Preparation method of conductive glass

Abstract

The invention provides a preparation method of conductive glass, which comprises the following steps: S1) mixing silica sand, feldspar, limestone, dolomite and sodium carbonate, and melting at high temperature to obtain molten glass; mixing a nano conductive material with a solvent to obtain a conductive solution; s2) molding the molten glass, and spraying the conductive solution to the surface and / or the interior of the molten glass in a pressurized manner in the molding process to obtain a conductive glass ribbon; and S3) annealing the conductive glass tape to obtain the conductive glass. The invention also provides a preparation method of the conductive glass. The invention provides a preparation method of conductive glass, which comprises the following steps: pumping a conductive solution into molten glass by a pressurized spraying method in a float glass melting and forming process, and curing together in the glass forming process to obtain the conductive glass. The method is simple in process and low in cost, and the conductivity and the stability of the conductive glass can be remarkably improved.

Description

Technical Field

[0001] The present invention relates to the technical field of glass preparation, and in particular to a method for preparing conductive glass. Background Art

[0002] Float glass is a widely used type of glass. It is generally made from raw materials such as sea sand, quartz sandstone powder, soda ash, and dolomite. After being melted at high temperatures in a melting furnace, the resulting molten glass flows continuously from the furnace and floats on the surface of the molten metal. It is spread into a glass ribbon with uniform thickness and is flame-polished. After cooling and hardening, it is separated from the molten metal and then annealed and cut into transparent, colorless flat glass. Float glass has the advantages of good flatness, uniform thickness, and flat and parallel upper and lower surfaces, making it suitable for a variety of applications. However, traditional float glass does not have electrical conductivity, which limits its application in certain specific fields (such as electronic displays and solar cells).

[0003] To address the non-conductivity of float glass, researchers have attempted to create conductive glass by adding conductive materials to the surface or interior of the glass. However, the preparation of conductive glass often presents complex processes, high costs, and, in particular, unstable conductivity. Therefore, developing a simple, efficient, and low-cost method for preparing conductive glass is of great significance. Summary of the Invention

[0004] The technical problem solved by the present invention is to provide a method for preparing conductive glass. The preparation method provided in this application can improve the conductivity and stability of conductive glass.

[0005] In view of this, the present application provides a method for preparing conductive glass, comprising the following steps:

[0006] S1) mixing silica sand, feldspar, limestone, dolomite and soda ash, and melting them at high temperature to obtain glass liquid;

[0007] mixing the nano-conductive material and the solvent to obtain a conductive solution;

[0008] S2) forming the glass liquid, and during the forming process, spraying the conductive solution under pressure onto the surface and / or inside of the glass liquid to obtain a conductive glass ribbon;

[0009] S3) annealing the conductive glass ribbon to obtain conductive glass.

[0010] In some specific embodiments, the conductive glass ribbon is prepared as follows:

[0011] The glass liquid is placed in a tin bath to obtain a conductive glass ribbon with smooth and parallel surfaces on both sides.

[0012] In some specific embodiments, in step S1), the nano-conductive material includes one or more of carbon nanotubes, silver nanowires, carbon black, graphene, copper nanowires, black phosphorus, and graphyne;

[0013] And / or, the solvent includes one or more of ethanol, water, ethylene glycol, propanol and methanol.

[0014] In some specific embodiments, in step S1), the particle size of the nano-conductive material is 1 to 10 nm;

[0015] And / or, the concentration of the nano-conductive material in the conductive solution is 1-10 mg / ml.

[0016] In some specific embodiments, in step S1), the conductive solution is prepared by:

[0017] The nano-conductive material and the solvent are subjected to a first ultrasonic treatment, centrifuged and then subjected to a second ultrasonic treatment to obtain a conductive solution.

[0018] In some specific embodiments, the first ultrasonic treatment time is 15 to 25 minutes, the centrifugal speed is 2000 to 5000 rpm, the centrifugal time is 2 to 5 minutes, and the second ultrasonic treatment time is 15 to 25 minutes.

[0019] In some specific embodiments, in step S1), based on the total mass of silica sand, feldspar, limestone, dolomite and soda ash, the content of the silica sand is 55-70wt%, the content of the feldspar is 10-18wt%, the content of the limestone is 3-8wt%, the content of the dolomite is 6-12wt%, and the content of the soda ash is 10-25wt%.

[0020] In some specific embodiments, the high-temperature melting temperature is 1500-1800°C, and the temperature of the glass liquid is reduced from 1200-1500°C to 600-800°C during the forming process.

[0021] In some specific embodiments, the pressure spraying is 50-100 MPa, the spraying speed is 2-10 cm / s, and the spraying amount is 0.2-1.0 mg / cm 2 .

[0022] The present application also provides a method for preparing conductive glass, comprising the following steps:

[0023] S1) mixing silica sand, feldspar, limestone, dolomite and soda ash, and melting them at high temperature to obtain glass liquid;

[0024] mixing the nano-conductive material and the solvent to obtain a conductive solution;

[0025] S2) spraying the conductive solution onto the surface and / or interior of the glass liquid under pressure to obtain a conductive glass ribbon;

[0026] S3) annealing the conductive glass ribbon to obtain conductive glass.

[0027] The present application provides a method for preparing conductive glass, which comprises first mixing silica sand, feldspar, limestone, dolomite and soda ash, and melting them at high temperature to obtain a glass liquid, and then mixing a nano-conductive material and a solvent to obtain a conductive solution, and then molding the glass liquid. During the molding process, the conductive solution is sprayed under pressure onto the surface and / or the interior of the glass liquid to obtain a conductive glass ribbon, and finally, the conductive glass ribbon is annealed to obtain the conductive glass. During the preparation of the conductive glass, the present application sprays the conductive solution onto the surface and / or the interior of the glass liquid during the molding process by pressurized spraying, thereby effectively ensuring the uniform distribution of the nano-conductive material in the glass, thereby improving the conductivity and stability of the conductive glass.

[0028] Furthermore, during the preparation of the conductive solution, the nano-conductive material and the solvent are sequentially subjected to a first ultrasonic treatment, centrifugation, and a second ultrasonic treatment, so that the nano-conductive material is uniformly dispersed in the solvent without agglomeration, thereby facilitating the uniform distribution of the nano-conductive material in the glass.

[0029] Furthermore, the present application adjusts the pressure, speed and spraying amount of pressurized spraying, which is more conducive to the uniform distribution of nano-conductive materials in the glass, thereby further improving the conductivity and stability of the conductive glass. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 Schematic diagram of the process for preparing the conductive glass of the present invention. DETAILED DESCRIPTION

[0031] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

[0032] In view of the problems of complex process, high cost and unstable conductive performance of conductive glass in the prior art, the present application provides a method for preparing conductive glass, which adopts a pressurized spraying method to spray nano-conductive materials onto the surface and / or inside of the glass liquid, so that the nano-conductive materials are evenly distributed in the obtained conductive glass, thereby improving the conductivity and stability of the conductive glass. Specifically, the embodiment of the present invention discloses a method for preparing conductive glass, and the flow diagram is shown as follows: Figure 1 As shown, the specific steps include:

[0033] S1) mixing silica sand, feldspar, limestone, dolomite and soda ash, and melting them at high temperature to obtain glass liquid;

[0034] mixing the nano-conductive material and the solvent to obtain a conductive solution;

[0035] S2) forming the glass liquid, and during the forming process, spraying the conductive solution under pressure onto the surface and / or inside of the glass liquid to obtain a conductive glass ribbon;

[0036] S3) annealing the conductive glass ribbon to obtain conductive glass.

[0037] In the preparation process of conductive glass, the present application first prepares raw materials, specifically: silica sand, feldspar, limestone, dolomite and soda ash are mixed and melted at high temperature to obtain glass liquid, and at the same time, nano-conductive material and solvent are mixed to obtain conductive solution; in the preparation process of the above-mentioned glass liquid, the silica sand provides SiO2, the feldspar provides Al2O3, the limestone provides CaO, the dolomite provides MgO, and the soda ash provides Na2O; the silica sand, the feldspar, the limestone, the dolomite and the soda ash are raw materials well known to those skilled in the art, and this application does not elaborate on them. Special restrictions: In this application, based on the total weight of the silica sand, feldspar, limestone, dolomite, and soda ash, the silica sand content is 55-70wt%, the feldspar content is 10-18wt%, the limestone content is 3-8wt%, the dolomite content is 6-12wt%, and the soda ash content is 10-25wt%. Specifically, the silica sand content is 67wt%, the feldspar content is 15wt%, the limestone content is 6wt%, the dolomite content is 10wt%, and the soda ash content is 2wt%. After the silica sand, feldspar, limestone, dolomite, and soda ash are uniformly mixed, they are preferably melted in a melting furnace at a high temperature of 1500-1800°C, specifically 1600-1700°C. In the preparation process of the conductive solution, the nanoconductive material includes one or more of carbon nanotubes, silver nanowires, carbon black, graphene, copper nanowires, black phosphorus, and graphyne. Specifically, the nanoconductive material is selected from one or more of carbon nanotubes, silver nanowires, carbon black, graphene, copper nanowires, black phosphorus, and graphyne. More specifically, the nanoconductive material is selected from carbon nanotubes, silver nanowires, carbon black, graphene, copper nanowires, black phosphorus, and graphyne. The solvent includes one or more of ethanol, water, ethylene glycol, propanol, and methanol. Specifically, the solvent is selected from one or more of ethanol, water, ethylene glycol, propanol, and methanol. More specifically, the solvent is selected from ethanol, water, ethylene glycol, propanol, or methanol. To ensure that the nanoconductive material is uniformly dispersed in the solvent and does not agglomerate, the concentration of the nanoconductive material in the conductive solution is 1 to 10 mg / ml. Specifically, the concentration of the nanoconductive material in the conductive solution is 2 to 5 mg / ml. More specifically, the concentration of the nanoconductive material in the conductive solution is 3 to 4 mg / ml.The particle size of the nano-conductive material is 1 to 10 nm, specifically, the particle size of the nano-conductive material is 2 to 7 nm, and further, the particle size of the nano-conductive material is 3 to 6 nm; the particle size of the nano-conductive material is relatively small, and if a large amount of it is added to the solvent, it will agglomerate in the solution, affecting the preparation of the conductive glass; in view of this, the preparation of the conductive solution described in the present application is preferably obtained by sequentially performing a first ultrasonic treatment, centrifugation, and a second ultrasonic treatment, so as to facilitate the uniform dispersion of the nano-conductive material in the solvent without agglomeration. The first ultrasonic treatment lasts for 15 to 25 minutes, specifically, 16 to 23 minutes, and more specifically, 20 to 22 minutes. The centrifugal speed is 2000 to 5000 rpm, and the centrifugal time is 2 to 5 minutes, specifically, 3000 to 4000 rpm, and the centrifugal time is 3 to 4 minutes. The second ultrasonic treatment lasts for 15 to 25 minutes, specifically, 18 to 23 minutes, and more specifically, 20 to 22 minutes. The conductive solution is prepared in an atmospheric environment without requiring a special environmental atmosphere.

[0038] The present application then shapes the glass liquid, and during the shaping process, the conductive solution is pressurized and sprayed onto the surface and / or interior of the glass liquid to obtain a conductive glass ribbon; in the above process, during the shaping of the glass liquid, the conductive solution is evenly sprayed onto the surface and / or interior of the semi-formed glass ribbon by a pressurized spraying device, and the pressurized spraying device includes a nozzle and a pressurizing device, the nozzle is arranged above or below the semi-formed glass ribbon, and the pressurizing device is used to spray the conductive solution onto the surface and / or interior of the semi-formed glass ribbon at a certain pressure and speed; the semi-formed glass ribbon indicates that the glass liquid is not completely solidified and is in a partially melted and partially solidified state. The conductive glass ribbon preferably flows the glass liquid into a tin bath, and under the action of its own gravity and surface tension, it spreads out into a double-sided flat parallel continuous glass ribbon that moves slowly forward. The spraying pressure of the pressurized spraying is 50-100 MPa, the spraying speed is 2-10 cm / s, and the spraying amount is 0.2-1.0 mg / cm 2 Specifically, the pressure spraying pressure is 60-90 MPa, the spraying speed is 3-8 cm / s, and the spraying amount is 0.4-0.8 mg / cm 2 More specifically, the pressure spraying pressure is 70-80 MPa, the spraying speed is 4-6 cm / s, and the spraying amount is 0.5-0.6 mg / cm 2. In the process of pressurized spraying mentioned above, the content of nano-conductive material in the glass ribbon is controlled by adjusting the spraying amount, thereby affecting the conductivity of the conductive glass; the distribution uniformity of the conductive solution on the glass ribbon is controlled by adjusting the spraying speed, and too fast a speed may cause uneven distribution of the nano-conductive material, thereby affecting the conductive performance; the spraying pressure determines whether the conductive solution can effectively penetrate into the interior of the glass ribbon or evenly adhere to the surface, which has an important influence on the distribution and conductive performance of the nano-conductive material. The present application can achieve uniform distribution of nano-conductive materials in the glass ribbon by precisely controlling the spraying amount, spraying speed, and spraying pressure, thereby improving the conductive performance and stability of the conductive glass.

[0039] Finally, the conductive glass ribbon is annealed to obtain conductive glass. The annealing is performed to gradually cool and solidify the conductive glass ribbon, and at the same time, the nano-conductive material is also completely solidified along with the glass liquid to form conductive glass.

[0040] The present application also provides a method for preparing conductive glass, comprising the following steps:

[0041] S1) mixing silica sand, feldspar, limestone, dolomite and soda ash, and melting them at high temperature to obtain glass liquid;

[0042] mixing the nano-conductive material and the solvent to obtain a conductive solution;

[0043] S2) spraying the conductive solution onto the surface and / or interior of the glass liquid under pressure to obtain a conductive glass ribbon;

[0044] S3) annealing the conductive glass ribbon to obtain conductive glass.

[0045] The preparation method of the conductive glass is almost the same as the preparation method of the conductive glass described above, except that the conductive solution is directly sprayed on the surface and / or inside of the completely molten glass liquid under pressure, and then annealed and solidified to obtain the conductive glass.

[0046] This application provides a method for preparing conductive glass. During the float glass melt forming process, a conductive solution is injected into the molten glass via pressure spraying, which solidifies during the glass forming process to form the conductive glass. This method is not only simple and cost-effective, but also significantly improves the conductive properties and stability of the conductive glass. Furthermore, by precisely controlling the relevant parameters of the pressure spraying, the present application can achieve uniform distribution of the nano-conductive material in the glass, thereby improving the conductive properties and stability of the conductive glass. The conductive glass prepared by this application has broad market prospects for use in a variety of fields, such as electronic displays, solar cells, and touch screens.

[0047] In order to further understand the present invention, the preparation method of the conductive glass provided by the present invention is described in detail below with reference to the examples. The protection scope of the present invention is not limited by the following examples.

[0048] Example 1

[0049] Silica sand, feldspar, limestone, dolomite and soda ash are mixed in mass percentages of 67 wt%, 15 wt%, 6 wt%, 10 wt% and 2 wt%, and the mixture is put into a melting furnace and melted at 1600° C. to obtain molten glass;

[0050] 6 mg of carbon nanotubes with a particle size of 2 nm were dispersed in 3 ml of ethanol. The resulting solution was sonicated for 20 minutes, centrifuged at 2000 rpm for 5 minutes, and then sonicated for another 20 minutes to obtain a carbon nanotube solution with a concentration of 2 mg / ml.

[0051] The glass liquid flows into the tin bath and spreads out under the action of its own gravity and surface tension to form a double-sided parallel continuous glass ribbon that moves slowly forward. During this process, the carbon nanotube solution is sprayed on the surface and inside of the glass liquid at a spraying rate of 0.3 mg / cm 2 , spraying speed is 2cm / s, spraying pressure is 60MPa;

[0052] The obtained glass liquid continues to move forward and enters the annealing furnace for annealing treatment, so that the glass ribbon is gradually cooled and solidified to obtain conductive glass;

[0053] The conductive glass obtained above was tested for its conductivity. The results showed that the resistivity of the conductive glass was 20 Ω·m. After long-term use (one month), the resistivity changed by less than 5%, indicating that the conductive glass had stable conductivity. The square resistance of different areas of the conductive glass tested was 20 ohms per square, indicating that the nano-conductive material was evenly distributed in the glass.

[0054] Example 2

[0055] The preparation method is the same as that of Example 1, except that: the conductive solution is prepared by dispersing 6 mg of graphene with a particle size of 3 nm in 3 ml of water. The resulting solution is ultrasonically treated for 16 min, centrifuged at 3000 rpm for 4 min, and ultrasonically treated for another 18 min to obtain a graphene solution with a concentration of 2 mg / ml.

[0056] The conductive glass obtained above was tested for its conductivity. The results showed that the resistivity of the conductive glass was 30 Ω·m, and the resistivity changed by less than 5% after long-term use (one month). The square resistance of different areas of the conductive glass was 30 ohms per square, indicating that the nano-conductive material was evenly distributed in the glass.

[0057] Example 3

[0058] The preparation method is the same as that of Example 1, except that the parameters of the pressurized spraying are as follows: the spraying amount is 0.5 mg / cm 2 , the spraying speed is 6cm / s and the spraying pressure is 70MPa.

[0059] The conductive glass obtained above was tested for its conductivity. The results showed that the resistivity of the conductive glass was 26Ω·m. After long-term use (one month), the square resistance of different areas of the conductive glass tested did not differ by more than 3 ohms per square, indicating that the nano-conductive material was evenly distributed in the glass.

[0060] Comparative Example 1

[0061] The preparation method is the same as that of Example 1, except that the spraying amount is adjusted to 0.1 mg / cm 2 .

[0062] Conductive performance testing of the conductive glass obtained above showed that the resistivity of the conductive glass was 24 Ω·m, and the resistivity changed by 6% after long-term use (one month). The square resistance of different areas of the conductive glass tested varied by 10 ohms per square, indicating that the nano-conductive material was not evenly distributed in the glass.

[0063] Comparative Example 2

[0064] The preparation method is the same as that of Example 1, except that the spraying speed is adjusted to 3 cm / s.

[0065] Conductive performance testing of the conductive glass obtained above showed that the resistivity of the conductive glass was 26 Ω·m, and the resistivity changed by 7% after long-term use (one month). The square resistance of different areas of the conductive glass tested varied by 9 ohms per square, indicating that the nano-conductive material was not evenly distributed in the glass.

[0066] Comparative Example 3

[0067] The preparation method is the same as that of Example 1, except that the spraying pressure is adjusted to 30 MPa.

[0068] Conductive performance testing of the conductive glass obtained above showed that the resistivity of the conductive glass was 34 Ω·m, and the resistivity changed by 20% after long-term use (one month). The square resistance of different areas of the conductive glass tested varied by 21 ohms per square, indicating that the nano-conductive material was not evenly distributed in the glass.

[0069] It can be seen from the above comparative examples that when the parameters of pressurized spraying such as spraying amount, spraying speed or spraying pressure are not within the scope of this application, it will affect the uniform distribution of nano-conductive materials, thereby causing the conductive performance and stability of the conductive glass to decrease.

[0070] The above embodiments are only intended to help understand the method and core concept of the present invention. It should be noted that, without departing from the principles of the present invention, a number of improvements and modifications may be made to the present invention by those skilled in the art, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

[0071] The above description of the disclosed embodiments is intended to enable one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention is not limited to the embodiments shown herein but is intended to conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing conductive glass, comprising the following steps: S1) mixing silica sand, feldspar, limestone, dolomite and soda ash, and melting them at high temperature to obtain glass liquid; mixing the nano-conductive material and the solvent to obtain a conductive solution; S2) forming the glass liquid, and during the forming process, spraying the conductive solution under pressure onto the surface and / or inside of the glass liquid to obtain a conductive glass ribbon; S3) annealing the conductive glass ribbon to obtain conductive glass.

2. The preparation method according to claim 1, characterized in that The conductive glass ribbon is prepared as follows: The glass liquid is placed in a tin bath to obtain a conductive glass ribbon with smooth and parallel surfaces on both sides.

3. The preparation method according to claim 1 or 2, characterized in that In step S1), the nano-conductive material includes one or more of carbon nanotubes, silver nanowires, carbon black, graphene, copper nanowires, black phosphorus and graphyne; And / or, the solvent includes one or more of ethanol, water, ethylene glycol, propanol and methanol.

4. The preparation method according to claim 1 or 2, characterized in that In step S1), the particle size of the nano-conductive material is 1 to 10 nm; And / or, the concentration of the nano-conductive material in the conductive solution is 1-10 mg / ml.

5. The preparation method according to claim 1 or 2, characterized in that In step S1), the preparation method of the conductive solution is specifically as follows: The nano-conductive material and the solvent are subjected to a first ultrasonic treatment, centrifuged and then subjected to a second ultrasonic treatment to obtain a conductive solution.

6. The preparation method according to claim 5, characterized in that The first ultrasonic treatment lasts for 15 to 25 minutes, the centrifugal speed is 2000 to 5000 rpm, the centrifugal time is 2 to 5 minutes, and the second ultrasonic treatment lasts for 15 to 25 minutes.

7. The preparation method according to claim 1 or 2, characterized in that In step S1), based on the total mass of silica sand, feldspar, limestone, dolomite and soda ash, the content of the silica sand is 55-70wt%, the content of the feldspar is 10-18wt%, the content of the limestone is 3-8wt%, the content of the dolomite is 6-12wt%, and the content of the soda ash is 10-25wt%.

8. The preparation method according to claim 1 or 2, characterized in that The temperature of the high-temperature melting is 1500-1800°C, and the temperature of the glass liquid is reduced from 1200-1500°C to 600-800°C during the forming process.

9. The preparation method according to claim 1 or 2, characterized in that: The pressure spraying is 50-100 MPa, the spraying speed is 2-10 cm / s, and the spraying amount is 0.2-1.0 mg / cm 2 .

10. A method for preparing conductive glass, comprising the following steps: S1) mixing silica sand, feldspar, limestone, dolomite and soda ash, and melting them at high temperature to obtain glass liquid; mixing the nano-conductive material and the solvent to obtain a conductive solution; S2) spraying the conductive solution onto the surface and / or interior of the glass liquid under pressure to obtain a conductive glass ribbon; S3) annealing the conductive glass ribbon to obtain conductive glass.

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