Long-acting anti-wear glass polishing powder and preparation method thereof

Abstract

The present application relates to the technical field of inorganic glass polishing powder preparation, in particular to a long-acting anti-abrasion glass polishing powder and a preparation method thereof. The present application overcomes the problems of traditional cerium-based polishing powder, such as easy settlement and pipeline blockage during processing, and lack of long-acting anti-abrasion protection after polishing. By in-situ combination and addition of sodium lignosulfonate and double-end epoxy polyethylene glycol in the precursor liquid, cross-linking reaction is carried out, and particle settlement is inhibited by steric hindrance and electrostatic repulsion. In addition, calcium metaborate or barium metaborate is added as a boron-containing fluxing component during pyrolysis and multiphase eutectic calcination, which locks the lamellar wear-reducing component in the inorganic skeleton, and integrates the cutting phase and the lubricating phase. Finally, the continuity of the processing flow is improved, and under the shear force, the glass surface migrates to form a film to play a dynamic lubrication role, effectively reducing the scratch width and inhibiting the rise of haze after long-term sand particle erosion.

Description

Technical Field

[0001] This invention relates to the field of inorganic glass polishing powder preparation technology, specifically to a long-lasting wear-resistant glass polishing powder and its preparation method. Background Technology

[0002] Traditional cerium-based polishing powders are widely used in the processing of optical glass and liquid crystal display glass due to their excellent chemical cutting activity and regular grain morphology. With the rapid development of industrial technology, electronic and optical device surfaces have placed higher demands on long-term planarization and protective capabilities. However, the glass surface processed by traditional cerium-based polishing powders is a pure hard inorganic crystalline phase system, lacking a friction-reducing and slip-resistant protective layer with dynamic lubrication function. In subsequent service, when faced with high-frequency reciprocating friction or long-term erosion by solid abrasive particles, it is prone to surface brittle spalling and crack propagation, leading to a serious degradation of the material's long-term wear resistance and protective performance.

[0003] In terms of process, physical compounding with low-friction coefficient solid lubricants or solid-phase sintering with low-melting-point components are used to construct an anti-wear barrier on the processed surface. However, traditional wet fluorination, wet ball milling, or direct calcination methods, when used to process these compounded substances, lack effective local confinement during high-temperature calcination. This easily leads to significant phase separation between the hard cutting phase and the soft lubricating phase, as well as uncontrolled coarsening of rare earth grains. Consequently, the final composite particle structure is loose and the bonding fails. Under the high-shear fluid field of chemical mechanical polishing, components are prone to premature loss, making it impossible to effectively form a film on the glass surface. It is difficult to achieve both stable slurry suspension and long-term anti-wear performance after polishing. Therefore, a long-lasting anti-wear glass polishing powder and its preparation method are proposed. Summary of the Invention

[0004] The purpose of this invention is to provide a long-lasting wear-resistant glass polishing powder and its preparation method. This invention overcomes the problems of traditional cerium-based polishing powders, which easily settle and clog pipelines during processing and lack a long-lasting wear-resistant protective layer on the polished glass.

[0005] The following technical solutions are adopted to solve the above problems: This invention provides a method for preparing a long-lasting wear-resistant glass polishing powder. The preparation method is as follows: 1) Preparation of organic-inorganic composite dispersion of wear-reducing phase: Sodium lignosulfonate and sodium pyrophosphate are mixed and dissolved in a liquid system, and then a double-ended epoxy crosslinking agent is pumped in to carry out a polycondensation reaction to build a stable material flow layer; after the reaction is completed, the layered component is added, and the mixture is subjected to high-frequency ultrasonic peeling and shear dispersion to obtain a stable composite dispersion emulsion.

[0006] 2) In-situ bonding of multiphase inorganic abrasive matrix: Transition metal oxide powder and amorphous borate fluxing phase powder are emulsified and dispersed in deionized water, and then introduced into rare earth salt solution. Under high shear stirring, the composite dispersion emulsion prepared in step 1) is introduced to carry out composite physical co-precipitation and in-situ blending to obtain multiphase composite slurry.

[0007] 3) Pressure atomization, granulation and drying: The multiphase composite slurry is pumped into a pressure spray drying tower for flash dehydration and granulation, and the composite precursor powder is collected.

[0008] 4) Pyrolysis and multiphase eutectic calcination: The composite precursor powder is placed in a protective atmosphere kiln for gradient heat treatment: During the pyrolysis and carbonization stage, the outer organic reaction products are transformed into an in-situ amorphous carbon structure transition layer; then the temperature is raised to solid-phase eutectic reaction to activate the local solid-phase eutectic phase transformation and phase recombination between the amorphous borate flux phase, rare earth phase, sodium pyrophosphate and inorganic abrasive matrix, forming borate multiphase composite particles with high polishing activity containing rare earth, and the layered components are wrapped and embedded in the composite skeleton. After discharge and cooling, a long-lasting anti-wear polishing powder precursor is obtained.

[0009] 5) Airflow deagglomeration and classification: The long-lasting anti-wear polishing powder precursor is fed into a supersonic airflow pulverizer, where it is deagglomerated and classified under the impact of the high-speed flow field, and ultrafine long-lasting anti-wear glass polishing powder with narrow particle size distribution is collected.

[0010] Preferably, in step 1), a quaternary ammonium salt catalyst with a mass fraction of 0.2wt%-0.8wt% of sodium lignosulfonate solid is added to the system, and a sodium hydroxide solution with a mass fraction of 5wt% is added dropwise to adjust the pH value of the liquid phase system to 9.5-10.5; the amount of sodium lignosulfonate solid powder added is 35 parts, the amount of anhydrous sodium pyrophosphate added is 10 parts, and the amount of deionized water added is 30 to 35 times the mass of sodium lignosulfonate; the mechanical stirring speed is 700 rpm to 900 rpm, the stirring temperature is 40°C to 50°C, and the stirring time is 20 min to 30 min.

[0011] Preferably, the quaternary ammonium salt catalyst is tetrabutylammonium bromide.

[0012] Preferably, in step 1), the double-ended epoxy crosslinking agent is selected from one of double-ended epoxy polyethylene glycol or neopentyl glycol diglycidyl ether; the dropping time is controlled within 8 min to 15 min, and after the dropping is completed, the rotation speed is increased to 1400 rpm to 1600 rpm, and the reaction is carried out at a constant temperature of 40°C to 50°C for 35 min to 45 min.

[0013] In this invention, by limiting the molecular ratio of sodium lignosulfonate and the bi-terminal epoxy crosslinking agent and the thermal field reaction kinetics, the phenolic hydroxyl groups, sulfonic acid groups and epoxy end groups on the sodium lignosulfonate molecular chain undergo an in-situ ring-opening nucleophilic substitution reaction, and in-situ self-assembles and polymerizes in the liquid phase system to form a high-viscosity, sedimentation-resistant organic protective body.

[0014] Preferably, in step 1), the layered component is selected from one of hexagonal boron nitride or titanium pyrophosphate, or a mixture thereof in any proportion. Hexagonal boron nitride is abbreviated as h-BN, and titanium pyrophosphate has the chemical formula TiP2O7. Its input amount is 1.1 to 1.8 times the mass of sodium lignosulfonate; the ultrasonic power of the high-frequency ultrasonic disperser is set to 750W to 850W, the ultrasonic frequency is 38kHz to 42kHz, the temperature field during treatment is controlled at 32℃ to 42℃, and the treatment time is 45min to 55min.

[0015] By using high-frequency ultrasound, combined with the physical adsorption and encapsulation barrier effect of the polymer products, large sheet materials are dispersed into micro-nano scale micro-sheets, which are then stably encapsulated in situ at the center of the micelles to prevent secondary overlap.

[0016] Preferably, in step 2), the transition metal oxide powder is selected from nano-barium titanate powder. The amorphous borate fluxing phase powder is selected from either calcium metaborate powder or barium metaborate powder; the mass ratio of the two is controlled between 6.5:1 and 8.5:1; the amount of deionized water added is 1.6 to 1.8 times the total mass of the inorganic powder.

[0017] Preferably, in step 2), the speed of the high-shear emulsifier is controlled at 3200 rpm to 3800 rpm, and the continuous high-speed dispersing and shearing time is 25 min to 35 min; the industrial-grade lanthanum cerium nitrate solution has a mass fraction of 28 wt% to 32 wt% based on rare earth oxides, wherein the rare earth oxides are abbreviated as REO, the atomic ratio of La to Ce is stable at 1:1.8 to 1:2.2, and the continued shearing and stirring time after its addition is 12 min to 18 min.

[0018] Preferably, in step 2), during the in-situ binding reaction in step S2, the pumping flow rate of the composite dispersion emulsion is strictly limited to 55 ml / min to 105 ml / min; after pumping is completed, the stirring speed of the emulsifier is adjusted back to 550 rpm to 650 rpm, the heating is turned on to raise the system temperature to 70°C to 80°C, and the system is kept at a constant temperature or stirred at low speed for 2.5 h to 3.5 h.

[0019] In this invention, since nano-barium titanate and calcium metaborate have high unsaturated surface energy on high shear surfaces, when the composite dispersion emulsion is pumped in at a constant low flow rate, the charged lignin reaction liquid components will be oriented towards the adsorption of lanthanum and cerium components and inorganic abrasive surfaces, thereby forming a dense and uniform organic and inorganic blended shell layer around the multiphase inorganic abrasive particles.

[0020] Preferably, in step 3), the solid suspended matter content of the multiphase composite slurry is controlled between 20wt% and 25wt%, and the solid suspended matter is abbreviated as SS. The process control parameters of the industrial pressure spray drying tower are as follows: the inlet air temperature is controlled between 215℃ and 235℃, the outlet air temperature is controlled between 93℃ and 102℃, and the pressure of the atomizing nozzle at the top of the tower is stabilized between 0.38MPa and 0.42MPa; the collected composite precursor powder has a moisture content ≤1.0wt% and an average particle size span controlled between 15μm and 30μm.

[0021] By controlling the specific temperature gradient and axial pressure distribution of the spray tower, the surface of the atomized droplets and the shell layer are rapidly dehydrated and shaped, and the moisture evaporates evenly from the inside to the outside, avoiding shell cracking caused by local overheating and ensuring the acquisition of a non-hollow, dense precursor.

[0022] Preferably, in step 4), the protective atmosphere kiln is a sealed industrial rotary kiln, and pure nitrogen with a purity ≥99.95% is continuously introduced for atmosphere replacement to adjust the residual oxygen concentration in the kiln to ≤20ppm. The specific operating parameters of the gradient heating program are as follows: during the pyrolysis carbonization stage, the temperature is increased to 510℃ to 530℃ at a rate of 2.2℃ / min to 2.8℃ / min, and then held at this temperature for 2.2h to 2.8h. Subsequently, the heating program is switched, and during the solid-phase eutectic crystallization stage, the temperature is increased to 710℃ to 800℃ at a rate of 4.5℃ / min to 5.5℃ / min. This temperature can be, for example, 720℃, 740℃, 760℃, 770℃, 790℃, etc., and the high-temperature calcination is held for 3.0h to 4.0h. Finally, the kiln is naturally cooled to the room under nitrogen protection.

[0023] Under an oxygen-deficient confined temperature field ranging from 510℃ to 530℃, the outer lignin flexible polymer chains undergo controlled pyrolysis and are transformed in situ into a high-density carbon network. This in-situ generated amorphous carbon structure transition layer serves both as a microscopic barrier and a physical confinement isolation, limiting long-distance grain boundary migration and disordered coarse sintering between internal inorganic particles (as observed in SEM morphology). Figure 1 , Figure 2(A clear change in grain boundaries can be observed). On the other hand, when the kiln temperature further exceeds the eutectic point and rises to 710℃ to 800℃, the activated carbon layer undergoes thermodynamic compatibility softening with boron-containing fluxing components such as calcium metaborate or barium metaborate, significantly reducing the diffusion resistance of the solid-phase reaction and inducing and promoting a highly localized solid-phase eutectic reaction between rare earth oxides, barium titanate matrix surface microcrystals, and sodium pyrophosphate. This results in the in-situ generation of borate composite crystalline particles with high polishing and cutting activity, while simultaneously and firmly mechanically embedding and locking the highly friction-reducing and lubricating lamellar components within the micropores and gaps of these multiphase particles.

[0024] Preferably, in step 5), the operating parameters of the all-ceramic-lined supersonic airflow pulverizer are controlled as follows: the operating pressure of the high-pressure dry air of the pulverizing medium is 0.65MPa to 0.75MPa; the rotation speed of the pulverizer and classifier in the classification zone is adjusted to 3800rpm to 4600rpm; and under the final gas flow of the pulverizing and collecting system, the long-lasting wear-resistant glass polishing powder with a central particle size D50 stable in the range of 0.52μm to 0.75μm is collected and retained.

[0025] The use of a ceramic liner prevents the introduction of metallic foreign matter, such as iron, nickel, and chromium, during the pulverization process. Under the intense opposing collision forces of a high-pressure supersonic flow field (0.65 MPa to 0.75 MPa), the slightly sintered necks formed under the confinement of the in-situ carbon layer undergo brittle fracture and rapid deagglomeration. Because the internal framework grains do not undergo anisotropic coarsening during the calcination stage, the powder exhibits high brittleness and deagglomeration properties, achieving shear fractionation even at low pulverization strength.

[0026] In addition, the main physicochemical properties of the raw and auxiliary materials used in this invention are as follows: Nitrogen purity ≥ 99.95%; REO mass fraction in industrial-grade lanthanum nitrate cerium solution 30 wt%; Nano barium titanate powder purity ≥ 99.2%, average primary particle size 30 nm–50 nm; Calcium metaborate purity ≥ 98.5%, CAS number 13701-64-9, Aladdin C119380; Barium metaborate purity ≥ 99.0%, CAS number 13701-59-2; Sodium lignosulfonate purity ≥ 95.0%, CAS number 8061-51-6; Anhydrous sodium pyrophosphate purity ≥ 99.95%. 9.0%, CAS No. 7722-88-5; Titanium pyrophosphate purity ≥98.0%, CAS No. 13470-09-2; Hexagonal boron nitride purity ≥99.3%, layered particle size ≤1.5μm, CAS No. 10043-11-5; Bi-terminated epoxy polyethylene glycol with an average molecular weight of 600–2000 Da and an epoxy equivalent of 300–1000 g / eq, or products from Henan Alpha Chemical Co., Ltd.; Neopentyl glycol diglycidyl ether CAS No. 17557-23-2.

[0027] This invention also provides a long-lasting anti-wear glass polishing powder, which is prepared by any of the above-mentioned preparation methods. By mass, the raw materials include 780 parts of transition metal oxide powder, 90-140 parts of amorphous borate fluxing phase powder, 450-600 parts of lanthanum cerium nitrate solution, 35 parts of sodium lignosulfonate solid powder, 10 parts of anhydrous sodium pyrophosphate, 12-20 parts of a double-terminated epoxy crosslinking agent, and 40-65 parts of layered components.

[0028] This polishing powder not only maintains a clear supernatant volume of 7.1 mL–11.5 mL after standing in a 20 wt% high-solids-content aqueous suspension for 48 hours, but also exhibits "non-agglomerated" anti-agglomeration stability. When used for chemical mechanical polishing of silicate glass, standard 50 mm × 50 mm, 2.0 mm thick quartz silicate glass was selected as the substrate. The initial surface roughness Ra of the glass surface before polishing remained stable within the range of 0.15 μm–0.18 μm. The finished polishing powders from each group were weighed and prepared into a polishing slurry with a solids content of 12 wt% using deionized water. The pH of the polishing slurry was adjusted to a stable 10.0 using a 2 wt% KOH solution or dilute nitric acid. Polishing was performed using an industrial single-sided chemical mechanical polishing machine with an LP57 polyurethane foam polishing pad (1.0). The polishing pressure was 35 kPa, the polishing disc speed was 75 rpm, and the workpiece loading head rotation speed was 70 rpm. The polishing slurry was pumped through a peristaltic pump at a constant flow rate of 120 mL / min. The material was continuously dripped into the center area of ​​the polishing pad, and the continuous constant temperature polishing process lasted for 45 minutes. After polishing, the glass substrate was transferred to a multi-tank industrial ultrasonic cleaning line for continuous cleaning: first, it was ultrasonically cleaned for 10 minutes in a 0.5 wt% surfactant DBSA aqueous solution tank to remove residual abrasives, with an ultrasonic power of 600 W, a frequency of 40 kHz, and a temperature of 45 °C; then, it was ultrasonically rinsed for 8 minutes in each of two continuous deionized water tanks; finally, the glass substrate was placed in an isopropanol vapor tank for dehydration and slow drying for 3 minutes to obtain the surface to be tested. After treatment, not only was the horizontal scratch width controlled within the range of 1.54 μm–2.25 μm under the severe friction and scratch test of 1000 high-frequency reciprocating diamond needle tip (load 30 N), but also, after long-term scouring and abrasion by 3 kg of natural quartz sand, the change value (Δ) of the light transmittance haze of the glass surface was reduced to a loss level of 0.28%–0.46%, demonstrating the industrial technical effect of combining high dispersion stability and long-term anti-defect protection.

[0029] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. In the in-situ liquid-phase bonding process of the precursor, sodium lignosulfonate is introduced to undergo a liquid-phase polymerization reaction with polyethylene glycol with double-epoxy groups. Through steric hindrance and electrostatic repulsion, the rapid sedimentation of multiphase micro and nano particles in the aqueous medium is inhibited. This not only improves the suspension and dispersion stability of the polishing powder during processing and avoids clogging of the processing pipeline, but also endows the precipitate with excellent anti-caking properties, ensuring the processing continuity in the chemical mechanical polishing process.

[0030] 2. During pyrolysis and multiphase eutectic roasting, calcium metaborate or barium metaborate is added as a boron-containing fluxing component. The resulting amorphous carbon transition layer activates the eutectic reaction between the rare earth phase, the barium titanate matrix, and sodium pyrophosphate. The resulting inorganic multiphase matrix effectively locks in lamellar anti-friction components such as hexagonal boron nitride or titanium pyrophosphate. The microscopic integration of the hard cutting phase and the soft lubricating phase is achieved during the heat treatment stage, preventing the premature loss of free anti-friction particles under high-speed polishing fluid polishing.

[0031] 3. The friction-reducing components sandwiched in the porous skeleton undergo directional migration under the drive of frictional shear stress and are embedded in situ on the glass processing surface to form a film. During subsequent stress, they play a dynamic sliding lubrication role. Although the absolute depth of its surface resistance to the micro-indentation of rigid needle tips is inferior to that of pure hard phase rare earth polishing powder due to the introduction of flexible lubricating phase, it can alleviate and disperse the lateral pressure of the friction interface, prevent brittle peeling and cracking of the glass on both sides of the micro-scratching trajectory, reduce the width of the scratch after friction, and suppress the increase in haze after long-term high-energy sand particle scouring. Attached Figure Description

[0032] Figure 1 The image shows the scanning electron microscope (SEM) morphology of the long-lasting wear-resistant glass polishing powder prepared in Example 1 of this invention. Figure 2 The image shows the SEM morphology of the glass polishing powder prepared by calcination under conventional air atmosphere in Comparative Example 3 of this invention. Figure 3 This is a kinetic curve showing the change in the volume of the upper clarified liquid of the glass polishing powder prepared in Example 1, the control group, and Comparative Example 3 of the present invention over time when the slurry is in a static state. Detailed Implementation

[0033] The technical solution of the present invention will be further illustrated below with reference to the embodiments, but the present invention is not limited to the scope described in the embodiments. Example

[0034] S1. Preparation of organic-inorganic composite dispersions with reduced wear resistance Weigh 35g of sodium lignosulfonate solid powder, 10g of sodium pyrophosphate, and 0.2g of quaternary ammonium salt catalyst, dissolve them in 1200g of deionized water, and mechanically stir at 800rpm for 25min at 45℃ to obtain a homogeneous liquid. Slowly add 15g of di-epoxy polyethylene glycol dropwise to the above liquid over 10min, increase the stirring speed to 1500rpm, and maintain the reaction at 45℃ for 40min. Maintain the pH at 9.5 during the reaction. After the reaction is complete, add 50g of hexagonal boron nitride to the system, transfer the material to a high-frequency ultrasonic disperser, set the ultrasonic power to 800W and the ultrasonic frequency to 40kHz, and continuously sonicate at 35℃–40℃ for 50min to obtain a composite dispersion emulsion.

[0035] S2. In-situ bonding of multiphase inorganic abrasive matrix: 780g of nano-barium titanate powder and 110g of calcium metaborate powder were blended and added to 1500g of deionized water, placed in a 10L reaction vessel, and mechanically dispersed using a high-shear emulsifier at 3500rpm for 30min. Then, 550g of industrial-grade lanthanum cerium nitrate solution (30wt% REO, atomic ratio La:Ce=1:2) was added to the reaction vessel, and mechanical dispersion and stirring continued for 15min. While maintaining emulsification and stirring, the composite dispersion emulsion prepared in step S1 was pumped into the reaction vessel at a constant flow rate of 80ml / min. After pumping, the mechanical stirring speed was adjusted to 600rpm, and heating was turned on to raise the material temperature to 75℃. The reaction was maintained at this temperature for 3h to obtain a multiphase composite slurry.

[0036] S3. Pressure atomization, granulation and drying The multiphase composite slurry obtained in step S2 is pumped into an industrial pressure spray drying tower. The inlet air temperature of the spray tower is controlled at 215℃, and the outlet air temperature is controlled at 95℃. The pressure of the atomizing nozzle at the top of the tower is set to 0.40MPa. After the slurry is dehydrated by high-pressure spray granulation, a composite precursor powder with a moisture content ≤1.0wt% and an average particle size distribution between 15–30μm is collected at the bottom of the tower.

[0037] S4. Pyrolysis and multiphase eutectic roasting The composite precursor powder collected in step S3 was loaded into a corundum crucible and fed into a sealed industrial rotary kiln. Pure nitrogen gas with a purity ≥99.95% was continuously introduced into the kiln for atmosphere replacement, maintaining a residual oxygen concentration ≤20ppm. A gradient heating program was initiated: during the pyrolysis and carbonization stage, the temperature was increased to 520℃ at a rate of 2.5℃ / min, and then held at this temperature for 2.5 hours, during which the outer organic segments were converted into an amorphous carbon structure. During the solid-state eutectic crystallization stage, the temperature was increased to 760℃ at a rate of 5℃ / min, and then held at this high temperature for 3.5 hours. Calcium metaborate, lanthanum cerium oxide, sodium pyrophosphate, and barium titanate surface components underwent a solid-state eutectic reaction, which was observed in detail. Figure 1 It can be seen that after calcination, the overall central particle size distribution is uniform, the grain boundaries are clear, and a borate crystal phase containing rare earth high polishing activity abrasive phase is formed, and hexagonal boron nitride is solidified in the composite structure. The morphology is regular and there are no obvious large hard agglomerates. After calcination, it is naturally cooled to room temperature with the kiln to obtain a long-lasting anti-wear polishing powder precursor.

[0038] S5. Airflow de-aggregation stage The material from the kiln is fed into a fully ceramic-lined supersonic airflow mill for pulverization and deagglomeration. The working medium is 0.7 MPa high-pressure dry air. Inside the pulverization chamber, the high-pressure dry air is injected into the pulverization zone through supersonic nozzles, creating a high-speed airflow field. The material, driven by the high-speed airflow, undergoes frequent and intense collisions and friction, and then rises with the airflow to the classification zone. The pulverizer in the classification zone rotates at 4200 rpm. Under the combined action of the centrifugal force field generated by the rotating classification wheel and the centripetal pull of the airflow, ultrafine particles reaching the set particle size pass through the classification wheel and enter the collection system. Coarse particles that do not reach the set fineness return to the pulverization zone for further pulverization under centrifugal force. After airflow classification, glass polishing powder with a center particle size D50 of 0.58-0.68 μm is collected. Example

[0039] S1. Preparation of organic-inorganic composite dispersions with reduced wear resistance Weigh 35g of sodium lignosulfonate solid powder, 10g of sodium pyrophosphate, and 0.25g of quaternary ammonium salt catalyst, dissolve them in 1200g of deionized water, and mechanically stir at 800rpm for 25min at 45℃ to obtain a homogeneous liquid. Slowly add 12g of liquid di-epoxy polyethylene glycol dropwise to the above liquid over 8min, increase the stirring speed to 1500rpm, and maintain the reaction at 45℃ for 40min. Maintain the pH at 10.0 during the reaction. After the reaction is complete, add 65g of hexagonal boron nitride to the system, transfer the material to a high-frequency ultrasonic disperser, set the ultrasonic power to 800W and the ultrasonic frequency to 40kHz, and continuously sonicate at 35℃–40℃ for 50min to obtain a composite dispersion emulsion.

[0040] S2. In-situ bonding of multiphase inorganic abrasive matrix on surface 780g of nano-barium titanate powder and 140g of calcium metaborate powder were mixed and added to 1450g of deionized water, placed in a 10L reaction vessel, and mechanically dispersed using a high-shear emulsifier at 3500rpm for 30min. Then, 600g of industrial-grade lanthanum nitrate solution (30wt% REO, atomic ratio La:Ce=1:2) was added to the reaction vessel, and mechanical dispersion and stirring continued for 15min. While maintaining emulsification and stirring, the composite dispersion emulsion prepared in step S1 was pumped into the reaction vessel at a constant flow rate of 60ml / min. After pumping, the mechanical stirring speed was adjusted to 600rpm, and heating was turned on to raise the material temperature to 80℃. The reaction was maintained at this temperature for 3h to obtain a multiphase composite slurry.

[0041] S3. Pressure atomization, granulation and drying The multiphase composite slurry obtained in step S2 is pumped into an industrial pressure spray drying tower. The inlet air temperature of the spray tower is controlled at 230℃, and the outlet air temperature is controlled at 100℃. The pressure of the atomizing nozzle at the top of the tower is set to 0.40MPa. After the slurry is dehydrated by high-pressure spray granulation, a composite precursor powder with a moisture content ≤1.0wt% and an average particle size distribution between 15–30μm is collected at the bottom of the tower.

[0042] S4. Pyrolysis and multiphase eutectic roasting The composite precursor powder collected in step S3 was loaded into a corundum sagger and fed into a sealed industrial rotary kiln. Pure nitrogen gas with a purity ≥99.95% was continuously introduced into the kiln for atmosphere replacement, maintaining a residual oxygen concentration ≤20ppm. A gradient heating program was initiated: during the pyrolysis carbonization stage, the temperature was increased to 520℃ at a rate of 2.5℃ / min, and held at this temperature for 2.5 hours, transforming the outer organic chain segments into an amorphous carbon structure. During the solid-phase eutectic crystallization stage, the temperature was increased to 720℃ at a rate of 5℃ / min, and held at this high temperature for 3.5 hours. After calcination, the kiln was allowed to cool naturally to room temperature.

[0043] S5. Airflow de-aggregation stage The material exiting the kiln after calcination is fed into an air jet mill for pulverization and deagglomeration, using 0.7 MPa high-pressure dry air as the working medium. Inside the air jet mill chamber, high-pressure dry air is injected into the pulverization zone through supersonic nozzles, creating a high-speed airflow field. The material, driven by the high-speed airflow, undergoes frequent and intense collisions and friction, and then rises with the airflow to the classification zone. The pulverizer and classifier in the classification zone rotates at 4500 rpm. Under the combined action of the strong centrifugal force field generated by the rotating classifying wheel and the centripetal pull of the airflow, ultrafine particles reaching the set particle size pass through the classifying wheel and enter the collection system. Coarse particles that do not reach the set fineness return to the pulverization zone for further pulverization under centrifugal force. After air jet classification, glass polishing powder with a center particle size D50 of 0.52-0.62 μm is collected. Example

[0044] S1. Preparation of organic-inorganic composite dispersions with reduced wear resistance Weigh 35g of sodium lignosulfonate solid powder, 10g of sodium pyrophosphate, and 0.2g of quaternary ammonium salt catalyst, dissolve them in 1200g of deionized water, and mechanically stir at 800rpm for 25min at 45℃ to obtain a homogeneous liquid. Add 20g of liquid di-epoxy polyethylene glycol dropwise to the above liquid over 15min, increase the stirring speed to 1500rpm, and maintain the reaction at 45℃ for 40min. Maintain the pH at 10.0 during the reaction. After the reaction is complete, add 40g of hexagonal boron nitride to the system, transfer the material to a high-frequency ultrasonic disperser, set the ultrasonic power to 800W and the ultrasonic frequency to 40kHz, and continuously sonicate at 35℃–40℃ for 50min to obtain a composite dispersion emulsion.

[0045] S2. In-situ bonding of multiphase inorganic abrasive matrix on surface 780g of nano-barium titanate powder and 90g of calcium metaborate powder were mixed and added to 1600g of deionized water, placed in a 10L reaction vessel, and mechanically dispersed using a high-shear emulsifier at 3500rpm for 30min. Then, 450g of industrial-grade lanthanum nitrate solution (30wt% REO, atomic ratio La:Ce=1:2) was added to the reaction vessel, and mechanical dispersion and stirring continued for 15min. While maintaining emulsification and stirring, the composite dispersion emulsion prepared in step S1 was pumped into the reaction vessel at a constant flow rate of 100ml / min. After pumping, the mechanical stirring speed was adjusted to 600rpm, and heating was turned on to raise the material temperature to 70℃. The mixture was kept at this temperature for 3h to obtain a multiphase composite slurry.

[0046] S3. Pressure atomization, granulation and drying The multiphase composite slurry obtained in step S2 is pumped into an industrial pressure spray drying tower. The inlet air temperature of the spray tower is controlled at 215℃, and the outlet air temperature is controlled at 93℃. The pressure of the atomizing nozzle at the top of the tower is set to 0.40MPa. After the slurry is dehydrated by high-pressure spray granulation, a composite precursor powder with a moisture content ≤1.0wt% and an average particle size distribution between 15–30μm is collected at the bottom of the tower.

[0047] S4. Pyrolysis and multiphase eutectic roasting The composite precursor powder collected in step S3 was loaded into a corundum sagger and fed into a sealed industrial rotary kiln. Pure nitrogen gas with a purity ≥99.95% was continuously introduced into the kiln for atmosphere replacement, maintaining a residual oxygen concentration ≤20ppm. A gradient heating program was initiated: during the pyrolysis carbonization stage, the temperature was increased to 520℃ at a rate of 2.5℃ / min, and held at this temperature for 2.5 hours, transforming the outer organic chain segments into an amorphous carbon structure. During the solid-phase eutectic crystallization stage, the temperature was increased to 780℃ at a rate of 5℃ / min, and held at this high temperature for 3.5 hours. After calcination, the kiln was allowed to cool naturally to room temperature.

[0048] S5. Airflow de-aggregation stage The material exiting the kiln after calcination is fed into an air jet mill for pulverization and deagglomeration, using 0.7 MPa high-pressure dry air as the working medium. Inside the air jet mill chamber, high-pressure dry air is injected into the pulverization zone through supersonic nozzles, creating a high-speed airflow field. The material, driven by the high-speed airflow, undergoes frequent and intense collisions and friction, and then rises with the airflow to the classification zone. The pulverizer and classifier in the classification zone rotates at 3900 rpm. Under the combined action of the strong centrifugal force field generated by the rotating classification wheel and the centripetal pull of the airflow, ultrafine particles reaching the set particle size pass through the classification wheel and enter the collection system, while coarse particles that do not reach the set fineness return to the pulverization zone for further pulverization under centrifugal force. After air jet classification, glass polishing powder with a center particle size D50 of 0.64-0.75 μm is collected. Example

[0049] S1. Preparation of organic-inorganic composite dispersions with reduced wear resistance Weigh 35g of sodium lignosulfonate solid powder, 10g of sodium pyrophosphate, and 0.15g of quaternary ammonium salt catalyst, dissolve them in 1200g of deionized water, and mechanically stir at 800rpm for 25min at 45℃ to obtain a homogeneous liquid. Add 18g of liquid di-epoxy polyethylene glycol dropwise to the above liquid over 10min, increase the stirring speed to 1500rpm, and maintain the reaction at 45℃ for 40min. Maintain the pH at 10.5 during the reaction. After the reaction is complete, add 60g of hexagonal boron nitride to the system, transfer the material to a high-frequency ultrasonic disperser, set the ultrasonic power to 800W and the ultrasonic frequency to 40kHz, and continuously sonicate at 35℃–40℃ for 50min to obtain a composite dispersion emulsion.

[0050] S2. In-situ bonding of multiphase inorganic abrasive matrix on surface 780g of nano-barium titanate powder and 125g of calcium metaborate powder were mixed and added to 1530g of deionized water, placed in a 10L reaction vessel, and mechanically dispersed using a high-shear emulsifier at 3500rpm for 30min. Then, 520g of industrial-grade lanthanum cerium nitrate solution (30wt% REO, atomic ratio La:Ce=1:2) was added to the reaction vessel, and mechanical dispersion and stirring continued for 15min. While maintaining emulsification and stirring, the composite dispersion emulsion prepared in step S1 was pumped into the reaction vessel at a constant flow rate of 70ml / min. After pumping, the mechanical stirring speed was adjusted to 600rpm, and heating was turned on to raise the material temperature to 78℃. The mixture was kept at this temperature for 3h to obtain a multiphase composite slurry.

[0051] S3. Pressure atomization, granulation and drying The multiphase composite slurry obtained in step S2 is pumped into an industrial pressure spray drying tower. The inlet air temperature of the spray tower is controlled at 235℃, and the outlet air temperature is controlled at 100℃. The pressure of the atomizing nozzle at the top of the tower is set to 0.40MPa. After the slurry is dehydrated by high-pressure spray granulation, a composite precursor powder with a moisture content ≤1.0wt% and an average particle size distribution between 15–30μm is collected at the bottom of the tower.

[0052] S4. Pyrolysis and multiphase eutectic roasting The composite precursor powder collected in step S3 was loaded into a corundum sagger and fed into a sealed industrial rotary kiln. Pure nitrogen gas with a purity ≥99.95% was continuously introduced into the kiln for atmosphere replacement, maintaining a residual oxygen concentration ≤20ppm. A gradient heating program was initiated: during the pyrolysis carbonization stage, the temperature was increased to 520℃ at a rate of 2.5℃ / min, and held at this temperature for 2.5 hours, transforming the outer organic chain segments into an amorphous carbon structure. During the solid-phase eutectic crystallization stage, the temperature was increased to 740℃ at a rate of 5℃ / min, and held at this high temperature for 3.5 hours. After calcination, the kiln was allowed to cool naturally to room temperature.

[0053] S5. Airflow de-aggregation stage The material exiting the kiln after calcination is fed into an air jet mill for pulverization and deagglomeration, using 0.7 MPa high-pressure dry air as the working medium. Inside the air jet mill chamber, high-pressure dry air is injected into the pulverization zone through supersonic nozzles, creating a high-speed airflow field. The material, driven by the high-speed airflow, undergoes frequent and intense collisions and friction, and then rises with the airflow to the classification zone. The pulverizer and classifier in the classification zone rotates at 4400 rpm. Under the combined action of the strong centrifugal force field generated by the rotating classification wheel and the centripetal pull of the airflow, ultrafine particles reaching the set particle size pass through the classification wheel and enter the collection system, while coarse particles that do not reach the set fineness return to the pulverization zone for further pulverization under centrifugal force. After air jet classification, glass polishing powder with a center particle size D50 of 0.55-0.64 μm is collected. Example

[0054] S1. Preparation of organic-inorganic composite dispersions with reduced wear resistance Weigh 35g of sodium lignosulfonate solid powder, 10g of sodium pyrophosphate, and 0.2g of quaternary ammonium salt catalyst, dissolve them in 1200g of deionized water, and mechanically stir at 800rpm for 25min at 45℃ to obtain a homogeneous liquid. Add 14g of liquid di-epoxy polyethylene glycol dropwise to the above liquid over 12min, increase the stirring speed to 1500rpm, and maintain the reaction at 45℃ for 40min. Maintain the pH at 9.5 during the reaction. After the reaction, add 45g of hexagonal boron nitride to the system, transfer the material to a high-frequency ultrasonic disperser, set the ultrasonic power to 800W and the ultrasonic frequency to 40kHz, and continuously sonicate at 35℃–40℃ for 50min to obtain a composite dispersion emulsion.

[0055] S2. In-situ bonding of multiphase inorganic abrasive matrix on surface 780g of nano-barium titanate powder and 105g of calcium metaborate powder were mixed and added to 1580g of deionized water, placed in a 10L reaction vessel, and mechanically dispersed using a high-shear emulsifier at 3500rpm for 30min. Then, 480g of industrial-grade lanthanum nitrate solution (30wt% REO, atomic ratio La:Ce=1:2) was added to the reaction vessel, and mechanically dispersed and stirred for 15min. While maintaining emulsification and stirring, the composite dispersion emulsion prepared in step S1 was pumped into the reaction vessel at a constant flow rate of 90ml / min. After pumping, the mechanical stirring speed was adjusted to 600rpm, and heating was turned on to raise the material temperature to 72℃. The mixture was kept at this temperature for 3h to obtain a multiphase composite slurry.

[0056] S3. Pressure atomization, granulation and drying The multiphase composite slurry obtained in step S2 is pumped into an industrial pressure spray drying tower. The inlet air temperature of the spray tower is controlled at 220℃, and the outlet air temperature is controlled at 102℃. The pressure of the atomizing nozzle at the top of the tower is set to 0.40MPa. After the slurry is dehydrated by high-pressure spray granulation, a composite precursor powder with a moisture content ≤1.0wt% and an average particle size distribution between 15–30μm is collected at the bottom of the tower.

[0057] S4. Pyrolysis and multiphase eutectic roasting The composite precursor powder collected in step S3 was loaded into a corundum sagger and fed into a sealed industrial rotary kiln. Pure nitrogen gas with a purity ≥99.95% was continuously introduced into the kiln for atmosphere replacement, maintaining a residual oxygen concentration ≤20ppm. A gradient heating program was initiated: during the pyrolysis carbonization stage, the temperature was increased to 520℃ at a rate of 2.5℃ / min, and held at this temperature for 2.5 hours, transforming the outer organic chain segments into an amorphous carbon structure. During the solid-phase eutectic crystallization stage, the temperature was increased to 790℃ at a rate of 5℃ / min, and held at this high temperature for 3.5 hours. After calcination, the kiln was allowed to cool naturally to room temperature.

[0058] S5. Airflow de-aggregation stage The material exiting the kiln after calcination is fed into an air jet mill for pulverization and deagglomeration, using 0.7 MPa high-pressure dry air as the working medium. Inside the air jet mill chamber, high-pressure dry air is injected into the pulverization zone through supersonic nozzles, creating a high-speed airflow field. The material, driven by the high-speed airflow, undergoes frequent and intense collisions and friction, and then rises with the airflow to the classification zone. The pulverizer and classifier in the classification zone rotates at 4000 rpm. Under the combined action of the strong centrifugal force field generated by the rotating classification wheel and the centripetal pull of the airflow, ultrafine particles reaching the set particle size pass through the classification wheel and enter the collection system. Coarse particles that do not reach the set fineness return to the pulverization zone for further pulverization under centrifugal force. After air jet classification, glass polishing powder with a center particle size D50 of 0.61-0.71 μm is collected. Example

[0059] S1. Preparation of organic-inorganic composite dispersions with reduced wear resistance Weigh 35g of sodium lignosulfonate solid powder, 10g of sodium pyrophosphate, and 0.2g of quaternary ammonium salt catalyst, dissolve them in 1200g of deionized water, and mechanically stir at 800rpm for 25min at 45℃ to obtain a homogeneous liquid. Slowly add 16g of neopentyl glycol diglycidyl ether to the above liquid over 15min, increase the stirring speed to 1500rpm, and maintain the reaction at 45℃ for 40min. Maintain the pH at 9.5 during the reaction. After the reaction is complete, add 55g of titanium pyrophosphate to the system, transfer the material to a high-frequency ultrasonic disperser, set the ultrasonic power to 800W and the ultrasonic frequency to 40kHz, and continuously sonicate at 35℃–40℃ for 50min to obtain a composite dispersion emulsion.

[0060] S2. In-situ bonding of multiphase inorganic abrasive matrix on surface 780g of nano-barium titanate powder and 120g of barium metaborate powder were blended and added to 1550g of deionized water, placed in a 10L reaction vessel, and mechanically dispersed using a high-shear emulsifier at 3500rpm for 30min. Then, 500g of industrial-grade lanthanum nitrate solution (30wt% REO, atomic ratio La:Ce=1:2) was added to the reaction vessel, and mechanical dispersion and stirring continued for 15min. While maintaining emulsification and stirring, the composite dispersion emulsion prepared in step S1 was pumped into the reaction vessel at a constant flow rate of 85ml / min. After pumping, the mechanical stirring speed was adjusted to 600rpm, and heating was turned on to raise the material temperature to 76℃. The reaction was maintained at this temperature for 3h to obtain a multiphase composite slurry.

[0061] S3. Pressure atomization, granulation and drying The multiphase composite slurry obtained in step S2 is pumped into an industrial pressure spray drying tower. The inlet air temperature of the spray tower is controlled at 225℃, and the outlet air temperature is controlled at 100℃. The pressure of the atomizing nozzle at the top of the tower is set to 0.40MPa. After the slurry is dehydrated by high-pressure spray granulation, a composite precursor powder with a moisture content ≤1.0wt% and an average particle size distribution between 15–30μm is collected at the bottom of the tower.

[0062] S4. Pyrolysis and multiphase eutectic roasting The composite precursor powder collected in step S3 was loaded into a corundum sagger and fed into a sealed industrial rotary kiln. Pure nitrogen gas with a purity ≥99.95% was continuously introduced into the kiln for atmosphere replacement, maintaining a residual oxygen concentration ≤20ppm. A gradient heating program was initiated: during the pyrolysis carbonization stage, the temperature was increased to 520℃ at a rate of 2.5℃ / min, and held at this temperature for 2.5 hours, transforming the outer organic chain segments into an amorphous carbon structure. During the solid-state eutectic crystallization stage, the temperature was increased to 770℃ at a rate of 5℃ / min, and held at this high temperature for 3.5 hours. Barium metaborate reacted with sodium pyrophosphate, titanium pyrophosphate, and barium titanate surface components in a solid-state eutectic reaction, forming a borate crystal phase and solidifying titanium pyrophosphate within the composite structure. After calcination, the kiln was allowed to cool naturally to room temperature.

[0063] S5. Airflow de-aggregation stage The material exiting the kiln after calcination is fed into an air jet mill for pulverization and deagglomeration, using 0.7 MPa high-pressure dry air as the working medium. Inside the air jet mill chamber, high-pressure dry air is injected into the pulverization zone through supersonic nozzles, creating a high-speed airflow field. The material, driven by the high-speed airflow, undergoes frequent and intense collisions and friction, and then rises with the airflow to the classification zone. The pulverizer and classifier in the classification zone rotates at 4100 rpm. Under the combined action of the strong centrifugal force field generated by the rotating classification wheel and the centripetal pull of the airflow, ultrafine particles reaching the set particle size pass through the classification wheel and enter the collection system, while coarse particles that do not reach the set fineness return to the pulverization zone for further pulverization under centrifugal force. After air jet classification, glass polishing powder with a center particle size D50 of 0.60-0.70 μm is collected.

[0064] control group Specifically, it is a glass polishing powder prepared according to the scheme of Example 1 in CN111978869B.

[0065] Comparative Example 1 Referring to Example 1, in process step S1, hexagonal boron nitride is not added, that is, only sodium lignosulfonate, sodium pyrophosphate and bi-epoxy polyethylene glycol undergo cross-linking reaction in the liquid phase. In subsequent step S2, the emulsion is directly pumped into a deionized water suspension containing 780g of nano barium titanate powder, 110g of calcium metaborate powder and 550g of industrial-grade lanthanum cerium nitrate solution (deionized water is reduced to 1500g accordingly). The remaining formulation amounts and process parameters remain unchanged.

[0066] Comparative Example 2 The technical solution is the same as in Example 1, but in process step S2, the amount of calcium metaborate is adjusted from 110g to 15g, while the amounts of other components, process steps, and operating parameters remain unchanged.

[0067] Comparative Example 3 The technical solution is based on Example 1, except that in process step S4, the atmosphere control method during calcination is changed: instead of pure nitrogen, the temperature is directly raised to 520°C at a rate of 2.5°C / min and held for 2.5 hours under a conventional air atmosphere, followed by a further increase in temperature to 760°C at a rate of 5°C / min and high-temperature calcination for 3.5 hours. The remaining process formula and parameters remain unchanged. The long-lasting anti-wear polishing powder precursor obtained in S4 exhibits coarsened recrystallization, forming a large number of amorphous, multi-faceted, disordered, blocky hard agglomerates. Heat treatment under a conventional air atmosphere causes the lignin cross-linking network on the precursor surface to undergo violent oxidation and combustion during pyrolysis at 520°C, converting entirely into gas and escaping. This results in the loss of the microscopic local confinement of the amorphous carbon skeleton and the isolation and support between phases, leading to uncontrolled disordered contact sintering of the precursor particles during subsequent temperature-raising crystallization. Ultimately, this results in poor subsequent suspension and reduced wear resistance of the glass obtained after polishing.

[0068] Comparative Example 4 The technical solution is the same as in Example 1, but in the solid-state eutectic crystallization stage of process step S4, the high-temperature calcination temperature is reduced from 760°C to 610°C, while the holding time is still maintained at 3.5h. The heating rate, pyrolysis stage temperature and other steps remain unchanged.

[0069] The test examples included tests for dispersion and glass abrasion resistance. The suspension dispersibility test method is as follows: Weigh 100g of polishing powder samples from each example, comparative example, and control group, add 400g of deionized water, and prepare an aqueous suspension with a solid content of 20wt%. Place the slurry on a magnetic stirrer and continuously stir and disperse at 800rpm for 30min to achieve a uniform suspension state. Quickly pour the uniformly stirred slurry into a 100mL stoppered graduated cylinder to the 100mL mark and record the initial time. After standing for 2h, 24h, and 48h, visually read and record the volume (unit: mL) of the clear liquid on the upper layer of the graduated cylinder. The smaller the volume of the clear liquid on the upper layer, the better the suspension dispersibility and anti-agglomeration performance of the powder in the aqueous phase. After standing for 48h, remove the stopper of the graduated cylinder and invert the graduated cylinder stably 180°. Observe the flow state of the precipitate at the bottom. If the precipitate flows out directly in a fluid state, or can be completely poured out with just a gentle shake, it is judged as "no hard lumps"; if the precipitate is firmly adhered to the bottom of the graduated cylinder and cannot be poured out even after continuous tapping or shaking, it is judged as "hard lumps". The test results are shown in Table 1 and... Figure 3 As shown, the results are expressed as the data mean ± relative standard deviation.

[0070] Initial microhardness testing was performed according to GB / T 37900-2019 with adjustments. Standard chemical mechanical polishing was conducted on silicate glass substrates of the same specifications using polishing powders of each group. After processing, the substrates were cleaned with deionized water and ultrasonically, and then dried. A micro Vickers hardness tester was used, equipped with a standard diamond pyramid indenter. A defect-free area was selected on the glass surface, and a fixed test load of 200g (1.96N) was set, with a holding time of 10s. After unloading, the lengths of the two diagonals of the indentation were measured under a microscope. The initial micro Vickers hardness value of the glass surface was calculated using the Vickers hardness calculation formula or the system's built-in software. Five points were randomly measured on each sample, and the average value was taken.

[0071] The method for reciprocating friction and scratch testing is as follows: a reciprocating friction and wear testing machine is used, and the friction pair is equipped with diamond scratching needles with a radius of curvature R=0.2mm. The glass samples, after polishing treatment for each group, are fixed on a horizontal test platform, and a vertical gradient load of 30N is applied. The reciprocating stroke is set to 50mm, and the reciprocating frequency is 2Hz. The testing machine is started, and 1000 reciprocating wiping tests are continuously performed on the same trajectory on the glass surface. After the test, a white light interferometer is used to perform a three-dimensional scan of the cross-sectional morphology of the wiping area, and the vertical scratch depth (μm) and horizontal scratch width (μm) at the center of the scratch trajectory are measured and read.

[0072] Table 1-1 Test Results of Suspension Dispersion and Dispersion Indicators During Processing Example 1 1.5±4.2% 6.8±3.5% 8.2±3.1% No hard lumps Example 2 1.2±4.5% 5.9±3.8% 7.1±3.3% No hard lumps Example 3 2.2±4.1% 8.4±3.6% 10.2±3.0% No hard lumps Example 4 1.7±4.3% 7.2±3.4% 8.7±3.2% No hard lumps Example 5 2.0±4.0% 7.9±3.7% 9.5±3.1% No hard lumps Example 6 1.4±4.6% 6.3±3.9% 7.6±3.4% No hard lumps control group 8.5±3.8% 27.2±2.9% 31.0±2.5% hard lumps Comparative Example 1 3.8±4.8% 13.5±4.0% 15.4±3.6% hard lumps Comparative Example 2 1.8±4.4% 7.5±3.5% 9.0±3.2% No hard lumps Comparative Example 3 3.2±4.3% 12.1±3.7% 14.2±3.3% hard lumps Comparative Example 4 1.6±4.2% 7.0±3.6% 8.5±3.1% No hard lumps Depend on Figure 3 The volume change curve of the clarified liquid over time shows that the sedimentation behavior of each group of powders in the aqueous medium exhibits nonlinear rheology and sedimentation that conforms to the laws of physicochemical processes. That is, in the early stage of 0–24h settling, there is relatively significant rapid free sedimentation and regional sedimentation. In the later stage of 24–48h settling, due to the densification of the bottom sediment, the volume growth rate slows down significantly and gradually tends to a gentle saturated compaction plateau.

[0073] The long-term sand-fall abrasion test method is as follows: Strictly selected natural quartz sand is used as the abrasive medium, with particle size controlled between 0.5 and 1.0 mm. The polished glass sample is fixed on the sample holder of a standard sand-fall tester, with the glass's light-receiving surface tilted at a 45° angle to the horizontal plane. A conduit is connected, allowing 3 kg of quartz sand to fall freely from a fixed height of 1 m through the vertical conduit, continuously scouring the tilted glass surface. The sand flow rate is controlled to be uniform using a gravity regulating valve. Before and after the sand-fall abrasion test, the light transmittance haze in the central wear area of ​​the sample is measured using a fully automatic haze meter. The haze difference before and after scouring is calculated as Δ = Δafter wear - Δinitial. The smaller the Δ value, the stronger the long-term resistance to environmental friction and erosion of the chemical / modified protective layer formed on the glass surface during polishing.

[0074] Table 1-2 Test Results of Scratch Resistance and Long-Term Abrasion Resistance of Glass Surface Example 1 632.4±1.5% 0.15±4.8% 1.82±3.9% 0.35±5.1% Example 2 645.1±1.3% 0.11±5.2% 1.54±4.2% 0.28±5.5% Example 3 610.8±1.6% 0.21±4.5% 2.25±3.7% 0.46±4.8% Example 4 625.2±1.4% 0.17±4.9% 1.98±4.0% 0.38±5.2% Example 5 618.5±1.5% 0.19±4.7% 2.10±3.8% 0.42±5.0% Example 6 638.7±1.2% 0.13±5.0% 1.68±4.1% 0.31±5.3% control group 715.0±2.1% 0.08±3.6% 3.65±2.8% 0.95±4.2% Comparative Example 1 692.1±1.8% 0.12±4.2% 2.92±3.3% 0.68±4.6% Comparative Example 2 608.4±2.0% 0.28±3.8% 2.98±3.0% 0.78±4.4% Comparative Example 3 612.6±1.9% 0.25±3.9% 2.84±3.1% 0.73±4.5% Comparative Example 4 620.3±1.7% 0.22±4.1% 2.34±3.4% 0.52±4.3% The above test results show that the polishing powder dispersibility and the resulting glass abrasion resistance of the embodiments are good. The embodiments represented by Examples 1 and 2, while maintaining excellent processing dispersibility, improve the long-term wear resistance and scratch resistance of the polished glass surface. In steps S1 and S2, sodium lignosulfonate and di-epoxy polyethylene glycol undergo in-situ liquid-phase polymerization, constructing a composite protective layer in situ on the precursor surface. This structure inhibits the disordered aggregation of multiphase abrasive particles through physical barrier and spatial shielding effects, maintaining the sedimentation volume of the 20wt% high-solids suspension at a low level of 8.0–9.2 mL after standing for 48 hours, demonstrating good slurry dispersion stability. In step S4, during gradient calcination, calcium metaborate or barium metaborate, as a boron-containing fluxing component, softens and reduces... The diffusion resistance of the interfacial solid-phase reaction promotes a local solid-phase eutectic reaction between the rare earth active phase, barium titanate matrix, and sodium pyrophosphate, resulting in the in-situ growth of borate multiphase composite particles with moderate hardness. Hexagonal boron nitride or titanium pyrophosphate slip phases are strongly locked and anchored within the particle skeleton. During CMP polishing, these multiphase composite particles migrate to the glass surface under interfacial shear force. In 1000 high-frequency reciprocating friction tests, the protective material on the glass surface effectively disperses the normal stress and reduces the interfacial friction coefficient. Although the absolute depth of its surface resistance to micro-indentation by the needle tip is slightly less than that of the pure hard phase control group due to the introduction of the flexible lubricating phase, it effectively inhibits macroscopic brittle fracture and microcrack propagation on both sides of the scratch. Therefore, its scratch width and the increase in haze from sand erosion are at the lowest levels.

[0075] In contrast, the control group was prepared according to the existing technology CN111978869B. The product is a pure hard inorganic crystalline phase system consisting of lanthanum oxyfluoride, lanthanum phosphate, and cerium-rich active cerium dioxide, which are fully crystallized and recrystallized. It does not contain any low-hardness organic modified carbonized products or flexible friction-reducing slip phases. Therefore, the abrasive has high overall rigidity, and the glass surface after polishing has a hardness as high as 715.0 kgf / mm². 2 The initial micro Vickers hardness of the sample exhibited strong vertical indentation resistance in the early stage of the reciprocating friction scratch test, resulting in a scratch depth of 0.08 μm. However, due to the lack of a spatial barrier layer in its precursor, its 48-hour settling volume in the suspension was significantly higher. Furthermore, because the system did not contain any solid anti-friction components, it could not provide physical slip modification in the polishing area, leading to a high-friction state for the friction pair. In the later stage of 1000 consecutive reciprocating friction cycles and the long-term scouring of 3 kg of high-energy quartz sand, the lack of a physical anti-friction modification layer resulted in surface friction shear stress concentration. Consequently, the haze change value and reciprocating scratch width after sand scouring were inferior to those of the other embodiments.

[0076] For each comparative example, Comparative Example 1, lacking a solid slip hexagonal boron nitride component with a low coefficient of friction, undergoes sintering of calcium metaborate and rare earth components into a pure hard composite crystalline phase during calcination. It is not occupied or diluted by the soft phase, so its initial microhardness and reciprocating scratch depth exhibit high rigidity characteristics approaching those of the control group. However, in the later stages of friction and during the sand drop test, due to the lack of physical barrier protection from the friction-reducing modification layer, the horizontal friction shear force causes local micro-tensile cracks and micro-peeling. The scratch width and sand drop haze changes fail to reach the protection level of the examples. Comparative Example 2 reduced the amount of calcium metaborate. Due to the lack of sufficient low-melting-point eutectic liquid medium during calcination at 760℃, the resistance to solid-phase diffusion kinetics increased, preventing efficient in-situ bonding into multiphase borate particles. This resulted in insufficient binding force of the inorganic structure to hexagonal boron nitride, causing slipped particles to become free during polishing and prematurely lost with the waste liquid. These particles failed to accumulate and form a protective layer in the processing zone, leading to a significant degradation in the initial microhardness and long-term wear resistance of the glass surface. Comparative Example 3, calcined in a conventional air atmosphere, caused the lignin reaction liquid products on the precursor surface to undergo violent oxidation and combustion during pyrolysis at 520℃, converting into gas and escaping. This resulted in the loss of the microscopic barrier and physical confinement isolation provided by the carbon layer, leading to significant degradation in scanning electron microscopy (SEM). Figure 2 The sintered material exhibits an extremely uneven, malignantly disordered contact morphology, and the sedimentation properties of the suspension deteriorate after depolymerization. Specifically... Figure 3 It is evident that the sedimentation is the fastest. Simultaneously, the rare earth active phase, due to a lack of reduction or carbon layer buffering, exhibits uncontrolled, non-uniform crystal coarsening. Furthermore, the loss of the physical confinement of hexagonal boron nitride by the carbon layer leads to the collapse and phase separation of the final coating structure. During polishing, the anisotropic, coarse, hard particles easily cause microscopic scratches on the glass surface, significantly worsening the depth of reciprocating scratches and the increase in sand haze. Comparative Example 4 lowers the solid-phase eutectic reaction temperature, below the eutectic point temperature at which the inorganic multiphase system induces interfacial solid-phase eutectic and crystallization recombination. Due to insufficient thermal driving force, the inorganic phases only exhibit a loose physical accumulation state, failing to fully form a high-density, rigid, wear-resistant structure. Under the high shear stress of CMP processing, abrasive particles with obvious structural defects undergo severe fragmentation and disintegration, resulting in the inability to maintain chemical shearing and mechanical cutting efficiency for a long period. The initial hardness of the glass surface after polishing is low, and all long-term scratch resistance and wear resistance indicators are lower than those of the normally calcined examples.

Claims

1. A long-lasting anti-wear glass polishing powder, characterized in that, The preparation materials, by mass parts, include the following: 90-140 parts of transition metal oxide powder and amorphous borate fluxing phase powder, 450-600 parts of lanthanum cerium nitrate solution, sodium lignosulfonate solid powder, anhydrous sodium pyrophosphate, 12-20 parts of double-ended epoxy crosslinking agent, and 40-65 parts of layered components.

2. The long-lasting anti-wear glass polishing powder according to claim 1, characterized in that, The transition metal oxide powder is nano-barium titanate powder; the amorphous borate fluxing phase powder is either calcium metaborate powder or barium metaborate powder; the layered component is either hexagonal boron nitride or titanium pyrophosphate.

3. A method for preparing the long-lasting wear-resistant glass polishing powder as described in claim 1, characterized in that, The preparation method includes: dissolving sodium lignosulfonate and sodium pyrophosphate in a liquid system, pumping in a double-ended epoxy crosslinking agent within 8 to 15 minutes, adding the layered component after polycondensation and crosslinking reaction, and obtaining a composite dispersion emulsion after peeling and shearing dispersion. Transition metal oxide powder and amorphous borate flux phase powder are emulsified and dispersed in deionized water, and then introduced into a rare earth salt solution. The mixture is then pumped into the composite dispersion emulsion at a flow rate of 55 ml / min to 105 ml / min to obtain a multiphase composite slurry.

4. The method for preparing long-lasting wear-resistant glass polishing powder according to claim 3, characterized in that, The transition metal oxide powder is selected from nano-barium titanate powder, and the amorphous borate fluxing phase powder is selected from calcium metaborate powder and barium metaborate powder; the amount of deionized water added is 1.6 to 1.8 times the total mass of the inorganic powder; the rare earth salt solution is lanthanum nitrate and cerium nitrate solution, and the mass fraction of lanthanum nitrate and cerium nitrate solution based on rare earth oxides is 28 wt% to 32 wt%, and the atomic ratio of La to Ce is 1:1.8 to 1:2.

2.

5. The method for preparing long-lasting wear-resistant glass polishing powder according to claim 3, characterized in that, The multiphase composite slurry is dehydrated, dried, and subjected to gradient heat treatment to obtain a precursor for long-lasting wear-resistant glass polishing powder, which is then crushed and collected to obtain the long-lasting wear-resistant glass polishing powder.

6. The method for preparing long-lasting wear-resistant glass polishing powder according to claim 5, characterized in that, The inlet air temperature of the pressure spray drying tower used for dehydration and drying is controlled between 215°C and 235°C, the outlet air temperature is between 93°C and 102°C, and the pressure of the atomizing nozzle at the top of the tower is stabilized between 0.38MPa and 0.42MPa.

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