently regulated, and technical guarantee is provided for ejection of a melt. In addition, the hard phase ZrN formed in the powder product can improve the mechanical property and the electronic conductivity of the material. Take the preparation of nano composite alumina/zirconia eutectic ceramic as an example. When the content of zirconia is lower (20 wt% -40 wt%), the strength can reach 800MPa, and the toughness can reach 9 MPa.m1/2(ii) a When the content of zirconia is medium (40 wt% -60 wt%), the strength can reach 900MPa, and the toughness can reach 11 MPa.m1/2(ii) a When the content of zirconia is higher (60 wt% -80 wt%), the strength can reach 1200MPa, and the toughness can reach 13 MPa.m1/2。
The method has low requirement on the granularity of the raw materials, so micron-sized powder is adopted, and the cost is greatly reduced.
The nano eutectic powder prepared by the method is compact through sintering, and a high-density, fine and uniform nano eutectic tissue structure is obtained, so that the large-size, fine and dense nano eutectic composite ceramic is prepared. The method for preparing the nano eutectic composite ceramic through the new technical route of preparing the sintering compact by the eutectic powder solves the contradiction between large-size and fine organization structures in the traditional process.
The microstructure of the powder depends on the cooling speed, different cooling speeds can be obtained by selecting proper melt temperature, ejection speed and gas-phase cooling medium, and solid solution powder of a corresponding system can be prepared. The method can obtain the oxide-based eutectic ceramic powder with better microstructure and uniform particles. Generally, the diameter of the obtained eutectic powder is 1 to 50 μm.
The method has the advantages of simple process, high purity, rapid reaction (reaction time is only a few seconds to a few minutes), short preparation period, high yield, capability of spraying 1-30 kg of powder each time, capability of realizing industrialized mass production, low cost, environmental protection and high efficiency, and capability of realizing industrialized production.
Drawings
FIG. 1 is a schematic diagram of the structure of a high-pressure reactor used in the process of the present invention;
FIG. 2 is a schematic view of the structure of a nozzle holder in a high-pressure reactor for use in the process according to the invention;
FIG. 3 shows Al prepared in example 12O3/ZrO2The shape of the nano eutectic micro powder;
FIG. 4 is an enlarged view of FIG. 3;
FIG. 5 is a cross-sectional microstructure of an embodiment of 6 nm eutectic differentiation;
FIG. 6 is a cross-sectional microstructure of the embodiment 9 nm eutectic differential;
fig. 7 is a cross-sectional structure of the embodiment 7 nm eutectic differential.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the method for preparing the alumina-based nano eutectic composite micro powder by the combustion synthesis aerosol method comprises the following steps:
respectively drying the raw materials, uniformly mixing, loading into a high-pressure reactor, igniting the raw materials in a reaction atmosphere, performing high-temperature combustion synthesis reaction, obtaining a high-temperature melt after complete reaction, keeping the temperature for 1-60 s, opening a nozzle of the high-pressure reactor, spraying the melt at a high flow rate under the action of high-pressure gas in the high-pressure reactor, and rapidly cooling in a gas phase to obtain Al2O3Base nanometer eutectic composite micro powder; the aluminum powder is composed of 10-35 parts by mass of aluminum powder, 10-40 parts by mass of nitrate and 25-80 parts by mass of diluent.
The embodiment is described with reference to fig. 1 and 2, the high-pressure reaction vessel includes a reactor 1, a tablet 4, a nozzle 5, a nozzle support 6, a sealing preload member 8, an upper slide plate 10, a lower slide plate 11, a resistance wire 13 and a dragging device 9, a two-stage stepped circular hole is formed along the thickness direction of the reactor bottom of the reactor 1, the first stepped circular hole 2 is located at the upper part of the second stepped circular hole 3, and the diameter of the first stepped circular hole 2 is larger than that of the second stepped circular hole 3;
the nozzle support 6 is of a coaxial integrated structure formed by a circular plate-shaped support body part 6-1 and a cylindrical part 6-2, an insertion hole 6-3 is formed along the central axis of the nozzle support 6, a circular ring groove 6-4 is formed in the end face of the cylindrical part 6-2, the nozzle support 6 is inserted and embedded into a two-stage stepped circular hole, the cylindrical part 6-2 is matched with a second stepped circular hole 3, the circular plate-shaped support body part 6-1 is matched with a first stepped circular hole 2, the lower surface of the circular plate-shaped support body part 6-1 is lapped on the stepped surface of the two-stage stepped circular hole, and a sealing preload piece 8 is embedded in the circular ring groove 6-4;
the pressing sheet 4 is arranged on the upper surface of the circular plate-shaped frame body 6-1, the pressing sheet 4 is in threaded connection with the first stepped round hole 2, and a pressing sheet through hole is formed in the center of the pressing sheet 4;
the nozzle 5 is arranged in a pressing sheet through hole of the pressing sheet 4 and a jack 14 of the nozzle support 6, a graphite core is arranged in the nozzle 5, the bottom surface of the nozzle 5 abuts against the upper surface of the sealing preload part 8, the upper plate surface of the upper sliding plate 10 is in contact with the outer surface of the bottom of the reactor 1, the lower sliding plate 11 is in contact with the lower part of the upper sliding plate 10, sliding plate through holes are respectively formed in the upper sliding plate 10 and the lower sliding plate 11, the sealing preload part 8 is guaranteed to pass through the hole diameter of the sliding plate through hole, the sliding plate through hole in the lower sliding plate 11 is right opposite to the sealing preload part 8, and the upper sliding. The nozzle opening size of the nozzle is phi 1-20 mm.
The present embodiment adopts a combustion synthesis aerosol method, which is a technique for synthesizing an inorganic refractory material by heat emitted from the raw material itself during the reaction without using an external heat source. Generally, solidification in an equilibrium state allows only a system corresponding to a eutectic point to form a complete eutectic structure, and another phase appears at other composition points. When the system is rapidly cooled from the liquid phase to the pseudo eutectic region surrounded by the extensions of the two liquidus lines when solidification is away from the equilibrium state, 100% eutectic structure may occur in the system even if the two-phase components in the eutectic system do not satisfy the composition corresponding to the eutectic point. The combustion synthesis gas-spray method has extremely high cooling rate, which not only refines eutectic organization structure, but also greatly expands pseudo eutectic area. In the invention, the system generates exothermic reaction to generate a high-temperature and high-pressure environment, so that the raw materials reach above the melting point to form a melt. The melt is sprayed out from a nozzle in a high-pressure environment and is quenched by a gas-phase cooling medium to form the nano eutectic ceramic powder.
In the present embodiment, the combustion temperature and pressure are for producing Al2O3Based on the important parameters of the nano micro powder, the melting, the spraying and the atomizing can be realized only when the combustion temperature is higher than the melting point of the system; meanwhile, the temperature of the melt has an important influence on the subsequent processes of spraying, atomizing and fast cooling. In addition, pressure is a key factor that affects the melt jet velocity. When the temperature of the melt is lower and the pressure is higher, the ejection speed is higher, the cooling speed of the melt is relatively higher, and the eutectic structure is fine; when the melt temperature is high and the pressure is small, the ejection speed is low, the cooling speed is relatively slow, and the eutectic structure is relatively thick. The ejection speed affects not only the microstructure result of the powder but also the particle size of the powder, and the ejection speed is high, the particle size of the powder is small, the ejection speed is low, and the particle size of the powder is large. The size of the particle diameter is notDepending only on the jet velocity and also on the nozzle configuration, the nozzle inner diameter, aspect ratio affect the flow resistance and flow coefficient of the nozzle and thus can affect the fluid jet velocity.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the nitrate is one or a mixture of more of aluminum nitrate, zirconium nitrate, magnesium nitrate, cerium nitrate, yttrium nitrate, terbium nitrate, holmium nitrate, erbium nitrate, dysprosium nitrate, thulium nitrate, ytterbium nitrate, samarium nitrate, gadolinium nitrate, samarium nitrate and europium nitrate according to any ratio. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the diluent is a mixture consisting of one or more of aluminum oxide, zirconium oxide, magnesium oxide, zinc oxide, yttrium oxide, cerium oxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, yttrium oxide, samarium oxide, europium oxide and erbium oxide in any ratio. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the third difference between the present embodiment and the specific embodiment is that: when the combustion synthesis reaction product contains zirconia, yttria is 0-20 mol% of the molar content of zirconia in the product, ceria is 0-30 mol% of the molar content of zirconia in the product, magnesia is 0-28 mol% of the molar content of zirconia in the product, calcia is 0-33.45 mol% of the molar content of zirconia in the product, titania is 0-44.41 mol% of the molar content of zirconia in the product, and scandia is 0-20 mol% of the molar content of zirconia in the product. The rest is the same as the third embodiment.
Control of t-ZrO by addition of phase change stabilizers (yttrium oxide, cerium oxide, magnesium oxide, calcium oxide, titanium oxide)2The content of the zirconium oxide can stabilize the tetragonal phase zirconium oxide to the room temperature, and the phase change and the toughness can be improved.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and (3) preheating the raw materials before igniting the raw materials, wherein the preheating temperature is 25-600 ℃. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the reaction atmosphere is vacuum, air, inert gas and O2、N2One or more mixed gases composed according to any ratio. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the sixth embodiment is different from the sixth embodiment in that: the pressure of the air is 0-20MPa, and the pressure of the air is O2The pressure of (A) is 0-30MPa, the said N2The pressure of (2) is 0-20MPa, and the pressure of the inert gas is 0-5 MPa. The rest is the same as the sixth embodiment.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
The following embodiments are all performed by using a high-pressure reaction vessel, which is described with reference to fig. 1 and 2, and includes a reactor 1, a tablet 4, a nozzle 5, a nozzle bracket 6, a sealing preload piece 8, an upper slide plate 10, a lower slide plate 11, a resistance wire 13 and a dragging device 9, wherein a two-stage stepped circular hole is formed along the thickness direction of the reactor bottom of the reactor 1, the first stepped circular hole 2 is located at the upper part of the second stepped circular hole 3, and the diameter of the first stepped circular hole 2 is larger than that of the second stepped circular hole 3;
the nozzle support 6 is of a coaxial integrated structure formed by a circular plate-shaped support body part 6-1 and a cylindrical part 6-2, an insertion hole 6-3 is formed along the central axis of the nozzle support 6, a circular ring groove 6-4 is formed in the end face of the cylindrical part 6-2, the nozzle support 6 is inserted and embedded into a two-stage stepped circular hole, the cylindrical part 6-2 is matched with a second stepped circular hole 3, the circular plate-shaped support body part 6-1 is matched with a first stepped circular hole 2, the lower surface of the circular plate-shaped support body part 6-1 is lapped on the stepped surface of the two-stage stepped circular hole, and a sealing preload piece 8 is embedded in the circular ring groove 6-4;
the pressing sheet 4 is arranged on the upper surface of the circular plate-shaped frame body 6-1, the pressing sheet 4 is in threaded connection with the first stepped round hole 2, and a pressing sheet through hole is formed in the center of the pressing sheet 4;
the nozzle 5 is arranged in a pressing sheet through hole of the pressing sheet 4 and a jack 14 of the nozzle support 6, a graphite core is arranged in the nozzle 5, the bottom surface of the nozzle 5 abuts against the upper surface of the sealing preload part 8, the upper plate surface of the upper sliding plate 10 is in contact with the outer surface of the bottom of the reactor 1, the lower sliding plate 11 is in contact with the lower part of the upper sliding plate 10, sliding plate through holes are respectively formed in the upper sliding plate 10 and the lower sliding plate 11, the sealing preload part 8 is guaranteed to pass through the hole diameter of the sliding plate through hole, the sliding plate through hole in the lower sliding plate 11 is right opposite to the sealing preload part 8, and the upper sliding.
The raw materials are loaded into a reactor, and after the raw material system is ignited, a rapid exothermic reaction is generated to generate a high-temperature environment, so that the melting point of all the raw materials is reached to form a melt. The reactor is closed, a high-pressure environment is formed in the reactor due to gas expansion and the like under the action of high temperature, and the melt is sprayed out from the nozzle to form powder after a certain heat preservation time under the action of the high-pressure environment. The reactor is designed to be of a 'gate valve' type, and a sealing structure ensures sealing under high pressure. The graphite nozzle is used as a heat insulation material to ensure the structural strength at high temperature, and the flashboard, the ejection part, the hydraulic cylinder or the cylinder is used as a power and execution element to perform ejection instant ejection, so that the ejection function of the molten liquid at high temperature and high pressure is completed under the condition of not damaging any device. The reactor can resist the high temperature of 1600-4000 ℃ and the high pressure of 5-100 MPa.
Example 1:
this example is a combustion synthesis aerosol process for preparing Al2O3The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 80 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 12 hours, and the vacuum degree is 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, mixing 170.65g of Al powder and 203.42g of Zr (NO)3)4315.36g of Al2O3And 310.56g of ZrO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 4mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 30s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
As can be seen from FIGS. 3 and 4, the prepared alumina-based eutectic ceramic is differentiated into spherical particles and is submicron powder. It can be seen from fig. 5-7 that the internal microstructure of the powder appears as a nano-sized eutectic microstructure.
Example 2:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 14 hours, and the vacuum degree is 0.07 MPa; the diluent is ZrO2；
Thirdly, 1207.9g of Al powder, 1439.8g of Zr (NO)3)4And 7244.1g of ZrO2Mixing, ball-milling in a ball-milling tank at a ball-to-material ratio of 3:1 for 4hThen sieving the mixture by a 100-mesh sieve to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 10mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the heat is preserved for 25s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 3:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 8 hours, and the vacuum degree is 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 175.19g of Al powder, 208.84g of Zr (NO)3)4128.41g of Al2O3And 487.56g of ZrO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 3mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, and heat preservation is carried out for 30sOpening a nozzle of the high-pressure reactor, and reacting Al in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
The nano eutectic composite micro powder prepared in the embodiment is subjected to hot-pressing sintering densification treatment, and a three-point bending test is performed on the material, wherein the performance of the nano eutectic composite micro powder is as follows: fracture toughness 10.58MPa m1/2The flexural strength was 860 MPa.
Example 4:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Al (NO)3)3·9H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Al (NO)3)3And adding Al (NO)3)3Sieving with 40 mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 12 hours, and the vacuum degree is 0.06 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 215.21g of Al powder, 253.69g of Al (NO)3)3337.32g of Al2O3And 193.78g of ZrO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 6mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 30s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
The reaction principle of this example:
when N is introduced2Al powder and aluminum nitrate are used as raw materials, and the final product is Al2O3/ZrO2The combustion synthesis reaction formula is as follows:
16Al+2Al(NO3)3→3N2+9Al2O3
8Al+3N2+6ZrO2→4Al2O3+6ZrN
example 5:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(Y2O3) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder, diluent and Y2O3Drying in a vacuum drying oven at 80 deg.C for 10 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 193.79g of Al powder, 231.00g of Zr (NO)3)4249.98g of Al2O3325.23g of ZrO2And 2.87g Y2O3Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is put into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 5mm, the reaction vessel is arranged above an air cooling device, and resistance wires are communicated in the air atmosphereElectrically igniting raw materials, carrying out high-temperature combustion synthesis reaction to obtain high-temperature melt after the reaction is completed, keeping the temperature for 60s, opening a nozzle of the high-pressure reactor, and carrying out Al reaction under the action of high-pressure gas in the high-pressure reactor2O3/ZrO2(Y2O3) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(Y2O3) Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 6:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(Y2O3) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder, diluent and Y2O3Drying in a vacuum drying oven at 80 deg.C for 12 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 196.09g of Al powder, 233.75g of Zr (NO)3)474.58g of Al2O3495.58g of ZrO2And 17.75g Y2O3Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 6h, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 1mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 40s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2(Y2O3) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(Y2O3) Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 7:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(Y2O3) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder, diluent and Y2O3Drying in a vacuum drying oven at 80 deg.C for 12 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 123.30g of Al powder, 146.98g of Zr (NO)3)422.04g of Al2O3707.69g of ZrO2And 32.71g Y2O3Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 5 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 3mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 35s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2(Y2O3) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(Y2O3) Nanometer eutectic compound micropowder. The above-mentionedThe air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
The nano eutectic composite micro powder prepared in the embodiment is subjected to hot-pressing sintering densification treatment, and a three-point bending test is performed on the material, wherein the performance of the nano eutectic composite micro powder is as follows: fracture toughness 13.07MPa m1/2The flexural strength was 1270 MPa.
Example 8:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(CeO2) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder, diluent and CeO2Drying in a vacuum drying oven at 70 deg.C for 12 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 179.99g of Al powder, 214.56g of Zr (NO)3)4288.97g of Al2O3316.48g of ZrO2And 8.91g of CeO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 3mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 30s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2(CeO2) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(CeO2) Nanometer eutectic compound micropowder. The air cooling device is filled with airAnd the phase medium is air.
The nano eutectic composite micro powder prepared in the embodiment is subjected to hot-pressing sintering densification treatment, and a three-point bending test is performed on the material, wherein the performance of the nano eutectic composite micro powder is as follows: fracture toughness 8.31MPa m1/2The flexural strength was 780 MPa.
Example 9:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(CeO2) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder, diluent and CeO2Drying in a vacuum drying oven at 70 deg.C for 12 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 175.19g of Al powder, 208.84g of Zr (NO)3)4128.41g of Al2O3487.56g of ZrO2And 37.18g of CeO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 5 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 4mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 20s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2(CeO2) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(CeO2) Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with gas-phase mediumWherein the gas phase medium is air.
Example 10:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(CeO2) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder, diluent and CeO2Drying in a vacuum drying oven at 70 deg.C for 12 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 1537.9g of Al powder 1833.2g of Zr (NO)3)41835.4g of Al2O34793.4g of ZrO2And 1438.83g CeO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 6h, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 8mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 45s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2(CeO2) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(CeO2) Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 11:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 8 hours, and the vacuum degree is 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 141.91g of Al powder, 119.16g of Zr (NO)3)4396.58g of Al2O3And 292.35g of ZrO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is put into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 1mm, the reaction vessel is placed above an air cooling device, and 10MPa O is introduced2The resistance wire is electrified to ignite the raw materials to carry out high-temperature combustion synthesis reaction, high-temperature melt is obtained after the reaction is completed, the temperature is kept for 30s, then the nozzle of the high-pressure reactor is opened, and Al is added under the action of high-pressure gas in the high-pressure reactor2O3/ZrO2The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 12:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(Y2O3) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 80 deg.C for 8 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, the mixture is mixed withMetallic Al powder, diluent and Y2O3Drying in a vacuum drying oven at 80 deg.C for 8 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 162.41g of Al powder and 178.60g of Zr (NO)3)4161.33g of Al2O3482.65g of ZrO2And 124.46g Y2O3Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is put into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 5mm, the reaction vessel is arranged above an air cooling device, and 5MPa N is introduced2The resistance wire is electrified to ignite the raw materials to carry out high-temperature combustion synthesis reaction, high-temperature melt is obtained after the reaction is completed, the temperature is kept for 25s, then the nozzle of the high-pressure reactor is opened, and Al is added under the action of high-pressure gas in the high-pressure reactor2O3/ZrO2(Y2O3) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(Y2O3) Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
The reaction principle of this example:
introduction of N2In the time, the combustion synthesis reaction formula is as follows:
20Al+3Zr(NO3)4→6N2+10Al2O3+3ZrO2
8Al+3N2+6ZrO2→4Al2O3+6ZrN
example 13:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the (MgO) nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying in a drying ovenDrying at 60 deg.C for 12h to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, putting metal Al powder, a diluent and MgO in a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 8 hours, and the vacuum degree is 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 182.04g of Al powder, 217.00g of Zr (NO)3)4173.18g of Al2O3427.77g of ZrO2Mixing with 24.36g of MgO, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 4mm, the reaction vessel is placed above an air cooling device, 2MPa Ar is introduced, resistance wires are electrified to ignite raw materials, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 30s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2The (MgO) melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(MgO) Nano eutectic composite micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 14:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 8 hours, and the vacuum degree is 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 179.41g of Al powder, 190.87g of Zr (NO)3)4117.54g of Al2O3And 489.18g of ZrO2Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 2mm, the reaction vessel is placed above an air cooling device, 10MPa compressed air is introduced, a resistance wire is electrified to ignite the raw materials, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, after the temperature is kept for 25s, the nozzle of the high-pressure reactor is opened, and Al is reacted in the high-pressure reactor under the action of high-pressure gas in the high-pressure reactor2O3/ZrO2The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 15:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(Y2O3) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder and Al2O3And Y2O3Drying in a vacuum drying oven at 70 deg.C for 12 hr under 0.07 MPa;
thirdly, 159.99g of Al powder, 190.71g of Zr (NO)3)4232.00g of Al2O3417.31g of ZrO2And 10.16g of Y2O3Mixing, and ball-milling with a planetary ball mill at a ball-to-material ratio of 3:1 for 6hSieving with 100 mesh sieve to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 5mm, the reaction vessel is placed above an air cooling device, the raw material powder is preheated to 600 ℃, 3MPa Ar mixed gas is introduced, resistance wires are electrified to ignite the raw materials, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after complete reaction, after the temperature is kept for 35s, the nozzle of the high-pressure reactor is opened, and Al is reacted in the high-pressure reactor under the action of the high-pressure gas2O3/ZrO2(Y2O3) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(Y2O3) Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 16:
this example is a combustion synthesis aerosol process for preparing Al2O3/CeAlO3The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidant powder Ce (NO)3)4·6H2Drying O in a drying oven at 80 deg.C for 12 hr to obtain Ce (NO)3)4And Ce (NO)3)4Sieving with 40 mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 80 ℃, the drying time is 12 hours, and the vacuum degree is 0.07 MPa; the diluent is Al2O3And CeO2A mixture of components;
thirdly, 268.04g of Al powder and 306.53g of Ce (NO)3)4218.52g of Al2O3And 221.91g of CeO2Mixing, ball-milling by adopting a planetary ball mill with a ball-material ratio of 3:1 for 4 hours, and sieving by using a 100-mesh sieve after ball-milling to obtain mixed powder;
fourthly, the mixed powder is put into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 2mm, the reaction vessel is arranged above an air cooling device, and resistance wires are arranged in the air atmosphereElectrifying to ignite the raw materials, performing high-temperature combustion synthesis reaction to obtain high-temperature melt after the reaction is completed, keeping the temperature for 50s, opening a nozzle of the high-pressure reactor, and performing Al reaction under the action of high-pressure gas in the high-pressure reactor2O3/CeAlO3The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/CeAlO3Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 17:
this example is a combustion synthesis aerosol process for preparing Al2O3The method for preparing the/ErAG nano eutectic composite micro powder comprises the following steps:
firstly, putting oxidant powder erbium nitrate into a drying oven for drying at 60 ℃ for 12 hours to obtain dried erbium nitrate, and sieving the erbium nitrate with a 40-mesh sieve;
secondly, putting the metal Al powder and the diluent into a vacuum drying oven for drying, wherein the drying temperature is 60 ℃, the drying time is 12 hours, and the vacuum degree is 0.07 MPa; the diluent is Al2O3And Er2O3A mixture of components;
thirdly, 243.17g of Al powder, 278.51g of erbium nitrate powder and 162.27g of Er2O3And 246.52g of Al2O3Mixing, ball-milling by adopting a planetary ball mill with a ball-material ratio of 3:1 for 4 hours, and sieving by using a 100-mesh sieve after ball-milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 1mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 30s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3The ErAG melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ErAG nano eutectic composite micro powder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 18:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder and Al2O3、ZrO2Drying in a vacuum drying oven at 70 deg.C for 12 hr under 0.07 MPa;
thirdly, 210.19g of Al powder, 250.56g of Zr (NO)3)4357.24g of Al2O3And 182.02g of ZrO2Mixing, ball-milling by adopting a planetary ball mill with a ball-material ratio of 3:1 for 6h, and sieving by a 100-mesh sieve after ball-milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 3mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the heat is preserved for 25s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 19:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2(Y2O3) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying at 80 deg.C in a drying ovenDrying at 8h to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder, diluent and Y2O3Drying in a vacuum drying oven at 80 deg.C for 8 hr under 0.07 MPa; the diluent is Al2O3And ZrO2A mixture of components;
thirdly, 166.69g of Al powder and 198.71g of Zr (NO)3)4150.30g of Al2O3484.30g of ZrO2And 12.37g Y2O3Mixing, then putting into a ball milling tank for ball milling, wherein the ball-material ratio is 3:1, the ball milling time is 4 hours, and sieving by a 100-mesh sieve after ball milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 2mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 40s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2Y2O3) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2(Y2O3) Nanometer eutectic compound micropowder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
When introducing O2/N2When the gas mixture is mixed, the combustion synthesis equation is (taking the final product as Al)2O3/ZrO2For example):
4Al+3O2→2Al2O3
20Al+3Zr(NO3)4→6N2+10Al2O3+3ZrO2
8Al+3N2+6ZrO2→4Al2O3+6ZrN
the nano eutectic composite micro powder prepared in the embodiment is compacted by hot-pressing sinteringChemical treatment, namely performing three-point bending test on the material, wherein the performance is as follows: fracture toughness 10.67MPa m1/2The flexural strength was 924 MPa.
Example 20:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2/YAG(Y2O3) The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, oxidizing agent powder Zr (NO)3)4·5H2Drying O in a drying oven at 60 deg.C for 12 hr to obtain Zr (NO)3)4And Zr (NO)3)4Sieving with 40 mesh sieve;
secondly, mixing metal Al powder and Al2O3、ZrO2And Y2O3Drying in a vacuum drying oven at 70 deg.C for 12 hr under 0.07 MPa;
thirdly, 231.00g of Al powder, 272.31g of Zr (NO)3)4186.67g of Al2O362.12g of ZrO2And 247.90g of Y2O3Mixing, ball-milling by adopting a planetary ball mill with a ball-material ratio of 3:1 for 6h, and sieving by a 100-mesh sieve after ball-milling to obtain mixed powder;
fourthly, the mixed powder is placed into a high-pressure reaction vessel, the nozzle size of a nozzle in the high-pressure reaction vessel is phi 2mm, the reaction vessel is placed above an air cooling device, resistance wires are electrified to ignite raw materials in air atmosphere, high-temperature combustion synthesis reaction is carried out, high-temperature melt is obtained after the reaction is completed, the nozzle of the high-pressure reactor is opened after the temperature is kept for 35s, and Al is reacted in the high-pressure reactor under the action of high-pressure gas2O3/ZrO2(Y2O3) The melt is sprayed out at high flow rate and is rapidly cooled by air to obtain Al2O3/ZrO2YAG nanometer eutectic composite micro powder. The air cooling device is a cooling cavity filled with a gas-phase medium, wherein the gas-phase medium is air.
Example 21:
this example is a combustion synthesis aerosol process for preparing Al2O3/ZrO2The method for preparing the nano eutectic composite micro powder comprises the following steps:
firstly, mixing Al powder and Al2O3And ZrO2Drying in a vacuum drying oven at 80 deg.C for 10 hr under 0.06 MPa; then 134.30g of dried Al powder, 2.31g of Zr (NO)3)4233.25g of ZrO2And 640.27g of Al2O3Putting the mixture into a ball milling tank for ball milling, controlling the mass ratio of ball materials to be 3:1, and the ball milling time to be 4 hours, sieving the mixture through a 60-mesh sieve after ball milling, and uniformly mixing to obtain mixed powder;
secondly, the mixed powder obtained in the step one is put into a pressure-resistant reactor with a nozzle at the lower end, the nozzle size of the nozzle is phi 6mm, and O with the pressure of 12MPa is introduced2Then the pressure-resistant reactor is arranged on an air cooling device, the theoretical adiabatic temperature is set to be 2400K, the mixed powder is ignited to initiate the synthesis reaction, the temperature is kept for 30s, then the nozzle of the pressure-resistant reactor is opened, and Al in the pressure-resistant reactor is filled in2O3/ZrO2Spraying the composite melt, and cooling in gas phase to obtain Al2O3/ZrO2The composite eutectic micro powder is used in preparing composite eutectic oxide powder through combustion synthesis and aerosol process.
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