CN108675336A - The method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave - Google Patents
The method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave Download PDFInfo
- Publication number
- CN108675336A CN108675336A CN201810781167.4A CN201810781167A CN108675336A CN 108675336 A CN108675336 A CN 108675336A CN 201810781167 A CN201810781167 A CN 201810781167A CN 108675336 A CN108675336 A CN 108675336A
- Authority
- CN
- China
- Prior art keywords
- ultrasonic wave
- microwave
- double
- rare earth
- outfields
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- 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
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention has captured a kind of method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave, specially：Using the rare-earth chlorination solution of a concentration of 0.02~0.1molL 1 as stoste, using urea as precipitating reagent, stoste and precipitating reagent are stirred evenly, obtain mixed liquor；By above-mentioned mixed liquor, microwave and the double outfield concerted reactions of ultrasonic wave are carried out, sediment is obtained；Gained sediment is subjected to heat filtering, washing, drying successively again；Then it is thermally decomposed, obtains target product.Compared with general homogeneous precipitation method, the method for the present invention, reaction speed is fast, without the hydro-thermal method of supercharging；Without adding the coating materials such as any activating agent, dispersant and template, you can obtain high purity rare earth oxides, avoid coating material and impacted to product purity.
Description
Technical field
The invention belongs to technical field of material.It is related to a kind of system of specific physical performance RE oxide powder material
Standby technology, and in particular to one kind is cooperateed with using microwave with the double outfields of ultrasonic wave using nitric acid rare earth or rare-earth chlorination liquid as raw material
The method of liquid phase synthesis nano rareearth oxidate powder body material.
Background technology
Rare earth oxide makes it have unique chemistry and physical property because of its special electron structure, light,
Electricity, magnetic, sound, power etc. show the characteristic better than non-rare earth material.And the rare earth oxide of nanosizing have it is original
Outside rare earth property, while having both the exclusive characteristic of nano material；Further, after oxide nano rare earth spheroidization, will have
Higher specific surface area, surface energy and better mobility and dispersibility, and the performances such as its light, electricity, magnetic, power is made to obtain into one
Step is promoted, to be widely used in optical material, catalysis material, magnetic material, glass and ceramic material, alloy or composite wood
Material etc. field.
At present prepare superfine rare-earth oxide method still based on liquid phase method, include the precipitation method, sol-gel method,
Hydro-thermal method, microemulsion method, spray pyrolysis etc., wherein again the most universal with the application of the precipitation method.
The common precipitation method mainly have direct precipitation method, homogeneous precipitation method, alcohol Hydrolyze method and complexed-precipitation method.It is wherein straight
It connects the precipitation method and homogeneous precipitation method is easier to industrialization.
It is well known that homogeneous precipitation method is more easy to obtain spherical oxide nano rare earth, thus researcher is numerous.But at present
There are still some technical problems for the phase precipitation method：(1) existing precipitation from homogeneous solution be by heat slowly and equably release structure crystalline substance from
Son, make its combined with rare earth ion generate presoma precipitation, thus reaction speed and its slowly, even if its use collaboration be pressurized
Hydro-thermal method also tends to take for ten a few houres；(2) this method usually requires to introduce activating agent, dispersant, inhibitor or template etc.
Dressing agent not only increases manufacturing cost, and may affect to the purity of product.
Invention content
Goal of the invention：The present invention is to solve above-mentioned homogeneous precipitation method long preparation period, the technical problems such as dressing agent need to be added,
There is provided that a kind of reaction speed is fast, prepares rare earth without be added the dressing agents such as any activating agent, dispersant, inhibitor or template
The liquid precipitation of oxide nano sphere powder body material.
Inventive principle：Microwave frequency makes polar molecule in solution is per second to generate 24.5 hundred million times up to 2450 megahertzs of height
Orientation, resonance motion, not only make heating more rapidly, evenly, no temperature gradient, without hysteresis effect etc., and and play soft template
The effect of agent avoids the agglomeration of small grains to greatly shorten liquid phase crystallization nucleation induction period and crystallization reaction time.
Ultrasonic wave refers to sound wave of the frequency range in 15k~10MHz, is mainly derived from using power in chemical field
The cavitation effect of ultrasonic wave and its strong shock wave of initiation and speed are higher than 110ms-1Microjet, and then generate machinery effect
Answer (acoustic streaming, shock wave, microjet etc.), fuel factor (5000K, 1800atm localized hyperthermia high pressure, whole to heat up), luminous effect
(sonoluminescence) and activating effect (hydroxyl radical free radical is generated in aqueous solution), four kinds of effects and non-orphaned, but interact, phase
Mutually promote, accelerates reaction process.This cavitation of ultrasonic wave greatly improves heterogeneous reaction rate, realizes heterogeneous reaction object
Between uniform mixing, accelerate the diffusion of reactants and products, promote the formation of solid cenotype, control size and the distribution of particle.
Thus ultrasonic wave plays the role of similar dispersant, activating agent in crystallization process.
Microwave generates " non-thermal effect " with the double outfield synergistic effects of ultrasonic wave, reduces nucleation activation energy, urges in other words
Change the effect of " induction " fast nucleation, it is uniform and fast for the shortening of induction period, the quick formation of nucleus, the rearrangement of lattice, crystal
Speed grows up, the removing of the crystallization water, the refinement of crystal grain create advantage.Thus, microwave acts synergistically with the double outfields of ultrasonic wave
More than single microwave or ul-trasonic irradiation, can with auxiliary liquid phase synthesis Monodispersed nanometer rare earth oxide ball.
Technical solution：Microwave provided by the present invention cooperates with auxiliary liquid phase synthesis rare earth oxide to receive with the double outfields of ultrasonic wave
The method of rice ball, specially：With a concentration of 0.02~0.1molL-1Rare-earth chlorination solution be stoste, with urea be precipitation
Agent stirs evenly stoste and precipitating reagent, obtains mixed liquor；By above-mentioned mixed liquor, microwave and the double outfields of ultrasonic wave are carried out
Concerted reaction obtains sediment；Gained sediment is subjected to heat filtering, washing, drying successively again；Then it is thermally decomposed, is obtained
To target product.
Specifically, the rare-earth chlorination solution can be lanthanum chloride, dysprosium chloride, erbium chloride etc..
Specifically, the mol ratio of the precipitating reagent urea and ammonium hydroxide is 1:0~3:10-8, and urea and rare-earth chlorination
The mol ratio of solution is 20~100.
Specifically, the microwave and the double outfield concerted reactions of ultrasonic wave, reaction condition are：70~95 DEG C of reaction temperature,
0.5~1.5h of reaction time.The Cooperative Mode of microwave/ultrasonic wave is 1:2 or 2:1, i.e., while microwave field continuous action, surpass
Sound wave is interval 1s after interval 2s or pulse 2s after pulse 1s, and as the period, cycle operation is until reaction terminates.Described is super
The frequency of sound wave is 25~40kHz.Microwave power is 500~700W.
Specifically, the thermal decomposition is to carry out 2~3h of thermal decomposition at 700~900 DEG C of temperature.
Specifically, rare earth in the nanometer rare earth oxide ball include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium,
Any one element in holmium, erbium, thulium, ytterbium, lutetium.
Advantageous effect：(1) product regular appearance prepared by the method for the present invention, dispersion degree is high, has both nanometer and spherical rare earth
The superiority of oxide powder material.
(2) compared with general homogeneous precipitation method, the method for the present invention, reaction speed is fast, without the hydro-thermal method of supercharging；Nothing
The coating materials such as any activating agent, dispersant and template need to be added, you can obtain high purity rare earth oxides, avoid table
Face dressing agent impacts product purity.
(3) present invention process flow is simple, can directly utilize the rare earth chlorine of the extraction and separation of existing Rare Earth Separation enterprise
It is that raw material prepares spherical nano rareearth oxidate powder body material to change liquid, is easy to industrialization promotion application.
Description of the drawings
Fig. 1 is the techniqueflow chart of the present invention.
Fig. 2 is lanthana product transmission electron microscope (TEM) figure of embodiment 1.
Fig. 3 is dysprosia product transmission electron microscope (TEM) figure of embodiment 2.
Fig. 4 is erbium oxide product transmission electron microscope (TEM) figure of embodiment 3.
Specific implementation mode：
The present invention is further illustrated with reference to the accompanying drawings and examples.
Rare earth chloride stoste in the embodiment of the present invention is all obtained with south jiangxi ion type rareearth ore through full extraction and separation
Strip liquor diluted with pure water；The microwave of use cooperates with the model XH- of Liquid-phase reactor with the double outfields of ultrasonic wave
300A, ultrasonic frequency 25KHz.
It is involved in the present invention to product average grain diameter be to scheme in conjunction with its SEM or TEM, pass through Image Tool softwares and calculate
Obtained from.
Embodiment 1.
Microwave cooperates with auxiliary homogeneous precipitation method to prepare lanthana nanosphere with the double outfields of ultrasonic wave, by following steps：
(1) 0.05molL is taken-1Lanthanum chloride stoste and 2.5molL-1Each 200mL of urea liquid is sufficiently mixed uniformly,
Obtain mixed liquor；
(2) mixed liquor is put into microwave with the double outfields of ultrasonic wave in the reaction chamber of microwave synergistic extraction instrument, instills ammonia
The pH that water adjusts mixed liquor is 6.5, and control microwave/ultrasonic synergistic pattern is 2:1, ultrasonic power 900W, microwave power
650W, reaction time 0.9h, 90 DEG C of reaction temperature；
(3) reaction solution is centrifuged to the end of reaction and is that 70 DEG C of deionized water washs 3 times and obtains filter cake with temperature；Again
It is placed in 120 DEG C of drying box dry 3h, obtains lanthana presoma；
(4) then presoma is thermally decomposed in programmable high temperature furnace, controls 700 DEG C of decomposition temperature, soaking time
2h is cooled to room temperature, and obtains lanthana nanosphere.
The TEM for obtaining lanthana nanosphere schemes as shown in Fig. 2, it is about 30nm to measure its average grain diameter.
Embodiment 2.
Microwave cooperates with auxiliary homogeneous precipitation method to prepare dysprosia nanosphere with the double outfields of ultrasonic wave, by following steps：
(1) 0.075molL is taken-1Dysprosium chloride stoste and 3molL-1Each 200mL of urea liquid is mixed evenly,
Obtain mixed liquor；
(2) mixed liquor is put into microwave and the reaction chamber of the double outfields of ultrasonic wave and microwave synergistic extraction instrument, uncomfortable pH,
It is 1 to control microwave/ultrasonic synergistic pattern:2, ultrasonic power 900W, microwave power 600W, reaction time 0.75h, reaction temperature
90 DEG C of degree；
(3) reaction solution is centrifuged and washs 3 times with deionized water at a temperature of 90 °C to the end of reaction and obtain filter cake；Again
It is placed in 100 DEG C of drying box dry 4h, obtains dysprosia presoma；
(4) then presoma is thermally decomposed in programmable high temperature furnace, controls 850 DEG C of decomposition temperature, soaking time
1.5h is cooled to room temperature, and obtains dysprosia nanosphere.
The TEM for obtaining dysprosia nanosphere schemes as shown in Fig. 2, it is about 85nm to measure its average grain diameter.
Embodiment 3.
Microwave cooperates with auxiliary homogeneous precipitation method to prepare erbium oxide nanosphere with the double outfields of ultrasonic wave, by following steps：
(1) 0.05molL is taken-1Erbium chloride stoste and 2molL-1Each 200mL of urea liquid is mixed evenly, and obtains
To mixed liquor；
(2) mixed liquor is put into microwave with the double outfields of ultrasonic wave in the reaction chamber of microwave synergistic extraction instrument, instills ammonia
The pH that water adjusts mixed liquor is 6, and control microwave/ultrasonic synergistic pattern is 1:2, ultrasonic power 900W, microwave power
600W, reaction time 0.75h, 90 DEG C of reaction temperature；
(3) reaction solution is centrifuged and washs 3 times with deionized water at a temperature of 90 °C to the end of reaction and obtain filter cake；Again
It is placed in 120 DEG C of drying box dry 3h, obtains erbium oxide presoma；
(4) then presoma is thermally decomposed in programmable high temperature furnace, controls 850 DEG C of decomposition temperature, soaking time
1.5h is cooled to room temperature, and obtains erbium oxide nanosphere.
The TEM for obtaining erbium oxide nanosphere schemes as shown in figure 4, it is about 65nm to measure its average grain diameter.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
It, for those skilled in the art, still can be with although describing the invention in detail with reference to the foregoing embodiments
Technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.It is all
The present invention design under the premise of, made by it is any modification, improve etc., should all be included in the protection scope of the present invention.
Claims (8)
1. the method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave, it is characterised in that with dense
Degree is 0.02~0.1molL-1Rare-earth chlorination solution be stoste, using urea as precipitating reagent, stoste and precipitating reagent are stirred equal
It is even, obtain mixed liquor；By above-mentioned mixed liquor, microwave and the double outfield concerted reactions of ultrasonic wave are carried out, sediment is obtained；Again will
Gained sediment carries out heat filtering, washing, drying successively；Then it is thermally decomposed, obtains target product.
2. microwave according to claim 1 cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave
Method, it is characterised in that the mol ratio of the precipitating reagent urea and ammonium hydroxide is 1:0~3:10-8, and urea and rare-earth chlorination
The mol ratio of solution is 20~100.
3. microwave according to claim 1 cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave
Method, it is characterised in that the double outfield concerted reactions of the microwave and ultrasonic wave, reaction condition are：70~95 DEG C of reaction temperature,
0.5~1.5h of reaction time.
4. microwave according to claim 1 cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave
Method, it is characterised in that the Cooperative Mode of microwave/ultrasonic wave is 1:2 or 2:1, i.e., while microwave field continuous action, ultrasound
Wave is interval 1s after interval 2s or pulse 2s after pulse 1s, and as the period, cycle operation is until reaction terminates.
5. microwave according to claim 1 cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave
Method, it is characterised in that the frequency of the ultrasonic wave is 25~40kHz.
6. microwave according to claim 1 cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave
Method, it is characterised in that the microwave power is 500~700W.
7. microwave according to claim 1 cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave
Method, it is characterised in that the thermal decomposition is to carry out 2~3h of thermal decomposition at 700~900 DEG C of temperature.
8. microwave according to claim 1 cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave
Method, it is characterised in that rare earth in the nanometer rare earth oxide ball include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium,
Any one element in holmium, erbium, thulium, ytterbium, lutetium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810781167.4A CN108675336A (en) | 2018-07-17 | 2018-07-17 | The method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810781167.4A CN108675336A (en) | 2018-07-17 | 2018-07-17 | The method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108675336A true CN108675336A (en) | 2018-10-19 |
Family
ID=63814261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810781167.4A Pending CN108675336A (en) | 2018-07-17 | 2018-07-17 | The method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108675336A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647310A (en) * | 2018-12-17 | 2019-04-19 | 横店集团东磁股份有限公司 | A method of the spray pyrolysis unit with microwave heating and ternary precursor is prepared with it |
| CN111056564A (en) * | 2019-12-27 | 2020-04-24 | 广西科学院 | Microwave preparation method of lanthanum cerium terbium oxide fluorescent powder |
| CN113105889A (en) * | 2021-03-26 | 2021-07-13 | 华南理工大学 | Method for preparing europium and dysprosium co-doped strontium aluminate fluorescent powder with assistance of ultrasonic waves |
| CN113909485A (en) * | 2021-10-11 | 2022-01-11 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN115286379A (en) * | 2022-08-03 | 2022-11-04 | 景德镇陶瓷大学 | Method for preparing barium titanate-based ceramic powder by external field-promoted polycondensation non-aqueous precipitation process |
-
2018
- 2018-07-17 CN CN201810781167.4A patent/CN108675336A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 欧阳成: "微波与超声波对液相合成氧化铈形貌的影响研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109647310A (en) * | 2018-12-17 | 2019-04-19 | 横店集团东磁股份有限公司 | A method of the spray pyrolysis unit with microwave heating and ternary precursor is prepared with it |
| CN111056564A (en) * | 2019-12-27 | 2020-04-24 | 广西科学院 | Microwave preparation method of lanthanum cerium terbium oxide fluorescent powder |
| CN111056564B (en) * | 2019-12-27 | 2022-05-13 | 广西科学院 | Microwave preparation method of lanthanum-cerium-terbium oxide fluorescent powder |
| CN113105889A (en) * | 2021-03-26 | 2021-07-13 | 华南理工大学 | Method for preparing europium and dysprosium co-doped strontium aluminate fluorescent powder with assistance of ultrasonic waves |
| CN113909485A (en) * | 2021-10-11 | 2022-01-11 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN113909485B (en) * | 2021-10-11 | 2023-11-17 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN115286379A (en) * | 2022-08-03 | 2022-11-04 | 景德镇陶瓷大学 | Method for preparing barium titanate-based ceramic powder by external field-promoted polycondensation non-aqueous precipitation process |
| CN115286379B (en) * | 2022-08-03 | 2023-02-10 | 景德镇陶瓷大学 | Method for preparing barium titanate-based ceramic powder by external field-promoted polycondensation non-aqueous precipitation process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108675336A (en) | The method that microwave cooperates with auxiliary liquid phase synthesis nanometer rare earth oxide ball with the double outfields of ultrasonic wave | |
| Yang et al. | Microwave-assisted synthesis of ceria nanoparticles | |
| Xu et al. | Synthesis of monodispersed spherical yttrium aluminum garnet (YAG) powders by a homogeneous precipitation method | |
| Yang et al. | Synthesis, crystal growth, and photoluminescence properties of YAG: Eu3+ phosphors by high-energy ball milling and solid-state reaction | |
| CN109019656B (en) | Method for producing nano rare earth oxide powder | |
| CN109371308B (en) | The method for preparing multi-principal elements alloy toughened aluminum oxide base metal-ceramic composite powder end | |
| CN102659149A (en) | Preparation method for monodisperse high-purity alpha-Al2O3 powder | |
| CN108083316A (en) | A kind of preparation method of nano rareearth oxidate powder body | |
| Wang et al. | Microwave synthesis of homogeneous YAG nanopowder leading to a transparent ceramic | |
| CN103420428A (en) | Preparation method of magnesium ferrite nano-particles | |
| Kudryashova et al. | Synthesis of yttrium–aluminum garnet using a microreactor with impinging jets | |
| CN103193472A (en) | Method for synthesizing subsphaeroidal barium ferrite superfine powder by using ultrasound-assisted coprecipitation method | |
| RU2404125C2 (en) | Method of preparing zirconium dioxide nanopowder | |
| CN109516490B (en) | Preparation method of cerium dioxide nano particles with controllable structures | |
| CN102557151B (en) | Method for preparing nanometer ferroferric oxide powder by reducing at one step | |
| CN106745303A (en) | A kind of three-dimensional flower ball-shaped cadmium ferrite bismuth meal body and preparation method thereof | |
| CN102190484A (en) | Preparation method for YAG (yttrium aluminum garnet) transparent ceramic | |
| CN104843802A (en) | Preparation method for micron-sized superparamagnetic ferroferric oxide microspheres | |
| CN107021520B (en) | A kind of yttrium oxide powder and preparation method thereof | |
| CN104973624A (en) | Preparation method of meshy tetragonal phase zirconia nano powder | |
| CN108640144B (en) | Yttrium oxide double-stage nanosphere and preparation method thereof | |
| CN106673426A (en) | Porous-microsphere nanoscale bioglass material doped with rare earth element as well as preparation method and application of porous-microsphere nanoscale bioglass material | |
| KR20100016887A (en) | Manufacturing method of nano zinc oxide powders by hydrothermal method | |
| CN109465464A (en) | A method of preparing alumina-based ceramic metal nano composite powder | |
| CN107188214B (en) | A kind of preparation method of yttrium oxide nano-powder and nanostructure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zeng Qingyun Inventor after: Liu Yong Inventor after: Zhang Hua Inventor after: Zhang Xiangliang Inventor after: Xue Liyan Inventor before: Zhang Xiangliang Inventor before: Zhang Hua Inventor before: Liu Yong |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20181019 |