A composite glass material containing a nano-reinforcing component

Abstract

The application relates to the technical field of composite glass material preparation, and discloses a composite glass material containing a nano reinforcing component, which comprises a glass matrix, a nano reinforcing component and a dispersing agent, the glass matrix is composed of the following components in mass fractions: 60-70 parts of silicon dioxide, 10-15 parts of sodium oxide, 5-10 parts of calcium oxide, 1-3 parts of aluminum oxide and 0.5-2 parts of zinc oxide, and the preparation method comprises the following steps: mixing and melting of glass matrix raw materials; preparation of a nano particle dispersion liquid; dropwise addition of the dispersion liquid and micro-bubble injection; stirring and shaping; and annealing treatment. The application introduces an argon micro-bubble disturbance mechanism, so that the nano particles form a more uniform spatial distribution in the glass, and the wear resistance and structural consistency of the material are significantly improved; the application avoids the problems of particle accumulation and stress concentration areas, and effectively breaks through the technical bottleneck that particles are prone to sedimentation in the ordinary melting composite method.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of composite glass material preparation, in particular to a composite glass material containing a nano-enhanced component. BACKGROUND

[0002] With the increasing demand for advanced functional materials, composite glass materials have gradually attracted widespread attention in the field of high-performance structural materials due to their excellent optical, mechanical and thermal stability. In particular, in optoelectronic packaging, wear-resistant windows, precision instruments and special building glass, the demand for comprehensive performance of materials is increasing, which makes it difficult for traditional single glass systems to meet the application requirements under complex working conditions.

[0003] The preparation method of composite glass mainly focuses on melt doping, which usually involves directly adding nano-oxides or ceramic particles to the glass raw materials, and then obtaining the target material through conventional high-temperature melting, casting and annealing process. This kind of technology has the advantages of mature process and good equipment compatibility in industry, and has been applied in some high-temperature-resistant and wear-resistant components.

[0004] However, in the existing composite glass material preparation technology, nano-particles are prone to agglomeration or sedimentation in high-temperature melt, resulting in large local performance deviation in the finished product, unstable structure, weak interfacial bonding between particles and glass matrix, often forming stress concentration points, easily causing micro-cracks or falling off, and lacking effective melt dynamic disturbance mechanism, so that the particle distribution is difficult to achieve balance on the macro scale, and the annealing process design is too simple to fully release the processing stress. Therefore, the present application provides a composite glass material containing a nano-enhanced component to solve the problems existing in the prior art. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a composite glass material containing a nano-enhanced component, which solves the problems of serious particle agglomeration, uneven distribution, weak interfacial bonding and difficult release of structural stress in the existing composite glass material preparation technology.

[0006] To achieve the above purpose, the present application is realized by the following technical scheme: a composite glass material containing a nano-enhanced component, comprising a glass matrix, a nano-enhanced component and a dispersant, the glass matrix is composed of the following components in mass fraction:

[0007] Silicon dioxide: 60-70 parts;

[0008] Sodium oxide: 10-15 parts;

[0009] Calcium oxide: 5-10 parts;

[0010] Aluminum oxide: 1-3 parts;

[0011] Zinc oxide: 0.5-2 parts.

[0012] Silicon dioxide: 60-70 parts, Silicon dioxide is the main component of the composite glass material, which plays a role in providing the matrix structure. Silicon dioxide has strong chemical stability and thermal stability, and has a low thermal expansion coefficient, which helps to maintain the stability of the glass material under high temperature conditions. In the glass matrix, silicon dioxide forms a network structure, which provides mechanical strength and chemical stability to the glass matrix. 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.

[0013] Sodium oxide: 10-15 parts, Sodium oxide exists in the glass matrix as a network modifier. Its main role is to reduce the glass melting point and promote the flowability of the glass, thereby reducing the melting temperature of the glass and optimizing the processing performance of the glass. As an alkali oxide, sodium oxide can replace part of the network oxygen atoms of the silicon-oxygen tetrahedron in the glass, breaking the strong connection of the silicon-oxygen network and forming non-bridging oxygen. The introduction of these non-bridging oxygen reduces the tightness of the network structure, promotes the melting of the glass, and makes it more easily flowable at low temperatures.

[0014] Calcium oxide: 5-10 parts, Calcium oxide, as an alkaline earth metal oxide, is mainly used to adjust the physical properties of the glass, such as refractive index and thermal expansion coefficient. The addition of calcium oxide can also help improve the chemical stability of the glass, especially in terms of improving its resistance to acid and alkali corrosion. Calcium oxide plays a similar role to sodium oxide in the glass matrix as a network modifier, which further changes the network structure of the glass by forming a bond between calcium oxide and the silicon-oxygen tetrahedron. The addition of calcium oxide not only improves the mechanical strength of the glass, but also makes it more resistant to heat and chemical corrosion by improving the network structure of the glass.

[0015] Aluminum oxide: 1-3 parts, Aluminum oxide, as an important reinforcing component, helps to improve the heat resistance, corrosion resistance of the glass material, and increase the strength of the glass. Aluminum oxide can strengthen the three-dimensional network structure of the glass and improve its thermal shock resistance. The addition of aluminum oxide can effectively enhance the stability of the glass network. Aluminum oxide forms Al-O-Si bonds by combining with silicon dioxide, promoting the compactness of the glass structure. Aluminum oxide can inhibit the expansion of the glass, enhance the hardness and heat resistance of the glass.

[0016] Zinc oxide: 0.5-2 parts, Zinc oxide in glass is used to adjust the refractive index and thermal expansion coefficient, and improve the transparency of the glass. Zinc oxide can also enhance the ultraviolet resistance of the glass. Zinc oxide, as a special oxide, is mainly used to adjust the optical properties of the glass. By introducing zinc oxide into the glass, the refractive index of the glass can be adjusted, thereby improving its optical performance.

[0017] Zirconia nanoparticles: 2-6 parts, Zirconia nanoparticles are introduced as reinforcing components, which can significantly improve the mechanical properties of the composite glass, especially its hardness and wear resistance. Zirconia particles have a high melting point and strong thermal stability, which can enhance the strength and rigidity of the glass material at high temperature. Zirconia nanoparticles as nanoscale reinforcing substances, its main role is to enhance the strength and wear resistance of the glass matrix. In the glass matrix, zirconia particles are uniformly distributed at the nanoscale, and form a composite material with the glass matrix through interfacial action. These nanoparticles can effectively improve the impact strength, hardness and wear resistance of the glass.

[0018] Polyvinylpyrrolidone: 2-5 parts, polyvinylpyrrolidone as a dispersant, mainly plays a role in helping zirconia nanoparticles to disperse uniformly during preparation, preventing agglomeration. Polyvinylpyrrolidone molecules have hydrophilicity and lipophilicity in solution, and can coat zirconia particles through intermolecular interaction to form a stable dispersion. During preparation, the molecular chain of PVP is physically adsorbed on the surface of zirconia, reducing the interparticle attraction force and preventing agglomeration, maintaining uniform distribution of particles. Preferably, the nanoreinforcing component is zirconia nanoparticles, the addition amount is 2-6 parts, the particle size is 20-50 nanometers, and the purity is not less than 99.9%.

[0019] Preferably, the dispersant is polyvinylpyrrolidone, the addition amount is 2-5 parts, and the molecular weight is 10,000-50,000.

[0020] 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 and structure of the glass melt.

[0021] Preferably, the aluminum oxide and zinc oxide are used to adjust the types and proportions of cations in the matrix oxide system.

[0022] A preparation method of a composite glass material containing a nanoreinforcing component is also provided, comprising the following steps:

[0023] S1, weigh the glass matrix raw material components, mix uniformly, and melt at 1350-1450℃ for 30-60 minutes to obtain a glass matrix melt;

[0024] S2, add 2-6 parts of zirconia nanoparticles and 2-5 parts of polyvinylpyrrolidone to a mixed solution of ethanol and deionized water with a volume ratio of 7:3, adjust the pH to 9-11, and stir for 30-45 minutes to form a stable dispersion;

[0025] S3, while the glass melt is kept at a high temperature, the dispersion liquid is slowly added to the melt over a period of 15-30 minutes, and argon gas is introduced into the melt at a flow rate of 50-200 mL / min to form microbubbles with a diameter of 50-200 microns for dispersion;

[0026] S4, continue to stir the glass melt at 30-60 rpm and keep for 10 minutes, and pour into a preheated mold at 400-500°C after the particles interface is combined and uniformly distributed;

[0027] S5, the shaped glass is annealed by holding at 530-550°C for 60-90 minutes, cooling to 450°C at a rate of 1-2°C / min for 30-60 minutes, and then cooling to room temperature at a rate of 1-3°C / min, to obtain the composite glass material.

[0028] For step S1, the required mass of glass matrix raw material components, including silicon dioxide, sodium oxide, calcium oxide, aluminum oxide and zinc oxide, is weighed and mixed uniformly according to the specified mass fraction, ensuring uniform distribution of each component. The mixed raw materials are placed in a platinum crucible or high-temperature resistant container and heated to a high temperature range of 1350-1450°C, and maintained at a melting temperature for 30-60 minutes until the raw materials are completely melted and a uniform glass melt is formed.

[0029] For step S2, zirconium oxide nanoparticles and polyvinylpyrrolidone are added to a mixture of ethanol and deionized water in a mass ratio, and the pH value of the solution is adjusted to 9-11 using ammonia water. The nanoparticles and PVP are completely dispersed by stirring for 30-45 minutes to form a stable nanoparticle dispersion liquid, avoiding particle agglomeration and maintaining uniform distribution of the particles in the solution.

[0030] For step S3, the prepared stable dispersion liquid is added to the glass melt in a slow dropwise manner. During the dropwise addition, argon gas is introduced into the melt through a microporous ceramic rod or other appropriate device at a flow rate of 50-200 mL / min to form microbubbles with a diameter of 50-200 microns. The injection of argon gas helps to uniformly disperse the zirconium oxide particles in the glass matrix, avoids particle settling and agglomeration, and enhances the interface contact and bonding between the particles and the glass matrix.

[0031] For step S4, continue to stir the melt and keep stirring for at least 10 minutes to ensure uniform distribution of the zirconium oxide nanoparticles in the glass melt and sufficient interface bonding. After uniform distribution is completed, the melt is poured into a preheated mold with a temperature control of 400-500°C for shaping. The mold should be selected to have good thermal stability and appropriate thermal conductivity, such as a graphite mold or a quartz mold.

[0032] For step S5, the formed glass is subjected to annealing treatment, first, the temperature is raised to 530-550℃ and kept for 60-90 minutes to release internal stress and promote the initial stability of the glass structure. Then, by slowly reducing the temperature to 450℃ at a rate of 1-2℃ / min and keeping for 30-60 minutes, the residual stress in the glass is further eliminated and its internal molecular structure is perfected. Finally, continue to cool the glass to room temperature at a cooling rate of 1-3℃ / min, to ensure that the glass material does not break or deform during the cooling process, so as to finally obtain a stable composite glass material.

[0033] Preferably, the zirconium oxide nanoparticles 2-6 parts and polyvinylpyrrolidone 2-5 parts are added to a mixed solution of ethanol and deionized water in a volume ratio of 7:3.

[0034] The mass ratio of zirconium oxide nanoparticles to polyvinylpyrrolidone is 1:1.0-1:1.8;

[0035] The total liquid mass of the stable dispersion is 8-12 times the mass of the added solids;

[0036] The stirring temperature is controlled at 25-40℃ using a magnetic stirrer or a propeller type stirring device.

[0037] Preferably, the argon gas is introduced at a flow rate of 50-200 mL / min, which includes the following steps:

[0038] The argon gas used to form microbubbles is injected through a ceramic microporous diffusion rod, and the injection depth is 10-20 mm;

[0039] The diameter of the microbubbles is controlled within the range of 50-200 microns by the pore size of the diffusion rod;

[0040] The argon gas is continuously introduced during the entire dropping process to maintain a uniform bubble flow field.

[0041] Preferably, after the particle interface is combined and uniformly distributed, it is poured into a preheated mold at 400-500℃, which includes the following steps:

[0042] The temperature rise and fall rate of the mold is controlled at 10-20℃ / min;

[0043] After the melt is poured into the mold, the stirring speed during the forming process is kept at 30-60 rpm for 10-15 minutes.

[0044] Preferably, the preheated 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 cavity.

[0045] In summary, the present application includes at least one of the following beneficial technical effects:

[0046] 1. The present application introduces an argon micro-bubble disturbance mechanism, which allows nanoparticles to form a more uniform spatial distribution within the glass, significantly improving the material's wear resistance and structural consistency. Unlike traditional processes where particles rely on natural diffusion for dispersion, the present application avoids the problem of particle accumulation and stress concentration areas, effectively breaking through the technical bottleneck of ordinary melt compounding methods where particles tend to settle.

[0047] 2. The present application uses polyvinylpyrrolidone to disperse and coat the nano-zirconia particles, establishing a stable dispersion state before entering the melt, ensuring that the particles do not easily agglomerate at high temperatures and maintaining long-term dispersion. In traditional methods, particles are mixed directly with glass, and after heat treatment, local agglomeration and performance instability problems often occur. This treatment method completely changes the particle surface state, making it more suitable for the glass matrix environment and improving the overall uniformity of the material.

[0048] 3. The present application sets a low-speed stirring step during the melting stage, which not only maintains the fluidity of the melt but also effectively disperses particles in local concentrated areas, achieving dynamic fusion of the reinforcing phase and the glass network. Unlike existing static melting methods, which result in performance differences due to uneven heat distribution, this treatment makes the material more balanced in stress, significantly improves thermal shock resistance, and has stronger thermal stability.

[0049] 4. The present application introduces a multi-stage temperature control annealing strategy, which allows for more complete thermal stress release and more coordinated structural shrinkage, resulting in a significant reduction in the incidence of cracks in the final product. Compared to the material cracking problem caused by single-stage holding and rapid cooling in existing technologies, this method ensures efficiency while achieving more stable thermal degradation control, which is one of the key points for improving the yield of composite glass. BRIEF DESCRIPTION OF DRAWINGS

[0050] Figure 1 is a preparation method flowchart of the present application. DETAILED DESCRIPTION

[0051] The following will be described in detail in conjunction with the accompanying Figure 1 , the present application will be further described.

[0052] Please refer to the accompanying Figure 1 :

[0053] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0054] Example 1:

[0055] Raw material components (by mass fraction):

[0056] Silicon dioxide (SiO2): 65 parts;

[0057] Sodium oxide (Na2O): 12.5 parts;

[0058] Calcium oxide (CaO): 7.5 parts;

[0059] Aluminum oxide (Al2O3): 2 parts;

[0060] Zinc oxide (ZnO): 1 part.

[0061] Nano-enhanced component:

[0062] Zirconium oxide (ZrO2) nanoparticles: 4 parts;

[0063] Polyvinylpyrrolidone (PVP): 3 parts.

[0064] Preparation method:

[0065] Glass matrix raw material mixing and melting: The raw materials are weighed according to the above mass fractions, and the silicon dioxide, sodium oxide, calcium oxide, aluminum oxide, and zinc oxide are mixed uniformly. The mixed raw materials are placed in a platinum crucible and heated to 1350°C, and the temperature is maintained for 60 minutes to ensure complete melting of the raw materials and obtain a uniform glass melt.

[0066] Preparation of nanoparticle dispersion liquid: 4 parts of zirconium oxide nanoparticles and 3 parts of polyvinylpyrrolidone are added to ethanol and deionized water (volume ratio 7:3), the pH is adjusted to 9.5, and a stirrer is used to stir for 30 minutes to form a stable dispersion liquid.

[0067] Dispersion liquid dropping and microbubble injection: The glass melt is kept at 1350°C, and the dispersion liquid is slowly added to the melt at a rate of 15 minutes. During this process, argon gas is injected into the melt at a flow rate of 100 mL / min, and the diameter of the microbubbles is controlled at about 100 microns to ensure uniform dispersion.

[0068] Stirring and shaping: Continue to stir the glass melt at a stirring speed of 50 rpm for 10 minutes. Then pour the melt into a preheated quartz mold at 400°C for shaping.

[0069] Annealing treatment: The shaped glass is subjected to annealing treatment. The annealing process includes holding at 530°C for 90 minutes, then reducing the temperature to 450°C at a rate of 1°C / min and holding for 30 minutes, and finally reducing the temperature to room temperature at a rate of 2°C / min to obtain a composite glass material.

[0070] Example 2:

[0071] Raw material components (by mass fraction):

[0072] Silicon dioxide (SiO2): 60 parts;

[0073] Sodium oxide (Na2O): 10 parts;

[0074] Calcium oxide (CaO): 5 parts;

[0075] Aluminum oxide (Al2O3): 1 part;

[0076] Zinc oxide (ZnO): 0.5 parts.

[0077] Nano-enhanced component:

[0078] Zirconium oxide (ZrO2) nanoparticles: 2 parts;

[0079] Polyvinylpyrrolidone (PVP): 2 parts.

[0080] Preparation method:

[0081] Glass matrix raw material mixing and melting: The raw materials are weighed according to the above mass fractions, and the silica, sodium oxide, calcium oxide, aluminum oxide, and zinc oxide are mixed uniformly. The mixed raw materials are placed in a platinum crucible and heated to 1450°C, and the temperature is maintained for 30 minutes to ensure complete melting of the raw materials and obtain a uniform glass melt.

[0082] Preparation of nanoparticle dispersion liquid: 2 parts of zirconium oxide nanoparticles and 2 parts of polyvinylpyrrolidone are added to ethanol and deionized water (volume ratio 7:3), the pH is adjusted to 10, and a stirrer is used to stir for 35 minutes to form a stable dispersion liquid.

[0083] Dispersion liquid dropping and microbubble injection: The glass melt is maintained at 1450°C, and the dispersion liquid is slowly added to the melt at a rate of 20 minutes. During this process, argon gas is injected into the melt at a flow rate of 50 mL / min, and the diameter of the microbubbles is controlled at about 50 microns.

[0084] Stirring and shaping: Continue to stir the glass melt at a stirring speed of 40 rpm for 15 minutes. Then pour the melt into a preheated quartz mold at 450°C for shaping.

[0085] Annealing treatment: The shaped glass is subjected to annealing treatment. The annealing process includes maintaining at 540°C for 70 minutes, then reducing the temperature to 460°C at a rate of 2°C / min and maintaining for 40 minutes, and finally reducing the temperature to room temperature at a rate of 1°C / min to obtain a composite glass material.

[0086] Example 3:

[0087] Raw material components (by mass fraction):

[0088] Silicon dioxide (SiO2): 70 parts;

[0089] Sodium oxide (Na2O): 15 parts;

[0090] Calcium oxide (CaO): 10 parts;

[0091] Aluminum oxide (Al203): 3 parts;

[0092] Zinc oxide (ZnO): 2 parts.

[0093] Nano-reinforcing component:

[0094] Zirconium oxide (Zr02) nanoparticles: 6 parts;

[0095] Polyvinylpyrrolidone (PVP): 5 parts.

[0096] Preparation method:

[0097] Glass matrix raw material mixing and melting: The raw materials are weighed according to the above mass fractions, and the silicon dioxide, sodium oxide, calcium oxide, aluminum oxide, and zinc oxide are mixed uniformly. The mixed raw materials are placed in a platinum crucible and heated to 1400°C, and the temperature is maintained for 45 minutes to ensure complete melting of the raw materials and obtain a uniform glass melt.

[0098] Preparation of nanoparticle dispersion liquid: 6 parts of zirconium oxide nanoparticles and 5 parts of polyvinylpyrrolidone are added to ethanol and deionized water (volume ratio 7:3), the pH is adjusted to 11, and a stirrer is used to stir for 40 minutes to form a stable dispersion liquid.

[0099] Dispersion liquid dropping and microbubble injection: The glass melt is kept at 1400°C, and the dispersion liquid is slowly added to the melt at a rate of 30 minutes. During this process, argon gas is injected into the melt at a flow rate of 200 mL / min, and the diameter of the microbubbles is controlled at about 200 microns to ensure uniform dispersion.

[0100] Stirring and shaping: Continue to stir the glass melt at a stirring speed of 60 rpm for 15 minutes. Then pour the melt into a 500°C preheated quartz mold for shaping.

[0101] Annealing treatment: The shaped glass is subjected to annealing treatment. The annealing process includes holding at 550°C for 60 minutes, then reducing the temperature to 460°C at a rate of 2°C / min and holding for 50 minutes, and finally reducing the temperature to room temperature at a rate of 3°C / min to obtain a composite glass material.

[0102] Comparative Example 1:

[0103] The difference compared with Example 1 is that polyvinylpyrrolidone (PVP) is not added, and the rest is the same.

[0104] Comparative Example 2:

[0105] The difference from Example 1 is that the amount of zirconia nanoparticles added is 1 part, and the rest is the same.

[0106] Comparative Example 3:

[0107] The difference from Example 1 is that the amount of zirconia nanoparticles added is 8 parts, and the rest is the same.

[0108] Comparative Example 4:

[0109] The difference from Example 1 is that the argon injection step is not performed, and the rest is the same.

[0110] Comparative Example 5:

[0111] The difference from Example 1 is that the pH value of the nanoparticle dispersion is not adjusted, and the rest is the same.

[0112] Comparative Example 6:

[0113] The difference from Example 1 is that the glass melt is not stirred, and the rest is the same.

[0114] Experiment 1:

[0115] Purpose of the experiment: To evaluate the change in surface hardness of the composite glass material under different conditions of adding nano-enhanced components.

[0116] Experimental samples:

[0117] Example 1;

[0118] Comparative Example 1: (without PVP);

[0119] Comparative Example 2: (zirconia addition is too low);

[0120] Comparative Example 3: (zirconia addition is too high);

[0121] Experimental steps:

[0122] Sample preparation:

[0123] Each glass sample is made into a polished block with a size of 20mm x 20mm x 3mm, and the surface is polished to a mirror state to ensure that the test area is flat, free of pores and scratches.

[0124] Hardness test parameter settings:

[0125] Loading force: 100gf;

[0126] Hold time: 10 seconds;

[0127] Number of measurement points: 6 points are randomly selected for testing for each sample, and the readings are recorded;

[0128] Test temperature: room temperature (about 25℃).

[0129] Hardness test operation:

[0130] Place the sample on the hardness tester stage, adjust the focus and indenter position, and align the sample surface for loading test. After each loading is completed, record the corresponding reading.

[0131] Data recording and arrangement:

[0132] After collecting the hardness readings of 6 points of each sample, the variation range and trend are calculated and compared (the experimental results are shown in Table 1).

[0133] Table 1: Vickers hardness test data of different formula samples of composite glass materials (unit: HV)

[0134] Sample No. 1st point 2nd point 3rd point 4th point 5th point 6th point Average 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

[0135] In this experiment, by comparing the hardness performance of different samples, it can be seen that the effective dispersion of nano-zirconium oxide particles in the glass matrix has a direct enhancing effect on the hardness of the overall material. When the particles are uniformly distributed in the matrix and the particle size is fine, the propagation path of the crack in the matrix can be limited on the microscale, forming a "crack blunting" effect, thereby enhancing the material's deformation resistance and surface load capacity. In contrast, when the particle addition amount is insufficient or the dispersion is poor, this enhancing effect is difficult to realize, resulting in a material with low hardness.

[0136] The uniform distribution effect of the particles is closely related to the stability of the dispersion system. After adding polyvinylpyrrolidone in the implementation, the molecular chain can form an adsorption layer on the surface of the nano-zirconium oxide, significantly improving its dispersibility in the solution and preventing particle agglomeration. During the subsequent melt addition process, this coating structure further promotes the effective combination of particles and glass network structure at high temperature, allowing the nano-particles to remain in a fine distribution state in the matrix, thereby effectively enhancing the overall structural stability and hardness of the glass.

[0137] In addition, the content control of nano-particles also plays a key role. An appropriate amount of zirconium oxide not only helps to form an effective strengthening lattice structure, but also can share external loads in the matrix. Experimental results show that when the addition amount exceeds the appropriate range, the particle spacing is too small, which can easily lead to stress concentration, which is not conducive to performance; while when the content is too low, the strengthening effect is insufficient. Therefore, on the basis of surface modification and distribution strategy of nano-particles, controlling the reasonable addition amount is a key technical element for preparing high-hardness composite glass.

[0138] Experiment 2:

[0139] Purpose of the experiment:

[0140] The wear test was conducted on the composite glass materials prepared under different process conditions to comparatively evaluate the influence of micro-bubble assisted dispersion and pH adjustment on wear resistance.

[0141] Experimental samples:

[0142] Example 1;

[0143] Comparative Example 4: (without argon injection);

[0144] Comparative Example 5: (without pH adjustment).

[0145] Experimental procedure:

[0146] Sample preparation and pretreatment:

[0147] Each sample was cut into a round piece (about 25 mm in diameter and 3 mm in thickness) and polished to a mirror surface. The sample was cleaned by ultrasonic alcohol cleaning and dried for standby.

[0148] Initial weighing:

[0149] The mass of each sample before wear was weighed by a precision balance, and the initial value was recorded.

[0150] Wear test parameter setting:

[0151] Wear time: 5 minutes;

[0152] Vertical load: 10N;

[0153] Rotational speed: 200 rpm;

[0154] Each group of samples was tested in triplicate, and the average mass loss was calculated.

[0155] Test operation procedure:

[0156] The sample was placed on the grinding disc, and the equipment was started for timed wear. After the test, the sample was taken out, the surface residual abrasive particles were removed, and then the sample was weighed again after being wiped dry. The mass after wear was recorded.

[0157] Data arrangement:

[0158] The mass loss difference was calculated as the wear amount, and the results were recorded (the experimental results are shown in Table 2).

[0159] Table 2: Wear test mass loss data of composite glass material samples with different formulations (unit: mg)

[0160] Sample No. Test Sample 1 Test Sample 2 Test 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

[0161] From the wear resistance experiment results, it can be seen that the wear amount of the material surface is closely related to the dispersion state of the nanoparticles in the glass matrix. The introduction of micro-bubbles by argon injection creates a disturbance effect in the high-temperature melt, which helps to break the initial agglomeration state of the particles and allows them to have more sufficient spatial diffusion in the fluid. This disturbance mechanism allows the nanoparticles of zirconium oxide to be more uniformly distributed in the high-viscosity glass melt, which in turn forms a stable reinforcing structure during the forming and cooling process, significantly improving the material's ability to resist surface wear.

[0162] At the same time, during the preparation of the dispersion, the pH value is adjusted by the alkaline environment, effectively changing the charge state of the nanoparticle surface, enhancing the repulsion between them, and being conducive to the high stability of the particles in the liquid phase. This process ensures that the particles are in a good dispersion state before being added to the melt. Compared with the sample without pH adjustment, the stable precursor dispersion system significantly reduces the risk of particle agglomeration in the melt, thereby improving the uniformity of the particles in the finished product and enhancing their structural support for the glass surface during wear.

[0163] The effect of particle distribution uniformity on wear resistance is particularly evident. Zirconia particles in a good distribution state can effectively inhibit the peeling and fine scratches on the material surface when subjected to friction impact, and share the abrasive force, thereby delaying the wear process of the matrix material. On the contrary, if the dispersion is uneven or the particles are agglomerated, weak interfaces or local peeling are easily formed during wear, reducing the overall wear resistance. This verifies the key role of dispersion stability strategies and dynamic dispersion methods in improving the wear resistance of glass materials.

[0164] Experiment 3:

[0165] Purpose of the experiment:

[0166] By simulating the thermal shock test conditions, the crack resistance of the glass melt during the forming process with and without stirring steps is compared.

[0167] Experimental samples:

[0168] Example 1;

[0169] Comparative Example 6: (glass melt without stirring).

[0170] Experimental steps:

[0171] Sample preparation:

[0172] The two samples were cut into glass pieces of the same size (30mm x 10mm x 3mm), and the surface was polished to ensure no scratches or cracks.

[0173] Thermal shock test operation:

[0174] Put the sample into a dry box, heat to 500℃ and keep for 5 minutes;

[0175] Quickly remove the hot sample with tongs and immediately immerse vertically into a cold water bath;

[0176] After cooling, remove the sample, dry and visually or manually inspect for cracks or chipping.

[0177] Test repeatability:

[0178] Each sample is tested 5 times, and the presence and extent of cracking is recorded using a simple ranking system.

[0179] Data recording method:

[0180] Use the scoring system to judge the anti-cracking effect:

[0181] Intact: 0 points;

[0182] Cracks: 1 point;

[0183] Cracking or chipping: 2 points. Calculate the total score of each group of samples and take the average to obtain the anti-cracking score (experimental results are shown in Table 3).

[0184] Table 3: Anti-cracking test score results of composite glass samples with different processes

[0185] Sample No. 1st time 2nd time 3rd time 4th time 5th time Average Score Example 1 0 0 1 0 0 0.2 Comparative Example 6 1 2 1 2 1 1.4

[0186] The anti-cracking experiment results show that the stirring operation during the high-temperature melting stage has an important influence on the stability of the overall structure of the material. By continuous stirring, a certain convection state is maintained inside the glass melt, which helps to achieve dynamic and uniform distribution of nanoparticles in the melt, avoiding the phenomenon of particle sinking, floating or local aggregation. This dynamic distribution mechanism ensures that the reinforcing components better embed in the glass network structure during the cooling and solidification process, thereby providing an effective crack blocking path when subjected to thermal shock and enhancing the anti-cracking performance.

[0187] In contrast, in samples formed without stirring, particles tend to concentrate in local areas, leading to uneven distribution of the matrix structure. Once subjected to external temperature shock, local stress concentration phenomena are obvious, thereby inducing cracks or even chipping. Melt stirring not only improves the uniformity of particle distribution, but also improves the bonding state between particles and the glass matrix, making particles more stably embedded in the three-dimensional network, acting as "stress release points" in the stress conduction process, reducing the risk of local damage when subjected to thermal shock.

[0188] In addition, the melt stirring process is also beneficial to the formation of a more stable contact interface between the particles and the glass network framework at the microscale, reducing the fragile areas caused by poor interface transition. Experiments show that the composite glass prepared by stirring exhibits higher structural integrity during the severe cold and hot alternating process, indicating that the thermal stability and crack resistance of the material have been significantly optimized. This mechanism fully demonstrates the importance of introducing reasonable dynamic disturbance means in the melting process for obtaining high-performance composite glass materials.

[0189] The embodiments of the present specific implementation are the preferred embodiments of the present application, and are not intended to limit the protection scope of the present application, wherein the same parts are denoted by the same reference numerals. Therefore, any equivalent changes made according to the structure, shape, principle of the present application should be covered within the protection scope of the present application.

Claims

1. A method for preparing a composite glass material containing a nano-reinforcing component, the composite glass material comprising a glass matrix, a nano-reinforcing component and a dispersant, characterized in that, The glass matrix is composed of the following components in mass fraction: Silicon dioxide: 60-70 parts; Sodium oxide: 10-15 parts; Calcium oxide: 5-10 parts; Aluminum oxide: 1-3 parts; Zinc oxide: 0.5-2 parts; The nano-enhanced component is zirconium oxide nanoparticles, with an addition amount of 2-6 parts, a particle size of 20-50 nanometers, and a purity of not less than 99.9%; The dispersant is polyvinylpyrrolidone, with an addition amount of 2-5 parts and a molecular weight of 10,000-50,000; The preparation method of the composite glass material includes the following steps: S1, weigh the glass matrix raw material components, mix uniformly, and melt at 1350-1450℃ for 30-60 minutes to obtain a glass matrix melt; S2, add 2-6 parts of zirconium oxide nanoparticles and 2-5 parts of polyvinylpyrrolidone to a mixed solution of ethanol and deionized water with a volume ratio of 7:3, adjust the pH to 9-11, and stir for 30-45 minutes to form a stable dispersion; S3, slowly add the dispersion to the melt in a 15-30 minute time under the condition that the glass melt remains at a high temperature, and pass argon gas at a flow rate of 50-200 mL / min to form micro-bubbles with a diameter of 50-200 microns for dispersion; S4, continue to stir the glass melt at 30-60 rpm and keep for 10 minutes, then pour into a preheated mold at 400-500℃ for forming; S5, after annealing treatment, the formed glass is cooled to 450℃ at a rate of 1-2℃ / min, kept for 30-60 minutes, and then cooled to room temperature at a rate of 1-3℃ / min to obtain the composite glass material; The argon gas passed at a flow rate of 50-200 mL / min includes the following steps: The argon gas used to form micro-bubbles is injected through a ceramic microporous diffusion rod, with an injection depth of 10-20 millimeters; The diameter of the micro-bubbles is controlled within the range of 50-200 microns by the pore size of the diffusion rod; The argon gas is continuously passed throughout the whole process.

2. A method of making a nanoreinforced composite glass material according to claim 1, wherein, The sodium oxide is an alkaline oxide component, and the calcium oxide is an alkaline earth metal oxide component, which are used to introduce non-bridging oxygen and adjust the composition and structure of the glass melt.

3. The method of claim 1, wherein the nanoreinforced component comprises a plurality of nanoparticles dispersed in a matrix material. The aluminum oxide and zinc oxide are used to adjust the types and proportions of cations in the matrix oxide system.

4. The method of claim 1, wherein the nanoreinforced component comprises a plurality of nanoparticles dispersed in a matrix material. The addition of 2-6 parts of zirconium oxide nanoparticles and 2-5 parts of polyvinylpyrrolidone to a mixed solution of ethanol and deionized water with a volume ratio of 7:3 includes: The mass ratio of zirconium oxide nanoparticles to polyvinylpyrrolidone is 1:1.0-1:1.8; The total liquid mass of the stable dispersion is 8-12 times the mass of the added solids; Magnetic stirring or propeller stirring device is used, and the stirring temperature is controlled at 25-40℃.

5. The method of claim 1, wherein the nanoreinforced component comprises a plurality of nanoparticles dispersed in a matrix material. After the particle interfaces are combined and uniformly distributed, the glass melt is poured into a preheated mold at 400-500℃ for forming, which includes the following steps: The temperature rising and falling rate of the mold is controlled at 10-20℃ / min; After the melt is poured into the mold, the stirring speed during the forming process is kept at 30-60 rpm for 10-15 minutes.

6. The method of claim 1, wherein the nanoreinforced component comprises a plurality of nanoparticles dispersed in a matrix material. 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 composite glass material after annealing to room temperature is slowly completed in a closed furnace cavity.

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