CN103359788B - The low-temperature synthetic method of soilless sticking complete stable cubic phase nano zirconium oxide powder - Google Patents
The low-temperature synthetic method of soilless sticking complete stable cubic phase nano zirconium oxide powder Download PDFInfo
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Abstract
The invention discloses a kind of low-temperature synthetic method of soilless sticking complete stable cubic phase nano zirconium oxide powder.First stablizer concentrated nitric acid is dissolved, form stable clear solution.Solubility zirconates distilled water is dissolved simultaneously, form stable clear solution.Again by described two kinds of solution according to stablizer positively charged ion: Zr
4+mol ratio is that the ratio of 3:97 ~ 10:90 mixes, and about regulating pH value to 7 with ammoniacal liquor.Add the precipitation agent little over amount, obtain the mixed precipitation of stable homogeneous, i.e. presoma.Then by dry for the presoma obtained, grind for subsequent use.It is undertaken mixing by certain mass ratio with fused salt, dry, and be contained in ceramic crucible and calcine.Be incubated 1 hours and take out crucible, and the product distilled water repetitive scrubbing that will obtain, the soilless sticking complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.The inventive method technique is simple, energy consumption is low, pollution-free, the little and narrowly distributing of product cut size, dispersed and good stability.<!--1-->
Description
Technical field
What the present invention relates to is a kind of low-temperature synthetic method of soilless sticking complete stable cubic phase nano zirconium oxide powder.
Background technology
At present, ZrO
2raw powder's production technology mainly 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 by control carbon and catalyst levels and silicon is at high temperature separated from zircon sand.This technique is simple, flow process is short, product cost relative moderate.But also there are some significant problems in this technique.On the one hand, the zircon sand raw material sources used due to electric smelting method are extensive, and mineral composition, structure, dopant type etc. have very large difference, some impurity wherein, as Al
2o
3, TiO
2, Fe
2o
3be difficult to remove by ordinary method in electrosmelting process Deng impurity; On the other hand, at electric smelting ZrO
2in jet pelletising process, by the impact of melt viscosity, cause some melts could not jet into particle, and be piled into ZrO with bulk
2stick together, have impact on granular yield rate, cause and melt down product and increase.Meanwhile, comparatively slow owing to sending speed of cooling forth in system space, the granular size sending forth out often uniformity coefficient is poor, and color is also poor, directly affects the quality of product.In addition, comparatively large (the electric smelting ZrO of electric melting process energy consumption
2temperature >2300 DEG C), thus be unfavorable for cost control.
Compare electric smelting method, chemical method produces ZrO
2process be more prone to for controlling the performance of product.High-performance ZrO prepared by this technique
2current ZrO
2the first-selection that advanced science and technology material is applied, advances 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.But, produce ZrO at employing chemical method
2time, on the one hand, owing to usually needing to adopt high-temperature calcination technique to obtain ZrO in the later stage
2powder, therefore inevitably causes ZrO
2the particle diameter of particle increases concurrent stiff reunion; On the other hand, although can improve by carrying out ball milling to product the particle diameter increase and hard aggregation defect that cause due to calcining, this process not only easily introduces other impurity, and can make final Granularity Distribution broadening, reduces product performance; In addition, chemical process flow process is longer, and decomposing agents consumption is large, and product cost is higher, therefore cannot 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 the low-temperature synthetic method providing a kind of soilless sticking complete stable cubic phase nano zirconium oxide powder for the deficiencies in the prior art.
Technical scheme of the present invention is as follows:
First stablizer concentrated nitric acid is dissolved, form stable clear solution.Solubility zirconates distilled water is dissolved simultaneously, form stable clear solution.Again by described two kinds of solution according to stablizer positively charged ion: Zr
4+mol ratio is that the ratio of 3:97 ~ 10:90 mixes, and with about ammoniacal liquor adjust ph to 7.Add the precipitation agent little over amount, obtain the mixed precipitation of stable homogeneous, i.e. presoma.Then by dry for the presoma obtained, grind for subsequent use.Be presoma in mass ratio by itself and fused salt: the ratio of fused salt=1:1 ~ 1:4 carries out mixing, dry, and be contained in ceramic crucible and calcine in about 500 ~ 800 DEG C.Be incubated 1 hours and take out crucible, and the product distilled water repetitive scrubbing that will obtain, the soilless sticking complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.
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 yttrium oxide, magnesium oxide, the one of calcium oxide in hydrochloric acid or salpeter solution, 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
2one in 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.It is pointed out that the selection for precipitation agent and fused salt kind, need ensure can generate a small amount of NaCl or KCl in its coprecipitation process, otherwise, then need introduce a small amount of NaCl or KCl in fused salt.After reaction terminates, fused salt is recyclable recycling also.
The invention has the advantages that:
Compare electric smelting method, low (the electric smelting ZrO of energy consumption of the present invention
2temperature >2300 DEG C), be conducive to cost control.And comparing general chemical method, the present invention can avoid the ZrO occurred due to calcining
2the phenomenon of particle hard aggregation, therefore without the need to carrying out ball milling to the product after calcining, thus to be conducive to reducing in product impurity and to improve the defects such as product cut size distribution broadening.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the embodiment of the present 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:
First by Y
2o
3dissolve with concentrated nitric acid, form 0.2moll
-1y (the NO of stable transparent
3)
3solution.Zirconium sulfate distilled water is dissolved simultaneously, form 0.2moll
- 1the solution of stable transparent.Again by above-mentioned two kinds of solution according to Y
3+: Zr
4+mol ratio is that the ratio of 3:97 mixes, and with about ammoniacal liquor adjust ph to 7.Add the saturated urea soln little over amount, and be heated to about 75 DEG C, form the mixed precipitation (i.e. presoma) of stable homogeneous.Then by dry for the presoma obtained, grind for subsequent use.By KNO
3be KNO in mass ratio with precursor powder
3/ presoma=3:1 carries out proportioning, and introduces the KCl mixing, dry of about 1wt%, and is contained in ceramic crucible and calcines in about 600 DEG C.Be incubated 1 hours and take out crucible, and the product distilled water repetitive scrubbing that will obtain, the complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.TEM with reference to figure 2 sample schemes, and the particle size range that picture shows to synthesize the Zirconium powder obtained is 5-50nm narrow ditribution, and powder is without obvious reunion.XRD figure with reference to figure 3 sample is composed, and this collection of illustrative plates shows that the powder crystalline phase obtained by this technique is Emission in Cubic Y
0.15zr
0.85o
1.93.
Example 2:
First by Y
2o
3dissolve with concentrated nitric acid, form 0.2moll
-1y (the NO of stable transparent
3)
3solution.Simultaneously by ZrOCl
28H
2o distilled water dissolves, and forms 0.2moll
-1the solution of stable transparent.Again by two kinds of solution according to Y
3+: Zr
4+mol ratio is that the ratio of 3:97 mixes, and with about ammoniacal liquor adjust ph to 7.Add the saturated urea soln little over amount, and be heated to about 75 DEG C, form the mixed precipitation (i.e. presoma) of stable homogeneous.Then by dry for the presoma obtained, grind for subsequent use.By KOH-KNO
3composite fused salt (KOH:KNO
3mol ratio is 0.313:0.687) with precursor powder in mass ratio for composite fused salt: presoma=3:1 carries out proportioning, and introduces the KCl mixing, dry of about 1wt%, and is contained in ceramic crucible and calcines in about 500 DEG C.Be incubated 1 hours and take out crucible, and the product distilled water repetitive scrubbing that will obtain, the complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.
Example 3:
First by Y
2o
3dissolve with concentrated nitric acid, form 0.2moll
-1y (the NO of stable transparent
3)
3solution.Simultaneously by ZrOCl
28H
2o distilled water dissolves, and forms 0.2moll
-1the solution of stable transparent.Again by two kinds of solution according to (Y
3+: Zr
4+) mol ratio is that the ratio of 3:97 mixes, and adds 4moll
-1kOH solution, about adjust ph to 10, form the mixed precipitation (i.e. presoma) of stable homogeneous.Then by dry for the presoma obtained, grind for subsequent use.By KOH-KNO
3composite fused salt (KOH:KNO
3mol ratio is 0.313:0.687) with precursor powder in mass ratio for composite fused salt: the ratio of presoma=3:1 carries out mixing, dry, and is contained in ceramic crucible and calcines in about 500 DEG C.Be incubated 1 hours and take out crucible, and the product distilled water repetitive scrubbing that will obtain, the complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.
Example 4:
First by Y
2o
3dissolve with concentrated nitric acid, form 0.2moll
-1y (the NO of stable transparent
3)
3solution.Simultaneously by ZrOCl
28H
2o distilled water dissolves, and forms 0.2moll
-1the solution of stable transparent.Again by two kinds of solution according to (Y
3+: Zr
4+) mol ratio is that the ratio of 8:92 mixes, and adds 4moll
-1kOH solution, about adjust ph to 10, form the mixed precipitation (i.e. presoma) of stable homogeneous.Then by dry for the presoma obtained, grind for subsequent use.By KOH-KNO
3composite fused salt (KOH:KNO
3mol ratio is 0.313:0.687) with precursor powder in mass ratio for composite fused salt: the ratio of presoma=3:1 carries out mixing, dry, and is contained in ceramic crucible and calcines in about 500 DEG C.Be incubated 1 hours and take out crucible, and the product distilled water repetitive scrubbing that will obtain, the complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.
Example 5:
First by YC1
37H
2o distilled water dissolves, and forms 0.2moll
- 1the YCl of stable transparent
3solution.Zirconium sulfate distilled water is dissolved simultaneously, form 0.2moll
-1the solution of stable transparent.Again by above-mentioned two kinds of solution according to Y
3+: Zr
4+mol ratio is that the ratio of 3:97 mixes, and with about ammoniacal liquor adjust ph to 7.Add the saturated urea soln little over amount, and be heated to about 75 DEG C, form the mixed precipitation (i.e. presoma) of stable homogeneous.Then by dry for the presoma obtained, grind for subsequent use.By KNO
3be KNO in mass ratio with precursor powder
3: presoma=3:1 carries out proportioning, and introduces the KCl mixing, dry of about 1wt%, and is contained in ceramic crucible and calcines in about 600 DEG C.Be incubated 1 hours and take out crucible, and the product distilled water repetitive scrubbing that will obtain, the complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.
Example 6:
First by YC1
37H
2o distilled water dissolves, and forms 0.2moll
-1the YCl of stable transparent
3solution.Zirconium sulfate distilled water is dissolved simultaneously, form saturated clear solution.Again by two kinds of solution according to (Y
3+: Zr
4+) mol ratio is that the ratio of 8:92 mixes, and with about ammoniacal liquor adjust ph to 7.Add the saturated urea soln little over amount, and be heated to about 75 DEG C, form the white mixed precipitation (i.e. presoma) of stable homogeneous.By dry for the presoma obtained, grind for subsequent use.Then by NaOH-NaNO
3composite fused salt (NaOH and NaNO
3mol ratio is 0.285:0.715) carry out proportioning for composite fused salt/presoma=4:1 in mass ratio with precursor powder, and introduce NaCl mixing, the drying of about 1wt%, and be contained in ceramic crucible, in about 500 DEG C calcinings, and be incubated 1 hours.Finally take out crucible, and the product distilled water repetitive scrubbing that will obtain, the complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying.
Claims (2)
1. a low-temperature synthetic method for soilless sticking complete stable cubic phase nano zirconium oxide powder, is characterized in that, is first dissolved by stablizer concentrated nitric acid, forms stable transparent solution; Solubility zirconates distilled water is dissolved simultaneously, form the solution of stable transparent; Again by described two kinds of solution according to stablizer positively charged ion: Zr
4+mol ratio is that the ratio of 0:100 ~ 8:92 mixes, and by ammoniacal liquor adjust ph to 7; Add the precipitation agent little over amount, obtain mixed precipitation and the presoma of stable homogeneous; By dry for the presoma obtained, grind for subsequent use; Then be presoma in mass ratio by fused salt and precursor powder: the ratio of fused salt=1:1 ~ 1:4 carries out mixing, dry, and be contained in ceramic crucible, in 500 ~ 800 DEG C of calcinings; Be incubated 1 hour taking-up crucible, and the product distilled water repetitive scrubbing that will obtain, the complete stable cubic phase nano zirconium oxide powder that particle diameter is 5-50nm can be obtained after drying, described stablizer is the one in yttrium oxide, magnesium oxide, the hydrochloric acid of calcium oxide or salpeter solution, or the yttrium salt of solubility, magnesium salts, one in calcium salt; Described precipitation agent is the one in NaOH or KOH, ammoniacal liquor or urea.
2. low-temperature synthetic method according to claim 1, is characterized in that, described zirconates comprises zirconium sulfate, ZrOCl
28H
2o or Zr (NO
3)
45H
2o is at interior solubility zirconates; Described stablizer is the one in yttrium oxide, magnesium oxide, the hydrochloric acid of calcium oxide or salpeter solution, or the yttrium salt of solubility, magnesium salts, one in calcium salt; Described precipitation agent is the one in NaOH, KOH, ammoniacal liquor or 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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| 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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| CN101412529A (en) * | 2008-11-19 | 2009-04-22 | 中国科学院过程工程研究所 | Method for preparing rare-earth oxide or composite rare-earth oxide nano-powder by molten salt synthesis |
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| JPH04181155A (en) * | 1990-11-15 | 1992-06-29 | Nippon Steel Corp | Measuring sensor for oxygen partial pressure in molten salt |
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| CN101412529A (en) * | 2008-11-19 | 2009-04-22 | 中国科学院过程工程研究所 | Method for preparing rare-earth oxide or composite rare-earth oxide nano-powder by molten salt synthesis |
Non-Patent Citations (2)
| Title |
|---|
| Preparation of lanthanum zirconate nano-powders by Molten Salts method;Xueying Wang et al.;《Journal of Non-Crystalline Solids》;20100210;第356卷;第1049-1051页 * |
| Synthesis of solid materials in molten nitrates;P. Afanasiev et al.;《Coordination Chemistry Reviews》;19981231;第178-180卷;第1725-1752页 * |
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