CN101962168A - Method for preparing nano powder material - Google Patents
Method for preparing nano powder material Download PDFInfo
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- CN101962168A CN101962168A CN2009101573067A CN200910157306A CN101962168A CN 101962168 A CN101962168 A CN 101962168A CN 2009101573067 A CN2009101573067 A CN 2009101573067A CN 200910157306 A CN200910157306 A CN 200910157306A CN 101962168 A CN101962168 A CN 101962168A
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- 239000000463 material Substances 0.000 title claims abstract description 35
- 239000011858 nanopowder Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 16
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 45
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 30
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 18
- 150000001298 alcohols Chemical class 0.000 claims abstract description 17
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 14
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000975 co-precipitation Methods 0.000 claims abstract description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 43
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 31
- 238000002360 preparation method Methods 0.000 claims description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 239000013049 sediment Substances 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000008118 PEG 6000 Substances 0.000 claims description 4
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 4
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 3
- 229920002594 Polyethylene Glycol 8000 Polymers 0.000 claims description 3
- 238000013467 fragmentation Methods 0.000 claims description 3
- 238000006062 fragmentation reaction Methods 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 2
- 229940075630 samarium oxide Drugs 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 21
- 238000005245 sintering Methods 0.000 abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 10
- 238000004220 aggregation Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 150000007529 inorganic bases Chemical class 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 239000012716 precipitator Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000000446 fuel Substances 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 235000019441 ethanol Nutrition 0.000 description 23
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 12
- 238000001354 calcination Methods 0.000 description 9
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- WKVDRPZFTFFYDE-UHFFFAOYSA-N 2-aminoethanol butan-1-ol Chemical compound NCCO.CCCCO WKVDRPZFTFFYDE-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Abstract
The invention relates to a method for preparing a nano powder material, and belongs to the field of inorganic synthesis and material chemistry. In the method, a crystalline hydrate of nitrate is taken as a raw material, anhydrous C2 to C4 alcohols are taken as a solvent, ethanolamine is taken as a precipitator; and the nano powder material, such as zirconium oxide, cerium oxide and the like, is prepared by a coprecipitation method. The method overcomes the defects of nonuniform precipitation, easy aggregation, need of special drying method and equipment, and the like in the conventional coprecipitation method in which water is taken as the solvent, and an inorganic base or an inorganic salt is taken as the precipitator; and the prepared nano powder material, such as zirconium oxide and cerium oxide has the advantages of small grain size (the grain size is 6 to 20nm), small particle size, narrow particle size distribution range (the particle size distribution range is 50 to 150nm), no hard aggregation, high sintering activity and the like. The prepared nano powder material is suitable for the fields of a solid oxide fuel cell, a chemical sensor, a special functional ceramic, a catalyst or a catalyst carrier and the like.
Description
Technical field
The invention belongs to inorganic synthetic and materials chemistry field, particularly a kind of preparation method of nano-powder material.Crystalline hydrate with nitrate is a raw material specifically, makes solvent with anhydrous C2-C4 alcohols, and organic base---monoethanolamine is made precipitating reagent in use, adopts coprecipitation to prepare a kind of method of zirconia, cerium oxide type nano-powder material.
Background technology
The wet chemical preparation method commonly used of nano-powder mainly contains coprecipitation, alkoxide hydrolysis, sol-gel process, hydro-thermal method and firing method etc.Wherein, coprecipitation since have can accurately control each constituent content, cost is low, technology is simple, be easy to advantage such as large-scale production and at industrial circle application promise in clinical practice arranged.Yet, prepare in the powder process in coprecipitation, adopt the aqueous solution usually, this easily reunites because of the huge surface tension of water produces in the dry run in later stage, then form hard aggregation in calcination process, this has a strong impact on particle diameter, particle diameter distribution and the sintering character etc. of synthetic powder.Solve coprecipitation and prepare agglomeration traits in the powder process, key is to reduce the adsorbed water content in the sediment or adopt special drying means (supercritical drying, azeotropic distillation, vacuum freeze drying, microwave drying etc.).Reduce that moisture is a kind of method of reuniting that reduces from the source in the sediment, be mainly concerned with and adopt the alcohols solvent washing precipitate, be the raw material solvent and be methods such as solvent with anhydrous alcohols with alcohol-water.Wherein, be that the method for solvent can weaken the influence of water to the reunion degree to greatest extent with anhydrous alcohols especially.
Be that solvent is when preparing ceramic powder material with anhydrous alcohols, usually adopt the aqueous solution of ammoniacal liquor or other inorganic base and other inorganic precipitant to make precipitating reagent, although this has weakened the reunion degree of powder to a certain extent, but the reunion of institute's synthetic powder is still more serious, so that powder granularity distributes, sintering activity is not ideal enough.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming, a kind of preparation method of nano-powder material is provided, reduce the reunion degree of powder, obtain that particle diameter is little, narrow particle size distribution, nano-powder material that sintering activity is high.
The objective of the invention is to be achieved through the following technical solutions:
Nano-powder material of the present invention comprises following material: zirconia (ZrO
2), Yttrium oxide doping zirconium oxide (YSZ), scandium oxide doped zirconia (ScSZ), scandium oxide and cerium oxide codope zirconia (10ScSZ-1CeO
2), magnesia doped zirconia (MgSZ), calcium oxide doped zirconia (CaSZ), cerium oxide (CeO
2), gadolinium oxide doped cerium oxide (GDC), samarium oxide doped cerium oxide (SDC).
The preparation method of nano-powder material of the present invention is that the nitrate with the respective metal of prepared each powder body material is raw material, with monoethanolamine (HOCH
2CH
2NH
2) make precipitating reagent, be solvent with anhydrous C2-C4 alcohols (ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol), adopt coprecipitation to prepare nano-powder material, may further comprise the steps:
1) is solvent with anhydrous C2-C4 alcohols, prepares the nitrate solution that total concentration of metal ions is 0.05～0.5mol/L;
2) use and 1) identical solvent, preparation monoethanolamine concentration is the ethanolamine solutions of 0.25～5mol/L;
3) above-mentioned 1) and 2) in add in any one solution by final synthetic powder quality and count 0～3% polyethylene glycol (PEG) as surfactant, the ethanolamine solutions that stir, heating for dissolving obtains containing the nitrate solution of polyethylene glycol or contains polyethylene glycol;
4) under constantly stirring, with 1) nitrate solution and 3 that obtains) ethanolamine solutions that contains polyethylene glycol that obtains, or 3) nitrate solution that contains polyethylene glycol and 2 that obtains) a kind of the joining in isopyknic another kind of solution in the ethanolamine solutions that obtains obtains precipitating suspension;
5) continue to stir still aging 0～12 hour 0～30 minute;
6) filter and obtain sediment, drying, fragmentation with C2-C4 alcohols solvent washing several;
7) calcined 2～5 hours down at 600～800 ℃ through above-mentioned washing, drying, broken sediment;
8) be solvent with ethanol or isopropyl alcohol,, obtain required nano-powder through separation, drying at rotating speed ball milling 2～48h of 400～1500rpm;
9) used C2-C4 alcohols solvent reclaims, purifies, and is recycling.
Above-mentioned steps 1) described nitrate when preparation zirconia class nano-powder material, adopts the ZrO (NO that contains the crystallization water
3)
2XH
2O or Zr (NO
3)
4XH
2O (x is a crystallization water number) is the zirconium source, the nitrate Y (NO of corresponding doped chemical
3)
3, Sc (NO
3)
3, Ce (NO
3)
3, Mg (NO
3)
2, Ca (NO
3)
2Deng crystalline hydrate be raw material; When preparation cerium oxide type nano-powder material, adopt the Ce (NO that contains the crystallization water
3)
3XH
2O (x is a crystallization water number) is the cerium source, the nitrate Sm (NO of corresponding doped chemical
3)
3, Gd (NO
3)
3Deng crystalline hydrate be raw material.The crystallization water in the nitrate helps the hydrolysis of monoethanolamine, discharges OH
-, promote precipitation reaction to take place.
Above-mentioned steps 2) described ethanolamine solutions, its preferred concentration is that monoethanolamine/metal ion mol ratio is 5～10.
Above-mentioned steps 3) described polyglycol surfactants can be any one among PEG2000, PEG4000, PEG6000, the PEG8000.
Above-mentioned steps 6) described anhydrous C2-C4 alcohols solvent can be any one in ethanol, normal propyl alcohol, isopropyl alcohol, the n-butanol, can with step 1) and 2) used solvent is identical, also can be different; Described drying can adopt vacuum drying, also can adopt common drying means, and the preferred temperature of its drying is 60～120 ℃; Described fragmentation can be adopted grinding, also can adopt ball milling, helps to weaken powder and reunites in follow-up calcination process.
Prepared nano zircite class, the cerium oxide type powder body material of the present invention has crystallite dimension, and little (crystallite dimension is 6～20nm), particle size is little, (particle diameter is distributed as 50～150nm) to narrow diameter distribution, hard aggregation-free, sintering activity advantages of higher, wherein zirconia class material can realized sintering densification below 1300 ℃, and the cerium oxide type material can be at densified sintering product below 1200 ℃.
The prepared nano-powder material of the present invention is applicable to fields such as SOFC, chemical sensor, specific function pottery, catalyst or catalyst carrier.
The present invention adopts the C2-C4 alcohols of non-water to make solvent, with organic base---monoethanolamine is made precipitating reagent, with usually be that the coprecipitation that solvent, inorganic base or inorganic salts are made precipitating reagent is compared with water, overcome and precipitated inhomogeneous, easy reunion, need deficiencies such as special drying means and equipment, its technology is simple, small investment, process environmental protection, product quality height, is all preparation methods of significant nano-powder material of a kind of social benefit and economic benefit.
Description of drawings
Fig. 1 is the XRD spectra of the present invention through the 8YSZ powder of 700 ℃ of calcining 4h.
Fig. 2 for the present invention through 700 ℃ of calcining 4h the SEM photo of 8YSZ powder.
Fig. 3 for the present invention through 600 ℃ of calcining 4h the XRD spectra of SDC powder.
Fig. 4 for the present invention through 600 ℃ of calcining 4h the SEM photo of SDC powder.
The specific embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is described further:
Embodiment 1
Nanometer 8YSZ (8mol%Y
2O
3-92mol%ZrO
2) preparation:
At first with Y (NO
3)
36H
2O and ZrO (NO
3)
28H
2O is a raw material, is solvent with the absolute ethyl alcohol, prepares the yttrium nitrate that total concentration of metal ions is 0.10mol/L and the nitrate mixed solution 400mL of zirconyl nitrate.With ethanol is solvent, and preparation monoethanolamine concentration is the monoethanolamine ethanolic solution 400mL of 1.0mol/L, and add count 1.5wt.% by final synthetic powder quality PEG6000 as surfactant, stir, heating makes it dissolving and form clear solution.Under constantly stirring, above-mentioned nitrate mixed solution is joined in the monoethanolamine ethanolic solution, obtain precipitating suspension; Continuation was stirred 30 minutes, and still aging 12 hours, filter then, and obtain sediment 3 times with absolute ethanol washing, in 75 ℃ of following vacuum drying 6h, grind the back and calcined 4 hours down at 700 ℃; With ethanol is solvent, at the rotating speed ball milling 24h of 700rpm, obtains required nanometer 8YSZ powder through separation, drying.Used alcohol solvent is through rectification and purification, and is recycling.
Adopt the crystal structure of X-ray diffraction analysis instrument (XRD) powder, observe morphology microstructure by field emission scanning electron microscope (FESEM).Fig. 1 is the XRD spectra through 700 ℃ of calcining 8YSZ after 4 hours.As shown in Figure 1, prepared powder has single cubic structure, does not have any dephasign, and the crystallite dimension of being calculated by Scherrer formula D=0.89 λ/β cos θ is 8.4nm.Fig. 2 is the FESEM photo of prepared 8YSZ powder.As seen from Figure 2, powder dispersity can be good, do not have obvious hard aggregation, and even particle distribution, profile are even sphere, and the particle average grain diameter is about 100nm.This 8YSZ powder has good sintering activity, can be behind 400MPa pressure compressing tablet at 1250 ℃ of following densified sintering products, and relative density reaches more than 97%.
Embodiment 2
Nanometer ZrO
2Preparation:
At first with ZrO (NO
3)
28H
2O is a raw material, is solvent with the anhydrous isopropyl alcohol, prepares the yttrium nitrate that total concentration of metal ions is 0.05mol/L and the nitrate mixed solution 400mL of zirconyl nitrate.With the isopropyl alcohol is solvent, and preparation monoethanolamine concentration is the monoethanolamine aqueous isopropanol 400mL of 0.25mol/IL, and add count 0.5wt.% by final synthetic powder quality PEG2000 as surfactant, stir, heating makes it dissolving and form clear solution.Under constantly stirring, above-mentioned nitrate mixed solution is joined in the monoethanolamine aqueous isopropanol, obtain precipitating suspension; Continue stirring 30 minutes, still aging 6 hours, filter then, and obtain sediment 3 times with the anhydrous normal butyl alcohol washing, in 110 ℃ of following vacuum drying 6h, grind the back and calcined 4 hours down at 600 ℃; With ethanol is solvent, at the rotating speed ball milling 24h of 400rpm, obtains required nanometer ZrO through separation, 80 ℃ of dryings
2Powder.Used alcohol solvent is through rectification and purification, and is recycling.
Adopt the crystal structure of X-ray diffraction analysis instrument (XRD) powder, observe morphology microstructure by field emission scanning electron microscope (FESEM).The XRD test result shows, prepared powder be the four directions mutually and monocline mutually, be 6.8nm by the crystallite dimension of Scherrer formula D=0.89 λ/β cos θ calculating.By the FESEM photo as can be known, powder dispersity can be good, do not have obvious hard aggregation, and even particle distribution, profile are even sphere, and the particle average grain diameter is about 80nm.
Embodiment 3
Nanometer 10ScSZ-1CeO
2(10mol%Sc
2O
3-89mol%ZrO
2-1mol%CeO
2) preparation:
At first with Sc (NO
3)
34H
2O, Ce (NO
3)
36H
2O and ZrO (NO
3)
28H
2O is a raw material, is solvent with the absolute ethyl alcohol, prepares the yttrium nitrate that total concentration of metal ions is 0.25mol/L and the nitrate mixed solution 400mL of zirconyl nitrate.With ethanol is solvent, and preparation monoethanolamine concentration is the monoethanolamine ethanolic solution 400mL of 1.5mol/L, and add count 3.0wt.% by final synthetic powder quality PEG6000 as surfactant, stir, heating makes it dissolving and form clear solution.Under constantly stirring, above-mentioned nitrate mixed solution is joined in the monoethanolamine ethanolic solution, obtain precipitating suspension; Continue to stir 15 minutes, still aging 2 hours, filter then, and obtain sediment 3 times with absolute ethanol washing, dry 8h under 80 ℃, ball milling under the rotating speed of 600rpm was calcined 4 hours down in 800 ℃ then; With ethanol is solvent, at the rotating speed ball milling 12h of 1000rpm, obtains required nanometer 10ScSZ-1CeO through separation, drying
2Powder.
Adopt the crystal structure of X-ray diffraction analysis instrument (XRD) powder, observe morphology microstructure by field emission scanning electron microscope (FESEM).The XRD test result shows, prepared 10ScSZ-1CeO
2Powder has single cubic structure, does not have any dephasign, and the crystallite dimension of being calculated by Scherrer formula D=0.89 λ/β cos θ is 12.5nm.By the FESEM photo as can be known, powder dispersity can be good, do not have obvious hard aggregation, and even particle distribution, profile are even sphere, and the particle average grain diameter is about 120nm.
Embodiment 4
Nanometer SDC (20mol%Sm
2O
3-80mol%CeO
2) preparation:
At first with Sm (NO
3)
35H
2O and Ce (NO
3)
36H
2O is a raw material, is solvent with the absolute ethyl alcohol, prepares the yttrium nitrate that total concentration of metal ions is 0.20mol/L and the nitrate mixed solution 400mL of zirconyl nitrate.With ethanol is solvent, and preparation monoethanolamine concentration is the monoethanolamine ethanolic solution 400mL of 2.0mol/L, and add count 1.0wt.% by final synthetic powder quality PEG8000 as surfactant, stir, heating makes it dissolving and form clear solution.Under constantly stirring, above-mentioned nitrate mixed solution is joined in the monoethanolamine ethanolic solution, obtain precipitating suspension; Still aging 2 hours, filter then, and obtain sediment 3 times with absolute ethanol washing, in 75 ℃ of following vacuum drying 8h, grind the back and calcined 4 hours down at 600 ℃; With ethanol is solvent, and ball milling 24h under the rotating speed of 800rpm obtains required nanometer SDC powder through separation, 80 ℃ of dryings.
Adopt the crystal structure of X-ray diffraction analysis instrument (XRD) powder, observe morphology microstructure by field emission scanning electron microscope (FESEM).Fig. 3 is the XRD spectra through 600 ℃ of calcining SDC after 4 hours.As shown in Figure 3, prepared powder has single cubic structure, does not have any dephasign, and the crystallite dimension of being calculated by Scherrer formula D=0.89 λ/β cos θ is 7.8nm.Fig. 4 is the FESEM photo of prepared SDC powder.As seen from Figure 4, powder dispersity can be good, do not have obvious hard aggregation, and even particle distribution, profile are even sphere, and the particle average grain diameter is about 80nm.This SDC powder has good sintering activity, can be behind 400MPa pressure compressing tablet at 1100 ℃ of following densified sintering products, and relative density reaches more than 95%.
Embodiment 5
Nano Ce O
2Preparation:
At first with Ce (NO
3)
36H
2O is a raw material, is solvent with anhydrous normal propyl alcohol, prepares the yttrium nitrate that total concentration of metal ions is 0.5mol/L and the nitrate mixed solution 400mL of zirconyl nitrate.With the normal propyl alcohol is solvent, and preparation monoethanolamine concentration is the monoethanolamine normal propyl alcohol solution 400mL of 2.5mol/L.Under constantly stirring, above-mentioned nitrate mixed solution is joined in the monoethanolamine normal propyl alcohol solution, obtain precipitating suspension; Filter then, and obtain sediment 3 times,, calcined 4 hours down at 600 ℃ then in 70 ℃ of following vacuum drying 10h with absolute ethanol washing; With the isopropyl alcohol is solvent, at the rotating speed ball milling 12h of 1000rpm, obtains required nano Ce O through separation, 80 ℃ of dry 12h
2Powder.
Adopt the crystal structure of X-ray diffraction analysis instrument (XRD) powder, observe morphology microstructure by field emission scanning electron microscope (FESEM).The XRD test result shows, prepared CeO
2Pure cube of phase structure of powder, the crystallite dimension of being calculated by Scherrer formula D=0.89 λ/β cos θ is 8.5nm.By the FESEM photo as can be known, powder dispersity can be good, do not have obvious hard aggregation, and even particle distribution, profile are even sphere, and the particle average grain diameter is about 100nm.
Embodiment 6
Nanometer GDC (10mol%Gd
2O
3-90mol%CeO
2) preparation:
At first with Gd (NO
3)
35H
2O and Ce (NO
3)
36H
2O is a raw material, is solvent with the anhydrous normal butyl alcohol, prepares the yttrium nitrate that total concentration of metal ions is 0.15mol/L and the nitrate mixed solution 400mL of zirconyl nitrate.With the n-butanol is solvent, and preparation monoethanolamine concentration is the monoethanolamine butanol solution 400mL of 1.0mol/L, and add count 1.0wt.% by final synthetic powder quality PEG4000 as surfactant, stir, heating makes it dissolving and form clear solution.Under constantly stirring, above-mentioned nitrate mixed solution is joined in the monoethanolamine butanol solution, obtain precipitating suspension; Continue to stir after 10 minutes still aging 4 hours, and filtered then, and obtain sediment 3 times,, grind the back 700 ℃ of calcinings 4 hours down in 80 ℃ of following vacuum drying 5h with the anhydrous normal butyl alcohol washing; With the isopropyl alcohol is solvent, and ball milling 10h under the rotating speed of 1200rpm obtains required nanometer GDC powder through separation, 100 ℃ of dryings.
Adopt the crystal structure of X-ray diffraction analysis instrument (XRD) powder, observe morphology microstructure by field emission scanning electron microscope (FESEM).The XRD test result shows, pure cube of phase structure of prepared GDC powder, and the crystallite dimension of being calculated by Scherrer formula D=0.89 λ/β cos θ is 9.6nm.By the FESEM photo as can be known, powder dispersity can be good, do not have obvious hard aggregation, and even particle distribution, profile are even sphere, and the particle average grain diameter is about 110nm.This SDC powder has good sintering activity, can be behind 400MPa pressure compressing tablet at 1200 ℃ of following densified sintering products, and relative density reaches more than 96%.
Claims (6)
1. the preparation method of a nano-powder material is characterized in that, is raw material with the nitrate of prepared powder body material respective metal, make precipitating reagent with monoethanolamine, with anhydrous C2-C4 alcohols is solvent, adopts coprecipitation to prepare nano-powder material, may further comprise the steps:
1) is solvent with anhydrous C2-C4 alcohols, prepares the nitrate solution that total concentration of metal ions is 0.05～0.5mol/L;
2) use and 1) identical solvent, preparation monoethanolamine concentration is the ethanolamine solutions of 0.25～5rnol/L;
3) above-mentioned 1) and 2) in add in any one solution count 0～3.0wt.% by final synthetic powder quality polyethylene glycol as surfactant, the ethanolamine solutions that stir, heating for dissolving obtains containing the nitrate solution of polyethylene glycol or contains polyethylene glycol;
4) under constantly stirring, with 1) nitrate solution and 3 that obtains) ethanolamine solutions that contains polyethylene glycol that obtains, or 3) nitrate solution that contains polyethylene glycol and 2 that obtains) a kind of the joining in isopyknic another kind of solution in the ethanolamine solutions that obtains obtains precipitating suspension;
5) continue to stir still aging 0～12 hour 0～30 minute;
6) filter and obtain sediment, drying, fragmentation with anhydrous C2-C4 alcohols solvent washing several;
7) calcined 2～5 hours down at 600～800 ℃ through above-mentioned washing, drying, broken sediment;
8) be solvent with ethanol or isopropyl alcohol,, obtain required nano-powder through separation, drying at rotating speed ball milling 2～48h of 400～1500rpm;
9) used C2-C4 alcohols solvent reclaims, purifies, and is recycling.
2. the preparation method of a kind of nano-powder material according to claim 1, it is characterized in that described nano-powder material is a kind of in the following material: zirconia, Yttrium oxide doping zirconium oxide, scandium oxide doped zirconia, scandium oxide and cerium oxide codope zirconia, magnesia doped zirconia, calcium oxide doped zirconia, cerium oxide, gadolinium oxide doped cerium oxide, samarium oxide doped cerium oxide.
3. the preparation method of a kind of nano-powder material according to claim 1 is characterized in that, described nitrate raw material comprises the crystalline hydrate of following one or more nitrate: ZrO (NO
3)
2, Zr (NO
3)
4, Y (NO
3)
3, Sc (NO
3)
3, Ce (NO
3)
3, Mg (NO
3)
2, Ca (NO
3)
2, Sm (NO
3)
3, Gd (NO
3)
3
4. the preparation method of a kind of nano-powder material according to claim 1 is characterized in that, described step 2) in ethanolamine solutions, its preferred concentration is that monoethanolamine/total metal ion mol ratio is 5～10.
5. the preparation method of a kind of nano-powder material according to claim 1 is characterized in that, the polyglycol surfactants in the described step 3) is any one among PEG2000, PEG4000, PEG6000, the PEG8000.
6. the preparation method of a kind of nano-powder material according to claim 1 is characterized in that, described C2-C4 alcohols solvent comprise following one or more: ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol.
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