Composite glass material containing nano reinforced component

Abstract

The invention relates to the technical field of preparation of composite glass materials, and discloses a composite glass material containing a nanometer reinforcing component, the composite glass material comprises a glass matrix, the nanometer reinforcing component and a dispersant, the glass matrix comprises the following components by mass: 60-70 parts of silicon dioxide; 10 to 15 parts of sodium oxide; 5-10 parts of calcium oxide; 1-3 parts of aluminum oxide; the preparation method comprises the following steps: mixing and melting the raw materials of the glass matrix; preparing a nano-particle dispersion liquid; dropwise adding dispersion liquid and injecting microbubbles; stirring and forming; and annealing treatment. According to the preparation method, an argon microbubble disturbance mechanism is introduced, so that nanoparticles form more uniform spatial distribution in the glass, the wear resistance and the structural consistency of the material are remarkably improved, the problems of particle accumulation and stress concentration areas are avoided, and the technical bottleneck that particles are easy to settle in a common fusion compounding method is effectively broken through.

Description

Technical Field

[0001] The present application relates to the technical field of composite glass material preparation, and in particular to a composite glass material containing nano-reinforced components. Background Art

[0002] With the growing demand for advanced functional materials, composite glass materials are gaining widespread attention in the field of high-performance structural materials due to their excellent optical, mechanical, and thermal stability properties. In particular, in optoelectronic packaging, wear-resistant windows, precision instruments, and specialized architectural glass, the requirements for comprehensive material performance continue to rise, making it increasingly difficult for traditional single-glass systems to meet the demands of complex applications.

[0003] The preparation of composite glass primarily relies on melt doping, typically by directly adding nano-oxide or ceramic particles to raw glass. The target material is then produced through conventional high-temperature melting, casting, and annealing processes. This technology boasts mature processes and good equipment compatibility in industry, and has been applied in some high-temperature and wear-resistant components.

[0004] However, in the existing composite glass material preparation technology, nanoparticles are very easy to agglomerate or settle in the high-temperature melt, resulting in large local performance deviations in the finished product, structural instability, weak interface bonding between the particles and the glass matrix, and often forming stress concentration points that easily induce microcracks or shedding. In addition, there is a lack of an effective dynamic perturbation mechanism for the melt, and the particle distribution is difficult to achieve balance on a macroscopic scale. The annealing process design is overly simplified, making it difficult to fully release processing stress. Therefore, the present invention provides a composite glass material containing a nano-reinforced component to address the shortcomings of the existing technology. Summary of the Invention

[0005] In response to the shortcomings of the existing technology, the purpose of this application is to provide a composite glass material containing nano-reinforced components, which solves the problems of severe particle agglomeration, uneven distribution, weak interface bonding and difficulty in releasing structural stress in the existing composite glass material preparation technology.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solutions: A composite glass material containing a nano-reinforced component comprises a glass matrix, a nano-reinforced component and a dispersant, wherein the glass matrix is ​​composed of the following components in parts by mass: Silicon dioxide: 60-70 parts; Sodium oxide: 10-15 parts; Calcium oxide: 5-10 parts; Alumina: 1-3 parts; Zinc oxide: 0.5-2 parts.

[0007] Silicon dioxide: 60-70 parts. Silicon dioxide is the primary component of the composite glass material, providing the matrix structure. Silicon dioxide has strong chemical and thermal stability, and a low coefficient of thermal expansion, which helps maintain the stability of the glass material under high-temperature conditions. Within the glass matrix, silicon dioxide forms a network structure, providing mechanical strength and chemical stability. During the high-temperature melting process, silicon dioxide reacts with other metal oxides to form a silicon oxide matrix with a three-dimensional network structure.

[0008] Sodium oxide: 10-15 parts. Sodium oxide acts as a network modifier in the glass matrix. Its primary function is to lower the melting point of the glass, promoting its fluidity, thereby reducing its melting temperature and optimizing its processing properties. As an alkaline oxide, sodium oxide can replace some of the network oxygen atoms of the silicon-oxygen tetrahedrons in the glass, breaking the strong connections of the silicon-oxygen network and forming non-bridging oxygen atoms. The introduction of these non-bridging oxygen atoms reduces the tightness of the network structure, promoting the melting of the glass and making it easier to flow at low temperatures.

[0009] Calcium oxide: 5-10 parts. Calcium oxide, an alkaline earth metal oxide, is primarily used to adjust the physical properties of glass, such as its refractive index and coefficient of thermal expansion. The addition of calcium oxide can also help improve the chemical stability of glass, particularly its resistance to acid and alkali corrosion. Similar to sodium oxide, calcium oxide acts as a network modifier within the glass matrix, further altering the glass's network structure by forming bonds between calcium oxide and silicon-oxygen tetrahedrons. The addition of calcium oxide not only improves the mechanical strength of glass but also enhances its heat and chemical resistance by modifying its network structure.

[0010] Alumina: 1-3 parts. Alumina, as an important reinforcing component, helps improve the heat resistance and corrosion resistance of glass, as well as increasing its strength. Alumina strengthens the three-dimensional network structure of glass and improves its thermal shock resistance. The addition of alumina effectively enhances the stability of the glass network. Alumina forms Al-O-Si bonds with silica, contributing to the density of the glass structure. Alumina also inhibits the expansion of glass, enhancing its hardness and heat resistance.

[0011] Zinc oxide: 0.5-2 parts. Zinc oxide in glass adjusts the refractive index and thermal expansion coefficient, and improves the transparency of the glass. Zinc oxide also enhances the glass's UV resistance. As a special oxide, zinc oxide's main function is to adjust the optical properties of glass. By introducing zinc oxide into glass, the refractive index of the glass can be adjusted, thereby improving its optical performance.

[0012] Zirconia nanoparticles: 2-6 parts. Zirconia nanoparticles, when introduced as a reinforcing component, can significantly improve the mechanical properties of the composite glass, particularly its hardness and wear resistance. Zirconia particles have a high melting point and strong thermal stability, and their addition can enhance the strength and rigidity of the glass material at high temperatures. As a nanoscale reinforcing material, zirconia nanoparticles primarily enhance the strength and wear resistance of the glass matrix. Within the glass matrix, the zirconia particles are uniformly distributed at the nanometer scale and form a composite material with the glass matrix through interfacial interactions. These nanoparticles can effectively improve the impact strength, hardness, and wear resistance of the glass.

[0013] Polyvinylpyrrolidone: 2-5 parts. As a dispersant, polyvinylpyrrolidone primarily helps disperse zirconium oxide nanoparticles evenly and prevents them from agglomerating during the preparation process. Polyvinylpyrrolidone molecules are both hydrophilic and lipophilic in solution, and through intermolecular interactions, they can coat zirconium oxide particles to form a stable dispersion. During the preparation process, the PVP molecular chains physically adsorb onto the zirconium oxide surface, reducing the mutual attraction between particles, preventing agglomeration, and maintaining a uniform distribution of particles. Preferably, the nano-reinforcement component is zirconium oxide nanoparticles, added in an amount of 2-6 parts, with a particle size of 20-50 nanometers and a purity of no less than 99.9%.

[0014] Preferably, the dispersant is polyvinyl pyrrolidone, the addition amount is 2-5 parts, and the molecular weight is 10,000-50,000.

[0015] Preferably, the sodium oxide is an alkaline oxide component, and the calcium oxide is an alkaline earth metal oxide component. The sodium oxide and calcium oxide are used to introduce non-bridging oxygen and adjust the composition structure of the glass melt.

[0016] Preferably, the aluminum oxide and zinc oxide are used to adjust the type and ratio of cations in the matrix oxide system.

[0017] A method for preparing a composite glass material containing a nano-reinforced component is also provided, comprising the following steps: S1. Weighing glass matrix raw material components, mixing them evenly, and melting them at 1350-1450° C. for 30-60 minutes to obtain a glass matrix melt; S2. Add 2-6 parts of zirconium oxide nanoparticles and 2-5 parts of polyvinyl pyrrolidone to a mixed solution of ethanol and deionized water in a volume ratio of 7:3, adjust the pH to 9-11, and stir for 30-45 minutes to form a stable dispersion; S3. While the glass melt is kept at a high temperature, the dispersion liquid is slowly added dropwise to the melt over a period of 15-30 minutes, and argon gas is introduced at a flow rate of 50-200 mL / min to form microbubbles with a diameter of 50-200 μm for dispersion; S4. Continue stirring the glass melt at 30-60 rpm for 10 minutes to allow the particles to bond and distribute evenly, then pour into a 400-500°C preheated mold for molding; S5. The formed glass is annealed by keeping the temperature at 530-550° C. for 60-90 minutes, cooling the temperature to 450° C. at a rate of 1-2° C. / min and keeping the temperature for 30-60 minutes, and then cooling the temperature to room temperature at a rate of 1-3° C. / min to prepare a composite glass material.

[0018] In step S1, the required mass of the glass matrix raw materials, including silicon dioxide, sodium oxide, calcium oxide, aluminum oxide, and zinc oxide, is weighed and mixed in the specified mass fractions to ensure uniform distribution of each component. The mixed raw materials are placed in a platinum crucible or a high-temperature container and heated to a high temperature range of 1350-1450°C. The melting temperature is maintained for 30-60 minutes until the raw materials are completely melted and a uniform glass melt is formed.

[0019] In step S2, zirconium oxide nanoparticles and polyvinyl pyrrolidone were added to a mixture of ethanol and deionized water in the appropriate mass ratio. The pH of the solution was adjusted to 9-11, finely adjusting with ammonia. Stirring was performed for 30-45 minutes to ensure complete dispersion of the nanoparticles and PVP, forming a stable nanoparticle dispersion, preventing particle agglomeration and maintaining uniform distribution of the particles in the solution.

[0020] In step S3, the prepared stable dispersion is slowly added dropwise to the glass melt. During this addition, argon gas is introduced into the melt via a microporous ceramic rod or other suitable device at a controlled rate of 50-200 mL / min, forming microbubbles with a diameter of 50-200 microns. The injection of argon gas helps evenly disperse the zirconium oxide particles in the glass matrix, preventing particle sedimentation and agglomeration, while also enhancing interfacial contact and bonding between the particles and the glass matrix.

[0021] In step S4, continue stirring the melt for at least 10 minutes to ensure uniform distribution of the zirconium oxide nanoparticles within the glass melt and sufficient interfacial bonding. Once uniform distribution is achieved, the melt is poured into a preheated mold controlled at 400-500°C for molding. The mold should be selected to ensure good thermal stability and adequate heat conductivity, such as a graphite or quartz mold.

[0022] In step S5, the formed glass is annealed. First, the temperature is raised to 530-550°C and held for 60-90 minutes to release internal stress and promote initial stabilization of the glass structure. Next, the temperature is slowly lowered to 450°C at a rate of 1-2°C / min and held for 30-60 minutes to further eliminate residual stress in the glass and improve its internal molecular structure. Finally, the glass is cooled to room temperature at a cooling rate of 1-3°C / min to ensure that the glass material does not crack or deform during the cooling process, ultimately obtaining a stable composite glass material.

[0023] Preferably, the step of adding 2-6 parts of zirconium oxide nanoparticles and 2-5 parts of polyvinyl pyrrolidone to a mixed solution of ethanol and deionized water in a volume ratio of 7:3 comprises: The mass ratio of the zirconium oxide nanoparticles to polyvinyl pyrrolidone is 1:1.0-1:1.8; The total liquid mass of the stable dispersion is 8-12 times the mass of the added solid; Use a magnetic stirring or propeller stirring device, and control the stirring temperature at 25-40℃.

[0024] Preferably, the step of introducing argon at a flow rate of 50-200 mL / min comprises the following steps: The argon gas used to form microbubbles is injected through a ceramic microporous diffusion rod with an injection depth of 10-20 mm; The diameter of the microbubbles is controlled by the aperture of the diffusion rod to be within the range of 50-200 microns; The argon gas is continuously introduced during the entire dropwise addition process to maintain a uniform bubble flow field.

[0025] Preferably, the step of allowing the particles to interface and distribute evenly and then pouring the particles into a preheated mold at 400-500° C. for molding comprises the following steps: Control the mold temperature rise and fall rate at 10-20℃ / min; After the melt is poured into the mold, the stirring speed is maintained at 30-60 rpm during the molding process for 10-15 minutes.

[0026] Preferably, the preheating mold is a graphite mold or a quartz mold, the annealing treatment is performed in an inert atmosphere, and the cooling process of the annealed composite glass material to room temperature is slowly completed in a closed furnace chamber.

[0027] In summary, this application includes at least one of the following beneficial technical effects: 1. This invention incorporates an argon microbubble perturbation mechanism, resulting in a more uniform spatial distribution of nanoparticles within the glass, significantly improving the material's wear resistance and structural consistency. Unlike traditional processes where particles rely on natural diffusion to disperse, this method avoids particle accumulation and areas of stress concentration, effectively overcoming the technical bottleneck of particle sedimentation in conventional melt-compounding methods.

[0028] 2. This invention uses polyvinyl pyrrolidone to perform a precursor dispersion coating on the nano-zirconia particles, establishing a stable dispersion state before entering the melt. This ensures that the particles are less likely to agglomerate at high temperatures and maintains a long-lasting dispersion. Traditional methods, where the particles are directly mixed with glass, are prone to localized agglomeration and performance instability after heat treatment. This treatment completely changes the surface state of the particles, making them more adaptable to the glass matrix environment and improving the overall uniformity of the material.

[0029] 3. This invention incorporates a low-speed stirring step during the melting phase, which not only maintains melt fluidity but also effectively disperses particles in locally concentrated areas, achieving dynamic fusion of the reinforcement phase with the glass network. Unlike existing static melting methods, which suffer from uneven thermal field distribution and lead to performance differences, this process results in more balanced stress distribution on the material, significantly improving thermal shock resistance and enhancing thermal stability.

[0030] 4. This invention incorporates a multi-stage temperature-controlled annealing strategy, which allows for more complete thermal stress release, more coordinated structural shrinkage, and significantly reduces the incidence of cracks in the finished product. Compared to the existing single-stage, rapid cooling method that can lead to material cracking, this method achieves more stable thermal degradation control while maintaining efficiency, a key factor in improving the yield rate of composite glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is a flow chart of the preparation method of this application. DETAILED DESCRIPTION

[0032] The following is combined with Figure 1 , further details of this application are given.

[0033] Please see the attached Figure 1 : Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0034] Example 1: Raw material components (by mass fraction): Silicon dioxide (SiO2): 65 parts; Sodium oxide (Na2O): 12.5 parts; Calcium oxide (CaO): 7.5 parts; Alumina (Al2O3): 2 parts; Zinc oxide (ZnO): 1 part.

[0035] Nano-enhanced components: Zirconium oxide (ZrO2) nanoparticles: 4 parts; Polyvinylpyrrolidone (PVP): 3 parts.

[0036] Preparation method: Mixing and melting the glass matrix raw materials: Weigh the raw materials according to the above mass fractions and mix silicon dioxide, sodium oxide, calcium oxide, aluminum oxide, and zinc oxide evenly. Place the mixed raw materials in a platinum crucible and heat at 1350°C. Maintain this temperature for 60 minutes to ensure complete melting of the raw materials and obtain a uniform glass melt.

[0037] Preparation of nanoparticle dispersion: 4 parts of zirconium oxide nanoparticles and 3 parts of polyvinyl pyrrolidone were added to ethanol and deionized water (volume ratio 7:3), the pH was adjusted to 9.5, and stirred with a stirrer for 30 minutes to form a stable dispersion.

[0038] Dispersion dropwise addition and microbubble injection: The glass melt is maintained at 1350°C, and the dispersion is slowly added dropwise over 15 minutes. During this process, argon gas is injected into the melt at a flow rate of 100 mL / min. The diameter of the microbubbles is controlled at approximately 100 microns to ensure uniform dispersion.

[0039] Stirring and molding: Continue stirring the glass melt at 50 rpm for 10 minutes. Then pour the melt into a quartz mold preheated at 400°C for molding.

[0040] Annealing: The formed glass was annealed at 530°C for 90 minutes, then cooled to 450°C at a rate of 1°C / min and held there for 30 minutes, and finally cooled to room temperature at a rate of 2°C / min to obtain a composite glass material.

[0041] Example 2: Raw material components (by mass fraction): Silicon dioxide (SiO2): 60 parts; Sodium oxide (Na2O): 10 parts; Calcium oxide (CaO): 5 parts; Alumina (Al2O3): 1 part; Zinc oxide (ZnO): 0.5 parts.

[0042] Nano-enhanced components: Zirconium oxide (ZrO2) nanoparticles: 2 parts; Polyvinylpyrrolidone (PVP): 2 parts.

[0043] Preparation method: Mixing and melting the glass matrix raw materials: Weigh the raw materials according to the above mass fractions and mix silicon dioxide, sodium oxide, calcium oxide, aluminum oxide, and zinc oxide evenly. Place the mixed raw materials in a platinum crucible and heat at 1450°C. Maintain this temperature for 30 minutes to ensure complete melting of the raw materials and obtain a uniform glass melt.

[0044] Preparation of nanoparticle dispersion: 2 parts of zirconium oxide nanoparticles and 2 parts of polyvinyl pyrrolidone were added to ethanol and deionized water (volume ratio 7:3), the pH was adjusted to 10, and stirred with a stirrer for 35 minutes to form a stable dispersion.

[0045] Dispersion dropwise addition and microbubble injection: The glass melt is maintained at 1450°C, and the dispersion is slowly added dropwise over 20 minutes. During this process, argon is injected into the melt at a flow rate of 50 mL / min, and the diameter of the microbubbles is controlled to be around 50 microns.

[0046] Stirring and molding: Continue stirring the glass melt at 40 rpm for 15 minutes. Then pour the melt into a quartz mold preheated at 450°C for molding.

[0047] Annealing: The formed glass was annealed. The annealing process included maintaining the temperature at 540°C for 70 minutes, then decreasing the temperature to 460°C at a rate of 2°C / min and maintaining the temperature for 40 minutes, and finally decreasing the temperature to room temperature at a rate of 1°C / min to obtain a composite glass material.

[0048] Example 3: Raw material components (by mass fraction): Silicon dioxide (SiO2): 70 parts; Sodium oxide (Na2O): 15 parts; Calcium oxide (CaO): 10 parts; Alumina (Al2O3): 3 parts; Zinc oxide (ZnO): 2 parts.

[0049] Nano-enhanced components: Zirconium oxide (ZrO2) nanoparticles: 6 parts; Polyvinylpyrrolidone (PVP): 5 parts.

[0050] Preparation method: Mixing and melting the glass matrix raw materials: Weigh the raw materials according to the above mass fractions and mix silica, sodium oxide, calcium oxide, aluminum oxide, and zinc oxide evenly. Place the mixed raw materials in a platinum crucible and heat at 1400°C for 45 minutes to ensure complete melting of the raw materials and obtain a uniform glass melt.

[0051] Preparation of nanoparticle dispersion: 6 parts of zirconium oxide nanoparticles and 5 parts of polyvinyl pyrrolidone were added to ethanol and deionized water (volume ratio 7:3), the pH was adjusted to 11, and stirred with a stirrer for 40 minutes to form a stable dispersion.

[0052] Dispersion dropwise addition and microbubble injection: The glass melt is maintained at 1400°C, and the dispersion is slowly added dropwise over 30 minutes. During this process, argon gas is injected into the melt at a flow rate of 200 mL / min. The diameter of the microbubbles is controlled at around 200 microns to ensure uniform dispersion.

[0053] Stirring and molding: Continue stirring the glass melt at 60 rpm for 15 minutes. Then pour the melt into a quartz mold preheated at 500°C for molding.

[0054] Annealing: The formed glass was annealed at 550°C for 60 minutes, then cooled to 460°C at a rate of 2°C / min and held there for 50 minutes, and finally cooled to room temperature at a rate of 3°C / min to obtain a composite glass material.

[0055] Comparative Example 1: Compared with Example 1, the difference is that polyvinyl pyrrolidone (PVP) is not added, and the rest are the same.

[0056] Comparative Example 2: Compared with Example 1, the difference is that the added amount of zirconium oxide nanoparticles is 1 part and the rest are the same.

[0057] Comparative Example 3: Compared with Example 1, the difference is that the added amount of zirconium oxide nanoparticles is 8 parts, and the rest are the same.

[0058] Comparative Example 4: Compared with Example 1, the difference is that the argon injection step is not performed, and the rest are the same.

[0059] Comparative Example 5: Compared with Example 1, the difference is that the pH value of the nanoparticle dispersion is not adjusted, and the rest are the same.

[0060] Comparative Example 6: Compared with Example 1, the difference is that the glass melt is not stirred, and the rest are the same.

[0061] Experiment 1: Experimental purpose: To evaluate the changes in surface hardness of composite glass materials under different conditions of adding nano-reinforcement components.

[0062] Experimental samples: Example 1; Comparative Example 1: (without PVP); Comparative Example 2: (ZrO2 addition amount is too low); Comparative Example 3: (ZrO2 addition amount is too high); Experimental steps: Sample preparation: Each glass sample was made into a polished block with a size of 20 mm × 20 mm × 3 mm, and the surface was polished to a mirror finish to ensure that the test area was flat and free of pores and scratches.

[0063] Hardness test parameter settings: Loading force: 100gf; Hold time: 10 seconds; Number of measuring points: 6 points are randomly selected for testing on each sample, and the readings are recorded; Test temperature: room temperature (about 25°C).

[0064] Hardness test operation: Place the sample on the hardness tester stage, adjust the focus and indenter position, and load the sample surface. After each load, record the corresponding reading.

[0065] Data recording and organization: After collecting hardness readings at 6 points of each sample, the variation range and trend were statistically analyzed and compared (the experimental results are shown in Table 1).

[0066] Table 1: Vickers hardness test data of composite glass material samples with different formulas (unit: HV) Sample number Point 1 Point 2 Point 3 Point 4 Point 5 Point 6 average value Example 1 689 701 714 693 709 698 701.0 Comparative Example 1 598 583 605 590 596 579 591.8 Comparative Example 2 563 570 548 556 561 552 558.3 Comparative Example 3 618 601 610 605 599 623 609.3 In this experiment, by comparing the hardness properties of different samples, it was shown that the effective dispersion of nano-zirconia particles in the glass matrix has a direct effect on improving the overall hardness of the material. When the particles are evenly distributed in the matrix and have a fine particle size, they can limit the propagation path of cracks in the matrix at the microscale, creating a "crack passivation" effect, thereby enhancing the material's resistance to deformation and surface load-bearing capacity. In contrast, when the particles are insufficiently added or poorly dispersed, this strengthening effect is less pronounced, resulting in a lower hardness of the material.

[0067] The uniform distribution of particles is closely related to the stability of the dispersion system. When polyvinyl pyrrolidone is added, the molecular chains form an adsorption layer on the surface of the nanozirconia, significantly improving its dispersibility in the solution and preventing particle agglomeration. During the subsequent addition of the melt, this coating further promotes the effective bonding of the particles within the glass network at high temperatures, maintaining a fine distribution of nanoparticles within the matrix, thereby effectively enhancing the overall structural stability and hardness of the glass.

[0068] Furthermore, controlling the nanoparticle content also plays a key role. An appropriate amount of zirconia not only facilitates the formation of an effective reinforcing lattice structure but also shares external loads within the matrix. Experimental results show that when the addition exceeds the appropriate range, the small interparticle spacing can easily lead to stress concentration, which is detrimental to performance. Meanwhile, when the content is too low, the strengthening effect is insufficient. Therefore, controlling the appropriate addition amount, based on the nanoparticle surface modification and distribution strategy, is a key technical element in achieving the preparation of high-hardness composite glass.

[0069] Experiment 2: Purpose of the experiment: By conducting wear tests on composite glass materials prepared under different process conditions, the effects of microbubble-assisted dispersion and pH adjustment on wear resistance were compared and evaluated.

[0070] Experimental samples: Example 1; Comparative Example 4: (without argon injection); Comparative Example 5: (pH not adjusted).

[0071] Experimental steps: Sample preparation and pretreatment: Each sample was cut into discs (approximately 25 mm in diameter and 3 mm in thickness), polished to a mirror finish, ultrasonically cleaned with alcohol, and dried for later use.

[0072] Initial weighing: Use a precision balance to weigh the mass of each sample before wear and record the initial value.

[0073] Wear test parameter setting: Wear time: 5 minutes; Vertical load: 10N; Rotation speed: 200 rpm; Each group of samples was tested three times and the average loss mass was calculated.

[0074] Test operation process: Place the sample on the grinding wheel and start the equipment for timed wear. After the test, remove the sample, clean the residual abrasive particles on the surface, wipe it dry, and weigh it again, recording the post-wear mass.

[0075] Data collation: Calculate the difference in mass loss as the wear amount and record the results (the experimental results are shown in Table 2).

[0076] Table 2: Mass loss data of abrasion resistance test of composite glass materials with different formulas (unit: mg) Sample number Sample 1 Sample 2 Sample 3 Average mass loss Example 1 4.8 5.2 4.9 4.97 Comparative Example 4 6.5 6.1 6.8 6.47 Comparative Example 5 5.9 6.0 6.3 6.07 Wear resistance test results show that the amount of surface wear on the material is closely related to the dispersion of the nanoparticles within the glass matrix. Argon injection, introducing microbubbles, creates a disturbance in the high-temperature melt, helping to break up the initial agglomeration of the particles and allowing them to diffuse more freely within the fluid. This disturbance mechanism ensures a more uniform distribution of the nanozirconia within the high-viscosity glass melt, forming a stable, reinforced structure during the molding and cooling process, significantly enhancing the material's resistance to surface wear.

[0077] Furthermore, during the dispersion preparation process, adjusting the pH in an alkaline environment effectively alters the surface charge state of the nanoparticles, enhancing repulsion and promoting high particle stability in the liquid phase. This process ensures that the particles are well dispersed before being added to the melt. Compared to samples without pH adjustment, the stable precursor dispersion significantly reduces the risk of particle agglomeration in the melt, thereby improving particle uniformity in the finished product and enhancing their structural support for the glass surface during wear.

[0078] The influence of particle distribution uniformity on wear resistance is particularly pronounced. Well-distributed zirconia particles effectively suppress flaking and minor scratches on the material surface during frictional impact, distributing the abrasive force and thus slowing the wear of the substrate. Conversely, uneven dispersion or particle agglomeration can easily lead to the formation of weak interfaces or localized delamination during wear, reducing overall wear resistance. This demonstrates the critical role of dispersion stabilization strategies and dynamic dispersion methods in improving the wear resistance of glass materials.

[0079] Experiment 3: Purpose of the experiment: By simulating thermal shock test conditions, the crack resistance of glass melts during the molding process with and without a stirring step was compared.

[0080] Experimental samples: Example 1; Comparative Example 6: (glass melt was not stirred).

[0081] Experimental steps: Sample preparation: The two samples were cut into glass pieces of the same size (30 mm × 10 mm × 3 mm), and the surfaces were polished to ensure that there were no scratches or cracks.

[0082] Thermal shock test operation: Place the sample in a drying oven, heat it to 500°C and keep it for 5 minutes; Quickly remove the hot sample with tongs and immediately immerse it vertically in a cold water bath; After cooling, remove the sample, wipe it dry and inspect it visually or manually for cracks or breakage.

[0083] Test repeatability: Each sample was tested 5 times, and the presence and extent of rupture were recorded each time, with simple grade judgment adopted.

[0084] Data recording method: Use a scoring system to judge the anti-cracking effect: Intact: 0 points; Cracks appear: 1 point; Crack or break: 2 points. The total score of each group of samples was calculated and the average was taken to obtain the crack resistance score (the experimental results are shown in Table 3).

[0085] Table 3: Thermal shock crack resistance test scores of composite glass samples with different processes Sample number 1st time 2nd time 3rd time 4th time 5th Average rating Example 1 0 0 1 0 0 0.2 Comparative Example 6 1 2 1 2 1 1.4 Crack resistance experiments demonstrate that stirring during the high-temperature melting stage significantly impacts the stability of the material's overall structure. Continuous stirring maintains a certain convection state within the glass melt, which helps achieve a dynamic and uniform distribution of nanoparticles within the melt, preventing particle sinking, floating, or localized aggregation. This dynamic distribution mechanism ensures that the reinforcing components are better embedded in the glass network during cooling and solidification, providing an effective crack-blocking path during thermal shock and enhancing crack resistance.

[0086] In contrast, in samples formed without stirring, particles tend to concentrate in localized areas, leading to uneven matrix structure distribution. Once subjected to external temperature shocks, localized stress concentration becomes apparent, inducing cracks or even breakage. Melt stirring not only improves particle distribution uniformity but also strengthens the bond between the particles and the glass matrix, allowing them to more firmly embed within the three-dimensional network. These particles act as "stress release points" during stress conduction, reducing the risk of localized damage from thermal shock.

[0087] Furthermore, the melt stirring process facilitates the formation of a more stable interface between the particles and the glass network at the microscale, reducing fragile areas caused by poor interface transitions. Experiments have shown that the composite glass produced by stirring exhibits enhanced structural integrity during intense thermal cycling, demonstrating significant improvements in the material's thermal stability and crack resistance. This mechanism demonstrates the importance of incorporating appropriate dynamic perturbations into the melting process for obtaining high-performance composite glass materials.

[0088] The examples of this specific embodiment are all preferred embodiments of this application and are not intended to limit the scope of protection of this application. Identical components are represented by the same reference numerals. Therefore, any equivalent changes made based on the structure, shape, and principle of this application should be included in the scope of protection of this application.

Claims

1. A composite glass material containing a nano-reinforced component, comprising a glass matrix, a nano-reinforced component and a dispersant, characterized in that: The glass matrix is ​​composed of the following components in parts by mass: Silicon dioxide: 60-70 parts; Sodium oxide: 10-15 parts; Calcium oxide: 5-10 parts; Alumina: 1-3 parts; Zinc oxide: 0.5-2 parts.

2. The composite glass material containing nano-reinforced components according to claim 1, characterized in that: The nano-reinforcement component is zirconium oxide nanoparticles, the addition amount is 2-6 parts, the particle size is 20-50 nanometers, and the purity is not less than 99.9%.

3. The composite glass material containing nano-reinforced components according to claim 1, characterized in that: The dispersant is polyvinyl pyrrolidone, the addition amount is 2-5 parts, and the molecular weight is 10,000-50,000.

4. The composite glass material containing nano-reinforced components according to claim 1, characterized in that: The sodium oxide is an alkaline oxide component, and the calcium oxide is an alkaline earth metal oxide component. The sodium oxide and calcium oxide are used to introduce non-bridging oxygen and adjust the composition structure of the glass melt.

5. The composite glass material containing nano-reinforced components according to claim 1, characterized in that: The aluminum oxide and zinc oxide are used to adjust the type and ratio of cations in the matrix oxide system.

6. A method for preparing a composite glass material containing a nano-reinforced component, for preparing a composite glass material containing a nano-reinforced component according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Weighing glass matrix raw material components, mixing them evenly, and melting them at 1350-1450° C. for 30-60 minutes to obtain a glass matrix melt; S2. Add 2-6 parts of zirconium oxide nanoparticles and 2-5 parts of polyvinyl pyrrolidone to a mixed solution of ethanol and deionized water in a volume ratio of 7:3, adjust the pH to 9-11, and stir for 30-45 minutes to form a stable dispersion; S3. While the glass melt is kept at a high temperature, the dispersion liquid is slowly added dropwise to the melt over a period of 15-30 minutes, and argon gas is introduced at a flow rate of 50-200 mL / min to form microbubbles with a diameter of 50-200 μm for dispersion; S4. Continue stirring the glass melt at 30-60 rpm for 10 minutes to allow the particles to bond and distribute evenly, then pour into a 400-500°C preheated mold for molding; S5. The formed glass is annealed by keeping the temperature at 530-550° C. for 60-90 minutes, cooling the temperature to 450° C. at a rate of 1-2° C. / min and keeping the temperature for 30-60 minutes, and then cooling the temperature to room temperature at a rate of 1-3° C. / min to prepare a composite glass material.

7. The composite glass material containing nano-reinforced components according to claim 6, characterized in that: The step of adding 2-6 parts of zirconium oxide nanoparticles and 2-5 parts of polyvinyl pyrrolidone to a mixed solution of ethanol and deionized water in a volume ratio of 7:3 comprises: The mass ratio of the zirconium oxide nanoparticles to polyvinyl pyrrolidone is 1:1.0-1:1.8; The total liquid mass of the stable dispersion is 8-12 times the mass of the added solid; Use a magnetic stirring or propeller stirring device, and control the stirring temperature at 25-40℃.

8. The composite glass material containing nano-reinforced components according to claim 6, characterized in that: The step of introducing argon at a flow rate of 50-200 mL / min comprises the following steps: The argon gas used to form microbubbles is injected through a ceramic microporous diffusion rod with an injection depth of 10-20 mm; The diameter of the microbubbles is controlled by the aperture of the diffusion rod to be within the range of 50-200 microns; The argon gas was continuously introduced during the entire dropwise addition process.

9. The composite glass material containing nano-reinforced components according to claim 6, characterized in that: The process of forming the particles by combining the particles at the interface and distributing them uniformly into a mold preheated at 400-500°C comprises the following steps: Control the mold temperature rise and fall rate at 10-20℃ / min; After the melt is poured into the mold, the stirring speed is maintained at 30-60 rpm during the molding process for 10-15 minutes.

10. The composite glass material containing nano-reinforced components according to claim 6, characterized in that: The preheating mold is a graphite mold or a quartz mold, the annealing treatment is carried out in an inert atmosphere, and the cooling process of the annealed composite glass material to room temperature is slowly completed in a closed furnace chamber.

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