CN116040668A - Submicron alpha-Al with uniform nucleation 2 O 3 Preparation method of powder - Google Patents
Submicron alpha-Al with uniform nucleation 2 O 3 Preparation method of powder Download PDFInfo
- Publication number
- CN116040668A CN116040668A CN202211717177.4A CN202211717177A CN116040668A CN 116040668 A CN116040668 A CN 116040668A CN 202211717177 A CN202211717177 A CN 202211717177A CN 116040668 A CN116040668 A CN 116040668A
- Authority
- CN
- China
- Prior art keywords
- powder
- submicron
- alpha
- precursor
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010899 nucleation Methods 0.000 title claims abstract description 25
- 230000006911 nucleation Effects 0.000 title claims abstract description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 80
- 239000002243 precursor Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 50
- 238000001556 precipitation Methods 0.000 claims abstract description 45
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 24
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000004202 carbamide Substances 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims description 81
- 238000001354 calcination Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 12
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- -1 PEG-2000 Polymers 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [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 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 3
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 150000004677 hydrates Chemical class 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 33
- 239000012071 phase Substances 0.000 abstract description 12
- 239000007791 liquid phase Substances 0.000 abstract description 9
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 230000001376 precipitating effect Effects 0.000 abstract description 4
- 239000013049 sediment Substances 0.000 abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 31
- 239000001099 ammonium carbonate Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 239000002244 precipitate Substances 0.000 description 14
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 235000012501 ammonium carbonate Nutrition 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- JVKRKMWZYMKVTQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JVKRKMWZYMKVTQ-UHFFFAOYSA-N 0.000 description 1
- 241000134884 Ericales Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- IOGARICUVYSYGI-UHFFFAOYSA-K azanium (4-oxo-1,3,2-dioxalumetan-2-yl) carbonate Chemical compound [NH4+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O IOGARICUVYSYGI-UHFFFAOYSA-K 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KSCFJBIXMNOVSH-UHFFFAOYSA-N dyphylline Chemical compound O=C1N(C)C(=O)N(C)C2=C1N(CC(O)CO)C=N2 KSCFJBIXMNOVSH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910006636 γ-AlOOH Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/441—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by calcination
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application provides a submicron alpha-Al with uniform nucleation 2 O 3 The preparation method of the powder comprises the steps of firstly, uniformly nucleating on the basis of a liquid phase precipitation method, and uniformly precipitating Al in supersaturated solution of aluminum salt by utilizing the slow release characteristic of urea 2 O 3 Precursor crystal nucleus, which can be performed under the auxiliary condition of microwave heating to quickly nucleate; and then, a large amount of sediment is quickly generated in the system by adding an alkaline pH regulator, so that the crystal nucleus is prevented from growing continuously due to overlong reaction time. Al prepared by the two-step nucleation mode 2 O 3 The precursor is calcined at a lower temperature (950-1150 ℃) and then converted into crystal grainsFine, uniformly dispersed alpha-Al 2 O 3 The alpha phase purity of the superfine powder is higher than 95 percent, and the grain diameter is between 100 and 300 nm. The method has the advantages of low production cost, environmental friendliness, high production efficiency, suitability for large-scale production and the like.
Description
Technical Field
The application relates to the technical field of inorganic nonmetallic materials, in particular toRelates to a submicron alpha-Al with uniform nucleation 2 O 3 A method for preparing powder.
Background
α-Al 2 O 3 Is an inorganic nonmetallic material with wide application, which has various crystal phases such as alpha, gamma, chi, eta, rho, delta, theta, kappa and the like, and the transition phase is finally converted into alpha-Al with the rise of temperature 2 O 3 . Thus, the alpha phase is the most stable one of Al 2 O 3 And (5) a crystal form. alpha-Al 2 O 3 The superfine powder is an important ceramic powder material, and has high melting point (2050 ℃), high hardness (Mohs hardness is 9.0) and low water absorption rate (less than or equal to 2.5% H) 2 O), good wear resistance, high electrical insulation performance, corrosion resistance and the like, has been widely applied to the production field of tip products such as lithium battery diaphragms, fine ceramics, rare earth fluorescent powder, precise parts of semiconductor equipment, monocrystalline sapphire substrates, biological ceramics and the like, and the demand amount shows a trend of increasing in successive years.
α-Al 2 O 3 The superfine powder is usually obtained by using a precursor under the condition of high-temperature calcination, wherein the precursor mainly comprises gamma-AlOOH and Al (OH) 3 Aluminum ammonium sulfate, aluminum Ammonium Carbonate (AACH), and the like. Wherein, the aluminum ammonium sulfate thermal decomposition method can generate a reaction byproduct NH 3 、SO 2 The gas causes serious pollution to the air, so the aluminum ammonium sulfate precursor is gradually eliminated. In addition, the precursor can generate a series of Al during the calcination process 2 O 3 The transition crystal forms experienced by the different precursors are also different. Without exception, transition phase Al 2 O 3 All require a phase change at a high temperature of about 1200-1400 ℃ to convert to alpha-Al 2 O 3 . However, in the high temperature stage, alpha-Al 2 O 3 The agglomeration is extremely serious, and the high temperature increases the production cost, which is not beneficial to the promotion of national energy conservation and emission reduction strategies. At such high calcination temperatures, al 2 O 3 The sintering process of the powder has already started. Therefore, once the crystal form transformation is completed at a higher temperature, α -Al 2 O 3 The particles will grow up immediately and,accompanied by the generation of sintering necks, a hard agglomerate structure of dendritic shape is easily formed. Thus, lowering the transformation temperature of the alpha phase is to produce fine, non-agglomerated alpha-Al 2 O 3 Key factors of the superfine powder.
When adopting monodisperse superfine Al with fine grains 2 O 3 Preparation of Al from powder 2 O 3 In the case of ceramic materials, the specific surface area of the powder is large, the surface activity is high, the diffusion distance of particles in the sintering process is greatly shortened, and the required sintering activation energy is also reduced. At a lower sintering temperature, dense high-purity Al with excellent performance can be obtained 2 O 3 A ceramic material. Thus, alpha-Al is reduced 2 O 3 Is to reduce Al 2 O 3 Reducing Al on the premise of ceramic sintering temperature 2 O 3 Calcination temperature and Al of powder 2 O 3 The sintering temperature of the ceramic is of great significance to the control of the production cost of enterprises.
It is mentioned in the prior art that the alpha-Al can be reduced by coarse grinding and micronization by ball milling, air-stream crushing, sand milling, etc 2 O 3 The agglomeration degree of the original powder and better particle size distribution are obtained. However, the additional adoption of the powder crushing technology is undoubtedly to add a production process, so that the energy consumption is increased, the control of the production cost of enterprises and the improvement of the production efficiency are not facilitated, and certain dust pollution is generated to the environment.
Therefore, in order to respond to the important strategic tasks of national energy conservation, emission reduction, cost reduction and synergy, al 2 O 3 The calcination temperature of the powder needs to be further reduced, and post-treatment processes such as crushing of the powder should be reduced as much as possible.
Disclosure of Invention
In view of this, the present application proposes a uniformly nucleated submicron alpha-Al 2 O 3 The preparation method of the powder can obtain submicron alpha-Al with fine grains at a lower calcination temperature 2 O 3 The superfine powder is used for overcoming the defects of the existing preparation method.
The application provides a submicron alpha-Al with uniform nucleation 2 O 3 The preparation method of the powder comprises the following steps:
s1: preparing an aluminum salt supersaturated solution with metastable state characteristics;
s2: adding urea to the supersaturated solution of aluminum salt to form Al (OH) 3 Sol;
s3: regulating said Al (OH) 3 The pH of the sol to obtain Al 2 O 3 A precipitation system;
s4: for the Al 2 O 3 Separating and drying the precipitation system to obtain Al 2 O 3 A precursor;
s5: calcining the Al 2 O 3 Precursor, alpha-Al is prepared 2 O 3 And (3) powder.
In one embodiment, in the step S1, the aluminum salt in the supersaturated solution of aluminum salt includes one or more of aluminum sulfate, aluminum nitrate, aluminum chloride, and hydrates of the above compounds.
In one embodiment, in the step S1, al in the supersaturated solution of aluminum salt 3+ The concentration of (C) is 1.0-2.0 mol/L.
In one embodiment, in the step S1, the final pH of the supersaturated solution of aluminum salt is controlled to be 3.0 to 4.0.
In one embodiment, in the step S1, after the supersaturated solution of aluminum salt is prepared, a dispersant is added to the supersaturated solution of aluminum salt, wherein the dispersant comprises one or more of PEG-600, PEG-2000, PEG-20000, and water-soluble starch.
In one embodiment, the temperature of the reaction system in the step S1 is controlled to be 35-55 ℃.
In one embodiment, in the step S2, the concentration of urea is 0.01 to 1.0mol/L.
In one embodiment, the temperature of the reaction system in the step S2 is controlled to be 40-70 ℃.
In one embodiment, in the step S3, the pH of the mixed solution is controlled to be 5.0 to 6.0 when the precipitation reaction reaches the end point.
In one embodiment, in the step S4, the Al is obtained 2 O 3 After the precursor, to the Al 2 O 3 Mixing alpha-Al into the precursor 2 O 3 One or more additives selected from seed crystal, ammonium nitrate, aluminum fluoride and magnesium oxide.
In one embodiment, in the step S5, the Al 2 O 3 The calcination temperature of the precursor is 950-1150 ℃.
In one embodiment, the Al 2 O 3 The precursor is kept at the calcination temperature for 1 to 6 hours.
In summary, the present application provides a uniformly nucleated submicron alpha-Al 2 O 3 The preparation method of the powder comprises the steps of firstly, uniformly nucleating on the basis of a liquid phase precipitation method, and uniformly precipitating Al in supersaturated solution of aluminum salt by utilizing the slow release characteristic of urea 2 O 3 Precursor crystal nucleus (i.e. Al (OH) 3 Sol) which can be carried out under the auxiliary condition of microwave heating to quickly nucleate; and then, a large amount of sediment is quickly generated in the system by adding an alkaline pH regulator, so that the crystal nucleus is prevented from growing continuously due to overlong reaction time. Al prepared by the two-step nucleation mode 2 O 3 The precursor is calcined at a lower temperature (950-1150 ℃) to be converted into alpha-Al with fine grains and uniform dispersion 2 O 3 The alpha phase purity of the superfine powder is higher than 95 percent, and the grain diameter is between 100 and 300 nm. The application makes up for the prior submicron alpha-Al 2 O 3 The defect of the powder preparation technology can obtain submicron alpha-Al with fine grains at a lower calcination temperature 2 O 3 The superfine powder has uniform appearance and narrow particle size distribution, and is used for reducing Al 2 O 3 The sintering temperature of the ceramic lays a good foundation. The method has the advantages of low production cost, environmental friendliness, high production efficiency, suitability for large-scale production and the like.
Drawings
FIG. 1 is a uniform nucleation of submicron order alpha-Al prepared in example 1 2 O 3 XRD spectrum of powder;
FIG. 2 is an embodiment1 the uniformly nucleated submicron alpha-Al prepared 2 O 3 SEM image of powder;
FIG. 3 is a submicron order alpha-Al of uniform nucleation prepared in example 2 2 O 3 XRD spectrum of powder;
FIG. 4 is a uniformly nucleated submicron alpha-Al prepared in example 2 2 O 3 SEM image of powder;
FIG. 5 is a submicron order alpha-Al of uniform nucleation prepared in example 3 2 O 3 XRD spectrum of powder;
FIG. 6 is a uniformly nucleated submicron alpha-Al prepared in example 3 2 O 3 SEM image of powder;
FIG. 7 is a submicron order alpha-Al of uniform nucleation prepared in example 4 2 O 3 XRD spectrum of powder;
FIG. 8 is a submicron order alpha-Al of uniform nucleation prepared in example 4 2 O 3 SEM image of powder;
FIG. 9 is a uniformly nucleated submicron alpha-Al prepared in example 5 2 O 3 XRD spectrum of powder;
FIG. 10 is a uniformly nucleated submicron alpha-Al prepared in example 5 2 O 3 SEM image of powder;
FIG. 11 is a submicron order alpha-Al of uniform nucleation prepared in example 6 2 O 3 XRD spectrum of powder;
FIG. 12 is a submicron order alpha-Al of uniform nucleation prepared in example 6 2 O 3 SEM image of powder;
FIG. 13 is a uniformly nucleated submicron alpha-Al prepared in example 7 2 O 3 XRD spectrum of powder;
FIG. 14 is a uniformly nucleated submicron alpha-Al prepared in example 7 2 O 3 SEM image of powder;
FIG. 15 is a uniformly nucleated submicron alpha-Al prepared in example 8 2 O 3 XRD spectrum of powder;
FIG. 16 is a photograph of a sample of the preparation of example 8Even nucleated submicron alpha-Al 2 O 3 SEM image of powder.
Detailed Description
The present application is further illustrated below with reference to specific examples and figures, but the examples are not intended to be limiting in any way. The embodiments are implemented on the premise of the technical scheme of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the following embodiments.
In the prior art, al 2 O 3 The precursor typically requires calcination at a higher temperature to ensure alpha-Al 2 O 3 The crystal transformation is completed, and alpha-Al is carried out at a high temperature stage 2 O 3 Agglomeration is extremely severe. The adoption of higher calcination temperature is not different from the increase of the production cost of enterprises, and is not beneficial to the promotion of national energy conservation and emission reduction strategies. In some prior patents, it is mentioned that Al can be reduced by high energy ball milling, air stream crushing, sand milling, etc 2 O 3 The particle size of the powder can forcedly improve the aggregation state and the particle size distribution of the powder, but the additional crushing process is undoubtedly added with a production procedure, which is not beneficial to the improvement of the production efficiency and even brings a certain dust pollution to the environment.
The morphology of the precursor will greatly influence the alpha-Al obtained by final calcination 2 O 3 Morphology of the powder. To obtain ultrafine alpha-Al with smaller particle size and uniform distribution 2 O 3 Powder, al is controlled by adjusting different reaction parameters 2 O 3 The precursor is nucleated and grown to obtain superfine uniform precursor powder, and then the precursor powder is calcined to obtain superfine alpha-Al 2 O 3 And (3) powder. The precursor with fine grains and uniform dispersion has larger reactivity, so that the transformation from the crystal form to the alpha phase can be completed at a lower temperature.
The precipitation process of precursor particles in the liquid phase is classified into reaction, nucleation and growth processes. As the concentration of the product (precursor) increases, the precursor starts to nucleate after reaching the critical nucleation concentration, and the primary nuclei also start to grow. The precursor solid-phase particles separated from the liquid phase must undergo nucleation and growth processes, if the two processes can be separated, the nucleation stage ensures that enough crystal nuclei are uniformly and rapidly generated everywhere in the reaction system, and the growth stage can control the crystal nuclei to synchronously grow without generating new crystal nuclei, thereby obtaining the precursor particles with fine granularity and uniform size. At present, the difficulty of the idea is how to regulate and control the reaction parameters such as concentration, temperature, reaction time, pH, supersaturation degree and the like so as to realize the uniform and rapid nucleation of the precursor in the liquid phase system.
Based on this, the present application proposes a uniformly nucleated submicron alpha-Al that can effectively reduce the calcination temperature 2 O 3 The preparation method of the powder can make up for the existing submicron alpha-Al 2 O 3 The defect of the powder preparation technology can realize the acquisition of submicron alpha-Al with fine grains at a lower calcination temperature 2 O 3 Ultrafine powder, uniform morphology and narrow particle size distribution. The method has the advantages of simple technical method, wide sources of production raw materials, higher yield of the final product, low energy consumption in the process, low production cost, environmental friendliness, high production efficiency, suitability for large-scale production and the like.
Specifically, the method is based on a liquid phase precipitation method, firstly, uniformly nucleating, and uniformly precipitating Al in supersaturated solution of aluminum salt by utilizing slow release characteristic of urea 2 O 3 Precursor nuclei (i.e. Al (OH) hereinafter) 3 Sol), which may be performed with the aid of microwave heating; and then, quickly nucleating, and quickly generating a large amount of precipitates in the system by adding an alkaline pH regulator so as to avoid the continuous growth of crystal nucleus caused by overlong reaction time. Al prepared by the two-step nucleation mode 2 O 3 The precursor can be converted into alpha-Al with fine crystal grains and uniform dispersion after being calcined at a lower temperature (950-1150 ℃) 2 O 3 The alpha phase purity of the superfine powder is higher than 95 percent, and the grain diameter is between 100 and 300 nm.
The application provides a submicron alpha-Al with uniform nucleation 2 O 3 The preparation method of the powder comprises the following steps:
s1: preparing an aluminum salt supersaturated solution with metastable state characteristics;
s2: adding urea to the supersaturated solution of aluminum salt to form Al (OH) 3 Sol;
s3: regulating said Al (OH) 3 The pH of the sol to obtain Al 2 O 3 A precipitation system;
s4: for the Al 2 O 3 Separating and drying the precipitation system to obtain Al 2 O 3 A precursor;
s5: calcining the Al 2 O 3 Precursor, alpha-Al is prepared 2 O 3 And (3) powder.
In a preferred embodiment, the preparation method specifically comprises the following steps:
s1: a supersaturated solution of aluminum salt having metastable properties is configured to reach a saturation concentration. For example, in a rapid stirring apparatus, an alkaline pH adjustor is rapidly dropped into an aluminum salt solution to obtain an aluminum salt supersaturated solution, and a certain amount of a dispersing agent is added.
Further, the aluminum salt solution in S1 may be prepared from one or more of aluminum-containing compounds such as aluminum sulfate, aluminum nitrate, aluminum chloride or hydrates of the above compounds and deionized water in proportion.
Further, al in the supersaturated solution of aluminum salt prepared in S1 3+ The concentration of (C) is 1.0-2.0 mol/L.
Further, the alkaline pH adjuster in S1 may be ammonium bicarbonate, ammonium carbonate, potassium carbonate, sodium carbonate, or the like.
Further, the temperature of the reaction system in S1 is controlled between 35 and 55 ℃.
Further, the final pH of the supersaturated solution of aluminum salt prepared in S1 is controlled to 3.0 to 4.0.
Further, the dispersing agent in S1 can be a single-component dispersing agent such as PEG-600, PEG-2000, PEG-20000, water-soluble starch and the like or any compound dispersing agent.
S2: adding urea into the supersaturated solution of aluminum salt to generate Al (OH) with continuous distribution 3 The addition of urea, i.e. sol, promotes uniform nucleation. For example, the supersaturated solution of the aluminum salt obtained in S1 is mixed withMixing urea solution, slowly hydrolyzing urea under microwave heating to release OH continuously - With Al 3+ Uniformly reacting in the system to generate Al (OH) with continuous distribution 3 And (3) sol.
Further, the concentration of the urea solution in S2 is 0.01-1.0 mol/L.
Further, the temperature of the microwave heating in S2 is controlled between 40 and 70 ℃.
S3: adjusting the Al (OH) obtained in S2 3 The pH of the sol causes Al to 3+ Fast reaction and complete precipitation to obtain Al 2 O 3 A precipitation system. For example, al (OH) obtained under ultrasonic and rapid stirring conditions to S2 3 And rapidly adding an alkaline pH regulator into the sol, generating a large amount of bubbles in the system, and stopping the reaction when the bubbles basically disappear.
Further, the pH of the mixed solution is controlled to be between 5.0 and 6.0 when the precipitation reaction in S3 reaches the end point.
Further, the alkaline pH regulator in S3 can be added rapidly by adopting methods of direct pouring, liquid phase atomization, peristaltic pump addition and the like.
Further, the alkaline pH adjuster in S3 may be ammonium bicarbonate, ammonium carbonate, potassium carbonate, sodium carbonate, or the like.
S4: separating and drying the Al obtained in S3 2 O 3 Precipitation system to obtain Al 2 O 3 A precursor. For example, al obtained in S3 2 O 3 The precipitate is subjected to solid-liquid separation, and the separated precipitate is respectively washed twice or more by deionized water and ethanol to remove surface impurities. Completely drying the washed precipitate to obtain Al 2 O 3 A precursor.
Further, the precipitation separation in S4 may be achieved by suction filtration or centrifugation.
Further, the precipitate separated in S4 may be dried by various means such as microwave drying, vacuum drying, etc.
Further, al obtained in S4 2 O 3 The precursor may be prepared by mixing alpha-Al 2 O 3 Additives such as seed crystal, ammonium nitrate, aluminum fluoride, magnesium oxide, etcThe calcination temperature is reduced.
S5: calcining Al obtained in S4 2 O 3 Precursor, alpha-Al is prepared 2 O 3 Ultrafine powder. For example, al obtained by S4 2 O 3 The precursor is put into a box furnace for calcination, thus obtaining submicron alpha-Al 2 O 3 Ultrafine powder.
Further, al in S5 2 O 3 The calcination temperature of the precursor is 950-1150 ℃.
Further, al in S5 2 O 3 The heat preservation time of the precursor at the calcination temperature is 1-6 h.
The following examples are set forth to illustrate in detail uniformly nucleated submicron alpha-Al of the present application 2 O 3 A method for preparing powder.
Example 1
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 40 ℃, and generating turbidity in the mixture to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 Adding 1L and 1.0mol/L ammonium carbonate solution into the sol in a rapid pouring way to enable the inside of the system to rapidly react, and rapidly completing the precipitation process after the pH reaches 5.0 to obtain Al 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the precursor at 1100 deg.c for 2 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in fig. 1 and 2, respectively, submicron-order α -Al prepared according to the above method 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The SEM image shows that the product has uniform morphology and good dispersibility.
Example 2
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L of 1mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 55 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 4.0 to form supersaturated solution; 15% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 40 ℃, and generating turbidity in the mixture to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 Adding 1L and 1.0mol/L ammonium carbonate solution into the sol in a rapid pouring way to enable the inside of the system to rapidly react, and rapidly completing the precipitation process after the pH reaches 5.0 to obtain Al 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the precursor at 1150 deg.c for 2 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in figures 3 and 4Respectively submicron alpha-Al prepared according to the method 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 。
Example 3
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 70 ℃, and uniformly generating white sol at all positions in the mixture, namely generating Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 Adding 1L and 1.0mol/L ammonium carbonate solution into the sol in a rapid pouring way to enable the inside of the system to rapidly react, and rapidly completing the precipitation process after the pH reaches 5.0 to obtain Al 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the precursor at 1100 deg.c for 2 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in fig. 5 and 6, respectively, submicron-order α -Al prepared according to the above method 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 。
Example 4
In this example, the following procedure was followedUniformly nucleated submicron alpha-Al 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 1mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 70 ℃, and uniformly generating white sol at all positions in the mixture to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 Adding 1L and 1.0mol/L ammonium carbonate solution into the sol in a rapid pouring way to enable the inside of the system to rapidly react, and rapidly completing the precipitation process after the pH reaches 5.0 to obtain Al 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the precursor at 1100 deg.c for 2 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in fig. 7 and 8, respectively, submicron-order α -Al prepared according to the above method 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The SEM image shows that the product has uniform morphology and good dispersibility.
Example 5
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 40 ℃, and generating turbidity in the mixture to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 2L of ammonium carbonate solution with the concentration of 0.5mol/L is added into the sol in a rapid pouring way, so that the internal reaction of the system is rapid, and after the pH reaches 6.0, the precipitation process is rapidly completed, and Al is obtained 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the precursor at 1100 deg.c for 2 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in fig. 9 and 10, submicron-order α -Al prepared according to the above method, respectively 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The SEM image shows that the product has uniform morphology and good dispersibility.
Example 6
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L,heating the mixed solution by microwaves until the temperature of the mixed solution reaches 40 ℃, and generating turbidity in the mixed solution to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 Adding 1L and 1.0mol/L ammonium carbonate solution into the sol in a liquid phase atomizing mode to enable the inside of the system to rapidly react, and rapidly completing the precipitation process after the pH reaches 5.0 to obtain Al 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the precursor at 1100 deg.c for 1 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in fig. 11 and 12, submicron-order α -Al prepared according to the above method, respectively 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The SEM image shows that the product has uniform morphology and good dispersibility.
Example 7
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 40 ℃, and generating turbidity in the mixture to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 1L of 1.0mol/L of the sol is added by rapid pouringThe ammonium carbonate solution enables the inside of the system to react rapidly, and after the pH reaches 5.0, the precipitation process is completed rapidly to obtain Al 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor; al to be obtained 2 O 3 Precursor and 5% of alpha-Al 2 O 3 The seed crystals are thoroughly mixed.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the mixture of the precursor and the seed crystal at 950 ℃ for 6 hours to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in fig. 13 and 14, respectively, submicron-order α -Al prepared according to the above-described method 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 。
Example 8
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 40 ℃, and generating turbidity in the mixture to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 Adding 1L and 1.0mol/L ammonium carbonate solution into the sol in a rapid pouring way to enable the inside of the system to rapidly react, and rapidly completing the precipitation process after the pH reaches 5.0 to obtain Al 2 O 3 A precipitation system.
Step four, theAl obtained in step three 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the precursor at 1050 deg.c for 4 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
As shown in fig. 15 and 16, submicron-order α -Al prepared according to the above method, respectively 2 O 3 XRD spectrum and SEM (scanning electron microscope) graph of powder show that the product is alpha-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The SEM image shows that the product has uniform morphology and good dispersibility.
Example 9
In this example, uniformly nucleated submicron alpha-Al was prepared as follows 2 O 3 And (3) powder.
Step one, dropwise adding 1mol/L ammonium bicarbonate solution into 0.5L and 0.5mol/L aluminum sulfate solution in a rapid stirring device, heating through a water bath, and keeping the temperature of the system at 35 ℃; controlling the addition amount of ammonium bicarbonate until the pH reaches 3.0 to form supersaturated solution; 10% PEG-600 was added as a dispersant.
Step two, uniformly mixing the supersaturated solution obtained in the step one with 1L of urea solution with the concentration of 0.01mol/L, heating the mixture by microwaves until the temperature of the mixture reaches 40 ℃, and generating turbidity in the mixture to generate Al (OH) 3 And (3) sol.
Step three, the Al (OH) obtained in step two is added 3 Adding 1L and 1.0mol/L ammonium carbonate solution into the sol in a rapid pouring way to enable the inside of the system to rapidly react, and rapidly completing the precipitation process after the pH reaches 5.0 to obtain Al 2 O 3 A precipitation system.
Step four, the Al obtained in the step three is processed 2 O 3 Separating the precipitation system by suction filtration, washing the precipitate with water and ethanol twice respectively, and rapidly dehydrating by microwave heating to obtain Al 2 O 3 A precursor; al to be obtained 2 O 3 The precursor was thoroughly mixed with 5% ammonium nitrate.
Fifthly, the Al obtained in the fourth step 2 O 3 Calcining the mixture of the precursor and ammonium nitrate as sintering aid at 1000 deg.c for 4 hr to obtain submicron alpha-Al 2 O 3 And (3) powder.
Table 1 shows the products alpha-Al corresponding to examples 1-8 above 2 O 3 Grain size and grain size of the particles.
TABLE 1
As can be seen in conjunction with fig. 1-16 and table 1, submicron-sized α -Al using uniform nucleation in accordance with the present application 2 O 3 alpha-Al prepared by the powder preparation method under the condition of low-temperature calcination 2 O 3 The powder has fine crystal grains, uniform dispersion, particle size of 100-300 nm, narrow particle size distribution, high alpha phase purity, uniform morphology and good dispersibility.
In summary, the present application provides a uniformly nucleated submicron alpha-Al 2 O 3 The preparation method of the powder comprises the steps of firstly, uniformly nucleating on the basis of a liquid phase precipitation method, and uniformly precipitating Al in supersaturated solution of aluminum salt by utilizing the slow release characteristic of urea 2 O 3 Precursor crystal nucleus (i.e. Al (OH) 3 Sol) which can be carried out under the auxiliary condition of microwave heating to quickly nucleate; and then, a large amount of sediment is quickly generated in the system by adding an alkaline pH regulator, so that the crystal nucleus is prevented from growing continuously due to overlong reaction time. Al prepared by the two-step nucleation mode 2 O 3 The precursor is calcined at a lower temperature (950-1150 ℃) to be converted into alpha-Al with fine grains and uniform dispersion 2 O 3 The alpha phase purity of the superfine powder is higher than 95 percent, and the grain diameter is between 100 and 300 nm. The application makes up for the existing submicronMeter grade alpha-Al 2 O 3 The defect of the powder preparation technology can obtain submicron alpha-Al with fine grains at a lower calcination temperature 2 O 3 The superfine powder has uniform appearance and narrow particle size distribution, and is used for reducing Al 2 O 3 The sintering temperature of the ceramic lays a good foundation. The method has the advantages of low production cost, environmental friendliness, high production efficiency, suitability for large-scale production and the like.
The concepts described herein may be embodied in other forms without departing from the spirit or characteristics thereof. The particular embodiments disclosed are illustrative and not restrictive. The scope of the application is, therefore, indicated by the appended claims rather than by the foregoing description. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (12)
1. Submicron alpha-Al with uniform nucleation 2 O 3 The preparation method of the powder is characterized by comprising the following steps:
s1: preparing an aluminum salt supersaturated solution with metastable state characteristics;
s2: adding urea to the supersaturated solution of aluminum salt to form Al (OH) 3 Sol;
s3: regulating said Al (OH) 3 The pH of the sol to obtain Al 2 O 3 A precipitation system;
s4: for the Al 2 O 3 Separating and drying the precipitation system to obtain Al 2 O 3 A precursor;
s5: calcining the Al 2 O 3 Precursor, alpha-Al is prepared 2 O 3 And (3) powder.
2. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 The preparation method of the powder is characterized in that in the step S1, the aluminum salt in the supersaturated solution of the aluminum salt comprises one or more of aluminum sulfate, aluminum nitrate, aluminum chloride and hydrates of the above compounds.
3. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 A process for producing a powder, characterized in that in the step S1, al is contained in the supersaturated solution of aluminum salt 3+ The concentration of (C) is 1.0-2.0 mol/L.
4. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 The preparation method of the powder is characterized in that in the step S1, the final pH value of the supersaturated solution of the aluminum salt is controlled to be 3.0-4.0.
5. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 The preparation method of the powder is characterized in that in the step S1, after the supersaturated solution of the aluminum salt is prepared, a dispersing agent is added into the supersaturated solution of the aluminum salt, and the dispersing agent comprises one or more of PEG-600, PEG-2000, PEG-20000 and water-soluble starch.
6. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 The preparation method of the powder is characterized in that the temperature of the reaction system in the step S1 is controlled to be 35-55 ℃.
7. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 The preparation method of the powder is characterized in that in the step S2, the concentration of the urea is 0.01-1.0 mol/L.
8. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 The preparation method of the powder is characterized in that the temperature of the reaction system in the step S2 is controlled to be 40-70 ℃.
9. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 The preparation method of the powder is characterized by comprising the following steps ofIn S3, the pH of the mixed solution is controlled to be 5.0-6.0 when the precipitation reaction reaches the end point.
10. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 A method for producing a powder, characterized in that in step S4, the Al is obtained 2 O 3 After the precursor, to the Al 2 O 3 Mixing alpha-Al into the precursor 2 O 3 One or more additives selected from seed crystal, ammonium nitrate, aluminum fluoride and magnesium oxide.
11. Uniformly nucleated submicron α -Al as described in claim 1 2 O 3 A method for producing a powder, characterized in that in step S5, the Al is 2 O 3 The calcination temperature of the precursor is 950-1150 ℃.
12. Uniformly nucleated submicron α -Al according to claim 11 2 O 3 The preparation method of the powder is characterized in that the Al 2 O 3 The precursor is kept at the calcination temperature for 1 to 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211717177.4A CN116040668B (en) | 2022-12-29 | 2022-12-29 | Submicron alpha-Al with uniform nucleation2O3Preparation method of powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211717177.4A CN116040668B (en) | 2022-12-29 | 2022-12-29 | Submicron alpha-Al with uniform nucleation2O3Preparation method of powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116040668A true CN116040668A (en) | 2023-05-02 |
| CN116040668B CN116040668B (en) | 2024-09-03 |
Family
ID=86132649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211717177.4A Active CN116040668B (en) | 2022-12-29 | 2022-12-29 | Submicron alpha-Al with uniform nucleation2O3Preparation method of powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116040668B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6913926A (en) * | 1968-09-14 | 1970-03-17 | ||
| CN101885500A (en) * | 2010-07-09 | 2010-11-17 | 西安交通大学 | Process for preparing catalysis nano Al2O3 by using starch gel- |
| CN102659149A (en) * | 2012-02-28 | 2012-09-12 | 山东大学 | Preparation method for monodisperse high-purity alpha-Al2O3 powder |
| CN112758968A (en) * | 2021-01-05 | 2021-05-07 | 中国铝业股份有限公司 | Alumina precursor and preparation method thereof, submicron alumina and preparation method thereof |
| CN113479918A (en) * | 2021-08-04 | 2021-10-08 | 郑州大学 | Preparation method of nano spherical alpha-alumina powder |
-
2022
- 2022-12-29 CN CN202211717177.4A patent/CN116040668B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6913926A (en) * | 1968-09-14 | 1970-03-17 | ||
| CN101885500A (en) * | 2010-07-09 | 2010-11-17 | 西安交通大学 | Process for preparing catalysis nano Al2O3 by using starch gel- |
| CN102659149A (en) * | 2012-02-28 | 2012-09-12 | 山东大学 | Preparation method for monodisperse high-purity alpha-Al2O3 powder |
| CN112758968A (en) * | 2021-01-05 | 2021-05-07 | 中国铝业股份有限公司 | Alumina precursor and preparation method thereof, submicron alumina and preparation method thereof |
| CN113479918A (en) * | 2021-08-04 | 2021-10-08 | 郑州大学 | Preparation method of nano spherical alpha-alumina powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116040668B (en) | 2024-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Colloidal processing of Gd2O3: Eu3+ red phosphor monospheres of tunable sizes: Solvent effects on precipitation kinetics and photoluminescence properties of the oxides | |
| Zhang et al. | Co-precipitation synthesis and luminescence behavior of Ce-doped yttrium aluminum garnet (YAG: Ce) phosphor: The effect of precipitant | |
| JP3936986B2 (en) | Method for producing single crystal zinc sulfide powder for phosphor | |
| CN108910932B (en) | Method for preparing narrow-distribution superfine yttrium oxide by sodium carbonate precipitation | |
| CN110629288B (en) | Method for preparing whisker-shaped gadolinium aluminate powder material by hydrothermal technology | |
| Jinqing et al. | Preparation of nanoscaled yttrium oxide by citrate precipitation method | |
| CN112266244A (en) | Preparation method of high-sintering-activity zirconium oxide powder | |
| JP7564823B2 (en) | Nano-barium titanate microcrystals and method for producing same, barium titanate powder and method for producing same | |
| EP1461289A1 (en) | METHOD FOR PREPARING OF a-ALUMINA NANO POWDER | |
| Wang et al. | Synthesis of monodisperse and high-purity α-Si3N4 powder by carbothermal reduction and nitridation | |
| Wu et al. | Solvothermal synthesis of spherical YAG powders via different precipitants | |
| CN116040668B (en) | Submicron alpha-Al with uniform nucleation2O3Preparation method of powder | |
| CN116462490B (en) | High-hardness alumina grinding powder and preparation method thereof | |
| CN116199270B (en) | Treatment process for reducing wastewater in cobalt oxide production process | |
| CN115196970B (en) | Preparation method of high-fluidity AlON spherical powder | |
| CN116715260A (en) | Submicron spheroidal alumina and preparation method thereof | |
| CN1858022A (en) | Gel combustion synthesis method for preparing neodymium-doped gadolinium-gallium garnet nano powder | |
| CN112340758A (en) | Preparation of high-purity alpha-Al by low-temperature calcination of aluminum ammonium sulfate2O3Method for producing powder | |
| CN115818687B (en) | Superfine alpha-Al2O3Method for preparing nano powder | |
| CN116639972B (en) | Tetragonal phase nano barium titanate powder and preparation method and application thereof | |
| CN116495766B (en) | Preparation method of spherical nanometer yttrium oxide | |
| CN116986625A (en) | Preparation method of in-situ precipitation self-dispersion indium oxide powder | |
| CN115784292B (en) | Basic cerium carbonate and preparation method and application thereof | |
| Hua et al. | Green synthesis of NdOHCO3 via a carbon dioxide carbonatation process in mild conditions | |
| CN117945449A (en) | Polycrystalline nanometer spherical yttrium europium oxide red fluorescent powder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Chang Zixuan Inventor after: Zhang Juxian Inventor after: Yao Congxue Inventor before: Chang Zixuan Inventor before: Zhang Juxian Inventor before: Yao Congxue |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |