CN103359788A - Low-temperature synthesis method of non-agglomeration fully stabilized cubic-phase nano-grade zirconium oxide powder - Google Patents

Low-temperature synthesis method of non-agglomeration fully stabilized cubic-phase nano-grade zirconium oxide powder Download PDF

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CN103359788A
CN103359788A CN2013103003280A CN201310300328A CN103359788A CN 103359788 A CN103359788 A CN 103359788A CN 2013103003280 A CN2013103003280 A CN 2013103003280A CN 201310300328 A CN201310300328 A CN 201310300328A CN 103359788 A CN103359788 A CN 103359788A
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zirconium oxide
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CN103359788B (en
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邓义群
沈针
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Jiangxi University of Science and Technology
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Abstract

The invention discloses a low-temperature synthesis method of non-agglomeration fully stabilized cubic-phase nano-grade zirconium oxide powder. According to the invention, a stabilizing agent is first dissolved by using concentrated nitric acid, such that a stable transparent solution is obtained; simultaneously, soluble zirconium salt is dissolved by using distilled water, such that a stable transparent solution is formed; the two solutions are mixed according to a molar ratio of stabilizing agent cations to Zr<4+> of 3:97 to 10:90; the pH value is regulated to approximately 7 by using ammonia water; a slight excess of precipitant is added, such that uniform and stable mixed precipitation which is a precursor is obtained; the precursor is dried and grinded, and is prepared for later use; the precursor is mixed with molten salt according to a certain mass ratio, and the mixture is dried; the mixture is calcined in a ceramic crucible; the temperature is maintained for approximately 1h, and a product is obtained; the obtained product is repeatedly washed by using distilled water, and is dried, such that the non-agglomeration total-stable cubic-phase nano-grade zirconium oxide powder with a particle size of 5-50nm is obtained. The method provided by the invention has the advantages of simple process, low energy consumption, and no pollution. The product has the advantages of small particle size, narrow particle size distribution, good dispersibility, and good stability.

Description

Low-temperature synthetic method without reunion complete stable cubic phase nano zirconium oxide powder
Technical field
What the present invention relates to is a kind of low-temperature synthetic method without reunion complete stable cubic phase nano zirconium oxide powder.
Background technology
At present, ZrO 2The preparation method of powder mainly is electric smelting method and chemical method.Electric smelting method ZrO 2Be the principle by zircon sand carbonizing reduction silica removal, adopt a step arc melting that silicon is at high temperature separated from zircon sand by control carbon and catalyst levels.This technique is simple, flow process short, product cost is relatively cheap.But also there are some significant problems in this technique.On the one hand, because the employed zircon sand raw material sources of electric smelting method are extensive, mineral composition, structure, dopant type etc. have very large difference, and some impurity wherein is such as Al 2O 3, TiO 2, Fe 2O 3Be difficult to remove by ordinary method in the electrosmelting process Deng impurity; On the other hand, at electric smelting ZrO 2In jet pelletising process, be subjected to the impact of melt viscosity, cause some melts to fail to jet into particle, and be piled into ZrO with bulk 2Stick together, affected granular yield rate, cause and melt down product and increase.Simultaneously, because it is slower to send speed of cooling forth in the system space, the granular size of sending forth out often uniformity coefficient is relatively poor, and color is also relatively poor, has directly affected the quality of product.In addition, large (the electric smelting ZrO of electric smelting process energy consumption 2Temperature〉2300 ° of C), thereby be unfavorable for cost control.
Compare the electric smelting method, chemical method is produced ZrO 2Process for control product performance be more prone to.The high-performance ZrO of this technique preparation 2Present ZrO 2First-selection in that the advanced science and technology material is used has advanced ZrO to a certain extent 2Application prospect.With electric smelting ZrO 2Compare the ZrO that chemical method is produced 2The performance index such as its chemical constitution, purity, fineness of powder and homogeneity (size distribution), phase structure, loose density, specific surface area are all more excellent.Yet, adopting chemical method to produce ZrO 2The time, on the one hand, owing to usually need to adopt high-temperature calcination technique to obtain ZrO in the later stage 2Therefore powder can cause ZrO inevitably 2The particle diameter of particle increases concurrent stiff reunion; On the other hand, although ball milling can improve because the particle diameter that calcining causes increases and the hard aggregation defective, and this process is not only introduced other impurity easily by product is carried out, and meeting is so that final Granularity Distribution broadening reduces product performance; In addition, the chemical process flow process is longer, and the decomposing agents consumption is large, and product cost is higher, therefore can't be used widely in fields such as conventional ceramic, refractory materials and glaze materials.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of low-temperature synthetic method without reunion complete stable cubic phase nano zirconium oxide powder for the deficiencies in the prior art.
Technical scheme of the present invention is as follows:
At first stablizer is dissolved with concentrated nitric acid, form stable clear solution.Simultaneously the solubility zirconates is dissolved with distilled water, form stable clear solution.Again with described two kinds of solution according to stablizer positively charged ion: Zr 4+Mol ratio is that the ratio of 3:97～10:90 is mixed, and regulates about pH value to 7 with ammoniacal liquor.Add slightly excessive precipitation agent, obtain the mixed precipitation of stable homogeneous, i.e. presoma.Then the presoma drying, the grinding that obtain is for subsequent use.With its with fused salt in mass ratio for the ratio of presoma: fused salt=1:1～1:4 is mixed, drying, and be contained in the ceramic crucible and in about 500～800 ° of C, calcine.Be incubated and took out crucible in about 1 hour, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying and be 5-50nm without reunion complete stable cubic phase nano zirconium oxide powder.
The zirconates that the present invention adopts is zirconium sulfate, ZrOCl 28H 2O or Zr (NO 3) 45H 2The solubility zirconates such as O.Stablizer both can be a kind of in hydrochloric acid or salpeter solution of yttrium oxide, magnesium oxide, calcium oxide, also can be yttrium salt, magnesium salts, the calcium salt of solubility, as: YC1 37H 2O, Y (NO 3) 36H 2O, MgCl 26HzO, Mg (NO 3) 26H 2O, CaC1 2, Ca (NO 3) 24H 2A kind of among the O etc.Precipitation agent is NaOH, KOH, ammoniacal liquor or urea etc.Fused salt can adopt such as NaOH-NaNO 3, KOH-KNO 3, KNO 3, NaNO 3Etc. composite fused salt or single fused salt.After reaction finished, fused salt is recyclable recycling also.
The invention has the advantages that:
Compare the electric smelting method, low (the electric smelting ZrO of energy consumption of the present invention 2Temperature〉2300 ° of C), be conducive to cost control.And comparing general chemical method, the present invention can avoid the ZrO that occurs owing to calcining 2Therefore the phenomenon of particle hard aggregation need not the product after the calcining is carried out ball milling, thereby is conducive to reduce in the product impurity and improves the defective such as product cut size distribution broadening.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention 1;
Fig. 2 is the TEM figure of sample;
Fig. 3 is the XRD figure spectrum of sample.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Example 1:
At first with Y 2O 3Dissolve with concentrated nitric acid, form 0.2 mol l -1Y (the NO of stable transparent 3) 3Solution.Simultaneously zirconium sulfate is dissolved with distilled water, form 0.2 mol l -1The solution of stable transparent.Again with above-mentioned two kinds of solution according to Y 3+: Zr 4+Mol ratio is that the ratio of 3:97 is mixed, and regulates about pH value to 7 with ammoniacal liquor.Add slightly excessive saturated urea soln, and be heated to about 75 ° of C, form the mixed precipitation (being presoma) of stable homogeneous.Then the presoma drying, the grinding that obtain is for subsequent use.With KNO 3With precursor powder be KNO in mass ratio 3The ratio of/presoma=3:1 is mixed, drying, and is contained in the ceramic crucible and calcines in about 600 ° of C.Be incubated and took out crucible in about 1 hour, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying is the complete stable cubic phase nano zirconium oxide powder of 5-50nm.With reference to the TEM figure of figure 2 samples, picture shows that the particle size range of the synthetic Zirconium powder that obtains is the narrow distribution of 5-50nm, and powder is without obvious reunion.With reference to the XRD figure spectrum of figure 3 samples, this collection of illustrative plates shows that the powder crystalline phase that obtains by this technique is Emission in Cubic Y 0.15Zr 0.85O 1.93
Example 2:
At first with Y 2O 3Dissolve with concentrated nitric acid, form 0.2 mol l -1Y (the NO of stable transparent 3) 3Solution.Simultaneously with ZrOCl 28H 2O dissolves with distilled water, forms 0.2 mol l -1The solution of stable transparent.Again with two kinds of solution according to Y 3+: Zr 4+Mol ratio is that the ratio of 3:97 is mixed, and regulates about pH value to 7 with ammoniacal liquor.Add slightly excessive saturated urea soln, and be heated to about 75 ° of C, form the mixed precipitation (being presoma) of stable homogeneous.Then the presoma drying, the grinding that obtain is for subsequent use.With KOH-KNO 3Composite fused salt (KOH:KNO 3Mol ratio is 0.313:0.687) with precursor powder in mass ratio for the ratio of composite fused salt: presoma=3:1 is mixed, drying, and be contained in the ceramic crucible and in about 500 ° of C, calcine.Be incubated and took out crucible in about 1 hour, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying is the complete stable cubic phase nano zirconium oxide powder of 5-50nm.
Example 3:
At first with Y 2O 3Dissolve with concentrated nitric acid, form 0.2 mol l -1Y (the NO of stable transparent 3) 3Solution.Simultaneously with ZrOCl 28H 2O dissolves with distilled water, forms 0.2 mol l -1The solution of stable transparent.Again with two kinds of solution according to (Y 3+: Zr 4+) mol ratio is that the ratio of 3:97 is mixed, and adds 4 mol l -1KOH solution, regulate about pH value to 10, form the mixed precipitation (being presoma) of stable homogeneous.Then the presoma drying, the grinding that obtain is for subsequent use.With KOH-KNO 3Composite fused salt (KOH:KNO 3Mol ratio is 0.313:0.687) with precursor powder in mass ratio for the ratio of composite fused salt: presoma=3:1 is mixed, drying, and be contained in the ceramic crucible and in about 500 ° of C, calcine.Be incubated and took out crucible in about 1 hour, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying is the complete stable cubic phase nano zirconium oxide powder of 5-50nm.
Example 4:
At first with Y 2O 3Dissolve with concentrated nitric acid, form 0.2 mol l -1Y (the NO of stable transparent 3) 3Solution.Simultaneously with ZrOCl 28H 2O dissolves with distilled water, forms 0.2 mol l -1The solution of stable transparent.Again with two kinds of solution according to (Y 3+: Zr 4+) mol ratio is that the ratio of 8:92 is mixed, and adds 4 mol l -1KOH solution, regulate about pH value to 10, form the mixed precipitation (being presoma) of stable homogeneous.Then the presoma drying, the grinding that obtain is for subsequent use.With KOH-KNO 3Composite fused salt (KOH:KNO 3Mol ratio is 0.313:0.687) with precursor powder in mass ratio for the ratio of composite fused salt: presoma=3:1 is mixed, drying, and be contained in the ceramic crucible and in about 500 ° of C, calcine.Be incubated and took out crucible in about 1 hour, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying is the complete stable cubic phase nano zirconium oxide powder of 5-50nm.
Example 5:
At first with YC1 37H 2O dissolves with distilled water, forms 0.2 mol l -1The YCl of stable transparent 3Solution.Simultaneously zirconium sulfate is dissolved with distilled water, form 0.2 mol l -1The solution of stable transparent.Again with above-mentioned two kinds of solution according to Y 3+: Zr 4+Mol ratio is that the ratio of 3:97 is mixed, and regulates about pH value to 7 with ammoniacal liquor.Add slightly excessive saturated urea soln, and be heated to about 75 ° of C, form the mixed precipitation (being presoma) of stable homogeneous.Then the presoma drying, the grinding that obtain is for subsequent use.With KNO 3With precursor powder be KNO in mass ratio 3: the ratio of presoma=3:1 is mixed, drying, and is contained in the ceramic crucible and calcines in about 600 ° of C.Be incubated and took out crucible in about 1 hour, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying is the complete stable cubic phase nano zirconium oxide powder of 5-50nm.
Example 6:
At first with YC1 37H 2O dissolves with distilled water, forms 0.2 mol l -1The YCl of stable transparent 3Solution.Simultaneously zirconium sulfate is dissolved with distilled water, form saturated clear solution.Again with two kinds of solution according to (Y 3+: Zr 4+) mol ratio is that the ratio of 8:92 is mixed, and regulates about pH value to 7 with ammoniacal liquor.Add slightly excessive saturated urea soln, and be heated to about 75 ° of C, form the white mixed precipitation (being presoma) of stable homogeneous.The presoma drying, the grinding that obtain is for subsequent use.Then with NaOH-NaNO 3Composite fused salt (NaOH and NaNO 3Mol ratio is 0.285:0.715) mix for the ratio of composite fused salt/presoma=4:1 in mass ratio with precursor powder, drying, and be contained in the ceramic crucible, in about 500 ° of C, calcine, and be incubated about 1 hour.Take out at last crucible, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying is the complete stable cubic phase nano zirconium oxide powder of 5-50nm.

Claims (2)

1. the low-temperature synthetic method without reunion complete stable cubic phase nano zirconium oxide powder is characterized in that, at first stablizer is dissolved with concentrated nitric acid, forms stable transparent solution; Simultaneously the solubility zirconates is dissolved with distilled water, form the solution of stable transparent; Again with described two kinds of solution according to stablizer positively charged ion: Zr 4+Mol ratio is that the ratio of 3:97～10:90 is mixed, and regulates pH value to 7 with ammoniacal liquor; Add slightly excessive precipitation agent, the mixed precipitation that obtains stable homogeneous is presoma; The presoma drying, the grinding that obtain is for subsequent use; Then with fused salt and precursor powder in mass ratio for the ratio of presoma: fused salt=1:1～1:4 is mixed, drying, and be contained in the ceramic crucible, in about 500～800 ° of C, calcine.Be incubated and took out crucible in about 1 hour, and with the product that obtains distilled water repetitive scrubbing, can obtain particle diameter after the drying is the complete stable cubic phase nano zirconium oxide powder of 5-50nm.
2. low-temperature synthetic method according to claim 1 is characterized in that, described zirconates is to comprise zirconium sulfate, ZrOCl 28H 2O or Zr (NO 3) 45H 2O is at interior solubility zirconates; Described stablizer is a kind of in the hydrochloric acid of yttrium oxide, magnesium oxide, calcium oxide or the salpeter solution, or a kind of in the yttrium salt of solubility, magnesium salts, calcium salt; Described precipitation agent is a kind of in NaOH, KOH, ammoniacal liquor or the urea; Fused salt adopts and comprises NaOH-NaNO 3, KOH-KNO 3, KNO 3, NaNO 3At interior composite fused salt or single fused salt.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105503178A (en) * 2015-12-10 2016-04-20 江西理工大学 Method for rapidly sintering fully stabilized zirconia powder under low temperature and normal pressure
CN109437296A (en) * 2018-12-06 2019-03-08 洛阳理工学院 A kind of method that molten-salt growth method prepares tetragonal phase zirconia nanorod
CN116969506A (en) * 2023-09-25 2023-10-31 中石油深圳新能源研究院有限公司 Electrolyte material for solid oxide fuel cell and preparation method thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105503178A (en) * 2015-12-10 2016-04-20 江西理工大学 Method for rapidly sintering fully stabilized zirconia powder under low temperature and normal pressure
CN105503178B (en) * 2015-12-10 2018-09-11 江西理工大学 A kind of method of low-temperature atmosphere-pressure Fast Sintering fully stabilized zirconia powder
CN109437296A (en) * 2018-12-06 2019-03-08 洛阳理工学院 A kind of method that molten-salt growth method prepares tetragonal phase zirconia nanorod
CN109437296B (en) * 2018-12-06 2021-03-30 洛阳理工学院 Method for preparing tetragonal-phase zirconia nanorod by molten salt growth method
CN116969506A (en) * 2023-09-25 2023-10-31 中石油深圳新能源研究院有限公司 Electrolyte material for solid oxide fuel cell and preparation method thereof

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