Narrow-distribution small-particle cerium oxide polishing solution and ball-milling preparation method thereof

Abstract

The invention relates to the technical field of preparation of polishing solutions, in particular to a narrow-distribution small-particle cerium oxide polishing solution and a ball-milling preparation method thereof. Cerium oxide, ethylene glycol, a wetting dispersant 1252, an aqueous dispersant Y-181 and deionized water are uniformly stirred and then are ground by a grinding machine to obtain the narrow-distribution small-particle cerium oxide polishing solution. According to the cerium oxide polishing solution prepared by the invention, the final pH value can be respectively controlled to be alkaline or neutral, but the pH value of the conventional cerium oxide polishing solution needs to be adjusted by using an acidity regulator after the conventional cerium oxide polishing solution is prepared, so that the chemical properties of the original polishing solution are influenced. The prepared polishing solution is uniform in particle and narrow in distribution, and the surface smoothness of a polished material can be greatly controlled.

Description

Technical Field

[0001] The invention relates to the technical field of polishing liquid preparation, in particular to a narrow distribution small-particle cerium oxide polishing liquid and a ball milling preparation method thereof. Background Art

[0002] Cerium oxide has high hardness, high polishing efficiency and good chemical stability, and is widely used as a polishing agent for optical glass, crystals and semiconductor materials. It can remove scratches, stains and microscopic defects on the surface of materials, make the surface flat and smooth, and improve the transparency and imaging quality of optical components.

[0003] As a cerium oxide polishing liquid, when the particle distribution is narrow and the particles are small, it can produce a more delicate cutting action during the polishing process, so that the microscopic undulations of the polished surface can be removed more finely, thereby reducing the surface roughness. If the polishing liquid contains larger particles, deeper scratches may be produced on the surface during polishing, resulting in increased surface roughness.

[0004] On the other hand, at alkaline pH values, the alkaline environment can promote certain chemical reactions, help remove specific surface contaminants or improve surface wettability. However, too high alkalinity may also cause corrosion, discoloration and other problems on the surface of the material. For example, in glass polishing, moderate alkalinity can improve the affinity between the polishing liquid and the glass surface and enhance the polishing effect, but too high alkalinity may cause the glass surface to fog.

[0005] For some optical components, the surface roughness is required to reach below the nanometer level. Some existing cerium oxide polishing liquids may not be able to stably achieve such precision, and problems such as scratches and polishing liquid residue may occur, affecting the optical performance of the components. Summary of the invention

[0006] The purpose of the present invention is to improve the polishing effect while reducing the corrosive effect of the alkaline cerium oxide polishing liquid on the polishing material, thereby providing two narrow distribution small particle cerium oxide polishing liquids with different pH values.

[0007] Dilute CeCl3 to 0.2-0.4 mol / L, stir with a stirrer for 0.5 h, add 1%-2% Tween 60 and stir for another 0.5 h, prepare 0.2-0.4 mol / L ammonia solution and add dropwise until the pH value reaches 12, stop adding dropwise, age for 4 h, wash with hot water above 80°C according to the mass ratio of 1:1000 for preparing cerium oxide, drain the moisture of the filter cake with a suction pump, put it into a pot and calcine at 700-800°C for 2-4 h to obtain cerium oxide with a pH value of 12-14.

[0008] Take CeCl3 and dilute it to 0.2-0.4 mol / L. After stirring with a stirrer for 0.5 h, add 1%-2% Tween 60 and stir for another 0.5 h. Add dropwise oxalic acid solution with a concentration of 0.2-0.4 mol / L (the molar ratio of cerium oxide (according to the stoichiometric ratio) to oxalic acid is 1:1.6). Age for 4 h. Wash with hot water above 80°C according to the mass ratio of 1:1000 for preparing cerium oxide. After draining the moisture of the filter cake with a suction pump, put it into a pot and calcine at 700-800°C for 2-4 h to obtain cerium oxide with a pH value of 7-9.

[0009] Take 10%-20% cerium oxide with a pH value of 12-14, 10%-20% ethylene glycol, 58%-79.8% deionized water, 0.1%-1% wetting dispersant 1252, and 0.1%-1% aqueous dispersant Y-181, mix well and grind in a grinder (the grinder is Shanghai Topaz Bedroom 2C sand mill), the ball milling medium is zirconia beads 0.3mm-0.5mm 5kg, and grinding at 800r / min for 6-8h can obtain a narrow distribution small particle cerium oxide polishing liquid with D100 less than 400nm and a pH value of 12-14.

[0010] Take 10%-20% cerium oxide with a pH value of 7-9, 10%-20% ethylene glycol, 58%-79.8% deionized water, 0.1%-1% wetting dispersant 1252, and 0.1%-1% aqueous dispersant Y-181, mix well and grind in a grinder (the grinder is Shanghai Topaz Bedroom 2C sand mill), the ball milling medium is zirconia beads 0.3mm-0.5mm 5kg, and grinding at 800r / min for 6-8h can obtain a narrow distribution small particle cerium oxide polishing liquid with D100 less than 400nm and a pH value of 7-9.

[0011] The application method of the polishing liquid of the present invention is: firstly polishing the base glass lens with cerium oxide polishing liquid with pH value of 12-14, and then polishing it again with cerium oxide polishing liquid with pH value of 7-9. The base glass lens is a lens of a microscope, a telescope, or a camera.

[0012] Beneficial effects: The cerium oxide polishing liquid prepared by the present invention can control the final pH value of the prepared polishing liquid to be alkaline or neutral, while the conventional cerium oxide polishing liquid needs to use an acidity regulator to adjust the pH value of the polishing liquid after preparation, which affects the chemical properties of the original polishing liquid. The polishing liquid prepared by the present invention has uniform particles and narrow distribution, and can greatly control the surface finish of the polished material. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is an electron microscope image of cerium oxide with a pH value of 12-14 prepared in Example 1;

[0014] Figure 2This is an electron microscope image of cerium oxide with a pH value of 7-9 prepared in Example 1;

[0015] Figure 3 This is an electron microscope image of cerium oxide with a pH value of 12-14 prepared in Comparative Example 1;

[0016] Figure 4 This is an electron microscope image of cerium oxide with a pH value of 7-9 prepared in Comparative Example 1;

[0017] Figure 5 This is a diagram of the polishing liquid 1 prepared in Comparative Example 4 after being allowed to stand;

[0018] Figure 6 The particle size distribution diagram of the polishing liquid 1 prepared in Example 1;

[0019] Figure 7 The particle size distribution diagram of the polishing liquid 2 prepared in Example 1;

[0020] Figure 8 The particle size distribution diagram of the polishing liquid 1 prepared in Example 6;

[0021] Fig. 9 The particle size distribution diagram of the polishing liquid 2 prepared in Example 6;

[0022] Fig.10 The particle size distribution diagram of the polishing liquid 1 prepared in Comparative Example 1;

[0023] Fig.11 This is a particle size distribution diagram of the polishing liquid 2 prepared in comparative example 1. DETAILED DESCRIPTION

[0024] The technical solution of the present invention is further described in detail below in conjunction with specific embodiments.

[0025] Example 1

[0026] Preparation of 100g of cerium oxide with a pH value of 12-14: prepare 2.9L of 0.2mol / L CeCl3 aqueous solution and stir for 0.5h, add 2g of Tween 60 and stir for another 0.5h, prepare 0.4mol / L ammonia water and add dropwise at a flow rate of 120g / min until the pH reaches 12, then stop adding dropwise, age for 4h, wash with 100kg of hot water above 80℃ 10 times, drain the filter cake with a suction pump and put it into a bowl and calcine at 800℃ for 2h, sieve the material through 80 mesh to obtain cerium oxide with a pH value of 12-14.

[0027] Preparation of 100 g of cerium oxide with a pH value of 7-9: prepare 2.9 L of 0.2 mol / L CeCl3 aqueous solution and stir for 0.5 h, add 2 g of Tween 60 and stir for another 0.5 h, take 83.66 g of oxalic acid and dissolve it in 2.32 L of deionized water, add it all dropwise at a rate of 120 g / L, age it for 4 h after the addition is completed, wash it with 100 kg of hot water above 80°C in 10 times, drain the filter cake with a suction pump and put it into a bowl and calcine it at 800°C for 2 h, sieve it through 80 mesh after discharge to obtain cerium oxide with a pH value of 7-9.

[0028] Take 100g of the cerium oxide with a pH value of 12-14 prepared above, 200g of ethylene glycol, 694g of deionized water, 3g of wetting dispersant 1252, and 3g of aqueous dispersant Y-181, stir them evenly, and then put them into a grinder for grinding. The grinding speed is 800r / min and the grinding is carried out for 6.5 hours. The particle size of the cerium oxide polishing liquid is detected by a Malvern 2000 laser particle size analyzer to obtain a narrow distribution small particle cerium oxide polishing liquid 1 with a D100 less than 400nm and a pH value between 12-14.

[0029] Take 100g of the cerium oxide with a pH value of 7-9 prepared above, 200g of ethylene glycol, 694g of deionized water, 3g of wetting dispersant 1252, and 3g of aqueous dispersant Y-181, stir them evenly, and then put them into a grinder for grinding. The grinding speed is 800r / min and the grinding is carried out for 6.5 hours. The particle size of the cerium oxide polishing liquid is detected by a Malvern 2000 laser particle size analyzer to obtain a narrow distribution small particle cerium oxide polishing liquid 2 with a D100 less than 400nm and a pH value between 7-9.

[0030] The application method of the polishing liquid is: firstly polish the glass lens with a cerium oxide polishing liquid (polishing liquid 1) having a pH value of 12-14, and then polish it again with a cerium oxide polishing liquid (polishing liquid 2) having a pH value of 7-9.

[0031] The testing method of the present invention is as follows:

[0032] Removal rate: Profilometer measurement method, the profilometer's stylus moves on the surface of the optical glass to measure the surface profile curve before and after polishing, determine the material removal thickness at different locations, and calculate the removal rate based on the measurement area and polishing time.

[0033] Roughness: measured by contact profilometer. The stylus of the contact profilometer passes over the surface of the optical glass, converting the microscopic surface fluctuations into electrical signals, which are then processed to obtain the roughness parameters.

[0034] Flatness: Coordinate measuring machine measurement method. The coordinate measuring machine collects a large number of point coordinate data on the optical glass plane to be measured through a contact probe. These data can accurately reflect the shape of the plane. Then the software is used to process these data and determine the flatness through mathematical methods such as fitting the plane and calculating the distance from the point to the plane.

[0035] Example 2

[0036] Preparation of 100g cerium oxide with a pH value of 12-14: 0.3mol / L CeCl3 was prepared in 1.93L and stirred for 0.5h, 1.5g Tween 60 was added and stirred for 0.5h, 0.3mol / L ammonia water was prepared and added dropwise at a flow rate of 120g / min until the pH value was 12, and then the addition was stopped, aged for 4h, washed with 100kg of hot water above 80°C for 10 times, the filter cake was drained by a suction pump and then placed in a bowl and calcined at 750°C for 2h, and the material was sieved through 80 mesh to obtain cerium oxide with a pH value of 12-14;

[0037] Preparation of 100g of cerium oxide with a pH value of 7-9: 0.3mol / L CeCl3 was prepared in 1.93L and stirred for 0.5h, 1.5g Tween 60 was added and stirred for 0.5h, 83.66g of oxalic acid was dissolved in 2.32L of deionized water, and all was added dropwise at a flow rate of 120g / L. After the addition was completed, it was aged for 4h, and washed with 100kg of hot water above 80°C for 10 times. After the filter cake was drained by a suction pump, it was placed in a bowl and calcined at 800°C for 2h. After the material was discharged, it was sieved through 80 mesh to obtain cerium oxide with a pH value of 7-9;

[0038] The grinding conditions and application methods of the cerium oxide polishing liquid 1 with a pH value of 12-14 and the cerium oxide polishing liquid 2 with a pH value of 7-9 are the same as those in Example 1.

[0039] Example 3

[0040] The preparation of cerium oxide with a pH value of 12-14 and cerium oxide with a pH value of 7-9 is the same as in Example 1;

[0041] Take 200g of cerium oxide with a pH value of 12-14, 100g of ethylene glycol, 684g of deionized water, 8g of wetting dispersant 1252, and 8g of aqueous dispersant Y-181, stir them evenly, put them into a grinder, grind them at a grinding speed of 800r / min for 7.5h to obtain a narrow distribution small particle cerium oxide polishing liquid 1 with a D100 less than 400nm and a pH value between 12-14;

[0042] Take 200g cerium oxide with a pH value of 7-9, 100g ethylene glycol, 684g deionized water, 8g wetting dispersant 1252, and 8g aqueous dispersant Y-181, stir them evenly, and then put them into a grinder for grinding. The grinding speed is 800r / min and the grinding is carried out for 7.5 hours to obtain a narrow distribution small particle cerium oxide polishing liquid 2 with a D100 less than 400nm and a pH value between 7-9.

[0043] The grinding conditions and application methods of the cerium oxide polishing liquid 1 with a pH value of 12-14 and the cerium oxide polishing liquid 2 with a pH value of 7-9 are the same as those in Example 1.

[0044] Example 4

[0045] The preparation of cerium oxide with a pH value of 12-14 and cerium oxide with a pH value of 7-9 is the same as in Example 1;

[0046] Take 120g of cerium oxide with a pH value of 12-14, 180g of ethylene glycol, 698g of deionized water, 1g of wetting dispersant 1252, and 1g of aqueous dispersant Y-181, mix well, and then put into a grinder for grinding at a grinding speed of 800r / min for 7 hours to obtain a narrow distribution small particle cerium oxide polishing liquid 1 with a D100 less than 400nm and a pH value between 12-14;

[0047] Take 120g of cerium oxide with a pH value of 7-9, 180g of ethylene glycol, 698g of deionized water, 1g of wetting dispersant 1252, and 1g of aqueous dispersant Y-181, mix them evenly, and then put them into a grinder for grinding. The grinding speed is 800r / min and the grinding is carried out for 7 hours to obtain a narrow distribution small particle cerium oxide polishing liquid 2 with a D100 less than 400nm and a pH value between 7-9.

[0048] The grinding conditions and application method of the cerium oxide polishing liquid with a pH value of 12-14 and the cerium oxide polishing liquid 2 with a pH value of 7-9 are the same as those in Example 1.

[0049] Example 5

[0050] The preparation of cerium oxide with a pH value of 12-14 and cerium oxide with a pH value of 7-9 is the same as in Example 1;

[0051] Take 120g of cerium oxide with a pH value of 12-14, 180g of ethylene glycol, 692g of deionized water, 3g of wetting dispersant 1252, and 5g of aqueous dispersant Y-181, mix well, and then put into a grinder for grinding at a grinding speed of 800r / min for 6.3 hours. Use Malvern 2000 laser particle size analyzer to detect the particle size of the cerium oxide polishing liquid, and obtain a narrow distribution small particle cerium oxide polishing liquid 1 with a D100 less than 400nm and a pH value between 12-14;

[0052] Take 120g cerium oxide with a pH value of 7-9, 180g ethylene glycol, 692g deionized water, 3g wetting dispersant 1252, and 5g aqueous dispersant Y-181, mix them evenly, and then put them into a grinder for grinding. The grinding speed is 800r / min and the grinding time is 6.3 hours to obtain a narrow distribution small particle cerium oxide polishing liquid 2 with a D100 less than 400nm and a pH value between 7-9.

[0053] The grinding conditions and application methods of the cerium oxide polishing liquid 1 with a pH value of 12-14 and the cerium oxide polishing liquid 2 with a pH value of 7-9 are the same as those in Example 1.

[0054] Example 6

[0055] The preparation of cerium oxide with a pH value of 12-14 and cerium oxide with a pH value of 7-9 is the same as in Example 1;

[0056] Take 120g of cerium oxide with a pH value of 12-14, 180g of ethylene glycol, 692g of deionized water, 4g of wetting dispersant 1252, and 4g of aqueous dispersant Y-181, mix well, and then put into a grinder for grinding at a grinding speed of 800r / min for 6.3 hours. Use Malvern 2000 laser particle size analyzer to detect the particle size of the cerium oxide polishing liquid, and obtain a narrow distribution small particle cerium oxide polishing liquid 1 with a D100 less than 400nm and a pH value between 12-14;

[0057] Take 120g of cerium oxide with a pH value of 7-9, 180g of ethylene glycol, 692g of deionized water, 4g of wetting dispersant 1252, and 4g of aqueous dispersant Y-181, mix them evenly, and then put them into a grinder for grinding. The grinding speed is 800r / min and the grinding time is 6.3 hours to obtain a narrow distribution small particle cerium oxide polishing liquid 2 with a D100 less than 400nm and a pH value between 7-9.

[0058] The grinding conditions and application methods of the cerium oxide polishing liquid 1 with a pH value of 12-14 and the cerium oxide polishing liquid 2 with a pH value of 7-9 are the same as those in Example 1.

[0059] Table 1

[0060]

[0061] Comparative Example 1

[0062] Preparation of cerium oxide with a pH value of 12-14 and cerium oxide with a pH value of 7-9: CeCl3 concentration is 0.5 mol / L, ammonia concentration is 0.5 mol / L, oxalic acid concentration is 0.5 mol / L, and the rest is the same as Example 1. The pH value of the obtained cerium oxide polishing liquid meets the production requirements, but some large particles exist in the particle distribution and cannot be removed.

[0063] Comparative Example 2

[0064] Take 300g of cerium oxide with a pH value of 12-14, cerium oxide with a pH value of 7-9, 200g of ethylene glycol, 500g of deionized water, 3g of wetting dispersant 1252, and 3g of aqueous dispersant Y-181 respectively. The other conditions are the same as those in Example 1. The obtained polishing liquid is relatively viscous. It cannot be further ground after grinding for 2 hours, and some large particles cannot be ground into small pieces.

[0065] Comparative Example 3

[0066] Take 100g of cerium oxide with a pH value of 12-14, 100g of cerium oxide with a pH value of 7-9, 300g of ethylene glycol, and 600g of deionized water respectively. The other conditions are the same as those in Example 1. The slurry obtained by grinding has too many small bubbles, and sampling and detection cannot be performed, and a normal liquid cannot be formed.

[0067] Comparative Example 4

[0068] Take 100g of cerium oxide with a pH value of 12-14, 100g of cerium oxide with a pH value of 7-9, 894g of deionized water, 3g of wetting dispersant 1252, and 3g of aqueous dispersant Y-181 respectively. The other conditions are the same as those in Example 1. The particle size and pH value of the polishing liquid can meet the requirements, but stratification occurs within 2 hours and it cannot be stored for a long time.

[0069] Comparative Example 5

[0070] 100 g of cerium oxide with a pH value of 12-14 and 100 g of cerium oxide with a pH value of 7-9, 200 g of ethylene glycol, 694 g of deionized water, and 6 g of wetting and dispersing agent 1252 were taken respectively. Other conditions were the same as those in Example 1. The obtained particle distribution had some large particles that could not be removed.

[0071] Comparative Example 6

[0072] 100 g of cerium oxide with a pH value of 12-14 and 100 g of cerium oxide with a pH value of 7-9, 200 g of ethylene glycol, 694 g of deionized water, and 6 g of aqueous dispersant BYK-154 were taken respectively. Other conditions were the same as those in Example 1. The obtained particle distribution had some large particles that could not be removed.

Claims

1. A ball milling preparation method for a cerium oxide polishing liquid, characterized in that: The preparation method comprises the following steps: taking cerium oxide, ethylene glycol, wetting dispersant 1252, water-based dispersant Y-181 and deionized water, stirring them evenly, and then grinding them with a grinder to obtain a cerium oxide polishing liquid with narrow distribution and small particles.

2. The ball milling preparation method of cerium oxide polishing liquid according to claim 1, characterized in that: The composition of the cerium oxide polishing liquid according to mass percentage is: cerium oxide 10-20%, ethylene glycol 10-20%, wetting dispersant 1252 0.1-1.0%, water-based dispersant Y-181 0.1-1.0% and deionized water 58-79.8%.

3. The ball milling preparation method of cerium oxide polishing liquid according to claim 1, characterized in that: The ball milling medium is zirconia beads 0.3mm-0.5m, the grinding speed is 800r / min, and the grinding time is 6-8h.

4. The ball milling preparation method of cerium oxide polishing liquid according to claim 1, characterized in that: The preparation method of cerium oxide is as follows: dilute CeCl3 to 0.2-0.4 mol / L, add 1%-2% Tween 60 after stirring for 0.5h, and then stir for another 0.5h, then add ammonia solution with a concentration of 0.2-0.4 mol / L until the pH value is 12, age for 4h, wash with hot water of >80°C at a mass ratio of 1:1000, drain the moisture of the filter cake and calcine in a pot to obtain cerium oxide with a pH value of 12-14.

5. The ball milling preparation method of cerium oxide polishing liquid according to claim 1, characterized in that: The preparation method of cerium oxide is as follows: dilute CeCl3 to 0.2-0.4 mol / L, add 1%-2% Tween 60 after stirring for 0.5h, and then add 0.2-0.4 mol / L oxalic acid solution dropwise, age for 4h, wash with hot water of >80°C at a mass ratio of 1:1000, drain the filter cake and calcine in a pot to obtain cerium oxide with a pH value of 7-9.

6. The ball milling preparation method of cerium oxide polishing liquid according to claim 5, characterized in that: According to the stoichiometric ratio, the molar ratio of cerium oxide to oxalic acid is 1:1.

6.

7. The ball milling preparation method of cerium oxide polishing liquid according to claim 4 or 5, characterized in that: The burning temperature is: 700-800℃, and the burning time is: 2-4h.

8. A cerium oxide polishing liquid prepared according to the method according to any one of claims 1 to 7, characterized in that: The polishing liquid D100 is less than 400nm, and the pH value is 7-9 or 12-14.

9. A method for applying the cerium oxide polishing liquid prepared according to any one of claims 1 to 7, characterized in that: The application method of the polishing liquid is: firstly polishing the substrate glass lens with the cerium oxide polishing liquid with a pH value of 12-14, and then polishing it again with the cerium oxide polishing liquid with a pH value of 7-9.

10. The use of the cerium oxide polishing liquid according to claim 9, characterized in that: The matrix glass lens is a lens for a microscope, a telescope, or a camera.

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