Method for preparing red sunlight control film on borosilicate plate glass

Abstract

The invention discloses a method for preparing a red sunlight control film on borosilicate plate glass, and relates to the technical field of glass production, and the method comprises the following steps: in a borosilicate float plate glass production line, a glass substrate runs in a tin bath, and then enters an annealing kiln front area through a transition roller way; through film layer structure design and an online film coating process in a specific area of an annealing kiln of a borosilicate float glass production line, the defect of coloring of a glass body is avoided, the stability and the high efficiency of production are ensured, the selected film coating materials such as ferric oxide, silicon oxide and tin oxide are low in cost and stable in quality, and the red sunlight control film is successfully prepared; the borosilicate plate glass has red appearance and energy-saving and sunlight control functions, the inorganic metal film is not limited by the service life and can be subjected to hot working, various products can be produced by adjusting the ratio of raw materials, the market variety of the borosilicate plate glass is enriched, and the requirement of the market for special borosilicate plate glass is met.

Description

Technical Field

[0001] The invention relates to the technical field of glass production, in particular to a method for preparing a red sunlight control film on borosilicate flat glass. Background Art

[0002] In glass production, borosilicate flat glass is widely used due to its unique properties, but the borosilicate flat glass on the market is almost colorless. With the growing market demand for diversified colors and high-performance borosilicate flat glass, glass coloring technology has become a research hotspot. Glass coloring mainly includes two methods: body coloring and surface coating film. However, due to the high boron content and strong oxidizing properties of borosilicate flat glass, and the fact that it is mostly produced in electric melting furnaces, many common glass colorants such as selenium, manganese, copper, sulfur, carbon, gold, and silver cannot be used normally. These colorants will change in value under the action of the electric field in the electric melting furnace, or cannot be colored normally in the borosilicate system. In addition, adding colorants to the glass raw materials will seriously interfere with the electric field of the borosilicate electric melting furnace, reduce the melting rate, disrupt the liquid flow, and affect the uniformity of the glass liquid, which will lead to a decrease in melting quality and product defects. Therefore, the method of producing colored borosilicate flat glass by coloring the glass body is greatly limited.

[0003] In the prior art, the products that can produce red glass are mainly packaging bottle glass, which uses glass body coloring, copper or gold as colorant, and undergoes secondary crystallization treatment to present red. However, due to the high cost, gold as a colorant has almost no practical application. Although copper red glass can be subjected to secondary crystallization treatment in bottle glass production due to the production and processing methods, the difficulty is relatively low, but for the continuous production line of borosilicate float flat glass, it is impossible to achieve online secondary crystallization technology. Offline crystallization is not only extremely expensive, but also difficult to ensure the deformation quality of the glass. On the other hand, in terms of the way of coating thin films on the glass surface, although there are currently a variety of coating products on soda-lime-silicon flat glass, there is no mature technology and method for producing red thin films on borosilicate flat glass. Whether it is the existing technology of glass body coloring or surface coating thin films, it cannot meet the demand for producing red borosilicate flat glass. Therefore, it is necessary to propose a method for preparing a red sunlight control film on borosilicate flat glass to solve the problems in the prior art. Summary of the invention

[0004] The purpose of the present invention is to make up for the shortcomings of the prior art and to provide a method for preparing a red sunlight control film on borosilicate flat glass, which can solve the problem that the existing borosilicate flat glass cannot produce red body colored glass, so that the glass has both the red appearance beauty and the dual functions of energy saving and sunlight control, and meets the market demand for distinctive and high-performance borosilicate flat glass.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a method for preparing a red sunlight control film on borosilicate flat glass, the method comprising the following steps: In the borosilicate float flat glass production line, the glass substrate runs in the tin bath and then enters the front area of ​​the annealing furnace through a transition roller; A stainless steel reactor is used to perform the first layer coating operation in the area where the glass substrate temperature is 660-680°C in the front area of ​​the annealing furnace. The interior of the stainless steel reactor is composed of 3 air inlet chambers and 2 exhaust chambers. The interior of the stainless steel reactor is composed of an upstream nitrogen gas-sealed air inlet chamber, an upstream reaction waste gas exhaust chamber, a coating gas air inlet chamber, a downstream reaction waste gas exhaust chamber, and a downstream nitrogen gas-sealed air inlet chamber from upstream to downstream. The bottom surface of the stainless steel reactor is composed of a mineral oil circulation channel, a coating reactor exhaust port, an upstream module of the coating reactor, an air inlet of the coating reactor, and a downstream module of the coating reactor, wherein the upstream module of the coating reactor and the downstream module of the coating reactor are asymmetrically designed; Using tetraethyl orthosilicate TEOS, triethyl phosphite TEP, monobutyltin trichloride MBTC, methyl isobutyl ketone MIBK, deionized water, nitrogen and air as raw materials, a 40-50nm thick SnO2+SiO2 step transition mixed film layer is plated on the surface of a borosilicate glass substrate by chemical vapor deposition. The film layer has a high silicon dioxide content close to the glass substrate in the thickness direction and a high tin dioxide content away from the glass substrate. In the area where the temperature of the glass substrate in the front area of ​​the annealing furnace is 560-590°C, an online high-temperature spray coating reactor is used to coat a 100-150nm thick Fe2O3 film on the glass substrate that has been coated with the first layer of film, using ferric acetylacetonate, ferrous lactate, ferric citrate, deionized water, surfactant, and compressed air as raw materials; After coating, the glass sheets are sent to the annealing kiln for annealing before being cut, quality inspected and packaged.

[0006] Furthermore, the coating gas inlet chamber of the stainless steel reactor transports the liquid coating raw materials through pipelines, metering, high-temperature vaporization and mixing to form a coating gas to the space between the glass substrate, and the coating gas undergoes a chemical vapor deposition reaction during movement, and the reacted gas and unreacted gas enter the exhaust chamber through the exhaust port and are discharged, wherein the steps of transporting, metering, vaporizing and mixing the liquid coating raw materials are specifically as follows: TEOS, TEP, MBTC, MIBK and deionized water are transported through pipelines and metered by flow meters, then vaporized into a gaseous state by an evaporator, and then transported to the stainless steel reactor at high temperature with nitrogen and air as carriers, and before the coating gas raw materials enter the pipeline system, all pipeline systems are purged and purified with high-pressure nitrogen.

[0007] Furthermore, in the process of chemical vapor deposition coating of SnO2+SiO2 step transition mixed film layer, the gradient distribution of film layer composition is achieved through the asymmetric design of upstream and downstream modules of the stainless steel reactor and the addition of catalyst pure water and TEP to the coating raw material reaction gas. The width of the upstream module of the coating reactor is twice the width of the downstream module of the coating reactor. After the coating reaction gas enters the space between the reactor and the glass substrate, the path of upstream movement is long and the path of downstream movement is short. The reaction rate of MBTC is increased under the action of the catalyst, while the reaction rate of TEOS is slower, forming a gradient change in the film layer composition.

[0008] Furthermore, when the SnO2+SiO2 step transition mixed film layer is deposited by chemical vapor deposition, the height of the stainless steel reactor from the glass substrate surface is maintained at 2.0-6.0 mm, and the dosage range of TEOS is 4.0-8.5 Kg / Hr, the dosage range of TEP is 1.0-2.5 Kg / Hr, the dosage range of MBTC is 4.5-7.5 Kg / Hr, the dosage range of MIBK is 0.20-0.50 Kg / Hr, the dosage range of deionized water is 0.5-1.5 Kg / Hr, the dosage range of nitrogen is 200-400 Nm³ / hr, and the dosage range of air is 0-120 Nm³ / hr.

[0009] Furthermore, when coating the SnO2+SiO2 step-transition mixed film layer, the tin bath outlet temperature and the electric heating device are controlled, and the temperature of the glass substrate in the coating reaction area is adjusted to 665-675°C. At the same time, the mineral oil in the mineral oil circulation channel at the bottom of the stainless steel reactor is heated to 180°C and the thermal cycle is started. After the temperature of the stainless steel reactor stabilizes, it is inserted into the annealing kiln, the height is adjusted to the coating position, the coating inlet pipe and exhaust pipe are connected, and the sealing work around the stainless steel reactor is done.

[0010] Furthermore, in the process of coating the SnO2+SiO2 step-transition mixed film layer, by controlling the running distance of the coating reaction gas of the stainless steel reactor and the difference in reaction rate, the silicon dioxide content is high near the glass substrate, and the tin dioxide content is high in the direction away from the glass substrate, and the enriched silicon dioxide on the side close to the glass substrate forms a chemical bond network structure with the silicon dioxide in the glass substrate body. When the stainless steel reactor is coating the SnO2+SiO2 step-transition mixed film layer, the upstream and downstream nitrogen gas seals ensure the stability of the atmosphere in the coating area to prevent the coating gas from overflowing. The coating gas moves upstream and downstream in a laminar manner, and a chemical vapor deposition reaction occurs on the surface of the hot glass substrate to form a film layer.

[0011] Furthermore, when coating the Fe2O3 film, the coating raw material usage is 1.2-2.4 liters / minute, the high-pressure air usage is 350-650Nm³ / hour, and the coating raw material is configured as follows: ferric acetylacetonate is added to deionized water at a weight ratio of 1:4-1:10, and then 0.05-0.15% of the weight of the solution is added as a surfactant, and after mixing evenly, the raw material particle size is ground to less than 6μm by a grinder to complete the raw material preparation.

[0012] Furthermore, when coating the Fe2O3 film, the tin bath outlet temperature is adjusted to control the surface temperature of the glass substrate to 585-595°C when coating the film. An online high-temperature spray coating reactor is used for coating. According to the film thickness required for production and the operating speed of the glass substrate, 8 spray guns are configured with an operating speed of 6-12 rpm. The waste gas generated by the reaction is discharged from the coating area by the waste exhaust system on both sides of the online high-temperature spray coating reactor, and the height of the online high-temperature spray coating reactor from the glass substrate surface is maintained at 150-300 mm.

[0013] Compared with the prior art, the method for preparing a red sunlight control film on borosilicate flat glass has the following beneficial effects: The present invention avoids the disadvantage of coloring the glass body through film layer structure design and an online coating process in a specific area of ​​the annealing furnace of a borosilicate float glass production line, ensures the stability and efficiency of production, selects iron oxide, silicon oxide, tin oxide and other coating materials with low cost and stable quality, and successfully prepares a red sunlight control film, so that the borosilicate flat glass has a red appearance and energy-saving and sunlight control functions. The inorganic metal film has no service life limit and can be heat-processed. Moreover, a variety of products can be produced by adjusting the raw material ratio, enriching the market types of borosilicate flat glass, meeting the market demand for special borosilicate flat glass, and promoting the progress of glass manufacturing technology.

[0014] Other advantages, objectives and features of the present invention will be set forth in part in the following description and, in part, will be apparent to those skilled in the art based on an examination of the following or may be taught from the practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the prior art descriptions are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0016] Figure 1 This is a schematic diagram of the film structure of the red sunlight control film; Figure 2 Schematic diagram of the process of online preparation of red film layer on borosilicate flat glass; Figure 3 is a cross-sectional schematic diagram of a stainless steel reactor; Figure 4 This is a schematic diagram of the spraying trajectory of the high-temperature spray coating reactor; Figure 5 The present invention is a flow chart of a method for preparing a red solar control film on borosilicate flat glass.

[0017] In the figure: 1. glass substrate; 2. SnO2+SiO2 step transition mixed film layer; 3. Fe2O3 film layer; 4. tin bath; 5. transition roller; 6. stainless steel reactor; 601. upstream nitrogen gas seal air inlet chamber; 602. upstream reaction waste gas exhaust chamber; 603. coating gas air inlet chamber; 604. downstream reaction waste gas exhaust chamber; 605. downstream nitrogen gas seal air inlet chamber; 606. mineral oil circulation channel; 607. coating reactor exhaust port; 608. coating reactor upstream module; 609. coating reactor air inlet; 610. coating reactor downstream module; 7. online high temperature spray coating reactor. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Embodiment 1

[0019] In a professional borosilicate flat glass manufacturer, the preparation of red solar control film was carried out.

[0020] First, in the borosilicate float glass production line, the glass substrate 1 runs in the tin bath 4, and then enters the annealing furnace through the transition roller 5. In the front area of ​​the annealing furnace of the borosilicate float glass production line, the environment here needs to be carefully controlled to ensure the stability and effectiveness of the entire coating process. During the operation, the staff closely monitors the temperature of the glass substrate 1. When the temperature is stabilized at 665°C, it is ready to be coated using the stainless steel reactor 6.

[0021] In order to ensure the best working state of the stainless steel reactor 6, a series of preparatory work was carried out before coating. The mineral oil was heated to 180°C and the thermal circulation system of the mineral oil was turned on so that all parts of the reactor could be heated evenly to ensure the stability of the reactor temperature. When the reactor reached the required temperature, it was accurately inserted into the annealing furnace and its position was adjusted so that the height of the reactor from the glass substrate 1 was accurately adjusted to 4.5 mm. This height was determined after many experiments and optimizations, and it can ensure the reaction efficiency and film uniformity between the coating gas and the glass substrate 1. At the same time, the connecting parts of the reactor were carefully inspected and sealed, the coating inlet pipe and the exhaust pipe were firmly connected, and special sealing materials were used to make peripheral seals to prevent gas leakage from affecting the coating quality.

[0022] Next, prepare the coating raw materials. For the first layer of SnO2+SiO2 step transition mixed film layer 2, accurate measurement and transportation of raw materials are very important. Tetraethyl orthosilicate TEOS at a flow rate of 5.033Kg / Hr, triethyl phosphite TEP at a flow rate of 1.427Kg / Hr, monobutyltin trichloride MBTC at a flow rate of 5.650Kg / Hr, methyl isobutyl ketone MIBK at a flow rate of 0.284Kg / Hr, and deionized water at a flow rate of 0.862Kg / Hr are transported through pipelines and measured by flow meters. They are then vaporized into gaseous state through evaporators. In this process, the vaporization temperature and time are strictly controlled to ensure that the raw materials are completely vaporized and stable in nature. Then, they are transported to the stainless steel reactor 6 at high temperature with 240Nm³ / hr of nitrogen and 86Nm³ / hr of air as carriers. Moreover, before the coating gas raw materials enter the pipeline system, all pipeline systems are purged and purified with high-pressure nitrogen. This step can effectively remove impurities and residual gases in the pipeline to avoid adverse effects on the coating quality.

[0023] A SnO2+SiO2 step transition mixed film layer 2 is plated on the surface of a borosilicate glass substrate 1 by chemical vapor deposition. The film layer has a thickness of 43.6 nm. In the thickness direction, the silicon dioxide content is high near the glass substrate 1, and the tin dioxide content is high away from the glass substrate 1. This composition gradient is achieved through the unique design of the reactor and the reaction conditions. Specifically, the interior of the stainless steel reactor 6 is composed of 3 air inlet cavities and 2 exhaust cavities. The interior of the stainless steel reactor 6 is composed of upstream nitrogen gas seal air inlet cavities, downstream nitrogen gas seal air inlet cavities, and downstream nitrogen gas seal air inlet cavities. The bottom surface of the coating reactor is composed of a mineral oil circulation channel 606, a coating reactor exhaust port 607, a coating reactor upstream module 608, a coating reactor air inlet 609, and a coating reactor downstream module 610. Moreover, the upstream and downstream modules of the stainless steel coating reactor are asymmetrically designed, wherein the width of the upstream module is twice that of the downstream module, and in the coating raw material reaction gas, the coating reactor has a plurality of chambers 601, an upstream reaction waste gas exhaust chamber 602, a coating gas inlet chamber 603, a downstream reaction waste gas exhaust chamber 604, and a downstream nitrogen gas seal inlet chamber 605. The addition of catalyst pure water and TEP controls the running distance and reaction rate difference of the coating reaction gas. When the coating reaction gas enters the space between the reactor and the glass substrate 1, the path moving upstream is long and the path moving downstream is short. Under the action of the catalyst, the reaction rate of monobutyltin trichloride MBTC is increased, and the rapid reaction reduces its concentration in the coating gas, while the reaction rate of tetraethyl orthosilicate TEOS is slow and the initial deposition is small. However, as the gas moves upstream and the MBTC reaction decreases, the TEOS concentration increases relatively and enters the rapid reaction stage, thereby depositing a silicon dioxide film layer dominated by TEOS reaction at a distance from the coating gas inlet, realizing a gradient change in the film layer composition. This design can not only isolate the sodium ions in the glass from migrating to the film layer and prevent the sodium ions from destroying the film layer structure, but also eliminate the reflective interference color that may be generated when the second film layer is subsequently plated. At the same time, the enriched silicon dioxide close to the glass side can form a chemical bond network structure with the silicon dioxide in the glass body, significantly enhancing the adhesion and wear resistance of the film layer.

[0024] When the glass substrate 1 continues to run to the area where the temperature of the front zone of the annealing furnace is 587°C, the second Fe2O3 film layer 3 is plated using an online high-temperature spray coating reactor 7. First, the coating raw materials are carefully configured. Ferric acetylacetonate is added to deionized water at a weight ratio of 1:6, and then a surfactant of 0.06% by weight of the solution is added. After mixing evenly, the raw material particle size is ground to less than 6 microns by a grinder to prepare the coating raw material. In this process, the grinding operation ensures that the raw material particle size is small enough to ensure the uniformity and density of the film layer. The coating raw material is passed through a reactor configured with a flow rate of 1.56 liters / minute. A reactor with 8 spray guns and a running speed of 10 rpm sprays toward the glass substrate 1, and 550Nm³ / hr of high-pressure air is introduced at the same time. During the coating process, the coating raw materials are uniformly attached to the glass substrate 1 in the form of spray, and the waste gas generated by the reaction is discharged from the coating area by the exhaust system on both sides of the coating machine to ensure the cleanliness of the coating area and the continuous reaction. Finally, a 109.8nm thick Fe2O3 film layer 3 is plated on the glass substrate 1 that has been coated with the first layer of film. Through special reaction process and conditions, the entire coating film layer presents a bright red color and has good sunlight control function.

[0025] After coating, the glass plate enters a normal annealing kiln for annealing. The annealing process is a key link, which can eliminate the internal stress of the film layer, form a tighter bond between the film layer and the glass substrate 1, and improve the bonding strength and stability between the film layer and the glass substrate 1. During the annealing process, the performance of the film layer and the flatness of the glass are guaranteed by accurately controlling the annealing temperature curve and annealing time.

[0026] Afterwards, the coated glass is cut. According to the size requirements of the architectural glass, high-precision cutting equipment is used to cut the large-sized coated glass into the required size specifications. During the cutting process, attention is paid to the control of the cutting speed and cutting pressure to avoid damage to the film layer. After the cutting is completed, strict quality inspection is carried out. Through various testing methods, such as optical performance testing, film thickness measurement, corrosion resistance testing, abrasion resistance testing, etc., ensure that the product meets high quality standards. Finally, packaging is carried out. Special packaging materials are used to package the coated glass to prevent scratches, bumps and other damage during transportation and storage.

[0027] The effects brought about by this embodiment are as follows: the successfully prepared red sunlight control thin film borosilicate flat glass presents a pure and bright red color in appearance, and has extremely high visual appeal. In terms of performance, it can effectively control the penetration and reflection of sunlight, and achieve good energy-saving effects. Moreover, after strict tests on film wear resistance, acid resistance and alkali resistance, the film layer shows excellent durability and can maintain stable performance during long-term use. In actual application scenarios, this high-quality red borosilicate flat glass product can significantly reduce indoor heat absorption and reduce indoor air conditioning energy consumption when used on the facade of a building. At the same time, its unique red appearance adds a unique visual identity and artistic charm to the building, making it stand out from many buildings. In exhibition venues and commercial window displays, it can create a unique red light and shadow effect, which not only meets the market demand for distinctive and energy-saving color borosilicate flat glass, but also brings significant economic benefits and market competitiveness to enterprises, and provides strong support for product innovation and technological development in the glass industry. Embodiment 2

[0028] In a laboratory environment focused on the development of new materials, work was also ongoing on the preparation of red solar control films on borosilicate flat glass, with the aim of further optimizing the process parameters and verifying its feasibility at different scales.

[0029] At the initial stage of the borosilicate float glass production line, the staff strictly controls the quality of raw materials to ensure the purity and stability of the borosilicate glass, laying the foundation for the subsequent coating process. In the borosilicate float glass production line, the glass substrate 1 runs in the tin bath 4, and then enters the annealing kiln through the transition roller 5. When the glass substrate 1 enters the front area of ​​the annealing kiln and the temperature reaches 670°C, the first layer of film coating is started using the stainless steel reactor 6.

[0030] When preparing the stainless steel reactor 6, carefully check the sealing and smoothness of the mineral oil circulation channel to ensure that the mineral oil can stably maintain the reactor temperature. Heat the mineral oil to 182°C and maintain thermal circulation. After the reactor temperature stabilizes, accurately install it in the annealing furnace, adjust the distance between the reactor and the surface of the glass substrate 1 to 4.8mm, then connect the coating inlet pipe and exhaust pipe, and perform double sealing detection to prevent any gas leakage from affecting the coating effect.

[0031] For the preparation of coating raw materials, they are strictly mixed according to the proportion: tetraethyl orthosilicate TEOS at 6.5Kg / Hr, triethyl phosphite TEP at 2.0Kg / Hr, monobutyltin trichloride MBTC at 6.0Kg / Hr, methyl isobutyl ketone MIBK at 0.35Kg / Hr, and deionized water at a flow rate of 1.2Kg / Hr are transported to the evaporator through pipelines. In the evaporator, the vaporization temperature and time are precisely controlled to fully vaporize the raw materials into gaseous state, and then transported to the stainless steel reactor 6 with 300Nm³ / hr of nitrogen and 100Nm³ / hr of air as carriers. Before the raw materials enter the pipeline system, high-pressure nitrogen is used for long-term and high-intensity purging and purification to ensure that there are no impurities remaining in the pipeline.

[0032] When chemical vapor deposition is used for coating, the asymmetric design of the upstream and downstream modules of the reactor and the effects of catalyst pure water and TEP are fully utilized. The width of the upstream module is twice the width of the downstream module. When the coating reaction gas enters the space between the reactor and the glass substrate 1, due to the difference in paths and the influence of the catalyst, MBTC reacts rapidly to reduce the concentration, while TEOS gradually increases the reaction rate during the gas movement, and finally forms a SnO2+SiO2 step transition mixed film layer 2 with a thickness of 46nm on the glass substrate 1. The film layer has a high silicon dioxide content near the glass substrate 1, which effectively prevents the migration of sodium ions and enhances the bonding strength between the film layer and the glass. The tin dioxide content increases away from the substrate, forming a good optical match with the subsequent film layer and reducing the reflected interference color.

[0033] When the glass substrate 1 runs to the position where the temperature of the front zone of the annealing furnace is 590°C, the online high-temperature spray coating reactor 7 is activated to coat the second Fe2O3 film 3, ferric acetylacetonate is added to deionized water at a weight ratio of 1:7, and a surfactant is added at a weight of 0.08% of the solution. After mixing evenly, the raw material particle size is ground to less than 5 microns by a fine grinder to prepare high-quality coating raw materials, which are sprayed onto the glass substrate 1 at a flow rate of 2.0 liters / minute through a reactor equipped with 8 spray guns and running at a speed of 11 revolutions / minute. At the same time, 600Nm³ / hr of high-pressure air is introduced. During the coating process, the spray angle and pressure of the spray gun are closely monitored to ensure that the coating raw materials are evenly covered on the first film. The waste gas generated by the reaction is quickly discharged from the coating area through the efficient waste exhaust system, and finally a 115nm thick Fe2O3 film 3 is formed on the glass substrate 1, so that the entire coated glass presents a bright and uniform red color and has excellent sunlight control capabilities.

[0034] After coating, the glass plate enters the annealing kiln for precise annealing. Through an advanced temperature control system, annealing is carried out strictly according to a predetermined annealing curve to effectively eliminate the internal stress of the film layer and improve the bonding strength and stability between the film layer and the glass substrate 1.

[0035] Subsequently, high-precision cutting equipment is used to cut the coated glass into samples of standard size. Special cooling and lubrication techniques are adopted during the cutting process to avoid any damage to the film layer. Then a comprehensive quality inspection is carried out, using spectrometers, electron microscopes, hardness testers and other equipment to conduct detailed inspections of the optical properties, microstructure, hardness and wear resistance of the film layer.

[0036] After testing, the prepared red sunlight control thin film borosilicate flat glass has good visible light transmittance and good wear resistance of the film layer. In the wear test simulating long-term use, the mass loss is very small. The acid and alkali resistance are also excellent. After immersion in a strong acid and alkali environment for a certain period of time, the film layer structure is still intact and the performance is stable.

[0037] The effects brought about by this embodiment are as follows: This embodiment once again proves the reliability and stability of the method under different conditions, provides strong support for its promotion in large-scale industrial production and high-end application fields, further enriches the product types of borosilicate flat glass, and meets the market's diversified needs for high-quality, high-performance red sunlight control film borosilicate flat glass. It has broad application prospects in energy-saving buildings, high-end decoration and other fields, and is expected to promote technological innovation and development in related industries.

[0038] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the same elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for preparing a red sunlight control film on borosilicate flat glass, characterized in that: The method comprises the following steps: In a borosilicate float flat glass production line, a glass substrate (1) runs in a tin bath (4) and then enters a front area of ​​an annealing furnace through a transition roller (5); A stainless steel reactor (6) is used to perform a first layer coating operation in an area where the temperature of the glass substrate (1) in the front area of ​​the annealing furnace is 660-680° C. The interior of the stainless steel reactor (6) is composed of three air inlet chambers and two exhaust chambers. The interior of the stainless steel reactor (6) is composed of an upstream nitrogen gas-sealed air inlet chamber (601), an upstream reaction waste gas exhaust chamber (602), a coating gas air inlet chamber (603), a downstream reaction waste gas exhaust chamber (604), and a downstream nitrogen gas-sealed air inlet chamber (605) from upstream to downstream. The bottom surface of the stainless steel reactor (6) is composed of a mineral oil circulation channel (606), a coating reactor exhaust port (607), a coating reactor upstream module (608), a coating reactor air inlet port (609), and a coating reactor downstream module (610), wherein the coating reactor upstream module (608) and the coating reactor downstream module (610) are of asymmetric design; Using tetraethyl orthosilicate (TEOS), triethyl phosphite (TEP), monobutyltin trichloride (MBTC), methyl isobutyl ketone (MIBK), deionized water, nitrogen and air as raw materials, a 40-50 nm thick SnO2+SiO2 step transition mixed film layer (2) is plated on the surface of a borosilicate glass substrate (1) by chemical vapor deposition, wherein the film layer has a high silicon dioxide content close to the glass substrate (1) in the thickness direction and a high tin dioxide content away from the glass substrate (1); In the area where the temperature of the glass substrate (1) in the front area of ​​the annealing furnace is 560-590° C., an online high-temperature spray coating reactor (7) is used to coat a 100-150 nm thick Fe2O3 film (3) on the glass substrate (1) coated with the first film, using ferrous acetylacetonate, ferrous lactate, ferric citrate, deionized water, a surfactant, and compressed air as raw materials; After coating, the glass sheets are sent to the annealing kiln for annealing before being cut, quality inspected and packaged.

2. A method for preparing a red sunlight control film on borosilicate flat glass according to claim 1, characterized in that: The coating gas inlet chamber (603) of the stainless steel reactor (6) transports the liquid coating raw materials through pipelines, meters, vaporizes at high temperature and mixes them into coating gas to the space between the glass substrate (1). The coating gas undergoes a chemical vapor deposition reaction during movement, and the reacted gas and unreacted gas enter the exhaust chamber through the exhaust port and are discharged. The steps of transporting, metering, vaporizing and mixing the liquid coating raw materials are as follows: TEOS, TEP, MBTC, MIBK and deionized water are transported through pipelines, metered by a flow meter, vaporized into a gaseous state by an evaporator, and then transported to the stainless steel reactor (6) at high temperature using nitrogen and air as carriers. Before the coating gas raw materials enter the pipeline system, all pipeline systems are purged and purified using high-pressure nitrogen.

3. A method for preparing a red sunlight control film on borosilicate flat glass according to claim 1, characterized in that: In the process of chemical vapor deposition coating of SnO2+SiO2 step transition mixed film (2), the gradient distribution of film layer composition is achieved by asymmetric design of upstream and downstream modules of the stainless steel reactor (6) and addition of catalyst pure water and TEP to the coating raw material reaction gas, wherein the width of the upstream module (608) of the coating reactor is twice the width of the downstream module (610) of the coating reactor. After the coating reaction gas enters the space between the reactor and the glass substrate (1), the upstream movement path is long and the downstream movement path is short. The reaction rate of MBTC is increased under the action of the catalyst, while the reaction rate of TEOS is slower, forming a gradient change in the film layer composition.

4. A method for preparing a red sunlight control film on borosilicate flat glass according to claim 1, characterized in that: When the SnO2+SiO2 step transition mixed film layer (2) is deposited by chemical vapor deposition, the height of the stainless steel reactor (6) from the surface of the glass substrate (1) is maintained at 2.0-6.0 mm, and the dosage range of TEOS is 4.0-8.5 Kg / Hr, the dosage range of TEP is 1.0-2.5 Kg / Hr, the dosage range of MBTC is 4.5-7.5 Kg / Hr, the dosage range of MIBK is 0.20-0.50 Kg / Hr, the dosage range of deionized water is 0.5-1.5 Kg / Hr, the dosage range of nitrogen is 200-400 Nm³ / hr, and the dosage range of air is 0-120 Nm³ / hr.

5. A method for preparing a red sunlight control film on borosilicate flat glass according to claim 1, characterized in that: When coating the SnO2+SiO2 step transition mixed film layer (2), the outlet temperature of the tin bath (4) and the electric heating device are controlled to adjust the temperature of the glass substrate (1) in the coating reaction area to 665-675°C. At the same time, the mineral oil in the mineral oil circulation channel (606) at the bottom of the stainless steel reactor (6) is heated to 180°C and the thermal cycle is started. After the temperature of the stainless steel reactor (6) is stabilized, it is inserted into the annealing kiln and the height is adjusted to the coating position. The coating air inlet pipe and exhaust pipe are connected, and the sealing work around the stainless steel reactor (6) is done.

6. A method for preparing a red sunlight control film on borosilicate flat glass according to claim 1, characterized in that: During the process of coating the SnO2+SiO2 step transition mixed film layer (2), the running distance of the coating reaction gas of the stainless steel reactor (6) and the difference in reaction rate are controlled so that the silicon dioxide content is high near the glass substrate (1), the tin dioxide content is high away from the glass substrate (1), and the enriched silicon dioxide on the side close to the glass substrate (1) forms a chemical bond network structure with the silicon dioxide in the glass substrate (1). When the stainless steel reactor (6) is coating the SnO2+SiO2 step transition mixed film layer (2), the nitrogen gas seals at the upstream and downstream ensure the stability of the atmosphere in the coating area to prevent the coating gas from overflowing. The coating gas moves upstream and downstream in a laminar manner, and a chemical vapor deposition reaction occurs on the surface of the hot glass substrate (1) to form a film layer.

7. A method for preparing a red sunlight control film on borosilicate flat glass according to claim 1, characterized in that: When coating the Fe2O3 film (3), the coating raw material usage is 1.2-2.4 liters / minute, the high-pressure air usage is 350-650 Nm³ / hour, and the coating raw material is configured as follows: ferric acetylacetonate is added to deionized water at a weight ratio of 1:4-1:10, and then 0.05-0.15% of the weight of the solution is added with a surfactant, and after mixing evenly, the raw material particle size is ground to less than 6 μm by a grinder to complete the raw material preparation.

8. A method for preparing a red sunlight control film on borosilicate flat glass according to claim 1, characterized in that: When coating the Fe2O3 film layer (3), the outlet temperature of the tin bath (4) is adjusted to control the surface temperature of the glass substrate (1) at 585-595°C when coating the film layer. The film is coated using an online high-temperature spray coating reactor (7). According to the film thickness required for production and the operating speed of the glass substrate (1), 8 spray guns are configured with an operating speed of 6-12 revolutions per minute. The waste gas generated by the reaction is discharged from the coating area by the waste exhaust system on both sides of the online high-temperature spray coating reactor (7), and the height of the online high-temperature spray coating reactor (7) from the surface of the glass substrate (1) is maintained at 150-300 mm.

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