CN102040381A - Preparation method of superfine zirconia powder - Google Patents
Preparation method of superfine zirconia powder Download PDFInfo
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- CN102040381A CN102040381A CN2009101880084A CN200910188008A CN102040381A CN 102040381 A CN102040381 A CN 102040381A CN 2009101880084 A CN2009101880084 A CN 2009101880084A CN 200910188008 A CN200910188008 A CN 200910188008A CN 102040381 A CN102040381 A CN 102040381A
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- 239000000843 powder Substances 0.000 title claims abstract description 61
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims description 79
- 238000002360 preparation method Methods 0.000 title claims description 37
- 239000000243 solution Substances 0.000 claims abstract description 61
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 29
- 238000001354 calcination Methods 0.000 claims description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003483 aging Methods 0.000 claims description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 5
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010533 azeotropic distillation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 18
- 238000001556 precipitation Methods 0.000 abstract description 15
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000012266 salt solution Substances 0.000 abstract description 6
- 150000003754 zirconium Chemical class 0.000 abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 abstract description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000003607 modifier Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 14
- 239000012071 phase Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 239000012716 precipitator Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002892 organic cations Chemical group 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 1
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Abstract
A process for preparing superfine zirconium oxide powder features that the quaternary ammonium alkali is used as precipitant and special precipitation method is used. The special precipitation method is to add the two solutions into a reaction kettle simultaneously under the condition of rapid stirring, react and nucleate rapidly, and directly wash the solution without aging, thereby achieving the purpose of controlling the growth of nuclei. The quaternary ammonium hydroxide is an alkaline substance and can separate out hydrous zirconium oxide (zirconium hydroxide gel) from a zirconium salt solution, the surface modifier can change the interfacial tension so as to achieve the effect of dispersion, the addition of a dispersing agent is omitted, the cost is saved, and simultaneously, tetragonal-phase and cubic-phase zirconium oxide powder can be prepared by controlling the amount of yttrium-containing compounds added under the condition of need.
Description
Technical field
The present invention relates to a kind of preparation method of superfine zirconia powder, particularly select for use special precipitation agent to carry out the method that rapid precipitation prepares the superfine zirconia powder, belong to the stupalith field.
Background technology
Zirconium white is as a kind of stupalith, and the physicochemical property that it is good are as high temperature resistant, wear-resistant, corrosion-resistant, the acid-basicity of itself, oxidation-reduction quality, under different conditions, have again light, electricity, sound, the sensitivity characteristic of gas and temperature etc., make it be widely used in electronic ceramics, in the high-technology fields such as function ceramics and structural ceramics.In recent years, in the continuous development along with preparation nano zircite technology, it is used as heterogeneous catalyst or adsorbing agent carrier also receives great concern.Zirconium white mostly exists with monocline at normal temperatures mutually, changes cubic phase when being heated to 1170-2370 ℃ into, is a cube phase by tetragonal phase converting more than 2370 ℃.As stupalith, zirconium white is accompanied by the contraction of volume along with the rising of temperature, volumetric expansion then appears in process of cooling, therefore can cancel each other for the stress that its volume change is caused in use and prevent the material cracking, must control the amount of these phase transformations, obtain PSZ, obtain PSZ, some other oxide compound that will mix in zirconium white is as yttrium oxide, magnesium oxide, aluminum oxide, cerium oxide etc. form zirconic mixture, have higher bending strength, also have fracture toughness property preferably, play phase transformation and strengthen toughness reinforcing effect.The spy is that the zirconium white of stabilized with yttrium oxide has general application at structural ceramics and function ceramics field fully.
The nano zirconium oxide powder preparation method mainly contains vapor phase process and liquid phase method.Relatively liquid phase method has more certain competitive edge, because the commercial run relevant with this method control is comparatively ripe with the amplifying technique of equipment, and cost is lower.Liquid phase method is divided into the precipitator method (Stichert W substantially now, Schuth F, J.Catal., 1998,174:242), sol-gel method (Ward D A, Ko E I, J.Catal.1995,157:321), hydrothermal method (Tani E, Yoshimura M, Somiya S, J.Am.Ceram.Soc.1983,66 (1): 11) etc. wherein liquid-phase coprecipitation is to be added drop-wise in the zirconium salt solution or zirconium salt solution is added drop-wise in the alkali lye by alkali lye, utilize alkali lye from zirconium salt solution, to be settled out oxidizing aqueous zirconium (zirconium hydroxide gel), again by ageing, washing, drying, calcining obtains Zirconium powder.But the precipitator method have the defective of himself, grow up as the nuclear that ageing brings, and the existence of hard aggregation, the uncontrollable grade of grain size all is to be badly in need of industrial production problem to be solved.Chinese patent CN 1170786C and CN 100391853C once reported by adding dispersion agent such as tensio-active agent or playing the dispersive effect by ultrasonic technique, reached the minimizing hard aggregation, thus control grain size size.But the dispersion agent kind is various, and ultrasonic technique all can restrict manufacturing enterprise with respect to industrial unrealistic property.
Summary of the invention
In order to overcome above-mentioned defective, the present invention is by improving the raw material and the technology of being used to have, thereby reaches a kind of preparation method of preparation superfine zirconia powder.
The present invention proposes a kind of preparation method of superfine zirconia powder, and wherein precipitation agent is selected quaternary ammonium hydroxide for use, and adopts the special precipitator method preparation superfine zirconia powder that combines.The special precipitator method are about to two kinds of solution adding simultaneously in the reactor under the condition of stirring fast, react nucleation rapidly, without ageing, and directly washing, thus reach the purpose that control nuclear is grown up.Quaternary ammonium hydroxide is that alkaline matter can be separated out oxidizing aqueous zirconium (zirconium hydroxide gel) from zirconium salt solution, also be thereby that surface-modifying agent can change interfacial tension and reaches the dispersive effect, saved the interpolation of dispersion agent, save cost, under the situation of needs, can also prepare simultaneously by the amount that the compound that contains yttrium is added in control the four directions mutually with cube mutually Zirconium powder.
Technical scheme of the present invention: the preparation method of superfine zirconia powder carries out according to following steps successively:
(1) preparation zirconium hydroxide presoma: basic zirconium chloride is dissolved in the zirconium oxychloride solution that is made into 0.1-1.0mol/L concentration in the deionized water, quaternary ammonium hydroxide is dissolved in is made into the quaternary ammonium hydroxide aqueous solution that massfraction is 10%-45% in the deionized water, with two solution low whipping speeds greater than mixing rapidly under 400 rev/mins the situation, by accurate pH test paper the pH value of reaction solution is remained between the 9-13, reaction times is 5-25 minute, and temperature of reaction is 30-70 ℃;
(2) preparation zirconium hydroxide filter cake: the zirconium hydroxide presoma that will react generation is without ageing, and direct filtration is separated, and washs with deionized water, does not have Cl until detecting filtrate with silver nitrate solution
-
(3) preparation zirconium hydroxide presoma powder: with gained zirconium hydroxide filter cake dispersed with stirring in propyl carbinol or Pentyl alcohol, with azeotropic distillation drying it is carried out drying, be under the condition of 0.1MPa promptly in vacuum tightness, 50-90 ℃ dry 5-15 hour, make exsiccant zirconium white presoma powder;
(4), obtain particle diameter less than 1.5 microns superfine zirconia powder through airflow milling again with exsiccant zirconium white presoma powder temperature lower calcination 1-6 hour at 500-900 ℃.
Wherein, the preferred concentration of described zirconium oxychloride solution is 0.5-1.0mol/L;
The preferred mass mark of the described quaternary ammonium hydroxide aqueous solution is 20%-25%;
Existing organic cation part (R4 in the described quaternary ammonium hydroxide structure
+) anionicsite (OH arranged again
-), be preferably Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH or (2-hydroxyethyl) trimethylammonium hydroxide;
The pH value of described reaction solution is preferably 9-12;
The described reaction times is preferably 5-15 minute.
Described calcining temperature is preferably 600-700 ℃, and described calcination time is preferably 2-4 hour;
In order not only to guarantee production efficiency but also can guarantee that the zirconium white presoma of gained is a nanoparticle, zirconium oxychloride solution concentration is advisable at 0.5-1.0mol/L, and the massfraction of the quaternary ammonium hydroxide aqueous solution is advisable at 20%-25%.
In order to prepare the yttria-stabilized zirconia powder, can in zirconium oxychloride solution, add YCl
3Perhaps Y (NO
3)
3, by control YCl
3Perhaps Y (NO
3)
3Content prepare cubic phase (t-ZrO
2) with (c-ZrO cube mutually
2) Zirconium powder.Work as YCl
3Perhaps Y (NO
3)
3Amount be controlled at the Y of its generation
2O
3Account for ZrO
2During the 2--3% of mole number, finally make cubic phase (t-ZrO
2) Zirconium powder, and work as Y
2O
3Account for ZrO
2During the 7--8% of mole number, finally make a cube phase (c-ZrO
2) Zirconium powder.
Because the present invention adopts quaternary ammonium hydroxide as precipitation agent, its OH
-With Zr4 in the zirconium salt solution
+Separate out, its moieties has also hindered the growth of nuclear to a certain extent simultaneously, plays dispersion effect.Cooperate again between nuclear that the rapid precipitation method makes and the nuclear to be difficult to grow up, so it is even to obtain particle diameter, the Zirconium powder of controllable size.In addition, adopting the special precipitator method to be about to zirconium oxychloride solution and precipitation agent low whipping speed in the present invention reacts greater than simultaneously will two solution under 400 rev/mins the situation adding in the reactor, like this, zirconium oxychloride solution and precipitation agent be rapid hybrid reaction nucleation under quick condition of stirring, reaction back digestion time is short, also can be without ageing, direct filtration, washing.
Description of drawings
Fig. 1: the transmission electron microscope photo of Zirconium powder
Fig. 2: the X-ray diffraction spectrogram (XRD) of Zirconium powder
Fig. 3: the X-ray diffraction spectrogram (XRD) of the Zirconium powder of 3% mole of stabilized with yttrium oxide
Embodiment
Embodiment 1
The preparation method of superfine zirconia powder comprises following step:
(1) with 16.27gZrOCl
28H
2O is dissolved in and is made into the 1mol/L zirconium oxychloride solution in the 50ml deionized water, takes by weighing 100.32g tetraethyl ammonium hydroxide (C8H20NOH 25%); Two kinds of solution are mixed reaction at rotating speed under greater than 400 rev/mins situation fast, and temperature is controlled at 40 ℃, by accurate pH test paper pH is controlled between the 11-12, reacts 10 minutes, makes the zirconium hydroxide presoma;
(2) with deionized water presoma is filtered, washing does not have Cl until detecting filtrate with silver nitrate solution
-, make preparation zirconium hydroxide filter cake;
(3) with gained zirconium hydroxide filter cake dispersed with stirring in propyl carbinol, under vacuum tightness is the condition of 0.1MPa, be heated to 80 ℃ then, vacuum component distillation 5h reclaims aqueous alcohol under condition of stirring, makes zirconium white presoma powder;
(4) zirconium white presoma powder is put into retort furnace, at 700 ℃ of calcining 2h; Make the superfine zirconia powder through grinding.
Embodiment 2
The step of superfine zirconia powder preparation method has been adjusted precipitation agent and has been adopted Tetramethylammonium hydroxide (25%) 70.83g as described in the embodiment 1; 16.21gZrOCl
28H
2O is dissolved in and is made into 1mol/L zirconium oxychloride solution temperature of reaction in the 50ml deionized water and is controlled at 50 ℃; PH remains between the 12-13, reacts 15 minutes; 80 ℃ of drying temperatures, component distillation 8h; Calcining temperature is controlled at 600 ℃ of calcining 3h.Make the superfine zirconia powder.
Embodiment 3
The step of superfine zirconia powder preparation method has been adjusted the concentration of basic zirconium chloride, with 16.12gZrOCl as described in the embodiment 1
28H
2O is dissolved in and is made into the 0.8mol/L zirconium oxychloride solution in the 62.5ml deionized water; Precipitation agent adopts Tetramethylammonium hydroxide (25%), has taken by weighing 70.12g; Temperature is controlled at 50 ℃, and pH remains between the 12-13, reacts 5 minutes; The alcohol that component distillation adopts is Pentyl alcohol, 80 ℃ of drying temperatures, component distillation 8h; 700 ℃ of calcining 2h; Make the superfine zirconia powder.
Embodiment 4
The step of superfine zirconia powder preparation method has been adjusted the concentration of basic zirconium chloride, with 16.14gZrOCl as described in the embodiment 1
28H
2O is dissolved in and is made into the 0.5mol/L zirconium oxychloride solution in the 100ml deionized water; Precipitation agent adopts Tetramethylammonium hydroxide (25%) to take by weighing 69.98g; 80 ℃ of drying temperatures, component distillation 8h; Calcining temperature is controlled at 600 ℃ of calcinings 3 hours; Make the superfine zirconia powder.
Embodiment 5
The step of superfine zirconia powder preparation method has been adjusted the concentration of basic zirconium chloride, with 16.18gZrOCl as described in the embodiment 1
28H
2O is dissolved in and is made into the 0.5mol/L zirconium oxychloride solution in the 100ml deionized water; Precipitation agent adopts TPAOH (12.5%), has promptly taken by weighing 150.32g TPAOH (25%) solution, to the deionized water that has wherein added 150ml join the TPAOH solution of massfraction 12.5%; Temperature of reaction is controlled at 50 ℃, and pH remains between the 10-11; The alcohol that component distillation adopts is Pentyl alcohol, 80 ℃ of drying temperatures, component distillation 10h; Calcining temperature is controlled at 500 ℃ of calcining 4h.Make the superfine zirconia powder.
Embodiment 6
The step of superfine zirconia powder preparation method has been adjusted the concentration of basic zirconium chloride, with 16.19gZrOCl as described in the embodiment 1
28H
2O is dissolved in and is made into the 0.3mol/L zirconium oxychloride solution in the 167g deionized water; Precipitation agent adopts TBAH (20%), promptly takes by weighing 200.02g TBAH (25%), and the deionized water that adds 50g to TBAH (25%) solution is made into 20% TBAH solution; Temperature of reaction is controlled at 60 ℃, and pH remains between the 9-10; 80 ℃ of drying temperatures, component distillation 10h; 800 ℃ of calcining 1h; Make the superfine zirconia powder.
Embodiment 7
The step of superfine zirconia powder preparation method is as described in the embodiment 1, and the mass percent of having adjusted tetraethyl ammonium hydroxide is 12.5%, promptly adds the deionized water of 100g in 100.12g tetraethyl ammonium hydroxide solution; 16.17gZrOCl
28H2O is dissolved in and is made into the 1mol/L zirconium oxychloride solution in the 50ml deionized water; Temperature of reaction is controlled at 30 ℃; PH remains between the 10-11; 80 ℃ of drying temperatures, component distillation 10h; Calcining temperature is controlled at 800 ℃ of calcining 2h.Make the superfine zirconia powder.
Embodiment 8
The step of superfine zirconia powder preparation method has been adjusted the concentration of basic zirconium chloride as described in the embodiment 1,16.13gZrOCl28H2O is dissolved in be made into the 0.5mol/L zirconium oxychloride solution in the 100ml deionized water; Take by weighing 100.22g tetraethyl ammonium hydroxide (C8H20NOH 25%), add the 66.88g deionized water, be made into the tetraethyl ammonium hydroxide solution of massfraction 15% to it; The alcohol that component distillation adopts is Pentyl alcohol, 80 ℃ of drying temperatures, component distillation 9h; Calcining temperature is controlled at 900 ℃ of calcining 3h.Make the superfine zirconia powder.
Embodiment 9
The step of superfine zirconia powder preparation method is as described in the embodiment 1, adjust precipitation agent and selected (2-hydroxyethyl) trimethylammonium hydroxide (45%) for use, take by weighing (2-hydroxyethyl) trimethylammonium hydroxide (45%) 40.12g, basic zirconium chloride 16.19g is dissolved in and is made into the 1mol/L zirconium oxychloride solution in the 50ml deionized water; Temperature of reaction is controlled at 40 ℃; The pH value is controlled between the 10-11; The alcohol that component distillation adopts is Pentyl alcohol, 90 ℃ of drying temperatures, component distillation 9h; Calcining temperature is controlled at 600 ℃ of calcining 3h.Make the superfine zirconia powder.
The preparation method of superfine zirconia powder comprises following step:
(1) with 32.27gZrOCl
28H
2O is dissolved in and is made into the 1mol/L zirconium oxychloride solution in the 100ml deionized water, adds the YCl of 1.17g to zirconium oxychloride solution
3(Y
2O
3Account for ZrO
2Mole number 3%), stir; Take by weighing 202.58g tetraethyl ammonium hydroxide (C
8H
20NOH 25%); Greater than rapid hybrid reaction 15 minutes under 400 rev/mins the situation, temperature is controlled at 40 ℃ with two kinds of solution low whipping speeds, and pH is controlled between the 11-12, makes zirconium hydroxide and yttrium hydroxide composite precursor;
(2) with deionized water presoma is filtered, washing does not have Cl until detecting filtrate with silver nitrate solution
-, make the compound filter cake of zirconium hydroxide and yttrium hydroxide;
(3) with gained filter cake dispersed with stirring in propyl carbinol, under vacuum tightness is the condition of 0.1MPa, be heated to 50 ℃ then, vacuum component distillation 15h reclaims aqueous alcohol under condition of stirring, makes the presoma powder;
(4) the presoma powder is put into retort furnace, at 600 ℃ of calcining 2h; Make ultra-fine tetragonal phase zirconium oxide powder through grinding.
The preparation method of superfine zirconia powder comprises following step:
(5) with 32.27gZrOCl
28H
2O is dissolved in and is made into the 1mol/L zirconium oxychloride solution in the 100ml deionized water, adds the YCl of 1.12g to zirconium oxychloride solution
3(Y
2O
3Account for ZrO
2Mole number 2%), stir; Take by weighing 202.58g tetraethyl ammonium hydroxide (C
8H
20NOH 25%); Greater than rapid hybrid reaction 15 minutes under 400 rev/mins the situation, temperature is controlled at 40 ℃ with two kinds of solution low whipping speeds, and pH is controlled between the 11-12, makes zirconium hydroxide and yttrium hydroxide composite precursor;
(6) with deionized water presoma is filtered, washing does not have Cl until detecting filtrate with silver nitrate solution
-, make the compound filter cake of zirconium hydroxide and yttrium hydroxide;
(7) with gained filter cake dispersed with stirring in propyl carbinol, under vacuum tightness is the condition of 0.1MPa, be heated to 50 ℃ then, vacuum component distillation 15h reclaims aqueous alcohol under condition of stirring, makes the presoma powder;
The presoma powder is put into retort furnace, at 600 ℃ of calcining 2h; Make ultra-fine tetragonal phase zirconium oxide powder through grinding.
Embodiment 12
With 32.38gZrOCl
28H
2O is dissolved in and is made into the 1mol/L zirconium oxychloride solution in the 100ml deionized water, adds the Y (NO of 4.27g to zirconium oxychloride solution
3)
3(Y
2O
3Account for ZrO
2Mole number 7%), stir; Take by weighing 225.58g tetraethyl ammonium hydroxide (C
8H
20NOH 25%); Greater than rapid hybrid reaction 15 minutes under 400 rev/mins the situation, temperature is controlled at 50 ℃ with two kinds of solution low whipping speeds, and pH is controlled between the 11-12, makes zirconium hydroxide and yttrium hydroxide composite precursor; With deionized water presoma is filtered, washing does not have Cl until detecting filtrate with silver nitrate solution
-Gained filter cake dispersed with stirring in propyl carbinol, is heated to 80 ℃ then under vacuum tightness is the condition of 0.1MPa, vacuum component distillation 8h reclaims aqueous alcohol under condition of stirring, makes the presoma powder; The presoma powder is put into retort furnace, at 700 ℃ of calcining 6h; Through grinding, subsequent disposal such as ball milling make superfine cubic phase zircite powder.
Embodiment 13
With 32.38gZrOCl
28H
2O is dissolved in and is made into the 1mol/L zirconium oxychloride solution in the 100ml deionized water, adds the Y (NO of 4.39g to zirconium oxychloride solution
3)
3(Y
2O
3Account for ZrO
2Mole number 8%), stir; Take by weighing 225.58g tetraethyl ammonium hydroxide (C
8H
20NOH 25%); Greater than rapid hybrid reaction 15 minutes under 400 rev/mins the situation, temperature is controlled at 50 ℃ with two kinds of solution low whipping speeds, and pH is controlled between the 11-12, makes zirconium hydroxide and yttrium hydroxide composite precursor; With deionized water presoma is filtered, washing does not have Cl until detecting filtrate with silver nitrate solution
-Gained filter cake dispersed with stirring in propyl carbinol, is heated to 80 ℃ then under vacuum tightness is the condition of 0.1MPa, vacuum component distillation 8h reclaims aqueous alcohol under condition of stirring, makes the presoma powder; The presoma powder is put into retort furnace, at 700 ℃ of calcining 6h; Through grinding, subsequent disposal such as ball milling make superfine cubic phase zircite powder.
Embodiment 14
Take by weighing 5kgZrOCl
28H
2O is dissolved in the deionized water of 31L and is made into the 0.5mol/L zirconium oxychloride solution, takes by weighing 12kg Tetramethylammonium hydroxide (C
8H
20NOH 25%); Greater than rapid hybrid reaction 20 minutes under 400 rev/mins the situation, temperature is controlled at 40 ℃ with two kinds of solution low whipping speeds, and pH is controlled between the 11-12, makes the zirconium hydroxide presoma; With deionized water presoma is filtered, washing does not have Cl until detecting filtrate with silver nitrate solution
-Gained filter cake dispersed with stirring in propyl carbinol, is heated to 80 ℃ then under vacuum tightness is the condition of 0.1MPa, vacuum component distillation 12h reclaims aqueous alcohol under condition of stirring, makes the presoma powder; The presoma powder is put into retort furnace, at 700 ℃ of calcining 2h; Through grinding, ball milling, subsequent disposal such as airflow milling make the superfine zirconia powder.
Embodiment 15
With 16.27gZrOCl
28H
2O is dissolved in and is made into the 0.1mol/L zirconium oxychloride solution in the 500ml deionized water, takes by weighing 100.32g tetraethyl ammonium hydroxide (C
8H
20NOH 25%) add deionized water 150g and be diluted to 10% concentration; Greater than rapid hybrid reaction under 400 rev/mins the situation, temperature is controlled at 70 ℃ with two kinds of solution low whipping speeds, and pH is controlled between the 11-12, reacts 25 minutes, makes the zirconium hydroxide presoma; With deionized water presoma is filtered, washing does not have Cl until detecting filtrate with silver nitrate solution
-Gained filter cake dispersed with stirring in propyl carbinol, is heated to 80 ℃ then under vacuum tightness is the condition of 0.1MPa, vacuum component distillation 6h reclaims aqueous alcohol under condition of stirring, makes the presoma powder; The presoma powder is put into retort furnace, at 500 ℃ of calcining 3h; Through grinding, subsequent disposal such as airflow milling make the superfine zirconia powder.
Claims (9)
1. the preparation method of a superfine zirconia powder is characterized in that comprising following step:
(1) preparation zirconium hydroxide presoma: basic zirconium chloride is dissolved in the zirconium oxychloride solution that is made into 0.1-1.0mol/L concentration in the deionized water, quaternary ammonium hydroxide is dissolved in is made into the quaternary ammonium hydroxide aqueous solution that massfraction is 10%-45% in the deionized water, with two solution low whipping speeds greater than mixing rapidly under 400 rev/mins the situation, by accurate pH test paper the pH value of reaction solution is remained between the 9-13, reaction times is 5-25 minute, and temperature of reaction is 30-70 ℃;
(2) preparation zirconium hydroxide filter cake: the zirconium hydroxide presoma that will react generation is without ageing, and direct filtration is separated, and washs with deionized water, does not have Cl until detecting filtrate with silver nitrate solution
-
(3) preparation zirconium white presoma powder: with gained zirconium hydroxide filter cake dispersed with stirring in propyl carbinol or Pentyl alcohol, with azeotropic distillation drying it is carried out drying, be under the condition of 0.1MPa promptly in vacuum tightness, 50-90 ℃ dry 5-15 hour, make exsiccant zirconium white presoma powder;
(4), obtain particle diameter less than 1.5 microns superfine zirconia powder through grinding again with exsiccant zirconium white presoma powder temperature lower calcination 1-6 hour at 500-900 ℃.
2. according to the preparation method of the described Zirconium powder of claim 1, it is characterized in that described zirconium oxychloride solution concentration is 0.5-1.0mol/L.
3. according to the preparation method of the described Zirconium powder of claim 1, the massfraction that it is characterized in that the described quaternary ammonium hydroxide aqueous solution is 20%-25%.
4. according to the preparation method of the described Zirconium powder of claim 1, it is characterized in that described quaternary ammonium hydroxide is a Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH, TBAH or (2-hydroxyethyl) trimethylammonium hydroxide.
5. according to the preparation method of the described Zirconium powder of claim 1, it is characterized in that the pH value of described reaction solution is 9-12.
6. according to the preparation method of the described Zirconium powder of claim 1, it is characterized in that the described reaction times is 5-15 minute.
7. according to the preparation method of the described Zirconium powder of claim 1, it is characterized in that described calcining temperature is between 600-700 ℃, calcination time is 2-4 hour.
8. according to the preparation method of each described Zirconium powder among the claim 1-7, it is characterized in that adding YCl in the zirconium oxychloride solution in step (1)
3, YCl
3Consumption be controlled at the Y that makes its generation
2O
3Account for ZrO
2The 2-3% of mole number finally makes particle diameter less than 1.5 microns ultra-fine cubic phase (t-ZrO
2) Zirconium powder.
9. according to the preparation method of each described Zirconium powder among the claim 1-7, it is characterized in that adding Y (NO in the zirconium oxychloride solution in step (1)
3)
3, Y (NO
3)
3Consumption be controlled at the Y that makes its generation
2O
3Account for ZrO
2The 7-8% of mole number finally makes particle diameter less than 1.5 microns superfine cubic phase (c-ZrO
2) Zirconium powder.
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