Preparation method of heat-insulating glass based on E-51 / ATO

Abstract

The invention relates to the field of heat-insulating glass preparation, in particular to a heat-insulating glass preparation method based on E-51 / ATO, which comprises the following steps: 1, pouring tin tetrachloride pentahydrate and antimony trichloride as precursors into a stainless steel high-pressure kettle with a para-polyphenol lining, and sealing to obtain an ATO dispersion solution; 2, the ATO dispersion solution is centrifuged and washed with ethyl alcohol and deionized water respectively, and dried nanometer ATO powder is obtained; 3, weighing E-51, an amine curing agent and acetone, uniformly mixing, pouring the nano ATO powder, and continuously stirring to obtain uniform ATO / E-51 slurry; and 4, fixing the pretreated glass substrate on a platform, injecting the ATO / E-51 slurry into a spray pen material cup, spraying the ATO / E-51 slurry on the surface of the glass substrate, and drying and curing a sprayed sample to obtain the ATO / E-51 heat-insulating glass with a compact surface structure. ATO nano-particles with the particle size of 10 nm are directly prepared through an optimized solvothermal method, and then agglomeration of the nano-particles is effectively prevented through an accurate mass ratio and high-speed stirring synergistic dispersion process.

Description

Technical Field

[0001] This invention relates to the field of heat-insulating glass manufacturing, and more specifically to a method for manufacturing heat-insulating glass based on E-51 / ATO. Background Technology

[0002] With the increasing demand for energy-efficient buildings, the development of high-efficiency heat-insulating glass has become an urgent need. Ordinary glass has high transmittance of near-infrared rays (780-2500nm) in sunlight, leading to a significant increase in indoor temperature and energy consumption. Existing heat insulation technologies such as Low-E glass have good performance, but they are expensive due to their reliance on silver film and complex coating processes. Furthermore, the film layer must be sealed within a hollow structure, making it impossible to use single panes, significantly increasing the difficulty of processing and application.

[0003] Nanoscale thermal insulation coating technology, particularly using antimony-doped tin oxide (ATO), has attracted significant attention due to its substantial comprehensive advantages. Compared to traditional precious metals (such as silver) or scarce materials (such as indium, used in ITO), ATO, using abundant tin and antimony as raw materials, possesses a significant cost advantage, making large-scale commercial applications possible. Furthermore, ATO nanomaterials exhibit excellent chemical and thermal stability, demonstrating great application potential in energy-efficient building windows, automotive insulated glass, and other specialized fields requiring heat conduction. However, despite the excellent properties of ATO materials themselves, key challenges remain in their coating applications. Nanoscale ATO particles are prone to agglomeration, making uniform dispersion in coatings difficult and affecting thermal insulation efficiency. Simultaneously, the adhesion strength between pure inorganic nanoparticles and glass substrates is poor, and the mechanical durability and environmental stability of the coating often fail to meet practical application requirements. These factors severely restrict the full realization and widespread application of ATO materials' advantages.

[0004] Therefore, how to leverage the advantages of ATO materials in chemical and thermal stability in the field of insulating glass is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of the problems existing in the prior art, the purpose of the present invention is to provide a method for preparing heat-insulating glass based on E-51 / ATO that can combine the excellent properties of ATO material with a suitable resin matrix (epoxy resin E-51) and prepare a coating with good heat insulation and durability through a simple and controllable process.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a method for preparing heat-insulating glass based on E-51 / ATO, comprising the following steps: Step 1: Using tin tetrachloride pentahydrate and antimony trichloride as precursors, after stirring, pour into a stainless steel autoclave with a para-polyphenol liner and seal. Place in a high-temperature forced-air drying oven and heat to allow the precursors to react fully. After natural cooling, obtain an ATO dispersion solution. Step 2: Centrifuge the ATO dispersion solution to remove the supernatant, wash with ethanol and deionized water respectively, and vacuum dry to obtain dry nano-ATO powder; Step 3: Weigh epoxy resin E-51, amine curing agent, and acetone, mix them evenly, pour them into the nano ATO powder, and continue stirring until there are no visible particle agglomerates in the system to obtain a uniform ATO / E-51 slurry. Step 4: Fix the pretreated glass substrate on the platform, inject the ATO / E-51 slurry into the spray gun cup, adjust the distance between the spray gun and the glass substrate, and spray the ATO / E-51 slurry onto the surface of the glass substrate at a constant moving speed. After the spraying is completed, the sample is dried and cured to obtain ATO / E-51 heat-insulating glass with a dense surface structure.

[0007] The above-mentioned method for preparing heat-insulating glass based on E-51 / ATO, wherein step 1 includes: Step 1-1: Prepare ATO solution using the solvothermal method. Weigh 50 mL of ethanol and divide it into two equal portions. Dissolve 2.00 g of SnCl4·5H2O solution and the calculated amount of SbCl3 solution in each portion. Stir magnetically at 1500 rpm for 10 min until completely dissolved. Steps 1-2: Mix SnCl4·5H2O solution and SbCl3 solution and continue stirring for 10 min to obtain precursor solution; Steps 1-3: Pour the precursor solution into a 100 mL stainless steel autoclave lined with para-polyphenol, seal it, and place it in a high-temperature drying oven at 180°C. Heating at C for 8 h allows the precursor to react fully, and after natural cooling, a gray-green ATO dispersion solution is obtained.

[0008] In the above-described method for preparing heat-insulating glass based on E-51 / ATO, in step 2, the ATO dispersion solution is centrifuged at 5000 rpm for 2 min to remove the supernatant, washed three times each with ethanol and deionized water, and then... Dry nano-ATO powder was obtained by vacuum drying at -0.1 MPa for 12 h.

[0009] In the above-mentioned method for preparing heat-insulating glass based on E-51 / ATO, step 3 includes: Step 3-1: Weigh 1.00 g of E-51 and 0.50 g of amine curing agent using an electronic balance, transfer them to a 25 mL beaker, and stir manually with a glass rod for 3 min until they are evenly mixed. Step 3-2: Add 10 mL of acetone solvent and stir magnetically at 1500 rpm for 10 min to obtain epoxy resin dilution. Step 3-3: Add 0.50 g-1.25 g of the nano ATO powder to the epoxy resin diluent and stir continuously until there are no visible particle agglomerates in the system to obtain a uniform ATO / E-51 slurry.

[0010] In the above-mentioned method for preparing heat-insulating glass based on E-51 / ATO, step 4, the glass substrate pretreatment includes: Step a: Select a glass slide as the substrate and reference, and immerse the glass slide in a beaker containing concentrated sulfuric acid: hydrogen peroxide = 7:3; Step b: Wait for the solution to reach 60 After cooling, ultrasonic treatment for 30 minutes is used to remove impurities from the surface of the glass slide; Step c: Rinse the slide 5 times with deionized water at 80°C. Bake at 30°C for 30 minutes, then place in a clean petri dish for later use.

[0011] In the above-mentioned method for preparing heat-insulating glass based on E-51 / ATO, step 4 includes: Step 4-1: Adjust the distance between the airbrush and the glass substrate to 15 cm; Step 4-2: After injecting ATO / E-51 slurry into the spray gun cup, continuously spray the glass substrate at a constant moving speed of 15 s / piece. Step 4-3: Immediately transfer the coated glass substrate to a forced-air drying oven at 100°C. Curing at C for 40 min yields ATO / E-51 heat-insulating glass with a dense surface structure.

[0012] The beneficial effects of the present invention's method for preparing heat-insulating glass based on E-51 / ATO are: This invention eliminates the need for expensive vacuum coating equipment (such as magnetron sputtering technology required for preparing Low-E glass), and combines a solvothermal method with an atmospheric pressure spraying process. It has low equipment requirements, is easy to operate, significantly reduces production costs, and is simple and inexpensive, which is conducive to large-scale industrial application.

[0013] Particle size was directly prepared by an optimized solvothermal method. 10 nm ATO nanoparticles were then dispersed using a precise mass ratio and high-speed stirring process, which effectively prevented the agglomeration of the nanoparticles, ensured the uniform dispersion of ATO in the resin matrix, optimized the dispersibility of nano ATO, and laid the foundation for the good thermal insulation performance of the coating.

[0014] Chemical etching of the glass substrate using a mixture of concentrated sulfuric acid and hydrogen peroxide significantly enhances the activity and roughness of the glass surface, improving the interfacial adhesion between the coating and the glass substrate. Epoxy resin E-51, known for its excellent adhesion, is selected as the film-forming agent, and a dense cross-linked network is formed with an amine curing agent through programmed temperature curing, resulting in excellent adhesion and mechanical strength of the coating. This significantly improves the coating's adhesion and durability. Attached Figure Description

[0015] Figure 1 This is a transmission electron microscope (TEM) image of ATO nanoparticles obtained in an embodiment of the present invention. Detailed Implementation

[0016] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described below in conjunction with specific embodiments and accompanying drawings.

[0017] Example 1 A method for preparing heat-insulating glass based on E-51 / ATO includes the following steps.

[0018] Step 1: Using tin tetrachloride pentahydrate and antimony trichloride as precursors, after stirring, pour into a stainless steel autoclave with a para-polyphenol liner and seal. Place in a high-temperature forced-air drying oven and heat to allow the precursors to react fully. After natural cooling, obtain an ATO dispersion solution. ATO solution was prepared using a solvothermal method. 50 mL of 95% ethanol was divided into two equal portions, and 2.00 g of SnCl₄·5H₂O (solution A) and a calculated amount of SbCl₃ (solution B) were dissolved in each portion. The solutions were magnetically stirred at 1500 rpm for 10 min until completely dissolved. A and B were then mixed and stirred for another 10 min to obtain precursor solution C. The molar ratio of tin(IV) tetrachloride pentahydrate to antimony trichloride precursor compound was 4:1. 1.

[0019] Pour solution C into a 100 mL stainless steel autoclave lined with para-polyphenol and seal. Place in a high-temperature drying oven at 180°C. Heating at C for 8-10 hours allows the precursor to react fully. After natural cooling, a grayish-green ATO dispersion is obtained.

[0020] Step 2: Centrifuge the ATO dispersion solution to remove the supernatant, wash with ethanol and deionized water respectively, and vacuum dry to obtain dry nano-ATO powder.

[0021] The ATO dispersion was centrifuged at 5000 rpm for 2-5 minutes to remove the supernatant, and washed three times each with ethanol and deionized water. It was then vacuum dried for 12 hours at a temperature of 70°C. C, -0.1 MPa, 12 h, to obtain dried nano-ATO powder.

[0022] Step 3: Weigh epoxy resin E-51, amine curing agent, and acetone, mix them evenly, pour them into the nano ATO powder, and continue stirring until there are no visible particle agglomerates in the system to obtain a uniform ATO / E-51 slurry.

[0023] Weigh 1.00 g of E-51 and 0.50 g of amine curing agent using an electronic balance, transfer them to a 25 mL beaker, and manually stir with a glass rod for 3 min until uniformly mixed. Then add 10 mL of acetone solvent and magnetically stir at 1500 rpm for 10 min to obtain an epoxy resin diluent. Add 0.50 g of antimony-doped tin oxide (ATO) powder to the epoxy diluent and continue stirring until no visible particle agglomerates are visible, obtaining a uniform ATO / E-51 slurry.

[0024] Before mixing, the mass ratio of ATO:E-51:curing agent:acetone in the ATO / E-51 slurry is 1:1:0.5:8. The ultrasonic treatment parameters are 50 Hz and 30°C. C, 10 min. Stirring parameters: 2000 rpm, 10 min.

[0025] Step 4: Fix the pretreated glass substrate on the platform, inject the ATO / E-51 slurry into the spray gun cup, adjust the distance between the spray gun and the glass substrate, and spray the ATO / E-51 slurry onto the surface of the glass substrate at a constant moving speed. After the spraying is completed, the sample is dried and cured to obtain ATO / E-51 heat-insulating glass with a dense surface structure.

[0026] Commercially available glass slides were used as the substrate. They were immersed in a mixed solution of concentrated sulfuric acid and hydrogen peroxide (7:3, v / v). After the solution cooled naturally to 60°C, the entire system was treated in an ultrasonic cleaner for 30 minutes to remove impurities from the slide surface. The slides were then rinsed five times with deionized water at 80°C. Bake at 30°C for 30 minutes, then place in a clean petri dish for later use.

[0027] Fix the pretreated glass substrate on the platform and adjust the distance between the spray gun and the glass substrate to 15 cm. After injecting an appropriate amount of ATO / E-51 slurry into the spray gun cup, spray continuously at a constant moving speed (15 s / piece), with a cup capacity of 10 mL, a carrier gas pressure of 0.1-0.2 MPa, and an air flow rate of 10.5 L / min.

[0028] The coated samples were immediately transferred to a forced-air drying oven at 100°C. Curing at C for 40 min yields ATO / E-51 heat-insulating glass with a dense surface structure.

[0029] Example 2 The method for preparing E-51 / ATO heat-insulating glass is the same as in Example 1, except that the 0.50 g ATO powder in Example 1 is replaced with 0.75 g ATO powder to prepare heat-insulating glass.

[0030] Example 3 The method for preparing E-51 / ATO heat-insulating glass is the same as in Example 1, except that the 0.50 g ATO powder in Example 1 is replaced with 1.00 g ATO powder to prepare heat-insulating glass.

[0031] Example 4 The method for preparing E-51 / ATO heat-insulating glass is the same as in Example 1, except that the 0.50 g ATO powder in Example 1 is replaced with 1.25 g ATO powder to prepare heat-insulating glass.

[0032] Comparative Example 1 The method for preparing E-51 / ATO heat-insulating glass is the same as in Example 1, except that the 0.50 g ATO powder in Example 1 is replaced with 0 g ATO powder to prepare heat-insulating glass.

[0033] Performance testing Table 1 below shows test samples with different E-51 to ATO mass ratios prepared according to the methods described in the above examples and comparative examples.

[0034] Glass surface temperature: Irradiation was performed using a 220V, 150W infrared heating lamp at a room temperature of 28.07°C. Irradiation was carried out at C for 10 minutes. The temperature data obtained by using a Teens K / J / T type thermocouple thermometer with adhesive temperature sensing wire are shown in Table 1.

[0035] Temperature inside the foam box: An indoor insulation device was constructed using a polystyrene (PS) foam box and an infrared heating lamp. A 40cm x 40cm sample opening was made at the top of the foam box, and the heating lamp was positioned 20cm above the opening. Different glass samples were placed over the sample opening, and the heating lamp was turned on to allow light to pass through. One end of a probe-type temperature measuring wire was inserted into the insulation box and sealed, while the other end was connected to a thermocouple thermometer to measure the internal temperature of the device and record the data in real time, as shown in Table 1.

[0036] Table 1: Comparison of the effects of different ATO concentrations .

[0037] Test results show that the near-infrared shielding performance of the heat-insulating glass is significantly enhanced with the increase of the mass ratio of ATO nanoparticles in E-51. This is manifested in the increased glass surface temperature and decreased temperature inside the foam box under near-infrared lamp irradiation, confirming the effective blocking effect of ATO on infrared radiation. When the mass ratio of ATO to E-51 is 1:1, the coating solution exhibits optimal stability and dispersibility, ensuring uniform film formation and durability. Simultaneously, the heat insulation performance is close to saturation at this ratio, and further increases in ATO dosage result in limited temperature changes. This demonstrates that the present invention, through optimized formulation, achieves an optimal balance between material utilization efficiency and preparation economy while ensuring high performance.

[0038] Through the comparison of the effects of the above embodiments and comparative examples, the preparation method of the present invention has the advantages of material system innovation and process integration innovation.

[0039] A functional-structural integrated coating system was constructed by combining ATO nanoparticles with excellent near-infrared absorption properties with an epoxy resin E-51 matrix. This system leverages the strong adhesion of E-51 resin and the selective thermal insulation properties of ATO to enhance the near-infrared blocking capability of glass and the adhesion of the coating. This delays the performance degradation of the coating during use, improving its service life and environmental adaptability.

[0040] A multi-stage process, encompassing surface etching, solvothermal synthesis, dispersion and compounding, spraying, and programmed curing, was employed to achieve complete process control from the controllable preparation of nanoparticles to uniform coating. The solvothermal method ensured the uniformity of ATO particle size. Ultrasonic-mechanical dispersion improved the uniformity of ATO distribution in the resin. Combining surface activation and spray curing processes, a feasible process route for the large-scale preparation of thermal insulation coatings was preliminarily explored.

[0041] The preparation method of this invention is a systematic innovation at both the material design and process integration levels, providing material system and methodological support for the development of energy-saving glass and possessing good industrialization prospects.

[0042] The above embodiments are merely illustrative of the structural concept and features of the present invention, intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and should not be construed as limiting the scope of protection of the present invention. All equivalent changes or modifications made based on the essence of the present invention should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing heat-insulating glass based on E-51 / ATO, characterized in that, Includes the following steps: Step 1: Using tin tetrachloride pentahydrate and antimony trichloride as precursors, after stirring, pour into a stainless steel autoclave with a para-polyphenol liner and seal. Place in a high-temperature forced-air drying oven and heat to allow the precursors to react fully. After natural cooling, obtain an ATO dispersion solution. Step 2: Centrifuge the ATO dispersion solution to remove the supernatant, wash with ethanol and deionized water respectively, and vacuum dry to obtain dry nano-ATO powder; Step 3: Weigh epoxy resin E-51, amine curing agent, and acetone, mix them evenly, pour them into the nano ATO powder, and continue stirring until there are no visible particle agglomerates in the system to obtain a uniform ATO / E-51 slurry. Step 4: Fix the pretreated glass substrate on the platform, inject the ATO / E-51 slurry into the spray gun cup, adjust the distance between the spray gun and the glass substrate, and spray the ATO / E-51 slurry onto the surface of the glass substrate at a constant moving speed. After the spraying is completed, the sample is dried and cured to obtain ATO / E-51 heat-insulating glass with a dense surface structure.

2. The method for preparing heat-insulating glass based on E-51 / ATO according to claim 1, characterized in that, Step 1 includes: Step 1-1: Prepare ATO solution using the solvothermal method. Weigh 50 mL of ethanol and divide it into two equal portions. Dissolve 2.00 g of SnCl4·5H2O solution and the calculated amount of SbCl3 solution in each portion. Stir magnetically at 1500 rpm for 10 min until completely dissolved. Steps 1-2: Mix SnCl4·5H2O solution and SbCl3 solution and continue stirring for 10 min to obtain precursor solution; Steps 1-3: Pour the precursor solution into a 100 mL stainless steel autoclave lined with para-polyphenol, seal it, and place it in a high-temperature drying oven at 180°C. Heating at C for 8 h allows the precursor to react fully, and after natural cooling, a gray-green ATO dispersion solution is obtained.

3. The method for preparing heat-insulating glass based on E-51 / ATO according to claim 2, characterized in that, In step 2, the ATO dispersion was centrifuged at 5000 rpm for 2 min to remove the supernatant, and washed three times each with ethanol and deionized water. Dry nano-ATO powder was obtained by vacuum drying at -0.1 MPa for 12 h.

4. The method for preparing heat-insulating glass based on E-51 / ATO according to claim 3, characterized in that, Step 3 includes: Step 3-1: Weigh 1.00 g of E-51 and 0.50 g of amine curing agent using an electronic balance, transfer them to a 25 mL beaker, and stir manually with a glass rod for 3 min until they are evenly mixed. Step 3-2: Add 10 mL of acetone solvent and stir magnetically at 1500 rpm for 10 min to obtain epoxy resin dilution. Step 3-3: Add 0.50 g-1.25 g of the nano ATO powder to the epoxy resin diluent and stir continuously until there are no visible particle agglomerates in the system to obtain a uniform ATO / E-51 slurry.

5. The method for preparing heat-insulating glass based on E-51 / ATO according to claim 4, characterized in that, In step 4, the glass substrate pretreatment includes: Step a: Select a glass slide as the substrate and reference, and immerse the glass slide in a beaker containing concentrated sulfuric acid: hydrogen peroxide = 7:3; Step b: Wait for the solution to reach 60 After cooling, ultrasonic treatment for 30 minutes is used to remove impurities from the surface of the glass slide; Step c: Rinse the slide 5 times with deionized water at 80°C. Bake at 30°C for 30 minutes, then place in a clean petri dish for later use.

6. The method for preparing heat-insulating glass based on E-51 / ATO according to claim 5, characterized in that, Step 4 includes: Step 4-1: Adjust the distance between the airbrush and the glass substrate to 15 cm; Step 4-2: After injecting ATO / E-51 slurry into the spray gun cup, continuously spray the glass substrate at a constant moving speed of 15 s / piece. Step 4-3: Immediately transfer the coated glass substrate to a forced-air drying oven at 100°C. Curing at C for 40 min yields ATO / E-51 heat-insulating glass with a dense surface structure.

Images