Tin liquid capable of reducing glass surface strength, preparation method and application thereof

Abstract

The present invention provides a tin solution capable of reducing the surface strength of glass. The solution comprises the following components by weight: 90-99 parts tin powder, 0.5-4 parts stabilizer, 0.1-3 parts antioxidant, and 0.1-3 parts functional additive. The present invention also provides a preparation method and application of the tin solution capable of reducing the surface strength of glass. The tin solution provided by the present invention can reduce the surface strength of glass, thereby lowering the HIC value, without changing the optical properties of the glass.

Description

Technical Field

[0001] The invention relates to a tin liquid, in particular to a tin liquid capable of reducing the surface strength of glass, and a preparation method and application thereof. Background Art

[0002] The car windshield is one of the most important safety components in a vehicle, its primary function being to protect the driver and passengers from external objects. In a collision between a car and a pedestrian, the pedestrian's head is highly susceptible to colliding with the windshield. Therefore, while ensuring the proper quality of the windshield, reducing the HIC value is a key research area in the automotive safety field. Currently, methods for reducing the HIC value of windshields can be employed to modify the thickness, curvature, and strength of the glass. However, these methods present certain challenges, such as compromising the transparency and surface strength of the glass, failing to meet penetration resistance standards, and reducing the glass's service life and safety performance.

[0003] At present, most manufacturers mainly reduce the HIC of automobile windshields through three aspects: (1) Setting up impact absorption areas: Installing impact absorption devices around the windshield can absorb part of the energy during a collision, thereby reducing the degree of head impact; (2) Treating the surface of the automobile windshield: Micro-treating the surface of the glass to form a weakened area on the glass surface, thereby reducing the surface strength of the glass. During a collision, the glass surface becomes more easily broken, thereby reducing the impact intensity on pedestrians; (3) Increasing the energy absorption effect of the connecting material of the automobile windshield: Improving the PVB film and increasing the elastic modulus of the PVB film. When a pedestrian collides with a car, the high-strength and high-modulus PVB film absorbs part of the energy of the pedestrian collision, thereby reducing the impact on the head.

[0004] The existing patents based on the above three technical directions are as follows:

[0005] (1) Patent CN207389137U designs a windshield cover assembly, which is a design with pedestrian protection. This windshield cover assembly includes a front windshield and a windshield water channel, as well as an upper end surface provided with an engine hood sealing strip and an engine hood support section. A constriction portion is provided on the vertical support section of the windshield cover. When colliding with a pedestrian, the constriction portion can alleviate the downward impact force on the pedestrian's head, thereby reducing damage to the pedestrian's head. Verification and analysis have shown that the front windshield cover with a constriction portion can significantly reduce the head HIC value, thereby achieving a protective effect on the pedestrian's head. This patent sets an impact-absorbing area on the vertical support section of the front windshield cover, which alleviates the downward impact force on the pedestrian's head when hitting a pedestrian and improves the protection of the pedestrian's head. However, this patent destroys the integrity and original structural design of the car body when setting the impact-absorbing area near the car's windshield, and reduces the strength of the car body. In addition, when the car is driving on a bumpy road, the parts in the impact-absorbing area may become loose, which not only reduces the service life of the car, but also causes the strength of the car body to be reduced and cannot ensure the safety of pedestrians.

[0006] (2) Patent CN1839059B provides a PVB film for automobile windshields. Laminated glass manufactured by high-pressure lamination using this PVB film can rely on the high-strength and high-modulus PVB film to absorb impact and reduce the impact damage suffered by pedestrians, thereby achieving the purpose of pedestrian protection. This patent uses an improved high-strength and high-modulus PVB film. When a collision occurs between a pedestrian and a car, the laminated glass and the laminated glass intermediate film absorb the impact. From a numerical point of view, the HIC value can be reduced to below 600; however, from the analysis of the actual collision process, the greatest damage to pedestrians is the process from the collision of the pedestrian's head with the first glass of the automobile windshield until it breaks. During this period, the speed and acceleration changes are the greatest, and the impact and damage to the pedestrian are the greatest. Although the use of high-strength and high-modulus PVB film to absorb impact can reduce the damage suffered by pedestrians, it fails to provide effective protection.

[0007] (3) Patent DE202021106914U uses a laser to perform micro-processing on a portion of the surface of the automobile windshield to create surface defects. When the windshield is impacted, the surface defects reduce the impact borne by the surface defects due to the presence of microcracks. Therefore, when a windshield made of this glass is subjected to a large impact, it will break in the surface defect area and then the entire glass will break. The presence of the surface defect reduces the strength of the automobile windshield, achieving the purpose of reducing impact and protecting pedestrians. However, the use of lasers to directly process the curved glass raw sheet has a processing accuracy of micrometers or even nanometers, resulting in a slow processing speed. High-precision processing inevitably requires high-precision processing equipment, which increases production costs and is not conducive to large-scale production. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to provide a tin liquid that can reduce the surface strength of glass, which can reduce the surface strength of glass and thus reduce the HIC value without changing the optical properties of the glass.

[0009] In order to solve the above technical problems, the technical solution of the present invention is:

[0010] A tin solution that can reduce the surface strength of glass is composed of the following components by weight: 90-99 parts of tin powder, 0.5-4 parts of stabilizer, 0.1-3 parts of antioxidant, and 0.1-3 parts of functional additives. The stabilizer is used to adjust the viscosity and density of the tin solution, improve stability, reduce the surface tension of the tin solution, and improve surface smoothness; the antioxidant is used to prevent the tin solution from being oxidized to form Sn. 2+ And tin infiltration into glass affects the surface quality of the glass; functional additives do not react with other components in the tin liquid under high-temperature catalysis to cause the tin liquid to deteriorate, but can exchange ions with the molten glass under high-temperature catalysis to change certain properties of the glass, such as surface strength, transmittance to infrared light, etc.

[0011] The process of a pedestrian colliding with a car's windshield can be divided into four stages: (1) The head contacts the windshield, the speed decreases sharply, and the acceleration increases sharply; (2) The first layer of glass of the windshield is shattered, the speed change amplitude decreases, and the acceleration decreases; (3) The PVB film contacts the head, and the acceleration changes slowly; (4) The glass is completely broken and the speed changes slowly. Among these four stages, the speed change in stage (1) is the largest, and the impact load on the pedestrian's head and the damage to the pedestrian are the largest. In this regard, the present invention reduces the HIC value of the windshield by reducing the strength of the glass sheet, thereby reducing the impact load on the pedestrian in stage (1), and providing the greatest protection for the pedestrian:

[0012] Furthermore, the stabilizer of the present invention is formed by mixing oxides, fluorides and chlorides in a weight ratio of (3-30):(3-42):(3-28).

[0013] Furthermore, the oxide of the present invention is a mixture of one or more of antimony oxide, aluminum oxide, and sodium oxide; the fluoride is one of lithium fluoride, sodium fluoride, ammonium fluoride, aluminum fluoride, and magnesium fluoride; and the chloride is a mixture of one or more of ammonium chloride, ferric chloride, sodium chloride, magnesium chloride, and silver chloride.

[0014] Furthermore, the oxide of the present invention is formed by mixing sodium oxide and aluminum oxide in a weight ratio of (5-45): (3-55), which can effectively adjust the viscosity of the tin liquid and improve the stability of the tin liquid; the fluoride is ammonium fluoride or sodium fluoride, which can reduce the surface tension of the tin liquid, improve the surface smoothness, and help improve the surface quality of the glass; the chloride is formed by mixing sodium chloride and magnesium chloride in a weight ratio of (5-50): (3-50), which can effectively improve the fluidity of the tin liquid and help improve the surface quality of the glass.

[0015] Furthermore, the antioxidant of the present invention is a mixture of one or more of phosphorus, gallium and germanium. These three elements react preferentially with Sn and oxygen, which can effectively reduce Sn. 2+ The production of.

[0016] Furthermore, the functional additive of the present invention is a mixture of one or more of titanium dioxide, cerium dioxide, cerium trioxide, boron nitride, boron carbide, and silicon carbide.

[0017] The functional additives described in the present invention can achieve the purpose of reducing the surface strength of glass in two ways: (1) During the float glass forming stage, the molten glass floats on the tin liquid. Under high-temperature catalysis, the glass and the functional additives in the tin liquid undergo ion exchange. The ions of the functional additives enter the glass, thereby reducing the surface strength of the glass. For example, titanium dioxide can improve the ultraviolet absorption capacity of the glass and promote the formation of crystals, thereby changing the physical properties of the glass and making it more susceptible to damage. In addition, the ions of the functional additives can form a local network with the loosely structured areas, reducing the surface stress to a certain extent. Therefore, by adding an appropriate amount of titanium dioxide to the tin liquid preparation, the titanium ions can enter the molten glass under high-temperature catalysis, making the glass brittle, thereby achieving the purpose of reducing the surface strength of the glass. (2) Some extremely stable substances will neither melt nor produce ion exchange with the glass surface and enter the molten glass surface under high-temperature catalysis. They will gradually precipitate on the glass surface as the glass is formed, forming small stress concentration points everywhere on the glass surface. For example, silicon carbide will be fixed to each other on the glass surface during the preparation process of high-temperature heating to form a sharp softening zone. This area is often prone to glass structure fracture. Due to the special physical properties of silicon carbide, it can accelerate the formation and propagation of fractures, thereby achieving glass weakening treatment and reducing the surface strength of the glass.

[0018] The present invention also provides a method for preparing the above-mentioned tin liquid capable of reducing the surface strength of glass, comprising the following steps:

[0019] S1. Under argon protection, add tin powder into an autoclave and heat it to 900-1100°C to convert the tin powder into gaseous tin;

[0020] S2. The gaseous tin obtained in step S1 is passed into a mixing vessel, and the stabilizer, antioxidant, and functional additive are added to the mixing vessel, heated to 350-500°C and stirred for 1-3h to obtain a mixed solution;

[0021] S3. Cooling the mixed solution obtained in step S2 to 280° C. to obtain a tin solution capable of reducing the surface strength of the glass.

[0022] Furthermore, in step S2 of the present invention, the stirring speed is 200-1000 rad / min.

[0023] The present invention also provides the use of the above-mentioned tin liquid capable of reducing the surface strength of glass in preparing a glass sheet, comprising the following steps:

[0024] (1) Feeding:

[0025] Put silica sand, sandstone, dolomite, limestone, soda ash, sodium sulfate and coal powder into a mixing and screening machine and mix for 2-5 minutes to obtain a mixture. The mixture is then transferred to a silo and then fed into the melting furnace from the silo.

[0026] (2) Melting:

[0027] The melting furnace is heated to 1550-1600℃ to melt the mixture to obtain molten glass. The molten glass is then transferred to a cooling kiln, cooled to 1100-1150℃, and then transferred to a tin bath for molding. The heat source for melting the mixture comes from the flame of the heating furnace in the melting furnace. The flame direction is reversed every 20 minutes to optimize the thermal balance.

[0028] (3) Molding:

[0029] The glass liquid goes through four stages during the forming process:

[0030] The first stage: the glass liquid flows into the tin liquid tank at 1100-1150℃, floats on the tin liquid and spreads naturally;

[0031] The second stage: The glass liquid floating on the surface of the tin liquid shrinks and thickens under the action of surface tension, reducing the surface area. At the same time, it becomes thinner and spreads out under the action of gravity. Under the mutual balance of these two forces, it reaches a stable thickness.

[0032] The third stage: the glass liquid is cooled to 960-1080℃ and kept at this temperature for 70s to obtain a smooth surface;

[0033] The fourth stage: Under the balance of gravity and surface tension, the glass liquid is naturally formed into a 7mm thick glass ribbon on the tin liquid. The glass ribbon is then pulled by a stretching machine at 765-850℃ and a stretching speed of 600m / h to obtain thinned glass, and then cooled to 600℃.

[0034] (4) Annealing:

[0035] The glass obtained in step (3) is transferred to an annealing furnace, and the temperature is reduced from 600° C. to 480° C., and then to 50-80° C. to obtain cooled glass; the glass is gradually cooled in the annealing furnace and internal stress is released to avoid micro cracks caused by cutting;

[0036] (5) Cutting:

[0037] Use a cross-cutting machine and a longitudinal cutting machine to create scratches on the surface of the cooled glass, then set an upper mechanism at the breaking point below the scratch to break it at the scratch by its own weight, and then use a grinding wheel to process the edge, break the surface scratch on the edge of the glass to the required width, and finally obtain the original glass sheet.

[0038] Furthermore, in step (1) of the present invention, by weight, 23-25.2 parts of silica sand, 35.4-39.5 parts of sandstone, 15-18.4 parts of dolomite, 2.3-2.6 parts of limestone, 17-18 parts of soda ash, 1.1-1.6 parts of sodium sulfate, and 0.05-0.13 parts of coal powder are used; the vibration frequency of the mixing screen is 55-75 Hz, and the specification of the screening mesh used in the mixing screen is 57-81 holes / cm 2 .

[0039] Furthermore, in the third stage of step (3) of the present invention, the cooling rate of the glass liquid is 1.4-1.6°C / s.

[0040] Furthermore, in step (3) of the present invention, N is continuously added to the tin liquid tank through the air pressure pipe. 2 and H 2 A mixed gas is used as the protective gas. Tin is easily oxidized into tin oxide and stannous oxide. Tin oxide and stannous oxide will seriously contaminate the glass, causing defects such as tin droplets and fog points on the glass surface. Therefore, the tin liquid tank must be introduced into the protective gas; the pressure at the surface of the tin liquid in the tin liquid tank is 3-5Pa. If the pressure of the tin liquid tank is too high, the balance of the protective gas will be destroyed, which will have an adverse effect on production. If the pressure is too low, external gas will enter, causing oxygen to enter and react with the tin liquid to form tin oxide or stannous oxide. Tin ions can easily enter the glass surface and cause "tin seepage", which will affect the quality of the glass surface.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] 1. This invention does not affect the transparency of glass and is highly scalable. Ion exchange can not only reduce the surface strength of glass, but also enhance it. It is particularly suitable for strengthening ultra-thin glass. Ion exchange treatment does not produce directional optical distortion. For example, in Na2O-Al2O3-SiO2 glass, Li ions can be used instead of Na ions to reduce the thermal expansion coefficient of the glass, forming a compressive stress layer on the surface to enhance surface strength. Furthermore, exchanging different ions can enhance the corrosion resistance of the glass, increase its transmittance to visible light, or increase its transmittance to infrared light.

[0043] 2. The present invention can adjust the surface strength and HIC value of the glass sheet by changing the type and percentage of substances added to the tin solution to meet the needs of different car models and different markets.

[0044] 3. The present invention is simple and easy to implement, has low cost, does not change the original process, does not require additional production equipment, and can be directly mass-produced on the original production line, with almost no impact on the original float glass production line. Therefore, it can rely on mature float glass production equipment for mass production, and the functional additives used are commonly used industrial raw materials with a wide range of sources. DETAILED DESCRIPTION

[0045] The present invention will be described in detail below with reference to specific embodiments. The exemplary embodiments and descriptions of the present invention are used to explain the present invention but are not intended to limit the present invention.

[0046] Example 1

[0047] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 95 parts tin powder, 0.6 parts stabilizer, 2.4 parts phosphorus, and 2 parts cerium dioxide. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 10:20:10; the oxide is a mixture of sodium oxide and aluminum oxide in a weight ratio of 25:25; the fluoride is ammonium fluoride; and the chloride is a mixture of sodium chloride and magnesium chloride in a weight ratio of 25:25.

[0048] The preparation method of the tin liquid capable of reducing the surface strength of glass comprises the following steps:

[0049] S1. Under argon protection, tin powder is added to an autoclave and the temperature is raised to 1000°C to convert the tin powder into gaseous tin;

[0050] S2. The gaseous tin obtained in step S1 is passed into a mixing vessel, and the stabilizer, antioxidant, and functional additive are added to the mixing vessel. The mixture is heated to 400°C and stirred at a speed of 600 rad / min for 2h to obtain a mixed solution.

[0051] S3. Cooling the mixed solution obtained in step S2 to 280° C. to obtain a tin solution capable of reducing the surface strength of the glass.

[0052] The application of the tin liquid for reducing the surface strength of glass in preparing a glass sheet comprises the following steps:

[0053] (1) Feeding:

[0054] Silica sand, sandstone, dolomite, limestone, soda ash, thenardite, and coal powder were put into a mixing and screening machine with a vibration frequency of 65 Hz and mixed for 3 minutes to obtain a mixture. The mixture was transferred to a silo and then fed into a melting furnace from the silo. The mixture consisted of 24 parts of silica sand, 38 parts of sandstone, 16.5 parts of dolomite, 2.4 parts of limestone, 17.5 parts of soda ash, 1.3 parts of thenardite, and 0.09 parts of coal powder in parts by weight. The sieve mesh used in the mixing and screening machine had a specification of 70 holes / cm. 2 ;

[0055] (2) Melting:

[0056] The melting furnace is heated to 1580℃ to melt the mixture to obtain molten glass, which is then fed into a cooling kiln and cooled to 1120℃ before being fed into a tin bath for molding.

[0057] (3) Molding:

[0058] The glass liquid goes through four stages during the forming process:

[0059] The first stage: The glass liquid flows into the tin liquid tank at 1120℃, floats on the tin liquid and spreads naturally, and the tin liquid tank is continuously replenished with N through the air pressure pipe. 2 and H 2 The mixed gas is used as the protective gas, and the pressure at the surface of the tin liquid in the tin liquid tank is 4Pa;

[0060] The second stage: The glass liquid floating on the surface of the tin liquid shrinks and thickens under the action of surface tension, reducing the surface area. At the same time, it becomes thinner and spreads out under the action of gravity. Under the mutual balance of these two forces, it reaches a stable thickness.

[0061] The third stage: the glass liquid is cooled to 1000℃ at a cooling rate of 1.5℃ / s and kept at this temperature for 70s to obtain a smooth surface.

[0062] The fourth stage: Under the balance of gravity and surface tension, the glass liquid is naturally formed into a 7mm thick glass ribbon on the tin liquid. The glass ribbon is then pulled by a stretching machine at 850℃ and a stretching speed of 600m / h to obtain thinned glass, and then cooled to 600℃.

[0063] (4) Annealing:

[0064] The glass obtained in step (3) is transferred to an annealing furnace, and the temperature is reduced from 600° C. to 480° C., and then to 60° C. to obtain cooled glass; the glass is gradually cooled in the annealing furnace and internal stress is released to avoid microcracks caused by cutting;

[0065] (5) Cutting:

[0066] Use a cross-cutting machine and a longitudinal cutting machine to create scratches on the surface of the cooled glass, then set an upper mechanism at the breaking point below the scratch to break it at the scratch by its own weight, and then use a grinding wheel to process the edge, break the surface scratch on the edge of the glass to the required width, and finally obtain the original glass sheet.

[0067] Example 2

[0068] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 97 parts tin powder, 1 part stabilizer, 1 part phosphorus, and 1 part cerium oxide. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 20:10:20; the oxide is a mixture of sodium oxide and aluminum oxide in a weight ratio of 5:5; the fluoride is ammonium fluoride; and the chloride is a mixture of sodium chloride and magnesium chloride in a weight ratio of 5:5.

[0069] The preparation method and application of the tin liquid capable of reducing the surface strength of glass described in Example 2 are the same as those in Example 1.

[0070] Example 3

[0071] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 99 parts tin powder, 0.6 parts stabilizer, 0.2 parts gallium, and 0.2 parts boron carbide. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 30:10:20; the oxide is a mixture of sodium oxide and aluminum oxide in a weight ratio of 45:45; the fluoride is ammonium fluoride; and the chloride is a mixture of sodium chloride and magnesium chloride in a weight ratio of 50:50.

[0072] The preparation method and application of the tin liquid capable of reducing the surface strength of glass described in Example 3 are the same as those in Example 1.

[0073] Example 4

[0074] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 99 parts tin powder, 0.6 parts stabilizer, 0.15 parts germanium, 0.1 parts gallium, and 0.15 parts titanium dioxide. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 14:4:6; the oxide is a mixture of sodium oxide and aluminum oxide in a weight ratio of 45:30; the fluoride is ammonium fluoride; and the chloride is a mixture of sodium chloride and magnesium chloride in a weight ratio of 15:15.

[0075] The preparation method and application of the tin liquid capable of reducing the surface strength of glass described in Example 4 are the same as those in Example 1.

[0076] Example 5

[0077] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 98 parts tin powder, 1 part stabilizer, 0.25 parts germanium, 0.25 parts gallium, and 0.5 parts titanium dioxide. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 10:4:6; the oxide is a mixture of sodium oxide and aluminum oxide in a weight ratio of 5:5; the fluoride is ammonium fluoride; and the chloride is a mixture of sodium chloride and magnesium chloride in a weight ratio of 5:5.

[0078] The preparation method and application of the tin liquid capable of reducing the surface strength of glass described in Example 5 are the same as those in Example 1.

[0079] Performance Testing

[0080] The test method refers to GB / T9656-2021. The glass sheets obtained in Examples 1-5 were laminated to obtain laminated glass, and then a human head simulation experiment was conducted. The experimental data are shown in Table 1:

[0081]

[0082]

[0083] Table 1

[0084] As shown in Table 1, when the amount of tin powder is reduced and the amount of thermal stabilizer, antioxidant, and functional additive is increased, as shown in Examples 1 and 2, the HIC value is reduced due to severe damage to the surface microstructure of the original glass sheet, but the flexural modulus strength required for protecting vehicle occupants is also significantly reduced. Furthermore, compared with Examples 1 and 2, Examples 3, 4, and 5 increase the amount of tin powder and reduce the amount of antioxidant and functional additive, and the HIC value is significantly reduced without significantly reducing the flexural modulus strength.

[0085] Example 6

[0086] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 90 parts tin powder, 4 parts stabilizer, 3 parts phosphorus, and 3 parts boron nitride. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 30:42:28; the oxide is a mixture of antimony oxide and aluminum oxide in a weight ratio of 45:55; the fluoride is lithium fluoride; and the chloride is a mixture of sodium chloride and ammonium chloride in a weight ratio of 47:3.

[0087] The preparation method of the tin liquid capable of reducing the surface strength of glass comprises the following steps:

[0088] S1. Under argon protection, tin powder is added to an autoclave and the temperature is raised to 1100°C to convert the tin powder into gaseous tin;

[0089] S2. The gaseous tin obtained in step S1 is passed into a mixing vessel, and the stabilizer, antioxidant, and functional additive are added to the mixing vessel. The mixture is heated to 500°C and stirred at a speed of 200 rad / min for 1h to obtain a mixed solution.

[0090] S3. Cooling the mixed solution obtained in step S2 to 280° C. to obtain a tin solution capable of reducing the surface strength of the glass.

[0091] The application of the tin liquid for reducing the surface strength of glass in preparing a glass sheet comprises the following steps:

[0092] (1) Feeding:

[0093] Silica sand, sandstone, dolomite, limestone, soda ash, thenardite, and coal powder were put into a mixing and screening machine with a vibration frequency of 55 Hz and mixed for 5 minutes to obtain a mixture. The mixture was transferred to a silo and then fed into a melting furnace. The mixture consisted of 23 parts of silica sand, 35.4 parts of sandstone, 15 parts of dolomite, 2.6 parts of limestone, 17 parts of soda ash, 1.1 parts of thenardite, and 0.05 parts of coal powder in parts by weight. The sieve mesh used in the mixing and screening machine had a specification of 81 holes / cm 2 ;

[0094] (2) Melting:

[0095] The melting furnace is heated to 1550℃ to melt the mixture to obtain molten glass, which is then fed into a cooling kiln and cooled to 1100℃ before being fed into a tin bath for molding.

[0096] (3) Molding:

[0097] The glass liquid goes through four stages during the forming process:

[0098] The first stage: The glass liquid flows into the tin liquid tank at 1100℃, floats on the tin liquid and spreads naturally, and the tin liquid tank is continuously replenished with N through the air pressure pipe. 2 and H 2 The mixed gas is used as the protective gas, and the pressure at the surface of the tin liquid in the tin liquid tank is 3Pa;

[0099] The second stage: The glass liquid floating on the surface of the tin liquid shrinks and thickens under the action of surface tension, reducing the surface area. At the same time, it becomes thinner and spreads out under the action of gravity. Under the mutual balance of these two forces, it reaches a stable thickness.

[0100] The third stage: the glass liquid is cooled to 960℃ at a cooling rate of 1.4℃ / s and kept at this temperature for 70s to obtain a smooth surface.

[0101] The fourth stage: Under the balance of gravity and surface tension, the glass liquid naturally forms into a 7mm thick glass ribbon on the tin liquid. The glass ribbon is then pulled by a stretching machine at 765℃ and a stretching speed of 600m / h to obtain thinned glass, and then cooled to 600℃.

[0102] (4) Annealing:

[0103] The glass obtained in step (3) is transferred to an annealing furnace, and the temperature is reduced from 600° C. to 480° C., and then to 50° C. to obtain cooled glass; the glass is gradually cooled in the annealing furnace and internal stress is released to avoid microcracks caused by cutting;

[0104] (5) Cutting:

[0105] Use a cross-cutting machine and a longitudinal cutting machine to create scratches on the surface of the cooled glass, then set an upper mechanism at the breaking point below the scratch to break it at the scratch by its own weight, and then use a grinding wheel to process the edge, break the surface scratch on the edge of the glass to the required width, and finally obtain the original glass sheet.

[0106] Example 7

[0107] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 94 parts tin powder, 3 parts stabilizer, 2 parts gallium, and 1 part silicon carbide. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 3:3:3; the oxide is a mixture of sodium oxide and antimony oxide in a weight ratio of 7:3; the fluoride is aluminum fluoride; and the chloride is a mixture of sodium chloride and ferric chloride in a weight ratio of 30:20.

[0108] The preparation method of the tin liquid capable of reducing the surface strength of glass comprises the following steps:

[0109] S1. Under argon protection, tin powder is added to an autoclave and the temperature is raised to 900°C to convert the tin powder into gaseous tin;

[0110] S2. The gaseous tin obtained in step S1 is passed into a mixing vessel, and the stabilizer, antioxidant, and functional additive are added to the mixing vessel. The mixture is heated to 350°C and stirred at a speed of 1000rad / min for 3h to obtain a mixed solution.

[0111] S3. Cooling the mixed solution obtained in step S2 to 280° C. to obtain a tin solution capable of reducing the surface strength of the glass.

[0112] The application of the tin liquid for reducing the surface strength of glass in preparing a glass sheet comprises the following steps:

[0113] (1) Feeding:

[0114] Silica sand, sandstone, dolomite, limestone, soda ash, sodium sulfate, and coal powder were put into a mixing and screening machine with a vibration frequency of 75 Hz and mixed for 2 minutes to obtain a mixture. The mixture was transferred to a silo and then fed into a melting furnace. The mixture consisted of 25.2 parts of silica sand, 39.5 parts of sandstone, 18.4 parts of dolomite, 2.3 parts of limestone, 18 parts of soda ash, 1.6 parts of sodium sulfate, and 0.13 parts of coal powder in parts by weight. The sieve mesh used in the mixing and screening machine had a specification of 57 holes / cm. 2 ;

[0115] (2) Melting:

[0116] The melting furnace is heated to 1600℃ to melt the mixture to obtain molten glass, which is then fed into a cooling kiln and cooled to 1150℃ before being fed into a tin bath for molding.

[0117] (3) Molding:

[0118] The glass liquid goes through four stages during the forming process:

[0119] The first stage: The glass liquid flows into the tin liquid tank at 1150℃, floats on the tin liquid and spreads naturally, and the tin liquid tank is continuously replenished with N through the air pressure pipe. 2 and H 2 The mixed gas is used as the protective gas, and the pressure at the surface of the tin liquid in the tin liquid tank is 5Pa;

[0120] The second stage: The glass liquid floating on the surface of the tin liquid shrinks and thickens under the action of surface tension, reducing the surface area. At the same time, it becomes thinner and spreads out under the action of gravity. Under the mutual balance of these two forces, it reaches a stable thickness.

[0121] The third stage: the glass liquid is cooled to 990℃ at a cooling rate of 1.6℃ / s and kept at this temperature for 70s to obtain a smooth surface.

[0122] The fourth stage: Under the balance of gravity and surface tension, the glass liquid is naturally formed into a 7mm thick glass ribbon on the tin liquid. The glass ribbon is then pulled by a stretching machine at 800℃ and a stretching speed of 600m / h to obtain thinned glass, and then cooled to 600℃.

[0123] (4) Annealing:

[0124] The glass obtained in step (3) is transferred to an annealing furnace, and the temperature is reduced from 600° C. to 480° C., and then to 80° C. to obtain cooled glass; the glass is gradually cooled in the annealing furnace and internal stress is released to avoid microcracks caused by cutting;

[0125] (5) Cutting:

[0126] Use a cross-cutting machine and a longitudinal cutting machine to create scratches on the surface of the cooled glass, then set an upper mechanism at the breaking point below the scratch to break it at the scratch by its own weight, and then use a grinding wheel to process the edge, break the surface scratch on the edge of the glass to the required width, and finally obtain the original glass sheet.

[0127] Example 8

[0128] A tin solution capable of reducing the surface strength of glass comprises the following components by weight: 96 parts tin powder, 2 parts stabilizer, 1 part germanium, and 1 part cerium dioxide. The stabilizer is a mixture of oxide, fluoride, and chloride in a weight ratio of 4:6:10; the oxide is a mixture of antimony oxide and aluminum oxide in a weight ratio of 15:25; the fluoride is magnesium fluoride; and the chloride is a mixture of sodium chloride and silver chloride in a weight ratio of 25:25.

[0129] The preparation method of the tin liquid capable of reducing the surface strength of glass comprises the following steps:

[0130] S1. Under argon protection, tin powder is added to an autoclave and the temperature is raised to 950°C to convert the tin powder into gaseous tin;

[0131] S2. The gaseous tin obtained in step S1 is passed into a mixing vessel, and the stabilizer, antioxidant, and functional additive are added to the mixing vessel. The mixture is heated to 400°C and stirred at a speed of 800rad / min for 2.5h to obtain a mixed solution.

[0132] S3. Cooling the mixed solution obtained in step S2 to 280° C. to obtain a tin solution capable of reducing the surface strength of the glass.

[0133] The application of the tin liquid for reducing the surface strength of glass in preparing a glass sheet comprises the following steps:

[0134] (1) Feeding:

[0135] Silica sand, sandstone, dolomite, limestone, soda ash, thenardite, and coal powder were put into a mixing and screening machine with a vibration frequency of 60 Hz and mixed for 4 minutes to obtain a mixture. The mixture was transferred to a silo and then fed into a melting furnace from the silo. The mixture consisted of 23.5 parts of silica sand, 38 parts of sandstone, 16 parts of dolomite, 2.5 parts of limestone, 18 parts of soda ash, 1.2 parts of thenardite, and 0.1 parts of coal powder in parts by weight. The sieve mesh used in the mixing and screening machine had a specification of 80 holes / cm 2 ;

[0136] (2) Melting:

[0137] The melting furnace is heated to 1560℃ to melt the mixture to obtain molten glass, which is then fed into a cooling kiln and cooled to 1140℃ before being fed into a tin bath for molding.

[0138] (3) Molding:

[0139] The glass liquid goes through four stages during the forming process:

[0140] The first stage: The glass liquid flows into the tin liquid tank at 1140℃, floats on the tin liquid and spreads naturally, and the tin liquid tank is continuously replenished with N through the air pressure pipe. 2 and H 2 The mixed gas is used as the protective gas, and the pressure at the surface of the tin liquid in the tin liquid tank is 4Pa;

[0141] The second stage: The glass liquid floating on the surface of the tin liquid shrinks and thickens under the action of surface tension, reducing the surface area. At the same time, it becomes thinner and spreads out under the action of gravity. Under the mutual balance of these two forces, it reaches a stable thickness.

[0142] The third stage: the glass liquid is cooled to 1080℃ at a cooling rate of 1.5℃ / s and kept at this temperature for 70s to obtain a smooth surface.

[0143] The fourth stage: Under the balance of gravity and surface tension, the glass liquid is naturally formed into a 7mm thick glass ribbon on the tin liquid. The glass ribbon is then pulled by a stretching machine at 840℃ and a stretching speed of 600m / h to obtain thinned glass, and then cooled to 600℃.

[0144] (4) Annealing:

[0145] The glass obtained in step (3) is transferred to an annealing furnace, and the temperature is reduced from 600° C. to 480° C., and then to 70° C. to obtain cooled glass; the glass is gradually cooled in the annealing furnace and internal stress is released to avoid microcracks caused by cutting;

[0146] (5) Cutting:

[0147] Use a cross-cutting machine and a longitudinal cutting machine to create scratches on the surface of the cooled glass, then set an upper mechanism at the breaking point below the scratch to break it at the scratch by its own weight, and then use a grinding wheel to process the edge, break the surface scratch on the edge of the glass to the required width, and finally obtain the original glass sheet.

[0148] The above descriptions are merely embodiments of the present invention and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. A tin solution capable of reducing the surface strength of glass, characterized in that: The invention is composed of the following components in parts by weight: 90-99 parts of tin powder, 0.5-4 parts of a stabilizer, 0.1-3 parts of an antioxidant, and 0.1-3 parts of a functional additive; the stabilizer is a mixture of oxides, fluorides, and chlorides in a weight ratio of (3-30):(3-42):(3-28), the oxides are a mixture of one or more of antimony oxide, aluminum oxide, and sodium oxide, the fluorides are one of lithium fluoride, sodium fluoride, ammonium fluoride, aluminum fluoride, and magnesium fluoride, and the chlorides are a mixture of one or more of ammonium chloride, ferric chloride, sodium chloride, magnesium chloride, and silver chloride; and the functional additives are a mixture of one or more of titanium dioxide, cerium dioxide, cerium trioxide, boron nitride, boron carbide, and silicon carbide.

2. The tin liquid capable of reducing the surface strength of glass according to claim 1, characterized in that: The oxide is formed by mixing sodium oxide and aluminum oxide in a weight ratio of (5-45): (3-55); the fluoride is ammonium fluoride or sodium fluoride; and the chloride is formed by mixing sodium chloride and magnesium chloride in a weight ratio of (5-50): (3-50).

3. The tin liquid capable of reducing the surface strength of glass according to claim 1, characterized in that: The antioxidant is a mixture of one or more of phosphorus, gallium and germanium.

4. The method for preparing a tin liquid capable of reducing the surface strength of glass according to any one of claims 1 to 3, characterized in that: The following steps are involved: S1. Under argon protection, add tin powder into an autoclave and heat it to 900-1100°C to convert the tin powder into gaseous tin; S2. The gaseous tin obtained in step S1 is passed into a mixing vessel, and the stabilizer, antioxidant, and functional additive are added to the mixing vessel, heated to 350-500°C and stirred for 1-3h to obtain a mixed solution; S3. Cooling the mixed solution obtained in step S2 to 280° C. to obtain a tin solution capable of reducing the surface strength of the glass.

5. The method for preparing a tin liquid capable of reducing the surface strength of glass according to claim 4, characterized in that: In step S2, the stirring speed is 200-1000 rad / min.

6. Use of the tin liquid capable of reducing the surface strength of glass according to any one of claims 1 to 3 in preparing a glass blank, characterized in that: The following steps are involved: (1) Feeding: Put silica sand, sandstone, dolomite, limestone, soda ash, sodium sulfate and coal powder into a mixing and screening machine and mix for 2-5 minutes to obtain a mixture. The mixture is then transferred to a silo and then fed into the melting furnace from the silo. (2) Melting: The melting furnace is heated to 1550-1600℃ to melt the mixture to obtain molten glass, which is then fed into a cooling kiln and cooled to 1100-1150℃ before being fed into a tin bath for molding. (3) Molding: The glass liquid goes through four stages during the forming process: The first stage: the glass liquid flows into the tin liquid tank at 1100-1150℃, floats on the tin liquid and spreads naturally; The second stage: The glass liquid floating on the surface of the tin liquid shrinks and thickens under the action of surface tension, reducing the surface area. At the same time, it becomes thinner and spreads out under the action of gravity. Under the mutual balance of these two forces, it reaches a stable thickness. The third stage: the glass liquid is cooled to 960-1080℃ and kept at this temperature for 70s to obtain a smooth surface; The fourth stage: Under the balance of gravity and surface tension, the glass liquid is naturally formed into a 7mm thick glass ribbon on the tin liquid. The glass ribbon is then pulled by a stretching machine at 765-850℃ and a stretching speed of 600m / h to obtain thinned glass, and then cooled to 600℃. (4) Annealing: The glass obtained in step (3) is transferred to an annealing furnace, and the temperature is reduced from 600°C to 480°C, and then to 50-80°C to obtain cooled glass; (5) Cutting: Use a cross-cutting machine and a longitudinal cutting machine to create scratches on the surface of the cooled glass, then set an upper mechanism at the breaking point below the scratch to break it at the scratch by its own weight, and then use a grinding wheel to process the edge, break the surface scratch on the edge of the glass to the required width, and finally obtain the original glass sheet.

7. The use according to claim 6, characterized in that: In the step (1), by weight, 23-25.2 parts of silica sand, 35.4-39.5 parts of sandstone, 15-18.4 parts of dolomite, 2.3-2.6 parts of limestone, 17-18 parts of soda ash, 1.1-1.6 parts of sodium sulfate, and 0.05-0.13 parts of coal powder are used; the vibration frequency of the mixing screen is 55-75 Hz, and the specification of the screening mesh used in the mixing screen is 57-81 holes / cm².

8. The use according to claim 6, characterized in that: In the third stage of step (3), the cooling rate of the glass liquid is 1.4-1.6°C / s.

9. The use according to claim 6, characterized in that: In the step (3), a mixed gas of N2 and H2 is continuously added to the tin liquid tank through an air pressure pipe as a protective gas; the pressure at the surface of the tin liquid in the tin liquid tank is 3-5Pa.

Images