A method for preparing a red solar control film on borosilicate flat glass

Abstract

The present invention discloses a method for preparing a red solar control film on borosilicate flat glass, relating to the technical field of glass production. The method comprises: in a borosilicate float flat glass production line, a glass substrate is run in a tin bath, and then enters the front area of an annealing lehr via a transition roller. The present invention avoids the disadvantages of coloring the glass itself through film layer structure design and an online coating process in a specific area of the annealing lehr of the borosilicate float glass production line, ensuring stable and efficient production. The red solar control film is successfully prepared by selecting low-cost and stable-quality coating materials such as iron oxide, silicon oxide, and tin oxide, giving the borosilicate flat glass both a red appearance and energy-saving and solar control functions. The inorganic metal film has no service life limit and can be thermally processed. Furthermore, by adjusting the raw material ratio, a variety of products can be produced, enriching the market variety of borosilicate flat glass and meeting the market demand for specialty borosilicate flat glass.

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 all 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 will not be able to display color normally in the borosilicate system. Moreover, 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, thereby leading to a decline 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 main product capable of producing red glass is packaging container glass. This glass is tinted using copper or gold as a colorant and then undergoes a secondary crystallization process to produce a red color. However, due to its high cost, gold as a colorant has little practical application. While copper-red glass can undergo secondary crystallization in container glass production due to its production and processing methods, it is relatively easy to achieve this. However, for continuous production lines for borosilicate float glass, online secondary crystallization technology is not feasible. Offline crystallization is not only extremely expensive but also difficult to ensure the deformation quality of the glass. Furthermore, regarding the method of coating thin films on the glass surface, although there are currently various coating products for soda-lime-silica flat glass, there is no mature technology or method for producing red thin films on borosilicate flat glass. Whether it is the existing technology for tinting the glass body or coating the thin films on the surface, neither can meet the demand for producing red borosilicate flat glass. Therefore, it is necessary to propose a method for preparing a red solar 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 existing technology and provide a method for preparing a red sunlight control film on borosilicate flat glass. It 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, meeting 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:

[0006] 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;

[0007] A stainless steel reactor is used for the first layer coating operation in the area of the front section of the annealing furnace where the glass substrate temperature is 660-680°C. The interior of the stainless steel reactor is composed of three air inlet chambers and two exhaust chambers. From upstream to downstream, the interior of the stainless steel reactor is composed of an upstream nitrogen gas seal 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 seal air inlet chamber. 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. The upstream module of the coating reactor and the downstream module of the coating reactor are asymmetrically designed.

[0008] A 40-50 nm thick SnO2+SiO2 step-transition mixed film is deposited on a borosilicate glass substrate using tetraethyl orthosilicate (TEOS), triethyl phosphite (TEP), monobutyltin trichloride (MBTC), methyl isobutyl ketone (MIBK), deionized water, nitrogen, and air by chemical vapor deposition. The film has a high silicon dioxide content near the glass substrate in the thickness direction and a high tin dioxide content away from the glass substrate.

[0009] In the area in front of the annealing furnace where the temperature of the glass substrate 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;

[0010] After coating, the glass sheets are sent to the annealing kiln for annealing, followed by cutting, quality inspection and packaging.

[0011] Furthermore, the coating gas inlet chamber of the stainless steel reactor transports the liquid coating raw materials through pipelines, meters, and vaporizes them at high temperature to form a coating gas mixed therewith to the space between the glass substrate. 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 specific 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 and measured by flow meters, then vaporized into a gaseous state through an evaporator, and then transported to the stainless steel reactor at high temperature using nitrogen and air as carriers. Before the coating gas raw materials enter the pipeline system, all pipeline systems are purged with high-pressure nitrogen.

[0012] 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 upstream movement path is long and the downstream movement path is short. The reaction rate of MBTC increases under the action of the catalyst, while the reaction rate of TEOS is slower, forming a gradient change in the film layer composition.

[0013] 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 TEOS dosage range is 4.0-8.5 Kg / Hr, the TEP dosage range is 1.0-2.5 Kg / Hr, the MBTC dosage range is 4.5-7.5 Kg / Hr, the MIBK dosage range is 0.20-0.50 Kg / Hr, the deionized water dosage range is 0.5-1.5 Kg / Hr, the nitrogen dosage range is 200-400 Nm³ / hr, and the air dosage range is 0-120 Nm³ / hr.

[0014] Furthermore, when coating the SnO2+SiO2 step-transition mixed film layer, the tin bath outlet temperature and the electric heating device are controlled to adjust the temperature of the glass substrate in the coating reaction area 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 air inlet pipe and exhaust pipe are connected, and the surrounding area of the stainless steel reactor is sealed.

[0015] Furthermore, during 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 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.

[0016] 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 solution weight of a surfactant is added. After mixing evenly, the raw material is ground to a particle size of less than 6μm using a grinder to complete the raw material preparation.

[0017] Furthermore, when coating the Fe2O3 film, the tin bath outlet temperature is adjusted to control the surface temperature of the glass substrate at 585-595°C when coating the film. An online high-temperature spray coating reactor is used for coating. Based on 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 through 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.

[0018] Compared with the existing technology, the method for preparing a red sunlight control film on borosilicate flat glass has the following beneficial effects:

[0019] 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, ensuring production stability and efficiency. The coating materials such as iron oxide, silicon oxide, and tin oxide are selected with low cost and stable quality, and a red sunlight control film is successfully prepared, so that the borosilicate flat glass has both 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 variety of borosilicate flat glass, meeting the market demand for special borosilicate flat glass, and promoting the progress of glass manufacturing technology.

[0020] Other advantages, objects and features of the present invention will be described 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 learned from the practice of the invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort.

[0022] Figure 1 Schematic diagram of the film structure of the red sunlight control film;

[0023] Figure 2 Schematic diagram of the process for online preparation of red film layer on borosilicate flat glass;

[0024] Figure 3 is a cross-sectional schematic diagram of a stainless steel reactor;

[0025] Figure 4 This is a schematic diagram of the spray trajectory of the high-temperature spray coating reactor;

[0026] Figure 5 The present invention is a flow chart of a method for preparing a red solar control film on borosilicate flat glass.

[0027] 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 inlet chamber; 602. Upstream reaction waste gas exhaust chamber; 603. Coating gas inlet chamber; 604. Downstream reaction waste gas exhaust chamber; 605. Downstream nitrogen gas seal 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

[0028] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention. Example 1

[0029] The preparation of red solar control film was carried out in a professional borosilicate flat glass manufacturer.

[0030] 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 stabilizes at 665°C, the stainless steel reactor 6 is prepared for coating.

[0031] To ensure the optimal working condition 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 mineral oil heat circulation system was turned on to ensure that all parts of the reactor were heated evenly and the reactor temperature was stable. 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 surface of the glass substrate 1 was accurately adjusted to 4.5mm. This height was determined after multiple experiments and optimizations to ensure the reaction efficiency between the coating gas and the glass substrate 1 and the uniformity of the film layer. At the same time, the connecting parts of the reactor were carefully inspected and sealed. The coating inlet and exhaust pipes were firmly connected, and the surrounding seals were made with special sealing materials to prevent gas leakage from affecting the coating quality.

[0032] Next, prepare the coating raw materials. For the first layer of SnO2+SiO2 step-transition mixed film 2, accurate measurement and delivery of the raw materials are crucial. Tetraethyl orthosilicate (TEOS) at a flow rate of 5.033 kg / Hr, triethyl phosphite (TEP) at a flow rate of 1.427 kg / Hr, monobutyltin trichloride (MBTC) at a flow rate of 5.650 kg / Hr, methyl isobutyl ketone (MIBK) at a flow rate of 0.284 kg / Hr, and deionized water at a flow rate of 0.862 kg / Hr are transported through pipelines and measured by flow meters. They are then vaporized into gaseous form through an evaporator. In this process, the vaporization temperature and time are strictly controlled to ensure that the raw materials are completely vaporized and their properties are stable. They are then transported to the stainless steel reactor 6 at high temperature using 240 Nm³ / hr of nitrogen and 86 Nm³ / hr of air as carriers. In addition, 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.

[0033] A SnO2+SiO2 step transition mixed film layer 2 is deposited 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 consists of three air inlet cavities and two exhaust cavities. From upstream to downstream, the interior of the stainless steel reactor 6 is the upstream nitrogen gas seal air inlet. The bottom surface of the chamber 601, the upstream reaction waste gas exhaust chamber 602, the coating gas inlet chamber 603, the downstream reaction waste gas exhaust chamber 604, and the downstream nitrogen gas seal inlet chamber 605 are 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 stainless steel coating reactor is asymmetrically designed in that the upstream module width is twice the width of the downstream module, and in the coating raw material reaction gas, the coating reactor is asymmetrically designed in that the upstream module width is twice the width of the downstream module. The addition of catalysts, pure water and TEP, controls the travel distance and reaction rate differences of the coating reaction gas. When the coating reaction gas enters the space between the reactor and the glass substrate 1, the upstream path is long and the downstream path 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. However, the reaction rate of tetraethyl orthosilicate (TEOS) is slower, with less initial deposition. However, as the gas moves upstream, the MBTC reaction decreases, while the TEOS concentration increases relatively and enters a rapid reaction phase. As a result, a silicon dioxide film layer dominated by TEOS reaction is deposited at a distance from the coating gas inlet, achieving a gradient change in the film layer composition. This design not only isolates sodium ions in the glass from migrating to the film layer, preventing sodium ions from damaging the film layer structure, but also eliminates the reflective interference color that may be generated when the second film layer is subsequently deposited. At the same time, the enriched silicon dioxide near 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.

[0034] When the glass substrate 1 continues to run to the area where the temperature of the front zone of the annealing furnace is 587℃, the second layer of Fe2O3 film 3 is coated using an online high-temperature spray coating reactor 7. First, the coating raw materials are carefully prepared. Ferric acetylacetonate is added to deionized water at a weight ratio of 1:6, and then a surfactant is added at a weight ratio of 0.06% of the solution. After mixing evenly, the raw material is ground to a particle size of less than 6 microns using 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 equipped with a flow rate of 1.56 liters / minute. A reactor equipped with eight spray guns operating at 10 rpm sprays onto a glass substrate 1 while simultaneously introducing 550 Nm³ / hr of high-pressure air. During the coating process, the coating material adheres evenly to the glass substrate 1 in the form of a spray. Exhaust gases generated by the reaction are discharged from the coating area via exhaust systems on both sides of the coating machine, ensuring a clean coating area and continuous reaction. Ultimately, a 109.8nm thick Fe2O3 film 3 is deposited on the glass substrate 1 that has already been coated with the first layer of film. Through a special reaction process and conditions, this film exhibits a vibrant red color and provides excellent sunlight control.

[0035] After the coating is completed, the glass plate enters the normal annealing furnace for annealing. The annealing process is a key link. It can eliminate the stress in 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 precisely controlling the annealing temperature curve and annealing time.

[0036] 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 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, wear resistance testing, etc., it is ensured that the product meets high quality standards. Finally, it is packaged. Special packaging materials are used to package the coated glass to prevent scratches, bumps and other damage during transportation and storage.

[0037] 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 in appearance, with extremely high visual appeal. In terms of performance, it can effectively control the transmission and reflection of sunlight, achieving good energy-saving effects. Moreover, after rigorous film wear resistance, acid resistance and alkali resistance tests, 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 among 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 the company, and provides strong support for product innovation and technological development in the glass industry. Example 2

[0038] In a laboratory environment focused on the research and development of new materials, work is also underway on the preparation of red solar control films on borosilicate flat glass, with the aim of further optimizing process parameters and verifying their feasibility at different scales.

[0039] 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.

[0040] 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 into 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 and exhaust pipes and perform double sealing tests to prevent any gas leakage from affecting the coating effect.

[0041] 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 the pipeline. In the evaporator, the vaporization temperature and time are precisely controlled to fully vaporize the raw materials into gaseous state. Then, they are 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, they are purged for a long time and with high intensity using high-pressure nitrogen to ensure that there are no impurities remaining in the pipeline.

[0042] When using chemical vapor deposition 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 path difference 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.

[0043] When the glass substrate 1 reaches a temperature of 590°C in the front zone of the annealing lehr, the online high-temperature spray coating reactor 7 is activated to apply 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 0.08% by weight of the solution. After mixing, the raw material is ground to a particle size of less than 5 microns using a fine grinder to prepare a high-quality coating material. The material is then sprayed onto the glass substrate 1 at a flow rate of 2.0 liters / minute through a reactor equipped with eight spray guns operating at 11 rpm. Simultaneously, high-pressure air at 600 Nm³ / hr is introduced. During the coating process, the spray gun spray angle and pressure are closely monitored to ensure that the coating material evenly covers the first film layer. Exhaust gases generated by the reaction are rapidly discharged from the coating area via a high-efficiency exhaust system. Ultimately, a 115 nm thick Fe2O3 film 3 is formed on the glass substrate 1, giving the entire coated glass a vibrant and uniform red color and excellent sunlight control capabilities.

[0044] After the coating is completed, the glass plate enters the annealing furnace for precise annealing treatment. Through the advanced temperature control system, annealing is carried out strictly according to the predetermined annealing curve, which effectively eliminates the stress in the film layer and improves the bonding strength and stability between the film layer and the glass substrate 1.

[0045] 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 tests on the optical properties, microstructure, hardness and wear resistance of the film layer.

[0046] After testing, the prepared red sunlight control thin film borosilicate flat glass has good visible light transmittance and good wear resistance. In the wear test simulating long-term use, the mass loss is extremely small. The acid and alkali resistance are also excellent. After soaking in a strong acid and alkali environment for a certain period of time, the film structure remains intact and the performance is stable.

[0047] 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.

[0048] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as illustrative and non-restrictive, and the scope of the invention is defined by the appended claims, not the foregoing description, and all variations within the meaning and scope of the same elements of the claims are intended to be included therein. Any reference sign in a claim should not be construed as limiting the claim to which it relates.

Claims

1. A method for preparing a red solar 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 the front area of an annealing furnace through a transition roller (5); A stainless steel reactor (6) is used to perform the first layer coating operation in the 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) consists of three air inlet chambers and two exhaust chambers. The interior of the stainless steel reactor (6) is composed of an upstream nitrogen gas seal 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 seal air inlet chamber (605) from upstream to downstream. The bottom surface of the stainless steel reactor (6) consists 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), wherein the coating reactor upstream module (608) and the coating reactor downstream module (610) are asymmetrically designed. A 40-50 nm thick SnO2+SiO2 step transition mixed film layer (2) is deposited on the surface of a borosilicate glass substrate (1) using tetraethyl orthosilicate TEOS, triethyl phosphite TEP, monobutyltin trichloride MBTC, methyl isobutyl ketone MIBK, deionized water, nitrogen and air by chemical vapor deposition. 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). ) process, the gradient distribution of the film layer composition is achieved by the asymmetric design of the upstream and downstream modules of the stainless steel reactor (6) and the 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 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 slow, forming a gradient change in the film layer composition; 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 ferric 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, followed by cutting, quality inspection and packaging.

2. The method for preparing a red solar 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 them, vaporizes them at high temperature and then transports the mixed coating gas to the space between the stainless steel reactor and 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 specific 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 with high-pressure nitrogen.

3. The method for preparing a red solar 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.

4. The method for preparing a red solar 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 is heated to 180°C in the mineral oil circulation channel (606) at the bottom of the stainless steel reactor (6) and the thermal cycle is started. After the temperature of the stainless steel reactor (6) stabilizes, it is inserted into the annealing furnace, the height is adjusted to the coating position, the coating air inlet pipe and exhaust pipe are connected, and the surrounding of the stainless steel reactor (6) is sealed.

5. The method for preparing a red solar 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), by controlling the running distance of the coating reaction gas of the stainless steel reactor (6) and the difference in reaction rate, 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 near the side of the glass substrate (1) forms a chemical bond network structure with the silicon dioxide in the glass substrate (1) body. 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 that the atmosphere in the coating area is stable to prevent the coating gas from overflowing. The coating gas moves upstream and downstream in a laminar flow manner, and a chemical vapor deposition reaction occurs on the surface of the hot glass substrate (1) to form a film layer.

6. The method for preparing a red solar 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 solution weight of a surfactant is added, 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.

7. The method for preparing a red solar 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 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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