Glass glaze for resistor disc and preparation method of glass glaze

Abstract

The invention relates to the technical field of electronic components, and particularly discloses a glass glaze for a resistor disc and a preparation method thereof, the glass glaze comprises the following raw materials by weight: 25-35 parts of pure new glass powder, 25-35 parts of recycled glass powder, 20-30 parts of water, and 4-6 parts of a water-based adhesive; the recycled glass powder is glass glaze waste which is not attached to a substrate in a resistor disc spraying process and is subjected to surface modification treatment; the water-based adhesive is prepared from the following components in parts by weight: 20 to 30 parts of water and 0.5 to 1 part of hydroxyethyl cellulose, and the pure new glass powder is prepared from the following components in parts by weight: 12.5 to 24.5 parts of bismuth trioxide, 0.75 to 5.25 parts of boric oxide, 1.25 to 7.0 parts of zinc oxide, 1.25 to 3.5 parts of aluminum oxide, 1.25 to 6.3 parts of silicon oxide, 0.025 to 1.75 parts of copper oxide and 0.025 to 1.05 parts of magnesium oxide. The glass glaze provided by the invention can be used for protecting the surface of a resistor disc, and has the advantages of good electrical insulating property and good stability.

Description

Technical Field

[0001] The present application relates to the technical field of electronic components, and more specifically, to a glass glaze for resistors and a preparation method thereof. Background Art

[0002] Resistor glass glaze is a material widely used in the manufacture of electronic components. Its excellent insulation, heat resistance, and mechanical strength make it widely used in the manufacture of electronic components such as resistors and capacitors, protecting them and improving their stability and reliability. The performance of resistor glass glaze directly affects the quality and lifespan of electronic components. Therefore, its preparation process and performance optimization have long been research hotspots in the electronic materials field.

[0003] The manufacturing process for resistors often uses a slurry spraying process to apply glass glaze to the sides of the resistors. However, this process has a low material utilization rate, resulting in a large amount of glass waste that has not adhered to the substrate, resulting in a significant waste of resources. Traditionally, recycling this waste is relatively simple, simply crushing it for reuse, but this recycling method has many drawbacks.

[0004] First, recycled glass powder may contain impurity ions. Directly adding this raw material to glass glaze can significantly reduce the insulation and withstand voltage performance of the glass glaze, seriously affecting the proper operation and safety of electronic components. Furthermore, the presence of hydroxyl groups on the surface of recycled glass powder can increase the porosity within the glaze layer, causing resistance drift and reducing the performance stability of the resistor. These issues in recycled glass powder can affect the performance of the glass glaze, thereby limiting its application in the preparation of glass glaze for resistors.

[0005] Therefore, how to recycle glass powder while maintaining the good performance of glass glaze has become an urgent problem that needs to be solved. Summary of the Invention

[0006] In order to solve the above problems, the present application provides a glass glaze for resistors.

[0007] In a first aspect, the present application provides a glass glaze for a resistor, which adopts the following technical solution: A glass glaze for resistors, comprising the following raw materials in parts by weight: 25-35 parts of pure new glass powder, 25-35 parts of recycled glass powder, 20-30 parts of water, 4-6 parts of water-based adhesive; The recycled glass powder is the waste glass glaze that is not attached to the substrate during the resistor spraying process and has undergone surface modification treatment; The water-based adhesive includes 20-30 parts of water and 0.5-1 part of hydroxyethyl cellulose. The pure new glass powder comprises 12.5-24.5 parts of bismuth trioxide, 0.75-5.25 parts of boron oxide, 1.25-7.0 parts of zinc oxide, 1.25-3.5 parts of aluminum oxide, 1.25-6.3 parts of silicon oxide, 0.025-1.75 parts of copper oxide, and 0.025-1.05 parts of magnesium oxide.

[0008] By adopting the above technical solution and introducing recycled glass powder that has undergone surface modification, resource utilization is effectively improved and production costs are reduced. Low-melting-point components such as bismuth trioxide and boron oxide in pure new glass powder promote the fracture and reconstruction of the glass network during the firing process, reduce the melting temperature, and accelerate the formation of the liquid phase. At the same time, fluxing agents such as zinc oxide further improve the fluidity and densification of the glass. After the surface modification of the recycled glass powder, its surface activity is improved, and the interface bonding with the pure new glass powder is tighter, reducing the degradation of electrical properties caused by impurity ions or interface defects, while avoiding powder agglomeration and the generation of surface microcracks. The hydroxyethyl cellulose in the water-based adhesive ensures the uniformity and stability of the slurry during the coating process through thickening and bonding effects, which is conducive to the dense coverage of the glass glaze on the surface of the resistor, and ultimately forms a glass glaze layer with excellent insulation properties, heat resistance and mechanical strength. While achieving effective resource recycling, the quality and life of electronic components are improved.

[0009] Specifically, the bismuth trioxide in the pure new glass powder formula, with its low melting point, lowers the melting temperature of the glass glaze, providing a foundation for low-temperature sintering. Its high polarizability and lone-pair electron properties regulate the glass network structure and the electronic structure of the resistor interface, respectively, enhancing the dielectric and nonlinear conductivity. Boron oxide and silicon oxide form a stable basic network skeleton, giving the glaze layer mechanical strength and chemical stability. Zinc oxide promotes microstructural homogenization during sintering, while copper oxide further reduces the sintering temperature by forming a low-melting phase with bismuth trioxide and synergistically optimizes nonlinear conductivity with zinc oxide. Aluminum oxide and magnesium oxide act as network modifiers to fill structural voids, improving density and chemical durability. Magnesium oxide inhibits bismuth volatilization and ensures sintering stability. The final formula achieves dense sintering at low temperatures while imparting excellent electrical insulation and thermal stability to the glass glaze layer.

[0010] Optionally, the recycled glass powder is subjected to surface modification treatment, specifically comprising the following steps: S1. The recycled glass powder was collected and dried at 100-110 ° C to a water content of ≤ 0.3wt%, sieved, and depolymerized by ball milling with magnesium stearate to obtain a mixed powder; S2. The mixed powder and the reducing solution were mixed in a mass ratio of 1:4-6 and placed in a water bath at 65-75 ° C with stirring, maintaining the pH between 3.3-3.8. The reaction was terminated when the redox potential was ≤-150mv, and the mixture was filtered and washed to neutral to obtain a reduced powder; S3. The reduced powder was mixed with silane hydrolyzate in a mass ratio of 1:3-5, stirred at room temperature for 10-20 minutes, filtered, dried, heated and cured, and air-classified to obtain a surface-modified recycled glass powder.

[0011] By adopting the above technical solution, firstly, drying and dehydration and magnesium stearate ball milling deagglomeration can remove adsorbed water and weakly bound impurities on the powder surface. At the same time, the lubricating effect of magnesium stearate effectively destroys the powder agglomeration structure and improves the dispersibility. Secondly, in the weakly acidic reducing solution, the oxidizing metal ions (such as high-valent ions such as iron and copper) present on the powder surface are reduced to a low-valent state, avoiding the formation of conductive channels or catalytic glass phase crystallization during the subsequent sintering process. At the same time, the maintained acidic environment can further inhibit the dissolution of impurity ions. Finally, the silanol groups in the silane hydrolyzate react with the hydroxyl groups on the powder surface to form stable siloxane bonds, and the amino groups form hydrogen bonds or covalent bonds with the hydroxyethyl cellulose in the adhesive to construct an active surface layer, which significantly improves the interfacial binding energy. At the same time, the coating with magnesium stearate reduces powder agglomeration, and the cured silane layer fills the surface microcracks, further strengthening the microstructure. Finally, the modification treatment significantly changed the surface energy of the powder. The increase in polarity promoted liquid phase wetting, reduced the sintering activation energy, achieved low-temperature densification, lowered the densification starting temperature, and greatly reduced the porosity at the same sintering temperature, significantly improving its filling effect in glass glaze and electrical performance stability.

[0012] Optionally, the reducing solution includes 110-130 g / L of citric acid, 40-60 g / L of ascorbic acid, and 3-8 g / L of ferrous sulfate.

[0013] By adopting the above technical solution, efficient reduction and impurity control are achieved: citric acid, as a complexing agent, can form a stable soluble complex with metal ions to prevent the secondary precipitation of impurity ions. At the same time, its acidic environment promotes ascorbic acid to reduce high-valent metal ions to low-valent states, avoiding the formation of conductive channels or catalytic crystallization during subsequent sintering; ascorbic acid, as a strong reducing agent, quickly consumes dissolved oxygen in the solution and directly reduces metal ions, lowering the redox potential; ferrous sulfate, as a catalyst, its Fe 2+ It can participate in the electron transport chain, accelerate the reaction process, and at the same time be oxidized to Fe 3+The system can still maintain stability through citric acid complexation. With the synergistic effect of the three, the reducing solution not only deeply removes oxidative impurities, but also fixes metal ions through complexation, significantly improving the insulation resistance and breakdown strength of the glass glaze. At the same time, it maintains a stable pH value in the system to prevent corrosion of equipment caused by excessive acidity, achieving a balance between reduction efficiency and process safety.

[0014] Optionally, the silane hydrolyzate comprises 2-5 parts of γ-aminopropyltriethoxysilane and 95-98 parts of a 90% ethanol aqueous solution, and the pH is adjusted to 4.2-4.8 with glacial acetic acid.

[0015] By employing this technical solution, γ-aminopropyltriethoxysilane undergoes controlled hydrolysis in a weakly acidic ethanol solution to generate silanol groups, which react with the hydroxyl groups on the glass powder surface through dehydration condensation to form strong Si-O-Si covalent bonds. Simultaneously, the amino groups at the silane termini impart positive charge to the powder surface, neutralizing the inherent negative surface potential of the glass powder to inhibit agglomeration and forming strong hydrogen bonds with the hydroxyl and carboxyl groups in the subsequent water-based adhesive. The ethanol-water solution serves as the reaction medium, ensuring full dissolution of the silane and controlling the hydrolysis rate. Ultimately, a dense monomolecular modified layer is formed on the powder surface, bringing the dispersibility and interfacial bonding strength of the recycled powder to levels comparable to those of virgin material.

[0016] Optionally, the particle size of the pure new glass powder is 0.7-1.2 μm, and the particle size of the recycled glass powder is 4-6 μm.

[0017] By employing this technical solution, pure new glass powder (0.7-1.2μm) preferentially melts during the initial sintering phase. The high surface energy generated by its fine particle size promotes low-temperature densification, allowing the melt to fully envelop the surface of the coarse 4-6μm recycled powder particles, forming a wetted bond. The rigid network formed by the coarse particles suppresses sintering shrinkage stress and prevents cracking in the glaze layer. This bimodal distribution system allows the fine powder to fill the voids in the coarse powder, reducing porosity to its theoretical minimum. Furthermore, the microstructured channels formed by the coarse particles facilitate gas evacuation during sintering, ultimately resulting in a dense, defect-free glass glaze layer.

[0018] Optionally, polyvinyl pyrrolidone is further added to the water-based adhesive, and the mass ratio of the hydroxyethyl cellulose to the polyvinyl pyrrolidone is (2.5-3):1.

[0019] By adopting the above technical solution, hydroxyethyl cellulose is used as a thickener and film-forming agent, and the hydroxyl groups on its molecular chain can form hydrogen bonds with the surface of the glass powder. At the same time, a three-dimensional network structure is built through intermolecular entanglement, giving the adhesive good adhesion and water retention. Polyvinyl pyrrolidone is used as a non-ionic polymer dispersant. Its lactam group effectively prevents the agglomeration of glass powder through steric hindrance effect and electrostatic repulsion, and enhances its compatibility with the organic matrix. When the two are compounded in a specific mass ratio, the network structure of hydroxyethyl cellulose provides basic strength for the system, and the dispersing effect of polyvinyl pyrrolidone further optimizes the powder distribution. At the same time, its hydrophilic groups form hydrogen bonds with hydroxyethyl cellulose to synergistically improve the rheological properties and anti-settling properties of the adhesive, and ultimately form a uniform and dense interface layer in the composite material during the curing process, reducing pores and defects.

[0020] Optionally, 0.2-0.5 parts of a sintering aid is further added to the raw materials, which is composed of ammonium molybdate and bismuth citrate in a mass ratio of 0.5-1:1.

[0021] By adopting the above technical solution, ammonium molybdate decomposes at high temperature to form molybdenum oxide. Its low melting point promotes the formation of liquid phase, accelerates the rearrangement and densification of glass powder particles, and at the same time, molybdenum oxide can inhibit abnormal grain growth; bismuth citrate releases bismuth ions during the sintering process, and its low melting point and high polarizability characteristics further reduce the sintering temperature, regulate the glass network structure, and enhance the dielectric properties; when the two are compounded in a specific mass ratio, the liquid phase promoting effect of ammonium molybdate and the structural regulating effect of bismuth citrate complement each other, which not only accelerates the densification process but also avoids the weakening of grain boundaries. At the same time, bismuth ions and molybdenum ions synergistically inhibit the migration of impurity ions, reduce leakage current channels, and ultimately enable the glass glaze to achieve high density and uniform crystal phase at low temperature, significantly improving its electrical properties and thermal stability.

[0022] In a second aspect, the present application provides a method for preparing glass glaze for resistors, which adopts the following technical solution: A method for preparing glass glaze for resistor chips comprises the following steps: (1) melting pure new glass powder raw material at 1100-1200°C, quenching with water, crushing and air-flow classifying to 0.7-1.2 μm, and obtaining pure new glass powder for use; (2) Dissolve hydroxyethyl cellulose in water at 60-70°C in a water bath and stir until completely dissolved to form a water-based adhesive; (3) Mixing pure new glass powder, recycled glass powder, water-based adhesive and water, and aging at room temperature for 3-5 hours to obtain a slurry; (4) The slurry is coated on the surface of the resistor and then vitrified to obtain a glass glaze for the resistor.

[0023] Step sintering is used in the vitrification process: a) Heating to 200℃ and holding time ≥ 60min; b) Raise the temperature to 450°C within 40-60 minutes and keep at this temperature for ≥30 minutes; c) Raise the temperature to 500-530℃ within 60 minutes and keep it at this temperature for 60-90 minutes.

[0024] By adopting the above technical solution, glass powder of suitable particle size is obtained by precisely controlling the steps of melting, water quenching, crushing and grading of pure new glass powder. The prepared water-based adhesive can improve the stability of the slurry. The pure new and recycled glass powders are mixed and aged to make the slurry performance better. The step-by-step sintering process is adopted, the temperature is gradually increased and the insulation time of each stage is reasonably controlled, which can effectively remove moisture and organic matter from the slurry, promote the full melting and sintering of the glass powder, form a dense and uniform glass glaze layer, and improve the quality and performance of the glass glaze for resistors. At the same time, the use of recycled glass powder also helps to reduce costs and recycle resources.

[0025] In summary, this application has the following beneficial effects: 1. This application effectively improves resource utilization and reduces production costs by introducing recycled glass powder that has undergone surface modification, solving the problem of resource waste caused by a large amount of glass waste that is not attached to the substrate in the resistor spraying process.

[0026] 2. After surface modification, the recycled glass powder in this application has a tighter interface with the pure new glass powder, reducing the degradation of electrical properties caused by impurity ions or interface defects, while avoiding powder agglomeration and the generation of surface microcracks, ensuring the excellent insulation performance and heat resistance of the glass glaze on the resistor.

[0027] 3. By precisely controlling the melting, crushing and grading steps of pure new glass powder and adopting a step-by-step sintering process, the moisture and organic matter in the slurry are effectively removed, which promotes the full melting and sintering of the glass powder, forming a dense and uniform glass glaze layer, improving the quality and performance of the glass glaze for resistors, and at the same time meeting the high quality and long life requirements of electronic components. DETAILED DESCRIPTION

[0028] The present application is further described in detail below with reference to the examples. It is particularly noted that if no specific conditions are specified in the following examples, the reactions are carried out according to conventional conditions or the conditions recommended by the manufacturer. Unless otherwise specified, the raw materials used in the following examples can be obtained from common commercial sources.

[0029] Polyvinylpyrrolidone was purchased from Jinan Zhengkang Chemical Co., Ltd., K30. Preparation example of raw materials

[0030] Preparation Example

[0031] Preparation Example 1 A recycled glass powder that has undergone surface modification is prepared by the following steps: S1. The recycled glass powder was collected and dried at 105°C to a water content of ≤0.3wt%, and 0.3% of the mass of the recycled glass powder was added to magnesium stearate, and ball milled at 300r / min for 30min to obtain a mixed powder; S2. Take 40kg of the mixed powder and the reducing solution in a mass ratio of 1:5 and place it in a water bath at 70 ° C and stir the reaction, maintaining its pH between 3.3-3.8. The reaction is terminated when the redox potential is ≤-150mv, and the mixture is filtered and washed to neutrality to obtain a reduced powder; the reducing solution includes 120g / L of citric acid, 50g / L of ascorbic acid, and 5g / L of ferrous sulfate. After adding an appropriate amount of water and turning on the stirring device, citric acid, ascorbic acid and ferrous sulfate are slowly added in sequence. After one substance is completely dissolved, the next substance is added until all components are completely dissolved to obtain a uniform reducing solution; S3. Take 35 kg of the above-mentioned reduced powder and mix it with the prepared silane hydrolyzate in a mass ratio of 1:4, stir and react at room temperature for 15 minutes, filter, dry, heat and solidify, and air flow classify to collect powder with a particle size of 4-6 μm to obtain recycled glass powder after surface modification; the silane hydrolyzate is obtained by dissolving 4.9 kg of γ-aminopropyltriethoxysilane in 135.1 kg of 90% v / v ethanol aqueous solution and stirring to fully disperse it, and adjusting the pH to 4.5 with glacial acetic acid.

[0032] Preparation Example 2 A recycled glass powder that has undergone surface modification is prepared by the following steps: S1. The recycled glass powder was collected and dried at 110 ° C to a water content of ≤0.3wt%, and 0.2% of the mass of the recycled glass powder was added to magnesium stearate, and ball milled at 300r / min for 30min to obtain a mixed powder; S2. Take 40kg of the mixed powder and the reducing solution in a mass ratio of 1:6 and place it in a water bath at 75 ° C with stirring to react, maintaining its pH between 3.3-3.8. The reaction is terminated when the redox potential is ≤-150mv, and the mixture is filtered and washed to neutrality to obtain a reduced powder; the reducing solution includes 130g / L of citric acid, 60g / L of ascorbic acid, and 8g / L of ferrous sulfate. After adding an appropriate amount of water and turning on the stirring device, citric acid, ascorbic acid and ferrous sulfate are slowly added in sequence. After one substance is completely dissolved, the next substance is added until all components are completely dissolved to obtain a uniform reducing solution; S3. Take 35 kg of the reduced powder and add it to the prepared silane hydrolyzate in a mass ratio of 1:5, stir and react at room temperature for 20 minutes, filter, dry, heat and solidify, and air flow classify to collect powder with a particle size of 4-6 μm to obtain recycled glass powder after surface modification; the silane hydrolyzate is obtained by dissolving 3.6 kg of γ-aminopropyltriethoxysilane in 171.4 kg of 90% v / v ethanol aqueous solution and stirring to fully disperse it, and adjusting the pH to 4.8 with glacial acetic acid.

[0033] Preparation Example 3 A recycled glass powder that has undergone surface modification is prepared by the following steps: S1. The recycled glass powder was collected and dried at 100°C to a water content of ≤0.3wt%, and 0.4% of the mass of the recycled glass powder was added to magnesium stearate, and ball milled at 300r / min for 30min to obtain a mixed powder; S2. Take 40kg of the mixed powder and the reducing solution in a mass ratio of 1:4 and place it in a water bath at 65 ° C and stir the reaction, maintaining its pH between 3.3-3.8. The reaction is terminated when the redox potential is ≤-150mv, and the mixture is filtered and washed to neutrality to obtain a reduced powder; the reducing solution includes 110g / L of citric acid, 40g / L of ascorbic acid, and 3g / L of ferrous sulfate. After adding an appropriate amount of water and turning on the stirring device, citric acid, ascorbic acid and ferrous sulfate are slowly added in sequence. After one substance is completely dissolved, the next substance is added until all components are completely dissolved to obtain a uniform reducing solution; S3. Take 35 kg of the above-mentioned reduced powder and mix it with the prepared silane hydrolyzate in a mass ratio of 1:3, stir the reaction at room temperature for 10 minutes, filter, dry, heat and solidify, and air flow classify to collect powder with a particle size of 4-6 μm to obtain recycled glass powder after surface modification; the silane hydrolyzate is obtained by dissolving 5.1 kg of γ-aminopropyltriethoxysilane in 99.9 kg of 90% v / v ethanol aqueous solution and stirring to fully disperse it, and adjusting the pH to 4.2 with glacial acetic acid.

[0034] Preparation Example 4 A surface-modified recycled glass powder is prepared by the following steps, which is different from Preparation Example 1 in that the recycled glass powder is not treated with a reducing liquid in this Preparation Example: S1. The recycled glass powder was collected and dried at 105°C to a water content of ≤0.3wt%, and magnesium stearate accounting for 0.3% of the mass of the recycled glass powder was added, and ball milled at 300r / min for 30min to obtain a mixed powder; S2. Take 35kg of the above mixed powder and mix it with the prepared silane hydrolyzate in a mass ratio of 1:4, stir and react at room temperature for 15 minutes, filter, dry, and heat to cure to obtain recycled glass powder after surface modification; the silane hydrolyzate is obtained by dissolving 4.9kg of γ-aminopropyltriethoxysilane in 135.1kg of 90% v / v ethanol aqueous solution and stirring to fully disperse it, and adjusting the pH to 4.5 with glacial acetic acid.

[0035] Preparation Example 5 A surface-modified recycled glass powder is prepared by the following steps: S1. The recycled glass powder was collected and dried at 105°C to a water content of ≤0.3wt%, and magnesium stearate accounting for 0.3% of the mass of the recycled glass powder was added and ball milled at 300r / min for 30min to obtain a mixed powder; S2. Take 40kg of the above-mentioned mixed powder and the reducing liquid in a mass ratio of 1:5, mix them, and place them in a water bath at 70°C for stirring and reacting, maintaining the pH between 3.3-3.8. When the redox potential is ≤-150mv, terminate the reaction, filter and wash until neutral to obtain a reduced powder, dry, heat and solidify, and collect the powder with a particle size of 4-6μm by air flow classification to obtain recycled glass powder that has been surface modified; the reducing liquid includes 120g / L of citric acid, 50g / L of ascorbic acid, and 5g / L of ferrous sulfate. First, add an appropriate amount of water and turn on the stirring device, then slowly add citric acid, ascorbic acid and ferrous sulfate in sequence. After one substance is completely dissolved, add the next substance until all components are completely dissolved to obtain a uniform reducing liquid.

[0036] Example

[0037] Example 1

[0038] A glass glaze for resistor sheets is prepared by the following steps: (1) Melting the pure new glass powder raw material at 1200°C, quenching it with water, and crushing it to a particle size of 0.7-1.2 μm to obtain pure new glass powder for use; the pure new glass powder includes 18.5 kg of bismuth trioxide, 3 kg of boron oxide, 4.12 kg of zinc oxide, 2.34 kg of aluminum oxide, 3.8 kg of silicon oxide, 0.9 kg of copper oxide, and 0.54 kg of magnesium oxide; (2) Dissolve 0.8 kg of hydroxyethyl cellulose in 20 kg of water in a 65 °C water bath and stir evenly to form a water-based adhesive; (3) 30 kg of pure new glass powder, 30 kg of recycled glass powder obtained in Preparation Example 1, 5 kg of water-based adhesive and 25 kg of water were stirred and mixed, and aged at room temperature for 4 hours to obtain a slurry; (4) The above slurry is electrostatically coated on the surface of the zinc oxide resistor and then vitrified to obtain a glass glaze for the resistor; the weight of the glass slurry sprayed per square centimeter of the side area is 0.15g; Step sintering is used in the vitrification process: a) Heat to 200°C and keep warm for 60 minutes; b) Raise the temperature to 450°C within 50 minutes and keep it at that temperature for 30 minutes; c) Heat to 500°C within 60 minutes and keep at this temperature for 75 minutes.

[0039] Example 2

[0040] A glass glaze for resistor sheets is prepared by the following steps: (1) Melting the pure new glass powder raw material at 1100°C, quenching it with water, and crushing it to a particle size of 0.7-1.2 μm to obtain pure new glass powder for use; the pure new glass powder includes 12.5 kg of bismuth trioxide, 0.75 kg of boron oxide, 1.25 kg of zinc oxide, 3.5 kg of aluminum oxide, 6.3 kg of silicon oxide, 1.75 kg of copper oxide, and 0.025 kg of magnesium oxide; (2) Dissolve 1 kg of hydroxyethyl cellulose in 30 kg of water in a 70°C water bath and stir until completely dissolved to form a water-based adhesive; (3) 25 kg of pure new glass powder, 35 kg of recycled glass powder obtained in Preparation Example 2, 6 kg of water-based adhesive and 20 kg of water were stirred and mixed, and aged at room temperature for 5 hours to obtain a slurry; (4) The above slurry is electrostatically coated on the surface of the zinc oxide resistor and then vitrified to obtain a glass glaze for the resistor; the weight of the glass slurry sprayed per square centimeter of the side area is 0.15g; Step sintering is used in the vitrification process: a) Heat to 200°C and keep warm for 60 minutes; b) Raise the temperature to 450°C within 60 minutes and keep it at that temperature for 30 minutes; c) Raise the temperature to 530°C within 60 minutes and keep at this temperature for 60 minutes.

[0041] Example 3

[0042] A glass glaze for resistor sheets is prepared by the following steps: (1) The pure new glass powder raw material is melted at 1150°C and then quenched with water, and then crushed and air-graded to 0.7-1.2 μm to obtain pure new glass powder for use; the pure new glass powder includes 24.5 kg of bismuth trioxide, 5.25 kg of boron oxide, 7 kg of zinc oxide, 1.25 kg of aluminum oxide, 1.25 kg of silicon oxide, 0.025 kg of copper oxide, and 1.05 kg of magnesium oxide; (2) Dissolve 0.5 kg of hydroxyethyl cellulose in 25 kg of water in a 60 °C water bath and stir until completely dissolved to form a water-based adhesive; (3) 35 kg of pure new glass powder, 25 kg of recycled glass powder obtained in Preparation Example 3, 4 kg of water-based adhesive and 30 kg of water were stirred and mixed, and aged at room temperature for 3 hours to obtain a slurry; (4) The above slurry is electrostatically coated on the surface of the zinc oxide resistor and then vitrified to obtain a glass glaze for the resistor; the weight of the glass slurry sprayed per square centimeter of the side area is 0.15g; Step sintering is used in the vitrification process: a) Heat to 200°C and keep warm for 60 minutes; b) Raise the temperature to 450°C within 40 minutes and keep it at that temperature for 30 minutes; c) Raise the temperature to 515°C within 60 minutes and keep at this temperature for 90 minutes.

[0043] Example 4

[0044] A glass glaze for resistors is different from Example 1 in that: this example uses the recycled glass powder prepared in Preparation Example 4 and subjected to surface modification.

[0045] Example 5

[0046] A glass glaze for resistors is different from Example 1 in that: this example uses the recycled glass powder prepared in Preparation Example 5 and subjected to surface modification.

[0047] Example 6

[0048] A glass glaze for a resistor, which differs from Example 1 in that 2 kg of polyvinyl pyrrolidone is further added to the water-based adhesive in this embodiment, specifically as follows: Wherein (2) 0.5 kg of hydroxyethyl cellulose and 2 kg of polyvinyl pyrrolidone were dissolved in 25 kg of water in a 60°C water bath and stirred until completely dissolved to form a water-based adhesive; the rest was the same as in Example 1.

[0049] Example 7

[0050] A glass glaze for resistor sheets is different from Example 6 in that 3 kg of polyvinyl pyrrolidone is further added to the water-based adhesive in this example.

[0051] Example 8

[0052] A glass glaze for resistor sheets is different from Example 6 in that 1.4 kg of polyvinyl pyrrolidone is further added to the water-based adhesive in this example.

[0053] Example 9

[0054] A glass glaze for a resistor, which differs from Example 1 in that 0.35 kg of a sintering aid is further added in this example. The sintering aid is composed of ammonium molybdate and bismuth citrate in a mass ratio of 1:1 and is prepared by the following steps: Wherein (3) 30 kg of pure new glass powder, 30 kg of recycled glass powder prepared in Preparation Example 1, 0.35 kg of sintering aid, 5 kg of water-based adhesive and 25 kg of water were stirred and mixed, and aged at room temperature for 4 hours to obtain a slurry; The remaining steps are the same as in Example 1.

[0055] Example 10

[0056] A glass glaze for resistors is different from Example 9 in that: in this example, 0.21 kg of a sintering aid is further added, which is composed of ammonium molybdate and bismuth citrate in a ratio of 0.5:1.

[0057] Example 11

[0058] A glass glaze for resistors is different from Example 9 in that: in this example, 0.495 kg of a sintering aid is further added, which is composed of ammonium molybdate and bismuth citrate in a ratio of 0.65:1.

[0059] Comparative Example

[0060] Comparative Example 1 A glass glaze for resistor chips is different from Example 1 in that: in this comparative example, pure new glass powder of equal mass is used instead of recycled glass powder.

[0061] Comparative Example 2 A glass glaze for resistors is different from Example 1 in that the recycled glass powder added in this comparative example has not been surface-modified. Performance testing

[0062] Insulation withstand voltage: Conduct a high current impulse withstand test according to the method specified in GB / T 11032-2020 standard, and detect the maximum withstand value of its impulse capability at a high current of 4 / 10μs; Aging test: According to the method specified in IEC 60216-1-2013, the resistance change rate is measured after 1000 hours at 85℃ / 85%RH.

[0063] Table 1 Test data

[0064] From Examples 1-3 and Comparative Example 1 and Table 1, it can be seen that the final properties of the glass glaze made entirely of pure new glass powder are consistent with the properties of the modified recycled glass powder in this application, indicating that the modification of the recycled glass powder in this application can effectively improve the performance of the recycled glass powder, so that it can achieve electrical performance reliability equivalent to that of new powder.

[0065] Combining Examples 1-3 and Comparative Example 2 and Table 1, it can be seen that the test data of Examples 1-3 are significantly better than those of Comparative Example 2, indicating that modifying the recycled glass powder can effectively remove metal impurities and repair surface defects, thereby avoiding insulation degradation and resistance drift caused by the recycled material.

[0066] Comparing Example 1 with Examples 4-5 and Table 1, it can be seen that the various test data for Example 1 are significantly superior to those for Examples 4-5. This demonstrates that the reduction of the reducing solution with the silane in combination with the formation of a chemically bonded interface significantly enhances the interfacial bonding between the components of the glass glaze, improving the mechanical strength and structural stability of the glass glaze. The reducing solution removes impurities such as the surface oxide layer to enhance its activity, while the silane reacts chemically with the surface of the glass powder to form a stable chemical bond. The synergistic effect of the two effectively improves the interfacial state, thereby enhancing the performance of the glass glaze.

[0067] Combining Example 1 with Examples 6-8 and Table 1, it can be seen that the various test data of Examples 6-8 are significantly better than those of Example 1, indicating that the addition of polyvinyl pyrrolidone can optimize the rheological properties of the slurry, reduce the microscopic pores of the glass glaze, and improve the uniformity of sintering, thereby obtaining a glass glaze with higher density and better performance.

[0068] Combining Example 1 with Examples 9-11 and Table 1, it can be seen that the various test data of Examples 9-11 are significantly better than those of Example 1. Ammonium molybdate and bismuth citrate cooperate with each other to reduce the sintering temperature while promoting the growth and orderly arrangement of crystals in the glass glaze, forming a more stable crystal structure, thereby improving the thermal stability and electrical insulation properties of the glass glaze.

[0069] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A glass glaze for a resistor, characterized in that: It includes the following raw materials in parts by weight: 25-35 parts of pure new glass powder, 25-35 parts of recycled glass powder, 20-30 parts of water, 4-6 parts of water-based adhesive; The recycled glass powder is the waste glass glaze that is not attached to the substrate during the resistor spraying process and has undergone surface modification treatment; The water-based adhesive includes 20-30 parts of water and 0.5-1 part of hydroxyethyl cellulose. The pure new glass powder comprises 12.5-24.5 parts of bismuth trioxide, 0.75-5.25 parts of boron oxide, 1.25-7.0 parts of zinc oxide, 1.25-3.5 parts of aluminum oxide, 1.25-6.3 parts of silicon oxide, 0.025-1.75 parts of copper oxide, and 0.025-1.05 parts of magnesium oxide.

2. The glass glaze for resistor according to claim 1, characterized in that: The recycled glass powder is subjected to surface modification treatment, which specifically includes the following steps: S1. The recycled glass powder was collected and dried at 100-110 ℃ to a water content of ≤0.3wt%, and magnesium stearate was added to the ball mill to obtain a mixed powder; S2. The mixed powder and the reducing solution were mixed in a mass ratio of 1:4-6 and placed in a water bath at 65-75 ° C with stirring, maintaining the pH between 3.3-3.

8. The reaction was terminated when the redox potential was ≤-150mv, and the mixture was filtered and washed to neutral to obtain a reduced powder; S3. The reduced powder was mixed with silane hydrolyzate in a mass ratio of 1:3-5, stirred at room temperature for 10-20 minutes, filtered, dried, heated and cured, and air-classified to obtain a surface-modified recycled glass powder.

3. The glass glaze for resistor according to claim 1, characterized in that: The added amount of magnesium stearate accounts for 0.2-0.4% of the mass of the recycled glass powder.

4. The glass glaze for resistor according to claim 1, characterized in that: The reducing solution comprises 110-130 g / L of citric acid, 40-60 g / L of ascorbic acid, and 3-8 g / L of ferrous sulfate.

5. The glass glaze for resistor according to claim 1, characterized in that: The silane hydrolyzate comprises 2-5 parts of gamma-aminopropyltriethoxysilane and 95-98 parts of a 90% ethanol aqueous solution, and the pH value is adjusted to 4.2-4.8 with glacial acetic acid.

6. The glass glaze for resistor according to claim 1, characterized in that: The particle size of the pure new glass powder is 0.7-1.2 μm, and the particle size of the recycled glass powder is 4-6 μm.

7. The glass glaze for resistor according to claim 1, characterized in that: Polyvinyl pyrrolidone is also added into the water-based adhesive, and the mass ratio of the hydroxyethyl cellulose to the polyvinyl pyrrolidone is (2.5-3):

1.

8. The glass glaze for resistor according to claim 1, characterized in that: 0.2-0.5 parts of a sintering aid is further added to the raw materials, which is composed of ammonium molybdate and bismuth citrate in a mass ratio of 0.5-1:

1.

9. A method for preparing a glass glaze for a resistor according to any one of claims 1 to 6, characterized in that: The following steps are involved: (1) The pure new glass powder raw material is melted at 1100-1200℃ and then water quenched, crushed and air-graded to 0.7-1.2μm to obtain pure new glass powder for use; (2) Dissolve hydroxyethyl cellulose in water at 60-70°C in a water bath and stir until completely dissolved to form a water-based adhesive; (3) Mixing pure new glass powder, recycled glass powder, water-based adhesive and water, and aging at room temperature for 3-5 hours to obtain a slurry; (4) coating the above slurry on the surface of the resistor and then vitrifying it to obtain a glass glaze for the resistor; Step sintering is used in the vitrification process: a) Heating to 200℃ and holding time ≥ 60min; b) Raise the temperature to 450°C within 40-60 minutes and keep at this temperature for ≥30 minutes; c) Raise the temperature to 500-530℃ within 60 minutes and keep it at this temperature for 60-90 minutes.

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