CN115403064A - Cerium oxide and preparation method thereof - Google Patents
Cerium oxide and preparation method thereof Download PDFInfo
- Publication number
- CN115403064A CN115403064A CN202211143453.0A CN202211143453A CN115403064A CN 115403064 A CN115403064 A CN 115403064A CN 202211143453 A CN202211143453 A CN 202211143453A CN 115403064 A CN115403064 A CN 115403064A
- Authority
- CN
- China
- Prior art keywords
- cerium
- cerium oxide
- ceo
- nano
- polishing
- 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.)
- Granted
Links
Images
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
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
- 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
- C01F17/10—Preparation or treatment, e.g. separation or purification
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to the field of nano materials, in particular to cerium oxide and a preparation method thereof. The invention provides a preparation method of cerium oxide, which takes ammonium hydrogen oxalate and ammonia water as coprecipitators to prepare a cerium oxide nano material, can eliminate the influence of particle agglomeration in the preparation process, obtains nano cerium oxide with uniformly distributed particles, and obtains the spherical nano cerium oxide with uniform and compact structure, thereby being beneficial to being used as polishing powder, and having simple method and low cost. Experiments show that the CeO is prepared by a chemical precipitation method 2 Monomers are synthesized into C with controllable particle size and morphology by adjusting the addition amount of each medicine, the dripping sequence of the precipitator, the calcination temperature and other experimental conditionseO 2 And (3) nano materials. The synthesis technology can be used for large-scale production, and the prepared CeO can be amplified in large scale 2 The nano material has higher consistency and stability.
Description
Technical Field
The invention relates to the field of nano materials, in particular to cerium oxide and a preparation method thereof.
Background
With the rapid development of technologies such as optics, electronics, network technology, communication engineering, etc., the requirement for the precision of chemical mechanical polishing is higher and higher due to the high surface quality of the integrated circuits, the integrated circuit chips are gradually increased, the single transistor elements are gradually decreased, and the multilayer integrated circuit chip is the inevitable trend of chemical mechanical polishing in the technology development. Different from the traditional pure mechanical or pure chemical polishing method, the technology avoids the defects of surface damage caused by pure mechanical polishing, low polishing speed, low surface flatness, poor polishing consistency and the like easily caused by single-purification chemical polishing by means of the mechanical grinding effect of superfine grinding particles in slurry and the chemical corrosion effect of materials, and in the process, the polishing slurry plays a role of playing a role, and the grinding particles are important factors influencing the properties of the polishing slurry.
The ultra-precise rare earth polishing material is mainly used for Chemical Mechanical Polishing (CMP) of precise optical materials and chip semiconductor materials. The high-quality polishing solution should break through the following three technologies, namely abrasive manufacturing technology, abrasive dispersing technology and polishing solution formulation technology.
The purity, hardness, granularity, shape and the like of the polishing powder can influence the polishing capability, and the physical properties of the cerium-based rare earth compound are controlled in a targeted manner by combining with the actual polishing requirement to ensure the quality of the polishing process, so that the cerium-based rare earth compound has the characteristics of nanoscale size, sphericity, narrow particle size distribution, strong cutting force, high polishing precision, good polishing quality, long service life and the like, and is more suitable for the polishing powder and the polishing solution of semiconductor materials. The physical properties (the size of particles, the size distribution of particles, the morphological characteristics of nanoparticles, the surface properties of particles, the aggregation or dispersion state of particles, and the like), the purity and the stability of the solid polishing abrasive, the production cost, the batch repeatability, and particularly the consistency and stability of the polishing abrasive after large-scale production are key problems which currently restrict the difficult industrialization of the polishing abrasive.
In the last forty years, cerium oxide has become an important glass polishing material instead of iron oxide. Compared with the conventional polishing material, the cerium-based rare earth polishing powder has the advantages of high polishing speed, high smoothness and long service life. To date, cerium-based rare earth polishing powders have been widely used for various glass products. In the field of high-precision optical lenses, high smoothness and light transmittance are required, and higher requirements are provided for the particle size distribution, the grinding force and the scratch rate of polishing powder. The high-cerium rare earth polishing powder has high applicability, but the raw material cost is too high, and the high-cerium rare earth polishing powder is rarely adopted at present. At present, cerium-based polishing powder is prepared by a precipitation-roasting method taking rare earth chloride as a raw material in the market, the rare earth polishing powder prepared by the method has uniform components, moderate particle size and good crystal form consistency, and the product is widely applied to the fields of optical glass, photomasks, liquid crystal displays and the like. However, the method is complex and the process is difficult to control. How to prepare rare earth polishing powder suitable for the optical field has become a topic of intense research.
Through continuous practice, people continuously deepen the understanding of the polishing powder. With the development of rare earth industry, the application field of rare earth is continuously expanded, and people begin to try to use rare earth oxide as polishing powder. Currently, cerium-based polishing powders are the most widely used polishing powders. Compared with other polishing powder, the cerium-based polishing powder has the advantages of good crystal form, small and uniform particle size, strong chemical activity, high polishing efficiency, small usage amount, long service life, high qualification rate of workpieces, easiness in cleaning, no pollution and the like. Thus, cerium-based polishing powders are also known as "King of polishing powders".
The polishing powder on the market at present has uneven polishing granularity, irregular appearance, poor cutting force, easy scratch generation during polishing and low polishing speed. Therefore, the surface of the polishing powder is modified by adjusting the precipitation reaction condition and the composite system, and the influence of the modified polishing powder on the polishing performance is researched through experimental comparison and data analysis, so that the optimal modification scheme is determined, the polishing performance of the polishing powder is improved, and a basis and an idea are provided for improving and developing a new polishing powder production process. The improvement idea of the preparation process is to perform physical property control (improve the physical chemistry and application characteristics) aiming at an application target, analyze the states and properties of various substances related to the polishing powder by using an advanced analytical instrument, understand from a plurality of subject fields of surface chemistry, physics, colloid chemistry and the like, provide a process method for effectively controlling the production process, provide theoretical basis and guidance for industrial application and industrial design of the polishing powder, and have important significance for future development of the preparation process, promotion of a polishing powder product suitable for a silicon wafer and development of the polishing powder with high performance and wide particle size gradient.
Cerium dioxide (formula CeO) 2 ) Has very wide application. For example, the catalyst can be used for a ternary purification catalyst for automobile exhaust, has the advantages of high activity, low price, long service life and the like, replaces most of noble metals, and has the annual dosage of thousands of tons; ceO (CeO) 2 And can be used for electronic ceramics and solid electrolytes: ceO (CeO) 2 The powder has extremely strong absorption performance on ultraviolet rays, can be used for preparing ultraviolet absorption materials, such as 185pm short-wave ultraviolet rays in fluorescent lamps to prolong the service life of the lamps, and is also used for sunscreen cosmetics, sunscreen fibers, automobile glass and the like: the plastic product is easy to age and become brittle under the action of ultraviolet rays, and the surface of the plastic product is coated with a coating containing cerium oxide particles (which are transparent to sunlight) to prevent the plastic from aging; resin and rubber paints are required to be coated on the surfaces of tanks, automobiles, ships, oil storage tanks and the like, the paints are easy to age and become brittle due to the irradiation of sunlight ultraviolet rays, and the ultraviolet-proof coating prepared by adding cerium oxide powder into the paints has obviously improved ageing resistance: ceO (CeO) 2 Is also a good glass polishing agent; ceO (CeO) 2 Is a good ultraviolet light catalytic material and can degrade organic pollutants in the environment. In summary, ceO 2 The method is applied to factories, has huge potential, high added value and good commercial prospect. But CeO 2 In the using process, soft agglomeration is easy to occur, and the agglomeration is serious along with the reduction of the central particle size of the powder, so that the suspension performance is poor, the particle distribution is not uniform, a circulating pipeline of grinding slurry is easy to block, and the polishing quality and the grinding efficiency of the material are influenced.
CeO 2 The preparation method mainly comprises a precipitation method, a sol-gel method, a hydrothermal method, a micro-emulsion method, an electrochemical method and the like. The liquid phase method is mainly to form a precursor in a liquid phase system by controlling the conditions of liquid phase chemical reaction, such as reactant concentration, reaction temperature and time, stirring speed, hydrolysis speed, coprecipitation and the likeA method. The liquid phase method is between a gas phase method and a solid phase method, compared with the gas phase method, the liquid phase method has the advantages of simple equipment, no need of harsh physical conditions such as high vacuum and the like, easy amplification and the like, and simultaneously has the advantages of purity and less agglomeration compared with powder prepared by the solid phase method, thereby being easy to realize industrial production and being the most common method for preparing nano particles at present. However, the conventional liquid phase method for preparing CeO 2 Aggregates are easy to generate, and the existence of the aggregates has many adverse effects on the performance of the material, such as directly influencing the forming of the material, so that the sintered body can not obtain the material with uniform and compact microstructure; agglomerates can also directly influence the sintering behavior of the material.
In addition, the existing method needs high-temperature and high-pressure equipment, is expensive and has no economic value of mass production; some are not suitable for large-scale production. For example, chinese patent No. 1821314a discloses a method for preparing ultrafine cerium oxide, which comprises using an alkaline substance as a precipitant, controlling the pH of the reaction suspension to generate a precipitate, then converting the suspension with oxalic acid, controlling the pH at the end of the reaction, finally filtering, washing, drying the precipitate, burning at 600-1000 ℃ to obtain ultrafine cerium oxide, and using the ultrafine cerium oxide for polishing. But the product prepared by the method also has wider particle size distribution between 10nm and 30um, and the specific surface area reaches 50m 2 (g), it is poor in reusability as a polishing powder. For another example, taiwan patent No. 328068 discloses that cerium oxide powder of 10 to 80nm is obtained by mixing cerium nitrate and rapidly heating to 70 to 100 ℃, adjusting the pH to 5 to 10, and maintaining the temperature at the temperature for 0.2 to 20 hours. The precursor of the method is also cerium hydroxide, and the daily particle size is too fine, so that the method is not suitable for being used as polishing powder.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a cerium oxide and a preparation method thereof, the method provided by the present invention can eliminate the influence of particle agglomeration in the preparation process, and obtain a spherical nano cerium oxide with a uniform and compact particle structure, and the method is simple and low in cost.
The invention provides a preparation method of cerium oxide, which comprises the following steps:
a) Mixing a precipitator, cerium salt and a surfactant, and reacting and aging to obtain a cerium oxide precursor; the precipitator comprises ammonia water and ammonium hydrogen oxalate;
b) And B) calcining the cerium oxide precursor obtained in the step A) to obtain cerium oxide.
Firstly, mixing a precipitator, a cerium salt and a surfactant, and carrying out reaction and aging to obtain a cerium oxide precursor, specifically, the method comprises the following steps:
a1 Adding the precipitant solution into the cerium salt solution and the surfactant, and mixing to react;
a2 Aging the reaction product obtained in the step A1) to obtain a precursor.
In some embodiments of the invention, the cerium salt solution and the surfactant are first mixed, the precipitant is added while stirring, the reaction is started to generate a precipitate, and the precipitate is completely aged, washed and dried to obtain the precursor.
In one embodiment, the surfactant is added into the cerium salt solution, a mixed solution of the cerium salt solution and the surfactant is obtained through stirring, the mixed solution of the cerium salt solution and the surfactant is transferred into a heating stirrer, then the precipitator is dripped into the mixed solution of the cerium salt solution and the surfactant through a multi-channel constant flow pump, the reaction is carried out at a certain temperature, precipitation is generated, the precipitate is completely sealed and aged, and the precipitate is washed with water and ethanol for three times and then dried, so that the precursor is obtained. In one embodiment, the stirring speed is 400r/min to 1000r/min, preferably 500r/min. In one embodiment, the temperature of the reaction is between 50 ℃ and 80 ℃, preferably 60 ℃. In one embodiment, the temperature of aging is 50 ℃ to 80 ℃; the aging time is 0-5 h.
The precipitating agent comprises ammonia water and ammonium hydrogen oxalate, and the inventor creatively discovers that spherical nano cerium oxide with uniform and compact particles can be prepared by adopting a mixed solution of ammonia water and ammonium hydrogen oxalate as a coprecipitator to precipitate and dropwise prepare cerium oxide.
In certain embodiments of the invention, the molar ratio of ammonia to ammonium hydrogen oxalate is 0.1:0.1 to 0.4, preferably 0.1:0.4. in one embodiment, the precipitant is obtained by mixing 0.4mol/L ammonium hydrogen oxalate and 0.1mol/L ammonia water. In certain embodiments of the invention, the precipitant solution is added at a rate of 1mL/min to 5mL/min, preferably 2mL/min.
The cerium salts of the present invention may be commercially available or may be prepared. In one embodiment, the cerium salt is selected from at least one of cerium nitrate, cerium chloride, cerium oxalate, cerium sulfate, cerium carbonate, cerium phosphate, cerium methanesulfonate, cerium pyrophosphate, cerous cyanogen phosphate, preferably from cerium nitrate. In one embodiment, 10g to 15g of cerium carbonate is dissolved in 5mL to 10mL of concentrated nitric acid, and water is added to prepare a cerium salt solution. In one embodiment, the concentration of the cerium salt solution is 0.1mol/L to 0.5mol/L, preferably 0.4mol/L.
In certain embodiments of the present invention, the surfactant is selected from at least one of polyethylene glycol 8000, polyethylene glycol 10000, polyethylene glycol 20000, polyvinylpyrrolidone, polypropylene glycol, polyacrylamide, hydroxyethyl cellulose, polyoxyethylene alkyl ether, preferably selected from polyethylene glycol 20000, wherein the polyoxyethylene alkyl ether comprises polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether or polyoxyethylene cetyl ether. In one embodiment, the surfactant is 0.4wt% to 1.0wt%, preferably selected from 0.4wt%, of the cerium salt solution.
The invention can add the precipitant solution into the cerium salt solution and the surfactant to mix, and then can add the fluorinating agent. In one embodiment, the fluorinating agent is selected from at least one of ammonium fluoride, hydrofluoric acid, ammonium bifluoride, chlorine fluoride, sulfur tetrafluoride, preferably from ammonium fluoride.
The method comprises the steps of mixing a precipitator, a cerium salt and a surfactant, reacting and aging to obtain a cerium oxide precursor, and calcining the cerium oxide precursor to obtain the cerium oxide. In one embodiment, the temperature of the calcination is 500 ℃ to 800 ℃, preferably 700 ℃; the calcining time is 2h to 4h, preferably 2h.
The invention also provides cerium oxide prepared by the preparation method. In one embodiment, the cerium oxide has a particle size of 30nm to 800nm. In one embodiment, the cerium oxide is spherical.
The invention provides a preparation method of cerium oxide, which comprises the following steps: a) Mixing a precipitator, cerium salt and a surfactant, and reacting and aging to obtain a cerium oxide precursor; the precipitating agent comprises ammonia water and ammonium hydrogen oxalate; b) And B) calcining the cerium oxide precursor obtained in the step A) to obtain cerium oxide. According to the preparation method provided by the invention, the ammonium hydrogen oxalate and the ammonia water are used as coprecipitates to prepare the cerium oxide nano material, the influence of particle agglomeration in the preparation process can be eliminated, the nano cerium oxide with uniformly distributed particles is obtained, and the obtained nano cerium oxide is spherical nano cerium oxide with a uniform and compact structure, so that the cerium oxide nano material is favorable for being used as polishing powder, and is simple in method and low in cost. Experiments show that the CeO is prepared by a chemical precipitation method 2 The monomer is used for synthesizing the CeO with controllable particle size and morphology by adjusting the addition amount of each medicine, the dripping sequence of the precipitator, the calcining temperature and other experimental conditions 2 And (3) nano materials. The synthesis technology can be used for large-scale production, and the prepared CeO can be amplified in large scale 2 The nano material has higher consistency and stability.
Drawings
FIG. 1 shows CeO prepared in example 1 2 SEM image of nano material;
FIG. 2 shows CeO prepared in example 2 2 SEM image of the nanometer material;
FIG. 3 shows CeO prepared in example 3 2 SEM image of the nanometer material;
FIG. 4 shows CeO prepared in example 4 2 SEM image of the nanometer material;
FIG. 5 shows CeO prepared in example 5 2 SEM image of the nanometer material;
FIG. 6 shows CeO prepared in example 6 2 SEM image of the nanometer material;
FIG. 7 shows CeO prepared in comparative example 1 2 SEM image of the nanometer material;
FIG. 8 shows CeO prepared in comparative example 2 2 SEM image of the nanometer material;
FIG. 9 is a CeO prepared in comparative example 3 2 SEM image of the nanometer material;
FIG. 10 shows CeO prepared in example 1 2 XRD diffractogram of (a);
FIG. 11 shows CeO prepared in example 1 2 An infrared spectrum of (2);
FIG. 12 shows CeO prepared in example 1 2 Thermogravimetric plot of precursor.
Detailed Description
The invention discloses cerium oxide and a preparation method thereof. Those skilled in the art can modify the process parameters appropriately to achieve the desired results with reference to the disclosure herein. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
A series of cerium oxides are prepared and characterized through condition optimization experiments.
Influencing of CeO 2 The morphology and the granularity are various, and the method carries out condition optimization aiming at each factor to finish the CeO 2 Controllable preparation of morphology and size, mainly investigating the influence of the factors of cerium nitrate concentration, ammonia water concentration, ammonium hydrogen oxalate concentration, reaction temperature, the type and adding amount of a surfactant, aging time and concentration and calcining temperature. The experimental influence factors are shown in table 1:
TABLE 1
| Factors of the fact | Level 1 | Level 2 | Level 3 | Level 4 |
| Cerium nitrate concentration/(mol/L) | 0.1 | 0.2 | 0.3 | 0.4 |
| Concentration of Ammonia/(mol/L) | 1 | 2 | 3 | 4 |
| Ammonium hydrogen oxalate concentration/(mol/L) | 0.1 | 0.2 | 0.3 | 0.4 |
| Reaction temperature/(. Degree.C.) | 50 | 60 | 70 | 80 |
| Surfactant species | PEG(8000) | PEG(10000) | PEG(20000) | PVP |
| Surfactant addition/(%) | 1.0 | 0.8 | 0.6 | 0.4 |
| Aging temperature/(. Degree.C.) | 50 | 60 | 70 | 80 |
| Aging time/(h) | 0 | 1 | 2 | 3 |
| Calcination temperature/(. Degree. C.) | 500 | 600 | 700 | 800 |
The invention uses a scanning electron microscope (SEM, hitachi S4800) with the acceleration voltage of 30kV to characterize the sample and observe the appearance and the structure of the sample. An X-ray powder diffraction (XRD) pattern in the range of 20 DEG to 90 DEG was photographed by a D8 type focusing diffractometer (Bruker) at a scanning speed of 2 DEG min -1 . The samples were subjected to Fourier transform Infrared Spectroscopy (FT-IR) using a Thermo FisherNicolet-6700 spectrometer, and the resultant samples were subjected to structural analysis. Thermogravimetric analysis (TGA) was carried out using a thermogravimetric analyzer (TG/SDTQ 600) at a temperature ranging from 0 ℃ to 1000 ℃.
The invention is further illustrated by the following examples:
example 1
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.4 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 0.345g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 60 ℃, and the stirring speed is 500 r-min -1 。
0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 The ammonia water solution is mixed to prepare a mixed precipitator B. The mixed precipitator B is added with 2 mL-min by a multi-channel constant flow pump -1 The mixture was added dropwise to the mixed solution A at the rate of (1), and after completion of the addition, 0.15g of ammonium fluoride was added to conduct a reaction.
After the reaction is finished, the beaker is sealed by a plastic film and then is placed in an oven at the temperature of 60 ℃ for aging for 2 hours. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 700 ℃ for 2h to obtain spherical CeO with the particle size of 30nm 2 And (3) nano materials. Subjecting the obtained CeO to SEM 2 The morphology analysis was carried out, the results are shown in FIG. 1, FIG. 1 is the CeO prepared in example 1 2 SEM image of the nano material.
Example 2
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.4 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 0.345g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 60 ℃, and the stirring speed is 500 r-min -1 。
0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 The ammonia water solution is mixed to prepare a mixed precipitator B. The mixed precipitator B is added with 2 mL-min by a multi-channel constant flow pump -1 The mixture was added dropwise to the mixed solution A at the rate of (1), and after completion of the addition, 0.3g of ammonium fluoride was added to conduct a reaction.
After the reaction is finished, the beaker is sealed by a plastic film and then is put into an oven at 60 ℃ for aging for 1 hour. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 800 ℃ for 2h to obtain spherical CeO with the particle size of 50nm 2 And (3) nano materials. Obtained CeO was subjected to SEM 2 The morphology analysis was carried out, the results are shown in FIG. 2, and FIG. 2 shows the CeO prepared in example 2 2 SEM image of the nano material.
Example 3
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.4 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 0.345g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 60 ℃, and the stirring speed is 500 r.min -1 。
0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 The ammonia water solution is mixed to prepare a mixed precipitator B. The mixed precipitator B is added with 2.5 mL-min by a multi-channel constant flow pump -1 The mixture was added dropwise to the mixed solution A at the rate of (1), and after completion of the addition, 0.3g of ammonium fluoride was added to conduct a reaction.
After the reaction is finished, the beaker is sealed by a plastic film and then is put into an oven at 60 ℃ for aging for 2 hours. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 700 ℃ for 2h to obtain spherical CeO with the particle size of 80nm 2 A nano-material. Subjecting the obtained CeO to SEM 2 The morphology analysis was carried out, the results are shown in FIG. 3, and FIG. 3 shows the CeO prepared in example 3 2 Nanomaterial SEM image.
Example 4
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.4 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 0.345g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A to heatingIn the stirrer, the heating temperature is 70 ℃, and the stirring speed is 500 r.min -1 。
0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 The ammonia water solution is mixed to prepare a mixed precipitator B. The mixed precipitator B is added with 2.5 mL-min by a multi-channel constant flow pump -1 The mixture was added dropwise to the mixed solution A at the rate of (1), and after completion of the addition, 0.3g of ammonium fluoride was added to conduct a reaction.
After the reaction, the beaker is sealed by a plastic film and then put into an oven at 70 ℃ for aging for 1h. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 600 ℃ for 2h to obtain spherical CeO with the particle size of 100nm 2 A nano-material. Obtained CeO was subjected to SEM 2 The morphology analysis was carried out, the results are shown in FIG. 4, and FIG. 4 is the CeO prepared in example 4 2 SEM image of the nano material.
Example 5
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.4 mol. L -1 The cerium nitrate solution of (2) was stirred at room temperature. While stirring was maintained, 0.5g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 60 ℃, and the stirring speed is 500 r.min -1 。
0.3 mol/L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 The ammonia water solution is mixed to prepare a mixed precipitator B. The mixed precipitator B is added with 2.5 mL-min by a multi-channel constant flow pump -1 Was added dropwise to the above mixed solution A at a rate of 0.6g, and after completion of the dropwise addition, ammonium fluoride was added to conduct a reaction.
After the reaction is finished, the beaker is sealed by a plastic film and then is put into an oven at 60 ℃ for aging for 3 hours. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 700 ℃ for 2h to obtain spherical CeO with the particle size of 200nm 2 And (3) nano materials. Obtained CeO was subjected to SEM 2 The morphology analysis was carried out and the results are shown in FIG. 5, which is a graph5 is CeO prepared in example 5 2 Nanomaterial SEM image.
Example 6
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.4 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 0.7g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 60 ℃, and the stirring speed is 500 r-min -1 。
0.3 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 The ammonia water solution is mixed to prepare a mixed precipitator B. The mixed precipitator B is heated to 3 mL/min by using a multi-channel constant flow pump -1 Was added dropwise to the mixed solution A at the rate of 0.6g of ammonium fluoride.
After the reaction is finished, the beaker is sealed by a plastic film and then is put into an oven with the temperature of 80 ℃ for aging for 3 hours. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 800 ℃ for 2h to obtain spherical CeO with the particle size of 800nm 2 And (3) nano materials. Obtained CeO was subjected to SEM 2 The morphology analysis was carried out, and the results are shown in FIG. 6, where FIG. 6 is the CeO prepared in example 6 2 SEM image of the nano material.
Comparative example 1
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.3 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 1g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 80 ℃, and the stirring speed is 600 r-min -1 。
Firstly, 0.3 mol.L is firstly mixed by a multi-channel constant flow pump -1 The ammonia solution (2.5 mL. Min.) -1 Is added dropwise to the mixed solution A at a rate of 0.3 mol. L -1 Ammonium hydrogen oxalate was added dropwise. After the dropwise addition, 1g of ammonium fluoride was added to conduct a reaction.
After the reaction was completed, the beaker was sealed with a plastic film and then placed at 80 deg.CAging in an oven at the temperature of 1 ℃ for 1 hour. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 700 ℃ for 4h to obtain micron-sized spindle CeO 2 And (3) nano materials. Subjecting the obtained CeO to SEM 2 The morphology analysis was performed, and the results are shown in FIG. 7, and FIG. 7 shows the CeO prepared in comparative example 1 2 SEM image of the nano material.
Comparative example 2
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.3 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 1g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 70 ℃, and the stirring speed is 500 r.min -1 。
Firstly, 0.3 mol.L is firstly mixed by a multi-channel constant flow pump -1 The ammonia solution (2) was dissolved at 3 mL/min -1 Is added dropwise to the mixed solution A at a rate of 0.3 mol. L -1 Ammonium hydrogen oxalate (iv) was added dropwise. After the dropwise addition, 1.2g of ammonium fluoride was added to conduct a reaction.
After the reaction, the beaker was sealed with a plastic film and then placed in an oven at 70 ℃ for aging. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at 700 ℃ for 2h to obtain flower-shaped CeO 2 And (3) nano materials. Subjecting the obtained CeO to SEM 2 The morphology analysis was carried out, and the results are shown in FIG. 8, where FIG. 8 is the CeO prepared in comparative example 2 2 SEM image of the nano material.
Comparative example 3
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and ultrapure water was added thereto to prepare 0.4 mol. L -1 Stirring the cerium nitrate solution at normal temperature. While stirring was maintained, 1.5g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 60 ℃, and the stirring speed is 500 r-min -1 。
Firstly, 0.3 mol.L is firstly mixed by a multi-channel constant flow pump -1 Of grass ofThe ammonium acid hydride solution is added at a concentration of 3 mL/min -1 Is added dropwise to the mixed solution A at a rate of 0.3 mol. L -1 The ammonia water of (2) is added dropwise. After the dropwise addition, 0.8g of ammonium fluoride was added to conduct a reaction.
After the reaction is finished, the beaker is sealed by a plastic film and then is put into an oven at 60 ℃ for aging for 3 hours. And washing the aged sample for three times by distilled water and absolute ethyl alcohol, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor at the temperature of 600 ℃ for 3h to obtain flaky CeO 2 And (3) nano materials. Subjecting the obtained CeO to SEM 2 The morphology analysis was performed, and the results are shown in FIG. 9, where FIG. 9 is the CeO prepared in comparative example 3 2 Nanomaterial SEM image.
As can be seen from FIGS. 1 to 6, ceO prepared in examples 1 to 6 2 Are uniformly dispersed fine spherical particles with the particle sizes of 30nm, 50nm, 80nm, 100nm, 200nm and 800nm respectively, and the method shows that the CeO is realized by adjusting the reaction condition and the calcination temperature 2 And controlling the size of the nano particles. As can be seen from FIGS. 7 to 9, ceO prepared in comparative examples 1 to 3 2 CeO in the size of micron 2 The two-step precipitation method is adopted in comparative examples 1 to 3, and the dropping sequence and the dropping amount of ammonium hydrogen oxalate and ammonia water are adjusted to prepare three CeO with different morphologies, namely, fusiform, floriform and flaky CeO 2 A material. In conclusion, the invention initially realizes CeO by optimizing and regulating the competitive kinetics of oxide crystal nucleus growth and crystal nucleus formation 2 And controlling the size, shape, distribution and aggregation state of the material.
Example 7
For CeO prepared in example 1 2 XRD analysis was performed, and the analysis result is shown in FIG. 10, in which FIG. 10 is the CeO prepared in example 1 2 XRD diffractogram of (a). As can be seen from FIG. 10, ceO 2 Diffraction peaks of the sample at 2 θ =28.58 °, 33.13 °, 47.53 °, 56.37 °, 59.10 °, 69.46 °, 76.74 ° and 79.11 ° correspond to CeO, respectively 2 The crystal planes of (111), (200), (220), (311), (222), (440), (331), and (420) of (a) are cubic fluorite structures. The peak value and the position are found and compared with the standard card JCPDSN.34.0394The cards are consistent, the diffraction peak intensity is higher, the peak shape is sharper, no impurity peak appears, which indicates that the synthesized CeO 2 Has high purity and good crystallinity.
For CeO prepared in example 1 2 Infrared spectroscopic analysis (FT-IR) was conducted, and the results are shown in FIG. 11, in which FIG. 11 shows the CeO prepared in example 1 2 An infrared spectrum of (1). As can be seen from FIG. 11, the nano CeO 2 The spectra of (A) are present at 3750cm -1 ，2349cm -1 ，1630cm -1 And 750cm -1 4 absorption peaks at position (3), wherein 3750cm -1 Near absorption peak is nano CeO 2 Caused by stretching vibration of-OH groups in free water of the powder at 2349cm -1 And 667cm -1 The absorption peak is mainly attributed to CO adsorbed on the surface of the sample 2 . At 750cm -1 Due to CeO 2 The absorption peak caused by vibration shows a significant blue shift, mainly because the volume of the nanoparticles is too small, so that the surface tension of the particles is increased, and the inside of the particles is distorted, so that the Ce-O bond length is shortened, and the vibration frequency is increased. Peak position and shape of full-range infrared spectrum and CeO 2 The Sadler standard spectrum of the CeO is matched, and the CeO is shown 2 The successful preparation.
For CeO prepared in example 1 2 TGA analysis was performed, and the analysis results are shown in FIG. 12, and FIG. 12 shows the CeO prepared in example 1 2 Thermogravimetric plot of precursor. As can be seen from fig. 12, at 200 ℃, the precursor shows a large endothermic peak with a peak value of 73 ℃. At about 218 ℃, the reaction is finished, which indicates that the precursor is subjected to a great amount of structural water separation at 200 ℃, the weight loss rate of the process is 8.2%, and the weight loss curve shows that a great amount of thermal decomposition reaction exists in the process. An exothermic peak appeared at 278 ℃, indicating that the decomposition reaction of the precursor continued, with a weight loss of 14.8%. The weight loss curve after 398 ℃ becomes stable gradually, which indicates that the decomposition of the precursor is finished. The total weight loss of the whole decomposition process is about 23%.
In conclusion, ceO was prepared by the chemical precipitation method in examples 1 to 6 and comparative examples 1 to 3 2 A material. By aiming at eachThe addition amount of the medicine, the dripping sequence of the precipitator, the calcining temperature and other experimental conditions are adjusted to synthesize the CeO with controllable particle size and morphology 2 A material. In examples 1 to 6, spherical CeO particles having a uniform particle distribution and a uniform and dense microstructure were successfully synthesized 2 And (3) nano materials. The synthesis technology can be used for large-scale production, and the prepared CeO can be amplified in large scale 2 The nano material has higher consistency and stability.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A method for preparing cerium oxide, comprising the steps of:
a) Mixing a precipitator, cerium salt and a surfactant, and reacting and aging to obtain a cerium oxide precursor; the precipitating agent comprises ammonia water and ammonium hydrogen oxalate;
b) And B) calcining the cerium oxide precursor obtained in the step A) to obtain cerium oxide.
2. The method according to claim 1, wherein the molar concentration ratio of ammonia to ammonium hydrogen oxalate in the precipitant is 0.1:0.1 to 0.4.
3. The method according to claim 2, wherein step a) comprises in particular:
a1 Adding the precipitant solution into the cerium salt solution and the surfactant, and mixing to react;
a2 Aging the reaction product obtained in the step A1) to obtain a precursor.
4. The method according to claim 3, wherein the precipitant solution is added at a rate of 1 to 5mL/min.
5. The method according to claim 3, wherein the concentration of the cerium salt solution is 0.1 to 0.5mol/L;
the surfactant accounts for 0.4-1.0 wt% of the cerium salt solution.
6. The method for preparing the compound of claim 1, wherein the reaction temperature is 50-80 ℃;
the aging temperature is 50-80 ℃; the aging time is 0-5 h;
the calcining temperature is 500-800 ℃; the calcining time is 2-4 h.
7. The method according to claim 1, wherein the cerium salt is at least one selected from the group consisting of cerium nitrate, cerium chloride, cerium oxalate, cerium sulfate, cerium carbonate, cerium phosphate, cerium methanesulfonate, cerium pyrophosphate, cerous phosphate;
the surfactant is at least one selected from polyethylene glycol 8000, polyethylene glycol 10000, polyethylene glycol 20000, polyvinylpyrrolidone, polypropylene glycol, polyacrylamide, hydroxyethyl cellulose, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether and polyoxyethylene cetyl ether.
8. The method according to claim 3, wherein the step A1) further comprises adding a fluorinating agent after mixing;
the fluorinating agent is at least one of ammonium fluoride, hydrofluoric acid, ammonium bifluoride, chlorine fluoride and sulfur tetrafluoride.
9. Cerium oxide obtainable by the process according to any one of claims 1 to 8.
10. The cerium oxide according to claim 9, wherein the particle size of the cerium oxide is 30 to 800nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211143453.0A CN115403064B (en) | 2022-09-20 | 2022-09-20 | Cerium oxide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211143453.0A CN115403064B (en) | 2022-09-20 | 2022-09-20 | Cerium oxide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115403064A true CN115403064A (en) | 2022-11-29 |
| CN115403064B CN115403064B (en) | 2023-10-13 |
Family
ID=84165952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211143453.0A Active CN115403064B (en) | 2022-09-20 | 2022-09-20 | Cerium oxide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115403064B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118125492A (en) * | 2024-02-29 | 2024-06-04 | 北京炜烨创新科技有限公司 | Preparation method of cerium oxide, cerium oxide and application of cerium oxide |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704339A (en) * | 2004-06-03 | 2005-12-07 | 中南大学 | Process for preparing high purity active nano ceria |
| CN1785815A (en) * | 2005-08-28 | 2006-06-14 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN1821314A (en) * | 2005-12-26 | 2006-08-23 | 内蒙古科技大学 | Process for preparing super fine cerium oxide for polishing |
| KR20080111796A (en) * | 2007-06-20 | 2008-12-24 | 주식회사 엘지화학 | Spherical nano-ceria particle method which being capable of controlling surface-area |
| CN101608097A (en) * | 2009-07-14 | 2009-12-23 | 上海华明高纳稀土新材料有限公司 | Nano cerium oxide seriflux for chemical mechanical polishing and preparation method thereof |
| CN103145168A (en) * | 2013-02-28 | 2013-06-12 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Particle-size-controllable nano and sub-micron CeO2 preparation method |
| CN104877573A (en) * | 2015-06-08 | 2015-09-02 | 四川大学 | Preparation method of spherical nano fluorine-doped CeO2 polishing powder |
| CN106146894A (en) * | 2015-03-23 | 2016-11-23 | 李佳怡 | A kind of preparation method of the high transparent hot phase-change material of high thermal insulation |
| KR20190063989A (en) * | 2017-11-30 | 2019-06-10 | 솔브레인 주식회사 | Method of preparing cerium oxide particles, cerium oxide particles and composition of slurry for polishing compring the same |
| CN112266730A (en) * | 2020-12-04 | 2021-01-26 | 内蒙古科技大学 | Preparation method of fluorinated cerium dioxide polishing powder under microwave condition |
| CN114539928A (en) * | 2022-03-16 | 2022-05-27 | 深圳市瑞来稀土材料有限公司 | Rare earth polishing powder for optical glass polishing treatment and preparation method thereof |
| CN115058199A (en) * | 2022-08-18 | 2022-09-16 | 广东粤港澳大湾区黄埔材料研究院 | High-dispersion ball-like nano cerium oxide polishing solution and application thereof |
-
2022
- 2022-09-20 CN CN202211143453.0A patent/CN115403064B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1704339A (en) * | 2004-06-03 | 2005-12-07 | 中南大学 | Process for preparing high purity active nano ceria |
| CN1785815A (en) * | 2005-08-28 | 2006-06-14 | 内蒙古科技大学 | Preparation method of high specific surface area nano-cerium oxide |
| CN1821314A (en) * | 2005-12-26 | 2006-08-23 | 内蒙古科技大学 | Process for preparing super fine cerium oxide for polishing |
| KR20080111796A (en) * | 2007-06-20 | 2008-12-24 | 주식회사 엘지화학 | Spherical nano-ceria particle method which being capable of controlling surface-area |
| CN101608097A (en) * | 2009-07-14 | 2009-12-23 | 上海华明高纳稀土新材料有限公司 | Nano cerium oxide seriflux for chemical mechanical polishing and preparation method thereof |
| CN103145168A (en) * | 2013-02-28 | 2013-06-12 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Particle-size-controllable nano and sub-micron CeO2 preparation method |
| CN106146894A (en) * | 2015-03-23 | 2016-11-23 | 李佳怡 | A kind of preparation method of the high transparent hot phase-change material of high thermal insulation |
| CN104877573A (en) * | 2015-06-08 | 2015-09-02 | 四川大学 | Preparation method of spherical nano fluorine-doped CeO2 polishing powder |
| KR20190063989A (en) * | 2017-11-30 | 2019-06-10 | 솔브레인 주식회사 | Method of preparing cerium oxide particles, cerium oxide particles and composition of slurry for polishing compring the same |
| CN112266730A (en) * | 2020-12-04 | 2021-01-26 | 内蒙古科技大学 | Preparation method of fluorinated cerium dioxide polishing powder under microwave condition |
| CN114539928A (en) * | 2022-03-16 | 2022-05-27 | 深圳市瑞来稀土材料有限公司 | Rare earth polishing powder for optical glass polishing treatment and preparation method thereof |
| CN115058199A (en) * | 2022-08-18 | 2022-09-16 | 广东粤港澳大湾区黄埔材料研究院 | High-dispersion ball-like nano cerium oxide polishing solution and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 周国永等: "碳酸氢铵-氨水-草酸共沉淀法制备微米稀土CeO2工艺的研究", 《化工新型材料》, vol. 40, no. 9, pages 138 - 140 * |
| 王喜龙等: "纳米氧化铈制备技术进展", 《天津化工》, vol. 27, no. 4, pages 3 * |
| 赵朗等: "稀土超精密抛光材料", 《中国稀土学会2021学术年会论文摘要集》, pages 438 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118125492A (en) * | 2024-02-29 | 2024-06-04 | 北京炜烨创新科技有限公司 | Preparation method of cerium oxide, cerium oxide and application of cerium oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115403064B (en) | 2023-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101356870B1 (en) | A process for making cerium oxide nanoparticle | |
| EP1948568B1 (en) | Method for preparing cerium carbonate powder | |
| KR100691908B1 (en) | Coating method of metal oxide superfine particles on the surface of metal oxide and coating produced therefrom | |
| JP6493207B2 (en) | Method for producing cerium oxide abrasive | |
| JP4917098B2 (en) | Cerium carbonate powder and production method, cerium oxide powder produced therefrom and production method, and CMP slurry containing the same | |
| CN112266730B (en) | Preparation method of fluorinated cerium dioxide polishing powder under microwave condition | |
| US20080305025A1 (en) | Methods for Production of Metal Oxide Nano Particles, and Nano Particles and Preparations Produced Thereby | |
| WO2012101871A1 (en) | Fine abrasive particles and process for producing same | |
| Tunusoğlu et al. | Surfactant-assisted formation of organophilic CeO2 nanoparticles | |
| US20080311031A1 (en) | Methods For Production of Metal Oxide Nano Particles With Controlled Properties, and Nano Particles and Preparations Produced Thereby | |
| DE102006011965A1 (en) | Process for producing fine alpha-alumina particles | |
| CN115403064B (en) | Cerium oxide and preparation method thereof | |
| CN115259205A (en) | Preparation method and application of nano cerium oxide | |
| CN108975378A (en) | A kind of dysprosia raw powder's production technology | |
| CN109678506A (en) | A kind of preparation method of erbium oxide crystalline ceramics | |
| CN100427395C (en) | Preparation method of mono dispersion nano-alpha aluminium oxide particle powder | |
| CN102858684A (en) | Method for the mass production of silver nanoparticles having a uniform size | |
| JP2010521405A (en) | Method for producing cerium carbonate powder using urea | |
| Wang et al. | Synthesis of CeO2 nanoparticles derived by urea condensation for chemical mechanical polishing | |
| CN1237006C (en) | In2O3 and ITO monodisperse nano powder hydrothermal preparation method | |
| CN102796493A (en) | Spherical monodisperse high-cerium polishing powder and preparation method thereof | |
| CN115160935A (en) | Octahedral cerium oxide abrasive particle polishing solution and preparation method and application thereof | |
| CN112079379B (en) | ZnTiO compound 3 Material and method for producing same | |
| KR20080054580A (en) | Novel synthetic method of cerium carbonate and ceria, and abrasive liquid containing the said ceria | |
| CN115028451B (en) | Preparation method of terbium oxide nano powder |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |