Glass insulator gluing process using anti-aging reinforced adhesive

Abstract

This invention discloses a glass insulator bonding process using an aging-resistant reinforced adhesive, relating to the field of electrical insulation materials technology. By uniformly mixing ceramic powder, glass powder, and additives in parts by weight, followed by ball milling, molding, pre-sintering, and hot-pressing sintering, a dense insulator effectively composited with ceramic and glass is obtained. The resulting suspension insulator exhibits significantly improved flexural strength, density, and thermal shock stability, while maintaining excellent electrical insulation performance. This invention overcomes the technical defects of insufficient mechanical strength and service reliability in existing composite insulators, and is suitable for applications in high-voltage overhead line suspension insulation devices under high mechanical load conditions.

Description

Technical Field

[0001] This invention relates to the field of electrical insulation materials technology, and in particular to a glass insulator bonding process using an aging-resistant reinforced adhesive. Background Technology

[0002] Suspension insulators for high-voltage overhead transmission lines are crucial components in power systems, used to support and insulate high-voltage conductors. Their primary function is to isolate conductors at different potentials from the ground, ensuring the safe flow of current along a predetermined path, while also bearing loads such as mechanical tension, wind, and snow loads. Suspension insulators are mainly classified into three categories based on their material: ceramic insulators, glass insulators, and composite insulators. Ceramic and glass insulators have a long history and mature technology, and have been widely used in power grids of all voltage levels across the country for a long time. However, they each also have significant limitations in terms of mechanical and environmental resistance.

[0003] Traditional ceramic insulators have good dielectric strength, heat resistance and long service experience, but ceramic materials are inherently brittle and are prone to cracking and breaking when subjected to mechanical or thermal shock. Especially in high-voltage and high-tonnage environments, their flexural strength and impact resistance are insufficient, posing certain operational safety hazards.

[0004] Glass insulators have high resistance to flashover voltage and the fragments are not fatally damaged when they "explode," which reduces the risk of flashover caused by deterioration to a certain extent. However, glass itself is also a brittle material, and its ability to withstand impact and bending loads is relatively limited. Moreover, it is susceptible to the accumulation of microcracks due to environmental factors during long-term service.

[0005] To address the limitations of single ceramic or glass insulators in terms of mechanical and durability under high voltage and high load conditions, domestic and international technological developments have gradually moved towards composite insulators, optimizing overall performance by combining different material systems. For example, CN100481276C discloses a suspension composite insulator. This technology points out that existing ceramic and glass insulators are prone to brittleness, contamination, and high-voltage flashover and cylinder shattering accidents, and proposes a composite structure to improve flexural strength.

[0006] The earlier patent WO2003107360A1 also pointed out the problems of traditional ceramic insulators being fragile, heavy, and easily damaged during transportation and installation, emphasizing the development of composite structure insulators to improve their mechanical strength and installation reliability.

[0007] In addition, in the disc-shaped suspension porcelain or glass composite insulator shown in Chinese patent CN102522162A, in order to improve the creepage distance and anti-pollution flashover performance of the existing structure, a combined inorganic material barrier structure is adopted, but it still mainly focuses on the local structural optimization of traditional materials.

[0008] Although existing ceramic, glass, and composite insulators have been widely used in power system operation, there is still room for improvement in terms of high mechanical strength, thermal shock resistance, density, and long-term stability. Especially in ultra-high voltage and extra-high voltage power grid environments, higher demands are placed on suspension insulator materials and manufacturing processes; existing technologies struggle to significantly improve mechanical strength and crack resistance while ensuring high electrical insulation performance. Summary of the Invention

[0009] Based on the problems raised in the background art, the present invention proposes a glass insulator bonding process using an aging-resistant and reinforced adhesive.

[0010] The technical solution is as follows: A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Prepare raw material powder by mixing alumina powder, borosilicate glass powder, yttrium oxide stabilized zirconium oxide powder, and silica powder in the following mass ratios: 100 parts, 10-40 parts, 5-20 parts, and 5-20 parts, respectively. (2) Add 0.1-2.0 parts of organic dispersant and 3.0-10.0 parts of binder to the mixed powder, and ball mill it for 8-16 hours with 145-180 parts of isopropanol as solvent so that the particle D50 of the mixed powder is in the range of 1-5μm; (3) After drying and pulverizing the ball-milled slurry, add 1.0-5.0 parts of plasticizer to make a plastic molding material; (4) Isostatic pressing or injection molding is used to form the molding material into a suspension insulator blank, and a pressure of 80-200MPa is applied. (5) The blank is pre-sintered at a temperature of 450-800℃ for 1-4 hours to remove organic matter and improve initial strength. (6) The pre-sintered body is placed in a vacuum or argon protective atmosphere for hot pressing sintering. The heating rate is 5-20℃ / min, the sintering temperature is 1250-1500℃, and the holding time is 0.5-3h. At the same time, a hot pressing pressure of 10-40MPa is applied to fully combine the ceramic matrix with the glass phase to form a dense composite structure. (7) The sintered body is machined, deburred, polished and cleaned to obtain the final suspension insulator.

[0011] Preferably, the alumina powder is α-Al2O3 with an average particle size D50 of 0.5-3 μm.

[0012] Preferably, the borosilicate glass powder is composed of 60-75 wt% SiO2, 10-20 wt% B2O3, and 5-15 wt% Na2O, with an average particle size D50 of 1-5 μm.

[0013] Preferably, the yttrium-stabilized zirconia powder is 3-8 mol% Y₂O₃-stabilized zirconia.

[0014] Preferably, the D50 of the silica powder is 0.5-3 μm.

[0015] Preferably, the organic dispersant is polyvinyl alcohol, polyacrylate, or a mixture thereof.

[0016] Preferably, the adhesive is prepared by the following method: Mix 100-120 parts of bisphenol F type epoxy resin, 3-6 parts of 4-amino-3-mercaptopyridine (CAS: 52334-54-0), 5-9 parts of 4-fluoro-1-aminonaphthalene, and 2-5 parts of γ-glycidoxypropyltrimethoxysilane, add 0.4-0.7 parts of triethylamine, and react at 75-95℃ for 80-140 minutes. After the reaction, adjust the pH to 7-8 with sodium bicarbonate solution, add 0.8-2.5 parts of nano-silica with a particle size of 15-30 nm, and ultrasonically disperse for 40-120 minutes to obtain the binder.

[0017] Preferably, the bisphenol F type epoxy resin is DER354LV with a viscosity of 2500-3500.

[0018] Preferably, the plasticizer is di(2-ethylhexyl) phthalate, polyethylene glycol, or glycerin.

[0019] Preferably, the molding temperature during injection molding is 50-80℃, and the mold holding time is 30-120s.

[0020] Preferably, the pre-sintering adopts a heating rate of 2-10℃ / min, and the pre-sintering atmosphere is air or an oxygen-enriched atmosphere.

[0021] Adhesive reaction mechanism: The epoxy groups of bisphenol F epoxy resin can undergo ring-opening addition reactions with the amino and mercapto groups in 4-amino-3-mercaptopyridine, respectively, and simultaneously form an amine-cured crosslinking structure with the amino group in 4-fluoro-1-aminonaphthalene, thus constructing a multi-component crosslinking framework. γ-glycidoxypropyltrimethoxysilane participates in the crosslinking reaction through its epoxy groups, and its siloxane segments optimize the interfacial compatibility between the inorganic powder and the organic phase. Triethylamine acts as a catalyst to accelerate the reaction process. The subsequently added nano-silica is uniformly embedded into the crosslinking network through ultrasonic dispersion, further filling the structural voids, and finally forming a dense, stable, and highly insulating adhesive system with strong interfacial bonding.

[0022] Adhesive effect: The synergistic effect of multi-component cross-linking reaction and nanoparticle filling significantly improves the mechanical strength and structural density of the binder, effectively enhancing the crack resistance and load-bearing capacity of the insulator.

[0023] The specific reaction of amino, mercapto, and epoxy groups, combined with the introduction of fluorinated monomers, endows the binder with excellent electrical insulation and aging resistance properties, meeting the long-term service requirements under high-voltage conditions.

[0024] The precise reaction between thiol-containing and fluorine-containing functional monomers and epoxy groups optimizes the interfacial bonding efficiency of the binder, reduces interfacial defects, and significantly improves the thermal shock resistance stability of the insulator.

[0025] Compared with the prior art, the present invention has the following advantages: 1. The dense ceramic-glass composite structure improves the overall flexural strength and crack resistance of the material; 2. Glass can penetrate the ceramic interface during high-temperature hot pressing, improving interfacial bonding and enhancing mechanical properties; 3. The electrical insulation performance of composite insulators is not significantly affected, and they have excellent resistance to thermal shock. 4. The preparation method has strong process controllability and is suitable for large-scale production. Detailed Implementation

[0026] The features of the present invention are further illustrated below through embodiments, but the scope of protection of this patent is not limited to the embodiments. Example 1

[0027] A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Preparation of raw material powders: Select 100 kg of α-Al2O3 alumina powder (average particle size D50 = 0.5 μm, purity ≥ 99.8%), 10 kg of borosilicate glass powder (composition: 60 wt% SiO2, 20 wt% B2O3, 15 wt% Na2O, average particle size D50 = 1 μm), 5 kg of 3 mol% Y2O3 stabilized zirconium oxide powder (purity ≥ 99.5%), and 5 kg of ultrafine SiO2 powder (D50 = 0.5 μm, specific surface area 200 m²). 2 / g); Add the above powder to a three-dimensional mixer (model SYH-100, speed 150r / min) and mix for 40 minutes to obtain a uniformly mixed powder.

[0028] (2) Ball milling to prepare slurry: Add 0.1 kg of organic dispersant (polyvinyl alcohol, degree of polymerization 1700, purity ≥99.0%) and 3.0 kg of binder to the mixed powder, and then add 145 kg of isopropanol (purity ≥99.7%) as solvent, and send them together into a planetary ball mill (model QM-6SP4, ball milling jar volume 10L); use zirconia balls as the ball milling medium (ball diameter 10 mm, medium to powder weight ratio 5:1), set the ball milling speed to 300 r / min, and the ball milling time to 8 hours; after the ball milling is completed, take a sample for testing, and the particle size D50 of the mixed powder is 1 μm, which meets the requirements.

[0029] The adhesive is prepared as follows: 100 kg of bisphenol F epoxy resin (DER354LV, viscosity 2500 mPa·s, 25℃), 3 kg of 4-amino-3-mercaptopyridine (CAS: 52334-54-0, purity ≥98.5%), 5 kg of 4-fluoro-1-aminonaphthalene (purity ≥98.0%), and 2 kg of γ-glycidyl etheroxypropyltrimethoxysilane (purity ≥98.5%) are weighed and added to a 500 L reactor; 0.4 kg of triethylamine (purity ≥99.0%) is added to the reactor, the stirrer is turned on (speed 80 r / min), and the temperature is raised to 75℃ and kept constant for 80 minutes; after the reaction, the pH of the system is adjusted to 7 with 5 wt% sodium bicarbonate solution, 0.8 kg of nano silica (particle size 15 nm) is added, and the mixture is placed in an ultrasonic disperser (power 1000W) and ultrasonically dispersed for 40 minutes to obtain a high-insulation adhesive, which is then sealed for later use.

[0030] (3) Preparation of molding material: The ball-milled slurry is sent to a vacuum drying oven (model DZF-6050), set at 60℃ and vacuum degree -0.08MPa, and dried for 8 hours until constant weight; after drying, the material is put into a high-speed pulverizer (model FS-100, speed 12000r / min) for pulverization and passed through a 200-mesh sieve; 1.0kg of plasticizer (di(2-ethylhexyl) phthalate, purity ≥99.0%) is added to the pulverized powder, and then put into a three-dimensional mixer (speed 160r / min) for 30 minutes to make a molding material with good plasticity.

[0031] (4) Molding process: Cold isostatic pressing is used to load the molding material into the rubber mold (size...). Place the blank into a cold isostatic press (model YLB-630); set the forming pressure to 80MPa and the holding time to 5 minutes to form a suspension insulator blank; after forming, remove the blank and observe its appearance for defects such as cracks and missing material.

[0032] (5) Pre-sintering treatment: The insulator blank is placed in a box-type sintering furnace (model SX-1200) and pre-sintered in an air atmosphere; the heating rate is set to 2℃ / min, and the temperature is raised from room temperature to 450℃. After reaching the set temperature, it is kept at the temperature for 1 hour; during the pre-sintering process, organic dispersants, binders and other organic substances in the blank are removed. After cooling to room temperature, the blank is taken out and the initial strength of the blank is tested to be ≥5MPa.

[0033] (6) Hot pressing sintering: Place the pre-sintered body into a vacuum hot pressing sintering furnace (model HP-1600), close the furnace door, and evacuate to 1×10⁻⁶. -3 Pa; set the heating rate to 5℃ / min, heat to 1250℃, hold at the sintering temperature for 0.5 hours, and apply hot pressing pressure of 10MPa at the same time; ensure that the ceramic matrix and glass phase are fully wetted and bonded during the sintering process to form a dense composite structure; after sintering, maintain a vacuum state and cool naturally to below 200℃.

[0034] (7) Machining and post-processing: The sintered body is taken out and machined using a CNC lathe (model CK6150) to remove excess edges and corners; then the surface burrs are removed using a deburring machine (model QM-200), and then polished by a surface grinder (model M7130) (surface roughness Ra≤0.8μm); finally, the machined insulator is placed in an ultrasonic cleaner (model KQ-1000) and ultrasonically cleaned with deionized water for 20 minutes, and then dried to obtain the final suspension insulator. Example 2

[0035] A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Preparation of raw material powders: 100 kg of α-Al2O3 alumina powder (average particle size D50 = 1.5 μm, purity ≥ 99.8%), 22.5 kg of borosilicate glass powder (composition: 66 wt% SiO2, 16 wt% B2O3, 12 wt% Na2O, average particle size D50 = 2.5 μm), 11.25 kg of 5 mol% Y2O3 stabilized zirconia powder (purity ≥ 99.5%), and 11.25 kg of ultrafine SiO2 powder (D50 = 1.5 μm, specific surface area 250 m²). 2 / g); Add the above powder to a three-dimensional mixer (model SYH-100, speed 155r / min) and mix for 45 minutes to obtain a uniformly mixed powder.

[0036] (2) Ball milling to prepare slurry: Add 0.8 kg of organic dispersant (polyvinyl alcohol and polyacrylate are compounded in a mass ratio of 1:1, and the molecular weight of polyacrylate is 5000) and 5.75 kg of binder to the mixed powder, and then add 157.5 kg of isopropanol (purity ≥99.7%) as solvent. Then feed them into a planetary ball mill (model QM-6SP4, ball milling jar volume 10L); use zirconia balls as the ball milling medium (ball diameter 10 mm, medium to powder weight ratio 5:1), set the ball milling speed to 320 r / min, and the ball milling time to 11 hours; after the ball milling is completed, take a sample for testing. The particle size D50 of the mixed powder is 2.2 μm, which meets the requirements.

[0037] The adhesive is prepared as follows: 105 kg of bisphenol F epoxy resin (DER354LV, viscosity 2800 mPa·s, 25℃), 4 kg of 4-amino-3-mercaptopyridine (CAS: 52334-54-0, purity ≥98.5%), 6 kg of 4-fluoro-1-aminonaphthalene (purity ≥98.0%), and 3 kg of γ-glycidyl etheroxypropyltrimethoxysilane (purity ≥98.5%) are weighed and added to a 500 L reactor; 0.5 kg of triethylamine (purity ≥99.0%) is added to the reactor, the stirrer is turned on (speed 85 r / min), and the temperature is raised to 82℃ and kept constant for 100 minutes; after the reaction, the pH of the system is adjusted to 7.2 with 5 wt% sodium bicarbonate solution, 1.4 kg of nano silica (particle size 20 nm) is added, and the mixture is ultrasonically dispersed in an ultrasonic disperser (power 1000W) for 65 minutes to obtain a high-insulation adhesive, which is then sealed for later use.

[0038] (3) Preparation of molding material: The ball-milled slurry is sent to a vacuum drying oven (model DZF-6050), set at 65℃ and vacuum degree -0.085MPa, and dried for 9 hours until constant weight; after drying, the material is put into a high-speed pulverizer (model FS-100, speed 12000r / min) for pulverization and passed through a 200-mesh sieve; 2.5kg of plasticizer (polyethylene glycol, molecular weight 400, purity ≥99.0%) is added to the pulverized powder, and then put into a three-dimensional mixer (speed 165r / min) for 35 minutes to make a molding material with good plasticity.

[0039] (4) Molding process: Injection molding is adopted. The molding material is fed into the injection molding machine (model HTF-80X); the molding temperature is set to 60℃, the mold temperature to 40℃, the injection pressure to 120MPa, and the mold holding time to 60s. The molded part is a suspension insulator blank (dimensions). After molding, the blank is removed from the mold and its appearance is inspected to ensure there are no defects such as cracks or missing material.

[0040] (5) Pre-sintering treatment: The insulator blank is placed in a box-type sintering furnace (model SX-1200) and pre-sintered in an oxygen-rich atmosphere (oxygen content 25 vol%). The heating rate is set to 4.5℃ / min, and the temperature is raised from room temperature to 562.5℃. After reaching the set temperature, it is held for 2 hours. During the pre-sintering process, organic dispersants, binders and other organic substances in the blank are removed. After cooling to room temperature, the blank is taken out and the initial strength of the blank is tested to be ≥8MPa.

[0041] (6) Hot pressing sintering: Place the pre-sintered body into a vacuum hot pressing sintering furnace (model HP-1600), close the furnace door and introduce argon gas (purity ≥99.99%) to maintain the furnace pressure at 0.05MPa; set the heating rate to 9.5℃ / min, heat to 1337.5℃, hold at the sintering temperature for 1.3 hours, and apply a hot pressing pressure of 20MPa at the same time; during the sintering process, ensure that the ceramic matrix and the glass phase are fully wetted and bonded to form a dense composite structure; after sintering, maintain the argon atmosphere and cool down to below 200℃.

[0042] (7) Machining and post-processing: The sintered body is taken out and machined using a CNC lathe (model CK6150) to remove excess edges and corners; then the surface burrs are removed using a deburring machine (model QM-200), and then polished by a surface grinder (model M7130) (surface roughness Ra≤0.6μm); finally, the machined insulator is placed in an ultrasonic cleaner (model KQ-1000) and ultrasonically cleaned with deionized water for 25 minutes, and then dried to obtain the final suspension insulator. Example 3

[0043] A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Preparation of raw material powders: 100 kg of α-Al2O3 alumina powder (average particle size D50 = 2.2 μm, purity ≥ 99.8%), 32.5 kg of borosilicate glass powder (composition: 70 wt% SiO2, 13 wt% B2O3, 9 wt% Na2O, average particle size D50 = 3.8 μm), 16.25 kg of 7 mol% Y2O3 stabilized zirconium oxide powder (purity ≥ 99.5%), and 16.25 kg of ultrafine SiO2 powder (D50 = 2.2 μm, specific surface area 300 m²). 2 / g); Add the above powder to a three-dimensional mixer (model SYH-100, speed 160r / min) and mix for 50 minutes to obtain a uniformly mixed powder.

[0044] (2) Ball milling to prepare slurry: Add 1.4 kg of organic dispersant (polyacrylate, molecular weight 8000, purity ≥99.0%) and 8.0 kg of binder to the mixed powder, and then add 167.5 kg of isopropanol (purity ≥99.7%) as solvent, and send them together into a planetary ball mill (model QM-6SP4, ball milling jar volume 10L); use zirconia balls as the ball milling medium (ball diameter 10 mm, medium to powder weight ratio 5:1), set the ball milling speed to 350 r / min, and the ball milling time to 13.5 hours; after the ball milling is completed, take a sample for testing, and the particle size D50 of the mixed powder is 3.8 μm, which meets the requirements.

[0045] The adhesive is prepared as follows: 112 kg of bisphenol F epoxy resin (DER354LV, viscosity 3200 mPa·s, 25℃), 5 kg of 4-amino-3-mercaptopyridine (CAS: 52334-54-0, purity ≥98.5%), 7.5 kg of 4-fluoro-1-aminonaphthalene (purity ≥98.0%), and 4 kg of γ-glycidyl etheroxypropyltrimethoxysilane (purity ≥98.5%) are weighed and added to a 500 L reactor; 0.6 kg of triethylamine (purity ≥99.0%) is added to the reactor, the stirrer is turned on (90 r / min), and the temperature is raised to 90℃ and kept constant for 120 minutes; after the reaction, the pH of the system is adjusted to 7.6 with 5 wt% sodium bicarbonate solution, 2.0 kg of nano silica (particle size 25 nm) is added, and the mixture is ultrasonically dispersed in an ultrasonic disperser (power 1000 W) for 90 minutes to obtain a high-insulation adhesive, which is then sealed for later use.

[0046] (3) Preparation of molding material: The ball-milled slurry is sent to a vacuum drying oven (model DZF-6050), set at 70℃ and vacuum degree -0.09MPa, and dried for 10 hours until constant weight; after drying, the material is put into a high-speed pulverizer (model FS-100, speed 12000r / min) for pulverization and passed through a 200-mesh sieve; 3.8kg of plasticizer (glycerin, purity ≥99.5%) is added to the pulverized powder, and then put into a three-dimensional mixer (speed 170r / min) for 40 minutes to make a molding material with good plasticity.

[0047] (4) Molding process: Cold isostatic pressing is used to load the molding material into the rubber mold (size...). Place the blank into a cold isostatic press (model YLB-630); set the forming pressure to 160MPa and the holding time to 7 minutes to form a suspension insulator blank; after forming, remove the blank and observe its appearance for defects such as cracks and missing material.

[0048] (5) Pre-sintering treatment: The insulator blank is placed in a box-type sintering furnace (model SX-1200) and pre-sintered in an oxygen-rich atmosphere (oxygen content 30 vol%). The heating rate is set to 7.5℃ / min, and the temperature is raised from room temperature to 687.5℃. After reaching the set temperature, it is held for 3 hours. During the pre-sintering process, organic dispersants, binders and other organic substances in the blank are removed. After cooling to room temperature, the blank is taken out and the initial strength of the blank is tested to be ≥12MPa.

[0049] (6) Hot pressing sintering: Place the pre-sintered body into a vacuum hot pressing sintering furnace (model HP-1600), close the furnace door and introduce argon gas (purity ≥99.99%) to maintain the furnace pressure at 0.08MPa; set the heating rate to 14.5℃ / min, heat to 1412.5℃, hold at the sintering temperature for 2.2 hours, and apply a hot pressing pressure of 30MPa at the same time; during the sintering process, ensure that the ceramic matrix and the glass phase are fully wetted and bonded to form a dense composite structure; after sintering, maintain the argon atmosphere and cool down to below 200℃.

[0050] (7) Machining and post-processing: The sintered body is taken out and machined using a CNC lathe (model CK6150) to remove excess edges and corners; then the surface burrs are removed using a deburring machine (model QM-200), and then polished by a surface grinder (model M7130) (surface roughness Ra≤0.4μm); finally, the machined insulator is placed in an ultrasonic cleaner (model KQ-1000) and ultrasonically cleaned with deionized water for 30 minutes, and then dried to obtain the final suspension insulator. Example 4

[0051] A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Preparation of raw material powders: Select 100kg of α-Al2O3 alumina powder (average particle size D50=3μm, purity ≥99.8%), 40kg of borosilicate glass powder (composition: 75wt%SiO2, 10wt%B2O3, 5wt%Na2O, average particle size D50=5μm), 20kg of 8mol%Y2O3 stabilized zirconium oxide powder (purity ≥99.5%), and 20kg of ultrafine SiO2 powder (D50=3μm, specific surface area 350m²). 2 / g); Add the above powder to a three-dimensional mixer (model SYH-100, speed 165r / min) and mix for 55 minutes to obtain a uniformly mixed powder.

[0052] (2) Ball milling to prepare slurry: Add 2.0 kg of organic dispersant (polyvinyl alcohol and polyacrylate are compounded at a mass ratio of 2:1, and the molecular weight of polyacrylate is 10000) and 10.0 kg of binder to the mixed powder, and then add 180 kg of isopropanol (purity ≥99.7%) as solvent. Then feed them into a planetary ball mill (model QM-6SP4, ball milling jar volume 10L); use zirconia balls as the ball milling medium (ball diameter 10 mm, medium to powder weight ratio 5:1), set the ball milling speed to 380 r / min, and the ball milling time to 16 hours; after the ball milling is completed, take a sample for testing. The particle size D50 of the mixed powder is 5 μm, which meets the requirements.

[0053] The adhesive is prepared as follows: 120 kg of bisphenol F epoxy resin (DER354LV, viscosity 3500 mPa·s, 25℃), 6 kg of 4-amino-3-mercaptopyridine (CAS: 52334-54-0, purity ≥98.5%), 9 kg of 4-fluoro-1-aminonaphthalene (purity ≥98.0%), and 5 kg of γ-glycidyl etheroxypropyltrimethoxysilane (purity ≥98.5%) are weighed and added to a 500 L reactor; 0.7 kg of triethylamine (purity ≥99.0%) is added to the reactor, the stirrer is turned on (speed 95 r / min), and the temperature is raised to 95℃ and kept constant for 140 minutes; after the reaction, the pH of the system is adjusted to 8 with 5 wt% sodium bicarbonate solution, 2.5 kg of nano silica (particle size 30 nm) is added, and the mixture is placed in an ultrasonic disperser (power 1000W) and ultrasonically dispersed for 120 minutes to obtain a high-insulation adhesive, which is then sealed for later use.

[0054] (3) Preparation of molding material: The ball-milled slurry is sent to a vacuum drying oven (model DZF-6050), set at 75℃ and vacuum degree -0.095MPa, and dried for 11 hours to constant weight; after drying, the material is put into a high-speed pulverizer (model FS-100, speed 12000r / min) for pulverization and passed through a 200-mesh sieve; 5.0kg of plasticizer (di(2-ethylhexyl) phthalate, purity ≥99.0%) is added to the pulverized powder, and then put into a three-dimensional mixer (speed 175r / min) for 45 minutes to make a molding material with good plasticity.

[0055] (4) Molding process: Injection molding is used. The molding material is fed into the injection molding machine (model HTF-80X); the molding temperature is set to 80℃, the mold temperature to 45℃, the injection pressure to 150MPa, and the mold holding time to 120s, forming a suspension insulator blank (dimensions...). After molding, the blank is removed from the mold and its appearance is inspected to ensure there are no defects such as cracks or missing material.

[0056] (5) Pre-sintering treatment: The insulator blank is placed in a box-type sintering furnace (model SX-1200) and pre-sintered in an air atmosphere; the heating rate is set to 10℃ / min, and the temperature is raised from room temperature to 800℃. After reaching the set temperature, it is kept at the temperature for 4 hours; during the pre-sintering process, organic dispersants, binders and other organic substances in the blank are removed. After cooling to room temperature, the blank is taken out and the initial strength of the blank is tested to be ≥15MPa.

[0057] (6) Hot pressing sintering: Place the pre-sintered body into a vacuum hot pressing sintering furnace (model HP-1600), close the furnace door, and evacuate to 1×10⁻⁶. -3 Pa; set the heating rate to 20℃ / min, heat to 1500℃, hold at the sintering temperature for 3 hours, and apply hot pressing pressure of 40MPa at the same time; ensure that the ceramic matrix and glass phase are fully wetted and bonded during the sintering process to form a dense composite structure; after sintering, maintain a vacuum state and cool naturally to below 200℃.

[0058] (7) Machining and post-processing: The sintered body is taken out and machined using a CNC lathe (model CK6150) to remove excess edges and corners; then the surface burrs are removed using a deburring machine (model QM-200), and then polished by a surface grinder (model M7130) (surface roughness Ra≤0.2μm); finally, the machined insulator is placed in an ultrasonic cleaner (model KQ-1000) and ultrasonically cleaned with deionized water for 35 minutes, and then dried to obtain the final suspension insulator.

[0059] Comparative Example 1 A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Preparation of raw material powders: Select 100 kg of α-Al2O3 alumina powder (average particle size D50 = 0.5 μm, purity ≥ 99.8%), 10 kg of borosilicate glass powder (composition: 60 wt% SiO2, 20 wt% B2O3, 15 wt% Na2O, average particle size D50 = 1 μm), 5 kg of 3 mol% Y2O3 stabilized zirconium oxide powder (purity ≥ 99.5%), and 5 kg of ultrafine SiO2 powder (D50 = 0.5 μm, specific surface area 200 m²). 2 / g); Add the above powder to a three-dimensional mixer (model SYH-100, speed 150r / min) and mix for 40 minutes to obtain a uniformly mixed powder.

[0060] (2) Ball milling to prepare slurry: Add 0.1 kg of organic dispersant (polyvinyl alcohol, degree of polymerization 1700, purity ≥99.0%), 3.0 kg of sodium carboxymethyl cellulose binder, and 145 kg of isopropanol (purity ≥99.7%) as solvent to the mixed powder, and send them together into a planetary ball mill (model QM-6SP4, ball milling jar volume 10L); use zirconia balls as the ball milling medium (ball diameter 10 mm, medium to powder weight ratio 5:1), set the ball milling speed to 300 r / min, and the ball milling time to 8 hours; after the ball milling is completed, take a sample for testing, and the particle size D50 of the mixed powder is 1 μm, which meets the requirements.

[0061] (3) Preparation of molding material: The ball-milled slurry is sent to a vacuum drying oven (model DZF-6050), set at 60℃ and vacuum degree -0.08MPa, and dried for 8 hours until constant weight; after drying, the material is put into a high-speed pulverizer (model FS-100, speed 12000r / min) for pulverization and passed through a 200-mesh sieve; 1.0kg of plasticizer (di(2-ethylhexyl) phthalate, purity ≥99.0%) is added to the pulverized powder, and then put into a three-dimensional mixer (speed 160r / min) for 30 minutes to make a molding material with good plasticity.

[0062] (4) Molding process: Cold isostatic pressing is used to load the molding material into the rubber mold (size...). Place the blank into a cold isostatic press (model YLB-630); set the forming pressure to 80MPa and the holding time to 5 minutes to form a suspension insulator blank; after forming, remove the blank and observe its appearance for defects such as cracks and missing material.

[0063] (5) Pre-sintering treatment: The insulator blank is placed in a box-type sintering furnace (model SX-1200) and pre-sintered in an air atmosphere; the heating rate is set to 2℃ / min, and the temperature is raised from room temperature to 450℃. After reaching the set temperature, it is kept at the temperature for 1 hour; during the pre-sintering process, organic dispersants, binders and other organic substances in the blank are removed. After cooling to room temperature, the blank is taken out and the initial strength of the blank is tested to be ≥5MPa.

[0064] (6) Hot pressing sintering: Place the pre-sintered body into a vacuum hot pressing sintering furnace (model HP-1600), close the furnace door, and evacuate to 1×10⁻⁶. -3 Pa; set the heating rate to 5℃ / min, heat to 1250℃, hold at the sintering temperature for 0.5 hours, and apply hot pressing pressure of 10MPa at the same time; ensure that the ceramic matrix and glass phase are fully wetted and bonded during the sintering process to form a dense composite structure; after sintering, maintain a vacuum state and cool naturally to below 200℃.

[0065] (7) Machining and post-processing: The sintered body is taken out and machined using a CNC lathe (model CK6150) to remove excess edges and corners; then the surface burrs are removed using a deburring machine (model QM-200), and then polished by a surface grinder (model M7130) (surface roughness Ra≤0.8μm); finally, the machined insulator is placed in an ultrasonic cleaner (model KQ-1000) and ultrasonically cleaned with deionized water for 20 minutes, and then dried to obtain the final suspension insulator.

[0066] Comparative Example 2 A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Preparation of raw material powders: Select 100 kg of α-Al2O3 alumina powder (average particle size D50 = 0.5 μm, purity ≥ 99.8%), 10 kg of borosilicate glass powder (composition: 60 wt% SiO2, 20 wt% B2O3, 15 wt% Na2O, average particle size D50 = 1 μm), 5 kg of 3 mol% Y2O3 stabilized zirconia powder (purity ≥ 99.5%), and 5 kg of ultrafine SiO2 powder (D50 = 0.5 μm, specific surface area 200 m²). 2 / g); Add the above powder to a three-dimensional mixer (model SYH-100, speed 150r / min) and mix for 40 minutes to obtain a uniformly mixed powder.

[0067] (2) Ball milling to prepare slurry: Add 0.1 kg of organic dispersant (polyvinyl alcohol, degree of polymerization 1700, purity ≥99.0%) and 3.0 kg of binder to the mixed powder, and then add 145 kg of isopropanol (purity ≥99.7%) as solvent, and send them together into a planetary ball mill (model QM-6SP4, ball milling jar volume 10L); use zirconia balls as the ball milling medium (ball diameter 10 mm, medium to powder weight ratio 5:1), set the ball milling speed to 300 r / min, and the ball milling time to 8 hours; after the ball milling is completed, take a sample for testing, and the particle size D50 of the mixed powder is 1 μm, which meets the requirements.

[0068] The adhesive is prepared as follows: 100 kg of bisphenol F epoxy resin (DER354LV, viscosity 2500 mPa·s, 25℃), 3 kg of 4-amino-3-mercaptopyridine (CAS: 52334-54-0, purity ≥98.5%), and 2 kg of γ-glycidyl etheroxypropyltrimethoxysilane (purity ≥98.5%) are weighed and added to a 500 L reactor; 0.4 kg of triethylamine (purity ≥99.0%) is added to the reactor, the stirrer is turned on (speed 80 r / min), and the temperature is raised to 75℃ and kept constant for 80 minutes; after the reaction, the pH of the system is adjusted to 7 with 5 wt% sodium bicarbonate solution, 0.8 kg of nano silica (particle size 15 nm) is added, and the mixture is placed in an ultrasonic disperser (power 1000 W) and ultrasonically dispersed for 40 minutes to obtain a high-insulation adhesive, which is then sealed for later use.

[0069] (3) Preparation of molding material: The ball-milled slurry is sent to a vacuum drying oven (model DZF-6050), set at 60℃ and vacuum degree -0.08MPa, and dried for 8 hours until constant weight; after drying, the material is put into a high-speed pulverizer (model FS-100, speed 12000r / min) for pulverization and passed through a 200-mesh sieve; 1.0kg of plasticizer (di(2-ethylhexyl) phthalate, purity ≥99.0%) is added to the pulverized powder, and then put into a three-dimensional mixer (speed 160r / min) for 30 minutes to make a molding material with good plasticity.

[0070] (4) Molding process: Cold isostatic pressing is used to load the molding material into the rubber mold (size...). Place the blank into a cold isostatic press (model YLB-630); set the forming pressure to 80MPa and the holding time to 5 minutes to form a suspension insulator blank; after forming, remove the blank and observe its appearance for defects such as cracks and missing material.

[0071] (5) Pre-sintering treatment: The insulator blank is placed in a box-type sintering furnace (model SX-1200) and pre-sintered in an air atmosphere; the heating rate is set to 2℃ / min, and the temperature is raised from room temperature to 450℃. After reaching the set temperature, it is kept at the temperature for 1 hour; during the pre-sintering process, organic dispersants, binders and other organic substances in the blank are removed. After cooling to room temperature, the blank is taken out and the initial strength of the blank is tested to be ≥5MPa.

[0072] (6) Hot pressing sintering: Place the pre-sintered body into a vacuum hot pressing sintering furnace (model HP-1600), close the furnace door, and evacuate to 1×10⁻⁶. -3Pa; set the heating rate to 5℃ / min, heat to 1250℃, hold at the sintering temperature for 0.5 hours, and apply hot pressing pressure of 10MPa at the same time; ensure that the ceramic matrix and glass phase are fully wetted and bonded during the sintering process to form a dense composite structure; after sintering, maintain a vacuum state and cool naturally to below 200℃.

[0073] (7) Machining and post-processing: The sintered body is taken out and machined using a CNC lathe (model CK6150) to remove excess edges and corners; then the surface burrs are removed using a deburring machine (model QM-200), and then polished by a surface grinder (model M7130) (surface roughness Ra≤0.8μm); finally, the machined insulator is placed in an ultrasonic cleaner (model KQ-1000) and ultrasonically cleaned with deionized water for 20 minutes, and then dried to obtain the final suspension insulator.

[0074] Comparative Example 3 A glass insulator bonding process using an aging-resistant reinforced adhesive includes the following steps: (1) Preparation of raw material powders: Select 100 kg of α-Al2O3 alumina powder (average particle size D50 = 0.5 μm, purity ≥ 99.8%), 10 kg of borosilicate glass powder (composition: 60 wt% SiO2, 20 wt% B2O3, 15 wt% Na2O, average particle size D50 = 1 μm), 5 kg of 3 mol% Y2O3 stabilized zirconium oxide powder (purity ≥ 99.5%), and 5 kg of ultrafine SiO2 powder (D50 = 0.5 μm, specific surface area 200 m²). 2 / g); Add the above powder to a three-dimensional mixer (model SYH-100, speed 150r / min) and mix for 40 minutes to obtain a uniformly mixed powder.

[0075] (2) Ball milling to prepare slurry: Add 0.1 kg of organic dispersant (polyvinyl alcohol, degree of polymerization 1700, purity ≥99.0%) and 3.0 kg of binder to the mixed powder, and then add 145 kg of isopropanol (purity ≥99.7%) as solvent, and send them together into a planetary ball mill (model QM-6SP4, ball milling jar volume 10L); use zirconia balls as the ball milling medium (ball diameter 10 mm, medium to powder weight ratio 5:1), set the ball milling speed to 300 r / min, and the ball milling time to 8 hours; after the ball milling is completed, take a sample for testing, and the particle size D50 of the mixed powder is 1 μm, which meets the requirements.

[0076] The adhesive is prepared as follows: 100 kg of bisphenol F epoxy resin (DER354LV, viscosity 2500 mPa·s, 25℃), 5 kg of 4-fluoro-1-aminonaphthalene (purity ≥98.0%), and 2 kg of γ-glycidyl etheroxypropyltrimethoxysilane (purity ≥98.5%) are weighed and added to a 500 L reactor; 0.4 kg of triethylamine (purity ≥99.0%) is added to the reactor, the stirrer is turned on (speed 80 r / min), and the temperature is raised to 75℃ and kept constant for 80 minutes; after the reaction, the pH of the system is adjusted to 7 with 5 wt% sodium bicarbonate solution, 0.8 kg of nano silica (particle size 15 nm) is added, and the mixture is ultrasonically dispersed in an ultrasonic disperser (power 1000 W) for 40 minutes to obtain a high-insulation adhesive, which is then sealed for later use.

[0077] (3) Preparation of molding material: The ball-milled slurry is sent to a vacuum drying oven (model DZF-6050), set at 60℃ and vacuum degree -0.08MPa, and dried for 8 hours until constant weight; after drying, the material is put into a high-speed pulverizer (model FS-100, speed 12000r / min) for pulverization and passed through a 200-mesh sieve; 1.0kg of plasticizer (di(2-ethylhexyl) phthalate, purity ≥99.0%) is added to the pulverized powder, and then put into a three-dimensional mixer (speed 160r / min) for 30 minutes to make a molding material with good plasticity.

[0078] (4) Molding process: Cold isostatic pressing is used to load the molding material into the rubber mold (size...). Place the blank into a cold isostatic press (model YLB-630); set the forming pressure to 80MPa and the holding time to 5 minutes to form a suspension insulator blank; after forming, remove the blank and observe its appearance for defects such as cracks and missing material.

[0079] (5) Pre-sintering treatment: The insulator blank is placed in a box-type sintering furnace (model SX-1200) and pre-sintered in an air atmosphere; the heating rate is set to 2℃ / min, and the temperature is raised from room temperature to 450℃. After reaching the set temperature, it is kept at the temperature for 1 hour; during the pre-sintering process, organic dispersants, binders and other organic substances in the blank are removed. After cooling to room temperature, the blank is taken out and the initial strength of the blank is tested to be ≥5MPa.

[0080] (6) Hot pressing sintering: Place the pre-sintered body into a vacuum hot pressing sintering furnace (model HP-1600), close the furnace door, and evacuate to 1×10⁻⁶. -3 Pa; set the heating rate to 5℃ / min, heat to 1250℃, hold at the sintering temperature for 0.5 hours, and apply hot pressing pressure of 10MPa at the same time; ensure that the ceramic matrix and glass phase are fully wetted and bonded during the sintering process to form a dense composite structure; after sintering, maintain a vacuum state and cool naturally to below 200℃.

[0081] (7) Machining and post-processing: The sintered body is taken out and machined using a CNC lathe (model CK6150) to remove excess edges and corners; then the surface burrs are removed using a deburring machine (model QM-200), and then polished by a surface grinder (model M7130) (surface roughness Ra≤0.8μm); finally, the machined insulator is placed in an ultrasonic cleaner (model KQ-1000) and ultrasonically cleaned with deionized water for 20 minutes, and then dried to obtain the final suspension insulator.

[0082] Test method: 1. Three-point bending strength test Test Standards and Methods: A three-point bending test (refer to ISO 178 or ASTM C674 / C790) was conducted on a universal testing machine. Specimen dimensions were prepared according to standard specifications, and the support span L, loading rate, and fixtures were all controlled according to standards. Bending Strength Calculate using the following formula: Where F is the peak load, and b and d are the sample width and thickness, respectively; see the introduction to the three-point bending test principle.

[0083] 2. Dielectric strength (breakdown voltage) test Test standards and methods: Refer to IEC60243-1 / ASTM D149 and other standards for testing the dielectric strength of solid insulating materials. Apply a gradually increasing AC voltage to the sample until electrical breakdown occurs, record the breakdown voltage, and calculate the breakdown strength (kV / mm). The ambient temperature should be controlled at 20±2℃.

[0084] Density and compaction determination Test method: The density was determined using the standard Archimedes method, and the volumetric density was obtained by comparing it with the theoretical density. The theoretical density was calculated based on the weighted average of the constituent phases.

[0085] 4. Thermal shock cycling test Test method: The sample is subjected to a heating / cooling cycle between high temperature (500℃) and room temperature for more than 10 times to check for cracks or structural damage (isothermal residence and rapid cooling cycles are performed according to the requirements of GB / T 775.1 / IEC 61109 thermal cycling). Test results: This adhesive innovatively introduces two functional monomers, 4-amino-3-mercaptopyridine and 4-fluoro-1-aminonaphthalene. Through their multi-component synergistic reaction with epoxy groups, combined with interfacial regulation by silane coupling agents and filling modification with nano-silica, a high-performance crosslinking system is constructed. Compared with traditional adhesives, it achieves breakthroughs in mechanical strength, insulation reliability, and environmental stability. In particular, the specific reaction between the novel monomers and epoxy groups provides an innovative path for upgrading the adhesive's performance, successfully meeting the stringent requirements of high-voltage overhead line insulators under high mechanical loads and complex environments.

[0086] The technical principles of the present invention have been described above with reference to specific embodiments. These descriptions are merely for explaining the principles of the invention and should not be construed as limiting the scope of protection of the invention in any way. Based on this explanation, those skilled in the art can readily conceive of other specific embodiments of the invention without inventive effort, and these embodiments will all fall within the scope of protection of the present invention.

Claims

1. A glass insulator bonding process using an aging-resistant reinforced adhesive, characterized in that, Includes the following steps, measured in parts by weight: (1) Prepare raw material powder by mixing alumina powder, borosilicate glass powder, yttrium oxide stabilized zirconium oxide powder, and silica powder in the following mass ratios: 100 parts, 10-40 parts, 5-20 parts, and 5-20 parts, respectively. (2) Add 0.1-2.0 parts of organic dispersant and 3.0-10.0 parts of binder to the mixed powder, and ball mill it for 8-16 hours with 145-180 parts of isopropanol as solvent so that the particle D50 of the mixed powder is in the range of 1-5μm; (3) After drying and pulverizing the ball-milled slurry, add 1.0-5.0 parts of plasticizer to make a plastic molding material; (4) Isostatic pressing or injection molding is used to form the molding material into a suspension insulator blank, and a pressure of 80-200MPa is applied. (5) The blank is pre-sintered at a temperature of 450-800℃ for 1-4 hours to remove organic matter and improve initial strength. (6) The pre-sintered body is placed in a vacuum or argon protective atmosphere for hot pressing sintering. The heating rate is 5-20℃ / min, the sintering temperature is 1250-1500℃, and the holding time is 0.5-3h. At the same time, a hot pressing pressure of 10-40MPa is applied to fully combine the ceramic matrix with the glass phase to form a dense composite structure. (7) The sintered body is machined, deburred, polished and cleaned to obtain the final suspension insulator; The adhesive is prepared by reacting bisphenol F type epoxy resin with 4-amino-3-mercaptopyridine, 4-fluoro-1-aminonaphthalene, γ-glycidyl etheroxypropyltrimethoxysilane, triethylamine, and nano-silica.

2. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The alumina powder is α-Al2O3 with an average particle size D50 of 0.5-3 μm.

3. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The borosilicate glass powder is composed of 60-75wt% SiO2, 10-20wt% B2O3, and 5-15wt% Na2O, with an average particle size D50 of 1-5μm.

4. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The yttrium-stabilized zirconia powder is 3-8 mol% Y₂O₃-stabilized zirconia.

5. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The silica powder has a D50 of 0.5-3 μm.

6. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The organic dispersant is polyvinyl alcohol, polyacrylate, or a mixture thereof.

7. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The adhesive is prepared by the following method: Mix 100-120 parts of bisphenol F type epoxy resin, 3-6 parts of 4-amino-3-mercaptopyridine (CAS: 52334-54-0), 5-9 parts of 4-fluoro-1-aminonaphthalene, and 2-5 parts of γ-glycidoxypropyltrimethoxysilane, add 0.4-0.7 parts of triethylamine, and react at 75-95℃ for 80-140 minutes. After the reaction, adjust the pH to 7-8 with sodium bicarbonate solution, add 0.8-2.5 parts of nano-silica with a particle size of 15-30 nm, and ultrasonically disperse for 40-120 minutes to obtain the binder.

8. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The plasticizer is di(2-ethylhexyl) phthalate, polyethylene glycol, or glycerin.

9. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The molding temperature during injection molding is 50-80℃, and the mold holding time is 30-120s.

10. The glass insulator bonding process using an aging-resistant reinforced adhesive according to claim 1, characterized in that: The pre-sintering process employs a heating rate of 2-10℃ / min, and the pre-sintering atmosphere is air or an oxygen-enriched atmosphere.

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