CN108147456A - A kind of preparation method of monodisperse zirconium dioxide microballoon - Google Patents
A kind of preparation method of monodisperse zirconium dioxide microballoon Download PDFInfo
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- CN108147456A CN108147456A CN201611094181.4A CN201611094181A CN108147456A CN 108147456 A CN108147456 A CN 108147456A CN 201611094181 A CN201611094181 A CN 201611094181A CN 108147456 A CN108147456 A CN 108147456A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a kind of preparation methods of monodisperse zirconium dioxide microballoon, belong to chemical technology field.This method includes：Using water-soluble inorganic zirconium salts as zirconium source, water is as solvent, alcohols is as dispersant, add in surfactant, precipitating reagent etc. after mixing, by the way that nano zirconium dioxide spheric granules is prepared under non-contact external control methods hydrolysis, monodispersed spherical Zirconium dioxide powder is then obtained after dry, roasting.The nano zirconium dioxide microspherulite diameter that preparation method using the present invention obtains is distributed between 0.3~2um, and particle size distribution is uniform, soilless sticking between particle, and cost of material is low, is easy to get, preparation method is easy, and reaction efficiency is high, repeatability and stablize, can batch continuous production.
Description
Technical field
The invention belongs to chemical technology field, more particularly to a kind of preparation method of monodisperse zirconium dioxide microballoon.
Background technology
The appearance of nano material is a kind of new discovery of Material Field, and the size of nano material is small, pattern is specific, ultra-fine point
The special construction of cloth etc. determines that nano material has some special effects, can possess some that conventional material does not have
Property, such as small-size effect, quantum size effect and macro quanta tunnel effect etc., therefore nano material can significantly improve
The performance of light, electricity, sensing and the catalysis of material etc..Wherein, nanometer titanium dioxide zirconia material is that one kind is widely studied and answers
Multi-functional nanometer material, in electronics, magnetism, optics, biology, electrode, sensor, catalyst, pharmaceuticals, pigment and coating
Etc. have special application prospect.Granule-morphology, size, uniformity coefficient and the dispersibility of nano material directly determine
The purposes and quality of nano material.Wherein, the purposes of spherical nanometer zirconium dioxide material is very extensive, may be widely used for
In the preparation of the materials such as fiber, film, coating, fuel cell, lambda sensor and chromatographic packing material, therefore, research and development
The preparation method of nano zirconium dioxide particle that a kind of good dispersion, uniformity are excellent, sphericity is high has great importance.
The method for preparing zirconium dioxide material at present mainly has vapor phase method, solid phase method, the precipitation method, solvent heat/hydro-thermal method, micro-
Emulsion method.A kind of method that vapor phase method prepares zirconium dioxide material, used gas are disclosed in patent CN103739014A
Phase method cost of equipment is expensive, and technics comparing is complicated, and obtained valuable product, is not suitable for industrialized production；Specially
A kind of solid phase method for preparing zirconium dioxide persursor material is disclosed in sharp CN101708862A, used in method need item
Part is harsher, and reaction raw materials cost is higher, and obtained powdery product is easily reunited sintering；It is public in patent CN101830507A
The conditions such as a kind of precipitation method for preparing zirconium dioxide material, temperature, the pH value of the precipitation method have been opened to the hydrolysis of precipitation and had been polymerize
Journey suffers from critically important influence, so pattern more difficult to control and size, while obtained product can also be mixed with being not readily separated
Impurity also has that precipitation is reunited and crystal mixed precipitation in process of production；Therefore, prepared by above-mentioned preparation process
Zirconium dioxide particle is not suitable for nano zirconium dioxide because of complex process, particle agglomeration, inhomogenous and of high cost etc. reasons
The preparation of particle.
At present, nano zirconium dioxide particle is prepared using sol-gal process the most extensive, operation side simple with equipment
Just the advantages that.But traditional sol-gal process, the method that zirconium dioxide is prepared for example, by using zirconium-n-propylate hydrolysis, although energy
The preferable monodisperse zirconium dioxide microballoon of sphericity is enough prepared, still, the raw material of this method is very expensive, can not be used as system
Preparation Method is produced in batches；Using conventional inorganic zirconium salts as the sol-gal process of zirconium source, water phase as reaction medium, although former
Expect it is at low cost, but prepare particle agglomeration it is very serious, sphericity is poor.
Invention content
The present invention is directed to be directed to the above-mentioned deficiency for preparing zirconium dioxide material, it is single to propose prepared by a kind of new sol-gal process
Disperse the method for zirconium dioxide microballoon.
A kind of preparation method of monodisperse zirconium dioxide microballoon, the specific steps are：
(1) inorganic salts of water-soluble zirconium with aqueous solution are mixed evenly, add in precipitant material and stirred evenly
To solution A；
(2) solution B is obtained after surfactant and alcohol solution being mixed evenly；
(3) solution A in above-mentioned steps with solution B is mixed evenly, is placed in microwave environment, is heated in microwave
It is reacted to certain temperature, the suspension of spherical nanometer zirconium dioxide particle is obtained after being aged a period of time；
(4) suspension obtained in step (3) is filtered, washed, dries and calcination process obtains ball shaped nano dioxy
Change zirconium particle.
Water soluble zirconium salt described in step (1) mainly includes in zirconium oxychloride, zirconium nitrate, zirconyl nitrate, zirconium chloride
It is one or more of.
Precipitant material described in step (1) mainly includes urea, triethylene diamine, diethylenetriamines, six methylenes
One or more of urotropine, ammonium citrate, ammonium acetate.
The molar ratio of water-soluble inorganic zirconium salts, precipitating reagent and water described in step (1) is preferably 1:2~5:55~
277。
Surfactant described in step (2) mainly include cetyl trimethylammonium bromide, lauryl sodium sulfate,
One kind in neopelex, ethylenediamine, tetraacethyl sodium, ethanol amine, diethanol amine, polyvinyl alcohol, tween, cellulose
It is or several.
Alcohols in step (2) mainly includes one or more of methanol, ethyl alcohol, isopropanol, normal propyl alcohol, n-butanol.
The molar ratio of surfactant and alcohol solution described in step (2) is 1:600~1300.
Precipitation reaction is carried out using microwave heating in the step (3), the temperature of reaction is 25~300 DEG C, the reaction time
It is 0.01~2 hour；And the pH value after ageing reaction is controlled 5~13, wherein it is preferred that 6~10；
Drying mode in the step (4) is predominantly dried in vacuo, and drying temperature is preferably 60~80 DEG C；Dry humidity
Preferably 50~90%；Calcination temperature is preferably 600~900 DEG C.
The size of zirconium dioxide microsphere particle prepared by the present invention be 0.3~2um, obtained zirconium dioxide microballoon uniformity
High, crystal form is monocline type and zirconium dioxide microsphere features smooth surface, almost without pore structure.
The principle of this method is：The nucleation process of early period is for synthesizing uniform nano zirconium dioxide spherical particles to pass
It is important.Outburst nucleation theory in crystal nucleation theory, crystal nucleation and crystal growth are in the forming process of crystal
With competitive relation, the nucleus number that core can be erupted within the same time is more, and crystal more can be equal in the same time
One growth, the crystal of difference nucleation result in that crystal growth time is different, and the particle size differential as a result obtained is with regard to bigger.
Nucleation initial stage is broken out in crystal, using heterogeneity of the surfactant in water and alcoholic solution, hydrophobic group proper alignment is inhaled
Crystal grain surface is attached to, avoids the reunion of particle, the mode of heating regulated and controled using non-contact external (can be microwave, photo-induction
Lead excitation, magnetic force induction etc.), transmit even heat.In this way, the process of a homogeneous nucleation is just obtained, in controllable momentum
It transmits, in the case of heat transfer and mass transfer, the initial reactant nucleus size of generation is uniform, by the late growth of nucleus, nucleus
Growth becomes larger, and granular precursor is accumulated and be combined with each other, and forms granular precursor, passes through the shearing force in solution and drawing force
Effect, granular grows become spherical, and granular precursor finally deposits to form spherical zirconium dioxide nanoparticles.
Beneficial effects of the present invention are：Can be with fast reaction using the method for the present invention, the zirconium dioxide that is prepared
Grain sphericity is high, uniformity is good, dispersibility is excellent, and technological operation is easy, cost of material is low, raw material is easy to get, repeated and stability
It is good.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram (SEM) of embodiment 1.
Fig. 2 is the scanning electron microscope diagram (SEM) of embodiment 3.
Fig. 3 is monodispersity index (PDI) figure of embodiment 1.
Specific embodiment
Embodiment 1
In the environment of 20 ± 5 DEG C, 5ml deionized waters, 3.22g zirconium oxychlorides and 1.502g urea are measured, it will be above-mentioned anti-
Object is answered to mix, is stirred evenly with the mode of magnetic agitation, obtains solution A.100ml ethanol solutions are measured, add in 0.3759g 12
Sodium alkyl sulfate, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirring 30
Minute, stop stirring, stand a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 2 hours, take out
Then product is cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution, then use ethyl alcohol
It cleans, filters repeatedly with isopropanol, obtained product is positioned in vacuum drying chamber, and 60 DEG C are dried in vacuo 24 hours.Then will
Product is placed in Muffle kiln roasting, is warming up to 450 DEG C for 25 DEG C from room temperature with the heating rate of 5 DEG C/min, 3 is small at 450 DEG C of holding
When, 750 DEG C are warming up to from 450 DEG C with the heating rate of 5 DEG C/min later, keeps at 750 DEG C 5 hours, drops naturally later later
Temperature obtains the zirconium dioxide microballoon that average grain diameter is 1000nm, monodispersity index (PDI) value is 0.214.Scanning electron microscope
(SEM) is schemed as shown in Figure 1, monodispersity index (PDI) figure is as shown in Figure 3.
Embodiment 2
In the environment of 20 ± 5 DEG C, 10ml deionized waters, 3.22g zirconium oxychlorides and 2.1g urea are measured, by above-mentioned reaction
Object mixes, and is stirred evenly with the mode of magnetic agitation, obtains solution A.120ml ethanol solutions are measured, add in 0.3811g ethylenediamines
Tetraacethyl, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirred 30 minutes,
Stop stirring, stand a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 90 minutes, take out production
Then object is cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution, then with ethyl alcohol and
Isopropanol cleans repeatedly, and filtering, obtained product is positioned in vacuum drying chamber, and 80 DEG C are dried in vacuo 24 hours.It then will production
Object is placed in Muffle kiln roasting, is warming up to 400 DEG C for 25 DEG C from room temperature with the heating rate of 3 DEG C/min, keeps at 450 DEG C 3 hours,
750 DEG C are warming up to from 450 DEG C with the heating rate of 3 DEG C/min later, is kept at 700 DEG C 5 hours later, Temperature fall later,
After testing, the zirconium dioxide microballoon that average grain diameter is 1500nm, monodispersity index (PDI) value is 0.398 is obtained.
Embodiment 3
In the environment of 20 ± 5 DEG C, 5ml deionized waters, 4.29g zirconium nitrates and 2.1g urea are measured, by above-mentioned reactant
Mixing, is stirred evenly with the mode of magnetic agitation, obtains solution A.100ml ethanol solutions are measured, add in 0.3759g dodecyls
Sodium sulphate, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirred 30 minutes,
Stop stirring, stand a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 1 hour, take out product,
Then it is cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution, then with ethyl alcohol and different
Propyl alcohol cleans repeatedly, and filtering, obtained product is positioned in vacuum drying chamber, and 60 DEG C are dried in vacuo 24 hours.Then by product
Muffle kiln roasting is placed in, 450 DEG C is warming up to for 25 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps at 450 DEG C 3 hours, it
750 DEG C are warming up to from 450 DEG C with the heating rate of 5 DEG C/min afterwards, is kept at 750 DEG C later 5 hours, Temperature fall, passes through later
Detection obtains the zirconium dioxide microballoon that average grain diameter is 2000nm, monodispersity index (PDI) value is 0.336.Scanning electron microscopy
Mirror figure (SEM) is as shown in Figure 3.
Embodiment 4
In the environment of 20 ± 5 DEG C, 5ml deionized waters, 3.22g zirconium oxychlorides and 2.1g urea are measured, by above-mentioned reaction
Object mixes, and is stirred evenly with the mode of magnetic agitation, obtains solution A.100ml ethanol solutions are measured, add in 0.4757g hexadecanes
Base trimethylammonium bromide, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirred
It mixes 30 minutes, stops stirring, stand a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 150 points
Clock takes out product, is then cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution,
It is cleaned, filtered repeatedly with ethyl alcohol and isopropanol again, obtained product is positioned in vacuum drying chamber, and 60 DEG C of vacuum drying 24 are small
When.Then product is placed in Muffle kiln roasting, is warming up to 500 DEG C for 25 DEG C from room temperature with the heating rate of 3 DEG C/min, keeps
3 hours at 450 DEG C, 750 DEG C are warming up to from 450 DEG C with the heating rate of 3 DEG C/min later, is kept at 800 DEG C 5 hours later,
Temperature fall later after testing, it is micro- to obtain the zirconium dioxide that average grain diameter is 1200nm, monodispersity index (PDI) value is 0.291
Ball.
Embodiment 5
In the environment of 20 ± 5 DEG C, 15ml deionized waters, 3.55g zirconium sulfates and 1.8g urea are measured, by above-mentioned reactant
Mixing, is stirred evenly with the mode of magnetic agitation, obtains solution A.100ml ethanol solutions are measured, add in 0.3811g ethylenediamine tetraacetics
Acetic acid, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirs 30 minutes, stops
It only stirs, stands a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 30 minutes, take out product,
Then it is cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution, then with ethyl alcohol and different
Propyl alcohol cleans repeatedly, and filtering, obtained product is positioned in vacuum drying chamber, and 60 DEG C are dried in vacuo 24 hours.Then by product
Muffle kiln roasting is placed in, 450 DEG C is warming up to for 25 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps at 450 DEG C 3 hours, it
750 DEG C are warming up to from 450 DEG C with the heating rate of 5 DEG C/min afterwards, is kept at 750 DEG C later 5 hours, Temperature fall, passes through later
Detection obtains the zirconium dioxide microballoon that average grain diameter is 2000nm, monodispersity index (PDI) value is 0.362.
Embodiment 6
In the environment of 20 ± 5 DEG C, 10ml deionized waters, 2.31g zirconyl nitrates and 2.4g urea are measured, by above-mentioned reaction
Object mixes, and is stirred evenly with the mode of magnetic agitation, obtains solution A.150ml ethanol solutions are measured, add in 0.4757g hexadecanes
Base trimethylammonium bromide, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirred
It mixes 30 minutes, stops stirring, stand a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 30 points
Clock takes out product, is then cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution,
It is cleaned, filtered repeatedly with ethyl alcohol and isopropanol again, obtained product is positioned in vacuum drying chamber, and 60 DEG C of vacuum drying 24 are small
When.Then product is placed in Muffle kiln roasting, is warming up to 450 DEG C for 25 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps
3 hours at 450 DEG C, 750 DEG C are warming up to from 450 DEG C with the heating rate of 5 DEG C/min later, is kept at 750 DEG C 5 hours later,
Temperature fall later after testing, it is micro- to obtain the zirconium dioxide that average grain diameter is 2500nm, monodispersity index (PDI) value is 0.411
Ball.
Embodiment 7
In the environment of 20 ± 5 DEG C, 20ml deionized waters, 2.33g zirconium chlorides and 3.0g urea are measured, by above-mentioned reactant
Mixing, is stirred evenly with the mode of magnetic agitation, obtains solution A.120ml ethanol solutions are measured, add in 0.3811g ethylenediamine tetraacetics
Acetic acid, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirs 30 minutes, stops
It only stirs, stands a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 30 minutes, take out product,
Then it is cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution, then with ethyl alcohol and different
Propyl alcohol cleans repeatedly, and filtering, obtained product is positioned in vacuum drying chamber, and 60 DEG C are dried in vacuo 24 hours.Then by product
Muffle kiln roasting is placed in, 450 DEG C is warming up to for 25 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps at 450 DEG C 3 hours, it
750 DEG C are warming up to from 450 DEG C with the heating rate of 5 DEG C/min afterwards, is kept at 750 DEG C later 5 hours, Temperature fall, passes through later
Detection obtains the zirconium dioxide microballoon that average grain diameter is 1800nm, monodispersity index (PDI) value is 0.637.
Embodiment 8
In the environment of 20 ± 5 DEG C, 3ml deionized waters, 2.31g zirconyl nitrates and 2.1g urea are measured, by above-mentioned reaction
Object mixes, and is stirred evenly with the mode of magnetic agitation, obtains solution A.120ml ethanol solutions are measured, add in 0.4757g hexadecanes
Base trimethylammonium bromide, mixing, stirs evenly, obtains solution B in the same way later.Solution A and solution B are mixed, stirred
It mixes 30 minutes, stops stirring, stand a period of time, be then placed into micro-wave oven, adjust microwave heating power, heat 60 points
Clock takes out product, is then cleaned repeatedly with deionized water, until filtrate can not detect chlorion with silver nitrate solution,
It is cleaned, filtered repeatedly with ethyl alcohol and isopropanol again, obtained product is positioned in vacuum drying chamber, and 60 DEG C of vacuum drying 24 are small
When.Then product is placed in Muffle kiln roasting, is warming up to 450 DEG C for 25 DEG C from room temperature with the heating rate of 5 DEG C/min, keeps
3 hours at 450 DEG C, 750 DEG C are warming up to from 450 DEG C with the heating rate of 5 DEG C/min later, is kept at 750 DEG C 5 hours later,
Temperature fall later after testing, it is micro- to obtain the zirconium dioxide that average grain diameter is 1800nm, monodispersity index (PDI) value is 0.596
Ball.
Claims (9)
1. a kind of preparation method of monodisperse zirconium dioxide microballoon, it is characterised in that this method the specific steps are：
(1) inorganic salts of water-soluble zirconium with water are mixed evenly, add in precipitating reagent and are uniformly mixing to obtain solution A；
(2) solution B is obtained after surfactant and alcohol solution being mixed evenly；
(3) solution A in above-mentioned steps with solution B is mixed evenly, is placed in microwave environment, one is heated in microwave
Determine thermotonus, the suspension of spherical nanometer zirconium dioxide particle is obtained after being aged a period of time；
(4) suspension obtained in step (3) is filtered, washed, dries and calcination process obtains spherical nanometer zirconium dioxide
Particle.
2. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claim 1, it is characterised in that：Step (1)
Described in water soluble zirconium salt mainly include zirconium oxychloride, zirconium nitrate, zirconyl nitrate, one or more of zirconium chloride.
3. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claim 1, it is characterised in that：Step (1)
Described in precipitant material be urea, triethylene diamine, diethylenetriamines, hexa, ammonium citrate or acetic acid
One or more of ammonium.
4. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claim 1, it is characterised in that：Step (1)
Described in water-soluble inorganic zirconium salts, precipitating reagent and water molar ratio be 1:2~5:55~277.
5. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claim 1, it is characterised in that：Step (2)
Described in surfactant for cetyl trimethylammonium bromide, lauryl sodium sulfate, neopelex, second two
One or more of amine, tetraacethyl sodium, ethanol amine, diethanol amine, polyvinyl alcohol, tween or cellulose.
6. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claim 1, it is characterised in that：Step (2)
In alcohols one or more of for methanol, ethyl alcohol, isopropanol, normal propyl alcohol or n-butanol.
7. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claims 1, it is characterised in that：Step
(2) molar ratio of surfactant and alcohol solution described in is 1:600~1300.
8. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claims 1, it is characterised in that：The step
Suddenly precipitation reaction is carried out using microwave heating in (3), the temperature of reaction is 25~300 DEG C, and the reaction time is 0.01~2 hour；
And the pH value after ageing reaction is controlled 5~13, wherein it is preferred that 6~10.
9. a kind of preparation method of monodisperse zirconium dioxide microballoon according to claim 1, it is characterised in that：The step
(4) drying mode in is predominantly dried in vacuo, and drying temperature is 60~80 DEG C；Dry humidity is 50~90%；Calcination temperature
It is 600~900 DEG C.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108675348A (en) * | 2018-07-04 | 2018-10-19 | 江苏大学 | A method of preparing superfine zirconia powder |
| CN111056569A (en) * | 2020-01-21 | 2020-04-24 | 绵竹市金坤化工有限公司 | Method for preparing nano zirconium oxide by alcohol method |
| CN112374514A (en) * | 2020-11-11 | 2021-02-19 | 广州大学 | Method for rapidly preparing bayer stone microspheres with uniform particle size by double hydrolysis at room temperature |
| CN113004034A (en) * | 2021-02-06 | 2021-06-22 | 苏州润纳斯纳米科技有限公司 | High sintering activity composite nano Zr02Preparation method of powder microspheres |
| CN114751451A (en) * | 2022-05-19 | 2022-07-15 | 美轲(广州)新材料股份有限公司 | Preparation method of nano zirconia |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108675348A (en) * | 2018-07-04 | 2018-10-19 | 江苏大学 | A method of preparing superfine zirconia powder |
| CN111056569A (en) * | 2020-01-21 | 2020-04-24 | 绵竹市金坤化工有限公司 | Method for preparing nano zirconium oxide by alcohol method |
| CN111056569B (en) * | 2020-01-21 | 2022-04-01 | 绵竹市金坤化工有限公司 | Method for preparing nano zirconium oxide by alcohol method |
| CN112374514A (en) * | 2020-11-11 | 2021-02-19 | 广州大学 | Method for rapidly preparing bayer stone microspheres with uniform particle size by double hydrolysis at room temperature |
| CN112374514B (en) * | 2020-11-11 | 2022-09-30 | 广州大学 | Method for rapidly preparing bayer stone microspheres with uniform particle size by double hydrolysis at room temperature |
| CN113004034A (en) * | 2021-02-06 | 2021-06-22 | 苏州润纳斯纳米科技有限公司 | High sintering activity composite nano Zr02Preparation method of powder microspheres |
| CN114751451A (en) * | 2022-05-19 | 2022-07-15 | 美轲(广州)新材料股份有限公司 | Preparation method of nano zirconia |
| CN114751451B (en) * | 2022-05-19 | 2024-01-30 | 美轲(广州)新材料股份有限公司 | Preparation method of nano zirconia |
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