CN115403064B - Cerium oxide and preparation method thereof - Google Patents
Cerium oxide and preparation method thereof Download PDFInfo
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- CN115403064B CN115403064B CN202211143453.0A CN202211143453A CN115403064B CN 115403064 B CN115403064 B CN 115403064B CN 202211143453 A CN202211143453 A CN 202211143453A CN 115403064 B CN115403064 B CN 115403064B
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- C—CHEMISTRY; METALLURGY
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- 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
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- C01F17/235—Cerium oxides or hydroxides
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The application relates to the field of nano materials, in particular to cerium oxide and a preparation method thereof. The application provides a preparation method of cerium oxide, which uses ammonium hydrogen oxalate and ammonia water as coprecipitators to prepare cerium oxide nano material, can eliminate the influence of particle agglomeration in the preparation process, and obtains nano cerium oxide with uniform particle distribution, and the obtained nano cerium oxide is spherical nano cerium oxide with uniform and compact structure, thereby being beneficial to being applied as polishing powder, and having simple method and low cost. Experiments show that the CeO is prepared by a chemical precipitation method 2 The monomer is synthesized into CeO with controllable particle size and morphology by adjusting experimental conditions such as the addition amount of each medicine, the dropping sequence of the precipitant, the calcination temperature and the like 2 A nanomaterial. The synthesis technology can be used for large-scale production, and CeO prepared after large-scale amplification 2 The nanometer material has high consistency and stability.
Description
Technical Field
The application 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 optical, electronic, network technologies and communication engineering, the requirements of the high surface quality of the integrated circuits on the precision of chemical mechanical polishing are higher and higher, the integrated circuit chips are gradually increased, the individual product body pipe elements are gradually reduced, and the multilayer integrated circuit chips are the necessary trend of technological development. Unlike traditional mechanical or pure polishing method, the technology avoids the disadvantages of low polishing speed, low surface flatness, poor polishing consistency and the like caused by simple mechanical polishing by means of mechanical polishing action of superfine abrasive particles in slurry and chemical corrosion action of materials, and the polishing slurry plays a role in playing a role in influencing the properties of the polishing slurry in the process, so that the optimal abrasive is determined according to different polishing substrates, and the technological process parameters are controlled to meet different requirements of integrated circuit production on chemical mechanical polishing technology in different scales.
Ultra-precise rare earth polishing materials are mainly used for Chemical Mechanical Polishing (CMP) of precision optical materials and chip semiconductor materials. The high-quality polishing solution can break through the following three technologies, namely an abrasive manufacturing technology, an abrasive dispersing technology and a 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 purposefully controlled by combining the actual polishing requirements to ensure the polishing process quality, so that the polishing powder 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 polishing liquid of semiconductor materials. Around the physical properties of the CMP abrasive particles (the size of the particles, the size distribution of the particles, the morphological characteristics of the nanoparticles, the surface properties of the particles, the aggregation or dispersion state of the particles, etc.), the purity, the stability of the solid polishing abrasive, the production cost, the batch repeatability, and especially the consistency and stability of the polishing abrasive after large-scale production are key problems which restrict the difficult industrialization of the polishing abrasive at present.
In the forty of the last century, cerium oxide was 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. Cerium-based rare earth polishing powder has been widely used in various glass products until now. For the field of high-precision optical lenses, high smoothness and light transmittance are required, and higher requirements are put on the particle size distribution, grinding force and scratch rate of polishing powder. The applicability of the high cerium rare earth polishing powder is higher, but the cost of raw materials is too high, and the high cerium rare earth polishing powder is rarely adopted at present. At present, a precipitation-roasting method which takes rare earth chloride as a raw material is generally adopted in the market to prepare cerium-based polishing powder, and the rare earth polishing powder prepared by the method has the advantages of uniform components, moderate particle size and good crystal form consistency, and 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 subject of intense research.
Through continuous practice, people have increasingly recognized polishing powder. With the development of the rare earth industry, the application field of rare earth is expanding, and attempts are beginning 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 many advantages of good crystal form, small and uniform granularity, strong chemical activity, high polishing efficiency, small usage amount, long service life, high work piece qualification rate, easy cleaning, no pollution and the like. Thus, cerium-based polishing powder is also referred to as "king of polishing powder".
The polishing powder on the market at present has uneven polishing granularity, irregular shape or poor cutting force, is easy to produce scratches during polishing and has 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 from experimental comparison and data analysis, so that the optimal modification scheme is determined, the polishing performance of the polishing powder is further improved, and a foundation and thinking are provided for improving and developing a new polishing powder production process. The improved thought of the preparation process aims at physical property control (improving physical chemistry and application characteristics) of an application target, an advanced analytical instrument is utilized to analyze various substance states and performances related to polishing powder, the process method for effectively controlling the production process is provided from the fields of surface chemistry, physics, colloid chemistry and the like, theoretical basis and guidance are provided for industrial application and industrial design, and the method has important significance for future development of the preparation process and development of polishing powder products applicable to silicon wafers and development of polishing powder with high-performance wide particle size gradient.
Ceria (of the formula CeO) 2 ) Has very wide application. For example, it can be used for automobilesThe tail gas ternary purifying catalyst has the advantages of high activity, low price, long service life and the like, replaces most noble metals, and uses thousands of tons each year; ceO (CeO) 2 Can be used for electronic ceramics and solid electrolyte: ceO (CeO) 2 The powder has extremely strong ultraviolet absorption performance, and can be used for preparing ultraviolet absorption materials, such as 185pm short wave ultraviolet rays in fluorescent tubes, so as to improve the service life of the tubes, and also used for sun-proof cosmetics, sun-proof 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 is transparent to sunlight) so as to prevent the plastic from aging; resin and rubber paint are required to be coated on the surfaces of tanks, automobiles, ships, oil storage tanks and the like, and the paint is extremely easy to age and become brittle due to irradiation of sunlight ultraviolet rays, and the anti-ultraviolet paint prepared by adding cerium oxide powder into the paint 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 short, ceO 2 The application of the method has huge potential, high added value and good commercial prospect. But CeO 2 Soft agglomeration easily occurs in the use process, and the agglomeration is serious along with the reduction of the central particle size of powder, so that the suspension performance is poor, the particles are unevenly distributed, the circulating pipeline of the grinding slurry is easily blocked, and the polishing quality and the grinding efficiency of the material are affected.
CeO 2 The preparation method mainly comprises a precipitation method, a sol-gel method, a hydrothermal method, a microemulsion method, an electrochemical method and the like. The liquid phase method is mainly a method for forming 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 like. The liquid phase method is between the gas phase method and the 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, easy amplification and the like, and meanwhile, compared with the powder prepared by the solid phase method, the liquid phase method is pure and less in agglomeration, and is easy to realize industrial production, thus being the most commonly used method for preparing nano particles at present. However, the existing liquid phase method is used for preparing CeO 2 Easy generation of agglomerates and storage of agglomeratesThe material performance is affected by a plurality of adverse effects, such as direct influence on the molding of the material, so that the sintered body cannot finally obtain a material with uniform and compact microstructure; agglomerates can also directly affect the sintering behavior of the material.
In addition, the existing method needs high-temperature high-pressure equipment, is high in price and has no economic value of mass production; some are not suitable for mass production. For example, chinese patent 1821314a discloses a method for preparing ultra-fine cerium oxide, which comprises using an alkaline substance as a precipitant, controlling pH of a reaction suspension to form a precipitate, then converting the suspension with oxalic acid, controlling pH of a reaction end point, finally filtering, washing, drying the precipitate, firing at 600-1000 ℃ to obtain ultra-fine cerium oxide, and polishing. But the particle size distribution of the product prepared by the method is also wider between 10nm and 30um, and the specific surface area reaches 50m 2 And/g, which is poor in recyclability as a polishing powder. For another example, taiwan patent 328068 discloses that mixed cerium nitrate is rapidly heated to 70-100 ℃, the pH value is adjusted to 5-10, and the mixture is kept at the temperature for 0.2-20 hours, thereby obtaining cerium oxide powder of 10-80 nanometers. The precursor of the method is cerium hydroxide, and the daily granularity is too fine to be suitable for polishing powder.
Disclosure of Invention
In view of the above, the technical problem to be solved by the application is to provide a cerium oxide and a preparation method thereof, wherein the method provided by the application can eliminate the influence of particle agglomeration in the preparation process, and the spherical nano cerium oxide with uniform and compact particle structure is obtained, and the method is simple and low in cost.
The application provides a preparation method of cerium oxide, which comprises the following steps:
a) Mixing a precipitator, cerium salt and a surfactant, reacting, and aging to obtain a cerium oxide precursor; the precipitant comprises ammonia water and ammonium hydrogen oxalate;
b) And C), calcining the cerium oxide precursor obtained in the step A) to obtain cerium oxide.
Firstly, mixing a precipitator, cerium salt and a surfactant, reacting and ageing to obtain a cerium oxide precursor, and specifically, the method comprises the following steps:
a1 Adding the precipitant solution into cerium salt solution and surfactant, mixing, and reacting;
a2 And (3) aging the reaction product obtained in the step A1) to obtain a precursor.
In some embodiments of the present application, the cerium salt solution and the surfactant are first mixed, the precipitant is added while stirring, the reaction starts to produce precipitate, and the precipitate is aged, washed and dried to obtain the precursor.
In one embodiment, the method comprises the steps of firstly adding the surfactant into the cerium salt solution, stirring to obtain a mixed solution of the cerium salt solution and the surfactant, transferring the mixed solution of the cerium salt solution and the surfactant into a heating stirrer, then dropwise adding the precipitant into the mixed solution of the cerium salt solution and the surfactant by using a multichannel constant flow pump, reacting at a certain temperature to start to generate precipitate, sealing and aging after the precipitate is completely precipitated, washing with water and ethanol for three times, and drying to obtain a precursor. In one embodiment, the stirring speed is 400r/min to 1000r/min, preferably 500r/min. In one embodiment, the temperature of the reaction is 50 ℃ to 80 ℃, preferably 60 ℃. In one embodiment, the aging temperature is from 50 ℃ to 80 ℃; the aging time is 0-5 h.
The application discloses a method for preparing cerium oxide by precipitation titration, which comprises the steps of preparing a mixed solution of ammonia water and ammonium hydrogen oxalate, wherein the mixed solution is used as a coprecipitator for preparing the cerium oxide by precipitation titration.
In certain embodiments of the application, the molar concentration ratio of the aqueous ammonia to the 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 with 0.1mol/L aqueous ammonia. In certain embodiments of the application, the precipitant solution is added at a rate of 1mL/min to 5mL/min, preferably 2mL/min.
The cerium salts of the present application are 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 mesylate, cerium pyrophosphate, and cerium cyanophosphate, preferably selected from cerium nitrate. In one embodiment, 10 g-15 g of cerium carbonate is dissolved in 5 mL-10 mL of concentrated nitric acid, and water is added to prepare 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 application, 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 comprises 0.4wt% to 1.0wt% of the cerium salt solution, preferably selected from 0.4wt%.
The application adds the precipitant solution into cerium salt solution and surfactant to mix, and can also add 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 application mixes the precipitant, cerium salt and surfactant, reacts and ages to obtain cerium oxide precursor, and then calcines the cerium oxide precursor to obtain cerium oxide. In one embodiment, the temperature of the calcination is 500 ℃ to 800 ℃, preferably 700 ℃; the calcination time is 2 to 4 hours, preferably 2 hours.
The application 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 application provides a preparation method of cerium oxideThe preparation method comprises the following steps: a) Mixing a precipitator, cerium salt and a surfactant, reacting, and aging to obtain a cerium oxide precursor; the precipitant comprises ammonia water and ammonium hydrogen oxalate; b) And C), calcining the cerium oxide precursor obtained in the step A) to obtain cerium oxide. According to the preparation method provided by the application, ammonium hydrogen oxalate and ammonia water are used as coprecipitators for preparing the cerium oxide nano material, so that the influence of particle agglomeration in the preparation process can be eliminated, the nano cerium oxide with uniform particle distribution can be obtained, and the obtained nano cerium oxide is spherical nano cerium oxide with uniform and compact structure, so that the application of the nano cerium oxide as polishing powder is facilitated, and the method is simple and low in cost. Experiments show that the CeO is prepared by a chemical precipitation method 2 The monomer is synthesized into CeO with controllable particle size and morphology by adjusting experimental conditions such as the addition amount of each medicine, the dropping sequence of the precipitant, the calcination temperature and the like 2 A nanomaterial. The synthesis technology can be used for large-scale production, and CeO prepared after large-scale amplification 2 The nanometer material has high consistency and stability.
Drawings
FIG. 1 shows CeO prepared in example 1 2 SEM images of the nano materials;
FIG. 2 shows CeO prepared in example 2 2 SEM images of the nano materials;
FIG. 3 is a CeO prepared in example 3 2 SEM images of the nano materials;
FIG. 4 is a CeO prepared in example 4 2 SEM images of the nano materials;
FIG. 5 is a CeO prepared in example 5 2 SEM images of the nano materials;
FIG. 6 is a CeO prepared in example 6 2 SEM images of the nano materials;
FIG. 7 shows CeO prepared in comparative example 1 2 SEM images of the nano materials;
FIG. 8 is a CeO prepared in comparative example 2 2 SEM images of the nano materials;
FIG. 9 is a CeO prepared in comparative example 3 2 SEM images of the nano materials;
FIG. 10 shows CeO prepared in example 1 2 XRD diffractogram of (2);
FIG. 11 shows CeO prepared in example 1 2 Is a infrared spectrogram of (2);
FIG. 12 shows CeO prepared in example 1 2 Thermal weight profile of precursor.
Detailed Description
The application discloses cerium oxide and a preparation method thereof. Those skilled in the art can, with the benefit of this disclosure, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present application. While the methods and applications of this application have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the application can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the application.
According to the application, a series of cerium oxides are prepared and characterized through a condition optimization experiment.
Influence of CeO 2 The application optimizes the conditions aiming at various factors to finish CeO 2 The controllable preparation of morphology and size mainly examines the influence of cerium nitrate concentration, ammonia water concentration, ammonium hydrogen oxalate concentration, reaction temperature, the type and addition amount of surfactant, aging time and concentration, and calcination temperature. The experimental influencing factors are shown in table 1:
TABLE 1
| Factors of | Level 1 | Level 2 | Level 3 | Level 4 |
| Cerium nitrate concentration/(mol/L) | 0.1 | 0.2 | 0.3 | 0.4 |
| Ammonia concentration/(mol/L) | 1 | 2 | 3 | 4 |
| Concentration of ammonium Hydrogen oxalate/(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 dosage/(%) | 1.0 | 0.8 | 0.6 | 0.4 |
| Aging temperature/(DEGC) | 50 | 60 | 70 | 80 |
| Aging time/(h) | 0 | 1 | 2 | 3 |
| Calcination temperature/(. Degree.C.) | 500 | 600 | 700 | 800 |
The application uses a scanning electron microscope (SEM, hitachi S4800) with acceleration voltage of 30kV to characterize the sample, and observe the appearance and structure of the sample. X-ray powder diffraction (XRD) patterns in the range of 20 DEG to 90 DEG were taken with 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) testing with a Thermo FisherNicolet-6700 spectrometer, and the synthesized samples were subjected to structural analysis. Thermogravimetric analysis (TGA) was performed using a thermogravimetric analyzer (TG/SDTQ 600) in the temperature range of 0 ℃ to 1000 ℃.
The application is further illustrated by the following examples:
example 1
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.4 mol.L of ultrapure water was added thereto to prepare -1 Cerium nitrate solution (b) is stirred at normal temperature. Stirring was maintained, and 0.345g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solutionA. Transferring the mixed solution A into a heating stirrer, wherein the heating temperature is 60 ℃, and the stirring rotating speed is 500 r.min -1 。
Will be 0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 Mixing the aqueous ammonia solution of (2) to prepare the mixed precipitant B. The mixed precipitant B is pumped by a multichannel constant flow pump at the speed of 2mL min -1 Is added dropwise to the above mixed solution A at a rate of 0.15g of ammonium fluoride after the completion of the addition, and the reaction is carried out.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 60 ℃ for aging for 2 hours. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 2 hours at 700 ℃ to obtain spherical CeO with the particle size of 30nm 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 1, FIG. 1 is CeO prepared in example 1 2 SEM images of nanomaterial.
Example 2
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.4 mol.L of ultrapure water was added thereto to prepare -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 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 rotating speed is 500 r.min -1 。
Will be 0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 Mixing the aqueous ammonia solution of (2) to prepare the mixed precipitant B. The mixed precipitant B is pumped by a multichannel constant flow pump at the speed of 2mL min -1 Is added dropwise to the above mixed solution A at a rate of 0.3g of ammonium fluoride after the completion of the addition, and the reaction is carried out.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 60 ℃ for aging for 1 hour. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 2 hours at 800 ℃ to obtain spherical CeO with the particle size of 50nm 2 A nanomaterial. SEM is adopted to obtain CeO 2 Proceeding withMorphology analysis, the results are shown in FIG. 2, FIG. 2 is CeO prepared in example 2 2 SEM images of nanomaterial.
Example 3
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.4 mol.L of ultrapure water was added thereto to prepare -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 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 rotating speed is 500 r.min -1 。
Will be 0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 Mixing the aqueous ammonia solution of (2) to prepare the mixed precipitant B. The mixed precipitant B is pumped by a multichannel constant flow pump at a concentration of 2.5 mL.min -1 Is added dropwise to the above mixed solution A at a rate of 0.3g of ammonium fluoride after the completion of the addition, and the reaction is carried out.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 60 ℃ for aging for 2 hours. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 2 hours at 700 ℃ to obtain spherical CeO with the particle size of 80nm 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 3, and FIG. 3 is CeO prepared in example 3 2 SEM images of nanomaterial.
Example 4
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.4 mol.L of ultrapure water was added thereto to prepare -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 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 70 ℃, and the stirring rotation speed is 500 r.min -1 。
Will be 0.4 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 Mixing the aqueous ammonia solution of (2) to prepare the mixed precipitant B. The mixed precipitant B is pumped by a multichannel constant flow pump at a concentration of 2.5 mL.min -1 Is added into the mixed solution A at a speed of 0.3g of ammonium fluoride after the completion of the addition, and the reaction is carried outShould be.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 70 ℃ for aging for 1 hour. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 2 hours at 600 ℃ to obtain spherical CeO with the particle size of 100nm 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 4, and FIG. 4 is CeO prepared in example 4 2 SEM images of nanomaterial.
Example 5
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.4 mol.L of ultrapure water was added thereto to prepare -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 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 rotating speed is 500 r.min -1 。
Will be 0.3 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 Mixing the aqueous ammonia solution of (2) to prepare the mixed precipitant B. The mixed precipitant B is pumped by a multichannel constant flow pump at a concentration of 2.5 mL.min -1 Is added dropwise to the above mixed solution A at a rate of 0.6g of ammonium fluoride after the completion of the addition, and the reaction is carried out.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 60 ℃ for aging for 3 hours. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 2 hours at 700 ℃ to obtain spherical CeO with the particle size of 200nm 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 5, and FIG. 5 is CeO prepared in example 5 2 SEM images of nanomaterial.
Example 6
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.4 mol.L of ultrapure water was added thereto to prepare -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 0.7g of polyethylene glycol (PEG) was added to the cerium nitrate solution to obtain a mixed solution A. Transferring the mixed solution A toIn the heating stirrer, the heating temperature is 60 ℃, and the stirring rotating speed is 500 r.min -1 。
Will be 0.3 mol.L -1 Ammonium hydrogen oxalate and 0.1 mol.L -1 Mixing the aqueous ammonia solution of (2) to prepare the mixed precipitant B. The mixed precipitant B is pumped by a multichannel constant flow pump at 3mL min -1 Is added dropwise to the above mixed solution A at a rate of 0.6g of ammonium fluoride.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 80 ℃ for aging for 3 hours. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 2 hours at 800 ℃ to obtain spherical CeO with the particle size of 800nm 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 6, FIG. 6 is CeO prepared in example 6 2 SEM images of nanomaterial.
Comparative example 1
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.3 mol.L of ultrapure water was added thereto -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 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 rotating speed is 600 r.min -1 。
The multichannel constant flow pump is utilized to firstly pump 0.3 mol.L -1 The ammonia solution of (2) was used in an amount of 2.5 mL/min -1 Is added dropwise to the above mixed solution A at a rate of 0.3 mol.L -1 The ammonium hydrogen oxalate is added dropwise. After the completion of the dropwise addition, 1g of ammonium fluoride was added to carry out the reaction.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 80 ℃ for aging for 1 hour. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 4 hours at 700 ℃ to obtain micron-sized shuttle CeO 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 7, and FIG. 7 is CeO prepared in comparative example 1 2 SEM images of nanomaterial.
Comparative example 2
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.3 mol.L of ultrapure water was added thereto -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 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 rotating speed is 500 r.min -1 。
The multichannel constant flow pump is utilized to firstly pump 0.3 mol.L -1 The ammonia solution of (2) was used in an amount of 3 mL/min -1 Is added dropwise to the above mixed solution A at a rate of 0.3 mol.L -1 The ammonium hydrogen oxalate is added dropwise. After the completion of the dropwise addition, 1.2g of ammonium fluoride was added to carry out a reaction.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 70 ℃ for aging. And washing the aged sample with distilled water and absolute ethyl alcohol for three times, filtering, and drying at 100 ℃ to obtain a precursor. Calcining the precursor for 2 hours at 700 ℃ to obtain flower-like CeO 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 8, and FIG. 8 is CeO prepared in comparative example 2 2 SEM images of nanomaterial.
Comparative example 3
11.5g of cerium carbonate was dissolved in 7.2mL of concentrated nitric acid, and 0.4 mol.L of ultrapure water was added thereto to prepare -1 Cerium nitrate solution (b) is stirred at normal temperature. While stirring, 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 rotating speed is 500 r.min -1 。
The multichannel constant flow pump is utilized to firstly pump 0.3 mol.L -1 Ammonium hydrogen oxalate solution of 3 mL/min -1 Is added dropwise to the above mixed solution A at a rate of 0.3 mol.L -1 Dropwise adding ammonia water of (2). After completion of the dropwise addition, 0.8g of ammonium fluoride was added to carry out a reaction.
After the reaction was completed, the beaker was sealed with a plastic film, and then placed in an oven at 60 ℃ for aging for 3 hours. Washing the aged sample with distilled water and absolute ethanol three times, and filtering to obtainDrying at 100 ℃ to obtain a precursor. Calcining the precursor for 3 hours at 600 ℃ to obtain flaky CeO 2 A nanomaterial. SEM is adopted to obtain CeO 2 Morphology analysis was performed, the results are shown in FIG. 9, and FIG. 9 shows CeO prepared in comparative example 3 2 SEM images of nanomaterial.
As can be seen from FIGS. 1 to 6, ceO prepared in examples 1 to 6 2 The particles are uniformly dispersed fine spherical particles, and the particle diameters are respectively 30nm, 50nm, 80nm, 100nm, 200nm and 800nm, which shows that the CeO is realized by adjusting the reaction conditions and the calcination temperature 2 And controlling the dimension of the nano particles. As can be seen from FIGS. 7 to 9, ceO prepared in comparative examples 1 to 3 2 CeO of micron-sized dimensions 2 The preparation method has a shuttle shape, a flower shape and a sheet shape respectively, and shows that the comparative examples 1 to 3 prepare the CeO with three different shapes such as the shuttle shape, the flower shape and the sheet shape by utilizing a two-step precipitation method and adjusting the dropping sequence and the dropping amount of the ammonium hydrogen oxalate and the ammonia water 2 A material. In conclusion, the application preliminarily realizes CeO by optimizing and controlling the growth of oxide crystal nucleus and the competitive kinetics of crystal nucleus formation 2 Control of the dimensions, morphology, distribution and aggregation state of the material.
Example 7
For CeO prepared in example 1 2 XRD analysis was performed, the analysis results are shown in FIG. 10, and FIG. 10 shows CeO prepared in example 1 2 Is a XRD diffractogram of (c). As can be seen from FIG. 10, ceO 2 Diffraction peaks of the sample at 2θ=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 (111), (200), (220), (311), (222), (440), (331), and (420) are cubic fluorite structures. Compared with the standard card JCPSSN.34.0394, the synthesized CeO has the peak value and the position consistent with the card, the diffraction peak intensity is higher, the peak shape is sharper, and no impurity peak appears, which indicates the synthesized CeO 2 The purity of the product is high, and the crystallinity is good.
For CeO prepared in example 1 2 Infrared spectroscopic analysis (FT-IR) was conducted, and the analysis result was shown in FIG. 11, and FIG. 11 is CeO prepared in example 1 2 Is a spectrum of infrared light of (a) is obtained. As can be seen from FIG. 11, nano CeO 2 Is present in the spectrum at 3750cm respectively -1 ，2349cm -1 ，1630cm -1 And 750cm -1 4 absorption peaks at 3750cm -1 The nearby absorption peak is nano CeO 2 Stretching vibration of-OH groups in free water of powder at 2349cm -1 And 667cm -1 The absorption peak at the position is mainly attributed to CO adsorbed on the surface of the sample 2 . At 750cm -1 Where due to CeO 2 The absorption peak caused by vibration shows remarkable blue shift mainly because the volume of the nano particles is too small, so that the surface tension of the particles is increased, the interior of the particles is distorted, the length of Ce-O bonds is shortened, and the vibration frequency is increased. Peak position and peak shape of full-segment infrared spectrum and CeO 2 The Sadler standard spectra of (C) agree with each other, indicating CeO 2 Is a successful preparation of (a).
For CeO prepared in example 1 2 TGA analysis was performed and the analysis results are shown in FIG. 12, FIG. 12 being CeO prepared in example 1 2 Thermal weight profile of precursor. As can be seen from fig. 12, at 200 ℃, the precursor exhibits a large endothermic peak, which peak is 73 ℃. At about 218 ℃, the reaction is complete, indicating that the precursor has undergone significant structural water detachment at 200 ℃, a weight loss of 8.2% for this process, and a weight loss curve indicating the presence of significant thermal decomposition reactions in the process. An exothermic peak was present at 278 c, indicating that the decomposition reaction of the precursor continued and the weight loss was 14.8%. The weight loss curve after 398 ℃ becomes gradually smooth, indicating that the decomposition of the precursor has been completed. The total weight loss during the whole decomposition process was about 23%.
In summary, examples 1 to 6 and comparative examples 1 to 3 prepared CeO by chemical precipitation 2 A material. CeO with controllable particle size and morphology is synthesized by adjusting experimental conditions such as the addition amount of each medicine, the dropping sequence of the precipitant, the calcination temperature and the like 2 A material. Wherein examples 1 to 6 successfully synthesize spherical CeO with uniform particle distribution and uniform and compact microstructure 2 A nanomaterial. The synthesis technology can be used for large-scale production, and CeO prepared after large-scale amplification 2 The nano material has a higher oneSex and stability.
The foregoing is only a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art, who is within the scope of the present application, should make equivalent substitutions or modifications according to the technical scheme of the present application and the inventive concept thereof, and should be covered by the scope of the present application.
Claims (7)
1. A method for preparing cerium oxide polishing powder, comprising the following steps:
a1 Adding a precipitant into the cerium salt solution and the surfactant, mixing, and reacting; the molar concentration ratio of the precipitant is 0.1: 0.1-0.4 of a mixed solution of ammonia water and ammonium hydrogen oxalate;
a2 Aging the reaction product obtained in the step A1) to obtain a cerium oxide precursor;
b) Calcining the cerium oxide precursor obtained in the step A2) to obtain spherical cerium oxide, wherein the particle size of the spherical cerium oxide is 30-800 nm.
2. The method of claim 1, wherein the precipitant solution is added at a rate of 1mL/min to 5 mL/min.
3. The preparation method according to claim 1, wherein the concentration of the cerium salt solution is 0.1mol/L to 0.5 mol/L;
the surfactant accounts for 0.4-wt-1.0-wt% of the cerium salt solution by mass.
4. The method according to claim 1, wherein the temperature of the reaction is 50 ℃ to 80 ℃;
the aging temperature is 50-80 ℃; the aging time is 1-5 hours;
the calcining temperature is 500-800 ℃; the calcination time is 2-4 h.
5. 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 methane sulfonate, cerium pyrophosphate, and cerium cyanide 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.
6. The method according to claim 1, wherein the step A1) further comprises adding a fluorinating agent after mixing;
the fluorinating agent is at least one selected from ammonium fluoride, hydrofluoric acid, ammonium bifluoride, chlorine fluoride and sulfur tetrafluoride.
7. A spherical cerium oxide obtained by the production method according to any one of claims 1 to 6.
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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 |
|---|
| 碳酸氢铵-氨水-草酸共沉淀法制备微米稀土CeO2工艺的研究;周国永等;《化工新型材料》;第40卷(第9期);第138-140页 * |
| 稀土超精密抛光材料;赵朗等;《中国稀土学会2021学术年会论文摘要集》;第438页 * |
| 纳米氧化铈制备技术进展;王喜龙等;《天津化工》;第27卷(第4期);第3页第2段 * |
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