CN113817412A - Preparation method of nano polishing powder - Google Patents

Preparation method of nano polishing powder Download PDF

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CN113817412A
CN113817412A CN202111304295.8A CN202111304295A CN113817412A CN 113817412 A CN113817412 A CN 113817412A CN 202111304295 A CN202111304295 A CN 202111304295A CN 113817412 A CN113817412 A CN 113817412A
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lanthanum
graphene
powder
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王玉利
刘洪宝
薄俊东
苗培生
苗鸿波
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Bayannaoer Yixin New Material Co ltd
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    • 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
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • 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
    • 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
    • C01F17/241—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
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    • C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

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Abstract

The invention discloses a preparation method of nano polishing powder, wherein the size of lanthanum-cerium oxide polishing powder prepared by multiple slow deposition and hydrothermal methods is nano-grade, the size is uniform, the fluidity is good, small-particle precipitated crystals are introduced by ammoniated graphene, the obtained oxide particles are highly dispersed, and lanthanum is prepared into lanthanum-cerium oxide by a strong alkaline hydrothermal method, so that lanthanum enters a cerium oxide crystal lattice, the technical problem of poor polishing effect caused by different components in the polishing powder can be effectively shielded, and the hardness of the polishing powder is improved.

Description

Preparation method of nano polishing powder
Technical Field
The invention relates to the technical field of cerium oxide preparation, in particular to a preparation method of nano polishing powder.
Background
With the improvement of the performance requirements of high and new materials in industry, the interest of preparing cerium oxide powder materials with different physical properties is more and more aroused. Therefore, the preparation of cerium oxide ultrafine powder materials with controllable physical properties becomes a focus of research on inorganic powder materials. The small-granularity rare earth oxide powder serving as a functional material has the advantages of high specific surface area, high surface activity, high chemical reaction speed, quick dissolution, high sintered body strength and remarkable effects on refractory materials, semiconductor materials, sensors, ultra-high temperature heat-resistant alloys and the like due to small granularity, uniform granules and narrow distribution. For many years, the production process technology of cerium oxide mainly comprises methods such as an extraction method, an electrolytic oxidation method, an extraction separation method and the like, but the existing process is complex in operation and high in cost, and the prepared cerium oxide is uneven in particle size, poor in flowability and not beneficial to industrial application.
Application CN202110300454 discloses a preparation method of small-particle-size cerium oxide, which comprises the following specific steps: (1) preparing graphene by a hummer method and carrying out high-speed ball milling; (2) the concentration of the prepared ammoniated graphene is 2-7 g/L; (3) slowly titrating; (4) adding ammonia water with the concentration of 7-8mol/L into the cerium chloride solution according to the ratio of the REO mass (g) of the cerium chloride solution to the volume (mL) of the ammonia water of 1:1.5-2, and continuously stirring; (5) ammonium bicarbonate deposition to prepare grey white solid powder for later use; (6) and (4) delivering the grey white powder into a kiln for high-temperature calcination. The method improves the preparation efficiency of the small-granularity cerium oxide, lays a raw material foundation for large-scale industrial application, and particularly has cerium oxide particles with high specific surface area and uniform particle size. In the experimental process, the hardness, polishing rate, scratching effect and particle size distribution of the cerium oxide prepared by the method are all to be improved.
In addition, CN201410256001 discloses a preparation method of rare earth polishing powder, comprising the following steps: (1) precipitating the mixed rare earth by a mixed solution of ammonium bicarbonate and ammonia water, aging, and adding mixed fluoric acid for fluorination to obtain fluoridated basic rare earth carbonate, wherein the mixed rare earth is lanthanum cerium rare earth chloride or lanthanum cerium praseodymium chloride rare earth, and the mixed fluoric acid is mixed acid of hydrofluoric acid and fluosilicic acid; (2) roasting the fluoridized basic rare earth carbonate obtained in the step 1 in multiple stages to obtain a mixed rare earth oxide, wherein the mixed rare earth oxide is a mixture of cerium oxyfluoride and cerium oxide, or a mixture of lanthanum cerium oxyfluoride and cerium oxide; (3) and (3) crushing and grading the mixed rare earth oxide obtained in the step (2) to obtain the rare earth polishing powder, wherein the particle size of the rare earth polishing powder is 0.3-0.5 mu m. The invention can prepare superfine rare earth polishing powder which can reach angstrom level on the glass polishing surface, is uniformly dispersed and has small grain size. It can be seen that the polishing powder mixture of lanthanum oxide and cerium oxide obtained by the above preparation, i.e. the polishing powder contains two polishing materials with different amounts, and the polishing effects of the two polishing materials are different due to the hardness difference of the two polishing materials, which finally results in the polishing effect being less than expected.
Disclosure of Invention
Based on the problems or improvement points of the cerium oxide polishing powder in the prior art, the invention provides a preparation method of nano polishing powder, CeLaOx oxide is prepared by a high-temperature high-pressure strong alkaline hydrothermal method, and the product does not show the XRD diffraction peak of lanthanum oxide, namely La3+ (larger than Ce) with large ionic radius is enabled to pass through an extreme environment4+) Into CeO2In the crystal lattice, CeLaOx oxide is obtained, and the oxide polishing powder has small grain size, pure components, variable hardness, less scratches and higher polishing rate.
A preparation method of nano polishing powder comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruption instrument, and raising the temperature of the ammonia water solution to 80-90 ℃ when the ammonia water solution is oscillatedoC, stopping ultrasonic oscillation, and keeping the temperature at 80-90 DEGoC, refluxing for 4-6 h; naturally cooling, filtering once, diluting, and centrifugally separating to obtain a supernatant to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8-8.5, and the concentration of the prepared ammoniated graphene is 2-7 g/L;
(3) adding water into the cerium chloride stock solution to dilute until REO is 60-90g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 150-;
(4) heating the solution to 30-35 ℃, adding lanthanum cerium chloride, adding ammonia water with the concentration of 7-8mol/L according to the TREO mass (g) of the lanthanum cerium chloride solution and the volume (mL) ratio of the ammonia water of 1:1.5-2, and continuously stirring, wherein the molar ratio of lanthanum to cerium in the lanthanum cerium chloride is 1: (5-7);
(5) heating the solution obtained in the step (4) to 45-55 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of TREO mass (g) of the solution obtained in the step (4) to mass (g) of the solid ammonium bicarbonate of 1:0.7-1, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6-7, and continuously stirring;
(6) transferring the solution into a hydrothermal reaction kettle, adding proper amounts of polyvinylpyrrolidone, sodium citrate, sodium hydroxide and sodium carbonate, wherein the amount of NaOH is 9-12mol/L, the amount of sodium carbonate is 1-2mol/L, the amount of citric acid is 0.5-1mol/L, the amount of polyvinylpyrrolidone is 0.3-0.7g/L, sealing, and increasing the temperature at 5 ℃/min to 290 ℃ -oC, carrying out hydrothermal reaction for 12-24h, naturally cooling, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
(6) and (4) delivering the grey white powder into a kiln for high-temperature calcination, and performing temperature programmed calcination.
Further, the polishing powder is CeLaOx oxide, and the product does not show an XRD diffraction peak of lanthanum oxide.
Furthermore, the D50 of the polishing powder is less than or equal to 100nm, and the D90 is less than or equal to 230 nm.
Further, the specific surface area of the cerium oxide is 20-30m2/g。
Further, the centrifugation in the step (2) is performed by adopting a high-speed centrifuge, the ion speed is 5000rpm, and supernatant is taken.
Further, the temperature programming roasting is 2 to 3oC/min, up to 300-oC, keeping the temperature for 1-2h, and then 10-15oC/min heating to 900-1000oAnd C, keeping the constant temperature for 1.5-2 h.
The present invention is explained as follows:
firstly, graphene is prepared by a typical hummer method, the preparation method is simple, a single-layer graphene sheet layer can be prepared easily, but the long side of the sheet layer is large and exceeds the particle size of cerium oxide, so that subsequent pore-forming is not facilitated, and meanwhile, the graphene sheet layer is large and is not beneficial to obtaining dispersed graphene and needs to be ground.
And then reducing the long edges of the sheet layers by ball milling, dispersing the graphene sheet layers re-bonded by the ball milling again by a cell disruptor, if the ultrasonic oscillation of the cell disruptor is cancelled, the thickness of the graphene sheet layers is extremely large, the aperture is larger than 100nm after pore formation, and the contrast surface area does not contribute, so that the long edges, the thickness and the dispersity of the graphene sheet layers need to be controlled.
Secondly, through the aqueous ammonia backward flow, introduce the amino on graphite alkene surface, mainly there are three effects, one, improve the hydrophilicity of graphite alkene, make things convenient for the abundant contact of cerium oxide and graphite alkene, two, adsorbed amino, be favorable to cerium ion and graphite alkene to pass through amino and be connected, three, avoid agglomerating again through the graphite alkene of cell disruption appearance ultrasonic oscillation dispersion, should pay attention to the concentration of pH concentration and graphite alkene in this process, too high pH can lead to too big in the precipitate crystal of subsequent cerium chloride formation, the dispersity is low, during pH is too low can not form the precipitate crystal, the concentration of graphite alkene is too big, be unfavorable for the deposit to take place, the concentration of graphite alkene is too low, be unfavorable for the promotion of specific surface area.
Compared with the prior application of the applicant, the centrifugal separation is added in the process of obtaining the ammoniated graphene aqueous solution to obtain the supernatant, the particle size of the polishing powder prepared by the hydrothermal method is smaller, so that the requirement on the size of the pore-forming graphene is smaller, and the graphene in the centrifugal supernatant is smaller in sheet layer and is beneficial to obtaining the nano-pore.
Then, adding water to dilute the cerium chloride stock solution until the REO is 60-90g/L to prepare a cerium chloride solution, slowly titrating the cerium chloride solution into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, and the dropwise addition amount is 150-The dropping time is 20-30min, the stirring is continued for 10-20min after the dropping is finished, in the process, the titration should be slow, a needle tube which is pushed quantitatively is recommended to be used for titration, or the titration is performed by gravity, metal ions in the cerium chloride are concentrated and directionally distributed on the surface of amino groups of the graphene by stirring after the titration, and precipitation is generated to form tiny Ce (OH)2Depositing seed particles, a process known as Ce (OH)2Primary precipitation seed crystal process.
And then heating the solution to 30-35 ℃, adding lanthanum cerium chloride, adding ammonia water with the concentration of 7-8mol/L according to the TREO mass (g) of the lanthanum cerium chloride solution and the volume (mL) ratio of the ammonia water of 1:1.5-2, and continuously stirring, wherein the molar ratio of lanthanum to cerium in the lanthanum cerium chloride is 1: (5-7); continuing to deposit large particles of Ce (OH) on the very small precipitated seed particles2The particles can be coated with graphene in the deposition process, so that the deposition and separation of Graphene (GE) and rare earth oxide are effectively avoided, the high specific surface area of the polishing powder is facilitated, a lanthanum cerium chloride solution in the process is called as the deposition and growth process of cerium lanthanum hydroxide, and if the oxidation roasting is carried out in the process, the obtained oxide is a simple mixture of lanthanum oxide and cerium oxide.
Then, after the solution obtained in the step (4) is heated to 45-55 ℃, according to the proportion of 1:0.7-1 of the REO mass (g) of the solution obtained in the step (4) and the mass (g) of solid ammonium bicarbonate, slowly adding the solid ammonium bicarbonate while stirring, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6-7, and then centrifugally drying the precipitated precipitate to obtain off-white solid powder for later use, wherein the reaction mainly occurs in the process, namely, the reaction is 2RE3++6HCO3 -=RE2(CO3)3+3CO2+3H2O,
The RE is lanthanum, cerium, Ce (La) Cl3+6NH4HCO3=Ce(La)(CO3)3+NH4Cl; that is, CeLa (CO) is mainly formed in the process3)xPrecipitating as anisotropic secondary precipitate, directly roasting, and still making lanthanum oxide and oxideA simple mixture of cerium.
(6) Transferring the solution into a hydrothermal reaction kettle, adding proper amounts of polyvinylpyrrolidone, sodium citrate, sodium hydroxide and sodium carbonate, wherein the amount of NaOH is 9-12mol/L, the amount of sodium carbonate is 1-2mol/L, the amount of citric acid is 0.5-1mol/L, the amount of polyvinylpyrrolidone is 0.3-0.7g/L, sealing, and increasing the temperature at 5 ℃/min to 290 ℃ -oC, carrying out hydrothermal reaction for 12-24h, naturally cooling, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
in the general hydrothermal reaction, for example, the reaction temperature is 110-.
In the roasting process, the roasting is temperature programmed roasting: 2-3oC/min, up to 300-oC, keeping the temperature for 1-2h, and then 10-15oC/min heating to 900-oC roasting for 1.5-2h at constant temperature, except dehydration, mainly performing oxidation combustion of the aminated graphene in the first stage, wherein the temperature rise speed is low, the graphene is conveniently and fully combusted, the obtained pore channel is not more than 10nm, the aminated graphene used by the method is selected from centrifugal supernatant fluid, the pore channel is small, and in the second stage, the pore channel is 10-15 hoC/min heating to 900-oC is kept at the constant temperature for 1.5-2h, the temperature rising speed is high, the situation that the pore passages are completely closed due to slow roasting is avoided, the pore passages can be obviously shrunk through fast roasting, the density of the polishing powder is effectively increased, namely the hardness of the polishing powder is increased, and meanwhile, the obtained specific surface area is 20-30m2The specific surface area of the polishing powder is higher than that of the polishing powder of the same kind, namely the adsorption capacity effect is good, and the obtained polishing powder is spherical, as shown in figure 2.
The invention has the advantages and positive effects that:
1. the cerium lanthanum oxide polishing powder prepared by multiple times of slow deposition and a hydrothermal method has the advantages of nanometer-level size, uniform size and good fluidity.
2. The resulting oxide particles are highly dispersed by introducing small particles of precipitated crystals through ammoniated graphene.
3. The lanthanum-cerium oxide is prepared by a hydrothermal method, the oxide is not a mixture, lanthanum enters a cerium oxide lattice, and the technical problem of poor polishing effect caused by different components in the polishing powder can be effectively shielded.
4. By adjusting the entering amount of lanthanum, the hardness of cerium oxide can be effectively improved, and the polishing powder with high removal rate can be obtained.
5. The specific surface area and the pore volume of the cerium oxide are improved by introducing the graphene to be extremely high, and the adsorption capacity is better when the cerium oxide is used as a polishing agent.
Drawings
FIG. 1, XRD patterns of polishing powders of example 2 of the present invention and comparative example;
FIG. 2 is a TEM image of the polishing powder obtained in example 2 of the present invention and an enlarged view thereof.
Detailed Description
For further understanding of the contents, features and effects of the present invention, the following embodiments are exemplified and described in detail with reference to the accompanying drawings, which are intended to be illustrative and not limiting, and the scope of the present invention shall not be limited thereby.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available unless otherwise specified.
Example 1
A preparation method of nano polishing powder comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) placing the graphene in an ammonia solution containing 25wt.% of ammonia water for cell disruptionUltrasonic oscillating the pulverizer, and heating the ammonia water solution to 80 deg.C while oscillatingoC, stopping ultrasonic oscillation, and keeping the temperature at 80 DEG CoC, refluxing for 4 h; naturally cooling, filtering once, diluting, and centrifugally separating at 5000rpm to obtain a supernatant to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8, and the concentration of the prepared ammoniated graphene is 2 g/L;
(3) adding water into the cerium chloride stock solution to dilute until REO is 60g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 150ml, the dropping time is 20min, and continuously stirring for 10min after the dropping is finished;
(4) heating the solution to 30 ℃, adding lanthanum cerium chloride, adding ammonia water with the concentration of 7mol/L according to the TREO mass (g) of the lanthanum cerium chloride solution and the volume (mL) ratio of the ammonia water of 1:1.5, and continuously stirring, wherein the molar ratio of lanthanum to cerium in the lanthanum cerium chloride is 1: 5;
(5) heating the solution obtained in the step (4) to 45 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of TREO mass (g) of the solution obtained in the step (4) to mass (g) of the solid ammonium bicarbonate of 1:0.7, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6, and continuously stirring;
(6) transferring the solution into a hydrothermal reaction kettle, adding appropriate amounts of polyvinylpyrrolidone, sodium citrate, sodium hydroxide and sodium carbonate, wherein the amount of NaOH is 9mol/L, the amount of sodium carbonate is 1mol/L, the amount of citric acid is 0.5mol/L, the amount of polyvinylpyrrolidone is 0.3g/L, sealing, and heating to 290 deg.C/min at 5 deg.C/minoC, carrying out hydrothermal reaction for 12 hours, naturally cooling, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 2oC/min, increasing to 300oC, keeping the temperature for 1h, and then 10oC/min heating to 900oC, keeping the constant temperature for 1.5 h.
Example 2
A preparation method of nano polishing powder comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 27.5wt.%, carrying out ultrasonic oscillation of a cell disruptor, and raising the temperature of the ammonia water solution to 85 ℃ when the oscillation is carried outoC, stopping ultrasonic oscillation, and keeping the temperature at 85 DEGoC, refluxing for 5 hours; naturally cooling, filtering once, diluting, and centrifugally separating at 5000rpm to obtain a supernatant to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8.25, and the concentration of the prepared ammoniated graphene is 4.5 g/L;
(3) adding water into the cerium chloride stock solution to dilute until REO is 75g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 175ml, the dropping time is 25min, and continuously stirring for 15min after the dropping is finished;
(4) heating the solution to 32.5 ℃, adding lanthanum cerium chloride, adding ammonia water with the concentration of 7.5mol/L according to the TREO mass (g) of the lanthanum cerium chloride solution and the volume (mL) ratio of the ammonia water of 1:1.75, and continuously stirring, wherein the molar ratio of lanthanum to cerium in the lanthanum cerium chloride is 1: 6;
(5) heating the solution obtained in the step (4) to 50 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of TREO mass (g) of the solution obtained in the step (4) to mass (g) of the solid ammonium bicarbonate of 1:0.8, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6.5, and continuously stirring;
(6) transferring the solution to a hydrothermal reaction kettle, adding appropriate amounts of polyvinylpyrrolidone, sodium citrate, sodium hydroxide and sodium carbonate, wherein the amount of NaOH is 10.5mol/L, the amount of sodium carbonate is 1.5mol/L, the amount of citric acid is 0.75mol/L, the amount of polyvinylpyrrolidone is 0.5g/L, sealing, and heating to 305 deg.C/min at 5 deg.C/minoC, carrying out hydrothermal reaction for 18h, naturally cooling, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 2.5oC/min, increasing to 325oC, keeping the temperature for 1.5h, and then 12.5oC/min heating to 950oC is kept for 1.75h at constant temperature.
Example 3
A preparation method of nano polishing powder comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 28wt.%, carrying out ultrasonic oscillation of a cell disruption instrument, and raising the temperature of the ammonia water solution to 90 ℃ when the ammonia water solution is oscillatedoC, stopping ultrasonic oscillation, and keeping the temperature at 90 DEGoC, refluxing for 6 h; naturally cooling, filtering once, diluting, and centrifugally separating at 5000rpm to obtain a supernatant to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8.5, and the concentration of the prepared ammoniated graphene is 7 g/L;
(3) adding water into the cerium chloride stock solution to dilute until REO is 90g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 200ml, the dropping time is 30min, and continuously stirring for 20min after the dropping is finished;
(4) heating the solution to 35 ℃, adding lanthanum cerium chloride, adding ammonia water with the concentration of 8mol/L according to the proportion of TREO mass (g) of the lanthanum cerium chloride solution to volume (mL) of the ammonia water of 1: 2, and continuously stirring, wherein the molar ratio of lanthanum to cerium in the lanthanum cerium chloride is 1: 7;
(5) heating the solution obtained in the step (4) to 55 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of TREO mass (g) of the solution obtained in the step (4) to mass (g) of the solid ammonium bicarbonate of 1:1, detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 7, and continuously stirring;
(6) transferring the solution into a hydrothermal reaction kettle, adding appropriate amounts of polyvinylpyrrolidone, sodium citrate, sodium hydroxide and sodium carbonate, wherein the amount of NaOH is 12mol/L, the amount of sodium carbonate is 2mol/L, the amount of citric acid is 1mol/L, the amount of polyvinylpyrrolidone is 0.7g/L, sealing, and heating to 320 deg.C/min at 5 deg.C/minoC, hydrothermal reaction for 24 hours, and naturalAfter cooling, centrifugally drying the separated precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and temperature programming calcination is carried out, wherein the temperature programming calcination is 3oC/min, increased to 350oC, keeping the temperature for 2 hours, and then 15oC/min heating to 1000oAnd C, keeping the constant temperature for 2 hours.
Comparative example 1
A preparation method of nano polishing powder is characterized by comprising the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 27.5wt.%, carrying out ultrasonic oscillation of a cell disruptor, and raising the temperature of the ammonia water solution to 85 ℃ when the oscillation is carried outoC, stopping ultrasonic oscillation, and keeping the temperature at 85 DEGoC, refluxing for 5 hours; naturally cooling, filtering once, diluting, and centrifugally separating at 5000rpm to obtain a supernatant to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8.25, and the concentration of the prepared ammoniated graphene is 4.5 g/L;
(3) adding water into the cerium chloride stock solution to dilute until REO is 75g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 175ml, the dropping time is 25min, and continuously stirring for 15min after the dropping is finished;
(4) heating the solution to 32.5 ℃, adding ammonia water with the concentration of 7.5mol/L according to the TREO mass (g) of the lanthanum cerium chloride solution and the volume (mL) ratio of the ammonia water of 1:1.75, and continuously stirring, wherein the molar ratio of lanthanum to cerium in the lanthanum cerium chloride is 1: 6;
(5) heating the solution obtained in the step (4) to 50 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of TREO mass (g) of the solution obtained in the step (4) to mass (g) of the solid ammonium bicarbonate of 1:0.8, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6.5, and continuously stirring;
(6) transferring the solution to a hydrothermal reaction kettle, and adding appropriate amounts of polyvinylpyrrolidone and citric acidSodium, sodium hydroxide and sodium carbonate, wherein the dosage of NaOH is 0.5mol/L, the dosage of citric acid is 0.75mol/L, the dosage of polyvinylpyrrolidone is 0.5g/L, sealing is carried out, and the temperature is raised to 150 ℃ at the rate of 5 ℃/minoC, carrying out hydrothermal reaction for 18h, naturally cooling, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 2.5oC/min, increasing to 325oC, keeping the temperature for 1.5h, and then 12.5oC/min heating to 950oC is kept for 1.75h at constant temperature.
Comparative example 2
A preparation method of nano polishing powder comprises the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruptor, wherein the frequency of the cell disruptor is 30KHz, the power is 800W, the longest edge of a graphene sheet layer is controlled to be not more than 2 μm, the thickness is not more than 10nm, and when the ammonia water solution is oscillated and heated to 85 DEG, the ammonia water solution is subjected to ultrasonic oscillationoC, stopping ultrasonic oscillation, and keeping the temperature at 85 DEGoC, refluxing for 5 hours; naturally cooling, filtering once, diluting to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8.25, and the concentration of the ammoniated graphene is 4.5 g/L;
(3) and (3) adding water into the lanthanum cerium chloride stock solution to dilute until REO is 75g/L to prepare a lanthanum cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 175ml/L, the dropping time is 25min, and continuously stirring for 15min after the dropping is finished.
(4) Heating the solution to 32.5 ℃, adding 7.5mol/L ammonia water according to the ratio of the REO mass (g) of the lanthanum cerium chloride solution to the volume (mL) of the ammonia water of 1:1.75, and continuously stirring;
(5) heating the solution obtained in the step (4) to 50 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of the REO mass (g) of the solution obtained in the step (4) to the mass (g) of the solid ammonium bicarbonate of 1:0.85, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6.5, and then carrying out centrifugal drying on the precipitated precipitate to obtain off-white solid powder for later use;
(6) the grey white powder is sent into a kiln for high-temperature calcination, and the temperature programming calcination is carried out, wherein the temperature programming calcination is 2.5oC/min, increasing to 325oC, keeping the temperature for 1.5h, and then 12.5oC/min heating to 950oAnd C, roasting and keeping the constant temperature for 1.75 h.
For inventive example 2 and comparative example 1 (CeO), respectivelyX-LaOX) Comparative example 2(CeO2), comparative example 3 (LaO)x) When XRD test is performed, as shown in fig. 1, it can be clearly seen that, as can be seen from example 2 and comparative example 2, the diffraction peaks of the lanthanum cerium polishing powder prepared by the present invention are completely consistent with those of the cerium polishing powder prepared by comparative example 2, and correspond to the (111), (200), (220), and (311) crystal faces (the first four distinct diffraction peaks) of the cubic fluorite structured lanthanum cerium oxide, it can be clearly found that, in the hydrothermal process, La enters the crystal lattice of the cerium oxide, the position of the diffraction peak of the cerium oxide is not changed, and similarly, after the hydrothermal treatment, the diffraction peak obtained by the present invention has high intensity and high crystallinity. By comparing example 2 with comparative example 1, it can be clearly seen that when the hydrothermal temperature is reduced and the hydrothermal solution is in a non-strong alkali condition, the obtained polishing powder is a mixture of lanthanum oxide and cerium oxide, and the obtained polishing effect is poor due to the difference in hardness between the lanthanum oxide and the cerium oxide, and by comparing example 2 with comparative example 1 and comparative example 3, the obtained lanthanum oxide and cerium oxide polishing powder has high purity under the conditions of high temperature, high pressure and high alkali.
Polishing rate test: directly dispersing a certain mass of polishing powder into deionized water to prepare polishing solution, polishing quartz glass, setting the rotating speed of a polishing machine to be 100r/min and the pressure to be 9.8KPa, and performing polishing rate test on example 2 and comparative example 1, wherein the polishing rate of the example 2 is 0.08123mg/min.cm2Comparative example 1 had a polishing rate of 0.0623mg/min.cm2It was found that the hardness of the polishing powder of the present invention was higher than that of the mixture of comparative example 1,the efficiency is higher.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims (6)

1. A preparation method of nano polishing powder is characterized by comprising the following steps:
(1) preparing graphene by a hummer method to obtain graphene powder, and carrying out high-speed ball milling on the graphene powder;
(2) putting the graphene into an ammonia water solution containing 25-28wt.%, carrying out ultrasonic oscillation of a cell disruption instrument, and raising the temperature of the ammonia water solution to 80-90 ℃ when the ammonia water solution is oscillatedoC, stopping ultrasonic oscillation, and keeping the temperature at 80-90 DEGoC, refluxing for 4-6 h; naturally cooling, filtering once, diluting, and centrifugally separating to obtain a supernatant to obtain an ammoniated graphene aqueous solution, wherein the pH value of the aqueous solution is 8-8.5, and the concentration of the prepared ammoniated graphene is 2-7 g/L;
(3) adding water into the cerium chloride stock solution to dilute until REO is 60-90g/L to prepare a cerium chloride solution, slowly titrating into the aqueous solution obtained in the step (2), wherein the temperature is normal temperature, the dropping amount is 150-;
(4) heating the solution to 30-35 ℃, adding lanthanum cerium chloride, adding ammonia water with the concentration of 7-8mol/L according to the TREO mass (g) of the lanthanum cerium chloride solution and the volume (mL) ratio of the ammonia water of 1:1.5-2, and continuously stirring, wherein the molar ratio of lanthanum to cerium in the lanthanum cerium chloride is 1: (5-7);
(5) heating the solution obtained in the step (4) to 45-55 ℃, slowly adding solid ammonium bicarbonate while stirring according to the proportion of TREO mass (g) of the solution obtained in the step (4) to mass (g) of the solid ammonium bicarbonate of 1:0.7-1, simultaneously detecting the pH value, stopping adding the solid ammonium bicarbonate when the pH value is 6-7, and continuously stirring;
(6) transferring the solution into a hydrothermal reaction kettle, and adding appropriate amounts of polyvinylpyrrolidone, sodium citrate and hydrogenSodium oxide and sodium carbonate, wherein the dosage of NaOH is 9-12mol/L, the dosage of sodium carbonate is 1-2mol/L, the dosage of citric acid is 0.5-1mol/L, the dosage of polyvinylpyrrolidone is 0.3-0.7g/L, sealing is carried out, and the temperature is increased to 290 ℃ at 5 ℃/minoC, carrying out hydrothermal reaction for 12-24h, naturally cooling, and then carrying out centrifugal drying on the precipitate to obtain off-white solid powder for later use;
(6) and (4) delivering the grey white powder into a kiln for high-temperature calcination, and performing temperature programmed calcination.
2. The method of claim 1, wherein the polishing powder is CeLaOx oxide, and the product does not show XRD diffraction peak of lanthanum oxide.
3. The method of claim 1, wherein the polishing powder has a D50 of 100nm or less and a D90 of 230nm or less.
4. The method of claim 1, wherein the cerium oxide has a specific surface area of 20 to 30m2/g。
5. The method of claim 1, wherein the centrifugation in step (2) is performed by using a high speed centrifuge at a centrifugation rate of 5000rpm, and collecting the supernatant.
6. The method of claim 1, wherein the temperature-programmed calcination is 2 to 3oC/min, up to 300-oC, keeping the temperature for 1-2h, and then 10-15oC/min heating to 900-oAnd C, keeping the constant temperature for 1.5-2 h.
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