CN103588246A - Preparation process for nano zirconia powder - Google Patents
Preparation process for nano zirconia powder Download PDFInfo
- Publication number
- CN103588246A CN103588246A CN201210286093.XA CN201210286093A CN103588246A CN 103588246 A CN103588246 A CN 103588246A CN 201210286093 A CN201210286093 A CN 201210286093A CN 103588246 A CN103588246 A CN 103588246A
- Authority
- CN
- China
- Prior art keywords
- powder
- zirconium oxide
- preparation technology
- oxide powder
- zirconium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation process for nano zirconia powder. The preparation process comprises the steps of adding an alkaline precipitating agent in a zircon salt-containing aqueous solution to obtain a hydroxide precipitate; and then filtering, washing, dehydrating, drying and sintering to obtain zirconia powder. A colloidal solution obtained by dehydration with an azeotropic distillation method is dried in a distillation apparatus; and the colloidal solution is continuously stirred during dehydration and drying. The preparation process has the advantages of short reaction time, few procedures, large production capacity and high security, is suitable for large-scale production and can greatly reduce production cost.
Description
Technical field
The present invention relates to a kind of preparation technology of high dispersion nanometer oxide zirconium powder body, be specially a kind of preparation work of nano zirconium oxide powder.
Background technology
Zirconium white is due to essential propertys such as its intrinsic chemical composition and crystalline structure, thereby has the advantages such as chemical stability is good, heat-conduction coefficient is little, hardness is large, is a kind of important structure and function stupalith.Common zirconium white exists with monoclinic phase at normal temperature to 1170 ℃, changes Tetragonal while being heated to 1170 ℃-2370 ℃ into, when more than 2370 ℃, by tetragonal phase converting, becomes Emission in Cubic (2700 ℃ of left and right meltings).Because the high-temperature-phase (Emission in Cubic or Tetragonal) of pure zirconia is along with the reduction of temperature can be transformed into low-temperature phase (monoclinic phase), obtain high-temperature-phase zirconium white stable under room temperature, some other oxide compound just need to adulterate in zirconium white, as yttrium oxide, calcium oxide, magnesium oxide, Scium trioxide etc., form composite oxides.Partially stabilized or the complete stable zirconium white of the Tetragonal of this doping transformation toughening and tiny crack toughness reinforcing aspect excellent property, there is high room temperature strength and fracture toughness property.Research in recent years shows, with the tetragonal phase zirconium oxide (Y-TZP) of stabilized with yttrium oxide when crystal size is controlled at nano level (being less than 100nm), may bring the sudden change of material property, as significantly improving of the strength of materials and fracture toughness property, realize superplasticity under normal temperature etc.Meanwhile, the zirconium white of stabilized with yttrium oxide or a kind of good gas sensitive (for oxygen sensor) and solid state battery material, be one of focus of current Material Field research.Utilizing the character of nano zirconium oxide powder, work out mechanical property better or possess matrix material and the functional materials of some specific function, be applied to different fields, is the final purpose of preparing Zirconium powder research work.One of main prerequisite that improves zircite product performance is requirement crystal size tiny (nano level), the even particle size distribution of preparing Zirconium powder, purity is high, reunions is few, and the cost of preparing low, be easy to suitability for industrialized production.
Prepare at present the technique of nano zirconium oxide powder and divide liquid phase method and vapor phase process.Wherein liquid phase method has coprecipitation method, hydrothermal method, sol-gel method, microemulsion method etc.These techniques respectively have its feature, but also exist a lot of not enough.As coprecipitation method, be containing adding precipitation agent in the solution of zirconates (as zirconium oxychloride, zirconium sulfate, zirconium carbonate acyl etc.), obtain precipitation of hydroxide, more after filtration, washing, dehydration, dry, calcination, obtain Zirconium powder.This technique is relatively simple, can make that granularity is little, the more manageable multicomponent nanocomposite powder of composition, and JP96000698 has the report of this respect.Weak point is that the powder making often exists more hard agglomeration, affects sintering temperature and the mechanical property of goods.CN1253120A be take zirconium oxychloride as raw material, in order to solve the agglomeration traits of powder, adopts the technique that adds dispersion agent and control temperature ageing in ethanol, has prepared low sintering nano zirconium oxide powder.Hydrothermal method is prepared nano zircite, and generally to take the inorganic or organic compound of zirconium be raw material, can make that particle diameter is little, the powder of high dispersive, and CN1253119A has introduced the technique that hydrothermal method is prepared nano zircite colloidal sol.The weak point of hydrothermal method is that preparation condition is harsher, and cost is higher, and output is lower.Sol-gel method and alkoxide hydrolysis are used the organic compound of zirconium, exist equally raw material sources difficulty, and price is higher, and hydrolysis method long reaction time, productive rate be too low, be difficult to the defects such as suitability for industrialized production.Vapor phase process is produced nano zirconium oxide powder, and products therefrom is better dispersed, can continuous production.But vapor phase process is suitable for, do not prepare multicomponent mixture oxide powder, and the controllability of component is also relatively poor, the cost of material using is higher, and output is lower.As CN1259488A, take zirconium tetrachloride as raw material, in high-temperature reactor, mix, be hydrolyzed with water vapour, prepare nano zirconium oxide powder.But, obtain the stable Zirconium powder of Tetragonal by this technique, also need the pure zirconia powder that vapor phase process is obtained to immerse in metal salt solution, evaporation, dry, calcination.
Summary of the invention
Technical problem solved by the invention is to provide a kind of preparation technology of nano zirconium oxide powder, to solve the problem in above-mentioned background technology.
Technical scheme of the present invention is: a kind of preparation technology of nano zirconium oxide powder, containing in the aqueous solution of zirconates, adding alkaline precipitating agent, obtain precipitation of hydroxide, washing more after filtration,, dehydration, dry, satin burning, obtain Zirconium powder, adopt the colloidal solution after azeotropic distn dehydration dry in water distilling apparatus, dehydration and constantly stirring when dry.This scheme can overcome oneself has technology to dry with baking oven or microwave oven, and when sediment separate out and alcohol, what when fractional dose is large, the alcohol of evaporation caused catches fire and explode.Meanwhile, can reduce operation steps and program.Thereby can carry out large batch of suitability for industrialized production, at least can produce more than 10 kilograms for every batch.
The preparation technology of described nano zirconium oxide powder, first adding alcohol containing in the aqueous solution of zirconates, mixes rear horse back and adds alkaline precipitating agent.With this alcohol dispersing method, can make the agglomeration of precipitation improve, and save time, enhance productivity.
The preparation technology of described nano zirconium oxide powder, containing the aqueous solution of zirconates, be, selecting cheap zircon sand is raw material, adopt caustic alkali melting method through roasting, embathe, leaching, purging by crystallization and obtain.With zircon sand, be that raw material is directly produced the precursor solution containing zirconium ion, be that the precursor solution that waste contains zirconium ion is compared with zirconium oxychloride by crystal state or other zirconates, can save the step that makes zirconates crystal state, and from crystal state, be returned as again the step of solion state.
The preparation technology of described nano zirconium oxide powder, the satin after powder for drying burns temperature at 650-1000 ℃.Be conducive to like this remove completely the organism in powder, can improve the purity of product.
The preparation technology of described nano zirconium oxide powder, alcohol used is butanols, Virahol, primary isoamyl alcohol, propyl alcohol, glycol ether, ethylene glycol, ethanol.
The preparation technology of described nano zirconium oxide powder, containing adding after crystal phase stablizer in the aqueous solution of zirconates, then add alkaline precipitating agent.Can obtain Tetragonal crystal stable under normal temperature.Described stablizer can be yttrium oxide, calcium oxide, magnesium oxide etc.
The preparation technology of nano zirconium oxide powder of the present invention, the zircon sand of take is exemplified below as raw material: adopt sodium hydroxide to mix with zircon sand fine ore, roasting, the six side's phase sodium zirconates that zirconium silicate are converted into can be decomposed by hydrochloric acid, burn till material and wash the impurity such as divided silicon, aluminium, sodium with water, use again dissolving with hydrochloric acid, through condensing crystal separation of iron, calcium, the impurity such as admire, with oxyethane (or polyacrylamide) secondary silica removal, with ketone or amine extractant extraction iron, prepare the precursor solution of highly purified zirconium.This solution be directly used in prepare monoclinic phase, Tetragonal is partially stabilized or full stabilized nanoscale Zirconium powder.Prepare the partially stabilized or full stabilized nanoscale zirconium white of Tetragonal, adopt the method for other oxide stabilizer of doping (yttrium oxide, calcium oxide, magnesium oxide etc.), as dissolving with hydrochloric acid yttrium oxide for (or Yttrium trinitrate is water-soluble) mixes with zirconium solution afterwards.PH value with ammoniacal liquor regulator solution under strong stirring makes zirconium and yttrium form oxyhydroxide co-precipitation, washes precipitation with water.Precipitation of hydroxide is mixed with alcohol, in high temperature dehydration moisture eliminator, under certain temperature, dewater, calcination, obtains nano zirconium oxide powder.This preparation technology adopts azeotropic distn dehydration, utilize alcohol oxygen based structures and the hydrophobic grouping of alcohol molecule, make it to replace the water molecules in hydroxide colloid, before powder for drying, all remove water molecules wherein, greatly reduce powder at the agglomeration of calcination stage, the nano zirconium oxide powder high dispersing, the agglomeration that obtain are little, have very large specific surface area and sintering activity.
This preparation technology's gordian technique is, colloidal solution after dehydration is dry in water distilling apparatus, dehydration and constantly stirring when dry, and this technology can overcome for prior art baking oven or microwave oven is dried, when sediment separate out and alcohol, what when fractional dose is large, the alcohol of evaporation caused catches fire and explodes.Meanwhile, can reduce operation steps and program.Thereby can carry out large batch of upper industryization and produce, at least can produce more than 10 kilograms for every batch.
What described preparation technology gave an example is described below step by step:
1. zircon sand decomposes: zircon sand fine ore is mixed to 650-800 ℃ of pyrolytic decomposition 1.5-3 hour in High Temperature Furnaces Heating Apparatus by 1:1.2-1.6 (weight ratio) with sodium hydroxide.
2. the preparation of zirconium precursor liquid solution: degradation production is through repeatedly washing, filter, separating impurity.Material after water washing, through dissolving with hydrochloric acid, is controlled salt acidacidity 2.5-4.0 mol/L, and adding polyethylene oxide (or polyacrylamide) to make its concentration is 0.1-0.3 grams per liter, precipitation separation, and cooling solution makes zirconium with ZrOCl
2form crystallization.Adopt the method for polyethylene oxide (or polyacrylamide) secondary silica removal and ketone or amine extractant extraction iron to be further purified.ZrOCl
2the water-soluble precursor solution that obtains zirconium.In solution, the concentration of zirconium ion is controlled between 0.2-1.0 mol/L.
3. precipitate: in the zirconium solution of preparation, add a certain amount of yttrium solution (controlling the doping of yttrium oxide in Zirconium powder is 2-8mo1%), and a certain amount of alcohol.Add again ammoniacal liquor, with ammonia neutralization, generate precipitation of hydroxide.PH value in precipitation process is controlled between 9-11, and strong stirring, to guarantee ruthenium ion precipitation completely and evenly to mix with zirconium hydroxide.
4. solid-liquid separation and washing: precipitation of hydroxide, through centrifugal or press filtration and liquid separation, adopts distilled water wash precipitation, to remove foreign ion wherein.
5. dehydration: the precipitation of hydroxide after washing mixes with alcohol, with milling treatment of colloid mixture or strong stirring.The add-on of alcohol is 2.0-5.0:1 with respect to the weight ratio of precipitation of hydroxide.Alcohol herein can be butanols, Virahol, primary isoamyl alcohol, propyl alcohol, glycol ether, ethylene glycol, ethanol.Wherein preferentially adopt butanols and Virahol.The mixture of oxyhydroxide and alcohol is placed in to distillation dehydration drying installation, and heating process temperature is controlled at (alcohol water azeotropic point temperature) between 70 ℃-180 ℃, to guarantee completing of reaction, the water in precipitation of hydroxide is all removed.
6. dry: after planar water is removed completely, rising temperature is evaporated alcohol and collected.Convection drying powder in distillation dehydration drying installation, the time is 1-5 hour.In drying process, constantly stir, make powder drying temperature even.
7. calcination: control calcination temperature between 450-1000 ℃ according to the granularity of required powder, the time is 1-5 hour.The object of calcination is that the dry powder crystallization obtaining is become to crystalline oxide.
Beneficial effect:
1. the reaction times is short.Take zirconium oxychloride as raw material, and the time that makes nano zirconium oxide powder is no more than 6 hours, take zircon sand as raw material, and the time that makes nano zirconium oxide powder is no more than 20 hours;
2. drying treatment amount is large, safe, can suitability for industrialized production; When in enormous quantities dry, isolated alcohol can not catch fire and explode, thus can tens, being dried of hundreds of kilogram;
3. flow process is few, and equipment is simple, and processing parameter is easy to control, and is easy to large-scale industrial production;
4. adopt alcohol to disperse and azeotropic distn dewatering process, reduced the agglomeration of powder, gained powder granularity is little, be evenly distributed, pattern is regular, it is less to reunite;
5. the zirconium white of preparation has large specific surface area;
6. the oxide stabilizer of doping can suppress the grain growth in calcination process effectively.
After the powder drying that adopts above technique to prepare, be loose shape, the granularity of the Zirconium powder after calcination can be as small as several nanometer to tens nanometers, the less and hard aggregation-free body of reuniting.
Accompanying drawing explanation
Fig. 1 is the TEM photo of embodiments of the invention 2 powders.
Fig. 2 is the TEM photo of embodiments of the invention 3 powders.
Embodiment
In order to make technique means of the present invention, creation characteristic, workflow, operation reach object and effect is easy to understand, enumerate following specific embodiment.
EXAMPLE l
30 kilograms of zirconium oxychlorides getting lenticular are water-soluble, and making zirconium ion concentration in the aqueous solution is 0.2 mol/L, adds the solution of 0.1 mol/L, and controlling the doping of oxidation in Zirconium powder is 3mol.Add a certain amount of alcohol, under strong stirring, drip 50% ammoniacal liquor (volume ratio), until pH is greater than 9.The separated precipitation of hydroxide of press filtration, distilled water wash precipitates until can't detect chlorion (Silver Nitrate check).
Precipitation of hydroxide is mixed with the butanols (weight ratio) of 2 times, with milling treatment of colloid or strong stirring.Be placed in distillation dehydration drying installation, in 150 ℃ of dehydrations, until powder complete drying, in High Temperature Furnaces Heating Apparatus, 400 ℃ of calcination powders are 4 hours.By BET method, measure the specific surface area of powder, the granularity of transmissioning electric mirror determining powder, size-grade distribution and crystal morphology, the crystalline structure of X ray powder crystal diffraction powder and the mean particle size of primary particle.Result is as shown in table 1.
Table 1 embodiment 1 obtains the test data of nano zirconium oxide powder
| Morphology microstructure | Tetragonal proportion/% | Monoclinic phase proportion/% | Primary particle mean particle size/nm | Specific surface area (BET)/m 2/g |
| Sub-circular | 95 | 5 | 5.6 | 135.2 |
Embodiment 2
Get 1000 grams of zircon sand fine ores and mix with 1400 grams of sodium hydroxide, in corundum ware in High Temperature Furnaces Heating Apparatus 700 ℃ decompose 1.5 hours.Degradation production, through washing, dissolving with hydrochloric acid, silica removal, iron, aluminium, sodium etc., is prepared into 4 liters of solution.Mandelic acid gravimetric determination wherein in the precursor solution of zirconium zirconic concentration be 0.915 mol/L, in zircon sand, the zirconic rate of recovery is 69.4%.In the precursor solution of zirconium, add a certain amount of alcohol, under strong stirring, drip 50% ammoniacal liquor (volume ratio), until pH is for being greater than 9.Centrifugation precipitation of hydroxide, distilled water wash precipitates until can't detect chlorion (Silver Nitrate check).
Precipitation of hydroxide is mixed with the butanols (weight ratio) of 3 times, use milling treatment of colloid.Be placed in distillation drying and dehydrating device, in 150 ℃ of dehydrations, until powder complete drying, in High Temperature Furnaces Heating Apparatus, 650 ℃ of calcination powders are 2 hours.By BET method, measure the specific surface area of powder, the granularity of transmissioning electric mirror determining powder, size-grade distribution and crystal morphology, the crystalline structure of X ray powder crystal diffraction powder and the mean particle size of primary particle.Result is as shown in table 2.Transmission electron microscope photo is shown in Fig. 2
Table 2 embodiment 2 obtains the test data of nano zirconium oxide powder
| Morphology microstructure | Tetragonal proportion/% | Monoclinic phase proportion/% | Primary particle mean particle size/nm | Specific surface area (BET)/m 2/g |
| Sub-circular | 3 | 97 | 10.0 | 90.1 |
Embodiment 3
By the technique in embodiment 2, prepare hydroxide colloid precipitation (doping of oxidation in Zirconium powder is 6mol%).Precipitation of hydroxide is mixed with the ethanol (weight ratio) of 2 times, and strong stirring.Centrifugation, with the same ethanol repeated washing of measuring once, then centrifugation.Be placed in distillation drying and dehydrating device, in 100 ℃ of dehydrations, until powder complete drying, in High Temperature Furnaces Heating Apparatus, 500 ℃ of calcination powders are 3 hours.By BET method, measure the specific surface area of powder, the granularity of transmissioning electric mirror determining powder, size-grade distribution and crystal morphology, the crystalline structure of X ray powder crystal diffraction powder and the mean particle size of primary particle.
Result is as shown in table 3, and transmission electron microscope is shown in Fig. 2.
Table 3 embodiment 3 obtains the test data of nano zirconium oxide powder
| Morphology microstructure | Tetragonal proportion/% | Monoclinic phase proportion/% | Primary particle mean particle size/nm | Specific surface area (BET)/m 2/g |
| Sub-circular | 100 | 0 | 7.5 | 110.2 |
Embodiment 4
By the technique in embodiment 2, prepare hydroxide colloid precipitation (doping of yttrium oxide in Zirconium powder is 8mol%).Precipitation of hydroxide is mixed with the butanols (weight ratio) of 4 times, and strong stirring.Centrifugation, with the same butanols repeated washing of measuring once.Be placed in distillation drying and dehydrating device, in 120 ℃ of dehydrations, until powder complete drying, in High Temperature Furnaces Heating Apparatus, 1000 ℃ of calcination powders are 2 hours.The granularity of transmissioning electric mirror determining powder is 43nm, and the crystalline structure of X ray powder crystal diffraction powder is Tetragonal.Purity is that zirconium white (hafnium, yttrium) is greater than 99. 9 %.
The protection domain of present patent application is not subject to above-mentioned restriction of giving an example.The nano zirconium oxide powder of being prepared by the disclosed technique of present patent application has good performance, thereby has in many aspects important application.For example, utilize its granularity tiny, reunite few, 300 ℃ of left and right of sintering temperature that can reduce ceramic.Utilize its high strength, high rigidity and toughness, for making sintex, bearing, valve, abrasive material.Utilize low, the high temperature resistant and wear resistance of its heat-conduction coefficient, for the spraying of plasma body ceramic layer and the high-temperature fuel gas turbine components material of cylinder sleeve of engine.Due to the superplasticity that nanometer zirconium oxide ceramic occurs, being desirably in easily processing aspect of ceramic has important application.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. the preparation technology of a nano zirconium oxide powder, containing in the aqueous solution of zirconates, adding alkaline precipitating agent, obtain precipitation of hydroxide, washing more after filtration,, dehydration, dry, calcination, obtain Zirconium powder, it is characterized in that adopting the colloidal solution after azeotropic distn dehydration dry in water distilling apparatus, dehydration and constantly stirring when dry.
2. the preparation technology of a kind of nano zirconium oxide powder according to claim 1, is characterized in that, first adding alcohol containing in the aqueous solution of zirconates, mixing rear horse back and adding alkaline precipitating agent.
3. the preparation technology of a kind of nano zirconium oxide powder according to claim 1 and 2, is characterized in that containing the aqueous solution of zirconates being, selecting cheap zircon sand is raw material, adopt caustic alkali melting method through roasting, embathe, leaching, purging by crystallization and obtain.
4. the preparation technology of a kind of nano zirconium oxide powder according to claim 1 and 2, is characterized in that calcination temperature after powder for drying is at 650 ℃-1000 ℃.
5. the preparation technology of a kind of nano zirconium oxide powder according to claim 1 and 2, is characterized in that alcohol used is butanols, Virahol, primary isoamyl alcohol, propyl alcohol, glycol ether, ethylene glycol, ethanol.
6. the preparation technology of a kind of nano zirconium oxide powder according to claim 1 and 2, is characterized in that adding after crystal phase stablizer containing in the aqueous solution of zirconates, then adds alkaline precipitating agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210286093.XA CN103588246A (en) | 2012-08-13 | 2012-08-13 | Preparation process for nano zirconia powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210286093.XA CN103588246A (en) | 2012-08-13 | 2012-08-13 | Preparation process for nano zirconia powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103588246A true CN103588246A (en) | 2014-02-19 |
Family
ID=50078613
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210286093.XA Pending CN103588246A (en) | 2012-08-13 | 2012-08-13 | Preparation process for nano zirconia powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103588246A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922399A (en) * | 2014-03-27 | 2014-07-16 | 中国船舶重工集团公司第七二五研究所 | Preparation method of zirconium oxide nanospheres |
| CN105712399A (en) * | 2016-01-20 | 2016-06-29 | 淄博晶泽光学材料科技有限公司 | Method for preparing zirconium dioxide polishing powder |
| CN105753047A (en) * | 2016-04-21 | 2016-07-13 | 常州大学 | Novel method of preparing nano zirconium oxide powder for dentistry |
| CN105923651A (en) * | 2016-04-21 | 2016-09-07 | 常州大学 | New method for preparing dental colored nano zirconium oxide powder |
| CN106698510A (en) * | 2016-12-20 | 2017-05-24 | Tcl集团股份有限公司 | Doped ZrO2 and preparation method, and QLED device and preparation method |
| CN106986381A (en) * | 2017-05-10 | 2017-07-28 | 国标（北京）检验认证有限公司 | A kind of loose preparation method containing zirconium hydroxide or nm-class powder of zirconium oxide |
| CN108997010A (en) * | 2018-10-06 | 2018-12-14 | 景德镇陶瓷大学 | A kind of zero-emission oxide ceramic powder body preparation method and its production system |
| CN116063081A (en) * | 2023-02-16 | 2023-05-05 | 西北工业大学 | ZrO synthesis by sol-gel method 2 Coated ZrB 2 Preparation method of particle composite powder |
-
2012
- 2012-08-13 CN CN201210286093.XA patent/CN103588246A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922399A (en) * | 2014-03-27 | 2014-07-16 | 中国船舶重工集团公司第七二五研究所 | Preparation method of zirconium oxide nanospheres |
| CN103922399B (en) * | 2014-03-27 | 2016-01-20 | 中国船舶重工集团公司第七二五研究所 | A kind of preparation method of zirconia nanopowder ball |
| CN105712399A (en) * | 2016-01-20 | 2016-06-29 | 淄博晶泽光学材料科技有限公司 | Method for preparing zirconium dioxide polishing powder |
| CN105753047A (en) * | 2016-04-21 | 2016-07-13 | 常州大学 | Novel method of preparing nano zirconium oxide powder for dentistry |
| CN105923651A (en) * | 2016-04-21 | 2016-09-07 | 常州大学 | New method for preparing dental colored nano zirconium oxide powder |
| CN105753047B (en) * | 2016-04-21 | 2018-05-01 | 常州大学 | A kind of new method for preparing dental nano zirconium oxide powder |
| CN106698510A (en) * | 2016-12-20 | 2017-05-24 | Tcl集团股份有限公司 | Doped ZrO2 and preparation method, and QLED device and preparation method |
| CN106698510B (en) * | 2016-12-20 | 2019-11-12 | Tcl集团股份有限公司 | Adulterate ZrO2And preparation method, QLED device and preparation method |
| CN106986381A (en) * | 2017-05-10 | 2017-07-28 | 国标（北京）检验认证有限公司 | A kind of loose preparation method containing zirconium hydroxide or nm-class powder of zirconium oxide |
| CN108997010A (en) * | 2018-10-06 | 2018-12-14 | 景德镇陶瓷大学 | A kind of zero-emission oxide ceramic powder body preparation method and its production system |
| CN116063081A (en) * | 2023-02-16 | 2023-05-05 | 西北工业大学 | ZrO synthesis by sol-gel method 2 Coated ZrB 2 Preparation method of particle composite powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103588246A (en) | Preparation process for nano zirconia powder | |
| Manivasakan et al. | Synthesis of monoclinic and cubic ZrO2 nanoparticles from zircon | |
| CN100503450C (en) | Method for preparing powder of zirconium oxide in high purity | |
| CN102757222B (en) | Composite stable microcrystal zirconium oxide ceramic mixed powder and manufacturing process | |
| CN101973578A (en) | Water-based sol-gel method for preparing high-purity monodisperse barium titanate nanopowder | |
| CN112745105B (en) | High-sintering-activity alumina ceramic powder and preparation method thereof | |
| CN109721357A (en) | A kind of Zirconium oxide powder and its preparation method and application that the nanometer yttrium that monodisperse granularity is controllable is stable | |
| CN103058278A (en) | Preparation method of tin antimony oxide nano-powder | |
| CN108557883B (en) | Preparation method of nano antimony trioxide | |
| CN106830051A (en) | A kind of method for preparing nanometer Zinc oxide powder as raw material with industrial zinc oxide | |
| CN1168785C (en) | Process for preparing nano zirconium oxide powder | |
| JP6149039B2 (en) | Ultrafine titanium dioxide and method for producing the same | |
| CN105129834B (en) | A kind of nanometer level RE oxide raw powder's production technology | |
| CN108706618A (en) | Utilize the method for micro-emulsion method for preparing nano aluminium oxide | |
| CN108609652A (en) | A method of preparing Zirconium dioxide nano powder using fused salt | |
| CN108083334A (en) | A kind of preparation method of monodisperse spherical nano zirconium dioxide powder body material | |
| CN112573570A (en) | Scandium-cerium-doped zirconium oxide superfine powder and preparation method thereof | |
| Zhang et al. | CTAB-assisted hydrothermal synthesis of nano-sized tetragonal zirconium dioxide | |
| Khomane et al. | Synthesis and characterization of lithium aluminate nanoparticles | |
| CN107445202B (en) | A kind of small size, super-dispersed nano zirconium oxide base coating raw powder's production technology | |
| WO2001000530A1 (en) | Processing aqueous titanium solutions to titanium dioxide pigment | |
| CN105819517A (en) | Method for preparing iron oxide red from coal ash | |
| CN104528824B (en) | A kind of produce Zirconium powder and the method for ammonium salt and product simultaneously | |
| CN103708549B (en) | Nano level ZrO 2the preparation method of powder | |
| CN108083332A (en) | It is a kind of to be given up the method that zirconium prepares zirconium oxide with solid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140219 |