CN101823765B - Preparation method of high dispersion rod type nanometer zirconium oxide - Google Patents
Preparation method of high dispersion rod type nanometer zirconium oxide Download PDFInfo
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- CN101823765B CN101823765B CN2010101825713A CN201010182571A CN101823765B CN 101823765 B CN101823765 B CN 101823765B CN 2010101825713 A CN2010101825713 A CN 2010101825713A CN 201010182571 A CN201010182571 A CN 201010182571A CN 101823765 B CN101823765 B CN 101823765B
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Abstract
The invention provides a preparation method of high dispersion rod type nanometer zirconium oxide, belonging to the technical field of nanometer material preparation. The preparation method is characterized by comprising the following steps of firstly, under the stirring condition, preparing gel by dripping 0.05-1mol/L of sodium borohydride solution into 0.05-1mol/L of zirconium oxychloride solution, continuously titrating to produce white precipitate, stirring for 0.5-12h, and suction filtering and washing the precipitate for many times by using distilled water or absolute ethyl alcohol until washing liquid is neutral; secondly, adding camphene into the precipitate, heating to 60-100 DEG C, and stirring and mixing to form slurry; and thirdly, carrying cooling formation on the slurry under the temperature lower than 20 DEG C, putting the solidified slurry at room temperature, staying 4-10 days, putting the solidified slurry into a sintering furnace after the camphene is completely exerted, and obtaining the high dispersion rod type nanometer zirconium oxide by calcining for 2h under the temperature of 500-900 DEG C. The invention has the advantages of simple process, safe operation and low cost. The length-diameter ratio of the synthesized rod type nanometer zirconium oxide is bigger than 3 times.
Description
Technical field
The invention provides a kind of preparation method of high dispersion rod type nanometer zirconium oxide, belong to the nano material preparation technical field.
Background technology
Zirconium dioxide is a kind of high temperature resistant, wear-resistant, corrosion resistant ceramic, and except that being applied to traditional refractory materials and beramic color, it also is widely used in high-tech areas such as electronic ceramics, function ceramics and structural ceramicss.Nano structural material as nano wire, nanometer rod, nanometer sheet, shows new physicals, has potential to use in a lot of fields.From at present both at home and abroad to nano level ZrO
2Research, the nanometer ZrO of preparation
2Particle is spherical and bar-shaped.At present about rod-like nano ZrO
2The preparation method has following technology report: 1, the paper of Sun Xiaofei, Song Xiuqin " direct precipitation method prepares bar-shaped zirconium white " adopts EDTA as complexing agent, the bar-shaped zirconium white of in ethanolic soln, preparing, and every rod all is to be formed by many thin rods " binding ", and every thin rod all is to be piled up by many small-particles to form, particle is the spheroidal particle of 13nm, shortcoming is: must react the cost height under the condition of alcoholic solution; The excellent homogeneity that generates is bad, and rod is piled up for the ball shaped nano particulate, is not real nanometer rod.2, Gao Lin, the paper of Song Xiuqin " Controlled preparation and spectral analysisof nanorod andnanocluster ZrO
2" adopt sulphosalicylic acid as the masterplate agent, in ethanolic soln, prepare bar-shaped zirconium white, diameter is 50～400nm, assembles druse, shortcoming: must react the cost height under the condition of alcoholic solution; The excellent homogeneity that generates, dispersed bad.3, paper " Synthesis and crystallization of anisotropic shaped ZrO
2Nanocrystalline powdersby hydrothermal process " adopt hydro-thermal synthesis process, with ZrOCl
28H
2O is a raw material, 1～5mol/L NaOH solution is the hydro-thermal medium, at 250 ℃ of insulation 24h, prepare bar-shaped zirconium white, diameter is 300nm, and length is 0.8～1 μ m, and paper " Synthesis; microstructure and optical characterization of zirconium oxide nanostructures " adopts hydro-thermal synthesis process, with ZrO (NO
3)
2χ H
2O is that raw material, 5mol/LNaOH solution are the hydro-thermal medium, at 250 ℃ of insulation 24h, prepares bar-shaped zirconium white, and diameter is 100nm, and long is 425nm, and shortcoming is: the hydro-thermal reaction time is long, and efficient is low; The High Temperature High Pressure operational hazards is unfavorable for suitability for industrialized production; The NaOH consumption is big, and is seriously polluted.4, patent CN1171798C " a kind of synthetic method of zirconium oxide nano wire array ", adopt template to prepare nano wire, prepare zirconium colloidal sol with oxalic acid titration zirconyl chloride solution, under 1.3MPa, pressurize, allow zirconium colloidal sol by multiaperture pellumina, after the colloidal sol drying under argon gas atmosphere roasting prepare nano wire, shortcoming: must adopt multiaperture pellumina as template, zirconium colloidal sol is extruded by nanoporous, and efficient is low, is difficult to suitability for industrialized production.5, paper " the auxiliary synthetic ZrO of ionic liquid at room temperature
2Nano wire " and paper " Synthesis of ZrO
2Nanowires byionic-liquid route " use 1-butyl-3-methyl imidazolium tetrafluoroborate ([BMIm] BF
4) solion is as template, ethylene glycol is as the hydro-thermal medium, and in autoclave, 160 ℃ of insulation 46h prepare diameter 50nm, are about the ZrO of 25 μ m
2Nano wire, shortcoming: solion preparation difficulty costs an arm and a leg; The High Temperature High Pressure operational hazards is unfavorable for suitability for industrialized production; And the space appears in 500 ℃ of roastings, and the intensity of nano wire is low, is the nano particle polymer.
In addition, because nano particle is active high, the nano-powder of preparation is reunited serious, need to use special technology to eliminate and reunite, as supercritical drying, vacuum lyophilization, microwave drying and component distillation, equipment requirements is higher, and by convection drying, agglomeration is serious.
Summary of the invention
The purpose of this invention is to provide a kind ofly can overcome that above-mentioned defective, technology are simple, operational safety, cost are low, the preparation method of the high dispersion rod type nanometer zirconium oxide that do not pollute, its technical scheme is:
A kind of preparation method of high dispersion rod type nanometer zirconium oxide, it is characterized in that adopting following steps: (1) is under agitation condition, 0.05～1mol/L sodium borohydride solution is splashed in 0.05～1mol/L zirconyl chloride solution, generate gel, continue titration and generate white precipitate, stir 0.5～12h, will precipitate then with distilled water or dehydrated alcohol filtering and washing several, till washing lotion shows neutrality; (2) in precipitation, add amphene, be heated to 60～100 ℃, mix the formation slip; (3) be lower than freeze forming in 20 ℃ the environment in temperature, the slip that will solidify is placed on and stopped in the air at room temperature environment 4～10 days, treat to be put in the sintering oven after amphene volatilizees fully, and 500～900 ℃ of calcining 2h, diffusing rod type nanometer zirconium oxide promptly secures satisfactory grades.
Precipitation is 1: 1～3 with the mass ratio of amphene among the preparation method of described a kind of high dispersion rod type nanometer zirconium oxide, step (2).
The preparation method of described a kind of high dispersion rod type nanometer zirconium oxide, temperature is lower than 20 ℃ environment in the step (3), as in refrigerated tank or the liquid nitrogen cryogenics environment.
Principle of work of the present invention is: because the fusing point of amphene is lower, and fusing about 45 ℃, and be solid under the normal temperature state, the mold temperature of base substrate is low.In process of setting, there are the temperature head that can regulate in slip internal temperature and exterior cooling medium, reach the purpose of its directional freeze of control, help the formation of club shaped structure; Simultaneously, amphene is as easy evaporable material, and the formation hole that just can volatilize naturally in air improves powder dispersity.
The present invention compared with prior art has following advantage:
1, do not add any tensio-active agent, promptly form rod type nanometer zirconium oxide;
2, the present invention adopts direct precipitation method to prepare presoma, with respect to hydro-thermal synthesis process, does not use high-temperature high-pressure apparatus, and is simple to operate, safety; As reaction medium, cost is low with respect to alcoholic solution.
3, the nm-class powder of zirconium oxide good dispersity of the present invention's preparation, the low reunion.
Description of drawings
Fig. 1 is the XRD spectrum of the embodiment of the invention after 700 ℃ of calcinings;
Fig. 2 is the SEM photo of the embodiment of the invention after 700 ℃ of calcinings.
Embodiment
Embodiment 1
(1) ZrOCl of 3.2g
28H
2The water that O is dissolved in 100ml is configured to the 0.1mol/L zirconyl chloride solution, then the 0.2mol/L sodium borohydride solution is titrated in the zirconyl chloride solution, till regeneration white precipitate not, stir 2h, to precipitate for several times, till washing lotion shows neutrality, obtain precipitating 12g with the distilled water filtering and washing; (2) in precipitation, add the 12g amphene, be heated to 60 ℃, mix the formation slip; (3) at the liquid nitrogen environment freeze forming, the slip that will solidify is placed in the air at room temperature environment and stopped 7 days, treat to be put in the sintering oven after amphene volatilizees fully, and 700 ℃ of calcining 2h, diffusing rod type nanometer zirconium oxide promptly secures satisfactory grades.
By the XRD test, visible powder crystal type is a monocline phase (see figure 1); By the SEM test, visible Zirconium powder is bar-shaped, and about diameter 40nm, long is the 150nm (see figure 2).
Embodiment 2
(1) ZrOCl of 1.6g
28H
2The water that O is dissolved in 100ml is configured to the 0.05mol/L zirconyl chloride solution, then the 0.6mol/L sodium borohydride solution is titrated in the zirconyl chloride solution, till regeneration white precipitate not, stir 0.5h, to precipitate for several times with the dehydrated alcohol filtering and washing, till washing lotion shows neutrality, obtain precipitating 5g; (2) in precipitation, add the 10g amphene, be heated to 100 ℃, mix the formation slip; (3) at-40 ℃ of freeze formings, the slip that will solidify is placed in the air at room temperature environment and stopped 10 days, treat to be put in the sintering oven after amphene volatilizees fully, and 900 ℃ of calcining 2h, diffusing rod type nanometer zirconium oxide promptly secures satisfactory grades.
Embodiment 3
(1) ZrOCl of 32g
28H
2The water that O is dissolved in 100ml is configured to the 1mol/L zirconyl chloride solution, then the 0.05mol/L sodium borohydride solution is titrated in the zirconyl chloride solution, till regeneration white precipitate not, stir 12h, to precipitate for several times, till washing lotion shows neutrality, obtain precipitating 95g with the distilled water filtering and washing; (2) in precipitation, add the 200g amphene, be heated to 80 ℃, mix the formation slip; (3) in 15 ℃ of environment moulding of room temperature, the slip that will solidify is placed in the air at room temperature environment and stopped 4 days, treat to be put in the sintering oven after amphene volatilizees fully, and 500 ℃ of calcining 2h, diffusing rod type nanometer zirconium oxide promptly secures satisfactory grades.
Claims (2)
1. the preparation method of a high dispersion rod type nanometer zirconium oxide, it is characterized in that adopting following steps: (1) is under agitation condition, 0.05～1mol/L sodium borohydride solution is splashed in 0.05～1mol/L zirconyl chloride solution, generate gel, continue titration and generate white precipitate, stir 0.5～12h, will precipitate then with distilled water or dehydrated alcohol filtering and washing several, till washing lotion shows neutrality; (2) add amphene in precipitation, precipitation is 1: 1～3 with the mass ratio of amphene, is heated to 60～100 ℃, mixes the formation slip; (3) be lower than freeze forming in 20 ℃ the environment in temperature, the slip that will solidify is placed on and stopped in the air at room temperature environment 4～10 days, treat to be put in the sintering oven after amphene volatilizees fully, and 500～900 ℃ of calcining 2h, diffusing rod type nanometer zirconium oxide promptly secures satisfactory grades.
2. the preparation method of a kind of high dispersion rod type nanometer zirconium oxide as claimed in claim 1 is characterized in that: temperature is lower than 20 ℃ environment in the step (3), as in refrigerated tank or the liquid nitrogen cryogenics environment.
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| CN103864085B (en) * | 2014-03-26 | 2017-12-19 | 山东理工大学 | The preparation method of bar-shaped zirconium boride powder |
| CN104386745B (en) * | 2014-11-03 | 2015-12-30 | 安徽工业大学 | A kind of preparation method of nano zirconium oxide powder |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358670A (en) * | 2002-01-11 | 2002-07-17 | 清华大学 | Method for synthesizing zirconium oxide nano wire |
| CN1733611A (en) * | 2005-08-12 | 2006-02-15 | 安泰科技股份有限公司 | Zirconium dioxide nano powder material preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358670A (en) * | 2002-01-11 | 2002-07-17 | 清华大学 | Method for synthesizing zirconium oxide nano wire |
| CN1733611A (en) * | 2005-08-12 | 2006-02-15 | 安泰科技股份有限公司 | Zirconium dioxide nano powder material preparation method |
Non-Patent Citations (3)
| Title |
|---|
| Liangrong Li et al..Synthesis and characterization of monoclinic ZrO2 nanorods by a novel and simple precursor thermal decomposition approach.《Solid State Communications》.2003,第127卷639-643. * |
| Yingkai Liu et al..Synthesis and Characterization of Zirconia Nanorods.《J. Am. Ceram. Soc.》.2002,第85卷(第12期),3120-3122. * |
| 魏春城等.硼化锆粉体的制备与表征.《材料导报》.2009,第23卷196-201. * |
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