CN108640151A - Zirconia hollow microsphere containing aluminium and preparation method thereof - Google Patents
Zirconia hollow microsphere containing aluminium and preparation method thereof Download PDFInfo
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- CN108640151A CN108640151A CN201810599788.0A CN201810599788A CN108640151A CN 108640151 A CN108640151 A CN 108640151A CN 201810599788 A CN201810599788 A CN 201810599788A CN 108640151 A CN108640151 A CN 108640151A
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- aluminium
- hollow microsphere
- zirconia hollow
- zirconia
- containing aluminium
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 154
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 99
- 239000004411 aluminium Substances 0.000 title claims abstract description 97
- 239000004005 microsphere Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004202 carbamide Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 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 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 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 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 10
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 235000011167 hydrochloric acid Nutrition 0.000 description 13
- 125000005909 ethyl alcohol group Chemical group 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 7
- NZSLBYVEIXCMBT-UHFFFAOYSA-N chloro hypochlorite;zirconium Chemical class [Zr].ClOCl NZSLBYVEIXCMBT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 description 2
- 239000012720 thermal barrier coating Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of zirconia hollow microspheres containing aluminium, and it is (1~4) that this, which contains aluminium zirconia hollow microsphere comprising molar ratio: 8 aluminium element and zr element, this contains a diameter of 0.1~10 μm of aluminium zirconia hollow microsphere.The invention also discloses a kind of methods preparing the zirconia hollow microsphere containing aluminium, including：Aluminium presoma, zirconium precursor body, urea and strong acid are uniformly mixed in ethanol, form clear solution；Clear solution is placed in closed reactor, 6~18h of solvent thermal reaction at 160~200 DEG C, it is cooling, the white precipitate in product is collected, is washed, it is dry；1~4h is calcined at 800~1000 DEG C.The present invention introduces aluminium element in zirconia hollow microsphere, effectively reduce the diffusion rate of zirconium oxide at high temperature, tiny balloon is set still to keep stablizing at 1300 DEG C or more, and the introducing of aluminium element is simple for process, cost of material is low, the prepared hollow microsphere structure of zirconium oxide containing aluminium is stablized, good dispersion.
Description
Technical field
The invention belongs to heat-barrier material fields, and in particular to one kind zirconia hollow microsphere containing aluminium and preparation method thereof.
Background technology
Bubble zirconia is because with density is low, specific surface area is high, thermal conductivity is low, chemical stability is good and heat-resist
Etc. characteristics, have a wide range of applications in heat-insulated field.Bubble zirconia is applied to prepare thermal boundary painting in heat-insulated field more
The raw material of layer or block body stephanoporate ceramics, prepared heat-barrier material show excellent heat-proof quality.
The grain size and heat resistance of Bubble zirconia drastically influence the heat-proof quality of end product.In general, working as thermal boundary
One timing of coating or block body stephanoporate ceramics porosity, raw materials used Bubble zirconia diameter is smaller, and product thermal conductivity is lower.This
It is because when one timing of material porosity, the reduction of Bubble zirconia diameter will cause internal total interfacial area to increase.It is internal
The increase of interfacial area can reduce material heat radiation, and the transfer route for keeping heat total in solid phase greatly prolongs, and reduces material
The heat transfer of material.Therefore, Bubble zirconia diameter is smaller, and prepared heat-barrier material heat-proof quality is better.But small particle
Bubble zirconia heat resistance it is usually poor, as the patent application of Publication No. CN103086700A and CN1259453C make
Thermal barrier coating is prepared with 10-150 μm of zirconia hollow microsphere of diameter is raw material, prepared thermal barrier coating meets basic nature
It can require.The patent application of Publication No. CN107805065A is passed through using the zirconia hollow microsphere of 1-5 μm of diameter for raw material
Gel casting process prepares porosity height, and density is low, the excellent porous ceramics of heat-proof quality.Prepared by both techniques every
Hot material heat-proof quality is preferable, but due to the use of zirconia hollow microsphere high temperature resistance it is poor, usually less than 1200 DEG C, limit
Its use under higher temperature environment is made.Therefore, research High-temperature-reszirconium zirconium oxide tiny balloon can lead it in high temperature insulating
The use in domain is particularly important.
Invention content
The object of the present invention is to provide a kind of stable structure, the excellent zirconia hollow microsphere containing aluminium of high temperature resistance.
It is a further object of the present invention to provide a kind of cost of material is low, simple for process to prepare above-mentioned zirconium oxide containing aluminium hollow
The method of microballoon.
Technical solution：The present invention provides a kind of zirconia hollow microsphere containing aluminium, and it includes to rub that this, which contains aluminium zirconia hollow microsphere,
You are than being (1~4): 8 aluminium element and zr element, this contains a diameter of 0.1~10 μm of aluminium zirconia hollow microsphere.
Preferably, above-mentioned zirconia hollow microsphere containing aluminium is made of aluminium oxide and zirconium oxide, a diameter of 0.1~5 μm, wall thickness
For 150-250nm.The preparation method of the above-mentioned zirconia hollow microsphere containing aluminium includes the following steps：
1) aluminium presoma, zirconium precursor body, urea and strong acid are uniformly mixed in ethanol, form clear solution；
2) clear solution made from step 1) is placed in closed reactor, solvent thermal reaction 6 at 160~200 DEG C~
18h, it is cooling, the white precipitate in product is collected, is washed, it is dry；
3) product of the step 2) after dry is calcined into 1~4h at 800~1000 DEG C.
Another aspect of the present invention provides a kind of method preparing the above-mentioned zirconia hollow microsphere containing aluminium, includes the following steps：
1) aluminium presoma, zirconium precursor body, urea and strong acid are uniformly mixed in ethanol, form clear solution；
2) clear solution made from step 1) is placed in closed reactor, solvent thermal reaction 6 at 160~200 DEG C~
18h, it is cooling, the white precipitate in product is collected, is washed, it is dry；
3) product of the step 2) after dry is calcined into 1~4h at 800~1000 DEG C.
During solvent thermal reaction, urea can hydrolyze, and discharge hydroxide ion, to adjust the pH of reaction system,
Strong acid catalyst ethanol dehydration and it is in situ generate small ether oil droplet, aluminium presoma and zirconium precursor body are selectively deposited in small second
Ether oil droplets form the hollow ball being made of aluminium presoma and zirconium precursor body；The organic matter in hollow ball is removed by calcining
With absorption water, and converts aluminium presoma and zirconium precursor to aluminium oxide and zirconium oxide, it is hollow to obtain stable zirconium oxide containing aluminium
Microballoon.
In step 1), aluminium presoma, zirconium precursor body, urea molar ratio be (1~4): 8: (12~24)；The aluminium forerunner
Body is one or more mixtures in aluminum nitrate, aluminium chloride, alumina silicate, aluminum sulfate and Aluminum sol；The zirconium precursor body is
One or more mixtures in zirconium oxychloride, zirconium-n-butylate and zirconium oxycarbonate；The volume ratio of ethyl alcohol and strong acid be (2~
8)∶1；The strong acid is one or more mixtures in hydrochloric acid, nitric acid and sulfuric acid, and hydrogen ion concentration is 10 in the strong acid
~15mol/L；For ethyl alcohol as reaction dissolvent, addition should be able to be such that aluminium presoma, zirconium precursor body and urea fully dissolves, excellent
Selection of land, concentration of the zirconium precursor body in clear solution should be within the scope of 0.05~0.15mol/L；In addition, can by ultrasound and/or
The mode of 60~80 DEG C of heating stirrings accelerates aluminium presoma, zirconium precursor body, urea to dissolve in ethanol and forms clear solution.
In step 2), it is water or absolute ethyl alcohol to wash the cleaning solution used, and drying is in 60~100 DEG C of dry 24~48h.
Advantageous effect：The present invention introduces aluminium element in zirconia hollow microsphere, and the introducing of aluminium element effectively reduces
The diffusion rate of zirconium oxide at high temperature makes tiny balloon still keep stablizing at 1300 DEG C or more, solves prior art institute
The problem of zirconia hollow microsphere non-refractory of preparation.Also, the introducing of aluminium element is simple for process in the method for the present invention, former
Expect that the hollow microsphere structure of zirconium oxide containing aluminium at low cost, prepared is stablized, good dispersion is zirconia hollow microsphere at higher temperature
Use under environment realizes breakthrough.
Description of the drawings
Fig. 1 (a) is the SEM figures of the zirconia hollow microsphere containing aluminium prepared by embodiment 2；Fig. 1 (b) is prepared by embodiment 2
SEM figure of the zirconia hollow microsphere containing aluminium after 1300 DEG C of high-temperature process；
Fig. 2 is the EDS figures of the zirconia hollow microsphere containing aluminium prepared by embodiment 2；
Fig. 3 (a) is the SEM figures without aluminium zirconia hollow microsphere prepared by comparative example；Fig. 3 (b) is prepared by comparative example
SEM figures without aluminium zirconia hollow microsphere after 1300 DEG C of high-temperature process.
Specific implementation mode
Embodiment 1
The preparation method of the zirconia hollow microsphere containing aluminium is as follows：
0.008mol aluminum nitrates, 0.016mol zirconium oxychlorides, 0.032mol urea are added in 200ml absolute ethyl alcohols,
And 50ml concentrated hydrochloric acids (hydrogen ion concentration is 12mol/L in concentrated hydrochloric acid) are slowly added in whipping process, in 60 DEG C of water baths
Lower magnetic agitation is to clear solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE),
After sealing 12h is heated in 160 DEG C of baking ovens.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, with anhydrous second
After alcohol washing three times, it is put into 60 DEG C of baking ovens for 24 hours to being completely dried.The powder obtained after drying is calcined 2h at 1000 DEG C to obtain
Zirconia hollow microsphere containing aluminium, and take a part of zirconia hollow microsphere containing aluminium high-temperature process 2h at 1300 DEG C.
Embodiment 2
The preparation method of the zirconia hollow microsphere containing aluminium is as follows：
0.004mol aluminum nitrates, 0.016mol zirconium oxychlorides, 0.032mol urea are added in 200ml absolute ethyl alcohols,
And 50ml concentrated hydrochloric acids (hydrogen ion concentration is 12mol/L in concentrated hydrochloric acid) are slowly added in whipping process, in 60 DEG C of water baths
Lower magnetic agitation is to clear solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE),
After sealing 12h is heated in 160 DEG C of baking ovens.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, with anhydrous second
After alcohol washing three times, it is put into 60 DEG C of baking ovens for 24 hours to being completely dried；The powder obtained after drying is calcined 2h at 1000 DEG C to obtain
Zirconia hollow microsphere containing aluminium, and take a part of zirconia hollow microsphere containing aluminium high-temperature process 2h at 1300 DEG C.
Embodiment 3
The preparation method of the zirconia hollow microsphere containing aluminium is as follows：
0.002mol aluminum nitrates, 0.016mol zirconium oxychlorides, 0.032mol urea are added in 200ml absolute ethyl alcohols,
And 50ml concentrated hydrochloric acids (hydrogen ion concentration is 12mol/L in concentrated hydrochloric acid) are slowly added in whipping process, in 60 DEG C of water baths
Lower magnetic agitation is to clear solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE),
After sealing 12h is heated in 160 DEG C of baking ovens.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, with anhydrous second
After alcohol washing three times, it is put into 60 DEG C of baking ovens for 24 hours to being completely dried；The powder obtained after drying is calcined 2h at 1000 DEG C to obtain
Zirconia hollow microsphere containing aluminium, and take a part of zirconia hollow microsphere containing aluminium high-temperature process 2h at 1300 DEG C.
Embodiment 4
The preparation method of the zirconia hollow microsphere containing aluminium is as follows：
0.004mol aluminum nitrates, 0.016mol zirconium oxychlorides, 0.032mol urea are added in 200ml absolute ethyl alcohols,
And 50ml concentrated hydrochloric acids (hydrogen ion concentration is 12mol/L in concentrated hydrochloric acid) are slowly added in whipping process, in 60 DEG C of water baths
Lower magnetic agitation is to clear solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE),
After sealing 18h is heated in 160 DEG C of baking ovens.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, with anhydrous second
After alcohol washing three times, it is put into 60 DEG C of baking ovens for 24 hours to being completely dried；The powder obtained after drying is calcined 2h at 1000 DEG C to obtain
Zirconia hollow microsphere containing aluminium, and take a part of zirconia hollow microsphere containing aluminium high-temperature process 2h at 1300 DEG C.
Embodiment 5
The preparation method of the zirconia hollow microsphere containing aluminium is as follows：
0.004mol aluminum nitrates, 0.016mol zirconium oxychlorides, 0.032mol urea are added in 200ml absolute ethyl alcohols,
And 50ml concentrated hydrochloric acids (hydrogen ion concentration is 12mol/L in concentrated hydrochloric acid) are slowly added in whipping process, in 60 DEG C of water baths
Lower magnetic agitation is to clear solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE),
After sealing 18h is heated in 200 DEG C of baking ovens.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, with anhydrous second
After alcohol washing three times, it is put into 60 DEG C of baking ovens for 24 hours to being completely dried；The powder obtained after drying is calcined 2h at 1000 DEG C to obtain
Zirconia hollow microsphere containing aluminium, and take a part of zirconia hollow microsphere containing aluminium high-temperature process 2h at 1300 DEG C.
Embodiment 6
The preparation method of the zirconia hollow microsphere containing aluminium is as follows：
0.004mol aluminium chloride, 0.016mol zirconium-n-butylates, 0.024mol urea are added in 200ml absolute ethyl alcohols,
And 50ml sulfuric acid (hydrogen ion concentration is 10mol/L in sulfuric acid), the magnetic under 60 DEG C of water baths are slowly added in whipping process
Power stirs to clarify solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), sealing
Afterwards 6h is heated in 200 DEG C of baking ovens.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, is washed with absolute ethyl alcohol
After washing three times, it is put into 60 DEG C of baking ovens for 24 hours to being completely dried；The powder obtained after drying is calcined 1h at 1000 DEG C must contain aluminium
Zirconia hollow microsphere, and take a part of zirconia hollow microsphere containing aluminium high-temperature process 2h at 1300 DEG C.
Embodiment 7
The preparation method of the zirconia hollow microsphere containing aluminium is as follows：
0.002mol aluminum sulfate, 0.008mol zirconium oxycarbonates, 0.048mol urea are added to 200ml absolute ethyl alcohols
In, and 60ml nitric acid (hydrogen ion concentration is 15mol/L in nitric acid) is slowly added in whipping process, under 60 DEG C of water baths
Magnetic agitation is to clear solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), it is close
It is honored as a queen and heats 10h in 180 DEG C of baking ovens.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, absolute ethyl alcohol is used
After washing three times, it is put into 60 DEG C of baking ovens for 24 hours to being completely dried；The powder obtained after drying is calcined 4h at 800 DEG C to be contained
Aluminium zirconia hollow microsphere, and take a part of zirconia hollow microsphere containing aluminium high-temperature process 2h at 1300 DEG C.
Comparative example
The preparation method of zirconia hollow microsphere is as follows：
0.016mol zirconium oxychlorides, 0.032mol urea are added in 200ml absolute ethyl alcohols, and delayed in whipping process
Slow that 50ml concentrated hydrochloric acids (hydrogen ion concentration is 12mol/L in concentrated hydrochloric acid) are added, magnetic agitation is extremely clarified under 60 DEG C of water baths
Solution.The clear solution prepared is poured into the stainless steel cauldron that liner is polytetrafluoroethylene (PTFE), in 160 DEG C of baking ovens after sealing
Middle heating 12h.After reaction finishes natural cooling, the precipitation that reaction generates is filtered out, after being washed three times with absolute ethyl alcohol, is put into
For 24 hours to being completely dried in 60 DEG C of baking ovens；The powder obtained after drying is calcined 2h at 1000 DEG C must be free of the zirconium oxide sky of aluminium
Heart microballoon, and take zirconia hollow microsphere of the part without aluminium high-temperature process 2h at 1300 DEG C.
It summarizes：
(1) the embodiment 1-3 main distinctions are that the aluminium content added is different, are (1 in the molar ratio of aluminium element and zr element
~4): prepared zirconia hollow microsphere containing aluminium shows excellent high temperature resistance in 8 ranges.Fig. 1 (a) is embodiment
The SEM of the zirconia hollow microsphere containing aluminium prepared by 2 schemes, and tiny balloon preserves completely, and surface is smooth.Fig. 1 (b) is embodiment 2
SEM of the prepared zirconia hollow microsphere containing aluminium after 1300 DEG C of high-temperature process schemes, the equal nothing of tiny balloon after high-temperature process
Significant change shows excellent high temperature resistance.Fig. 2 is the EDS figures of the zirconia hollow microsphere containing aluminium prepared by embodiment 2,
And the molar ratio of aluminium element and zr element is 1: 4, and this demonstrates the aluminium elements in precursor to be completely incorporated into zirconium oxide sky
In heart microballoon.
(2) embodiment 2,4~embodiment of embodiment, 7 main distinction are that the conditions such as reaction time, temperature difference, comparison are real
It applies example 2, embodiment 4 and embodiment 5 and finds that the change of hydrothermal condition influences less hollow ball heat resistance.
(3) comparative example is the zirconia hollow microsphere without aluminium, and Fig. 3 (a) is to be free of aluminium zirconium oxide prepared by comparative example
The SEM of tiny balloon schemes, and tiny balloon preserves completely, and surface is smooth.Fig. 3 (b) is to be not added with aluminium zirconium oxide prepared by comparative example
SEM of the tiny balloon after 1300 DEG C of high-temperature process schemes, and the aluminium tiny balloon that is not added with after high-temperature process destroys seriously, and surface is in engrave
Empty shape adds its heat resistance of the zirconia hollow microsphere of aluminium to want very different compared to embodiment 2.Therefore, add aluminium to zirconium oxide sky
Heart microballoon high temperature resistance is obviously improved.
Claims (10)
1. a kind of zirconia hollow microsphere containing aluminium, which is characterized in that this contain aluminium zirconia hollow microsphere include molar ratio for (1~
4): 8 aluminium element and zr element, this contains a diameter of 0.1~10 μm of aluminium zirconia hollow microsphere.
2. zirconia hollow microsphere containing aluminium according to claim 1, which is characterized in that this contains aluminium zirconia hollow microsphere packet
Salic and zirconium oxide.
3. zirconia hollow microsphere containing aluminium according to claim 1, which is characterized in that this contains aluminium zirconia hollow microsphere
A diameter of 0.1~5 μm, wall thickness is 150~250nm.
4. zirconia hollow microsphere containing aluminium according to claim 1, which is characterized in that this contains aluminium zirconia hollow microsphere
Preparation method includes the following steps：
1) aluminium presoma, zirconium precursor body, urea and strong acid are uniformly mixed in ethanol, form clear solution；
2) clear solution made from step 1) is placed in closed reactor, 6~18h of solvent thermal reaction, cold at 160~200 DEG C
But, the white precipitate in product is collected, is washed, it is dry；
3) product of the step 2) after dry is calcined into 1~4h at 800~1000 DEG C.
5. a kind of method preparing the zirconia hollow microsphere containing aluminium, which is characterized in that this approach includes the following steps：
1) aluminium presoma, zirconium precursor body, urea and strong acid are uniformly mixed in ethanol, form clear solution；
2) clear solution made from step 1) is placed in closed reactor, 6~18h of solvent thermal reaction, cold at 160~200 DEG C
But, the white precipitate in product is collected, is washed, it is dry；
3) product of the step 2) after dry is calcined into 1~4h at 800~1000 DEG C.
6. the method according to claim 5 for preparing the zirconia hollow microsphere containing aluminium, which is characterized in that in step 1), aluminium
Presoma and zirconium precursor body molar ratio are (1~4): 8；The aluminium presoma be aluminum nitrate, aluminium chloride, alumina silicate, aluminum sulfate and
One or more mixtures in Aluminum sol；The zirconium precursor body is in zirconium oxychloride, zirconium-n-butylate and zirconium oxycarbonate
One or more mixtures.
7. the method according to claim 6 for preparing the zirconia hollow microsphere containing aluminium, which is characterized in that in step 1), second
The volume ratio of alcohol and strong acid is (2~8): 1；The strong acid is one or more mixtures in hydrochloric acid, nitric acid and sulfuric acid, institute
It is 10~15mol/L to state hydrogen ion concentration in strong acid；Aluminium presoma, zirconium precursor body, urea molar ratio be (1~4): 8: (12
~24).
8. the method according to claim 6 for preparing the zirconia hollow microsphere containing aluminium, which is characterized in that in step 1), institute
State a concentration of 0.05~0.15mol/L of zirconium precursor body in clear solution.
9. the method according to claim 5 for preparing the zirconia hollow microsphere containing aluminium, which is characterized in that in step 1), lead to
The mode for crossing ultrasound and/or 60~80 DEG C of heating stirrings accelerates aluminium presoma, zirconium precursor body, urea and strong acid to be formed in ethanol
Clear solution.
10. the method according to claim 5 for preparing the zirconia hollow microsphere containing aluminium, which is characterized in that in step 2), institute
It is water or absolute ethyl alcohol to state the cleaning solution that washing uses, and the drying is in 60~100 DEG C of dry 24~48h.
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