CN1214986C - Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate - Google Patents
Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate Download PDFInfo
- Publication number
- CN1214986C CN1214986C CN 03109840 CN03109840A CN1214986C CN 1214986 C CN1214986 C CN 1214986C CN 03109840 CN03109840 CN 03109840 CN 03109840 A CN03109840 A CN 03109840A CN 1214986 C CN1214986 C CN 1214986C
- Authority
- CN
- China
- Prior art keywords
- zirconium dioxide
- carbon nano
- powder
- zirconium
- zirconyl nitrate
- 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.)
- Expired - Fee Related
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 63
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 title claims abstract description 20
- 230000003301 hydrolyzing effect Effects 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 32
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 12
- 239000011858 nanopowder Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000005496 tempering Methods 0.000 claims description 4
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- HYYSOWPMTGSPEQ-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Zr+4] Chemical compound [C+4].[O-2].[O-2].[Zr+4] HYYSOWPMTGSPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 230000033444 hydroxylation Effects 0.000 claims description 3
- 238000005805 hydroxylation reaction Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 238000010992 reflux Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- 239000003985 ceramic capacitor Substances 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 abstract 1
- 239000003758 nuclear fuel Substances 0.000 abstract 1
- 239000005304 optical glass Substances 0.000 abstract 1
- 239000007784 solid electrolyte Substances 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 22
- 239000002105 nanoparticle Substances 0.000 description 9
- 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 7
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 150000003754 zirconium Chemical class 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910021512 zirconium (IV) hydroxide Inorganic materials 0.000 description 1
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention discloses a technology for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate, which belongs to the technical field of chemical raw materials and nuclear fuel preparing technologies. Carbon nanotubes are added in a water solution of concentrated zirconium oxynitrate, and after the processes of refluxing, drying and sintering, 7 to 20 nanometers of zirconium dioxide nanometer powder is obtained. The technology for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate has the advantages of simple technology and filtration saving, and stable cubic phases can be obtained under low temperature by a washing process. The obtained zirconium dioxide nanometer powder can be widely used for fabricating piezoelectric elements, ceramic capacitors, gas sensitive elements, solid electrolyte batteries, ceramic engines of internal combustion engines, optical glass, zirconium dioxide fibers, zirconium catalysts, etc.
Description
Technical Field
The invention belongs to the technical field of chemical raw material preparation, and particularly relates to a process for preparing zirconium dioxide nano powder by hydrolyzing zirconyl nitrate.
Background
Zirconium dioxide has excellent heat resistance, corrosion resistance and plasticity, and is an important basic raw material in the field of new materials. The superfine zirconium dioxide powder with high purity, superfine performance and uniform dispersion performance can be used as a raw material for preparing toughened ceramics with high strength, high toughness and excellent plasticity. By utilizing the semiconductor oxide characteristics of zirconium dioxide in oxygen atmosphere, the superfine powder of zirconium dioxide can also be used for manufacturing functional ceramic materials such as chemical sensors and the like. The superfine zirconia powder is one kind of catalyst carrier with excellent application foreground and has special active phase action and chemical property higher than that of gamma-Al carrier2O3Silica gel is more inert, and has both acidity and alkalinity and oxidation-reduction property, and the prepared catalyst has outstanding activity and selectivity.
Zirconium dioxide has different crystalline phases in different temperature ranges, is monoclinic at room temperature, starts to appear tetragonal phase when the temperature is raised to over 1000 ℃, and gradually takes the tetragonal phase as the main phase, and is transformed into cubic phase at over 2300 ℃. When the temperature of the sample is lowered, since the cubic phase and the tetragonal phase are metastable at room temperature, a phase transition occurs from the cubic phase or the tetragonal phase to a monoclinic phase. Zirconium dioxide of different structures has different properties, and also volume expansion occurs during phase transformation due to the high density of the cubic phase compared to the tetragonal phase, and thus it is necessary to control the crystal phase of zirconium oxide.
The zirconium dioxide ultrafine powder is prepared by a liquid phase synthesis method such as a precipitation method, a sol-gel method, a hydrothermal synthesis method, a microemulsion method, a vapor phase hydrolysis method, or a cracking method of an organic compound. Wherein the hydrolysis precipitation method is carried out by boiling the zirconium salt solution for a long timeLiquid, volatile acid HCl or HNO generated by hydrolysis3The evaporation is continued and the hydrolysis equilibrium is shifted to the right as follows:
filtering, washing, drying and calcining to obtain ZrO2And (3) powder. The process flow is as follows:
the zirconium salt solution is hydrolyzed, precipitated (boiling for 48 hours at 100 ℃), filtered, washed and dried (100-120℃)ZrO) is calcined (700-900 ℃) to obtain ZrO2Powder of which ZrOCl2The concentration is controlled to be 0.2-0.3 mol/L. The method has the advantages of simple operation and the disadvantages of long reaction time (more than48 hours), large energy consumption and agglomeration of the obtained powder. See literature: huangyuexing et al, characteristics of hydrous zirconia gels prepared by different processes, silicates bulletin, 1993, 5: 32 to 37; the patent: kato, Etsu (Nissan chemical industries Ltd.). Powder of synthetic resinous particles and processes for producing the m, United States Patent: 4,873,064, respectively; the methods of the present invention include, but are not limited to, the methods of the present invention, Obitsuet (Nissan Chemical Industries Ltd.). Process for manufacturing a Finezierium oxide powder, United States Patent: 4,985,229.
Disclosure of Invention
The invention aims to provide a process for preparing zirconium dioxide nano powder by hydrolyzing zirconyl nitrate, which is characterized by comprising the following steps: adding carbon nano tubes into a concentrated zirconyl nitrate aqueous solution, heating and boiling, utilizing hydroxylation of nitric acid on the surfaces of the carbon nano tubes to stably suspend the carbon nano tubes in the solution, promoting the zirconyl nitrate solution to hydrolyze to obtain zirconium hydroxide attached to the carbon nano tubes on the hydroxylated surfaces, drying and roasting to obtain zirconium dioxide-carbon nano tube composite powder, and controlling sintering atmosphere to obtain zirconium dioxide nano powder with different structures; the process comprises the following steps:
(1) adding carbon nano tubes into the zirconyl nitrate solution with the concentration of 0.2mol/L to 1mol/L, wherein the mass ratio of the carbon nano tubes to the zirconyl nitrate converted into zirconia is 1: 1-1: 20, and adjusting the mass ratio of the carbon nano tubes to the zirconyl nitrate to control the particle size of the produced zirconia;
(2) the mixed solution is refluxed and boiled for 2 to 5 hours, or directly heated and boiled for 45 minutes to 2 hours, and then dried at the temperature of 100 ℃ and 140 ℃;
(3) calcining for 2 hours at the temperature of 450-700 ℃ under the protective atmosphere, or introducing oxygen to remove carbon, and tempering for 2 hours at the temperature of 600-700 ℃ in the air after sintering to obtain the zirconium dioxide nano powder with different structures.
The invention has the beneficial effects that: the agglomeration phenomenon of the nano powder is solved, the reaction time is shortened, and the process flow is simplified. Meanwhile, the phase structure of the nano zirconium dioxide can be controlled. The process is simple, the boiling time is short, and the operability is strong; because the raw material is zirconyl nitrate, the residue of the zirconyl nitrate can be decomposed to generate zirconia, and no other raw material is introduced in the process, and the filtering and washing are not needed; the carbon nano tube is introduced, so that the agglomeration of particles can be effectively prevented; carbon enters the zirconia in the sintering process, and a stable cubic phase can be obtained at low temperature; the zirconium oxide with different structures can be obtained by changing the process parameters.
Drawings
Fig. 1 shows the surface morphology (TEM) of the zirconia nanoparticles obtained in example 1.
Fig. 2 is the surface morphology (TEM) of the zirconia nanoparticles obtained in example 2.
FIG. 3 shows the sintering of the single crystals of the zirconia nanoparticles of example 2 into a network structure.
FIG. 4 shows the surface morphology of the powder of example 3 consisting of zirconia nanoparticles and carbon nanotubes.
Detailed Description
The invention relates to a process for preparing zirconium dioxide nano powder by hydrolyzing zirconyl nitrate. Adding carbon nano tubes into a concentrated aqueous solution of zirconyl nitrate, heating and boiling, utilizing hydroxylation of nitric acid on the surface of the carbon nano tubes to stably suspend the carbon nano tubes in the solution, promoting the zirconyl nitrate solution to hydrolyze to obtain zirconium hydroxide attached to the carbon nano tubes on the hydroxylated surface, drying and roasting to obtain zirconium dioxide-carbon nano tube composite powder, and controlling sintering atmosphere to obtain zirconium dioxide nano powder with different structures. The process comprises the following steps:
(1) adding carbon nano tubes into the zirconyl nitrate solution with the concentration of 0.2mol/L to 1mol/L, wherein the mass ratio of the carbon nano tubes to the zirconyl nitrate converted into zirconia is 1: 1-1: 20; the mass ratio of the carbon nano tube to the zirconium oxynitrate is adjusted to control the particle size of the generated zirconium oxide.
(2) The mixed solution is refluxed and boiled for 2 to 5 hours or directly heated and boiled for 45 minutes to 2 hours, and then dried at 100 ℃ and 140 ℃.
(3) Calcining for 2 hours at the temperature of 450-700 ℃ under the protective atmosphere, or introducing oxygen to remove carbon, and tempering for 2 hours at the temperature of 600-700 ℃ in the air after sintering to obtain the zirconium dioxide nano powder with different structures.
The following is illustrated by way of example:
example 1: ZrO (NO)3)2·2H2Preparing 0.3mol/L solution from O, adding 0.3g of carbon nano tube into 50ml of the solution, refluxing and boiling the mixed solution for 3 hours, and drying; adding 20ml of water, directly heating and boiling for 1 hour twice, drying, grinding the dried sample, then roasting in Ar atmosphere, heating to 600 ℃ and roasting for 2 hours to obtain zirconia nano particles with the size of 7-10 nanometers, wherein the zirconia structure is a cubic phase structure. Its zirconium oxide sodiumThe TEM surface morphology of the rice particles is shown in fig. 1.
Example 2: ZrO (NO)3)2·2H2Preparing 0.5mol/L solution from O, adding 0.3g of carbon nano tube into 50ml of the solution, refluxing and boiling the mixed solution for 4 hours, and drying; adding 20ml of water, directly heating and boiling for 1 hour twice, drying, grinding the dried sample, and then roasting for 2 hours at 600 ℃ under Ar atmosphere to obtain the cubic phase structure zirconium oxide nano powder. Heating the obtained powder in air to 690 ℃, and carrying out tempering and roasting for 2 hours to obtain the nano zirconia with a tetragonal porous structure and a particle size of 7-12 nanometers. Zirconia nanoparticles thereofThe TEM surface morphology of the particles is shown in fig. 2; fig. 3 shows a TEM image of a network structure inter-single-crystal sintered with zirconia nanoparticles.
Example 3: ZrO (NO)3)2·2H2Preparing 1mol/L solution from O, adding 0.5g of carbon nano tube into 20ml of the solution, directly heating and boiling the mixed solution for 45 minutes (without reflux boiling), drying, grinding the dried sample, then baking under Ar atmosphere, and heating to 450 ℃ for 2 hours. The obtained nano particles have the size of 15-20 nanometers, and because the particles have large size, the diffusion of carbon atoms does not occur at 450 ℃, and the zirconia structure is a mixed structure of a tetragonal phase and a monoclinic phase. Fig. 4 shows the surface morphology of the powder composed of zirconia nanoparticles and carbon nanotubes, in which the bright lines are carbon nanotubes.
Claims (1)
1. A process for preparing zirconium dioxide nano powder by hydrolyzing zirconyl nitrate is characterized in that: adding carbon nano tubes into a concentrated zirconyl nitrate aqueous solution, heating and boiling, utilizing hydroxylation of nitric acid on the surfaces of the carbon nano tubes to stably suspend the carbon nano tubes in the solution, promoting the zirconyl nitrate solution to hydrolyze to obtain zirconium hydroxide attached to the carbon nano tubes on the hydroxylated surfaces, drying and roasting to obtain zirconium dioxide-carbon nano tube composite powder, and controlling sintering atmosphere to obtain zirconium dioxide nano powder with different structures; the process comprises the following steps:
(1) adding carbon nano tubes into the zirconyl nitrate solution with the concentration of 0.2mol/L to 1mol/L, wherein the mass ratio of the carbon nano tubes to the zirconyl nitrate converted into zirconia is 1: 1-1: 20, and adjusting the mass ratio of the carbon nano tubes to the zirconyl nitrate to control the particle size of the produced zirconia;
(2) the mixed solution is refluxed and boiled for 2 to 5 hours, or directly heated and boiled for 45 minutes to 2 hours, and then dried at the temperature of 100 ℃ and 140 ℃;
(3) calcining for 2 hours at the temperature of 450-700 ℃ under the protective atmosphere, or introducing oxygen to remove carbon, and tempering for 2 hours at the temperature of 600-700 ℃ in the air after sintering to obtain the zirconium dioxide nano powder with different structures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03109840 CN1214986C (en) | 2003-04-15 | 2003-04-15 | Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03109840 CN1214986C (en) | 2003-04-15 | 2003-04-15 | Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1482065A CN1482065A (en) | 2004-03-17 |
| CN1214986C true CN1214986C (en) | 2005-08-17 |
Family
ID=34152357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03109840 Expired - Fee Related CN1214986C (en) | 2003-04-15 | 2003-04-15 | Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1214986C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304280C (en) * | 2004-06-25 | 2007-03-14 | 中国科学院上海硅酸盐研究所 | Cobaltosic oxide nano-crystalline coated carbon nano-tube composite powder and preparation method thereof |
| CN100404176C (en) * | 2004-12-21 | 2008-07-23 | 哈尔滨工程大学 | Preparation of zirconia superfine powder by hydrolysis method |
| CN1329291C (en) * | 2005-02-18 | 2007-08-01 | 中国科学院上海硅酸盐研究所 | Crystal phase controllable zirconium dioxide/carbon nanometer composite powder and its prepn process |
| CN101339872B (en) * | 2008-08-15 | 2011-04-06 | 西安交通大学 | Double layer mixing structure carbon nano tube membrane field emission cathode and preparation thereof |
| CN101955224B (en) * | 2009-07-20 | 2012-09-26 | 焦作市维纳精细陶瓷有限公司 | Preparation method of zirconium oxide nanotube |
| CN102173452B (en) * | 2011-03-04 | 2012-12-26 | 北京工业大学 | ZrO2 nanometer points of single material, and preparation method and application thereof |
| CN103787394B (en) * | 2012-11-01 | 2016-02-03 | 中国石油化工股份有限公司 | A kind of preparation method of aluminum oxide |
| CN107337235B (en) * | 2017-07-18 | 2018-11-23 | 中国计量大学 | A kind of multi-stage porous ZrO2The preparation method of nano-powder |
| CN108726567B (en) * | 2018-08-13 | 2020-08-18 | 上海施迈尔精密陶瓷有限公司 | Environment-friendly high-strength easily-dispersible nano zirconium oxide material |
| CN110182807A (en) * | 2019-04-23 | 2019-08-30 | 宁波中车新能源科技有限公司 | A kind of zirconium doped porous carbon material and the preparation method for preparing lithium-ion capacitor battery anode composite |
-
2003
- 2003-04-15 CN CN 03109840 patent/CN1214986C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1482065A (en) | 2004-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Self-assembly of flowerlike AlOOH (boehmite) 3D nanoarchitectures | |
| CN1214986C (en) | Process for preparing nanometer zirconium dioxide powder by hydrolyzing zirconium oxynitrate | |
| CN1094467C (en) | Nm-class compound Ce-Zr oxide and its preparing process and application | |
| US6030914A (en) | Zirconia fine powder and method for its production | |
| CN110203969A (en) | A kind of high dispersive cubic phase nano zirconium oxide and preparation method thereof | |
| CN110092414A (en) | One kind has the metal oxide materials and preparation method thereof of special microstructure | |
| CN100445209C (en) | Preparation method of new type nano-titanium dioxide powder | |
| JP4963820B2 (en) | Method for producing sol using Zr-O-based particles as dispersoid | |
| CN109399711A (en) | A kind of preparation method of rutile phase hypovanadic oxide nano-powder | |
| Hirano et al. | Hydrothermal synthesis and phase stability of new zircon-and scheelite-type ZrGeO4 | |
| CN103641165A (en) | Method for preparing titanium dioxide nanotube by using natural mineral as formwork | |
| CN1868894A (en) | Preparation method of stable zirconium oxide nanometer material doped with samarium oxide | |
| CN109865535B (en) | Metastable state cerium oxide or cerium-zirconium solid solution nano material | |
| CN113877586A (en) | Preparation method and application of morphology-controllable hierarchical cerium-iron bimetal composite oxide | |
| CN105883910A (en) | Preparation method and product for perovskite SrTiO3 porous nano particles | |
| CN1477059A (en) | Preparation method of nano alumina material | |
| CN104891559B (en) | With titanium dioxide for titanium source synthesis Li doping PbTiO3the method of nano-particle and product and application | |
| JP2004315356A (en) | Acicular titanium oxide particulate, method for manufacturing the same and application for the same | |
| CN1301933C (en) | Ammonium hydrogen coprecipitation method for preparing nano powder of yttrium aluminum garnet and transparent ceramics | |
| CN109704402A (en) | A kind of synthetic method of the ultra-fine uniform cubic zirconia nanocrystals body material of ambient-temp-stable | |
| CN1634802A (en) | Preparation of magnesia alumina spinel nanopowder by using coprecipitation method | |
| CN105692694B (en) | Ti3O5/TiO2The preparation method of mixed crystal nanofiber | |
| CN114873640A (en) | Method for preparing fibrous zirconium dioxide aerogel | |
| CN1171798C (en) | Method for synthesizing zirconium oxide nano wire | |
| CN108855041B (en) | Preparation method of cerium oxide-zirconium oxide solid solution catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |